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FluidizedCatalyticCracking

Chapter6

JohnJechura jjechura@mines.edu
Updated:July30,2014

Gases
Polymerization

Sulfur
Plant

Gas

Butanes
Alkyl
Feed
Gas
Separation &
Stabilizer

Fuel Gas
LPG

Alkylation

Polymerization
Naphtha

Isomerization

Light Naphtha

Alkylate

Isomerate

Aviation
Gasoline
Automotive
Gasoline

Reformate
Naphtha
Hydrotreating

Heavy
Naphtha

Sulfur

LPG

Sat Gas
Plant

Naphtha
Reforming

Solvents

Naphtha

Atmospheric
Distillation

Crude
Oil

Jet Fuels

Kerosene

Kerosene

Desalter

Distillate

Hydrocracking

AGO

LVGO
Vacuum
Distillation

Gas Oil
Hydrotreating

Fluidized
Catalytic
Cracking

Cat
Naphtha

Solvents
Distillate
Hydrotreating

Cat
Distillates

Treating &
Blending

Heating Oils
Diesel

Fuel Oil

HVGO

Cycle Oils

Residual
Fuel Oils

DAO
Solvent
Deasphalting

Visbreaking

Vacuum
Residuum

Coker
Naphtha

Heavy
Coker
Gas
Oil

SDA
Bottoms

Asphalts

Naphtha

Distillates
Fuel Oil
Bottoms
Lube Oil

Lubricant
Greases

Solvent
Dewaxing

Waxes
Waxes
Coking

Light Coker
Gas Oil

Coke

OverviewofCatalyticCracking
FCCheartofamodernUSrefinery
NearlyeverymajorfuelsrefineryhasanFCCU

Oneofthemostimportant&sophisticatedcontributionstopetroleumrefining
technology

Capacityusually1/3ofatmospheric
crudedistillationcapacity

Contributesthehighestvolume
tothegasolinepool

EIA,Jan.1,2014database,publishedJune2014
http://www.eia.gov/petroleum/refinerycapacity/

U.S.RefineryImplementation
Top 10 combined Cat Cracking

EIA,Jan.1,2014database,publishedJune2014
http://www.eia.gov/petroleum/refinerycapacity/
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Purpose
Catalyticallycrackcarboncarbonbondsingasoils
Finecatalystinfluidizedbedreactorallowsfor
immediateregeneration
Lowersaveragemolecularweight&produceshigh
yieldsoffuelproducts
Producesolefins

Attractivefeedcharacteristics
Smallconcentrationsofcontaminants
Poisonthecatalyst
Smallconcentrationsofheavyaromatics
Sidechainsbreakoffleavingcorestodepositascoke
oncatalyst
Mustbeintentionallydesignedforheavyresid feeds

Productsmaybefurtherprocessed
Furtherhydrocracked
Alkylatedtoimprovegasolineantiknockproperties

CharacteristicsofPetroleumProducts

Largeconversiontolightproductsrequiressomecokeformation
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000

TypicalFCCComplex

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

TypicalFCCComplex

KochGlitsch BulletinKGSS1,Rev.32010,
http://www.kochglitsch.com/Document%20Library/KGSS.pdf
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History Fixed,Moving,&FluidizedBedCracking
Cyclicfixedbedcatalyticcracking
commercializedinlate1930s
1st Houdry ProcessCorporationcatalyst
crackerstartedupatSunOilsPaulsboro,
NewJersey,refineryinJune1936
Threefixedbedreactors&processed
2,000barrels/day

Otheradoptees:Sun,Gulf,Sinclair,
StandardOilofOhio,&TheTexas
Company

Sun&Houdry starteddevelopingmoving
bedprocessin1936
1stcommercial20,000barrel/dayunit
commissionedatMagnoliasBeaumont
Refineryin1943

Fluidizedbedcatalyticcracking
Upflowdensephaseparticulatesolid
processcreditedtoW.K.Lewis,MIT
Earlyadopters:StandardOilofNewJersey,
StandardOilofIndiana,M.W.Kellogg,Shell
Oil,TheTexasCompany,&others
Densephase backmixedreactor
ModelIFCCUatStandardOilofNew
JerseysBatonRougeRefinery,1942
ModelIIdominatedcatalyticcracking
duringearlyyears

Dilutephase riserreactordesign
Molecularsievebasedcatalysts 1960s
Significantlyhighercrackingactivity&
gasolineyields lowercarbononcatalyst
Plugflow drasticallyreducedresidence
time&90%feedconversions
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FCCFeedstocks
Considerationsduetochemicalspecies
Aromaticringstypicallycondensetocoke
Nohydrogenaddedtoreducecokeformation
Amountofcokeformedcorrelatestocarbonresidueoffeed
o

Feedsnormally37wt%CCR

Catalystssensitivetoheteroatompoisoning
Sulfur&metals(nickel,vanadium,&iron)
Feedsmaybehydrotreated

Atmospheric&vacuumgasoilsareprimaryfeeds
Couldberoutedtothehydrocrackerfordieselproduction
Notasexpensiveaprocessashydrocracking

Dictatedbycapacities&ofgasoline/dieseleconomics

Hydrotreated feedresultsincleanerproducts,nothighinsulfur

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FCCProducts
Primarygoal makegasoline&diesel,
minimizeheavyfueloilproduction

Catgasolinecontributeslargestvolume
tothegasolinepool
Frontendrichinolefins,backend
aromatics
DoesnotcontainmuchC6&C7olefins
veryreactive&formlighterolefins&
aromatics

Cokeproductionsmallbutveryimportant
Burnedinregenerator&providesheatfor
crackingreactions

Lightendshighinolefins
Goodforchemicalfeedstock
Canrecoverrefinerygradepropylene
Propylene,butylene,&C5olefinscanbe
alkylatedforhigheryieldsofhighoctane
gasoline

Catkerosene&jetfuel
Lowcetane numberbecauseofaromatics
lowersqualitydieselpool

Gasoils cycleoils
Essentiallysameboilingrangeasfeedstock

Slurry
Heavyresiduefromprocess
Highinsulfur,smallring&polynuclear
aromatics,&catalystfines
Usuallyhashighviscosity
Disposition
Blendedintotheheavyfueloil(Bunker
FuelOilorMarineFuelOil)
Hydrocracked
Blendedintocoker feed canhelpmitigate
shotcokeproblems
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ProductYields
Produceshighyieldsofliquids&smallamountsofgas&coke
Massliquidyieldsareusually90% 93%;liquidvolumeyieldsareoftenmorethan100%
(volumeswell)
(Ruleofthumb)Remainingmassyieldsplitbetweengas&coke

Theyieldpatternisdeterminedbycomplexinteractionoffeedcharacteristics&
reactorconditionsthatdetermineseverityofoperation
Roughyieldestimationchartsgivenintextpp.117 130&pp.144156

Conversiondefinedrelativetowhatremainsintheoriginalfeedstockboiling
range
Conversion 100% GasOilYield

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FCCUYieldExample
ProductYieldsfromFCCU
OperationInfo:

Conversion=

Yields

Fraction
FCCUFeed(TotalGasOil)
Lightgases(C2)
Propane(C3)
Propylene(C3=)
Isobutane(IC4)
nbutane(NC4)
Butylenes(C4=)
Gasoline(C5+)
LightCycleOil(LCO)
HeavyCycleOil(HCO)
Coke
Total
CycleOils
TotalLPG

Propane(C3)
Propylene(C3=)
Isobutane(IC4)
nbutane(NC4)
Butylenes(C4=)
Total

72.0 vol%
StandardDensities

bbl/day
25,000

lb/day
7,915,013

vol%
100.0%

wt%
100.0%

API
25.0

SpGr
0.9042

lb/gal
7.538

639
1,451
1,397
491
1,902
14,263
5,300
1,700

389,994
113,468
264,749
275,362
100,375
399,959
3,732,025
1,631,053
620,576
387,452

2.56%
5.80%
5.59%
1.96%
7.61%
57.05%
21.20%
6.80%

4.93%
1.43%
3.34%
3.48%
1.27%
5.05%
47.15%
20.61%
7.84%
4.90%

147.6
140.1
119.9
110.8
104.1
57.9
29.5
4.2

0.5070
0.5210
0.5629
0.5840
0.6005
0.7473
0.8789
1.0425

4.227
4.344
4.693
4.869
5.006
6.230
7.327
8.692

27,143
7,000
5,880

7,915,013
2,251,629
1,153,913

108.57% 100.00%
28.00%
28.45%
23.52%
14.58%

22.5

0.9186

7.659

Yields[vol%]
Unnormalized Normalized
2.92%
2.56%
6.63%
5.80%
6.38%
5.59%
2.24%
1.96%
8.69%
7.61%
26.87%
23.52%

WatsonK
Factor
12.00

SulfurDistribution
Content
Recovery
wt%
lb/day
wt%
0.50 39,575
2.5%
2.7%
1.1%
1.1%
3.0%
0.8%
0.1%
0.4%
1.0%
0.1%

9,846
3,027
3,027
3,027
3,027
3,027
2,010
6,095
6,095
396

24.9%
7.6%
7.6%
7.6%
7.6%
7.6%
5.1%
15.4%
15.4%
1.0%

39,575
12,189
15,134

100.0%
30.8%
38.2%

Example
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BoilingPointRangesforProducts
Kaes's Example FCC Problem
3,000
net.cso
31a
lco.product

2,500

unstab.gasol
Incremental Yield [bpd]

wet.gas
53-total.feed

2,000

1,500

1,000

500

100

200

300

400

500

600

700

800

900

1000

1100

1200

BPT [F]

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CatalyticCrackingCatalysts&Chemistry
Acidsitecatalyzedcracking&hydrogentransferviacarbonium mechanism
Basicreaction carboncarbonscissionofparaffins &cycloparaffins toformolefins&
lowermolecularweightparaffins &cycloparaffins

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

CH3CH2CH2CH2CH2CH2CH2CH3
CH3CH2CH2CH2CH3 CH=CHCH3
Olefinsexhibitcarboncarbonscission&isomerizationwithalkylparaffins toform
branchedparaffins
Cycloparaffins willdehydrogenate(condense)toformaromatics
Smallamountofaromatics&olefinswillcondensetoultimatelyformcoke
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CatalyticCrackingCatalysts&Chemistry
Zeolitecatalysts
Highactivity
Highgasoline&lowcokeyields
Goodfluidizationproperties
Sizebetweenflour&grainsof
sand.
Balancebetweenstrength(so
itdoesntbreakapartasit
movesthroughsystem)but
doesntabradetheequipment
internals.
o

70tons/mintypical
circulationrate

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

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CatalyticCrackingCatalysts&Chemistry
Researchcontinuesbycatalyst
suppliers&licensors

Recognitionthatbothcrackability of
feed&severityofoperationsare
factors
Theoreticalbasisforcracking
reactionsleadtomoreprecisecatalyst
formulation
Catalysttailoredtomaximizea
particularproduct
Focususedtobeongasoline
nowmorelikelydieselyieldor
increasedolefinproduction

Additives
Bottomscracking

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

ZSM5forincreasedC3production
COcombustionpromotersin
regenerator

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OperatingConditions&DesignFeatures
Designedtoprovidebalanceofreactor&regeneratorcapabilities
Usuallyoperatetooneormoremechanicallimits
Commonlimitiscapacitytoburncarbonfromthecatalyst
Ifaircompressorcapacityislimit,capacitymaybeincreasedatfeasiblecapitalcost
Ifregeneratormetallurgyislimit,designchangescanbeformidable.
Regeneratorcyclonevelocitylimit

SlidevalvePlimit

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FCCRiser/RegeneratorCombination
Risers
Inlettypically1300F,outlet950 1000F
Increasedreactortemperaturetoincrease
severity&conversion
Mayneedtoreversetolowerolefincontent
(gasolineformulationregulations)

Reactorpressurecontrolledbythefractionator
overheadgascompressor
Typically10to30psig

Highgasvelocityfluidizesfinecatalystparticles.
Currentdesignshaverisercontacttimestypically
2to3seconds.
Importantdesignpoint:quick,even,&complete
mixingoffeedwithcatalyst
Licensorshaveproprietaryfeedinjectionnozzle
systemstoaccomplishthis
Atomizefeedforrapidvaporization
Canimproveperformanceofanexistingunit

PetroleumRefiningTechnology&Economics 5th Ed.


byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

21

FCCRiser/RegeneratorCombination
Cyclones
Gas/solidseparationincyclones
Increasedcrosssectionalareadecreasesgas
velocity.
Normally2stagecyclones.

Rapidseparationtopreventovercracking.

Regenerators
Regeneratorsoperate1200 1500oF
Limitedbymetallurgyorcatalystconcerns

Temperaturedetermineswhethercombustion
gasesprimarilyCOorCO2
PartialBurn.Under1300F.HighCOcontent.
OutlettoCOboilers&HRSG(heat
recovery/steamgeneration).
FullBurn.Hightemperaturesproducevery
littleCO.simplerwasteheatrecoversystems.
PetroleumRefiningTechnology&Economics 5th Ed.
byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

22

FCCRiser/RegeneratorCombination
Heatbalance
Reactor&regeneratoroperateinheatbalance
Moreheatreleasedintheregenerator,highertemperatureofregeneratedcatalyst,&
higherreactortemperatures.

Heatmovedbycatalystcirculation.

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Resid CatalyticCracking
Economicsfavoringdirectcrackingofheavier
crudes&resids
Insteadofnormal58%cokeyieldcanreach15%
withresid feeds

Requiresheatremovalinregenerator
Catalystcoolersonregeneratorto
Produceshighpressuresteam
Speciallydesignedverticalshell&tubeheat
exchangers

Proprietaryspecializedmechanicaldesigns
availablewithtechnologylicense

PetroleumRefiningTechnology&Economics 5th Ed.


byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

24

ImprovingCatCrackingProcessMonitoring
MassBalance
Hydrocarbonbalance canyouaccount
foryourprocessstream?
Catalystbalance Canyouaccountfor
everypoundofcatalystfrominjectionto
regeneratorspentcatalyst
toslurrycatalystcontent?

PressureBalance
Drivesreliability&longterm
safeoperation
Understandpressureprofiles
including:airblower,regenerator,
reactor,&wetgascompressor
Helptroubleshootmechanicalissuesair
grids&cyclones
Ref:http://www.refinerlink.com/blog/Cat_Cracking_Process_Monitoring

HeatBalance
Importantforkineticreactionsoftheplant
aswellasdistillationandheat
recover/integrationintheunit

YieldBalance
Understandtheeconomic
implicationsoftheunit&helpfocus
onkeyindicators
Catalystcost/usageimpactstheoperating
expenseoftheCatCracker?
Impactoffeedqualityvariationsonyields?

FCCvs.HydrocrackerInstalledCost

FCCstendtobelessexpensivethanHydrocrackers
50,000bpddistillateFCC $150millioninstalledcost
50,000bpd@2000scf/bbl $350millioninstalledcost

PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
26

SupplementalSlides
Phillips66capacities
Fluidizedcatalyticcrackingtechnologyproviders
FCCriser/regeneratorcombination
OtherRCCconfigurations

27

Phillips66Statistics

U.S.informationfromEIA,Jan.1,2014database,publishedJune2014
http://www.eia.gov/petroleum/refinerycapacity/

28

FluidizedCatalyticCrackingTechnologies

Provider
Shaw
ExxonMobilResearch&Engineering
KBR
LummusTechnology
Shaw
ShellGlobalSolutions
UOP
LummusTechnology
KBR
KBR
HaldorTopsoeA/S
Shaw
Axens

Features
Deepcatalyticcracking
Fluidcatalyticcracking
Fluidcatalyticcracking
Fluidcatalyticcracking
Fluidcatalyticcracking
Fluidcatalyticcracking
Fluidcatalyticcracking
Fluidcatalyticcrackingformaximumolefins
Fluidcatalyticcracking,higholefincontent
Fluidcatalyticcracking,residual
Fluidcatalyticcrackingpretreatment
Residcracking
Residcracking

29

FCCRiser/RegeneratorCombination

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000

30

OtherFCCConfigurations

PetroleumRefiningTechnology&Economics 5th Ed.


byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

31

ExxonFlexicracking IIRFCCUnit
PetroleumRefiningTechnology&Economics 5th Ed.
byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

M.W.KelloggDesign

32