CHE 246

SEPARATION PROCESS

CHAPTER 4

LIQUID-LIQUID
EXTRACTION
ARBANAH MUHAMMAD
FACULTY OF CHEMICAL ENGINEERING
UiTM PASIR GUDANG

1
 LEARNING OUTCOME

4.1 Define liquid-liquid extraction, partially

immiscible system and immiscible system
4.2 Describe ternary phase diagram
4.3 Calculate for single–stage Liquid-liquid
extraction
4.4 Perform mass balance calculation for multi-
stage counter current flow systems in
4.4.1 Partially immiscible system
4.3.2 Immiscible system

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3
4.1 DEFINITION & APPLICATIONS

The transfer of solute-A of a liquid solution-B (diluent/carrier) by contact with another

insoluble liquid-C (solvent).

Transfer is based on the preferential solubility of solutes-A in the liquid-C (solvent).

.
Two streams result from this contact:
a) Extract is the solvent rich solution containing the desired extracted solute.
b) Raffinate is the residual feed solution containing little solute

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 Liquid-liquid Extraction Principle

C - solvent (blue)

A-solute (black)
B-liquid solution(green)

When Liquid-liquid extraction is carried out in a test tube or flask the

two immiscible phases are shaken together to allow molecules to
partition (dissolve) into the preferred solvent phase.

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DEFINITION & APPLICATIONS
Common production processes using LLE i.e:-

i. Food processing
ii. Pharmaceutical separation
iii. Oil purification
.

The difference between LLE and distillation process in the separation of liquid mixture:-

♦ LLE depends on solubilities between the liquid components and produces new
solution which in turn has to be separated later, whereas;

♦ Distillations depends on the differences in A/B / P of substances. It also

requires heat supply.

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Table 4.1: Industrial Liquid –Liquid Extraction (LLE) Processes

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(CHAPTER 3 ) 7
CDIO ACTIVITY 1

You are required to suggest preferred

separation operation (LLE or distillation) in
your plant.

Debate this topic between 2 GROUPS of

Aff. : Affirmative team (preffer LLE)
Opp. : Opposition team

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-
The advantages of LLE vs distillation process:-

a) Recovery of heat-sensitive materials, where low to moderate processing

temperatures are needed. Thermal decomposition might occur.

b) Separation of mixture which the components have close boiling point (vapor
pressure)

c) Separation of mixture which it’s relative volatility nearly to unity

d) Presence of azeotropic mixture/solution

e) If distillation utilizes excessive amount of steam generation – cost ↑

f) Solvent recovery easily maintained and energy saving can be realized.

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10
Solvent is the key point need to consider for optimized LLE separation. The criterias are as follows:

a) Distribution coefficient - the ratio (at equilibrium) of solute’s concentration in extract and
raffinate phases. It gives a measure of the affinity of the solute for
the 2 phases.
b) Solubility - the solutes are soluble in solvent but insoluble (low solubility) in the
feed solution. For example, if there is significant solubility of
solvent in the raffinate stream, an additional separation is required
to recover the solvent.
c) Recoverability - necessary to recover the solvent for re-use purposes.
d) Density - A large difference in density between extract and raffinate phases
permits high capacities in equipment. This especially important for
extraction equipments that utilizing gravity for phase separation.
e) Chemical Reactivity - Chemically stable and inert towards other components of the
system & construction
f) Viscosity / P - Low  & P for ease in handling & storage. E.g. high  leads to
difficulties in pumping, dispersion & mass transfer rate.
g) Availability & ↓cost.
h) selectivity
i) interfacial tension

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 PROCESS FLOW DIAGRAM LIQUID-LIQUID EXTRACTION

VN+1 Solvent
V1 Extract yAO
yA1 yBO
yB1 yCO
yC1

1 2 3 N

Lo Feed LN Raffinate
XAO XAN
XBO XBN
XCO XCN

Percentage of A being removed: LoXAo-LnXn1 x100%

LoXAo

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 Principles of Liquid-Liquid Equilibrium

Extraction involves the use of systems composed of at least 3 substances, and

generally all 3 components appear at least to some extent in both phases. The
graphical way to represent concentrations in ternary (i.e. 3-components) systems
are right triangular diagram or equilateral-triangular diagram

0.9

0.8

0.7

0.6
xC,yC

0.5

0.4

0.3
M
0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xA, yA

Right triangular diagram Equilateral triangular diagram

Coordinate point M (0.3,0.5,0.2) coordinate point M (0.4,0.3,0.3)
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4.1.2 DIFFERENT WAYS TO DRAW THE LLE PHASE DIAGRAMS
(a) Equilateral triangular diagram

One liquid phases

M (0.3, 0.3, 0.4)

Two liquid phases

(B)

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Figure 3.1.3 Ternary diagram of ethylene glycol-water-furfural (25ºC)
(b) Right triangular diagram

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(CHAPTER 3 ) 15
 EQUILIBRIUM CURVE
Dot line …… Dash line ---
1 Raffinate layer Extract layer
(water layer) (isopropyl ether layer)
0.9
water layer Isopropyl ether layer

0.8 Acetic isopropyl Acetic isopropyl

acid water ether acid water ether
0.7 0 0.988 0.012 0 0.006 0.994
coordinate 0.0069 0.981 0.012 0.0018 0.005 0.993
0.6
(0.311,0.108,0.581)
0.0141 0.971 0.015 0.0037 0.007 0.989
xC,yC

0.5 coordinate 0.0289 0.955 0.016 0.0079 0.008 0.984

(0.362,0.151,0.487
0.0642 0.917 0.019 0.0193 0.01 0.971
0.4
0.133 0.844 0.023 0.0482 0.019 0.933
0.3
0.255 0.711 0.034 0.114 0.039 0.847

coordinate 0.367 0.589 0.044 0.216 0.069 0.715

0.2
(0.464,0.371,0.165) 0.443 0.451 0.106 0.311 0.108 0.581
0.1
coordinate
(0.443,0.451,0.106) 0.464 0.371 0.165 0.362 0.151 0.487

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xA, yA

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Tie line
A pair of extract and raffinate coordinate
1
water layer Isopropyl ether layer
0.9
Acetic isopropyl Acetic isopropyl
0.8
acid water ether acid water ether

0 0.988 0.012 0 0.006 0.994 0.7

0.0069 0.981 0.012 0.0018 0.005 0.993 0.6

xC,yC
0.0141 0.971 0.015 0.0037 0.007 0.989 0.5

0.0289 0.955 0.016 0.0079 0.008 0.984 0.4

0.0642 0.917 0.019 0.0193 0.01 0.971
0.3
0.133 0.844 0.023 0.0482 0.019 0.933
0.2
0.255 0.711 0.034 0.114 0.039 0.847
0.1
0.367 0.589 0.044 0.216 0.069 0.715
0
0.443 0.451 0.106 0.311 0.108 0.581 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xA, yA
0.464 0.371 0.165 0.362 0.151 0.487

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4.2 SINGLE STAGE OF LLE
- Solvent and feed streams are contacted each other in single stage producing the raffinate
and extract streams which are in equilibrium states.

- Feed stream normally consists of binary solution containing solute (A) dissolved in a
diluent/carrier (B).

- The extracting solvent (C) can be either pure solvent or may content low concentration of
solute (A) (recycle solvent).

- When feed mixed with solvent, an intermediate phase M momentarily forms as the light
liquid moves through heavily liquid in the form of bubbles. These bubbles provide a large
surface area for contact between the feed solution and the solvent that speed up the mass
transfer process

- In most single stage LLE, it is interested to determine the equilibrium composition and
mass flowrates of extract and raffinate by using ternary phase diagram and mass balance
principle.

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 Figure 4.2.1. Single stage equilibrium LLE
(a) Schematic diagram of LLE (b) Ternary phase diagram
- The material balance for the diagram’s boundary in Fig 3.2.1.1 can be written as:-
Overall mass balance : LO + V2 = L1 + V1 = M ……(3.1)
Mass balance on comp. A : LOxAO + V2yA2 = L1xA1 + V1yA1 = MxAM ……(3.2)
Mass balance on comp. C : LOxCO + V2yC2 = L1xC1 + V1yC1 = MxCM …...(3.3)
- The points Lo, V2 and M can be plotted as shown in Fig 3.2.1.1 (b).
- Then using trial and error method to find tie line which can be drawn through the point M, that locates the
compositions of L1 and V1
- The amounts of L1 and V1 can be determined by substitution into Eqs. (3.1) - (3.3)
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EXERCISE 4.1
A single stage extraction is performed in which 400kg/h of a solution containing 40 wt% acetic acid in
water is contacted with 400kg/h of pure isopropyl ether. Determine:-

i. The compositions of raffinate and extract

ii. The flowrates of raffinate and extract
iii. The percentage of acetic acid removal in the system

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 V2=400kg/h
Solution Exercise 4.1 yAo=0
yBo=0
V1 yCo=1

L1
Lo=400kg/h
xAo=0.4
xBo=0.6
xCo=0

1 Plot coordinate Lo and V2

2 Find M coordinate
3 Overall balance Lo + V2 = L1 + V1 = M
400 + 400 =M =800

balance on A Lo xAo+ V2yA2 = MXAM

(400x0.4) + (400x0) =800XAM
XAM = 0.2
balance on c Lo xco+ V2yc2 = MXcM
(400x0) + (400x1) =800XcM
XcM = 0.5

M coordinate (0.2,0.3,0.5), make sure this point align with Lo-V2 line 21
 V2 (0,0,1) = (yA2, yA2 yC2)

Answer (i) V1 (yA1, yB1 yC1)

L1-V1 line is drawn through point M M(0.2,0.3,0.5) = (xAM, xCM xCM)

by trial and error
L1 (xA1, xB1 xC1)

V1 = (0.14,0.05,0.81) M
L1 = (0.29,0.68,0.03) L0(0.4,0.6,0) = (xA0, xB0, xC0)

Answer (ii)

V1 = 480 kg/h
L1 = 320 kg/h

Answer (iii)

% Removal=LoXAo-L1XA1 x100%=42%
LoXAo
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 4.3 MULTIPLE STAGES OF LLE
4.3 .1 PARTIALLY IMMICIBLE SYSTEM
Figure 4.3.1 : Schematic
diagram of counter-current
multistages LLE

- The material balance for the diagram’s boundary in Fig 4.3.1 can be written as:-
Overall mass balance : LO + VN+1 = LN + V1 = M ……(4.4)
Mass balance on comp. A : LOxAO + VN+1yAN+1 = LNxAN + V1yA1 = MxAM ……(4.5)
Mass balance on comp. C : LOxCO + VN+1yCN+1 = LNxCN + V1yC1 = MxCM …..(4.6)
- Determination of LN and V1 flowrates will be as follows (Fig. 4.3.1 -a):-
i. Plot the ternary diagram of the system
ii. Calculate the M coordinate (xAM, xCM) by using eq (3.2 & 3.3) & locate the M coordinate accordingly on
the ternary diagram
iii. Locate the coordinates of VN+1 (yAN+1, yCN+1); LO (xAO, yCO) & LN (xAN,xCN). Coordinates of VN+1 & LN
must lie on the phase envelope/ boundary. Normally xAN (composition of solute at raffinate) will be
given.
iv. Plot line from LN to M → V1( yA1, yC1). V1 coordinate must lie on the phase boundary.
v. Finally calculate the LN and V1 flowrates value by substituting the respective value using eq.( 4.4 – 4.6)
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Determination of no of theoretical (graphical method) will be as follows (Fig. 4.3.1):-
i. Find  reference coordinate. It is interception point between 2 operating lines:-
a) LO & V1 - Initial
b) LN & VN+1 - Final
ii. Start iteration from V1 to equilibrium diagram then back to ternary diagram to give L1 coordinate.
iii. Draw tie line from V1 to L1 → 1 stage
iv. Continue iteration from L1 to  reference coordinate to give V2 → 2nd operating line
v. Continue the same procedure until the tie line intercept the final operating line.
vi. Finally, calculate the quantity of tie line in the diagram which represent the no of theoretical stages.

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EXERCISE 4.2
An aqueous feed of 200 kg/h containing 40 wt % acetic acid is being extracted by pure isopropyl ether
at the rate of 600 kg/h in a countercurrent multistage system. The exit acid concentration in the
aqueous phase is to contain 10 wt % acetic acid. The equilibrium data is provided in the appendix.
Determine:
i. Schematic diagram of the system
ii. Construct the ternary phase diagram and equilibrium diagram for acetic acid (A)-water(B)-
isopropyl ether(C) system by using the given equilibrium data.
iii. The compositions of the extract and raffinate.
(V1 (0.1,0.03, 0.87), Ln(0.1, 0.88, 0.02)
iv. The amounts of the extract and raffinate
(V1: 663.63 kg/h, Ln:136.36 kg/h)
v. Percentage of the acetic acid is being removed from the system.
82.9% .
vi. The number of theoretical stages
(2.2-2.56)

M (0.1, 0.15, 0.75)

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 V1 VN+1
Lo 1 N
LN

1. Plot the ternary diagram of the system

2. Locate the coordinates of LO, VN+1, & LN (must lie on the equilibrium curve).

3. Calculate the M coordinate (xAM, xCM)

4. Plot line from LN to M → V1 is located at the intersection of line LN-M with the
phase boundary
5. Line LoV1 and LNVN+1 are drawn and the intersection is the operating line ∆
6. From V1 find the L1 ( using 45 line or tie line)

7. Line L1∆ is next drawn locating V2

8. From V2 find the L2 ( using 45 line or tie line)

9. Line L2∆ is next drawn locating V3

10. Stop when you get L is over the LN

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 C V1 VN+1
1. Plot the ternary diagram of the system Lo 1 N
Vn+1 LN
2. Locate the coordinates of LO, VN+1, &
LN (must lie on the equilibrium curve). V2

V1
3. Plot line from Lo to VN+1

4. Calculate the M coordinate (xAM, xCM), m

where M point located at line Lo VN+1

5. Plot line from LN to M → V1 is located

at the intersection of line LN-M with the
phase boundary L2
B L1 A
6. Line LoV1 and LNVN+1 are drawn and LN Lo
the intersection is the operating line ∆

7. From V1 find the L1 ( using 45 line or

tie line)

8. Line L1∆ is next drawn locating V2

9. From V2 find the L2 ( using 45 line or tie

line)

10. Line L2∆ is next drawn locating V3

11. Stop when you get L is over the LN

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3.3 LLE FOR IMMISCIBLE SOLVENT

Figure 3.3.1 : Schematic diagram of counter-current multistages LLE

for immiscible liquid

- For the immiscible LLE, the material balance for the diagram’s boundary in Fig 3.3 can be written as:-

xAO yAN+1 xAN yA1

L’ 1 - xAO + V’ 1-y = L’ 1 - x + V’ 1- y ……(3.4)
AN+1 AN A1

OPERATING LINE
Where;
L’ = kg inert B/ h
V’ = kg inert C/ h

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- No. of theoretical stages are determine through the graphical method ( Fig. 3.3.2) from:-
i. Equilibrium line
ii. Operating line

yA1

yAN+1

xAN xo
Figure 4.3.2 : Graphical method for immiscible LLE
- Refer to example 12.7- 3 (P796) for further understanding.

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 3.4 LIQUID-LIQUID EXTRACTION (LLE) EQUIPMENT
- 2 main classes of LLE equipment:-
a) Vessels in which mechanical agitation is provided for mixing
b) Vessels in which the mixing is done by the flow of the fluid themselves
- Both classes can be operated in batch or continuous.

Figure 3.4.1 (a) Compartmented mixing Figure 3.4.1(b) Horizontal gravity-settling vessel.
vessel with variable-speed turbine agitators
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(a) Scheibel column-first design (b) Scheibel column-second design

(c) Scheibel column-third design

(d) Oldshue-Rushton (Mixco) column (e) Rotating-disk-contactor (RDC)

Figure 3.4.2 Commercial extractors with mechanical assisted agitation
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CHE 347/ 251: UNIT OPERATIONS
(CHAPTER 3 )
 Extraction equipment
Batch: Continuous:

single-stage: column:

separatory funnel

mixer-settler
rotating-disk contacter
a. agitator; b. stator disk
Table 3.4.1: Advantages and Disadvantages of Different LLE Equipments

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(CHAPTER 3 ) 33
The End

TQ
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