07 Catalytic Cracking PDF

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 treating
Reforming
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
Updated: July 12, 2018
2
Copyright © 2017 John Jechura (jjechura@mines.edu)
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
Reformer
Alkylation
Isomerization
EIA, Jan. 1, 2018 database, published June 2018
http://www.eia.gov/petroleum/refinerycapacity/
3
U.S. Refinery Implementation
EIA, Jan. 1, 2018 database, published June 2018
http://www.eia.gov/petroleum/refinerycapacity/
4
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
5
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
6
Fluid Catalytic Cracker
“Benecia Refinery Tour,” Valero Energy Corp., July 9, 2007
http://flowexpertblog.com/2013/09/05/fccu‐in‐todays‐refineries/ http://www.secinfo.com/dsvrp.uEe6.d.htm#1stPage
8
Typical FCC Complex
Figure modified from Koch‐Glitsch Bulletin KGSS‐1, Rev. 3‐2010,
http://www.koch‐glitsch.com/Document%20Library/KGSS.pdf
9
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
10
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: October 24, 2018
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Boiling Point Ranges for Products
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]
Based on example problem in:
Refinery Process Modeling, A Practical Guide to Steady State Modeling of Petroleum Processes, 1st 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
18
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”
19
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
• 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
20
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
21
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
22
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
Petroleum Refining Technology & Economics – 5th Ed.
• Atomize feed for rapid vaporization by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007
• Can improve performance of an existing unit
23
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 by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007
little CO. simpler waste heat recover systems.
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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.
25
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

by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007
26
Summary
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
FCC vs. Hydrocracker Installed Cost
FCCs tend to be less expensive than Hydrocrackers
 50,000 bpd distillate FCC – $150 million installed cost Petroleum Refining Technology & Economics, 5th ed.
Gary, Handwerk, & Kaiser
 50,000 bpd @ 2000 scf/bbl – $350 million installed cost CRC Press, 2007
30
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

32
Exxon Flexicracking IIR FCC Unit

M.W. Kellogg Design
33
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
http://www.refinerlink.com/blog/FCC_Catalyst_Selection_Considerations/
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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
35
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)
36
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
37
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: http://www.refinerlink.com/blog/Cat_Cracking_Process_Monitoring
38

07 Catalytic Cracking PDF

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Fluidized Catalytic Cracking

Butanes Fuel Gas

Visbreaking Heavy Distillates

Primary goal – make gasoline & diesel, Cat kerosene & jet fuel – rarely made

Petroleum Refining Technology & Economics – 5th Ed.

Axens Resid cracking

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

Petroleum Refining Technology & Economics – 5th Ed.

Petroleum Refining Technology & Economics – 5th Ed.

Resid cracking Additives

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