DelayedCoking

Chapter5
Purpose
Processheavyresiduumtoproduce
distillates(naphtha&gasoils)thatmay
becatalyticallyupgraded
Hydrotreating,catalyticcracking,and/or
hydrocracking
Attractiveforheavyresiduumnot
suitableforcatalyticprocesses
Largeconcentrationsofresins,
asphaltenes,&heteroatomcompounds
(sulfur,nitrogen,oxygen,metals)
Metals,sulfur,&othercatalystpoisons
generallyendupincoke
Soldforfuel&otherpurposes
Carbonrejectionprocess
Fired Heater
Fractionator
Coke Drums
Gas
Naphtha
Light Gas O
Heavy Gas O
Fresh Feed
Steam
Coke
3
DevelopmentofCoking
Cokingcapacityismeasuredintermsofbothcokeproductionintonsperday&
residualoilfeedrateinbarrelsperday
EIAdatabaseasofJanuary1,2009:
4
Unit bblperstreamday RelativeCapacity
CrudeUnits 18.2MMbpd
VacuumUnits 8.8MMbpd 48%
DelayedCokingUnits 2.5MMbpd 14%
FluidCokingUnits 0.2MMbpd 1%
U.S.RefineryImplementation
5
Top 10 Delayed Cokers; all Fluidized Cokers.
CORPORATION State Site
Atmospheric
CrudeDistillation
Capacity(barrels
perstreamday)
Vacuum
Distillation
Downstream
ChargeCapacity,
CurrentYear
(barrelsper
streamday)
ThermCracking,
DelayedCoking
Downstream
ChargeCapacity,
CurrentYear
(barrelsper
streamday)
ThermCracking,
FluidCoking
Downstream
ChargeCapacity,
CurrentYear
(barrelsper
streamday)
Petcoke,Market
Production
Capacity,Current
Year(barrelsper
steamdayexcept
sulfurand
hydrogen)
EXXONMOBILCORP Louisiana BATONROUGE 523,200 246,100 123,500 0 31,525
PDVAMERICAINC Louisiana LAKECHARLES 440,000 230,000 110,000 0 30,000
CHEVRONCORP Mississippi PASCAGOULA 360,000 314,000 105,000 0 35,500
VALEROENERGYCORP Texas PORTARTHUR 415,000 219,000 99,700 0 32,240
ACCESSINDUSTRIES Texas HOUSTON 302,300 202,000 97,500 0 29,250
DEERPARKREFININGLTDPTNRSHP Texas DEERPARK 340,000 180,000 89,300 0 38,701
MARATHONPETROLEUMCORP Louisiana GARYVILLE 518,000 268,000 87,000 0 29,000
WRBREFININGLP Illinois WOODRIVER 345,000 199,000 83,000 0 28,500
CONOCOPHILLIPS Texas SWEENY 260,000 132,100 78,700 0 22,800
CHEVRONCORP California ELSEGUNDO 290,500 169,100 77,600 0 25,500
CORPORATION State Site
Atmospheric
CrudeDistillation
Capacity(barrels
perstreamday)
Vacuum
Distillation
Downstream
ChargeCapacity,
CurrentYear
(barrelsper
streamday)
ThermCracking,
DelayedCoking
Downstream
ChargeCapacity,
CurrentYear
(barrelsper
streamday)
ThermCracking,
FluidCoking
Downstream
ChargeCapacity,
CurrentYear
(barrelsper
streamday)
Petcoke,Market
Production
Capacity,Current
Year(barrelsper
steamdayexcept
sulfurand
hydrogen)
PBFENERGYCOLLC Delaware DELAWARECITY 190,200 104,600 0 54,500 13,620
EXXONMOBILCORP Texas BAYTOWN 584,000 297,000 54,000 42,000 22,750
VALEROENERGYCORP California BENICIA 150,000 81,300 0 29,500 6,800
ROYALDUTCH/SHELLGROUP California MARTINEZ 158,000 102,000 25,000 22,500 8,600
EXXONMOBILCORP Montana BILLINGS 62,200 28,900 0 10,400 4,000
CharacteristicsofPetroleumProducts
6
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
Conversiontolightproductsw/oextrahydrogenrequiressignificantcokeformation
DevelopmentofCoking
AfterWorldWarIIrailroadsshiftedfromsteamtodiesellocomotives
Demandforheavyfueloilsharplydeclined
Cokingincreasesdistillateproduction&minimizesheavyfueloil
1950to1970cokingcapacityincreasedfivefold
Morethantwicetherateofincreaseincrudedistillationcapacity
Increaseinheavyhighsulfurcrudecombineddecreaseinheavyfueloil
7
CokingChemistry
Carbonrejectionprocess
Cokehasverylittlehydrogen shiftstothelighter
products
Metals(hydrotreatingcatalystpoisons)concentrate
incoke
Cycleofcracking&combining
SidechainscrackedoffofPNA(Polynuclear
Aromatic)cores
Heteroatomsinsidechainsendupinlightproducts
PNAscombine(condense)toformasphaltenes&
coke
Metals&heteroatomsinPNAcoresendupincoke
Conditions
Hightemperatures&lowpressuresfavorcracking
Moredistillateliquids
Loweryieldsofcoke&hydrocarbongas
Highresidencetimefavorthecombiningreactions
Overconversionwillreducedistillates&produce
cokeandhydrocarbongases
8
CokingTechnologies
9
Provider Features
Bechtel
KBR
LummusTechnology
UOP/FosterWheeler
ExxonMobil Fluidizedbed
DelayedCokingwithuniquefeaturesof:furnacedesign;
cokedrumstructure,design,layout,&scheduling;coke
handling
DelayedCoking
Predominatecokingtechnology
DelayedCokingtechnologyisrelativelyinexpensive
Openartavailable
Companiesdolicensetechnologyemphasizingcokefurnaces,specialprocessingmodes,
&operations
10
FeedfortheDelayedCoker
DelayedCokercanprocessawidevarietyoffeedstocks
Canhaveconsiderablemetals(nickel&vanadium),sulfur,resins,&asphaltenes
Mostcontaminantsexitwithcoke
Typicalfeedisvacuumresid
Atmosphericresidoccasionallyused
Typicalfeedcomposition
6%sulfur
1,000ppm(wt)metals
ConradsonCarbonResidue(CCR)of2030wt%ormore
Feedultimatelydependsontypeofcokedesired
11
SolidProducts
Cokewithlargeamountsofmetals&sulfurmayposeadisposalproblem
Oilsandspileitup
Productgrades
Needlecoke
Anodegrade
Fuelgrade
ProductMorphology
Needlecoke
Spongecoke
Shotcoke
12
SolidProducts
Highqualityproducts
Needlecoke
FCCcycleoils&gasoils
Usedforelectrodesinsteelmanufacturing
Anodegradecoke
Residswithsmallringaromatics,lowmetals,&lowsulfur
Usedforelectrodesinaluminumproduction
Hydroprocessingupstreamofdelayedcokermaybeusedtomakehighqualitycoke
Fuelgradecoke
About8590%carbon,4%hydrogen,47%sulfur,1%nitrogen,oxygen,vanadium&nickel
Feedstock residhighinpolynucleararomatics&sulfur
Valuesimilartocoal
13
SolidProducts
Morphology
Needlecoke
Verydense&crystallineinstructure
Spongecoke
Isspongelikeinstructure
Shotcoke
Cannotavoid basedonasphaltene content
offeed
Fromsizeofsmallballbearingstobasketball
Operationaladjustmentsrequiredincutting
&handlingofcoke
14
ShotCoke:Design&Operations,JohnD.Elliott
http://www.fwc.com/publications/tech_papers/oil_gas/shotcoke.pdf
LightProducts
Vaporlightendsprocessedinrefinerygasplant
Liquids
Naphthafraction
Maybeusedascatalyticreformerfeedafterhydrotreating
Smallfractionofgasolinepool
LightGasOil
Usedindieselpoolafterhydrotreating
Hydrocrackerprocessesaromaticrings
HeavyGasOilfedtocatalyticcrackerorhydrocracker(preferred)
FlashZoneGasOil
Increasesliquidyield&reducescokemake
Composition
Reducedaromaticsbuthigholefincontent
Thoughheteroatomsareconcentratedincokestillhighinsulfur
15
FeedstockSelection
Amountofcokerelatedtocarbonresidueoffeed
Correlatestohydrogen/carbonratio&indicatescokingtendency
Threemaintests
ConradsonCarbon(ASTMD189)
Ramsbottommethod(ASTMD524)
MicrocarbonResidueTest(ASTMD4530)
16
Yields
Lowyieldsofliquidsrelativetohydrocracking
Massconversionofvacuumresidstoliquidsabout55% about90%for
hydrocracking
Coke&liquidyieldsmaybeestimatedbysimpleequations
(misprintpg.104 seepg.117)
17

CokeYield(wt%)=1.6 (wt%CCR)
Gas(C4)(wt%)=7.8+0.144 (wt%CCR)
Gasoline(wt%)=11.29+0.343 (wt%CCR)
GasOil(wt%)=100(wt%Coke)(wt%Gas)(wt%Gasoline)
186.
Gasoline(vol%)=

5
(wt%Gasoline)
131.5+API
155.5
GasOil(vol%)= (wt%GasOil)
131.5+API
ProductLightEnds&SulfurDistribution
Estimatedproductdistribution Tables5.8&5.9
18
TypicalGasComposition
Component Mole%
Methane 51.4
Ethene 1.5
Ethane 15.9
Propene 3.1
Propane 8.2
Butenes 2.4
IButane 1.0
NButane 2.6
H2 13.7
CO2 0.2
Total 100.0
TypicalDistributions
Sulfur(%) Nitrogen(%)
Gas 30
Light
Naphtha
1.7
Heavy
Naphtha
3.3 1
LCGO 15.4 2
HCGO 19.6 22
Coke 30 75
Total 100 100
UseofYieldEquations
LiquidVol% Weight% Mole% StandardLiquid
Density
MolecularWeight
G
a
s

(
C
4

)
H2
7
.
8

0
.
1
4
4

%
C
C
R
Calc 13.7* Pure
H2S Calc * Pure Pure
CO2 Calc 0.2 Pure Pure
C1 Calc 51.4 Pure
C2= Calc 1.5 Pure Pure
C2 Calc 15.9 Pure Pure
C3= Calc 3.1 Pure Pure
C3 Calc 8.2 Pure Pure
C4=s Calc 2.4 Pure Pure
IC4 Calc 1.0 Pure Pure
NC4 Calc 2.6 Pure Pure
Gasoline
(Wt%)*186.5/
(131.5+API)
11.29+
0.343*%CCR
Calculate
GasOil
(wt%)*155.5/
(131.5+API)
Calculate
Coke 1.6*%CCR
Total 100% 100%
19
Notes:
Sulfur in gas as H
2
S. Decrease H
2
amount to account for amount H
2
S.
Interrelate the mass of non-sulfur gas using the mol% values above.
ExampleYieldProblem
CCR Sul fur (wt%) Yi el d Yi el d
bbl /day l b/day SpGr l b/gal API wt% wt% wt% vol %
Crude Charge 100,000 31,899,718 0.9110 7.595 23.8
Vac Resid Feed 41,900 14,730,456 1.0040 8.371 9.4 13.20 2.89 46.2 41.9
Coker Gas 1,428,972 8.94 9.70
Coker Gasoline 8,770 2,330,005 0.7587 6.326 55.0 0.009 15.82 20.93
Coker Gas Oil 24,669 7,860,407 0.9100 7.587 24.0 0.019 53.36 58.88
Coke 3,111,072 4.11 21.12
Coker Total 14,730,456 100.00
Sufl ur Di stri buti on Coker Gas Composi ti on
Sul fur (%) l b/day mol /day Corrected Corrected Corrected
Gas 30.0 127,713 3,983 Component Mol % Mol Wt mol /day mol /day Mol % l b/day
Light Naphtha 1.7 7,237 Methane 51.4 16.043 30,167 30,167 51.4 483,962
Heavy Naphtha 3.3 14,048 Ethene 1.5 28.054 880 880 1.5 24,697
LCGO 15.4 65,559 Ethane 15.9 30.070 9,332 9,332 15.9 280,604
HCGO 19.6 83,439 Propene 3.1 42.081 1,819 1,819 3.1 76,562
Coke 30.0 127,713 Propane 8.2 44.097 4,813 4,813 8.2 212,220
Total 100.0 425,710 Butenes 2.4 56.108 1,409 1,409 2.4 79,032
I-Butane 1.0 58.123 587 587 1.0 34,113
N-Butane 2.6 58.123 1,526 1,526 2.6 88,694
H2 13.7 2.016 8,041 4,058 6.9 8,180
CO2 0.2 44.010 117 117 0.2 5,166
H2S 34.080 3,983 6.8 135,742
Sulfur 32.064 3,983
Total 100.0 62,674 58,691 100.0 1,428,972
w/o Sulfur 22.171 58,691
20
Examplesteps
BoilingPointRangesforProducts
21
Kaes's Example Coker Problem
-
100
200
300
400
500
600
700
800
900
1,000
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
BPT [F]
I
n
c
r
e
m
e
n
t
a
l

Y
i
e
l
d

[
b
p
d
]
42-hcgo
53+55
40-lcgo
37-unstab
33-wetgas
lab-vac-resid
Configuration
Typicalequipment
Heater(furnace)&Preheattrain
Cokedrumvessels
Fractionator
Downstreamvaporprocessing
vessels
Cokedrumsrunintwobatch
modes
Filling
Decoking
Bothmodesofoperation
concurrentlyfeedtothe
fractionator
22
TypicalDelayedCokingUnit
23
OriginalSource:
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
TypicalDelayedCokingUnit
FreshFeed&Furnace
Freshfeedtobottomoffractionator
Totalfeed(freshfeed+recycle)heatedinfurnace
Furnace
Outlettemperatureabout925
o
F crackingstartsabout800
o
F
Endothermicreactions
Superheatallowscrackingreactionstocontinueincokedrums DelayedCoking
Steaminjectedintofurnace
Reduceoilpartialpressure&increasevaporization
Maintainshighfluidvelocities
24
TypicalDelayedCokingUnit
CokeDrumConfiguration
Flowupfrombottom
Cokingreactionarecompletedindrum
Vaporsouttopofdrumtofractionator
Evennumberofcokedrums
Typicallytwoorfour
Operateaspairs,onefillingwhiletheotherdecoked
25
TypicalDelayedCokingUnit
CokeDrumCyclicOperation
FillCokeDrum
Cokingreactionindrums&solidcoke
deposited
Gasfromtopofcokedrumtofractionator
Fullcycletimetillcokedrumfull
Decoking
Offlinedrumdecoked
Quenchstep hotcokequenchedwith
steamthenwater.Givesoffsteam&
volatilehydrocarbons
Initialsteampurgefedtofractionator.
Furtherpurgedirectedtoblowdown
system.
Cokedrilledoutwithwaterdrills
CokeCollectionSystems
Directdischargetohoppercar
Padloading
Pit&craneloading
26
27
http://www.glcarbon.com/ref/delayed.PDF
CokeDrumSchedule 1Pair
28
DrumBeingFilled DrumBeingDecoked Fractionator
1hourSteamout
4hoursQuench
1.5hoursDehead
4hoursDrilloutcoke
1hourRehead
4.5hoursTest,Warmup,&Standby
16hoursFilldrumwithcoke
45hoursUpsetfromswitchover
11hoursLinedout&steady
CokeDrumSchedule 3Pairs
29
HandbookofPetroleumRefiningProcesses
RobertMeyers
McGrawHill,Inc,1986
Deheading
Transitioningfrommanualtoautomaticdeheading
Totallyenclosedsystemfromthetopofcokedrumtothedrainpit,railcar,orsluiceway
Eliminateexposurerisktopersonnel,equipment,&theunheadingdeck
Remotelyoperated
fromcontrolroom
Allsafetyinterlocks
incorporated
Isolation&controlof
adrumdump
30
http://www.processengr.com/ppt_presentations/coking_101.pdf
Decoking
Eachcokedrumhasadrillingrigthat
raises&lowersarotatingcuttinghead
Useshighpressure(4,000psig)water
Steps
Drumcooled&displacedwithwaterto
removevolatiles
Pilotholeisdrilledthroughthecoketo
bottomhead
Pilotdrillbitreplacedwithamuchlarger
highpressurewaterbit
Cutdirection predominantlytopto
bottom
Bottomupcuttingrisksstuckdrillifbed
collapses
Thecokefallsfromcokedrumintoa
collectionsystem
31
Automateddecokingsolvescokersafetychallenges
I.Botros,HydrocarbonProcessing,pp4750,November2011
Decoking
32
HandbookofPetroleumRefiningProcesses
RobertMeyers
McGrawHill,Inc,1986
Decoking
33
HandbookofPetroleumRefiningProcesses
RobertMeyers
McGrawHill,Inc,1986
TypicalDelayedCokingUnit
Fractionator
Vaporscompressed&senttogasplant
Naphthaiscondensedfromfractionatoroverhead
Gasoilsaresidestreamdrawsfromthefractionator
FlashZoneGasinternallyrecycledtocokedrumsorrecoveredasadditionalliquid
product.
34
CokeProducts
GreenCoke
Directlyproducedbyarefineryifnofurtherprocessingdone
Fuelcoke
CalcinedCoke
Greencokeheatedtofinishcarbonizingcoke&reducevolatilemattertoverylowlevels
Anode&needlecoke
35
Calcining
Greencokeheatedtofinishcarbonizing
coke&reducevolatilemattertoverylow
levels
Calcining doneinrotarykilnorrotary
hearth
Heated1800 2400
o
F
Calcining doesnotremovemetals
Uncalcined spongecokehasheating
valuesof14,000Btu/lb
Primarilyusedforfuel
Crushed&drainedoffreewater
contains10%moisture,10%volatiles,&
therestcoke
36
GreenCoke
Calcined
Coke
Fixedcarbon 86% 92% 99.5%
Moisture 6% 14% 0.1%
Volatilematter 8% 14% 0.5%
Sulfur 1% 6% 1% 6%
Ash 0.25% 0.40%
Silicon 0.02% 0.02%
Nickel 0.02% 0.03%
Vanadium 0.02% 0.03%
Iron 0.01% 0.02%
FluidBedCoking&Flexicoking
FluidCoking&Flexicokingareexpensiveprocessesthathaveonlyasmallportion
ofthecokingmarket
Continuousfluidizedbedtechnology
Cokeparticlesusedasthecontinuousparticulatephasewithareactorandburner
ExxonResearchandEngineeringlicensorofFlexicokingprocess
ThirdgasifiervesselconvertsexcesscoketolowBtufuelgas
37
FluidBedCoking CokeRecycledtoExtinction
38
Figurefromhttp://www.exxonmobil.com/refiningtechnologies/fuels/mn_fluid.html
Flexicoking
39
Figurefromhttp://www.exxonmobil.com/refiningtechnologies/fuels/mn_fluid.html
DelayedCokerInstalledCost
Includes
Cokerfractionator
Hydraulicdecokingequipment
Cokedewatering,crushing,&separation
3dayscoveredcokestorage
Cokedrums50 60psig
Blowdown condensation&wastewater
purification
Liquidproductheatexchangetoambient
temperature
Excludes
Lightendsfacilities
Lightendssulfurremoval
Productsweetening
Coolingwater,steam&powersupply
Offgascompression
40
PetroleumRefiningTechnology&Economics,5
th
ed.
Gary,Handwerk,&Kaiser
CRCPress,2007