FluidizedCatalyticCracking

Chapter6

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

Purpose
Catalyticallycrackcarboncarbonbondsin
gasoils

Finecatalystinfluidizedbedreactor
allowsforimmediateregeneration
Lowersaveragemolecularweight&
produceshighyieldsoffuelproducts
Producesolefins

Attractivefeedcharacteristics
Smallconcentrationsofcontaminants
Poisonthecatalyst

Smallconcentrationsofheavyaromatics
Sidechainsbreakoffleavingcoresto
depositascokeoncatalyst
Mustbeintentionallydesignedfor
heavyresid feeds

Productsmaybefurtherprocessed
Furtherhydrocracked
Alkylated toimprovegasolineantiknock
properties

CharacteristicsofPetroleumProducts

Largeconversiontolightproductsrequiressomecokeformation
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000

OverviewofCatalyticCracking
FCCheartofamodernUSrefinery
NearlyeverymajorfuelsrefineryhasanFCCU

Oneofthemostimportant&sophisticatedcontributionstopetroleumrefiningtechnology
Capacityusually1/3ofatmosphericcrudedistillationcapacity
Contributesthehighestvolumeto
thegasolinepool

U.S.RefineryImplementation

Company

ExxonMobil Refining
ExxonMobil Refining
BP
BP
PDVSA
Hovensa LLC
ConocoPhillips
Sunoco
Marathon Petroleum
Motiva Enterprises

State

Site

Louisiana
Texas
Texas
Indiana
Louisiana
Virgin Islands
New Jersey
Pennsylvania
Louisiana
Louisiana

BATON ROUGE
BAYTOWN
TEXAS CITY
WHITING
LAKE CHARLES
KINGSHILL
LINDEN
PHILADELPHIA
GARYVILLE
NORCO

Vacuum
Cat Cracking:
Cat Cracking:
Distillation
Fresh Feed
Recycled Feed
Atmospheric
Downstream
Downstream
Downstream
Crude Distillation
Charge Capacity, Charge Capacity, Charge Capacity,
Capacity (barrels
Current Year
Current Year
Current Year
per stream day)
(barrels per
(barrels per
(barrels per
stream day)
stream day)
stream day)
524,000
596,400
475,000
420,000
440,000
525,000
250,000
355,000
275,000
250,000

242,500
288,600
237,000
247,000
235,000
225,000
75,000
163,200
142,000
95,000

242,000
215,500
175,000
165,000
147,000
149,000
145,000
138,500
131,000
120,000

0
8,000
8,000
4,000
3,000
0
0
0
0
0

Top 10 combined Cat Cracking

TypicalFCCComplex

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

FCCRiser/RegeneratorCombination

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000

OtherFCCConfigurations

PetroleumRefiningTechnology&Economics 5th Ed.

byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

10

OtherFCCConfigurations
Bayway configuration?

PetroleumRefiningTechnology&Economics 5th Ed.

byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

11

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

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&diesel

whileminimizingproductionofheavyfuel
oil
Catgasolinecontributeslargestvolume
tothegasolinepool
Frontendrichinolefins
Backendhighlyaromaticwithsome
olefins
DoesnotcontainmuchC6&C7olefins
veryreactive&formlighterolefins&
aromatics

Cokeproductionsmallbutveryimportant
Burnedinregenerator&providesheatfor
crackingreactions

Lightendscontainlargeamountsofolefins
Goodforchemicalfeedstock

Catkerosene&jetfuel
Lowcentanenumberbecauseofaromatics
lowersqualitydieselpool

Gasoils cycleoils
Sameboilingrangeasinitialgasoil
feedstock

Slurry
Heavyresiduefromprocess
Highinsulfur,smallring&polynuclear
aromatics,&catalystfines
Usuallyhashighviscosity
Disposition

Canrecoverchemicalgradepropylene&
ethylene

Blendedintotheheavyfueloil(Bunker
FuelOilorMarineFuelOil)

Propylene,butylene,&C5olefinscanbe
alkylatedforhigheryieldsofhighoctane
gasoline

Hydrocracked
Blendedintocokerfeed canhelp
mitigateproblemswithshotcoke
production

16

ProductYields
Produceshighyieldsofliquids&smallamountsofgas&coke
Massliquidyieldsareusually90%93%;liquidvolumeyieldsareoftenmorethan100%
(volumeswell)
(Ruleofthumb)Remainingmassyieldsplitbetweengas&coke

Theyieldpatternisdeterminedbycomplexinteractionoffeedcharacteristics&
reactorconditionsthatdetermineseverityofoperation
Roughyieldestimationchartsgivenintextpp.117130pp.144156

Conversiondefinedrelativetowhatremainsintheoriginalfeedstockboiling
range
Conversion 100% GasOilYield

17

UseofYieldCharts
Vol%

Wt%

FuelGas

6.19
C3

6.21

Ratio

Pure

C3=

6.21

Ratio

Pure

6.22

Ratio

Pure

NC4

6.22

Ratio

Pure

C4=s

6.22

Ratio

Pure

LPG

IC4

6.20

Gasoline
CycleOils

LCO
HCO

6.23
100%
Conv

Ratio

6.24/25

6.27

Coke
Total

Density

Ratio

Ratio

Ratio
6.27

6.18
100%

100%

18

FCCUYieldExample
Product Yields from FCCU
Feed Information:

Ave BPT
F
825.4

Specific
Gravity
0.9042

API
Gravity
25.0

Watson
K Factor
12.0

Sulfur
Content
wt%
0.500

Water density @ 60F =

8.33718 lb/gal

Product Distribution:
Conversion =
Fraction

72.0 vol%
Yields
vol%
wt%
100.0%
100.0%

bbl/day
25,000

lb/hr
329,791

636
1,444
1,390
488
1,893
14,311
5,300
1,700

16,134
4,704
10,977
11,417
4,162
16,605
156,021
67,968
25,857
15,947

2.54%
5.78%
5.56%
1.95%
7.57%
57.24%
21.20%
6.80%

4.89%
1.43%
3.33%
3.46%
1.26%
5.03%
47.31%
20.61%
7.84%
4.84%

Total
Cycle Oils

27,162
7,000

329,791
93,825

108.65%
28.00%

100.00%
28.45%

Total LPG

5,851

Feed
Light gases (C2-)
Propane (C3)
Propylene (C3=)
Iso-butane (IC4)
n-butane (NC4)
Butylenes (C4=)
Gasoline (C5+)
Light Cycle Oil (LCO)
Heavy Cycle Oil (HCO)
Coke

Standard Densities
API
SpGr
lb/gal
25.0
0.9042
7.538

lb/bbl
316.6

147.6
140.1
119.9
110.8
103.8
57.9
29.5
4.2

0.5070
0.5210
0.5629
0.5840
0.6013
0.7473
0.8790
1.0425

4.227
4.344
4.693
4.869
5.013
6.230
7.328
8.692

177.5
182.4
197.1
204.5
210.6
261.7
307.8
365.0

22.5

0.9187

7.659

321.7

Sulfur Distribution
Product
Recovery
wt%
lb/hr
wt%
0.50%
1,649
2.54%
2.68%
1.15%
1.10%
3.03%
0.76%
0.054%
0.37%
0.98%
0.10%

410
126
126
126
126
126
84
254
254
16

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

1,649
508

100.0%
30.8%

631

38.2%

Un-Normalized Yields:

Propane (C3)
Propylene (C3=)
Iso-butane (IC4)
n-butane (NC4)
Butylenes (C4=)

Total

23.41%
2.92%
6.63%
6.38%
2.24%
8.69%
26.87%

Example

19

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]

20

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

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

CH3CH2CH2CH2CH2CH2CH2CH3
CH3CH2CH2CH2CH3 CH=CH2CH3
Olefinsexhibitcarboncarbonscission&isomerization withalkylparaffins toform
branchedparaffins
Cycloparaffins willdehydrogenate(condense)toformaromatics
Smallamountofaromatics&olefinswillcondensetoultimatelyformcoke

21

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

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&regeneratorcapabilities
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.

PetroleumRefiningTechnology&Economics 5th Ed.

byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

27

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

PetroleumRefiningTechnology&Economics 5th Ed.

byJamesGary,GlennHandwerk,&MarkKaiser,CRCPress,2007

29

FCCvs.HydrocrackerInstalledCost

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

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

30