VaporLiquidEquilibriumCalculationsUsingKValues

ThevaporliquidequilibriumconstantordistributioncoefficientforcomponentA
isdefinedas
y
KA=xA
A (31)
where yA=molefractionofAinthevaporphaseandx A=molefractionofAin
theliquidphase

For light hydrocarbon systems (methane to decane), the K values have been
determinedsemiempericallyandcanbeevaluatedfromtheequationsgiveninTable
3.13.Ingeneral,Kisafunctionoftemperature,pressure,andcomposition.

Table3.1.EquilibriumKvaluesforlighthydrocarbonsystems
=============================================================
(1)lnK=A/T2+BCln(P)+D/P2
(2)lnK=A/T2+BCln(P)+D/P
(3)lnK=A/T+BCln(P),wherePisinpsia,TisinoR
compound A B C D Form
=============================================================
Methane 292860 8.2445 .8951 59.8465 (1)
Ethylene 600076.9 7.90595 .84677 42.94594 (1)
Ethane 687248.2 7.90694 .866 49.02654 (1)
Propylene 923484.7 7.71725 .87871 47.67624 (1)
Propane 970688.6 7.15059 .76984 6.90224 (2)
iButane 1166846 7.72668 .92213 0 (1)
nButane 1280557 7.94986 .96455 0 (1)
iPentane 1481583 7.58071 .93159 0 (1)
nPentane 1524891 7.33129 .89143 0 (1)
nHexane 1778901 6.96783 .84634 0 (1)
nHeptane 2013803 6.52914 .79543 0 (1)
nOctane 7646.816 12.48457 .73152 (3)
nNonane 2551040 5.69313 .67818 0 (1)
nDecane 9760.457 13.80354 .7147 (3)
=============================================================

The relative volatility i for each individual component in a multicomponent

mixtureisdefinedwithrespecttoareferencecomponentC.
y /x
i = i i = Ki
yC/xC KC (32)

Thevaluesof i willbelessdependentontemperaturethanthevaluesofK i
sincetheKiallincreasewithtemperatureinasimilarmanner.

Boiling(Bubble)pointcalculationusingKvalues
 Theliquidcompositionxi ofamixtureisgivenataspecifiedpressureP,the
temperatureTandcompositionyi ofthevaporinequilibriumwiththeliquidcanbe
calculatedwiththefollowingprocedure:
ChooseacomponentCtobethereference(base)component.
AssumeatemperatureT(T= xi Tbi )
Tbi=BoilingpointofpurecomponentiatpressureP.IfanequationforK
isgivenasfunctionoftemperatureandpressure,thistemperaturecanbeobtainedby
settingK=1.

Iterationsteps:
1.LetTsave=T.DetermineKi(Fromtable7.1).yi=Kixi
2.EvaluateSumy= yi
3.LetKC=KC/Sumy
4.DetermineTfromKCandP
5.Ifabs(TTsave)>1oRgotostep1elseyi=yi/Sumy

DewpointcalculationusingKvalues

Thevaporcompositionyi ofamixture isgivenataspecifiedpressureP,the

temperatureTandcompositionxi oftheliquidinequilibriumwiththevaporcanbe
calculatedwiththefollowingprocedure:
ChooseacomponentCtobethereference(base)component.
AssumeatemperatureT(T= yi Tbi )
Tbi=BoilingpointofpurecomponentiatpressureP.IfanequationforK
isgivenasfunctionoftemperatureandpressure,thistemperaturecanbeobtainedby
settingK=1.

Iterationsteps:
1.LetTsave=T.DetermineKi(Fromtable7.1).xi=yi/Ki
2.EvaluateSumx= xi
3.LetKC=KCSumx
4.DetermineTfromKCandP
5.Ifabs(TTsave)>1oRgotostep1elsexi=xi/Sumy

Example 3.1
A mixture contains 35 mole % isobutane, 35 mole % isopentane, and 30 mole
% n-hexane is at 30 psia. The K values for these co mpoundcanbeobtainedfrom
ln K = A/T2 + B + C ln P where T is in oR and P is in psia
Compound A B C
Isobutane -1,166,846 7.72668 -.92213
Isopentane -1,481,583 7.58071 -.93159
n-hexane -1,778,901 6.96783 -.84634

The boiling point of (pure) n-hexane at 30 psia is 659.6 oR

This mixture is flashed at 582.74 oR where 60 % of the feed is evaporated and at this
conditions KiC4 = 3.1718, KiC5 = 1.051, KnC6 = 0.3169

Let isopentane be the reference compound and T = 582.74 oR be a guessed

value for the bubble point calculation (for the above mixture), the next calculated
temperature Tcal can be determined from
yi = 0.66814
KiC5 (at Tcal) = KiC5 (at 582.74oR) /

Let isopentane be the reference compound and T = 582.74 oR be a guessed

value for the dew point calculation (for the above mixture), the next calculated
temperature Tcal can be determined from

KiC5 (at Tcal) = KiC5 (at 582.74oR) * xi = 1.4609

FlashdistillationofmulticomponentmixtureusingKvalues

A liquid mixture is partially vaporized and the vapor is allowed to come to

equilibriumwiththeliquid.TheprocessflowdiagramisshowninFig.3.1.Thevapor
andliquidphasesarethenseparated.

V,yi

F,xiF
Q

L,xi

Fig. 3.1 Flash distillation.

Makingacomponentibalance,
FxiF=Vyi+Lxi=Vyi+(FV)xi (33)
Definingf=V/F,eq.(7.3)becomes
xiF=fyi+(1f)xi (34)
Theaboveequationcanbesolvedforyi,
yi =Ki xi =f1 xi +xiF (35)
f f
orforxi,
xiF
xi = (36)
f Ki 1 +1

ThefeedcompositionxiF andthefractionfofthefeedvaporizedaregivenata
specified separator pressure P, the temperature T and compositions x i and yi can be
calculatedwiththefollowingprocedure:
AssumeatemperatureT=fTd+(1f)Tb
Tb,Td=BubblepointanddewpointofmixtureatpressureP.
xiF

LetT1=TandSumx1= f Ki (T1 ,P)1 +1
xiF
f K (T ,P)1 +1
LetT2=T1 Sumx1andSumx2= i 2
Iterationsteps:
1.T=(T1T2T1 Sumx2+T2 Sumx1)/(Sumx1Sumx2)
2.EvaluateSumx= xi atT,P
3.LetT1=T2,T2=T,Sumx1=Sumx2,andSumx2=Sumx
 4.Ifabs(Sumx1)>.001
thengotostep1
elseT=(T1T2T1 Sumx2+T2 Sumx1)/(Sumx1Sumx2)
EndIf

xiF
xi =
f Ki 1 +1 andyi =Ki xi

IfthefeedcompositionxiF,temperatureTandpressurePofseparatoraregiven,
thenthefractionofthefeedvaporizedV/Fandcompositionsx iandyicanbecalculated.
Eqs.(35)and(36)canbearrangedsothatf=V/Fistheonlyunknown.
yi xi=0 (37)
Ki xiF xiF
f Ki1 +1 f Ki1 +1 =0 (38)
Ki 1 xiF
=0
F= f Ki 1 +1 (39)

Equation(39),whichisknownastheRachfordRiceequation,hasexcellentconvergent
propertiesandcanbesolvedbyNewtonsmethod.TakethederivativeofthefunctionF
withrespecttoV/F(orf),

2
dF = Ki 1 xiF
df f Ki 1 +1 2 (310)

ThefollowingprocedurecanbeusedtosolveforV/F:

ChecktoseeifTisbetweenTbandTd.
f=(TTb)/(TdTb)

Iterationsteps:
Ki 1 xiF

1.EvaluateF= f Ki 1 +1
2
dF = Ki 1 xiF
2.Evaluate df f Ki 1 +1 2
dF
3.LetER=F/ df .f=fER
4.Ifabs(ER)>.001gotostep1

xiF
xi =
f Ki 1 +1 andyi =Ki xi