FluidizedCatalyticCracking

Chapter6
 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
Catalyticallycrackcarboncarbon
bondsingasoils
Finecatalystinfluidizedbedreactor
allowsforimmediateregeneration
Lowersaveragemolecularweight&
produceshighyieldsoffuelproducts
Producesolefins
Attractivefeedcharacteristics
Smallconcentrationsof
contaminants
Poisonthecatalyst
Smallconcentrationsofheavy
aromatics
Sidechainsbreakoffleavingcores
todepositascokeoncatalyst
Mustbeintentionallydesignedfor
heavyresid feeds
Productsmaybefurtherprocessed
Furtherhydrocracked
Alkylated toimprovegasolineanti
knockproperties

3
CharacteristicsofPetroleumProducts

Largeconversiontolightproductsrequiressomecokeformation

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000

4
OverviewofCatalyticCracking

FCCheart ofamodernUSrefinery
NearlyeverymajorfuelsrefineryhasanFCCU
Oneofthemostimportant&sophisticatedcontributionstopetroleum
refiningtechnology
Capacityusually35%to40%ofthecrudedistillationcapacity
Contributesthehighestvolumetothegasolinepool
Isomerization

Vol%
FCCU 35% FC C U

Reformer 30% Alkylation

Alkylation 20%
Isomerization 15%

Reformer

5
 U.S.RefineryImplementation

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
TypicalFCCComplex

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

9
FCCRiser/RegeneratorCombination

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000

10
OtherFCCConfigurations

PetroleumRefiningTechnology&Economics 5th Ed.

byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

11
OtherFCCConfigurations
Bayway configuration?

PetroleumRefiningTechnology&Economics 5th Ed.

byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

12
FluidizedCatalyticCrackingTechnologies

Provider Features
Shaw Deepcatalyticcracking
ExxonMobileResearch&Engineering Fluidcatalyticcracking
KBR Fluidcatalyticcracking
LummusTechnology Fluidcatalyticcracking
Shaw Fluidcatalyticcracking
ShellGlobalSolutions Fluidcatalyticcracking
UOP Fluidcatalyticcracking
LummusTechnology Fluidcatalyticcrackingformaximumolefins
KBR Fluidcatalyticcracking,higholefincontent
KBR Fluidcatalyticcracking,residual
HaldorTopsoeA/S Fluidcatalyticcrackingpretreatment
Shaw Residcracking
Axens Residcracking

13
EarlyFixed&MovingBedCatalyticCracking
Cyclicfixedbedcatalyticcrackingcommercializedinlate1930s
Houdry ProcessCorporationformedin1930
FirstHoudry catalystcrackerstartedupatSunOilsPaulsboro,New
Jersey,refineryinJune1936
Threefixedbedreactors&processed2,000barrels/day

12,000barrels/daycommercialunitwentonstreamatSunsMarcus
HookRefineryin1937
Otheradoptees:Gulf,Sinclair,StandardOilofOhio,&TheTexas
Company
Sun&Houdry ProcessCorporationstarteddevelopmentonamoving
bedprocessin1936
PilotThermofor catalyticcrackerwasstartedin1941
Firstcommercial20,000barrel/dayunitcommissionedatMagnolias
BeaumontRefineryin1943

14
FluidizedCatalyticCracking
UpflowdensephaseparticulatesolidprocesscreditedtoW.K.Lewis,MIT
OriginallydevelopedastheWinklercoalgasificationprocess
StandardOilofNewJersey,StandardOilofIndiana,M.W.Kellogg,ShellOil,The
TexasCompany,&others
Densephase backmixedreactor
ModelIFCCUatStandardOilofNewJerseysBatonRougeRefinery,1942
ModelIIdominatedcatalyticcrackingduringearlyyears
DesignedbeforefirstModelIoperating

Dilutephase riserreactordesign
Catalystsbasedonmolecularsieve 1960s
Significantlyhighercrackingactivity&gasolineyields lowercarbononcatalyst
Plugflow drasticallyreducedresidencetime&90%feedconversions

15
FeedsforCatalyticCracking
Aromaticringstypicallycondensetocoke
Nohydrogenaddedtoreducecokeformation
Amountofcokeformedcorrelatestocarbonresidueoffeed
Feedsnormally37wt%CCR
Catalystssensitivetoheteroatompoisoning
Sulfur&metals(nickel,vanadium,&iron)
Feedsmaybehydrotreated
Atmospheric&vacuumgasoilsareprimaryfeeds
Couldberoutedtothehydrocrackerfordieselproduction
Notasexpensiveaprocessashydrocracking
Dictatedbycapacities&ofgasoline/dieseleconomics
Hydrotreated feedresultsincleanerproducts,nothighinsulfur

16
FCCProducts
Primarygoaltomakegasoline&diesel
whileminimizingproductionofheavyfuel
oil
Catgasoline contributeslargestvolume
tothegasolinepool
Frontendrichinolefins
Backendhighlyaromaticwithsome
olefins
DoesnotcontainmuchC6&C7olefins
veryreactive&formlighterolefins&
aromatics
Cokeproductionsmallbutveryimportant
Burnedinregenerator&providesheatfor
crackingreactions
Lightendscontainlargeamountsofolefins
Goodforchemicalfeedstock
Canrecoverchemicalgradepropylene&
ethylene
Propylene,butylene,&C5olefinscanbe
alkylated forhigheryieldsofhighoctane
gasoline
Catkerosene&jetfuel
Lowcentane numberbecauseofaromatics
lowersqualitydieselpool
Gasoils cycleoils
Sameboilingrangeasinitialgasoil
feedstock
Slurry
Heavyresiduefromprocess
Highinsulfur,smallring&polynuclear
aromatics,&catalystfines
Usuallyhashighviscosity
Disposition
Blendedintotheheavyfueloil(Bunker
FuelOil orMarineFuelOil)
Hydrocracked
Blendedintocoker feed canhelp
mitigateproblemswithshotcoke
production
17
ProductYields
Produceshighyieldsofliquids&smallamountsofgas&coke
Massliquidyieldsareusually90%93%;liquidvolumeyieldsareoften
morethan100%(volumeswell)
(Ruleofthumb)Remainingmassyieldsplitbetweengas&coke
Theyieldpatternisdeterminedbycomplexinteractionoffeed
characteristics&reactorconditionsthatdetermineseverityof
operation
Roughyieldestimationchartsgivenintextpp.117130pp.144156
Conversiondefinedrelativetowhatremainsintheoriginalfeedstock
boilingrange
Conversion = 100% ( GasOilYield)

18
UseofYieldCharts
Vol% Wt% Density
FuelGas 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% Ratio
CycleOils Ratio
HCO Conv 6.24/25 Ratio 6.27
Coke 6.18
Total 100% 100%

19
 FCCUYieldExample
Product Yields from FCCU
Watson Sulfur Water density @ 60F = 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
BoilingPointRangesforProducts
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
CatalyticCrackingCatalysts&Chemistry
Acidsitecatalyzedcracking&hydrogentransferviacarbonium
mechanism
Basicreaction carboncarbonscissionofparaffins&cycloparaffins to
formolefins&lowermolecularweightparaffins&cycloparaffins

Paraffin
Paraffin+Olefin
AlkylNaphthene
Naphthene+Olefin
AlkylAromatic
Aromatic+Olefin
Example

CH3CH2CH2CH2CH2CH2CH2CH3
CH3CH2CH2CH2CH3 + CH=CH2CH3

Olefinsexhibitcarboncarbonscission&isomerization withalkyl
paraffinstoformbranchedparaffins
Cycloparaffins willdehydrogenate(condense)toformaromatics
Smallamountofaromatics&olefinswillcondensetoultimatelyform
coke

22
CatalyticCrackingCatalysts&Chemistry
Zeolite catalysts
Highactivity
Highgasoline&lowcokeyields
Goodfluidizationproperties
Sizebetweenflour&grainsofsand.
Balancebetweenstrength(soitdoesntbreakapartasitmovesthroughsystem)butdoesnt
abradetheequipmentinternals.
- 70tons/mintypicalcirculationrate

Researchcontinuesbycatalystsuppliers&licensors
Recognitionthatbothcrackability offeed&severityofoperationsarefactors
Theoreticalbasisforcrackingreactionsleadtomoreprecisecatalystformulation
Catalysttailoredtomaximizegasolineordieselyieldorincreaseolefinproduction
Additives
Bottomscracking
ZSM5forincreasedC3production
COcombustionpromoters(inregenerator)

23
Zeolite Structure

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

24
TrendsinCatalysts

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

25
OperatingConditions&DesignFeatures
Designedtoprovidebalanceofreactor&regeneratorcapabilities
Usuallyoperatetooneormoremechanicallimits
Commonlimitiscapacitytoburncarbonfromthecatalyst
Ifaircompressorcapacityislimit,capacitymaybeincreasedatfeasible
capitalcost
Ifregeneratormetallurgyislimit,designchangescanbeformidable.
Regeneratorcyclonevelocitylimit

SlidevalvePlimit

26
FCCRiser/RegeneratorCombination
Risers
Inlettypically1300F,outlet950 1000F
Increasedreactortemperaturetoincreaseseverity&
conversion
Mayneedtoreversetolowerolefincontent(gasoline
formulationregulations)
Reactorpressurecontrolledbythefractionator
overheadgascompressor
Typically10to30psig
Highgasvelocityfluidizesfinecatalystparticles.
Currentdesignshaverisercontacttimestypically2to3
seconds.
Timeslessthan0.25secondsreported
Importantdesignpoint:quick,even,&complete
mixingoffeedwithcatalyst
Licensorshaveproprietaryfeedinjectionnozzle
systemstoaccomplishthis
Atomizefeedforrapidvaporization
Canimproveperformanceofanexistingunit
PetroleumRefiningTechnology&Economics 5th Ed.
byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

27
FCCRiser/RegeneratorCombination
Cyclones
Gas/solidseparationincyclones
Increasedcrosssectionalareadecreasesgas
velocity.
Normally2stagecyclones.
Rapidseparationtopreventovercracking.
Regenerators
Regeneratorsoperate1200 1500F
Limitedbymetallurgyorcatalystconcerns
Temperaturedetermineswhethercombustion
gasesprimarilyCOorCO2
PartialBurn.Under1300F.HighCOcontent.
OutlettoCOboilers&HRSG(heat
recovery/steamgeneration).
FullBurn.Hightemperaturesproduceverylittle
CO.simplerwasteheatrecoversystems.

PetroleumRefiningTechnology&Economics 5th Ed.

byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

28
FCCRiser/RegeneratorCombination
Heatbalance
Reactor&regeneratoroperateinheatbalance
Moreheatreleasedintheregenerator,highertemperatureof
regeneratedcatalyst,&higherreactortemperatures.
Heatmovedbycatalystcirculation.

29
Resid CatalyticCracking
Economicsfavoringuseofheaviercrudes&direct
crackingofresids
Insteadofanormal58%cokeyield,itcanreach
15%withresid feeds
Requiresheatremovalinregenerator
Catalystcoolers onregeneratorto
Produceshighpressuresteam
Speciallydesignedverticalshell&tubeheat
exchangers
Proprietaryspecializedmechanicaldesigns
availablewithtechnologylicense

PetroleumRefiningTechnology&Economics 5th Ed.

byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

30