OILREFINERYPROCESSES

by
A A
A P O G

D
SRM U

E E

OUTLINE

1.
2.
3.
4.
5.
6.

Introduction
PhysicalProcesses
ThermalProcesses
CatalyticProcesses
ConversionofHeavyResidues
TreatmentofRefineryGasStreams

INTRODUCTION

OilrefiningisakeyactivityintheCPI.
Over600refineriesworldwidehaveatotalannual
capacityofmorethan3500x106 tonnes.
Goalofoilrefiningistwofold:
i.

productionoffuelsfortransportation,powergeneration
andheating;and
ii. productionofrawmaterialsfortheCPI.

Oilrefineriesarecomplexplantsbutarerelatively
matureandhighlyintegrated.
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Overview
Afterdesalting anddehydration,crudeisseparated
intofractionsbydistillation.
Thedistilledfractionscannotbeuseddirectly.
Thereasonforsuchacomplexsetofprocessesisthe
differencebetweenthecrudeoilpropertiesandthe
needsofthemarket.
Anotherreasonforcomplexityisenvironmental.
Legislationdemandscleanerproductsandisthe
majordriveforprocessimprovementand
developmentofnovelprocesses.
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Refiningoperations
Petroleumrefiningprocessesandoperationscanbeseparatedintofive
basicareas:
Fractionation (distillation)istheseparationofcrudeoilinatmosphericand
vacuumdistillationtowersintogroupsofhydrocarboncompoundsof
differingboilingpointrangescalled"fractions"or"cuts."
ConversionProcesses changethesizeand/orstructureofhydrocarbon
molecules.Theseprocessesinclude::
Decomposition (dividing)bythermalandcatalyticcracking;
Unification (combining)throughalkylationandpolymerization;and
Alteration (rearranging)withisomerizationandcatalyticreforming.

TreatmentProcesses topreparehydrocarbonstreamsforadditional
processingandtopreparefinishedproducts.Treatmentmayinclude
removalorseparationofaromaticsandnaphthenes,impuritiesand
undesirablecontaminants.Treatmentmayinvolvechemicalorphysical
separatione.g. dissolving,absorption,orprecipitationusingavarietyand
combinationofprocessesincludingdesalting,drying,hydrodesulfurizing,
solventrefining,sweetening,solventextraction,andsolventdewaxing.

Refiningoperations
FormulatingandBlending istheprocessofmixingand
combininghydrocarbonfractions,additives,andother
componentstoproducefinishedproductswithspecific
performanceproperties.
OtherRefiningOperations include:

lightendsrecovery;
sourwaterstripping;
solidwaste,processwaterandwastewatertreatment;
cooling,storageandhandlingandproductmovement;
hydrogenproduction;
acidandtailgastreatment;
andsulfurrecovery.
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PHYSICALPROCESSES

Desalting/dehydration
Howdoesdistillationwork?
Crudedistillation
Propanedeasphalting
Solventextractionanddewaxing
Blending

Desalting/dehydration

Crudeoiloftencontainswater,inorganicsalts,suspendedsolids,and
watersolubletracemetals.
Step0 intherefiningprocessistoremovethesecontaminantssoas
toreducecorrosion,plugging,andfoulingofequipmentandto
preventpoisoningcatalystsinprocessingunits.
Thetwo mosttypicalmethodsofcrudeoildesalting arechemical and
electrostaticseparation,andbothusehotwaterastheextraction
agent.
Inchemicaldesalting,waterandchemicalsurfactant (demulsifiers)
areaddedtothecrude,whichisheatedsothatsaltsandother
impuritiesdissolveorattachtothewater,thenheldinatanktosettle
out.
Electricaldesaltingistheapplicationofhighvoltageelectrostatic
chargestoconcentratesuspendedwaterglobulesinthebottomof
thesettlingtank.Surfactantsareaddedonlywhenthecrudehasa
largeamountofsuspendedsolids.
Athird(andrare)processfiltershotcrudeusingdiatomaceousearth.
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Desalting/dehydration

Thecrudeoilfeedstockisheatedto65180C toreduceviscosityand
surfacetensionforeasiermixingandseparationofthewater.The
temperatureislimitedbythevaporpressureofthecrudeoilfeedstock.
Inbothmethodsotherchemicalsmaybeadded.Ammoniaisoftenused
toreducecorrosion.CausticoracidmaybeaddedtoadjustthepHofthe
waterwash.

Desalting/dehydration

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Howdoesdistillationwork?
Distillationisdefinedas:
aprocessinwhichaliquidorvapourmixtureoftwoormore
substancesisseparatedintoitscomponentfractionsofdesired
purity,bytheapplicationandremovalofheat.

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Howdoesdistillationwork?
Distillationisbasedonthefactthatthevapourofaboiling
mixturewillbericherinthecomponentsthathavelower
boilingpoints.
Thus,whenthisvapouriscooledandcondensed,the
condensatewillcontainthemorevolatilecomponents.At
thesametime,theoriginalmixturewillcontainmoreof
thelessvolatilecomponents.
Distillationisthemostcommonseparationtechniqueand
itconsumesenormousamountsofenergy,bothinterms
ofcoolingandheatingrequirements.
Distillationcancontributetomorethan50%ofplant
operatingcosts.
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Howdoesdistillationwork?
Distillationcolumnsareclassifiedbythemannerin
whichtheyareoperated:
1. Batch,inwhichthefeedtothecolumnisintroduced
batchwise.Thatis,thecolumnischargedwitha'batch'
andthenthedistillationprocessiscarriedout.Whenthe
desiredtaskisachieved,anextbatchoffeedis
introduced.
2. Continuouscolumnsprocessacontinuousfeedstream.
Nointerruptionsoccurunlessthereisaproblemwith
thecolumnorsurroundingprocessunits.Theyare
capableofhandlinghighthroughputsandarethemost
commonofthetwotypes.
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Continuousdistillationcolumns
1.

Classifiedaccordingto:
Natureofthefeedthattheyareprocessing:

2.

Numberofproductstreamstheyhave:

3.

multiproduct column columnhasmorethantwoproductstreams.

Whereextrafeedexitswhenusedtohelpwiththeseparation:

4.

binary column feedcontainsonlytwocomponents;

multicomponent column feedcontainsmorethantwocomponents.

extractive distillation wheretheextrafeedappearsinthebottom

productstream;
azeotropic distillation wheretheextrafeedappearsatthetopproduct
stream.

Typeofcolumninternals:

tray column traysofvariousdesignsusedtoholduptheliquidto

providebettercontactbetweenvapourandliquid;
packedcolumn packingsareusedtoenhancevapourliquidcontact.
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MainComponentsofDistillationColumns

Averticalshell whereseparation
ofliquidcomponentsisdone.
Columninternalse.g.trays/plates
and/orpackings whichareused
toenhancecomponent
separations.
Areboiler toprovidethe
necessaryvaporizationforthe
distillationprocess.
Acondenser tocooland
condensethevapourleavingthe
topofthecolumn.
Arefluxdrum toholdthe
condensedvapourfromthetop
ofthecolumnsothatliquid
(reflux)canberecycledbackto
thecolumn.
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Traysandplates
Bubblecaptrays
Ariserorchimneyisfitted
overeachhole,andacap
coverstheriser.Thecap
ismountedwithaspace
toallowvapourtorise
throughthechimneyand
bedirecteddownwardby
thecap,finallydischarging
throughslotsinthecap,
andbubblingthroughthe
liquidonthetray.

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Traysandplates
Valvetrays
Perforationsarecoveredbycaps
liftedbyvapour,whichcreatesa
flowareaanddirectsthevapour
horizontallyintotheliquid.

Sievetrays
Sievetraysaresimplymetal
plateswithholesinthem.Vapour
passesstraightupwardthrough
theliquidontheplate.The
arrangement,numberandsizeof
theholesaredesignparameters.
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Liquidandvapourflowsinatraycolumn

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Basicoperation

Thefeed isintroducedsomewhere
nearthemiddleofthecolumntoa
tray knownasthefeedtray.
Thefeedtraydividesthecolumn
intoatop(enriching orrectification)
andabottom(stripping)section.
Thefeedflowsdownthecolumn
whereitiscollectedinthereboiler.
Heat(usuallyassteam)issupplied
tothereboilertogeneratevapour.
Thevapourfromthereboilerisre
introducedintotheunitatthe
bottomofthecolumn.
Theliquidremovedfromthe
reboilerisknownasthebottoms
product orsimply,bottoms.
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Basicoperation
Vapourmovesupthecolumn,exitsthetop,andiscooledina
condenser.Thecondensedliquidisstoredinaholdingvesselknown
astherefluxdrum.Someofthisliquidisrecycledbacktothetopof
thecolumnandthisiscalledthereflux.Thecondensedliquidthatis
removedfromthesystemisknownasthedistillate ortopproduct.
Thus,thereareinternalflows ofvapourandliquidwithinthecolumn
aswellasexternalflowsoffeedsandproductstreams,intoandoutof
thecolumn.

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Crudedistillation
Step1 intherefiningprocessistheseparationofcrudeoilinto
variousfractionsorstraightruncuts bydistillationinatmospheric and
vacuum towers.Themainfractionsor"cuts" obtainedhavespecific
boilingpointrangesandcanbeclassifiedinorderofdecreasing
volatilityintogases,lightdistillates,middledistillates,gasoils,and
residuum.
Atmosphericdistillation
Thedesaltedcrudefeedstockispreheatedusingrecoveredprocess
heat.Thefeedstockthenflowstoadirectfiredcrudechargeheater
thenintotheverticaldistillationcolumnjustabovethebottom,at
pressuresslightlyaboveatmosphericandattemperaturesranging
from340370C(abovethesetemperaturesundesirablethermal
crackingmayoccur).Allbuttheheaviestfractionsflashintovapor.
Asthehotvaporrisesinthetower,itstemperatureisreduced.Heavy
fueloilorasphaltresidueistakenfromthebottom.Atsuccessively
higherpointsonthetower,thevariousmajorproductsincluding
lubricatingoil,heatingoil,kerosene,gasoline,anduncondensedgases
(whichcondenseatlowertemperatures)aredrawnoff.

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Atmosphericdistillation

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Simplecrudedistillation

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Vacuumdistillation

Tofurtherdistilltheresiduum ortoppedcrude fromtheatmospheric

towerwithoutthermalcracking,reducedpressureisrequired.
Theprocesstakesplaceinoneormorevacuumdistillationtowers.
Theprinciplesofvacuumdistillationresemblethoseoffractional
distillationexceptthatlargerdiametercolumnsareusedtomaintain
comparablevaporvelocitiesatthereducedpressures.Theinternal
designsofsomevacuumtowersaredifferentfromatmospheric
towersinthatrandompackinganddemisterpadsareusedinsteadof
trays.
Atypicalfirstphasevacuumtowermayproducegasoils,lubricating
oilbasestocks,andheavyresidualforpropanedeasphalting.
Asecondphasetoweroperatingatlowervacuummaydistillsurplus
residuumfromtheatmospherictower,whichisnotusedforlube
stockprocessing,andsurplusresiduumfromthefirstvacuumtower
notusedfordeasphalting.
Vacuumtowersaretypicallyusedtoseparatecatalyticcracking
feedstockfromsurplusresiduum.
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Vacuumdistillation

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Solventdewaxingunit

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Blending
Blendingisthephysicalmixtureofanumberofdifferentliquid
hydrocarbonstoproduceafinishedproductwithcertaindesired
characteristics.
Productscanbeblendedinlinethroughamanifoldsystem,orbatch
blendedintanksandvessels.
Inlineblendingofgasoline,distillates,jetfuel,andkeroseneis
accomplishedbyinjectingproportionateamountsofeachcomponent
intothemainstreamwhereturbulencepromotesthoroughmixing.
Additivesincludingoctaneenhancers,antioxidants,antiknock
agents,gumandrustinhibitors,detergents,etc.areaddedduring
and/orafterblendingtoprovidespecificpropertiesnotinherentin
hydrocarbons.

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THERMALPROCESSES

Whenahydrocarbonisheatedtoasufficientlyhigh
temperaturethermalcracking occurs.Thisis
sometimesreferredtoaspyrolysis (especiallywhen
coalisthefeedstock).Whensteamisuseditis
calledsteamcracking.Wewillexaminetwo
thermalprocessesusedinrefineries.
Visbreaking
Delayedcoking

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Visbreaking

Visbreaking is a mild form of thermal cracking that lowers the

viscosity of heavy crude-oil residues without affecting the
boiling point range.
Residuum from the atmospheric distillation tower is heated
(425-510C) at atmospheric pressure and mildly cracked in a
heater.
It is then quenched with cool gas oil to control over-cracking,
and flashed in a distillation tower.
Visbreaking is used to reduce the pour point of waxy residues
and reduce the viscosity of residues used for blending with
lighter fuel oils. Middle distillates may also be produced,
depending on product demand.
The thermally cracked residue tar, which accumulates in the
bottom of the fractionation tower, is vacuum-flashed in a
stripper and the distillate recycled.

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Visbreaking

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Visbreaking

Alternatively,vacuumresiduecanbecracked.Theseverityofthe
visbreakingdependsupontemperatureandreactiontime(18min).
Usually<10wt%ofgasolineandlighterproductsareproduced.

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DelayedCoking

Cokingisaseveremethodofthermalcrackingusedtoupgradeheavy
residualsintolighterproductsordistillates.
Cokingproducesstraightrungasoline(Cokernaphtha)andvarious
middledistillatefractionsusedascatalyticcrackingfeedstock.
Theprocesscompletelyreduceshydrogensothattheresidueisa
formofcarboncalled"coke."
Threetypicaltypesofcokeareobtained(spongecoke,honeycomb
coke,andneedlecoke)dependinguponthereactionmechanism,
time,temperature,andthecrudefeedstock.
Indelayedcokingtheheatedcharge(typicallyresiduumfrom
atmosphericdistillationtowers)istransferredtolargecokedrums
whichprovidethelongresidencetimeneededtoallowthecracking
reactionstoproceedtocompletion.

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DelayedCoking

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CATALYTICPROCESSES

FluidCatalyticCracking(FCC)
Hydrotreating
Hydrocracking
CatalyticReforming
Alkylation

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CatalyticCracking
Mainincentiveforcatalyticcrackingistheneedto
increasegasolineproduction.
Feedstocksaretypicallyvacuumgasoil.
Crackingiscatalyzedbysolidacidswhichpromotethe
ruptureofCCbonds.Thecrucialintermediatesare
carbocations (+vechargedHCions)formedbytheaction
oftheacidsitesonthecatalyst.
BesidesCCcleavagemanyotherreactionsoccur:
isomerization
protonationanddeprotonation
alkylation
polymerization
cyclizationandcondensation
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CatalyticCracking
Catalyticcrackingcomprisesacomplexnetworkof
reactions,bothintramolecularandintermolecular.
Theformationofcoke isanessentialfeatureofthe
crackingprocessandthiscokedeactivates thecatalyst.
Catalyticcrackingisoneofthelargestapplicationsof
catalysts:worldwidecrackingcapacityexceeds500
milliont/a.
Catalyticcrackingwasthefirstlargescaleapplicationof
fluidizedbedswhichexplainsthenamefluidcatalytic
cracking (FCC).
Nowadaysentrainedflowreactors areusedinsteadof
fluidizedbedsbutthenameFCCisstillretained.
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FluidCatalyticCracking

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FluidCatalyticCracking

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Hydrocracking

Hydrocracking is a twostage process combining catalytic cracking and

hydrogenation, wherein heavier feedstock is cracked in the presence
of hydrogen to produce more desirable products.

The process employs high pressure, high temperature, a catalyst, and

hydrogen. Hydrocracking is used for feedstock that are difficult to
process by either catalytic cracking or reforming, since these
feedstock are characterized usually by a high polycyclic aromatic
content and/or high concentrations of the two principal catalyst
poisons, sulfur and nitrogen compounds.

The process largely depends on the nature of the feedstock and the
relative rates of the two competing reactions, hydrogenation and
cracking. Heavy aromatic feedstock is converted into lighter products
under a wide range of very high pressures (70140 bar) and fairly high
temperatures (400800C), in the presence of hydrogen and special
catalysts.

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Hydrocracking

Whenthefeedstockhasahighparaffiniccontent,theprimaryfunctionof
hydrogenistopreventtheformationofpolycyclicaromaticcompounds.

Anotherimportantroleofhydrogeninthehydrocrackingprocessisto
reducetarformationandpreventbuildupofcokeonthecatalyst.

Hydrogenationalsoservestoconvertsulfurandnitrogencompounds
presentinthefeedstocktohydrogensulfideandammonia.

Hydrocrackingproducesrelativelylargeamountsofisobutanefor
alkylationfeedstockandalsoperformsisomerizationforpourpoint
controlandsmokepointcontrol,bothofwhichareimportantinhigh
qualityjetfuel.

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Hydrocracking

Preheated feedstock is mixed with recycled hydrogen and sent to the first
stage reactor, where catalysts convert sulfur and nitrogen compounds to
H2S and NH3. Limited hydrocracking also occurs.

After the hydrocarbon leaves the first stage, it is cooled and liquefied and
run through a separator. The hydrogen is recycled to the feedstock.

The liquid is charged to a fractionator.

The fractionator bottoms are again mixed with a hydrogen stream and
charged to the second stage. Since this material has already been
subjected to some hydrogenation, cracking, and reforming in the first
stage, the operations of the second stage are more severe (higher
temperatures and pressures). Again, the second stage product is
separated from the hydrogen and charged to the fractionator.

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CatalyticReforming

Catalyticreformingisanimportantprocessusedtoconvertlow
octanenaphthasintohighoctanegasolineblendingcomponents
calledreformates.

Reformingrepresentsthetotaleffectofnumerousreactions suchas
cracking,polymerization,dehydrogenation,andisomerizationtaking
placesimultaneously.

Dependingonthepropertiesofthenaphthafeedstock(asmeasured
bytheparaffin,olefin,naphthene,andaromaticcontent)and
catalystsused,reformatescanbeproducedwithveryhigh
concentrationsofbenzene,toluene,xylene,(BTX)andother
aromaticsusefulingasolineblendingandpetrochemicalprocessing.

Hydrogen,asignificantbyproduct,isseparatedfromthereformate
forrecyclinganduseinotherprocesses.

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CatalyticReforming

Acatalyticreformercomprisesareactorandproductrecovery
section.

Thereisafeedpreparationsectioncomprisingacombinationof
hydrotreatmentanddistillation.

MostprocessesusePtastheactivecatalyst.SometimesPtis
combinedwithasecondcatalyst(bimetalliccatalyst)suchasrhenium
oranothernoblemetal.

Therearemanydifferentcommercialprocessesincludingplatforming,
powerforming,ultraforming,andThermoforcatalyticreforming.

Some reformers operate at low pressure (313 bar), others at high

pressures (up to 70 bar). Some systems continuously regenerate the
catalyst in other systems. One reactor at a time is taken offstream for
catalyst regeneration, and some facilities regenerate all of the
reactors during turnarounds.

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THANK YOU

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