FluidizedCatalyticCracking

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
4
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
Largeconversiontolightproductsrequiressomecokeformation
OverviewofCatalyticCracking
FCCheartofamodernUSrefinery
NearlyeverymajorfuelsrefineryhasanFCCU
Oneofthemostimportant&sophisticatedcontributionstopetroleumrefining
technology
Capacityusually35%to40%ofthecrudedistillationcapacity
Contributesthehighestvolumeto
thegasolinepool
5
U.S.RefineryImplementation
6
Top 10 combined Cat Cracking
CORPORATION State Site
Atmospheric
CrudeDistillation
Capacity(barrels
perstreamday)
Vacuum
Distillation
Downstream
ChargeCapacity,
CurrentYear
(barrelsper
streamday)
CatCracking:
FreshFeed
Downstream
ChargeCapacity,
CurrentYear
(barrelsper
streamday)
CatCracking:
RecycledFeed
Downstream
ChargeCapacity,
CurrentYear
(barrelsper
streamday)
EXXONMOBILCORP Louisiana BATONROUGE 523,200 246,100 243,000 0
EXXONMOBILCORP Texas BAYTOWN 584,000 297,000 215,000 8,000
BPPLC Texas TEXASCITY 475,000 237,000 182,000 8,000
BPPLC Indiana WHITING 430,000 247,000 175,400 7,000
HOVENSALLC VirginIslands KINGSHILL 525,000 225,000 149,000 0
PDVAMERICAINC Louisiana LAKECHARLES 440,000 230,000 145,000 3,000
CONOCOPHILLIPS NewJersey LINDEN 251,000 75,000 145,000 0
MARATHONPETROLEUMCORP Louisiana GARYVILLE 518,000 268,000 141,000 0
SUNOCOINC Pennsylvania PHILADELPHIA 355,000 163,200 138,500 0
CONOCOPHILLIPS Texas SWEENY 260,000 132,100 107,700 12,000
TypicalFCCComplex
8
Ref:http://www.osha.gov/dts/osta/otm/otm_iv/otm_iv_2.html
FCCRiser/RegeneratorCombination
9
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
OtherFCCConfigurations
10
PetroleumRefiningTechnology&Economics 5
th
Ed.
byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007
OtherFCCConfigurations
11
PetroleumRefiningTechnology&Economics 5
th
Ed.
byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007
Bayway configuration?
FluidizedCatalyticCrackingTechnologies
12
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
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
minimizingproductionofheavyfueloil
Catgasolinecontributeslargestvolumetothe
gasolinepool
Frontendrichinolefins
Backendhighlyaromaticwithsomeolefins
DoesnotcontainmuchC6&C7olefins very
reactive&formlighterolefins&aromatics
Cokeproductionsmallbutveryimportant
Burnedinregenerator&providesheatfor
crackingreactions
Lightendscontainlargeamountsofolefins
Goodforchemicalfeedstock
Canrecoverchemicalgradepropylene&ethylene
Propylene,butylene,&C5olefinscanbe
alkylatedforhigheryieldsofhighoctanegasoline
Catkerosene&jetfuel
Lowcentane numberbecauseofaromatics
lowersqualitydieselpool
Gasoils cycleoils
Sameboilingrangeasinitialgasoilfeedstock
Slurry
Heavyresiduefromprocess
Highinsulfur,smallring&polynuclear aromatics,
&catalystfines
Usuallyhashighviscosity
Disposition
Blendedintotheheavyfueloil(BunkerFuelOil
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
( )
= Conversion 100% GasOilYield
UseofYieldCharts
Vol% Wt% Density
FuelGas 6.19
LPG
C3
6.20
6.21 Ratio Pure
C3= 6.21 Ratio Pure
IC4 6.22 Ratio Pure
NC4 6.22 Ratio Pure
C4=s 6.22 Ratio Pure
Gasoline 6.23 Ratio 6.27
CycleOils
LCO
100%
Conv
A
A
A
Ratio
Ratio
HCO 6.24/25 Ratio 6.27
Coke 6.18
Total 100% 100%
18
FCCUYieldExample
19
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%
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%
Yields Standard Densities
Sulfur Distribution
Product Yields from FCCU
Example
BoilingPointRangesforProducts
20
Kaes's Example FCC Problem
-
500
1,000
1,500
2,000
2,500
3,000
0 100 200 300 400 500 600 700 800 900 1000 1100 1200
BPT [F]
I
n
c
r
e
m
e
n
t
a
l

Y
i
e
l
d

[
b
p
d
]
net.cso
31a
lco.product
unstab.gasol
wet.gas
53-total.feed
CatalyticCrackingCatalysts&Chemistry
Acidsitecatalyzedcracking&hydrogentransferviacarbonium mechanism
Basicreaction carboncarbonscissionofparaffins &cycloparaffins toformolefins&
lowermolecularweightparaffins &cycloparaffins
Example
Olefinsexhibitcarboncarbonscission&isomerizationwithalkylparaffins toform
branchedparaffins
Cycloparaffins willdehydrogenate(condense)toformaromatics
Smallamountofaromatics&olefinswillcondensetoultimatelyformcoke
21

Paraffin Paraffin+Olefin
AlkylNaphthene Naphthene+Olefin
AlkylAromatic Aromatic+Olefin
+
3 2 2 2 2 2 2 3 3 2 2 2 3 2 3
CH CH CH CH CH CH CH CH CH CH CH CH CH CH=CH CH
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
23
Ref:http://thor.tech.chemie.tumuenchen.de/index.php?option=com_frontpage&Itemid=1
TrendsinCatalysts
24
Ref:http://thor.tech.chemie.tumuenchen.de/index.php?option=com_frontpage&Itemid=1
OperatingConditions&DesignFeatures
Designedtoprovidebalanceofreactor&regeneratorcapabilities
Usuallyoperatetooneormoremechanicallimits
Commonlimitiscapacitytoburncarbonfromthecatalyst
Ifaircompressorcapacityislimit,capacitymaybeincreasedatfeasiblecapitalcost
Ifregeneratormetallurgyislimit,designchangescanbeformidable.
Regeneratorcyclonevelocitylimit
SlidevalveAPlimit
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
26
PetroleumRefiningTechnology&Economics 5
th
Ed.
byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007
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
PetroleumRefiningTechnology&Economics 5
th
Ed.
byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007
FCCRiser/RegeneratorCombination
Heatbalance
Reactor&regeneratoroperateinheatbalance
Moreheatreleasedintheregenerator,highertemperatureofregeneratedcatalyst,&
higherreactortemperatures.
Heatmovedbycatalystcirculation.
28
ResidCatalyticCracking
Economicsfavoringuseofheaviercrudes&direct
crackingofresids
Insteadofanormal58%cokeyield,itcanreach
15%withresidfeeds
Requiresheatremovalinregenerator
Catalystcoolersonregeneratorto
Produceshighpressuresteam
Speciallydesignedverticalshell&tubeheat
exchangers
Proprietaryspecializedmechanicaldesigns
availablewithtechnologylicense
29
PetroleumRefiningTechnology&Economics 5
th
Ed.
byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007
Hydrocrackervs.FCCInstalledCost
HydrocrackerstendtobemoreexpensivethanFCCs
50,000bpddistillateFCC $150millioninstalledcost
50,000bpd@2000scf/bbl $350millioninstalledcost
30
PetroleumRefiningTechnology&Economics,5
th
ed.
Gary,Handwerk,&Kaiser
CRCPress,2007