LiquidLiquidExtractions

Lastlecturecovered:
UsingasimplespreadsheettoapplytheRachfordRice
Procedure
BubblepointandDewPointtemperatureandpressure
calculations
Anexampleofadewpointtemperaturecalculation

Thislecturewillcover:
TernaryLiquidLiquidextractions.
Ternaryphasediagrams.
Aproceduretodeterminetheproductcompositionsand
flowratesofaliquidliquidextractionseparation.

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 LiquidLiquidTernarySingleEquilibriumStage

WelastcoveredtheFlashCalculationswherealiquidphaseandavaporphasewere
inequilibrium.Forthatsystemweneededequilibriumdata,forexample,froma
Depriestercharttodeterminethedistributionofcomponentsbetweenthetwophases.

Nowwellanalyzethefollowingsystem:

TernaryLiquidLiquidExtraction
Inthiscase:
Wecreatetwoliquidphasesbyintroducingasolvent(C)(MSA)toaliquidmixtureofacarrier(A)
andasolute(B)
Solvent(C)andcarrier(A)haveverylittlesolubilityineachother

LiquidLiquidExtraction
SolventFeed
SolventRichLiquidOut
S,C E,A,B,C
LiquidFeed CarrierRichLiquidout
F,A,B R,A,B,C

Definetheraffinateastheexitingphaserichincarrier.
Definetheextractastheexitingphaserichinsolvent.

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 LiquidLiquidTernarySingleEquilibriumStage

Ifthesolventandcarrierhavesomesolubilityineachother,thentheraffinatewillhave
asmallamountofsolventinitandtheextractwillhaveasmallconcentrationof
carrier:

LiquidLiquidExtraction

SolventFeed
Extractout
S,XC(S),T,P
E,XA(E),XB(E),XC(E),T,P
LiquidFeed
F,XA(F),XB,T,P Raffinateout
R,XA(R),XB(R),XC(R),T,P

Theraffinateistheexitingphaserichincarrier.
Theextractistheexitingphaserichinsolvent.

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 LiquidLiquidTernarySingleEquilibriumStage

Ifthesolventandcarrierhavenosolubilityineachother,thentheraffinatewill
havenosolventinitandtheextractwillhavenocarrierinit:

Allofsolventexits
intheextract

LiquidLiquidExtraction

SolventFeed
Extractout
S,XC(S),T,P
E,XB(E),XC(E),T,P
LiquidFeed
F,XA(F),XB,T,P Raffinateout
R,XA(R),XB(R),T,P

Allofcarrierexits
intheraffinate
Theraffinateistheexitingphaserichincarrier.
Theextractistheexitingphaserichinsolvent.

4
 MassandMoleRatios

Oftentheconcentrationsareasmassormoleratios,ratherthanmassormolefractions.
Thisisgenerallydonetosimplifytheexpressionsusedintheanalysis.

MassratioXB:TheratioofmassofcomponentBtoanothercomponentofthestream.
MoleratioXB:TheratioofmolesofcomponentBtoanothercomponentofthestream.

Notethatthebasis(choiceofcomponent)forthemassormoleratiomustbechosen.

MassRatioExample:
SolventFeed Extractout
S,XC(S),T,P E,XB(E),XC(E),T,P
LiquidFeed
Raffinateout
F,XA(F),XB,T,P R,XA(R),XB(R),T,P

(F )
FB =XB FA RateofBinthefeedistheratioofBtoA,timesfeedrateofA.

EB =X(BE )EC =X(BE )S RateofBintheextractistheratioofBtoC,timesrateofC.

( R) (R)
RB =XB RA =XB FA RateofBintheraffinateistheratioofBtoA,timesrateofA.

SB =X(BS)SC =0 RateofBinthesolventistheratioofBtoC,timesfeedrateofC.

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 MaterialBalances

SoluteMaterialBalance:
SolventFeed Extractout
S,XC(S) E,XB(E),XC(E)
LiquidFeed
Raffinateout
F,XA(F),XB R,XA(R),XB(R)

(F )
FB =XB FA RateofBinthefeedistheratioofBtoA,timesfeedrateofA.

EB =X(BE )EC =X(BE )S RateofBintheextractistheratioofBtoC,timesrateofC.

( R) (R)
RB =XB RA =XB FA RateofBintheraffinateistheratioofBtoA,timesrateofA.

SB =X(BS)SC =0 RateofBinthesolventistheratioofBtoC,timesfeedrateofC.

SoluteMaterialBalance: FB +SB =RB +EB

X(BF )FA +XB

(S) (R)
SC =XB RA +X(BE )EC

X(BF )FA =X(BR)FA +X(BE )S

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 EquilibriumDistribution

Thewaythesolutewilldistributeitselfbetweentheextractandraffinateat
equilibriumisgivenbytheKValue:
NotethattheKvalueis
primedtosignifythatthis
(E) (R)
XB =K 'DB XB isaratioofmassormole
ratios,notaratioofmole
fractions.

SolventFeed
Extractout
S,XC(S) E,XB(E),XC(E)
B
LiquidFeed
Raffinateout
F,XA(F),XB R,XA(R),XB(R)

Notethatconcentrations
ofexitingstreamsfrom
anequilibriumstagearealways
relatedbyequilibrium.

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 TheExtractionFactor

Thedegreeofseparationofthesolutebetweentheexitingstreamsisexpressedasthe
extractionfactor:

ExtractionFactor:Theratioofsoluteflowin
theextracttosoluteflowintheraffinate.

EB =X(BE )EC =X(BE )S EB

(E )
XB S
B = ( R)
( R) (R) RB XB FA
RB =XB RA =XB FA

Combiningthisdefinitionwiththeequilibriumrelationship:

X(BE ) =K 'DB XB
(R)

resultsinanotherexpressionfortheextractionfactor:
Thelargertheequilibrium
K'DB S drivingforcetoseparateB,and
B = thelargertheratioofsolventto
FA feed,thelargertheextraction
factor.
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 ExtractionEfficiency

Wecandeterminetheamountnotextractedstartingwiththematerialbalanceofthesolute:

(F ) ( E) ( R)
XB FA =XB S+XB FA

WesubstituteintheKvalueratio:

X(BF )FA =K 'DB XB

(R) (R)
S +XB FA

Andsimplify:

Thisratiogivestheamount (R)
ofsoluteleftintheraffinate XB FA
=
( F ) K ' S+F
totheamountoriginallyin
thefeedstream,
XB DB A

(R)
XB 1 1 Theamountnotextractedincreases
(F )
= ' =
XB K DB S B +1 withthefeedrate,andsmaller
+1 ratiodistributionbetweenextract
FA andraffinateandlesssolvent.

9
 TernaryPhaseDiagrams

Itisconvenienttoconstructternaryphasediagramsona
C
GibbsTriangle(shownatright).Notethatthevariables
forthesediagramsareonlycompositionandthat
pressureandtemperatureareheldconstant(thatisthat
thesediagramsareslicesthroughafourdimensional
spacewithconstantTandP).

A B

10
 TernaryPhaseDiagrams

Compositionsarereadasfollows:
C
Drawthreelinesfromthecomposition
[94%C,3%B,3%A]
pointparalleltothecompositionlines.
Readthecompositionsoffofthethree
axes.

Note:Onlytwomolefractionsare
needed(usethethirdasacheck).
Compositionscanbemolefractions [33%C,33%B,33%A]
ormassfractions.

[20%C,20%B,60%A]
[30%C,70%B]

[100%A]

A B

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 ConstructionofTernaryPhaseDiagrams

12
 TernaryEutecticPhaseDiagrams

G G
L L

13
 TernaryEutecticPhaseDiagrams

C
TaboveTofthe
ternaryeutectic,but
belowthebinary
eutectics.

T
L

+L

+

+
+
+
+ +L +L 0 XB 1
+L
L
+L +L

++L

+
A B

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 TernaryPhaseDiagrams

+L
L

A B

15
 PartiallySolubleTernarySystems
Ifthetwophasesbothhaveapartialsolubilityoftheothercomponent,thenthe
analysisissomewhatmorecomplicated:

Thedifficultyisthatnowequilibriumdatamustbeobtainedfortheternary
whichrelatesthepartialsolubilities.Equilibriumdatacanbeobtainedgraphically,or
fromtables.Theternaryphasediagramisatypicalwayofrepresentingtheequilibrium
compositionsofthetwophases:

Solute

66%EthGly
7%Furfural
27%Water
Acompositionwhere
EthyleneGlycol Water onlyasingleliquid
exists.

50%EthGly 17%EthGly
50%Furfural 27%Furfural
56%Water
Acompositionwhere
100%Furfural twoliquidphases
coexist.
Solvent Carrier
Furfural
16
 SpecificationofLiquidLiquidEquilibrium
Fortwophaseequilibrium(eithercompleteinsolubility,orpartiallysolubility):
theequilibriumisbetweentwoliquidsphases (=2)
threecomponents(ternary)distributebetweenthetwophases (C=3)

Forthestaticequilibriumcasewecanspecify3variables:

IfwespecifyTandPweareleftwithoneadditionalvariable:

Thusifwespecifytheconcentrationofonecomponentineitherofthephases
thiscompletelydefinesthestateofthesystem.

EthyleneGlycol Water

TieLines:
Showthecompositions
oftheequilibriumphases.

Furfural
17
 PartiallySolubleTernarySystems
Example:Considerafeedof200kgof30%ethyleneglycolinwater.Add300kgofpure
furfuralsolvent.
SolventFeed Extractout
S,XC(S) E,XB(E),XC(E)
LiquidFeed
Raffinateout
F,XA(F),XB R,XA(R),XB(R)

EthyleneGlycol Water

Furfural

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 PartiallySolubleTernarySystems
Example:Considerafeedof200kgof30%ethyleneglycolinwater.Add300kgofsolvent
whichispurefurfural.

Step1:LocatetheSolventandFeedpoints

EthyleneGlycol Water
F
60kgEG
140kgwater

S Furfural
300Kg

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 PartiallySolubleTernarySystems
Step2:LocatethemixingpointM:

X(BF )FA +XB

(E )
S 0.3200kg+0300kg
= =0.12
F +S 500kg

EthyleneGlycol Water

F60kgEG
140kgwater

S
Furfural
300Kg

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 PartiallySolubleTernarySystems
Step3:Usethetielinetogettheraffinateandextractcompositions.

Extract(4%water,14%EG,82%furfural)
Raffinate(87%water,5%EG,8%furfural)

EthyleneGlycol Water

F60kgEG
140kgwater
M
E
R

S
Furfural
300Kg

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 PartiallySolubleTernarySystems
Step4:Determinetheamountofextractandraffinate(canuseleverrule)
( M)
XC XC(E )0.630.82 Extract(4%water,14%EG,82%furfural)
Rf = ( R) ( E)
= =0.257 Raffinate(87%water,5%EG,8%furfural)
XC XC 0.080.82
R =0.257500kg=128.4kg
E =(10.257) 500kg=371.6kg

EthyleneGlycol Water

F60kgEG
140kgwater
M
E
R

S
Furfural
300Kg

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 PartiallySolubleTernarySystems
Step5:Determinethesolventfreeextract:MixturesofEandS.ExtendlinefromSthrough
EtosolventfreepointatH.

SolventfreeextractH(20%water,80%EG)

( R)
XB
(F )
=
H XB

EthyleneGlycol Water

F60kgEG
140kgwater
M
E
R

S
Furfural
300Kg

23
 Summary

Thislecturecovered:
TernaryLiquidLiquidextractions.
Ternaryphasediagrams.
Aproceduretodeterminetheproductcompositionsand
flowratesofaliquidliquidextractionseparation.

Nextlecturewillcover:
Leaching
Crystallization

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