3/12/2018

EKC 217
Liquid-Liquid Extraction
Dr Fadzil

Introduction – Liquid Extraction

• Liquid – liquid extraction –
Extraction of solute from liquid
carrier by immiscible or partially
miscible liquid (solvent).
• No vaporization is needed, thus
can be performed at low
temperatures.
• Suitable for extraction of heat
sensitive solutes (denatured at
elevated temperatures)

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Introduction – Industrial application

Solute Carrier Solvent
• Liquid extraction commonly use for; Acetic acid Water Ethyl acetate
• Removal of aromatic and sulfur Ammonia Butenes Water
compounds from liquid kerosene
using liquid sulfur dioxide. Aromatics Paraffins Diethylene
• Extraction of acetic acid in aqueous glycol
solution using ethyl acetate. Aromatics Kerosene Sulfur dioxide
• Extraction of penicillin or antibiotic Formaldehyde Water Isopropyl ether
from the broth (liquid media for Formic acid Water Tetrahydrofuran
biological conversion by microbial)
Methyl ethyl Water Trichloroethane
• Liquid extraction is attractive for ketone
the recovery of solutes because less Phenol Water Chlorobenzene
energy intensive compared to
Penicillin Broth Butyl acetate
distillation.
Vanilla Oxidized liquors Toluene
Vitamin A,E Fish/vegetable oil Propane

Process Flow Diagram of Liquid – Liquid

Extraction
• Liquid extractor normally coupled with a Extract
solvent recovery unit for recycling the solvent Raffinate (Solute rich)
back to the extractor.
• The feed contains solute dissolved in a carrier
solvent.
Recovery

• Another solvent which is immiscible or Liquid -

Solvent

Liquid
partially miscible is used to recover or extract Extraction
the solute from the carrier solvent
• The carrier solvent and the remaining solute
leaving the extractor is called “raffinate
phase”. Solvent
Feed Solute
• The solvent rich with solute leaving the (Carrier + Solute)
extractor is called “extract phase”.

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Type of Liquid – Liquid Extractor

• Mixer Settler
• Two liquid phase are mixed in a vessel.
• The liquids are agitated with multiple
plate/blade to form dispersed liquid
phase.
• The dispersion of the liquids gives
more surface area and enhances mass
transfer of solute.
• Then dispersed liquids (emulsion) will
be separated by gravity induced
settling.
• Mixture settler can be arranged in
series to form multi-stage extractor.

Mixer Settler

Type of Liquid – Liquid Extractor

• Spray Column
• Light and heavy phase is flowing counter-
currently.
• Either heavy phase or liquid phase is
dispersed in the column.
• The dispersed phase is generated at the
inlet by using a nozzle.

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Type of Liquid – Liquid Extractor

• Plate tower
• Similar to gas absorption column.
• Heavy phase and light phase is
flowing counter-currently.

• Agitated extraction tower

• Gravitational force alone is in
adequate for phase dispersal.
• Agitator is used to promote the
formation of dispersed phase and
enhance mass transfer.

Liquid – Liquid Extraction (LLE) Process

• LLE
• Immiscible LLE
• Counter current
• Diluted solute
• Concentrated solute
• Cross flow
• Diluted solute
• Concentrated solute
• Partially miscible LLE
• Counter current
• Cross flow

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Immiscible LLE – Counter-current

Extract phase
• Raffinate and extract phases are fed in the
opposite direction. E1 E2 EN S
y1 y2 yN
• The design equation for immiscible LLE is yN+1
comparable to gas-liquid adsorption (both
phases do not mix) 1 2 N
• At high solute concentration; F R1 R2 RN
𝐹 = 𝐹(1 − 𝑥 ) 𝐹≠𝑅 xο x1 x2 xN
𝑆 = 𝑆(1 − 𝑦 ) 𝑆≠𝐸 Raffinate phase
Where;
• At low solute concentration; 𝐸 – is the extract phase
𝐹=𝐹 =𝑅 𝑆=𝑆 =𝐸 𝑅 – is the raffinate phase
𝑆 – is the solvent feed
• For immiscible liquids, 𝐹′ and 𝑆′ are constants 𝐹 – is the feed (carrier solvent + solute)
𝑁 – is the number of contacts (stages)

Immiscible LLE – Counter-current (diluted

solute)
Extract phase
• Solute mass balance;
𝐹𝑥 + 𝑆𝑦 =𝑅 𝑥 +𝐸 𝑦 E1 E2 EN S
𝑅 𝐸 𝐹 y1 y2 yN
𝑦 = 𝑥 + 𝑦 − 𝑥 yN+1
𝑆 𝑆 𝑆
• For diluted solute; 1 2 N
𝐹=𝐹 =𝑅 𝑆=𝑆 =𝐸
F R1 R2 RN
• Thus; xο x1 x2 xN
𝐹 𝐹 Operating Raffinate phase
𝑦 = 𝑥 +𝑦 − 𝑥 Line (diluted)
𝑆 𝑆 Where;
𝐸 – is the extract phase
𝑅 – is the raffinate phase
𝑆 – is the solvent feed
𝐹 – is the feed (carrier solvent + solute)
𝑁 – is the number of contacts (stages)

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Immiscible LLE – Counter-current (diluted

solute) McCabe-Thiele E1
Extract phase

E2 EN S
approach y1 y2 yN yN+1
• The operating line for diluted solute;
1 2 N
𝑅 𝑅
𝑦 = 𝑥 +𝑦 − 𝑥
𝐸 𝐸 F R1 R2 RN
xο x1 x2 xN
• To estimate the number of contactors/stages, Raffinate phase

required partition coefficient data or

distribution ratio given by;
𝑦=𝐾 𝑥
𝑦
• Where, 𝐾 is the distribution ratio of solute in 4
the extract phase over raffinate phase.

Extract phase
3
𝑅
𝑆𝑙𝑜𝑝𝑒 =
2 𝐸
Stages= 4
1
𝑦
𝑥 𝑥
Raffinate phase

Immiscible LLE – Counter-current

(concentrated solute)
Extract phase
• Solute mass balance;
𝐹𝑥 + 𝑆𝑦 =𝑅 𝑋 +𝐸 𝑦 E1 E2 EN S
y1 y2 yN yN+1
• For concentrated solute;
𝐹≠𝐹 ≠𝑅 𝑆≠𝑆 ≠𝐸 1 2 N
𝐹 = 𝐹 1−𝑥 =𝑅 1−𝑥
F R1 R2 RN
𝑆 =𝑆 1−𝑦 =𝐸 1−𝑦 x1 xN
xο x2
• Substitution of 𝐹, 𝑆, 𝑅 and 𝐸 into the solute Raffinate phase
mass balance gives; Where;
𝑥 𝑦 𝑥 𝑦 𝐸 – is the extract phase
𝐹′ + 𝑆′ = 𝐹′ + 𝑆′ 𝑅 – is the raffinate phase
1−𝑥 1−𝑦 1−𝑥 1−𝑦 𝑆 – is the solvent feed
𝐹 – is the feed (carrier solvent + solute)
𝐹′𝑋 + 𝑆′𝑌 = 𝐹′𝑋 + 𝑆 𝑌 𝑁 – is the number of contacts (stages)
XN, Y1, Xo and YN+1 are the
mol ratio

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Immiscible LLE – Counter-current

(concentrated solute)
• Thus, the operating line in mol ratio is;
𝐾 𝑋
𝐹′ 𝐹′ Operating 𝑌=
𝑌 = 𝑋 +𝑌 − 𝑋 1+𝑋−𝐾 𝑋
𝑆′ 𝑆′ Line (concentrated)

• The conversion of distribution ratio from mol

fraction to mol ratio gives; 𝑌
3

Extract phase
𝑦 𝑌
𝑌= 𝑦=
1−𝑦 1+𝑌 Stages = 3
𝑥 𝑋 2
𝑋= 𝑥=
1−𝑥 1+𝑋 𝐹′
1 𝑆𝑙𝑜𝑝𝑒 =
𝑆′
𝑦=𝐾 𝑥
𝑌
𝑌 𝑋 𝑋 𝑋
=𝐾
1+𝑌 1+𝑋 Raffinate phase
𝐾 𝑋 Equilibrium
𝑌= Line (concentrated) Note:
1+𝑋−𝐾 𝑋 Conversion of straight Eq line in mol fraction
to mol ratio will give slightly curved Eq line

Immiscible LLE – Cross-Flow Extraction

(Diluted solute) 𝑆 ,𝑦 , 𝑆 ,𝑦 , 𝑆 ,𝑦 ,

• For cross-flow extraction, fresh solvent is used for

each stages. 1 2 N
𝐹, 𝑥 𝑅 ,𝑥 𝑅 ,𝑥 𝑅 ,𝑥
• For immiscible liquids and diluted solute;
𝐹=𝐹 =𝑅 𝑆 = 𝑆′ = 𝐸 𝐸 ,𝑦 , 𝐸 ,𝑦 , 𝐸 ,𝑦 ,

• Material balance for any stages are given by;

𝐹𝑥 + 𝑆 𝑦 , = 𝐹𝑥 + 𝑆 𝑦 ,
𝐹𝑥 + 𝑆 𝑦 , = 𝐹𝑥 + 𝑆 𝑦 ,

𝐹𝑥 +𝑆 𝑦 , = 𝐹𝑥 + 𝑆 𝑦 ,

• Solve for 𝑦 ,
𝐹 𝐹 Operating
𝑦 , =− 𝑥 + 𝑥 +𝑦 ,
𝑆 𝑆 Line for any stages

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Immiscible LLE – Cross-Flow Extraction

(Diluted solute) 𝑆 ,𝑦 , 𝑆 ,𝑦 , 𝑆 ,𝑦 ,

𝐹 𝐹 Operating
𝑦 , =− 𝑥 + 𝑥 +𝑦 , Line (mol frac.)
𝑆 𝑆 for any stages 𝐹, 𝑥
1 𝑅 ,𝑥
2 𝑅 ,𝑥
N 𝑅 ,𝑥
• Operating line (OL) above gives a correlation 𝐸 ,𝑦 𝐸 ,𝑦 𝐸 ,𝑦
, , ,
between the composition of the extract 𝑦 ,
and raffinate 𝑥 with a negative slope of 𝑭/𝑺𝑵.
𝒚
• The OL for each stages of cross-flow extraction can
be illustrated as showed in the Figure. Where, the
𝑥 ,𝑦
feed solvent for each stages are pure solvent. 𝑦 ,
,

• It is assumed that the extract and raffinate phases 𝑥 ,𝑦 ,

are at equilibrium for each stages. Thus, the 𝑦 ,

𝑥 ,𝑦
composition of solute in the extract and raffinate 𝑦 ,
,
𝑠𝑙𝑜𝑝𝑒 = −
𝐹
𝑆
located at the equilibrium line (EL).

𝒙
𝑥 ,𝑦 , 𝑥 ,𝑦 , 𝑥 ,𝑦 ,

Immiscible LLE – Cross-Flow Extraction

(Concentrated solute) 𝑆 ,𝑦 , 𝑆 ,𝑦 , 𝑆 ,𝑦 ,

• For cross-flow extraction of concentrated solute;

𝐹
𝐹 =𝐹 1−𝑥 = 𝑅 1−𝑥 𝐹, 𝑥
1 𝑅 ,𝑥
2 𝑥 N 𝑅 ,𝑥
𝑆′ = 𝑆 1−𝑦 , = 𝐸 1−𝑦
𝐸 ,𝑦 , 𝐸 ,𝑦 , 𝐸 ,𝑦 ,
• Thus, the operating line (OL) can be expressed in
mol ratio with a negative slope of 𝑭′/𝑺′𝑵. 𝒀 EL, 𝑦 = 𝐾 𝑥
𝐹′ 𝐹′ Operating
𝑌 , =− 𝑋 + 𝑋 +𝑋 , Line (in mol ratio) 𝐾 𝑋
𝑆′ 𝑆′ for any stages 𝑋 ,𝑌 , 𝑌=
𝑌, 1+𝑋−𝐾 𝑋

𝑋 ,𝑌 ,
𝑌,
𝑋 ,𝑌 ,
𝑌 , 𝐹′
𝑠𝑙𝑜𝑝𝑒 = −
𝑆′

𝑿
𝑋 ,𝑌 , 𝑋 ,𝑌 , 𝑋 ,𝑌 ,

NOTE:
A straight EL will be slightly curved after conversion to mol ratio

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Partially miscible LLE

• Most LLE involves two partially
miscible liquids.
• For miscible LLE, solution through
the McCabe-Thiele approach is
unreliable.
• Ternary liq-liq diagram composed a
mixture of solute, solvent and
carrier solvent has to be analysed
• Two types of ternary diagram
• Equilateral triangle
• Right triangle
Equilateral triangle Right triangle

Ternary Liquid-Liquid Phase Diagram

Solute
• Give liq-liq equilibrium data for three (100%)
component system (composed of solute-
carrier-solvent)
• On the ternary diagram
• At the vertex is the pure component
• At the base is the mixture of two
component.
• The composition of the component
from the vertex to the opposite base
is reduced from 100% to 0%

0% Solute
Carrier Solvent
Carrier-Solvent mixture
(100%) (100%)

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Ternary Liquid-Liquid Phase Diagram

Solute (A)
• Composition of solute-carrier- (100%)
solvent in the ternary diagram is
read by reading composition of
each component, from the Mixture Composition
30% A, 30% C, 40% S
vertices to the opposite bases.
• The composition of a mixture is
located at the intersect of the 30% A

three lines.

Carrier (C) Solvent (S)

(100%) (100%)

Ternary Liquid-Liquid Phase Diagram

• In a Liquid-Liquid Phase Diagram Solute (A)
have two region
• Single phase region – where all
components are dissolved in a single
phase
• Two phases region – where the Equilibrium
components are separated into two Single phase
curve
liquid phases
• The boundary between single phase
and two phases regions is
represented by an equilibrium Two phases
curve/saturation curve/binodal
curve.
Carrier (C) Solvent (S)

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Ternary Liquid-Liquid Phase Diagram

• At the two phases regions, there Solute
are tie lines that connecting the
composition of raffinate phase and
extract phase
• On the diagram
• Point R to P on an equilibrium line is Plait Point Equilibrium
curve
representing a composition of
raffinate phase P
• Point E to P on an equilibrium line is
representing a composition of extract
phase
• Point P is a plait point – where the
composition of raffinate phase is
equal to composition of extract phase
R E
Carrier Solvent

Ternary Liquid-Liquid Phase Diagram

• For example – a liquid mixture Solute
with composition M will separate
into two phases
• Raffinate phase with composition
of R Equilibrium
curve
• Extract phase with composition of P
E E
M
• The compositions of raffinate
R
and extract phases are read by
following the tie line to the
equilibrium curve. Carrier Solvent

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Ternary Liquid-Liquid Phase Diagram

• Point M also represent the total Solute
composition of the Feed mixture F
M
(Carrier + Solute) and pure solvent. S
• If the feed with a composition of F is
mixed with pure solvent S, the Feed
composition of the resulted mixture or F
point M can be found on a straight line
E
between point F (feed) and S (pure M
solvent)
R

S
Carrier Solvent
Pure Solvent

Ternary Liquid-Liquid Phase Diagram

• Point M can be calculated by Solute
F
using Inverse Lever Arm Rule; M
S
• From total mass balance &
component balance of C;
𝑀 =𝐹+𝑆 (Total mass balance)
F Extract

(Component mass balance) Feed

𝑀𝑥 = 𝐹𝑥 + 𝑆𝑥 E
𝐹 + 𝑆 𝑥 = 𝐹𝑥 + 𝑆𝑥 (Substitution & rearrangement) Raffinate M

𝐹 𝑥 −𝑥
= R
𝑆 𝑥 −𝑥
Where; S
𝐹 𝑆𝑀 C is mass fraction
= SM & MF is the distance (cm) Carrier Solvent
𝑆 𝑀𝐹
Pure Solvent

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Ternary Liquid-Liquid Phase Diagram

• Inverse Lever Arm Rule also can Solute
F
be applied on line R, M & E M
S
𝑀 =𝑅+𝐸 (Total mass balance)

𝑀𝐶 = 𝑅𝐶 + 𝐸𝐶 (Component mass balance)

𝑅 + 𝐸 𝐶 = 𝑅𝐶 + 𝐸𝐶 (Substitution & rearrangement)

F Extract
𝑅 𝐶 −𝐶 Feed
= E
𝐸 𝐶 −𝐶 M
Where; Raffinate
𝑅 𝐸𝑀 C is mass fraction
= EM & MR is the distance (cm)
𝐸 𝑀𝑅 R

S
Carrier Solvent
Pure Solvent

Ternary Liquid-Liquid Phase Diagram

• Basically for Inverse Lever Arm Rule; Solute
F
𝐹 𝑆𝑀 𝑅 𝐸𝑀 M
= = S
𝑆 𝑀𝐹 𝐸 𝑀𝑅

• The mass ratio is equivalent to length

ratio on the phase diagram, thus;
F Extract
𝐸 𝑀𝑅 𝐹 𝑀𝑆 Feed
= = E
𝑀 𝑅𝐸 𝑀 𝑆𝐹 Raffinate M

• This rule applied on any location in the R

phase diagram (single and two phase
S
region)
Carrier Solvent
Pure Solvent

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Single-Stage Example: Find the Raffinate & Extract

Compositions from a given feed conditions
S = 200 g Ethylene Glycol
Water Extract

M
F = 100 g Raffinate
LLE System
35% EG
65% Furfural

Furfural Water

Operating line & Operating Point

• Liquid-liquid extraction frequently being
operated in multi stages.
• Operating point (P) need to be located in A E1 E2 E3 S
the phase diagram for estimating no. of
stages.
• Draw two operating line which is F R1 R2 R
connecting point E→F and S→R. The • Operating point is the mass
intersection between these operating line is differences between passing
known as operating point. stream, thus;
𝑃 = 𝐸1 − 𝐹 = 𝐸2 − 𝑅1 = 𝐸3 − 𝑅2
Operating
Point
P E
F
M
R
S
C S

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Multi-stage Example: Draw the operating

lines
S = 200 g Ethylene Glycol
Water E

F = 50 g R
LLE System 5% EG
25% EG
75% Furfural

a) Find an operating point to achieve 5% of

ethylene glycol in the raffinate ?
b) Estimate the required number of
contacts/stages?

Furfural Water

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