Fluidized Catalytic Cracking

Chapter 6
 Gases

Polymer- Sulfur
ization Plant
Sulfur

LPG
Sat Gas
Gas Plant

Butanes Fuel Gas

Alkyl
Feed LPG
Alkylation

Gas Polymerization
Separation & Naphtha
Stabilizer Isom-
erization
Light Naphtha
Alkylate
Aviation
Isomerate
Gasoline
Automotive
Gasoline
Reformate
Naphtha Solvents
Heavy Naphtha
Hydro-
Naphtha Reforming
treating Naphtha
Atmospheric
Distillation

Jet Fuels
Kerosene
Crude
Desalter Kerosene
Oil
Distillate Cat Solvents
AGO Hydro- Naphtha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
treating
Gas Oil Fluidized
Cat Diesel
LVGO Hydro- Catalytic
treating Cracking Distillates
Vacuum
Distillation
Fuel Oil
HVGO
Cycle Oils
Residual
Fuel Oils
DAO
Solvent
Deasphalting SDA
Coker Asphalts
Bottoms
Naphtha Naphtha

Visbreaking Heavy Distillates

Fuel Oil
Coker Bottoms
Vacuum Gas
Lube Oil Lubricant
Residuum Oil
Solvent Greases
Dewaxing
Waxes
Waxes
Coking Light Coker
Gas Oil

Coke

2
Purpose
• Catalytically crack carbon‐carbon 
bonds in gas oils 
ƒ Fine catalyst in fluidized bed reactor 
allows for immediate regeneration
ƒ Lowers average molecular weight & 
produces high yields of fuel products
ƒ Produces olefins
• Attractive feed characteristics
ƒ Small concentrations of 
contaminants
• Poison the catalyst
ƒ Small concentrations of heavy 
aromatics
• Side chains break off leaving cores 
to deposit as coke on catalyst
• Must be intentionally designed for 
heavy resid feeds
• Products may be further processed
ƒ Further hydrocracked
ƒ Alkylated to improve gasoline anti‐
knock properties

3
Characteristics of Petroleum Products

Large conversion to light products requires some coke formation

Refining Overview – Petroleum Processes & Products, 
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000

4
Overview of Catalytic Cracking

• FCC “heart” of a modern US refinery
ƒ Nearly every major fuels refinery has an FCCU
• One of the most important & sophisticated contributions to petroleum 
refining technology
• Capacity usually 35% to 40% of the crude distillation capacity
• Contributes the highest volume to the gasoline pool
Isomerization

Vol%
FCCU 35% FC C U

Reformer 30% Alkylation

Alkylation 20%
Isomerization 15%

Reformer

5
 U.S. Refinery Implementation

Vacuum Cat Cracking: Cat Cracking:

Distillation Fresh Feed Recycled Feed
Atmospheric
Downstream Downstream Downstream
Crude Distillation
Company State Site Charge Capacity, Charge Capacity, Charge Capacity,
Capacity (barrels
Current Year Current Year Current Year
per stream day)
(barrels per (barrels per (barrels per
stream day) stream day) stream day)

ExxonMobil Refining Louisiana BATON ROUGE 524,000 242,500 242,000 0

ExxonMobil Refining Texas BAYTOWN 596,400 288,600 215,500 8,000
BP Texas TEXAS CITY 475,000 237,000 175,000 8,000
BP Indiana WHITING 420,000 247,000 165,000 4,000
PDVSA Louisiana LAKE CHARLES 440,000 235,000 147,000 3,000
Hovensa LLC Virgin Islands KINGSHILL 525,000 225,000 149,000 0
ConocoPhillips New Jersey LINDEN 250,000 75,000 145,000 0
Sunoco Pennsylvania PHILADELPHIA 355,000 163,200 138,500 0
Marathon Petroleum Louisiana GARYVILLE 275,000 142,000 131,000 0
Motiva Enterprises Louisiana NORCO 250,000 95,000 120,000 0

Top 10 combined Cat Cracking

6
Typical FCC Complex

Ref: http://www.osha.gov/dts/osta/otm/otm_iv/otm_iv_2.html

9
FCC Riser/Regenerator Combination

Refining Overview – Petroleum Processes & Products, 
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000

10
Other FCC Configurations

Petroleum Refining Technology & Economics – 5th Ed.

by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007

11
Other FCC Configurations
Bayway configuration?

Petroleum Refining Technology & Economics – 5th Ed.

by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007

12
Fluidized Catalytic Cracking Technologies

Provider Features
Shaw Deep catalytic cracking
ExxonMobile Research & Engineering Fluid catalytic cracking
KBR Fluid catalytic cracking
Lummus Technology Fluid catalytic cracking
Shaw Fluid catalytic cracking
Shell Global Solutions Fluid catalytic cracking
UOP Fluid catalytic cracking
Lummus Technology Fluid catalytic cracking for maximum olefins
KBR Fluid catalytic cracking, high olefin content
KBR Fluid catalytic cracking, residual
Haldor Topsoe A/S Fluid catalytic cracking ‐‐ pretreatment
Shaw Resid cracking
Axens Resid cracking

13
Early Fixed & Moving Bed Catalytic Cracking
• Cyclic fixed bed catalytic cracking commercialized in late 1930s
ƒ Houdry Process Corporation formed in 1930
ƒ First Houdry catalyst cracker started up at Sun Oil’s Paulsboro, New 
Jersey, refinery in June 1936
• Three fixed bed reactors & processed 2,000 barrels/day

ƒ 12,000 barrels/day commercial unit went on stream at Sun’s Marcus 
Hook Refinery in 1937
ƒ Other adoptees: Gulf, Sinclair, Standard Oil of Ohio, & The Texas 
Company
• Sun & Houdry Process Corporation started development on a moving 
bed process in 1936
ƒ Pilot Thermofor catalytic cracker was started in 1941
ƒ First commercial 20,000‐barrel/day unit commissioned at Magnolia’s 
Beaumont Refinery in 1943

14
Fluidized Catalytic Cracking
• Up‐flow dense phase particulate solid process credited to W.K. Lewis, MIT
• Originally developed as the Winkler coal gasification process
ƒ Standard Oil of New Jersey, Standard Oil of Indiana, M.W. Kellogg, Shell Oil, The 
Texas Company, & others
• Dense phase – back mixed reactor 
ƒ Model I FCCU at Standard Oil of New Jersey’s Baton Rouge Refinery, 1942
ƒ Model II dominated catalytic cracking during early years
• Designed before first Model I operating

• Dilute phase — riser reactor design
ƒ Catalysts based on molecular sieve – 1960s 
ƒ Significantly higher cracking activity & gasoline yields – lower carbon on catalyst
ƒ Plug flow – drastically reduced residence time & 90% feed conversions

15
Feeds for Catalytic Cracking
• Aromatic rings typically condense to coke
ƒ No hydrogen added to reduce coke formation
ƒ Amount of coke formed correlates to carbon residue of feed
• Feeds normally 3‐7 wt% CCR
• Catalysts sensitive to heteroatom poisoning
ƒ Sulfur & metals (nickel, vanadium, & iron)
ƒ Feeds may be hydrotreated
• Atmospheric & vacuum gas oils are primary feeds
ƒ Could be routed to the hydrocracker for diesel production
• Not as expensive a process as hydrocracking
ƒ Dictated by capacities & of gasoline/diesel economics
• Hydrotreated feed results in cleaner products, not high in sulfur 

16
FCC Products
• Primary goal to make gasoline & diesel  • Cat kerosene & jet fuel
while minimizing production of heavy fuel 
oil ƒ Low centane number because of aromatics 
ƒ “Cat gasoline” contributes largest volume  – lowers quality diesel pool
to the gasoline pool
• Gas oils – “cycle oils”
• Front end rich in olefins
ƒ Same boiling range as initial gas oil 
• Back end highly aromatic with some 
olefins feedstock
• Does not contain much C‐6 & C‐7 olefins – • “Slurry”
very  reactive & form lighter olefins & 
aromatics ƒ Heavy residue from process
• Coke production small but very important ƒ High in sulfur, small ring & polynuclear
ƒ Burned in regenerator & provides heat for  aromatics, & catalyst fines
cracking reactions
ƒ Usually has high viscosity
• Light ends contain large amounts of olefins
ƒ Good for chemical feedstock ƒ Disposition 

ƒ Can recover chemical grade propylene &  • Blended into the heavy fuel oil (“Bunker 
ethylene Fuel Oil” or Marine Fuel Oil)
ƒ Propylene, butylene, & C5 olefins can be  • Hydrocracked
alkylated for higher yields of high‐octane 
gasoline • Blended into coker feed – can help 
mitigate problems with shot coke 
production

17
Product Yields
• Produces high yields of liquids & small amounts of gas & coke
ƒ Mass liquid yields are usually 90%‐93%; liquid volume yields are often 
more than 100% (volume swell)
ƒ (Rule of thumb) Remaining mass yield split between gas & coke
• The yield pattern is determined by complex interaction of feed 
characteristics & reactor conditions that determine severity of 
operation
ƒ Rough yield estimation charts given in text pp. 117‐130 pp. 144‐156
• Conversion defined relative to what remains in the original feedstock 
boiling range 
Conversion = 100% − ( Gas Oil Yield)

18
Use of Yield Charts
Vol% Wt% Density
Fuel Gas 6.19
C3 6.21 Ratio Pure
C3= 6.21 Ratio Pure
LPG IC4 6.20 6.22 Ratio Pure
NC4 6.22 Ratio Pure
C4=s 6.22 Ratio Pure
Gasoline 6.23 Ratio 6.27
LCO 100% ‐ Δ Δ Ratio
Cycle Oils Δ Ratio
HCO Conv 6.24/25 Ratio 6.27
Coke 6.18
Total 100% 100%

19
 FCCU Yield Example
Product Yields from FCCU
Watson Sulfur Water density @ 60°F = 8.33718 lb/gal
Feed Information: Ave BPT Specific API K Factor Content
°F Gravity Gravity wt%
825.4 0.9042 25.0 12.0 0.500
Product Distribution:
Conversion = 72.0 vol% Sulfur Distribution
Yields Standard Densities Product Recovery
Fraction bbl/day lb/hr vol% wt% °API SpGr lb/gal lb/bbl wt% lb/hr wt%
Feed 25,000 329,791 100.0% 100.0% 25.0 0.9042 7.538 316.6 0.50% 1,649

Light gases (C2-) 16,134 4.89% 2.54% 410 24.9%

Propane (C3) 636 4,704 2.54% 1.43% 147.6 0.5070 4.227 177.5 2.68% 126 7.6%
Propylene (C3=) 1,444 10,977 5.78% 3.33% 140.1 0.5210 4.344 182.4 1.15% 126 7.6%
Iso-butane (IC4) 1,390 11,417 5.56% 3.46% 119.9 0.5629 4.693 197.1 1.10% 126 7.6%
n-butane (NC4) 488 4,162 1.95% 1.26% 110.8 0.5840 4.869 204.5 3.03% 126 7.6%
Butylenes (C4=) 1,893 16,605 7.57% 5.03% 103.8 0.6013 5.013 210.6 0.76% 126 7.6%
Gasoline (C5+) 14,311 156,021 57.24% 47.31% 57.9 0.7473 6.230 261.7 0.054% 84 5.1%
Light Cycle Oil (LCO) 5,300 67,968 21.20% 20.61% 29.5 0.8790 7.328 307.8 0.37% 254 15.4%
Heavy Cycle Oil (HCO) 1,700 25,857 6.80% 7.84% 4.2 1.0425 8.692 365.0 0.98% 254 15.4%
Coke 15,947 4.84% 0.10% 16 1.0%

Total 27,162 329,791 108.65% 100.00% 1,649 100.0%

Cycle Oils 7,000 93,825 28.00% 28.45% 22.5 0.9187 7.659 321.7 508 30.8%

Un-Normalized Yields:
Total LPG 5,851 23.41% 631 38.2%

Propane (C3) 2.92%

Propylene (C3=) 6.63%
Iso-butane (IC4) 6.38%
n-butane (NC4) 2.24%
Butylenes (C4=) 8.69%
Total 26.87%

Example

20
Boiling Point Ranges for Products
Kaes's Example FCC Problem

3,000

net.cso
31a
2,500 lco.product
unstab.gasol
wet.gas
53-total.feed
Incremental Yield [bpd]

2,000

1,500

1,000

500

-
0 100 200 300 400 500 600 700 800 900 1000 1100 1200
BPT [°F]

21
Catalytic Cracking Catalysts & Chemistry
• Acid site catalyzed cracking & hydrogen transfer via carbonium
mechanism 
ƒ Basic reaction — carbon‐carbon scission of paraffins & cycloparaffins to 
form olefins & lower molecular weight paraffins & cycloparaffins

Paraffin ⎯⎯
→Paraffin+Olefin
Alkyl Naphthene ⎯⎯
→Naphthene+Olefin
Alkyl Aromatic ⎯⎯
→ Aromatic+Olefin
• Example

CH3CH2CH2CH2CH2CH2CH2CH3 ⎯⎯
→ CH3CH2CH2CH2CH3 + CH=CH2CH3

ƒ Olefins exhibit carbon‐carbon scission & isomerization with alkyl 
paraffins to form branched paraffins
ƒ Cycloparaffins will dehydrogenate (condense) to form aromatics
ƒ Small amount of aromatics & olefins will condense to ultimately form 
coke

22
Catalytic Cracking Catalysts & Chemistry
• Zeolite catalysts
ƒ High activity
ƒ High gasoline & low coke yields
ƒ Good fluidization properties
• Size between flour & grains of sand. 
• Balance between strength (so it doesn’t break apart as it moves through system) but doesn’t 
abrade the equipment internals.
- 70 tons/min typical circulation rate

• Research continues by catalyst suppliers & licensors 
ƒ Recognition that both crackability of feed & severity of operations are  factors
ƒ Theoretical basis for cracking reactions lead to more precise catalyst formulation
ƒ Catalyst tailored to maximize gasoline or diesel yield or increase olefin production
ƒ Additives
• Bottoms cracking
• ZSM‐5 for increased C3 production
• CO combustion promoters (in regenerator)

23
Zeolite Structure

Ref: http://thor.tech.chemie.tu‐muenchen.de/index.php?option=com_frontpage&Itemid=1

24
Trends in Catalysts

Ref: http://thor.tech.chemie.tu‐muenchen.de/index.php?option=com_frontpage&Itemid=1

25
Operating Conditions & Design Features
• Designed to provide balance of reactor & regenerator capabilities
• Usually operate to one or more mechanical limits
ƒ Common limit is capacity to burn carbon from the catalyst
• If air compressor capacity is limit, capacity may be increased at feasible 
capital cost
• If regenerator metallurgy is limit, design changes can be formidable.
• Regenerator cyclone velocity limit

ƒ Slide valve ΔP limit

26
FCC Riser/Regenerator Combination
• Risers
ƒ Inlet typically 1300°F, outlet 950 ‐ 1000°F
ƒ Increased reactor temperature to increase severity & 
conversion
• May need to reverse to lower olefin content (gasoline 
formulation regulations)
ƒ Reactor pressure controlled by the fractionator 
overhead gas compressor
• Typically 10 to 30 psig
ƒ High gas velocity fluidizes fine catalyst particles. 
ƒ Current designs have riser contact times typically 2 to 3 
seconds.
• Times less than 0.25 seconds reported
ƒ Important design point: quick, even, & complete 
mixing of feed with catalyst
• Licensors have proprietary feed injection nozzle 
systems to accomplish this
• Atomize feed for rapid vaporization
• Can improve performance of an existing unit
Petroleum Refining Technology & Economics – 5th Ed.
by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007

27
FCC Riser/Regenerator Combination
• Cyclones
ƒ Gas/solid separation in cyclones 
• Increased cross sectional area decreases gas 
velocity.
• Normally 2 stage cyclones. 
ƒ Rapid separation to prevent “over cracking.”
• Regenerators
ƒ Regenerators operate 1200 – 1500°F
• Limited by metallurgy or catalyst concerns
ƒ Temperature determines whether combustion 
gases primarily CO or CO2
• Partial Burn. Under 1300°F. High CO content. 
Outlet to CO boilers & HRSG (heat 
recovery/steam generation).
• Full Burn. High temperatures produce very little 
CO. simpler waste heat recover systems.

Petroleum Refining Technology & Economics – 5th Ed.

by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007

28
FCC Riser/Regenerator Combination
• Heat balance
ƒ Reactor & regenerator operate in heat balance
• More heat released in the regenerator, higher temperature of 
regenerated catalyst, & higher reactor temperatures.
ƒ Heat moved by catalyst circulation.

29
Resid Catalytic Cracking
• Economics favoring use of heavier crudes & direct 
cracking of resids
ƒ Instead of a normal 5‐8% coke yield, it can reach 
15% with resid feeds
• Requires heat removal in regenerator 
ƒ “Catalyst coolers” on regenerator to 
ƒ Produces high‐pressure steam
ƒ Specially designed vertical shell & tube heat 
exchangers
ƒ Proprietary specialized mechanical designs 
available with technology license

Petroleum Refining Technology & Economics – 5th Ed.

by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007

30