Fluidized Catalytic Cracking

Chapter 6
Petroleum Refinery Block Flow Diagram

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Overview of Catalytic Cracking
FCC “heart” of a modern US refinery
▪ Nearly every major fuels refinery has an
FCCU
One of the most important & sophisticated
contributions to petroleum refining
technology
Capacity usually 1/3 of atmospheric
crude distillation capacity
Contributes the highest volume
to the gasoline pool

FCCU
Alkylation EIA, Jan. 1, 2019 database, published June 2019
[Link]
Reformer
Isomerization

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U.S. Refinery Implementation

EIA, Jan. 1, 2019 database, published June 2019

[Link]

Updated: July 1, 2019

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Purpose
Catalytically crack carbon-carbon bonds Products may be further processed
in gas oils ▪ Further hydrotreated
▪ Fine catalyst in fluidized bed reactor ▪ Olefins used as feedstock to alkylation
allows for immediate regeneration process
▪ Lowers average molecular weight &
produces
▪ high yields of fuel products
▪ Produces olefins

Attractive feed characteristics

▪ Small concentrations of contaminants
• Poison the catalyst
▪ 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

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 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

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What is a fluidized bed?

[Link] [Link]

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Fluid Catalytic Cracker

[Link] “Benecia Refinery Tour,” Valero Energy Corp., July 9, 2007

[Link]

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Typical FCC Complex

Figure modified from Koch-Glitsch Bulletin KGSS-1, Rev. 3-2010,

[Link]

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FCC Riser/Regenerator Combination

“Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis”
E.T.C. Vogt & B.M. Weckhuysen, Chem Soc Rev, 2015, 44, 7342-7370

Updated: July 1, 2019

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CFD Simulation of an FCC Riser

[Link]

Updated: July 1, 2019

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History – Fixed, Moving, & Fluidized Bed
Cracking
Cyclic fixed bed catalytic cracking Fluidized bed catalytic cracking
commercialized in late 1930s ▪ Up-flow dense phase particulate solid process
▪ 1st Houdry Process Corporation catalyst cracker credited to W.K. Lewis, MIT
started up at Sun Oil’s Paulsboro, New Jersey, ▪ Early adopters: Standard Oil of New Jersey,
refinery in June 1936 Standard Oil of Indiana, M.W. Kellogg, Shell Oil,
▪ Three fixed bed reactors & processed 2,000 The Texas Company, & others
barrels/day ▪ Dense phase – back mixed reactor
▪ Other adoptees: Sun, Gulf, Sinclair, Standard ▪ Model I FCCU at Standard Oil of New Jersey’s
Oil of Ohio, & The Texas Company Baton Rouge Refinery, 1942
▪ Model II dominated catalytic cracking during
Sun & Houdry started developing moving bed
early years
process in 1936
▪ 1st commercial 20,000-barrel/day unit Dilute phase — riser reactor design
commissioned at Magnolia’s Beaumont ▪ Molecular sieve based catalysts – 1960s
Refinery in 1943
▪ Significantly higher cracking activity & gasoline
yields – lower carbon on catalyst
▪ Plug flow – drastically reduced residence time
& 90% feed conversions

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FCC Feedstocks
Chemical species considerations Atmospheric & vacuum gas oils are
▪ Aromatic rings typically condense to primary feeds
coke ▪ Could be routed to the hydrocracker
• Feedstock can be hydrotreated to for diesel production
reduce the aromatic content • Not as expensive a process as
• Amount of coke formed correlates to hydrocracking
carbon residue of feed ▪ Dictated by capacities & of
o Feeds normally 3-7 wt% CCR gasoline/diesel economics
▪ Catalysts sensitive to heteroatom
poisoning Hydrotreated feed results in cleaner,
• Sulfur & metals (nickel, vanadium, & low-sulfur products
iron) ▪ If feedstock not hydrotreated then
• Feeds may be hydrotreated to reduce the products must be separately
poisons hydrotreated to meet ultra low
sulfur specs

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FCC Products
Primary goal – make gasoline & diesel, Cat kerosene & jet fuel – rarely made
minimize heavy fuel oil production ▪ Low cetane number because of aromatics –
▪ “Cat gasoline” contributes largest volume to lowers quality diesel pool
the gasoline pool ▪ Poor cold properties
• Front-end rich in olefins, back-end aromatics
• Does not contain much C-6 & C-7 olefins – very Gas oils – “cycle oils”
reactive & form lighter olefins & aromatics ▪ Essentially same boiling range as feedstock

Coke production relatively small but very “Slurry”

important ▪ Heavy residue from process
▪ Burned in regenerator & provides heat for ▪ High in sulfur, small ring & polynuclear
cracking reactions aromatics, & catalyst fines
▪ Largest single source of CO2 in refinery ▪ Usually has high viscosity
Light ends high in olefins ▪ Disposition
• Blended into the heavy fuel oil (“Bunker Fuel Oil”
▪ Good for chemical feedstock or Marine Fuel Oil)
▪ Can recover refinery grade propylene • Hydrocracked
▪ Propylene, butylene, & C5 olefins can be • Blended into coker feed – can help mitigate shot
alkylated for higher yields of high-octane coke problems
gasoline

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Product Yields
Produces high yields of liquids & small amounts of gas & coke
▪ Mass liquid yields are usually 90% – 93%; liquid volume yields are often more than
100% (volume swell)
▪ (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
▪ Rough yield estimation charts given in text pp. 117 – 130 & pp. 144-156
Conversion (per the text book) defined relative to what remains in the original
feedstock boiling range:
% Product Yield = 100 × (Product Volume) / (Feed Volume)
Conversion = 100% - (% Cycle Oil Yield)

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FCCU Yield Example

Updated: July 1, 2019

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Boiling Point Ranges for Products Kaes's Example FCC Problem

3,000

[Link]
31a
2,500 [Link]
[Link]
[Link]
[Link]
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]

Based on example problem in:

Refinery Process Modeling, A Practical Guide to Steady State Modeling of Petroleum Processes, 1 st ed.
Gerald Kaes, Athens Printing Company, 02004

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Catalytic Cracking Catalysts & Chemistry
Composites – zeolite dispersed in amorphous matrix
▪ Zeolite – 10-50 wt % – provides activity, stability, & selectivity
▪ Matrix – 50-90% – provides desirable physical properties & some catalytic activity

Acid site catalyzed cracking & hydrogen transfer via carbonium mechanism
▪ Basic reaction — carbon-carbon scission of paraffins & cycloparaffins to form olefins & lower molecular
weight paraffins & cycloparaffins
Paraffin → Paraffin + Olefin
Alkyl Napthene → Naphthene + Olefin
Alky Aromatic → Aromatic + Olefin
▪ Example
CH3CH2CH2CH2CH2CH2CH2CH3 → CH3CH2CH2CH2CH3 + CH=CHCH3
▪ Olefins exhibit carbon-carbon scission & isomerization with alkyl paraffins to form branched paraffins
▪ Cycloparaffins will dehydrogenate (condense) to form aromatics
▪ Small amount of aromatics & olefins will condense to ultimately form coke

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Complex System of Chemical Reactions

“Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis”
E.T.C. Vogt & B.M. Weckhuysen, Chem Soc Rev, 2015, 44, 7342-7370

Updated: July 1, 2019

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Catalysts & Chemistry
FCC catalysts consists of a number of components to
meet demands of FCC system
▪ High activity, selectivity, & accessibility; coke
selectivity
• High gasoline & low coke yields
▪ Good fluidization properties & attrition resistance
• 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.
o 70 tons/min typical circulation rate

▪ Hydrothermal stability
▪ Metals tolerance

Main active component is a zeolite

▪ Internal porous structure with acid sites to crack
larger molecules to desired size
range “Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis”
E.T.C. Vogt & B.M. Weckhuysen, Chem Soc Rev, 2015, 44, 7342-7370

Updated: July 1, 2019

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Catalysts & Chemistry
Research continues by catalyst suppliers
& licensors
▪ Recognition that both crackability of feed
& severity of operations are factors
▪ Theoretical basis for cracking reactions
lead to more precise catalyst formulation
▪ Catalyst tailored to maximize a particular
product
• Focus used to be on gasoline…
• now more likely diesel yield or …
• increased olefin production
▪ Additives
• Bottoms cracking
“Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis”
• ZSM-5 for increased C3 production E.T.C. Vogt & B.M. Weckhuysen, Chem Soc Rev, 2015, 44, 7342-7370
• CO combustion promoters in regenerator

FCC catalyst cost

▪ Generally the 2nd highest operating
expense, after crude oil purchases
▪ May pay upwards of $3,000 per ton

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Yields are catalyst dependent

New Resid Fluid Catalytic Cracking (FCC) Catalyst Technology for Maximum Distillates Yield Demonstrated in Big West
Oil’s Salt Lake City Refinery, BASF Technical Note

Updated: July 1, 2019

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Operating Conditions & Design Features
Designed to provide balance of reactor & regenerator capabilities
Usually operate to one or more mechanical limits
▪ 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
▪ Slide valve ΔP limit

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FCC Riser/Regenerator Combination
Risers
▪ Inlet typically 1300oF, outlet 950 – 1000oF
▪ Increased reactor temperature to increase severity &
conversion
• May need to reverse to lower olefin content (gasoline
formulation regulations)
▪ Reactor pressure controlled by the fractionator
overhead gas compressor
• Typically 10 to 30 psig
▪ High gas velocity fluidizes fine catalyst particles.
▪ Current designs have riser contact times typically 2
to 3 seconds.
▪ 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
Petroleum Refining Technology & Economics – 5th Ed.
• Can improve performance of an existing unit by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007

Updated: July 1, 2019

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FCC Riser/Regenerator Combination
Cyclones
▪ Gas/solid separation in cyclones
• Increased cross sectional area decreases gas
velocity.
• Normally 2 stage cyclones.
▪ Rapid separation to prevent “over cracking.”
Regenerators
▪ Regenerators operate 1200 – 1500oF
• Limited by metallurgy or catalyst concerns
▪ Temperature determines whether
combustion gases primarily CO or CO2
• Partial Burn. Under 1300oF. High CO content.
Outlet to CO boilers & HRSG (heat
recovery/steam generation).
• Full Burn. High temperatures produce very Petroleum Refining Technology & Economics – 5th Ed.
little CO. simpler waste heat recover systems. by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007

Updated: July 1, 2019

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

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Resid Catalytic Cracking
Economics favoring direct cracking of heavier
crudes & resids
▪ Instead of normal 5-8% coke yield can reach 15%
with resid feeds

Requires heat removal in regenerator

▪ “Catalyst coolers” on regenerator to
• Produces high-pressure steam
• Specially designed vertical shell & tube heat exchangers
▪ Proprietary specialized mechanical designs available
with technology license

Petroleum Refining Technology & Economics – 5th Ed.

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

Updated: July 1, 2019

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Summary

Updated: July 1, 2019

Copyright © 2016-2019 John Jechura (jjechura@[Link])
Summary
Heart of a gasoline-oriented Extremely active catalyst
refinery systems
▪ Deactivate with coke in the
Catalytically cracks feedstocks
matter of seconds
that are too heavy to blend ▪ Requires the use of fluidized bed
into the diesel pool systems to regenerate catalyst
▪ Special designs required to crack ▪ The heat liberated from burning
resids off the coke provides the heat to
drive the cracking reactions

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Supplemental Slides

Updated: July 1, 2019

Copyright © 2016-2019 John Jechura (jjechura@[Link])
 FCC vs. Hydrocracker Installed Cost

FCCs tend to be less expensive than Hydrocrackers Petroleum Refining Technology & Economics, 5th ed.
Gary, Handwerk, & Kaiser
▪ 50,000 bpd distillate FCC – $150 million installed cost CRC Press, 2007
▪ 50,000 bpd @ 2000 scf/bbl – $350 million installed cost
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Fluidized Catalytic Cracking Technologies
Provider Features

Axens Resid cracking

ExxonMobil Research & Fluid catalytic cracking

Engineering
Haldor Topsoe A/S Fluid catalytic cracking – pretreatment

KBR Fluid catalytic cracking; FCC – high olefin content; resid cracking

Lummus Technology Fluid catalytic cracking; FCC for maximum olefins

Shaw Fluid catalytic cracking; deep catalytic cracking; resid cracking

Shell Global Solutions Fluid catalytic cracking

UOP Fluid catalytic cracking

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 Other FCC Configurations

Petroleum Refining Technology & Economics – 5th Ed.

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

Updated: July 1, 2019

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Other FCC Configurations

Exxon Flexicracking IIR FCC Unit

Petroleum Refining Technology & Economics – 5th Ed.

by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007
M.W. Kellogg Design

Updated: July 1, 2019

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Catalyst Considerations
Adjustment of active catalytic components (zeolite & active matrix) can achieve
various refinery objectives
Considerations
▪ Bottoms Cracking
▪ Octane
▪ Coke selectivity
▪ ZSM-5 additive
▪ Resid cracking
▪ Additives
▪ FCC catalyst cost
• Generally the 2nd highest operating expense, after crude oil purchases
• May pay upwards of $3,000 per ton

FCC Catalyst Selection Considerations, Hoyer, March 2015

[Link]

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Catalyst Considerations
Bottoms Cracking Octane
▪ Large-pore matrix permits easy ▪ Sodium content & amount of rare
access of large molecules earth exchange effects degree of
▪ Large molecule cracking octane enhancement
mechanisms ▪ Trade offs
• Matrix cracking • Increased FCC conversion & gasoline
o Most efficient upgrading into yield can be at the expense of octane
higher-valued gasoline & light number
cycle oil • Increased gasoline olefin content can
• Cracking on the external zeolite improve RON
surface • Increased branching & aromatic
o Minimal bottoms upgrading, very content improves MON
small fraction of total zeolite
surface
• Thermal cracking
o Nonselective – tends to produce
to gas & coke
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Catalyst Considerations
Coke selectivity ZSM-5 additive
▪ A coke-selective catalyst reduces the ▪ Does not require complete catalyst
regenerator temperature change out – small amount, 1-5% of
• Could allow for a higher reactor total catalyst
temperature to increase octane w/o ▪ Enhances gasoline octane
exceeding regenerator temperature
• Selectively cracks straight chain
or air compressor limits
paraffins & olefins (low-octane ) to
mainly C3 and C4 olefins.
• Some olefins isomerized to more
highly branched (high octane)
• Does not affect aromatics or
naphthenes (high octane)

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Catalyst Considerations
Resid cracking Additives
▪ No single optimum catalyst for all ▪ Passivation agents to mitigate nickel
resid processing applications and vanadium
▪ Allow for greater selectivity in ▪ SOx-reduction additives for
products compared to thermal regenerator emissions
cracking ▪ High-density fines used as
• Must cope with high levels of coke fluidization aids.
precursors & metals in resid feeds
▪ Requires coke-selective & metals-
resistant catalysts, metals
passivators, and SOx emission-
reducing catalysts
▪ Feed’s CCR issues w/o cat cooler
• Increased CCR, increased regenerator
temperature, decreased C/O ratio, &
declining conversion

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Improving Cat Cracking Process Monitoring
Mass Balance Heat Balance
▪ Hydrocarbon balance – can you account ▪ Important for kinetic reactions of the
for your process stream? plant as well as distillation and heat
▪ Catalyst balance – Can you account for recover/integration in the unit
every pound of catalyst from injection to
Yield Balance
regenerator spent catalyst to slurry
catalyst content? ▪ Understand the economic implications of
the unit & help focus on key indicators
Pressure Balance ▪ Catalyst cost/usage impacts the
▪ Drives reliability & long-term safe operating expense of the Cat Cracker?
operation ▪ Impact of feed quality variations on
▪ Understand pressure profiles including: yields?
air blower, regenerator, reactor, & wet
gas compressor
▪ Help troubleshoot mechanical issues –air
grids & cyclones

Ref: [Link]

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