DelayedCoking

Chapter5
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
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
EIAdatabaseasof
January1,2012
4
U.S.RefineryImplementation
5
Top 10 Delayed Cokers; all Fluidized Cokers.
CharacteristicsofPetroleumProducts
6
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
Conversiontolightproductsw/oextrahydrogenrequiressignificantcokeformation
HistoricalDevelopmentofCoking
AfterWorldWarIIrailroadsshiftedfromsteamtodiesellocomotives
Demandforheavyfueloilsharplydeclined
Cokingincreasesdistillateproduction&minimizesheavyfueloil
1950to1970cokingcapacityincreasedfivefold
Morethantwicetherateofincreaseincrudedistillationcapacity
Increaseinheavyhighsulfurcrudecombineddecreaseinheavyfueloil
7
CokingChemistry
Carbonrejectionprocess
Cokehasverylittlehydrogen containedinlighter
products
Metals(catalystpoisons)concentrateincoke
Cycleofcracking&combining
SidechainscrackedoffofPNA(Polynuclear
Aromatic)cores
Heteroatoms insidechainsendupinlightproducts
PNAscombine(condense)toformasphaltenes &
coke
Metals&heteroatoms inPNAcoresendupincoke
Conditions
Hightemperatures&lowpressuresfavorcracking
Moredistillateliquids
Loweryieldsofcoke&hydrocarbongas
Highresidencetimefavorthecombiningreactions
Overconversionwillreducedistillates&produce
cokeandhydrocarbongases
8
Figure:Comparisonofthermalcrackingandhydrocracking yielddistributions,Sayles&Romero
http://www.digitalrefining.com/article_1000070.pdf
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&sulfur
mayposeadisposalproblem
Oilsandspileitup
Productgrades
Needlecoke
Anodegrade
Fuelgrade
ProductMorphology
Needlecoke
Spongecoke
Shotcoke
Highqualityproducts
Needlecoke
Feedstock FCCcycleoils&gasoils
Usedforelectrodesinsteelmanufacturing
Anodegradecoke
Feedstock resids withsmallring
aromatics,lowmetals,&lowsulfur
Usedforelectrodesinaluminum
production
Hydroprocessing upstreamofdelayed
coker maybeusedtomakehighquality
coke
Fuelgradecoke
Feedstock resid highinpolynuclear
aromatics&sulfur
Valuesimilartocoal
12
SolidProducts
Morphology
Needlecoke
Verydense&crystallineinstructure
Spongecoke
Isspongelikeinstructure
Shotcoke
Cannotavoid basedonasphaltene content
offeed
Fromsizeofsmallballbearingstobasketball
Operationaladjustmentsrequiredincutting
&handlingofcoke
13
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
Someofthelowestqualityintherefinery
Reducedaromaticsbuthigholefincontent
Thoughheteroatoms areconcentratedincokestillhighinsulfur
14
FeedstockSelection
Amountofcokerelatedtocarbonresidueoffeed
Correlatestohydrogen/carbonratio&indicatescokingtendency
Threemaintests
ConradsonCarbon(ASTMD189)
Ramsbottommethod(ASTMD524)
MicrocarbonResidueTest(ASTMD4530)
15
Yields
Lowyieldsofliquidsrelativetohydrocracking
Massconversionofvacuumresidstoliquidsabout55% about90%for
hydrocracking
Coke&liquidyieldsmaybeestimatedbysimpleequations
(misprintpg.104 seepg.117)
16

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
17
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%
18
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
19
Examplesteps
BoilingPointRangesforProducts
20
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
21
TypicalDelayedCokingUnit
22
OriginalSource:
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
TypicalDelayedCokingUnit
FreshFeed&Furnace
Freshfeedtobottomoffractionator
Totalfeed(freshfeed+recycle)heatedin
furnace
Furnace
Outlettemperatureabout925F
Crackingstartsabout800F
Endothermicreactions
Superheatallowscrackingreactionsto
continueincokedrums DelayedCoking
Steaminjectedintofurnace
Reduceoilpartialpressure&increase
vaporization
Maintainshighfluidvelocities
CokeDrumConfiguration
Flowupfrombottom
Cokingreactionarecompletedindrum
Vaporsouttopofdrumtofractionator
Evennumberofcokedrums
Typicallytwoorfour
Operateaspairs,onefillingwhiletheother
decoked
23
TypicalDelayedCokingUnit
CokeDrumCyclicOperation
FillCokeDrum
Cokingreactionindrums&solid
cokedeposited
Gasfromtopofcokedrumto
fractionator
Fullcycletimetillcokedrumfull
Decoking
Offlinedrumdecoked
Quenchstep hotcokequenched
withsteamthenwater.Givesoff
steam&volatilehydrocarbons
Initialsteampurgefedto
fractionator.Furtherpurgedirected
toblowdown system.
Cokedrilledoutwithwaterdrills
CokeCollectionSystems
Directdischargetohoppercar
Padloading
Pit&craneloading
24
Improvecoker efficiencywithreliablevalveautomation
B.Deters&R.Wolkart,HydrocarbonProcessing,April2013
25
http://www.glcarbon.com/ref/delayed.PDF
CokeDrumSchedule 1Pair
26
DrumBeingFilled DrumBeingDecoked Fractionator
1hourSteamout
4hoursQuench
1.5hoursDehead
4hoursDrilloutcoke
1hourRehead
4.5hoursTest,Warmup,&Standby
16hoursFilldrumwithcoke
45hoursUpsetfromswitchover
11hoursLinedout&steady
CokeDrumSchedule 3Pairs
27
HandbookofPetroleumRefiningProcesses
RobertMeyers
McGrawHill,Inc,1986
Deheading
Transitioningfrommanualtoautomaticdeheading
Totallyenclosedsystemfromthetopofcokedrumtothedrainpit,railcar,orsluiceway
Eliminateexposurerisktopersonnel,equipment,&theunheadingdeck
Remotelyoperated
fromcontrolroom
Allsafetyinterlocks
incorporated
Isolation&controlof
adrumdump
28
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
29
Automateddecokingsolvescoker safetychallenges
I.Botros,HydrocarbonProcessing,pp4750,November2011
Decoking
30
HandbookofPetroleumRefiningProcesses
RobertMeyers
McGrawHill,Inc,1986
Decoking
31
HandbookofPetroleumRefiningProcesses
RobertMeyers
McGrawHill,Inc,1986
TypicalDelayedCokingUnit
Fractionator
Vaporscompressed&senttogasplant
Naphthaiscondensedfromfractionatoroverhead
Gasoilsaresidestreamdrawsfromthefractionator
FlashZoneGasinternallyrecycledtocokedrumsorrecoveredasadditionalliquid
product.
32
CokeProducts
GreenCoke
Directlyproducedbyarefinery
ifnofurtherprocessingdone
Primarilyusedforfuel
Uncalcined spongecoke
typically14,000Btu/lb
heatingvalue
Crushed&drainedoffree
water
Calcined Coke
Greencokeheatedtofinish
carbonizingcoke&reduce
volatilemattertoverylow
levels
Anode&needlecoke
33
GreenCoke CalcinedCoke
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%
Calcining
Greencokeheatedtofinish
carbonizingcoke&reduce
volatilemattertoverylow
levels
Calcining doneinrotarykilnor
rotaryhearth
Heated1800 2400
o
F
Calcining doesnotremove
metals
34
FluidBedCoking&Flexicoking
FluidCoking&Flexicokingareexpensiveprocessesthathaveonlyasmallportion
ofthecokingmarket
Continuousfluidizedbedtechnology
Cokeparticlesusedasthecontinuousparticulatephasewithareactorandburner
ExxonResearchandEngineeringlicensorofFlexicokingprocess
ThirdgasifiervesselconvertsexcesscoketolowBtufuelgas
35
FluidBedCoking
36
Figurefromhttp://www.exxonmobil.com/refiningtechnologies/fuels/mn_fluid.html
Flexicoking
37
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
38
PetroleumRefiningTechnology&Economics,5
th
ed.
Gary,Handwerk,&Kaiser
CRCPress,2007