Fluid Catalytic
Cracking Process
Process Technology Manual
ORPIC
Sohar, Oman
September 2012
LIMITED DISTRIBUTION
This material is UOP LLC technical information of a confidential nature for use only by personnel within your
organization requiring the information. The material shall not be reproduced in any manner or distributed for any
purpose whatsoever except by written permission of UOP LLC and except as authorized under agreements with
UOP LLC.
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Table of Contents
Page 1
TABLE OF CONTENTS
I.
INTRODUCTION
II.
PROCESS FLOW
Reactor Regenerator
Main Column
Gas Concentration and Recovery
III.
PROCESS CONTROL
Reactor Regenerator
Main Column
Gas Concentration
IV.
EQUIPMENT
Process Equipment and Its Use
Metallurgical Corrosion
V.
FLUIDIZED SOLIDS
Theory
Applications to Fluid Catalytic Cracking
VI.
CATALYST
History
Modern FCC Catalysts
Time and Temperature Effects
Poisons
Catalyst Management
Catalyst Properties and Testing
VII.
PROCESS VARIABLES
Reactor and Regenerator Process Variables
Feedstock
VIII.
PROCESS CALCULATIONS
FCC Flow Corrections and Mass Balance
Liquid Product Cutpoint Corrections
Reactor and Regenerator Heat Balance
FCC Unit Mechanical Summaries
Additional FCC Unit Calculations
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Table of Contents
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IX.
X.
ANALYTICAL METHODS
Minimum Sample Size
Typical Sampling Schedule
Outline of FCCU Laboratory Methods
XI.
PROCEDURES
Refractory Dryout
Startup
Shutdown
Emergencies
Catalyst Handling
FCC Unit Evaluation
XII.
SAFETY
General
Additional Safety Precautions for Entering Vessels
High Temperature Problems
Chemical Hazards
XIII.
ENVIRONMENTAL
Emissions Sources and Solutions
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Introduction
Page 1
Introduction
UOP Company History
For more than 80 years, UOP has been one of the worlds leading licensors of new
and innovative technology. Today, UOP continues in this role with 30 offices on 4
continents and 9 manufacturing facilities worldwide. UOP currently licenses and
designs more than 60 different processes and has a total of 5,500 units licensed
worldwide. For the last 50 years, the fluid catalytic cracking (FCC) process has
been an important and successful part of UOP's licensing activities.
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Introduction
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During this stage, the company benefited immensely by the addition to its research
staff of Prof. Vladimir Ipatieff, a famous Russian scientist known internationally for
his work in high-pressure catalysis. His contributions in catalytic chemistry gave
UOP a position of leadership in the development of catalysis as applied to petroleum processing. The first project of Ipatieff and his research team was catalytic
polymerization. Other eminent scientists were also attracted to UOPs research
center in Riverside during this period.
With the outbreak of World War II, UOP scientists and engineers focused their
knowledge and talents on developing new catalytic processes, notably alkylation
that helped meet wartime energy requirements, especially for aviation fuel. UOP
also cooperated with other companies to develop the FCC process.
In 1944, the owners of UOP divested themselves of their holdings in the company,
and UOPs stock was placed in trust. The American Chemical Society was named
as the beneficiary. Thus, the Petroleum Research Fund was created with the
understanding that income from the trust was to be used for advanced scientific
education and fundamental research in the petroleum field.
In spite of some financial and legal setbacks suffered by UOP during this period,
strong management succeeded in steering the company back to its original course:
taking creative research from concept to commercial reality. UOP was recognized
as a company employing the worlds most knowledgeable scientific and technical
personnel, who understood petroleum refining and the need for improved processing methods and techniques.
In 1949, UOP's research staff developed a radically different refining process that
used a catalyst containing platinum. Called the Platforming process, it revolutionized the art of reforming to produce gasoline with substantially improved octane
number. The process was also instrumental in making benzene available in a
quality and quantity never before realized on a commercial scale. With the
Platforming process and other innovative processes, UOP became a vital
contributor to the emergence and growth of the petrochemical industry.
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Introduction
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In the early 1950s, UOP also began to manufacture its own proprietary catalysts
and a variety of refining chemicals at a newly constructed plant in Shreveport,
Louisiana. Later UOP built manufacturing plants at McCook, Illinois; Brimsdown,
U.K.; and other locations. In 1952, UOP moved its headquarters and engineering
activities to Des Plaines, a suburb of Chicago. Soon after, the construction of a new
research center at the same location was begun.
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Introduction
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Table 1
UOP's History
1914
1915
Name changed to Universal Oil Products Company -patents for Dubbs cracking process issued
1921
1930
Ipatieff joins UOP beginning a wave of new process developments: alkylation, catalytic polymerization, C4 isomerization
1941
1949
Late 1950s
1961
Early 1970s
Hydrocracking introduced
First Sorbex unit licensed
CCR Platforming introduced
1988
UOP merged with the EP&P and CAPS groups of Union Carbide
1995
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Introduction
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In the last 20 years, UOP has developed and commercialized a variety of new and
innovative processes for the refining and petrochemical industry including the
Penex, Molex, BenSat, Oleflex, Ethermax, Merox, Styro-Plus,
Alkylene, Isal, Isomar and Detalprocesses.
UOP transfers this technology to its clients through its licensing activity. In the
technology transfer process, UOP licenses technology; assists in the planning,
design, engineering and commissioning of new installations; provides management
services and advises on the efficient performance of processing facilities throughout
the world.
Behind the successful performance record of UOP is a highly qualified and strong
team continuously at work on ideas and projects. The scientific disciplines are
strongly represented in UOP's team of personnel. UOP has about 4,000 employees
worldwide. With a wide array of highly specialized talents, UOP offers its clients the
complete capability necessary in meeting the demands of today, and the challenges
of the future.
UOP licenses or maintains a position of technical expertise for more than 60 different processes in the petroleum and petrochemical industry. Approximately 175
process units are licensed yearly, and to date UOP has licensed more than 5,500
individual process units and provided technical know-how in designs for more than
1,000 additional non-licensed units. UOP presently holds in excess of 9,000
unexpired patents.
UOP's worldwide licensing activities are supported by a network of offices and
representatives. UOP is centered in Des Plaines, Illinois, and has a district office in
Houston. UOP Limited, a 100% UOP owned subsidiary for operations in Europe,
Africa and the Middle East, has its main European office in Guildford (near London)
and district offices in New Delhi, Jakarta, Jeddah, Beijing and Moscow. UOP Asia
Pacific, located in Tokyo, is an affiliate company of UOP for the licensing of UOP
processes in Japan and certain other areas in the Far East and Southeast Asia.
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Introduction
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UOP has catalyst manufacturing facilities in the United States and in Europe. UOP
Asia Pacific operates a catalyst plant in Japan.
The international scope of UOP activities is evidenced by the fact that process units
have been designed for installation in more than 80 countries around the world.
UOP activities related to these installations have ranged from preparation of
engineering designs for single process units to extensive planning studies involving
market analyses, feasibility and optimization studies, designs for entire grassroots
refineries (both process units and offsites), and complete plant commissioning
services.
The services provided by UOP for these units includes plant design, inspection,
commissioning, performance testing, and training of refinery operating personnel.
Since 1955, UOP has provided, or is providing, engineering designs for more than
125 grassroots refineries and petrochemical complexes. UOP also provided design
specifications for all offsite equipment for many of these installations.
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Introduction
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Table 2
Historical Origins of Fluid Catalytic Cracking
1913 - 1936
Thermal cracking
Burton thermal cracking process (1913)
Dubbs thermal cracking process (1915)
Current use visbreaking, coking
1936 - 1941
1941 - 1955
Thermal Cracking
The first thermal conversion process was the Burton process first practiced
commercially in 1913 by Standard Oil of Indiana. In the original Burton process, oil
was exposed batch-wise to high temperature at elevated pressure to achieve
thermal conversion to lighter products. Because of the batch nature of the Burton
process, commercial units contained a large number of individual cracking stills in
order to achieve acceptable daily throughputs.
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Introduction
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Following the commercialization of the Burton process, the Dubbs thermal cracking
process was developed and patented in 1915 (UOP). The Dubbs process was a
continuous process for the thermal conversion of oil to lighter products at elevated
temperature and pressure. The Dubbs process was widely used in refineries
through the 1920s and into the 1930s.
Thermal cracking processes continue to be used in refining today. Examples of
currently used thermal processes are visbreaking and various forms of coking.
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Introduction
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Introduction
Page 10
back up to the catalyst surge vessel by bucket elevators. Later units employed
pneumatic air lift systems to transfer the regenerated catalyst back up to the surge
vessel.
Socony-Vacuum was the principle developer of the TCC process and the first semi
commercial unit started up at the Paulsboro refinery in 1941. The TCC units were
licensed and operated by Socony-Vacuum and others from 1941 to about 1955
when the TCC gave way to the more versatile FCC process developed in the during
the late 1930s and early 1940s. A few TCC units still continue to operate today.
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Introduction
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Standard-NJ's Baton Rogue refinery in May 1942. Two other Model I FCCs were
designed but were not built as the improved Model II FCC design came very
quickly. When Standard-NJ announced the construction and imminent startup of the
first FCC Model I, they also announced that Universal Oil Products (UOP) and M.
W. Kellogg would be designing and licensing the new FCC technology. In the threeyear period between 1942 and 1945, 34 new FCC units came on stream in the
refineries of 20 different oil companies. The installed capacity of these new FCC
units was over 500,000 BPD. Thirteen of these units were licensed from UOP.
Following the commercialization of the Model I and Model II FCC units within the
CRA partnership, the FCC unit design and development diverged with the partner
companies largely going their separate ways with regard to future FCC technology
development and commercialization.
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Introduction
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silica-alumina catalysts then in use. The availability of the zeolitic catalysts served
as the basis for most of the process innovations that have developed in recent
years.
The continuing sequence of advances in both catalyst activity and process design
culminated in the most significant concept to date in the field of the FCC process
the achievement of transport-phase cracking entirely in the riser, or all-riser cracking. The key to all-riser cracking is the design of a system that initiates a plug-flow
reaction and then stops the cracking reaction at the optimum yield of desired
products. UOP commercialized a new design based on this concept in 1971. This
design was also applied to existing unit revamps. Commercial results confirmed the
expected advantages of the system compared to the older designs. The quick
quench design provided the desired high selectivity to gasoline, reduced coke yield,
and a reduction of secondary cracking of desired products to lighter, less valuable
material.
The next major improvement in the FCC technology was the development of
catalysts and regenerator systems for the complete internal combustion of carbon
monoxide (CO) to carbon dioxide (CO2). In 1973, an existing UOP unit was
revamped to include a new combustor concept in regeneration technology to
achieve direct conversion of CO within the unit. This was followed by the start-up in
1974 of a new FCC unit specifically designed to incorporate the combustor
regenerator technology.
This development in regenerator design and operating technique resulted in
reduced coke yields, lower CO emissions which satisfy environmental standards
and higher circulating catalyst activity that improved product distribution and quality.
Table 3 summarizes some of the major achievements in UOP's FCC process
technology development and commercialization.
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Introduction
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Table 3
Milestones in FCC Technology
1942
1945
1947
1950s
1973
1983
1983
1991 - 1995
1994
1994
2006
Recent Developments
Advances in riser termination devices occurred at a rapid rate in the 1980s to the
mid 1990s. Early riser termination devices such as the open Tee resulted in very
long residence times for the hydrocarbon products in the reactor vessel. This
extended residence time resulted in nonselective thermal cracking and secondary
catalytic cracking reactions. Recent improvements have resulted in better containment of the hydrocarbon vapor to the riser and therefore lower post riser residence
time. This reduced delta coke and dry gas and improved gasoline selectivity. Early
versions of these high containment riser terminations included the vented riser and
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Introduction
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SCSS (suspended catalyst solids separation) devices. In 1991, the first VDS
(vortex disengager stripper) was commissioned. This technology further minimized
the post-riser residence time resulting in further improvements in product yields. In
1995, the first VSS (vortex separation system) was commissioned.
Improvements in feed distribution systems also occurred rapidly in the late 1980s
and 1990s. Elevated, radially oriented feed distributors minimize nonselective
thermal cracking reactions by providing more uniform feed/catalyst contacting with
less back mixing than the earlier wye feed distributors. Acceleration zone
technology which pre-accelerates the catalyst into a uniform, moderate density flow
pattern for optimum oil penetration and uniform catalyst/oil contacting further
improved the performance of the elevated feed distributors. The first UOP elevated
feed distributors were commissioned in 1983. Developments in spray nozzle
technology resulted in the Optimix feed distributor which has a smaller, more
uniform oil droplet size and a spray pattern that distributes the oil uniformly over the
entire riser area for superior catalyst/oil contacting and performance. The first
Optimix feed distributor was commissioned in 1994. Since then, the number of
refiners using Optimix feed distributors has grown to over 80.
Resid processing in FCC units began in the mid-1970s. During this same period,
reactor temperatures were being increased to maximize gasoline octane. The need
for higher conversion, combined with the desire to process residue feeds significantly increased coke yields and ultimately limited the FCC regenerator capacity.
The RCC, or Reduced Crude Conversion, process was developed jointly by UOP
and Ashland Oil in the late 1970s to address residue processing. It is an extension
of UOP's FCC design experience that incorporates many innovations and modifications from the UOP-Ashland Oil development program. In addition to cold-flow
modeling work, a large-scale pilot plant was constructed at Ashland's Catlettsburg,
Kentucky refinery. Testing in this 200 BPSD plant examined processing variables
and new mechanical designs on a wide range of residual feedstocks. In 1983,
Ashland commissioned a 40,000 BPSD RCC unit at the Catlettsburg refinery.
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Introduction
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Several major innovations from the pilot plant testing and first commercial design at
Ashland have become the foundation of UOP's technical offering for catalytic
cracking of residue feedstocks, including the following.
Acceleration zone and feed distribution system
Higher containment riser termination devices for quick disengagement
Two-stage catalyst regeneration
Catalyst cooler
Since 1983, eight grass-root RCC units licensed by UOP have been commissioned.
In addition, resid feedstocks are being processed in more than 30 existing UOP
FCC units. In present times, the distinction between a gasoil FCC unit and a resid
FCC unit has blurred to the point where most modern FCC units are capable of
processing some level of resid. The term RFCC is used by UOP today to designate
a new unit utilizing a 2 stage regenerator designed for the specific intent of
processing resid feeds. Table 4 shows a brief summary of resid processing and
UOP's activity in the area of resid processing.
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Introduction
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Table 4
Resid Processing Milestones
1940s
1950s
1975
1976
1983
1984 - 2006
Commercial Experience
Since commercialization of the FCC process, UOP has licensed more than 210
units, or over 50% of all non-captive installations. More than 140 of these units
continue to operate throughout the world. The superior technology and operational
reliability built into UOP FCC units are some of the reasons why 58 refineries
worldwide have licensed new UOP FCC units since 1980, which is more than all
other licensors combined during this period. UOP's commercial activity in the
FCC/RCC/MSCC processes since 1980 is as follows:
63
40
330
180
30+
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Introduction
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process. The ability to continuously circulate fluidized catalyst between the reactor
and the regenerator allows the FCC unit to operate efficiently as a continuous
process.
The FCC units are large-scale processes and unit throughputs are typically in the
range of about 10,000 to 130,000 barrels per day. This corresponds to catalyst
circulation rates of around 7 to 130 tons per minute. The largest commercial FCC
unit in operation was designed at 130,000 BPSD, pushed to ~184,000 BPSD, and
in 2005 was revamped to a nominal 200,000 BPSD with a catalyst circulation rate in
excess of 170 metric tons per minute. These large circulation rates of hot, abrasive
catalyst constitute a very significant challenge to the mechanical integrity of the
reactor, the regenerator and their associated internal equipment. Thus, mechanical
design considerations are critical to the ultimate success of an FCC unit as a
prominent refinery process unit. The main features of an FCC unit are:
Catalytic process
Mechanical process
Cracks heavy molecules to lighter ones
Pressure: 15-45 psig (1-3 kg/cm2g)
Temperature:
Reactor:
915-1050F (490-565C)
Regenerator: 1200-1450F (650-790C)
Reaction and regeneration sections intimately
linked by heat balance and catalyst circulation
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Introduction
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In addition, the FCC units commonly process heavy fractions from other conversion
units as part of the combined FCC feed blend. Examples of these types of streams
are coker gasoil and hydrocracker fractionator bottoms. The types of heavy hydrocarbon streams that are commonly charged to an FCC unit are:
Atmospheric gasoil
Vacuum gasoil
Atmospheric resid
Coker gasoil
Demetallized oil
Hydroprocessed gasoil
Hydroprocessed resid
Lube oil extracts
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FCC Products
The products obtained from the FCC unit are light hydrocarbon gases (C2-) which
are normally used within the refinery as fuel gas, light olefins and paraffins (C3s
and C4s) also referred to as LPG, gasoline, LCO and clarified oil commonly
referred to as main column bottoms. In addition, flue gas is generated from the
burning of coke in the regenerator. Heat is recovered from the flue gas and is used
to make steam and in some cases power is also recovered from the flue gas in the
form of electricity via a power recovery expander coupled to a motor/generator.
Products produced from an FCC unit are:
Light gas
Light olefins
LPG
Light paraffins
Gasoline
Light cycle oil
Main Column Bottoms
Coke (burned in unit as fuel)
Most of the FCC product streams undergo further processing before leaving the
refinery as marketable products. Figure 2 shows typical routes for the FCC product
steams going to further processing and ultimately to blending into the refinery
product pools.
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Figure 2
Typical Use of FCC Products
Flue Gas
Reactor
&
Regen.
C3/C4
Paraffins
Fuel Gas
Alkylation
LPG
Merox
Gasoline Gasoline
Merox
LCO
CLO
Alkylate
Gasoline
Pool
C3/C4
Splitter
Main
Column
&
Gas Con
LPG Pool
MTBE
Distillate
Hydrotreater
Diesel
Pool
Heavy Fuel
Oil Pool
The light liquid products from the FCC process are LPG and gasoline. The LPG
from an FCC unit is highly olefinic and has become an increasingly valuable stream
for further processing in the present movement toward reformulated gasoline and
as petrochemical unit feedstocks. The FCC olefins are an important feedstock for
the production of MTBE and alkylate as gasoline blending components and for the
production of polypropylene. The FCC gasoline generally has good octane properties (90-95 RON and 80-83 MON) and may make up 30 vol-% or more of the
refinery gasoline pool. Some typical characteristics of light FCC products from highconversion operations (VGO Feed, 1.0 wt% sulfur) are:
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Introduction
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LPG:
500 - 1500 wppm total sulfur
30 - 40 vol-% C3 olefins
34 - 45 vol-% total C4 olefins
The heavy liquid products from an FCC unit are normally LCO and clarified oil. The
LCO product is normally used as a blending component in the diesel pool and/or in
the heavy fuel oil pool. It is becoming increasingly common for LCO destined for
diesel blending to be hydrotreated first for sulfur reduction. Clarified oil is usually
blended off to the heavy fuel oil pool. In some cases, the FCC unit clarified oil is
used in coker feed, for asphalt production or sold as feed for carbon black production. Some characteristics of heavy FCC products from high conversion operations
(VGO Feed, 1.0 wt% sulfur) are:
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Introduction
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ACFM
activity
adjusted
afterburning
AGO
atmospheric gasoil
Al
aluminum
Al2O3
alumina
APS
AR
ash
as produced
ASTM
behind in burning
BPD
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Introduction
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BS & W
C1, C2
C3=
olefin (propylene)
caustic
sodium hydroxide
CCR
CFR
CN-
cyanide ion
CO2/CO
cold regenerator
conversion
COS
carbonyl sulfide
CRC
CSO
Cu
copper
DA, DS, DG
P, DP
dry gas
EP
F-1
F-2
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Introduction
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Fe
iron
Fines
Fm
Gasoline efficiency
GC, GLC
Gb
Gf
gpm
H2/C1
H2S
hydrogen sulfide
HC
hydrocarbon
HCN
HCO
HPS
IBP
K (UOP K)
lb/Bbl (#/Bbl)
LCO
LV-%
MC
main column
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Introduction
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MCB
MON
MW
molecular weight
N (or N2)
nitrogen
Na
sodium
NH3
ammonia
Ni
nickel
NOx
nitrogen oxides
O (or O2)
oxygen
ppm
Pf
recycle
RE (or Re2O3)
Rg
regenerator
RON
RSH
mercaptan sulfur
RVP
Rx
reactor
SA
surface area
SCF/Bbl (SCFB)
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SCFD
selectivity
severity
Si
silicon
Si2O3
silica
sintering
SOX
sulfur oxides
spillback
SS
Tf
vanadium
VGO
vacuum gasoil
vol-%
volume percent
wt-%
weight percent
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Introduction
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Analysis Recorder
ARC
DR
FA
Flow Alarm
FE
FFRC
Fl
Flow Indicator
FIC
FIF
FQI
FR
Flow Recorder
FRA
FRC
FRCF
FRCQI
FRQI
FRQIA
HC
Hand Control
II
Current Indicator
LA
Level Alarm
LC
Level Controller
LG-B
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LG-R
LG-RLT
LG-T
LG-TK
LG-TLT
Ll
Level Indicator
LIA
LIC
LR
Level Recorder
LRA
LRC
PA
Pressure Alarm
PC
Pressure Controller
PDC
PDI
PDIC
PDR
PDRA
PDRC
PDRCA
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PI
Pressure Indicator
PIA
PIC
PR
Pressure Recorder
PRA
PRC
SI
Speed Indicator
SR
Speed Recorder
TA
Temperature Alarm
TC
Temperature Controller
TDR
TDRA
TDRC
TI
Temperature Indicator
TIC
TIX
TR
Temperature Recorder
TRA
TRC
TRX
TW
Thermowell
Zl
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Introduction
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Indicates High
HH
Indicates Low
LL
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Process Flow
Page 1
PROCESS FLOW
INTRODUCTION
The modern Fluid Catalytic Cracking unit is a large and complex process for
cracking heavy gas oil to lighter hydrocarbons. FCC has largely replaced the old
thermal crackers because it is a more efficient process, i.e. more production of
valuable products at a lower overall cost by using catalyst and heat instead of
simply heat.
In its simplest form, the process consists of a reactor, a catalyst regenerator, and
product separation. This is shown in Figure 1. Catalyst circulation is continuous, at
very large mass flow rates. For this reason, the reactor and regenerator are usually
discussed as one section. The product separation is usually divided into its low and
high pressure components, i.e. the main column section, and the gas concentration
and recovery section.
Figure 1:
Fluid Catalytic Cracking Process
Flue Gas
Regenerator
Air
Catalyst
Transfer
Lines
Products
Reactor
Raw Oil
Product
Separation
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Process Flow
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Reactor-Regenerator
This is the heart of the process, where the heavy feed is cracked. The reaction
products range from oil which is heavier than the charge to a light fuel gas. The
catalyst is continuously regenerated by burning off the coke deposited during the
cracking reaction. This provides a large measure of the heat required for the
process.
Main Column
The main column cools the reactor vapors and begins the separation process. A
heavy naphtha fraction and light and heavy fuel oils (LCO and CLO) come off the
tower as products; gasoline and lighter materials leave the top of the tower together
and are cooled and separated further into product streams in the gas concentration
section.
Raw
Oil
Catalyst
Section
MCB
HCO
Steam
Light
Naphtha
Fuel
Gas
Flue
Gas
FCC-PF002
LPG
Flue Gas
Cooler
BFW
Heavy
Naphtha
LCO
Main Column
Section
Power Recovery
Section
Figure 2
FCC Block Flow Diagram
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Process Flow
Page 3
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Process Flow
Page 4
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Process Flow
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Figure 3:
Model I FCC
Cottrell
Precipitator
Flue Gas
Catalyst
Fines
Products to
Main Column
Cyclones
Hoppers
Air or
Steam
Steam
Standpipes
Regenerator
Reactor
Steam
Regenerator
Riser
Water
Catalyst
Recycle
Cooler
Raw Oil
Charge
Reactor
Riser
Fired
Heater
FCC-PF003
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Figure 4
Down-flow Model II Catalytic Cracking Unit
Flue
Gas
Cottrell
Precipitator
Waste
Heat
Boiler
Multicyclones
Regenerator
Products to
Main Column
Reactor
Steam to
Stripping
Section
Raw Oil
Charge
MCB
Recycle
Air
FCC-PF004
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Process Flow
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Figure 5
UOP Stacked Fluid Catalytic Cracking Unit
To Main Column
Cyclone
Flue Gas
Reactor
Orific
Chamber
Spent Catalyst
Stripper
Flue Gas
Slide Valve
Stripping
Steam
Regenerator
Spent Catalyst
Slide Valve
Regenerated Catalyst
Slide Valve
Air
Slurry Recycle
Raw Oil
Charge
HCO Recycle
FCC-PF005
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Process Flow
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The next advance in reactor-regenerator design was the Side-by-Side unit, shown
in Figure 6. This design was better for larger units, where stacking the reactor on
top of the regenerator became more expensive. The Side-by-Side layout has also
been used for many of the new small units. The straight riser showed less erosion
than the curved riser of the Stacked unit. Some of the Side-by-Side units were
designed with a reactor dense bed. This bed was eliminated with the advent of
zeolite cracking catalysts, and the riser was extended within the reactor to minimize
thermal and catalytic cracking by reducing vapor residence time in the vessel.
Initially, cyclones were installed on the riser to separate the oil and catalyst, but this
was not particularly successful due to poor cyclone performance. The riser cyclones
were replaced by a "Tee" shaped termination at the top of the riser. The riser
cyclone could then be moved over to allow room for the addition of another cyclone
at the reactor outlet, providing two stages of cyclone separation. Later advances in
riser termination devices concentrated on maximizing hydrocarbon containment or
minimizing the post-riser residence time in the reactor shell where non-selective,
thermal and secondary cracking reactions occur. Side-by-Side units have won
good acceptance by the industry and over 75 UOP designed Side-by-Side FCC
units have been built.
Zeolite cracking catalysts were developed in 1963 and gradually accepted by the
industry over the next ten years. These catalysts proved to be much more active
than amorphous catalysts and were ideally suited for the short contact time riser
cracker. Conversion levels rose as high as 80% without requiring excessive reactor
temperature.
Another significant improvement in FCC reactor technology was the use of elevated
feed distributors. The older wye feed distributors injected the raw oil charge into a
highly back-mixed catalyst flow that resulted in non-uniform oil/catalyst mixing and
excessive light gas and coke formation. In newer systems, multiple, radially oriented
feed distributors elevated in the riser inject raw oil more uniformly to maximize
selectivity to desired products.
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Process Flow
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New regenerator designs were also developed over the years. The old perforated
plate air distributor was changed to a pipe grid for better air distribution. Two stage
cyclones replaced single stage cyclones and reduced catalyst losses.
The burning of coke in the old regenerators was not complete, i.e., not all the
carbon went to CO2, and the flue gas normally contained 6-10 vol-% CO. The unit
ran with no excess oxygen. This prevented afterburning in the cyclones and the
resultant heat damage to the cyclones. An extra furnace to generate steam, the CO
boiler, was added to utilize heat that would otherwise be lost. All of the excess CO
in the flue gas could be burned in the CO boiler, but capital costs were high. The
obvious solution to this problem was to burn all of the CO to CO2 in the regenerator,
where the catalyst can absorb the heat.
Although this could be done in a standard bubbling bed regenerator, a new, high
efficiency type regenerator design proved more efficient. In the high efficiency or
combustor style regenerator, shown in Figure 7, the air and catalyst is mixed in a
fast fluidized environment in the lower part of the regenerator or combustor. The
fluidized catalyst is then carried up the combustor riser to the upper regenerator.
The fluidization in the combustor provides excellent air/catalyst mixing and heat
transfer to maximize coke burning kinetics. The high efficiency regenerators on
stream average less than 100 ppm CO, and less than 40 ppm NOx in the flue gas.
This design enables refineries to get greater thermal efficiency from the unit while
simultaneously meeting more stringent air quality standards.
157048
Process Flow
Page 10
Figure 6
UOP Side by Side Fluid Catalytic Cracking Unit
Rxn Products to
Main Column
Reactor
Down-Turned
Arm
Flue
Gas
Flue Gas
Slide Valve
Stripping
Steam
Bubbling Bed
Regenerator
Spent
Catalys
Slide Valve
Main
Distributo
Air
Regenerated
Catalys
Slide Valve
Wy
Section
Raw
Oil Feed
157048
Process Flow
Page 11
Figure 7
Modern UOP Side by Side Fluid Catalytic Cracking Unit
With High Efficiency Regenerator, Elevated Feed Distributors and
Vortex Separation System Riser Termination
157048
Process Flow
Page 12
The process flow of the reactor and regenerator section of a typical, modern FCC
unit with a high efficiency regenerator can be described as follows:
Lift steam and/or light hydrocarbon is injected at the base of the riser or Wye to
accelerate the catalyst from towards the elevated feed distributors, which are
located about 1/3 the way up the riser. The preheated raw oil charge is pumped
through the feed distributors and atomized with the addition of steam then injected
into the regenerated catalyst stream. The heat from the catalyst and reduced
hydrocarbon partial pressure in the riser both act to help vaporizes the oil. The
catalyst, oil and steam travel up the riser to a region of lower pressure in the reactor
where the cracked hydrocarbon products are separated from the catalyst in the riser
termination device and cyclones before going to the main column for initial product
separation.
During the cracking reaction, a carbonaceous by-product called coke is deposited
on the circulating catalyst. This catalyst (referred to as spent catalyst) drops from
the reactor disengager and cyclones into the stripping section where a
countercurrent flow of steam is used to remove both interstitial and some adsorbed
hydrocarbon vapors. The stripped catalyst flows from the reactor stripper through
the spent catalyst standpipe to the regenerator, where the coke is continuously
burned off. The catalyst flow through the spent catalyst standpipe is controlled to
balance the circulating catalyst flow by maintaining a constant catalyst level in the
reactor.
In the regenerator, the spent catalyst mixes with air and hot regenerated catalyst
from the recirculation catalyst standpipe at the base of the combustor. Here the
coke deposited during in the reactor is burned off to reactivate the catalyst and
provide heat for the net endothermic cracking reactions. The heat of combustion
raises the catalyst temperature in the regenerator to a range of 1200F-1375F
(648C-746C). The catalyst and air flow up the combustor riser and separate at a
"Tee" shaped head. The flue gas is further "cleaned" of catalyst in the cyclones in
the upper regenerator. The recirculation catalyst standpipe returns some of the hot
regenerated catalyst to the combustor either on temperature or density control to
provide heat for initiation of the carbon burn. The remainder or the regenerated
157048
Process Flow
Page 13
157048
Process Flow
Page 14
the catalyst. A portion of the partially regenerated catalyst entering the lower or
second stage regenerator flows through the catalyst cooler(s) where heat is
removed from the catalyst to generate steam. The cooled catalyst and the
remainder of the hot catalyst from the first stage regenerator mix in the second
stage regenerator where the coke burning is completed under conditions of
complete CO combustion in the presence of excess O2. Carbon is burned off the
catalyst to low levels in the second stage regenerator at moderate temperature to
maximize catalyst activity. The combustion gases from the second stage
regenerator pass into the first stage regenerator where the pre-heated excess O2
improves coke burn kinetics, and is completely consumed. The combined flue gas
exits through two stages of cyclones in the first stage regenerator and out through a
single common flue gas line. The overall mode of combustion for the two stage
regenerator is partial burn with the additional benefit that all of the catalyst returning
to the reactor is fully regenerated due to the full burn environment of the second
stage regenerator.
Figure 8 shows the arrangement of the regenerator of an RFCC unit. The reactor is
the same as the modern Side by Side unit shown in Figure 7.
Figure 9 shows the process flow for a catalyst cooler. Although catalyst coolers are
not a new idea for FCC service, past attempts to employ catalyst coolers on FCCs
have been largely unsuccessful from both mechanical and process points of view.
UOPs catalyst cooler represents an improved design developed and refined to
provide both mechanical reliability and a wide range of heat removal flexibility. Heat
removal varies with the rate of fluidization air injected to the cooler and the catalyst
slide valve opening.
The operation of the catalyst cooler is as follows; catalyst enters the cooler shell
where the tube bundle is immersed in hot fluidized catalyst. Fluidization air is
injected at the bottom of the cooler shell to control the fluidization and heat transfer.
Annular bayonet type water tubes are used in the tube bundle. Water entering the
bundle flows up through the inner tube, flows out the top of the inner tube and down
through the annular space between the inner and outer tubes where heat transfer
occurs and water is vaporized to steam. In flow-through style coolers cooled
catalyst exits the cooler shell through a standpipe and slide valve and is returned to
157048
Process Flow
Page 15
the regenerator to allow hot catalyst to enter the top of the cooler to maximize the
cooler duty. Back-mix type coolers rely only on fluidization and back-mixing to
transfer hot catalyst from the regenerator rather than using catalyst flow through a
standpipe. Back-mix coolers have a simpler mechanical configuration but can only
remove approximately 70% of the heat transfer capable through a flow-through
cooler.
A large excess of water is circulated through the tubes where heat transfer
generates steam to ensure that the tube walls are always wet and cooled. The
steam and water mixture returns from the cooler bundle to a steam drum where the
steam and water are separated. Water from the drum is circulated back to the
cooler and the saturated steam from the steam drum is routed to the refinery steam
system.
157048
Process Flow
Page 16
Figure 8
UOP RFCC Regenerator Process Flow
Flue Gas
Spent Catalyst
from Reactor
1st Stage
Regenerator
Vent Tubes
Catalyst
Cooler
First
Stage Air
2nd Stage
Regenerator
Water/
Steam
Water
Recirculation
Catalyst
Standpipe
Regenerated
Catalyst to
Reactor
Second Stage
Air
157048
Process Flow
Page 17
Figure 9
UOP FCC Catalyst Cooler Process Flow
Water and
Steam
Saturated
Steam to
Superheater
Fluffing
Air
Makeup
BFW
Blowdown
Cooled Catalyst
Slide Vlave
Circulating
Water
FCC-PF009
157048
Process Flow
Page 18
Main Column
The main column is the first step in the separation and recovery of the cracked
hydrocarbon vapors from the FCC reactor. The reaction products enter the column
at high temperatures, 900-1022F (480-550C). The main column is similar to a
crude tower, with two important differences: 1) The vapors must be cooled before
fractionation can begin, and 2) a large quantity of lighter gas passes overhead with
the gasoline. Figure 10 shows the general process flow for an FCC main column.
Large quantities of heavy oil are circulated over a series of disc and doughnut trays
to cool the vapors and wash down entrained catalyst. The heat removed by the
main column bottoms and the heavy cycle oil is used for feed preheat, steam
generation, reboiler heat in the rest of the unit, or some combination of the three.
The catalyst washed out of the reactor is concentrated in the main column bottoms
stream.
Most of the bottoms flow is directed through exchangers for heat removal and
returned to the disc and doughnut trays. The return line must be free draining to
avoid plugging problems with catalyst fines settling in low points. Some of the
cooled bottoms material from the steam generators may be returned directly to the
bottom of the tower as quench to reduce the temperature of the liquid and minimize
coking and fouling in the bottoms system. Figure 11 shows a typical process flow
for the main column bottoms pumparound and product circuit.
Many older units used a slurry settler to separate and return catalyst fines to the
reactor with a slurry stream off the bottom of the settler. The main column bottoms
product comes off the top of the settler and is normally called clarified slurry oil. In
reactors with two stages of cyclones and in units with modern riser termination
devices, the use of slurry settlers has normally been discontinued. Heavy bottoms
product comes directly from the main column bottoms circulating stream, as does
any slurry recycle to the reactor.
157048
Process Flow
Page 19
Figure 10
UOP FCC Main Column
To Wet Gas
Compressor
CW
To Sour
Water
To Primary
Absorber
1
5
6
Gas
Concentration
Unit
FI
7
19
21
FI
22
Equalizing
Line to/from
Feed Drum
Steam
26
27
29
30
Heavy
Naphtha
Product
Gas
Concentration
Unit
Steam
32
Light Cycle
Oil Product
33
Flushing Oil
34
35
Gas
Concentration
Unit
36
Flushing Oil
37
Torch Oil
38
Reactor
Vapors
Steam
BFW
Main Column
Bottoms Product
CW
Raw Oil to
Reactor
157048
Process Flow
Page 20
Figure 11
UOP FCC Main Column Bottoms Process Flow
6
Minimum
Spillback
E
FRC
Main Column
Rx
Overhead
MCB
Product
Pumps
Tempered
Water
Quench
Steam
Steam
Main Column
Bottoms Circulation
Pumps
MCB
Product
MCB
Steam
Generators
Water
Raw
Oil
Water
Circulating
Bottoms/
Raw Oil
Exchanger
Raw
Oil
Net
Bottoms/
Raw Oil
Exchanger
157048
Process Flow
Page 21
As previously mentioned, most FCC units with modern riser terminations and
reactor cyclones do not require the use of a slurry settler and new units currently
being designed do not include settlers. If a refiner has strict specifications on the
ash content of the main column bottoms product, then more advanced alternate
fines removal equipment is usually employed to reduce the catalyst fines to very low
levels. The two most common types of catalyst removal equipment used today are
the micromesh filter and the electrostatic separator. Cyclonic separation devices
have also been used, but are typically limited to smaller capacity installations.
A typical micromesh filter system will have 2 or 3 vessels with up to 100 filter
elements in each. When multiple filtration vessels are used, each filtration vessel is
sized for 100% of the design flow rate. One vessel is typically in filtration mode
while another is in backflush mode to remove the filter cake from the elements.
When enough catalyst fines have deposited on the filter elements to increase the
pressure drop across the filter to a pre set limit, the vessel is taken off line for back
flushing. Once the filter vessel is off line and drained the vessel is filled with
backflush liquid, either HCO or LCO, and allowed to soak to help dissolve any
heavy aromatic compounds on the elements. The top of the vessel is then
pressured up with either fuel gas or nitrogen to provide the driving force for a high
velocity back flush. The back flush material is collected in a receiver vessel and
pumped back to the reactor riser. A typical process flow for the micromesh filtration
system is shown in Figure 12.
A typical electrostatic slurry oil filtration unit consists of 4-16 skid mounted
cylindrical shells (modules) depending on the volume of filtrate to be process. Each
module contains a high voltage cylindrical electrode surrounded by conductive glass
beads, with a ground rod located in the center of the module assembly. During the
separation cycle, the glass beads are ionized in an electrostatic field. As catalyst
particles flow between the beads, they are electrostatically collected on the surface
of the beads. Each module is sequentially back-flushed while the remaining
modules in the system continue the separation. In the backflush cycle, the electrode
is de-energized and the beads are fluidized, resulting in a circulating motion up
through the center of a 9-inch annular electrode and down the outside. The
circulation up the center annulus and down the walls of the module creates a
scrubbing action, to mechanically scrub the beads clean. Mechanically scrubbing
157048
Process Flow
Page 22
the beads as opposed to solvent soaking as with the micro-mesh filters, raw oil
feed, or any compatible oil can be used as the backflush medium to an electrostatic
filter. The back flush material is directed back to the reactor riser.
Figure 12
Main Column Bottoms Product Filtration System
Backwash Gas
(N2 or Fuel Gas)
Clean MCB
Product to
Storage
Filter
#1
Filter
#2
Filter
#3
N2 or Fuel Gas
Vent
Back Flush
Liquid
(LCO/HCO)
MCB
Product
Receiver
Vessel
Catalyst
Backwash
to Reactor
157048
Process Flow
Page 23
There are typically three side-cuts withdrawn from the main column, heavy cycle oil
(HCO), light cycle oil (LCO), and heavy naphtha (HCN). The refiner may withdraw
all three, only two or one, depending on product needs and tower design. On
relatively rare occasions, the main column is designed with a fourth side-cut to
discretely fractionate a heavy LCO cut and a light LCO cut. The side-cut streams
that go out as product are usually stripped to meet flash-point specifications.
Pumparound loops from these side-draws are used to heat balance the main
column by exchanging heat with the gas concentration unit reboilers, the raw oil
charge or boiler feed water. The heat removed in the bottom and side pumparounds determines the amount of reflux in each section of the tower and must be
properly balanced for proper column operation. Gasoline and light gases pass up
through the main column and leave as vapors. After being cooled and condensed,
unstabilized gasoline is pumped back to the top of the column as reflux to control
the top temperature in the column. Figures 13, 14, 15 and 16 show typical process
flows for the HCO pumparound, the LCO pumparound, the Heavy Naphtha
pumparound and the Main Column Overhead system, respectively.
157048
Process Flow
Page 24
Figure 13
Main Column HCO Pumparound
Main Column
LIC
HCO Internal
Reflux
(Pumped)
To MCB/Feed
Exchanger Outlet
(for startup)
Filling Line
(from feed pump)
To Feed
Surge Drum
(normally no flow)
To Pump
Flushing Oil
Supply Header
157048
Process Flow
Page 25
Figure 14
Main Column LCO Pumparound and Product
FI
FIC
LIC
Steam
FIC
LCO
Product
BFW
CW
Preheater
FIC
LCO to
Flushing Oil
Debutanizer Feed
Exchanger
FIC
Stripper
Reboiler
Rich Oil from
Sponge Absorber
Lean Oil to
Sponge Absorber
FCC-PC403
157048
Process Flow
Page 26
Figure 15
Main Column Heavy Naphtha Pumparound and Product
Main Column
C3/C4 Splitter
Reboiler
Circulating Naphtha/
Debutanizer Feed
Exchanger
Steam
E
FRC
Heavy
Naphtha
Stripper
LCO
Stripper
Reflux
(Gravity Flow)
LIC
Heavy Naphtha
Circulation
Pumps
Heavy Naphtha
Product Pumps
Heavy Naphtha
Product Cooler
HeavyNaphtha
to and from
NHT Unit
Signal from HCN
Hydrotreater
CW
FRC
E
Hydrotreated
Heavy Naphtha
Product
157048
Process Flow
Page 27
Figure 16
FCC/DS-R00-37
157048
Process Flow
Page 28
The raw oil feed system is included in the main column section for better process
efficiency, i.e. to take advantage of the heat from the main column. Feed enters the
unit from storage or directly from upstream processes, such as a vacuum tower or a
hydrotreater. The latter scheme is more efficient because the feed will not have to
be cooled before storage and then reheated flowing into the FCC. The number and
type of exchangers used will depend on cost and process factors that will vary with
each refinery.
Most newer units do not use fired charge heaters. Fired charge heaters have
become unpopular due to the increases in fuel costs, operational safety and impact
on overall refinery stack emissions. The feed goes directly to the riser after the raw
oil/main column bottoms exchanger. Figures 17 and 18 show typical process flow
schemes for the FCC feed preheat system without a fired charge heater and with a
fired charge heater, respectively.
Figure 17
Feed Preheat
Equalizing
Line To/From
Main Column
To
Reactor
LCO
Product
MCB
Product
Circ.
MCB
MCB
Recycle
HCO
Recycle
FCC-PF401
157048
Process Flow
Page 29
Figure 18
Feed Preheat with Fired Heater
Equalizing Line
To/From Main
Column
Fired
Heater
Raw Oil from
Storage/
Upstream Unit
MCB
Product
To
Reactor
Circ.
MCB
Fuel
Gas
FCC-PF401
157048
Process Flow
Page 30
D
HPR
IR
PA
SA
S
WGC
HPR
Wash Water to MC
OVHD Receiver
IR
Debutanizer
High Pressure Receiver
Interstage Receiver
Primary Absorber
Sponge Absorber
Stripper
Wet Gas Compressor
Legend:
Wash
Water
WGC
Gas from
MC Overhead
Receiver
Gasoline from
MC Overhead
Receiver
40
P
A
Rich Lean
Oil Oil
S
A
36
Figure 19:
40
Stabilized
FCC Gasoline
HCO
LPG
Fuel
Gas
157048
Process Flow
Page 31
Main
Column
Hydrocarbon
Water
Condensate
To Sour Water
Stripper
WGC
1st Stage
Main Column
Receiver
Interstage
Drum
Figure 20:
WGC
2nd Stage
High Pressure
Receiver
157048
Process Flow
Page 32
157048
Process Control
Page 1
PROCESS CONTROL
Reactor-Regenerator Control Systems
Most of the control systems in a Fluid Catalytic Cracking unit are similar to those used
elsewhere in the refinery.
Good control of the catalyst circulation through the reactor and regenerator is critical for
stable operation. The catalyst circulation control scheme is shown in Figure 1. This
figure shows a side by side unit with a bubbling bed regenerator but the catalyst
circulation control between the reactor and regenerator is the same on all FCC and
RFCC units.
The circulation of hot regenerated catalyst from the regenerator to the reactor is
controlled to maintain a constant reactor temperature with the regenerated catalyst slide
valve. The circulation of spent catalyst from the reactor to the regenerator is controlled
to maintain a constant catalyst level in the reactor with the spent catalyst slide valve.
The controls on both the spent catalyst and regenerated catalyst slide valves also
include a low differential pressure override. If the differential pressure across either slide
valve drops to a very low or negative value the override will close the slide valve. This
minimizes the possibility of reverse flow in the standpipes, either air entering the reactor
or hydrocarbon entering the regenerator, which are hazardous situations.
Figure 1 shows signals from the reactor temperature controller and level controllers
going to low level selectors (LSS). The low signal selectors also receive signals from the
differential pressure controllers on the corresponding slide valve. If the differential
pressure across the slide valve is greater than the override setpoint, typically 2 psi (0.14
kg/cm2) the LSS will select the process variable (level or temperature) to control the
slide valve. If the slide valve pressure drop falls below the override setpoint the LSS will
send that output to the slide valve which will start closing. The low differential pressure
override controllers should always be in automatic.
157048
Process Control
Page 2
Figure 1
Catalyst Circulation Controls
Products to
Main
Column
TIC
PDIC
Reactor
Riser
Termination
Device
HSS
>
LIC
Flue
Gas
PIC
Regenerator
LSS
LI
<
PDIC
XI
(Density)
Spent
Catalyst
Slide Valve
LSS
<
PDIC
Raw
Oil
Air
Regenerated
Catalyst Slide
Valve
Lift Gas/
Steam
FCC-PC001
157048
Process Control
Page 3
For steady control of the catalyst circulation between the reactor and regenerator the
differential pressure across the slide valves must be constant. To ensure steady slidy
valve DPs the differential pressure between the reactor and regenerator is controlled
with the double disc flue gas slide valves on the outlet of the regenerator. In addition to
the slide valves an orifice chamber is also used to take approximately 2/3 of the total
flue gas system pressure drop to minimize erosion in the flue gas slide valves.
A typical flue gas system without power recovery is shown in Figure 2. The reactor
pressure is not controlled directly and floats on the main column overhead pressure.
The reactor-regenerator differential pressure controller allows the regenerator pressure
to change along with the reactor pressure. Pressure control for units with power
recovery is discussed later.
Figure 2
Regenerator Pressure Control/
Flue Gas System
HSS
>
PIC
PDIC
Signal from
Reactor
Pressure Tap
Flue Gas
Flue Gas
Slide Valves
Orifice
Chamber
Steam
CO Boiler
Air
Air
Electrostatic
Precipitator
Water
FCC-PC002
157048
Process Control
Page 4
157048
Process Control
Page 5
Figure 3
Reactor Control and Instrumentation
PDI
TIC
LIC
LIC
SWITCH
LI (Density
Compensated)
XI
(Density)
XI
(Density)
Prestripping
Steam
PDIC
< LSS
Stripping
Steam
MPS
Fluffing
Steam
Spent
Catalyst
LSS
PDIC
Regenerated
Catalyst
<
Atomizing
Steam
For Feed/Steam
controls see Figure 4
Raw Oil
FIC
Lift Gas
FIC
Lift Steam
MPS
FIC
Start-up/Emergency
Steam
FCC-PC003
157048
Process Control
Page 6
The feed bypass system is also shown in Figure 4. When a situation requiring a quick
shutdown is encountered, a control board mounted switch is activated which trips a
solenoid valve controlling the pneumatic signals to the feed bypass valves, causing
these valves to move to their failure positions, i.e. the valve in the line to the riser closes
and the valve in the bypass line to the main column opens. Normally, the next course of
action is to open the emergency steam to the riser to either maintain catalyst circulation
if the regenerated catalyst slide valve remains open or to clear the riser of catalyst if the
regenerated catalyst slide valve is closed.
On units with elevated feed distributors, another important operating variable affecting
the yield pattern is the lift zone velocity. The lift zone velocity is a function of the lift
steam and/or lift gas flow rates which are controlled on straight flow control. As the lift
zone velocity is increased the catalyst density at the point of the feed injection
decreases allowing better penetration of the atomized oil droplets into the catalyst. The
optimum lift zone velocity is typically in the range of 10 15 ft/sec (3 4.5 m/sec).
Either lift gas, lift steam or a combination of both may be used to achieve the optimum
lift zone velocity.
Stripping steam flows are also controlled on straight flow control. The optimal total
stripping steam rate is typically 1.7 2.5 lb/M-lb catalyst circulation but this can vary
significantly with depending on the unit design. The stripping steam rate should be
changed when any process conditions are changed that result in a significant change in
the catalyst circulation rate. The stripping steam rate should also be tested occasionally
to ensure that the optimum steam rate is used.
157048
Process Control
Page 7
Figure 4
Feed/Atomizing Steam Control
FI
FI
FI
To other
nozzles
PI
Steam
FO
Local PI must be
readable from valve
PI
Local FI must
be readable
from valve
FI
FI
To other
nozzles
Local FI must
be readable
from valve
To other
nozzles
NORMALLY
NO FLOW
HEADER
PURGE
HS
Feed Bypass
Switch
S
Instrument
Air
FO
Vent
FC
FCC-PC004
157048
Process Control
Page 8
157048
Process Control
Page 9
The air rate to the regenerator is controlled either to maintain a minimum of excess
oxygen in the flue gas (typically 2%) for full combustion operation or to control the
CO2/CO ratio and therefore the heat of combustion and regenerator temperatures in
partial combustion operation.
High Efficiency Regenerator
The instrumentation and controls for a FCC unit with a high efficiency, combustor style
regenerator is shown in Figure 5.
The pressure, regenerated catalyst temperature and combustion air rate for the high
efficiency regenerator are the same as the bubbling bed regenerator described above.
The difference between the high efficiency regenerator and a conventional "bubbling
bed " regenerator is that the regenerator is divided into two sections. The lower section
is called the combustor and is where the spent catalyst and air mix and coke
combustion occurs. The combustor operates in the fast fluidized regime of fluidization.
All the catalyst entering the combustor is transported up the combustor riser into the
upper regenerator where the regenerated catalyst disengages from the flue gas. The
upper regenerator holds the cyclones, provides volume for the regenerated catalyst to
disengage from the flue gas and provides the surge capacity for catalyst in the system.
An important feature of the high efficiency regenerator is the recirculating catalyst
standpipe and slide valve. The recirculation of hot regenerated catalyst from the upper
regenerator to the combustor is important in controlling the coke combustion rate. By
controlling the amount of catalyst recirculated, the following parameters are controlled in
the combustor: the pre-combustion mixing temperature, the catalyst density, catalyst
flux and catalyst residence time. This, in turn, allows the coke combustion rate and
catalyst regeneration to be optimized. The recirculating catalyst slide valve is controlled
through a low signal selector and a slide valve PDIC, similarly to the other slide valves.
On early designs, this slide valve position was set on hand control. In current designs,
the recirculation slide valve position is controlled by a temperature or density controller
located in the upper section of the combustor. A switch is used to select the input signal
to the recirculation slide valve low signal selector.
157048
Process Control
Page 10
Figure 5
High Efficiency Regenerator Controls and
Instrumentation
>
TI's
(1 Each Cyclone)
PIC
PDIC
Signal from
Reactor Pressure
Tap
LI
XI
(Density)
Recirculating
Catalyst Slide
Valve
FIC
Fluffing Air
Regenerated
Catalyst to Reactor
PDIC
TIC
LSS
XIC
(Density)
Spent Catalyst
from Reactor
<
SWITCH
FCC-PC005
157048
Process Control
Page 11
In a high efficiency regenerator the dense bed catalyst level in the upper regenerator
provides the surge volume for the unit and is not controlled directly except by catalyst
additions and withdrawals.
A small flow of fluffing air to the upper regenerator on straight flow control is required to
ensure proper fluidization and flow into the regenerated and recirculation catalyst
standpipes.
157048
Process Control
Page 12
the CO2/CO ratio in the flue gas and therefore the heat of combustion is also used to
adjust the temperature of the regenerated catalyst.
Figure 6
RFCC Regenerator Controls and Instrumentation
LI
Spent Catalyst
from Reactor
XI
Side View
Vent Tubes
PDIC
PDIC
LIC
First
Stage Air
LSS
LSS
<
<
TIC
Recirculation
Catalyst
Standpipe
Cooled
Catalyst
Standpipe
Regenerated
Catalyst to
Reactor
Second
Stage Air
Second
Stage Air
FCC-PF006
157048
Process Control
Page 13
157048
Process Control
Page 14
Figure 7
Main Air Blower Control
Vent to
Atmosphere
Silencer
Snort
Valve
Low Flow
Shutdown
FO
FIC
(Temp, Pressure Corrected)
Instrument
Air
XIC
(Anti-Surge)
Steam
Vent
ST
SIC
Suction
Filter
Housing
T
TT PT
Air
Cylinder FT
TT PT
TT PT
FT
Air to
Regenerator
Special Check
Valve
FCC-PC007
Figure 8
RFCC Main Air Blower Control
(Anti Surge and Special Check Valve Details Not Shown)
Vent to
Atmosphere
Silencer
TT PT
ZIC
ZT
To First Stage
Regenerator
XIC
(Anti-Surge)
Steam
Suction
Filter
Housing
FO
Special Check
Valves
T
TT PT
ZT
To Second Stage
Regenerator
Stator Vanes
FCC-PC008
157048
Process Control
Page 15
The check valve in the air blower discharge line isolates the blower from the regenerator
if the blower trips. This minimizes the possibility of hot catalyst backing up into the
blower and minimizes the volume of air in the piping if surging occurs. The closing
action is assisted by a spring loaded air cylinder, which operates when the air flow falls
below a certain limit. When the flow drops below the low limit a solenoid valve deenergizers and vents the air from the cylinder allowing the spring to move a cam which
bumps the check valve to assist it in closing. An air line from the catalyst hoppers or
plant air is used to provide plant air to clear catalyst from the discharge line if the blower
is down. It can also be used to supply warm blower air to the catalyst hoppers.
157048
Process Control
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selector (HSS). The high signal selector directs the appropriate control signal (normally
the PDIC) to set the positions of the expander inlet and bypass butterfly valves via a
split range signal. The expander turbine is discussed further in the section covering
Equipment.
Modern power recovery controls, while controlling in the same manner, are more
complicated than discussed here. Power recovery controls and anti-surge controllers
are provided by specialized vendors. The additional functions performed by these
controllers are beyond the scope of this manual.
On units with power recovery, a steam turbine may be used for startup of the air blower.
The turbine can also provide auxiliary power if necessary. The motor/generator imports
or exports power to maintain a constant speed on the power recovery train. If more
energy is being supplied to the expander and the turbine than is required by the blower
there will be surplus electricity generated and exported. If the blower needs more power
than the expander is providing then electricity will be consumed to hold the train at
normal speed.
The flue gas leaving the regenerator flows through a series of small cyclonic devices in
the third stage separator for catalyst fines removal to minimize erosion in the expander.
The underflow catalyst stream from the third stage separator, carried by a small gas
flow, bypasses the expander and typically leaves the system with the main flue gas
stream downstream of the expander turbine. The underflow from the bottom of the
separator is controlled by a restriction orifice called the critical flow nozzle.
A flue gas quench system is also included on units with power recovery. If the flue gas
temperature exceeds the design temperature of the expander a flow of cooling steam is
started to the regenerator plenum through a split range controller. If the steam fails to
cool the flue gas sufficiently a flow of cooling water, typically BFW, is started to the
plenum. Most power recovery vendors also include an emergency steam quench at the
inlet of the expander for additional protection.
157048
Process Control
Page 17
Figure 9
Power Recovery Controls
Quench Connection See Detail Below
TIC
>
PIC
HSS
Split
Range
Flue
Gas
Orifice
Chamber
PDIC
Butterfly
Valves
Third
Stage
Separator
Flue Gas
Cooler
Critical
Flow
Orifice
Motor/
Air Blower
Generator
M
Electrostatic
Precipitator
Steam
T
Steam
Turbine
Expander
Air
TIC
Split
Range
LPS
Atomizing
Steam
FC
Purge
Steam
FI
BFW
Signal From
Regenerator
Temperature
Transmitter
To Other
Nozzles
FC
RO
Concentric
Sleeve Purge
Stuffing
Box
Plenum
Shell
Retracta
ble Tip
FCC-PC009
157048
Process Control
Page 18
157048
Process Control
Page 19
effectively causes the cooler to shutdown by closing the cooled catalyst slide valve and
closing the fluidization air control valve.
The mixture of steam and water exiting the cooler tube bundle flows to the steam drum
where the steam and water are separated. The saturated steam flow from the drum is
metered and flows out to the refinery steam system. Normally the saturated steam
leaving the steam drum is superheated in some type of downstream steam superheater.
The water returned to the steam drum is recirculated back to the cooler tube bundle. A
small continuous blowdown flow of water is removed from the drum to control
accumulation of impurities in the circulating water. The outputs of the steam product
flow meter and the steam drum level indicator are summed and control the flow of boiler
feed water (BFW) makeup entering the steam drum.
157048
Process Control
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Figure 10
Catalyst Cooler Controls
Steam and
Water
Steam
Low Low
Level (2/3
Voting)
LG
LT
FI
LI
PI
VENT
FIC
LT
TI
DE
PG
STEAM
SEPARATOR
Air
LIC
LT
TI
FI
Intermittent
Blowdown
Continuous
Blowdown
Low/Low
Low Flow
(2/3 Voting)
FIC
FI
Low Flow
Pump Auto
Start
FT
Makeup
BFW
VENT
S
DE
To Motor
Control
Circuit
To Motor
Control
Circuit
Steam
FO
FCC-PC010
I
Interlock System
157048
Process Control
Page 21
157048
Process Control
Page 22
157048
Process Control
Page 23
Figure 11
Torch Oil Control
Atomizing
Steam
PI
FC
Steam
Annular Sleeve
Purge Steam
STRAINERS
Split Range
(Steam Valve
Opens First)
Manifold
Purge Steam
FI MUST BE
READABLE
FROM CONTROL
VALVE
PI
RO
FI
FC
FIC
Regenerator
Shell and
Lining
PI MUST BE
READABLE FROM
CONTROL VALVE
Stuffing Box
Instrument
Air
FC
VENT
DE
Emergency Interlock
Unit Shutdown Logic
From Raw
Oil Pumps
From HCO
Oil Pumps
FCC-PC011
157048
Process Control
Page 24
Figure 12
Direct Fired Air Heater Control
To
Regenerator
Air
Ignitor
Start
Flame
Sensor
High Temperature
Shutdown
I
PDI Must Be
Readable
From Damper
TIC
Damper
Ignitor
Sight
Port
Burner
Pilot/
Ignitor
Sight
Port
Pilot Gas
PI
Sight Port
(sighting
flame)
PI
Sight Port
(sighting
opp. wall
PI
Pressure
Control
Valve
PI
PI
PIC
S
S
VENT
DE
FC
INSTRUMENT
AIR
Fuel
Gas
FCC-PC012
157048
Process Control
Page 25
157048
Process Control
Page 26
Figure 13
Catalyst Addition Control
Fresh Catalsyt
Hopper
INSTRUMENT
AIR
VENT
FC
Instrument
Air
Plant Air
Vent
Plant Air
FC
RO
Volume
Pot
RO
Instrument
Air
Plant Air
Vent
FC
FI
FI
Plant Air
To Regenerator
FCC-PC013
157048
Process Control
Page 27
157048
Process Control
Page 28
Figure 14
Main Column Overview
Wash Water
WGC Spillback
OVHD Vapor
to WGC
CW
HCN from
Gas Con
Sour Water
LCO from
Gas Con
Steam
HCN
Product
HCO from
Gas Con
Steam
LCO to
Flushing Oil
LCO
Product
HCN to
Gas Con
LCO to
Gas Con
HCO to
Gas Con
Reactor
Product
Vapor
Steam
Raw Oil to
Reactor
BFW
MCB
Product
FCC-PC400
157048
Process Control
Page 29
157048
Process Control
Page 30
Figure 15
Main Column Bottoms and HCO Flow and Control
FIC
FIC
LIC
HCN Stripper
Reboiler
Debutanizer
Reboiler
Torch Oil
Pump Flushing Oil
MCB
Quench
FIC
Reactor
Product
Vapor
Steam
FI
FIC
LIC
Raw
FIC
BFW
FIC
FIC
MCB
Product
CW
Raw
FCC-PC401
157048
Process Control
Page 31
During normal operations the heat input from the circulating main column bottoms to
reboilers and preheat exchangers will be set by product and process considerations.
This is true of the heat removed in the other pump around loops as well. Heat input to
the steam generators is generally the only variable available to the operator for
adjustment of the column heat balance and reflux rates. Increasing the bottoms flow
through the steam generators will cause more heat to be removed. This will reduce the
amount of hot vapor traffic up the column and eventually will reduce the overhead reflux
rate and the heat removed in the overhead system.
Each exchanger in the main column bottoms pumparound circuit is designed for oil
containing catalyst particles. Main column bottoms flows through the exchanger on the
tube side and the velocity should be kept between 3.75 ft/s and 7.0 ft/s (1.14 m/s and
2.13 m/s) for straight tubes and between 3.75 ft/s and 5.75 ft/s (1.14 m/s and 1.75 m/s)
for U-tubes. Below the minimum velocity, catalyst can accumulate on the tube walls
and slowly plug the tube while greatly reducing heat transfer. If the velocity is above 7
ft/s (2.13 m/s), there is a risk of erosion on the tube walls. If the circulating MCB is very
low in ash content (<0.15 wt-%) the risk of erosion is greatly reduced. The rates
required to meet these velocities must be calculated for each exchanger before startup.
Bottoms product is withdrawn on straight flow control adjusted manually by the operator
to maintain a steady bottoms level in the main column. The product is cooled, typically
in cooling water exchangers before being sent to tank. In many cases the bottoms
product is also exchanged with the raw oil.
Removal of catalyst fines from the bottoms product by filtration, settlers or hydroclones
is an option which may be included depending on the end use of the bottoms product. If
a slurry settler is used to reduce catalyst fines in the bottoms product, the settler inlet
flow is drawn upstream of any bottoms product coolers. Hot main column bottoms
enters the settler tangentially and the swirling motion imparted distributes the heavy oil
evenly as it moves up to the outlet. Settler superficial velocity is limited to 30 BPD/ft2
(50 m3/d/m2) or less in the settler so that the fines can settle to the bottom of the
vessel. Clarified oil product (CLO) leaves from the top of the settler. Diluent (cooled
main column bottoms, raw oil or HCO) is added at the bottom of the settler to carry the
157048
Process Control
Page 32
fines back to the riser. The diluent addition rate is always equal to or slightly less than
the slurry flow to the riser and the settler feed rate is normally equal to or greater than
the clarified product from the from the top of the settler so that net flow is downward
carrying the settled fines out of the settler. Figure 16 shows the slurry settler flow and
control. Slurry settlers are not as common today because of the improvement in reactor
riser terminations and cyclones.
Filtration of the slurry product is becoming more common either to produce carbon
black feed stock (which typically requires less than 100 wppm solids), to minimize
downstream problems in fired heaters or to minimize tank cleaning cost. Figure 17
shows a typical flow and control for a bottoms filtration unit.
Figure 16
Slurry Settler Flow and Control
FIC
Clarified
Slurry Oil
Product
PSV
FIC
Return to
Main Column
Main Column
Bottoms
Slurry
Settler
FI
FIC
Diluent
(HCO or
Raw Oil)
FIC
Sewer
Slurry
to Riser
FCC-PC402
157048
Process Control
Page 33
Figure 17
Main Column Bottoms Filter Flow and Control
PIC
Backwash Gas
(N2 or Fuel Gas)
FIC
Clean
MCB
Product to
Storage
Bypass
(normally
closed)
PDI LS
LS
Filter
#1
PDI
PDI LS
Filter
#2
Filter
#3
Split
Range
N2 or Fuel Gas
PIC
Solvent Fluid
(LCO/HCO)
Vent
Receiver
Vessel
MCB
Product
LIC
FIC
FI
FIC
Catalyst
Backwash
to
Reactor
157048
Process Control
Page 34
157048
Process Control
Page 35
157048
Process Control
Page 36
Figure 18
LCO Flow and Control
FI
FIC
LIC
Steam
FIC
LCO
Product
BFW
CW
Preheater
FIC
LCO to
Flushing Oil
Debutanizer Feed
Exchanger
FIC
Stripper
Reboiler
Rich Oil fromSponge
Absorber
Lean Oil to Sponge
Absorber
FCC-PC403
157048
Process Control
Page 37
Figure 19
HCN Flow and Control
FI
FIC
LIC
HCO FIC
HCN
Product
CW
FIC
C3/C4 Splitter
Reboiler
FCC-PC404
157048
Process Control
Page 38
157048
Process Control
Page 39
set at 0.3-0.5 psi (0.02-0.035 kg/cm2) above the setpoint for the primary pressure
controller will open venting some of the gas to flare or a low pressure fuel gas system.
This control system allows the unit to continue operating during a short duration
compressor failure and is useful during startup before sufficient gas is produced in the
reactor to run the compressor.
Figure 20
Main Column Overhead Flow and Control
Wet Gas
Compressor First
Stage Spillback
Signal to Wet
Gas Compressor
Controls
Cooling
Water
FC
PSV
Wash
Water
PRC
PIC
To Flare
Header
To Wet Gas
Compressor
Suction Drum
LIC
TIC
LIC
FIC
FIC
Net Overhead
Liquid to High
Pressure
Receiver
FI
Sour
Water
FCC-PC405
157048
Process Control
Page 40
Normal flow - at lower charge rates, the main column overhead receiver signal
will control the first stage spillback to hold receiver pressure constant. The
second stage spillback will be controlled by the anti-surge controller to satisfy the
minimum flow requirements of the surge curve. The turbine will be running at
minimum governor speed. As the charge rate is increased, there is a greater net
flow of gas, so the two spillbacks are gradually closed by the controllers. When
the spillbacks reach the fully closed position, the output signal from the overhead
receiver pressure controller will be high enough to begin increasing the
compressor speed. The speed will then be continuously varied to remove the gas
from the main column and hold the pressure constant. Throughout this, the flow
controllers will have no effect as long as there is sufficient gas flow to keep the
machine out of surge.
157048
Process Control
Page 41
2.
Abnormally low flow - there would be two main reasons for low gas flow. The first
would be insufficient gas from the main column, such as when the feed was
suddenly cut out. The second reason would be an abnormally high second stage
discharge pressure, caused by problems in the gas concentration unit. Whatever
the cause, when the flow falls below the point set by the operator on the FRC,
the output signal falls, which would then be transmitted by the low signal selector.
This opens the spillback valves to recycle gas back to the suction, allowing the
gas to be moved through the machine in sufficient quantities to keep it out of a
surge condition. When normal conditions are restored, the flow controller output
will rise, and the low signal selector will return the spillbacks to pressure control.
If the low flow is caused by high pressure in the gas concentration unit, opening
the first stage spillback will overpressure the main column. This condition will
open the overpressure control valve to flare, holding the receiver pressure at the
overpressure set point.
3.
Abnormally high flow - the main cause for very high flow rates would be operating
the FCC unit in such a fashion that the compressor could not handle the gas
flow. The machine would be at maximum governor speed with both spillbacks
closed. Pressure in the main column would rise, opening the overpressure
control valve to flare.
Modern anti-surge and pressure control systems take advantage of faster transmitters
and computer technology to allow monitoring of multiple variables and rapid calculation
of corrected flow rates to allow more efficient operation closer to the surge line with less
spillback. These inputs to the anti-surge controllers are shown in Figure 21.
157048
Process Control
Page 42
Figure 21
Wet Gas Compressor Control
Signal
from Main
Column
Overhead
PRC
From
Main
Column
Overhead
Receiver
FI
FI
Antisurge
Controller
Antisurge
Controller
To High
Pressure
Receiver
Antisurge
Signal Opens
Control Valve
TT
Nirogen
Purge
Nirogen
Purge
FO
FO
Steam
TT
TT
TI
SI
SC
PT
PT
PT
Antisurge
Signal Opens
Control
Valve
TT
PT
Speed
Sensor
First Stage
Spillback to
Main Coulumn
Overhead
To Surface
Condenser
First
Stage
Second
Stage
FCC-PC407
157048
Process Control
Page 43
157048
Process Control
Page 44
157048
Process Control
Page 45
Figure 22
Wash Water Control
Main Column
OVHD Vapors
FI
CW
Main Column
OVHD Rec.
CW
Liquid from
Primary Absorber
Vapor from
Stripper
To Primary
Absorber
Sour
Water
High Pressure
Receiver
M
First
Stage
Second
Stage
LIC
To Stripper
To Primary
Absorber
LIC
FIC
Condensate
Water Break
Drum
FCC-PC409
157048
Process Control
Page 46
157048
Process Control
Page 47
Figure 23
Feed Preheat System
Equalizing
Line To/From
Main Column
FIC
LIC
FIC
High Temperature
Closes Control
Valve
Split
Range
TIC
To
Reactor
FIC LSS
<
Split
Range
FIC
LCO
MCB
Product Product
Low Temperature
Closes Control
Valve
Circ.
MCB
MCB
Recycle
HCO
Recycle
FCC-PC411
157048
Process Control
Page 48
Figure 24
Feed Preheat with Fired Heater
Equalizing Line
To/From Main
Column
LIC
FIC
TIC
TIC
Fired
Heater
MCB
Product
To
Reactor
Circ.
MCB
Fuel
Gas
FCC-PC410
157048
Process Control
Page 49
157048
Process Control
Page 50
Figure 25
Gas Concentration Unit Flow
Lift Gas to
Reactor
Lean Gas
KO Drum
Unstabilized
Gasoline from
Main Column
OVHD
Wet Gas
Compressor
Discharge
Sponge
Gas to
Treating
CW
CW
Primary
Absorber
Sponge
Absorber
Rich Oil
to Main
Column
CW
High Pressure
Receiver
Stripper
Wash Water to
Main Column
OVHD Receiver
LCO from
Main
Column
Wash Water
from Interstage
Receiver
LPG to
Treating
Debutanizer
Circ.
HCO
Stabilized Gasoline to
Treating
CW
FCC-PC703
157048
Process Control
Page 51
157048
Process Control
Page 52
controller sets the pressure for the knockout drum, the sponge absorber, the primary
absorber, the high pressure receiver and the stripper column. The pressure of each
vessel depends upon the pressure drop between the vessel and the lean gas knockout
drum.
Figure 26
Gas Concentration Unit Absorber Section
Lift Gas to
Reactor
Lean Gas
KO Drum
Unstabilized
Gasoline from
Main Column
OVHD
Wet Gas
Compressor
Discharge
Sponge
Gas to
Treating
CW
CW
Primary
Absorber
Sponge
Absorber
Rich Oil
to Main
Column
CW
High Pressure
Receiver
Stripper
Wash Water to
Main Column
OVHD Receiver
LCO from
Main
Column
Wash Water
from Interstage
Receiver
LPG to
Treating
Debutanizer
Circ.
HCO
Stabilized Gasoline to
Treating
CW
FCC-PC703
157048
Process Control
Page 53
157048
Process Control
Page 54
Heat to the debutanizer reboiler is typically supplied by circulating HCO. The flow of
HCO is adjusted by the operator to adjust the reflux rate in the column and the quality of
fractionation. The temperature controller is adjusted to control the RVP (Reid Vapor
Pressure) of the gasoline. Stabilized gasoline flows from the column bottom to supply
heat to the stripper reboiler and then to the stripper feed exchanger. Gasoline from the
stripper feed exchanger can be split into two streams. Recycle gasoline is cooled and
pumped to the primary absorber on flow control. Net debutanizer bottoms (i.e., gasoline)
is cooled and pumped to the treating unit. The net gasoline flow controller is reset by the
debutanizer bottoms level controller to maintain the column bottom level.
157048
Process Control
Page 55
Figure 27
Gas Concentration Unit Fractionation Section
PIC
Vapor
to HPR
Debutanizer
LIC
FIC
Stripper
PDIC
TIC
18
19
LPG to
Treating
19
20
Circulating
LCO To/
From Main
Column
36
35
36
TIC
FIC
40
FIC
LIC
Circulating
HCO To/From
Main Column
Liquid
from
HPR
Split
Range
FI
FIC
Stabilized Gasoline
to Primary
Absorber
CW
FIC
Stabilized
Gasoline to
Treating
FCC-PC700
157048-1
Equipment
Page 1
EQUIPMENT
INTRODUCTION
The Fluid Catalytic Cracking unit is exposed to severe temperature, erosion and
corrosion effects. The equipment has been designed to withstand these conditions
for an acceptable mechanical life, but the life can be drastically shortened by abuse
or poor operations. Proper control and operation will avoid the unnecessary
problems which lead to premature failure.
The FCC unit should be inspected every turnaround. The inspection can be done by
a UOP inspector, the refinery inspection department, or both. Adequate record
keeping of these inspections is necessary to develop the unit history which will aid
the refiner to judge equipment life, determine potential problems and evaluate the
effect of different metallurgy and process conditions related to the equipment.
A good inspection will include the following:
1)
2)
3)
4)
Erosion and corrosion are not always obvious. A thorough inspection of the
equipment will reveal the extent of any damage and help determine the cause and
effect relationship. Also, because no equipment lasts forever, the inspection will
help the refiner determine when equipment must be replaced so advance orders
can be made.
157048-1
Equipment
Page 2
Minor repair work can prevent small problems from expanding to larger problems. It
is difficult to predict the amount of minor work which will be required. The desired
length of the next run will determine the extent of the repairs.
157048-1
Equipment
Page 3
be removed as necessary by water washing the equipment. Do not allow any water
in the wet gas compressor. Normal refinery safety practices should be followed for
toxic vapors, explosivity, oxygen content of vessels, etc. The refinery safety
engineer should follow the turnaround carefully.
AIR BLOWER
The main blower of an FCC unit supplies large quantities of air to the regenerator.
Advances in rotating machinery technology have led to the replacement of the old
positive displacement reciprocating air compressor with centrifugal and axial
machines. Blowers can be driven by steam or gas turbines, electric motors, or flue
gas turbines, usually referred to as power recovery expanders. Depending on the
mode of operation and other factors such as feed quality, the FCC unit needs 1014.5 pounds of air per pound of coke, which is approximately 2000-3000 SCF/bbl
(330-500 Nm3air/m3FF). Air is filtered through a screened suction housing that
should be designed for noise abatement. Compressed air leaves the blower at
about 300-450F (150-230C) and 30-60 psia (2.1-4.2 kg/cm2(a)).
CENTRIFUGAL MACHINE
Air flow rates on a centrifugal machine are controlled by varying the speed of
rotation, throttling the suction, or venting off excess air. Four to six stages are
common, with labyrinth seals used to prevent leakage between stages. These
machines normally use forced lubrication systems for the bearings and may be
equipped with temperature and vibration probes for early detection of mechanical
problems.
157048-1
Equipment
Page 4
AXIAL MACHINE
An axial blower, shown in Figure 1, uses rotating blades to move the air. The air
flows through the machine in a straight line, each successive stage adding pressure
energy much like a propeller blade. The air flow rate is most often controlled by
varying the shaft speed. This can be accomplished either through a turbine driver,
or by including a Variable Speed Drive (VSD) unit on a motor. If the machine is
designed for constant speed, other means of flow control must be provided. One
option is to snort (vent) excess air to atmosphere. However, for normal control this
would require power to compress air that is vented back to atmosphere, and is
simply not energy efficient. Practical options include the use of small variable pitch
blades known as stators on the blower housing. The variable pitch stators redirect
the air flow into the path of the rotating elements. When this redirection is at a
steeper angle, more air is transferred. These machines use forced lubrication
systems and are normally equipped with temperature and vibration probes.
Another option to control air flow from a fixed speed blower is to include a suction
throttle valve. This mode of operation is very common in older machines, but as
with a snort valve, it is not an energy efficient system. The suction throttle valves
on motor driven air blowers can be eliminated through the installation of a VSD unit
onto the motor.
Axial compressors are generally more efficient at larger capacities than centrifugal
machines. They are smaller and lighter than an equivalent size centrifugal unit.
Choice of machine depends on the individual refiner, but axial blowers are more
common for larger units.
Specific operation of these large machines is too complex to describe in this
manual. Individual manufacturer's instructions should be followed for each unit.
157048-1
Equipment
Page 5
Figure 1
Axial Compressor
BLOWER PROBLEMS
The problems encountered with an FCC blower can be divided into two groups;
operational and mechanical. Examples of mechanical problems are vibration, shaft
displacement and noise. These may result from manufacturing defects, construction
mistakes such as misalignment of the driver and blower, and routine wear of the
bearings. In most cases, however, mechanical problems are caused by operational
difficulties. An example is surge, which occurs when the air blower is not able to
produce enough head to overcome downstream resistance. A centrifugal
compressor curve, shown in Figure 2, gives a typical head-flow relationship, while
Figure 3 shows a curve for an axial machine.
At a fixed speed the compressor will follow the curve. Flow decreases with
increasing head, similar to a pump. Unlike a pump, however, the characteristic
curve begins to turn down toward the zero capacity region after reaching a peak in
157048-1
Equipment
Page 6
pressure. This peak is called the stability limit or surge point. The machine will thus
produce less head at the decreased capacity. The pressure downstream of the
machine is higher and the flow reverses through the blower. When the downstream
pressure is relieved, normal flow is restored. Resistance quickly builds again and
the machine surges. The condition can be recognized by a characteristic cycling
sound and a rapid rising and falling of the flow between normal and zero. When the
gas moves back into the machine, the rotor tends to stall, which can cause serious
damage as the machine is subjected to large unusual forces and increased gas
temperature across each surge cycle. Surge cycles can result in damage to the
thrust or axial bearings and labyrinth seals. In severe cases the rotor itself may
crack or rub against the casing. On an axial blower the blades may break.
To prevent this backflow condition, many blowers are fitted with an anti-surge
controller. The controller essentially compares pressure rise and flow against a
programmed operating map of the blower. The operating map includes a calibrated
surge line. As the machine approaches the surge line a blow-off valve, commonly
referred to as a snort valve, is opened slowly. Opening the snort increases flow
through the machine and prevents surging. Surge is generally considered more
dangerous to axial blowers than to centrifugal, but should be avoided for either.
Choke, or stonewalling, is a low pressure, high flow condition where the gas velocity
approaches the speed of sound. Dangerous vibrations result and can cause the
rotor to crack. This condition may also be seen on the characteristic curve at low
head. The line becomes almost vertical as the capacity increases and air velocity
approaches the sonic value. This condition is infrequent but care must be taken to
avoid it. Choke is more of a problem for axial than centrifugal machines. Rotating
stall is a somewhat rare phenomenon, indicated by an inability to build pressure
while the flow is more or less normal. It results when air moves around the axial
rotor, rather than through it. The best cure is to back down to starting conditions and
restart increasing the flow again.
The air blower suction line should be inspected for cleanliness. The suction hood or
housing should be cleaned. Except for vibration from the blower, this section of the
plant is not subject to any unusual stresses, and normally lasts for many years.
157048-1
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Inspection and maintenance on the blower and associated systems should follow
the manufacturer's recommendations. Replacement of the bearings, seals,
lubricating oil, etc. is required at certain intervals. The air filters on the suction
housing should be inspected during normal turnarounds and replaced or repaired
as required.
Performance (capacity) of the blower can diminish over time due to fouling of the
blades. Foulants may include dust and chemical contaminants drawn into the
machine through the filter housing. Episodes of blade fouling have been associated
with sudden and heavy rains, washing contaminants off of the suction filters and
into the blower. Performance decline of up to 10% of rated flow have been
associated with blade fouling. Most vendors offer a surfactant or solvent injection
system that can be added to the suction line of the machine to help remove blade
foulants from the blower.
The air blower discharge line is not subject to corrosion or metal loss. All air snort
valves should be checked by the instrument department; few problems are ever
encountered with the air snort valves.
In the event of an emergency trip, many modern machines require that they be
rotated while cooling down. If this procedure is not followed when required, serious
rotor deflection can result. Excessive rotor deflection can result in serious
mechanical damage to the compressor, requiring a major overhaul of the machine.
157048-1
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Figure 2
Centrifugal Air Blower Performance Curve
Figure 3
Axial Air Blower Performance Curve
157048-1
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POWER RECOVERY
The power consumed by the air blower is a significant part of an FCC unit's
operating expense. Utility costs continue to rise, only partially offset by more
efficient motors and turbines. Recovery of the energy in the hot flue gas from the
regenerator can increase the overall efficiency of the unit. This was first done with
steam generation systems. The flue gas exchanges heat with a circulating water
stream. A 30,000 BPD (195 m3/hr) FCCU without a CO boiler can produce 40-70 Mlb/hr (18-32 t/hr) of 600 psig (42 kg/cm2) steam. Heat recovery in this scheme is
somewhat limited by a minimum allowable flue gas temperature. Sulfur oxides and
water vapor in the stack gas can cause corrosion of the equipment if they condense
in the flue gas duct. The temperature at which the condensation occurs is known
as the acid gas condensation point, which shifts depending on the concentration
and distribution between the different oxides. The acid gas condensation point is
typically in the range of 400-600F (200-315C), although it may be higher for some
units. The maximum temperature limit of the flue gas is typically a function of
metallurgical design limits for downstream equipment, which may include an
electro-static precipitator, flue gas scrubber, and/or stack.
The major disadvantage of a straight steam generation energy recovery scheme is
that no power is recovered from gas pressure, normally 10-40 psi (0.7-2.81 kg/cm2)
above atmospheric pressure at the regenerator outlet. Another approach to
recovering energy from the flue gas was tried in 1950. This was a turbo expander,
driven directly by hot flue gas. Initial results were unsatisfactory; after only 750
hours of operation catalyst fines in the flue gas had substantially eroded away the
turbine blades and casing. The fines problem was solved by placing an additional
catalyst separator, known as a Third Stage Separator (TSS) outside of the
regenerator.
In the TSS, flue gas moves through a large number of small cyclone assemblies in
which the catalyst is centrifugally separated from the flowing gas stream. To
remove the separated catalyst fines from the TSS, a small amount of gas, typically
3% of the regenerator flue gas, is used to pneumatically sweep the catalyst fines
157048-1
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out the bottom of the vessel. The clean flue gas is then directed to the inlet of the
power recovery expander.
UOP has been designing power recovery systems since 1973. Between 1973 and
2004, UOP licensed 33 TSSs with 22 placed into operation. The original units were
designed by UOP under license from Shell. Over the years, UOP improved upon
the original design by implementing several modifications. Even with these
modifications incorporated into the base design, very little had actually changed in
the overall design of the TSS in 25 years. These TSS designs still suffered from the
limitations imposed by radial flow gas distribution and reverse flow in the cyclone
elements.
In 1996, UOP launched a development program to design and offer a smaller, more
economic, high efficiency TSS that could not only be utilized in power recovery
installations, but also be a viable alternative to electrostatic precipitators and wet
gas scrubbers for environmental applications.
The cold flow modeling (CFM) test program extended over 2 years, during which
both dimensional variables and process flow variables were studied. Based on a
thorough understanding of cyclone theory, and drawing on other sources of cyclone
expertise, the UOP program investigated the contribution of many variables on
catalyst separation efficiency. These variables included:
Over 200 individual tests were conducted on single and multiple cyclone models to
determine the highest efficiency and highest capacity design cyclone. The tests
were conducted with commercial FCC catalyst fines. Computational fluid dynamic
(CFD) computer modeling was used to validate and benchmark the CFM work, and
to quickly investigate potential improvements and guide the physical modeling
program.
157048-1
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The development work culminated in the new UOP TSS design (see Figure 9). The
most significant improvement in the design is that the UOP TSS utilizes axial flow
for catalyst/gas separation. The flue gas flow is maintained essentially in one
direction - in the top and out the bottom of the unit. Axial flow distribution minimizes
the potential for solids re-entrainment resulting from gas flow direction change and
resultant eddy current formation. The older style TSS utilizes radial flow distribution
in which the flue gas is distributed from the centerline of the TSS, radially outward
between the two tube-sheets. As such, the inner tubes see a higher gas and dust
loading than the outer tubes. The mal-distribution of flue gas and fines inherent in
this design results in varying efficiency across the older style TSS.
The new UOP TSS is about 40% smaller than other TSS offerings for the same
capacity; making it less expensive to fabricate, easier to install, and better suited
where plot space is a premium.
The first UOP TSS was commercialized in April 2002. Performance testing on the
unit was performed twice in 2002, following the unit startup in April and again in
December. The initial test showed that the UOP TSS discharged between 36-50
mg/Nm3 of particulates, depending on flue gas rate. The NSPS compliance testing
resulted in a particulate matter emission of 0.6 lbs/1000 lbs of coke burn, only 67%
of that allowed by NSPS standards. This performance showed that the UOP TSS
could not only provide power recovery expander erosion, but could also be used as
in the refiners particulate emission control strategy, by replacing more traditional,
costly, and hazardous means (electrostatic precipitators and wet gas scrubbers) of
controlling particulates exiting the flue gas stack.
A comparison of the older style TSS and newer style TSS is shown in Figure 4.
Both vessels are carbon steel vessel with 4" (100 mm) of refractory lining and
stainless steel internals. The cold-wall construction is more effective on both
erosion and cost basis than the early hot-wall stainless steel separators. A coarse
screen, or grate, covers the flue gas outlet entrance to trap large chunks of
refractory or other debris.
The overall efficiency of the separator depends on the efficiency of the regenerator
cyclones and the quantity of catalyst fines being generated in the reactorregenerator system. The separator should remove >70-90% of the particles for high
157048-1
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and low regenerator cyclone efficiency, respectively. Most of the fines which pass
through the separator are smaller than ten (10) microns. These small particles do
not cause much erosion to the expander blades but the smallest particles can
deposit on the expander blades and casing, causing vibration problems.
The pressure drop across the expander is on the order of 10-30 psi (0.7-2.1
kg/cm2), with a temperature drop of 200-250F (110-140C). After driving the
turbine, the flue gas goes to a steam generator for further energy recovery.
The majority of the catalyst is removed from the flue gas with the underflow from
the third stage separator which is typically routed back into the flue gas downstream
of the expander. If required, an electrostatic precipitator or flue gas scrubber may
be placed downstream of the steam generator to remove any remaining catalyst
fines before the flue gas is exhausted to atmosphere. Alternatively the underflow
may be filtered to achieve ~99.99% removal of the catalyst fines, or routed to a 4th
stage cyclone separator to achieve ~60-90% removal of the catalyst fines from the
underflow stream, depending on local environmental restrictions.
The power recovery train usually consists of five parts; the expander turbine,
motor/generator, air blower, and a steam turbine, and is commonly referred to as a
5-Body Train, see Figure 5. In this arrangement the expander turbine is coupled
to the main air blower shaft to directly supplement the power requirement of the
blower. The 5-body train requires a steam turbine or motor to get it started; in some
cases only one of them is provided.
The expander, shown in Figures 6 and 7, is a single stage machine because of the
low pressures involved. The gas to the expander is accelerated over a parabolic
nose cone. Pressure energy is converted to velocity energy, and the high velocity
gas drives the turbine.
Expander turbines designed in the past were generally limited to an inlet
temperature of 1200-1250F (650-675C) to prevent heat damage. This generation
of expanders however, still required quench injection systems in the regenerator
plenum chamber to protect the expanders in the event of a regenerator temperature
157048-1
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excursion. Quench systems essentially dumped steam and water into the
regenerator plenum to cool the flue gas. While this provided for thermal protection
of the expander, the increased steam and water in the flue gas often resulted in
sticky catalyst that agglomerated in cement-like deposits that increased blade
fouling on the expander. Newer expander turbines normally have a design
temperature in excess of 1375F (750C) and do not require a quench control
system.
For units with a power recovery system, butterfly valves in the flue gas line control
the differential pressure between the reactor and regenerator. The PDIC sends a
signal to the large butterfly valve which is located at the inlet to the expander. A
smaller butterfly valve will allow flue gas to bypass the expander when the large
butterfly valve is fully open because of an excessive flue gas rate or when the
expander is off line. This prevents over pressuring the regenerator.
In the traditional five piece power recovery train, the motor/generator is usually a
constant speed induction type machine that provides extra power to the blower
shaft when needed. If the expander produces more energy than is required by the
blower, the machine will act as a generator and feed power into the electrical grid.
This acts as a braking mechanism and provides some over-speed protection for the
machine.
157048-1
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Figure 4
Third Stage Separator
Old Style TSS
11' 6" OD
48 Tubes
29'
70 Tubes
23'
19' 3" OD
Figure 5
5-Body Power Recovery Train
Flue
Gas
Exhaust
Flue
Gas
Inlet
Air to
Air
In Regenerator
Inlet
Guide
Vanes
Steam
Turbine
Main Air
Blower
Expander
Steam
Inlet
Gear
Box
Motor /
Generator
Exhaust
Steam
Outlet
Electrical
Connection to
Power Grid
157048-1
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Page 15
Figure 6
Flue Gas Expander
Because power recovery trains are generally fitted on larger units, the blowers used
are of the higher efficiency axial type. The blower is a constant speed machine in
most cases, especially if used with an induction type motor/generator. Varying the
angle of the stator blades in the blower is the most economical control scheme.
Because the motor/generator has a large startup electrical power requirement, a
steam turbine may be used to bring the train up to speed. The turbine will normally
provide 50-75% of the power needed for the blower. Once the train is close to
design speed, the motor can be started without using excessive amounts of
electricity. This in turn decreases the size of the transformers and switch-gears
needed. When the expander is running the turbine is allowed to freewheel, or may
157048-1
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be used to provide extra power. If there is no steam turbine, the expander turbine
may be used to "bootstrap" the train up to speed.
In unit revamp situations where the main air blower is not to be replaced, the power
recovery train can be reduced to 3 parts; the expander, gear reducer and generator.
This configuration is known as a Gen Set power recovery installation. In this
configuration, the power recovery system is completely isolatable from the
remainder of the FCC unit. The electrical power generation from the system is
routed directly into the refinery power grid. The net power recovery capable through
a Gen Set system is lower than a 5-body train due to efficiency losses in the switch
gear, and motor. However, the capital expenditure of Gen Set systems is lower,
and they can be completely isolated from the remainder of the FCC unit should
there be any equipment problems with the power recovery system.
157048-1
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Figure 7
Flue Gas Expander
Outlet
Blades
Rotor
Bearing
Coupling
Inlet
Shaft
FCC-E001
157048-1
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Page 18
Figure 8
FCC Power Recovery
1300 F (704 C)
1600 F
(871 C)
1200 F (649 C)
1100 F (593 C)
1000 F (538 C)
44.7 psia
(3.14 kg/cm2a)
157048-1
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CHECK VALVE
The check valve is installed on the discharge of the air blower. It prevents backflow
of air or catalyst, which could cause serious damage to the blower. Fluidized
catalyst will easily flow back through the air heater if pressure is lost. If the blower
starts to surge, the large volume of the regenerator must be isolated from the
blower. Figures 9-11 show the check valve and its associated equipment.
Figure 9
Blower Discharge Check Valve
157048-1
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Page 20
Figure 10
Blower Discharge Check Valve - Side View
The special check valve is a swing style check valve with a spring loaded air
cylinder that provides spring force assisted closing. An oil filled dash pot provides a
damping action on opening. Construction is of heavy wall steel to resist temperature
and pressure stresses, with 11-13% Cr or stainless trim. The stainless steel shaft is
supported by hardened stainless steel bushings, with graphoil packing used to
prevent leakage. Older designs have incorporated asbestos packing that may need
to be addressed with the appropriate abatement procedures. The shaft is connected
to the dashpot and to a lever arm that has counterweights that support 75% of the
disc weight. These weights minimize the pressure drop through the valve, but
should never hold the disc open when there is no air flow. The lever arm is usually
cut to the proper length in the factory, and the weights set in the field.
157048-1
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The air cylinder consists of a small piston opposed by a spring. Under normal
conditions, air is supplied to the piston, which moves up to compress the spring.
The piston rod moves freely between two small lever arms attached to the check
valve shaft. As the piston rod rises, the valve is free to open. Air flow from the
blower forces the valve open. The air to the piston is supplied through a three-way
valve that will vent off cylinder pressure when actuated. For older units, a shutdown
of the blower would signal the valve to cut off the air supply. For the new units that
have venturi meters on the blower discharge line, a low flow signal will signal the
valve to cut off the air supply. A shutdown on the blower itself, low blowerregenerator differential pressure, or low air flow can all be configured to cut off the
air supply to the piston and activate the special check valve. Instrument air failure
will also vent off pressure from the cylinder. Upon initial venting, the spring provides
a sharp thump to the valve shaft to help free the disc in the event that it has become
slightly stuck in the open position. The force of the spring is not enough to close
against the normal operating air flow from the main air blower. As such, a spurious
activation of the special check valve, i.e., a loss of instrument signal to the solenoid
valve, would result in a higher pressure drop through the check, but would not force
a unit shutdown.
After initial actuation, with no air pressure to oppose it, the spring provides a
constant load on the valve shaft. As the piston rod comes down, it pulls on the lever
arms, which exert a closing force on the shaft. This provides a starting boost to
close the check valve and will bring the valve closer to the seat before the air flow to
the regenerator actually stops.
Following a solenoid trip, the three-way valve must be manually reset in the field.
This functionality is included in the system design to help ensure that movement of
the check valve disc is controlled and stable, rather than a sporadic situation that
would result if the air cylinder was pressured and depressured in a random fashion
during an upset.
Typical turnaround maintenance on the special check valve includes maintenance
of the air cylinder, refilling the dashpot oil, repacking of the stuffing box hinge
157048-1
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assembly, replacement of the accordion type protective piston rod cover. After the
check has been reassembled, the flapper should move freely and close normally
under its own weight. Proper seating of the check disc should be confirmed
internally with visual inspection. If the main air line is too small to facilitate internal
visual inspection, the approximate position of the disc can be verified by the position
of the counter-weight arm.
DASHPOT
The dashpot provides a resistance to a sudden opening of the check valve. It has a
loose fitting piston that rides in an oil filled cylinder. The valve in the bypass line
restricts oil flow from the top of the dashpot to the bottom as the piston moves up.
This restriction prevents the check valve from opening too quickly. As the piston
moves down on the check valve closure, the valve in the bypass on the dashpot
opens wide to allow rapid closing of the check valve. Some snubbing action remains
to prevent excessive slamming. The dashpot should be filled with a light lubricating
oil such as SAE 10W. It is also important to provide a "volume leg" in the oil piping
to account for the volume of the piston shaft in the closed position. The setting on
the oil dash pot needs to be verified on initial installation and subsequent
turnarounds by opening the disc and allowing it to fall closed. Proper setpoint of the
oil valve should result in a smooth controlled closure of the disc with no substantial
impact on the valve seat.
If the check valve is thrust open under low air flow conditions, it may fly up too far,
and then slam back onto the seat. This can cause damage to the valve seating
surfaces. As a result, the check valve should be examined for any unusual wear,
such as impact erosion on the seat during the turnaround.
157048-1
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157048-1
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Page 24
Figure 12
Direct Fired Air Heater
Air
Inlet
Air
Outlet
TI's
(2 Required)
Pilot/Ignitor
Assembly
Air
Purge
Air
Purge
Main
Gas
Sight Port
(2 Required Must Sight Pilot
and Main Burner)
Air
Purge
Baffle
Sight Port
Sighting
Burner
Sight Port
Sighting
Opposite Wall
4" Vacuum
Cleanout
Connection
Manway
FCC-E002
157048-1
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Page 25
AIR GRID
The original design for a conventional regenerator air distribution system was a
perforated plate. Air entered the base of the regenerator and then passed through a
large number of small holes in a large metal plate. In the late 1970's and early
1980's, the processing of more contaminated feedstocks increased air demand and
regenerator temperatures. Increased incidents of erosion, full CO combustion, and
the introduction of new regenerator designs lead to significant changes in the
design of the air grid.
The bubbling-bed regenerators feature a high catalyst entry point into the dense
bed relative to the air grid. Two basic types of air grid designs are used by UOP in
this style of regenerator: pipe grid and mushroom grid. The high-efficiency
regenerators have a low catalyst entry point relative to the air grid. On this design,
UOP uses a pipe grid.
The mushroom grid with extension arms is used in situations where a standpipe
inlet is below the air grid. A dome grid was used previously, but an exit in the grid
was needed to transfer catalyst to the regenerator standpipe. The mushroom air
grid with extension arms distributes air through jets located in the dome and arms.
A side view of the grid is shown in Figure 13. Figure 14 shows a plan of the
mushroom grid with arms.
The mushroom grid is constructed with 1" (25mm) lining on the dome and " (19
mm) lining on the extension arms. The lining minimizes the thermal stresses on the
grid wall resulting from the temperature differential between the inlet air and
regenerator.
157048-1
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Figure 13
Mushroom Air Grid with Extension Arms
157048-1
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Page 27
Figure 14
Plan View of Mushroom Air Grid with Arms
Plugged Nozzle
Open Nozzle
157048-1
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Page 28
The dome air grid distributes air through jets located on its dome. A side view of the
grid is shown in Figure 15.
Figure 15
Dome Air Distributor
157048-1
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Page 29
Some dome-type air distributors have experienced jet erosion. UOP believes that
the erosion on this type of air grid is due to catalyst from the spent and recirculating
catalyst standpipes impacting directly onto the surface of the distributor. When the
catalyst impacts the air grid in this fashion, the catalyst can be forced into the jets
resulting in erosion as the catalyst is blown out of the jets. Erosion can also occur
on the external portion of the jet from the catalyst impact.
Several methods of combating this type of erosion have been developed. One
method is to install extended catalyst deflectors, which distribute the catalyst over a
wide cross-sectional area of the regenerator to minimize the localized impact of
catalyst onto the grid. Another modification is to cover the surface of the air grid with
an abrasion-resistant lining so that the outlet of the jets is flush with the abrasionresistant lining. The dual-diameter jets have also been replaced with singlediameter, higher velocity jets.
Because of mechanical reliability the pipe grid is the most commonly designed type
of air grid today. The pipe grid distributes the air through two to four large laterals
into a number of small branches. A side view of the grid is shown in Figure 16.
Figure 17 shows a plan of the pipe air grid. Modern air grids use a dual diameter jet
(Figure 18) with a restriction orifice at the inlet. This allows a higher pressure drop
for better air distribution while minimizing the velocity out of the jet for minimum
catalyst attrition.
Air grids are designed for a total pressure drop between 0.8 and 1.2 psi (0.06-0.085
kg/cm2). The pressure drop must be maintained above 0.5 psi (0.035 kg/cm2) to
achieve even distribution and should be below 1.5 psi (1.05 kg/cm2) to minimize
main air blower discharge pressure.
Many of the pipe grid and supports designed for partial combustion units were low
alloy, such as 5% chrome. The higher temperatures encountered in a most modern
full CO burning units require 304 SS.
157048-1
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Pipe-grids designed by UOP in the early 1970's had experienced cracking at certain
butt welded joints, but otherwise worked well. UOP has modified the pipe-grid
design and the advantages of this style of air grid are as follows:
1)
2)
the 90 elbow is attached to the header arms and main hub with extruded
connections which moves the welds away from the highly stressed junction
3)
the branch arms pass through the header arms which increases the strength
of these joints
4)
external abrasion resistant lining protects against erosion and also provides a
smooth thermal gradient
Figure 16
Pipe Air Grid
157048-1
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Page 31
Figure 17
Plan of Pipe Air Grid
Figure 18
Dual Diameter Jet Detail
157048-1
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Page 32
A pipe grid is subject to severe catalyst erosion on the upper surface of the
branches. For this reason, older units had stainless steel retaining dams, Figure 19,
welded on top of each lateral. These dams held an insulating layer of catalyst which
alleviated both erosion and possible heat damage problems. Currently, UOP
designs the air distributor so the entire surface of the branches have abrasion
resistant lining. The lining provides both the erosion resistance and the thermal
barrier required.
Figure 19
Coffer Dam
Stiffener
Branch
157048-1
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Page 33
The jets on the pipe air grid and on the arms of the mushroom grid point down to
avoid channeling the catalyst bed, as seen in Figure 18. It should be noted that
some of the jets are normally plugged. This is done for three reasons:
1.
2.
To increase the pressure drop to the proper level if the grid has too many
holes (future design case).
3.
The pressure drop across the air grid can be calculated with the equation:
P =
2.238 * W2
P * V2
=
Cd2 * Ah2 *
2200 * T
where:
P
P
T
V
=
=
=
=
W =
Cd =
Ah =
157048-1
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REGENERATOR
The regenerator is an internally lined carbon steel vessel. The lining, called
refractory, is a concrete type material which is gunned onto reinforcing support
anchors. This lining is necessary to protect the metal wall of the vessel from the
high temperatures at which the regenerator operates and should keep the outer
shell of the regenerator below 650F (343C) at all times. The refractory is applied
over stainless steel hexmesh or steerhorn anchors. Different grades and depths are
applied depending on the service. In general, four - five inches (100 - 125mm) is
used in the regenerator when insulation is of primary importance.
Abrasion resistant refractory lining are used on all internal surfaces in the
regenerator to protect the base metal from the erosive environment. - 1 inch (19 25mm) of lining is typically used and is anchored by stainless steel hex mesh
anchors. This refractory is much harder and denser than the insulating refractory so
that it is provides more erosion protection but does not offer the same insulating
properties.
Instrument connections are inserted through the refractory. Thermowells, which are
used to measure catalyst or gas temperatures, are hard surfaced with a cobaltchrome stellite hard surfacing to protect them from the erosive conditions. Pressure
taps (and pressure taps used as level indicators) are protected by steam, gas, or air
purges. These are discussed later in this section. The purges provide a buffer
between the catalyst bearing gas in the regenerator and the small instrument taps
which can easily plug.
Figure 20 shows a conventional (bubbling bed) regenerator in detail. The air flows
from the grid up through a dense bed of catalyst where the carbon is burned off.
The catalyst enters the vessel from the spent catalyst standpipe, at the end of which
is a deflector baffle to distribute the catalyst evenly over the bed, not straight down
to the outlet. The design shown does not have an internal catalyst hopper, which is
a large diameter cone above the regenerated catalyst standpipe. The higher density
catalyst in the cone provides extra head pressure in the standpipe if needed by a
particular unit.
157048-1
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Combustion gases, excess air, and catalyst particles traveling from the dense
phase to the dilute phase are separated using two-stage cyclones. Flue gas leaving
the cyclones enters a plenum chamber at the top of the regenerator. The hot gases
travel through the double-disc slide valves, which are set to regulate the reactorregenerator differential pressure. The flue gas then travels through the orifice
chamber, where its pressure is dropped through a series of perforated plates.
Finally, the energy of the flue gas is recovered in a CO boiler (or steam generator
for a full combustion unit) where the CO is burned along with auxiliary fuel gas and
air to generate steam (or simply cooled to generate steam in a full combustion unit).
157048-1
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Figure 20
Conventional Regenerator
THERMOCOUPLES
(1each cyclone)
CYCLONE SUPPORTS
REGENERATOR PLENUM
REFRACTORY
LINING
MANWAYS
LEVEL AND
PRESSURE TAPS
TIs
FIRST STAGE
CYCLONES
REFRACTORY
LINING
SECOND STAGE
CYCLONES
EXTERNAL
LINING
TRICKLE
VALVES
TORCH OIL
OPEN PRIMARY
CYCLONE DIPLEG
TERMINATIONS
SPENT CATALYST
DEFLECTOR
SPENT CATALYST
STANDPIPE
LEVEL AND DENSITY
PRESSURE TAPS
MANWAY
AIR DISTRIBUTOR
CATALYST
WITHDRAWAL
REGENERATED
CATALYST
STANDPIPE
FCC-E003
157048-1
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Page 37
157048-1
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Page 38
Figure 21
Two Stage Regenerator
Flue Gas
Primary
Cyclone
Secondary
Cyclone
Mushroom
Grid
Distributor
Spent
Catalyst
First Stage
Regenerator
Spent Catalyst
Distributor
Ski-Jump
Recirculation
Catalyst
Standpipe
Catalyst
Cooler
Second Stage
Regenerator
(Side View)
Vent Tubes
First Stage Air Inlet
Second Stage
Regenerator
Cooled
Catalyst
Standpipe
Regen
Standpipe
Hopper
Regenerated
Catalyst
157048-1
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Figure 22
Updated RFCC First Stage Air Grid Design
First Stage
Air In
FCC-E004
157048-1
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Page 40
RFCC units will also have one or more catalyst coolers. The catalyst cooler slide
valve position is set by the signal from the second stage regenerator temperature
controller or the slide valve differential pressure controller over-ride via a low signal
selector. The recirculating catalyst slide valve position is set in a similar manner, by
signals from the lower regenerator level controller or the slide valve differential
pressure controller through a low signal selector. Each slide valve packing is steam
purged like the regenerated catalyst slide valve.
In the first stage the flue gas and catalyst are separated by two-stage cyclones. The
catalyst falls down the cyclone diplegs which are submerged in the catalyst bed to
provide a seal against gas passing up the diplegs. The primary cyclone diplegs are
typically open ended pipes with a splash plate and the secondary cyclones have
trickle valves. The catalyst flows into the annular zone around the mushroom air
distributor and into the recirculation catalyst standpipe and catalyst cooler(s). Air is
directed through nozzles on the underside of each arm of the upper air distributor to
help maintain proper fluidization of catalyst in this area.
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157048-1
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Figure 23
UOP Fluid Catalytic Cracking Process
High Efficiency Regenerator System
Cyclones
Upper
Regenerator
Combustor
Riser
Combustor
Regenerated
Catalyst
Fluffing Air Ring
Spent
Catalyst
Mixing Zone
Air Grid
157048-1
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Figure 24
High Efficiency Regenerator with External Mixing
Upper
Regenerator
Combustor
Riser
Combustor
Recirculation
Catalyst
Standpipe
Regenerated
Catalyst
Catalyst/Air
Distributor
Spent
Catalyst
Lift Riser
Air
157048-1
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COMBUSTOR CONE
Figure 25 illustrates the changes in regenerator cone design that have taken place
since the mid-1980s. UOP has developed a new cone detail (see Figure 26) that
eliminates the radial and axial constraint imposed by the hard refractory lining and
cold regenerator shell. The resulting stress is dissipated by incorporating a flexible
soft pack ceramic lining that permits both radial and circumferential expansion.
Additionally, the new cone detail minimizes thermal stresses due to radial
expansion by providing a flexible skirt section that connects to the regenerator wall.
The key feature of the new internal combustor cone design is the air space
incorporated between the cone skirt and the regenerator shell. The air space is
required to provide the optimal heat transfer medium between the cone and the
regenerator shell. By using this air space, it has been proven that the thermal
stresses in the cone are less than the stresses compared to other internal cone
designs that have experienced deformation.
In order to maintain this air space, it is mandatory to keep the air gap free of
catalyst. The catalyst seal device achieves this objective (see Figure 27). Some
characteristics of the catalyst seal are as follows:
1)
2)
3)
157048-1
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Figure 25
Combustor Cone Modifications
UOP 1906H-7
UOP 3110-4
157048-1
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Figure 26
Detail of Combustor Cone Design
Fiberfrax
Moist Pak-D
Abrasion
Resistant Lining
Refractory
Lining
Ceramic Fiber
Blanket Insulation
Retaining Ring
Air Space
157048-1
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Figure 27
Detail of Catalyst Seal Device
Ceramic Fiber
(2 layers)
4
(Cold Position)
2
(Hot Position)
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Figure 28
New Style Combustor Riser Arms
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Figure 29
Fluffing Air Distributor
STANDPIPES
ABRASION RESISTANT
LINING
ABRASION RESISTANT
RESTRICTION
ORIFICE
LINING
PIPE
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Figure 30
Torch Oil Nozzle
SPRAY NOZZLES
Spray nozzles are used to inject water through an atomizing nozzle to cool off the
flue gas in the plenum chamber if the unit has power recovery. The spray water
should be clean, such as steam condensate. Contaminants such as sodium will
cause problems by deactivating the catalyst or contributing to its breakup.
Mechanically, the spray nozzles are similar to the torch oil nozzles.
CATALYST COOLER
The ability to control and vary the amount of heat removed from the regenerator
creates an additional degree of freedom by moderating the regenerator temperature
as a limiting constraint. The catalyst cooler provides a variable heat sink, which
157048-1
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allows the refiner to vary the catalyst/oil ratio, reactor temperature, and feed
temperature independently of one another.
The catalyst cooler tube bundle is inserted into a refractory lined shell off the side or
bottom head of the regenerator. The tubes of this exchanger are the bayonet type.
The boiler feed water enters the cooler through the inner tubes and the mixture of
water and steam exits the cooler through the annulus between the inner and outer
tubes. The outer tubes are 3 inch (75mm) O.D. made from 1 Cr, Mo seamless
tube material. The inner tubes are 1-3/8 inch (35mm) O.D. made from carbon steel
seamless tubing.
The stainless steel fluidizing air lances distribute air into the cooler near the bottom
of the tubes. The air creates turbulence and increases heat transfer coefficient as
the bubbles travel upward. The backmixing created by the bubbles also brings hot
catalyst into the cooler from the regenerator. The air is delivered to a common
manifold supplying all the lances through a flow controller. The lances contain a
restriction orifice, located near the piping header at the top of each lance, to help
distribute the air uniformly over the cross sectional area of the cooler. The
countercurrent fluidizing air improves heat transfer by creating turbulence and
mixing in the region of contact between the hot catalyst and the tubes. A differential
pressure transmitter, with taps located above and below the cooler, gives a direct
indication of the density of the fluidized catalyst at various conditions of catalyst flow
and air injection.
Mechanical reliability is achieved by locating the cooler in the dense phase of the
regenerator. In the dense phase, the heat transfer coefficient is higher which
permits lower catalyst and fluidization air velocities. Lower velocities minimize
erosion within the cooler. In addition, the cooler tubes are located in the vertical
plane. This feature generates a uniform heat transfer coefficient over the entire tube
surface thereby preventing uneven surface temperatures which cause localized
stress.
Catalyst coolers have been designed and built to fit virtually every regenerator
configuration, including single-stage bubbling beds, high-efficiency combustors, and
two-stage regenerators. Three basic styles of UOP catalyst coolers are currently
available:
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Flow-through catalyst cooler The catalyst flows downward into the cooler shell
and exits into the cooled catalyst standpipe near the bottom of the tube bundle. The
standpipe transports the cooled catalyst through a slide valve and expansion joint
into the combustor on a high efficiency regenerator or to the second stage
regenerator on an RFCC. In a single stage bubbling bed regenerator the catalyst
can be lifted back into the regenerator with air through a lift riser. Both the catalyst
flow through the cooler and the fluffing air rate are used to control the cooler duty.
Backmix catalyst cooler This style contains no catalyst exit standpipe. Hot
catalyst enters the cooler by backmixing as a result of fluidization air injected near
the bottom of the tube bundle. The major advantage of this cooler design is that no
slide valve, expansion joint, or standpipe is required. This configuration also permits
the cooler to be lower to the ground if elevation is a limiting constraint. The duty of
a back mix cooler is ~60% of an equal sized flow through cooler and is controlled
only with the fluffing air.
Hybrid catalyst cooler The combination of flow-through and backmix operation
constitutes the hybrid catalyst cooler. In a hybrid, the catalyst exits into a standpipe
located at the midsection of the tube bundle (instead of at the bottom as in flowthrough coolers). In the hybrid cooler, the upper portion of the bundle operates in
the flow-through mode, and the bundle length below the catalyst outlet operates in
the backmix mode. This configuration achieves somewhat less heat-removal
capacity than a full flow-through cooler but still transfers cooled catalyst down to the
lower portion of the regenerator.
The catalyst cooler steam generation circuit includes the cooler, steam drum, and
circulation pumps. Boiler feedwater is pumped to the bottom head, enters the inner
tubes, then flows down through the annulus between the inner and outer tubes
where it absorbs heat to generate steam. The steam-water mixture leaves the
catalyst cooler to be separated in the steam drum. Makeup boiler feed water is
delivered to the steam drum through a flow controller which is cascaded to signals
from the drum level and steam generation flow transmitters. Steam flows from the
drum through a stop check non-return valve and a superheater (either part of the
flue gas cooler or a fired heater) before entering the refinery steam header.
157048-1
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Figures 31-35 show some examples of catalyst coolers and catalyst coolerregenerator configurations that have been constructed.
Figure 31
Flow Through Catalyst Cooler
UOP Catalyst Cooler General Arrangement
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Figure 32
UOP Backmix Catalyst Cooler
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Figure 33
Examples of Bubbling Bed Regenerators
with Catalyst Coolers
Flow Through
Backmixed
Aeration
Air
Aeration
Air
Lift Riser
Cooled
Catalyst
Standpipe
Water and
Steam
Water and
Steam
Water
Water
Air
Lift Air
Distributor
157048-1
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Figure 34
Examples of High Efficiency Regenerators
with Catalyst Coolers
157048-1
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Figure 35
RCC Regenerator with Catalyst Coolers
Example of an RCC Regenerator with Multiple Catalyst Coolers
Fluffing Air
Fluffing Air
Air
Backmix
Catalyst Cooler
Flow-Through
Catalyst Cooler
Air
UOP 2119-27
157048-1
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Operating the catalyst cooler with sufficient water circulation to ensure that the tube
walls are always wet so that they can not overheat and limiting the fluffing air so that
the tubes are not subjected to erosion are critical in ensuring mechanical integrity
and long life of the cooler. In new units the flow controller regulating the water flow
to the cooler has been eliminated so the water flow is set by the pump curve. The
spare pumps are instrumented to start automatically on low water flow. If the water
flow is not recovered by the auto start the cooler is shutdown by closing the cooled
catalyst slide valve and the fluffing air control valve. The fluffing air rate should
never exceed a flow that will result in a superficial velocity in the shell of more than
1 ft/sec (0.3 m/sec).
In recent years, as catalyst cooler reliability has improved, UOP has shifted from a
reactive to a proactive approach to catalyst cooler design. Several design
modifications have been developed recently.
Tie Rod Support
Previous designs had the tie rods, which support the eggcrate bracing, protrude
through a hole in the upper tubesheet. The tie rod was welded to the tubesheet on
the steam (bottom) side. While this method was acceptable under normal operating
circumstances, the tie rod could potentially push through the tubesheet if tie rod
growth was restricted due to an obstruction or thermal binding. This would create a
path for the steam to enter into the catalyst side of the cooler, having the same
effect as a tube leak. The current design eliminates the hole through the tubesheet,
using instead a cup into which the tie rod is inserted (see Figure 36). This cup is
countersunk and welded into the catalyst (top) side of the tubesheet. The tie rod is
welded around the rim of the cup above the refractory face providing easy access
for bundle maintenance or refurbishment. This design eliminates the possibility of
the tie rod creating a steam leak.
157048-1
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Figure 36
Modifications to Tie Rod Supports
Tie Rods
Bracing Bars
Egg-Crate
Support Bracing
Refractory Lining
Old Method
Upper Tubesheet
New Method
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The small additional cost of the flat tube caps is recovered in assembly time.
157048-1
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Figure 37
Modifications to Outer Tube Caps
Aeration Pipe Header
Aeration Lance
Lance Support
Arms
Pipe Support
Plate
Pipe Support
Stool
Old Method
Outer Tubes
New Method
157048-1
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Figure 38
Flat Tube Cap
157048-1
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required duty is slightly higher than the duty of a seven foot catalyst cooler, making
a single eight foot cooler a less expensive alternative to two smaller coolers.
Update: Debris Screens
Since 1991, debris screens have been installed in all existing units. Debris screens,
which are installed at the entrance to the cooler, have become standard supply for
all coolers mounted on the lower regenerator cone or head. The screens prevent
large refractory pieces or other loose debris from accumulating at the bottom of the
tube bundle where the debris can restrict or divert the flow of air from the air lance,
potentially causing catalyst impingement on a tube and an eventual tube leak. Aside
from some minor improvements in the anchoring method, the screens have held up
well in operation and have performed their function. There have not been any tube
leaks caused by accumulated debris in coolers with debris screens.
Update: Air Lance Pressure Testing
Because the internal air piping and lances are not subject to code requirements,
UOP implemented a required shop pressure test of the completed aeration
assembly in 1991. Since that time, there have been no reported air leaks or weld
failures in any operating coolers that have received this testing. Prior to the shop
testing, air leaks had occurred in at least five units, three of which lead to tube
leaks.
157048-1
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CYCLONES
The flue gas leaving the dense bed will entrain some of the catalyst particles with it.
Some of these settle back to the bed; others are carried higher. Measurements of
the entrained particles taken at increasing heights above the bed show a gradual
decrease in the amount of fines entrained. At some point above the bed, the
concentration of particles entrained levels out. This is called the Transport
Disengaging Height, or TDH.
Early FCC units used a number of small tubes, called multi-clones to remove
particles. These were not particularly effective and were difficult to maintain. The
cyclone design shown in Figure 39 was the next step. The shaveoff was intended
to increase efficiency, but also proved difficult to maintain. The cyclones used in the
modern FCC unit use a fairly simple principle to remove most of the particles. See
Figure 40. The catalyst bearing gas enters a cylinder through a tangential opening.
The catalyst is 500-1000 times as heavy as the gas, and is subjected to forces
several hundred times that of gravity as the gas swirls around the cylinder. The
larger particles are removed through centrifugal forces which force the particle
outward to collide with the wall. The collisions slow down the particle so that they
fall by gravity into the dust hopper and are returned to the vessel through the
diplegs. The viscous drag forces of the gas tend to carry some of the catalyst
particles with it. Generally only the smaller particles are light enough to stay with the
gas, because the inertial and centrifugal forces acting on them are small.
The catalyst separated from the gas stream swirls downward due to the force of
gravity. The chamber below the entrance of the cyclone tapers downward and tends
to keep the catalyst against the wall which is away from the cleaner area at the
center core (where the gas disengages and moves up). There is more disengaging
area in the hopper, which feeds catalyst to the dipleg; this disengaging area also
decreases the amount of erosion which could be created by the vortex of the
catalyst particles.
157048-1
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Figure 39
Cyclone-Catalyst Fines Collector with Shaveoff
Catalyst-Free
Gas Outlet
Gas Out
Catalyst
Shave-Off
Bypass
Catalyst Shave-Off
Bypass
Catalyst-Laden
Gas Inlet
Re-Entry
Opening
Note:
Because of the High Maintenance
Required on the Catalyst Shave-Off
(Caused by Erosion) many Refiners are
Choosing to remove this Device
Catalyst-Laden
Gas Inlet
Stream PatternLower Portion
Stream PatternUpper Portion
(Principally Finer Particles)
Disengaging
Hopper
Catalyst
Outlet
Dip Pipe
UOP 2119-28
157048-1
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Figure 40
Cyclone-Catalyst Fines Collector
There is a pressure drop between the cyclone inlet and dipleg outlet. If the catalyst
is to be returned to the bed, the dipleg must hold a head of catalyst sufficient to
overcome this differential. If the catalyst in the dipleg stops flowing, the gas will
simply carry the catalyst out the top. If the dipleg is submerged in the bed, then the
pressure at the bottom will increase and catalyst will be forced out as the level in
the leg rises. The required head will determine the dipleg length.
There are two general types of dipleg termination devices the trickle valve and
counterweighted flapper valve. The trickle valve in Figure 41 is generally used on
submerged diplegs. The valve is simply a flat plate held closed by gravity and
external pressure until the catalyst head in the dipleg is sufficient to open it. The leg
dumps, and the trickle valve swings shut. The counterweighted flapper valve in
157048-1
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Figure 42 is another method, with a better seal than the trickle valve. The
counterweight holds the flapper closed until the catalyst head is sufficient to open
the flapper.
UOP has updated the design of the counterweighted flapper valve to improve its
mechanical reliability and maximize the unit onstream efficiency.
The major revisions to the design are:
1.
Addition of a stop bar to prevent the valve from opening more than 45 (see
Figure 42).
2.
3.
4.
Requirement that the hard surfacing used on the pin and bushings be crack
free. There is some concern that surface cracking may contribute to
roughness and thus restrict smooth motion of the hinge mechanism.
Alternative hard surfacing such as Waspalloy, Wallex 50 and Triten should
be considered as options for hard surfacing of the pin and bushings.
5.
157048-1
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Figure 41
Trickle Valve
Hinge
Flapper Plate
Stop
157048-1
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Figure 42
Counterweighted Flapper Valve
STIFFENER
LUG
DETAIL
Closed Position
Open Position
157048-1
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3mm
+0.0625"
-0.000"
+1.6mm
-000mm
1/8 "
(BOTH SIDES)
(BOTH SIDES)
38mm PLUS/MIN.8mmID
Figure 43
Bushing Detail
3/8 "(10mm)
7/8 "
(22mm)
OF BUSHING
LUG ON DIPLEG
1/8 "
(3mm)
3"(75mm) DIA
HARD
1/8 "(3mm)
BUSHING
SURFACING
CONCENTRIC
DIA
2 9/32 "(58mm)
OF HOLE
OF BUSHING
7/8 "
3/8 "(10mm)
(INCLUDES 1/8 "(3mm)
OF BUSHING
HARD SURFACING)
3"(75mm) DIA
HARD
(22mm)
1/8 "(3mm)
DIA
2 9/32 "(58mm)
BUSHING
SURFACING
ECCENTRIC
38mm PLUS/MIN.8mmID
ECCENTRIC BUSHING
CONCENTRIC BUSHING
OF BUSHING
AND HOLE
157048-1
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TABLE 1
FLAPPER VALVE COUNTERWEIGHT
Dipleg
Diameter
6 (150 mm)
8" (200mm)
10" (250mm)
12" (300mm)
14" (350mm)
16" (400mm)
18" (450mm)
20" (500mm)
22" (550mm)
24" (600mm)
Counterweight
Lbs / Kg
1.9
3.3
5.4
7.8
9.6
12.8
16.4
20.5
25.0
30.0
0.9
1.5
2.4
3.6
4.4
5.8
7.4
9.3
11.4
13.6
Two important factors in cyclone efficiency are the velocity of the gas and the size
distribution of the particles. In general, the higher the velocity, the higher the
efficiency. It should be remembered, however, that higher cyclone velocities may
mean higher vessel velocities, with more catalyst carried up to the cyclones. If these
are larger particles, most of them will be collected, but in extreme cases, the
cyclones could be overloaded and the larger particles lost. Higher velocities also
means higher rates of erosion and catalyst attrition. The solids distribution is not
under immediate control, except by minimizing attrition of the catalyst by avoiding
areas of high velocity. In general, the small fines, less than 20 microns, will be lost,
with most of the larger size particles collected. The reactor cyclones generally do a
better job because here the coke on the catalyst fines makes them larger and
easier to collect.
The design of the cyclone is the important factor in its efficiency as well as the
resistance to erosion; it is normally handled by the cyclone manufacturers.
However, in the early 1980's, erosion in the cyclones and cyclone diplegs increased
noticeably. Units were beginning to process larger quantities of heavier and more
contaminated feeds. These feeds produce more coke, which increases air demand
and regenerator temperatures. The net result is increased erosion as a result of an
157048-1
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increase in catalyst loading and cyclone velocities. Competition among vendors was
another factor leading to an increase in instances of erosion. In some cases,
vendors supplied cyclones with key geometric ratios, such as L/D, minimized for
cost reasons.
To address these problems, UOP began to specify cyclone geometric relationships
and velocity criteria. The purpose was to ensure that all cyclone vendors bid on the
same basis and that the cyclones supplied met the process and mechanical
requirements set by UOP.
The requirements set forth in the "Mechanical Considerations In FCC Design" paper
presented at the 1996 UOP FCC Symposium have significantly reduced erosion
problems. These requirements are as follows:
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Second Stage
Both Stages
Ratio of the main cone outlet diameter to the barrel diameter shall be 0.4
minimum.
Ratio of cyclone height, measured from the roof of the cyclone to the outlet of
the dust hopper cone, to its barrel diameter shall be 5.0.
Projected apex point of the main cone shall terminate at a minimum distance of
0.3 x barrel diameter above the outlet of the dust hopper cone.
Ratio of the dust hopper diameter to the main cone outlet diameter shall be 1.5
minimum.
Ratio of the dust hopper cone height to the barrel diameter shall be 0.45
minimum.
The reactor cyclones are normally a low alloy steel, such as 1 Cr, Mo. Some
older partial CO combustion regenerator cyclones used 5 Cr or 12 Cr, with 1 Cr
diplegs sometimes. For the higher temperatures of modern, complete CO
combustion, Type 304 stainless steel (18 Cr, 8 Ni) is used. Abrasion resistant lining
is used on all cyclones to protect them from catalyst erosion. The inlet horn, the gas
outlet pipe, barrel, disengaging hopper, and part of the dipleg will be lined. The
157048-1
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extent of the dipleg lining will depend on accessibility and prior experience; erosion
in one area usually leads to a lining at the next turnaround. The exterior of the
diplegs must be protected with an abrasion lining where they are subject to catalyst
impingement, such as from the spent catalyst inlet or from another dipleg discharge.
ORIFICE CHAMBER
Orifice chambers (Figure 44) are used on FCC units when the regenerator pressure
is controlled by flue gas slide valves. The chamber is a cylindrical vessel with a
series of perforated grid plates (Figure 45). These plates hold a backpressure
downstream of the slide valves. By reducing the pressure drop across the valves,
their operating life is greatly extended because there is no sudden acceleration of
the catalyst bearing gas stream. The flow through the orifice chamber may be
upflow or downflow depending on downstream equipment. There are no moving
parts, so no adjustments can be made on stream. UOP designs the orifice chamber
as follows:
the flue gas slide valve is designed for approximately one-third of the pressure
drop and the orifice chamber is designed for the remaining two-thirds of the
pressure drop.
enough grids are installed to limit the pressure drop across each individual grid
while maintaining a specified velocity across each hole.
the distance between the top grid and the flue gas slide valve is kept at a
maximum. In revamp situations, this distance may be short and lining will be
required for the first grid only. Additionally, the installation of a shroud at the
inlet has proven to be beneficial in reducing erosion.
Given the UOP design philosophy of using cold wall construction whenever
possible, UOP has developed a cold wall orifice chamber. As a result, the chamber
walls are no longer prone to buckling, cracking, bulging and other phenomena
associated with high temperature stainless steel design.
Because of the high inlet temperature of the orifice chamber, the grids must be
designed for stainless steel metallurgy (if a waste heat boiler is installed upstream,
then carbon steel or low chrome can be used). The grids are supported by a
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cylindrical skirt section; typically two grids are supported from one skirt section. The
cylindrical skirt is supported by a tapered skirt section which is then welded to the
chamber wall. The tapered skirt requires a certain length to accommodate the
thermal expansion of the stainless steel grid relative to the cold wall shell. A gap is
also provided between the skirt and the refractory lining to allow for this expansion.
Blanket insulation is provided behind the tapered skirt to allow for the thermal
deflection.
The cold wall orifice chamber significantly reduces the amount of thermal growth of
the flue gas line (as compared to the hot wall design). This reduction will reduce or
eliminate the amount of expansion joints required. Given the change in thermal
movements, as well as the additional weight (due to the refractory), the entire flue
gas system should be reviewed for both support and flexibility for revamps.
Inspection
UOP has developed two types of orifice chambers to accommodate various revamp
inspection requirements. The first option allows external manway access to each
pair of top skirt grids (due to the skirt support scheme, external access to all grids is
not possible). To accommodate the external manways, extra tangent length for the
orifice chamber is required.
In the event there are space limitations, a shorter version has been developed.
Inspection access for this design requires the use of internal manways on each grid.
157048-1
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Figure 44
Cold Wall Orifice Chamber
Inlet Shrould
FLOW
Internal
Manways
157048-1
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Figure 45
Orifice Chamber Details
C GRID
RING NO 5
RING NO 4
RING NO 3
RING NO 2
RING NO 1
INTERNAL MANWAY
AIR SPACE
HIGH DENSITY
REFRACTORY
LINING
RING NO 5
RING NO 4
RING NO 3
STAGGER HOLES
WHERE POSSIBLE
CERAMIC FIBER
BLANKET
INSULATION
LINING TRANSITION
RING NO 2
RADIUS RING NO 1
C GRID
ABRASION
RESISTANT LINING
HIGH DENSITY
REFRACTORY LINING
+
- GAP
AIR
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ELECTROSTATIC PRECIPITATORS
Electrostatic precipitators (Figure 46) are used to remove catalyst fines from the
flue gas. The equipment consists of a large rectangular steel shell which contains a
number of wires called discharge electrodes, and a number of flat collecting plates.
The wires and plates are hung vertically, in alternating rows. A high electrical
potential is put on the discharge electrode wires, and the plates are electrically
grounded. A corona discharge surrounds the discharge electrode because of the
high potential. Gas ions formed by this corona move rapidly towards the collecting
electrode. When an ion strikes a catalyst fine, it becomes charged. The electrical
field between the electrodes causes the particle to deposit on the collecting
electrode. As more particles collect, a layer of fines builds up on the plate. A
mechanical rapper periodically strikes the frame of the collecting plate, and the
particles are knocked off. The fines tend to agglomerate into larger particles which
fall into dust hoppers under the electrodes. There is no physical change in the
particles, simply an agglomeration which makes them large enough for gravitational
forces to exceed the carrying force exerted by the gas.
Precipitators usually operate at pressures slightly above atmospheric. Inlet
temperatures range from 400-800F (205-425C). The temperature is especially
important if the flue gas has acidic components such as SOx or NOx. These may
condense and combine with water to form corrosive agents. The precipitator shell
may be insulated to hold the metal temperature high enough to prevent
condensation.
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Figure 46
Electrostatic Precipitator
Insulator
Discharge
Electrode
Rapper
Gas Out
Collecting
Surface
Gas Flow In
Hopper
UOP 2119-34
Discharge
Electrode
157048-1
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Collection efficiencies range from 70-99%, with 90-95% more common. The factors
affecting the efficiency are:
1.
2.
3.
4.
5.
6.
As the effective voltage increases, the efficiency increases. Too high of a voltage
can lead to arcing, which will damage the electrodes. Arcing can also occur if the
weights holding the discharge electrode wires fall off and allow the wires to swing
over towards the collecting plate. The precipitator should be designed with the
proper number of power supplies and control equipment to prevent excess
sparking.
The resistivity of the fines is approximately constant. It may be decreased for better
collection efficiency by adding small (<20 ppm) amounts of ammonia, but this is
usually not required. Spray water is also used in some cases.
The size distribution will be determined by cyclone performance in the regenerator.
Large solids rates to the precipitator, even with high efficiencies, may still lead to
emission problems, so it is better to have lower loadings to the unit. Larger particles
are easier to collect, because the smaller ones are more easily carried with the gas.
Typical gas flow rates are 5-6 ft/sec (1.5-1.8 M/s). Lower flow rates will give greater
efficiency. A higher collecting area will also increase efficiency.
The final factor, the rapping cycle, is normally designed for one strike from each
rapper every 1-3 minutes. Greater power and frequency of rapping will increase
efficiency, but must be balanced against cost. Both collecting and discharge
electrodes are fitted with rappers, most of them positioned on the collectors.
157048-1
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157048-1
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Figure 47
Catalyst Storage Hopper
Auto Gauge
Instrument
Vacuum
Nozzle
Grate with
Wire Mesh
Outlet
Manual
Gauge Hatch
Relief Valve
Inlet
Manway
Catalyst Makeup
(Fresh Catalyst Only)
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157048-1
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Figure 48
Expansion Joint Location
Top of Support
Spring Hangers
Spent Catalyst
Expansion Joint
Recirculation Catalyst
Expansion Joint
Regenerated Catalyst
Expansion Joint
Top of Support
Structural Bumper
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The typical components of a UOP specified expansion joint are shown in Figure 49.
Figure 49
Expansion Joint Components
Convolution
Liner
Root
Ring
Cover
Purge
Connection
Bellows
Flow
Bellows Design UOP presently specifies single ply bellows. Dual Ply bellows are
acceptable provided each ply is designed for full temperatures and pressure. Dual
Ply bellows should include a method for pressure leak detection (preferably a
positive pressure gage) as shown in Figure 50. When adding a dual ply
replacement to an existing expansion joint, the piping system should be reviewed
for the additional loads induced by the higher spring rates of the dual ply.
157048-1
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Figure 50
Two-Ply Bellows
WEEP HOLE
TWO-PLY TESTABLE
FOR LEAK
BELLOWS
DETECTION
PROCESS PIPE
ATTACHMENT
WELD
Control Rod Design The control rods are intended for control and stability of the
expansion joint and are not intended to take the full bellows pressure thrust force.
The control rods should be used for reference when determining the installed
position of the expansion joint as well as a reference during operation and shutdown
(for future trouble shooting information).
Equalizing Rings UOP presently specifies a self equalizing expansion joint. Root
rings are an acceptable alternative to equalizing rings. (UOP specifies a minimum
area requirement for root rings). Equalizing rings and root rings are intended for
added protection in the event of over pressure.
Bellows Packing Details Several methods of packing the bellows are shown in
Figure 51. External insulation is required on packed bellows to minimize the
potential of condensation during operation. UOP currently uses packed bellows for
all expansion joints except for the spent catalyst expansion joint which is
continuously steam purged to remove hydrocarbon and minimize coking. Several
refiners have successfully used packed bellows for the spent catalyst expansion
joint. UOP is currently evaluating several FCC units before packed bellows for this
service is incorporated in the project specifications.
157048-1
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Figure 51
Packing Details of Expansion Joints
157048-1
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expansion joint absorbs both axial compression and lateral offset. These forces are
due to the regenerator expanding upward, the spent catalyst stripper downward,
and the standpipe compressing during operation. This standpipe is relatively short
and therefore not subjected to out-of-plane movement that occurs on inlet and
outlet nozzles connected to large-diameter vessels. Early units used carbon steel
standpipes and slide valves for the spent catalyst to the regenerator. Most of the
newer units use 1 Cr, Mo; although a few have stayed with insulation lined
carbon steel.
On new units, the regenerated catalyst standpipe and the lower portion of the
reactor riser are of cold-wall construction. On this type of unit, the expansion joint
needs to absorb axial extension and lateral offset, mainly as a result of the large
thermal growth from the hot-wall stripper and upper reactor riser. On older units
having a hot-wall wye section and regenerated catalyst standpipe, the primary
movement during operation is still axial extension and lateral offset. However, on
shutdown of the unit, the expansion joint may need to absorb axial compression,
which occurs when the raw oil is cut from the unit, steam is added at the bottom of
the riser, and the regenerated catalyst slide valve is closed. The steam cools the
reactor riser while the regenerator standpipe remains at operating temperature
because of hot catalyst filling the standpipe above the closed slide valve. The
regenerated catalyst standpipe can also be subjected to additional movements
because of the long length of reactor riser and standpipe. Any bowing of the riser or
the stripper or sagging of the standpipe affects the amount of axial movement and
lateral offset the expansion joint has to absorb. The regenerated catalyst standpipes
and slide valves range from 5% Cr on conventional units to stainless steel (Type
304) in older higher temperature units and cold wall design in modern high
temperature units.
Thermal movement is absorbed within the expansion joints by means of a flexible
item referred to as bellows. The bellows are formed into a corrugated shape from
thin-gauge material of a metallurgy selected to perform in the process environment
encountered; the expansion joint bellows are normally Alloy 625. The geometry and
number of corrugations used relate to the total movement capacity of a bellows.
The bellows design is based on equations outlined in the Standards of the
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Figure 52
Bellows Movement
D
C
h
E
L
TAN =
=
2
h
L
A
B
Ratios:
C A F
= =
D B E
C-A
Tan ( 2 ) = ( 2 )( F )
or
( 2 )( D E- B )
157048-1
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Figure 53
How Motion is Absorbed by Bellows
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SLIDE VALVES
Slide valves are used to control catalyst flow. These are gate-type valves driven by
a hydraulic actuator. The primary problems encountered with slide valves were
associated with erosion and corrosion. The elimination of guide steam purges have
alleviated many of the corrosion problems. However, if guide steam purges are
present, then the steam purge can be used once or twice a shift to keep the guides
free of catalyst. In some cases, a continuous purge is used, but its flow should be
restricted to prevent erosion of the guides. To prevent erosion, the valve disc is
covered with an abrasion-resistant refractory anchored by stainless steel hexmesh.
Hard metal surfacing is used on other parts of the valve exposed to catalyst flow
(see Figures 54 and 55). The clearances between the support guides on the sides
of the valve and the disc are set by the manufacturer. The entire system will expand
when it gets hot, so these clearances should be checked to avoid binding or
sticking. The new slide valves are designed such that no guide purge is required.
Cold wall design which uses carbon steel (see Figure 54) has also eliminated some
corrosion problems as well as many of the cracking problems generally associated
with hot wall design (specifically polythionic attack on the stainless steel). By
working closely with many slide valve suppliers, UOP has also incorporated design
and geometry guidelines which minimize erosion during normal operation. These
changes include locating the orifice plate upstream of the valve and sloping the
bottom of the bonnet a minimum of 30 from the horizontal. The sloped bottom
prevents catalyst accumulation in the bonnet. The support guides for the disc are
recessed a minimum of 3" (75mm) from the sides of the inlet port. Other design
improvements recently developed are as follows:
1. Five second stroke time for normal operation.
2. Two second stroke time for emergency shutdown.
3. Emergency shutdown features are testable on stream.
4. Offset port to center flow during normal operation.
5. Development of cold wall valves for spent catalyst standpipe service.
6. In shop hot stroke test required to guarantee trouble free operation in the field.
157048-1
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Figure 54
CL Port
CL Port
CL Valve
CL Valve
Port Opening
Stem
Stuffing Box
Guide Bolting
Bonnet
Drain Slots
Guide
Bonnet
Carbon
Steel
Shell
Disc
Orifice
Plate
157048-1
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Figure 55
Hot Wall Slide Valve
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A typical FCC slide valve hydraulic oil system, used in earlier designs, is shown in
Figure 56. The hydraulic oil is pumped out of the low pressure tank through a filter
to the slide valve. It circulates back from the valve or from two flow by-passes. One
of these is a hand controlled valve at the end of the hydraulic header; the other is a
minimum flow bypass on automatic control. These keep the oil circulating and
prevent pump damage that might occur if the pump were to run against a closed
system, such as when the pilot valve is holding the valve in one position. A spare
pump with auto start is used to maintain flow if the first pump fails. The high
pressure oil tank will supply sufficient hydraulic oil to close the slide valves if both
pumps go down. This tank is not large enough to hold oil pressure for more than
one to two minutes. If both pumps are lost, the unit should be brought down until at
least one is running again. Modern plants are designed with a separate oil system
for each valve, but it is more common to have one hydraulic oil system for all slide
valves. Small multi-stage centrifugal pumps are gradually replacing the
reciprocating pumps on older plants.
157048-1
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Figure 56
FCC Slide Valve Hydraulic Oil System
N2
From Control
Instrument
IA
Must Drain
F
FV
RO
SV
HC
FH
PI
D
HPR
HV
LPR
F
FIC
F
F&W
Legend
D = Drain
F = Filter
FH = Flexible Hose
FIC = Flow Indicating Controller
F & W = Filling & Withdrawal
HC = Hydraulic Cylinder
HPR = High Pressure Receiver
HV = Hand Valve
IA = Instrument Air
LPR = Low Pressure Receiver
PV = Piolet Valve
RO = Restriction Orifice
SV = Safety Valve
UOP 2119-44
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Figure 57
Slide Valve Actuator
Component Arrangement and Hydraulic Circuitry
157048-1
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Figure 58
Reactor Riser Disengaging Devices
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Vented-riser systems, which use the momentum of the catalyst exiting the riser for
ballistic separation, have been successfully operating for more than 10 years and
are well proven in commercial applications. UOP has 11 vented-riser designs in
operation. On later vented riser designs, no mechanical or erosion problems have
been observed. However, limited erosion has been noticed on units revamped to a
vented-riser when the catalyst flux is high. As a preventative measure, UOP now
recommends additional " (19 mm) abrasion-resistant refractory lining to be
installed in the following areas on vented-riser reactor systems (Figure 59):
The reactor head extending approximately 3 ft beyond the tangent line. The
refractory lining is used to cover a target area on the head of the reactor
where the catalyst impacts directly. The lining is a precaution since erosion
has not been observed in this area.
DA points. Half-pipe shields coated with refractory lining are installed over
the DA points to protect them against erosion.
TI points. Half-pipe shields coated with refractory lining are installed over the
TI points to protect them against erosion. The thermowells are to be the hard
surfaced type. The control point is moved to the reactor plenum chamber.
The reactor shell above the cone section. A stainless steel taper bar should
be used to terminate the abrasion resistant lining being added. The angle of
this taper bar should be as small as possible. The abrasion resistant lining is
usually extended a minimum distance of 3' (0.9 M) above the reactor cone.
157048-1
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Figure 59
Extent of Reactor Cladding and Hex Lining
For Vented Riser Terminations
157048-1
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In this design, the combined catalyst and product vapor mixture exits the riser and
passes directly into the riser cyclones for separation. The product vapors exit the
riser cyclone gas tube and pass through a second stage of cyclones before exiting
the reactor. The catalyst flows down the cyclone diplegs into the catalyst stripper.
The vapors carried down the diplegs and the vapors from the catalyst stripper are
swept from the reactor system back into the cyclone system with steam into a vent
tube entering the cross over duct between the cyclone stages.
Because all of the catalyst flows into the cyclones, erosion was concern in the
design of a direct-connected cyclone system. Reports from the operating UOP
direct-connected cyclone systems that have undergone scheduled mechanical
turnarounds indicated only negligible erosion in the riser and cyclone areas.
Because of the transfer piping now incorporated between the primary and
secondary cyclones, the hydrocarbon vapor product and hot catalyst are no longer
in contact with the reactor shell. Consequently, a large thermal differential is
introduced between the reactor internals and the adjacent reactor shell at startup, at
shutdown, and during emergency situations. The mechanical design of the reactor
must accommodate this thermal gradient. UOP's standard design practice is to use
a thermal differential, which is based on the difference between the reactor design
temperature and the steam condensation temperature.
The thermal gradient is not limited to the reactor internals. The reactor riser, reactor
vapor manifold, and reactor vapor line are also subjected to the same thermal
differential. As a result, all guides, supports, and other attachments to the reactor
shell must be designed to accommodate this condition. UOP's experience has been
that all support guides, and sometimes the actual vapor line, require some type of
modification when the direct-connected cyclone system is incorporated into the
design. In summary, the addition of direct-connected cyclones affects the entire
reactor system and is not just limited to the internals.
During the 90's, UOP developed and put into commercial operation the suspended
catalyst separation system which combines the features of the vented riser
(allowing pressure upsets) and direct connect (high containment) systems (see
Figure 60). This system is a two cyclone vented riser which operates with a similar
flow pattern to the direct connect system, but the riser above the first stage is open.
157048-1
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The riser fills with a dense zone of catalyst above the inlet to the first stage cyclone
during normal operation, but during a pressure upset the catalyst is free to
discharge harmlessly into the reactor. It was also proven that the suspended
catalyst separation system had the same advantage as the direct connect system;
post riser cracking is minimized because all of the vapor goes to the first stage
cyclone.
Figure 60
Suspended Solids Separation Riser Design
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Figure 60
Vortex Separation System (VSS)
Vortex
Chamber
A
Prestripping
Section
Prestripping
Steam
Dipleg
Gas
Catalyst
Catalyst
Level
Internal
Riser
Spent Catalyst
Stripper
Vortex
Chamber
Section A-A
157048-1
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Figure 61
Vortex Disengager Stripper (VDS)
To Main
Column
Plenum
Cyclones
Vortex
Disengager
Riser
Counter Weighted
Flapper Valves
Support
Brackets
Gas Flow To
Cyclones
Fluffing
Steam Ring
Reactor Shell
Prestripping
Section
Catalyst Return
Slots
Spent
Catalyst
Stripper
Catalyst Flow to
Stripper
Stripping
Steam Ring
Fluffing
Steam Ring
Spent Catalyst To
Regenerator
157048-1
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REACTOR RISER
The reactor riser is a vertical pipe in which the desirable cracking reactions take
place. Hot catalyst enters the wye section at the bottom of the riser and is lifted up
to the feed injection point by the lift gas/steam mixture. Two wye designs, a hot wall
and a cold wall, have been used. The two wye sections differ in wall temperature
and resulting stresses. The modern cold wall wye with 5" (125 mm) of refractory
lining has a lower wall temperature and reduced stress, permitting the metallurgy to
be changed from 304H stainless steel to carbon steel. The cold wall wye and the
hot wall wye are illustrated in Figures 62 and 63. A mixture of lift gas and steam is
injected through the lift nozzle at the bottom of the wye section. Catalyst and lift
media travel up the riser to the feed distributors where the riser diameter increases.
This increase allows for the increased volume of hydrocarbon vapors as the oil is
injected and vaporized when it meets the catalyst. Because the riser volume is
small it limits the contact time between the catalyst and hydrocarbon. This prevents
overcracking of the products. Below the point where the riser enters the reactor
stripper, the riser is carbon steel with castable refractory lining. This lining is
abrasion resistant and insulates the carbon steel from the high catalyst
temperatures. Above the point at which the riser enters the reactor stripper, the riser
becomes hot wall so the metallurgy is upgraded to typically 1 Cr Mo.
157048-1
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Figure 62
Cold Wall Wye
Carbon Steel
Reinforcing Rings
Bumper
157048-1
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Figure 63
Hot Wall Wye
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Page 112
157048-1
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Figure 64
Reactor Riser Feed Distributor
Bayonet Type
157048-1
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Figure 65
Reactor Riser Feed Distributor
Jet Nozzle Type
157048-1
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Figure 66
Effect of Feed Distributor
UOP 3110-9
157048-1
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Figure 67
Premix Feed Distributor (Wye)
157048-1
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Figure 68
Premix Feed Distributor with Annular Lift (Wye)
157048-1
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157048-1
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Figure 69
Elevated Feed Injection System
Mix Zone
Feed &
Steam
Acceleration
Zone
Catalyst
Steam or Gas
UOP 2569B-1
157048-1
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Page 120
157048-1
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Page 121
Figure 70
Elevated Riser Premix Feed Distributor
157048-1
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The Optmix nozzles have been commercially proven in more than twenty units and
major performance benefits with the Optimix nozzle system have been achieved in
dry gas reduction and gasoline yield improvement.
The feature most recently added to the Optimix distributor is the DUR O LOK
coupling. This coupling provides a means for replacing the tips for maximum
flexibility in both maintenance and modification for changes in design charge rate.
157048-1
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Figure 71
UOP Optimix Feed Nozzle
Steam
DUR O LOCTM
Coupling
Oil
REACTOR PLENUM
The direct-connected cyclone reactor systems prompted the development of new
reactor plenum designs. In a direct-connected system, the area surrounding the
cyclones is relatively inactive. The traffic in this area is limited primarily to the
vapors being carried out of the reactor stripper. During startups and shutdowns, the
temperatures observed at the reactor shell and cyclones can therefore be
substantially different. To accommodate the large differences in thermal expansion,
new plenum designs were required. Different approaches to this problem are shown
in Figure 72. UOP typically uses an internal plenum design to minimize overall
vessel height and cost.
157048-1
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Figure 72
UOP Plenum Chamber Designs
External Plenum
Internal Plenum
External Manifold
157048-1
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temperatures. Alternatively, a lower coke yield for the same conversion can be used
to increase throughput on main air blower limited units.
In 1998 and 1999 UOP conducted an extensive research program to evaluate the
existing commercial stripper tray designs and develop a more efficient design. A
commercial scale Plexiglas model was built to allow visual observations of the
catalyst and gas flow patterns. Catalyst circulation rates greater than commercial
flux rates were possible in this model. Helium tracer gas injected to the catalyst
entering the top of the model was used to quantify the stripping efficiency for each
tray type.
The three stripper tray designs which were used commercially in the past by UOP
and tested in the model are shown in Figure 74.
The classic UOP tray, which had 2 rows or large holes on the top of the tray was
used up to the mid 1980s. The stripper tray style with three rows of holes in the
skirt was used from the mid 1908s to early 1990s. In the early 1990s the jets were
returned to the top of the trays with longer skirts which allowed more pressure drop
across the tray for better steam distribution. Each of these designs perform well at
low to moderate catalyst flux rates, up to ~60,000 lb/hr/ft2 (290 kg/hr/m2). Above
these rates the efficiency falls quickly and fluidization problems can occur which
limit the capacity of the stripper.
The modern tray design developed from the cold flow modeling is shown in Figure
75. This tray uses a larger number of smaller jets on the top of the tray spread out
over a larger percentage of the tray than in previous designs. This provides for
better steam/catalyst contacting resulting in improved stripping efficiency. Another
advantage resulting from this is that all areas of the bed are uniformly fluidized
resulting in smoother catalyst flows and uniform catalyst flux. This improved
fluidization has allowed the upper limits on catalyst flux to be pushed above 100,000
lb/hr/ft2 ( 490,000 kg/hr/m2) while maintaining very high stripping efficiency. The
catalyst flux is based on the annular area between the riser and stripper shell.
157048-1
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The modern stripper is also designed for higher catalyst residence times than the
early models. This residence time is important to allow completion of bed cracking
reactions of the absorbed hydrocarbons which continue to generate strippable
vapors that can be removed before the catalyst enters the regenerator. The uniform
catalyst flux in the modern stripper also increases the effective catalyst residence
time by eliminating areas of stagnant catalyst and areas of high catalyst flux.
Figure 73
High Efficiency Spent Catalyst Stripper
Insulation
Riser
Stripper Shell
Stripping
Steam
Stripping
Steam
Abrasion Resistant
Lining
Fluffing Steam
FCC-E005
157048-1
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Figure 74
Historical Stripper Tray Designs
157048-1
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Figure 75
Modern Stripper Tray Design
C
L Spent Catalyst
Stripper
Abrasion
Resistant Lining
Detail
12-14 Gage
Tubing
Riser
Stripper
Shell
FCC-E007
157048-1
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REFRACTORY LlNING
Refractory lining is used extensively in the reactor and regenerator. The types of
refractories generally fall into three categories: abrasion resistant, insulating, and
castable. Castable refractory lining exhibits both abrasion resistant and insulating
properties. In recent years, abrasion resistant plastic linings have entered the
market. Plastics have become popular for small repair jobs because of their ease of
application. The material is putty-like and comes ready for installation without
addition of water. A listing of the various applications is given in Table 2.
TABLE 2
REFRACTORY LlNING
Application
Reactor
Reactor Stripper
Upper Regenerator
Lower Regenerator
Standpipes
Upper Reactor Riser
Lower Reactor Riser
Cold Wall Wye
Hot Wall Wye
Feed Distributor
Expansion Joint
Slide Valve
Cyclones
External Mixer
Flue Gas Line
Catalyst Cooler
Abrasion
Resistant
X
X
X
X
X
X
X
X
X
X
X
X
X
Castable
Insulating
X
X
X
X
X
X
X
X
X
157048-1
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UOP has made several modifications to the refractory specifications to ensure the
proper use of materials, installation procedures, and inspection and testing
methods. Some of the major revisions to the UOP Standard Specifications include
the following:
The anchor spacing has been reduced from 12 (300) for high density
vibrocast refractory and gunned refractory:
Anchor Location
Top head of Vertical Vessels
Plenum Areas
Overhead Areas
Horizontal Shells
Catalyst Transfer Lines
Overhead Vapor Lines
Vertical Shells
Bottom Head of Vertical Vessels
Downhand Areas
Anchor Spacing
1.0 x Lining Thickness
The coating on the anchor has been reduced to the tip of the leg. Coating on
just the top " (13mm) of the anchor leg allows a greater bond and allows
thermal expansion of the tips without spalling the lining on the surface.
157048-1
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The heat drying procedure has been modified. The modified procedure is
required to ensure refractory quality by incorporating a controlled, slow heatdrying rate.
The installation temperatures are controlled to ensure that the lining is not
freezing or being subjected to incomplete hydration.
Figure 76
Steerhorn Anchors for Gunned and Vibrocast Refractory Lining
Cap
1(25 mm)
60
5/16 (8mm)
Diameter Anchor
3/8
(9 mm)
Radius
Shell
Weld
1/2
(13mm)
Radius
157048-1
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THERMOWELLS
Reactor thermowells are protected with a hard metal surfacing. The number will
depend upon the size of the unit. The most important temperatures are the riser
outlets for a modern unit, or the dense bed for an older unit. These can be checked
with the reactor over head and stripper bottom outlet thermowells. The catalyst in
the stripper usually is 5-10F (3-6C) hotter than the cyclone outlets, because heat
transfer from the catalyst to the oil is not perfect. Thermowells may inadvertently be
placed in a dead area, where false, usually low, readings are obtained. False
readings can be detected by comparing the different readings obtained around the
reactor.
The thermowells used in the regenerator are protected by a stellite hard surface
coating. Wear will vary, depending on location. During the inspection, each
thermowell should be carefully checked and replaced if necessary.
157048-1
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Figure 76
DA, DG and DS Piping
1/2" Pipe to Instrument
1/16" Restriction
Orifice
Strainer
P
Nozzle on Vessle
Or Standpipe
3/4 '' Instrument Air for "DA" Points
3/4 '' Purge Gas for "DG" Points
3/4 '' Purge Steam for "DS" Points
FCC-E008
157048-1
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During inspection, the pressure taps (and pressure taps used for level indication)
should be cleaned and the surrounding refractory should be checked. The reamer,
shown in Figure 77, can be used to clean out the taps when the unit is on stream,
or when it is down.
Figure 77
Pressure Tap Reamer
6'' (150) DIAMETER HANDWHEEL
FLEXIBLE GRAPHITE
PACKING
5'-0'' (1525)
ROUND HEAD
STEEL PLUG
FCC-E009
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MAIN COLUMN
The FCC main column is shown in Figure 78. The column may be divided into two
sections: the regular fractionator and the lower disc and doughnut trays. The bottom
six trays are designed for high vapor and liquid flow rates. The trays are shown
schematically in Figure 79. A coke trap, shown in Figure 80, prevents large pieces
of coke or other debris from entering the bottom line.
The steam ring may be used on some units to steam strip the bottoms material of
any lighter hydrocarbons. The column is fitted with three sample lines which are
normally called try lines; the bottom try line is also used as a sample line. These are
used to check the bottoms level because the level glass and indicator are subject to
occasional plugging by fines or coke particles. Both level instruments are protected
with an LCO flush which flows into the level instrument from the top.
The FCC main column is mounted on a table top instead of the skirt mounting seen
on most columns. Table top mounting simplifies maintenance work on the bottoms
lines, which are subject to plugging from coke or catalyst fines. A separate suction
line to each pump allows operation to continue through one line while the other is
cleaned. As an additional note, every valve in the bottoms circuit should be installed
with the stem up to keep catalyst fines out of the bonnet. If plant layout does not
allow a stem to be straight up, it should be as close to the vertical position as
possible.
The upper part of the tower is similar to any other fractionator. Sidecut streams
must be stripped to remove absorbed light material. Stacked heavy cat naphtha and
light cycle oil strippers are shown in Figure 81. Steam is the most common
stripping method, although reboiler strippers are sometimes used. Reboiler
strippers decrease the amount of sour water that must be treated. The overhead
vent from each stripper returns to the main column in a vapor space.
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The overhead from the column is condensed by air or water coolers, normally a
combination of the two. Water from the gas concentration section washes the
ammonia and some other salts from the last bank of condensers. If it were injected
before this, much of the water could vaporize, decreasing its effect. The sour water
is separated in the overhead receiver (see Figure 82) and sent to a sour water
stripper. Gasoline and gas go to the gas concentration section, with some gasoline
returned to the tower for reflux.
The main column is made of regular or killed carbon steel, with a 1/8 inch (3 mm)
thick Type 405 or 410 (12 Cr) cladding from below the naphtha or LCO draw tray to
the bottom outlet. Any nozzles or manways in this clad section should also be alloy
lined. All the trays and caps in the column are Type 410 stainless. The inspector
should look for any evidence of pitting, cracks or bulging in the alloy lining. Metal
thickness should be checked and recorded for future reference. A general
inspection should be made for loose caps, clips and bolts, and for general metal
loss or tray distortion. The upper part of the column is usually not subject to severe
corrosion. The bottom of the column should be checked for integrity of the lining
and for any signs of coke buildup. Excess amounts of coke may indicate that the
bottoms temperature was too high during operation. The coke trap and steam ring
should be cleaned and checked for corrosion. The steam ring should have the
nozzles pointing upward, to avoid erosion to the bottom head lining.
157048-1
Equipment
Page 137
Figure 78
Main Column
Manway and
Vent
Reflux
Vapor Out
HCN Liquid
Return
4
5
HCN Stripper
Vapor Return
HCN Reflux
Draw
HCN Reflux
Return
HCN Pumparound
and Product Draw
7
18
LCO Pumparound
Return
19
20
LCO Stripper
Vapor Return
LCO Reflux
Draw
LCO Reflux
Return
21
LCO Pumparound
and Product Draw
410S or 405
cladding
17
26
HCO Pumparound
Return
27
28
29
30
31
32
33
34
MCB Pumparound
Return
35
36
37
38
Try Lines
Quench
Steam Out
Coke Trap
Bottoms Pumaparound
and Product Draw
FCC-E400
157048-1
Equipment
Page 138
Figure 79
Typical Disc and Donut Pans
C VESSEL
1-3/8" DIAMETER HOLES
ON 5" EQUILATERAL
1-3/8" DIAMETER HOLES
ON 2-1/2" EQUILATERAL
TRIANGULAR PITCH
TRIANGULAR PITCH
SUPPORT
RING
C VESSEL
A
OPEN AREA
4" HIGH WEIR FOR
TOP DONUT ONLY
PLAN OF DONUT
C VESSEL
DOWNCOMER
OF TRAY
TRAY
SUPPORT
RING
DONUT TRAY
DISC TRAY
SECTION A-A
C VESSEL
1-3/8" DIAMETER HOLES
ON 2-1/2" EQUILATERAL
OPEN AREA
TRIANGULAR PITCH
C VESSEL
SYMMETRICAL
ABOUT CENTERLINE
PLAN OF DISC
NO HOLES AT FEED POINTS
FCC-E401
157048-1
Equipment
Page 139
Figure 80
Typical Coke Trap
120
40
150
SUPPORTS
OPENINGS
25 R
150
50 (TYPICAL)
OD OUTLET NOZZLE
100
PROVIDE 2 DRAIN
OPENINGS, LOCATED
180 DEG APART.
(BOTTOMS OUT)
FCC-E402
157048-1
Equipment
Page 140
Figure 81
Heavy Cat Naphtha Stripper (Top)
Light Cycle Oil Stripper (Bottom)
Manway and Vent
Stripping Steam
LC-LG
Vortex Breaker
Vent
Vapor to Main Column
Stripped HCN Product
1
LCO from Main Column
Stripping Steam
LC-LG
Vortex Breaker
FCC-E403
157048-1
Equipment
Page 141
Figure 82
Main Column Overhead Receiver
Vent and Ventilation
Vapor Outlet
Manway
PC
Steam Out
Inlet Distributor
(Detail)
LC & LG
LC & LG
Water
Water Boot
Water Outlet
Hydrocarbon
Outlet
Vortex Breakers
FCC-E404
157048-1
Equipment
Page 142
STEAM
LP
RETURN HEADER
TO CIRCULATING
STEAM
CONDENSATE
3/4 ''
MP
STEAM
TI
PUMP WARMUP/COOLDOWN
PUMP WARMUP/COOLDOWN
PDI
PG
MIN
TO CIRCULATING
MCB HEADER
MIN
COKE
STRAINER
OIL
FLUSHING
STEAM
OIL
FLUSHING
MIN
BLANKOFF
STEAM
MP
COKE
STRAINER
MIN
MIN
PG
PDI
TI
PUMP WARMUP/COOLDOWN
PUMP WARMUP/COOLDOWN
3/4 ''
Try Lines
MP STEAM
Figure 83
Main Column Bottoms Circulating Pumps
MOV
MIN
FCC-E405
OIL
FLUSHING
MOV
157048-1
Equipment
Page 143
MIN
157048-1
Equipment
Page 144
Besides the turnaround, the bottoms pumps usually require some repair work
during the course of the run. The seal flush system should be checked for
cleanliness, and the packing replaced if necessary. The packing is especially
vulnerable to the hot, erosive conditions. There may also be wear to the pump case
and rotor. If this is severe, a hard surfacing material may be applied to the rotor.
The inspector should also check the pump suction strainer for corrosion and holes.
157048-1
Equipment
Page 145
Figure 84
Slurry Service Orifice Meter Piping Assembly
Closed Coupled Above Orifice for ANSI Class 300/600
Screwed Cap
(do not seal
weld)
" Globe
"
minimum
Pipe
Transmitter
Mounting
Bracket
P
Capsule
Single
Valve
Equalizing
Manifold
minimum
Flange Adapters
" Gate
(Install on Vertical Tap)
" Pipe
Flow
Pipe Strap
" Solid Plug
FCC-E406
157048-1
Equipment
Page 146
SLURRY SETTLER
In earlier units when the cyclone efficiency was not as high, the main column
bottoms stream contained catalyst fines which had to be removed to meet certain
product specifications. Part of the bottoms stream was sent to the carbon steel
settler (sometimes called a clarifier) where the fines would settle out and were
returned to the reactor with a slurry recycle. Clarified oil came off the top of the
vessel. The settler operated liquid full, with a cross-sectional area designed for an
upward oil velocity of 30 BPD/ft2 (2.1 M3/hr/M2) or less at normal charge rates.
Heavy cycle oil or raw oil diluent could be used to flush the fines back to the reactor.
Figure 85
FCC Slurry Settler
Vent
Manway
Main Column
Bottoms Inlet
Nozzle and
Wear Plate
Dilute Oil
Inlet and
Distributor
Flushing
Nozzle
Steamout
Slurry Outlet
UOP 2119-67
157048-1
Equipment
Page 147
SLURRY FILTRATION
Filtration of the slurry product to achieve product specifications of 100 wppm total
solids or lower is becoming increasingly common. Sales of the slurry product as
carbon black feedstock and desire to minimize the increasing cost of tank cleaning
are driving this trend.
The most common type of filters use pourous, sintered metal filter elements. A
typical filter system will have 2 or 3 vessels with a number of filter elements in each.
One vessel is typically in filtration mode while another is in backflush mode to
remove the filter cake from the elements. When enough catalyst fines have
deposited on the filter elements to increase the pressure drop across the filter to a
pre set limit the vessel is taken off line for back flushing. Once the filter vessel is off
line and drained the vessel is filled with backflush liquid, either HCO or LCO, and
allowed to soak to help dissolve any heavy aromatic compounds on the elements.
The top of the vessel is then pressured up with either fuel gas or nitrogen to provide
the driving force for a high velocity back flush. The back flush material is collected in
receiver vessel and pumped back to the reactor riser or to the spent catalyst
stripper. A typical arrangement for the filtration equipment is shown in Figure 86.
157048-1
Equipment
Page 148
Figure 86
FCC Slurry Filter
BACKFLUSH
GAS
BACKFLUSH GAS
ACCUMULATOR
CLEAN
PRODUCT
OUT
FILTER
VESSEL
#1
FILTER
VESSEL
#2
FILTER
VESSEL
#3
VENT
SLURRY
IN
BACKFLUSH
RECEIVER
HCO or
LCO
SOAK IN
BACKFLUSH
TO
REACTOR
FCC-E407
157048-1
Equipment
Page 149
2.
3.
The first of these, hydrogen blistering, is the most common problem with general
metal attack by the various acids a close second. Hydrogen blistering occurs in
steel where surface corrosion is active. Blisters are formed by the diffusion of
atomic hydrogen into steel and then accumulate at slag or inclusions within dirty
steel. The atomic hydrogen then converts into molecular hydrogen, and the
resultant pressure forms the blister. Blisters may rupture to the thin side of the
defect. The presence of cyanides (Prussian blue) greatly increases susceptibility of
H2 blistering in steel. The inspector should look for a bluish color when the plant is
first opened, because this is a good indication of areas where corrosion and/or H2
blistering may be found. Hydrogen sulfide (H2S) also contributes to blistering and
corrosion; it is present in most gas concentration units. The inspector should look
for H2S pitting, blisters, and general metal loss. Inspection of the equipment should
be thorough, and when corrosion is found, the type and extent of the corroded
areas should be determined. It is not unusual to find one head or one particular
plate in a vessel full of blisters, with the remaining portion of the vessel in good
condition. Repairs can be made by replacing the damaged areas and still maintain
the equipment in service.
157048-1
Equipment
Page 150
157048-1
Equipment
Page 151
157048-1
Equipment
Page 152
CENTRIFUGAL MACHINES
Centrifugal compressors (Figure 87) are multi-stage machines, contained within the
two external stages. Each of the two stages is protected by an anti-surge device
which will over-ride normal controls to protect the machine. Gas leakage out of the
casing is prevented by suction and discharge end labyrinth seals. These seals are
backed by either buffer gas or seal oil, normally oil. The seal oil system runs 5 psi
above suction gas pressure, using a seal oil head tank or differential pressure
controller to hold this differential pressure even if suction pressure varies
somewhat. A balancing drum is used to offset axial thrust, so suction pressure is
maintained at both ends of the compressor. The seal oil system must be kept in
operation while the casing is under pressure or gas will leak out.
157048-1
Equipment
Page 153
Figure 87
Centrifugal Compressor
FCC/DS-R00-45
157048-1
Equipment
Page 154
RECIPROCATING MACHINES
Reciprocating compressors can be driven by gas engines, turbines, or electric
motors. They are usually constant speed machines. Suction valve unloaders and
clearance pockets are provided on some machines for greater operating flexibility.
A reciprocating machine should never be run with discharge valves blocked in.
Liquid slugging is also very dangerous, as the liquid is incompressible and will lead
to broken piston rods or a cracked head. Suction knockout drums should be
checked frequently for any liquid.
The reciprocating machine uses packing to prevent gas leakage from the
compressor. This simple system should work quite well as long as the packing is
tightened correctly. Over tightening will lead to excess wear and then leakage.
157048-1
Equipment
Page 155
Figure 88
Compressor Suction Drum
Ventilation and
Vent Nozzles
Gas Out
Mesh Blanket
(Demister Pad)
LC-LG
Manway
Steamout
Vortex breaker
Liquid Out
FCC-E700
157048-1
Equipment
Page 156
WASH WATER
The overhead stream from the main column contains various contaminants which
may cause corrosion, plugging, or fouling. These would include ammonia, sulfides,
cyanides, chlorides, and phenols. A wash water stream is used to remove them,
because most of them are ionic or polar species, readily soluble in water. Flow rates
are usually maintained at 6-7 vol% of the fresh feed rate.
The water should be clean, preferably steam condensate, to prevent adding more
problems such as salts or dissolved oxygen to the system. The water is injected
after the compressor first stage and is pumped out of the interstage suction drum to
the HPS. Here it collects in a water boot and is pressured back to the main column
overhead condensers. It collects in the overhead receiver water boot and is pumped
out to the sour water stripper for disposal.
There is always water present in the main column and gas concentration section
from stripping steam and other sources. If the wash water is not used to flush out
the sulfides, ammonia, cyanides, and other species, the water present can become
highly corrosive from absorption of these contaminants. Sulfide levels of greater
than 20,000 ppm have been reported in the overhead receiver water. Hydrogen
blistering and general corrosive attack may become quite severe, especially if feed
sulfur is greater than 1%, or nitrogen greater than 1000 ppm. Also, while the
overhead receiver water may be basic, pH >7, most of the ammonia that is
responsible for this will drop out in the main column receiver.
The water in the gas concentration section may become acidic from H2S and CN-. If
there is any oxygen present, elemental sulfur may be formed from oxidation of the
sulfides. This will cause problems in meeting gasoline product specifications. Wash
water will solve many of these problems by diluting the corrosives, and keeping the
water pH at 8-9, where sulfide oxidation is greatly reduced.
157048-1
Equipment
Page 157
Figure 89
High Pressure Separator
Inlet Pressure Relief
PI & PC
LI & LC
Ventilation
and Vent
Vapor Out
Slotted Pipe
Distributor
Manway
Steam Out
Vortex
Breaker
LI & LC
Liquid Out
Water Boot
Water Out
FCC-E701
157048-1
Equipment
Page 158
PRIMARY ABSORBER
The primary absorber (Figure 90)is a killed steel column with about 30-40 trays.
The trays are normally carbon steel with Type 410 stainless steel fittings. Valuable
light products such as LPG are absorbed from the gas as it travels from the bottom
to the top outlet. The most common tower design uses two intercoolers to remove
the heat of gas absorption from the gasoline as it fails down the tower. This
temperature rise is roughly 20-25F (11-14C). These intercoolers are located
roughly one-third and two-thirds of the way down the tower. The gasoline circulation
through the water coolers may be pumped or gravity driven. Water drain pots are
required on the gravity circulation systems to prevent accumulation of water as the
gasoline cools; a water head would stop gasoline circulation. Pumped systems are
better from a velocity, and thus heat transfer, viewpoint.
Another design that has become popular recently uses debutanized FCC gasoline
as a final wash before the gas leaves the tower. A cooled slipstream from the
bottom of the debutanizer is introduced at the top of the column, with the gasoline
from the main column overhead receiver entering the tower 5 to 7 trays lower. This
system allows the use of only one intercooler with the same or better C3 recovery
efficiency, i.e., the amount of C3 recovered in the debutanizer overhead compared
to the total amount produced. The gasoline from the bottom of the primary absorber
is pumped to the HPS; the gas flows to the sponge absorber.
Serious corrosion can occur in this column from H2 attack. Hydrogen blistering can
be severe in the upper section and top head, and is also seen occasionally in the
middle of the tower and in the intercoolers. The shell and heads should be
inspected at each turnaround. The inspection of the internals should pay particular
attention to stagnant areas around weirs, downcomers, and nozzle extensions.
Bolts and trays should be inspected for tightness and embrittlement of materials.
157048-1
Equipment
Page 159
Figure 90
Primary Absorber
Vent and Ventilation
Vapor Outlet
Distributor
Distributor
Unstabilized
Gasoline Inlet
Manway
12
13
14
26
27
28
40
LC & LG
Vapor Inlet
Liquid Outlet
FCC-E702
157048-1
Equipment
Page 160
SPONGE ABSORBER
The sponge absorber (Figure 91) is a "guard" tower which uses LCO to absorb any
remaining liquid from the gas. If any significant quantities of C5 or C6 remain in the
gas stream, these will cause problems with treating. If the gas is sent directly to the
fuel system, condensation of heavy material is dangerous.
The sponge absorber is fabricated with killed steel. It used to be designed with 25
carbon steel trays; the tray fittings were Type 410 stainless. Currently, UOP designs
all sponge absorbers with packing towers which minimizes the risk of foaming. A
mesh blanket, Type 304 stainless, is installed at the top of the absorber to trap any
entrained liquid.
The gas leaves the tower on pressure control. Absorption LCO is flow controlled,
with a lean oil/rich oil exchanger to heat the rich sponge oil as it leaves the
absorber. This decreases the temperature effects when the LCO is returned to the
main column. The lean oil is water cooled after it leaves the rich oil exchanger, to
100F (38C) maximum.
The inspector of the tower should follow the same pattern of inspection as the
primary absorber. The sponge absorber is subject to corrosion and hydrogen
blistering, but usually somewhat less than the primary.
157048-1
Equipment
Page 161
Figure 91
Sponge Absorber
Vent and Ventilation
Vapor Outlet
Mesh Blanket
Pre-Distributor
Re-Distributor
Hold Down Grid
Manway
Bed Support
Vapor Inlet
LC-LG
Steam Out
Liquid Out
FCC-E703
157048-1
Equipment
Page 162
STRIPPER
The stripper (Figure 92) removes light hydrocarbons and H2S from the gasoline. A
LCO reboiler is used to heat the tower and to preheat the gasoline feed. The off-gas
goes to the HPS; an FRC in the gas line controls the LCO to the reboiler.
The stripper is made of killed carbon steel with about 30-40 carbon steel trays. Tray
fittings are Type 410 stainless. Some units have experienced high corrosion rates in
the stripper. The reboiler is usually carbon steel, but may be 5% Cr % Mo in
cases where severe corrosion has occurred. This corrosion is not common and can
usually be corrected without the additional expense of a chrome reboiler. Inhibitor
has been used in some cases, but this protection can be lost with unstable
operating conditions. The inspector should check metal thickness and the reboiler
should be checked for unusual wear during the turnaround.
157048-1
Equipment
Page 163
Figure 92
Stripper
Vapor Outlet
Vent and Ventilation
Distributor
Liquid Inlet
1
18
Manway
19
36
Reboiler Return
Reboiler Draw Off Well
LC & LG
Steam Out
Liquid Out
Vortex Breaker
FCC-E704
157048-1
Equipment
Page 164
DEBUTANIZER
The stripped gasoline is pressured to the debutanizer for vapor pressure
adjustment. The LPG product after treating can be used for fuel or further
processed for petrochemicals. The gasoline product usually requires treatment for
sulfur, and the addition of inhibitors for better stability.
The most common method of pressure control is a hot vapor bypass around the
overhead condenser. The reflux back to the tower is temperature controlled by a
TRC device located on the fourth tray from the top. This scheme gives a better split
than overhead temperature control. Heat is supplied by a HCO reboiler,
occasionally supplemented by a main column bottoms reboiler. Hot fluid to the
reboiler tubes is FRC controlled. Insufficient heat will not give good fractionation,
too much heat will flood the tower.
The debutanizer (Figure 93) is killed steel with 35-40 carbon steel trays. Tray
fittings are Type 410 stainless. The overhead system is usually carbon steel, with
inhibited Admiralty tubes in the water condenser. The shell of the reboiler is carbon
steel; the tubes, tube sheet and floating head cover are 5% Cr % Mo. Carbon
steel clad with Type 410 stainless may be used instead of 5% Cr. Hot fluid flow is
through the tubes. This vessel and associated piping are occasionally subject to
severe corrosion and hydrogen blistering. The best solution to this and to the
corrosion problems of the other vessels is water injection at the interstage receiver.
As mentioned above, some refiners have also used alloy steel or monel instead of
carbon steel for severe cases of corrosion in the debutanizer.
157048-1
Equipment
Page 165
Figure 93
Debutanizer
Vent and
Ventilation
Vapor Outlet
Reflux
1
TIC
8
Stripper
Bottoms
Inlet
19
Manway
20
35
36
40
LC & LG
Vortex Breaker
Reboiler
Return
Manway
Steam Out
Liquid Out to
Reboiler and
Product
FCC-E705
157048-1
Equipment
Page 166
CORROSION
Steel Corrosion
It has been established that steel corrosion, hydrogen blistering, and weld cracking
problems come from a water, hydrogen sulfide, ammonia, and/or cyanide
environment. The overall corrosion reaction for steel is:
Fe + 2HS- = FeS + S-2 + 2H
(1)
The amount of bisulfide ion (HS-) formed depends on the pH, temperature, and
hydrogen sulfide (H2S) partial pressure and comes from the H2S dissociation:
H2S = H+ + HS-
(2)
The iron sulfide (FeS) scale provides some protection against corrosion if the
system pH is about 8. However, dissolved hydrogen cyanide (HCN) accelerates
corrosion by destroying the protective FeS film and converting it into soluble
ferrocyanide complexes:
FeS + 6CN- = Fe(CN)6-2 + S-2
(3)
The ferrocyanide (Fe(CN)6-4) is easily recognized by its blue color (Prussian blue)
when water samples are allowed to dry.
Hydrogen Blistering
Some portion of the hydrogen atoms formed in the corrosion process (Equation 1)
gradually penetrates the steel through surface imperfections and diffuse into the
steel as atomic hydrogen. This diffusing hydrogen reacts to form molecular
hydrogen:
2H = H2
157048-1
Equipment
Page 167
The hydrogen molecules are larger in size and are trapped in the steel cavities
causing local pressure to build up. The result is blistering and fissures in the metal.
High quality killed carbon steel usually has less inclusions today than in earlier
times, and blistering is usually less of a problem than before.
Water Wash
Most refiners feel that wash water is adequate for cyanide control. Hydrogen
blistering has not been a problem in most of the FCC Gas Concentration units.
Cyanide is effectively kept out of the Gas Concentration Unit through the use of an
adequate wash to the Main Column overhead receiver and to the wet gas
compressor Interstage suction drum. An effective water wash dilutes and scrubs the
corrosive species such as hydrogen sulfide, ammonia, chlorides, and cyanides from
the FCC light hydrocarbon streams.
As stated previously, the water wash rate should be at least 6-7 Vol% on fresh feed
to the FCC Unit. There should be no entrainment of water from the overhead
receiver to the primary absorber column. Recommended water wash sources
include oxygen free water, steam condensate, and boiler feed water before
alkalinity adjustment. If the wash water contains oxygen, gum formation will
increase and wet gas compressor fouling may occur. If the wash water contains
magnesium or calcium salts, these components will precipitate increasing the
fouling problems. Also, if oxygen is present, elemental sulfur may be formed
causing copper strip corrosion in the gasoline.
Condensate pH
Overhead streams in the fractionator and gas concentration section consist mainly
of hydrocarbon vapors, steam, and relatively small amounts of contaminants.
During condensation, the water phase absorbs some of the contaminants and can
become highly corrosive. The FCC Process condensate develops a pH of 7 to 9
because of the higher concentration of ammonia relative to the acid contaminants
and because ammonia is more soluble in water than hydrogen sulfide or hydrogen
cyanide.
157048-1
Equipment
Page 168
The pH of the system should be higher than 8.0. At lower pH values the
polysulfide decomposes into ammonia (NH3), hydrogen sulfide (H2S), and
elemental sulfur (S). The H2S will increase the corrosion rate and the
elemental sulfur (S) will give corrosive gasoline and equipment plugging
problems.
2)
The polysulfide will commence salting out at temperatures below 38F and
plug pump suction and discharge lines.
3)
157048-1
Equipment
Page 169
4)
5)
Wash water requirements are generally higher to assure that the polysulfide
stays in solution. If the polysulfide does not stay in solution equipment plugging
will increase. Also, processing the additional sour water can be costly.
157048
Fluidized Solids
Page 1
FLUIDIZED SOLIDS
Introduction
A fluidized bed is formed by passing a gas upwards through a bed of solid particles.
If the gas velocity (U) is above a minimum gas velocity, Umf, the solids become
fluidized and the mixture behaves like a liquid.
Figure 1
Fluidized Beds Behave Like a Liquid
No Flow
U Umf
Flow
U Umf
157048
Fluidized Solids
Page 2
157048
Fluidized Solids
Page 3
This behavior will change as more gas is pressured through the bed. Bubbles of gas
begin to appear in the bed. The point at which this occurs is defined as the
minimum bubbling velocity (Umb). The bubbles may be small ones which disappear
after a short rise, or larger ones that grow as they pass through the bed. As the
velocity is increased further, the bubbles begin to occupy more of the bed. The
bubbles bursting through the surface throw catalyst into the area above the bed.
The surface of the bed is violently disturbed by the slugs, yet remains fairly distinct.
As gas velocity is further increased, the bed enters a turbulent state, where the
upper surface of the bed is not well defined. Slugging by large gas bubbles
decreases. Bubbling bed regenerators typically operate in this region. Advantages
of this regime are high solids mixing and therefore high heat and mass transfer
rates, contributing to the combustion of coke off the catalyst. The mixing is primarily
in the vertical direction and is driven by catalyst particles being pushed upwards on
top of the bubbles then falling off and dropping down behind the bubbles as shown
in Figure 2.
Eventually, the gas velocity exceeds the terminal velocity of some of the particles in
the bed. This regime is known as fast fluidization. Combustors typically operate in
this regime. At this point, a fluidized bed is not maintained unless catalyst is
recycled to the bed. Further gas rate increase moves into the pneumatic conveying
regime. Without recirculation of catalyst, all catalyst will be blown out of the vessel.
157048
Fluidized Solids
Page 4
Figure 2
Bubble Driven Catalyst Mixing
Catalyst
Flow
Bubble
Wake
Drift
Gas
FCC-F001
157048
Fluidized Solids
Page 5
Figure 3 illustrates the pressure drop across a bed as a function of fluidization gas
superficial velocity. Initially, the pressure drop increases with velocity to the point of
initial fluidization, Umf. For typical FCC catalyst this value is around 0.01 ft/sec.
Once fluidized, the catalyst exerts a pressure profile similar to that of a liquid. The
pressure head exerted by the bed will be about equal the weight of catalyst and the
gas contained in it. As a result of frictional losses, the pressure drop across the bed
is slightly greater than its weight. Between the point of initial fluidization and the
point at which entrainment begins, the behavior of the catalyst may be described by
the following equation:
P = (cat + gas) * h where gas 0
P = Pressure Drop, psi
= Density, lbs/ft3
h=
Bed Height, ft/144
At higher velocities, we approach the pneumatic conveying regime in which the
entire bed is eventually entrained; hence a sharp pressure drop.
157048
Fluidized Solids
Page 6
Figure 3
Pressure Drop Across a Fluidized Bed
Bubbling
Bed
Regenerator
U>Umb
Combustor
U<Umf
Reactor
Riser
Particulate
Regime
Bubbling
Regime
Slug Flow
Regime
Turbulent
Regime
Fast
Fluidization
Fixed
Bed
Gas
Initiation of
Fluidization
Entrainment
Begins
gas 0
U = Gas Velocity
Umf = Minimum fluidization Velocity
Umb = Minimum bubbling velocity
Density, lbs/ft3
hBed Height, ft/144
Pneumatic
Conveying
157048
Fluidized Solids
Page 7
157048
Fluidized Solids
Page 8
Figure 4
Geldarts Particle Classification
10,000
5,000
3,000
2,000
D
B
1,000
500
300
200
100
10
20
50
100 200
500 1,000 2,000
dp, Microns
C: Cohesive
D: Spoutable
157048
Fluidized Solids
Page 9
Fluidization in Regenerator
Superficial velocities in the FCC regenerator are considerably higher than minimum
fluidization. This is because the air rate is set by the coke make in the unit, not the
fluidization requirements. Less air would leave the unit behind in burning, with most
of the coke still on the catalyst. The regenerator diameter could be increased to
drop the superficial velocity but this would add considerable cost in construction.
Additionally, uniform distribution of air is more difficult in very large vessels. The
FCC design takes into account the need to regenerate catalyst, maintain
fluidization, retain catalyst inventory, and minimize capital expenditures.
The conventional or Bubbling Bed regenerator, shown in Figure 5, generally
operates with superficial air velocities of 2-3.5 ft/sec. This velocity is in the turbulent
fluidization regime. This regime exhibits violent bubbling and gas slugging which
causes catalyst to be thrown upward into the freeboard area above the bed. Most of
the catalyst settles back to the bed by gravity. However, some of the catalyst,
especially fines, is carried up above the freeboard area. The regenerator vessel can
thus be divided into two sections, the dense bed and the dilute phase.
The dense bed is all the catalyst contained below the established bed level. The
dilute phase is where larger catalyst particles separate from the gas and fall back to
the bed. Any catalyst particles that do not separate in the dilute phase, enter into
the regenerator cyclones. Catalyst entering the cyclones is separated by centrifugal
force with the larger particles being returned to the bed via the cyclone diplegs.
Catalyst fines too small to be separated by the cyclones are carried out of the
regenerator with the flue gas.
In a bubbling bed regenerator it is important that the coke and air are evenly
distributed. The air bubbles rising through the bed result in thorough mixing in the
vertical direction but little mixing horizontally. Therefore if the spent catalyst, and
therefore the coke, is not uniformly distributed the areas with more coke may be
short of air allowing CO to breakthrough the bed. The other areas with less coke
operate with excess oxygen. This combination results in afterburning and high
157048
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temperatures in the dilute phase. For this reason a spent catalyst distributor or ski
jump is used on all spent catalyst standpipe outlets. In many cases the air grid jet
plugging pattern will be shifted to areas expected to have less coke present to
reduce the air in that area.
The design distance between the cyclone inlet and the surface of the dense bed is
determined by the Transport Disengaging Height, or TDH. The TDH is a function of
the superficial gas velocity, vessel diameter, and the particle size distribution. The
amount of catalyst entrained in the gas above a fluidized bed decreases with the
height above it. A given particle reaches a distance above the bed where
gravitational forces overcome the upward drag forces of the gas, and the particle
falls back to the bed. The smaller the particle, the greater the distance. A height is
reached where the amount of entrained solids becomes constant, no more particles
are overcome by gravitational forces. The particles here are to small to settle. This
height, the TDH, determines what minimum distance above the bed the cyclones
inlets must be placed. Other considerations for setting the cyclone design inlet level
include dense bed level variations and minimum required dipleg length. To account
for these considerations, the cyclone inlet height will be greater than the actual
TDH.
As illustrated in Figure 6, if a regenerator is operated in such a manner that the
distance between the catalyst bed and the cyclone inlet is less than the TDH, the
catalyst density at the cyclone inlet will be higher. This will increase the catalyst
loading to the cyclone and potentially increase catalyst losses from the cyclone.
In a bubbling bed regenerator the discharge of the primary cyclone diplegs which
are returning hot catalyst to the bed can be directed to heat colder areas of the bed,
typically near the spent catalyst inlet.
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Figure 5
Conventional FCC Regenerator
Flue
Gas
Transport
Disengaging
Height
Freeboard
Catalyst
Movement
Dense
Bed
Gas
Bubbles
Air
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TDH
Height
Figure 6
Schematic Depiction of TDH
Density of Solids
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This operating data demonstrates how flexible the system is in adjusting combustor
inventory/coke burning capacity for various operating conditions. Consider the
operating condition E at gas velocity B. If the superficial velocity is now increased to
C either by a change in regenerator pressure or air rate, the combustor density will
decrease to condition F at constant solids loading. However, if necessary, the
combustor density may be reestablished at condition G by means of increasing the
solids flux (opening the external recirculation slide valve). Note that an adjustment
in combustor density also changes the combustor inventory and a change in the
upper regenerator level (surge inventory).
The catalyst bed density in a regenerator is primarily a function of superficial
velocity. For typical bubbling bed regenerator velocities, bed densities would range
from 30 to 40 lb/ft3. By contrast, typical combustor densities range from 10 to 15
lb/ft3. Figure 8 gives a correlation between bed density and superficial velocity.
Figures 9, 10, & 11 show normal catalyst densities in various unit configurations.
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Figure 7
Combustor Operation
A
(Z)
3 3
Combustor Density, lb/ft
Combustor Catalyst
Inventory, I =
Density x Volume
D
(Y)
(Y)
(X)
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Figure 8
Catalyst Bed Density
60
50
40
30
20
10
0
0
0.1
1.0
3.0
10.0
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Figure 9
Catalyst Densities
Side by Side FCC with Bubbling Bed Regenerator/
Tee Disengager Riser Termination
2
(30)
40-45
(640-720)
3
(50)
35
(560)
35
(560)
5
(80)
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Figure 10
Catalyst Densities
High Efficiency Regenerator/ Highly Contained
Riser Termination/ Elevated Feed
<1
(<15)
1
(20)
3
(50)
40
(640)
40-45
(640-720)
35
(560)
5
(80)
8-12
(130-200)
15-20
(240-320)
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Figure 11
Catalyst Densities
RFCC 2 Stage Regenerator
<1
(<15)
40-45
(640-720)
3
(50)
5
(80)
35
(560)
3
(50)
35
(560)
35
(560)
15-20
(240-320)
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Fluidization in Standpipes
Fluidized catalyst can be made to flow through pipe in the same manner as a liquid.
Standpipes generate static head which allows transport of catalyst between the
reactor and regenerator. The static head generated must be enough to overcome
any pressure differences between the reactor and regenerator. As catalyst travels
down the standpipe it carries gas with it which keeps the catalyst fluidized and
flowing smoothly. The pressure will increase as the catalyst progresses down the
standpipe because of the additional head. This increase in pressure causes the
entrained gas to compress and the void volume to decrease. If the gas is
compressed too much the catalyst in the standpipe becomes dearated, it will no
longer flow smoothly and can cause circulation problems. A condition know as slipstick flow can ensue where the catalyst breaks away from the dearated mass and
passes down the standpipe. Reactor temperature and reactor level swings can be a
symptom of this phenomenon. Standpipe design criteria are set to ensure that
pressure head build up, flux rate and velocity, and aeration levels are adequate to
ensure stable operation.
Figure 12 illustrates the pressure profile in a standpipe. Troubleshooting of low or
erratic standpipe flow should start with a single gauge pressure survey to ensure
that the right amount of head is generated in the standpipe. The head generation
should be the density in the standpipe, typically 35 lb/ft3 (560 kg/m3) times the
elevation change. Another useful troubleshooting exercise is to check the flow
through the slide valve versus the expected flow predicted by the slide valve
equation:
A x Cd x (DP x )1/2
W=
1.5
Where:
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Figure 12
Standpipe Pressure Profile
Standpipe Entrance
Effects
Head Generation
Height
Slide Valve Entrance Effects
Slide Valve DP
Pressure
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diplegs this gas volume can be very large, as much as 6 wt% of the total product.
Once the catalyst exits the dipleg the entrained gas is exposed to high temperatures
for an extended period of time in the large reactor shell volume resulting in higher
light ends and coke make. This is one of the reasons for development of the vortex
separation technology which provides a highly contained riser termination without
the entrainment of hydrocarbons back into the reactor through the diplegs.
Fluidization in Reactor Stripper
The reactor stripper is similar in principle to a dense bed in the regenerator. The key
difference is that the fluidization, or stripping, medium is steam and not air. Steam is
introduced through pipe distributors and flows up through the bed displacing
hydrocarbons from the interstitial and void spaces of the catalyst. Roughly 1.5 to 2.5
pounds of steam per thousand pounds of catalyst is required for a well designed
stripper. The stripping action helps to recover valuable reaction products and
maintains proper fluidization of the catalyst as it moves back to the regenerator.
Typical superficial velocities are in the range of one to three feet per second.
Poor stripper design can result in uneven distribution of the vapor flow. As a result
of this, some of the catalyst may become defluidized while the catalyst flux in other
areas of the stripper increases. This can reduce stripping efficiency due to poor
catalyst/steam contacting, excessive gas entrainment down the stripper and lower
residence times in the active portion of the stripper. As the catalyst flux in the active
area of the stripper increases more gas can be entrained down the stripper and into
the standpipe resulting in lower densities, less standpipe head generation and lower
slide valve pressure drop.
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CATALYST
INTRODUCTION
The FCC catalysts in use today are a complex blend of technologies. The
workhorse catalyst in this complex system is, itself, a complex blend of
technologies. The main component in the workhorse catalyst is a crystalline silicaalumina material known as a zeolite, or alternatively known as a molecular sieve.
The quantity and the properties of the zeolite in the catalyst can be altered to fit the
individual activity and product yield requirements of the refinery. A second active
component in the workhorse catalyst is typically an active alumina, included in the
workhorse catalyst to provide conversion of the very large and heavy molecules in
the feed, which are difficult for the molecular sieve to process. This second
component also can protect the molecular sieve from contaminants in the FCCU
feed, which can damage the performance of the molecular sieve. A third component
is added to this catalyst cocktail to make the catalyst hard enough to meet the
stringent particulate emissions requirements of the FCCU.
In todays world, other catalytic components are frequently combined with the
workhorse catalyst, as catalyst additives. These additives can be included to
provide increased gasoline octane, increased yields of light olefins, principally
propylene, enhanced coke burning characteristics in the regenerator, and
decreased SOx and NOx emissions from the regenerator.
HISTORY
The first FCC catalysts were finely ground, naturally occurring clays. By today's
standards, these catalysts were inexpensive, but they suffered from poor stability,
activity, and integrity. Activity was less than half what it is today, and erosion caused
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There are over 30 different naturally occurring zeolites, but only 8 exist in sufficient
quantities to permit commercial exploitation. Over 100 have been synthesized in the
laboratory. The zeolite used in todays FCC catalyst is called a Type Y sieve and is
close to a rare natural mineral called faujasite. Large quantities of this material are
synthesized by the catalyst industry; roughly 50 million pounds per year are used for
FCC catalyst.
When zeolites were first tested as FCC catalysts, a pure zeolite was used. In the
pilot plants in operation at that time, this zeolite proved far too active, more than 100
times as active as amorphous catalysts. But when the zeolites were incorporated
into an amorphous base, the catalyst showed great promise. The first commercial
catalysts were made with 8-10% zeolites, and showed an activity 1.5 to 2 times that
of the amorphous types. To utilize this higher activity, UOP introduced the short
contact time, all riser cracking concept. The short contact time minimized
undesirable over cracking, while the high activity maintained good conversion.
Since virtually all the cracking could be done in one pass, it was no longer
necessary to recycle large quantities of heavy oil from the main column. Obviously,
the fresh feed rate was increased. However, for distillate operations, the low reactor
severity desired still required a high recycle rate.
The Y-zeolite is made up of regularly reoccurring cage-like structures. The cage has
openings into the cage of approximately 7 in diameter. The zeolite is, thus,
sometimes referred to as a molecular sieve, since the constrained entrance into the
zeolite cage acts as a sieve. Molecules up to a certain size can enter the cage while
larger molecules are kept out. Cracking occurs inside the cage at the locations of
the active sites, which are associated with the aluminum atoms inside the cage. The
cracked products must then exit the catalyst. At this time, the accepted theory is
that the reaction is not diffusion-controlled or limited, although the effect is present.
When exposed to the severe hydrothermal conditions that exist in the regenerator,
the crystalline structure of the zeolite is susceptible to significant destruction of its
structure, resulting in loss of catalytic activity. A major advancement in catalyst
technology occurred in the late 1960s, when it was discovered that a controlled
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hydrothermal pretreatment could improve the stability of the zeolite. The resulting
product was designated as ultra-stable Y-zeolite, commonly referred to as US-Y.
The 1970s ushered in the age of Environmental Sensitivity. Air pollution concerns
impacted the operations of the FCCU. This in turn ushered in the age of Catalyst
Additives. The first environmental concerns that effected FCC operations were in
the areas of CO pollution from the FCC regenerator and lead pollution from car
exhausts.
Prior to 1970, burning coke in the regenerator resulted in equal volumes of CO and
CO2 in the flue gas. It was impossible to convert the CO to CO2 in the FCCU without
creating unacceptable temperatures in the upper part of the regenerator.. A
modestly sized FCCU (20,000 BPD) without a CO boiler typically emitted over
20,000 lbs/hr of CO into the atmosphere. In the early 1970s it was discovered that a
small amount of platinum (~ 1ppm) in the FCC catalyst inventory allowed the CO to
be completely converted to CO2 without causing excessive temperatures in the
regenerator. In addition to eliminating CO, complete combustion had economic
advantages as well. Today, the 1 ppm of platinum is typically added as a catalyst
additive, which contains a high concentration of Pt (500 1000 ppm).
Prior to the 1970s, tetra ethyl lead (TEL) was used to increase gasoline octane but
concerns were raised that it also resulted in toxic lead emissions in automobile
exhaust. In the 1970s, legislation in the U.S. was passed that reduced, and
eventually eliminated, the amount of TEL that could be used in gasoline. Refiners
had to take steps to regain the lost octane. The use of US-Y zeolites in the FCCU
was found to help increase FCC gasoline octane. At the same time, a new zeolite
with a smaller pore than Y-zeolite, designated as ZSM-5, was developed which,
when added to the FCC catalyst inventory, was found to increase gasoline octane.
An additive containing ZSM-5 was frequently used for this purpose in the 1980s.
Sulfur oxide emissions (SOX) from the regenerator flue gas became an
environmental concern in the 1980s. This led to another catalyst additive which
refiners could blend with their FCC catalyst. The additive captured the SOX
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produced in the regenerator and carried it back to the reactor, where the sulfur was
released as H2S and left the FCCU with the product gases. The sulfur could then be
recovered as elemental sulfur in a Klaus plant.
In the late 1990s, concerns about nitric oxide (NOX) emissions from the regenerator
began to be raised. Catalyst suppliers began to provide additives that could be used
to reduce NOX. With the aid of the NOX additive NOX was converted to N2 and left
with the regenerator flue gas.
Also in the late 1990s, demand for propylene increased to the point where
propylene became an FCC product of considerably greater value than FCC
gasoline. Refiners who could produce a high quality propylene product began to run
their cat crackers to maximize propylene. The use of a ZSM-5 containing additive
became the variable that had the biggest impact upon increasing FCC propylene
yields. Whereas, in the 1980s, a ZSM-5 additive was used to increase gasoline
octane, at the start of the 21st century, ZSM-5 additives were primarily being used to
increase FCC propylene yields. The trend towards increasing value of propylene
continued during the period 2000 2005, during which time the price of propylene
increased from ~$500 / metric ton to ~$900/ metric ton. Refiners have increased
their use of ZSM-5 additives during this period and catalyst suppliers have
responded by increasing the content of ZSM-5 zeolite in their additives. In the
1980s, ZSM-5 additives typically contained 10% ZSM-5 zeolite. By 2005, additives
containing 40% ZSM-5 were common. Catalyst suppliers were also beginning to
supply a multi-functional catalyst which contained, within one catalyst particle, both
a Y-zeolite component and a ZSM-5 zeolite component.
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Heats the air from the air blower up to the temperature of the
regenerator
On the reactor side, the catalyst must have sufficient activity to carry out catalytic
conversion of the hydrocarbon feed before any significant amount of thermal
cracking occurs and must have the selectivity characteristics that provides the type
of products required by the refinery.
Thus, the catalyst must have the thermal stability to maintain particle and catalytic
integrity under severe regenerator conditions. It must have the physical strength to
maintain particle morphology under the severe impact and erosion forces so that it
remains in the unit, and it must have the proper flow characteristics to allow it to
readily flow between the regenerator and the reactor.
Thermal (free radical) cracking is the predominant cause for the removal of
hydrocarbon groups from the ends of a hydrocarbon chain, producing most of the
methane, and a large portion of the ethane and ethylene produced. Significant
quantities of the larger fragments (C3 and greater) are generally not produced by
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Cracking of the original large gas-oil molecule is a primary reaction. Such reactions
can be:
The secondary reactions are mainly associated with H-transfer reactions of one kind
or another and generally result in the saturation of an olefin:
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The isomerization of a straight-chain olefin, after the initial formation of the olefin, is
another important secondary reaction.
CATALYST COMPONENTS
To carry out its functions, the modern FCC catalyst is typically made up of four
separate but important components:
The inactive matrix component and the binder control the overall activity of the
catalyst by diluting the highly active components down to the proper activity level
and provide the proper particle strength and morphology. In the area of particle
strength, all catalyst suppliers have made major advances in catalyst attrition
resistance. In the 1990s, achieving good catalyst attrition resistance is generally not
a problem.
From a catalytic point of view, the zeolite and the active matrix components are the
items of principal interest.
The Zeolite
The zeolite provides controlled Brnsted (proton donor) acidity from its crystalline
structure and both Brnsted and Lewis (electron acceptor) acidity from the
nonframework alumina. Non-framework alumina exists as a result of the hydrothermal removal of alumina from the silica - alumina zeolite framework. Some basic
zeolite concepts help to understand how the zeolite functions.
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Initiation: nC10H22
CH3(CH2)6CH=CHCH3+H2
C7H 15 C C CH3
+
H
C7 H15 CH = CH CH3
O
O
|
Si O AL O
|
|
O
O
H+ O
O
|
|
Si O AL O
|
|
O
O
(Protonated Catalyst Surface)
O
O
|
Si O AL O
|
|
O
O
C6H 13 + CH 2 = CH CH 2 CH 3
O AL O
|
O
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In this illustration, the -CH3 fragment at the other C-C position can not generate
enough vibration to crack the bond.
The carbenium ion also promotes rapid skeletal isomerization to the tertiary carbon
location, which is the most stable configuration, as:
CH 3
C 2 H 5 CH 2 CH 2 CH 2
C 2 H 5 C CH 3
O AL O
|
O
O AL O
|
O
CH3
CH3
O AL O
O AL O
O O AL O
O
O AL O
-
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Zeolite Structure
The zeolite used in today's FCC catalyst is the Y-type faujasite. The tetrahedral
structure is the basis for the entire geometry of the Y-type faujasite. The tetrahedron
is present at the beginning when silicon and aluminum atoms are combined with
four oxygen atoms (Figure 1) in a tetrahedral arrangement. The silica and alumina
tetrahedra are then arranged at the vertices of a truncated octahedron known as the
sodalite cage. This cage has 8 hexagonal faces, 6 square faces (Figure 1), and 24
silica and alumina vertices.
Figure 1
Zeolite Molecular Structure
Tetrahedron
Sodalite
Silicon
or
Aluminum
Oxygen
The sodalite cages also combine tetrahedrally, through the hexagonal faces, with
other sodalite cages (Figure 2) to form the supercage, also known as the unit cell.
Eight sodalite cages make a unit cell. Some important dimensions of these
structures in a Y-type faujasite crystal are:
Sodalite cage
Entrance diameter 2.2
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Supercage
Entrance diameter 7.4
Internal diameter 13
Unit cell (as synthesized)
External diameter 24.67
Figure 2
Zeolite Molecular Structure
Sodalite
Cages
Supercage
Hexagonal
Prisms
Zeolites are frequently referred to as either a large pore zeolite, with a 12 member
ring pore entrance; as a medium pore zeolite, with a 10 member ring opening; or as
a small pore zeolite, with an 8 member ring pore opening. The Y-zeolite is a large
pore zeolite with a 12 member ring.
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Zeolite Dealumination
Under the conditions of steam and high temperature that exist in an FCC
regenerator, all Y-type faujasite zeolites dealuminate to some degree, even if fully
rare earth exchanged. The crystal structure is attacked by water molecules, which
extract the aluminum and deposit it within the supercage as Al(OH)3:
O
|
O Al- O
|
O
OH
+ 4 H+OH-
OH
OH
OH
+ Al(OH)3 + Cation OH
The non-framework alumina (NFA) that is deposited has catalytic activity (Lewis
acidity). It tends to catalyze the formation of C2 and lighter gases, olefins, and coke.
The hydroxyl nest, which is formed when aluminum is removed from the framework,
represents a point of framework weakness that can lead to crystal collapse. In some
cases, silicon atoms migrate from the crystal surface into the crystal lattice in an
annealing type of operation and fill the vacancies left by the departing aluminum
atoms. Also, in other cases, silicon atoms from a collapsed framework react with the
NFA to form silica-alumina compounds.
A further effect of dealumination is that the crystalline structure shrinks in size, the
O-Si-O bond being smaller than the O-Al-O bond. The greater the degree of
dealumination, the smaller the crystalline unit cell size. Also, as aluminum is
removed from the crystal structure, the ratio of SiO2 to Al2O3 in the remaining
framework increases. The measurement of unit cell size by X-ray diffraction
techniques then becomes a convenient way to determine the SiO2/Al2O3 ratio of
the zeolite in a catalyst. Such a relationship is shown in Figure 3.
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Figure 3
Effect of Dealumination on Unit Cell Size
24.70
24.66
24.60
24.50
24.52 (US-Y)
24.40
24.30
24.20
5 8
10
20
30
40
50
60
0 30 50 60
70
80
85
90
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Figure 4
Effect of Rare Earth Exchange on
24.45
24.40
24.35
24.30
24.25
24.20
0
10
12
14
16
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Figure 5
Delta Coke at 65 wt% Conversion
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Figure 6
Gasoline Olefin Content at 65 wt% Conversion
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Figure 7
C6-C8 Aromatics at 65 wt% Conversion
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Figure 8
Gasoline RONC at 65 wt% Conversion
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Figure 9
Gasoline MONC at 65 wt% Conversion
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Changing the degree of zeolite dealumination has some other subtle effects on the
cracking reaction and on FCC operating conditions. Increased dealumination (lower
unit cell size) increases the endothermic heat of cracking and also increases
cracking activation energy. The multiple effects of changing unit cell size are
illustrated in Figure 10. Although the higher heat of reaction and lower delta coke
resulting from lower unit cell size increases the catalyst circulation rate and lowers
regenerator temperature, it also increases coke yield because of the effect of
increased heat of reaction on the FCC heat balance.
Figure 10
Effect of Equilibrium Zeolite Unit Cell Size
Heat of Reaction
Octane
Activation Energy
24.25
24.30
24.35
24.40
24.45
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As the demand for propylene increased in the 1990s, ZSM-5 additives began to be
used to increase the yield of FCC derived C3=. That trend has continued to
accelerate in the 21st century. Placing a high concentration of ZSM-5 crystalline
zeolite into the FCC catalyst blend can produce high C3= yields. Yields of up to 20
wt% C3= can be achieved with the proper feed and operating conditions, compared
to a C3= yield of 3-4% at conventional FCC conditions.
Catalyst suppliers are actively working to produce more effective ZSM-5 additives.
The additives produced in the 1980s typically contained 10% ZSM-5 crystalline
zeolite. As the demand for C3= increased, the need arose for FCC catalyst blends
containing higher amounts of ZSM-5. However, using large quantities of the 10%
additive resulted in a dilution of the base Y-zeolite catalyst. Since only the Y-zeolite
could crack VGO, the dilution resulted in an unacceptable loss of VGO cracking
activity. Additives containing higher contents of ZSM-5 were developed. A second
generation of additives containing 25% ZSM-5 was provided to the industry. Going
higher in sieve content and maintaining adequate attrition resistance proved to be
difficult, but eventually that problem was resolved. Additives containing 40% ZSM-5
with good attrition resistance are now available. Catalyst suppliers are now working
on developing a single particle catalyst which contains both a Y-zeolite and a
ZSM-5 zeolite.
Todays ZSM-5 additives are modified by the addition of phosphorous to the zeolite.
Phosphorous combines with aluminum atoms in the zeolite crystal structure,
through an oxygen bond, and enhances the stability and acidity of that alumina site.
Catalyst suppliers now routinely include the equilibrium catalyst phosphorous
content on their equilibrium catalyst report. Knowing the phosphorous content of the
fresh additive allows the refiner to tract the amount of ZSM-5 additive in their
equilibrium catalyst blend.
A typical set of results for increasing amounts of ZSM-5 additive is shown in
Figures 11 and 12.
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Figure 11
20
50
18
48
16
46
14
44
Gasoline
12
42
10
40
Butylenes
8
6
38
36
Propylene
34
Ethylene
32
30
0
0.5
1.5
2.5
3.5
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Figure 12
Effect of ZSM-5 On Gasoline Octane
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The Matrix
The matrix is defined as the entire catalyst particle except the zeolite. Its function is
to provide catalyst hardness, as well as to adjust the catalyst activity to the proper
level by diluting the zeolite, and to provide some special properties, such as
bottoms cracking activity and metals traps.
Zeolites have one major drawback: their porosity. The pore opening is too small
(7 to 8 ) to allow the large molecules with high molecular weight to enter the
zeolite cage. For this reason, some precracking must occur before the zeolite can
play a major role.
To some extent, the zeolite itself can provide this precracking function. The zeolite
has some external, active surface area that can be reached through the large inert
pores provided by the kaolin-silica binder matrix. Some mesopores in the 20 to 50
region are also created within the zeolite as a result of sieve collapse. These
mesopores can then provide some access to the zeolite interior. Consequently, the
zeolite itself can precrack a large percentage of the paraffinic molecules in the feed.
The large, multi-ring aromatic molecules create a more-difficult problem.
Active Alumina Matrix
The active alumina matrix component provides the catalyst with the ability to crack
these large molecules. As seen in Figure 13, the active alumina matrix provides
significant surface area and hence active sites in the 50 to 200 region. These
pores are sufficiently large to provide easy access to the large molecules and thus
allow precracking to occur.
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Figure 13
Effect of Matrix on Pore Size Distribution
Figure 14
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27
Aromatic Feed
@ 60% Conversion
LCO, wt-%
25
23
21
Paraffinic Feed
@ 75% Conversion
19
17
15
20
40
60
20
100
120
140
160
The typical active alumina matrix achieves its activity to a large degree through
Lewis acid sites. These sites are well known to cause coke and H2 formation. Thus,
the selectivity achieved via active alumina cracking is expected to be substantially
poorer than with zeolitic cracking. This reaction occurs for both paraffinic feeds and
aromatic feeds (Figures 15 and 16).
Figure 15
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5.2
Coke, wt-% FF
4.4
Aromatic Feed
3.6
2.8
Paraffinic Feed
2.0
1.2
20
40
60
20
100
120
140
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Figure 16
Effect of Matrix on Dry Gas Yields
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Figure 17
Effect of Metals on Coke Factor
Coke Factor of Equil. Catalyst
3.0
C atalyst
F
A
B
C atalyst F
2.5
V /N i
3.3
2.4
0.5
2.0
C atalyst A & B
1.5
1.0
0.5
1,000
2,000
3,000
4,000
5,000
Figure 18
Effect of Metals on H2 Factor
H2 Factor of Equil. Catalyst
8 .0
7 .0
C a ta ly st
F
A
B
C a ta ly st F
6 .0
V /N i
3 .3
2 .4
0 .5
C a ta ly st A
5 .0
4 .0
C a ta ly st B
3 .0
2 .0
1 ,0 0 0
2 ,0 0 0
3 ,0 0 0
4 ,0 0 0
E q u iv a le n t N ic k el (N i + V /4 ), w t-p p m
5 ,0 0 0
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Extrapolation of Figures 17 & 18 would indicate that nickel levels above 10,000
ppmw would result in totally unacceptable H2 and Coke Factors. Recent experience
has shown that these factors do not continue to increase linearly with increasing
nickel content. Rather, as seen in Figure 19, they reach an upper limit, which
depends upon catalyst design. It is believed that there is a limiting catalyst surface
area for supporting the deposited nickel. Once the metal has covered the available
area, additional metal deposits on top of already deposited metal and does not
generate any additional catalytic metal surface area.
Figure 19
Effect of Nickel Upon E-Cat H2 & Coke
0.9
4.5
0.8
4
Coke
0.6
3.5
3
Hydrogen
0.5
2.5
0.4
0.3
1.5
0.2
0.1
0.5
0
0
5000
10000
15000
20000
0.7
0
25000
Metals Passivation
The FCC feed additives that form chemical complexes with nickel have been
successful in reducing the dehydrogenation activity of nickel. Antimony compounds,
which have been in use for more than 30 years, are effective chemical additives.
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Data showing the reduction in H2 yield as a result of using antimony are shown in
Table 1.
Bismuth-containing additives have also been found to reduce the dehydrogenation
activity of nickel. Although somewhat less effective than antimony, the bismuth
additives have the advantage of being less of a concern from an environmental
point of view.
TABLE 1
HYDROGEN YIELD DECREASE EXPERIENCED BY
PHILLIPS LICENSES USING METALS PASSIVATION
Hydrogen Yield, SCFB FF
License
Catalyst
4 Ni + V,
Ppm
Unpassivated
Passivated
% Charge
3,600
92
58
37
16,200
202
104
49
6,540
64
21
67
10,820
126
62
51
8,800
87
55
37
6,140
161
103
36
8,300
105
85
19
10,800
71
19
73
9,300
159
109
31
Average
44
Reference: W.C. McCarthy, et al. Paper No. 13, Katalistiks 3rd FCC Symposium, 1982.
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Perhaps the most-active area in catalyst development in recent years has been the
development of active matrices that minimize the adverse effect of metals. One
advancement has been achieved through pore-structure adjustments and alteration
of the surface chemistry of the aluminas, using a large-pore boehmite alumina.
Such a matrix alumina is believed to encapsulate the nickel, so that the nickel
surface is no longer exposed and cannot make contact with the hydrocarbons to
catalyze dehydrogenation. With this technology, antimony additives provide only a
small additional benefit. Equilibrium catalyst material data illustrating the
performance of such a nickel trap are seen in Figure 20.
Figure 20
Catalyst Performance with Nickel Trap and
Antimony
0.25
V=1,000-2,000
wt-ppm
H2 Yield, wt-%
0.20
0.15
Without Sb
With Nickel Trap
0.10
With Sb
0.05
0
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Figure 21
Effect of Vanadium on Catalyst Activity
70
68
66
64
62
60
58
56
54
52
3,000 3,500
4,000
4,500
5,000 5,500
6,000
6,500 7,000
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little loss in activity and with little increase in H2 and coke production. Unfortunately,
when placed in actual commercial use, the titanates appeared to be sensitive to
sulfur poisoning and have not lived up to their laboratory performance. As yet, they
have shown little trapping capability in refinery use.
Rare-earth-based vanadium traps, which are much less susceptible to permanent
sulfur poisoning, have been considerably more successful in commercial refinery
use. This technology, which was originally commercialized by Katalistiks in the late
1980s, is now being used by Grace, designated as their RV technology. Grace
catalysts that incorporate the RV trap are called Residcats. The RV trap can be
used either as a separate additive or incorporated into the cracking catalyst particle.
Because of its high mobility, vanadium readily jumps from particle to particle,
seeking those particle locations where it has a high affinity. Separate particle
vanadium traps thus work nearly as well as in-catalyst traps. An illustration of the
effectiveness of the rare earth vanadium trap is given in Figure 22.
Figure 22
Effect of Vanadium Trap
72
70
68
Vanadium
Trap
66
64
Base Case
62
60
58
1,000
2,000
3,000
4,000
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Sodium and other alkalis or alkaline earths such as calcium, potassium and lithium
are strong catalyst poisons which can have an immediate and significant impact on
catalyst activity. Sodium is usually present in the feed as salt resulting from
operational problems in the crude unit desalter or from purchased feeds from
tankers. Poor steam quality can also be a source of these contaminants. An
increase in sodium of just 0.1 wt% can cause a drop of up to 3 numbers in catalyst
activity.
Iron is another potential catalyst poison in high concentrations. If enough iron
accumulates on the surface of the catalyst the access to the active catalyst sites
may be blocked resulting in lower effective catalyst activity. Several units have
reported significant loss in catalyst activity when the iron on the equilibrium catalyst
exceeds ~3000 5000 wt ppm above the fresh catalyst iron level.
Basic nitrogen compounds in the FCC feed are temporary poisons that bond with
the active acid sites making them inaccessible for cracking reactions. The nitrogen
is oxidized off the catalyst during regeneration and leaves as NOx compounds in
the regenerator flue gas. The deactivation effect, thus, lasts only as long as the
basic nitrogen compounds are present in the feed. Typically, basic nitrogen
compounds make up about 1/3 of the total nitrogen compounds in the feed.
Coke can also be considered as a temporary catalyst poison, which sits on the
catalyst active sites and is removed during regeneration. If coke is not completely
removed during regeneration, a loss in actual catalyst activity will result. Typically a
loss of 1.0 1.5 activity numbers occurs for every 0.1wt% coke left on the catalyst.
Note that the activity numbers reported on a catalyst vendors equilibrium catalyst
report are determined after any remaining carbon is burned off. If the catalyst
leaving the regenerator does have a significant amount of unremoved coke, the
reported activity on the equilibrium catalyst sheet will thus not reflect the actual
lower, working activity in the reactor.
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CATALYST ADDITIVES
CO Combustion Promoters
In the early 1970s, researchers discovered that certain Group VIII metals,
particularly platinum, can be incorporated into an FCC catalyst system at low
concentrations (13 wt ppm) to catalyze the combustion of CO to CO 2 effectively.
Of even greater importance was their discovery that at this low incorporation, the
Group VIII metals did not catalyze undesirable dehydrogenation reactions during
the cracking reaction. The cracking-selectivity characteristics achieved by the
cracking catalyst in use in the FCCU are thus not altered when such a CO
combustion promoter is added to the catalyst inventory.
The use of 12 ppm platinum in FCCU circulating catalyst inventories is now widely
practiced throughout the world to catalyze the combustion of CO to CO2 in the
FCCU regenerator. The promoter is added to the FCC catalyst inventory either as
an integral part of the fresh FCC catalyst, where it is included in the fresh catalyst at
12 wt ppm, or as a separate additive. The additive, which typically contains
5001000 wt ppm of platinum, is added to the FCCU by a small metering system
that is independent of the fresh cracking-catalyst addition system. In the United
States, the separate additive approach is generally used; in Europe, the additive is
most commonly incorporated with the fresh cracking catalyst.
Through the use of a combustion promoter, CO combustion occurs readily in the
dense phase at temperatures well below 700C (1292F). It has been reported that
promoted CO combustion occurred as low as 650C (1202F) in a commercial
FCCU operation.
Promoted combustion has a number of important benefits. First, the afterburn
problem, i.e., burning in the dilute phase, is greatly reduced. By consuming CO in
the dense phase, the potential heat release from burning in the dilute phase is
significantly decreased. A commercial example of a 90F reduction in regenerator
afterburn by using a CO combustion promoter is as follows:
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Without promoter
With promoter
1290
1220
1225
+ 65
1245
- 25
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The amount of promoter used can also be a variable in influencing the degree of
CO combustion. A promoted catalyst system can be classified as fully or partially
promoted. A partially promoted system is one in which an increase in promoter
content results in a decrease in the dilute-dense T. Conversely, a fully promoted
system sees no effect on afterburn T when the promoter level is changed. An
increase in the promoter content increases the proportion of CO that is burned in
the regenerator dense phase, and decreases the dilute-dense T, as seen in
Figure 23 . The change in dilute-dense T is mainly because of changes in the
dilute-phase temperature. Changes in promoter concentration have only a small
effect on dense-phase temperature but greatly affect dilute-phase temperatures.
Figure 23
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Currently, many refiners find that the use of a SOx adsorbing additive is the most
effective way to comply with the EPA regulations.. With such an additive, the
following steps occur:
SO 2 is oxidized to SO3 in the regenerator:
2 SO2 + O2 2 SO3
SO3 is adsorbed in the regenerator by the SOx additive
SO3 + MO MSO4
MO = metal oxide and M is most commonly magnesium:
The metal sulfate is reduced in the reactor
MSO4 + CH4 MS + CO2 + 2 H2O
Release of H2S is released in the stripper
The metal oxide adsorbent is regenerated
MS + H2O MO + H2S
The H2S is carried out with the reactor products, goes through the product-recovery
system of the FCCU, and eventually to further processing for sulfur recovery. The
metal oxide adsorbent recirculates with the spent cracking catalyst back to the
regenerator for the next SOx adsorption cycle.
The first commercially effective metal oxide adsorbent consisted of a solid solution
of a pure magnesium aluminate spinel (MgAl2O4) with MgO. Such a solid solution (
Mg2AlO5) does not destroy the spinel framework. The adsorption activity of the
dispersed MgO in the spinel is much greater than that of pure MgO itself.
Cerium is effective in oxidizing SO2 to SO 3. Consequently, a cerium-impregnated
Mg2Al2O 5 actively converts the SO 2 to SO3, which is then strongly adsorbed by the
dispersed MgO as MgSO4. A completely cyclic SOx removal catalyst contains, in
addition to the above component, a fourth metal component such as vanadium to
catalyze the conversion of MgSO4 to MgO.
Multifunctional SOx removal catalyst systems have been in commercial use since
1985 in the United States. Such systems have successfully reduced SOx
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the regenerator conditions, than they are to the absolute content of N in the feed.
The amount of excess oxygen may have a more direct correlation with the final NOx
concentration leaving the regenerator. Increasing the O2 in the regenerator flue gas
from 0.1 to 1.6% has been reported to double NOx emissions when no CO
combustion promoter is present. Adding a platinum-based combustion promoter,
which increases the available atomic oxygen, can increase the NOx content much
more.
An emerging picture of the complex NOx chemistry in the FCCU regenerator
includes the following reaction networks:
Pyrolysis
Oxidation
N (Coke) HCN
N (Coke) NH3
NO Reduction
2NO + 2 CO coke N2 + 2 CO2
NO + CFAS* 1/2N2 + CO
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The latest additive development has been directed at reducing the sulfur content in
gasoline, which is believed to be largely due to the presence of thiophene and
alkylated thiophenes in the FCC gasoline. The additives are intended to
dehydrogenate the thiophenes which then can crack, releasing H2S. Zinc based
catalysts on an alumina support have had mixed results.
CATALYST SELECTION
An enormous amount of flexibility is available in the design of FCC catalysts. The
catalyst designer can choose from a large variety of zeolites. Depending on the
zeolite chosen, the designer can vary the amount of zeolite, the type of ion
exchange, and the type of active matrix and can include metals traps or additives.
This complexity is illustrated in Figure 24. Each unique combination of these factors
provides a uniquely different result, and each has some specific positive and some
negative benefits. Catalyst suppliers are continuously working to improve the
catalyst to provide more flexibility to meet the specific needs of each individual
refiner.
The catalyst advancements are mainly related to improved coke and gas selectivity
in the presence of contaminant metals and in the presence of increased matrix
activity for better bottoms cracking and LCO selectivity.
Because of the wide variability in catalyst options and the individuality of each
refinery's situation, generalizing as to which catalyst is best should be avoided. The
choice is best arrived at when the refiner and catalyst supplier work closely together
to take advantage of the catalyst flexibility available. UOP can also assist in this
selection process by providing an assessment of the various catalyst options based
on commercial experience in other UOP units and on standardized testing in UOP
pilot plants.
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Figure 24
Catalyst Formulation
ReHY
USY
Other Zeolite
Treatments
ZSM-5
Low-Activity Matrix
Active Alumina
Matrix
Nickel Trap
Vanadium Traps
Plus
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Figure 25
Catalyst Hydrothermal Deactivation
80
75
Catalyst A
Catalyst B
Catalyst C
70
65
60
1350
1400
1450
1500
Deactivation Temperature, F
5 hours - 100% Steam
1550
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Use of torch oil can also result in thermal deactivation if the oil is not properly
atomized.
CATALYST MANAGEMENT
The type of catalyst used in a particular FCC unit depends on feedstock properties,
the desired product make, and unit bottlenecks. The choice of catalyst should be
made after careful study of all factors, including cost. Any catalyst changeover will
take significant time to be effective. Varying feedstocks and operating conditions
may also change yields and cloud the results of catalyst changes.
Fresh catalyst is typically added to the unit for two reasons:
1.
2.
If the unit holds catalyst well, it may be necessary to withdraw equilibrium catalyst
and add fresh to maintain a desired activity. If the catalyst has been damaged by
excessive use of steam or torch oil, or contaminated by metals, it may be necessary
to increase the catalyst makeup rate.
The desired catalyst activity is based on several factors, the first of which is
economics. The refiner should examine.
1.
2.
3.
4.
5.
Cost of catalyst.
The addition of fresh catalyst should be done as evenly as possible. There are a
variety of continuous loaders on the market which make this quite easy.
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If a large batch of fresh catalyst is added too quickly, the relative activity increase
may cause overcracking with lower gasoline and higher dry gas yields.
The unit should be monitored with plots to follow:
1.
2.
3.
4.
5.
These procedures are required for routine monitoring of the unit. Moreover, without
them, it is impossible to make intelligent decisions on catalyst management.
It may be necessary to add catalyst to make up physical losses. These can be due
to excessive or improper steam usage, equipment damage such as a bypassed
cyclone If catalyst losses are severe, or fresh catalyst addition is not desirable,
equilibrium catalyst can be added, either from a newly purchased stock or from onhand stock.
In some units, low metals equilibrium catalyst is added to replace higher metals
catalyst from the inventory. This is an effective way to reduce the levels metals and
therefore minimize the negative effects of the metals without the high cost of adding
large amounts of fresh catalyst. This is especially true in units with resid feed stocks
which are typically higher in metals than VGO.
Catalyst loading and use should be reviewed periodically to ensure proper unit
operation. This review should normally be done about every two months. If there
are special problems such as metals, the policy will have to be reviewed more
often. Care should be taken, however, that other factors such as different
feedstocks do not lead to hasty, inappropriate decisions.
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2.
3.
4.
5.
6.
The retention factor is an index attrition number which accounts for the weight
fraction of fresh catalyst that is not lost from the regenerator during loading.
Generally, the retention factor will vary from 0.70 to 0.80 depending on the specific
catalyst.
1.
ACA
INV
CAR
=
=
=
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DC
Deactivation Constant
FCA
ECA
=
=
ACA
NAR
INV
DC
RF
FCA
DCA
=
=
=
=
=
=
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4.
Calculate the time required for 75% turnover at the new addition rate.
PCT
Inventory Turnover = - LN 1 INV / NAR RF
100
where:
PCT
NAR
RF
=
=
=
100
= 101 days
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20,000 BPD
0.9042
3 ppm
2.5 Short Tons/day
ppm
1,000 ppm
200 Short Tons
Find metals concentration after 100 days of operation at the above conditions.
EXP
EMF =
CAR
INV
CAR
where:
EMF
EMI
FCM
SG
FFR
=
=
=
=
=
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FFM
CAR
INV
TS
=
=
=
=
EXP
EMF =
2.5
200
2.5
EMF
2996 ppm
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A catalyst test report will include information on the physical, chemical, and catalytic
properties of the equilibrium catalyst.
Under the category of physical properties, information will frequently be found on:
Catalyst surface area total area, zeolite area, and matrix area
Zeolite unit cell size
Catalyst bulk density
Catalyst pore volume
Catalyst particle size distribution
Catalyst fluidization properties
Following is a description of the various tests performed by laboratories:
PHYSICAL PROPERTIES
Surface Area
The body of catalyst particles is made up of pores which contain the active sites
where the cracking reactions occur. Nearly all (90 95%) of the catalyst's surface
area is internal. The total surface area, measured in square meters per gram of
catalyst, is made up of two components, the zeolite surface area and the area of the
material around the zeolite, known as the matrix surface area.
The zeolite surface area is the larger of the two and is a good indicator of the
catalyst activity. The zeolite surface area measures the area within the pores of
about 50 or less. The matrix surface area measures the surface area in the pores
> 50, which provide the channels through which the hydrocarbons can reach the
zeolite. The active alumina incorporated for bottoms cracking is found in this higher
pore range.
Surface area is measured by nitrogen adsorption at very low pressure. Total
surface area is typically determined by the BET method which measures adsorption
at a single pressure. Matrix surface area is determined by the t-plot method, which
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Particle density is the weight per unit volume of catalyst. Particle density is defined
as:
Skeletal Density
+ 1
(Skeletal Density Pore Volume)
Particle density is always less than skeletal density. A comparison of density would
be:
Particle Density 2 ABD 1.7 CPD
Compacted Particle Density (CPD) is similar to ABD, but the catalyst is tapped until
it settles to a minimum volume.
Skeletal Density
Skeletal density is the density of the solid portion of the catalyst, exclusive of the
volume of pores or voids. The values are obtained with a pycnometer after
determining pore volume. Typical skeletal density for low alumina catalyst is 2.35
g/ml; for high alumina the density is 2.5 g/ml. The zeolites fall somewhere in
between these two.
Pore Volume
Pore volume is another indicator of the zeolite content of the catalyst. Higher pore
volume would usually indicate higher zeolite content for two catalysts of the same
type, but would not necessarily indicate higher activity. Pore volume can be
determined by N2 adsorption, or by water titration. The values reported on the
equilibrium catalyst sheet are obtained from a water titration.
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The pore volume of equilibrium catalyst generally ranges from 0.2-0.5 cc/gm. The
variation here is because of the many different types of catalyst, and because of
different manufacturing techniques. Hydrothermal deactivation causes a slight
decrease in pore volume, while thermal deactivation causes a greater decrease.
Pore Diameter
This is a convention used to describe the average pore size. The assumption is
made that the pores are in the form of minute cylinders of diameter, PD, and length,
L. By definition then, the following equations apply:
SA = (PD)L
Pore Volume (PV) =
Therefore:
(PD)2L
4
PV
(PD)2 1
PD
= L
=
SA
4
4 (PD) L
Therefore:
PD =
4 PV
SA
Using:
SA in m2/g
PV in cc/g
PD in Angstroms
The equation then becomes:
PORE DIAMETER (PD) =
4 PV 104
SA
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Attrition Resistance
The attrition resistance of catalyst is an indication of its strength and hardness. A
more attrition-resistant catalyst will erode at a lower rate as it circulates through the
unit. Each catalyst supplier has their own technique for measuring attrition
resistance. Comparing one suppliers attrition value with another suppliers value is
not recommended.
Typical FCCU catalyst loss due to attrition is approximately 1 wt% of the catalyst
inventory per day.
Particle Size Distribution
The fluid properties of the catalyst are largely a function of the range of particle size.
Typical particle size distributions are:
% under 20 microns
% under 40 microns
% under 60 microns
% under 80 microns
% under 100 microns
Average Particle Size (APS)
1
10
33
55
73
75 microns
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The test method does not duplicate commercial performance so the results are only
relative. By comparing the results to a standard, however, the performance of the
sample in a commercial unit can be predicted. It is important to remember that the
sample is tested after any remaining coke is burned off so in units with high carbon
on regenerated catalyst the reported activity will not correlate with the activity in the
commercial reactor.
SELECTIVITY
The selectivity values reported for an equilibrium catalyst relate its tendencies to
form coke, C1-C4 gases, and hydrogen to those of a standard reference catalyst
when corrected to the same conversion. Selectivity is affected by the catalyst type
as well as varying degrees of metals contamination.
The catalyst's coking characteristic is measured by the coke factor, CF, which is
dependent on the accumulated Ni + V level. This coke factor can be used to
separate the effect the catalyst type and its accumulated metals level has on coking
from the effects due to processing conditions such as the actual FCCU feedstock's
coking tendency and the FCCU reactor temperature.
Hydrogen (H2) production is also very sensitive to the catalyst metals
contamination. The H2 producing tendency is measured by the H2/CH4 factor which
usually varies from less than one up to two for metals levels up to 1500 ppm. Some
catalyst suppliers provide a H2 yield value from their standard test.
The other selectivity value which relates to the catalyst's gas yield is the gas factor,
GF. This, like the coke factor, varies with the fresh catalyst type, but it is not as
metals sensitive as is the coke factor or the H2 value . Generally, the gas factor will
not give an increasing trend until the metals accumulation exceeds 2000 ppm. This
factor is used to separate the effect the catalyst type and its contamination has on
light gas production from FCCU processing conditions such as reactor temperature,
regenerator temperature, or the feedstock quality.
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CO COMBUSTION TEST
Some catalyst suppliers test the equilibrium catalyst for its ability to combust CO to
CO2. The reported value is given as the performance of the catalyst relative to a
catalyst that is considered to be fully loaded with a CO combustion promoter.
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PROCESS VARIABLES
INTRODUCTION
Proper control of an FCC unit requires careful balancing of many variables. Within
certain limits, the system can be controlled to provide optimum performance. The
limits, or restrictions, include feedstock quality, equipment limitations, and environmental constraints.
Of primary interest is the unit enthalpy balance which results from the many unit
operating conditions. The amount of coke produced in the reactor is a direct result
of the operating conditions imposed on the unit by the operator and is relatively
independent of the feed quality. The unit yields are directly related to the quality of
the feed and the operating severity set by the enthalpy balance. As these topics are
developed in this chapter, it will become clear that many of the assumptions made
by FCC operators are incorrect and a better understanding of the relationships of
the process variables is necessary to properly predict unit operation.
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The amount of energy flowing in the unit operation can be summarized as:
Energy In + Energy Produced = Energy Out + Energy Consumed
Energy In
= Energy in the air to the Regenerator, raw oil, steam, and lift
gas
Energy Produced
Energy Out
Energy Consumed
At steady state the net heat of combustion must equal the heat consumed by the
reactor. Stated mathematically:
NET HEAT OF COMBUSTION
BTU
[Hcomb - Hair - Hloss]
LB COKE
MUST EQUAL
TOTAL REACTOR HEAT LOAD
BTU
[Hfeed + Hdiluent + Hrecycle + HRx]
LB FEED
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The coke yield from the unit can then be written as:
BTU
100 Hfeed + Hdiluent + H recycle + HRx
LB FEED
WT% COKE YIELD ON FEED =
BTU
Hcomb - H air - Hloss
LB COKE
Note that the coke yield depends on the energy balance of the unit and the only
term that represents feed quality is the heat of reaction. Thus as feed quality
changes and the heat of reaction changes, there will be a change in coke yield.
Otherwise, the coke yield is set by the operating conditions imposed by the
operator.
THE ENTHALPY OPERATING WINDOW
Let us take as an example a unit operating in full CO combustion with a heavy gas
oil feed in once-through (no recycle) operation. As shown in the calculation section,
the enthalpy changes for diluents and normal vessel heat losses are negligible, so
the coke yield equation can be simplified to:
WT% COKE =
100 H feed + H Rx
H Comb Net
The unit control variables then become the feed temperature and the reactor
temperature. The usual range of feed temperature is 350-520F and 970-990F for
the reactor so a table showing the enthalpy changes for these ranges is:
CONTROL VARIABLE
DEPENDENT VARIABLE
REACTOR TEMP.
970 - 990F
H REACTION
FEED TEMP.
350 - 520F
409 - 530
BTU/LB FEED
H FEED
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Thus, the maximum range in coke yield variability for these operating ranges is
4.8-5.8 wt%. The potential change in coke yield due to any variation in dependent
variable such as heat of reaction, flue gas temperature, feed enthalpy and heat of
reaction is extremely limited. The following table shows the range of coke yields for
various variable changes.
DEPENDENT
VARIABLE
HEAT REACTION
REGEN TEMP.
H2 IN COKE
RANGE
ENTHALPY
COKE YIELD
LOW/HIGH CONV.
100 - 200
BTU/Lb Fd
4.6 - 5.5
1250 - 1400F
3407 - 4010
BTU/Lb Coke
5.14 - 5.39
6.0 - 7.0
16547 - 17000
BTU/Lb Coke
5.5 - 5.3
The net coke yield is thus essentially independent of feed quality. The conversion
and the cat/oil ratio are the variables that change with varying feed quality. In
essence, conversion coke from the quality feed is replaced by contaminant coke
from the poor feed at a correspondingly lower conversion.
Another way to look at this balance is to look only at the components of the reactor
side heat balance.
BTU/Lb Feed
530
5
13
180
2
730
%
72.6
0.68
1.78
24.67
0.27
100
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Over 70% of the coke produced in the unit is used just to heat up and vaporize the
feed. Only about one fourth of the coke is used to provide the heat of reaction. As
we saw above, the heat of reaction does not vary very much from feed to feed, so
the range of coke production can be seen clearly to be limited to less than half of
25% or about 10% of its typical value. In most units this corresponds to 5.5 wt%
plus or minus 10% (5.0 to 6.05) even for wide swings in feed quality and conversion
level.
THE DELTA COKE OPERATING WINDOW
Now that the coke yield on feed is known to be set by the operating conditions in the
unit, the next important term in the heat balance is the 'delta coke'. Delta coke is the
difference in coke content between the regenerated catalyst and spent catalyst.
Another way to express this is the coke yield on feed divided by the catalyst/oil ratio.
DELTA COKE =
ENTHALPY COKE
(or COKE YIELD)
CAT/OIL
Since the coke yield is set by the operating conditions, the cat/oil and the delta coke
must vary proportionally opposite to each other. The delta coke term is strongly
related to the regenerator temperature and thus the product selectivities.
C
TRegen = TRx +
Hcomb - Hair - Hloss
Cp
where:
Rearranging the equation, the cat/oil ratio can be calculated knowing the
regenerator and reactor temperatures, and the coke yield from the heat balance
calculation.
Cat /Oil =
H Comb Net
TRegen
- TReactor
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DELTA COKE
0.5
0.775
0.928
1.137
REGEN TEMP F
1250
1330
1390
1470
CAT/OIL
11.4
7.6
6.5
5.4
5.7
5.91
6.03
6.18
BASIS: 980F Rx, 350F Feed, 190 BTU/Lb Feed HRx, FULL CO
COMBUSTION, 1.0 CFR
The delta coke function therefore impacts conversion and selectivity enormously
due to its influence on regenerator temperature and corresponding cat/oil. At the
same time, since the regenerator temperature has little influence on the enthalpy
coke, the coke yield changes very little for large variations in delta coke at constant
heat of reaction.
HEAT REMOVAL FROM THE REGENERATOR BY CATALYST COOLING
Since we have just seen that the coke yield is set by the operating conditions and
not the feed quality, what can be done when a poor quality feed must be processed
and the conversion is not sufficient at the current operating conditions? At the same
time, this poor quality feed usually will result in a higher regenerator temperature as
well, causing a decline in liquid product yield. If a constant coke yield is required
due to an air blower limitation, any heat input to the reactor side must be offset by a
similar heat removal on the regenerator side. With the installation of a catalyst
cooler, the feed preheat can be increased to reduce the coke make, and a
corresponding heat removal via catalyst cooling can be done in the regenerator to
increase the cat/oil ratio and increase conversion to maintain constant coke
157048
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production. The overall yields can be greatly improved through the increase in
catalyst circulation. The higher E-cat activity resulting from the lower temperature
also improves the yields.
COKE YIELD FLEXIBILITY FOR OPTIMUM PERFORMANCE
The prime objective of most FCC operations is the conversion of feedstock to
gasoline and other valuable products, while minimizing the production of less
valuable products such as clarified oil and coke. The unique feature of an FCC unit
is that it supplies its own fuel, not only for the conversion to the products it
produces, but also for the fractionation of the products as well. This fuel is the byproduct of the cracking reactions left on the catalyst, commonly referred to as coke.
It has been the quest of designers not only to minimize coke on catalyst from the
cracking reactions, but to minimize coke on catalyst from other sources as well. It
has been documented that coke on catalyst can come from feed contamination
such as metals, coke added by the high boiling fraction of the feed, and by
entrainment from the catalyst circulation through the reactor stripper. The objective
is to produce the most desirable yield pattern for a given feedstock with the least
amount of coke possible. Once a unit is designed, it has a certain coke burning
capability which the operator can utilize to increase cracking severity as much as
desired for each feedstock. With heavier feeds that contain less hydrogen and
inherently produce less liquid yield volume, high coke burning capabilities are
needed and a way to increase the coke yield to improve yields is needed. The key
is to produce enough coke to increase the conversion of the feed until the optimum
yield pattern is achieved.
QUALITY AND CONDITION OF CHARGESTOCK
The typical feed to an FCC unit is a heavy gas oil, such as heavy atmospheric, light
vacuum, and heavy vacuum gas oil. The unit can accommodate a range of different
rates and types of feed within its design limitations. Typically a unit may run at
design conditions, at a higher charge rate with moderate conversion, or at low
charge rates with very high conversion levels.
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Some FCC units recycle heavy oil from the main column back to the riser. The
amount is defined by the combined feed ratio:
CFR =
Typical combined feed ratios for riser cracking units operating with a higher activity
catalyst would be 1.0-1.10. Older units running on low activity catalyst could range
from 1.2 to 1.8. If the oil can be cracked on one pass and not recycled, more fresh
feed can be processed. The recycle is generally heavy material which tends to be
more difficult to crack, and when it does crack, it makes more coke and light gas
than does the fresh feed. Many refiners run only enough recycle to return catalyst
fines to the reactor from the main column. This generally means a CFR of 1.05 or
less.
Proper control of upstream units, such as the vacuum column, is essential to good
feed quality. This control is mentioned only briefly in the following discussion
because it is beyond the scope of this work, but will affect all the variables listed
below.
There are several important characteristics which are used to describe the raw oil
charge. These relate to its ease of cracking and to most potential problems. The
major elements are:
RAW OIL CHARGE CHARACTERISTICS
1.
2.
3.
4.
5.
6.
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API GRAVITY
API gravity is a specific gravity relating the density of oil to the density of water.
Feed to an FCC can range from 15 to 45 API, with 20-25 API the most common.
Any change in this number is due to a change in boiling range, crude type, or both.
If the API gravity increases because the feedstock is more saturated (paraffinic and
less aromatic), the following changes can be expected:
1.
The charge will crack more readily for the same reactor temperature and there
will be greater conversion.
2.
3.
(CABP)
UOP K =
SG60
1/3
where:
CABP = Cubic average boiling point, R
SG60 = Specific Gravity at 60F
A detailed example of this calculation is given earlier. A UOP K factor of 11.2 would
show a more aromatic stock, while a K factor of 12.5 would indicate a more highly
paraffinic stock. One key feature of the FCC unit is that the hydrogen in the product
streams must come from the hydrogen in the feed. There is no added hydrogen in
this process. One good way to check the quality of FCC data and yield estimates is
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70
60
50
11
12
13
157048
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higher for cracked gasoline, as compared to straight run material. Gasoline in the
FCC feed is not considered desirable because it occupies space which could be
used to process gas oil, and because it usually has a low octane number. It would
be better to remove this material in the crude unit and send it to a reformer.
The "percent at 650F" (343C) is a measure of the light fuel oil in the charge. The
boiling point of 650F is chosen because it corresponds to the normal LCO
endpoint. This material will crack, but not to the same extent as the heavier
molecules. It will produce more coke than will the gasoline, but again, less than the
heavier material.
The endpoint of FCC charge stock may vary, depending to some extent on the
suitability of the material for cracking operation. The presence of coke precursors,
such as polynuclear aromatics, organometallic compounds, and high sulfur material,
are, in many cases, good reasons for avoiding the inclusion of high boiling point
compounds in FCC feed. This depends very much on the individual stock.
AVERAGE BOILING POINT
The average boiling point of the FCC feed depends on the average molecular
weight. An increase in API and the molecular weight will typically cause the
following:
1.
3.
4.
5.
2.
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There are upper limits to these increases. An exceptionally heavy feed might prove
to be undesirable because of high Carbon Residue, Sulfur, and similar factors. The
exact changes will depend on the individual feedstock.
CARBON RESIDUE
The carbon residue of a feedstock is an indirect measure of its coke producing
nature. The value may be determined by either the Conradson or Ramsbottom
methods. An increase in residue of a feed from one crude source will generally
result in an increase in regenerator temperature. The exact nature of coke laydown
is somewhat complicated so this characteristic is not always reliable for comparing
feeds from different crudes.
The carbon residue can be a useful number for determining possible contamination
in storage, or of problems in the upstream feed preparation units. Because
entrainment in the vacuum tower is a common cause of increased carbon residue, a
higher metals level may be observed at the same time. Gas oil having a carbon
residue over 0.5% should be considered suspect.
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COLOR
Color may be used as a possible indication of problems. Darker stocks tend to have
higher carbon residues, sulfur, and metal problems. This method is especially
valuable because it is a relatively quick and easy test.
METALS
Organometallic compounds in the FCC feed can cause serious overcracking if the
metals deposit on the catalyst. The cleanliness of a chargestock is given by a
metals factor:
Fm = V + 10 (Ni + Cu)
where:
Fm
V
Ni
Cu
=
=
=
=
Metals factor
Vanadium concentration, wppm
Nickel concentration, wppm
Copper concentration, wppm
All metal concentrations are ppm by weight in the feed. A factor of 1.0 is considered
safe, over 3.0 indicates a danger of poisoning.
Normal dry gas make at 60-70% conversion is 50-100 SCF/bbl. A heavily
contaminated stock would produce 200 SCF/bbl or more. The ratio H2/C1 will
increase as dehydrogenation reactions are catalyzed by the metals, especially Ni.
An H2/C1 ratio of 1.0, as compared to the normal 0.3-0.5, would again indicate
metals poisoning. A third indication of metals would be an increase of 10-15% in the
olefin content of the C3 stream, to as high as 85%.
Sodium and vanadium pose a different threat to the catalyst than nickel. These
metals are mobile at high temperatures and can destroy the zeolite in the catalyst
causing low activity and conversion. Even with metal traps in the catalyst, high
157048
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catalyst usage will be required to flush these metals from the unit to maintain
reasonable activity, conversion and selectivity.
Proper control of the feed preparation units is necessary to prevent these metals
from contaminating the feed. Most of the metals are concentrated in the heavier
fractions, although a few may be volatile at lower temperatures. Keeping
entrainment in the feed towers to a minimum will keep metals level down to a safe
value.
SULFUR
Sulfur is as undesirable in cat cracker charge as it is in the feed to most refining
units, causing corrosion of the equipment and increased difficulty in treating
products. At 50% conversion, about 35% of the sulfur charged is converted to H2S,
and at 70%, this figure will rise to about 50%. The sulfur content of a 400F
endpoint cat gasoline will be about 10% of that of the raw oil charge, but this
fraction increases rapidly as the endpoint is raised above 400F. As would be
expected, the higher the sulfur content of the gasoline, the lower will be its lead
response, although lead response is no longer important in many parts of the world.
Hydrotreating will significantly improve FCC feedstock. The effect is twofold: the
removal of impurities and the hydrogen addition to saturate molecules. The first of
these is important when the charge is contaminated with sulfur, nitrogen or metals.
These poisons may cause both process and environmental problems. Hydrogen
addition to the feed, especially to the large polynuclear aromatics, will give higher
conversion and a decreased coke yield by making these heavy compounds easier
to crack.
The FCC product sulfur distribution is not even; it tends to concentrate in the heavy
products and as H2S. Table 1 is a typical product sulfur distribution for a nonhydrotreated feed.
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TABLE 1
COMMERCIAL SULFUR BALANCE
(80.7 LV-% CONVERSION)
STREAM
COMPOSITION
WT-% SULFUR
PERCENTAGE
OF FEED
SULFUR
FEED:
1.04
100.0
PRODUCTS:
SPONGE ABS. OH
DEBUT. OH
H2S
44.4
RSH
GASOLINE
LIGHT CYCLE OIL
CLARIFIED OIL
FLUE GAS
SOUR WATER
0.15
1.35
2.08
3.8
6.5
16.7
17.1
9.1
1.9
99.5
Much of the feed sulfur comes off as H2S because H2S, once formed, is fairly stable
under the conditions encountered in the reactor. This desulfurization is beneficial
because concentrating the feed sulfur in one product stream decreases the
difficulties in treating other products.
Higher sulfur feedstocks that are mildly hydrotreated will tend to produce a lesser
percentage of H2S, and leave a larger portion of the feed sulfur in the heavy
products. The effects are shown in Table 2 for cycle oil sulfur content.
157048
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The results of this sulfur concentration in heavy products will vary with the refinery's
needs. Product specifications and uses must be balanced against changes in
corrosion rates and required metallurgy, and should be examined on a case by case
basis.
TABLE 2
SULFUR DISTRIBUTION
EQUIVALENT PROCESSING CONDITIONS
SULFUR,
WT-%
TOTAL
CYCLE OIL
SULFUR
CONTENT,
WT-%
PERCENTAGE
OF FEED
SULFUR
IN CYCLE
OILS
RAW
2.68
4.31
43.7
HYDROTREATED
0.56
1.40
55.8
HYDROTREATED
0.26
0.76
67.6
FEEDSTOCK TYPE
Metals
The reduction of metals by hydrotreating follows the same pattern as nitrogen and
oxygen removal. It is possible to reduce the feed metals factor, Fm, by 50-90% in a
moderate severity hydrotreater.
Hydrogen Addition
Hydrotreating an FCC feedstock to improve quality is generally more attractive if
gasoline or LPG is the desired product. Moderate severity LCO production may not
justify hydrotreating unless there is a high concentration of feed sulfur or other
contaminants. Table 3 shows the yield changes for a charge stock under equivalent
cracking conditions at three levels of hydrotreating.
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TABLE 3
EFFECT OF FEEDSTOCK
HYDROTREATING: EQUIVALENT CRACKING CONDITIONS
FEED
RAW
HYDROTREATED
GRAVITY, API
SULFUR, WT-%
CONVERSION (LV-%)
C5+ GASOLINE (LV-%)
21.7
2.68
78.1
55.5
25.5
0.53
80.7
60.1
26.4
0.28
81.7
61.0
33.3
0.01
92.0
68.2
33.6
1.0
37.2
0.78
37.1
0.76
41.8
0.43
93.8
93.9
94.0
92.0
RATIO ISOBUTANE/BUTYLENES
IN C4 FRACTION (MOL-%)
0.68
0.72
0.79
0.81
GASOLINE EFFICIENCY
VOL-%, GASOLINE/CONVERSION
0.71
0.74
0.75
0.74
A detailed analysis for two different feedstocks is given in Table 4. Two obvious
changes are the increase in API gravity and UOP K, indicating a greater degree of
hydrogen saturation. There is some small degree of hydrocracking, as shown by the
decrease in average molecular weight and boiling point.
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TABLE 4
FCC FEEDSTOCK PROPERTIES
GACH SARAN
(HEAVY IRANIAN)
L. A. BASIN
SEVERELY
HYDROHYDROTREATED TREATED
RAW
HYDROTREATED
RAW
22.9
26.3
22.2
26.3
35.0
11.78
385
1.83
11.98
380
0.14
11.45
316
1.30
11.7
298
0.1
11.99
266
0.001
0.34
0.06
0.1
0.1
0.0
N2, PPM
1880
1570
3380
2190
AROMATICS, WT-%
48.5
42.1
53
51
30.5
ASTM D 1160
IBP
10
30
50
70
so
95
% RECOVERED
504
661
760
822
877
958
983
98
458
632
739
799
856
933
990
98
382
548
653
724
795
880
965
98
360
530
628
707
779
868
954
98
360
440
518
594
682
810
920
98
FM FACTOR
2.3
2.9
0.0
0.0
PILOT PLANT
CONVERSION VOL-%
77
83
68
76
89
API
K
MW
S, WT-%
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HIGHER CONVERSION
2.
3.
4.
5.
6.
J Cracking
A modification of feed hydrotreating is J cracking. This process treats the light cycle
oil stream, which is then recycled back to the riser with the raw feedstock. The
hydrotreated LCO can be cracked, increasing the yield of all the lighter products. J
cracking partially saturates the di-, tri-, and tetra-aromatics present in LCO. These
components then crack instead of forming coke when the stream is recycled. Table 6
compares the product yields for J cracking and normal operation for a hydrotreated
feed.
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TABLE 6
FCC YIELD COMPARISON FOR J CRACKING
FEED: HYDROTREATED 25 API MIDDLE EAST GAS OIL
OPERATION
NORMAL
+ J CRACKING
CONVERSION, VOL-%
85
95
H2S, WT-%
0.15
0.25
C2 MINUS WT-%
2.77
3.06
C3, VOL-%
12.5
13.7
C4, VOL-%
18.0
19.6
67.1
74.3
LCO, VOL-%
10.0
0.0
5.0
5.0
COKE, WT-%
5.0
6.1
32.8
34.5
110.2
120.1
92.5
92.6
93.2
93.3
85.3
85.2
YIELDS
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The amount of poisons removed again depends on what species are present, and
the severity of treatment. Moderate hydrotreating will remove 10-50% of the total
nitrogen. A high severity operation may run close to 100% removal. Treatment for
oxygen gives similar results.
PROCESSING OF RESIDUAL FEEDSTOCKS
There are several problems and penalties associated with processing residual
feedstocks. There is a loss of selectivity in liquid product yield since the feed
generally contains less hydrogen than the gas oil fraction. The increased boiling
range brings more contaminants into the unit, both as coke precursors and as
metals. The coke precursors will cause a higher delta coke on catalyst and will
result in a hotter regenerator and less conversion for the coke yield generated. The
higher metals will cause more light gas production as will the higher regenerator
temperatures. Catalyst activity will be effected by the high metals and by the
additional deactivation from the high regenerator temperature. The higher coke yield
will mean thruput will have to be reduced to stay within the coke burning capacity of
the unit.
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The following table from a commercial unit illustrates what happens as the feed is
changed from VGO to Resid.
Commercial Operations
Changing from Gas Oil to Residue Processing
Feed
100 / 0
38 / 62
25 / 75
0 / 100
0.16
2.25
2.96
3.95
1.0
9.6
9.0
6.3
Conversion, lv-%
86.2
82.2
79.7
76.5
62.6
60.3
59.5
57.4
Coke, wt-%
5.6
7.2
7.1
7.5
Commercial Performance
As the contamination in the feed increased as a reflection of the poorer feed quality,
the coke make required to maintain conversion increased. However, by careful
selection of the crudes purchased, the metal content of the resid was controlled so
that their effect on the operation was limited and the additional coke burning
requirement was the major change. Note that the gasoline yield was reduced by
almost 5 LV% due to the change in feed.
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This same dependency on feed quality is evident in the RCC unit as well. The
following tables show the performance of the unit on three different quality feeds:
API
Sulfur, wt-%
Nitrogen, wt-%
Conradson Carbon, wt-%
Metals
Nickel, wt-ppm
Vanadium, wt-ppm
Low
Carbon
Residue
22.8
0.9
0.12
4.8
8
17
Intermediate
Carbon
Residue
21.3
1.1
0.14
6.0
13
31
High
Carbon
Residue
19.2
1.2
0.19
7.9
17
52
Low
Carbon
Residue
3.4
25.2
59.1
Intermediate
Carbon
Residue
3.2
24.7
56.6
High
Carbon
Residue
4.0
23.9
55.6
15.0
14.2
15.0
7.5
8.4
106.4
91.9
10.2
9.1
105.7
93.2
10.9
10.8
105.4
93.3
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Figure 2 summarizes the effect that contaminated feed has on the unit's regenerator
temperature.
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These plots also summarize the experiences of most refiners, who found that the
units designed for VGO could not accommodate more than about 3.5 to 4.0 wt-%
Conradson carbon in the feedstock due to excessively high regenerator temperatures. The high temperatures also resulted in severe catalyst deactivation and poor
unit performance. This fact, i.e., that residual stocks deposit more carbonaceous
material during the cracking cycle than can be effectively used to fuel the
conversions reactions, led to the development of alternative technologies directed
at:
The first approach led to the development of the two-stage regeneration system that
is currently practiced in the Ashland RCC unit and the second to the development of
the catalyst cooler, also incorporated in the design of this unit.
Table 5 summarizes the relevant properties of an atmospheric resid that will be
used to illustrate the benefits that can be obtained by varying the heat removal in a
commercial unit. Case 1 found in Table 6 represents a very low coke make
operation where the regenerator temperature has been allowed to equilibrate at a
very high level, in the order of 1480F. The yield structure is poor and the gas make
extremely high. The subsequent cases illustrate the benefits that can be derived by
manipulating the heat balance forcing the unit to produce more coke. Even though
the unit is producing an additional amount of coke, the yield pattern improves. The
data in Table 6 is plotted graphically in Figure 3.
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TABLE 5
RCC FEEDSTOCK FOR COKE YIELD VS. CONVERSION STUDY
API
Conradson Carbon
Metals, wt-ppm
UOP K
Source
20.8
4.8
20.0
12.1
Atmospheric Resid
TABLE 6
RCC ESTIMATED YIELDS VS. UNIT COKE YIELD
Case
Coke Yield, wt-%
Conversion, LV-%
Dry Gas, wt-%
Gasoline, LV-%
LCO, LV-%
Slurry, LV-%
Total Liquid, LV-%
Heat Removal
1
7.3
68.3
7.2
46.0
16.9
14.8
101.6
No
2
8.57
77.2
4.2
56.3
13.4
9.4
106.6
No
9.73
80.9
3.4
58.5
11.4
7.7
107.6
Yes
11.10
83.0
3.3
59.1
9.7
6.4
107.5
Yes
Feed: Table 5
Gasoline, 380F at 90% Pt.
LCO, 600F at 90% Pt.
Installing a variable heat removal catalyst cooler enables the refiner to adjust the
heat removal required for a given feedstock to produce the optimum yield pattern.
Even though the coke yield has increased, the resulting yield pattern at the higher
coke make is more favorable than that which can be achieved at the lower coke
makes. These benefits are achieved at relatively low regenerator temperatures, of
less than 1350F, for good catalyst activity maintenance.
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No Cat Cooler
Base
Base
1410
85
Base
Base
No
Base
Base + 160
Base
1350
85
Base
0.5 Base
2500 Btu/lb coke
Base
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The preceding discussions have illustrated the benefits that can be derived with the
installation of a catalyst cooler. This flexible technology permits:
Adjustments in the unit conversion to achieve the optimal yield pattern for a
given feedstock
A more profitable unit operation while keeping the unit coke production
constant.
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REGENERATION SECTION
The main purpose of the regeneration zone is to oxidize the coke on spent catalyst
and reestablish the catalyst activity of the fluidized particles prior to being returned
to the reactor riser. The heat from this combustion of coke in turn provides the
energy to satisfy the process requirements. Thus, the regeneration section has a
very fundamental significance.
Over the years this section has undergone fundamental design and mechanical
improvements. One of the first big movements occurred during the 1970's, with the
advent of total combustion. UOP moved away from the conventional bubbling or
turbulent-bed regenerator to a fast-fluidized, high-efficiency style combustor. Since
then this design has become well established as shown in Figure 8, and more than
45 units in commercial operation. Contrasting a modern high efficiency combustor
design with a typical bed style configuration of the past, as in Figure 6, the major
regenerator improvements are aimed towards:
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FIGURE 4
FLUIDIZATION REGIMES
A) Bubbling
Fluidized Bed
(B)
Turbulent
Fluidized Bed
(C)
Fast
Fluidized Bed
Transport
Riser Reactor
Bed Density
(D)
Catalyst Flux
Gas Velocity
UOP 3106-6
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FIGURE 5
BUBBLING TO TURBULENT BED TRANSITION
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FIGURE 6
BUBBLING BED REGENERATOR
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FIGURE 7
MAXIMUM DILUTE PHASE ENTRAINMENT
IN VERTICAL GAS-SOLIDS UPFLOW
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FIGURE 8
HIGH EFFICIENCY REGENERATOR
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Figure 9 represents typical combustor hydraulics for various catalyst loadings and
superficial gas velocities. The combustor density is measured across the entire
combustor height and the solids loading W (lb/sec/ft2) is the summation of both the
spent catalyst circulation and the combustor external recirculation. The gas
superficial velocity (A) lies well below the catalyst transport velocity, but at a low
solids flux (region X-Y), dilute phase flow exists. At condition (Y), the solids flux is
sufficient to choke the system and any further increase in solids loading (region Y-Z)
results in a substantial density (inventory/residence time) increase.
FIGURE 9
COMBUSTOR OPERATION
A
Combustor
Catalyst
Inventory Is:
I = Density x V
(Z)
Where V Is
The Combustor
Volume, ft.3
D
(Y)
(Y)
(X)
At the higher gas velocities (B) and (C), choking takes place at much higher solids
flux which results in a less abrupt change in combustor density with further
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FIGURE 10
CATALYST PRE-COMBUSTION TEMPERATURE
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1.
2.
3.
Most of these intrinsic mixing problems were eliminated with the high efficiency style
combustor. Figure 11 compares the theoretical particle residence time distributions
of a modern high-efficiency style combustor with that of a conventional bubbling
bed. The basic difference in response curves is due to both the fluidization regime
(fast-fluidized) and the solids entry/exit configuration. The combustor regenerator
more closely approaches a plug flow reactor system where it is impossible for a
spent catalyst particle to leave the regenerator without passing through the dilute
phase combustion zone.
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FIGURE 11
THEORETICAL RESIDENCE TIME DISTRIBUTIONS
Regarding radial/axial mixing, it is still highly desirable for the lower (5 feet)
combustor section to be operated with a pseudo-dense phase acceleration zone.
The relatively high slip and low voidage enhances the effective fast-fluidized bed
thermal conductivity, allowing rapid heat transfer between the hot recycled and
relatively cold spent catalyst particles up to the pre-combustion temperature. This
produces uniform radial temperatures in the lower combustion zone.
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Where:
K
= Rate constant, hr-1 atm-1
C
= Wt-% carbon on catalyst
PO2 = oxygen partial pressure, atm
The reaction rate constant will be dependent on temperature and can be
represented via an Arrhenius type equation:
dC / dt Koe
E
CPo2
RT
(1)
where:
E =
R
=
T
=
Activation Energy
Gas Constant
Temperature, R
This relationship for the rate of carbon burning from fluid catalytic cracking catalysts
was found experimentally to hold over a wide range of temperatures with diffusional
limitation not controlling. A similar expression can be used for the hydrogen content
of the coke, with the oxidation of hydrogen proceeding more rapidly than that of
carbon:
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dH / dt K oe
E
HPo2
RT
(2)
Where:
Ko Ko
H = Wt-% hydrogen on catalyst
When discussing coke combustion rates and kinetics, it is important to differentiate
between net coke yield and coke concentration (analogous to heat and
temperature). The net coke yield is set by the unit enthalpy balance with little direct
impact on the rate of coke combustion of individual particles.
Delta Coke
FG
air
Hloss
With a few simplifying assumptions, such as a plug flow combustor and total
combustion of coke to CO2, the differential equations (1) and (2) can be solved
numerically in order to gain insight into the impact and optimization of such process
variables as:
Temperature
Catalyst recirculation
Oxygen partial pressure
Carbon and hydrogen concentration
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Pre-combustion temperature is the mix temperature of the cold spent catalyst, hot
recycled catalyst, and combustion air:
Tmix
Where:
B
F
CCR
TB
0.275
0.273
=
=
=
=
lb air/hr
Cat Recirculation, wt ratio of CCR
Cat Circulation Rate, lb/hr
Blower Temp, F
The table below shows the substantial impact of recirculated catalyst on the
combustion rates via the increased initiation temperature Tmix.
Recycle
Coke Concentration
Mix Temperature
Regen Time
Zero
913
121 sec's
1.5 CCR
1161
44 sec's
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These two parameters are strongly interdependent since the final regenerated
catalyst temperature is set by:
TRegen = TRx + C/Cp [HComb - HAir - Hlosses]
Where:
C = Cspent - Cregen
With Cregen --> 0 for most operations
The impact of temperature alone on the rate of carbon combustion is exponential
and quite dramatic:
Temperature
Relative combustion rate
1100F
1200F
1300F
1400F
2.5
18
10
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FIGURE 12
RELATIVE EFFECT OF EXCESS OXYGEN
CONCENTRATION ON REGENERATION TIME
AS A FUNCTION OF TEMPERATURE
1.
2.
3.
4.
100
5% Excess O2
2% Excess O2
10
1120
1140
1160
1180
1200
1220
Temperature, oF
1240
1260
1280
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FIGURE 13
Relative Effect of Total Pressure on Regeneration Time
Requirement at Various Temperatures
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
1150F
1200F
1250F
10
20
30
40
50
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With some simplifying assumptions, all the process variables and their interactions
can be mathematically modeled via equations (1) & (2) in order to achieve
additional understanding and optimization of the combustor performance.
As an example of the model's use, Figure 14 and Table 8 show the calculated time
dependent responses of the numerous products of combustion for the following set
of typical combustor operating conditions:
Regenerator pressure
lb air/lb coke
Hydrogen in coke
Coke on spent catalyst
Recycle catalyst temperature
Blower discharge temperature
Catalyst recycle
Reactor temperature
% oxygen in air
CO2/(CO2+CO)
30.0 psig
14.18
6.0 wt-%
0.8 wt-%
1344F
320F
1.5 Xs
980F
21 mol%
1.0
Particle Temperature, F
Carbon Concentration, wt-%
Hydrogen Concentration, wt-%
Flue Gas Oxygen Concentration, mol%
Assumptions:
1. Complete combustion
2. Plug flow regeneration
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FIGURE 14
COMBUSTOR COMPOSITION PROFILES
25
1500
1450
20
1400
10
1300
1250
W
t- %
1200
Ca
rbo
nW
Flue Ga
s
t- %
O2 mol
-%
1150
1100
0
10
15
20
25
30
Time (seconds)
35
40
45
50
55
60
Temperature
o
Temp, F
en
og
dr
Hy
Composition
1350
15
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TABLE 8
FCC COMBUSTOR MODEL
CALCULATED TIME-DEPENDENT VARIABLES
Time
Temp, F
Carbon
wt-%
0
1
2
3
4
5
10
15
20
25
30
35
40
45
50
55
60
1160
1177
1182
1206
1218
1230
1272
1295
1310
1319
1325
1330
1333
1335
1336
1338
1339
0.752
0.708
0.663
0.616
0.574
0.532
0.358
0.246
0.174
0.126
0.097
0.076
0.060
0.046
0.039
0.032
0.026
Hydrogen
wt-%
0.046
0.036
0.028
0.022
0.016
0.012
0.002
0.001
-------------------------------------------------------
Flue Gas O2
mol%
21.0
18.3
17.7
16.2
14.8
13.7
8.5
7.0
5.5
4.6
3.9
3.5
3.2
2.9
2.7
2.6
2.5
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This burning of CO in the dilute phase known as "afterburning" can produce large
flue gas temperature increases above those in the dense phase. This is due to the
relative heats of combustion:
C
CO 3,960 BTU/lb
Total Combustion
(16,500 BTU / lbCoke)
16000
15000
14000
13000
12000
11000
1
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15
Complete Combustion
with 2% Oxygen
in Flue Gas
14
13
Complete Combustion
with No Oxygen
in Flue Gas
12
11
10
1
In the absence of catalyst, a flue gas stream of 3/1 CO2/CO mol composition
undergoing complete combustion to CO2 could see a temperature increase
> 600F. (Note: this temperature increase is moderated due to the sensible heat of
any entrained catalyst.)
In the 1970's, in order to exploit the higher activity, more coke selective zeolite
catalysts, operations with high temperature, once through total combustion were
utilized for the processing of conventional high quality vacuum gas oils. Table 9
shows a comparison between old and modern operations.
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TABLE 9
CATALYST FORMULATION AND PROCESS DESIGN MODIFICATIONS
Components
H2S
C2
C3
C4
C5+ Gasoline
LCO
CLO
Coke
Amorphous Catalyst
Wt-%
LV-%
0.5
4.5
6.75
11.95
45.4
12.8
8.7
9.4
100
54.4
12.4
7.6
Process Conditions
Bed cracking = 935F
CFR = 1.3
Partial burn
Capacity = Base
RONC = 92.5
RE-Y Zeolite
Wt-%
LV-%
0.4
3.75
6.45
11.45
50.2
12.55
9.4
5.8
100
59.8
12.0
8.0
Process Conditions
Riser cracking = 980F
CFR = 1.0
Total combustion
Capacity = 1.7 x Base
RONC = 91.8
Hfeed
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Hcomb:
Hrecycle:
9055
14,150 BTU/lb coke
Zero BTU/lb feed
With the combustor operation, complete CO combustion (< 50 ppm CO in flue gas)
can be achieved thermally, without promoter at temperatures greater than 1270F
and 2 mol % excess oxygen in the flue gas.
However, Mobil discovered that certain Group VIII metals, particularly platinum,
could be used at very low levels (1-3 wt ppm) to effectively catalyze the combustion
of CO to CO2 either as an integral part of the fresh FCC catalyst or as a separate
additive. In the combustor operation these additives are also frequently used but at
lower concentrations than the conventional bubbling bed regenerators.
The optimization of the combustor operation is simply the optimization of coke
burning kinetics, with a slight twist over conventional bubbling bed systems because
of the fast-fluidization regime. The combustor operation is normally quite stable, and
with only a little attention from the operator, optimal conditions can be maintained
without difficulty.
The focus of where to begin lies in only two areas: carbon on regenerated catalyst
and afterburning control. If these are both within acceptable values, no further
optimization is required. To adjust these values, we need to examine the areas of
control for the combustor.
Temperature
The primary control point for optimization is the combustor temperature. Although
the other factors are important, the temperature can be considered the one truly
independent variable for the operator.
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The ability to increase temperature in the combustor is, however, limited. Once the
recirculation slide valve is full open, no further increase in temperature can be
gained with hot recycle catalyst. The effect of other factors, such as the use of CO
promoter or increased coke operation, can lead to additional temperature
increase.
It should be noted that a flow-through catalyst cooler can limit the effectiveness of
the recirculation catalyst to raise combustor temperature. The cooled catalyst flow
will require additional hot catalyst recycle to maintain desired temperatures.
Somewhat compensating is the high coke operation that calls for the catalyst
cooler in the first place. However, if it becomes necessary, the cooled catalyst slide
valve can be adjusted to help optimize the combustor temperature.
Density
Density and velocity together determine the residence time of the catalyst within the
combustor. It is desirable to maintain at least 6 lb/ft3 density in the combustor and if
possible, 9 - 10 lb/ft3 should be a normal operating target.
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The combustor density is a dependent variable, since the temperature controls the
recirculation slide valve, unit capacity determines the velocity based on air rate, and
spent catalyst flow is dependent on the catalyst/oil ratio. However, where possible
the density (residence time) should be increased for the following situations:
Increased density will promote better thermal mixing and will increase residence
time to help resolve these conditions. Also keep in mind that as density increases,
the combustor catalyst inventory increases and the upper regenerator level will
decrease.
Velocity
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Excess Oxygen
The air rate and regenerator pressure will determine the oxygen partial pressure in
the combustor. Although higher levels of excess oxygen via increased air rate are
beneficial to the combustion kinetics, they are counterproductive to the unit
economics. Velocity will increase as air rate is increased, negating some of the
advantages of higher oxygen partial pressure. Thus, flue gas oxygen should be
maintained at or below 2 mol%.
There are certain situations when an increase in oxygen beyond normal flue gas
levels may be warranted:
One element that can be considered to increase oxygen partial pressure in the
combustor without increasing air rate is the use of pure oxygen injection. In certain
situations this may be economically feasible.
CO Combustion Promoter
If all other conditions in the combustor are optimized, the use of promoter will not be
required. However, it is perhaps inevitable that the FCC unit will be pushed to the
limits such that the combustor conditions will generally exceed optimum values. In
this case, the use of promoter can provide an additional measure of safety for
controlling afterburn and avoiding excessive dilute phase temperatures.
Particularly when maximum unit capacity is required beyond design levels, the use
of promoter can be beneficial. The following conditions might suggest that promoter
should be considered:
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Maximum Capacity
Since many units operate on the basis of pushing the FCC capacity to the limit, it is
appropriate to discuss what will happen in the combustor. Prior comments on the
operating variables have addressed some of the concerns of higher capacity
operation, but an overall perspective is needed.
In general, pushing capacity to the maximum will result in a combustor operating at
high velocity, low density and low catalyst residence time. Directionally, this will tend
to increase afterburn and carbon on regenerated catalyst.
From earlier data shown regarding coke burning kinetics, carbon is reduced to
levels around 0.15 wt% very quickly, but to get to 0.05 wt% requires substantial
additional time. In a maximum capacity operation, there may not be sufficient time in
the combustor to reach carbon levels of 0.05 wt% or below.
It is important to point out that this is not all bad, and in fact may be economically
advantageous. With the use of promoter to maintain control of after burning, it is
possible to allow the CRC to increase as a trade off for more feed capacity.
Although effective catalyst activity is reduced, the reduction may be small enough to
justify the higher capacity operation.
Optimization Summary
All of the above variables need to be thoroughly understood, especially how they
interact with each other. Application of this knowledge properly will result in arriving
at the best operation for each particular unit. Optimization should be considered as
a continuous effort, since what is optimal in one set of circumstances may not be in
another.
As a final note, it should be emphasized that UOP is always interested in obtaining
feedback on the operation and experiences of these units from the refiner. Our
Technical Service department is always available to provide assistance or
consultation as needed. Only through working together can we hope to continue to
improve our designs and their performance capability.
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INTRODUCTION
The main column bottoms system on an FCC presents some unusual mechanical
and operating problems. The vapors entering the column are superheated and
contain catalyst fines which may cause erosion or plugging. Heavy oil cascading
down the disc and doughnut (side-to-side on some units) trays cool and condense
the heavy vapors so that they can be fractionated. The catalyst fines are washed
down to the bottom of the column by this cascading stream.
COKE
Many units have some coke buildup in the reactor, vapor line, and bottom of the
main column. The amount in the reactor and vapor line can be minimized by good
insulation. The coke buildup in the main column is influenced by three factors:
1.
Hydrocarbon characteristics
2.
Temperature
3.
Residence Time
Some hydrocarbons have a greater tendency to thermally crack and produce coke
than others. The Conradson or Ramsbottom carbon residue tests may be used to
get some idea of this tendency, but it is difficult to compare one stock with another.
The amount of catalytic cracking that has taken place in the reactor will influence
the coke production of the hydrocarbons in the main column. The operation of the
FCC unit and of the upstream units that produce FCC feed are controlled by other,
more important variables than the main column bottoms coke make. Temperature
and residence time control are used to minimize the bottoms coke problem.
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The maximum allowable temperature in the bottom of the tower is usually given as
700F (370C). Experience with a particular feed may raise or lower this somewhat,
but it is better to run lower to prevent coke problems. Many refiners use 680-700F
(360-370C) as the normal operating point.
The major control on the bottoms temperature is by the composition of the material,
but the quench line may also be used to sub-cool the bottoms material. This line
returns cool oil directly to the bottoms level, instead of to the disc and doughnut
trays. It is generally used at high throughput, when there is adequate flow to the
discs and doughnuts, and the heat input to the column is high.
Residence time refers only to the time spent in the column, not in the entire slurry
system. The oil begins to cool as soon as it leaves the tower. There may be some
minor coking in the slurry settler and associated piping, but usually this is not
enough to affect plant operations. If the oil is in the tower too long, at too high a
temperature, serious coking can plug the bottom. Removal is difficult, because
chipping away with hammers usually leads to lining damage. Other methods, such
as chemical cleaning, are usually ineffective.
At low charge rates, the bottoms circulation through the exchangers must be
reduced to heat balance the tower. The oil cascading down the discs and
doughnuts decreases to a point where the trays run dry. Because the hot reactor
vapors are not cooled, they can cause warping and distortion of both the disc and
doughnut trays and those above as this large volume of vapors tries to pass up the
column. Catalyst fines will be carried up into the HCO and LCO circuits, which can
be quite serious, because these areas are not designed for fines removal. Product
specifications will be adversely affected.
The solution to this problem and that of long residence times at low circulation rates
is to use the minimum flow line which bypasses the exchangers and returns oil
directly to the column, over the disc and doughnut trays. The flow over these trays
should be at least 50 gpm/ft tower ID (37.3 m3/hr/meter tower ID). This line is
usually used on startup, when the charge rate is low and the tower is cool. As
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charge rate increases, the flow rate through the minimum line is decreased to force
oil through the heat exchange circuits. There should always be a small amount of oil
flowing through the line, so that the oil does not set up. The same is true for the
quench line to the bottom of the fractionator.
Some units have used a large impingement baffle to break up the reactor vapors as
they enter the column. Many of these baffles proved to be a good starting point for
coke, and the baffles were removed. Inevitably, there is some coke buildup; pieces
may break off with thermal shock or other stresses. If a chunk of coke could enter
the bottom line, it could cause plugging or pump damage. A coke trap made of Type
405 or 410 stainless steel is used at the bottom of the column to keep these large
chunks out of the line. Smaller pieces of coke pass through it and are caught by the
pump suction screens. These can be cleaned on stream, while the larger chunks of
coke might prove difficult to remove from the line.
CATALYST CARRYOVER
The amount of catalyst carryover from the reactor will depend on unit design,
cyclone efficiency, catalyst type, and unit throughput. Unusual problems such as
high reactor level, cyclone failure through cracks or plugged diplegs, or pressure
surges can increase the catalyst carryover to unacceptable levels. A conventional
unit of older design (single stage cyclones) should lose less than 0.4 LB/bbl charge
over to the main column, with most of this returning with the slurry recycle. A new
unit with a riser "Tee" and high efficiency cyclones should lose less than 0.05
LB/bbl.
It is not practical to actually measure the catalyst content of the main column inlet
vapors. The catalyst content of the circulating bottom stream is, however, a good
indication of the catalyst losses. A general assumption may be made that very little
catalyst is entrained up into the HCO or LCO products. If this is not the case, the
bottoms circulation over the disc and doughnut trays should be increased as much
as possible, within the limits imposed by other operating variables. The lower part of
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the tower should be inspected carefully at the next turnaround to determine if the
problem is here.
The main column bottoms pump discharge manifold is constructed to direct the
catalyst fines and coke particles out of the circulating system. The lines to the
various exchangers come off the top of the manifold. The line to the slurry settler
will come off the end of the manifold from the bottom. If there is no settler, the
reactor recycle and bottoms product lines will both come off the bottom of the
manifold. This obviously will not achieve a complete removal of catalyst fines or
coke, but it will help prevent a buildup in the main column bottoms circulating
system.
SLURRY SETTLER
The slurry settler process flow is shown in Figure 16 in Process Control section.
Main column bottoms enter the settler through a tangential nozzle; this gives it a
swirling motion that promotes a more even distribution of the heavy oil as it moves
up towards the outlet. The catalyst fines settle out and are carried back to the
reactor. The carrying medium will depend upon the operation.
1.
This would be typical of older units that require the high recycle rates to get desired
conversion. The recycle consists of main column bottoms and HCO, which is cooler
and has a higher flowing specific gravity than the bottoms material. The HCO is
injected into the upper diluent point and flows down with some of the bottoms and
most of the catalyst that enters the settler. A plant operating in this mode would
have a CFR of 1.2 to 2.0.
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2.
The use of the new higher activity catalysts and better reactor design enable the
refiner to crack most of the feed on the first try. The heavy oil product make is
lower; it is also a more refractory material which tends to go to coke and dry gas
when recycled to the reactor. The carrying material used in this case may be HCO,
but for many units, raw oil is the better choice. The bottom diluent injection point is
used to minimize the amount of raw oil that will go up into the settler. If the raw oil
thermally cracks or goes out with the CSO, it may cause problems with the CSO
product specifications. To help prevent this, the flow back to the reactor should
always be higher than the diluent flow to the settler.
SETTLER OVERHEAD
The amount of CSO that comes off the top of the settler will also depend upon the
operation. The decreased heavy oil make of the newer units can lead to a buildup of
catalyst in the main column because there is less main column bottoms leaving the
tower to take it out. This refers to oil leaving the system, not to the bottoms
circulation streams. The concentration of fines in the tower may build up enough to
cause serious erosion and plugging problems. The most effective solution is to use
a return line from the top of the settler to the main column disc and doughnut trays.
The flow to the settler can then be increased by the amount of oil which is returned
to the main column relatively free of catalyst.
Typical settler flow rates are shown in Table 11. For this table, it was assumed that
catalyst is coming overhead from the reactor at a rate of 100 LB/day. The catalyst
can only leave the system through the outlet to the settler; therefore, the
concentration will be equal to the amount of catalyst (100 LB/day), divided by the
flow to the settler.
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TABLE 11
SLURRY SETTLER FLOW
CASE A
CASE B
CASE C
10,000
10,000
10,000
1500
500
1500
0.067
0.20
0.067
500
500
500
1,000
500
500
1,000
500
500
1,000
Diluent, BPD
Case A would be an operation with lower activity catalyst and a higher CSO product
make. Case B would be a conversion to higher activity operation, decreasing the
amount of recycle and the CSO product. Neither Case A or B uses a return line
from the top of the settler to the main column. Case C is similar to B in that a higher
activity catalyst is used, with a small amount of main column bottoms produced. The
use of the return line from the top of the settler back to the main column allows the
flow to the settler to be increased to 1500 BPD. A limit on flow to the settler is the
velocity of fines settling. The liquid velocity should never exceed 30 BPD/ft2 (50
m3/d/m2) of settler cross sectional area. Above this, there may be problems with
catalyst carry over into the overhead stream.
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Some of the new units have incorporated a reactor cyclone configuration which
decreases the amount of catalyst carryover to the main column. The reactor riser
ends with a pair of outlet arms, and a two stage cyclone system on the reactor
outlet eliminates most of the catalyst in the overhead vapors. With this system,
some refiners have elected not to use a slurry settler. The recycle to the reactor and
the bottoms product come directly from the main column bottoms pump discharge
manifold.
PLUGGING
There are occasional problems with plugging in the lines or exchangers of catalyst
bearing streams. If there is a plant upset which causes large amounts of catalyst to
go overhead, such as a sudden dip in column pressure, immediate action should be
taken to remove the extra catalyst from the system. Increased slurry recycle and
clarified oil product would be the two most important steps. These should be
continued until the laboratory confirms that the BS & W content of the bottoms
stream is back to normal.
In the event of a major upset that completely fills the bottoms of the column with
catalyst, care must be taken to avoid further complications. Catalyst holds heat fairly
well and conducts it poorly, so the cool-down period may be on the order of several
days. The thermocouples in the column will be well insulated by the catalyst close to
the wall, so the readings will probably be lower than the actual temperature of most
of the catalyst. Introduction of cold oil or wash water will produce severe pressure
surges that may damage the column internals. The oil soaked catalyst is both a fire
and breathing hazard. The shutdown for cleanout can be estimated at one week, a
good argument against hasty measures that could lead to excessive catalyst
carryover to the column.
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To prevent catalyst plugging or erosion in the exchangers, UOP calls for the
following velocities in the tubes:
1.
2.
The main column bottoms circulation rate is adjusted to control the column's heat
removal requirement. The bottoms stream generally exchanges heat with the raw oil
feed and is utilized in the production of superheated steam in the steam generators.
A reduction or increase in the bottoms heat removal must be compensated by an
increase or reduction in heat removal in another section. Provided no other changes
are made, the overhead reflux rate will compensate for any changes in bottoms
heat removal. As illustrated in Table 12, a decrease in the bottoms stream heat
removal results in an increase in reflux rate. The bottoms stream heat removal
should be adjusted to minimize the reflux rate and maintain good product
distillations.
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TABLE 12
17550
17550
10488
13.81
7973
42.81
11581
13.81
7993
45.24
2782
2782
12.32
12.32
1790
1790
10.17
10.17
967
967
31.0
28.57
GASOLINE/DISTILLATE PRODUCTION
The main column draw temperatures are dependent on the stream's composition
and vary with changes in draw rate. As the gasoline product draw is reduced, liquid
will drop down the column to the LCO draw tray and require an increase in LCO
product draw. The reduced gasoline draw rate will result in a lighter gasoline
product having a lower ASTM distillation end point and a lower draw tray
temperature. The LCO product also becomes lighter because of light material
dropping to the LCO draw tray. The LCO initial boiling point temperature will
decrease with a slight decrease in the draw tray temperature. Table 13 illustrates
the changes which result to the main column and product streams as the LCO yield
is increased by reducing the gasoline endpoint and yield.
157048
Process Variables
Page 71
TABLE 13
Gasoline:
API
Product rate, BPD
90% BP temp., F
RONC
MC overhead temp., F
57.9
15800
372
90.7
311
57.2
16200
381
90.6
316
56.3
16600
392
90.4
323
20.1
6000
198
462
624
664
482
19.8
5600
204
471
624
664
485
19.3
5200
212
482
624
664
499
Slurry
API
Product rate, BPD
6.2
2800
6.2
2800
6.2
2800
Gasoline or any other liquid stream can be broken up into numerous cuts, each
having distinct properties. Examining the cuts which comprise a typical gasoline
sample will show how overall product quality can be improved.
157048
Process Variables
Page 72
A FCCU gasoline sample from a high severity operation was broken up into nine
cuts, each having a narrow TBP range as illustrated in Table 14. The properties of
the individual cuts are shown in Figures 6 and 7.
TABLE 14
Cut No.
1
2
3
4
5
6
7
8
9
Cumulative
Vol -%
20
30
40
50
60
70
80
90
100
TBP Fraction, F
75 - 93
93 - 145
145 - 181
181 - 210
210 - 250
250 - 286
250 - 286
286 - 334
334 - 387
387+
157048
Process Variables
Page 73
400
300
200
100
0
1
Gasoline Cut
100
API Gravity
80
60
40
20
1
Gasoline Cut
100
RONC
96
92
88
84
80
1
Gasoline Cut
157048
Process Variables
Page 74
Sulfur, wt %
0.8
0.6
0.4
0.2
0
1
5
Gasoline Cut
100
Bromine
Number
90
80
70
60
50
40
30
20
10
0
1
80
Gasoline Cut
Paraffin/Naptha
70
Aromatic
Olefin
Liquid Vol %
60
50
40
30
20
10
0
1
Gasoline Cut
157048
Process Variables
Page 75
The sulfur content of gasoline increases sharply in the last 387+ TBP fraction as
indicated in the Wt-% SULFUR graph. The overall sulfur content of gasoline hence
could be reduced by lowering the gasoline end point temperature.
The RONC graph of the various cuts indicates a reduction in octane at CUT 4
(181-210 TBP) and CUT 9 (387+ TBP). A slight increase in the overall gasoline
octane can be obtained by reducing the end point temperature of the gasoline. If it
were possible to remove CUT 4, gasoline octane could be further increased.
157048
Process Variables
Page 76
Operating Conditions
As desired.
Normally at minimum.
Reactor temperature
Reactor pressure
157048
Process Variables
Page 77
Variable
Operating Conditions
Stripping steam
Regenerator dense
phase temperature
Regenerator pressure
(conventional)
Regenerator level
Reactor-regenerator
differential pressure
157048
Process Variables
Page 78
Variable
Operating Conditions
157048
Process Variables
Page 79
TABLE 15
MAIN COLUMN
Variable
Operating Conditions
Flush oil
157048
Process Variables
Page 80
Variable
Operating Conditions
Circulating top
reflux temperature
Overhead receiver
temperature
157048
Process Variables
Page 81
TABLE 16
GAS CONCENTRATION SECTION
Variable
Operating Conditions
On spillback control.
Pressure
Sponge absorber
Top temperature
Pressure
157048
Process Variables
Page 82
Variable
Operating Conditions
Pressure
Debutanizer
Top temperature
Reboiler heat
Pressure
157048
Process Calculations
Page 1
PROCESS CALCULATIONS
INTRODUCTION
Throughout the years the Fluid Catalytic Cracking process has been a very versatile
and flexible tool for the refiner, and has become the basic conversion step in the
modern refinery. This process has survived and prospered because of its ability to
handle the many changes in catalyst, operating conditions, and feedstocks that have
occurred over the years.
The FCC Unit produces large volumes of high octane gasoline, olefinic LPG, fuel oil
(LCO and MCB), fuel gas, steam, and electricity. The yields are mainly determined by
process variables (i.e. feedstock, operating conditions, mechanical features, and type of
catalyst). Process variables have varying degrees of interdependence and may change
frequently producing changes in the yield structure of the products. A performance test
conducted at least once a week is recommended to evaluate the effect of process
variables on yield. The tests can be used to chart a history of the unit and to find
conclusions at different operating conditions.
The performance test provides accurate yield structures at a particular set of operating
conditions and provides a base point for further testing. The Performance Test normally
includes a heat balance, material balance, and a pressure survey. In those cases where
more information is desired, a Mechanical Evaluation Test is recommended. The refiner
can use this test to assess the potential of the unit and determine possible bottlenecks.
This section explains how to accomplish an acceptable Heat and Material balance and
how to do some of the most important calculations in the FCC Unit. An FCC
Performance Test Procedure is available on request from the Technical Service
Department. This procedure explains in detail how to conduct a performance test in the
FCC Unit.
157048
Process Calculations
Page 2
MATERIAL BALANCE
A material balance on an FCC Unit is done by drawing an envelope around the unit in a
manner that flow rates are known for all streams. This envelope includes the Reactor,
Regenerator, Main Column, and Gas Concentration sections. Normally, the Gas
Concentration Unit includes the primary absorber, sponge absorber, stripper column,
and debutanizer column.
1.
Data
Flow rates, flowing temperatures and laboratory analyses are required for each stream.
Pressure is also needed for the gas streams. The following table shows the information
needed to do a material balance:
INPUT DATA FOR HEAT AND MATERIAL BALANCE
Stream
API
Distillation
Feed
Yes
Yes
Yes
D-1160
Air*
Yes
Yes
MCB
Yes
Yes
Yes
D-1160
Yes
LCO
Yes
Yes
Yes
D-86
Yes
Gasoline
Yes
Yes
Yes
D-86
LPG
Yes
Yes
Sponge Gas
Yes
Yes
Meter Factor
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Flue Gas
Notes
GC
The method for including extraneous streams is straight forward as long as flow rates
and analyses are known. These additional streams coming into the Main Column and
Gas Concentration Unit are subtracted from the product streams.
157048
Process Calculations
Page 3
2.
Liquid Streams
Q = flow rate
K = flow meter constant ("K" factor)
R = chart reading
Gb = base gravity @ 60F
Gf = gravity at flowing temperature
0.9545
Where:
Go = density at 60F in kg/m3
T = observed temperature in F
T= T - 60
o = coefficient of thermal expansion at 60F, (1/F)
926
173
113
The set of correlations for the coefficient of thermal expansion based on API Data
Tables are:
o = (Ko + K1 Go + K2 Go )/ Go
Where:
0.00039779
157048
Process Calculations
Page 4
Product
Crude Oils
API Range
0 100
Ko
K1
K2
341.0957
0.2438
Gasoline
52 85
192.4571
Gasoline/Jet
48 52
1489.0670
-0.0018684
Jet Fuels
37 48
330.3010
Fuel Oils
0 37
103.8720
0.2701
0.3488
Lubricating Oils
-10 45
0.1F
0.1 API or 0.5 kg/m3
five significant figures for computation
157048
Process Calculations
Page 5
=
=
=
=
Flowing Temperature, F
Specific Gravity @ 60F, in g/ml
2.64641798
1.40583481
157048
Process Calculations
Page 6
3.
Gas Streams
Q = flow rate
K = flow meter constant ("K" factor)
R = flow meter reading
Pf = Pressure at flowing conditions (absolute)
Tf = Temperature at flowing conditions (absolute)
SG = specific gravity of gas = MWgas/MWair (1.0 for air)
K = 91,848 scfh
R = 6.5 chart reading
Pf = 173 psig + 14.7 = 187.7 psia
Tf = 113F + 460 = 573R
SG = 0.7054 from Sponge gas calculations
MW = 18.9 from Sponge gas calculations
Similar calculations are done for all gas, vapor, and air streams.
157048
Process Calculations
Page 7
4.
Calculate Coke
The coke make is calculated from the Heat Balance. (Refer to Heat Balance calculation
section.)
5.
A product yield is defined as the product rate divided by the raw oil rate.
The volume percent of each product stream is:
Vol-% (A) = (A, bpsd)100/Fresh Feed, bpsd
The weight percent is:
Wt-% (A) = (A, lb/hr)100/Fresh Feed, lb/hr
Where:
157048
Process Calculations
Page 8
6.
Once the weight and the volume flows are known for each stream, the Weight recovery
and the Liquid volume recovery can be calculated. Proper data analysis requires that
the Weight recovery must be 100.0 2.0 wt-%. Errors outside this range are significant
and cast doubts on the validity of the test data. The Sponge Gas used to calculate the
Weight recovery should not include the inert gases (N2, O2, CO, CO2). In addition, the
as-produced Liquid Volume recovery does not include the C3+ from the sponge gas.
Weight % Recovery = (Products, lb/hr x 100)/(Fresh Feed + Extraneous Feeds) lb/hr
Liquid Volume % Recovery = (Products, bpsd x 100)/(Fresh Feed + Extraneous
Feeds)bpsd
7.
Conversion
Conversion is defined as the volume percentage of raw oil converted to gasoline and
lighter components. This is calculated as:
Conversion, Vol% =
It is important to correct the gasoline and LCO yields on a constant cut-point basis. It is
inaccurate to compare gasoline yields at different 90% or EP temperatures. The gasoline
yield must also be adjusted by removing the C4's and adding the C5's and C6's from the
LPG and Sponge Gas streams. The procedures to adjust the liquid yields and to calculate
the C4's in the gasoline are attached in this section.
157048
Process Calculations
Page 9
9.
Gasoline Selectivity
The gasoline selectivity is the corrected gasoline yield divided by the true conversion:
Gasoline Selectivity =
10.
These procedures use the mol percentage from the GC analysis, the molecular weight,
and the specific gravity to calculate the flow rate of each component. Also, the stream
specific gravity and molecular weight are calculated. The procedure is attached in this
section.
11.
C3 and C4 Recovery
The C3 and C4 recovery indicate how the Gas concentration is performing. The C3
recovery is calculated as:
C3 Recovery, Vol% =
C3 in LPG
100
(C3 in LPG + C3 in Fuel Gas)
C4 in LPG
100
(C4 in LPG C4 in Fuel Gas C4 in Gasoline)
157048
Process Calculations
Page 10
Location: _______________________
TI - Tag
FE - Tag
Gravity
Vol.Corr.
Flowing
Meter
Temp. F
Readings
Gb@60F
Factor
Gravity Gf
"K"
TI10
TI-20
lb/Hr
Vol%
Wt%
8.90
0.9260
0.9545
0.8839
3,380
30,538
412,601
4.80
1.0412
0.8806
0.9169
418
1,843
28,005
6.04
6.79
9.00
0.9200
0.9838
0.9051
700
6,515
87,450
21.33
21.19
7.60
0.7599
0.9489
0.7211
2,118
17,987
199,434
58.90
48.34
7.20
0.5612
0.9653
0.5418
632
5,964
48,833
19.53
11.84
0.00
0.00
FRC-20
462
TI-30
BPSD
FRC-10
173
Date: __________
FC-30
101
Gasoline (DebBt)
TI-40
FRC-40
LPG
TI-50
LPG (ELPG)
Extraneous Feed
TI-
Coke
148
FRC-50
87
FRC-
25,187
6.10
6,589
18,821
4.56
6,996
20,887
PE-Tag
Press, psig
8
TI-60
FC-60
113
Gas (HGas)
Extraneous Feed
TI-
9a
Air to Regenerator
(Dry Back)
TI-70
9b
1.00
5.00
1.00
W/o Inerts
0.00
44.5
46,000
81,721
374,251
56
325
520
2,382
56
635
1,260
5,771
83,502
382,405
PI-72
FIC-74
230
1,518
PI-70
6.83
FIC-72
TI-74
Air to Distributor 2
W/o Inerts
173
PRC-
FIC-70
230
9c
0.6519
FC-
TI-72
PRC-60
6.50
415
SCFM
PI-74
6.20
1.00
As produced Calculations
10
98.82
Wt%
11
105.8
Vol%
12
Conversion
72.6
Vol%
For Liquids
LV%
uop1292rc
157048
Process Calculations
Page 11
Location: ____________________
Yields Adjustment for Gasoline @ 380F - 90% and LCO @600F - 90%.
IBP, F
10%, F
70%, F
90%, F
EP, F
Gasoline
LCO
319
460
MCB
524
710
569
Date: _____________
API
BPSD
lb/hr
367
410
54.71
17,987
618
653
22.30
6,515
87,450
4.40
1,843
28,005
26,346
314,889
Totals
199,434
Gasoline
Gasoline Factor (F1)
= [(380-T90)/(EP-T90)](1/9)+1
(1/9) + 1=
= [(380-IBP)/(T10-IBP)](1/9)
(1/9) =
cGasoline, BPSD
18,587
1.034 F1
0.05 F2
cBPSD
60.9
cLV%
c API
52.13
c API
0.771
cSG
cGasoline, lb/hr
208,974
c lb/hr
50.6
cWt%
lb/hr
BPSD
C4's in Gasoline
3,390
380
423
46
248
26
= cGasoline-C4's+C5's+C6's Extr(C5+C6)
18,587
corrBPSD
60.9
corrLV%
= cGasoline-C4's+C5's+C6's-Extr(C5+C6)
208,974
corrlb/hr
50.6
corrWt%
15 Corrected API
= ((141.5*BPSD*14.591)/(lb/h*24))-131.5
52.13
corrAPI
LCO
LCO Factor (F3)
= [(600-T70)/(T90-T70)](0.2)+0.7 =
0.827 F3
0.041 F4
= Gasoline - cGasoline
[ ( 600 524
( 17,680) -
)/ (710-524)]
(0.1) =
(18,587) =
-907 F5
5,059
corrBPSD
16.6
corrLV%
23.42
corrAPI
0.913
corrSG
67,416
corrlb/hr
16.3
corrWt%
2,392
corrBPSD
7.8
corrLV%
35,780
corrlb/hr
8.7
corrWt%
MCB
19 Corrected MCB, BPSD
87,450+
21 Corrected API
6.5
corrAPI
22
75.6
corrVol%
True Conversion
Note- The Factor equations are valid only if the as produce 90% temperatures are between 360-400F for gasoline and 580-620F for LCO.
The Factor Equations were developed from the 90% plus 10% Method. Used this method if the 90% Temp. are not in the specified range.
157048
Process Calculations
Page 12
C=AxB
g/100mol
Ib/hr
sp gr
0.04
0.00
1.47
4.31
5.82
1.3
0.0
64.7
120.7
186.7
14
0
716
1,335
2065
28.29
2.57
28.21
15.83
15.55
0.48
1.48
0.59
0.25
0.24
0.25
0.12
0.06
0.00
0.00
0.00
0.00
0.26
94.18
100.00
57.0
87.6
452.6
476.0
436.2
21.2
62.3
34.3
14.5
13.5
14.0
6.7
3.4
0.0
0.0
0.0
0.0
22.4
1,702
1,888
Component
MW
mole%
O2
CO
CO2
N2
Total Inertes
32.00
28.01
44.01
28.01
(t)
H2
H2S
C1
C2
C2=
C3
C3=
iC4
nC4
1-C4=
i-C4=
t-C4=
c-C4=
1,3-C4==
i-C5
n-C5
C5=
C6+
Total Products
TOTAL
2.02
34.08
16.04
30.07
28.05
44.10
42.08
58.12
58.12
56.11
56.11
56.11
56.11
54.09
72.15
72.15
70.14
86.18
(T)
MW = TC/TB =
18.9
SG = MW/28.966 =
0.6519
Mole % Inerts=tB=
5.82
Wt% Inerts=100tD/TD= 9.89
Inerts = tD =
2,065 Ib/hr
F
bpsd (scfh)
(168)
(0)
(6,170)
(18,091)
(24,429)
631
969
5,006
5,265
4,825
234
689
379
161
149
155
74
37
0
0
0
0
248
18,821
20,887
0.5077
0.5220
0.5631
0.5844
0.6013
0.6004
0.6100
0.6271
0.6272
0.6248
0.6312
0.6496
0.6640
(118,745)
(10,787)
(118,409)
(66,445)
(65,270)
31.6
90.4
46.2
18.8
17.0
17.7
8.4
4.1
0.0
0.0
0.0
0.0
25.6
259.8
(404,086)
=14.7=psia
+ 460=R
187.7
573.0
18,821 Ib/hr
395,313 scfh
scfh = V x Mol%/TB
157048
Process Calculations
Page 13
MW
B
mole%
C=AxE
g/100mol
SG
E=C/D
F=MxCftC G=VxE/tE
cc/lOOmol
lb/hr
H2S
34.08
0.0
0.0
0.7871
C2
30.07
0.0
0.0
0.3563
C2=
28.05
0.0
0.0
0.3680
C3
44.10
12.1
533.6
0.5077
1,051
5,216
704
C3=
42.08
36.2
1523.3
0.5220
2,918
14,891
1,955
iC4
58.12
10.7
621.9
0.5631
1,104
6,080
740
nC4
58.12
3.8
220.9
0.5844
378
2,159
253
1-C4=
56.11
8.5
476.9
0.6013
793
4,662
531
i-C4=
56.11
12.4
695.7
0.6004
1,159
6,801
776
t-C4=
56.11
9.2
516.2
0.6100
846
5,046
567
c-C4=
56.17
6.2
347.9
0.6271
555
3,401
372
1,3-C4==
54.09
0.3
16.2
0.6272
26
159
17
i-C5
72.15
0.4
28.9
0.6248
46
282
31
n-C5
72.15
0.2
14.4
0.6312
23
141
15
C5=
70.14
0.0
0.0
0.6496
C6+
86.18
0.0
0.0
0.6640
100.0
4,996
TOTAL (t)
8,899
48,838
bpsd
0
5,962
LPG S.G. =
tC/tE = 0.5614
Temperature, 0F
87
LPG MW =
tC/tB = 50.0
0.9653
Flow Gravity, Gf
0.5419
Meter Units
Meter K
=
=
7.2
631.5
V=Vol.Flow=Units x K x [SQRT(Gf)]/SG
5,962 bpsd
48,838 lbs/hr
157048
Process Calculations
Page 14
bpsd
32
90
122
234
689
923
bpsd
704
1,956
2,660
lb/hr
5,215
14,888
20,103
(5)
(6)
Stabilized Gasoline
(Debut. Bottoms)
bpsd
lb/hr
0
0
0
0
0
0
iC4
nC4
1-C4=
i-C4=
t-C4=
c-C4=
1,3-C4= =
Total C4s (T)
46
19
17
18
8
4
0
112
379
161
149
155
74
37
0
956
740
253
531
776
567
372
17
3,257
6,078
2,159
4,661
6,800
5,045
3,400
159
28,301
0
47
34
34
112
44
109
380
lb/hr
(3)
(4)
Debutanizer Overhead
0
399
299
299
997
399
997
3,390
95.6
wt-%
97.1
wt-%
157048
Process Calculations
Page 15
This method uses the ASTM distillation of the liquid products to create a composite
curve and correct the yields to any specified 90% temperatures.
Procedure
1. Using the ASTM distillation and a straight line interpolation equation, calculate
the LV% distilled every 20F for all the product streams.
%x=[(Tx-Ta)/(Tb-Ta)](%b-%a)+%a
%a < %x < %b
Ta < Tx < Tb
2. Calculate the composite volume and percent every 20F using the following
equations:
Cumulative BPD @ Tx =
BPD = [(%Gasoline) (BPSD Gasoline) + (% LCO) (bpsd LCO) + (% MCB)
(bpsd MCB)}/100
Cumulative LV% @ Tx = 100 BPD/Total BPD
3. Calculate Corrected Gasoline 90% @ 380F or Specified 90% Temperature:
Corrected Gasoline (Composite Yield @ 380F)/(0.9)
4. Calculate Corrected LCO 90% @ 600F or Specified 90% Temperature:
Corrected LCO = (Composite Yield @ 600F)-(Corr Gasoline)/(0.9)
5. Calculate Corrected MCB by difference:
Corrected MCB = Total Liquid Yield Correct Gasoline Correct LCO
157048
Process Calculations
Page 16
Data:
(%)
IBP
10%
30%
50%
70%
90%
EP
BPSD
Gasoline
(F)
94
124
165
222
294
367
410
LCO
(F)
319
460
503
533
569
618
653
MCB
(F)
524
710
759*
807*
876*
1100*
1200*
Total
17,680
6,515
2,227
26,422
157048
Process Calculations
Page 17
Data:
Tx, F
80
100
120
140
160
180
200
220
240
260
280
300
320
340
360
367
380
400
410
420
440
460
480
500
520
540
560
580
600
618
620
640
660
680
700
Gasoline
LCO
MCB
%x
0.0
2.0
8.7
17.8
27.6
35.3
42.3
49.3
55.0
60.6
66.1
71.6
77.1
82.6
88.1
90.0
93.0
97.7
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
%x
%x
0.0
0.1
1.5
2.9
3.4
4.3
5.7
6.5
7.2
8.6
10.0
19.3
28.6
37.9
53.9
65.0
74.5
82.7
90.0
90.6
96.3
100.0
100.0
100.0
0.0
0.9
1.9
3.0
4.1
5.1
5.2
6.2
7.3
8.4
9.5
Composite
BPD*
0
354
1,532
3,148
4,873
6,235
7,475
8,716
9,724
10,706
11,688
12,667
13,640
14,701
15,726
16,134
16,728
17,643
18,100
18,147
18,239
18,332
18,938
19,544
20,150
21,210
21,958
22,600
23,156
23,656
23,696
24,092
24,358
24,382
24,406
Percent
0
1.34
5.80
11.91
18.44
23.60
28.29
32.99
36.80
40.52
44.24
47.94
51.62
55.64
59.66
61.06
63.31
66.77
68.51
68.68
69.03
69.38
71.67
73.97
76.26
80.27
83.10
85.54
87.64
89.53
89.68
91.18
92.19
92.28
92.37
Corrected Gasoline =
=
Corrected LCO
=
=
Corrected MCB
=
=
157048
Process Calculations
Page 18
Burning coke in the regenerator provides all the heat necessary for the operation of
the unit. Yet, roughly 30-40% of the heat generated by the combustion of coke exits
the regenerator in the form of hot flue gas. The remainder is absorbed by the
regenerated catalyst which carries it to the reactor riser where it is used to vaporize
and heat up the combined feed to the desired cracking temperature.
The amounts of energy associated with the unit's operation are determined from a
catalyst section heat balance. The energy balance equation at steady state may be
written as:
Energy in + Energy produced = Energy out + Energy consumed
(1)
Energy in
Energy produced
Energy out
Energy consumed
= 0
or:
157048
Process Calculations
Page 19
Energy in
Energy produced
= 0
Energy out
(3)
The enthalpy change for the spent and regenerated catalyst is given by
Hspent catalyst = mass flow Cp (Rg Temp - Rx Temp)
(4)
(5)
At steady conditions,
Hspent catalyst + Hregenerated catalyst = 0
(6)
157048
Process Calculations
Page 20
Regenerated Catal ys t
Air
H Reaction
Spent Catalyst
Coke
Feed
Diluents
Radiation Losses
157048
Process Calculations
Page 21
(7)
The equation (7) demonstrates that all the energy in the Reactor-Regenerator
system is provided by the combustion of coke. The radiation loss term in this
equation is not a major item, but since vessel insulation is not perfect, some
radiation losses do occur. The term Hremoved refers to the heat duty of catalyst
cooler(s). The heat of reaction is the energy required to convert the feed to products
via the catalytic reaction mechanism.
The heat produced by the combustion of coke, equation (7), can be calculated from
the coke product rate and the mode of the regeneration operation. If all the CO
were burned to CO2 in the regenerator, more heat would be available per pound of
carbon than when the unit runs in this normal partial combustion mode. The heat
liberated by carbon combustion to CO2 is 14,150 BTU/lb (7,860 kcal/kg or 32,910
kj/kg) of carbon whereas heat for combustion to CO is only 3,960 BTU/lb (2,200
kcal/kg or 9,210 kj/kg).
Conversion Factors:
kcal/kg 1.8 = BTU/lb
BTU/lb 2.326 = kJ/kg
kcal/kg 4.187 = kJ/kg
The heat of reaction is endothermic. Energy is consumed by the reaction which
breaks the heavy hydrocarbon molecules into smaller, light hydrocarbon products.
The heat of reaction must be calculated from the energy balance using equation (7).
The most important value that can be calculated from the energy balance is the
catalyst/oil weight ratio. This ratio is important because it is a major factor in
hydrocarbon conversion and coke lay-down.
157048
Process Calculations
Page 22
Data Required
This heat balance is for a 30,565 BPSD feed case with the FCC Unit in total
combustion mode. The process conditions are:
Temperatures:
Pressures:
Reactor
Combined Feed
Lift Gas
Lift Steam
Feed Steam
Stripping Steam
970F
375F
100F
380F
380F
380F
Regenerator
Regenerated Catalyst
Flue Gas
Average Hottest in Rg
Air Blower Discharge
HP Boiler Feed Water
Catalyst Cooler Steam
1371F
1368F
1375F
399F
220F
463F
452 psig
157048
Process Calculations
Page 23
Flow Rates:
Fresh Feed
(No Recycle)
Lift Gas
Lift Steam
Feed Steam
Stripping Steam
Total Air to Regenerator*
Catalyst Cooler Steam
Catalyst Cooler Blowdown
3,250 lb/hr
12,900 lb/hr
1,800 lb/hr
5,000 lb/hr
382,405 lb/hr
56,033 lb/hr
6,952 lb/hr
Total air includes: air to combustor, air to upper regenerator, and air to catalyst
cooler.
CO
CO2
O2 + Ar
N2
SO2
NO2
2.
412,923 lb/hr
=
=
=
=
=
=
0.0
15.50
3.47
81.03
0.0
0.0
Unlike an Orsat analysis, a GC analysis includes Argon with the Oxygen. The first
step is to adjust the flue gas O2 content for Argon (Ar). The Ar content is assumed
to be 1.2% of the nitrogen, therefore,
Ar = (0.012) (81.03) = 0.97 mol%.
157048
Process Calculations
Page 24
=
=
=
=
=
=
N2 + Ar
SO2
NO2
3.
0
15.50
3.47 - 0.97 = 2.5
0.01152 lb H2O
lb dry air
1 lb dry air
(1 + 0.01152) lb wet air
4.
The flue gas rate can be calculated from the regeneration air rate. These two
streams are related by the inert N2 + Ar content which remains constant through the
catalyst regeneration. From a Nitrogen balance,
Since, moles =
Weight
Molecular Weight
157048
Process Calculations
Page 25
Then
Dry Air = (375,870 lb/hr)/(28.966 MW) = 12,976 lb mol/hr
mol/hr (N2 + Ar) in dry air = mol/hr (N2 + Ar) in flue gas
79 mol inerts
lb mol FG
82 mol inerts
12, 976 lb mol
5.
The carbon (C) content of the coke is calculated from the flue gas composition. One
mol of C is burned for each mole of CO or CO2produced.
C + O2 + H2 + S + N = CO + CO2 + H2O + SO2 + NO2 + O2
C=
mol CO/CO2
hr FG
100 mol FG
6.
The hydrogen (H2) content of the coke must be calculated from an O2 balance:
O2 in regeneration air = excess O2 in flue gas +
+ O2 reacted to CO (0.5 mol O2/mol CO)
+ O2 reacted to CO2 (1 mol O2/mol CO2)
+ O2 reacted to H2O (0.5 mol O2/mol H2O)
+ O2 reacted to SO2 (1 mol O2/mol SO2)
+ O2 reacted to NO2 (1 mol O2/mol NO2)
157048
Process Calculations
Page 26
Where:
O2 in regen. air =
=
of O2
hr
hr
100 mol air
Excess O2 in FG =
O2 reacted to CO =
=
of O2
hr
hr
100 mol FG
12, 501 lb mol FG
0 mol CO
0.5 mol O2
hr
100 mol FG
mol CO
= 0 lb mol/hr O2
O2 reacted to CO2 =
hr
100 mol FG
mol CO2
= 1,938 lb mol/hr of O2
O2 reacted to SO2 =
hr
100 mol FG
mol SO2
= 0 lb mol/hr of O2
O2 reacted to NO2 =
hr
100 mol FG
mol NO 2
= 0 lb mol/hr of O2
O2 reacted to H2O (by difference) is:
O2 Reacted to H2O = 2,725 - 312 - 0 - 1,938 - 0 - 0 lb mol/hr O2 = 475 lb mol/hr of O2
The hydrogen burned by oxygen in the regenerator is:
H2 burned by O2 =
475 lb mol
2 mol H2
950 lb mol
=
hr O2
mol O2
hr H2
157048
Process Calculations
Page 27
7.
1, 938 lb mol
12.01 lb C
23, 275 lb
=
hr C
lb mol C
hr C
from hydrogen =
950 lb mol
2.016 lb H
1, 915 lb
=
hr H2
lb mol H2
hr H
8.
Coke Yield =
Coke, lb/hr100
FF,lb/hr
Coke Yield =
9.
H2 in Coke
H2 ,
lb/hr(100)
Coke, lb/hr
1,915 lb/hr H
25,190 lb/hr coke
157048
Process Calculations
Page 28
Air to Coke =
(Air, lb/hr)(100)
Coke, lb/hr
Air to Coke =
Combustion heats are calculated based on the average hottest temperature in the
regenerator. The dense, dilute, cyclones, and flue gas average temperatures are
calculated and the hottest is used as basis.
The average hottest temperature is 1375F.
Hc (2C + O2
= (0
BTU
lb mole
BTU
lb mole
lb mole
hr
= 0 BTU/hr
Hc (C + O2
= (1,938
BTU
lb mole
BTU
lb mole
lb mole
hr
157048
Process Calculations
Page 29
Hc (2H2 + O2
= (475
BTU
lb mole
BTU
lb mole
lb mole
hr
430.51 10 6 BTU/hr
25, 190 lb/hr coke
157048
Process Calculations
Page 30
Since H = mass Cp T
Air is heated from the main air blower discharge temperature of 399F to the
average hottest temperature of 1375F at an average specific heat of 0.26 BTU/lb
F.
375, 870 lb/hr air
0.26 BTU
HAir =
(1375- 399F)
= 3, 787 BTU/lb coke
25,190 lb/hr coke
lb F
157048
Process Calculations
Page 31
Blowdown out at 463F = (441 BTU/lb) (6,952 lb/hr) = 3.066 106 BTU/hr
Catalyst cooler duty = (67.52 + 3.066 - 11.841) 106 BTU/hr = 58.75 106 BTU/hr
Or
HRemoved =
157048
Process Calculations
Page 32
CCR =
CCR =
or
CCR =
CCR lb/hr
FF lb/hr
C/O =
Rg Heat 100
HCombustion of Coke
157048
Process Calculations
Page 33
Hraw oil
= 252 BTU/lb
Hvapor
= 760 BTU/lb
157048
Process Calculations
Page 34
Hcomb feed =
23. Heat Consumed to Heat Up Lift Steam, Feed Steam and Stripping Steam
Steam is heated up from the header temperature of 380F to the reactor
temperature at 970F at an average specific heat of 0.485 BTU/lb F.
Hsteam =
157048
Process Calculations
Page 35
157048
Process Calculations
Page 36
Date:
Flue Gas Composition Adjustment:
GC, mol-%
Corrected for Ar*
(i)
CO =
0.00 CO =
0.00
15.50 CO2 =
15.50
(j)
CO2 =
3.47 O2 - (0.012*N2) =
2.50
(k)
O2 =
81.03 N2 + O2 - Cor O2 =
82.00
(L)
N2 =
0.00 SO2 =
0.00
(m)
SO2 =
0.00
(n)
NO2 =
0.00 NO2 =
Total
100.00
100.00
*Correction required only for GC not for Orsat analysis.
Temperatures:
Rg=Regenerator, Rx=Reactor
(o) Flue Gas Line
=
1368
F
(p) Rg Avg Cyclone Outlet
=
1368
F
(q) Rg Avg Dilute
=
1375
F
=
1371
F
(r) Rg Avg Dense (RgT)
(s) Avg Hottest Rg Temp
=
1375
F
Oxygen Balance:
(y)
(L) * (2 * 21 ) / 79 2(n) - 2(m) - 2(k) - 2(j) - (i)
(z)
2.016*(y) =12.01[ (i) + (j) ] + 32.06*(m) + 46.01*(n)
(1a)
Hydrogen = 2.016 * (y) * 100 / (z)
(1b)
Air = 28.966 * 100 * (L) / [ 79 * (z) ]
(1c)
Coke = Dry Air / [ Air / Coke ] = (f) / (1b)
(1d)
Fresh Feed
S.G. = 0.926
(1e)
Coke Yield = (1c) * 100 / (1d)
(t)
(u)
(v)
(w)
=
=
=
=
=
=
=
Air to Rg
Rx Temp
Hot Rg T Air T
Rg Dense T Rx T
7.6
201.5
7.6
14.9
25,187
412,923
6.10
=
=
=
=
399
970
976
401
F
F
F
F
Combustion of Coke
Basis: Average Hottest Regenerator Temperature:
(1f)
Hc(CO) = 46,216 + 1.47 * (s)
=
48,237 BTU/lb-mol
(1g)
Hc(CO2) = 169,135 + 0.5 * (s)
=
169,823 BTU/lb-mol
(1h)
Hc(H2O) = 104,546 + 1.585 * (s)
=
106,725 BTU/lb-mol
H Comb = [ (1f) * (i) + (1g) * (j) + (1h) * (y) ] / (z)
=
17,091 BTU/lb-mol
(1i)
(1j)
Correction Factor = 1133 134.64 * (1a)
=
109
BTU/lb-mol
H Combustion Coke = (1i) + (1j)
=
17,200 BTU/lb-mol
(1k)
Regenerator Heat Balance
Basis: 1 lb of Coke
(1m)
H coke = 0.4 BTU/lb-mol F * (w)
H air = (1b) * 0.26 BTU/lb F * (v)
(1n)
H H2O = (h) / (1c) * 0.485 BTU/lb F * (v)
(1o)
H Radiant Losses
(1p)
(1q)
Cat Cooler Heat Duty
H removed = Cooler Duty / Coke = (1q) * 10^6 / (1c)
(1r)
(1s)
Rg Heat = (1k) (1m) (1n) (1o) (1p) (1r)
(1t)
Rg Eff = Rg Heat * 100 / HcombCoke = (1s) * 100 / (1k)
(1u)
Cat/Oil = (1s) * (1e) / 100 * (0.275 BTU/lb F) * (w)
(1v)
Cat Circ = (Cat/Oil) * (FF) / 60 = (1u) * (1d) / 60 min/hr)
Coke = 100 * Coke / (60 * Cat Circ) = 100 * (1c) / 60 * (1v)
(1w)
=
=
=
=
=
=
=
=
=
=
=
160
3,787
81
250
58.7
2,331
10,590
61.6
5.86
40,313
1.04
BTU/lb coke
BTU/lb coke
BTU/lb coke
BTU/lb coke
MM-BTU/hr (calculated separately)
BTU/lb coke
BTU/lb coke
% Regenerator Efficiency
Catalyst-to-Oil Ratio
Catalyst Circulation, lb/min
Coke, wt-%
157048
Process Calculations
Page 37
Date:
=
=
=
=
=
=
=
=
970
375
412,923
289
760
0
0
0
F
F
lb/hr
BTU/lb
BTU/lb
lb/hr
BTU/lb
BTU/lb
(2i)
(2j)
(2k)
(2m)
(2n)
(2o)
(2p)
(2q)
(2r)
(2s)
=
=
=
=
=
=
=
=
=
=
2,748
0.275
3,250
110
0.5
380
0.485
5,000
12,900
1,800
lb/hr
BTU/lb F
lb/hr
F
BTU/lb F
F
BTU/lb F
lb/hr
lb/hr
lb/hr
(2t)
(2u)
(2v)
(2w)
(2y)
(2z)
=
=
=
=
=
=
471
0
13.7
3.4
-0.7
2
BTU/lb FF
BTU/lb FF
BTU/lb FF
BTU/lb FF
BTU/lb FF
BTU/lb FF
(3a)
BTU/lb FF + H Reaction
(Rg Heat BTU/lb Coke) * (Coke lb/hr) / (FF lb/hr) = Rx Heat = BTU/lb + H Rxn
(3b)
H Rxn = [(Rg Heat BTU/lb Coke) * (Coke lb/hr) / (FF lb/hr)] BTU/lb =
157
H Rxn BTU/ lb FF
157048
Process Calculations
Page 38
ASTM Distillation:
Vol%
Temperature, F
10
660
30
781
50
887
70
1015
90
1075
Specific Gravity:
0.9258
1. Calculate the volumetric average boiling point as the average of the 10, 30, 50, 70
and 90 vol-% temperatures.
VABP = (T10% + T30% + T50% + T70% + T90%) / 5
VABP = (660 + 781 + 887 + 1015 + 1075) / 5
=
883.6
2. Calculate the Engler slope as F per percent (F/%) by subtracting the 10 vol-%
temperature from the 90 vol-% temperature, and dividing the difference by 80.
Slope = (T90% T10%)/80
5.1875
CABP 459.69
SG
= 11.89
157048
Process Calculations
Page 39
A1 =
A1 =
A1=
A1 / 1,000
A2 =
A3 =
The enthalpy of liquid FCC feedstock at the riser inlet conditions is:
Hin = A1 * (TE 259.67) + A2 * (TE 259.67) + A3 * (TE 259.67)
Where:
TE
SG
UOP K
Vapor Enthalpy Equation: Equation source is a curve fit from UOP PD Chart PD-189
F1 =
F2 =
F3 =
Reactor temperature, F
157048
Process Calculations
Page 40
77
1,100
1,200
1,250
1,300
1,350
1,400
CO
47,565
47,847
47,980
48,050
48,123
48,199
48,274
CO2
169,332
169,677
169,735
169,760
169,784
169,808
169,835
H2O Vapor
104,129
106,279
106,448
106,529
106,610
106,687
106,765
Equations:
Hc(CO)
=
Hc(CO2)
=
Hc(H2O)
=
Where:
T is in F
157048
Process Calculations
Page 41
MECHANICAL EVALUATION
The Mechanical Evaluation Test should cover all facets of the FCC Unit, including the
reactor, regenerator, main column, and the gas concentration unit. All major pieces of
equipment should be part of this test, including vessels, pumps, compressors, heat
exchangers, and piping hydraulics. The procedure for this test is long and involved,
but the information can be very useful for the Refiner and for UOP. If the Refiner
wants to revamp the unit, it is important to determine maximum throughput and actual
equipment limitations. Most of the information will be collected only once, although
parts of it (such as exchanger surveys) can be repeated to follow fouling or other
potential problems.
The lists and data sheets included in this section can be used as guidelines in
collecting the required data, although the Refiner may have to modify certain parts for
his particular unit. It is important to finish collecting the data within as short a time as
possible. A single survey is generally satisfactory and it is no necessary to use long
term average data. The Unit should be operating smoothly to get realistic and good
quality data. Label the data collected and prepare a report in an orderly fashion.
157048
Process Calculations
Page 42
2.
3.
Units used (USA, Imperial, Metric) and Standard Conditions (0C, 760 mm;
60F, 14.7 psia)
4.
Limiting Factors
a.
Environmental
Constraints
(CO
emissions,
special
specifications)
b.
Utility Limitation (shortage of steam or electricity, etc.)
5.
Performance Data
a.
Accurate Flow and Weight Balance including sample analyses
product
157048
Process Calculations
Page 43
2.
3.
Air blower suction and discharge pressures, total and net (to regenerator) flow
rates, relative humidity and temperature of air, with manufacturers data and
performance curve for comparison.
4.
5.
Power recovery units should add flue gas temperatures and pressures around
expander, butterfly valve positions, electrical power consumed or generated
and single gauge pressure survey of third stage separator.
6.
7.
Complete flue gas sample before and after flue gas treater.
8.
9.
Single gauge pressure survey of main column and gas concentration section
(use one low pressure and one high pressure gauge, depending on location, for
better accuracy). Include feed flow rate and temperature, reflux flow rate and
temperature, reboiler heat input, overhead temperature and pressure and
enough other data to calculate a heat and weight balance around the column.
10.
Samples of main column overhead receiver gas and liquid; and gas,
hydrocarbons, and water samples from high pressure receiver for phase
equilibrium studies.
157048
Process Calculations
Page 44
11.
12.
13.
All pump suction and discharge pressures, flow rates, liquid compositions or
boiling ranges, and power consumption of driver, with manufacturers
performance data for comparison.
14.
Data on streams not usually measured, such as LCO to the sponge absorber,
including flow rates, temperatures, composition or boiling range, and single
gauge pressure survey of circuit.
15.
Pressures, temperatures, and flow rates of flushing oil to instruments and pump
seals and glands.
16.
157048
Process Calculations
Page 45
Flow through exchangers on both sides (gas and liquid), composition or boiling
range, and mass flow.
2.
Temperatures in and out of both sides, also between shells and bundles.
3.
Pressures in and out of both sides, also between shells and bundles.
4.
5.
If air coolers: air temperatures in and out, air velocity out, motor amps, note any
belt slippage, variable pitch position, louver position, etc.
6.
157048
Process Calculations
Page 46
Process flow (volume and mass, composition, molecular weight and boiling
range).
2.
Single gauge pressure survey for both process and fuel system.
3.
Fuel type (gas or oil) and analysis (composition, sulfur, gravity, etc.), pressure
and temperature of fuel at heater.
4.
Fuel consumption.
5.
6.
7.
8.
9.
Burner data: rating, design, number. Note any unusual problems such as
plugged or inoperative burners.
10.
Refiner should obtain sufficient data to calculate heat flux from both process
and fire side, heat release, heater efficiency and steam balance.
157048
Process Calculations
Page 47
157048
Process Calculations
Page 48
Date:
Time:
By:
I
19 18 17 16 15 14
12
13
Steam
Generator
Orifice Chamber
Flue Gas
SV
11
20
10
ESP
Flue Gas to
Stack
G
8
Cat Cooler
Slidevalve
22
Feed
5
D
Process Flow
DFAH
Feed Rate
Air Rate
Main Air
Blower
1
Atmospheric
Air
11
12
13
14
15
16
17
18
A
B
C
D
E
F
G
H
157048
Process Calculations
Page 49
157048
Process Calculations
Page 50
157048
Process Calculations
Page 51
page ____________________________
date ____________________________
Item No.: _____________________________
by ____________________________
Service: __________________________________________________________________
Type of Operation: _________________________________________________________
No. of Trays: _________________ Reflux Ratio:_________________________________
Type of Trays: _____________________________________________________________
Main Column Bottoms
Circulating
HCO
LCO
Circ.
Quench
CSO
Other
Mass Flow
_______
_______
_______
_______
_______ ________
Temperature Out
Return
Pressure
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______ ________
_______ ________
_______ ________
Distillation
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
EP
API or S.G.
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
BS & W
_______
_______
_______
_______
_______ ________
Steam to Stripper
_______
_______
_______
_______
_______ ________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
157048
Process Calculations
Page 52
page _______________________________
date _______________________________
Item No.: ____________________________
by _______________________________
Service: _________________________________________________________________
Type of Operation: _________________________________________________________
No. of Trays: ________________ Reflux Ratio: ________________________________
Type of Trays: ____________________________________________________________
HCO
Product
LCO
Product
Naphtha
Product
Reflux
Net
Ovhd.
Liquid
Ovhd.
Gas
Mass Flow,
_______
_______
_______
Temperature
_______
_______
_______
Pressure
Composition, ______ %
H2
N2
H2S
H2O
C1
C2
C3/C3=
iC4
nC4/C4=
iC5
nC5
C6+
Avg. Mol. Wt.
Gravity
Distillation
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
________
________
________
________
________
________
________
________
________
________
________
________
________
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
Steam to Stripper
_______
_______
_______
Flash Point
_______
_______
_______
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
EP
157048
Process Calculations
Page 53
COLUMN SUMMARY
page _______________________________
date _______________________________
Item No.: _____________________________ by _______________________________
Service: __________________________________________________________________
Type of Operation: _________________________________________________________
No. of Trays: _________________ Reflux Ratio:_________________________________
Type of Trays: _____________________________________________________________
Net
Off
Ovhd.
Feed
Reflux
Gas
Btms.
Liquid
Other
Mass Flow
_______
_______
_______
_______
_______ ________
Temperature
Pressure
_______
_______
_______
_______
_______
_______
_______
_______
_______ ________
_______ ________
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
________
________
________
________
________
________
________
________
________
________
________
________
________
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
EP
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
157048
Process Calculations
Page 54
ABSORBER SUMMARY
page _______________________________
date _______________________________
Item No.: ____________________________
by _______________________________
Service: _________________________________________________________________
Type of Operation: _________________________________________________________
No. of Trays: ________________ Reflux Ratio: ________________________________
Type of Trays: ____________________________________________________________
Gas
In
Liquid
In
Gas
Out
Liquid
Out
Pumparound
Upper
Lower
Mass Fl
Temperature
_______
_______
_______
_______
_______
_______
Pressure
_______
_______
_______
Composition, ______ %
H2
N2
H2S
H2O
C1
C2
C3
iC4
nC4
iC5
nC5
C6+
Avg. Mol. Wt.
Gravity
Distillation, _______
IBP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
EP
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
________
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
_______
157048
Process Calculations
Page 55
Suction Temperature:
Discharge Temperature:
Power:
MW:
________
________
________
________
F
F
hp
Type of Seal:
_________________________________________
Lube/Seal Oil System: ________________________________________
Buffer Gas:
(yes/no)
Buffer Gas Rate: ______________ SCFH
Automatic Surge Control:
(yes/no)
DRIVER
Motor Manufacturer: _________________________________________
Rating:
____________________ Service Factor:
______________
Insulation Class: ____________________ Voltage/phase/cycle:
Turbine Manufacturer:_________________________________________
Speed:
______________
Steam Supply: _______ psig
Steam Rate: ______________
Steam Exhaust: _______ psig
Gear Manufacturer:
Rating:
Type:
______ F
______ F
_________________________________________
____________________ Service Factor: _____________
____________________ Power Loss:
_____________
157048
Process Calculations
Page 56
Operating Speed:
____________ rpm
Cylinder Diameters:
_________
Piston Speed:
____________ ft/s
# of Suction/Discharge Valves: _________
Actual Rod Loadings, T/C:
________________________________________ lbf
Max Allowable Rod Loadings, T/C: ________________________________________ lbf
DRIVER
Motor Manufacturer:
Rating:
Insulation Class:
________________________________________
____________________ Service Factor:
_____________
____________________ Voltage/phase/cycle:
______ F
______ F
________________________________________
____________________ Service Factor: _____________
____________________ Power Loss:
_____________
157048
Process Calculations
Page 57
by ___________________________
Service: __________________________________________________________________
Description of Valve: _____________________
Actual
Design
____________
Flow rate:
______________________
____________
__________
Upstream pressure:
______________________
____________
__________
____________
__________
Flowing temperature:
____________
__________
______________________
157048
Process Calculations
Page 58
page _______________________________
date _______________________________
Item No.: ____________________________
by _______________________________
Service: _________________________________________________________________
Manufacturer: _____________________________________________________________
Type, Model: _____________________________________________________________
No. of Bundles: _______________________ No. of Passes: _____________________
No. of Tubes per Pass: _________________ Fans/bundle: ______________________
Tube Size _______________ ID x _______________ Gauge x _____________ Length
Piping Geometry: ______________________ Type*: ____________________________
Overall Heat Transfer Coefficient: _____________________________________________
Inlet
Outlet
Air
In
Out
No. fans on__________________________
Louver position_______________________
Mass flow
Q (calc.)
Composition, ____ %
H2
N2
H2S
H2O
C1
C2
C3
iC4
nC4
iC5
nC5
C6+
Avg. Mol. Wt.
Relative Humidity
Pressure
______________
______________
Temperature
_____________
_____________
______________
_____________
______________
_____________
Pitch control ________________________
Air
______________
______________
______________
Process
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
_____________
157048
Process Calculations
Page 59
Gravity
Distillation, ______
IBP
10%
30%
50%
70%
90%
EP
_____________
_____________
_____________
_____________
_____________
_____________
_____________
157048
Process Calculations
Page 60
by ___________________________
Service: _________________________________________________________________
Type of Fluid: ___________________________
______________________________________
Type of Meter: ____________________________________________________________
________________
Temperature
________________
Sp. Gr.**
________________
Meter Factor
________________
________________
________________
________________
________________
157048
Process Calculations
Page 61
page _______________________________
date _______________________________
Item No.: _____________________________ by _______________________________
Service: __________________________________________________________________
Manufacturer: _____________________________________________________________
Type, Model: ______________________________________________________________
No. of Bundles: ____________________________________________________________
No. of Passes/Bundle: __________________ Tubes per Pass: ____________________
Tube Size ______________ ID x _______________ Gauge x ______________ Length
Heat Exchange Surface Area/Bundle: __________________________________________
Piping Geometry (sketch if necessary): _________________________________________
Length of Service: __________________________________________________________
Design Heat Transfer Coefficient: ______________________________________________
Shell Side
Inlet
Stream
A
Outlet
Tube Side
Inlet
Outlet
______________
______________
Composition, ______ %
H2
N2
H2S
H2O
C1
C2
C3
iC4
nC4
iC5
nC5
C6+
Mass Flow
Avg. Mol. Wt.
A
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
Pressure
______________
Temperature
_____________
______________
_____________
______________
______________
_____________
_____________
B
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
157048
Process Calculations
Page 62
Gravity
Distillation, _______
IBP
10%
30%
50%
70%
90%
EP
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
______________
157048
Process Calculations
Page 63
HEATER SURVEY
page _______________________________
date _______________________________
Item No.: _____________________________ by _______________________________
Service: __________________________________________________________________
Manufacturer: _____________________________________________________________
Type, Model: ______________________________________________________________
No. of Passes:_________________________ Tubes per Pass: ____________________
Tube Size ______________ ID x _______________ Wall x ________________ Length
Geometry (Process): ________________________________________________________
Geometry (Flue Gas): _______________________________________________________
Radiant
Inlet
Stream
A
Outlet
Pressure
______________
Temperature
_____________
______________
_____________
Convection I
Inlet
Outlet
______________
______________
_____________
_____________
Convection II
Inlet
Outlet
______________
______________
_____________
_____________
Convection III
Inlet
Outlet
______________
______________
_____________
_____________
Fuel Gas
______________
_____________
Fuel Oil
______________
_____________
______________
_____________
______________
_____________
______________
_____________
______________
_____________
______________
_____________
157048
Process Calculations
Page 64
HEATER SURVEY
page _______________________________
date _______________________________
by _______________________________
Stream
A
B
Mass Flow, ________
_____ _____
Composition, ______ %
_____ _____
H2
_____ _____
_____ _____
N2
_____ _____
O2
CO
_____ _____
_____ _____
CO2
_____ _____
H2S
_____ _____
SO2
_____ _____
C1
_____ _____
C2
_____ _____
C3
_____ _____
iC4
_____ _____
nC4
_____ _____
iC5
_____ _____
nC5
_____ _____
C6-205C (400F)
205C (400F)+
_____ _____
Avg. Mol. Wt.
_____ _____
Gravity
_____ _____
Viscosity
_____ _____
Total Sulfur, _______
_____ _____
Metals, ___________
_____ _____
Q (calc.) Absorbed
_____ _____
Q (calc.) Released
Heater Gross Efficiency
Excess Air, %
Tube Skin Temps:, _____
Burner Pressure ______________________
C
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
D
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
____
E
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
F
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
_____
G,H,
I,J,K
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
______
% of Rating ____________________
157048
Process Calculations
Page 65
Pressure
______________
Discharge
______________
Temperature
_____________
Other Information
Rated Flow (STP)
_____________
Seal Type? Single, Tandem, Double, Bellow
Sp. Gr.
_____________
Spillback? Yes/No
Viscosity
_____________
NPSHR?
_________________________
Static Suction Head _____________
Suction Specific Speed: ________________
Speed
_____________
Differential Head (flowing condition) _________________________________________
Driver Type:
___________________________________________________________
Manufacturer: ___________________________________________________________
No., Size, Rating and Style (Mfgrs. designation): __________________________________
Rating:
_________________
Insulation Class:
_________________
Service Factor: _________________
Voltage/Phase/Cycle: _________________
Motor:
Power consumption
Speed
Turbine:
Steam consumption
Steam supply
______________
______________
______________
Steam exhaust
Speed
Pressure
______________
Temperature
______________
______________
______________
______________
157048
Process Calculations
Page 66
157048
Process Calculations
Page 67
SUPPLEMENTAL CALCULATIONS
REGENERATOR VELOCITIES
The following procedure shows how to calculate the superficial velocity in the
combustor, upper regenerator, and cyclones. This section presents two methods to
calculate the velocities in the regenerator. The first method is more precise but
requires more information and it is more laborious than the second method.
Method A
1.
Required Information
The FCC Unit is in total combustion mode for this case and with no catalyst cooler.
The process conditions are:
Temperatures:
Average Dense
Average Dilute
Average Cyclones
Air to Regenerator
Ambient
Relative Humidity
1371F
1375F
1375F
399F
62F
97%
Pressures:
Regenerator
Combustor
Cyclones
32 psig
34 psig
31 psig
Areas:
300 ft2
452 ft2
24.5 ft2
21.3 ft2
157048
Process Calculations
Page 68
Flow Rates:
Flue Gas:
Air to Regenerator
83,615 scfm
= (scfm x 28.76 lb/mol x 60 min/hr)/(379.5 scf/mol)
= 380,200 lb/hr
CO
CO2
O2
N2 + Ar
SO2
NO2
2.
=
=
=
=
=
=
0
15.50
2.5
82.0
0
0
0.01152 lb H2O
lb dry air
1 lb dry air
(1 + 0.01152) lb wet air
157048
Process Calculations
Page 69
3.
The flue gas rate can be calculated from the regenerator air rate. These two
streams are related by the inert N2 + Ar content which remains constant through the
catalyst regeneration.
Since, moles =
Weight
Molecular Weight
then,
Water in Air = (4,330 lb/hr)/(18 MW) = 241 mol/hr
Dry Air = (375,870 lb/hr)/(28.966 lb/mol) = 12,976 lb mol/hr
mol/hr (N2 + Ar) in dry air = mol/hr (N2 + Ar) in flue gas
79 mol inerts
lb mol FG
82 mol inerts
12, 976 lb mol
4.
157048
Process Calculations
Page 70
The water produced by the hydrogen (H2) content of the coke can be calculated
from an O2 balance:
O2 in regeneration air = excess O2 in flue gas +
+ O2 reacted to CO (0.5 mol O2/mol CO)
+ O2 reacted to CO2 (1 mol O2/mol CO2)
+ O2 reacted to H2O (0.5 mol O2/mol H2O)
+ O2 reacted to SO2 (1 mol O2/mol SO2)
+ O2 reacted to NO2 1 mol O2/mol NO2
where:
O2 in regen. air =
=
of O2
hr
hr
100 mol air
Excess O2 in FG =
O2 reacted to CO =
=
of O2
hr
hr
100 mol FG
= 0 lb mol/hr O2
hr
100 mol FG
mol CO
O2 reacted to CO2 =
=1,938 lb mol/hr of O2
hr
100 mol FG
mol CO2
O2 reacted to SO2 =
= 0 lb mol/hr of O2
hr
100 mol FG
mol SO2
O2 reacted to NO2 =
= 0 lb mol/hr of O2
hr
100 mol FG
mol NO 2
157048
Process Calculations
Page 71
5.
475 lb mol
2 mol H2O
950 lb mol
=
hr O2
mol O2
hr H2
then
=
=
=
=
=
=
=
=
V = nRT/P
157048
Process Calculations
Page 72
6.
= 3.5 ft/sec
= 65.2 ft/sec
= 76.6 ft/sec
= 4.8 ft/sec
157048
Process Calculations
Page 73
Method B
1.
Required Information
This method does not require the flue gas analysis. The process conditions are:
Temperatures:
Pressures:
Area:
Flow Rates:
2.
Average Dense
Regenerator
Regenerator Cross sectional
Air to Regenerator
1371F
32 psig
452 ft2
83,615 scfm
The volumetric flue gas rate can be calculated by using the Ideal Gas equation of
state
PV = nRT
then
R = PV/nT
R = P1V1/n1T1
R = P2V2/n2T2
P1V1/n1T1 = P2V2/n2T2
Or
V2 = P1V1T2 x n2
T1P2
n1
Where:
P1
T1
V1
P2
T2
=
=
=
=
=
0 pisg + 14.7
60 F + 460
83,615 scfm/(60 s/m)
32 pisg + 14.7
1,371F + 460
=
=
=
=
=
14.7 psia
520 R
1,393.6 ft/s
46.7 psia
1,831 R
157048
Process Calculations
Page 74
n2/n1
Then
V2
3.
The superficial velocity is calculated by dividing the volumetric flow rate by the cross
sectional area:
1,606 ft3/s
=
3.6 ft/s
2
452 ft
The molar expansion factor n2/n1 can be approximated if the flue analysis is
available by using the following equation:
Rg Velocity
n2/n1
2 - (79/N2%)
Where N2% is the Nitrogen percent form the flue gas analysis.
157048
Process Calculations
Page 75
P =
q2
C2 A2 (2g) 144
where:
P
q
r
C
A
g
=
=
=
=
=
=
The perforated grid air distributor is designed for a pressure differential of about 0.71.2 psi. This will give good air distribution for fluidization without causing catalyst
attrition. If the pressure differential is too high, the high velocity can cause attrition.
If the pressure differential is too low, less than 0.5 psi, it can cause poor distribution
of air and distributor erosion problems.
157048
Process Calculations
Page 76
1.
2.
1
12 in
lb/in 2
144 in 2
lb
= 38.7 3
2
175.25 in
ft
27.705 in H 2 O
ft
ft
157048
Process Calculations
Page 77
Notes:
i)
ii)
In cases when the pressure taps are under the stripper baffles the distance
between taps should be replaced by the distance between the bottom edges of
the baffles.
157048
Process Calculations
Page 78
1.
2.
Data Required
Instrument Readout:
Instrument Span:
50%
0-300 inches H2O
157048
Process Calculations
Page 79
3.
= 21.51 ft of Catalyst
27.705 in H 2 O
36.25 lb
ft 2
4. Method B - This method is more precise than Method A since consider the
reactor vapor density.
X + Y = 60.18 ft => Y = 60.18 - X
Where:
X = Catalyst height.
y = Reactor vapor height from catalyst bed to upper pressure tap.
60.18 ft = distance between pressure taps.
lb
lb/in 2
144 in 2 X (36.25 lb)
+ (60.18 - X) 1 3
150 in H 2 O
2
3
27.705 in H 2 O
ft
ft
ft
157048
Process Calculations
Page 80
Notes:
i)
ii)
In cases when the lower pressure tap is under the stripper baffle the distance
between taps should be replaced by the distance between the bottom edge of
the baffle and the upper tap.
157048
Process Calculations
Page 81
= Volume of vaporized feed, steam, lift gas, water, and inerts calculated at
the average conditions at the point of feed injection, ft3/s.
VP
= Volume of vaporized products, steam, lift gas, water and inerts calculated
at the average conditions at the point of feed injection, ft3/s.
It should be noted that prior to the residence time calculation, the average
temperature and pressure at the point of feed injection must be estimated to obtain
VF and VP.
157048
Process Calculations
Page 82
The riser pressure at the point of feed injection can be approximated by assuming a
5 psig pressure drop, hence:
Riser Pressure = Reactor dome pressure + 5 psi
The average temperature at the point of feed injection is calculated as:
Tavg
Where:
C/O
S/O
W/O
L/O
TR
TO
TL
TS
TW
CPO
157048
Process Calculations
Page 83
CPL
HOL
HWL
HRX
Tavg
157048
Process Calculations
Page 84
HYDROGEN BALANCE
This document describes a manual method for calculating the Hydrogen balance for
an FCC Unit.
Data required:
A normalized to 100% recovery product summary in wt-%
A breakdown of the C4- components
The distillation and API of each C5+ product
The distillation and API of the feed
API Technical Data Book Figure 2B1.1
"Characterizing Boiling Points of Petroleum Fractions"
Figure 2 - UOP Chart 409B-12
"Hydrogen Content of Liquid Petroleum Hydrocarbons"
Step 3. Calculate the Volume Average Boiling Point (VABP) for each of the heavier
products (C5+ gasoline, LCO, and MCB). See Figure 2B1.1 comments for
procedure and definitions.
Step 4. Calculate the Engler Slope for each of the heavier products (C5+ gasoline,
LCO, and MCB). See Figure 2B1.1 comments for procedure and definitions.
157048
Process Calculations
Page 85
Step 5. Determine the Mean Average Boiling Point from API Figure 2B1.1.
Step 6. Determine the Hydrogen content of the hydrocarbon liquid from Figure 2.
See the lower half of column 5 in the attached example.
Step 7. Multiply the wt% normalized yield pattern for each component by the
percentage Hydrogen in each product component. In the attached example this is
column 2 times column 5. The result is given in column 6.
Step 8. Calculate the percentage of Feed Hydrogen in each component by dividing
the Wt% Hydrogen in each product component by the Wt% H2 in the feed. In the
attached example this is the value in column 6 divided by the Wt% H2 in the feed
(13%).
157048
Process Calculations
Page 86
Mass Balance
wt-%
#H/Molecule
MW
%H2
H2 wt-%
% Feed H2
Results
Feed:
100.00
13.00
100.00
H2S
0.04
2.0158
34.08
0.06
0.0021
0.02
H2
0.23
2.0158
2.02
1.00
0.2280
1.75
C1
0.89
4.0361
16.04
0.25
0.2245
1.73
C2
0.81
6.0474
30.07
0.20
0.1622
1.25
C2=
0.91
4.0316
28.05
0.14
0.1303
1.00
C3
1.30
8.0632
44.10
0.18
0.2375
1.83
C3=
4.64
6.0474
42.08
0.14
0.6662
5.12
IC4
2.69
10.0790
58.12
0.17
0.4665
3.59
NC4
0.63
10.0790
58.12
0.17
0.1094
0.84
C4=
4.88
8.0632
56.11
0.14
0.7007
5.39
C5+ Gasoline
44.55
LCO
27.60
MCB
Coke
Total Products
13.80
6.15
47.29
11.30
3.12
23.99
5.22
10.20
0.53
4.10
5.62
4.44
0.25
1.92
39.74
12.98
99.82
100.00
Total
(R)^1/3
SpGr
0.7286
IBP
96.8
556.8
---------
API
62.02
214.7
10%
131.9
591.9
8.3962
VABP
20%
145.4
605.4
8.4596
Engler Slope
2.40
30%
163.4
623.4
8.5426
Correction Factor
6.0
40%
182.3
642.3
8.6280
CABP, R Uncorrected
672.8
50%
203.9
663.9
8.7237
CABP, F Corrected
206.8
60%
230.9
690.9
8.8404
CABP, R Corrected
666.8
70%
259.7
719.7
8.9616
UOP K
11.99
80%
291.2
751.2
9.0904
0.0032
90%
323.6
786.3
9.2193
Octane (F1 C)
92
EP
371.3
831.3
---------
Recovered Volume
99.5
0.5
Residue Volume
39.6
157048
Process Calculations
Page 87
157048
Process Calculations
Page 88
157048
Process Calculations
Page 89
T90 T10
in degrees Fahrenheit per percent distilled.
90 10
The relationships between the various average boiling points given in Figure 2B1.1 for petroleum
fractions are analogous to those defined by equations (2-0.3) through (2-0.7) for mixtures of
identifiable hydrocarbons.
Special Comments:
For ASTM D86 distillation temperatures above 475F, use the following correction for cracking:
log D 1.587 0.00473 T
(2B1.1-1)
Where:
D = correction to be added to T, in degrees Fahrenheit
T = observed distillation temperature, in degrees Fahrenheit
If the available distillation data are not from ASTM Method D86, they must be converted by the
methods of Chapter 3 to calculate the volumetric average boiling point.
Literature Sources:
This figure was developed by Smith and Watson, Ind. Eng. Chem. 29 1408 (1937). Equation
(2B1.1-1) was given by S.T.Hadden, Gulf Research and Development Company, Pittsburgh, Pa.,
private communication (1964).
Example:
Determine the molal average boiling point, weighted average boiling point, cubic average boiling
point, and mean average boiling point of a petroleum fraction having the following ASTM D86
distillation properties:
Distillation, percent by volume
10
30
50
70
90
Temperature, degrees Fahrenheit:
149 230 282 325 371
VABP
Slope
371 149
2.78 F %
80
Using Figure 2B1.1, the average boiling points are calculated from the volumetric average boiling
point:
157048
Process Calculations
Page 90
Q max N S D 2 Fa Fc hm
Gb
Where:
Qmax
N
D
d
S
Fa
Fc
Gf
Gb
hm
Note:
=
=
=
=
=
=
=
=
=
=
N, S, Fa, and Fc can be found in L.Spinks Principles and Practices of Flow Meter Engineering
=
=
=
=
=
=
=
=
=
=
=
=
=
=
34,000
194.3
7.981 in
5.034 in
0.6307
0.2672
1.001 for type 304 stainless steel plate
10
39,292; Re = 92.235*bpsd / (viscosity*D)
1.015
100 in H2O
173F
0.9266
0.8854 Gf = Gb*VCF = 0.9260 * 0.9562 = 0.8854
0.8854
0
.
9266
Gf
;
Q 3,360 MR
Gb
Q _________ BPSD
157048
Process Calculations
Page 91
=
=
=
=
=
=
=
=
=
=
=
=
=
N, S, Fa, Fc, Y and Z can be found in L.Spinks Principles and Practices of Flow Meter Engineering
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
8,375
=
lb/hr
=
26,100
128.78 for scfm and psi
6.065 in
3.5834 in
0.5908
0.2284
1.0003, for type 304 stainless steel plate
0.011
2,472,487; Re = 6.32(lb/hr)/(viscosity*D)
0.988
0.9944; Y = 1-(0.41-0.35B^4)(h/2)/(27.67Pf*(p/Cv))
200 in H2O
187.7 psia
573R
1.27
0.7054
0.965 f(Tr,Pr)
Tr = Tf/Tc
Pr = Pf/Pc
Q max 10,490scfm
The K constant can be calculated by using the following equation:
Gb
Q max
1,539scm
K
Tf
10
Pf
Where: 10: maximum units meter reading, MR, then:
Q 1539 MR
Pf
Gb ;
Tf
Q _________ scfm
187.7
573 0.7054 0.965
157048
Treating
Page 1
FEED/PRODUCT TREATING
INTRODUCTION
FCC feeds contain a number of contaminants that affect yields, product quality,
plant emissions and corrosion in the main column and gas concentration unit.
These contaminants are handled by a combination of treating either the feed or
products as well as unit design. This subject is of increasing importance to refiners
with the ever tighter limits on emissions from the plant, especially SOx and NOx and
on limits in liquid product sulfur levels. The industry trend towards processing resid
feeds which typically have higher concentrations of sulfur, metals and carbon
residue makes this issue even more important.
In the United States new fuel specifications are will limit the sulfur concentration in
both gasoline and high speed diesel fuels to less than 50 wppm. This is an issue
critical to the FCC because in a typical refinery gasoline pool 98% of the total
gasoline pool sulfur comes from the FCC naphtha even though the FCC naphtha
makes up only 30-40% of the pool. Limits on fuel oil sulfur will also require a
reduction in the MCB product sulfur. In some areas the limits on SOx emissions will
be more restrictive requiring less than 300 ppm in the flue gas. In the coming years
these restrictions will likely become even more stringent.
FEED TREATING
Light and heavy vacuum gas oils are the most common FCC feedstock with an
increasing trend towards atmospheric resid. Also, there are economic incentives
towards processing lower priced crudes which typically contain higher levels of
contaminants.
Hydrotreating is the most common and effective method of improving the FCC feed
quality. Hydrotreating not only reduces the contaminant concentration but also
improves yields. Hydrogen addition to the feed, especially to the large polynuclear
aromatics, makes these molecules easier to crack resulting in higher conversion to
desired products with less coke and light gas make. Table 1 shows the impact of
hydrotreating on both the FCC feed properties and the FCC yields.
157048
Treating
Page 2
Table 1
Feed Hydrotreating Benefits
Feed Desulfurization
Feed Properties
Gravity, API
Sulfur, wt%
Nitrogen, wppm
Carbon Residue, wt%
Metals (Ni + V), wppm
Yields, wt%
H2S
C2LPG
Naphtha
LCO
MCB
Coke
Conversion, lv%
Key Product Properties
Naphtha RONC
Naphtha MONC
LCO Cetane Index
Product Sulfur, wppm
H2S
Naphtha
LCO
MCB
SOx , vppm in flue gas
Untreated
90%
98%
99%
20.5
2.6
880
0.4
5
23.5
0.25
500
0.25
2
24.8
0.06
450
0.1
1
26.0
0.02
400
0.1
<1
1.1
3.3
16.3
48.3
16.7
9.0
5.4
74.3
0.1
3.5
17.6
51.5
15.7
6.6
5.0
77.7
0.0
3.2
18.7
52.5
15.0
5.9
4.7
79.1
0.0
2.8
19.9
53.6
14.0
5.2
4.4
80.8
93.2
80.5
25.7
93.0
80.8
25.7
92.9
81.1
26.4
92.7
81.0
26.5
10,100
3,600
29,700
57,800
2,000
750
230
3,400
11,000
410
190
55
900
3,000
120
95
18
300
1,100
42
157048
Treating
Page 3
As more sulfur is removed the sulfur balance in the FCC shifts towards higher
percentage of the total feed sulfur going to the MCB product and SOx in the flue
gas. This is because the hardest to remove sulfur is in the heavy aromatic
compounds which tend to form coke or remain uncracked. From Table 1 the
percentage of sulfur in the feed ending up in the MCB product increases from 20 to
30% and the percentage of feed sulfur ending up in the naphtha decreases from 6.7
to 4.8% as the untreated feed is desulfurized by 98%.
Table 1 illustrates a case where hydrotreating is used primarily for reduction in
sulfur. In some units, especially those treating resid feeds, the reduction of carbon
residue and metals is more important. Hydrotreating can reduce feed metals and
carbon residue by 90% or more allowing processing of extremely contaminated
resid feeds in the FCC while still achieving good yields. This can also significantly
reduce the required fresh catalyst addition rate.
Nitrogen is also removed by feed hydrotreating. Some of the nitrogen in the FCC
feed is converted to ammonia which can cause salt formation and plugging in the
main column overhead. Basic nitrogen in the feed acts a temporary poison to the
FCC catalyst. Severely contaminated FCC feeds may contain as much as 4,000
wppm nitrogen while a clean feed may contain less than 500 wppm. Cyanides are
also formed from nitrogen in the feed which can cause blistering and corrosion in
the gas concentration unit. Wash water and proper control of the main column
overhead temperature is usually sufficient to prevent these plugging and corrosion
concerns so that these are usually not a significant factor when considering
hydrotreating as an option to improve profitability.
Oxygen may be present in the feed either chemically bonded in the hydrocarbon or
absorbed from storage. Dissolved oxygen may cause fouling of heat exchangers
when the temperature approaches 400F (200C). The best method for preventing
this is to blanket the raw oil tanks with either fuel gas or nitrogen. This is most
important for cracked feed stocks such as coker gas oil or highly olefinic feeds.
Once in the reactor the oxygen will quickly be converted to water, carbon oxides,
phenols, creosols or acids.
157048
Treating
Page 4
PRODUCT TREATING
1.
2.
3.
4.
5.
Diolefinic hydrocarbons.
157048
Treating
Page 5
157048
Treating
Page 6
Elemental sulfur has a harmful effect on alkyl lead susceptibility for gasoline octane
improvement. Free sulfur will remain as a deposit when LPG is evaporated.
Removal of elemental sulfur is very difficult; hydrotreating or redistillation are two
costly removal methods. Chemical treatments such as scrubbing with sodium or
potassium polysulfide solutions or caustic-sodium sulfide, or reverse doctor treating
may be used but may not be completely effective. Certain additives may be helpful
in masking the sulfur corrosivity test. They should be used with caution. The best
treatment method is to avoid elemental sulfur formation by preventing H2S
oxidation.
Hydrogen Sulfide
Hydrogen sulfide results from the decomposition of sulfur compounds during the
cracking reaction and concentrates in the fuel gas and LPG products. It has an
obnoxious odor at low concentration, and is very poisonous. It paralyzes the
involuntary breathing function, leading to asphyxiation, unconsciousness and death.
Hydrogen sulfide in fuel gas will burn in a heater to form SO2. This acid gas may
cause corrosion and environmental problems due to its acidity when it dissolves in
water. In the presence of oxygen, H2S may oxidize in a product stream to form
elemental sulfur. H2S has a deleterious effect on lead susceptibility of FCC
gasoline. It promotes peroxide formation and prevents oxidation inhibitors from
functioning, thus reducing gasoline stability in storage. It is undesirable in HF acid
alkylation feedstocks as one pound of sulfur consumes about five pounds of
process acid, and H2S, along with some mercaptans, is sufficiently volatile to stay
with the C3 and C4 streams.
157048
Treating
Page 7
Dilute caustic soda or soda ash will remove H2S as well as CO2. The aqueous
caustic soda solution must be sufficiently dilute to prevent formation of sodium
sulfide crystals as the NaOH is converted to Na2S, and in the case of a dry feed, as
the solution dehydrates. Normal caustic concentrations are in the range of
10-15 Be to avoid Na2S crystallization.
The other principal treating method for the removal of H2S is regenerative
monoethanolamine (MEA) or diethanolamine (DEA) scrubbing. The stream to be
treated is contacted countercurrently with the amine to remove H2S, CO2, and COS.
The amine is then steam stripped to regenerate it. Although this treatment can
reduce H2S concentrations below 6 wt. ppm, it is equilibrium limited and therefore it
is normal to provide a dilute batch caustic scrubber following the amine scrubber as
a final cleanup and guard in case of an amine unit upset, e.g., when treating LPG.
Aside from pollution abatement benefits when operated in tandem with a sulfur
recovery process, amine treating usually becomes economically attractive strictly on
a chemical consumption basis when H2S levels exceed roughly 1000 ppm.
Mercaptans (RSH)
Mercaptans are found in all cracked products streams. Some of these may be
naturally occurring in the feed, but most mercaptans are formed during the cracking
reactions. Decomposition of other sulfur compounds or recombination reactions
between H2S and olefins are the major sources. There are two distinct types: alkyl,
open chain mercaptans, and aryl, aromatic mercaptans in which the SH group is
linked to a benzene ring structure. The aryl mercaptans are also known as
thiophenols and thiocresols. They tend to predominate over alkyl mercaptans in
FCC product streams boiling over 300F (150C).
The lower molecular weight mercaptans have a very obnoxious odor, particularly
noticeable due to their low vapor pressure. All mercaptans, like most sulfur
compounds, have a deleterious effect on lead susceptibility of motor gasolines.
Thiophenols promote gum and sludge formation reactions and cause storage
problems. Mercaptans can react with copper, particularly if basic nitrogen is
present, to form oil soluble cuprow compounds which can be oxidized to insoluble
157048
Treating
Page 8
copper oxide. The soluble copper can also then react with some oxygenated
compounds to form gelatinous copper phenolates.
Low molecular weight mercaptans may be extracted to some degree with caustic or
be sweetened, in a process which converts the mercaptans to less odiferous
disulfides. Mercaptans may be extracted from LPG to very low values, 0.5 wt. ppm
in some cases. Extraction of 50-95% of the mercaptans from gasoline is possible,
depending on boiling range. However, as mercaptans in FCC gasoline generally
represent only 10 to 35% of the total sulfur present, partial gasoline desulfurization
by extraction is usually not economical. The majority of FCC gasolines are currently
only sweetened to essentially eliminate mercaptans and produce a doctor negative,
or sweet, gasoline. Cycle oil is sometimes sweetened, but if low sulfur is desired,
the cycle oil must be hydrotreated.
Non regenerable caustic scrubbing to extract mercaptans is an old and expensive
process which may create or compound waste disposal problems. In many cases it
is not very effective. The most successful treating process for either extraction or
sweetening is the UOP Merox process. This process uses small amounts of caustic
to remove or transform mercaptans. A catalyst and oxygen supplied from
atmospheric air are used to regenerate the caustic. Further information on the
Merox process may be obtained from UOP.
Total gasoline sulfur may also be reduced by undercutting or reducing the endpoint
of the FCC gasoline. The sulfur concentration in the FCC gasoline increases rapidly
as the boiling range exceeds ~400 (200C). By reducing the endpoint of the
gasoline so that the heaviest 20% is included in the light cycle oil product the
gasoline sulfur content can be reduce by as much as 60%. Unfortunately, there are
significant product value losses associated with this for most refiners.
157048
Treating
Page 9
157048
Treating
Page 10
reactions. Cracked distillates containing copper will form gum and gelatinous
precipitates in storage. Copper also contributes to distillate color stability problems
and catalyses oxidation of alkyl lead additives, leading to haze in some finished
gasolines.
Gross copper contamination can be removed by chemical treatment, such as dilute
acid scrubbing or clay percolation. If the copper does not exceed 1 mg/liter, it can
be rendered harmless with a copper deactivator. Dosage is roughly 10 wt. ppm
active agent for each mg/liter. The deactivator, a chelating agent, complexes with
the copper so that it cannot take part in any further reactions.
Nitrogen Compounds
There are usually two types of nitrogen found in gasoline and cycle oil. One type
would be neutral compounds such as pyrrole, and the other a basic compound such
as pyridine or quinoline. Ammonia is found in the reactor overhead vapors, but if
normal main column overhead water injection is maintained, the ammonia is
removed at this point.
Neutral nitrogen compounds are associated with sediment formation in fuel oils.
Basic compounds are typically more harmful. Pyridine has a characteristic odor
which is very unpleasant when combined with mercaptans. Both basic and neutral
nitrogen compounds are color precursors which affect distillate color stability. Their
effect on lead susceptibility and octane number varies between good and bad
depending on the particular compound in question. Both types of nitrogen
compounds may also promote oil soluble gum formation, but this has not been
firmly established at this time.
Neutral nitrogen compounds may be removed with either strong acid or strong
caustic-methanol solutions. Basic nitrogen compounds could be removed with dilute
acid in acid resistant equipment. If acid strength is too high, there may be problems
with olefin addition, sulfonation, and other acid catalyzed reactions. Hydrotreating
will decompose both types of nitrogen compounds to ammonia. This might be
157048
Treating
Page 11
suitable for cycle oils, but not for gasoline, because aromatics might be saturated,
with severe loss in octane number.
Oxygen
Oxygen compounds such as phenols and cresols are formed during the cracking
reaction from oxygenated compounds in the feed and from oxygen entrained with
the catalyst. They are generally not considered harmful and may be considered
beneficial as some act as oxidation inhibitors. Some of the phenols are suspected
of being color precursors. Caustic treating can be used to remove most of the
oxygen containing compounds, including most organic acids, when deemed
necessary.
Diolefins
Diolefins, especially conjugated diolefins, are reactive hydrocarbons which quickly
enter into gum and sediment forming reactions. These compounds are normally
found in significant concentrations only in thermally cracked products. However,
when FCC conditions allow cracking to occur in the absence of catalyst, diolefins
will be formed in amounts roughly proportional to the degree of thermal cracking
present.
A good example of this type of compound is butadiene. It stays in the C4 fraction as
it is concentrated through fractionation. If this stream is then used as alkylation
feed, the butadiene will polymerize to form tar. Higher order diolefins lead easily to
gum formation in the gasoline and cycle oil streams.
Diolefins can be removed without significant olefins removal by carefully controlled
mild hydrotreating or vapor phase clay treatment. Proper dosage of oxidation will
nullify their effects. Another solution would be to minimize formation of diolefins by
decreasing thermal cracking. This could be done by reducing the reactor
temperature, reducing the regenerated catalyst temperature or by mechanical
changes minimizes post riser residence time.
157048
Treating
Page 12
Concentration
Treatment
Copper
High
Elemental sulfur
Redistribution
Hydrotreating
Reverse Doctor
Prevent formation by
minimizing free oxygen
Low
Any
Mercaptans, R-SH
DEA-water scrubbing
Caustic-MEA-water scrubbing
(Batch operation only)
Silica-Alumina Adsorbents
PbO Treaters
Strong acid
Strong caustic-methanol
solution
157048
Treating
Page 13
Contaminant
Concentration
Treatment
Water Wash
Caustic soda
Diolefins
Mild hydrotreating
Vapor phase clay treating
Change FCC operations to
minimize formation
157048
Analytical Methods
Page 1
ANALYTICAL METHODS
Introduction
Good analyses of the feed and product streams are essential for control and
evaluation of a Fluid Catalytic Cracker. It is extremely difficult to optimize a unit if
potential problems are not defined through the laboratory and process variables.
The following sections give a typical FCC sampling schedule and a brief outline of
some of the more common analytical methods.
There are a large number of laboratory tests which may be used. FCC products
vary widely, from clarified oil to fuel gas. This in turn leads to markedly different
analytical methods, such as six different types of distillations. The product being
tested and the type of result desired will determine which test is used.
Distillation
There are six distillation methods listed in this book. Two of them, UOP 1 and
ASTM D 86, cover the lighter fractions, from gasoline to gas oils. The UOP 1
method goes further; it continues past the typical decomposition point of 700F
(371C) into a thermal cracking of the sample with a dry residue (coke) remaining.
Two other methods, UOP 77 and 79, are fractionations in addition to distillations.
Either one can be used to separate certain fractions of a product for further
analysis. UOP 77 is more commonly used. UOP 79 is a high precision distillation
method which is used to determine true boiling points of petroleum fractions. The
test requires special equipment and the information obtained from this test is not
frequently needed. The two vacuum distillation methods, UOP 76 and ASTM D
1160, are used for heavy material. Reduced pressures, down to 1 mm Hg absolute
for D 1160 and 0.3 mm Hg absolute for UOP 76, permit distillation when the
temperature used for atmospheric techniques would lead to thermal cracking.
Sulfur
157048
Analytical Methods
Page 2
The six analytical methods for sulfur analysis can be initially divided into two groups,
gases and liquids. The Tutwiler method, UOP 9, gives a quantitative determination
of H2S in a gas stream. A second method, UOP 212, measures H2S, mercaptans,
and COS in light gases and LPG. The Tutwiler method does not give as detailed a
test as does UOP 212, but takes less time. There are four methods given for hydrocarbon liquid analysis. The Doctor Test, UOP 41, gives a qualitative determination
of mercaptans and H2S. UOP 163 will give a breakdown of mercaptan and H2S in
liquid streams. For total sulfur of lighter oils, the Lamp method, ASTM D 1266, is
used. For oils boiling above 350F (177C), ASTM D 1552 may be used to
determine total sulfur.
Octane
The Motor octane method, ASTM D 2700, is more severe, i.e., gives a lower rating
than does the Research method, ASTM D 2699. The correlation between the two is
not exact, so it is generally not easy to predict one octane from another. For similar
feedstocks and plant operation, the refiner may be able to make some general
predictions from past data.
Gas Chromatography
To determine the composition of light hydrocarbon gases and LPG streams
containing small amounts of C3 and C6 material, either UOP 539 or UOP 709 may
be used. Neither of these will separate argon from oxygen, or butene-1 from
isobutylene. UOP 709 is easier to run than UOP 539 and requires less elaborate
equipment, but UOP 709 does not differentiate between ethane, ethylene and
carbon dioxide. For exact determination of fuel gas from an FCC, UOP 539 would
be the better method. UOP 725 can be used to determine concentration of C5 and
lighter material in FCC gasoline.
157048
Analytical Methods
Page 3
Identify each sample with refiner, location, unit, sample, date and technical
contact person at UOP responsible for the results. Make certain the sample
tag is well secured to the sample and remains legible, even if it is wet with
water or hydrocarbon.
2.
It has been found that gasoline or naphtha sample collection in clear bottles,
which are left exposed to sunlight (or ultraviolet lighting) either direct or
indirect, and whether or not the sample has been treated with oxidation
inhibitors, will result in a severe loss of octane rating within a very short time.
Every effort must therefore be made to see that only the brown or amber
sample bottles are used for daily samples and more important that all samples
shipped to UOP for analysis are taken in amber bottles, are kept in a cool dark
place until packaged for shipment, and are shipped as soon as possible after
sampling.
3.
When shipping samples, mail or phone shipping information (air waybill, flight
number, bill of lading, etc.) to UOP.
4.
Send a copy of the request for analysis with the samples; send the original to:
UOP
Technical Service Department
FCC Group
25 E. Algonquin Road
Des Plaines, IL 60017 USA
157048
Analytical Methods
Page 4
5.
6.
For larger Rush samples being sent to UOP by air, indicate the shipping
instructions as:
SHIP TO: UOP LLC
Chicago, Illinois 60017 USA
HOLD AT: O Hare Airport
CALL: (847) 391-3043 ON ARRIVAL
7.
All samples shipped from outside the United States require additional
paperwork to comply with the U.S. Environmental Protection Agencys Toxic
Substances Control Act (TSCA). The following are some of the guidelines for
importing samples into the United States. Always contact your customer
service or technical service representative for assistance before
shipping any samples to ensure that all regulations are followed.
The use of a freight forwarder (e.g. Burlington Air Express or Emery
Worldwide) is preferred for all imported samples.
Overnight couriers (e.g. DHL, Federal Express or UPS) may be used
only if the written TSCA certification authorized, signed and dated by
UOP is obtained prior to shipment and physically included with the
documentation in the shipped package.
All samples should be routed through Chicagos Ohare International
Airport
All imports must have the following documentation:
157048
Analytical Methods
Page 5
157048
Analytical Methods
Page 6
Attachment 1a
Proforma Invoice
International Shipper/Exporter (Name & Address)
Invoice No:
Invoice Date:
Terms: Pro-Forma Invoice
Reference No:
Contact Name:
Contact Phone No.
Fax No.
DESCRIPTION
* * * NO CHARGE INVOICE * * *
QUANTITY:
GROSS WEIGHT:
MARKET
VALUE -DECLARED
FOR CUSTOMS
CLEARANCE
PURPOSES
ONLY
BOX(ES)
KGS.
US DOLLARS
$
DESCRIPTION OF SAMPLE(S):
PACKED IN
AMOUNT
157048
Analytical Methods
Page 7
Attachment 1b
Example
Proforma Invoice
International Shipper/Exporter (Name & Address)
Mountain View Refining
1000 Mountain View Dr.
Boulder City
Refining Country
Contact Name: Joe R. Engineer
Contact Phone No. (12) 3 456 -7890 Fax No. (12) 3-098-7654
Invoice No:
Invoice Date:
Terms: Pro-Forma Invoice
Reference No:
DESCRIPTION
* * NO CHARGE INVOICE * * *
QUANTITY: Three 1 liter catalyst samples
AMOUNT
US DOLLARS
$
GROSS WEIGHT:
BOX(ES)
3.5
KGS.
Robert S. UOP
Joe R. Engineer
Refinery Representative Signature
Joseph R. Engineer
Refinery Representative Name: please print
MARKET
VALUE -DECLARED
FOR CUSTOMS
CLEARANCE
PURPOSES
ONLY
157048
Analytical Methods
Page 8
Attachment 2a
TSCA Certification Form
157048
Analytical Methods
Page 9
Attachment 2b
TSCA Certification Form
Example Form
Angelo P. Furfaro
157048
Analytical Methods
Page 10
Attachment 3
International Analytical Requisition Form - UOP Technical Service
TO: UOP Technical Service Sample Coordinator
391-2253
Phone 847-391-
Fax 847-
Phone
Fax
Customer:
Refinery
Address
Contact Name
Description
Check if
MSDS is
Included
Rush
or
Standard
Process or unit:
Catalyst Type
Regenerated or Coked
Standard
Billing Information:
Address:
Attention:
Sample Shipping Information:
Shipped Via:
Phone Number of Carrier:
Airwaybill No.:
Analysis Required
Check if
MSDS is
Included
Rush
or
157048
Analytical Methods
Page 11
Minimum
(cm3)
Heavy Oil (Clarified Oil, Slurry, Raw Oil, Heavy and Light Cycle Oil)
API
Distillation
Viscosity
Vacuum Distillation
Conradson Carbon
Ash (sample to be taken and shipped in a wide mouth sample container)
Sediment and Water
Sulfur
Nitrogen
Metals
Pour Point
Color
100
250
150
300
150
300
150
20
15
100
200
50
Gasoline, LPG
API
Distillation
Hydrocarbon Types by GC
C5- by GLC
RVP
Mercaptan Sulfur
Total Sulfur
Octane Research
Motor
Leaded or Clear
Catalyst
100
210
150
50
1000
100
100
1000
for each
type
1000
NOTE: Individual samples can be taken from one large sample of each product,
usually about 1-2 gallons (3.5-7.0 liters).
157048
Analytical Methods
Page 12
TEST NUMBER
FREQUENCY
Normal Startup
1/D
1/W
1/D
3/D
3/W
1/D
D-189 or D4530
D-4007
UOP 864 or D-1552 or D-2622
UOP 384 or D-4629
UOP 389 or D-5708
1/D
1/W
1/D
1/W
1/W
1/D
1/W
1/D
1/W
1/D
D-97
UOP 269
UOP 614
UOP 375
1/W
Occas
Occas
1/D
1/W
Occas
Occas
1/D
Occas
Occas
Occas
1/D
Control
1/D
3/D
1/W
1/D
1/D
1/W
1/W
3/D
1/W
1/D
Control
1/D
1/D
157048
Analytical Methods
Page 13
TEST NUMBER
FREQUENCY
Normal Startup
1/D
1/D
1/D
1/D
1/D
1/D
1/D
3/D
3/D
1/D
1/D
1/W
1/D
1/D
D-1298 or D-4052
D-86
D-97
D-93
D-445
UOP 864
D-976
1/D
1/D
1/D
1/D
1/D
1/D
1/D
3/D
3/D
1/D
1/D
1/W
1/D
1/D
1/D
1/D
1/W
1/D
3/W
1/D
1/D
1/D
3/D
3/D
1/W
1/D
1/D
1/D
1/D
1/D
D-1298 or D-4052
D-86
D-445
UOP 864 or D-1552
D-97
D-93
1/D
1/D
1/W
1/D
1/D
1/D
3/D
3/D
1/W
1/D
1/D
1/D
UOP 212
UOP 539
Occas
Occas
1/D
1/D
157048
Analytical Methods
Page 14
TEST NUMBER
FREQUENCY
Normal Startup
D-1298 or D-4052
D-86
UOP 725
UOP 163
Occas
Occas
Occas
Occas
Occas
Occas
Occas
Occas
1/D
Occas
Occas
Occas
3/D
Occas
Occas
Occas
Spent Catalyst
Percent Carbon
UOP 703
1/W
Regenerated Catalyst
Particle Size Distribution*
Surface Area*
Pore Volume*
Activity*
Metals by ICP*
Percent Carbon*
UOP 856
UOP 874
UOP 874
D-3907
UOP 546
UOP 703
1/W
1/W
1/W
1/W
1/W
1/D
2/W
2/W
2/W
2/W
2/W
Control
Occas
Occas
Occas
Occas
157048
Analytical Methods
Page 15
TEST NUMBER
UOP 314
UOP 262
UOP 682
UOP 683
UOP 740
D-3921
D-1293
D-1126
D-859
FREQUENCY
Normal Startup
Occas
Occas
1/M
1/M
Occas
Occas
1/D
1/W
1/M
Occas
Occas
Occas
Occas
Occas
Occas
3/D
Occas
Occas
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
1/W
Saturated Steam from Catalyst Cooler, Flue Gas Cooler, and Main Column
Bottoms Steam Generator Steam Drums
Impurities
D-2186-C
Occas Occas
Silica
D-859
Occas Occas
Sodium
D-1428
Occas Occas
Lean Gas Product
H2S
Composition
UOP 212
UOP 539
1/D
1/D
3/D
3/D
1/D
1/D
1/D
3/D
3/D
3/D
157048
Analytical Methods
Page 16
TEST NUMBER
FREQUENCY
Normal Startup
D-1298 or D-4052
D-86
UOP 163
D-323
D-2699
D-2700
UOP 725
UOP 864 or UOP 836
1/D
1/D
1/D
1/D
1/D
1/D
1/D
1/D
3/D
3/D
3/D
3/D
3/D
3/D
3/D
3/D
D-1298 or D-4052
D-86
D-2699
D-2700
UOP 864 or UOP 836
1/D
1/D
1/D
1/D
1/D
3/D
3/D
3/D
3/D
3/D
1/D
1/D
1/D
1/D
1/D
3/D
3/D
3/D
3/D
3/D
1/D
1/D
1/D
1/D
1/D
1/D
1/D
3/D
3/D
3/D
3/D
3/D
3/D
3/D
1/D
1/D
3/D
3/D
157048
Analytical Methods
Page 17
TEST NUMBER
FREQUENCY
Normal Startup
D-1298 or D-4052
D-86
UOP 163
D-323
D-2699
D-2700
UOP 725
UOP 864 or UOP 836
1/D
1/D
1/D
1/D
1/D
1/D
1/D
1/D
UOP 314
UOP 262
UOP 682
UOP 683
UOP 740
D-3921
D-1293
Occas
Occas
1/M
1/M
Occas
Occas
1/D
3/D
3/D
3/D
3/D
3/D
3/D
3/D
3/D
Occas
Occas
Occas
Occas
Occas
Occas
3/D
157048
Analytical Methods
Page 18
Number
D-3907
D 1298
UOP 254
UOP 740
D 482
UOP 155
UOP 703
UOP 212
UOP 233
D 1500
D 156
D 189
UOP 314
UOP 682
UOP 1
D 86
UOP 77
UOP 79
UOP 76
D 1160
UOP 41
D 93
D 92
UOP 79
157048
Analytical Methods
Page 19
Test Description
Flue Gas Analysis, (GC)
(Orsat)
Particulates, SOx, NOx
Gas Analysis GC
GC
- Pentenes and lighter in olefinic gasoline
Gravity API
Gum
Copper Dish
Existent (Steam Jet)
Hydrogen Sulfide (H2S)
in Gas Tutwiler
with Mercaptans
Induction Period of Gasoline
Iron in Water
Isokinetic Particle Determination in Flue Gas
Kinematic Viscosity
Loss of Ignition of Catalyst
Mercaptan Sulfur Gases
Liquid Hydrocarbons
Metals Trace, in Crackling Catalysts
Trace, in Oils
Trace, in Oils
Nitrogen in Heavy Distillate
Octane Motor
Research
Particle Size Distribution of Catalyst
pH, Iron and Copper in Refinery Water
Number
UOP 539
UOP 172
EPA #5,6,7
UOP 539
UOP 709
UOP 725
D 1298
UOP 11
UOP 277
UOP 9
UOP 212
UOP 6
UOP 314
D 3685
D 445
UOP 275
UOP 212
UOP 163
UOP 546
UOP 389
UOP 391
UOP 384
D 2700
D 2699
UOP 422
UOP 314
157048
Analytical Methods
Page 20
Test Description
Phenols in Petroleum Products
Pore Volume and Pore Diameter of Catalyst
Pour Point of Petroleum Oils
Reid Vapor Pressure
Sampling of Petroleum
Sediment and Water in Oil
Sintering Index of Catalyst
Sulfides in Refinery Waters
Sulfur in Heavy Oils
Sulfur Doctor Test (H2S and Mercaptans)
H2S in Gases (Tutwiler)
Mercaptan and H2S in Light Distillates
H2S, Mercaptans, and COS in Hydrocarbon Gases
in Heavy Distillates
Total, in Light Distillates
Total Sulfur Lamp
Quartz Tube
Surface area, Pore Volume, and Pore Diameter of Catalyst
UOP Characterization Factor K
Vacuum Distillation
Viscosity Kinematic
Water and Sediment in Oil
Weathering Test (Boilaway)
Number
UOP 262
UOP 425
D 97
D 323
UOP 516 or D 270
D 4007
UOP 424
UOP 683
D 1552
UOP 41
UOP 9
UOP 163
UOP 212
D 1552
D 1266
D 1266
D 1552
UOP 425
UOP 375
D-1160
D 445
D 4007
UOP 155
157048
Analytical Methods
Page 21
OUTLINE OF SELECTED
ANALYTICAL TEST METHODS NUMERICAL INDEX
Test Number
Description
UOP 1
UOP 6
UOP 9
UOP 11
UOP 41
UOP 76
UOP 77
UOP 79
D 86
D 92
D 93
D 97
UOP 155
D 156
UOP 163
Vacuum Distillation
Distillation of Petroleum
Distillation of Petroleum
Distillation of Petroleum
Flash Point, Open Cup
Flash Point, Closed Cup
Pour Point of Petroleum Oil
Weathering Test (Boilaway)
Saybolt Color
Mercaptans and H2S in Liquid Hydrocarbons
UOP 172
D 189
UOP 212
UOP 233
UOP 251
UOP 254
UOP 262
D 270
157048
Analytical Methods
Page 22
Test Number
Description
UOP 275
UOP 277
D 287
UOP 314
D 323
UOP 375
UOP 384
UOP 389
UOP 391
UOP 422
UOP 424
UOP 425
D 445
D 482
UOP 516
UOP 539
UOP 546
UOP 682
UOP 683
UOP 703
UOP 709
UOP 725
UOP 740
D 1160
D 1266
D 1500
D 1552
D 2699
D 2700
D 3685
D 4007
157048
Analytical Methods
Page 23
Scope
This method is for determining the distillation range of heavy petroleum oils. It is
applicable to petroleum products whose boiling range extends above that of
kerosene; e.g., crude oils, gas oils and fuel oils. The method differs from ASTM
Method D 86 in that a 200 ml flask is used and the distillation is continued past the
thermal decomposition point to a dry or coke residue. The test is particularly useful
in estimating gasoline, kerosene and/or distillate contents and the coking
characteristics of these oils.
Outline of Method
A 100-ml sample is distilled under prescribed conditions. Systematic observations
of thermometer readings and volumes of condensate are made, and the weight of
coke or residue is determined. The results of the test are calculated and reported
from these data. No corrections are applied to the data.
Precautions
Oils containing more than traces of water are very difficult to distill. However, if the
heat is applied to the flask correctly, water can be distilled from the oil without
bumping. When water is present, heat the flask evenly over its top and bottom
surfaces; do not concentrate heat on the bottom of the flask. Keep the top of the
flask hot enough to prevent water vapor from condensing there and allow time for
the temperature to drop to ambient before continuing the distillation. Do not include
water in the percentages reported for the temperatures named. The IBP obtained in
this manner on samples containing water may, or may not, be a true IBP owing to
the possibility of superheating the vapors when the flame is applied to the top
surface of the flask. Note this on the distillation sheet.
157048
Analytical Methods
Page 24
157048
Analytical Methods
Page 25
Scope
This method is for determining the induction period of gasolines. It is useful in
predicting the storage stability, in lieu of the more valuable storage tests and
accelerated gum determination. It is a valuable control test and an excellent
measure of inhibitor effectiveness.
This method does not give the same numerical induction periods as ASTM Method
D 525 because of differences in construction of the bombs and bath. However, the
results are parallel and this method is preferred for its speed and convenience.
Outline of Method
The sample is placed in a bomb at 60-70F (15-20C) and subjected to oxygen at
100 psig. The bomb is heated rapidly to 211.6F (99.7C). The pressure is recorded
continuously until the break point has been passed. The induction period is then
determined from the chart record.
Precautions
The bombs and bottles must be scrupulously clean to obtain reproducible results.
Precision
Repeatability should be considered suspect it results differ from the mean by more
than 5%.
157048
Analytical Methods
Page 26
Scope
This method is for the determination of hydrogen sulfide in gas mixtures. Mercaptan
sulfur, if present, is determined as hydrogen sulfide. The accuracy of this method is
not sufficient to obtain reliable results below 5 grains of H2S per 100 cu. ft.
Outline of Method
The sample is admitted to a Tutwiler buret, displacing a starch solution. A known
volume of starch solution is retained in the buret and a standard iodine solution is
admitted and measured from the buret until the starch solution assumes a taint
permanent blue color. The concentration of hydrogen sulfide is calculated from the
volume of iodine used and its known normality.
Precautions
It is recommended that gases to be analyzed for hydrogen sulfide content be
sampled directly from the plant stream into the buret. If the sample is to be
transported, it should be done in a dry glass or stainless steel container.
Do not confuse the blue color of the iodine-starch complex with the opalescent
milky appearance resulting from the separation of free sulfur.
157048
Analytical Methods
Page 27
Precision
Duplicate results by the same operator should be considered suspect it they differ
by more than the following amounts, depending on the iodine solution used:
Iodine Solution A:
10 grains*
Iodine Solution B:
20 grains*
Iodine Solution C:
5 grains*
157048
Analytical Methods
Page 28
Scope
This is a method for determining the weight of the residue obtained when a gasoline
or naphtha is evaporated in a copper dish. Considered in connection with the
induction period, it is an indication of the stability of the gasoline in storage.
Outline of Method
The sample is evaporated in a clean, copper dish under controlled conditions and
the weight of the residue is determined.
Report
Report the average weight of the residue as milligrams of copper dish gum per 100
ml of gasoline.
157048
Analytical Methods
Page 29
Scope
This is a qualitative test for the presence of hydrogen sulfide and mercaptans in
gasoline, jet fuel, kerosene and similar petroleum products.
Outline of Method
The sample is shaken with a sodium plumbite solution in a test tube. If hydrogen
sulfide is present the following reaction occurs:
Na2PbO2 + H2S
PbS + 2NaOH
The lead sulfide is black and readily visible. If this reaction does not appear, sulfur
is added to the test tube and the mixture shaken again. If mercaptans are present,
on shaking they undergo a series of reactions, coloring the hydrocarbon layer first
orange, then red and brown, and finally a black precipitate of lead sulfide appears.
The overall reactions may be written:
Na2PbO2 + 2RSH
(RS) 2Pb + S
157048
Analytical Methods
Page 30
Report
(a)
(b)
Sample sour.
If a brown or black precipitate forms, the sample contains a relatively high
concentration of mercaptans and is reported sour.
(c)
Report
Definitely discolored
Barely discolored
Not discolored
sour
borderline
sweet
Precaution
Use only sufficient sulfur to form a thin film floating on the interface between the
sample and the doctor solution.
157048
Analytical Methods
Page 31
Scope
The distillation apparatus described in this method was devised to provide a means
of determining the boiling range of heavy oils. It is intended for the determination, at
reduced pressures, of the boiling temperature ranges of petroleum products which
have an initial boiling point in excess of 460F (238C) and which decompose when
distilled at atmospheric pressure. The method is applicable to petroleum products
which can be partially or completely vaporized at a maximum liquid temperature of
750F (399C), at a pressure in the range of 0.2-0.3 mm of mercury absolute, and
which may be condensed as liquids at the pressure of the test.
Outline of Method
The sample is distilled at a pressure of 0.2-0.3 mm of mercury absolute under
conditions which provide approximately one theoretical plate fractionation. Data
obtained, converted to 760 mm mercury, allow the preparation of a distillation curve
relating volume distilled and boiling point.
157048
Analytical Methods
Page 32
Scope
This method is for determining the gasoline, naphtha and kerosene content of a
crude oil as a guide in operating crude oil topping facilities.
Outline of Method
The method employs a Hempel column to secure the desired precision in a manner
which simulates the results obtained from a commercial distillation. Directions are
given to obtain end point gasoline, or naphtha, and kerosene of either specified end
point or API gravity.
157048
Analytical Methods
Page 33
Scope
This method describes laboratory fractionation equipment and procedures used in
obtaining true boiling point data for petroleum distillates and crude oils. Procedures
are also given for obtaining specific boiling range distillates for further analysis.
Outline of Method
A known volume of a petroleum distillate or a crude oil sample is fractionated in a
high efficiency laboratory column. The distillation may consist of: (1) the precision
fractionation of normally liquid hydrocarbons to collect fractions for further
identification: (2) the quantitative separation of normally gaseous hydrocarbons,
such as C3 and/or C4 hydrocarbons from C5 and heavier gasoline or crude oil
fractions, and/or (3) the determination of true boiling point (TBP) distillation curves
at atmospheric and reduced pressures.
157048
Analytical Methods
Page 34
2.
End point (EP) maximum thermometer reading obtained during the test.
3.
5.
6.
Percent total recovery combined percent recovery and residue in the flask.
7.
8.
9.
157048
Analytical Methods
Page 35
Scope
This method covers determination of the flash and fire points of all petroleum
products except fuel oils and those having an open cup flash below 175F (79C).
Summary of Method
The test cup is filled to a specified level with the sample. The temperature of the
sample is increased rapidly at first and then at a slow constant rate as the flash
point is approached. At specified intervals a small test flame is passed across the
cup. The lowest temperature at which application of the test flame causes the
vapors above the surface of the liquid to ignite is taken as the flash point. To
determine the fire point, the test is continued until the application of the test flame
causes the oil to ignite and burn for at least 5 sec.
Precision
The following data should be used in judging the acceptability of results (95 percent
confidence).
Duplicate results by the same operator should be considered suspect if they differ
by more than the following amounts:
157048
Analytical Methods
Page 36
Repeatability
Flash point
Fire point
15F (8C)
15F (8C)
30F (17C)
25F (14C)
157048
Analytical Methods
Page 37
Scope
These methods cover the determination of the flash point by Pensky-Martens
closed-cup tester of fuel oils, lube oils, suspensions of solids, liquids that tend to
form a surface film under test conditions, and other liquids.
Summary of Method
The sample is heated at a slow, constant rate with continual stirring. A small flame
is directed into the cup at regular intervals with simultaneous interruption of stirring.
The flash point is the lowest temperature at which application of the test flame
causes the vapor above the sample to ignite.
157048
Analytical Methods
Page 38
Scope
This standard defines a primary centrifuge method and two alternatives for
determining the amount of water and sediment in crude oil. It further specifies a
base method to be used when centrifuging is not suitable or when the accuracy of a
centrifuge method is to be confirmed.
Summary of Method
The three centrifuge methods involve selection of number of factors such as type of
solvent, type and amount of demulsifier, temperature of the sample during testing,
and the duration of centrifuging. With many types of oil, the results are not
dependent on the selected factors. Those factors which are not the most convenient
can be used with good results.
157048
Analytical Methods
Page 39
Scope
The test for pour point is intended for use on any petroleum oil.
Summary of Method
After preliminary heating, the sample is cooled at a specified rate and examined at
intervals of 5F (or 3C) for flow characteristics. The lowest temperature at which
movement of the oil is observed is recorded as the pour point.
Definition
Pour point the lowest temperature, expressed as a multiple of 5F (or 3C) at
which the oil is observed to flow when cooled and examined under prescribed
conditions.
Calculation and Report
Add 5F (or 3C) to the temperature recorded and report the result as the Pour
Point, ASTM D 97.
Precision
Repeatability Duplicate results by the same operator should be considered
suspect if they differ by more than 5F (or 3C).
Reproducibility The results submitted by each of two laboratories should be
considered suspect only if the two results differ by more than 10F (or 6C).
157048
Analytical Methods
Page 40
Scope
This is a rapid procedure for the estimation of iso- and normal butane in liquefied
butane samples. Propane does not interfere with the analysis and is determined if
present in concentrations not exceeding 25%. Pentane and olefins will interfere in
the analysis, if present. The test is sufficiently accurate for routine control of plant
operations, the apparatus is inexpensive and the technique involved requires little
experience.
Outline of Method
A 94 ml sample of liquefied butanes is drawn into a precooled centrifuge tube. It is
then weathered in air to the 90 ml mark. The centrifuge tube and contents are then
transferred to a water bath maintained at 60-70F (15-20C). Temperature readings
are recorded when the liquid level has dropped to the 50- and 15-ml graduation
marks of the centrifuge tube. From these temperatures and weathering test curve,
the approximate concentrations of propane, isobutane and normal butane are
determined.
157048
Analytical Methods
Page 41
Precision
Duplicate results by the same operator should be considered suspect if they differ
by more than the following amounts:
Hydrocarbons
Propane
i-butane
n-butane
Maximum Deviation, %
+ 2.5
+ 1.5
+ 1.0
157048
Analytical Methods
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Scope
This method covers the determination of the color of refined oils such as undyed
motor and aviation gasoline, jet fuels, naphthas and kerosene. A sample of the
liquid is added to a tubular column through which a light source is seen. The color is
compared with specified glass standards. The height of the liquid sample is
decreased by levels until the color of the sample is lighter than that of the standard.
The color number above this level is reported. The range of number is +30 (lightest)
to -16 (darkest color). Color standards correspond to sample depth and color
number.
Precision
Duplicate results by the same operator should be considered suspect if they differ
by more than 1 color unit.
Results submitted by one laboratory should be considered suspect if they differ
from that of another laboratory by 2 color units.
157048
Analytical Methods
Page 43
3
16 10 A N
SV
32 103 (B - A) N
SV
157048
Analytical Methods
Page 44
where:
A = volume of silver nitrate solution used to reach the sulfide ion end point,
ml
B = volume of silver nitrate solution used to reach the mercaptide ion end
point, ml
N = normality of alcoholic silver nitrate solution
S = specific gravity of sample at the temperature at which the sample is
pipetted
V = volume of sample, ml
Precautions
Allow enough time for the titration cell to reach equilibrium before recording the
volume of silver nitrate solution and the emf when the manual titration is made.
When using a recording titrator, add the titrant at a rate of 3.0 ml per minute in the
vicinity of the end point, otherwise the end point will be overshot.
157048
Analytical Methods
Page 45
Scope
A known quantity of sample is introduced into a Kjeldahl flask, diluted with distilled
water, and made alkaline with 50% sodium hydroxide. The volatile nitrogen bases
are distilled in a Kjeldahl apparatus and the condensate collected in a boric acid
adsorbing solution. This solution is then titrated with standardized sulfur acid using
methyl purple indicator.
157048
Analytical Methods
Page 46
Scope
This method is for the quantitative determination of carbon dioxide, oxygen and
carbon monoxide in flue gases.
Outline of Method
Systematically, the gas sample is admitted into a series of pipets, each containing a
reagent for the removal of an individual component. After contact with each reagent,
the gas is returned to the buret. The difference in residual volume indicates the
amount of component absorbed. In this manner, percentages of carbon dioxide,
oxygen and carbon monoxide are determined.
Precision
Duplicate results by the same operator should be considered suspect if they differ
by more than the following amounts:
Carbon dioxide
+ 0.2%
Oxygen
+ 0.3%
Carbon monoxide
+ 0.3%
157048
Analytical Methods
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This method covers the determination of the amount of carbon residue left after
evaporation and pyrolysis of an oil, and is intended to provide some indication of
relative coke-forming propensities. The method is generally applicable to relatively
nonvolatile petroleum products which partially decompose on distillation at
atmospheric pressure. Petroleum products containing ash-forming constituents as
determined by ASTM Method D 482, Test for Ash from Petroleum Products, will
have an erroneously high carbon residue, depending upon the amount of ash
formed.
Summary of Method
Calculate the carbon residue of the sample or of the 10 percent distillation residue
as follows:
Carbon residue = (A 100)/W
where:
A = weight of carbon residue, g
W = weight of sample, g
157048
Analytical Methods
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Report
Report the value obtained as "Conradson carbon residue, percent" or as
"Conradson carbon residue on 10 percent distillation residue, percent," ASTM
D 189.
157048
Analytical Methods
Page 49
Scope
This method is for determining hydrogen sulfide, mercaptan sulfur and carbonyl
sulfide in gaseous hydrocarbons and in liquefied petroleum gas (LPG) of ordinary
properties. Also covered is the determination of mercaptan in non-ordinary LPG
which may contain a wide range of hydrocarbon types from ethane to such gasoline
boiling range hydrocarbons as pentane and hexane. The hydrogen sulfide
concentration range which can be determined is from 0.3 to several thousand
wt-ppm. The method is also applicable to LPG samples containing as little as 1.0
ppm mercaptan sulfur.
Outline of Method
The sample, taken either from a sample bomb or directly from a refinery stream, is
scrubbed first through a potassium hydroxide solution and then through a
monoethanolamine solution. A potentiometric titration of the absorbed hydrogen
sulfide and mercaptan sulfur follows. The monoethanolamine solution, which
contains the absorbed carbonyl sulfide, is titrated potentiometrically with alcoholic
silver nitrate in an acidic titration solvent. The concentration of each item sought is
estimated from the titration curve.
Precision
157048
Analytical Methods
Page 50
Type of Sample
LPG containing
appreciable concentrations
of pentane and higher
boiling materials
No. of
Pairs
Mercaptan
Level,
wt-ppm, S
esd,
wt-ppm,
S
6.0
0.28
Allowable
difference,
wt-ppm, S
1.1
157048
Analytical Methods
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Scope
In this procedure the oil-catalyst mixture is washed free of oil with cold benzene,
dried and weighed.
Note: Toluene may be substituted for benzene.
Precautions
Do not conduct the analysis near an open flame. It is preferably carried out under a
hood.
Be sure the crucible is dry before placing it in the oven. It is advisable to leave the
oven door ajar for 5-10 minutes immediately after introducing the crucible.
If the catalyst persists in adhering to the Erlenmeyer flask, dry and weigh the flask
and add the increase in weight to the catalyst weight in the crucible.
Precision
157048
Analytical Methods
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Scope
This method is for evaluating the activity of fluid catalytic cracking catalysts relative
to a reference catalyst by measuring the conversion of a Mid-continent gas oil to
gas and gasoline. The procedure is applicable to both fresh and used catalyst.
Outline of Method
A standard gas oil charge stock is cracked over the test catalyst in a fixed-bed
operation under carefully controlled standard operating conditions. The conversion
to gasoline and gas is measured. The activity, expressed as a percentage, is the
ratio of the liquid hourly space velocity used with the test catalyst to the liquid hourly
space velocity required with a primary reference catalyst to give the same
conversion as that obtained with the test catalyst. The latter value is read from an
experimentally-obtained reference catalyst calibration curve showing conversion as
a function of space velocity.
Notes
1.
Fresh and equilibrium synthetic catalysts are calcined prior to activity testing
for 2 hours at 1112F +25F (600C) in a muffle furnace having a vent in the
door to permit slow circulation of air. The catalyst is loaded in 150-ml tall-form
porcelain crucibles (without covers) filled about one-half full. Fresh catalyst is
first dried at about 400F (204C) for 2 hours to remove moisture and avoid the
spattering of catalyst which otherwise may occur if placed directly in the muffle
furnace at 1112F. Regenerated equilibrium catalysts have substantially all of
the carbonaceous deposit (except embedded carbon) removed in calcining.
For normal carbon deposits of 0.3 to 0.5 wt-% or less, the activity rating is not
157048
Analytical Methods
Page 53
affected by the carbon removal. Abnormal carbon deposits, up to 1 and 1.5 wt%, usually will reduce the weight activity by 1 to 2 numbers.
In calcining fresh or used natural catalysts, the temperature employed is that
used when regenerating the catalyst in commercial practice.
157048
Analytical Methods
Page 54
Scope
This is a procedure for determining the apparent bulk density (ABD) of loosely
packed fluid cracking catalyst.
Outline of Method
Apparent bulk density is defined as weight per unit volume. It is an empirical value
for the particular type of solid particles to which the determination applies; in this
case, fluid (powered) cracking catalyst in a size range of less than 200 m effective
diameter.
Calculations
where:
W = weight of the catalyst, g
157048
Analytical Methods
Page 55
Scope
This method is intended primarily for the quantitative determination of phenols and
thiophenols in gasoline and in refinery caustics, but it also is applicable to crude
cresylic acids derived from these refinery caustics. "Phenols" consist of a mixture of
phenol, cresols and xylenols. "Thiophenols" denotes the analogous sulfur
compounds.
Outline of Method
Phenols and thiophenols are extracted from the petroleum fraction with 10% sodium
hydroxide solution. The ultraviolet absorption spectrum of the caustic extract is then
recorded. A base-line technique is used to compensate for background absorption
of the sample. Calibration in a similar manner with known solutions and the
application of Beer's Law permits calculation of weight-percent phenols and weightpercent thiophenols.
In the presence of excessive concentrations of mercaptans, only the sum of the
phenols and thiophenols can be determined directly. However, an accurate value
for thiophenols can be obtained from the modified procedure described, involving
adsorption of the sample on silica gel followed by selective elution of the
thiophenols.
The procedure for refinery caustics and crude cresylic acids is identical to that for
petroleum fractions except that the extraction step is omitted.
157048
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Precautions
157048
Analytical Methods
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Scope
157048
Analytical Methods
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Scope
This method is for determining the loss on ignition of fresh or used catalyst or
catalyst bases of the various commercial shapes and sizes, when an ignition
temperature of 900C is specified. It is also applicable to other sample types, such
as catalyst fines.
A representative weighted sample is heated at 900C to constant weight and the
loss in weight calculated as percent loss on ignition.
Precision
Duplicate determinations should not differ by more than 0.2% absolute for values
below 3.0%, or more than 0.3% to 10.0%.
Based on 10 pairs at the 2% loss on ignition level, the standard deviation calculated
from the mean range was 0.072%.
Time for Analysis
Elapsed time per test is about 21/4 hours (5.0 hours when fines are being
analyzed).
157048
Analytical Methods
Page 59
Scope
The steam jet method is similar to ASTM Method D 381 for Existent Gum in Fuels
by Jet Evaporation. The sample in a tarred beaker is placed in a heated metal block
apparatus maintained at 325F (163C) and evaporated to dryness by a jet of steam
which has been superheated to 325F (163C). The residue is weighed and
reported as milligrams of gum per 100 ml of sample.
Precautions
The types of gasolines and naphthas for which this method is intended must be
sampled and handled carefully in order to prevent oxidation. For best results it is
recommended that: (1) the sample containers be purged with inert gas such as
nitrogen, carbon dioxide, or sweet refinery gas prior to taking the samples, (2) any
storage between time of sampling and analysis be in the dark (preferably
157048
Analytical Methods
Page 60
refrigerated storage), (3) the time lapse between sampling and analysis be as short
as possible.
Precision
Duplicate results by the same operator should not be considered suspect unless
they differ by more than approximately 25% of the result.
157048
Analytical Methods
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Scope
Using a glass hydrometer the API gravity of crude petroleum and petroleum
products which have Reid Vapor Pressures under 26 lbs. can be determined.
Gravities are determined at 60F (15C), or converted to 60F, by means of
standard tables. Conversion tables are not applicable to nonhydrocarbons or
essentially pure hydrocarbons such as the aromatics. Of interest: the ID of the
sample cylinder must be at least 25 mm greater than the OD of the hydrometer. The
height of the cylinder shall be such that the sample height is 25 mm more than the
submerged portion of the hydrometer.
Precision
Repeatability Duplicates should not differ by more than 0.2 degrees API.
Reproducibility Results should not differ by more than 0.5 degrees API when done
by different labs.
The above judgments are valid providing API gravities were obtained at a
temperature not differing from 60F by more than 18F (10C).
157048
Analytical Methods
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Scope
This method is designed for measuring the extent of corrosion caused by refinery
waters. Copper and iron are determined at a level of 0.1 ppm and higher. The
metals may be present as simple dissolved ions, as complex ions with cyanide or
other complexing agents, or as part of the suspended solids that often are present.
Ammonia, hydrogen sulfide, hydrogen cyanide and organic matter do not interfere.
The pH of the water is determined because it usually correlates with the extent of
corrosion.
Outline of Method
The water sample, including any suspended solids, is concentrated in the presence
of sulfuric acid until sulfur trioxide fumes appear and then treated successively with
nitric acid and aqua regia.
Iron is determined colorimetrically. The lower limit of detection is 0.1 ppm iron.
Copper is determined colorimetrically. The lower limit of detection is 0.1 ppm copper
in the water sample.
The pH of the original water sample is determined with a pH meter using a glasscalomel electrode system. Samples drawn for determination of pH at the refinery
should be taken in glass bottles, leaving little or no air space above the liquid, and
should be stoppered immediately with rubber or neoprene. The pH should be
measured as soon thereafter as possible as it is often subject to fairly rapid change
with time. Draw samples to be sent out of the refinery in polyethylene bottles to
avoid breakage.
157048
Analytical Methods
Page 63
Precision
Insufficient data available to calculate an esd with at least 3.7 degrees of freedom.
Time for Analysis
157048
Analytical Methods
Page 64
This method determines the absolute vapor pressure of volatile crude oil and
volatile nonviscous petroleum products, except LPG. The gasoline chamber of the
testing apparatus is filled with a chilled sample and connected to the air chamber
section which should be at 100F (37.8C). The container is then immersed in a
constant-temperature bath and shaken periodically until equilibrium is reached. A
manometer attached at the end of the cylinder like apparatus is read and corrected
if the air chamber temperature is initially at something other than 100F.
Precision
Repeatability
0-5 psi
5-16 psi
16-26 psi
0.1
0.2
0.3
0-5 psi
5-16 psi
16-26 psi
Repeatability
0.35
0.3
0.4
157048
Analytical Methods
Page 65
Scope
This method is for determining the UOP Characterization Factor, which is indicative
of the general origin and nature of a petroleum stock. Values of 12.5 or higher
indicate a material predominantly paraffinic in nature. Highly aromatic materials
have characterization factors of 10.0 or less.
This method also may be used to estimate the molecular weight of typical
petroleum fractions. It is not intended for estimating the molecular weight of a pure
hydrocarbon compound.
Outline of Method
2.
The UOP Characterization Factor from API gravity and kinematic viscosity at a
temperature of 100, 122 or 210F (37.8, 50 or 98.9C), and
3.
Definitions
157048
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157048
Analytical Methods
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Scope
Duplicate determinations run in the same laboratory by the same operator on the
same equipment should not differ from the mean by more than the percent relative
in the table below:
Total
Nitrogen, ppm
Percent,
Relative
0.5
5
45
500
20
11
5
2
The estimated standard deviation was calculated to be 0.35 at the 16-ppm level,
based on 5 replicate samples; 1.38 at the 54-ppm level, based on 6 replicates.
157048
Analytical Methods
Page 68
Scope
Cobalt and potassium are added to the oil sample as internal standards and
spectroscopic buffers. The oil sample is then coked with fuming sulfuric acid, ignited
and ashed at 1000F (538C), treated with aqua regia and the ash dissolved in
dilute hydrochloric acid. A spark spectrum of the solution is obtained by means of a
rotating-disk electrode technique. A microphotometer is used to measure the
densities of selected metal lines. Concentrations are determined from standard
calibration curves.
Precision
The estimated standard deviations (esd) for various concentration levels of the
metals determined by this method are shown below. Duplicate results by the same
operator should not be considered suspect unless they differ by more than the
amounts shown in the "allowable difference" column (95% probability).
157048
Analytical Methods
Page 69
Metal Level,
ppm
No. of
Pairs
esd,
ppm
1
10
50
200
5
5
5
5
0.09
0.59
3.2
13
Allowable
Difference, ppm
0.3
2.2
12
48
157048
Analytical Methods
Page 70
Scope
This method is for determining trace concentrations (parts per million) of vanadium,
nickel, iron, copper and sodium in petroleum products such as crude oils and
residues, and varied organic compounds (including nitroanilines, amines,
chlorobenzenes, phenols and other related materials) produced or used in chemical
manufacturing. Other elements commonly found in these materials do not interfere.
Outline of Method
The sample is wet-ashed with fuming sulfuric acid and the coke is burned off in a
muffle furnace. The inorganic residue remaining is dissolved in acid and diluted to a
given volume. Vanadium, nickel, iron and copper are determined
spectrophotometrically, and sodium is determined by flame photometry, using
aliquots from the acid solution.
Precaution
The sulfuric acid concentration in the standard sodium solutions must be the same
as that in the sample solutions. If a different concentration of sulfuric acid is used for
the sample solution than that specified in this method, the calibration curve must be
prepared with sodium standard solutions containing this same sulfuric acid
concentration.
157048
Analytical Methods
Page 71
Precision
Allowable
Difference for
Duplicates, ppm
Range, ppm
(Sodium)
0 to 2
>2
0.2 ppm
10% of the mean
Insufficient data are available to calculate a standard deviation for the metals listed.
157048
Analytical Methods
Page 72
Scope
This method is for the determination of particle sizes of fluid cracking catalysts by
means of calibrated sieves having uniform precise square openings. It may also be
used for determining particle sizes of other powdered materials. The method
provides for the classification of particles in a range of sizes from about 20 to 149
microns.
The method is a modification of Shell Development Company, Method EMS 5Z2/61.
Outline of Method
157048
Analytical Methods
Page 73
Scope
This method provides a means of separating and measuring a fraction of used fluid
cracking catalyst having a reduced apparent density resulting from the pores having
been sealed off by localized overheating.
Precision
Duplicate results by the same operator should be considered suspect if they differ
by more than 1% absolute. Duplicate results by different operators should be
considered suspect if they differ by more than 2% absolute.
157048
Analytical Methods
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Scope
157048
Analytical Methods
Page 75
Precision
Surface Area
Duplicate determinations should not differ by more than 8% from the mean.
Based on 2 sets of 5 replicate determinations, the standard deviation at the 500-600
m2/g level was 12.
Based on 2 sets of 5 replicate determinations, the standard deviation at the 100-200
m2/g level was 2.
Pore Volume
Duplicate determinations should not differ by more than 5% from the mean.
Based on 2 sets of 5 replicate determinations, the standard deviation at the 50-60
Angstrom level was 1.
Based on 2 sets of 5 replicate determinations, the standard deviation at the 90-130
Angstrom level was 3.5.
157048
Analytical Methods
Page 76
157048
Analytical Methods
Page 77
Scope
This method covers the determination of the kinematic viscosity of liquid petroleum
products, both transparent and opaque, by measuring the time for a volume of liquid
to flow under gravity through a calibrated glass capillary viscometer. The dynamic
viscosity can be obtained by multiplying the measured kinematic viscosity by the
density of the liquid.
Summary of Method
The time is measured in seconds for a fixed volume of liquid to flow under gravity
through the capillary of a calibrated viscometer under a reproducible driving head
and at a closely controlled temperature. The kinematic viscosity is the product of the
measured flow time and the calibration constant of the viscometer.
Precision
The following precision applies to clean, transparent oils tested between 60 and
212F (15 and 100C).
Repeatability Duplicate results by the same operator, using the same
viscometer, should be considered suspect if their difference is greater than 0.35
percent of their mean.
Reproducibility The results submitted by each of two laboratories should not be
considered suspect unless their difference is greater than 0.7 percent of their mean.
ASH FROM PETROLEUM PRODUCTS
157048
Analytical Methods
Page 78
ASTM D 482
Scope
This method covers the determination of ash from distillate and residual fuels, gas
turbine fuels, crude oils, lubricating oils, waxes, and other petroleum products, in
which any ash-forming materials present are normally considered to be undesirable
impurities or contaminants. The method is limited to petroleum products which are
free from added ash-forming additives, including certain phosphorus compounds.
Summary of Method
The sample contained in a suitable vessel is ignited and allowed to burn until only
ash and carbon remain. The carbonaceous residue is reduced to an ash by heating
in a muffle furnace at 1427F (775C), cooled and weighed.
Report
Report the result to two significant figures as the ash, ASTM D 482, stating the
weight of the sample taken.
157048
Analytical Methods
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Scope
Properly identify each sample by attaching a tag to the cylinder giving company
name and location, time and date of sampling, identity of stream sampled, sample
pressure and tests required. Crate the cylinder to protect the valves from being
opened or damaged in shipment. Affix a "Red Label" or other proper shipping label
to the crate.
157048
Analytical Methods
Page 80
Samples taken in containers found leaking either during or after sampling should be
discarded and new samples taken in leak-free cylinders.
Consult the current Interstate Commerce Commission or other appropriate
authorities for regulations for applicable specification for shipment. Consult ASTM
Methods D 270, D 1145 and D 1265, if necessary, for procedures for measurement
and sampling of petroleum and petroleum products.
For liquid samples taken in the above manner it is mandatory to immediately
provide a safe outage in the cylinder to prevent thermal expansion and cylinder
rupture. Follow the recommendations in this method to safely provide that outage.
157048
Analytical Methods
Page 81
Scope
157048
Analytical Methods
Page 82
TABLE 1
GAS ANALYSIS BY GAS CHROMATOGRAPHY
LEVEL,
MOL-%
ESD,
MOL-%
ALLOWABLE
DIFFERENCE,
MOL-%
HYDROGEN
NITROGEN
METHANE
CARBON MONOXIDE
10
20
10
10
0.10
0.02
0.03
0.14
0.36
0.07
0.09
0.49
CARBON DIOXIDE
ETHANE
PROPYLENE
n-BUTANE
10
10
10
10
0.03
0.04
0.02
0.03
0.10
0.14
0.05
0.09
3
4
0.03
0.04
0.11
0.14
COMPONENT
ISOPENTANE
C5 OLEFINS/C6 PLUS
157048
Analytical Methods
Page 83
Samples of the unknown diluted in graphite are burned to completion using a 6-amp
dc arc. The photographed spectra are then examined to determine the elements
sought.
Iron, nickel, and vanadium concentrations are quantitatively determined by
densitometry, using an internal standard, while the concentrations of the remaining
metals are semi-quantitatively determined by visual comparison with spectra from
known samples.
Precision
Duplicate determinations for Fe, Ni, and V should not differ from the mean by more
than 10% in the 0.01 to 1.0% range.
Based on 10 replicates, the estimated standard deviation (esd) was calculated to
be:
Elemental
Level
esd
Fe
Ni
V
0.6
0.02
0.05
0.047
0.0017
0.0075
157048
Analytical Methods
Page 84
Scope
This method is for determining cyanide and thiocyanate in refinery water, both of
which are then calculated as weight-ppm cyanide. The lower limit of detection is
about 0.02 wt-ppm in samples containing no sulfur and 0.8 wt-ppm in those
containing 1% sulfide.
Outline of Method
A sample of refinery water is placed in a flask and hydrogen sulfide added. The
sample is then acidified with hydrochloric acid, bromine water is added and the
mixture allowed to stand until clear.
(1)
HCN + Br2
CNBr + HBr
8 HBr + H2SO4
157048
Analytical Methods
Page 85
(2)
(a)
+ CNBr
N
Br
CN
(b)
+ 2H 2 NC 6 H 4 -C 6 H 4 -NH
N
CN
Br
NHC 6 H 4 C 6 H 4 -NH
+ (Br)
+ H 2 N-CN
C 6 H 4 -C 6 H 4 NH 2
157048
Analytical Methods
Page 86
Scope
This method is for determining sulfide in refinery waste water. It cannot be used on
caustic solutions. Good precision can be obtained when a titrant volume of 10 ml or
more is used. The estimated standard deviation of 0.013 was obtained on a sample
containing 0.8 wt-% S. However, with titrant volumes of less than 10 ml, the results
may be high by as much as 5% of the value found.
Outline of Method
Cd++ + (NH4)2S
CdS + 2NH4+
either (a)
Cd++ + (NH4)2S S4
(b)
Cd++ + (NH4)2S S4
CdS + 4S + 2NH4+
CdS3 + 2NH4+
However, in this method the sulfide is calculated to the second "break" with the
equivalent weight of sulfur being 16.
157048
Analytical Methods
Page 87
Precision
The estimated standard deviation (esd) at the 0.8% sulfur level is shown below.
Duplicate results by the same operator are not considered suspect unless they
differ by more than the amount shown in the "allowable difference" column (95%
probability).
Type of
Sample
Sulfur
Level,
wt-%
No. of
Replicates
esd,
wt-% S
Allowable
Difference,
wt -%
Solution of
(NH4)2S
0.8
11
0.013
0.026
157048
Analytical Methods
Page 88
Scope
This method gives supplementary instructions for the determination of 0.01 to 80.0
wt-% carbon on catalysts.
It is necessary that the analyst be provided with the history of the sample so that the
proper sample preparation can be applied.
Outline of Method
The sample is weighed in a ceramic crucible, mixed with accelerators and burned in
an induction furnace using oxygen carrier gas. The products of combustion pass
through a purifying train consisting of a dust trap, antimony metal for chloride
removal, manganese dioxide for sulfur removal, and a heated catalyst lube for
conversion of carbon monoxide to carbon dioxide and hydrogen to water. The
carbon dioxide is adsorbed on molecular sieves at ambient temperature. After the
adsorption period is ended, the molecular sieve column is rapidly heated to 600F
(316C) and the carbon dioxide eluted and carried through the measuring thermistor
by an auxiliary flow of oxygen. The output of the thermistor bridge is integrated and
read on a digital voltmeter and converted to percent carbon by calculation.
157048
Analytical Methods
Page 89
Precision
Carbon Level,
%C
Number of
Pairs Used
Number of
Replicates
esd,
%C
Allowable
Difference, % C
0.01-0.6
0.6-2
2-5
20
5
7
7
5
0.005
0.015
0.022
0.334
0.02
0.05
0.07
1.25
157048
Analytical Methods
Page 90
Scope
157048
Analytical Methods
Page 91
TABLE 2
GAS ANALYSIS BY GAS CHROMATOGRAPHY
USING A TWO-INJECTION TECHNIQUE
LEVEL,
MOL-%
ESD,
MOL-%
ALLOWABLE
DIFFERENCE,
MOL-%
HYDROGEN
21
0.186
0.68
NITROGEN
0.087
0.32
METHANE
12
0.180
0.66
CARBON MONOXIDE
0.266
0.97
PROPANE
0.077
0.28
PROPYLENE
0.203
0.74
ISOBUTANE
0.158
0.58
n-BUTANE
0.074
0.27
ISOBUTYLENE
0.264
0.96
COMPONENT
157048
Analytical Methods
Page 92
Oily material is extracted from water with carbon tetrachloride. The infrared
absorbances of the extract are determined at 2860 cm-1 (3.50 m) and 2930 cm-1
(3.42 m), and these are used to calculate the concentration of oily matter.
Definition
Oily material means any substance containing -CH, -CH2-, or -CH3 groups which
show infrared adsorption bands at 2860 cm-1 (3.50 m) and 2930 cm-1 (3.42 m)
and which is extractable from acidified water with carbon tetrachloride.
Sensitivity
The sensitivity of this method is about 1 ppm. The method can be extended to
include oil concentrations of less than 1 ppm by using cells of longer path length (5and 10-cm cells are common), larger samples of the water and smaller volumes of
carbon tetrachloride for the extraction.
Precision and Accuracy
Results are reported to the nearest part per million. Relative esd as reported in the
reference API method is 5%. Duplicate results should be considered suspect if they
differ by more than 20% of the average value.
157048
Analytical Methods
Page 93
Scope
157048
Analytical Methods
Page 94
Scope
157048
Analytical Methods
Page 95
Introduction
This method has replaced the former ASTM Method D 155, Test for Color of
Lubricating Oil and Petrolatum by Means of ASTM Union Colorimeter. Method D
155 was withdrawn as an ASTM Tentative on July 1,1960. Method D 1500 is better
than the former Method D 155 in three respects: (1) the glass standards are
specified in fundamental terms; (2) the differences in chromaticity between
successive glass standards are uniform throughout the scale; and (3) the lighter
colored standards more nearly match the color of petroleum products.
Scope
This method covers the visual determination of the color of a wide variety of
petroleum products such as lubricating oils, heating oils, diesel fuel oils, and
petroleum waxes.
Report
Report as the color of the sample, the designation of the glass producing a
matching color, for example: 7.5 ASTM Color.
If the color of the sample is intermediate between those of two standard glasses
record the designation of the darker glass preceded by the letter "L", for example:
"L7.5 ASTM Color". Never report the color as being darker than a given standard
except those darker than 8, for example: ASTM Color.
If the sample has been diluted with kerosene, report the color of the mixture
followed by the abbreviation "Dil," for example: "L7.5 Dil ASTM Color".
157048
Analytical Methods
Page 96
Precision
The results obtained by different operators in the same laboratory should not vary
by more than 0.5 number, and the same variation should apply for determinations
between different laboratories at the 96 percent confidence level.
157048
Analytical Methods
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Scope
This method covers two procedures for the determination of total sulfur in petroleum
products, including lubricating oils containing additives, and additive concentrates.
The method is applicable to samples boiling above 350F (177C) and containing
not less than 0.06 percent sulfur. Chlorine in concentrations less than 1 percent
does not interfere. Nitrogen when present in excess of 0.1 percent may interfere;
the extent of such interference may be dependent on the type of nitrogen
compound as well as the combustion conditions. The alkali and alkaline earth
metals, as well as zinc, phosphorus, and lead, do not interfere.
Summary of Method
157048
Analytical Methods
Page 98
Precision
The following criteria should be used for judging the acceptability of results (95
percent confidence):
Repeatability Duplicate results by the same operator should be considered
suspect if they differ by more than the following amounts:
Sulfur, weight percent
(Range)
Repeatability
0 to 0.5
0.5 to 1.0
1.0 to 2.0
2.0 to 3.0
3.0 to 4.0
4.0 to 5.0
0.05
0.07
0.10
0.16
0.22
0.24
Reproducibility
0 to 0.5
0.5 to 1.0
1.0 to 2.0
2.0 to 3.0
3.0 to 4.0
4.0 to 5.0
0.05
0.11
0.17
0.26
0.40
0.54
157048
Analytical Methods
Page 99
This method determines the knock characteristics of motor gasolines, intended for
use in spark-ignition engines. A Research octane number (RON) of 100 or lower is
the volume percent of iso-octane in a blend with n-heptane that matches the knock
intensity of the unknown sample. For numbers above 100, a comparison is made to
iso-octane and milliliters of tetraethyllead required to match knock intensity.
Summary of Method
Data for limits on duplicate results by the same operator have not been developed.
Reproducibility
Limits
80
85
90
95
100
105
1.2
0.9
0.7
0.6
0.7
1.1
157048
Analytical Methods
Page 100
Scope
This method covers the determination of the knock characteristics of motor and
aviation-type gasolines, intended for use in spark-ignition engines, in terms of
ASTM motor octane numbers.
Summary of Method
The ASTM Motor Octane Number of a fuel is determined by comparing its
knocking tendency with those for blends of ASTM reference fuels of known octane
number under standard operating conditions. This is done by varying the
compression ratio to obtain standard knock intensity, as measured by an electronic
detonation meter.
Definitions
ASTM Motor Octane Number of motor and aviation-type gasolines of 100 and
below The volume percent, to the nearest tenth, of iso-octane (equals 100.0) in a
blend with n-heptane (equals 0.0) that matches the knock intensity of the unknown
sample, when compared by this method.
ASTM Motor Octane Number of a motor gasoline above 100 The value, to the
nearest tenth, that corresponds to the equivalent engine rating in terms of milliliters
of tetraethyl lead in iso-octane.
157048
Analytical Methods
Page 101
Precision
80
85
90
95
99
100.1
105
1.2
1.1
1.0
1.1
1.5
1.1
1.8
157048
Analytical Methods
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Scope
This method covers the sampling and determination of particulate matter in stack
gases.
Significance
The following procedure describes a method of sampling in stacks and flues which
has been standardized within the limits of the many conditions which are
encountered in the normal course of sampling stacks. No one procedure or set of
apparatus will apply to all problems. The recognition of one set of apparatus which
will satisfy a number of commonly encountered conditions will often leave many
other problems unanswered. The objective has been to select apparatus that will
give a reliable answer when applied to a variety of problems.
For compliance with regulations in the United States EPA method #5 is usually
required. Check with local authorities before using any lab method required for
compliance with environmental regulations.
157048
Procedures
Page 1
PROCEDURES
INTRODUCTION
The procedures given in this section are general instructions which may serve as a
guide for each unit. They cannot be specific because of the variations in the design
and construction of each Fluid Catalytic Cracking Unit. These methods should be
used by each refiner to develop a detailed set of operating instructions for his
particular unit.
Although basic procedures will be fairly consistent from unit to unit, the FCC is such
a flexible process that several different strategies exist for operating an FCC unit.
Individual refinery requirements and product markets should be carefully considered
to determine the most economic strategy to employ for the FCC unit. These
procedures will cover the basic operating steps for startup, shutdown and
emergency situations. Specific operating strategies for maximum economic benefit
will be left to the individual refiner.
This section is divided according to topic. These subsections are:
A.
B.
C.
D.
E.
F.
G.
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Procedures
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157048
Procedures
Page 3
refractory must be cured and dried; be sure that air is directed to every part of the
reactor-regenerator system.
The dryout may be summarized as:
1.
Controlled heating of regenerator and reactor with hold steps for water
removal.
2.
3.
The source of heat for the dryout may be the air blower and direct fired air heater,
as in the following procedure, or it may be supplied with internal local heaters. The
choice may be dictated by the particular vendor preference and/or availability of
suitable equipment.
Procedure
The following procedure is intended to supplement the refractory vendor procedure.
During the dryout, several hold periods are maintained at a constant temperature.
The time period for the hold may vary depending on the type and thickness of the
refractory lining. Where the vendor procedure calls for more conservative steps,
those steps should be followed. Should the following steps be more conservative
than the vendor, further discussion is warranted to confirm that the dryout will be
adequate. In all cases, the procedure of the vendor responsible for the
application/performance of the refractory shall govern.
1.
The curing procedure shall begin immediately after installation and shall
last a minimum of 24 hours. For the 4" low density gunned lining in the
regenerator, water or membrane curing steps may also be included.
157048
Procedures
Page 4
b.
2.
3.
During the curing procedure, the temperature of the shell and lining shall
be kept above 60F (16C).
After curing, the refractory lining shall be tested by tapping with a one
pound hammer at one foot intervals over the entire lining surface. Any
voids or dry filled spaces will emit a dull sound and these areas shall be
removed and replaced.
b.
After the 24 hour curing period, the refractory lining shall be air dried for
at least another 24 hours by natural or forced ventilation.
Isolate the structure with blinds in the feed, torch oil, fuel or gas to the CO
boiler and air heater, steam to the riser and stripper, and reactor vapor
line.
b.
Double block and bleed the riser blast points, flue gas quench nozzles
and all steam purge points.
c.
Remove the blankoffs on the catalyst loading lines and the drain points in
the flue gas system.
d.
Remove the blankoff on the vent nozzle on top of the reactor shell and
install a gate valve. Attach a pipe stack approximately six feet (two
meters) long to the valve for personnel protection.
This valve will only be used if the reactor vapor line vent does not pass
enough hot air to adequately heat up the reactor or if the riser termination
device is highly contained so that there is little or no air flow through the
reactor shell. Open the vapor line vent valve upstream of the vapor line
blind.
157048
Procedures
Page 5
4.
5.
e.
f.
Open air purges to all instrument DA points and slide valve packing
glands.
g.
Commission the steam systems of the flue gas cooler and catalyst cooler,
if present. Steam drum boilout procedures can be combined with the
dryout as long as the dryout procedure governs. The cooler tubes must
have circulating water flow for protection during the dryout.
h.
Close the spent and regenerated catalyst slide valves. Check the blast
and sample connections on the catalyst standpipes and drain any free
water.
i.
j.
Prepare the direct fired air heater for firing. Prepare alternate internal
heaters if they are to be used.
b.
Begin closing the discharge snort valve, forcing air into the regenerator.
As the pressure of the regenerator rises, the power required to drive the
blower increases. Check the air blower's performance curve and keep the
machine out of the surge condition.
Refractory Dryout
a.
Open the blast and sample connections on the catalyst standpipes and
drain any free water.
157048
Procedures
Page 6
b.
c.
d.
e.
It is important that the air blower is used only for initial dryout in
the reactor. For later startups, only steam should be used to
heat up the reactor. During operation, coke will form on the
reactor internals and walls. There is a real danger of damaging
oxidation or fire if this material is exposed to air at high
temperature.
For the cold wall regenerated catalyst standpipe, wye section and riser
with 5" high density vibracast refractory lining, the minimum hold period at
250F (120C) is 8 hours. It may be that some of this cold wall lining has
already been installed and dried out in the shop. In that case, the
remaining reactor lining will dictate the hold period required. For the 3/4"
abrasion lining in the upper riser and reactor vessel, the minimum hold
period at 250F (120C) is 4 hours.
157048
Procedures
Page 7
f.
After the 250F (120C) hold period, light the direct fired air heater and
raise the temperature in the regenerator and reactor at 50F (30C) per
hour to 650F (350C) and hold for 12 hours for 4" gunned lining, 8 hours
for 5" vibracast lining, or 4 hours for 3/4" abrasion lining. An operator
should be stationed by the air heater any time it is in service.
g.
h.
While the reactor and regenerator are heating up, the equipment should
be checked for expansion problems. Completely inspect the vessels,
standpipes and structure every hour until the regenerator plenum has
reached its maximum, generally ~1200F (650C), and every two hours
thereafter. Check:
(1)
(2)
That expansion joint tie rods are loose and not binding.
(3)
(4)
i.
During the 650F (350C) hold period is a convenient time to perform the
first hot bolting step. Systematically hot bolt the entire reactor-regenerator
section.
j.
All slide valves should be hot stroked at all hold temperatures. Position
indicators should be checked with board readings and the valves checked
157048
Procedures
Page 8
6.
k.
l.
m.
(2)
The direct fired air heater lining has been cured and dried.
157048
Procedures
Page 9
(3)
7.
b.
c.
Begin closing the reactor vapor line vent valve and flue gas slide valve
and raise the reactor and regenerator pressure to approximately 28 psig
(2 kg/cm2) or to the value specified in the 314 Specification.
d.
After the high temperature field test is completed, reduce the reactor
regenerator pressure back to the previous level.
b.
Begin reducing the air heater outlet temperature at 100F (55C) per
hour. When the regenerator temperature reaches 500F (260C), stop the
steam purges to the torch oil guns and nozzles.
c.
Shutdown the DFAH when the temperature control becomes erratic due
to low fuel gas flow.
d.
Continue air flow through the vessels until the temperature is within 50F
(30C) of the blower discharge temperature and then shut down the main
air blower.
e.
Open all manways and vents. Use fans or other air moving equipment to
cool the vessel internals to ambient conditions.
157048
Procedures
Page 10
f.
Remove the distributor flange at the bottom of the wye section to allow
inspection of the wye section.
g.
Inspect all refractory linings in the catalyst system, including the reactor,
regenerator, riser, standpipes, cyclones, air heater, flue gas line and
orifice chamber. Lock each slide valve in position to prevent accidental
movement during inspection. Small hairline cracks will be present in the
refractory and do not present a problem. Large cracks greater than 3/8"
(10 mm) that extend all the way to the shell should be repaired.
h.
For the final flange assembly before startup, glue of ceramic blanket to
the refractory retaining collars on all cold wall manways or blind flanges
before they are closed (see UOP standard specification 3-24-2 Figure 4).
B. NORMAL STARTUP
The normal startup of the unit can be divided into the following steps:
1.
Steam out the reactor and main column, and heat up the catalyst section.
2.
3.
4.
5.
6.
7.
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Procedures
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It is assumed that the unit is cold and empty, and that all precommissioning
activities and refractory dryout have been completed. General guidelines are
given in these procedures and each refiner should develop specific startup
procedures for their particular unit. Variations from the steps given here are
acceptable as long as the basic intent is followed and safety matters are not
compromised.
1.
The following procedure starts from the condition that all equipment and
vessels are full of air. Steaming of the reactor and fractionation section is
used to free the unit of oxygen. The following items should be completed
before the steam out is begun:
(1)
The unit must be completely flushed, all vessels and piping closed
up, all orifice plates and instrumentation installed, and all equipment
ready for startup.
(2)
The reactor vapor line blind should be removed at this time (refer to
Figure 4). Some refiners prefer to leave this blind in place until later
in the startup sequence. This is acceptable but it is generally more
convenient to remove the blind now. The procedure following is
designed to use the reactor containing steam as a protection buffer
between the regenerator with air and the main column with
hydrocarbon.
(3)
If the vapor line blind is out, the vapor line vent should be blocked
and blinded.
(4)
Remove the blankoff from the main column high point vent and open
the valve a couple turns.
(5)
Isolate the wet gas compressor at the suction and discharge lines.
Steam should not be allowed to enter the compressor.
157048
Procedures
Page 12
(6)
Line up backup nitrogen to the DG purge gas header and start purge
gas to the reactor instrumentation DG points.
(7)
Make sure the regenerated and spent catalyst slide valves are fully
shut. All slide valves should be operational with hydraulic systems
commissioned.
(8)
b.
Start steam to the base of the riser, to the feed distributors, to the reactor
stripper, and to the spent catalyst standpipe blast point. As the reactor is
purged and heated, steam will flow through the vapor line into the main
column. Continually drain condensate at the riser, reactor, stripper, and
main column low point drains. The spent catalyst standpipe blast point will
have to be used as a drain after the initial steaming is completed.
c.
Start steam into the bottom of the main column and into the sidecut
strippers. Vent at the top of the main column and at the overhead
receiver. Do not run the condenser fans or water to the trim cooler during
this procedure.
d.
Steam through the overhead receiver to the wet gas compressor suction
drum. Vent at the drum and drain condensate from low points. Steam
through the spillback lines and the interstage receiver but make sure the
compressor remains isolated. Connect steam hoses as needed if there is
trouble achieving a good steam plume from vents.
e.
Continually drain condensate from all low points. As the vessels and
piping heat up, less steam will condense and the low points can be
throttled to match the condensate drain rate. Condensate collecting in the
overhead receiver water boot can be pumped out with the sour water
pumps.
157048
Procedures
Page 13
f.
When there is a good steam plume out the top of the main column, main
column receiver, compressor suction drum and interstage receiver for at
least two hours, the system should be free of air and the steamout is
complete.
g.
A quick leak check should be conducted on the system. Throttle all vent
and drain valves to raise the pressure in the system to 10-12 psig (0.7-0.8
kg/cm2). Check all flanges, valve packings, etc. for leaks. It may be that
too much steam is condensed in the main column condenser to permit
building pressure for this leak test.
h.
Check all low points to ensure that all water is drained. Verify that the
spent catalyst standpipe is being drained from the blast and sample
connection.
i.
Start injecting fuel gas at the LCO stripper vapor return line. Raise the
reactor and main column pressure to 10-12 psig (0.7-0.8kg/cm2) before
reducing the steam injection. This will ensure that air is not drawn into the
unit as the steam condenses.
j.
Close all vents and continue draining water from all low points. Never
leave a drain point unattended with fuel gas in the system.
NOTE: Fuel gas injection to the LCO stripper should be enough that the
pressure transmitter on the main column receiver will keep the
overpressure control valve to the flare open a small amount at all
times. This will ensure that any air that might enter the system
will be purged out to the flare. On older units which used air as
the purge gas to the reactor instrument taps, air from the DA
points in the reactor is carried by the steam flows to the main
column and receiver. If this air is not purged out, the
concentration of oxygen can build up in the receiver to a high
level.
157048
Procedures
Page 14
2.
k.
l.
Be sure all DA and DG purges and all instrumentation in the reactorregenerator section are in service.
b.
Start the main air blower after the fractionation section is pressured up
with fuel gas. Refer to the manufacturer's instruction manual for the
blower startup procedure.
c.
157048
Procedures
Page 15
3.
4.
d.
Open the recirculating catalyst slide valve and catalyst cooler slide valve
(if present) to allow heated air to flow up the standpipes to the upper
regenerator.
e.
f.
Begin water circulation through the catalyst cooler tubes (if present) and
flue gas cooler tubes.
When the flow from the main air blower has stabilized, light the direct fired
air heater according to the manufacturer's instructions.
b.
c.
Start fluidizing air to the upper regenerator fluffing rings and to the
catalyst cooler fluidizing lances (if present) at minimum flow.
b.
Since LCO and HCO will be unavailable for flushing oil to the instruments
and the main column bottoms pump flushes (gland seal, wear rings and
throat bushing), the flush header should be commissioned with raw oil or
157048
Procedures
Page 16
a light gas oil from outside the battery limits if the raw oil is very heavy.
When the LCO and HCO products become available, the flush systems
will be changed back to the proper stream.
c.
Start raw oil feed through the startup filling line to the bottom of the main
column. The addition of cold feed into the column will condense some
steam since it passes countercurrent with steam over the disk and donut
trays. Therefore, add raw oil to the column slowly until the column is hot.
Pay special care to removing free water from the low points in all vessels,
exchangers and piping because sudden water vaporization can damage
equipment.
d.
e.
Start the main column bottoms pump and send oil through one of the
steam generators. This circulation must be done slowly at first to avoid
cooling the bottom of the main column. Raise the raw oil outlet
temperature as high as possible, then start flow through the second
steam generator. Try to maintain the column overhead temperature high
enough to drive water overhead.
f.
When the column bottom temperature has stabilized at its highest level
from the steam heating, slowly start bottoms circulation through the other
bottoms circulation loops. Circulate through the cold sections of the
system slowly until they are heated to avoid cooling the column bottom
excessively. Watch the bottoms level and bring in more raw oil as the
total bottoms circuit is inventoried. Start flow from the net bottoms pumps
through the startup line back to the raw oil charge pumps to complete the
loop. Check for water at the low points throughout the bottoms system.
This circulation and heatup will slowly dry out the bottoms system.
157048
Procedures
Page 17
g.
After the bottoms circuit is hot and dry with good circulation flows, check
for free water in the LCO and HCO system low points. Check that the
sidecut strippers inlet level control valves are fully closed. Start a small
flow of hot raw oil from the main column bottoms up to the LCO circuit
return line via the startup filling line. This will put hot oil into the upper part
of the column. When the LCO draw tray is full, it will overflow to inventory
to HCO section and then overflow back to the bottom of the column. Add
raw oil as necessary to maintain the bottoms level as the LCO and HCO
sections are inventoried. Keep the bottoms temperature as hot as
possible with the steam generators.
h.
Drain all free water in the LCO and HCO circuits and slowly start oil flow
through the heat exchange circuits in the Gas Concentration Unit,
bypassing the exchangers. Check that the main column overhead
temperature is high enough to avoid steam condensation in the column.
Do not place the sidecut strippers into operation at this time.
i.
Circulate oil flow through the LCO and HCO circuits until the lines are hot
and all free water has been removed. Maintain a small flow from the hot
bottoms circuit up to the LCO section to keep these sections hot and
overflow the draw trays back to the bottoms.
j.
Inventory the main column receiver with startup naphtha. Don't start reflux
at this time as it will cool off the top of the column and cause additional
steam condensation.
k.
157048
Procedures
Page 18
5.
The heating of the main column and the regenerator can be taking place
at the same time. The regenerator is being heated with the direct fired air
heater and steam is flowing through the reactor. Completely inspect the
reactor-regenerator structure every hour until the maximum air heater
outlet has been reached, around 1200F (650C), and once every two
hours thereafter. Check:
(1)
(2)
That expansion joint tie rods are loose and not binding.
(3)
(4)
b.
c.
157048
Procedures
Page 19
drain the standpipe so that water does not accumulate. The desired
situation is that all of the condensate is kept drained, and if drained into
the regenerator, it is done slowly so that when the water vaporizes, it will
not cause a large pressure surge in the regenerator which could push air
into the reactor.
d.
When the air heater temperature reaches 600F (315C), start hot bolting
flanges and manways and systematically hot bolt the entire regenerator
and flue gas system. Repeat this procedure when the air heater
temperature exceeds 1000F (540C).
e.
f.
Check that all instrument purges have been started and contain the
proper RO throughout the reactor-regenerator section. Check that all
regenerator level and density transmitters are functioning. Ensure that air
flow is going to the upper regenerator fluffing rings and catalyst cooler air
lances (if present).
g.
157048
Procedures
Page 20
The cyclone inlet velocities in the regenerator should be maintained greater than 35
ft/sec (11 m/sec) as much as possible to ensure good catalyst separation efficiency.
Lower pressure during heatup and catalyst loading can help increase the velocity
when the regenerator is cool. For bubbling bed and RFCC regenerators the
superficial bed velocity should not exceed 3 ft/sec (0.9 m/sec) during startup to
minimize catalyst loading to the cyclones.
a.
Ensure that the following items have been accomplished before loading
catalyst into the regenerator:
(1)
(2)
Check that all instrument purges, slide valve packing purges, and
expansion joint purges are commissioned.
(3)
157048
Procedures
Page 21
(4)
(5)
Ensure that fluffing air is on to the upper regenerator rings and to the
catalyst cooler (if present). Water must be circulating through the
cooler tubes to keep them cool.
(6)
b.
Prepare the catalyst hoppers for transferring catalyst. Refer to the specific
procedures outlined in the Catalyst Handling section. Gauge the hoppers
before starting to establish the initial catalyst inventory.
c.
d.
For a high efficiency style regenerator, open the recirculation slide valve
further to increase the density in the combustor as the level increases in
the upper regenerator. The combustor density will remain low even with
the recirculation valve full open since there is no catalyst circulating
through the spent standpipe yet. If possible, try to establish a combustor
density of 4-7 lb/ft3 (65-110 kg/m3).
e.
Near the end of the catalyst loading step, when a high level exists in the
regenerator and the combustor density is as high as possible with the
recirculation slide valve open, it is advisable to reduce the main air blower
rate to around 50% of design. This will cause the combustor density to
157048
Procedures
Page 22
7.
At the completion of the catalyst loading step, gauge the hopper again to
determine the quantity of catalyst loaded.
As the cold catalyst is being loaded, it will cool the regenerator. Keep the
air heater firing at its maximum temperature to heat the catalyst. The rate
of heating the catalyst is not critical; the size of the catalyst inventory, the
speed of catalyst loading and the duty of the air heater will affect how fast
the temperature can be raised. A rate of 200-300F (110-170C) per hour
is a good target.
b.
c.
157048
Procedures
Page 23
8.
d.
e.
It is advisable to start the wet gas compressor early and have it operating
smoothly before circulating catalyst. Set the process controls in
preparation for compressor startup as follows:
(1)
157048
Procedures
Page 24
9.
(2)
(3)
b.
Start the compressor interstage cooler fans and open the cooling water to
the trim cooler.
c.
Increase the fuel gas makeup to the LCO stripper to provide an operating
cushion before starting the compressor.
d.
e.
157048
Procedures
Page 25
Once startup naphtha (if used) or feed is introduced to the unit the additional
heat required to vaporize the hydrocarbon increases the catalyst circulation
and therefore the cyclone loading quickly. Before starting these streams the
catalyst separation efficiency of the riser termination device and cyclones must
be increased to minimize losses to the main column.
For a direct connect, SCSS, VSS or VDS riser termination systems the cyclone
inlet velocity should be increased to 35 ft/sec (11 m/sec) or greater with the
startup steam to the wye before starting raw oil or startup naphtha to the riser.
Note that this velocity includes the stripping steam vapor flow. This is very
important for direct connect or SCSS systems. The vortex chamber on VSS
and VDS riser termination systems is less sensitive to changes in velocity than
other types of termination devices so that this is not as critical but it is still
recommended.
For vented risers the velocity out of the riser is critical for catalyst separation.
Catalyst should not be circulated with startup naphtha or feed with less than 35
ft/sec (11 m/sec) riser exit velocity. This velocity does not include the stripping
steam vapor flow.
a.
When the regenerator has reached 900F (480C), the unit is ready to
start catalyst circulation. Temporarily stop the flow of oil from the MCB
circulation up to the LCO and HCO sections of the main column.
Shutdown the HCO and LCO circulation pumps if the inventory in these
sections is lost. When catalyst circulation is first started, it is possible that
catalyst can be carried into the main column. It is best to contain these
fines in the bottoms rather than having them spread through the LCO and
HCO circuits.
b.
Check the spent catalyst standpipe for any condensate. Crack open the
spent slide valve occasionally to drain condensate into the regenerator.
The P controller for the reactor and regenerator should be set at a
negative (reactor higher) 1.5 psig (0.1 kg/cm2) or more if required to keep
the spent catalyst slide valve P positive to provide a steam buffer
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(reactor) between the air in the regenerator and hydrocarbon in the main
column.
c.
Set the lift and/or startup steam to the wye to maintain a velocity of 15
ft/sec (4.5 m/sec) throughout the riser. If sufficient fuel or natural gas is
available, lift gas flow can be started to help reduce the steam
requirement. This flow can come from the normal lift gas source (sponge
absorber) as recycle if the wet gas compressor is operating, or can be
piped in externally and vented at the main column overhead receiver if
the compressor is not operating.
d.
e.
Adjust the stripping steam and fluffing steam flows to design rates.
f.
Check the P across the regenerated catalyst slide valve and blast the
standpipe with air if there is low or no P. Slide valve differential
pressures will be erratic at low catalyst circulation rates.
g.
Start opening the regenerated catalyst slide valve with the reactor
temperature controller in manual. Closely watch the reactor temperature
which will rise as soon as catalyst begins to circulate. If no response is
observed after several minutes, blast the regenerated catalyst standpipe
again.
h.
The catalyst circulation from the reactor back to the regenerator should
be started as soon as possible to minimize any potential mud formation
(catalyst + condensate) in the spent catalyst standpipe. Do not wait until
the reactor level is fully established to start catalyst flow to the
regenerator. As soon as catalyst creates an increasing P across the
spent slide valve, open the valve on manual to start returning catalyst to
the regenerator. If the P does not increase across the valve, blast the
standpipe with steam.
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i.
k.
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b.
c.
d.
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when torch oil is fired (or the level is maintained above the torch oil guns
in a bubbling bed or RFCC regenerator).
e.
At some point after stable catalyst circulation has been established, and
both spent and regenerated catalyst slide valves have good P across
them, the reactor-regenerator P controller can be adjusted to a positive
value (regenerator pressure higher) to help balance the two slide valve
P's. Make sure the slide valve low P override controllers are
commissioned.
f.
Stop backing steam into the main column steam generators and fill them
with boiler feed water to prepare for eventual heat removal/steam
production. This should be done slowly to avoid excessive thermal shock
when the tubes are changed from hot steam to cooler BFW.
b.
Set the feed flow through the bypass valve to the main column at
approximately 10% of design charge rate. The flow may be lined up
through the main column bottoms recycle flow meter. The bottoms
recycle meter is convenient to use for starting feed to the riser because
the normal feed control valve is too large to accurately control such small
flows.
c.
Feed steam should be set at 150% of design. Stripping steam and fluffing
steam flows should be at design.
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Prior to starting feed to the riser, be sure to drain all free water from the
feed line between the diverter valve and the feed nozzle block valves.
Start feed to the riser by switching the feed bypass switch to the normal
position. This will close the valve on the line to the main column and open
the line to the riser. Begin opening the regenerated catalyst slide valve
further at the same time to provide the additional heat required to
maintain riser temperature and velocity.
NOTE: Start feed very slowly at first to avoid thermal shock to the feed
distributor tips. The feed distributor tips can be cracked if
subjected to excessive thermal shock.
When cutting in oil, catalyst circulation must be increased to
maintain the reactor temperature. Do not allow the temperature
to drop below 930F (500C). Should the reactor temperature
drop too low, feed can be reduced until the temperature is
increased again. Initially, the regenerator temperature may drop
until catalyst containing coke enters the regenerator. Try to
maintain the combustor temperature around 1250F (675C).
e.
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rates. The reduction should be done gradually so that riser velocity does
not suddenly drop.
f.
g.
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Control
As desired.
Lift Steam
And
Lift Gas
Feed Steam
Reactor Temperature
Reactor Pressure
Indirectly set
pressure.
by
main
column
receiver
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Reactor Variables
Control
Stripping Steam
Naphtha to Riser
HCO Recycle
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Regenerator Variables
Control
Combustor Temperature
Combustor Density
Regenerated Catalyst
Temperature
Reactor-Regenerator
Differential Pressure
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Regenerator Variables
Control
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Control
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Control
Flush Oil
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D. NORMAL SHUTDOWN
The shutdown of the FCC Unit is essentially the reverse of the startup steps. It
should be carried out in an orderly and planned sequence. Some main points to
remember are:
1.
Maintain good catalyst fluidization and circulation through the reactor and
regenerator throughout the shutdown. Increase riser steam to ensure
smooth catalyst circulation.
2.
Always decrease the charge rate before decreasing the air rate. Maintain
excess oxygen in the flue gas at all times and keep the regenerator hot to
ensure the catalyst is fully regenerated.
3.
Make sure all pumparound circuits are flushed out to eliminate problems
with heavy oils or catalyst fines.
During scheduled shutdowns, the catalyst section and the main column exchanger
circuits will usually be inspected and cleaned. Depending on the work to be done,
the main column might have to be water washed for entry. The Gas Concentration
Unit will be pumped out and purged with steam. If columns are to be entered, they
will need to be water washed.
Precautions must be taken to cool the reactor sufficiently before allowing air to enter
the vessel. This is done to guard against the possibility of auto-ignition of hot coke
deposits in the reactor or vapor line. The reactor should be cooled below 350F
(175C) before any manways or nozzles are opened. Riser and stripping steam
should be used to assist cooling the vessel as required.
The following procedure describes a full shutdown for maintenance entry to vessels.
Depending on the reason for the shutdown, the full procedure may not be followed,
and catalyst may or may not be left in the regenerator. In most cases, catalyst will
be transferred from the reactor to the regenerator during a shutdown. These
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Notify offsites and utility systems well in advance that the FCC Unit will be
shutting down. Prepare the regenerator by withdrawing catalyst to drop
the upper regenerator level to a low value. This will make room for the
eventual transfer of the catalyst in the reactor and reduce the time
needed to unload the unit catalyst inventory.
2.
3.
4.
Maintain the main column bottoms level low around 30%. Control the
level by drawing more or less bottoms product to storage.
5.
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As the raw oil charge rate is reduced, increase the lift steam and the feed
steam to assist catalyst circulation. Begin reducing the reactor pressure to
increase vapor velocity in the riser and the cyclones. Lift gas flow to the
riser may need to be reduced as the gas production is decreased. When
control of the lift gas becomes difficult or unstable, shutdown the flow and
block in the control valve.
7.
As the coke make decreases, the regenerator will cool off. Reduce the
catalyst cooler air rate and begin closing the cooled catalyst slide valve.
The slide valve may be closed completely but do not stop the fluidizing air
until catalyst is removed from the regenerator. Fire the air heater when
needed to hold the combustor temperature at 1225-1250F (665-675C).
Torch oil may be used but should be avoided if possible due to its harmful
effect on the catalyst.
8.
The main column overhead gas production will decrease as the reactor
temperature and charge rate are decreased. Check that the spillback
valves for the wet gas compressor remain in a controlling range. Start fuel
gas flow into the LCO stripper vapor return line if needed to maintain main
column pressure control as the unit is shut down.
9.
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10. Prepare to bypass feed from the riser. Make sure the main column has a
low level in the bottom. Keep the regenerator at a lower pressure than the
reactor and put the regenerated catalyst slide valve on manual control.
Increase riser steam to maintain catalyst circulation, bypass raw oil to the
main column, and reduce the flow of oil. Keep raw oil flowing in and out of
the main column until it is verified that any catalyst carried over to the
column during shutdown has been flushed out.
11. With the catalyst circulating on steam, begin dropping the reactor level to
transfer catalyst into the regenerator. Begin withdrawing catalyst from the
regenerator to the hopper to make room for the reactor inventory. Start
decreasing the air heater outlet temperature at 100-200F (50-100C) per
hour. When the regenerator temperatures have dropped below 1000F
(540C) close the regenerated catalyst slide valve and stop circulating
catalyst to the reactor. Maintain steam flow to the riser.
12. When oil is bypassed from the reactor, the gas make will decrease very
rapidly. Shutdown the wet gas compressor according to the
manufacturer's instructions and block it in. Nitrogen purge the compressor
casing.
13. After the wet gas compressor is shut down, block in the pressure
controller on the sponge absorber overhead line. Pressure as much liquid
as possible back to the main column or to the debutanizer from the other
gas concentration columns. After all the liquid is pumped out, depressure
the columns to the fuel gas system. When the fuel gas header pressure is
reached, depressure the remaining gas to flare.
14. As the main column starts to cool, stop the withdrawal of naphtha and
LCO to the sidecut strippers. The naphtha and cycle oils will then
overflow their accumulators, wash down the column, and dilute the
bottoms material. Open the bypass on the net bottoms product to the raw
oil line and start bottoms circulation as during startup. Switch the flushing
header source from LCO/HCO to the raw oil line. When the column and
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bottoms circuit is adequately flushed, pump out all circuits, the sidecut
strippers, and the column bottoms. Shut down the flushing headers.
When the column is empty, depressure it to flare. Pump out the overhead
receiver to the primary absorber column. Steam out the raw oil charge
line, the heat exchange train, and the reactor bypass line to the main
column from the raw oil pump discharge.
15. When all the catalyst has been transferred from the reactor into the
regenerator, close the spent catalyst slide valve. Lock both slide valves
closed. Unload catalyst from the upper regenerator to the hopper. Open
the recirculation and cooled catalyst slide valves to drop catalyst from the
standpipe and cooler into the combustor, where it will be carried back to
the upper regenerator. When all the catalyst is removed from the
regenerator, close the unloading valves, shut off the air heater and blind
the fuel gas line. Continue cooling the regenerator with the main air
blower. When the regenerator temperatures are slightly above the blower
discharge temperature, the air blower can be shutdown.
16. Connect vacuum hoses to the catalyst unloading connections throughout
the catalyst section and systematically clean out any remaining catalyst.
Vacuum catalyst from the unloading nozzles provided at the air heater,
the bottom of the riser, the bottom of the reactor stripper cone, and the
upper regenerator cone. When cleaning the reactor riser, the regenerated
catalyst slide valve should be temporarily opened to unload any
remaining catalyst from the regenerator standpipe.
17. When the main column is empty, start steam to the bottom and stripping
steam to the sidecut strippers. Be sure fuel gas to the LCO stripper is
shutoff and blinded. Maintain steam flow to the riser, feed distributors and
reactor stripper. Open the vents on top of the main column and overhead
receiver, and drain condensate from the low points.
18. When the reactor and main column are hydrocarbon free, decrease the
riser and column bottoms steam flows until only a trace is showing at the
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drains located at the vapor line blind. Remove the blind in the vapor line
vent, open the vent and install the vapor line blind. Increase the steam
flows and continue to steam out for several more hours. Drain
condensate from all low points.
19. Connect steam hoses and steam out all pumparound circuits. Drain
condensate from low points When the steamout is completed, be sure
vents and drains are fully open before stopping steam to avoid pulling a
vacuum.
20. When the main column has cooled to 100F (40C), start plant water to
the overhead receiver. Start the reflux pump and send water to the top of
the column. Drain at the bottoms and low points. When water flushing is
complete, blind where required for entry.
21. When the gas concentration columns are empty, steam out the unit as
required. Any column which will be opened for entry should be water
washed after steaming.
22. When the reactor and regenerator have cooled to 300F (150C), the
manways can be opened to ventilate and cool the vessels. Install air
movers as required. Note that when the reactor and regenerator are
entered, hot catalyst can still be present, particularly in any diplegs which
are closed by their flapper valves.
23. Install blinds to isolate all vessels to be entered. A specific blind list
should be prepared for each particular unit.
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E. EMERGENCY PROCEDURES
Emergencies on an FCC Unit may come in many forms. The operator must first
recognize the problem and then take quick action. Response will depend to a large
extent on plant design and individual features, the potential danger from the event,
and specific circumstances present at the time of the event. As it is impossible to
foresee every potential situation, operator judgment, anticipation and training are
key components for handling emergencies successfully. The best protection is a
thorough understanding of the process, the equipment and the potential dangers
involved.
The most important aspect of any emergency situation is how to make it safe;
personnel safety, environmental safety, and equipment safety are the major
objectives for any emergency handling program. Once the safety issues are under
control, then the less important concerns, such as maintaining or restoring unit
operation can be addressed.
Most FCC Unit emergencies will eventually involve a fundamental decision: should
raw oil charge to the riser be stopped for a period of time to correct the problem? If
this action is necessary, the basic steps to keep in mind are:
1.
2.
Bypass raw oil to the main column and stop lift gas.
3.
4.
These steps remove the hydrocarbon from the reactor, establish a steam
barrier between the regenerator and the main column, and maintain good
vapor velocity in the riser to assist catalyst circulation. Once these conditions
are established, the problem area can be investigated and corrected.
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Oil Reversal
This is one of the most severe emergency events which can develop on the
FCC unit, but thanks to built-in safety features in the design, is a very rare
event in today's modern unit.
A reversal can develop due to a sudden increase in reactor or main column
pressure, or a sudden decrease in regenerator pressure. The higher pressure
in the base of the riser can cause oil to backflow up the regenerated catalyst
standpipe into the regenerator. Once in the regenerator, the oil will burn
rapidly, resulting in extremely high temperatures. A severe reversal can cause
temperatures to exceed 2000F (1100C), well over the design temperature of
the regenerator internals. Fortunately, today's slide valves are designed to
close within 5 seconds and if the valve low P override is in service, the
amount of oil which could potentially reach the regenerator is considerably
reduced.
If a reversal occurs, the following actions should be taken:
a.
Bypass the raw oil charge, increase steam to the riser, increase feed
steam and close the regenerated and spent catalyst slide valves. Adjust
the reactor-regenerator P to a negative value (reactor pressure higher)
and reduce the reactor pressure. Stop lift gas and block in the control
valves.
b.
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c.
d.
If it is not possible to circulate catalyst with riser steam, decrease the air
rate as much as possible and wait for the oil to burn off and temperatures
to drop. Do not shutdown the air blower if it can be avoided, as a lengthy
unit shutdown may develop to clean coke out of the regenerator. Monitor
and record regenerator temperatures every five minutes.
e.
Add fuel gas to the LCO stripper to maintain main column and reactor
pressure. Shutdown the wet gas compressor if necessary and control the
pressure from the overhead receiver overpressure control valve.
f.
If it is expected that raw oil feed will be stopped for a long period, begin
pre-startup main column bottoms circulations. When temperatures drop
below 1300F (700C) in the regenerator, start increasing the air rate and
internal catalyst circulation. Use the air heater or torch oil if necessary to
hold the catalyst at 1200F (650C), then continue with the unit restart per
the normal procedures.
2.
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It is essential that the coke be burned off the catalyst at the same rate it is
produced. This is easily achieved in full CO combustion by maintaining a small
amount of excess oxygen in the flue gas. In partial CO combustion, however,
excess oxygen is not present and the burn characteristic is represented by the
CO2/CO ratio. It is much easier to change the coke production fast enough to
exceed the oxygen availability in partial combustion. When all the coke is not
burned, the unit gets "behind in burning" with the result that coke begins to
accumulate on the catalyst. The catalyst may turn dark gray or black in color
and will start to lose activity, causing a drop in conversion. Coke formation in
the reactor will continue and the overall coke accumulation on the catalyst can
snowball, eventually forcing feed to be bypassed.
Afterburn can be defined as CO combustion in the regenerator dilute phase.
There will always be some minor degree of afterburn and it is not a problem
until it becomes excessive. It is undesirable because there is little catalyst
present in this area to absorb the heat and very high temperatures can
develop.
Signs that the unit is behind in burning are:
a.
The temperature difference between the regenerator dilute phase and the
dense bed is less than usual, and
b.
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(2)
(3)
(4)
(5)
In the event that increasing the air rate does not correct the problem,
reduce the reactor temperature, drop the raw oil charge rate, and/or
start naphtha quench to the riser.
Increasing T between the regenerator dilute phase and the dense bed.
b.
(2)
(3)
(4)
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(5)
3.
Switch to the spare pump if this has not automatically occurred from the
low flow switch auto-start control.
If the flue gas cooler circulating water cannot be restored, bypass oil from
the riser immediately. This is required to prevent high temperatures in the
flue gas cooler tubes and downstream piping. The maximum allowable
temperature for the cooler tubes is usually 700F (370C).
c.
Increase lift steam and feed steam to the riser to maintain reactor
pressure so that air cannot enter from the regenerator. Stop the lift gas
and block in the control valve.
d.
Close the regenerated and spent catalyst slide valves to stop catalyst
circulation.
e.
f.
Start fuel gas to the LCO stripper. Continue running the wet gas
compressor on total spillback.
g.
If feed to the riser is stopped for more than four hours and the reactor
instruments are purged with air (DA), block in the purges. This will
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When the water circulation is restored, start the main air blower and bring
the unit back on stream following the normal startup procedure. Restart
the DA purges just prior to beginning catalyst circulation if these had been
stopped.
Catalyst Cooler:
4.
i.
Stop the fluidizing air and close the cooler slide valve. The catalyst in the
cooler should be allowed to become stagnant and cool off to minimize the
overheating of the tubes.
j.
It is not necessary to bypass feed from the riser. Unit operation will have
to be adjusted due to the loss of heat removal from the cooler. Reactor
severity will have to be reduced or the feedstock made lighter.
Immediately bypass oil from the riser to the main column. This must be
done quickly as the regenerator pressure will drop, causing a loss of
regenerated catalyst slide valve P which could set up the potential for an
oil reversal. Increase riser steam and feed steam.
b.
Check that the air blower discharge check valve closes completely
following the blower shutdown to ensure that no catalyst backs into the
blower.
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c.
Fully close the catalyst slide valves. The valves would eventually close
due to loss of differential pressure across them after the blower fails, but
they should be manually closed as fast as possible. Reduce fluidizing air
to the catalyst cooler to a minimum.
d.
Start fuel gas to the LCO stripper as quickly as possible. This may allow
the wet gas compressor to continue operating with the spillbacks fully
open. Reduce the main column receiver pressure as low as possible.
e.
f.
If feed to the riser is stopped for more than four hours and the reactor
instrumentation is purged with air (DA), block in the purges. This will
minimize the possibility of auto-ignition of coke due to an accumulation of
oxygen.
g.
Restart the main air blower when it is ready for service. Begin internal
catalyst circulation in the regenerator through the recirculation catalyst
slide valve. If the regenerator temperature is above 800F (430C), torch
oil can be used to reheat the catalyst back to 1200F (650C). If it is
below 750F (400C), light the air heater first. Be sure to raise the reactor
pressure above the regenerator pressure after the blower is restarted.
h.
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5.
6.
a.
Bypass oil from the riser to the main column and increase steam to the
riser and feed distributors. Keep catalyst circulating to the reactor if the
shutdown will be for a short duration. Establish a reactor pressure higher
than the regenerator.
b.
Continue internal catalyst circulation in the regenerator and use torch oil
to keep the catalyst at 1200F (650C).
c.
Start just enough fuel gas to the LCO stripper to maintain pressure control
on the main column.
d.
Reduce the main column pumparound flows to keep the main column hot.
Back steam into the bottoms steam generators as needed to heat the
circulating bottoms stream.
e.
Restart the wet gas compressor as soon as possible. Bring the unit back
on stream following the normal startup procedure.
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7.
a.
Increase riser steam and feed steam. Keep catalyst circulating to the
reactor if the shutdown will be for a short duration.
b.
Start fuel gas to the LCO stripper to maintain pressure in the main
column. Establish a reactor pressure higher than the regenerator.
c.
Keep the wet gas compressor running on total spillback in preparation for
restarting charge to the riser.
d.
Continue internal catalyst circulation in the regenerator and use torch oil
as needed to maintain the catalyst at 1200F (650C).
e.
When the charge pump is available, bring the unit back on stream
following the normal startup procedure.
The first priority is to get the material out of the column and try to keep
the bottoms temperature down. Try to start the spare pump immediately.
Reduce the charge rate to 75% of design and drop the reactor
temperature by 50F (30C). Decrease column product draws slightly to
aid in quenching the bottoms.
b.
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steam, bypass the raw oil charge to the main column, and stop the raw oil
feed. Establish a reactor pressure higher than the regenerator. Keep
catalyst circulating to the reactor if the shutdown will be for a short
duration.
8.
c.
Continue internal catalyst circulation in the regenerator and use torch oil
to maintain the catalyst at 1200F (650C).
d.
Add fuel gas to the LCO stripper as needed to maintain main column and
reactor pressure. Keep the wet gas compressor running on total spillback.
e.
When a bottoms pump can be restarted, pump the column bottoms down
to a normal level. Restart the normal bottoms circulation and follow the
normal startup procedure.
b.
Controller Malfunctions
c.
The slide valve has many redundant safety features to minimize the potential
for loss of control. Four methods are provided to move the slide valve:
1.
2.
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a.
3.
4.
For those cases where the hydraulic lines remain intact, the slide
valve main hydraulic oil accumulator will provide enough fluid to the
actuator to move the valve two full strokes. However, if the valve has
not moved within approximately four minutes, the accumulator will
have depressured and be unable to move the valve.
(2)
(3)
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(4)
(5)
b.
Controller Malfunctions
A slide valve will close upon the loss of its actuator electronic power or
instrument signal. There is no alarm for these failures and they will only
be apparent to the board operator when he sees the slide valve drifting to
the closed position. In this case, the slide valve should be operated using
the hydraulic oil system local manual positioner, the local handpump or
the handwheel. When operating the slide valve locally, care must be
taken to maintain a positive slide valve P. If the electronic input signal
can be reestablished quickly, put the valve back into regular operation.
For a prolonged failure, the unit will need to be shutdown.
c.
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the main column and shut down the charge pump. Establish a
reactor pressure higher than the regenerator and reduce the
main column pressure.
(2)
(b)
(c)
Shutdown the wet gas compressor and allow the main column
to cool down. Pump out as much oil as possible. Start steam to
the bottom of the column and vent from the overhead receiver
to flare. Maintain enough pressure to keep the reactor pressure
above the regenerator.
(d)
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(c)
(d)
When prepared, bypass the raw oil to the main column and
shut down the charge pump. Immediately shutdown the main
air blower, riser steam and feed steam. Maintain reactor
stripping steam. With no steam to transport the catalyst, it will
slump and plug the riser wye section. This is done to prevent
any air from entering the reactor. While this is less than
desirable for easily restarting operation, it is a necessary safety
protection for the unit.
(e)
(f)
(g)
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(3)
(4)
(b)
(c)
If the valve is stuck too far open, the catalyst density in the
combustor will increase which will increase the blower
discharge pressure. If the air flow becomes limited as a result,
adjustments can be made to the regenerator pressure to
compensate.
(d)
If the valve is stuck too far closed, the catalyst density and
temperature will decrease, and there may not be enough heat
to complete the coke combustion or enough catalyst to absorb
the heat from the combustion. This could lead to afterburning in
the upper regenerator. In this case, the air rate can be
decreased slightly to compensate. In severe cases, the charge
rate and reactor temperature should be reduced to decrease
the coke make.
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9.
Catalyst Cooler
a.
(2)
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b.
(3)
(4)
(5)
To avoid thermally shocking the tubes, let them cool to below 450F
(230C) before restarting the water circulation. Use the
thermocouples located in the cooler as an indication of the tube
temperature.
(6)
Restart water circulation and watch for a high BFW makeup rate
indicating a tube is leaking.
(7)
(2)
(3)
(4)
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(5)
It is possible to leave the cooler in this state and continue the FCC
operation indefinitely. The stagnant catalyst in the cooler will
eventually cool to protect the tubes against high temperature.
Shutdown of the FCC unit can be planned for a later date to repair
the ruptured tube.
In both of the above situations, loss of the catalyst cooler will require an
adjustment in FCC operating conditions to compensate for the lost heat
removal and limit regenerator temperature. This may require a reduction
in charge rate or a lighter feedstock. The FCC unit does not need to be
shutdown in either event.
10. Lift Gas Failure
Lift gas is not required to keep the FCC unit operating. Usually, lift steam can
be used to compensate for any loss of lift gas. The system is designed to shut
off lift gas to the riser when oil charge is bypassed.
a.
b.
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The raw oil charge is bypassed to the main column on air failure. The
charge pump should be shut down until air is restored.
b.
Steam to the riser and feed distributors opens fully on air failure. Lift gas
to the riser will fail closed.
c.
The main air blower governor will fail to the minimum speed and the antisurge snort valve will fail open. The catalyst slide valves will not fail as
they are electrohydraulic, so they must be closed by operator action. If
instrument air cannot be restored quickly, the blower may be left running
and the snort valve, recirculation catalyst slide valve and flue gas slide
valves and be adjusted to reestablish catalyst circulation in the
regenerator. The catalyst temperature can then be maintained at 1200F
(650C) using the air heater or torch oil in preparation for the unit restart.
d.
The wet gas compressor spillback valves will fail open. Unless sufficient
fuel gas can be put into the LCO stripper to maintain column pressure,
the compressor should be shut down.
e.
f.
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Increase lift steam and feed steam to the riser, bypass the raw oil charge
to the main column and close the raw oil charge control valve. If it is
expected that the power outage will be temporary, continue catalyst
circulation using steam. Stop lift gas flow. Establish a reactor pressure
higher than the regenerator and reduce the pressure in the main column.
b.
Close the catalyst cooler slide valve and reduce fluidizing air to minimum
flow to minimize heat removal in the regenerator. If catalyst circulation is
continued, use the air heater to maintain the catalyst at 1200F (650C).
The turbine driven circulating water pumps for the catalyst cooler and flue
gas cooler should continue operating.
c.
If the wet gas compressor is motor driven, it will shut down. If turbine
driven, keep the compressor running on total spillback. In either case,
start fuel gas to the LCO stripper to maintain column pressure.
d.
The main column bottoms pumps are turbine driven and will continue
operating. Maintain circulation but flow through the steam generators may
have to be stopped if BFW makeup has stopped. With all column
pumparounds and overhead reflux stopped, the column will hold heat for
some time.
e.
When power is restored, restart all pumps and follow the normal startup
procedure.
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Shutdown the wet gas compressor and bypass raw oil charge to the main
column. Increase lift steam and feed steam to the riser. Stop lift gas flow
and block in the control valve.
b.
c.
d.
Continue internal catalyst circulation in the regenerator and use torch oil
to maintain the catalyst at 1200F (650C).
e.
When cooling water is restored, bring the unit back on stream following
the normal startup procedure.
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F.
a.
Bypass raw oil charge to the main column and shutdown the charge
pump. Increase lift steam, feed steam and stripping steam to maximum
flows to purge the reactor quickly.
b.
Continue catalyst circulation on riser steam for a short period, then close
the regenerated and spent catalyst slide valves.
c.
Since the main column bottoms pumps are turbine driven, they will not be
operating for long. Therefore, cool the main column quickly to lighten the
material in the bottom to avoid coking when flow has been lost. Pump out
bottoms to hold a low level. Shutdown the wet gas compressor and begin
to depressure the main column to flare. Start steam to the main column
bottom to help purge the column.
d.
The main air blower is usually turbine driven and will eventually be
stopped. Internal catalyst circulation in the regenerator can be maintained
until that time. If it is expected that steam will be restored within a short
period, keep the catalyst hot with the air heater until the blower shuts
down.
e.
When steam is restored, start turbines carefully due to the potential for
condensate in the lines. Restart the unit according to the normal startup
procedures.
CATALYST HANDLING
Handling FCC catalyst is a relatively simple job. FCC catalyst is a relatively
strong material and will function quite well if not seriously abused. Because of
its characteristic of being easily fluidized, it is easily moved to and from the unit
using the principles of a pneumatic conveyor.
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Storage is provided usually in two large hoppers, one for fresh catalyst and the
other for equilibrium catalyst (removed from the unit). Capacity of these
hoppers may vary from 100-500 tons, depending on the size of the unit. The
fresh catalyst hopper will have an automatic catalyst loader, and is usually
slightly smaller than the equilibrium hopper. The equilibrium hopper must be
sized to hold the entire catalyst inventory of the unit, plus some contingency.
Both hoppers have relief valves to prevent overpressuring, and a variety of
loading and unloading lines. Instrumentation is limited to several pressure
gauges and a level gauging device. Both hoppers are usually built to withstand
a full vacuum. A steam ejector is used to provide this vacuum to unload
catalyst into the hopper. Refer to Figure 5.
1.
b.
Pressure taps are open and the level gauging devices are working.
c.
The lines and vessels are free of foreign material, especially water
or oil. The air lines should be checked by blowing all lines until they
are clean and dry. The large diameter loading lines can be blown
using the hot air from the regenerator during dryout. Any water in the
lines or hoppers will form a sticky mud which makes normal handling
impossible as this wet catalyst is extremely difficult to remove.
Prolonged blowing with air or cleanout by hand will work, but the
best method is prevention by keeping the system dry.
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hour. Then the gauging hatch is opened and the outage measured with a
hand tape.
2.
b.
c.
Line up the loading line from the hopper to the regenerator start the
carrying air to the line while leaving the block valve under the hopper
closed. Set the air rate to achieve a velocity of ~50 ft/sec (15 m/sec)
in the line or so that the pressure at the end of the line increases by
~1-2 psi (0.1-0.2 kg/cm2) if no FI is provided.
f.
Open the catalyst loading valve at the bottom of the hopper slowly
until the loading line pressure rises 10-15 psi (0.7-1.0 kg/cm2),
signifying that catalyst is flowing through the line. The catalyst block
valve should be 1/4 to 3/4 open. The operator can avoid plugging
the line by carefully watching the pressure gauge and/or carrying air
FI on the loading line at the base of the hopper. With normal loading,
the gauge will oscillate slightly around a pressure about 5-10 psi
(0.35 0.7 kg/cm2) above the regenerator pressure. If this gauge on
the loading line shows an increase in pressure, the catalyst hopper
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block valve should be closed. The carrying air can then clear the line
before excess catalyst can plug it. The optimum catalyst transfer
technique is best determined through trial and error operation for
each specific installation.
g.
h.
i.
Plugging Problems
If there is a problem with the catalyst bridging above the block valve at
the bottom of the hopper, quickly opening and closing the valve 1-2 turns
will usually break the bridge. If this fails, blast the bottom of the hopper
with air.
The catalyst loading line may plug occasionally. When this happens,
close the catalyst block valve at the base of the hopper. Starting at the
regenerator and working back to the hopper, fully open the blast points
one by one. If this fails, pounding on the line with a non-sparking hammer
will work as a last resort. When the pressure gauge on the loading line at
the base of the hopper falls to just above the regenerator pressure, the
line is clear. High pressure air or nitrogen may be used to clear a plug,
but do not exceed safe working pressure of the line.
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3.
4.
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5.
G. SPECIAL OPERATIONS
1.
Catalyst Sampling
When drawing hot catalyst samples, gloves, long sleeve clothing and face
shields should always be worn. Always use a metal container to collect
the sample. Refer to Figure 6 for the valve locations in the following
procedure for drawing catalyst samples.
a.
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Procedures
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b.
(2)
Check that all blast and sample connection valves are closed,
then open sample valve E and steam valve B. Vent steam to
the atmosphere until it is dry.
(3)
(4)
Open sample valve E and reduce the steam flow through valve
B until a small flow of catalyst is obtained. If catalyst does not
flow out of sample valve E, close valve E and blast the
standpipe through steam valve C. Repeat the step until catalyst
can be obtained.
(5)
(6)
(7)
(8)
(9)
(2)
Check that all blast and sample connection valves are closed,
then open sample valve E and air valve A. Vent air to the
atmosphere until it is dry.
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2.
(3)
Close sample valve E and open the nozzle valve F. Air purge
the sample line into the standpipe.
(4)
Open sample valve E and reduce the air flow through valve A
until a small flow of catalyst is obtained. If catalyst does not flow
out of sample valve E, close valve E and A, and blast the
standpipe through steam valve C. Repeat the step until catalyst
can be obtained.
(5)
(6)
(7)
(8)
(9)
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3.
b.
Check that all blast and sample valves are closed, then open sample
valve E and steam valve C. Vent steam to the atmosphere until it is
dry.
c.
Close sample valve E and open nozzle valve F. Purge steam into
the standpipe until the plug is cleared. Do not blast for extended
periods (more than several minutes) with the steam valve full open.
Potential erosion to the standpipe refractory is a concern. It is better
to use short intermittent blasts than one long continuous blast.
d.
e.
f.
Pull the blind in the air heater fuel gas line after the main air blower
is put in operation.
b.
c.
Adjust the inlet damper to direct less air behind the burner block.
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d.
Open the fuel gas line supplying gas to the pilot burner. Press the
button on the local panel supplying power to the pilot ignitor. Use the
observation ports to confirm that the pilot has been lit.
e.
When the pilot has been lit, slowly open the main burner gas valve
until a flame is obtained. Use the observation ports to confirm that
the main burner is firing.
f.
g.
(2)
If the air flow to the regenerator stops for any reason, the fuel
gas supply valves must be shut off immediately.
(3)
The fuel gas to the heater must be free of any liquid. Slugs of
liquid hydrocarbon
temperatures.
4.
can
cause
damage
due
to
high
Flushing System
The flushing oil system is required for two reasons:
a.
The main column bottoms contains catalyst fines which can settle
out and plug instruments and small piping, and which can erode
pumps and control valves.
b.
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The throat bushings and wear rings of the main column bottoms pumps
are flushed with hot heavy cycle oil taken from the circulating HCO pump
discharge. Hot material is used to avoid the thermal stresses which could
result if a cooled oil was injected into the hot pump casing. HCO is used
since LCO would flash and cause pump cavitation. The flush rate is
adjusted by closing the inlet flush valve, observing the static pressure,
and opening the flush valve until the pressure increases about 10 psi (0.7
kg/cm2).
Light cycle oil is used for all other flushing services with the exception that
raw oil is used during startup and can be used during an emergency. On
units with resid feed stocks light gas oil from storage should be used as a
backup instead of raw oil. The flushing oil is taken from the LCO product
cooler outlet and passes through a 30 mesh strainer, which should be
cleaned whenever the P exceeds 15 psi (1 kg/cm2).
The main column bottom level instrument and sight glass similarly flushed
to prevent the accumulation of catalyst. A 1/8 inch (3 mm) restriction
orifice is used to regulate the flow to each location.
The main column bottoms pump packing glands are flushed with LCO
through a lantern ring to cool the shaft and packing. The flush is returned
to the main column with the circulating HCO return. This flush is adjusted
by closing both the supply and return valves, and observing the lantern
ring pressure. The flushing supply valve should then be adjusted so that
the flush oil pressure is 15 psi (1 kg/cm2) higher, while the return valve is
adjusted to maintain the return temperature above 150F (65C). It is
advisable to mark the desired flush oil pressures on the gauges so that
adjustments can be easily made.
157048
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5.
Application
The main air blower discharge check valve is a swinging disc type
valve installed on the discharge of the air blower for safety reasons.
The weight of its disc is balanced to cause the valve to close when
air flow stops, preventing the reverse flow of air and catalyst through
the blower. The valve is equipped with a spring loaded air cylinder
and an oil dashpot. The air cylinder provides an automatic device
which assists the valve to close quickly, while the dashpot dampens
the excessive swinging of the disc under a low or pulsating flow
condition so that the disc does not slam on the seat.
b.
Counterweights
The steel disc of the valve is of heavy construction to resist distortion
from pressure loads or high temperatures. Counterweights are
provided so that the full weight of this disc will not have to be carried
by the gas stream going through the valve. By counterweighting
approximately 75% of the disc weight, the valve opens wide under
the design flow condition and results in minimum pressure drop
through the valve. Counterweighting to hold the valve open when
there is no gas flow through the valve must not be done as this
negates the safety protection of the valve. If the disc is moved off the
seat by manually pulling on the counterweight lever when there is no
gas flow through the valve, the disc should return to the seat freely
and rapidly upon release of the counterweight lever.
c.
Air Cylinder
The external spring loaded air cylinder is designed to assist in the
rapid closure of the valve under emergency conditions. It can not be
used to open the valve and under normal operating conditions with
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Oil Dashpot
The oil dashpot contains a loose fitting piston which moves through
an oil filled cylinder. As the check valve disc moves, it moves the
piston through the oil, forcing oil from one side to the other through a
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If all attempts fail, the lift or feed distributor in the wye should be pulled to
allow entry for manual removal of the catalyst.
NOTE: Always assume the catalyst will be hot and take all necessary
safety precautions.
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Figure 1:
Reactor/Regenerator Section
Products to
Main
Column
Flue
Gas
FIC
Prestripping
Steam
FIC
Stripping
Steam
FIC
Fluffing
Steam
FIC
Atomizing
Steam
Steam
HS
Split Range
Reactor Bypass to
Main Column
FO
FIC
Raw Oil
from Preheat
FC
Torch Oil
from HCO
or Raw Oil
Main Column
Bottoms Recycle
Air
Fuel
Gas
Pilot
Gas
FIC
FIC
Lift
Steam
Startup Naphtha
from Main Column
Overhead
Steam
FIC
Startup
Steam
FIC
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Procedures
Page 83
Figure 2:
Main Column Lower Section
Circulation
Bypass
FIC
LIC
Startup
Filling Line
To LCO
Pumparound
Return Line
Debutanizer
Reboiler
Torch Oil
FIC
MCB
Quench
Reactor
Product
Vapor
Steam to
Superheater
FIC
Startup
Steam
FIC
HS
FO
Raw Oil to
Reactor
FC
Startup Heating
Steam Trap
Startup
Circulation/
Recycle
FIC
FIC
MCB
Product
Torch
Oil
Raw Oil
from
Surge
Drum
Flushing
Oil
CW
FCC-P002
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Figure 3:
Main Column Upper Section
Wet Gas
Compressor First
Stage Spillback
Signal to Wet Gas
Compressor Controls
PRC
PIC
To Flare Header
FC
PSV
CW
LIC
TIC
FIC
FIC
Startup
Circulation
Bypass
FI
Gas
Concentration
Unit Heat
Exchangers
HCN
Stripper
FI
Startup
Fuel Gas
FIC
HCO
HCN
Product
LCO
Stripper
Steam
CW
FIC
LCO
Product
BFW
CW
Preheater
Gas
Concentration
Unit Heat
Exchangers
LCO to
Flushing Oil
Startup
Circulation
Bypass
FCC-P003
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Figure 4:
Reactor Vapor Line Blind
Reactor
Overhead
Vapor
Vent to
Safe
Location
Blind or
Spacer
Steam
DG
PI
Blind or
Spacer
Drains
FCC-P004
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Figure 5:
Catalyst Handling Facilities
To Atmosphere or
ESP Inlet
Ejector
Manual
Gauging
Hatch
Steam
LI
Air Purge
Catalyst
Hopper
GRATING
Plant Air
Plant
Air
Plant Air
RO
Catalyst
Volume Pot
Everlasting
Valves
Plant Air
Catalyst
Makeup
Logic
Controller
Sight Flow
Glass
FI
PG
FIC
Catalyst Loading
and Unloading
from Shipping
Containers
Catalyst Filling
and Withdrawal
To/From
Regenerator
"DA"
Plant
Air
Removable
Spoolpiece
(blankoff
when not
unloading
Ecat)
PI
"DA"
Catalyst Makeup to
Regenerator
FCC-P005
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Figure 6:
Catalyst Standpipe Blast and Sample Point
Plant
Air
Steam
A
B
Strainer
D
C
RO
E
Sample
Point
Catalyst
Standpipe
Min
FCC-P006
157048
Safety
Page 1
SAFETY
A.
GENERAL
Safety is a broad field that covers a variety of topics from fire fighting to toxic
chemicals. Awareness of safety in the refinery is extremely important. As a basis for
a safety program, regulations and guidelines from government and professional
groups should be studied for their effect on this unit and then implemented by the
refinery staff. The staff must develop its own coordinated plant-wide method of
implementing safe and proper procedures, and of handling emergencies, which
should include:
1.
2.
3.
B.
The reactor must be adequately cooled before air is admitted into the vessel. If the
reactor is not sufficiently cooled, auto-ignition of hot coke deposits in the reactor or
its vapor line may result. The reactor must be cooled to below 300F (150C) before
any manways or nozzles are opened. Riser or stripping steam can be used to help
cool the vessel.
157048
Safety
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2.
An air mover should be installed at the vessel's manway to sweep away any
vapors and provide a continuous supply of fresh air.
3.
Responsible personnel must test the atmosphere in the vessel for explosivity,
toxic fumes, oxygen content, dust, etc. Permission for vessel entry should be
given only after this testing has been done.
4.
5.
6.
Personnel entering the vessel should wear a safety harness with a properly
attached safety line.
7.
If the work is to be performed at a high level above the bottom of the vessel,
such as cyclone inspection, scaffolding and support flooring must be built to
prevent falls.
8.
157048
Safety
Page 3
9.
There should be spare pressure demand respirators, complete with their own
separate air supplies, to allow backup personnel to enter the vessel quickly in
case of an emergency. This spare equipment must be compact enough to
allow the users to enter through the manway while wearing the equipment.
10.
C.
D.
The danger of vaporizing water in a liquid-full vessel exists anywhere in the refinery
where a heating source exists and a water pocket can form. In the FCC unit, this is
most likely to occur in the main column bottoms circuit. Anytime a vessel such as a
slurry settler, or a bottoms coke strainer or filter is opened for maintenance,
particular care must be paid to removing all free water and slowly heating the vessel
back up to operating temperature. This is true for the bottoms heat exchangers as
well. If water is heated in a hydrostatically full vessel, it will follow its vapor liquid
equilibrium curve and begin increasing in pressure. If the vessel design pressure is
157048
Safety
Page 4
exceeded and the vessel cracks and relieves the internal pressure, the superheated
water will expand approximately 1600 times in volume, resulting in a catastrophic
failure of the vessel. This is similar to a classic boiler explosion mechanism.
Operating and maintenance procedures must be written and followed to prevent
equipment water pockets and rapid heating.
E.
CHEMICAL HAZARDS
The hydrocarbons, catalyst, and chemicals encountered in an RCC Unit are not
hazardous as long as they are handled according to safe refinery practices. If they
are mishandled, or allowed to escape into the atmosphere, some of them may be a
hazard to the health of anyone in the area. It is recommended that the refiner
determine the allowable safe limits according to laws, rules, and regulations issued
by various agencies which apply to the material in question.
It is suggested that methods ASTM D-170, ASTM E-300, and UOP 516 be followed
regarding sampling techniques.
Hazardous materials present in the RCC Unit, and their emergency treatments,
include:
1.
Catalyst
Fluid cracking catalyst is a fine dust capable of causing eye and lung irritation. When
unloading catalyst cars, drawing samples, etc., goggles or a face shield should be
worn. If the circumstances are such that the working atmosphere becomes dusty, a
dust mask should also be worn. The Material Safety Data Sheet provided by the
catalyst manufacturer needs to be consulted for additional detailed information.
When drawing hot regenerated catalyst samples, gloves and long sleeved clothing
should always be worn. In case of hot catalyst leaks, care must be exercised to
avoid the contact with hot catalyst on unprotected skin.
157048
Safety
Page 5
Loose catalyst is a relatively poor conductor of heat. While the surface of a pile of
catalyst may be cool, the interior may be very hot. Personnel should not walk over or
work around piles of spilled catalyst.
2.
Iron Sulfide
Iron sulfide is a black or gray powder deposit found in vessels where sulfur corrosion
has occurred. It is easily mistaken for coke. The danger of iron sulfide lies in its
"pyrophoric" properties. It will ignite spontaneously when exposed to air, which is
most likely to occur in recently opened refinery vessels.
A vessel suspected of containing iron sulfide must be thoroughly steamed out and
washed with water before air is permitted to enter. Any suspected deposits must be
kept wet until they can be removed and disposed of properly.
3.
Heavy cracked oils are skin irritants. When drawing samples, draining equipment,
and cleaning vessels or exchangers, suitable care should be exercised to avoid skin
contact. In case of actual contact, the skin should be thoroughly washed with hot
soapy water, and any oil-saturated clothing should be removed.
Should any hydrocarbon enter the eye, the recommended First Aid is to wash with a
copious amount of clean water and obtain trained medical assistance as quickly as
possible.
4.
Hydrocarbons in the gasoline boiling range will remove the natural oil from the skin,
leaving it unprotected and subject to irritation or infection. Those gasoline streams
which contain aromatics will be particularly dangerous. Benzene is a poison, and
heavier aromatics have a narcotic effect.
157048
Safety
Page 6
Aromatic Hydrocarbons
a.
Benzene2
The most toxic hydrocarbon present in the unit is benzene. The danger in
exposure to benzene lies in its carcinogenic effect on the body's blood-forming
organs, an effect which is cumulative with each exposure. This aromatic
component is contained in the gasoline and heavy naphtha streams in the unit.
If clothing, including gloves, becomes wet from benzene, immediately remove the
clothing. Wash the skin areas exposed to benzene with soap and water. Take a
complete bath if the body area is wetted with benzene. Do not wear clothing that
has been wet with benzene until the garment has been washed and dried.
Wearing clothing that has been wet with benzene almost assures that the person
will inhale benzene vapors over a long period of time with serious hazard to
health.
Avoid draining benzene on the ground or into the sewers where it can vaporize
and create a health hazard. If benzene is accidentally spilled, flush it from the
area and the sewer catch basin with large quantities of cold water. Do not use hot
water or steam which further vaporizes the benzene. If you must enter an area of
high benzene vapor concentration resulting from a spill, wear a pressure demand
respirator.
For detailed information to take on exposure and potential hazards, consult Chapter XVII of
OHSA Publication 1910.1028, Appendix A.
157048
Safety
Page 7
Though not specifically a health hazard, a problem resulting from benzene entering
the sewer is that benzene is much more soluble in water than any other
hydrocarbons. This places an extra load on the effluent treating system.
b.
These aromatic compounds are present in the gasoline and heavy naphtha streams
in the unit. These compounds are only mildly toxic and do not have the destructive
effect on the blood-forming organs as does benzene. Their principal effect is skin,
eye, and respiratory irritation. If clothing becomes wet with such aromatics, remove
the clothing, bathe, and put on fresh clothing. Avoid breathing aromatic vapors.
All employees should be alerted as to the early signs and symptoms of excessive
absorption of aromatics, and all workers should report such symptoms to the
Medical Department. In addition, all employees should, of course, be advised of the
hazards involved and precautions to be taken when working with aromatics.
6.
The inhalation of any light hydrocarbon vapor should be avoided. Such vapors can
be toxic, since they may contain aromatics, H2S, or other lethal compounds.
A person who has breathed quantities of hydrocarbon vapors should be removed
from the area and kept warm and quiet. If necessary, artificial respiration with or
without the use of oxygen should be administered and medical aid summoned.
Professional medical attention should be obtained at once.
157048
Safety
Page 8
7.
157048
Safety
Page 9
8.
Flue Gas
Flue gas from the regenerator contains little or no oxygen. Asphyxiation can result if
a person enters an improperly ventilated duct or a low area where the high density of
flue gas will cause it to accumulate.
Asphyxiation may be preceded by symptoms of dizziness, headache, or shortness of
breath.
RCC flue gas is very dangerous since it contains carbon monoxide, which is toxic. A
concentration of 0.4% can be fatal in about one hour. One visible symptom of carbon
monoxide poisoning is a bluish-red color of the skin.
First Aid in cases of flue gas asphyxiation or poisoning consists of keeping the victim
warm and administering artificial respiration and oxygen, if necessary, obtain
professional medical attention immediately.
157048
Safety
Page 10
HYDROGEN SULFIDE
EXPOSURE
CALL FOR MEDICAL AID.
VAPOR POISONOUS IF INHALED.
Irritating to eyes.
Move to fresh air.
If breathing has stopped, give artificial respiration.
If breathing is difficult, give oxygen.
IF IN EYES, hold eyelids open and flush with plenty of water.
HEALTH HAZARDS
PERSONAL PROTECTIVE EQUIPMENT: Rubber-framed goggles; approved
respiratory protection.
SYMPTOMS FOLLOWING EXPOSURE: Irritation of eyes, nose and throat. If high
concentrations are inhaled, hyperpnea and respiratory paralysis may occur. Very
high concentrations may produce pulmonary edema.
TREATMENT FOR EXPOSURE (THRESHOLD LIMIT VALUE): 10 ppm
SHORT-TERM INHALATION LIMITS: 200 ppm for 10 min., and 50 ppm for 60 min.
TOXICITY BY INGESTION: Hydrogen sulfide is present as a gas at room
temperature, so ingestion not likely.
LATE TOXICITY: Data not available.
VAPOR (GAS) IRRITANT CHARACTERISTICS: Vapor is moderately irritating such
that personnel will not usually tolerate moderate or high vapor concentration.
157048
Safety
Page 11
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Safety
Page 12
TOLUENE
EXPOSURE
CALL FOR MEDICAL AID.
VAPOR
Irritating to eyes, nose and throat.
If inhaled, will cause nausea, vomiting, headache, dizziness, difficult breathing, or
loss of consciousness.
Move to fresh air.
If breathing has stopped, give artificial respiration. If breathing is difficult, give
oxygen.
LIQUID
Irritating to skin and eyes.
If swallowed, will cause nausea, vomiting or loss of consciousness. Remove
contaminated clothing and shoes.
Flush affected areas with plenty of water.
IF IN EYES, hold eyelids open and flush with plenty of water.
IF SWALLOWED and victim is CONSCIOUS, have victim drink water or milk. DO
NOT INDUCE VOMITING.
HEALTH HAZARDS
PERSONAL PROTECTIVE EQUIPMENT: Air-supplied mask; goggles or face shield;
plastic gloves.
157048
Safety
Page 13
157048
Safety
Page 14
XYLENES
EXPOSURE
CALL FOR MEDICAL AID.
VAPOR
Irritating to eyes, nose and throat.
If inhaled, will cause headache, difficult breathing, or loss of consciousness.
Move to fresh air.
If breathing has stopped, give artificial respiration. If breathing is difficult, give
oxygen.
LIQUID
Irritating to skin and eyes.
If swallowed, will cause nausea, vomiting or loss of consciousness. Remove
contaminated clothing and shoes.
Flush affected areas with plenty of water.
IF IN EYES, hold eyelids open and flush with plenty of water.
IF SWALLOWED and victim is CONSCIOUS, have victim drink water or milk.
DO NOT INDUCE VOMITING.
HEALTH HAZARDS
PERSONAL PROTECTIVE EQUIPMENT: Approved canister or air-supplied mask;
goggles or face shield; plastic gloves and boots.
SYMPTOMS FOLLOWING EXPOSURE: Vapors cause headache and dizziness.
Liquid irritates eyes and skin. If taken into lungs, causes severe coughing, distress,
and rapidly developing pulmonary edema. If ingested, causes nausea, vomiting,
cramps, headache, and coma; can be fatal. Kidney and liver damage can occur.
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ENVIRONMENTAL
Introduction
The refiner today is facing ever tighter environmental regulations. This section will
discuss some of the normal FCCU pollutants and potential methods for their
reduction. It is assumed that each refiner will be familiar with the restrictions placed
on him by the appropriate authorities, as these widely varying and ever-changing
rules are beyond the scope of this book.
There are four primary sources of emissions from the FCCU. These are:
Sour Water
The major source is the regenerator flue gas, it will be discussed first.
Regenerator Flue Gas
The flue gas flow rate is about 105 - 110% (wt) of the inlet air rate on a dry basis.
The composition of the gas will vary with the mode of regeneration, i.e., partial or
complete combustion, and with other factors such as feedstock composition.
Typical uncontrolled emission concentrations are shown in Table 1. Normally, the
breakdown of the flue gas will be 75-80 vol% N2 + Argon, 15-22 vol% CO + CO2
and 8 -12% water vapor.
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TABLE 1
FCCU REGENERATOR UNCONTROLLED
FLUE GAS EMISSIONS FLUE GAS CONCENTRATIONS
Species
CO
Particulates
(note 2)
Bubbling Bed
Partial
Combustion
Bubbling Bed
Complete
Combustion
High Efficiency
Regenerator
Complete
Combustion
90,000 ppm
<500 ppm
<100 ppm
25-50%
20-50%
Opacity
(note 2)
SOx
200-2000 ppm
(note 3)
Hydrocarbons
<200 ppm
<10 ppm
<10 ppm
NH3
<200 ppm
<10 ppm
<10 ppm
NOx
50-100 ppm
150-350 ppm
<60 ppm
Notes:
1.
2.
3.
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2.
Unburned hydrocarbons
3.
4.
Water vapor
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Each of these would have a separate solution, and would normally be accompanied
by other problems. Large amounts of catalyst fines from the stack could indicate
excessive attrition or poor cyclone performance. If the plume were caused by
unburned hydrocarbons, this would indicate poor regenerator operation.
Control of condensables such as SOx are discussed elsewhere in this section.
Water vapor is sometimes mistaken for catalyst fines. This vapor usually does not
cause problems meeting environmental regulations and it should not be excessive;
large increases in water output should be investigated if the water vapor rate is
excessive.
Sulfur Oxides
The flue gas sulfur oxides are formed when sulfur in the coke is oxidized to SOx in
the regenerator. These oxides are primarily SO2 (~90%), with lesser amounts of
SO3 (~10%); the total SOx increases as feed sulfur increases and depends on the
type of compounds containing the sulfur.
There are basically two methods of reducing SOx besides feed pretreatment: using
a catalyst additive, i.e. a SOx control catalyst" and wet gas scrubbing (dry
scrubbing with limestone has also been used, but it is impractical for most refiners).
The SOx control catalyst additive is injected independent of the FCC catalyst (a
small injection device is required) and is typically 3-10% of the catalyst inventory.
The additive adsorbs SOx in an oxidizing environment (regenerator) and liberates
sulfur as H2S in a reducing environment (reactor). SOx control additives can
typically remove 10-20 lb SOx/lb additive down to a limit of ~300 vppm in the flue
gas. This process relies on oxidizing the SO2 to SO3 and is therefore typically more
effective in a complete combustion unit with excess oxygen present.
UOP has acquired the right to license the Exxon Wet Gas Scrubbing (WGS)
process (see Figure 1) to UOP-licensed FCC or RFCC units. The WGS process
removes both SOx and particulates from the FCC or RFCC flue gas. The WGS uses
a venturi device which provides intimate contacting of the flue gas with a mildly
alkaline solution. The system can also tolerate large solids carryover from the
regenerator if an upset should occur. The catalyst fines are removed as moist filter
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cakes and the water effluent contains dissolved salts (sodium sulfate). Wet gas
scrubbing can remove up to 90% of the SOx from the flue gas down to <50 vppm.
Precise economic comparisons between using a SOx control catalyst and the WGS
process are difficult because the value assigned to particulates removal has a major
effect on the selection. In general, the SOx control catalyst will be more attractive at
low-to-moderate amounts of SOx removal (below 1000 vol ppm) and the WGS is
more attractive for removing large quantities of SOx (above 1500 vol ppm) or for
meeting very low SOx emissions (<200 vppm). Between 1000 and 1500 ppm of SOx
removed, the choice depends on a number of factors including variability of installed
cost, presence of existing particulate removal equipment, local environmental laws,
utility and chemical costs and relative amount of SOx removal.
Nitrogen Oxides
The amount of NOx emitted from the regenerator is highly dependent upon several
variables such as mode of operation, regenerator style, excess O2, promoter
concentration, coke distribution, feed nitrogen, and dense bed temperature. Studies
have shown that about half of the feed nitrogen goes to coke on catalyst, but only
about 10% of the nitrogen in coke goes to NOx. It is believed that the NOx emission
is limited by the reaction of CO + NO to form N2 and CO2. Thus, when Pt CO
promoter is added to a unit, CO is converted to CO2 so quickly that there is less CO
available to react with the NOx and NOx emissions increase. In a partial burn
operation, there is always CO available to react with the NOx formed so emissions
are lower. Good coke and air distribution is important so that concentrations of CO,
O2 and NOx are evenly distributed throughout the regenerator. There are
fundamental differences in the operation of a bubbling bed operating in full
combustion with CO promoter and a high efficiency regenerator operating in full
combustion without the need for CO promoter.
Bubbling Bed Regenerator
The bubbling bed type regenerator burns coke from spent FCC catalyst in a backmixed dense phase fluidized bed. The regenerator consists of a closed cylindrical
pressure vessel sized to contain a dense phase fluidized bed of catalyst in the
bottom of the vessel and multiple sets of cyclone separators within the dilute phase
existing in the upper portion of the vessel.
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Spent catalyst enters the regenerator at the side of the vessel at the surface of the
fluidized dense phase of catalyst. Air for coke combustion is distributed uniformly
across the cross-section of the vessel near the bottom of the fluidized bed through
an air distributor. The carbon burning reactions proceed largely in series, with coke
burning to CO first and then CO burning to CO2. Since the fluidized bed is
substantially back-mixed, there is a rather wide distribution of residence times for
both the combustion reactants and products. Further, since fluidized dense beds
mix better vertically than laterally, it is difficult to mix reactants (air and coke)
uniformly across the cross-section of the vessel. This leads to non-uniform burning
profiles and requires longer average residence times, higher quantities of excess
oxygen and higher levels of Pt combustion promoter to assure that the catalyst is
burned clean (regenerated fully) and that CO is fully converted to CO2 to avoid
exceeding CO emission limits. This combination of factors, i.e. long residence
times, non-uniform burning profiles, higher required levels of excess oxygen (~2
mol%), and higher required levels of Pt combustion promoter, result in this style of
regenerator typically producing on the order of 3 to 4 times the NOx emissions
relative to the equivalent High Efficiency Combustor style regenerator.
Combustor Style Regenerator
The High Efficiency Combustor style regenerator burns coke from the spent catalyst
in a quasi-plug flow fast fluidization burning zone. The High Efficiency style
regenerator is divided into two separate zones. The lower section is the combustor
zone where the coke burning occurs. The upper section of the regenerator (second
zone) serves to hold a reservoir of regenerated catalyst and also contains multiple
sets of cyclones in the dilute phase of the upper regenerator. Very little, if any, coke
burning occurs in this upper portion of the regenerator vessel.
Spent catalyst (carrying the coke), air and a substantial quantity of hot clean
regenerated catalyst are mixed together in the bottom of the combustor. The
combustor vessel is sized so that it operates in the velocity and density regime
characterized as fast fluidization. This permits quasi-plug flow transport of material
from the bottom of the combustor vessel upward and out to the upper regenerator
through a vapor/catalyst disengaging device. The moderate operating density of the
combustor (burn zone) permits rapid and uniform mixing of material entering the
bottom of the combustor. The recycle of hot regenerated catalyst permits a degree
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of control over residence time and initial rates of coke combustion. The quasi-plug
flow behavior of the fast fluidized bed assures relatively narrow and controlled
residence time distributions. Overall, the High Efficiency Combustor style of
regenerator provides better control of the burning zone.
The results of the better (or more efficient) control of the burn zone in the
Combustor style regenerator are that:
Oxygen is used more efficiently so that lower levels of excess oxygen are
required to completely burn the coke to CO2 while minimizing CO emissions
Generally Pt combustion promoter is not needed (at design rates) to accelerate
the burn to completion because hot recycled catalyst is used to increase the
burning rate by preheating the combustion reactants (air and coke on spent
catalyst)
The preheating effect of recycling hot regenerated catalyst, combined with the
efficient mixing and uniform residence time distribution in the combustor permits
the time spent in the combustor to be minimized
Plant Upsets
The values given for pollutant concentration in Table 1 are for normal plant
operation. During upsets these numbers may be grossly exceeded. An example of
this would be an oil reversal into the regenerator. Massive amounts of hydrocarbons
may be emitted. While the FCCU has been designed for safe operation, something
as simple as a sticky slide valve may thwart initial corrective action. The best way to
minimize these upsets is careful attention to the unit, with well trained operators that
understand what action should be taken, and why it is done.
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Pollutant
Sulfide, ppm
Ammonia, ppm
Cyanide, ppm
Phenols, ppm
Hydrocarbons, ppm
3000 4000
1000 2000
40 150
100 300
100 2000
3000 4000
1000 2000
30 50
200 600
100 2000
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Some refiners do not show pollutant levels as high as the values given in Table 2,
especially if the feed sulfur or nitrogen is low. The difference between the partial
and complete combustion mode of regenerator operation would involve oxygen
carryover with the regenerated catalyst, different oxidation levels in the regenerator
and other factors. The normal disposal method for the sour water is a sour water
stripper. The overhead vapor stream from the stripper is normally sent to a Claustype unit, although in some cases it may be simply burned. The stripper bottoms is
sent to waste water treatment; it has also been used for the crude unit desalter.
MCB Catalyst Fines
Catalyst fines leaving the reactor with the hydrocarbon product are concentrated in
the bottom of the main column and leave the unit with the bottoms product. Some of
these fines settle out in the product tank so that the tank needs to be cleaned
occasionally. The oil soaked fines removed from the tanks are considered
hazardous waste and must be disposed of properly. Catalyst fines in the bottoms
product can also cause problems with heaters and boilers firing heavy fuel oil.
Because of the high cost of tank cleaning and problems with downstream heaters
catalyst fines removal technology is being added or considered by many refiners.
UOP, through an alliance with Pall Corporation, offers filtration technology capable
of reducing the fines in the bottoms product to less than 50 wppm. Cyclonic
separation devices and slurry settlers are also in use but are less effective.
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