FluidizedCatalyticCracking

Chapter6
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphalting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
J et Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
2
Purpose
Catalyticallycrackcarboncarbonbondsin
gasoils
Finecatalystinfluidizedbedreactor
allowsforimmediateregeneration
Lowersaveragemolecularweight&
produceshighyieldsoffuelproducts
Producesolefins
Attractivefeedcharacteristics
Smallconcentrationsofcontaminants
Poisonthecatalyst
Smallconcentrationsofheavyaromatics
Sidechainsbreakoffleavingcoresto
depositascokeoncatalyst
Mustbeintentionallydesignedfor
heavyresid feeds
Productsmaybefurtherprocessed
Furtherhydrocracked
Alkylated toimprovegasolineantiknock
properties
3
CharacteristicsofPetroleumProducts
4
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
Largeconversiontolightproductsrequiressomecokeformation
OverviewofCatalyticCracking
FCCheartofamodernUSrefinery
NearlyeverymajorfuelsrefineryhasanFCCU
Oneofthemostimportant&sophisticatedcontributionstopetroleumrefiningtechnology
Capacityusually1/3ofatmosphericcrudedistillationcapacity
Contributesthehighestvolumeto
thegasolinepool
5
U.S.RefineryImplementation
6
Top 10 combined Cat Cracking
Company State Site
Atmospheric
Crude Distillation
Capacity (barrels
per stream day)
Vacuum
Distillation
Downstream
Charge Capacity,
Current Year
(barrels per
stream day)
Cat Cracking:
Fresh Feed
Downstream
Charge Capacity,
Current Year
(barrels per
stream day)
Cat Cracking:
Recycled Feed
Downstream
Charge Capacity,
Current Year
(barrels per
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
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&diesel
whileminimizingproductionofheavyfuel
oil
Catgasolinecontributeslargestvolume
tothegasolinepool
Frontendrichinolefins
Backendhighlyaromaticwithsome
olefins
DoesnotcontainmuchC6&C7olefins
veryreactive&formlighterolefins&
aromatics
Cokeproductionsmallbutveryimportant
Burnedinregenerator&providesheatfor
crackingreactions
Lightendscontainlargeamountsofolefins
Goodforchemicalfeedstock
Canrecoverchemicalgradepropylene&
ethylene
Propylene,butylene,&C5olefinscanbe
alkylatedforhigheryieldsofhighoctane
gasoline
Catkerosene&jetfuel
Lowcentanenumberbecauseofaromatics
lowersqualitydieselpool
Gasoils cycleoils
Sameboilingrangeasinitialgasoil
feedstock
Slurry
Heavyresiduefromprocess
Highinsulfur,smallring&polynuclear
aromatics,&catalystfines
Usuallyhashighviscosity
Disposition
Blendedintotheheavyfueloil(Bunker
FuelOilorMarineFuelOil)
Hydrocracked
Blendedintocokerfeed canhelp
mitigateproblemswithshotcoke
production
16
ProductYields
Produceshighyieldsofliquids&smallamountsofgas&coke
Massliquidyieldsareusually90%93%;liquidvolumeyieldsareoftenmorethan100%
(volumeswell)
(Ruleofthumb)Remainingmassyieldsplitbetweengas&coke
Theyieldpatternisdeterminedbycomplexinteractionoffeedcharacteristics&
reactorconditionsthatdetermineseverityofoperation
Roughyieldestimationchartsgivenintextpp.117130pp.144156
Conversiondefinedrelativetowhatremainsintheoriginalfeedstockboiling
range
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&isomerization withalkylparaffins 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)butdoesnt
abradetheequipmentinternals.
o 70tons/mintypicalcirculationrate
Researchcontinuesbycatalystsuppliers&licensors
Testingforlowornorareearthcontent
Rareearthmaterialsincreasinginprice&decreasinginavailability
Recognitionthatbothcrackability offeed&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
FCCvs.HydrocrackerInstalledCost
HydrocrackerstendtobemoreexpensivethanFCCs
50,000bpddistillateFCC $150millioninstalledcost
50,000bpd@2000scf/bbl $350millioninstalledcost
30
PetroleumRefiningTechnology&Economics,5
th
ed.
Gary,Handwerk,&Kaiser
CRCPress,2007