Professional Documents
Culture Documents
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/
4
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
10
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
11
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
12
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
13
ProductYields
Produceshighyieldsofliquids&smallamountsofgas&coke
Massliquidyieldsareusually90% 93%;liquidvolumeyieldsareoftenmorethan100%
(volumeswell)
(Ruleofthumb)Remainingmassyieldsplitbetweengas&coke
Theyieldpatternisdeterminedbycomplexinteractionoffeedcharacteristics&
reactorconditionsthatdetermineseverityofoperation
Roughyieldestimationchartsgivenintextpp.117 130&pp.144156
Conversiondefinedrelativetowhatremainsintheoriginalfeedstockboiling
range
Conversion 100% GasOilYield
14
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
15
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]
16
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
17
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
18
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
19
OperatingConditions&DesignFeatures
Designedtoprovidebalanceofreactor®eneratorcapabilities
Usuallyoperatetooneormoremechanicallimits
Commonlimitiscapacitytoburncarbonfromthecatalyst
Ifaircompressorcapacityislimit,capacitymaybeincreasedatfeasiblecapitalcost
Ifregeneratormetallurgyislimit,designchangescanbeformidable.
Regeneratorcyclonevelocitylimit
SlidevalvePlimit
20
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
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®eneratoroperateinheatbalance
Moreheatreleasedintheregenerator,highertemperatureofregeneratedcatalyst,&
higherreactortemperatures.
Heatmovedbycatalystcirculation.
23
Resid CatalyticCracking
Economicsfavoringdirectcrackingofheavier
crudes&resids
Insteadofnormal58%cokeyieldcanreach15%
withresid feeds
Requiresheatremovalinregenerator
Catalystcoolersonregeneratorto
Produceshighpressuresteam
Speciallydesignedverticalshell&tubeheat
exchangers
Proprietaryspecializedmechanicaldesigns
availablewithtechnologylicense
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
31
ExxonFlexicracking IIRFCCUnit
PetroleumRefiningTechnology&Economics 5th Ed.
byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007
M.W.KelloggDesign
32