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3 Liquid Vapor Equilibrium
3 Liquid Vapor Equilibrium
INTRODUCTION
Thedrivingforceforproduc0onofreservoiruids(oil,water,gas) androckmatrixwhicharecontainedunderhightemperatures pressures;theyarecompressedrela0vetotheirdensi0esat standardtemperaturesandpressure. Areservoirdrivemechanismisasourceofenergyfordrivingthe uidsoutthroughthewellbore. ItisnotnecessarilytheenergyliCingtheuidstothesurface, althoughinmanycases,thesameenergyiscapableofliCingthe uidstothesurface.
IDEALSOLUTIONS
Behaviourofanidealsolu0on: nochemicalinterac0onoccurs nointermolecularforcesoccurwhenmixingcomponents resultinnohea0ngeectswhenidealsolu0onsaremixed thevolumeofthemixtureequalsthesumofthevolumesthepure componentswouldoccupyatthesamepressureandtemperature
RaoultsLaw
Raoultsequa0onstatesthatthepar0alpressureofacomponentinthe gasisequaltotheproductofthemolefrac0on,xjintheliquid,mul0plied bythevapourpressureofthepurecomponentpvj. p j=xjpvj
DaltonsLaw
LawDaltonslawstatesthatthepar0alpressureofacomponentpjis equaltothemolefrac0onofthatcomponentinthegas,yj0mesthe totalpressureofthesystemp. pj=yjp whereyjisthecomposi0onofthevapourandpisthepressureofthe system 2.3IdealEquilibriumRa0oBycombiningtheabovetwolaws,yjp=xjpvj (3)yxppjjvj=(4)
IdealEquilibriumRaDo
BycombiningtheRaoultsandDaltonsLaws:
y jp = x jp vj yj p vj = = Kj xj p
i.e.thera0oofthecomponentinthevapourandliquidphasesis givenbythera0oofthevapourpressureofthepurecomponentto thetotalpressureofthesystem.Thisra0oistermedtheEquilibrium raDo,Kj
z jn = x jnL + y jn g p vj z jn = x jnL + x j ng p z jn xj = p vj nL + ng p
Ifabasisofonemoleofmixtureisusedi.e. n L + n g = 1.0
zj xj = = 1.0 p vj 1+ n g 1 p zj xj = = 1.0 p 1+ nL 1 p vj
Usingtheseequa0onsinatrialanderrormethodthecomposi0ons ofvapourandliquidstreamsinaashsepara0oncanbe determined.
Theequilibriumra0oKjisdenedasthera0oofthecomposi0onofj inthevapourtoliquidphase,i.e.
yj Kj = xj
ClearlyKjisdenedatapar0cularpressureandtemperature.
OthernamesforEquilibriumra0o,includeKfactors,Kvalues, equilibriumvapourliquiddistribu0onra0os.
Fugacity
Theconceptoffugacityisintroduced,foruseinequilibriumcalcula0ons, toextrapolateorcorrectvapourpressures. Thisisrequiredsinceapurecomponentonlyhasavapourpressureupto itscri0calpoint. Thefugacityisathermodynamicquan0tydenedintermsofthechange infreeenergyinpassingfromonestatetoanother.Foranidealgas,the fugacityisequaltoitspressure,andthefugacityofeachcomponentis equaltoitspar0alpressure.Thera0ooffugacitytopressureistermed thefugacitycoecient,. Foramul0componetsystem,
fi = Pz i
Allsystemsbehaveasidealgasesatverylowpressures,hence>1 whenP>0 Whenfugaci0esarenot1,thenthisgivesanindica0onofnonideality. Fugacityhasbeenimaginedasameasureoftheescapingtendencyof moleculesfromonephasetoanadjacentphase.
Fugacity
Inmul0componentsystems,ifthefugacityofacomponentinadjacent phasesisthesame,thetwophaseswillbeinequilibriumwithnonet transferofmoleculesfromonephasetoanother.Atequilibriumtherefore
fg = fL
Thefugacitycoecient,ofapurecomponentcanbecalculatedfrom thefollowinggeneralequa0on.
p z 1 1 v RT ln = Pdv dp = (z 1) lnz + RT v 0 P
Thera0oofthefugacityatthestateofinteresttothatatareferencestate iscalledtheac0vity i = fi /fio Theac0vityisameasurethereforeofthefugacitycontribu0onor ac0venessofthecomponentinamixture fi = ifio Thera0oofac0vitytoconcentra0oniscalledtheac0vitycoecienti, where i i /x i =
Therefore : fi = ix ifio
NONIDEALSYSTEMS
Idealsolu0onassump0onscannotbeappliedtothesystemsrelevantto mul0componenthydrocarbonuidsinreservoirow,transportand processingcondi0ons. Theidealassump0onsonlyapplytolowpressuresandmoderate temperatures,chemicallyandphysicallysimilarcomponentsand behaviourbelowthecri0calpoint. Dierentmethodshavebeendevelopedfortrea0ngvapourliquid equilibriumfornonidealsystems.ThepreviousKvalueisbasedon bothidealandidealsolu0onslaws. Toextendtheprincipleofequilibriumra0otomul0component hydrocarbonmixturestothepressuresandtemperaturesrelevantto petroleumengineers,methodsoftrea0ngnonidealsystemsneedtobe established. WeassumeinthatKvaluesareavailableeitherfromwhateversource, experimental,NGPSAdatacharts,orfromequa0onsofstateandother predic0vemethods.
EQUATIONSFORCALCULATING EQUILIBRIUMRELATIONS
VapourLiquidCalculaDons
Thecalcula0onsfordeterminingtheamountofliquidandvapour presentinamixturewhenthepressureandtemperatureisknownare obviouslyimportant,forexample,inop0misingtheperformanceofa separatorprocess. Thecalcula0onsfordeterminingthe amountofliquidandvapourpresentina mixturewhenthepressureand temperatureisknownareobviously important,forexample,inop0misingthe performanceofaseparatorprocess. Theequilibriumequa0onswhichare usedforaprocessseparatorarethe sameasthosewithinagridblockor elementofareservoirsimulator. Figurerepresentssuchasepara0on.
z j = x jL + x jK jV zj
F = L + V = 1.0 z jF = x jL + y jV z j = x jL + y jV yj Kj = xj
m m j=1 j=1
z j = x j (L + K jV) xj =
m
(L + K jV)
m
y j = x jK j
m
j=1 m
xj = yj =
m
zj
j=1
(L + K jV)
zj
= 1.0 = 1.0
x j = y j = z j = 1.0
j=1
j=1
j=1
(V + L /K j )
j=1 m
zj
(L /V + K j )
zj
=V
j=1 L VK + 1 j
=V
ThemethodofcalculaDon: (1)SelectKjforeachcomponentatthetemperatureandpressureofthe system (2)Assumeavapourliquidspliti.e.V&LsuchthatV+L=1.0 (3)CalculateeitherV,L,xjoryjfromequa0ons (4)Either: (i)checkV&LcalculatedagainstassumedVorL (ii)determineifxjoryj=1.0 (5)Repeatthecalcula0onun0lassumedvalueiscalculatedvalueorun0l xjandyj=1.0.
z j = yj
z j = x jK j
j=1
xj =
zj
j=1 K j
= 1.0
Kj
Themixtureatthebubblepointisthereforeinequilibriumwitha quan0tyofliquidhavingacomposi0ondenedbytheaboveequa0on.
j=1
z y j = jK j = 1.0
j=1
SEPARATORPROBLEMS Inaseparatorastreamofuidisbroughttoequilibriumatseparator temperatureandpressure.Vapourandliquidareseparatedwithinthe unitandcon0nueasseparatestreams. Severalseparatorscanbeoperatedinserieseachreceivingtheliquid phasefromtheseparatoropera0ngatthenexthigherpressure. Eachcondi0onofpressureandtemperatureatwhichvapourandliquid areseparatediscalledastagesepara0on.Henceaprocessusingone separatorandastocktankisatwostageprocessathreestageprocess hastwoseparatorsandonestocktank.(seenextFigure). Separatorcalcula0onsareperformedtodeterminethecomposi0onof products,theoilforma0onvolumefactorandthevolumeofgasreleased perbarrelofoilandtodeterminetheop0mumseparatorcondi0onsfor thepar0cularcondi0onsofuid. Usingequilibriumcalcula0onsalreadyderivedwecancalculatethe separa0onachievedateachstage,thecomposi0onofthephases separated,thegas/oilra0o,andtheoilforma0onvolumefactor.
StageSeparaDon
sum of gas volumes (scf) Total Gas /Oil Ratio = = RT volume of stock tank oil (bbl)
(a) Calcula0onforStockTankOil,STO
nisthemolesofliquidinstocktankfornmolesintorstseparator:
nST = n1 L i
i=1
Ifn1=1.0
nST = L i
i=1 m
(b)Calcula0onofTotalGas
n gT = n gi = n1 Vi L j
i=1 i=1 j=1 m
i1
If n1 = 1 n gT = Vi L j
i=1 j=1
i1
OilFormaDonVolume FactorVolumeofstocktankoilpermoleoffeed
(VST ) m =
n ST MST ST
Ib.mol
OpDmumPressureofSeparatorSystem Theopera0ngcondi0onsofpressureandtemperatureofaseparator inuencetheamountofgasandstocktankoilproduced.Changeinthese valueswillchangetheGORandtheBo. Inquo0ngthesevaluesthereforeitisimportanttokeepnoteofthe associatedsepara0oncondi0onsofpressureandtemperature.Anumber ofunitsinseriesalsoinuencetheseparameters. Itistheroleoftheprocessdesignerstoop0misetheopera0ng condi0onsofsuchlimitsandthenumberofunitsrequired.Itisthe equilibriumcharacteris0csoftheindividualcomponentsasafunc0onof temperature,pressureandcomposi0onwhichinuencethesetotal separa0oncharacteris0csforthemixturesateachsepara0onstage.
OpDmumPressureofSeparatorSystem
Figurebelowillustratestheinuenceofachangeofpressureforatwostage separa0onprocessonGOR,Boandthedensityofstocktankoil.Equilibriumash calcula0ons,whichtheabovearecalled,areusedinmanyotherapplica0ons.In reservoirengineering,ashcalcula0onsareatthecoreofcomposi0onalsimula0on.
ExampleofSeparatorProblem ExamplefromMcCain(seehandout) IntegraDonoftheBlackOilandComposiDonalApproach Theexampleaboveillustratesthecombina0onofthecomposi0onal basedpredic0onofphasevolumesandassociatedproper0esandthat basedaroundtheblackoilmodel,centredaroundparametersofoil forma0onvolumefactorandgasoilra0o. Bysuchacombina0on,theweaknessesofthesimpletwocomponent blackoilmodelwhichisattheheartofdescribingoileldparameters, canbeovercomebyusingcomposi0onalderivedvaluesratherthan usingperhapsinappropriateempiricalcorrela0onsandcharts. InthenextchapterwewillexaminetheproceduresfordeterminingK.