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Liquid Liquid Extraction
 Feed + Solvent (immiscible)
= Extract (solvent Rich)+ Raffinate
• Applications:
(diluent rich)
• Separation of dilute aqueous solution as it is economic
compared to distillation
• Heat sensitive material as it is low temperature process –
long chain fatty acids from vegetable oils compared to high
vacuum distillation
• More economic compared to chemical method –Uranium&
Vanadium, Hafnium & Zirconium, Tungsten &
Molybdenum, purification of copper, phosphoric acid boric
acid
• Close boiling mixtures like aromatic and paraffinic
hydrocarbons
• From complex mixtures like penicillin
Equilateral triangular diagram
• If R kg of R is
mixed with E kg of
E. The resulting
composition will
lie on line RE at
M:
𝑅 𝑙𝑖𝑛𝑒 𝑀𝐸
=
𝐸 𝑙𝑖𝑛𝑒 𝑙𝑅𝑀
𝑥𝐸 − 𝑥𝑀
=
𝑥𝑀 − 𝑥𝑅
• C added to
original Mixture at
D varies along line
DC.
• 𝑅+𝐸 =𝑀
• 𝑅𝑥𝑅 + 𝐸𝑥𝐸 = 𝑀𝑥𝑀
• 𝑅𝑥𝑅 + 𝐸𝑥𝐸 = 𝑅𝑥𝑀 + 𝐸𝑥𝑀
𝑅 𝑥𝐸 −𝑥𝑀 𝐸𝑃 𝑀𝐸
• = = =
𝐸 𝑥𝑀 −𝑥𝑅 𝑃𝑆 𝑅𝑀
• Let A = diuent,B= solvent
and C= solute
• Equilibrium diagram –
Extract curve
• Raffinate curve [
• P= Plait point
• ab=tie line end point
gives composition in
extract phase and
raffinate phase
• Composiiton in raffinate x
• Compostion in extract y
System one pair partially miscible
two pairs fully miscible
 One pair partially miscible A-B
two pairs fully miscible A-C and B-C
• Effect of temperature
on equilibrium diagram
• t3>t2>t1
• As temperature
increases region of
homogeneity increases
Two pairs partially miscible A-B and B-C
one pair fully miscible A-C
Rectangular coordinates
 SELECTION OF SOLVENT
1. Selectivity should be more than 1
𝑊𝑡 𝐹𝑟𝑎𝑐 𝐶 𝑖𝑛𝐸 Τ𝑊𝑡 𝐹𝑟𝑎𝑐 𝐴 𝑖𝑛𝐸 𝑦𝐸 ∗ 𝑊𝑡 𝐹𝑟𝑎𝑐 𝐴 𝑖𝑛𝑅
𝛽= =
𝑊𝑡 𝐹𝑟𝑎𝑐 𝐶 𝑖𝑛𝑅Τ𝑊𝑡 𝐹𝑟𝑎𝑐 𝐴 𝑖𝑛𝑅 𝑥𝑅 ∗ 𝑊𝑡 𝐹𝑟𝑎𝑐 𝐴 𝑖𝑛𝐸
2. Distribution coefficient : Large value
𝑦𝐸 ∗
𝐷𝑒𝑖𝑠𝑡𝑟𝑖𝑏𝑢𝑡𝑖𝑜𝑛 𝑐𝑜𝑒𝑓𝑓 =
𝑥𝑅 ∗
3. Insoluble in solvent
4. Recoverable
5. Density – difference in densities of liquid phases.
6. Interfacial tension high – helps coalescence and separation
7. Chemically stable and inert to components
8. Low Viscosity, vapour press. , and freezing pt. for easy
handling and storage
9. Non toxic nonflammable and low cost
Determine
 Single stage extraction
𝐹 + 𝑆 = 𝐸1 + 𝑅1 = 𝑀
𝐹𝑥𝐹 + 𝑆𝑦𝑠 = 𝐸1 𝑦1 + 𝑅1 𝑥1 = 𝑀𝑥𝑀
𝐹𝑥𝐹 +𝑆𝑦𝑠
𝑥𝑀 =
𝑀
STEPS:
Locate F and S
Locate M on line FS at 𝑥𝑀
Draw tie line through M to
get𝐸1 𝑎𝑛𝑑 𝑅1
 Multistage Cross
Current Extraction
𝐹 + 𝑆1 = 𝐸1 + 𝑅1 = 𝑀1
𝐹𝑥𝐹 + 𝑆1 𝑦𝑠 = 𝐸1 𝑦1 + 𝑅1 𝑥1 = 𝑀1 𝑥𝑀1
2nd stage
𝑅1 + 𝑆2 = 𝐸2 + 𝑅2 = 𝑀2
𝑅1 𝑥1 + 𝑆2 𝑦𝑠 = 𝐸2 𝑦2 + 𝑅2 𝑥2 = 𝑀2 𝑥𝑀2
3rd stage
𝑅2 + 𝑆3 = 𝐸3 + 𝑅3 = 𝑀3
𝑅2 𝑥𝐹 + 𝑆3 𝑦𝑠 = 𝐸3 𝑦3 + 𝑅3 𝑥3 = 𝑀3 𝑥𝑀3
Final Extract
𝐸1 + 𝐸2 + 𝐸3 = 𝐸
𝐸𝑦𝐸 = 𝐸1 𝑦1 + 𝐸2 𝑦2 + 𝐸3 𝑦3
1. Locate F and S
Locate 𝑀1 on line FS at 𝑥𝑀1
Draw tie line through M1 to locate 𝐸1 𝑎𝑛𝑑 𝑅1
Find 𝑦1 𝑎𝑛𝑑𝑥1

2. Locate R1 and S
Locate 𝑀2 on line R1S at 𝑥𝑀2
Draw tie line through M2 to Locate 𝐸2 𝑎𝑛𝑑 𝑅2
Find 𝑦2 𝑎𝑛𝑑𝑥2

3. Locate R2 and S
Locate 𝑀3 on line R2S at 𝑥𝑀3
Draw tie line through M3 to locate 𝐸3 𝑎𝑛𝑑 𝑅3
Find 𝑦3 𝑎𝑛𝑑𝑥3
Multistage Counter current Extraction

• 𝐹 + 𝑆 = 𝑀 = 𝑅𝑁𝑝 + 𝐸1
• 𝐹𝑥𝐹 + 𝑆𝑦𝑠 = 𝑀𝑥𝑀 = 𝑅𝑁𝑝 𝑥𝑁𝑝 + 𝐸1 𝑦1
• 𝑅𝑁𝑝 − 𝑆 = 𝐹 − 𝐸1 = ∆𝑅 = 𝑅1 − 𝐸2 =
. . =Difference point ∆𝑅
• ∆𝑅 + 𝑆 = 𝑅𝑁𝑃 𝑎𝑛𝑑 ∆𝑅 + 𝐸1 = 𝐹
• Locate F,S,M, RNP
• Join RNP and M to get E1
• Join E1, F and extend
• Join S, RNp and extend to get ∆𝑅𝑝𝑝𝑜𝑖𝑛𝑡
• Draw tie line through E1 to get R1
• Join ∆𝑅 𝑎𝑛𝑑 𝑅1 𝑒𝑥𝑡𝑒𝑛𝑑 𝑡𝑜𝑔𝑒𝑡 E2
• Draw tie line through E2 to get R2
• Join ∆𝑅 𝑎𝑛𝑑 𝑅1 𝑒𝑥𝑡𝑒𝑛𝑑 𝑡𝑜𝑔𝑒𝑡 E2
• Repeat above two steps to get number of stages
Minimum solvent requirement
 LEACHING

Equilibrium relationship
Single stage leaching
Multistage counter current leaching
 Leaching Process
• Step I – solid containing solute and inert
mixed with solvent
• Step II – Agitation stopped and separated into
solid free overflow and underflow
• Overflow = solvent containing dissolved solute
• Underflow or slurry stream = inert solid and
adhering solution [containing solvent and
dissolved solute, generally of same
concentration as overflow]
 Symbols
• Solute = A
• Inert solid = B
• Solvent =C
• Concentration of Inert solid:
𝑘𝑔 𝑜𝑓 𝐵 𝑘𝑔 𝑜𝑓 𝑖𝑛𝑒𝑟𝑡
• 𝑁= =
𝑘𝑔 𝑜𝑓 𝐴+𝑘𝑔 𝑜𝑓 𝐶 𝑘𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
• Concentration of solute
𝑘𝑔 𝑜𝑓 𝐴 𝑘𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
• 𝐼𝑛 𝑜𝑣𝑒𝑟𝑓𝑙𝑜𝑤 𝑙𝑖𝑞𝑢𝑖𝑑, 𝑥𝐴 = 𝑘𝑔 𝑜𝑓 𝐴+𝑘𝑔 𝑜𝑓 𝐶
= 𝑘𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑘𝑔 𝑜𝑓 𝐴 𝑘𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
• 𝐼𝑛 𝑢𝑛𝑑𝑒𝑟𝑓𝑙𝑜𝑤 𝑙𝑖𝑞𝑢𝑖𝑑, 𝑦𝐴 = 𝑘𝑔 𝑜𝑓 𝐴+𝑘𝑔 𝑜𝑓 𝐶 = 𝑘𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
 Equilibrium diagram for variable
underflow and vertical tie line
• Equilibrium Diagram
• No solid in over flow-N=0 for
overflow curve
• No adsorption of solute by
solid
• concentration of withdrawn
solution is same as that of
solution associated with solid-
tie lines are vertical
• Distribution coefficient =1.
and Distribution curve is x=y
• Solution retention changes
with concentration – N varies
with y
Equilibrium diagram Constant
underflow and vertical tie line
• Equilibrium diagram for
case Constant
underflow:
• Solids settled or drained
to same extent at all
solute concentration
• Line KL is horizontal
 Equilibrium Diagram – non vertical tie line
[𝑦 ≠ 𝑥] variable under flow
• Equilibrium diagram for
case [tie lines are not
vertical]:
• Insufficient contact
time, so that all the
solute is not dissolved
• Adsorption of solute in
the solid.
Equilibrium diagram – solids in overflow

• Equilibrium diagram for

case Solids in the
overflow
• Solute adsorption on
solids
SINGLE STAGE LEACHING
• V= kg/h of overflow solution
(A+C)with composition x
• L= kg/h of liquid (solution) in
slurry(A+C) with composition y
• B= kg/hr of solute free inert
solid flow
• Total Mass Balance:
𝐿𝑜 + 𝑉2 = 𝐿1 + 𝑉1 = 𝑀
• Solute Balance
𝐿𝑜 𝑦𝑜 + 𝑉2 𝑥2 = 𝐿1 𝑦1 + 𝑉1 𝑥1
= 𝑀𝑥𝑀
M=Total flow rate kg (A+C)/hr
• Inert solid Balance
𝐵 = 𝑁0 𝐿0 + 0 = 𝑁1 𝐿1 + 0
= 𝑀𝑁𝑀
 m

• Refer Geankoplis

• 𝑉2 = 100 𝑘𝑔 𝑎𝑛𝑑
• 𝑥2 = 0,
• 𝐵 = 100 1 − 0.2 = 80𝑘𝑔,
• 𝐿0 = 100 1 − 0.8 = 20𝑘𝑔 𝑎𝑛𝑑 𝑦0 = 1.0
• 𝑁0 = 80Τ20 = 4.0 𝑘𝑔𝑠𝑜𝑙𝑖𝑑Τ𝑘𝑔𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
 𝐿𝑜 + 𝑉2 = 𝐿1 + 𝑉1 = 𝑀
𝐿𝑜 + 𝑉2 = 20 + 100 = 120𝑘𝑔 = 𝑀
𝐿𝑜 𝑦𝑜 + 𝑉2 𝑥2 = 𝐿1 𝑦1 + 𝑉1 𝑥2 = 𝑀𝑥𝑀
𝐿𝑜 𝑦𝑜 + 𝑉2 𝑥2 = 20 1.0 + 100 0
= 120𝑥𝑀
Or 𝑥𝑀 = 0.167

𝐵 = 𝑁0 𝐿0 + 0 = 𝑁1 𝐿1 + 0 = 𝑀𝑁𝑀
• 𝐵 = 4 20 = 80 = 𝑁𝑀 120
• 𝑁𝑀 = 0.667
Locate M on line noiningV2 and Lo
Draw veritcal line to get L1 and V1.
𝑦1 = 𝑥1 = 0.167 𝑎𝑛𝑑 𝑁1 = 1.5
𝐿1 = 53.3 𝑎𝑛𝑑 𝑉1 = 66.7𝑘𝑔
 COUNTERCURRENT MULTISTAGE LEACHING
• Total Mass Balance: 𝐿𝑜 + 𝑉𝑁+1 = 𝐿𝑁 + 𝑉1 = 𝑀
• Solute Balance
𝐿𝑜 𝑦𝑜 + 𝑉𝑁+1 𝑥𝑁+1 = 𝐿𝑁 𝑦𝑁 + 𝑉1 𝑥1 = 𝑀𝑥𝑀
Equation of Operating line:
𝐿𝑁 𝑉1 𝑥1 − 𝐿𝑜 𝑦𝑜
𝑥𝑁+1 = 𝑦𝑁 +
𝑉𝑁+1 𝑉𝑁+1
• Inert solid Balance
𝐵 = 𝑁0 𝐿0 + 0 = 𝑁1 𝐿1 + 0 = 𝑀𝑁𝑀
 COUNTERCURRENT
MULTISTAGE
LEACHING
• Material balance around
stage 1:
𝐿𝑜 + 𝑉2 = 𝐿1 + 𝑉1
• Stage n
𝐿𝑛−1 + 𝑉𝑛+1 = 𝐿𝑛 + 𝑉𝑛
• ∆= 𝐿0 − 𝑉1 = 𝐿1 − 𝑉2 =
𝐿𝑛 − 𝑉𝑛+1 = …
• 𝐿0 = 800 + 50 = 850
800
• 𝑦0 = = 0.941
850
• B= 2000
2000
• 𝑁0 = = 2.36
800+50
• 𝑉𝑁+1 = 1310 + 20 = 1330
20
• 𝑥𝑁+1 = = 0.015
1330
• Locate Lo and VN+1
• Locate LN
𝑁𝑁 𝑘𝑔 𝑖𝑛𝑒𝑟𝑡 𝑘𝑔 𝑠𝑜𝑙𝑛
• = 𝑥 =
𝑦𝑁 𝑘𝑔 𝑠𝑜𝑙𝑛 𝑘𝑔 𝑠𝑜𝑙𝑢𝑡𝑒
𝑘𝑔 𝑖𝑛𝑒𝑟𝑡 2000
= = 16.67
𝑘𝑔 𝑠𝑜𝑙𝑢𝑡𝑒 120
• Draw line through origin
with slope 16.67 and locate
LN
𝑁𝑁 = 1.95 𝑎𝑛𝑑 𝑦𝑁 = 0.118
• Overall Balance: • Locate L1, V2,L2.
• 𝐿0 + 𝑉𝑁+1 = 850 + 1330 • Determine LN and V1:
= 𝑀 = 2180𝑘𝑔/ℎ • 𝐿𝑁 + 𝑉1 = 𝑀 = 2180
• Solute Balance • 𝐿𝑁 𝑦𝑁 + 𝑉1 𝑥1 = 𝑀𝑥𝑀
• 850(0.941)+1330(0.015)=
2180𝑥𝑀 • 𝐿𝑁 (0.118) +𝑉1 0.6 =
2180 𝑥 0.376
• 𝑥𝑀 = 0.376
• Locate M • LN= 1016kg
• Join Lo, M and extend to • V1=1164kg
get V1, 𝑥1 = 0.6
• Locate ∆