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LIQUID EXTRACTION
CHAPTER / CONTENT
Definition & Application
Solvent selectivity
LLE for Partially Miscible Solvent
Solvent
Diluent
Carrier liquid
(denoted by component B)
Extract
Raffinate -
methylacrylate
from
organic
solution
with
Examples:
Extraction of methanol from LPG with water
Extraction of chloroacetic acid from methylchloroacetate with water.
The difference between LLE and distillation process in the separation of
liquid mixtures:
LLE depends on solubilities between the liquid components and
produces new solution which in turn has to be separated again,
whereas;
Solvent selectivity
The solvent is the key to a successful separation by LLE. The several criteria:
Distribution Coefficient.
This is the ratio (at equilibrium) of the concentration of solute in the
extract and raffinate phases. It gives a measure of the affinity of the solute
for the two phases.
A distribution coefficient other than unity implies that the solute must
have different affinity in the two phases. If only one solute is involved
(such as in the recovery of an impurity from an effluent stream), only the
distribution coefficient need to be considered, and it is desirable for this to
be as large as possible.
Solvent selectivity
Selectivity (Separation factor).
If there are more than one solutes (sat two solutes A and B), then
consideration should be given to the selectivity of the solvent for solutes A
against B.
The selectivity between two solutes A and B is defined as the ratio of
the distribution coefficient of A to the distribution coefficient of B. For all
useful extraction operation the selectivity must exceed unity. If the
selectivity is unity, no separation is possible.
Insolubility of Solvent.
The solvent should have low solubility in the feed solution, otherwise
the separation is not clean. For example, if there is significant solubility
of solvent in the raffinate stream, an additional separation step is required
to recover the solvent.
Solvent selectivity
Recoverability.
It is always necessary to recover the solvent for re-use, and this must
ordinarily be done by other means, e.g distillation. If distillation is to be
used, the solvent should form no azeotrope with the extracted solute and
mixtures should show high relative volatility. The solvent should also be
thermally stable under the distillation temperature.
Density.
A large difference in density between extract and raffinate phases
permits high capacities in equipment. This is especially important for
extraction devices utilizing gravity for phase separation.
Solvent selectivity
Interfacial tension.
The larger the interfacial tension, the more readily coalescence of
emulsions will occur but the more difficult the dispersion of one liquid in
the other will be. The more readily coalesces the emulsions the easier
phase separation will be.
Low interfacial tension aids dispersion and thus improves contacting
mass transfer efficiency. Coalescence is usually of greater importance, and
interfacial tension should therefore high.
Chemical Reactivity.
The solvent should be stable chemically and inert toward the other
components of the system and toward the common materials of
construction.
Solvent selectivity
Viscosity, Vapor pressure, Freezing Point.
These should be low for ease in handling and storage, for example, a
high viscosity leads to difficulties with pumping, dispersion and mass
transfer rate.
Availability and Cost.
An excellent solvent may not commercially available. Or it may
represent a large initial cost for charging the system, and a heavy
continuing expense for replacing inevitable operating losses.
Other Criteria.
Toxicity and flammability of the solvent are important occupational
health and safety consideration.
Stability of the solvent (i.e resistance to breakdown), particularly in the
recovery steps, is significant, especially if the breakdown products might
contaminate the products of the main separation.
Liquid-Liquid Extraction
Extracting Solvent, S
Intermediate, M
ys (A)
Feed Solution, F
xM (A)
Raffinate phase, R
x* (A)
xF (A)
F
E
M
yS
x*
Extract phase, E
y* (A)
S
R
xF
xM
y*
Note: Intermediate shown just for purpose of demonstration. Dont have to draw it when
answering the question
Eq. (1)
Eq. (2)
Using the calculated value of xM, locate point M (xM) on the FS line. Note that
point M must be on FS line.
Draw a new tie line that pass through point M. This new tie line must take shape
of the nearest given tie lines.
From the new tie line, you can locate point E and R and hence you can
determine the composition of raffinate, R and extract, E that are in equilibrium.
FS RE
Eq. (3)
Eq. (4)
% EG
% water
% furfural
% EG
% water
% furfural
0.0
5.0
95.0
0.0
92.0
8.0
8.5
4.5
87.0
2.0
89.6
8.4
14.5
4.5
81.0
5.5
86.0
8.5
21.0
6.0
73.0
7.0
84.4
8.6
29.0
7.0
64.0
8.0
83.3
8.7
42.0
8.5
49.5
14.0
77.2
8.8
50.0
14.0
36.0
31.0
60.0
9.0
51.0
33.0
16.0
51.0
33.0
16.0
S = 100 kg
xF=0.4
yS=0
FS M
100 100 M
M 200 kg
x M 0.2
Locate point F & S, draw line FS. Locate point xM on FS line. Draw new tie
line that pass through point xM. From that tie line, locate point E and R hence
you can determine the composition of R (x*) and E (y*) which is in equilibrium.
From the graph, y* = 0.26, x* = 0.075 (Solution for point 1)
F
M
R
F
E
M
R
100 100 R E
R 200 E
Eq. (i)
Normally numbering of the stages begin at the top down to the bottom.
Thus the top most stage is named as stage 1, stage directly below stage 1 is
stage 2 and so on.
Final extract, E
Feed solution, F
xF (A)
1
yE (A)
2
3
n
N-1
Extracting solvent, S
yS (A)
Final raffinate, R
XR (A)
Eq. (1)
Eq. (2)
Solute
Plait Point
E1
Feed
Operating Point
P
M
RN
S
Carrier
Solute
Plait Point
E1
E2
E3
E4
Feed
M
Operating Point
P
R1
E5
E6
RN
Carrier
Solvent C
Occurs when operating line touches the equilibrium curve at which the
separation requires infinite number of ideal stages.
Point M is dependent upon the solvent flow rate / amount. The larger the rate /
amount, the closer is point M to point S on the FS line.
xF = 0.30
RSF = 0.045
Emin
F
Mmin
RSF
S
yS = 0.015
Smin=1127.66 kg/h
S = 1409.58 kg/h
FS M
5300 1409.58 M
M 6409.58 kg
xM 0.24
E3
E4
E5
RSF
B kg diluent B in Raffinate
x kg A/kg diluent B
Solvent
N kg A in feed
S kg solvent C in Extract
y kg A/kg solvent C
y'
B
MN
x'
S
S
Eq. (3)
0.030
0.046
0.063
0.070
0.078
0.086
0.106
0.10
0.15
0.20
0.22
0.24
0.26
0.30
B = Water
C = Isopropyl ether
Feed solution
24.6 kg A
80 kg diluent B in Raffinate
x kg A/kg diluent B
Solvent
0 kg A in feed
The equilibrium data and equation above is plotted in figure next page.
From the intersection of lines, x = 0.062, y = 0.195
y'
0.2
0.15
0.1
0.05
0
0
0.02
0.04
0.06
0.08
x'
0.1
0.12
0.14
x2 kg A/kg pure B
1
2
3
n
N-1
N
xn kg A/kg pure B
The operating line equation for multi stage liquid liquid extraction:
y'
y' S x' 2 B
B
x' 2
S
S
Form of y = mx + c
Using the method similar to Mc Cabe Thiele diagram, the number of ideal
stages can be determined by drawing the triangular steps connecting equilibrium
line and the operating line.
0.000
0.025
0.050
0.100
0.150
0.200
0.220
0.240
0.260
0.300
y (kg acid/kg
isopropyl ether)
0.000
0.005
0.013
0.030
0.046
0.063
0.070
0.078
0.086
0.106
x2
y2
TOP (2)
BOTTOM (1)
20,000 kg/h isopropyl ether (C) in
y1
xF = 0.20
xBF = 0.80
S = 20,000 kg/h
Raffinate phase
x'1
A
A
B
A
A B 0.02
0.0204
B A B A B A B
B
0.98
y '1
0
0
20000
Extract
Mass of solute A = Mass of acid in Mass of acid in raffinate
Mass of solute A = 1600 - x1x B = 1600 0.0204 x 6400= 1469.44 kg/h
Mass of solvent C = 20 000 kg/h
1600
0.250
6400
y'2
1469 .44
0.0735
20000
B
S min
S min
B
m min
Example 5
Determine the minimum flow rate of isopropyl ether for the problem in
Example 4.
S min
B
0.8 8000
= 18 658.89 kg/h.
m min
0.343
2)
Vessels in which the mixing is done by the flow of the fluid themselves.
In figure 12.6 1(b) for combined mixer settler, sometimes used in extraction
of uranium salts or copper salts from aqueous solution.