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Phasebehaviorofmixtures

Contents

1EOSofamixtureContents 2Procedureforequilibriumcalculationsofamixture 3Nomenclature 4References 5NoteworthypapersinOnePetro

2Procedureforequilibriumcalculationsofamixture

3Nomenclature2Procedureforequilibriumcalculationsofamixture 4References 5NoteworthypapersinOnePetro 6Externallinks

4References2Procedureforequilibriumcalculationsofamixture 3Nomenclature 5NoteworthypapersinOnePetro 6Externallinks 7Seealso

5NoteworthypapersinOnePetro

6Externallinks2Procedureforequilibriumcalculationsofamixture 3Nomenclature 4References 5NoteworthypapersinOnePetro 7Seealso

7Seealso2Procedureforequilibriumcalculationsofamixture 3Nomenclature 4References 5NoteworthypapersinOnePetro 6Externallinks

EOSofamixture

ThethermodynamicpropertiesofamixturecanbecalculatedwiththesameEOSforapurefluid,withsomemodifications.Theprimarydifferenceisthatthemixturemolar volumeforaphaseiscalculatedwithEOSconstantsandtemperature­dependentfunctionsofthephasemolarcomposition,eitherx i ory i .Forexample,theSoaveRedlich­ KwongEOSwrittenforamixtureis

.Forexample,theSoaveRedlich­ KwongEOSwrittenforamixtureis (/File%3AVol1_page_0364_eq_001.png) wheresubscript m

wheresubscriptmindicatesamixtureproperty.Themixturepropertiesarecalculatedwithmixingrulesthatareoftenlinearorquadraticfunctionsofthephasemolefractions.

Forexample,fortheliquidphase,themixingrulefortheproduct,,isoftenthequadraticequation,

aα ,isoftenthequadraticequation, (/File%3AVol1_page_0364_eq_002.png) where
(/File%3AVol1_page_0364_eq_002.png) where (/File%3AVol1_page_0364_inline_001.png)

where (/File%3AVol1_page_0364_inline_001.png).Theparametersk ij arecalledbinaryinteractionparameters.Binaryinteractionparametersare

constantsthataredeterminedbyfittingthecubicEOStoexperimentalPVTdata.ThemixingruleforistheoreticallyjustifiedfromvirialEOS,whicharediscussedinseveral sources. [1][3][4][5][6][2] Forb m ,thelinearrelationship, (/File%3AVol1_page_0364_inline_002.png),isoftenused.

(/File%3AVol1_page_0364_inline_002.png) ,isoftenused.

Forequilibriumcalculations,thefugacityofeverycomponentineachphasemustbecalculated.Eq.1isusedforthispurpose.Forexample,substitutionoftheSoaveRedlich­

KwongEOSintoEq.1givesthefugacityofacomponentintheliquidphase,whichiswrittenas

(/File%3AVol1_page_0364_eq_003.png) (2) where

(2)

where

(/File%3AVol1_page_0364_eq_003.png) (2) where (/File%3AVol1_page_0364_inline_003.png)

(/File%3AVol1_page_0364_inline_003.png).Asimilarequationiswrittenforthevaporphase,wherex i isreplacedbyy i ,andsuperscriptLisreplacedbyV.

Procedureforequilibriumcalculationsofamixture

Theprocedureforequilibriumcalculationsofapotentialtwo­phasemixtureismorecomplexthanthatofapurefluid.Foranequilibriumflashcalculation,thepressureand

temperatureandoverallmolefractionsarespecified(i.e.,pressureandtemperaturearenowindependent,asspecifiedbytheGibbsphaserule).Thegeneralprocedureforaflash

calculationisdiscussednext.

1.MakeaninitialguessoftheK­values,where

(/File%3AVol1_page_0365_inline_001.png) .Whentheguessofthe K ­valuesisneartheequilibriumsolution,the (/File%3AVol1_page_0365_inline_001.png).WhentheguessoftheK­valuesisneartheequilibriumsolution,the

procedurewillconvergerapidly.Iftheguessisnotgood,theproceduremightnotconvergeatall.MostEOSprogramsusesomeempiricalcorrelationtoestimatethe

phasemolefractionsbasedonK­values.TheWilsonequation [7] isoftenused,where

[ 7 ] isoftenused,where (/File%3AVol1_page_0365_inline_002.png) . 2.Calculate x i

2.Calculatex i andy i withtheRachford­Riceprocedure. [8] OncetheK­valuesforeachcomponentarespecified,theRachford­Riceprocedureisusedtoestimatethephase molefractions.Amaterialbalanceoneachcomponentgivesz i =Lx i +(1­L)y i ,whereListhemolefractionliquid(seeEq.2).Substitutionofy i =K i x i intothematerial

).Substitutionof y i = K i x i intothematerial balanceequationgives,uponrearrangement,
).Substitutionof y i = K i x i intothematerial balanceequationgives,uponrearrangement,

gives

gives (/File%3AVol1_page_0365_inline_005.png)

(/File%3AVol1_page_0365_inline_006.png).ThisisanonlinearequationthatcanbestbesolvedbyasimpleNewton­Raphson

iteration,whereforeachiterationthenewvalueoftheliquidmolefractionisfoundfrom

(/File%3AVol1_page_0365_inline_007.png) .Forthe

firstiteration,chooseL=0.5anditerateuntil

.Forthe firstiteration,choose L =0.5anditerateuntil (/File%3AVol1_page_0365_inline_008.png) .
(/File%3AVol1_page_0335_eq_001.png) (2) 3.CalculatethecubicEOSparameters(e.g., a m and b m

(2)

3.CalculatethecubicEOSparameters(e.g.,a m andb m ).ThisstepisverystraightforwardanddependsontheselectedEOSanditsassociatedmixingrules.Thecritical temperatures,pressures,andacentricfactorsforeachcomponentareneededtocalculatetheEOSparameters. 4.SolvethecubicEOSforthephasemolarvolumesV mL andV mV .ThissteprequiressolutionofthecubicEOSforthecompressibilityfactor,Z,ofthevaporandliquid(or alternativelyforV V andV L ).Becausethecompositionsofthevaporandliquidaredifferent,twoseparatesolutionsfortherootsofthecubicEOSarerequired.Acubic equation­solveroriterationmethodshouldbeusedtoobtaintherootsoftheEOS.

TheprocedureforthisstepismorecomplexthanforapurefluidbecausesixrootsofthecubicEOSarecalculated(i.e.,threerootsfortheliquidandthreefor thevapor).Themiddlerootforthevaporandliquidarediscardedbecausethatsolutionleadstounstablephases,similartopurefluids.Oneoftheremaining twoliquidrootsispairedwithoneoftheothervaporrootstocalculatecomponentfugacitiesandequilibrium.Ifthewrongrootpairingisselected,thesolution couldbefalseinthatanunstableormetastablesolutioncouldbeobtained.ThecorrectequilibriumsolutionistheonethatminimizesthetotalGibbsenergy comparedwiththeotherpossibleroot­pairings.Firoozabadi [1] andWhitsonandBrule [2] provideagooddescriptionofhowtoselecttheliquidandvaporrootsso thatthetotalGibbsenergyofthetwo­phasemixtureisminimized.Formostcases,thecorrectrootfortheliquidistheonethatgivesthesmallestmolarvolume, andthecorrectrootforthevaporistheonethatgivesthelargestmolarvolume. Firoozabadi [1] andWhitsonandBrule [2] alsoexamineusingstabilityanalysestodeterminewhetheramixturewillformthreephasesinsteadofjustoneortwo phases.PhasediagramsforEORprocesses(/Phase_diagrams_for_EOR_processes)discussestheformationofthreeequilibriumphasesinCO 2 /crudeoil systems.

(/File%3AVol1_page_0366_inline_001.png)and

example).

6.Checktoseeifequilibriumhasbeenreached.Agoodcriterionis

6.Checktoseeifequilibriumhasbeenreached.Agoodcriterionis (/File%3AVol1_page_0366_inline_003.png)

(/File%3AVol1_page_0366_inline_003.png)forallcomponents.Ifthecriteriaare

satisfied,equilibriumhasbeenobtained.Thecorrectequilibriumsolutionisfoundwhen

Becausethesolutionisneverfoundexactly,weacceptthesolutionif

Becausethesolutionisneverfoundexactly,weacceptthesolutionif (/File%3AVol1_page_0366_inline_004.png) foreachcomponent.
Becausethesolutionisneverfoundexactly,weacceptthesolutionif (/File%3AVol1_page_0366_inline_004.png) foreachcomponent.

(/File%3AVol1_page_0366_inline_003.png)foreachcomponent.Thetoleranceof

10 ­5 canbedecreasedifbetteraccuracyisrequired.

7.Ifthecriteriahavenotbeensatisfied,theK­valuesshouldbeupdatedandstepstwothroughsixrepeated.Thisstepisalsoveryimportant;itaffectsboththerateof

(/File%3AVol1_page_0366_inline_005.png)and
(/File%3AVol1_page_0366_inline_005.png)and
(/File%3AVol1_page_0366_inline_005.png)and

canusethisratiotoestimatenewK­valuesfromtheoldones.Thatis,

determined,stepstwothroughsixarerepeateduntilconvergenceinstepsixisachieved.Convergencefromsuccessivesubstitutionscanbeslownearthecriticalregion. Othermethodsmayberequiredwhenconvergenceisslow. [1]

Nomenclature

[ 1 ] Nomenclature (/File%3AVol1_page_0367_inline_001.png) =

(/File%3AVol1_page_0367_inline_001.png)= fugacityofacomponentinamixture,mole 2 ­pressure/mole 2 ,Pa

k

=binaryinteractionparameter,dimensionless

K i

= K­valueofithcomponent,y i /x i ,dimensionless

L

=liquidmolefraction,molesliquid/totalmoles,dimensionless

p

=pressure,force/area,Pa

R

= gasconstant,pressure­volume/temperature/mole,Pa­m 3 /(Kelvin­mole)

t

=time,seconds

T

=temperature,Kelvin

V

= vapormolefraction,molesvapor/totalmoles,dimensionlessormolarvolumeoffluid,volume/mole,m 3 /mole

x

=x­coordinate,length,m

x i

=molefractionofithcomponentinliquid,molesithcomponentinliquid/totalmolesliquid,dimensionless

i thcomponentinliquid/totalmolesliquid,dimensionless (/File%3AVol1_page_0368_inline_001.png) =

(/File%3AVol1_page_0368_inline_001.png) = fugacitycoefficientforacomponentinamixture,mole 2 ­pressure/mole 2 ­pressure,dimensionless

References

1.↑ 1.0 1.1 1.2 1.3 1.4 Firoozabadi,A.1999.ThermodynamicsofHydrocarbonReservoirs.355.NewYorkCity:McGraw­HillBookCo.Inc 2.↑ 2.0 2.1 2.2 2.3 Whitson,C.H.,andBrule,M.R.2000.PhaseBehavior,Vol.20.Richardson,Texas:MonographSeries,SPE.

3.↑Prausnitz,J.M.,Lichtenthaler,R.N.,anddeAzevedo,E.G.1999.MolecularThermodynamicsofFluid­PhaseEquilibria,thirdedition.NewJersey:PrenticeHall.

4.↑Sandler,S.I.2000.ChemicalandEngineeringThermodynamics,thirdedition.NewYorkCity:JohnWiley&Sons.

5.↑Smith,J.M.,VanNess,H.C.,andAbbott,M.M.2001.ChemicalEngineeringThermodynamics,sixthedition.787.NewYorkCity:McGraw­HillBookCo.Inc.

6.↑Walas,S.M.1985.PhaseEquilibriainChemicalEngineering.671.Boston,Massachusetts:ButterworthPublishings.

7.↑Wilson,G.M.1969.AModifiedRedlich­KwongEquation­of­State,ApplicationtoGeneralPhysicalDataCalculations.Paper15cpresentedattheAIChENatl.Meeting,

Cleveland,Ohio,4–7May.

8.↑RachfordJr.,H.H.andRice,J.D.1952.ProcedureforUseofElectronicDigitalComputersinCalculatingFlashVaporizationHydrocarbonEquilibrium.JPetTechnol4

NoteworthypapersinOnePetro

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Externallinks

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