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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 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.
Evaluate
Sumy
3.LetKC=KC/Sumy
4.DetermineTfromKCandP
5.Ifabs(TTsave)>1oRgotostep1elseyi=yi/Sumy
DewpointcalculationusingKvalues
Thevaporcompositionyi ofamixture isgivenataspecifiedpressureP,the
temperatureTandcompositionxi oftheliquidinequilibriumwiththevaporcanbe
calculatedwiththefollowingprocedure:
ChooseacomponentCtobethereference(base)component.
Assume
temperature
Tbi=BoilingpointofpurecomponentiatpressureP.IfanequationforK
isgivenasfunctionoftemperatureandpressure,thistemperaturecanbeobtainedby
settingK=1.
Iterationsteps:
1.LetTsave=T.DetermineKi(Fromtable7.1).xi=yi/Ki
2.EvaluateSumx=
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
Isobutane
Isopentane
n-hexane
A
-1,166,846
-1,481,583
-1,778,901
B
7.72668
7.58071
6.96783
C
-.92213
-.93159
-.84634
KiC5
(at
Tcal)
KiC5
(at
582.74 oR)
= 0.66814
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) * = 1.4609
FlashdistillationofmulticomponentmixtureusingKvalues
A liquid mixture is partially vaporized and the vapor is allowed to come to
equilibriumwiththeliquid.TheprocessflowdiagramisshowninFig.3.1.Thevapor
andliquidphasesarethenseparated.
Makingacomponentibalance,
FxiF=Vyi+Lxi=Vyi+(FV)xi
Definingf=V/F,eq.(7.3)becomes
xiF=fyi+(1f)xi
Theaboveequationcanbesolvedforyi,
(33)
(34)
(35)
orforxi,
(36)
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.
Let
T1
and
Sumx1
Let
T2
T1
Sumx1
and
Sumx2
Iterationsteps:
1.T=(T1T2T1Sumx2+T2Sumx1)/(Sumx1Sumx2)
2.EvaluateSumx=atT,P
3.LetT1=T2,T2=T,Sumx1=Sumx2,andSumx2=Sumx
4.Ifabs(Sumx1)>.001
thengotostep1
elseT=(T1T2T1Sumx2+T2Sumx1)/(Sumx1Sumx2)
EndIf
and
IfthefeedcompositionxiF,temperatureTandpressurePofseparatoraregiven,
thenthefractionofthefeedvaporizedV/Fandcompositionsx iandyicanbecalculated.
Eqs.(35)and(36)canbearrangedsothatf=V/Fistheonlyunknown.
(37)
(39)
Equation(39),whichisknownastheRachfordRiceequation,hasexcellentconvergent
propertiesandcanbesolvedbyNewtonsmethod.TakethederivativeofthefunctionF
withrespecttoV/F(orf),
(310)
ThefollowingprocedurecanbeusedtosolveforV/F:
ChecktoseeifTisbetweenTbandTd.
f=(TTb)/(TdTb)
Iterationsteps:
1.
Evaluate
2.
Evaluate
3.LetER=F/.f=fER
4.Ifabs(ER)>.001gotostep1
and