Liquid-Liquid Extraction

One or more solutes are removed from a liquid by transferring into a

second liquid phase (solvent).

The solvent is a mass separating agent which normally must be

recovered later.

For LL extraction to work, the two liquid phases must be immiscible

or partially miscible.

Has the advantages of low temperature operation (since no

vaporization is required). Good for temperature sensitive materials
 Liquid-Liquid Extraction Equipment

Complete extraction process includes extraction unit and solvent recovery.

Often the recovery process is the more expensive step (e.g. distillation)
 Liquid-Liquid
Extraction Equipment
Compared with distillation, absorption and
stripping, a wide variety of equipment is
used for liquid-liquid extraction.

Heuristics:

1. If one or two equilibrium stages are

required, use mixer-settlers
2. If three equilibrium stages are required,
use mixer-settler, sieve tray column,
packed column or membrane contactor
3. If four or five are required, use sieve tray
column, packed column or membrane
contactor
4. For more than five stages, use a system
that applies mechanical energy (e.g.
rotating disk contactor)
 Liquid-Liquid Extraction Equipment
Solvent selection is critical for the design of an economical
extraction process

Solvent should be:

- Immiscible or partially miscible with process liquid

- Highly selective for solute and not for contaminants
- Non-toxic
- Non-corrosive
- Readily available
- Chemically stable
- Environmentally friendly
- Inexpensive

Solubility parameter is a simple approach for selecting solvents

with high selectivities:
1/ 2
 (Ev ) i  Latent heat of vaporization Liquids with close d values are
i    likely to be miscible
 Vi  Molal volume
 Counter-current extraction

Mass balance envelope for countercurrent cascade

- Most common arrangement for liquid-liquid extraction

- Liquids flow in opposite directions
- Each stage assumed to be an equilibrium stage, i.e. liquids leaving the
stage are in equilibrium
- Solvent (S) is used to extract solute (A) from the diluent (D)
- Stream with high concentration of solute is called the extract (E)
- Stream with high concentration of diluent is called the raffinate (R)
 McCabe-Thiele Method for Dilute Systems
Approach is very similar to dilute systems for absorption/stripping.

We assume:
1. System is isothermal
2. System is isobaric
3. Heat of mixing is negligible
4. Diluent and solvent are totally immiscible

FD  diluent flow rate, kg D/h  constant

FS  solvent flow rate, kg S/h  constant

These are flowrates of diluent and solvent, not total raffinate and extract.
However, in dilute systems, we can assume:
R  FD  const

E  FS  const
 McCabe-Thiele Method for Dilute Systems

The mass balance on the above envelope then becomes:

Ey j 1  Rx0  Ey 1  Rx j

Solving for yj+1 we get:

y j 1  (R/E)x j  [y1  (R/E)x0 ]

Since R/E is assumed to be constant, this plots as a straight line on a y

vs x graph.

Equilibrium data for dilute systems are normally represented as a

distribution ration, Kd: yA
Kd 
xA
McCabe-Thiele Method for Dilute Systems
For very dilute systems, Kd will be constant

At higher concentrations, Kd often becomes a function of concentration.

 McCabe-Thiele Method for Dilute Systems
Example
A feed of 100.0 kg/min of a 1.2 wt% mixture of acetic acid in water is to
be extracted with 1-butanol at 1 atm pressure and 26.7 oC. We desire an
outlet concentration of 0.1 wt% acetic acid in the exiting water. We have
available solvent stream 1 that is 44.0 kg/min of pure 1-butanol and
solvent stream 2 that is 30.0 kg/min of 1-butanol that contains 0.4 wt%
acetic acid. Devise a scheme to do this separation, find the outlet flow
rate and concentration of the exiting 1-butanol phase, and find the
number of equilibrium contacts needed.

Equilibrium data can be found in Table 13.3: y = 1.613 x

where y and x are acetic acid weight fractions in the solvent and diluent
phases, respectively.

Since mixing is the opposite of separation, it is best to keep the two feed
streams separate, with the pure solvent going in at the bottom and
solvent stream 2 going in at the middle.
 McCabe-Thiele Method for Dilute Systems
Balance on bottom of
extractor gives:
𝑅
𝐸 ( 𝑅
𝑦 = 𝑥 + 𝑦 𝑁 +1 − 𝑥 𝑁
𝐸 )
slope = = 100/44 = 2.273

and goes through point:

(0.001, 0)

Operating line for top of extractor:

𝑦=
𝑅
𝐸 ( 𝑅
𝑥 + 𝑦1 − 𝑥0
𝐸 ) slope = R/E = E/(E1+E2) = 100/(44+30)=1.35

and goes through point: (x0,y1)

McCabe-Thiele Method for Dilute Systems

We can find y1 from overall mass balance:

𝑅 𝑥 0 +𝐸1 𝑦 1 +𝐸 2 𝑦 2=𝑅 𝑥 𝑁 +𝐸 𝑦 1
(100)(0.012) + (44)(0) + (30)(0.004) = (100)(0.001) +(74)y 1
y1 = 0.01649
 McCabe-Thiele Method for Dilute Systems

The two operating lines intersect at the feed line, y = y solvent2 = 0.004

Substituting this into the bottom op. line gives xintersection = 0.00276

Stepping off stages from x = 0.001 gives 12 equilibrium contacts.

 Single-stage and cross-flow extraction

Counter-current is most common but occasionally can use croos-flow

Fresh extract streams are added to each stage

Extract product is removed
Prof. Adnan Alharahsheh CHE306 14
5 assumptions see for countercurrent case are also taken here

can use the McCabe-Thiele analysis

Prof. Adnan Alharahsheh CHE306 15

Mass balance around a single stage

Operating line is a straight line

Slope=-R/Ej (each stage will have a different operating line)

Intercept=(xj-1 *R/Ej + yj,in)

Prof. Adnan Alharahsheh CHE306 16

Two outlet streams are in equilibrium and on the operating line

Prof. Adnan Alharahsheh CHE306 17

 Extraction Equilibrium for Partially Miscible
Ternary Systems
All systems are partially miscible. When miscibility is very low, we can
assume immiscibility which means solvent and diluent flow rates constant
remain constant.

In reality, miscibility is often significant enough to require solving via a

method that allows for variable flow rates.

Ternary system equilibria can

be shown on a triangular graph.

Here is the acetone-chloroform-

water ternary system:
Mixing Calculations and the Lever Arm Rule

For the mixing operation shown, the flow rates F1 and F2 would be
given as well as the concentration of the two feeds, x A,F1, xD,F1, xA,F2 and
xD,F2.

We need to solve for 3 unknowns (M, xA,M and xA,D) so we need three
independent balances:
F1  F2  M

F1x A, F1  F2 x A, F2  Mx A, M

F1x D, F1  F2 x D, F2  Mx D, M
Mixing Calculations and the Lever Arm Rule

The concentrations of the mixed stream M are:

F1x A, F1  F2 x A, F2
x A, M 
F1  F2

F1x D, F1  F2 x D, F2
x D, M 
F1  F2

It can be shown (see textbook) that F1, F2 and M all lie along a straight
line on the triangular graph. This is called the lever-arm rule and is
useful for solving mixing problems.
Mixing Calculations and the Lever Arm Rule
Distance from F1 to M distance from M to F2

Distance from F1 to A distance from M to B

therefore

MF2 MB x D, M  x D, F2
 
F1M F1A x D, F1  x D, M

With some manipulation and combining

with the balance equations, this
becomes:

F1 MF2
 Lever-arm rule
F2 F1M
 Partially Miscible Single-Stage and Cross-
Flow Systems
Example
A solvent stream containing 10% by weight acetone and 90% by
weight chloroform is used to extract acetone from a feed containing 55
wt% acetone and 5% chloroform with the remainder being water. The
feed rate is 250 kg/h, while the solvent rate is 400 kg/h. Operation is at
25 oC and atmospheric pressure. Find the extract and raffinate
compositions and flow rates when one equilibrium stage is used for the
separation.

yA,S = 0.1
yS,S = 0.9 S = 400 xA,E
yD,S = 0 xD,E
xA,R
F = 250 xD,R
xA,F = 0.55
xS,F = 0.05
xD,F = 0.55
 Partially Miscible Single-Stage and Cross-
Flow Systems
Need equilibrium data for acetone-chloroform-water (obtained from
Table 13-4 and Figure 13-12)

Plot streams F and S

Find M from lever-arm rule

𝐹 𝑆𝑀 250
= = =0.385
𝑀 𝐹𝑆 250+ 400

or

Fx A,F  Sx A,S (250)(0.55)  400(0.1)

x A,M    0.273
F S 650
Partially Miscible Single-Stage and Cross-
Flow Systems
Next, construct a tie line through M by
trial and error.

The end points represent E and R

compositions.

Therefore: yA,E = 0.3

yD,E = 0.02
and
xA,R = 0.16
xD,R = 0.83

From mass balances: M = E + R

And MxA,M = EyA,E + RxA,R