8th Summer School on Petroleum Refining & Petrochemicals 3 7 June, 2013

FCC PROCESS FUNDAMENTALS & TECHNOLOGY EVOLUTION

June 3, 2013

Debasis Bhattacharyya
(bhattacharyad1@indianoil.in)

Outline
Process fundamentals
Catalytic cracking Fluidization regimes Position in refinery Process flow diagram Mode of catalyst regeneration Heat balance Process variables

Technology evolution
Reactor-Regenerator configuration Hardware internals Catalysts & Additives Resid processing Requirement specific developments

Summary

Refining Processes
Crude oil separation

Contaminant removal / product quality improvement

Refinery

Molecular rearrangement & combination

Molecular cracking: large to small

Cracking of Heavy Hydrocarbons

Cracking : Breaking large molecules by application of heat with or without catalyst with or without hydrogen

Thermal
High coke

Catalytic

Hydro
Low coke

Fluid Catalytic Cracking (FCC)

Dry gas Vacuum gas oil (VGO)

(H2, C1, C2)

Hydro-treated VGO
Hydro-cracker bottom Coker gas oil (CGO) De-asphalted oil (DAO) Reduced crude oil (RCO)

LPG
(C3, C4)

Light cracked naphtha (LCN)

(C5-150oC)

Heavy cracked naphtha (HCN)

(150 - 220oC)

Light cycle oil (LCO)

(220 - 370oC)

Vacuum residue (VR)

Clarified oil (CLO) or

Decant oil (DO)

Conversion wt% = (Feed- LCO- CLO)*100/Feed

. being continued till today 5

Position of FCC in Refinery

S T A B

Gas

LPG

Crude

C R U D E D I S T

Gasoline Blending

Gasoline

HDS

CCR Reformate HDS HDS Kerosene Jet fuel Diesel

V A C D I S T

Hydro-cracker/ Treater Visbreaker / Coker

BBU

FCC

Fuel Oil Coke Bitumen

6

Schematic of FCC
Products to Fractionator Flue Gas to WHRU Minimum fluidization (0.001-0.05 m/s) Reactor Bubbling (0.05-0.30 m/s) Stripper Steam Regenerator Turbulent (0.7-1.1 m/s) Air Fast fluidization/ Pneumatic transport (5-20 m/s)

SCSV

RCSV RCSV with Riser outlet temp. SCSV with reactor level
Steam

Riser Feed

Fluidization Regimes
P L P L

Umf

Umb

Uch

.. . . . ...
Fixed bed
Particulate regime Bubbling regime Slug flow regime Turbulent regime Fast fluidization

.... . . . ... . . .. . . . .. ....

Pneumatic conveying
8

Increasing Gas Velocity

Fluid Catalytic Cracking

Feed surge drum Pump Feed pre-heat furnace

Wet gas compressor

DDSV Orifice chamber CO boiler Waste heat recovery section Flue gas stack

FCC Internals
Reactor dome quench nozzle
Cyclone separator

Riser termination device

Regenerator dome quench nozzle Cyclone separator

Stripper internals Stripping steam distributor

Regenerator air distributor

Spent catalyst distributor

Feed injection nozzles 10

Main Catalytic Cracking Reactions

Paraffins
Cracking Cracking Cyclization Isomerization H Transfer Cyclization Condensation Dehydrogenation Cracking Dehydrogenation Isomerization Paraffins + Olefins LPG Olefins Naphthenes Branched Olefins Paraffins Coke Coke Coke

H Transfer

Branched Paraffins

Olefins

Naphthenes

Olefins Cyclo-olefins Dehydrogenation Naphthenes with different rings

Aromatics

Aromatics

Side chain cracking Trans alkylation Dehydrogenation Condensation

Unsubstituted aromatics + olefins Different alkyl aromatics Polyaromatics Alkylation Dehydrogenation Condensation

Coke

Hydrogen transfer Naphthene + Olefin Aromatic + Paraffin

11

Different Modes of FCC: Comparison

Mode Dry gas LPG Gasoline (C5-150oC) TCO (150-370oC) CLO ( 370oC+ ) Coke 216oC - Conversion LPG Gasoline Distillate

Typical product yields, wt% 6.5 4 2

40 25 10 4 6.5 90 18 45 22 6 5 81 10 30 44 10 4 50

Coke deposited on catalyst blocks the active site causes temporary deactivation needs burning to regenerate before circulating to riser
12

Types of Coke
Coke yield = Feed coke + Catalytic coke + Strippable coke + Contaminant coke Feed coke = 1 (feed CCR); where, 1 = f1(feed vaporization/distribution)

Catalytic coke = f2 (ROT, Cat/oil ratio, Catalyst/feed quality, Conversion level..)

Strippable coke = f3 (Stripper efficiency, Riser operation- temp.) Contaminant coke= Coke contributed by the contaminant metals in feed = f3 (metal level on catalyst, catalyst characteristics, operation severity, use of metal passivator)

Coke deposited on catalyst blocks the active site cause temporary deactivation of the catalysts Coke on catalyst needs to be burnt to regenerate before circulating to riser bottom Balancing coke is the most crucial in design of FCC unit

13

Mode of Catalyst Regeneration

Coke burning reactions
C + 1/2O2 CO (H = - 2200 kcal /kg)

CO + 1/2O2 CO2 (H = - 5600 kcal /kg)

H2 + 1/2O2 H2O (H = - 28900 kcal /kg)

Mode
Coke on regenerated catalyst, wt% Effective catalyst activity Regenerator temperature, oC CO in flue gas, ppm Requirement of CO Boiler Chances of Afterburning

Total Combustion
< 0.05 Higher Higher < 1000 No Lower

Partial Combustion
> 0.05 Lower Lower > 1000 Yes Higher
14

FCC Heat Balance

Flue gas Regenerator Spent Catalyst Heat of Coke Combustion Heat of Reaction Recycle Reactor Products Heat Losses

Heat losses

Regeneration Air

Regenerated Catalyst

Fresh Feed
Feed Pre-heater

15

FCC Heat Balance

Coke yield = Wcoke/Wfeed = Wcat*(CSC-CRC) / Wfeed = (Cat/Oil)*(Delta Coke)

Delta Coke = (Cpcat / DHcoke )*(Trg-Trc) (Trg-Trc) Coke yield = Reactor heat demand per unit total feed

Heat of Combustion per unit Coke = (Cat/Oil)*(Delta Coke)

Delta Coke (Trg-Trc)

For a given ROT, more is the Delata coke, more will be the regenerator dense bed temperature
16

Variables in FCC
Independent
Feed rate Recycle ratio Feed preheat Riser top temperature Reactor pressure Fresh catalyst activity / Selectivity

Major dependent
Regenerator temperature Catalyst circulation rate Regenerator air flow Coke on regenerated catalyst Product yields
17

Evolution of FCC Technology

1940s
Period 1936-1941 1941-1960 1942-today 1942

Fluid Catalytic Cracking Process for Gasoline

FCC process development Fixed bed Moving bed Fluid bed 1ST commercial FCCU was on stream at Baton Rouge Refinery of Standard Oil of New Jercy 33 FCCU were in operation Dense bed reactor

End of 1945 1955-1970s

Post 1970s

Short contact riser with pneumatic conveying become popular

18

Evolution of FCC Hardware Design

19

Exxons Model-IV FCC Unit

Flexi-cracking by ExxonMobil

20

Evolution of FCC Hardware Design

Kellogg Orthoflow FCC Converter

Orthoflow Resid FCC Converter

21

Resid FCC Units

Two-stage regenerator

Fast fluidized regenerator

UOP high efficiency regenerator RFCCU

UOP RFCC Unit

22

Two Stage Regeneration

RFCC unit by SWEC

R2R unit by Axens

23

Evolution of FCC Hardware Design

Source: www.kbr.com

24

Feed Injection System

Rapid feed vaporization and uniform mixing with catalyst
Reduce non-selective cracking &
thermal reaction

Better feed nozzle design using dispersion steam

Enhance vaporization Avoid backmixing of hydrocarbons

Avoid thermal cracking

Reduce hydrocarbon partial pressure

Feed coke = 1 (feed CCR) where, 1 = f1(feed vaporization/distribution)

Reduce coke make & improve yields

25

Effect of Feed Atomization

Parameter Oil droplet size, Relative no. of droplets Oil droplets/catalyst particle Vaporization time, milisec at 50% vorization 220 11 4 Case-1 500 1 0.001 Case-2 100 125 0.11 Case-3 30 4630 4

at 90% vaporization

400

20

26

Reactor Riser Disengaging Devices

T-Type Disengage r

Down Turned Arm

Vented Riser

Direct-Connected Cyclones
27

Reactor Riser Disengaging Devices

Source: www.kbr.com

Ramshorn type or Linear Disengaging Device (LD2)

Closed Cyclone Riser Termination

Vortex Separation System

28

Regenerator Cyclone System & Orifice Chamber

Source: www.hason-steel.com

Regenerator Cyclones

Orifice chamber

Regenerator Air Distributor

Air distributors
Minimizing gas bypassing or channeling Mass transfer diffusion resistance Erosion Thermal expansion mechanical reliability Mechanical integrity of supports

Commonly used
Pipe grid Air ring
Flat pipe grid preferred due to uniform coverage & lower discharge velocity

Efficient air grid

Total combustion regenerators least excess oxygen in flue gas Partial combustion regenerators minimum afterburning
30

FCC Catalyst Improvement

Catalysts Heart of FCC process undergone evolutionary changes
Colloidal binder

Zeolite pores 6.5-13. 5A Interparticle void clay Matrix pores 10-200A

Zeolite: Silica-alumina Amorphous matrix: Silica, silica-alumina, alumina Filler clay: Silica-alumina Other elements: Rare earth, Sodium

1942
1 micron

Natural clay, Synthetic low alumina catalyst

1948
1955 1961 1964 1980 1986

Micro-spheroidal catalyst (low alumina)

High alumina synthetic catalyst D5 zeolite TCC bead catalyst Spray dried fluid Y zeolites Coke selective Re-HY catalysts Improvement in Y-zeolites (USY) low coke selectivity, Higher octane (low non-framework alumina) 31

FCC Catalyst Improvement

Improvements in FCC catalysts Year 1950 1970 1990

Zeolite content, wt%

Particle density, g/cc Relative Attrition Index Todays FCC catalysts

0
0.9 20

10
1.0 5

40
1.4 1

Porous spray dried micro-spherical powder Particle size distribution of 20 -120 micron & particle density ~ 1400 kg/m3 Comprising Y zeolite in many derivatives of varying properties Supplied under various grades of particle sizes & attrition resistance Continuing improvement metal tolerance, coke selectivity Zeolite based catalyst improved yields of desired products with given feed & hardware
32

Use of Additives
ZSM-5 Additive
Increases yields of LPG / Light olefins Improves Gasoline RON Bottom Cracking Additive Upgrades bottom fraction of feed without proportional increase in coke make

GSR Additive
Reduces Gasoline Sulfur content by ~ 30%

CO Promoter
Enhances CO burning in regenerator dense bed

SOX Control Additive

Reduces SOx in regenerator flue gas

Ni passivator & V- Trap

Reduces detrimental effects of metals on product yields & catalyst health
33

Problems with Resid Processing in FCC

Ni S V &Na Basic N2 Aromatics
More H2, Dry Gas & Coke SOx Emmission, S in Product
Zeolite Destruction Zeolite Acidity Neutralization

More Coke & Low conversion

Con. Coke

High Regen temp, Low Cat/Oil High catalyst consumption to maintain activity
34

FCC Catalyst Cooler

External vertical shell & tube heat exchanger

Removal of heat Reduces regenerator temperature Retains catalysts activity Increases catalyst to oil ratios Better yields & enhanced profitability
35

Catalyst flows over entire cross sectional area of tube bundle in dense phase Provides variable heat sink & produces steam upto 850 psig

Shifting in objective of FCC operation

Operating Objective

Petrochemical feed stock

Alkylation& Isomerization feed

Product quality Resid Gasoline 1942 1970 1990 1995 2010

36

Technologies Developed by IndianOil

Technology Feed Heavy feedVGO, RCO, VR (part) Major products Challenges overcome

INDMAX

Light olefins, LPG, Deep cracking of heavier feed high octane with lesser Coke & Gas gasoline formation Unit heat balance Metal deactivation of catalyst

INDALIN

Naphtha

Light olefins, LPG, Cracking of low molecular gasoline weight hydrocarbon Unit heat balance Auto-grade LPG (saturated) & high octane gasoline Cracking of low molecular weight hydrocarbon Unit heat balance Saturation of LPG without using external hydrogen
Optimization of intermediate fraction with lower yield of bottom fraction

INDALIN Plus

Naphtha

Dist-Extra

Heavy feedVGO

Diesel component with higher cetane

Indmax Technology Resid to Olefins

Operational features High cat/oil ratio (15-25) Higher riser temperature (>550oC) High riser steam rate Relatively lower regen temp. Benefits LPG 35-55 wt% Propylene 17-25 wt% feed High octane gasoline (95+) Multifunctional proprietary catalyst Higher propylene selectivity Superior metal tolerance Lower coke make

Successfully commissioned at Guwahati refinery in June03 - Smoothest commissioning in IOCs FCC start-up

Indmax can handle high CCR, non-hydrotreated feed with attractive LPG / light olefins yield

38

Indmax-FCC Reactor-Regenerator
Direct-Coupled Cyclones Reaction Riser (Short Contact Time) Cyclone Containment Vessel (CCV) Direct-Coupled Cyclones Cyclone Containment Vessel (CCV)

MG Stripper

MG Stripper

Turbulent Regenerator Bed

Turbulent Regenerator Bed External Regenerated Catalyst Hopper

Being worldwide licensed by Lummus Technology, USA based on Basic Process Design data/information & catalyst from IndianOil
Micro-Jet Feed Injection Nozzles 39

INDMAX - Continual Development

Improvement of light olefins yield Setting up 85000 BPSD unit Collaboration with Lummus for global marketing & licensing Scale up & Commercialization

INDMAX
Yields of light olefins with paraffinic VGO feed (wt%):
Propylene: 27 Butylenes : 15 Ethylene : 14

Process development & pilot plant demonstration

IndianOils proven INDMAX technology can meet Refiners objectives of propylene maximization 40 &

Summary
FCC has been the most profitable & flexible refining process for more than seven decades because of its ability to meet changing demands FCC technology is still undergoing significant evolution

Beyond certain feed CCR, RFCC becomes too expensive due to high consumption of catalyst & inferior product yields
Increasing gap in propylene demand & supply drives orientation of FCC operation towards propylene maximization Scenario specific tailor made technology can be developed through proper understanding of fundamentals IndianOils proven INDMAX technology can meet the Refiners objectives of propylene maximization & residue upgradation in an cost effective manner
41

42