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Chapter6
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
FCCheartofamodernUSrefinery
NearlyeverymajorfuelsrefineryhasanFCCU
Oneofthemostimportant&sophisticatedcontributionstopetroleumrefining
technology
Capacityusually35%to40%ofthecrudedistillationcapacity
Contributesthehighestvolumeto
thegasolinepool
5
U.S.RefineryImplementation
6
TypicalFCCComplex
Ref:http://www.osha.gov/dts/osta/otm/otm_iv/otm_iv_2.html
8
FCCRiser/RegeneratorCombination
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
9
OtherFCCConfigurations
10
OtherFCCConfigurations
Bayway configuration?
11
FluidizedCatalyticCrackingTechnologies
Provider Features
Shaw Deepcatalyticcracking
ExxonMobilResearch&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
12
EarlyFixed&MovingBedCatalyticCracking
Cyclicfixedbedcatalyticcrackingcommercializedinlate1930s
Houdry ProcessCorporationformedin1930
FirstHoudry catalystcrackerstartedupatSunOilsPaulsboro,NewJersey,refineryin
June1936
Threefixedbedreactors&processed2,000barrels/day
12,000barrels/daycommercialunitwentonstreamatSunsMarcusHookRefineryin
1937
Otheradoptees:Gulf,Sinclair,StandardOilofOhio,&TheTexasCompany
Sun&Houdry ProcessCorporationstarteddevelopmentonamovingbed
processin1936
PilotThermofor catalyticcrackerwasstartedin1941
Firstcommercial20,000barrel/dayunitcommissionedatMagnoliasBeaumontRefinery
in1943
13
FluidizedCatalyticCracking
UpflowdensephaseparticulatesolidprocesscreditedtoW.K.Lewis,MIT
OriginallydevelopedastheWinklercoalgasificationprocess
StandardOilofNewJersey,StandardOilofIndiana,M.W.Kellogg,ShellOil,TheTexas
Company,&others
Densephase backmixedreactor
ModelIFCCUatStandardOilofNewJerseysBatonRougeRefinery,1942
ModelIIdominatedcatalyticcrackingduringearlyyears
DesignedbeforefirstModelIoperating
Dilutephase riserreactordesign
Catalystsbasedonmolecularsieve 1960s
Significantlyhighercrackingactivity&gasolineyields lowercarbononcatalyst
Plugflow drasticallyreducedresidencetime&90%feedconversions
14
FeedsforCatalyticCracking
Aromaticringstypicallycondensetocoke
Nohydrogenaddedtoreducecokeformation
Amountofcokeformedcorrelatestocarbonresidueoffeed
Feedsnormally37wt%CCR
Catalystssensitivetoheteroatompoisoning
Sulfur&metals(nickel,vanadium,&iron)
Feedsmaybehydrotreated
Atmospheric&vacuumgasoilsareprimaryfeeds
Couldberoutedtothehydrocrackerfordieselproduction
Notasexpensiveaprocessashydrocracking
Dictatedbycapacities&ofgasoline/dieseleconomics
Hydrotreated feedresultsincleanerproducts,nothighinsulfur
15
FCCProducts
Primarygoaltomakegasoline&dieselwhile Catkerosene&jetfuel
minimizingproductionofheavyfueloil
Lowcentane numberbecauseofaromatics
Catgasolinecontributeslargestvolumetothe
gasolinepool lowersqualitydieselpool
Frontendrichinolefins Gasoils cycleoils
Backendhighlyaromaticwithsomeolefins
Sameboilingrangeasinitialgasoilfeedstock
DoesnotcontainmuchC6&C7olefins very
reactive&formlighterolefins&aromatics Slurry
Cokeproductionsmallbutveryimportant Heavyresiduefromprocess
Burnedinregenerator&providesheatfor
crackingreactions Highinsulfur,smallring&polynuclear aromatics,
&catalystfines
Lightendscontainlargeamountsofolefins
Usuallyhashighviscosity
Goodforchemicalfeedstock
Canrecoverchemicalgradepropyleneðylene Disposition
Propylene,butylene,&C5olefinscanbe Blendedintotheheavyfueloil(BunkerFuelOil
alkylatedforhigheryieldsofhighoctanegasoline orMarineFuelOil)
Hydrocracked
Blendedintocoker feed canhelpmitigate
problemswithshotcokeproduction
16
ProductYields
Theyieldpatternisdeterminedbycomplexinteractionoffeedcharacteristics&
reactorconditionsthatdetermineseverityofoperation
Roughyieldestimationchartsgivenintextpp.117130pp.144156
Conversiondefinedrelativetowhatremainsintheoriginalfeedstockboiling
range
Produceshighyieldsofliquids&smallamountsofgas&coke
Massliquidyieldsareusually90%93%;liquidvolumeyieldsareoftenmorethan100%
(volumeswell)
(Ruleofthumb)Remainingmassyieldsplitbetweengas&coke
17
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%
18
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
Un-Normalized Yields:
Total LPG 5,851 23.41% 631 38.2%
Example
19
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]
20
CatalyticCrackingCatalysts&Chemistry
Acidsitecatalyzedcracking&hydrogentransferviacarbonium mechanism
Basicreaction carboncarbonscissionofparaffins &cycloparaffins toformolefins&
lowermolecularweightparaffins &cycloparaffins
Paraffin
Paraffin+Olefin
AlkylNaphthene
Naphthene+Olefin
AlkylAromatic
Aromatic+Olefin
Example
CH3CH2CH2CH2CH2CH2CH2CH3
CH3CH2CH2CH2CH3 CH=CH2CH3
Olefinsexhibitcarboncarbonscission&isomerizationwithalkylparaffins toform
branchedparaffins
Cycloparaffins willdehydrogenate(condense)toformaromatics
Smallamountofaromatics&olefinswillcondensetoultimatelyformcoke
21
CatalyticCrackingCatalysts&Chemistry
Zeolitecatalysts
Highactivity
Highgasoline&lowcokeyields
Goodfluidizationproperties
Sizebetweenflour&grainsofsand.
Balancebetweenstrength(soitdoesntbreakapartasitmovesthroughsystem)but
doesntabradetheequipmentinternals.
- 70tons/mintypicalcirculationrate
Researchcontinuesbycatalystsuppliers&licensors
Recognitionthatbothcrackabilityoffeed&severityofoperationsarefactors
Theoreticalbasisforcrackingreactionsleadtomoreprecisecatalystformulation
Catalysttailoredtomaximizegasolineordieselyieldorincreaseolefinproduction
Additives
Bottomscracking
ZSM5forincreasedC3production
COcombustionpromoters(inregenerator)
22
ZeoliteStructure
Ref:http://thor.tech.chemie.tumuenchen.de/index.php?option=com_frontpage&Itemid=1
23
TrendsinCatalysts
Ref:http://thor.tech.chemie.tumuenchen.de/index.php?option=com_frontpage&Itemid=1
24
OperatingConditions&DesignFeatures
Designedtoprovidebalanceofreactor®eneratorcapabilities
Usuallyoperatetooneormoremechanicallimits
Commonlimitiscapacitytoburncarbonfromthecatalyst
Ifaircompressorcapacityislimit,capacitymaybeincreasedatfeasiblecapitalcost
Ifregeneratormetallurgyislimit,designchangescanbeformidable.
Regeneratorcyclonevelocitylimit
SlidevalvePlimit
25
FCCRiser/RegeneratorCombination
Risers
Inlettypically1300F,outlet950 1000F
Increasedreactortemperaturetoincreaseseverity&
conversion
Mayneedtoreversetolowerolefincontent(gasoline
formulationregulations)
Reactorpressurecontrolledbythefractionator
overheadgascompressor
Typically10to30psig
Highgasvelocityfluidizesfinecatalystparticles.
Currentdesignshaverisercontacttimestypically2to3
seconds.
Timeslessthan0.25secondsreported
Importantdesignpoint:quick,even,&completemixing
offeedwithcatalyst
Licensorshaveproprietaryfeedinjectionnozzlesystems
toaccomplishthis
Atomizefeedforrapidvaporization
Canimproveperformanceofanexistingunit
PetroleumRefiningTechnology&Economics 5th Ed.
byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007
26
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.
27
FCCRiser/RegeneratorCombination
Heatbalance
Reactor®eneratoroperateinheatbalance
Moreheatreleasedintheregenerator,highertemperatureofregeneratedcatalyst,&
higherreactortemperatures.
Heatmovedbycatalystcirculation.
28
ResidCatalyticCracking
Economicsfavoringuseofheaviercrudes&direct
crackingofresids
Insteadofanormal58%cokeyield,itcanreach
15%withresidfeeds
Requiresheatremovalinregenerator
Catalystcoolersonregeneratorto
Produceshighpressuresteam
Speciallydesignedverticalshell&tubeheat
exchangers
Proprietaryspecializedmechanicaldesigns
availablewithtechnologylicense
29
Hydrocrackervs.FCCInstalledCost
HydrocrackerstendtobemoreexpensivethanFCCs
50,000bpddistillateFCC $150millioninstalledcost
PetroleumRefiningTechnology&Economics,5th ed.
50,000bpd@2000scf/bbl $350millioninstalledcost Gary,Handwerk,&Kaiser
CRCPress,2007
30