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Republic of Iraq

Ministry of Higher Education and


Scientific Research
University of Technology
Chemical Engineering Department

MODELING AND SIMULATION OF


FCC RISERS
A RESEARCH
SUBMITTED TO
THE CHEMICAL ENGINEERING DEPARTMENT
OF THE UNIVERSITY OF TECHNOLOGY IN THE
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE
OF
HIGHER DIPLOMA
IN CHEMICAL ENGINEERING
(PETROLEUM REFINING AND GAS TECHNOLOGY)

By
WALEED KHALID FADHIL
B.Sc. in Chem. Eng. 1998

March 2012

80

Dedicated to
My Family With My Deep Love

FCC riser
Plug flow reactor
VGO feed Light gases Gasoline
Coke Four lumps model .

.
UOP ,
.
MxR chamber ,
. worksheet

.

II

ACKNOWLEDGMENTS
First of all, thanks to Allah, who enabled me to achieve this research.
I wish to express my sincere gratitude and thankfulness to my
supervisor Dr. Shakir M. Ahmed for his kind supervision and continuous
advices during the research.
My grateful thanks to Prof. Dr. Mumtaz A. Zablouk, the Chairman of
the Department of Chemical Engineering at the University of Technology
for the provision of research facilities.
Special thanks to Assist. Prof. Dr. Mohammed F. Abid for his help
and support.
I would like to express my sincere appreciation to Assis. Lec. Farooq
A. Mehdi for his help. Also, my respectful regards to all the staff of
Chemical Engineering Department of University of Technology.
And finally my special thanks to my family for their support and
encouragement.

III

ABSTRACT
In the present work a mathematical model for the riser reactor of Fluid
Catalytic Cracking has been developed. The riser is considered as a plug
flow reactor incorporating the four lumps model for kinetics of cracking
reactions. Catalyst deactivation function is calculated based on linear
relationship between the catalyst coke content and its retention activity.
The model has been validated using the plant data of a commercial FCC
unit with RxCat technology developed by UOP. The model can predict the
mixing temperatures, at MxR chamber and riser inlet; also shows the
physical performance and productivity all over the riser height. An
interactive excel worksheet is constructed and used as a powerful tool for
solving the model equations and studying the effect of any change in
operating variableson the unit performance.

IV

CONTENTS

Certification

Acknowledgements

III

Abstract

IV

Contents

List of Figures

VII

List of Tables

IX

Nomenclature

CHAPTER 1Introduction

1.1.

Introduction

1.2.

Aim and scope of Work

CHAPTER 2Literature Survey

CHAPTER 3Mathematical Modeling

10

3.1.

Introduction

10

3.2.

Reactor / Regenerator Material & Energy Balances

10

3.2.1. Material Balance

11

3.2.1.1. Reactor Material Balance

11

3.2.1.2. Regenerator Materials Balance

12

3.2.2. Energy Balance

3.3.

13

3.2.2.1. Reactor Energy Balance

13

3.2.2.2. Regenerator Energy balance

13

Riser model

14

3.3.1. Model Assumptions

14

3.3.2. Cracking Reaction Kinetics

15

3.3.3. Concentration, Temperature, Pressure and Coking


time Profiles in the Riser

17

3.3.4. Catalyst Deactivation

18

3.3.5. Riser Hydrodynamics

19
V

3.3.6. Mixing Temperatures

21

3.4.

Heat of Combustion at the Regenerator

23

3.5.

Model Solution

23

CHAPTER 4 Results and Discussion

26

4.1.

Introduction

26

4.2.

Case Study

26

4.3.

Model Results

28

CHAPTER 5 Conclusions and Recommendations

38

5.1.

Conclusion

38

5.2.

Recommendations for FutureWork

39

Appendix A -Fluidized Catalytic Cracking Technologies

A-1

Appendix B - Variables of FCCunits

B-1

Appendix C - Computer Programs

C-1

Appendix D -Glossary of Terms Used In This Work

E-1

References

R-1

VI

LIST OF FIGURES
Figure No.

Title

Page No.

Figure 1.1

Fluid Catalytic Cracking Unit

Figure 3.1

schematic of FCCU reactor/regenerator system


used in present model

11

Figure 3.2

12

Figure 3.3

Input and output streams for reactor and


regenerator in FCCU
A volume element in the riser reactor

Figure 3.4

Schematic of four lumped reactions

16

Figure 3.5

Mathematical representation of reactor riser


used in the model

21

Figure 3.6

25

Figure 4.1

computational flow diagrams for riser reactor


model
Four lump concentration profile vs. riser height

Figure 4.2

Riser temperature profile

28

Figure 4.3

Riser pressure profile

30

Figure 4.4

Gas phase molecular weight vs. riser length

30

Figure 4.5

Gas phase density vs. riser height

30

Figure 4.6

Gas phase mass rate vs. riser height

31

Figure 4.7

Slip factor vs. riser height

32

Figure 4.8

Gas phase and catalyst velocities vs. riser


height
Gas phase and catalyst residence times vs. riser
height
Gas phase void fraction vs. riser height

32

Figure 4.9
Figure 4.10

VII

14

28

33
34

Figure No.

Title

Page No.

Figure 4.11

Predicted catalyst activity along the riser


height

34

Figure 4.12

Gasoline yield vs. feed conversion

35

Figure 4.13

Feed conversion vs. riser height

35

Figure A-1(a) Stacked Reactor regenerator configuration

A-2

Figure A-1(b) Side by side Reactor regenerator configuration

A-2

Figure A-2

KBRs counter-current regeneration design

A-5

Figure A-3

Lummus FCCU Process Flow Diagram

A-7

Figure A-4

S&W / IFP FCCU design

A-10

Figure A-5

Mix zone temperature control & Feed injection


nozzle

A-11

Figure A-6

Shells FCC & MILOS-FCC designs

A-13

Figure A-7

A-14

Figure A-8

PentaFlow Packing & Feed nozzels


configurations
UOPs reactor/regenerator FCCU design

Figure B-1

FCC reaction network

B-4

Figure B-2

Principal Reactions in Fluid Catalytic Cracking

B-5

Figure B-3

Evolution in structure of FCC catalysts before


1990
Catalyst activity retention vs. Carbon on
regenerated catalyst
Constructed Excel worksheet For FCC unit

B-6

Figure B-4
Figure C-1

VIII

A-16

B-8
C-8

LIST OF TABLES

Table No.

Title

Page No.

Table 1.1

Gasoline Pool Example

Table 4.1

Kinetic parameters with Modified frequency


factors used in present model

27

Table 4.2

Mixing temperatures at MxR chamber and


Riser inlet temperature

27

Table 4.3

Model predicted and plant values comparison

36

Table 4.4

Case study results

36

Table A-1

KBR & ExxonMobil FCCU Technologies

A-6

Table A-2

LUMMUS FCCU Technologies

A-8

Table A-3

S&W / IFP FCCU Technologies

A-11

Table A-4

Shells FCCU Technologies

A-14

Table B-1

Feedstock Crackability

B-2

Table B-2

Typical FCC unit products

B-3

Table B-3

Effect of operating Temperature of the reactor


on the performance of a fluidized bed cracking

B-11

Table C-1

Variables used in Polymath program

C-1

IX

NOMENCLATURES

Riser cross section area (m2)

Ar

Archimedes number (-)

Cp

Heat capacity (kJ/kg.K)

Riser diameter (m)

Particle diameter (m)

Ej

Activation energy (kJ/kmole)

Fr

Fround number

Heat enthalpy (kJ/s)

Hj

Heat enthalpy of jth reaction (kJ/kg)

Kj

Kinetic reaction rate constant of jth reaction

Koj

frequency factor or preexponential factor for jth reaction

Kuop

UOP characterization factor

Riser Height (m)

MW

Molecular weight (kg/kg mole)

Mass rate (kg/s)

Riser pressure (Pascal)

Universal ideal gas constant (atm m3/kmole K)

Re

Reynold number

Sulfur (kg/s)

Sph

Sphericity

SG

Feed specific gravity

Temperature (K)

Gas phase residence time (second)

tc

Catalyst residence time (second)

Velocity (m/s)

WHSV

Weighted hourly space velocity (1/hr)

Conversion (wt %)

yi

Weight fraction of ith lump


X

Axial position of riser height (m)

Greek letters

Voidage

Catalyst deactivation function

Density (kg/m3)

Slip factor
Catalytic cracker efficiency

Difference

Viscosity (Pa.s)

Ratio of frequency factor of jth lump reaction per frequency


factor of VGO to gasoline reaction

Subscripts
air

Air for regeneration

cok

Coke

cat

Catalyst

ds

Dispersion or Atomizing steam

Feed

fg

Flue gas

fl

Feed in the liquid phase

fv

Feed in the vapor phase

Gas phase

in

Flowing in

1,2,3,4 and 5 for the reactions VGO to GLN, VGO to LGS,


VGO to COK, GLN to LGS, and GLN to COK respectively

ls

Lifting steam

mix1

Mixing temperature at MxR chamber

mix2

Mixing temperature at riser inlet


XI

Superficial

out

Flowing out

Particle

pr

Products

rcat

Regenerated catalyst

rcoke

Coke on the regenerated catalyst

Steam

si

Riser and reactor inlet steam

so

Riser and reactor outlet steam

scat

Spent catalyst

scok

Coke on the spent catalyst

Terminal velocity

xcat

Carbonized catalyst

xcok

Coke of carbonized catalyst

Abbreviations
AF

Advanced Fluidization

BPSD

Barrel Per Stream Day

CB & I

Chicago Bridge & Iron

CCR

Conradson Carbon Residue or Catalyst Circulation Rate

CFD

Computational Fluid Dynamics

COK

Coke

CRC

Coke on the Regenerated Catalyst

CSC

Coke on the Spent Catalyst

C/O

Catalyst to Oil ratio

E-cat

Equilibrium Catalyst

EMRE

ExxonMobil Research and Engineering

FCC

Fluidized Catalytic Cracking

FCCU

Fluidized Catalytic Cracking

FEED

Front End Engineering Design


XII

FF

Fresh Feed

GLN

Gasoline

HCO

Heavy Cycle Oil

IFP

Institute France Petrol

KBR

Kellogg Brown & Root

LCO

Light Cycle Oil

LGS

Light Gases

LPG

Liquefied Petroleum Gas

MTC

Mix Temperature Control

RON

Research Octane Number

RSS

Riser Separator Stripper

ODE

Ordinary Differential Equation

TSS

Third Stage Separator

UOP

Universal Oil Products

VDS

Vortex Disengaging System

VGO

Vacuum Gasoil

VSS

Vortex Separation System

XIII

CHAPTER ONE

INTRODUCTION

Chapter One
1.1.

Introduction

INTRODUCTION

Fluid catalytic cracking (FCC) technology is a technology with more than


60 years of commercial operating experience. The process is used to
convert higher-molecular-weight hydrocarbons to lighter, more valuable
products through contact with a powdered catalyst at appropriate
conditions. The primary purpose of the FCC process has been to produce
gasoline, distillate, and C3/C4 olefins from low-value excess refinery gas
oils and heavier refinery streams. FCC is often the heart of a modern
refinery because of its adaptability to changing feedstocks and product
demands and because of high margins that exist between the FCC
feedstocks and converted FCC products. As oil refining has evolved over
the last 60 years, the FCC process has evolved with it, meeting the
challenges of cracking heavier, more contaminated feedstocks, increasing
operating flexibility, accommodating environmental legislation, and
maximizing reliability

[1]

. In the environmental protection field, FCC unit

play a significant role by producing the gasoline with lower benzene


content as clarified in the gasoline pool example (Table 1.1)
Refineries use fluid catalytic cracking to correct the imbalance between the
market demand for gasoline and the excess of heavy high boiling range
products resulting from the distillation of crude oil. [2]
The fluid catalytic cracking (FCC) unit consists of a reaction section and a
fractionating section that operate together as an integrated processing unit.
The reaction section includes two reactors, the riser reactor, where almost
all the endothermic cracking reactions and coke deposition on the catalyst
occur, and the regenerator reactor, where air is used to burn off the
accumulated coke. The regeneration process provides, in addition to
reactivating the catalyst powders, the heat required by the endothermic
cracking reactions, (Figure 1.1). [3]
1

Chapter One

Introduction

Figure 1.1: Fluid Catalytic Cracking Unit [4]

Table 1.1
Gasoline Pool Example [5, 6]
Gasoline
source
FCC
Reformate
Alkylate
Isomerate

% vol.
of Pool

% vol.
Bz.

RON

35
30
20
15

0.8
4.5
0
0.6

88
94
94
89

% vol
Pool
RON
33.8
31
20.6
14.6

Reformer

Alkylation

FCCU

Isomerization

Chapter One

Introduction

A modern FCC unit comprises different sections such as a riser reactor, a


stripper, a disengager, a regenerator, a main fractionator, catalyst transport
lines (spent catalyst standpipe and regenerated catalyst standpipe) and
several other auxiliary units such as: cyclones, air blower, expander, wet
gas compressor, feed pre-heater, air heater, catalyst cooler, etc

[7]

. The

proprietary new designs and technologies that have been developed by the
major FCC designers and licensors are briefly described in the
Appendix A.
Because of the importance of FCC unit in refining, a construction of
mathematical model that can describe the dynamic behavior of FCC unit
equipments in steady state is very important. Accurate model can be used
as a powerful tool to study the effect of process variables on the
performance and productivity of the system [7].
Simulation studies also provide guidance in the development of new
processes and can reduce both time and investment

[8]

. The effective

simulation of the fluid catalytic cracking operation requires knowledge of


reaction kinetics, fluid dynamics, feed and catalyst effects [9].
The riser reactor is probably the most important equipment in a FCC unit.
The modeling of a riser reactor is very complex due to complex
hydrodynamics and unknown multiple reactions, coupled with mass
transfer resistance, heat transfer resistance and deactivation kinetics. A
complete model of the riser reactor should include all the important
physical phenomena and detailed reaction kinetics [10].

Chapter One
1.2.

Introduction

AIMS AND SCOPE OF WORK


The main objectives of the present work are:

1. A short literature review of previous FCC riser modeling and


simulation studies.
2. Formulation of a mathematical model that can describe the reaction
kinetics and physical performance in the riser section of FCC unit by
using four lump model for kinetics description with linearly scaled
up frequency factors of Arrhenius equations.
3. The quantities of lifting and dispersion steam in all calculation steps
will be considered.
4. Model validation against a commercial scale FCC unit designed by
UOP is to be investigated.
5. An interactive excel worksheet for solving model equations and
studying the unit performance is to be constructed.

CHAPTER TWO

LITERATURE SURVEY

Chapter Two

Literature Survey

Modeling of riser reactor is very complex due to complex


hydrodynamics, unknown multiple reactions coupled with mass transfer and
heat transfer resistances. Also, the conditions keep changing all along the riser
height due to cracking which causes molar expansion in the gas phase and
influences the axial and radial catalyst density in the riser. In the literature,
numerous models of FCC riser are available with varying degrees of
simplifications and assumptions.
Ali et al. (1997)

[3]

; Arbel et al. (1995)

[11]

; Han et al. (2001)

[12]

developed a mathematical model of an industrial FCC unit, includes one


dimensional mass, energy, and species balance; their models was based on the
assumption of instantaneous and complete vaporization of the feed when
contacted with hot regenerated catalyst assuming modern high efficiency feed
injection systems. These types of modeling are normally simple to formulate
and to solve. They are more suitable when the interest is to explore the
influence of operating conditions, test a kinetic model or when the simulation
includes not only the riser, but also other equipments like the regenerator and
the stripper. The simplest kind of these models is the homogeneous version,
where both the vapor phase (hydrocarbon feed & products vapors) and the
solid phase (catalyst & coke) are moving at the same velocity. The
heterogeneous version considers different velocities for the two phases,
resulting in different residence times for each phase inside the riser.
The simplest hydrodynamic models assume steady state ideal plug flow
reactor.

Chapter Two

Ali et al.

Literature Survey
[3]

and Han et al.

[12]

used the four-lump kinetic models to

describe the behavior of cracking reactions, while Arbel et al.

[11]

used more

complex ten-lump model.


Theologos and Markatos (1993)

[13]

proposed a three dimensional

mathematical model considering two phase flow, heat transfer, and three lump
reaction scheme in the riser reactor. The authors developed the full set of
partial differential equations that describes the conservation of mass,
momentum, energy and chemical species for both phases, coupled with
empirical correlations concerning interphase friction, interphase heat transfer,
and fluid to wall frictional forces. The model can predict pressure drop,
catalyst holdup, interphase slip velocity, temperature distribution in both
phases, and yield distribution all over the riser. Theologos et al. (1997)
coupled the model of Theologos and Markatos (1993)

[13]

[14]

with a ten lump

reaction scheme to predict the yield pattern of the FCC riser reactor.
An integrated dynamic model for the complete description of the fluid
catalytic cracking unit (FCC unit) was developed by Bollas et al. (2002)

[15]

the model simulates successfully the riser and the regenerator of FCC and
incorporates operating conditions, feed properties and catalyst effects.
Erthal et al. (2003)

[16],

developed a one dimensional, mathematical

model, they considered in their model gas-solid flow that occurs in FCC risers,
two equations of momentum conservation applied to the compressible gas
flow and solid flow respectively, the model considers also the drag force and
heat transfer coefficient between two phases; four lump model used for
cracking reactions description.

Chapter Two

Literature Survey

Souzaa et al. (2003)

[17]

, combined a 2-D fluid flow field with a 6- lumps

kinetic model and used two energy equations (catalyst and gas oil) to simulate
the gas oil cracking process inside the riser reactor.
Das et al. (2003)

[18]

, performed the three-dimensional simulation of an

industrial-scale fluid catalytic cracking riser reactor using a novel densitybased solution algorithm. The particle-level fluctuations are modeled in the
framework of the kinetic theory of granular flow. The reactor model includes
separate continuity equations for the components in the bulk gas and inside the
solid phase.
Berry et al. (2004)

[19]

, modified the two-dimensional hydrodynamic

model to make it predictive by incorporating the slip factor for the calculation
of the cross-sectionally averaged voidage. The model has been coupled with
the four-lump kinetic model to predict the effect of operating conditions on
profiles of conversion, yield, temperature and pressure in the riser.
Hassan (2005)

[20]

, developed Material and energy balance calculations to

design Fluidized catalytic cracking (FCC) unit from Iraqi crude oil. She used
the visual basic program in her work.
With regard to reaction and kinetics, Xu et al. (2006)

[21]

proposed a

seven lump kinetic model to describe residual oil catalytic cracking, in which
products especially coke were lumped separately for accurate prediction.
Because in recent studies, kinetics was developed accounting for coke
formation leading to catalyst deactivation. The reactor block is modeled as a
combination of an ideal Plug Flow Reactor (PFR) and a Continuously Stirred
Tank Reactor (CSTR).

Chapter Two

Literature Survey

On the other hand, Krishnaiah et al. (2007) [22], a steady state simulation
for the fluid cracking was investigated, the riser reactor was modeled as a plug
flow reactor incorporating four lump model for cracking reactions; they
studied the effect of the operating variables on FCC unit performance, a
catalyst to oil ratio, air rate and gasoil inlet temperature have been chosen as
operating variables.
Souza et al. (2007)

[23]

, bi dimensional fluid flow combined with six

lumps kinetic model and two energy equations are used to model the gasoil
mixture flow and the cracking process inside the riser reactor.
Gupta et al. (2007)

[24]

proposed a new kinetic scheme based on

pseudocomponents cracking and developed a semi-empirical model for the


estimation of the rate constants of the resulting reaction network. Fifty
pseudocomponents (lumps) are considered in this scheme resulting in more
than 10,000 reaction possibilities. The model can be easily used to incorporate
other aspects of the riser modeling.
Ahari et al. (2008) [25], a one dimensional adiabatic model for riser reactor
of FCC unit was developed, the chemical reaction were characterized by a
four lump kinetic model, in their study, four cases of industrial riser operating
conditions have been adopted and the modified kinetic parameters are used to
eliminate the deviations between calculated and real values, also simulation
studies are performed to investigate the effect of changing process variables.
Based on Ahari et al. (2008) [25] study, Heydari et al. (2010) [26] performed
an excessive analysis to gasoline yield throughout the riser with respect to
different inlet mixing temperatures, different feed rates and different catalyst
to oil ratios.
8

Chapter Two

Shakoor (2010)

Literature Survey
[27]

developed a computer program using MATLAB 7

software to determine the rate constants of FCC unit cracking reactions


represented by six lump model and at any certain temperature.
Baurdez et al. (2010)

[28]

proposed a method for steady-state/transient,

two phase gassolid simulation of a FCC riser reactor. Authors used a simple
four lump kinetic model to demonstrate the feasibility of the method
Osman et al. (2010) [29] developed a kinetic model to simulate the riser of
a residue fluid catalytic cracking unit (RFCC) at steady state. The model based
on combination the material and energy balance equations with seven lump
model and a modified two dimensional hydrodynamic model. Simulation has
been performed based on the data from an operating unit at Khartoum
Refinery Company (KRC). MATLAB environment has been used to solve and
analyze the kinetic model and process variables.
A control system of a fluidized-bed catalytic cracking unit has been
developed by AL-Niami (2010)

[30]

. In this work the dynamic and control

system based on basic energy balance in the reactor and regenerator systems
have been carried out. For the control system, the important input variables
were chosen to be the reactor temperature and the regenerator temperature.

CHAPTER THREE

MATHEMATICAL
MODELING

Chapter Three
3.1.

Mathematical Modeling

INTRODUCTION

In this chapter, a mathematical model for the riser of an industrial FCC is


developed, based on the reactor/regenerator configuration presented in the
Figure 3.1. The preheated raw oil and steam are introduced into the reactor
riser at a point near the base of the riser above the MxR Chamber. Here, the
feed is contacted with a controlled amount of regenerated catalyst and lift
media from the MxR Chamber. The regenerated catalyst flow is controlled
to maintain a desired reactor temperature, and the spent catalyst
recirculation to the MxR Chamber is controlled manually or by ratio to the
regenerated catalyst flow. Feed and steam are mixed and injected through
the feed nozzles distributors. At the distributors the riser diameter increases
to allow for the expansion of hydrocarbon vapors as the oil is vaporized
when it meets the catalyst. As a result of feed vaporization, the cracking
reactions start and the density of the oil decreases causing an increase in the
velocity of the vapor/gas phase. The increasing gas phase velocity
accelerates the velocity of the catalyst and the riser behaves as a transport
bed reactor. The Gasoil is converted to gasoline range hydrocarbons, light
gases and coke. The cracking reactions by product (coke) gets deposited
on the catalyst surface and decreases its activity as the catalyst moves
toward the exit of the riser. Because the riser volume is small, it limits the
contact time between the catalyst and hydrocarbon to 5 seconds or less, and
prevents over cracking of the feed[10].

3.2.

REACTOR/REGENERATOR

MATERIAL

&

ENERGY

BALANCES
The material and energy balances around the reactor and the
regenerator can be calculated by defining the input and output streams
(Figure 3.2).

10

Chapter Three

Mathematical Modeling

Figure 3.1 schematic of FCC unit reactor/regenerator system used in


present model [31]
3.2.1. MATERIAL BALANCE
The material balance for any system at steady state is defined as:
Mass in = Mass out

3.2.1.1. REACTOR MATERIAL BALANCE


Mass in

= Mass of (feed + steam + regenerated catalyst)

Mass out = Mass of (reactor vapor + spent catalyst + steam)

Where, the oil feed contains small quantity of sulfur, portion of the sulfur
goes with spent catalyst and burned to SO2 in the regenerator, the
remainder exists with products; and steam inlet is equal to summation of
lifting steam, injection steam and stripping steam.

11

Chapter Three

Mathematical Modeling

Assuming steam inlet does not condense and is present in the exit vapor
products at the same rate, therefore reactor material balance can be
expressed as[33]:
mf + m si + mrcat = mpr + mso + mscat

(3.1)

Since, mscat = mrcat + mcokandm si = m so


Then, eq. (3.1) eliminated to:
mf = mpr + mcok

(3.2)

3.2.1.2. REGENERATOR MATERIAL BALANCE


Mass in

= Mass of (spent catalyst + air for coke burning)

Mass out = Mass of (flue gases + regenerated catalyst)


OR
mscat + mair = m fg + mrcat

Flue gases
(mfg)

Radiation losses

(3.3)

Reaction

mscat

Product
vapors
+ steam
(mpr+mso)

Radiation
losses

Combustion
of Coke

Heat removal
mrcat

Air
(mair)

FEED
(mf)
Steam
(msi)

Figure 3.2 Input and output streams for reactor and regenerator in FCCU

12

Chapter Three

Mathematical Modeling

3.2.2. ENERGY BALANCE


The hot regenerated catalyst supplies the bulk of the heat required to
vaporize the liquid feed to provide the overall endothermic heat of
cracking, and to raise the temperature of dispersion steam and inert gases to
the reactor temperature. [40] The energy balance equation at steady state may
be written as:
Energy in + Energy produced = Energy out + Energy consumed
3.2.2.1. REACTOR ENERGY BALANCE
Energy in

= Energy of (feed + regenerated catalyst + steam)

Energy produced

=0

Energy out = Energy of (reactor vapors + spent catalyst + radiation losses)


Energy consumed

= Heat of reaction

If the Reactor temperature is the reference base temperature, then


-Hfeed - Hsteam + Hregenerated catalyst = H radiation losses + HReaction
Or
Hregenerated catalyst = Hfeed + H steam + Hradiation losses +HReaction

(3.4)

3.2.2.2. REGENERATOR ENERGY BALANCE


Energy in

= Energy (air with moisture + spent catalyst + coke)

Energy produced = Combustion heat of coke


Energy out

= Energy (flue gas with moisture + regenerated catalyst


+removed by catalyst cooler + radiation losses)

Energy consumed = 0

If the Regenerator temperature is the reference temperature then,


Hcombustion of coke = Hcatalyst + Hair + Hsteam+ Hcoke+ H removed +
H radiation losses

(3.5)

13

Chapter Three

Mathematical Modeling

The enthalpy change for the spent and regenerated catalyst is given by
Hspent catalyst

= mcatCpcat(Regen. Temp.- Reactor Temp.)

Hregenerated catalyst = mcatCp cat(Reactor Temp. Regen. Temp.)


At steady conditions,
Hspent catalyst + Hregenerated catalyst = 0

3.3.

RISER MODEL
For numerical computation, riser is divided into equal sized segments

of thickness (dz), forming sequential equal sized volume elements (see


Figure 3.3).

Z=L

dz

Z=0

Figure 3.3 A volume element in the riser reactor

3.3.1. MODEL ASSUMPTIONS


In order to develop a mathematical model for the riser reactor, the
following assumptions are introduced:
14

Chapter Three

Mathematical Modeling

a. One dimensional transported plug flow reactor prevails in the riser


without radial and axial dispersion
b. Steady state operation
c. The riser wall is adiabatic.
d. Viscosities and heat capacities for all components in vapor phase are
constant along the riser.
e. The pressure change through the riser length is due to the static head of
catalyst in the riser.
f. The coke deposited on the catalyst does not affect the fluid flow
g. Instantaneous vaporization occurred in entrance of riser.
h. Each volume element is assumed to contain two phases (i) solid phase
(catalyst and coke) and (ii) gas phase (vapors of feed and product
hydrocarbon, and steam).
i. Each volume element, solid and gas phases are assumed to be well
mixed so that heat and mass transfer resistances can be ignored, and the
two phases have the same temperature.
j. The gas-solid flow is fully developed along all the riser height.

3.3.2. CRACKING REACTIONS KINETICS


The FCC process involves a network of reactions producing a large
number of compounds. Therefore, lumping models can be used to describe
the reaction system in terms of the feed and a defined number of products,
the agglomeration of many chemical compounds into a single compound
(called a lump),should exhibit some or several common properties(i.e.
boiling point, molecular weight, reactivity).In this work four lump model
scheme has been selected (Figure 3.4). This scheme consists of (VGO feed,
Light gases, Gasoline, and Coke), it is more realistic and simple to solve,
with more lumps, the mathematic becomes more complicated.

15

Chapter Three

Mathematical Modeling
K2

Light gases
K4

VGO

K1

Gasoline
K5

K3

Coke

Figure 3.4 Schematic of four lumped reactions

According to this scheme, a part of gasoline is also converted to light gases


and coke. It is assumed that cracking reaction rate is second order with
respect to Gasoil, and first order with respect to Gasoline, and the reactions
take place only in the vapor phase[3]. Rate constants (Kj) for cracking
reactions follow the Arrhenius dependence on temperature (equation 3.6).
(3.6)

Where, the kinetic parameters (Koj and Ej) for cracking reactions are
selected from the literatures[23, 25]. In order to fit the predicted gasoline yield
with industrial gasoline yield, the selected frequency factors can be scaled
linearly by dividing each one by the modified frequency factor (Ko1)ofthe
reaction feedstock gasoline:
(3.7)

While, the selected activation energies are used directly in the industrial
scale unit model. This approach has been adopted by Ancheyta (2011) [34].

16

Chapter Three

Mathematical Modeling

3.3.3. CONCENTRATION,

TEMPERATURE,

PRESSURE

AND

COKING TIME PROFILES IN THE RISER


In order to calculate the concentration profile for each lump
throughout the riser height, a differential material balance can be applied
along the riser, the following set of equations is obtained[3, 22, 33]:
For VGO lump:
=

For gasoline lump:

For light gases lump:

For coke lump:

(3.8)

(3.10)

(3.11)

(3.9)

The temperature profile along the riser can be calculated using following
energy balance equation [3, 22, 33]:
=

+ + )
+( + )

(3.12)

Where, the term { [(K1H1+K2H2+K3H3) y12 + (K4H4+K5H 5) y2]}


represents the energy absorbed by endothermic reaction of vapor phase in
the riser [16].
The pressure change throughout the riser can be predicted by[34]:
=

(1

(3.13)
17

Chapter Three

Mathematical Modeling

The catalyst residence time can be calculated using following equation [33]:
=

+[

(1

(3.14)

The variation of the vapor phase mass flow rate (m g) throughout the riser
can be predicted by the following equation [33]:
=

)+

(3.15)

Where, the quantities of dispersion steam (mds) and lifting steam (mls) that
inlets the riser are controlled as 1wt% and 3.5wt% of the feed rate,
respectively. The vapor phase density considered ideal gas and calculated
by:
=

101325

(3.16)

The average vapor phase molecular weight expressed as [16]:


=

)/

(3.17)

3.3.4. CATALYST DEACTIVATION


The catalyst deactivation function ( )due to coke deposition,
generally, there are two ways of its representation, one that depends on the
catalyst contact time and the other one depends on the catalyst coke
content. Since the functions that depend on the contact time do not account
for the efficiency of the regenerator, i.e. the catalyst activity at the riser
inlet. Therefore, in this work a single deactivation function depending on
the catalyst coke content has been formulated from (Figure B-4) in
appendix B using curve fit technique:
18

Chapter Three

Mathematical Modeling
= 1 45

)+

(3.18)

3.3.5. RISER HYDRODYNAMICS


After complete vaporization of feed, only solid phase (catalyst &
coke) and vapor phase (steam, hydrocarbon feed and product vapor) are
left. Based on the model assumption, the two phases in fully developed
flow, the empirical correlation (equation 3.19) developed by Patience et
al. (1992) for calculating slip factor can be applied. Slip factor, defined as
the ratio of interstitial gas velocity to average solids velocity.

=
Where
And

=1+

5.6

+ 0.47

(3.19)
(3.20)

(3.21)

The superficial gas velocity is calculated by:


=

(3.22)

And the average particle velocity calculated by [25]:


=

(1

(3.23)

By combination of equations (3.19),(3.22) and (3.23), the average void


fraction of the vapor phase can be evaluated by:

19

Chapter Three

Mathematical Modeling
=

Therefore, the gas and particle velocities can be evaluated by:


=

(3.24)
(3.25)

(3.26)

The residence time of the gas phase can be represented as the ratio of
distance and velocity as:
=

(3.27)

In order to calculate the particle terminal velocity, many correlations used


and can be found in the literatures. In general, the terminal velocity is
usually calculated for three zones: Stokes, intermediate and Newton zone,
and it classified according to Archimedes numbers which defines the
border between different zones. The Stokes regime holds for Ar< 32.9,
Intermediate regime is valid for 32.9 <Ar< 106.5, and the Newton regime is
defined for Ar> 106.5. In this work the simple correlation (equation3.29)
for intermediate regime has been employed for calculating Reynolds
number based on particle terminal velocity[35, 36, 37]:

=
=

18 + (2.3348 1.7439
=

20

(3.28)
.

(3.29)
(3.30)

Chapter Three

Mathematical Modeling

3.3.6. MIXING TEMPERATURES


In order to calculate the mixing temperature (Tmix1) at the MxR
chamber, where the hot regenerated catalyst is mixed with the carbonized
catalyst which has the same riser outlet temperature, and the mixed
catalysts are lifted by steam (Figure3.5). The energy balance around MxR
chamber can be applied to obtain the following equation:

+
(

+(
+(

(3.31)

mg
Tout

mscat
mscok
Tout

Regenerator

mcat
mcok
mg
Tmix2

Regenerated
catalyst

mds
Tds
mf
Tfl
API
Cpfv

mcat
mcok
mls
Tmix1

m rcat
m rcok
Trcat

MxR
chamber

mxcat
mxcok
Tout

Carbonized
catalyst

(Lifting steam)

mls
Tls
Figure 3.5 Mathematical representation of reactor riser used in the model
21

Chapter Three

Mathematical Modeling

For calculating the riser inlet mixing temperature (Tmix2), where the
lifting (regenerated/carbonized catalysts + steam) are mixed with injected
(feed + dispersion steam), the energy balance (equation3.32) around the
riser inlet can be formulated.
(

)+

[ 1(1.8

)+

) + 2.32

459.67) 2(1.8

459.67) + 3

(3.32)

Solving equation (3.32) for Tmix2, and taking the positive root for the
quadratic equation gives:
=
Where
= 2.32 3.24

1 2.32 1.8

= 2.32 (459.67)

+ 4
2

(3.33)

(3.34)

2.32 1654.812

1 + 2.32 459.67

3 2.32
+

(3.35)

2 + 2.32

(3.36)

Note that equation (3.33) represents the initial boundary condition to the
differential equation (3.12)

22

Chapter Three
3.4.

Mathematical Modeling

HEAT OF COMBUSTION AT THE REGENERATOR


At the regenerator where coke on the catalyst is burning off, the heat

consumed (kJ/s) for catalyst heating up inside the regenerator can be


calculated:

(3.37)

And the heat consumed (kJ/s) for heating up the coke, air and moisture plus
heat losses and removed are assumed 38% of total heat of combustion of
the coke. Therefore, equation 3.5 becomes:

1 0.38

(3.38)

Therefore, the heat of combustion at the regenerator per 1Kg of coke burnt,
can be calculated as follows:

3.5.

(3.39)

MODEL SOLUTION
A computer program presented in Appendix C for the model

simulation was developed using polymath version 5.1 and Microsoft Excel
worksheet 2007, based on the 4th order Runge Kutta method numerical
technique; and a sequential approach has been chosen in this solution. In
the present work the height of each volume element was kept 5cm. Further
decrease in the height of the volume element had no appreciable effect on
the results.
The sequence of calculation steps is listed below and the flow diagram for
the same sequence is given in Fig. 3.6. The model results and discussions
are presented in chapter four.

23

Chapter Three

Mathematical Modeling

Sequence of calculation steps:


1.

Read the input data required for calculation of MxR chamber


temperature.

2.

Calculate Tmix1 (equation 3.31)

3.

Read the input data required for calculation of riser inlet temperature.

4.

Calculate Tmix2 (equation 3.33)

5.

Read the input initial values of ODEs.

6.

Calculate the variable parameters (, K1, K2, K3, K4, K5, MWg, g,
mg, Uo, Ar, Ret, Ut, , g, U g, Up, X) using the appropriate
correlations. In this step all the calculated variable parameters are
represent the conditions of current volume element. As the conditions
at the exit of current volume element are the same as the conditions at
the inlet of the next volume element, therefore, use these calculated
values as an initial values for calculation the next volume element
conditions, equations (3.6) and (3.15) to (3.30).

7.

Go to the next volume element with (z = z + 0.05).

8.

Calculate the new values of ODEs depending on the calculated values


in step 6, equations (3.8) to (3.14).

9.

Repeat steps 6 - 8 until the sum of increment height equals the height
of the riser.

10. Calculate the yields and conversion at the exit of the riser.
11. Calculate the cracking efficiency, selectivity, WHSV, delta coke,
Hcombustion of coke.

24

Chapter Three

Mathematical Modeling
START

INPUT mrcat , mrcok,Trcat , mxcat , m xcok , Tout , mls , Tls , Cpcat , Cp cok , Cp s
From E. B. Calculate Tmix1, eq. (3.31)
INPUT mf , Tf , Kuop , API , SG , mds , Tds , Cpg
From E. B. Calculate Tmix2, eq. (3.33)
Z=0
INPUT initial values of ODEs from (3.8) to (3.14)
y1=1 , y2= y3= y4= 0 , tc= 0, T = Tmix2, P = Pin

Calculated and updated values , K1, K2 , K3 , K4 , K5, MWg , g


, mg , uo , Ar , Ret , ut , , g , ug , up , X, t
Equations (3.6) and (3.15) to (3.30)
Z = Z + 0.05
Solve above seven ODEs by Runge Kutta method

Z<L

YES

NO

Calculate the yields and conversion


END

Figure 3.6 computational flow diagrams for riser reactor model


25

CHAPTER FOUR

RESULTS AND
DISCUSSIONS

Chapter Four
4.1.

Results and discussion

INTRODUCTION
As discussed in previous chapter, the material and energy balance

equations were combined with reaction kinetics and the hydrodynamic


model equations to obtain a model capable to predicting the yield pattern
along the riser height. In this chapter the proposed model is validated
directly by comparing the model results with plant data. Model results are
plotted in the following figures with a brief discussion. An Excel worksheet
was developed for modeling of new and existing FCC unit, and to predict
the effect of any change in operating parameters on unit performance.

4.2.

CASE STUDY
For model validation, commercial FCC unit (30000 BPSD) designed

to handle hydrotreated VGO feed was selected. The unit operates for
maximum gasoline mode, therefore, no recycle occurs at normal operation
[1]

, with (0.5/1) mixing ratio of carbonized catalyst to regenerated catalyst

at MxR chamber.

Table 4.1 shows the kinetic parameters for cracking reactions with
adjustable frequency factors utilizing the productivity of studied case. This
approach has been adopted by many researchers[25, 26, 34].

26

Chapter Four

Results and discussion

Table 4.1
Kinetic parameters with Modified frequency factors used in present model
Frequency
Activation
Heat of
[16]
factor
energy
reaction[25]
Koj*
Ej
H j
(kJ/kmol)
(kJ/kg)
Gasoil to gasoline
12500
57359
393
Gasoil to light gases
1950
52754
795
Gasoil to coke
16
31820
1200
Gasoline to light gases
2650
65733
1150
Gasoline to coke
550
66570
151
*For feedstock cracking the Koj units are (wtfrac./s); for other lump
cracking the Koj units are (s-1)

4.3.

MODEL RESULTS
Table 4.2 lists the calculated and design values for mixing

temperatures at MxR chamber and riser inlet region.

Table 4.2
Mixing temperatures at MxR chamber and Riser inlet temperature
Present model
Licensor design data
MxR temperature (K)
912.74
912
Riser inlet temperature (K)
833.99
834
Product yield profiles and actual yield values have been modeled at the
riser exit shown in Figure 4.1. It shows the chemical reactions are faster
near the riser inlet where the higher gradients of the variables take place.

27

Chapter Four

Results and discussion


VGO present model
GLN present model
LGS present model
COK present model
Plant data
Plant data
Plant data
Plant data

1
0.9
0.8

wt fraction

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

10

15

20

25

30

35

Riser Height (m)

Figure 4.1 Four lump concentration profile vs. riser height

The riser temperature profile is plotted in Figure 4.2, where the


temperature drops quickly in the first few meters of the riser bottom zone,
indicating that most of the reactions occur at the riser bottom.
840
Present model

835

Plant data Tout

Temperature (K)

830

Plant data Tin

825
820
815
810
805
800
0

10

15

20

25

Riser Height (m)

Figure 4.2 Riser temperature profile


28

30

35

Chapter Four

Results and discussion

The predicted pressure profile of the riser is shown in Figure 4.3.The


pressure drops 15.3 kPa only, while the actual pressure drop that exists in
FCC risers is (35 62) kPa[40]. This difference is due to the simple
assumption of present model, where static head of catalyst prevails,
neglecting the frictions effect.

245000
Present model

243000
241000

Pressure (Pa)

239000
237000
235000
233000
231000
229000
227000
225000
0

10

15

20

25

30

35

Riser Height (m)

Figure 4.3 Riser pressure profile

The gas phase molecular weight along the riser height is shown in
Figure4.4, where the molecular weight decreases due to the increase of
light products percentage in the gas phase towards the riser exit. Although,
the steam quantity is 4.5% of the total gas phase, however, the model gives
better result of molecular weight when taking into account this small
quantity of steam. As a result of decreasing the gas phase molecular
weight, the gas density also decreases as shown in Figure 4.5.

29

Chapter Four

Results and discussion

200

Present Model

180

Plant data

160

Kg/Kmole

140
120
100
80
60
40
20
0
0

10

15

20

25

30

35

Riser Height (m)

Figure 4.4 Gas phase molecular weight vs. riser length

8
Present Model

Plant data

Density (Kg/m3)

6
5
4
3
2
1
0
0

10

15

20

25

Riser Height (m)

Figure 4.5 Gas phase density vs. riser height

30

30

35

Chapter Four

Results and discussion

The mass flow rate of the gas phase through the riser is plotted in
Figure4.6; it is decreases slightly due to the coke formation.
54
Present Model

Gas phase mass rate (Kg/s)

53.5

Plant data

53
52.5
52
51.5
51
50.5
0

10

15

20

25

30

35

Riser height (m)

Figure 4.6 Gas phase mass rate vs. riser height

The slip factor is plotted in the Figure 4.7; slip factor is high at the
beginning of the riser indicating the gas velocity is much greater than the
particle velocity, while the gas phase velocity increase due to cracking
reactions; it accelerates the catalyst velocity resulting decrease in slip
factor. The slip factor values may range from 1.2 to 4, where 2 considered a
typical in a commercial FCC unit[7].

The gas phase and solid phase velocities are plotted in Figure 4.8. The
figure shows the two phases at the maximum values at the riser exit.

31

Chapter Four

Results and discussion

6
Slip factor

3
2

0
0

10

15

20

25

30

35

Riser Height (m)

Figure 4.7 Slip factor vs. riser height

16
14

Velocity (m/s)

12
Model Gas Phase velocity

10

Model Solid phase velocity

8
6
4
2
0
0

10

15

20

25

30

Riser Height (m)

Figure 4.8 Gas phase and catalyst velocities vs. riser height

32

35

Chapter Four

Results and discussion

Figure 4.9 shows the gas phase and catalyst residence time in the riser.
The gas residence time is 2.2 seconds, and this agrees with riser design
criteria (1 to 5 seconds).While the catalyst is heavier than the gas, it stays
about 7 seconds inside the riser.
9
8

Residence time (sec.)

7
6
5
Vapor residence time

Catalyst residence time

3
2
1
0
0

10

15

20

25

30

35

Riser height (m)

Figure 4.9 Gas phase and catalyst residence times vs. riser height

Figure 4.10 indicates a molar expansion of the gas phase as a function


of cracking reaction. It shows that at 2m of the riser height is locally 92%
occupied by the gas phase, and this agrees with Figure 51 of Gauthier
(2009)

[41]

The catalyst deactivation function is plotted in Figure 4.11. The

catalyst activity at the beginning of the riser is around 0.8 indicates to the
effect of mixed carbonized catalyst of lower activity, while the catalyst
activity at the riser exit is around 0.44.

33

Chapter Four

Results and discussion

0.95
Present Model

0.9

0.85

g
0.8

0.75

0.7
0

10

15

20

25

30

35

Riser Height (m)

Figure 4.10 Gas phase void fraction vs. riser height


0.9
0.8
Present Model

0.7
0.6

0.5
0.4
0.3
0.2
0.1
0
0

10

15

20

25

30

Riser Height (m)

Figure 4.11Predicted catalyst activity along the riser height

34

35

Chapter Four

Results and discussion

Figure 4.12 shows the maximum gasoline yield occurs at 82.4wt% of feed
conversion; this conversion located at 31.65 m of riser height (Figure 4.13),
it agrees well with the riser size of a commercial FCC unit.
0.6
Present Model
Gasoline yield (wt fraction) feed

0.5

0.4

0.3

0.2

0.1

0
0

20

40

60

80

100

Conversion (wt %)

Figure 4.12 Gasoline yield vs. feed conversion


90
80

Conversion wt%

70
Present Model

60
50
40
30
20
10
0
0

10

15

20

25

Riser height (m)

Figure 4.13 Feed conversion vs. riser height


35

30

35

Chapter Four

Results and discussion

Table 4.3 shows a good agreement between predicted and plant data for
the variable parameters with acceptable deviation percentages; while
Table4.4 shows the case study results.

Table 4.3
Model predicted and Plant data comparison
Variable parameter
MxR chamber temperature (K)
Riser inlet temperature (K)

Model prediction
value
912.74
833.99

Plant data

% dev.

912
834

0.081
-0.0012

Light gases yield (kg/s)


Gasoline yield (kg/s)

14.0844
25.6186

14.65
25.7

- 3.86
- 0.32

Unconverted VGO yield (kg/s)

8.94922

8.9

- 0.55

Coke yield (kg/s)

2.54777

2.56

- 0.48

Riser outlet temperature (K)


Riser outlet pressure (kPa)
Gas phase outlet MW
(kg/kmole)
Gas phase outlet density
(kg/m3)
Gas phase outlet mass rate
(kg/s)

802.888
228.747

802
228.81

0.11
0.027

71.656

72.6

-1.3

2.457

2.43

1.11

50.9562

51

-0.086

Table 4.4
Case study results
Unit variable

value

Efficiency
Selectivity
Delta Coke
C/O ratio
WHSV (hr-1)
H combustion of coke (kJ/kg coke)

60.6
1.54
1.2
6.09
77.44
80459.8

36

CHAPTER FIVE

CONCLUSION
AND
RECOMMENDATION

Chapter Five
5.1.

Conclusions and Recommendations

CONCLUSIONS
In the present work a mathematical model has been developed for the

riser reactor of new reactor/regenerator configuration designed by UOP.


Based on the results of present study, the following conclusions can be
derived:

The formulated energy balance equation (3.31) for calculation of


the mixing temperature (Tmix1) at MxR chamber considers the effect
of coke content for both regenerated and circulated carbonized
catalysts, making the model flexible and more predictive.

The developed procedure for calculation of the riser inlet mixing


temperature (Tmix2) depends on defining specific gravity and Kuop
property of the feed into the energy balance equation (3.33). This
approach is more predictive than defining heat capacity, normal
boiling point and heat of vaporization of the feed which has adopted
by many others.

Considering the small quantity of the steam with hydrocarbons


inside the riser converges the model results to better values,
especially when calculating the gas phase molecular weight, where
the deviation percentage was reduced from 16% to -1.3%.

38

Chapter Five
5.2.

Conclusions and Recommendations

RECOMMENDATIONS FOR FUTURE WORK:


The following suggestions for future work can be considered:
Using CFD to visualize the unit performance in order to improve
design of internals.
Developing the model to include the cyclone, VSS, and regenerator
performance as well.
Developing the model using more lumps for kinetics, multidimensions for the riser, and multi-phase system.
Developing the model to taking account the friction effects between
phases with the wall of the riser and between phases itself.
Study the effect of change of any operating conditions variables on
unit performance, i.e. feed temperature, feed type and C/O ratio.

39

Appendix A

FCC technologies

APPENDIX A
A-1. Fluidized Catalytic Cracking Technologies
There are number of different proprietary designs that have been
developed for modern FCC units. Each design is available under a license that
must be purchased from the design developer by any petroleum refining
company desiring to construct and operate an FCC of a given design.
Basically, there are two different configurations for an FCC unit: the "stacked"
type, where the reactor and the catalyst regenerator are contained in a single
vessel with the reactor above the regenerator Figure A-1a, and "side-by-side"
type, where the reactor and catalyst regenerator are in two separate vessels
Figure A-1b. The major FCC designers and licensors are: [2, 42]
A- Stacked configuration:
Kellogg Brown & Root (KBR)
B- Side-by-side configuration:
CB&I Lummus
Stone & Webster Engineering Corporation (The Shaw Group) /
Institut Francais Petrole (IFP)
Shell Global Solutions International
ExxonMobil Research and Engineering (EMRE)
Universal Oil Products (UOP) - currently fully owned subsidiary
of Honeywell

A-1

Appendix A

FCC technologies

Figure A-1a Stacked


Reactor regenerator
configuration [43]

Figure A-1b Side by side


Reactor regenerator
configuration [43]
A-2

Appendix A

FCC technologies

These two different configurations can be classified into small scale and
large scale units as follows:
A stacked configuration of the reactor and regenerator, generally
applicable to small scale units processing less than 20,000 BPSD.
This was used for the small scale unit, with a feed rate of 2,500
BPSD.
A side-by-side configuration of the reactor and regenerator,
generally applicable to large scale units processing 20,000 or more
barrels per stream day of fresh feed. This was used for the large
scale unit, with a feed rate of 62,000 barrels per stream day (BPSD).

In general, all the major licensors agree that the stacked design requires
less plot space and less structural steel, thus lowering the installed cost. As
capacity increases, the vessel sizes also increase to a point where structural
cost exceeds this advantage. As a rule of thumb, a capacity of 20,000 BPSD is
the cut-off size where side-by-side design becomes more economical than
stacked design, according to UOP. There are other factors that affect the
cost/BPSD for the same capacity and thus affect the selection of the FCC
configuration. These factors include location, available land space, and local
building codes.
Over the years, with improvements in technology and increasing gasoline
demand, most of the refiners have modified their FCC units to increase
capacity. Several FCC units have been revamped to process more than
100,000 BPSD. According to the major licensors, the typical capacity of new
FCC units is 40,000 to 60,000 BPSD.

A-3

Appendix A

FCC technologies

Less vendor detail and previous design information was available for
estimation of the small scale FCC. In general, small scale FCC units are no
longer economic, and very few units under 20,000 BPSD are being built
today[43].
A-2. New designs for FCC units
The theory behind the design of any FCC unit configurations is the
same, unless the variations of design by the licensors, the component that
make up the FCC unit are the same: the riser, reactor, and regenerator [43].
A brief description of new technologies and advanced features identified by
each licensor is describing below.

A-2.1.

KBR and ExxonMobil


Feed enters through the proprietary ATOMAX-2 feed injection

system, (Figure A-2). Reaction vapors pass through a right angle turn and are
quickly separated from the catalyst in a positive pressure CLOSED
CYCLONE system which minimizes dry gas make and increases gasoline
yield. Spent catalyst flows to the regenerator through a stripper equipped with
DYNAFLUX baffles technology, featuring proprietary FLUX Tubes and
Lateral Mixing Elements which Reduces entrained hydrocarbons by 80
percent compared to conventional stripper designs and may achieve six
percent or less hydrogen in the coke.
REGENMAX Provides staged regeneration in a simple, single regenerator
vessel where counter-current flow of catalyst and air contacting is carried out;
spent catalyst is evenly distributed across the top of the regenerator bed,
causing a chemical reaction 2C + 2NO 2CO + N2 , only 5 to 7 percent of
the nitrogen in the coke escapes as NOx.
A-4

Appendix A

FCC technologies

Figure A-2 KBRs counter-current regeneration design [46]

Catalyst flow from the regenerator to the external vertical riser is controlled by
riser outlet temperature, which regulates the regenerated catalyst slide valve.
A plug valve located in the regenerator bottom head controls the level in the
stripper by regulating the catalyst flow from the spent catalyst standpipe.
Flue gas flows to an external plenum and then to the flue-gas system.
A Cyclofines Third Stage Separator (TSS) may be used to remove particulates
from the flue gas for protection of power recovery expander and/or
compliance with particulate emissions standards, where TSS is capable to
achieve less than 50 mg/Nm3 particulates in flue gas [44, 45].
A-5

Appendix A

FCC technologies

Riser Quench Technology consists of a series of nozzles uniformly spaced

around the upper section of riser. A portion of the feed or a recycle stream
from the main fractionator is injected through the nozzles into the riser to
rapidly reduce the temperature of the riser contents. The heat required to
vaporize the quench is supplied by increased fresh feed preheat or by
increased catalyst circulation. This effectively increases the temperature in the
lower section of the riser above that which would be achieved in a
nonquenched operation, thereby increasing the vaporization of heavy feeds,
increasing gasoline yield, olefin production, and gasoline octane [1].
The process features developed by KBR & ExxonMobil for FCCU and its
advantages are tabulated in Table A-1.

Table A-1
KBR & ExxonMobil FCCU Technologies [45]
Process features
Process benefits
ATOMAX-2 Feed Nozzles Produces 43 percent smaller droplet size than
the leading industry ATOMAX-1 nozzles
Riser Quench Technology
Improves gasoline yield and octane, and
prevents over-cracking that result in
undesirable products
Closed Cyclone Riser
Minimizes dry gas make and increases
Termination
gasoline yield using a simple compact
cyclone system
DynaFlux Stripping baffles Lower regenerator temperature, increase
catalyst circulation and higher conversion.
REGENMAX
Reduces
regenerator
emissions
and
entrainment and provides clean catalyst
burning under partial CO combustion at
minimum investment
MAXOFIN
Offers the ability to adjust propylene yield,
propylene/ethylene ratio and olefins/ liquid
fuels ratio as market conditions demand
A-6

Appendix A

A-2.2.

FCC technologies

LUMMUS, a CB&I company

The Lummus process incorporates an advanced reaction system, highefficient catalyst stripper and a mechanically robust, single stage fast fluidized
bed regenerator. Oil is injected into the base of the riser via proprietary
MICRO-Jet injection nozzles. Catalyst and oil vapor flow upwards through a
short-contacting time, all vertical riser where raw oil feedstock is cracked
under optimum conditions (Figure A-3).
Reaction products exiting the riser are separated from the spent catalyst in a
patented, DIRECT-COUPLED cyclone system. Product vapors are routed
directly to fractionation, thereby eliminating nonselective post-riser cracking
reactions and maintaining the optimum product yield slate. Spent catalyst
containing only minute quantities of hydrocarbons is discharged from the
diplegs of the direct-coupled cyclones into the cyclone containing vessel. The
catalyst flows down into the stripper containing proprietary MODULAR
GRID (MG) baffles.

Figure A-3 Lummus FCCU Process Flow Diagram [47]


A-7

Appendix A

FCC technologies

Trace hydrocarbons entrained with spent catalyst are removed in the MG


stripper using stripping steam. The MG stripper efficiently removes
hydrocarbons at low steam rate. The net stripper vapors are routed to the
fractionators via specially designed vents in the direct-coupled cyclones.

Table A-2
LUMMUS FCCU Technologies [47]
Process Features
Process Benefits
Micro-Jet feed injectors
Uniformly contact feed with catalyst
Minimal erosion and catalyst attrition
Low pressure drop
Short contact time riser reactor
Patented direct-coupled
cyclones at the end of the riser
reactor for quick and efficient
recovery of product vapors
Modular Grid (MG) catalyst
stripper design

Dual diameter catalyst


regenerator and turbulent bed
combustion
Regenerated catalyst standpipe
with external hopper
Spent catalyst square-bend
transfer line and distribution of
spent catalyst into the center of
the regenerator

Minimal back-mixing
Efficient catalyst/oil contacting
Minimal after- cracking
Low dry gas yield and delta coke
Minimal hydrocarbon loading in the
stripper
Highly efficient removal of hydrocarbon
product vapors from the catalyst
Reduced delta coke
Low stripping steam requirement
Low carbon on regenerated catalyst
Efficient use of combustion air
Reduced after-burning and NOx
emissions
Smooth, stable catalyst flow over a wide
operating range
Insensitive to unit upsets
Improved
slide
valve
pressure
differentials
Lower catalyst hydrothermal
deactivation
Stable spent catalyst flow
Lower capital and operating cost

A-8

Appendix A

FCC technologies

Catalyst from the stripper flows down the spent catalyst standpipe and through
the slide valve. The spent catalyst is then transported in dilute phase to the
center of the regenerator through a unique square bend spent catalyst transfer
line. This arrangement provides the lowest overall unit elevation. Catalyst is
regenerated by efficient contacting with air for complete combustion of coke.
The resulting flue gas exits via cyclones to energy recovery/flue gas treating.
The hot regenerated catalyst is withdrawn via an external withdrawal well.
The well allows independent optimization of catalyst density in the
regenerated catalyst standpipe. Maximizes slide valve pressure drop and
ensures stable catalyst flow back to the riser feed injection zone [44].
The process features developed by Lummus for FCCU and its advantages are
tabulated in Table A-2.
A-2.3.

Stone & Webster Engineering Corporation (The Shaw Group)/


AXENS, Institut Francais Petrole (The IFP Group)

Catalytic and selective cracking in a short contact time riser where oil
feed is effectively dispersed and vaporized through a proprietary feed
infection system. Operation is carried out at a temperature consistent with
targeted yields. The riser temperature profile can be optimized with the
proprietary Mixed Temperature Control (MTC) system, (Figure A-5).
Reaction products exit the riser reactor through a high efficiency, closecoupled, proprietary riser termination device RSS (Riser Separator Stripper).
Spent catalyst is pre-stripped followed by an advanced high-efficiency packed
stripper prior to regeneration, (Figure A-4). The reaction product vapor may
be quenched to give the lowest possible dry gas and maximum gasoline yield.

A-9

Appendix A

Riser Separator
Stripper

FCC technologies

RSS

Packed stripper

Figure A-4 S&W / IFP FCCU design [48]

Final recovery of catalyst particles occurs in cyclones before the product


vapor is transferred to the fractionation section.
Catalyst regeneration is carried out in a single regenerator equipped with
proprietary air and catalyst distribution systems, and may be operated for
either full or partial CO combustion.

A-10

Appendix A

FCC technologies

Figure A-5 Mix zone temperature control (left), Feed injection nozzle (right) [49]

Table A-3
S&W / IFP FCCU Technologies [1, 49]
Process Features
Process Benefits
Feed Injection
Primary Atomization: oil impact on target, Steam cross
shearing.
Secondary Atomization: Filamenting in barrel, spry
shaped by tip
Mix zone
Provide an independent control of the mix temperature
Temperature Control Achieve a high mix-zone temperature and lower riser
(MTC)
temperature
Riser Termination
Rapid separation of products and catalyst
Compact design
Easy start-up and operation
Reduces dry gas
Reduces coke
Sealed or open operation
Packed stripper
95% of the whole area is open to flow
Increased catalyst circulation rate and capacity
Stripping is more effective
Robust construction
Cold wall design

Allows the use of carbon steel for construction


Reduces the skin temperatures
Less thermal expansion of the components
Minimizing the need for expansion joints
Minimum capital investment

A-11

Appendix A

FCC technologies

The internals of the vessels and transfer lines are covered in insulating and
abrasion resistant refractory, Stone & Webester developed this technology to
make high temperature, high Olefins FCC a reality.
Reliable operation is ensured through the use of advanced fluidization
technology combined with a proprietary reaction system. Unit design is
tailored to the refiners needs and can include wide turndown flexibility [44].
The process features developed by Stone & Webster / IFP for FCCU and its
advantages are tabulated in Table A-3.

A-2.4.

SHELL Global Solution International B.V

Shells high-performance feed nozzle system feeds hydrocarbons to a short


contact-time riser. This design ensures good mixing and rapid vaporization
into the hot catalyst stream (Figure A-6).
Cracking selectivity is enhanced by the feed nozzles (Figure A-7) and
proprietary riser internals, which reduce catalyst back mixing while reducing
overall riser pressure drop.
Riser termination design incorporates reliable close-couple cyclones that
provide rapid catalyst/hydrocarbon separation. It minimizes post-riser cracking
and maximizes desired product yields, with no slurry clean up required.
Stripping begins in the staged stripper, equipped with high capacity baffle
structure, (Figure 2.7).

A-12

Appendix A

FCC technologies

Figure A-6 Shells FCCU design [44]

A single stage partial or full burn regenerator delivers excellent performance


at low cost. Proprietary internals are used at the catalyst inlet to disperse
catalyst, and the catalyst outlet to provide significant catalyst circulation
enhancement. Catalyst coolers can be added for more feedstock flexibility.
Cyclone systems in the reactor and regenerator use a proprietary design, thus
providing reliability, efficiency and robustness. Flue gas cleanup can be
incorporated with Shells third-stage separator [44], (Figure A-6).
The process features developed by Shell Global Solutions for FCC unit and its
advantages are tabulated in Table A-4.

A-13

Appendix A

FCC technologies

Figure A-7 PentaFlow Packing (left), Feed nozzels configurations (right)[50]

Table A-4
Shells FCCU Technologies [51]
Process Features
Feed injection system

Riser internals

Close-coupled reactor
cyclones with coke catcher

High-efficiency stripper

Catalyst circulation
enhancement technology

Third-stage separator (TSS)


technology

Process Benefits
Good riser coverage and mixing with the
catalyst. Resulting higher gasoline yields,
less dry gas, lower steam consumption and
reduced pressure requirements
improves catalyst distribution and reduces
spent catalyst reflux, which minimizes
nonselective thermal cracking
providing high separation efficiency,
minimizes post-riser cracking and reactor
vessel coking
PentaFlow stripper packing removes up to
95% of hydrocarbons, open design prevents
plugging, enhances catalyst flux and
facilitates access for maintenance.
Improves circulation rates by up to 50% and
is applicable to both the stripper and the
regenerator standpipes; it improves stability
and pressure build-up by optimizing the
catalyst condition near the inlets.
Reduces flue gas particulate emissions to
less than 50 mg/Nm3. It also protects the
flue gas system from erosion
A-14

Appendix A

A-2.5.

FCC technologies

Universal Oil Products UOP

UOPs process (Figure A-8) uses a side by side reactor/regenerator


configuration and a patented pre-acceleration zone to condition the
regenerated catalyst. Modern OPTIMIX feed distributors inject the feed into
the riser, which terminates in a vortex separation system (VSS). A high
efficiency stripper then separates the remaining hydrocarbons from the
catalyst, which is then reactivated in a combustor style regenerator, with
RxCat technology, a portion of the catalyst that is pre-stripped by the riser
termination device can be recycled back to the riser via a standpipe and the
MxR chamber.
The reactor zone features a short contact time riser, state of the art riser
termination device for quick separation of catalyst and vapor, with high
hydrocarbon containment (VSS/VDS technology) and RxCat technology,
wherein a portion of the pre-stripped (carbonized) catalyst from the riser
termination device is blended with the hotter regenerated catalyst in a
proprietary mixing chamber (MxR) for delivery to the riser.
With this technology, the reactor temperature can be lowered to reduce
thermal cracking with no negative impact on conversion, thus improving
product selectivity. The ability to vary the carbonized/regenerated catalyst
ratio provides considerable flexibility to handle changes in feedstock quality
and shortens the time for operating adjustments by enabling rapid switches
between gasoline, olefins or distillate operating modes. Since coke yield can
be decreased at constant conversion, capacity and reaction severity can be
increased, and CO2 emissions reduced. Furthermore, because the catalyst
delivered to the regenerator has a higher coke content, it requires less excess
oxygen at a given temperature to sustain the same kinetic combustion rate.
A-15

Appendix A

FCC technologies

Figure A-8 UOPs reactor/regenerator FCCU design [31]

The combustor style regenerator burns coke in a fast-fluidized environment


completely to CO2 with very low levels of CO.

UOP also offers two process technologies for maximizing propylene from
feedstocks traditionally processed in FCC units. The PetroFCC and RxPro
processes are specifically designed to meet increased propylene production
requirements but are flexible to also operate in maximum gasoline mode, if
required.

A-16

Appendix A

FCC technologies

Both processes utilize commercially proven technology and mechanical


features found in a conventional UOP FCC design, but are operated at process
conditions that promote light olefin and/or aromatics production for
petrochemical applications. The commercially-proven PetroFCC technology
provides a cost-effective means for producing moderate quantities of
propylene from moderate quality feedstocks. the newest entry to the enhanced
propylene platform at UOP, the RxPro process, employs a multi-stage reaction
system with targeted olefin recracking to achieve a highest yield of propylene
(>20 wt% FF) for a given reaction severity and feedstock quality[1, 44].

A-17

Appendix B

Variables of FCC units

APPENDIX B
VARIABLES OF FCC UNITS
B-1. FCC unit Feedstocks and Products
Modern FCC units can take a wide variety of feedstocks and can adjust
operating conditions to maximize production of gasoline, middle distillate
(LCO) or light olefins to meet different market demands. [42]
The FCC unit is also an important source of butene and pentene olefins used
in refinery processes such as the alkylation unit. [44]
B-1.1.

Feedstocks
The main feedstock used in FCC unit is the Gas Oil boiling between

316oC and 566 oC (600 oF and 1050 oF). FCC unit can accept a broad range of
gas oil feedstocks such as: [1]
v

Atmospheric gas oils.

Vacuum gas oils.

Coker gas oils.

Thermally cracked gas oils

Solvent deasphalted oils

Lube extracts

Hydrocracker bottoms

These gas oils can be considered mixtures of aromatic, naphthanic and


paraffinic molecules. There are also varying amounts of contaminants such as
sulphur, nitrogen and metals, particularly in the higher boiling fractions. These
differences in feed composition and in contaminants affect the operating
conditions required to obtain desired yields. To protect the catalyst, feed pretreatment by hydrotreating is required in order to remove contaminants and
improve cracking characteristics and yields.
B-1

Appendix B

Variables of FCC units

The principal limitation on charge stocks are the Conradson Carbon Residue
(CCR) and metal contaminants. The effect of Conradson carbon is to form a
deposit on the catalyst and reduce catalyst activity, promote coke and
hydrogen formation. [33]
Paraffinic atmospheric and vacuum gas oils takes as charge stocks because it's
more easily cracked in the catalytic cracker. [42]
Feedstocks can be ranked in terms of their Crackability, or easily to convert in
FCC unit. Crackability is a function of the relative proportions of paraffinic,
naphthenic, and aromatic species in the feed as shown in table B-1 [1].
Table B-1
Feedstock Crackability[1]
Range of

Relative Crackability

Feedstock type

High

Paraffinic

11.5 11.6

Intermediate

Naphthenic

< 11.3

Refractory

Aromatic

characteristic factor Kuop


> 12

FCC gasoline yield largely depends on changes in feed quality, catalyst


properties, and operating variables, for Feedstock Quality: Paraffinic
feedstocks produce the most gasoline yield (but the lowest octane). The
common indicators of any increase in feed paraffinicity are: [40]
Increase in the Kuop factor
Increase in the aniline point
Increase in the nickel-to-vanadium ratio
Decrease in the fraction of "cracked" material (Coker Gasoil)
B-2

Appendix B

B-1.2.

Variables of FCC units

Products

Table B-2 indicates the typical yields and the essential characteristics of the
products obtained by the catalytic of vacuum distillate (VGO) and the required
treatments.
Table B-2
Typical FCC unit products [53]
Products
GAS
C2 & H2S

Yield
wt%

Product characteristics Complementary


Treatments - Valorizations

35

Large amount of H2S produced with high


sulfur feeds
Requiring purification treatments (amine
washing Claus plant)

C3 CUT
- Propane
- Propylene

59

70% propylene in the C3 fraction


Propylene recovery by distillation for further
use in petrochemicals

C4 CUT
- Butanes
- Butenes

6 12

50 60% butenes in the C4 fraction


Possible valorization of butenes in
ALKYLATION plant to increase gasoline
production
Selective valorization of isobutene in MTBE
plant

GASOLINE
C5 C11

45 55

Most desirable product


Medium octane rating for unleaded gasoline
RON 92 93, MON 79 80
Relatively good stability
Corrosive and bad odor mercaptans require
sweetening by MEROX type process
Possibility to improve octane numbers by
separating a gasoline heart cut and then
processing it.

GAS OIL
(LCO)

15 20

Very aromatic
Low cetane number
S% generally high
Good diluents for heavy fuel oil

HEAVY streams
(HCO + SLURRY)

6 10

Very aromatic products


Diluents for heavy fuel oil

COKE

46

Self consumed as fuel in the regenerator


B-3

Appendix B

B-2.

Variables of FCC units

Catalytic Cracking Reactions

The main reaction in the FCC is the catalytic cracking of paraffin, olefins,
naphthenes and side chains in aromatics. A network of reactions occurring in
the FCC is illustrated in Figure B-1. The VGO undergoes the desired primary
cracking into gasoline and LCO. A secondary reaction also occurs, which
must be limited, such as a hydrogen transfer reaction which lowers the
gasoline yield and causes the cycloaddition reaction. The latter could lead to
coke formation (needed to provide heat for catalyst regeneration) [33].

Primary Cracking
Gases
Heavy
Gasoil

Primary
Cracking

Gasoline
+
LCO

H2, C1, C2,


C3, C4

Secondary
Cracking
Oligomerization

Dehydrogenation

Cycloaddition
Dehydrogenation

Residue
+
Coke

Figure B-1 FCC reaction network [54]

The main reactions occurs in the FCC riser reactor can be summarized in the
Figure B-2

B-4

Appendix B

Paraffins

Variables of FCC units


Cracking

Cracking
Cyclization
Isomerization
Olefins *

H Transfer
Cyclization
Condensation
Dehydrogenation

Cracking
Naphthenes

Dehydrogenation
Isomerization

Side-chain
Cracking
Aromatics

Transalkylation
Dehydrogenation
Condensation

Paraffins + Olefins

LPG Olefins
Naphthenes
Branched
Olefins

H Transfer

Branched
Paraffins

Paraffins
Coke

Olefins
Cyclo-Olefins

Dehydrogenation

Aromatics

Naphthenes with different rings

Unsubstitued aromatics + Olefins


Different alkylaromatics
Polyaromatics

Alkylation
Dehydrogenation
Condensation

* Mainly from cracking, very little in feed

Figure B-2 Principal Reactions in Fluid Catalytic Cracking [48, 55]


B-5

Coke

Appendix B

Variables of FCC units

FCC unit Operation Variables

B-3.

The primary variables available to the FCC unit operator for


maximizing unit conversion or specific desired product for a given feedstock
quality can be divided into two groups, catalytic and process.
B-3.1.

Catalytic activity and catalyst design

Earlier FCCU catalysts were natural occurring clays, which suffered from
low cracking activity, poor stability, and poor fluidization characteristics.
Later synthetic silica/alumina catalysts were developed, which were more
active and stable. These were replaced with present day zeolite (crystalline
silica alumina or molecular sieves) catalysts with greatly increased activity,
stability, and improved selectivity. It has been realized for some time that
better FCC unit yield could be achieved with shorter contact time between the
feedstock and the catalyst by using zeolite catalysts. With the earlier catalysts
of low activity and long residence time, some of the gasoline formed cracked
further in the catalyst bed to LPG resulting in lower gasoline yield [56].

Fig. B-3 Evolution in structure of FCC catalysts before 1990 [5, 57]
B-6

Appendix B

Variables of FCC units

Figure B-3 shows continuous improvements in the performance of FCC


catalysts from the beginning until 1990

Modern FCC catalysts are fine powders with a bulk density of 0.80 to
0.96g/cc, made up primarily of silica and alumina and containing acid sites
that enables the catalyst to crack reactions, and having a particle size
distribution ranging from 10 to 150 m and an average particle size of 60 to
100 m [2, 56].
Cracking catalysts for the fluid process are characterized by certain physical
and chemical properties. Physically, the catalyst must have: (a) satisfactory
fluidization characteristics, and (b) sufficient resistance to attrition so that
excessive loss of fine particles is not encountered. On the chemical side, the
catalyst must: (a) have adequate activity and maintenance of activity with age;
and (b) promote the formation of the desired reaction products with minimum
production of undesired by-products such as gas and coke. [58]
Amorphous catalysts have higher attrition resistance and are less costly than
zeolitic catalysts. Most commercial catalysts contain approximately 15%
zeolites and thus obtain the benefits of the higher activity and gasoline
selectivity of the zeolites and the lower costs and make-up rates of the
amorphous catalysts [42].
During the process, Catalyst deactivation occurs due to the metal content of
the feed such as Nickel and Vanadium, where vanadium can destroy the
zeolite activity, and coke deposition which temporarily block some of the
catalytic sites; The spent catalyst entering the regenerator contains between
0.4 to 2.5 wt% coke

[40]

, this coke is burned off in the regenerator and

Regenerated catalyst contains from 0.01 to 0.4%wt residual coke (CRC)


B-7

[42]

Appendix B

Variables of FCC units

this is an important parameter for a unit operator to monitor periodically. The


CRC is an indicator of regenerator performance (Figure B-4).
Catalyst loss also occurs due to the attrition, in order to maintain the catalyst
activity and replace the lost catalyst, daily makeup rate of fresh catalyst is
added, typically 0.045 to 0.14 Kg per barrel of fresh feed [40].

Figure B-4 Catalyst activity retention vs. Coke on regenerated catalyst [40]

In general, the deactivation in a given unit is largely a function of the units


mechanical configuration, its operating condition, the type of fresh catalyst
used, and the feed quality. The primary criterion for adding fresh catalyst is to
arrive at an optimum equilibrium catalyst activity level.

A too-high

equilibrium catalyst (E-cat) activity will increase delta coke on the catalyst,
resulting in a higher regenerator temperature. The higher regenerator
temperature reduces the catalyst circulation rate, which tends to offset the
activity increase. The amount of fresh catalyst added is usually a balance
between catalyst cost and desired activity [40, 59].
B-8

Appendix B

B-3.2.

Variables of FCC units

Process Variables

B-3.2.1. Independent variables: where directly regulated, usually with


control devices
B-3.2.1.1.

Feed Rate

As the flow rate of the feed decrease, the space velocity decrease and the
contact time increase, cause to increase conversion [60].
Conversion has been observed in some units to increase 1% absolute for a
3-5% relative decrease in fresh feed rate [61].
Charge rate is set as desired by the refiner based on the existing economics [31].
B-3.2.1.2.

Feed Preheat Temperature

Decreasing the feed preheat temperature at constant riser outlet


temperature will [31, 62]:
Increase the catalyst circulation rate
Slightly increase conversion
Increase the coke production rate 0.1 0.15 %wt on feed for every
10oC reduction in preheat temperature
Decrease the delta Coke (kg coke/kg catalyst)
Decrease the Regenerator temperature

B-3.2.1.3.

Reactor Pressure

According to UOP Operating Manual

[31]

, the pressure in the reactor is

normally varied very little. There is a trade off here as a higher reactor
pressure would reduce the Gas Concentration Unit gas compressor
horsepower requirements, but it would also increase the main air blower
horsepower. Higher pressure would also reduce the required size of the
vessels.
B-9

Appendix B

Variables of FCC units

The olefin content of the products will decrease with an increase in the
hydrocarbon partial pressure. Conversion will increase somewhat. Coke
laydown will increase slightly, an effect that may be offset by adding steam or
inert gas to reduce the hydrocarbon partial pressure. This may, however,
defeat the original purpose of raising the reactor pressure.
Reactor pressure normally varies slightly with changes in feed rate and
loading of the main column. The operator has some element of control, but
pressure must be kept within narrow limits around the design value to avoid
problems with riser and cyclone velocities. Normal first stage cyclone inlet
velocities are in the (20 m/s) range. Higher velocities are better for cyclone
efficiency, but worse with respect to the greater amount of catalyst carried up
to them as the vessel superficial velocity increases. Higher velocity also
increases cyclone erosion problems.
B-3.2.1.4.

Reactor Temperature

Reactor temperature is the prime control of reactor severity. Increasing the


reactor temperature set point will signal the regenerated catalyst valve to
increase the hot catalyst flow as necessary to achieve the desired riser outlet
temperature. The increased catalyst circulation rate results in increased
conversion.
Higher temperature accelerates intermolecular motions, and assists the
transformation of the rate of chemical process. The effect of temperature on
the rate constant is described by the Arrhenius equation:
=

exp(

( . 1)

The cracking rate constant is enhanced by the temperature of the riser and the
conversion of the feed into light products increases as a result [60].
B-10

Appendix B

Variables of FCC units

Higher cracking temperature also increase gasoline octane and LPG olefinicity
-with their potential for alkylation feed- , cracked gasoline from high
temperature operation are particularly useful blending components for leadfree gasoline

[54, 61]

. The higher octane is due to the higher rate of primary

cracking reactions relative to secondary hydrogen transfer reactions which


saturate olefins in the gasoline boiling range and lowers gasoline octane [61].

An increase in the unit conversion does not necessarily mean an increase in


gasoline yield, because Beyond a certain temperature, gasoline yield will be
negatively impacted [1, 42] (Table B 3).

Table B 3
Effect of operating Temperature of the reactor on the performance of a
fluidized bed cracking; Feed: Mid continent gasoil [60]
Aver. Reactor temperature, oC

510

538

558

Feed conversion, vol. %


yields Gasoline, vol. %

85

87

89

71

68

64

Propylene, vol. %

7.8

10.6

11.5

Butenes, vol. %

7.4

8.5

10.6

Coke, wt %

3.6

3.4

3.5

87

90

93

Research octane rating of gasoline, clear

However, cracking at higher temperatures also produces more gas and coke
which are less desirable products. The optimum temperature is when just
enough coke is formed on the catalyst so that the heat of combustion in the
regenerator can provide all the heat required for reaction when the catalyst
returns to the riser-reactor [43].
B-11

Appendix B

Variables of FCC units

B-3.2.2.

to changes in the

Dependent Variables: are responsive

independent variables
B-3.2.2.1.

Catalyst To Oil Ratio

Catalyst to Oil ratio (C/O) is the ratio of kg/hr of catalyst circulated to


kg/hr of fresh feed. It is dependent variable, where it increases with an
increase in reactor temperatures, and decreases with higher regenerator or feed
preheat temperatures.
With UOP RxCat Technology, the riser Catalyst/Oil ratio (riser-C/O), where it
is the ratio of kg/hr of both regenerated and recirculated spent (carbonized)
catalyst to kg/hr of fresh feed. This (riser-C/O) ratio can be directly
manipulated by the amount of spent catalyst that is recirculated to the MxR
chamber without affecting the heat balance of the reactor/regenerator system.
The increases in spent catalyst recirculation to riser at a constant reactor
temperature will [31]:
Increase conversion.
Decrease light gas yield.
Increase C3 and C4 yields.
Increase gasoline aromatic content.
Increase gasoline yield.
Decrease LCO.
Increase regenerator temperature.
Decrease C/O rate.
B-3.2.2.2.

Regenerator Temperature

The coke yield of a given cat cracker is essentially constant. However, a


more important term is delta coke. Delta coke controls the regenerator
temperature. Reducing delta coke will lower the regenerator temperature.
B-12

Appendix B

Variables of FCC units

Many benefits are associated with a lower regenerator temperature. The


resulting higher cat/oil ratio improves product selectivity and/or provides the
flexibility to process heavier feeds. Many factors influence delta coke, these
are [40]:
Feedstock quality. The quality of the FCC feedstock impacts the
concentration of coke on the catalyst entering the regenerator. A
"heavier" feed containing a higher concentration of coker gas oil will
directionally increase the delta coke as compared with a "lighter," residfree feedstock.
Feed/catalyst injection. A well-designed injection system provides a
rapid and uniform vaporization of the liquid feed. This will lower delta
coke by minimizing non-catalytic coke deposition as well as reducing
the deposits of heavy material on the catalyst.
Riser design. A properly designed riser will help reduce delta coke by
reducing the back-mixing of already "coked-up" catalyst with fresh
feed. The back-mixing causes unwanted secondary reactions.
Cat/oil ratio. An increase in the cat/oil ratio reduces delta coke by
spreading out some coke-producing feed components over more catalyst
particles and, thus, lowering the concentration of coke on each particle.
Reactor temperature. An increase in the reactor temperature will also
reduce delta coke by favoring cracking reactions over hydrogen transfer
reactions. Hydrogen transfer reactions produce more coke than cracking
reactions.
Catalyst activity. An increase in catalyst activity will increase delta
coke. As catalyst activity increases so does the number of adjacent sites,
which increases the tendency for hydrogen transfer reactions to occur.
Hydrogen transfer reaction.
B-13

Appendix C

Computer Programs
APPENDIX C
COMPUTER PROGRAMS

A Polymath Program for solution the FCC riser model is stated below. The
program may solve for any variable and flexible to accept different
operating conditions. Table C-1 lists some variables used in this program.
Excel worksheet is used as a powerful tool to solve the same equations
used in Polymath. Polymath solves the ODEs by Runge - kutta method
built inside its solver, while ODEs need to be introduced in details to Excel
and solved by iteration on cells using Runge - Kutta method. The main
interface simulator of an Excel worksheet is shown in Figure C-1.

Table C 1
Variables used in Polymath program
variable

Unit

Mug

Pa.s

Phy

Rhog
Rhocat

Description
Hydrocarbon vapor viscosity
Catalyst deactivation function

kg/m

kg/m

Density of gas phase


Density of catalyst particles

Sph

Sphericity

Voidage of gas phase

Slip factor

The programmed Equations in Polymath are:


Independent variable: z

Initial value: 0

Final value: 32

[1] d(y1)/d(z) = -J*(K1+K2+K3)*y1^2

Initial value: 1

[2] d(y2)/d(z) = J*((K1*y1^2-(K4+K5)*y2))

Initial value: 0

[3] d(y3)/d(z) = J*(K2*y1^2+K4*y2)

Initial value: 0

C-1

Appendix C

Computer Programs

[4] d(y4)/d(z) = J*(K3*y1^2+K5*y2)

Initial value: 0

[5] d(T)/d(z) = -S*((K1*H1+K2*H2+K3*H3)*y1^2+


(K4*H4+K5*H5)*y2)
[6] d(P)/d(z) = -RhoCat*9.81*(1-v)

Initial value: 834


Initial value: 258000

[7] d(tc)/d(z) = (A*RhoCat*w)/(mcat*w+((1/Mwtg)*mg*(1-y4)*RhoCat*


0.082*101325*T/P))

Initial value: 0

[8] Mwtg = 1/(y1/MwtVGO+y2/MwtGLN+y3/MwtLGS+


((mds+mls)/mf)/18)
[9] Rhog = (P*Mwtg)/(0.082*T*101325)
[10] mg = mf*(y1+y2+y3)+mds+mls
[11] Uo = mg/(A*Rhog)
[12] Ar = (Rhog*(RhoCat-Rhog)*9.81*dp^3)/Mug^2
[13] Ret = Ar/(18+(2.3348-1.7439*Sph)*Ar^0.5)
[14] Ut = (Ret*Mug)/(Rhog*dp)
[15] w = 1+5.6*(9.81*D)^0.5/Uo+0.47*(Ut/(9.81*D)^0.5)^0.41
[16] v = (RhoCat*mg)/(Rhog*mcat*w+RhoCat*mg)
[17] Ug = Uo/v
[18] Up = Ug/w
[19] J = A*v*phy*Rhog/mg
[20] S = A*v*Rhog*phy/(mcat*Cpcat+mg*Cpg)
[21] K1 = Ko1*exp(-E1/(8.3*T))
C-2

Appendix C

Computer Programs

[22] K2 = Ko2*exp(-E2/(8.3*T))
[23] K3 = Ko3*exp(-E3/(8.3*T))
[24] K4 = Ko4*exp(-E4/(8.3*T))
[25] K5 = Ko5*exp(-E5/(8.3*T))
[26] D = 1.37
[27] mf = 51.2
[28] mcat = mrcat+mxcat
[29] Mug = 1.179e-5
[30] RhoCat = 970
[31] dp = 60e-6
[32] Sph = 1
[33] MwtVGO = 360.04
[34] MwtGLN = 99
[35] MwtLGS = 46.5
[36] CpVGOgas = 3.56
[37] Cpg = CpVGOgas
[38] Cpcok = 1.675
[39] Cpcat = 2.3
[40] Ko1 = 12600
[41] Ko2 = 2070
[42] Ko3 = 25.1
C-3

Appendix C

Computer Programs

[43] Ko4 = 2735


[44] Ko5 = 0.006
[45] E1 = 57359
[46] E2 = 52754
[47] E3 = 31820
[48] E4 = 65733
[49] E5 = 66570
[50] H1 = 393
[51] H2 = 795
[52] H3 = 1200
[53] H4 = 1150
[54] H5 = 151
[55] L = 32
[56] A = 1.474
[57] phy = -45*(y4*mf+mxcok)/mcat+1
[58] x = (1-y1)*100
[59] mds = 0.01*mf
[60] mls = 0.035*mf
[61] mrcat = 208
[62] mxcat = 104
[63] mcok = mrcok+mxcok
C-4

Appendix C

Computer Programs

[64] mrcok = 0.013728


[65] mxcok = 1.28
[66] Trcat = 980
[67] Tout = 805
[68] Cps = 2.4
[69] Tls = 523
[70] Tmix1 = ((mrcat*Cpcat+mrcok*Cpcok)*Trcat+(mxcat*Cpcat+
mxcok*Cpcok)*Tout-mls*Cps*Tls)/ (mrcat*Cpcat+
mrcok*Cpcok+mxcat*Cpcat+mxcok*Cpcok+mls*Cps)
[71] A1 = -a1+ (a2+a3*SG)*Kuop
[72] A2 = A1+ (a4-a5*Kuop)/SG
[73] A3 = A2/1000
[74] A4 = (1+a6*Kuop)*(a7-a8/SG)/1000000
[75] A5 = -(1+a9*Kuop)*(a10-a11/SG)/1000000000
[76] HL = A3*(1.8*Tf-259.67)+A4*((1.8*Tf)^2-259.67^2)+
A5*((1.8*Tf)^3-259.67^3)
[77] F1 = f1*SG+f2*Kuop*(Kuop-f3)
[78] F2 = f4*SG+f5*Kuop*(Kuop-f6)
[79] F3 = f7*SG-f8*Kuop*(Kuop-f9)-f10
[80] a = 2.32*3.24*mf*F1
[81] b = mcat*Cpcat+mcok*Cpcok+mds*Cps+mls*Cps-2.32*1654.812*
mf*F1-2.32*1.8*mf*F2
C-5

Appendix C

Computer Programs

[82] c = 2.32*(459.67)^2*mf*F1+2.32*459.67*mf*F2+2.32*mf*F32.32*HL*mf-mds*Cps*Tds-(mcat*Cpcat+mcok*Cpcok+mls*
Cps)*Tmix1
[83] Tmix2 = (-b+ (b^2-4*a*c) ^0.5)/ (2*a)
[84] SG = 0.8841
[85] Kuop = 12.19
[86] Tf = 547
[87] Tds = 523
[88] t=z/Ug

POLYMATH Results
POLYMATH Report

,2012-10-02

Rev5.1.233

Calculated values of the DEQ variables


Variable
z
y1
y2
y3
y4
T
P
tc
MwtLGS
MwtGLN
mf
A
dp
Sph
mls
MwtVGO
mds
Mwtg
mg
mxcat
mrcat
E1
E2
E3
E4
E5
D
Rhog
mcat

initial value
0
1
0
0
0
834
2.44E+05
0
46.5
99
51.2
1.474
6.0E-05
1
1.792
360.04
0.512
189.48476
53.504
104
208
5.736E+04
5.275E+04
3.182E+04
6.573E+04
6.657E+04
1.37
6.6721777
312

minimal value
0
0.1747862
0
0
0
802.89656
2.287E+05
0
46.5
99
51.2
1.474
6.0E-05
1
1.792
360.04
0.512
71.656029
50.956315
104
208
5.736E+04
5.275E+04
3.182E+04
6.573E+04
6.657E+04
1.37
2.4570839
312

C-6

maximal value
32
1
0.5003684
0.2750897
0.0497595
834
2.44E+05
7.6269989
46.5
99
51.2
1.474
6.0E-05
1
1.792
360.04
0.512
189.48476
53.504
104
208
5.736E+04
5.275E+04
3.182E+04
6.573E+04
6.657E+04
1.37
6.6721777
312

final value
32
0.1747862
0.5003646
0.2750897
0.0497595
802.89656
2.287E+05
7.6269989
46.5
99
51.2
1.474
6.0E-05
1
1.792
360.04
0.512
71.656029
50.956315
104
208
5.736E+04
5.275E+04
3.182E+04
6.573E+04
6.657E+04
1.37
2.4570839
312

Appendix C
Mug
RhoCat
Ar
Ret
Ut
Uo
w
CpVGOgas
Cpg
Cpcok
Cpcat
Ko1
Ko2
Ko3
Ko4
Ko5
K1
K2
K3
K4
K5
H1
H2
H3
H4
H5
L
v
mxcok
x
Ug
Up
phy
J
S
mrcok
mcok
Trcat
Tout
Cps
Tls
Tmix1
Kuop
SG
A1
A2
A3
Tf
A4
A5
F1
a
F2
Tds
HL
b
F3
c
Tmix2
t

1.179E-05
970
97.97987
4.108341
0.1209933
5.4402789
4.8897177
3.56
3.56
1.675
2.3
1.26E+04
2070
25.1
2735
0.006
3.1747015
1.0144193
0.2531086
0.2055465
3.996E-07
393
795
1200
1150
151
32
0.8360283
1.28
0
6.5072905
1.3308111
0.8153846
0.1253032
0.0073829
0.013728
1.293728
980
805
2.4
523
912.74207
12.19
0.8841
-613.66162
45.266496
0.0452665
547
4.471E-04
-7.737E-08
1.856E-04
0.0714201
-0.443224
523
363.65147
783.58545
177.5477
-7.032E+05
833.99118
0

Computer Programs
1.179E-05
970
36.239765
1.681099
0.1209933
5.4402789
2.5803509
3.56
3.56
1.675
2.3
1.26E+04
2070
25.1
2735
0.006
2.3030001
0.7550937
0.2118213
0.1422815
2.753E-07
393
795
1200
1150
151
32
0.8360283
1.28
0
6.5072905
1.3308111
0.4479301
0.0306117
0.0017351
0.013728
1.293728
980
805
2.4
523
912.74207
12.19
0.8841
-613.66162
45.266496
0.0452665
547
4.471E-04
-7.737E-08
1.856E-04
0.0714201
-0.443224
523
363.65147
783.58545
177.5477
-7.032E+05
833.99118
0

C-7

1.179E-05
970
97.97987
4.108341
0.1344423
14.069561
4.8897177
3.56
3.56
1.675
2.3
1.26E+04
2070
25.1
2735
0.006
3.1747015
1.0144193
0.2531086
0.2055465
3.996E-07
393
795
1200
1150
151
32
0.9615194
1.28
82.521382
14.632633
5.6707921
0.8153846
0.1253032
0.0073829
0.013728
1.293728
980
805
2.4
523
912.74207
12.19
0.8841
-613.66162
45.266496
0.0452665
547
4.471E-04
-7.737E-08
1.856E-04
0.0714201
-0.443224
523
363.65147
783.58545
177.5477
-7.032E+05
833.99118
2.1868928

1.179E-05
970
36.239765
1.681099
0.1344423
14.069561
2.5803509
3.56
3.56
1.675
2.3
1.26E+04
2070
25.1
2735
0.006
2.3030001
0.7550937
0.2118213
0.1422815
2.753E-07
393
795
1200
1150
151
32
0.9615194
1.28
82.521382
14.632633
5.6707921
0.4479301
0.0306117
0.0017351
0.013728
1.293728
980
805
2.4
523
912.74207
12.19
0.8841
-613.66162
45.266496
0.0452665
547
4.471E-04
-7.737E-08
1.856E-04
0.0714201
-0.443224
523
363.65147
783.58545
177.5477
-7.032E+05
833.99118
2.1868928

FCCU SIMULATOR : Base case 30000 BPD FCCU

Notes :

Product

Input Value color

Riser diam. =
Riser Height =

Calculated Value color

1.37
32

Proportional value color

m
m

Kg/s
wt% feed
2.547766 4.976105
1.218287
wt%

wt% feed

14.08437
25.61864
8.949219

27.50854
50.03641
17.47894

WHSV
Tout
Pout
selectivity
Conv.
efficiency

77.44749
802.888
228747.2
1.540309

hr
K
Pa

82.5
60.63472

wt%
wt%

0.512
523

Kg/s
K

-1

Riser

Product
COK
Coke

Kg/s

LGS
GLN
TGO

Hcomb =

80459.84

KJ/Kg coke

Regenerator

mrcat
mrcok
Trcat

208
0.013728
980

mds
Tds

C/O
Tmix2
Pin

6.09375
833.9912
244000

K
Pa.

mcat
mcok
Tmix1

312
1.293728
912.7421

Kg/s
Kg/s
K

Kg/s
Kg/s
K

MxR

mls
Tls
mxcat
mxcok
Tout

104
1.28
805

mf
Tf
API
Kuop
Mwt

1.792
523

Kg/s
Kg/s
K

Figure C-1

Kg/s
K

51.2
547
28.55
12.19
360

Kg/s
K

Kg/Kmole

Appendix D

Glossary
APPENDIX D

GLOSSARY OF TERMS USED IN THIS WORK

Activity: is a measure of how fast one or more reactions proceed in


presence of the catalyst. High catalyst activity means fast reactions rates
and short contact time required (1 5 second) to achieve high conversion.

API Gravity: is an "artificial" scale of liquid gravity defined by: (141.5/SG)


- 131.5. The scale was developed for water = 10. The main advantage of
using API gravity is that it magnifies small changes in liquid density.

Back-Mixing: is the phenomena by which the catalyst travels more slowly


up the riser than the hydrocarbon vapors.
Carbonium Ion: is a positively charged (CH 5+) ion which is formed by
adding a hydrogen ion (H+) to paraffin.

Catalyst/oil ratio (C/O): The weight of circulating catalyst fed to the


reactor of a fluid-bed catalytic cracking unit divided by the weight of
hydrocarbons charged during the same interval.

Catalyst Cooler: is a heat exchanger that removes heat from the regenerator
through steam generation.

Catalyst Stability: resistance to time dependent deactivation by coke.

Conradson carbon: A test used to determine the amount of carbon residue


left after the evaporation and pyrolysis of oil under specified conditions.
Expressed as weight percent; ASTM D-189.
E-1

Appendix D

Glossary

Conversion: is often defined as the percentage of fresh feed cracked to


gasoline, lighter products, and coke. Raw conversion is calculated by
subtracting the volume or weight percent of the FCC products (based on
fresh feed) heavier than gasoline from 100, or:
Conversion = 100 (LCO + HCO + DO) vol% or wt%

Dense Phase: is the region where the bulk of the fluidized catalyst is
maintained.

Dilute Phase: is the region above the dense phase which has a substantially
lower catalyst concentration.

Decanted Oil, Slurry, Clarified Oil, or Bottoms: Are the heaviest and often
the lowest priced liquid product from a cat cracker.

Delta Coke: is the difference between the coke content of the spent catalyst
and the coke content of the regenerated catalyst.

Efficiency = (%Gasoline)/ (% Conversion) x 100

HCO: Heavy FCC cycle gas oil product.

LCO: Light FCC cycle gas oil product.

LHSV: Liquid hour space velocity; volume of feed per hour per volume of
catalyst.
Refractory: is a cement-like material used to stand abrasion and erosion.

Riser: is a vertical "pipe" where virtually all FCC reactions take place.
E-2

Appendix D

Glossary

Selectivity: the ratio of the yield of desirable product (gasoline) to the yield
of undesirable products (coke and gas).

Severity: The degree of intensity of the operating conditions of a process


unit. Severity may be indicated by percent disappearance of the feed, or
operating conditions alone.

Slip Factor: is the ratio of catalyst residence time to hydrocarbon vapors


residence time in the riser.

Space velocity: The volume (or weight) of gas and/or liquid passing
through a given catalyst or reactor space per unit time, divided by the
volume (or weight) of catalyst through which the fluid passes. High space
velocities correspond to short reaction times. See LHSV and WHSV.

WHSV: Weight hour space velocity; weight of feed per hour per weight of
catalyst.

E-3

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