LiquidLiquidExtractions

Liquidliquidextraction(alsoknownassolvent
extraction)involvestheseparationofthe
constituents(solutes)ofaliquidsolutionbycontact
withanotherinsolubleliquid.
Solutesareseparatedbasedontheirdifferent
solubilitiesindifferentliquids.
Separationisachievedwhenthesubstances
constitutingtheoriginalsolutionistransferredfrom
theoriginalsolutiontotheotherliquidsolution.
1

TheFigureshowedafeedliquid(the"first"liquid)containingthedesirablecompoundtobeseparated
togetherwithothercompounds.Thenanimmiscibleextractionliquid(the"second"liquid)isaddedand
mixedwiththefeedliquidthroughagitation.Thespeciesredistributethemselvesbetweenthe2liquid
phases.Agitationofthe2phasesiscontinueduntilequilibrium,andthenagitationisstoppedand
theliquidsareallowedtosettleuntilbothphasesareclear.The2phasescanthenbeseparated.that
is

Thesimplestliquidliquidextractioninvolvesonlyaternary(i.e.3components)system.The
solutionwhichistobeextractediscalledthefeed,andtheliquidwithwhichthefeedis
contactedisthesolvent.ThefeedcanbeconsideredascomprisingthesoluteAandthe
"carrier"liquidC.SolventSisapureliquid.Duringcontact,masstransferofAfromthe
feedtothesolventSoccurs,withlittletransferofCtoS.

OperasiPerpindahanMassaEkstraksiDalamIndustri
PengolahanMinyak

Thepurposeofsolventextractionistopreventcorrosion,protectcatalystin
subsequentprocesses,andimprovefinishedproductsbyremoving
unsaturated,aromatichydrocarbonsfromlubricantandgreasestocks.

Thesolventextractionprocessseparatesaromatics,naphthenes,and
impuritiesfromtheproductstreambydissolvingorprecipitation.The
feedstockisfirstdriedandthentreatedusingacontinuouscountercurrent
solventtreatmentoperation.

Application of Liquid-Liquid Extraction

Extraction processes are well suited to the petroleum industry because of the need to separate
heat-sensitive liquid feeds according to chemical type (e.g. aliphatic, aromatic, naphthenic) rather
than by molecular weight or vapour pressure.
Other major applications exist in the biochemical or pharmaceutical industry, where emphasis is on
the separation of antibiotics and protein recovery. In the inorganic chemical industry, they are used
to recover high-boiling components such as phosphoric acid, boric acid, and sodium hydroxide from
aqueous solutions.
Some examples are given below:
ExtractionofnitrobenzeneafterreactionofHNO3withtolueneinH2SO4
Extractionofmethylacrylatefromorganicsolutionwithperchlorethylene
Extractionofbenzylalcoholfromasaltsolutionwithtoluene
RemovingofH2SfromLPGwithMDEA
Extractionofcaprolactamfromammoniumsulfatesolutionwithbenzene
Removingresidualalkalisfromdichlorohydrazobenzenewithwater
ExtractionofmethanolfromLPGwithwater
Extractionofchloroaceticacidfrommethylchloroacetatewithwater
Extractionofacrylicacidfromwastewaterwithbutanol

Solventextraction

Inonetypeofprocess,thefeedstockiswashedwithaliquidinwhichthesubstancestobe
removedaremoresolublethaninthedesiredresultantproduct.Inanotherprocess,selected
solventsareaddedtocauseimpuritiestoprecipitateoutoftheproduct.Intheadsorption
process,highlyporoussolidmaterialscollectliquidmoleculesontheirsurfaces.

Thesolventisseparatedfromtheproductstreambyheating,evaporation,orfractionation,
andresidualtraceamountsaresubsequentlyremovedfromtheraffinatebysteamstrippingor
vacuumflashing.

Electricprecipitationmaybeusedforseparationofinorganiccompounds.
Thesolventisregeneratedforreusedintheprocess.
Themostwidelyusedextractionsolventsarephenol,furfural,andcresylicacid.
Othersolventslessfrequentlyusedareliquidsulfurdioxide,nitrobenzene,and2,2'dichloroethylether.
Theselectionofspecificprocessesandchemicalagentsdependsonthenatureofthefeedstockbeing
treated,thecontaminantspresent,andthefinishedproductrequirements.

LiquidLiquidTernarySingleEquilibriumStage
WelastcoveredtheFlashCalculationswherealiquidphaseandavaporphasewere
inequilibrium.Forthatsystemweneededequilibriumdata,forexample,froma
Depriestercharttodeterminethedistributionofcomponentsbetweenthetwophases.
Nowwellanalyzethefollowingsystem:
TernaryLiquidLiquidExtraction
Inthiscase:
Wecreatetwoliquidphasesbyintroducingasolvent(C)(MSA)toaliquidmixtureofacarrier(A)
andasolute(B)
Solvent(C)andcarrier(A)haveverylittlesolubilityineachother
LiquidLiquidExtraction
SolventFeed

S,C

E,A,B,C

LiquidFeed

F,A,B

SolventRichLiquidOut
CarrierRichLiquidout

R,A,B,C
Definetheraffinateastheexitingphaserichincarrier.
Definetheextractastheexitingphaserichinsolvent.

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.

LiquidLiquidTernarySingleEquilibriumStage
Ifthesolventandcarrierhavenosolubilityineachother,thentheraffinatewill
havenosolventinitandtheextractwillhavenocarrierinit:
Allofsolventexits
intheextract
LiquidLiquidExtraction
SolventFeed

S,XC(S),T,P

Extractout

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.

10

MassandMoleRatios
Oftentheconcentrationsareasmassormoleratios,ratherthanmassormolefractions.
Thisisgenerallydonetosimplifytheexpressionsusedintheanalysis.
MassratioXB:TheratioofmassofcomponentBtoanothercomponentofthestream.
MoleratioXB:TheratioofmolesofcomponentBtoanothercomponentofthestream.
Notethatthebasis(choiceofcomponent)forthemassormoleratiomustbechosen.

MassRatioExample:
SolventFeed

S,XC(S),T,P
LiquidFeed

F,XA(F),XB,T,P

FB XB F FA
EB X BE EC XBE S

RB XB R RA XB R FA
S B X BS SC 0

Extractout

E,XB(E),XC(E),T,P
Raffinateout

R,XA(R),XB(R),T,P
RateofBinthefeedistheratioofBtoA,timesfeedrateofA.
RateofBintheextractistheratioofBtoC,timesrateofC.
RateofBintheraffinateistheratioofBtoA,timesrateofA.
RateofBinthesolventistheratioofBtoC,timesfeedrateofC.

11

MaterialBalances
SoluteMaterialBalance:
SolventFeed

Extractout

S,XC(S)

E,XB(E),XC(E)

LiquidFeed

Raffinateout

F,XA(F),XB

R,XA(R),XB(R)

FB XB F FA

RateofBinthefeedistheratioofBtoA,timesfeedrateofA.

EB X BE EC XBE S
R
R
RB XB RA XB FA

S B X BS SC 0

SoluteMaterialBalance:

RateofBintheextractistheratioofBtoC,timesrateofC.
RateofBintheraffinateistheratioofBtoA,timesrateofA.
RateofBinthesolventistheratioofBtoC,timesfeedrateofC.

FB SB RB EB
S

X B FA XB SC XB RA X B EC
X BF FA XBR FA X BE S

12

EquilibriumDistribution
Thewaythesolutewilldistributeitselfbetweentheextractandraffinateat
equilibriumisgivenbytheKValue:

X BE K'DB XB R
SolventFeed

S,XC(S)
LiquidFeed

F,XA(F),XB

NotethattheKvalueis
primedtosignifythatthis
isaratioofmassormole
ratios,notaratioofmole
fractions.

Extractout
B

E,XB(E),XC(E)
Raffinateout

R,XA(R),XB(R)
Notethatconcentrations
ofexitingstreamsfrom
anequilibriumstagearealways
relatedbyequilibrium.

13

TheExtractionFactor
Thedegreeofseparationofthesolutebetweentheexitingstreamsisexpressedasthe
extractionfactor:
ExtractionFactor:Theratioofsoluteflowin
theextracttosoluteflowintheraffinate.

EB X BE EC XBE S
RB XB R RA XB R FA

XB E S
EB
B
R
RB X B FA

Combiningthisdefinitionwiththeequilibriumrelationship:

X BE K'DB XB R
resultsinanotherexpressionfortheextractionfactor:

K'DB S
FA

Thelargertheequilibrium
drivingforcetoseparateB,and
thelargertheratioofsolventto
feed,thelargertheextraction
factor.

14

ExtractionEfficiency
Wecandeterminetheamountnotextractedstartingwiththematerialbalanceofthesolute:

X BF FA XBE S X BR FA
WesubstituteintheKvalueratio:

X BF FA K'DB XB R S XB R FA
Andsimplify:
Thisratiogivestheamount
ofsoluteleftintheraffinate
totheamountoriginallyin
thefeedstream,

XB R

XB R

FA
F K' S F
XB
DB
A

1
1

F K' S
B 1
XB
DB
1
FA

Theamountnotextractedincreases
withthefeedrate,andsmaller
ratiodistributionbetweenextract
andraffinateandlesssolvent.

15

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

16

TernaryPhaseDiagrams
Compositionsarereadasfollows:
Drawthreelinesfromthecomposition
pointparalleltothecompositionlines.
Readthecompositionsoffofthethree
axes.
Note:Onlytwomolefractionsare
needed(usethethirdasacheck).
Compositionscanbemolefractions
ormassfractions.

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

C
[94%C,3%B,3%A]

[33%C,33%B,33%A]

[30%C,70%B]

[100%A]
A

17

ConstructionofTernaryPhaseDiagrams

18

TernaryEutecticPhaseDiagrams

19

TernaryEutecticPhaseDiagrams
C

TaboveTofthe
ternaryeutectic,but
belowthebinary
eutectics.

T
L
+L

+
+ +L
+L
L
+L

+
+L

XB

+L

++L

B
20

TernaryPhaseDiagrams
C

+L
L
A

B
21

PartiallySolubleTernarySystems
Ifthetwophasesbothhaveapartialsolubilityoftheothercomponent,thenthe
analysisissomewhatmorecomplicated:
Thedifficultyisthatnowequilibriumdatamustbeobtainedfortheternary
whichrelatesthepartialsolubilities.Equilibriumdatacanbeobtainedgraphically,or
fromtables.Theternaryphasediagramisatypicalwayofrepresentingtheequilibrium
compositionsofthetwophases:
Solute

EthyleneGlycol

Water

50%EthGly
50%Furfural

17%EthGly
27%Furfural
56%Water
Acompositionwhere
twoliquidphases
coexist.

100%Furfural

Solvent

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

Furfural

Carrier

22

SpecificationofLiquidLiquidEquilibrium
Fortwophaseequilibrium(eithercompleteinsolubility,orpartiallysolubility):
theequilibriumisbetweentwoliquidsphases
(=2)
threecomponents(ternary)distributebetweenthetwophases
(C=3)
Forthestaticequilibriumcasewecanspecify3variables:
IfwespecifyTandPweareleftwithoneadditionalvariable:
Thusifwespecifytheconcentrationofonecomponentineitherofthephases
thiscompletelydefinesthestateofthesystem.

EthyleneGlycol

Water

TieLines:
Showthecompositions
oftheequilibriumphases.

Furfural

23

TieLine
Tielineadalahgarisyangmenghubungkansatu
titikpadarafinatdanpadaextraktan
Campuranyangkomposisinyaterletakdalamtie
lineakanmemilikikesetimbangansamayaitu
padakeduatitikdiujungtieline
Tielinedibuatdengancaramembiarkansuatu
campuranyangdiketahuikomposisinya
mencapaikesetimbangan2fasa.

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EkstraksiKesetimbangan
Satutahap

Countercurrentsatutahapsepertidilukiskanpadagambarsebelahkiri
bawahinitidaklahadadalamaplikasinya(bisaandajelaskanmengapa?).
Namunbergunadalammemahamineracamasaperhitunganselanjutnya

L0 + V2 = L1 + V1 = M
L.xA + V.yA = M.xAM
L.xA + V.yA = M.xAM
L.xA + V.yA = M.xAM
L.xC + V.yC = M.xCM

L+V=M
L.xA + V.yA = M.xAM
L.xC + V.yC = M.xCM
Ekstrak E

V1

V2

L0

L1

Campuran

Rafinat R

25

Ekstraksijamak
1.

Buatlah garis yang menghubungkan VN+1,

M dan L0

VN+1

2.

Buat garis yg menghubungkan LN dan VN+1

3.

Buat pertemuan kedua garis tsb (1 & 2) >

4.

Buat tie line yg mengenai M,

5.

Pada sisi amplop fasa > L1 & V1

6.

Hubungkan L1 dengan , perpotongan pada

satu sisi amplop menjadi V2

7.

Buat tie line kedua dari V2,

8.

Dst sampai melewati LN,

9.

Jumlah tahap = jumlah garis yg menemui

V2

V1
M

L0
LN L1

26

27

28

29

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

30

PartiallySolubleTernarySystems
Example:Considerafeedof200kgof30%ethyleneglycolinwater.Add300kgofsolvent
whichispurefurfural.
Step1:LocatetheSolventandFeedpoints

EthyleneGlycol

S
300Kg

Water

F
60kgEG
140kgwater

Furfural

31

PartiallySolubleTernarySystems
Step2:LocatethemixingpointM:

X BF FA XBS S 0.3 200kg 0 300kg

0.12
FS
500kg

EthyleneGlycol

Water

F60kgEG
140kgwater

M
S
300Kg

Furfural

32

PartiallySolubleTernarySystems
Step3:Usethetielinetogettheraffinateandextractcompositions.
Extract(4%water,14%EG,82%furfural)
Raffinate(87%water,5%EG,8%furfural)

EthyleneGlycol

Water

F60kgEG
140kgwater

R
S
300Kg

Furfural

33

PartiallySolubleTernarySystems
Step4:Determinetheamountofextractandraffinate(canuseleverrule)

XC M XC E

0.63 0.82
R f R
E 0.08 0.82 0.257
XC XC

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

R 0.257 500kg 128.4kg

E 1 0.257 500kg 371.6kg
EthyleneGlycol

Water

F60kgEG
140kgwater

R
S
300Kg

Furfural

34

PartiallySolubleTernarySystems
Step5:Determinethesolventfreeextract:MixturesofEandS.ExtendlinefromSthrough
EtosolventfreepointatH.
SolventfreeextractH(20%water,80%EG)

X BR
XB

EthyleneGlycol

Water

F60kgEG
140kgwater

R
S
300Kg

Furfural

35

Differentialextractors
Extract

Extract
Feed

Extract

Feed

Feed

Extracting
solvent

Raffinate

Extract

Feed

Extracting
solvent

Raffinate

Extracting
solvent

Raffinate

Raffinate

36

EkstraksiDiferensial

Continuousprocess
Feedandextractingsolventflowpast
oneanother
Onephaseisdispersedintheother
Contactingandphaseseparationtakes
placewithinoneunit
Phasesarenotinequilibriumexcept
locallyi.eattheinterface

Extract
Feed

Extracting
solvent
Raffinate
37

Transportzatterlarutpadaekstraksi

Raffinate
side film

yi

Concentration
profile

Raffinate

Raffinate

Feed

Extract

x
xi

Extract
side film

Raffinate
side film

Extracting
solvent

Extract
side film
Interface

38

PemilihanPelarut(Solvent)

Selektivitas
Adalahkemampuanpelarutuntukmelarutkansuatuzatyangdikehendaki.Selektivitas
ditentukandenganmenghitung,yaitu

Koefisiendistribusi
Ketidaklarutansolven
Rekoverabilitas
Densitas
Teganganpermukaan
Reaktivitaskimia
Viskositas,tekananuapdantitikbeku
Toksisitas,nonflammabledanmurah

39

40

Summary
Thislecturecovered:
TernaryLiquidLiquidextractions.
Ternaryphasediagrams.
Aproceduretodeterminetheproductcompositionsand
flowratesofaliquidliquidextractionseparation.

Nextlecturewillcover:
Leaching
Crystallization

41

ALTERNATEVERSION
USINGSOLVENTFREEDIAGRAM

42

MASSBALANCEEQUATIONS
OVERALL&COMPONENT

La Vb Lb Va M
xa La y bVb x b Lb y aVa x m M

CANBEREARRANGEDTOSOLVEFORVaANDLbON
THEBASISOFLaANDVbFEDTOPROCESS

La
y b xm

Vb
xm xa

FROM LEVER RULE

43

MULTIPLECROSSCURRENTEXTRACTION

[xm,M]1 [xm,M]2
xA,La
[ya,Va]1
[ya,Va]2

[xb,Lb]1 = [xa,La]2
[xb,Lb]2

S
[yb,Vb]1,2

44

COUNTERCURRENTMULTISTAGEEXTRACTION

MINIMUMSOLVENTDETERMINATIONBASEDON
EQUILIBRIUMLINETHROUGHxa

xj,min
ya,min
xa
P,min

yb

xb

45

DESIGNSOLVENTRATES
GRAPHICALCALCULATIONOFNUMBEROFSTAGES

46

TRANSFERTOMcCABETHIELE

OPERATINGLINE
SLOPEBASEDON
L/V
PERRYSP.1518.

47