Professional Documents
Culture Documents
09 Liquid Liquid Extraction PDF
09 Liquid Liquid Extraction PDF
1
Examples of the uses of extraction are
The separation of penicillin from the
broth (the liquid phase obtained from
biological processes)
The separation of aromatic-ring hydro-
carbons (e.g., benzene, toluene) from
paraffins using sulpholane
2
Figure 9.1: A schematic diagram of a complete
liquid-liquid extraction process
(from “Separation Process Engineering” by Wankat, 2007)
4
Figure 9.2: Examples of extraction equipment
(from “Separation Process Engineering” by Wankat, 2007)
5
One of the most common types of extraction
is the counter-current system, depicted schema-
tically in Figure 9.3
6
In Figure 9.3, the raffinate phase consisting
of the solute A and the diluent D is fed into the
system from the right hand side (RHS), with
the total flow rate of Ro (or R ) and the concen-
tration (in mole or mass fraction of the solute)
of xo ; note that the flow rate of just the diluent
is FD
7
The raffinate phase exits the extraction sys-
tem with the concentration of the solute of x N ,
while the extract phase leaves the system with
the concentration of y1
8
However, for the dilute extraction system
(i.e. the extraction system in which the concen-
tration of the solute is low), we can assume that
R » FD
E » FS
Note that
R = raffinate flow rate
E = extract flow rate
FD = diluent flow rate
FS = solvent flow rate
9
In order to be able to use the McCabe-
Thiele approach for the extraction operation,
the following assumptions must be satisfied:
The system is isothermal
The system is isobaric
The heat of mixing is negligible
The diluent and the solvent are immiscible
10
Re-arranging Eq. 9.1 to obtain the opera-
ting equation for the extraction process yields
R æ R ö÷
y j +1 ç
= x j + çy1 - x o ÷÷ (9.2)
E çè E ÷ø
11
The equilibrium equation for the extraction
can be expressed as
yA
Kd =
xA
or
yA = Kd x A (9.3)
where Kd is the “distribution ratio”
12
Generally, the solvent should
be able to dissolve the solute more than
the diluent
be immiscible to the diluent
be highly selective for the desired solute
not be selective for contaminants
Kd
have a high value of a = desired
and
Kd
undesired
Kd
desired
13
Additionally, the solvent should also be
non-toxic
non-reactive or chemically stable
non-corrosive
non-flammable or non-explosive
readily available
inexpensive
environmentally friendly (i.e. “green”)
14
Example A feed of 100 kg/min of 1.2 wt% mix-
ture of acetic acid in water is to be extracted
with 1-butanol at 1 atm and 26.7 oC
The desired outlet concentration in the exiting
stream is 0.1 wt% of acetic acid
The solvent of pure 1-butanol is fed conter-
currently to the feed with the flow rate of 75
kg/min
Determine the composition of the exiting
1-butanol phase (i.e. the extract phase)
Also find the number of equilibrium contacts
(stages) needed
15
In this case,
the inlet concentration of the feed
(raffinate phase) is given as 1.2 wt% of
acetic acid (or xo = 0.012 )
the outlet concentration of the raffinate
phase is given as 0.1 wt% of acetic acid (or
x N = 0.001)
16
75
17
100 é æ100 ö ù
0= ( 0.001) + êy1 - çç ÷
÷ ( 0.012 )ú
75 ê çè 75 ÷÷ø ú
ë û
y1 = 0.015
( ) (
x N , yN +1 = 0.001, 0 )
(x , y ) = (0.012, 0.015)
o 1
19
0.025
0.020
0.015
yacetic acid
0.010
0.005
0.000
0.000 0.002 0.004 0.006 0.008 0.010 0.012 0.014
xacetic acid
20
9.2 Immiscible Single-stage and Cross-flow
Extraction
21
In this type of cascade, a fresh solvent (or
an extract stream) is fed to each stage
R æR ö
ç ÷÷
ç
y j = - x j + ç x j -1 + y j , in ÷ (9.6)
Ej çè E j ÷÷ø
22
which is the operating line for stage j of the
R
cross-flow extraction, with the slope of -
Ej
(x , y )
j j
23
Thus, one co-ordinate of the operating line is
( ) (
the point x j -1, y j , in or x j , y j +1, in )
The McCabe-Thiele diagram for the cross-
flow extraction can be depicted as Figure 9.5
24
Figure 9.5: The McCabe-Thiele diagram for the
cross-flow extraction
(from “Separation Process Engineering” by Wankat, 2007)
25
Example We want to extract a dilute solution
of the protein (or enzyme) alcohol dehydroge-
nase from an aqueous solution of 5 wt% poly-
ethylene glycol (PEG) with an aqueous solution
of 10 wt% dextran
The entering dextran solution contains no
protein, and the PEG solution has a flow rate
of 20 kg/h
Assume that the two aqueous phases are
immiscible; note that the dextran solution is
denser than the PEG solution
Determine the following:
a) If 10 kg/h of dextran is added to a
single-stage extractor, find the total
recovery fraction of alcohol dehydro-
genase in the dextran-solvent phase
26
b) If 10 kg/h is dextran is added to each
stage of a cross-flow cascade with 2
stages, find the total recovery
fraction of alcohol dehydrogenase in the
dextran solvent
Given the protein distribution coefficient as
(wt. fraction of protein in PEG, x )
K= = 0.12
(wt. fraction of protein in dextran, y )
27
The initial (inlet) amount of solute in the
raffinate phase is Rxo
28
Since the flow rate of the raffinate phase is
assumed to be constant (for the dilute immisci-
ble extraction), the total recovery faction can
be reduced to
xN
1-
xo
29
The equilibrium relationship is given as
x
K= = 0.12 (9.7)
y
and an equilibrium equation can be written as
follows (by re-arranging Eq. 9.7)
30
x
y= = 8.33x (9.8)
0.12
31
Unknowns:
xF
xz
y1, out
Eq. 9.6:
R æR ö
ç ÷
y j = - x j + çç x j -1 + y j , in ÷÷ (9.6)
Ej çè E j ÷÷ø
32
R æR ö
y1, out ç ÷
= - x z + çç x F + y in ÷÷ (9.9)
E1 çè E1 ÷ø
or
y = -2x + 2x F (9.10)
33
Drawing a straight line between the point
(x F
, 0) and the point (0, 2x F )
(x , y ) in this Example
z 1, out
34
8.33x + 2x = 2x F
10.33x = 2x F
x = x z = 0.194x F
35
(b) When both stages 1 and 2 are operated
36
The operating equation for stage 2 can be
written as follows
R æR ö
y2, out = - x 2 + çç x z + y in ÷÷÷
ç (9.12)
E2 çè E2 ÷ø
(0, 0.388x ) F
38
Solving for x yields
8.33x + 2x = 0.388x F
10.33x = 0.388x F
x = x 2 = 0.0376x F
39
9.3 Concentrated Immiscible Extraction
40
Accordingly, mole or mass fractions in both
raffinate (x i ) and extract (yi ) phases can be
used for species balance, as described and illus-
trated in the previous sections
41
To enable the mass or mole balance,
the flow rate of the raffinate phase (R )
must be replaced by the flow rate of the
diluent (FD )
the flow rate of the solvent (FS ) must be
used in lieu of the flow rate of the extract
phase
42
xi
Xi = (9.16)
1 - xi
yi
Yi = (9.17)
1 - yi
and the species balance (e.g., Eqs. 9.1 and 9.5)
and the operating-line equations (e.g., Eqs. 9.2
and 9.6) can be written as follows
FSYj +1 + FD Xo = FSY1 + FD X j
(9.18)
FD X j -1 + FS Yj , in = FD X j + FS Yj
j j
(9.19)
and
FD æ F ö
Yj +1 = X j + çççY1 - D Xo ÷÷÷ (9.20)
FS çè FS ÷ø
FD
(note that the slope for the operating line is )
FS
43
æ ö
FD çç FD ÷÷
Yj = - Xj + ç X j -1 + Yj , in ÷÷
FS çç F ÷÷ø
j è S j
(9.21)
FD
(note that the slope for the operating line is - )
FS
j
44
However, all extraction systems are, in fact,
partially miscible to some degree, and when the
miscibility is not negligible, the analysis using
the McCabe-Thiele approach is no longer appro-
priate (if we try to do so, it would not yield an
answer with an acceptable accuracy)
45
When a system consists of 3 components (or
species), mass (or mole) fraction of each com-
ponent/species can be shown as a three-compo-
nent diagram, which can be presented in the
form of
equilateral triangle, or
right triangle
demonstrated in the following Example
46
Example A liquid mixture of A, B, and C has
the mass fraction of A and B (at equilibrium)
at 25 oC as follows:
yA = 0.40
yB = 0.30
Locate the exact point of this mixture in a tree-
component diagram
47
Since this is a 3-component diagram, only 2
specified component is sufficient to locate the
exact point on the diagram
48
B
0.0 1.0
0.1 0.9
0.2 0.8
0.3 0.7
0.4 0.6
0.5 0.5
0.6 0.4
0.7 A yB =
0.3
0.8 0.2 0.30
0.9 0.1
1.0 0.0
C 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 A
yA = 0.40
49
B
0.9
0.8
0.7
0.6
0.5
0.4
A
0.3
yB =
0.2
0.30
0.1
yA = 0.40
Exercises
Try locating the following points yourself
1) yA = 0.40, yC = 0.60 Point P
2) yA = 0.20, yB = 0.50 Point Q
3) yB = 0.25, yC = 0.35 Point R
50
Let’s consider a simple liquid-liquid extrac-
tion (LLE) system below
A+B
51
could be divided into 2 phases as shown
below
C+B+A
A+B+C
53
Table 9.1: Equilibrium data for the water-chloro-
form-acetone system
Water phase Chloroform phase
(Raffinate phase) (Extract phase)
xD xS xA yD yS yA
Water Chloroform acetone Water Chloroform acetone
99.2 0.8 0 0.5 99.5 0
83.0 1.2 15.8 1.3 70.0 28.7
73.1 1.3 25.6 2.2 55.7 42.1
62.3 1.7 36.0 4.4 42.9 52.7
45.6 5.1 49.3 10.3 28.4 61.3
34.5 9.8 55.7 18.6 20.4 61.0
54
B
0.0 1.0
0.1 0.9
0.2 0.8
0.3 0.7
0.4 0.6
0.5 0.5
0.6 P 0.4
0.7 0.3
0.8 M 0.2
0.9 0.1
1.0 0.0
A 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 C
Tie line
Overall composition
of the mixture
55
Note that Point M is the composition of the
mixture of the raffinate phase and the extract
phase for a given tie-line (will be discussed in
detail later)
56
The composition in each phase for a given
point M is dictated by a tie-line
57
Point P in Figure 9.6 is the “plait point”,
which is the point where the composition in the
raffinate phase is equal to that of the extract
phase (note that the plait point is NOT neces-
sary to be the highest point of the solubility
curve)
58
R as the point on the raffinate phase and
the mass of the raffinate phase
E as the point on the extract phase and
the mass of the extract phase
M as the composition of the mixture and
the mass of the mixture
Thus,
R +E = M (9.22)
59
x B R + yB E = z B M (9.23)
x AR + yAE = z AM (9.24)
which can be re-arranged to
x B R + yB E x B R + yB E
zB = =
M R +E
(9.25)
x AR + yAE x AR + yAE
zA = =
M R +E
(9.26)
60
x B R + yB E = z B (R + E ) (9.27)
x AR + yAE = z A (R + E ) (9.28)
which can be re-arranged to
R (yB - z B )
= (9.29)
E (z B - x B )
R (yA - z A )
= (9.30)
E (z A - x A )
Since
yA - z A or yB - z B is the distance between
Point M and Point E (i.e. the distance
ME)
z A - x A or z B - x B is the distance between
Point R and Point M (i.e. the distance
RM)
Eqs 9.29 and 9.30 can be written as follows
61
R ME
= (9.31)
E RM
62
The values of R (the amount of the raffinate
phase) and E (the amount of the extract phase),
and the location of point M can be obtained by
measuring (using a ruler) the distance RE, RM,
and/or ME
63
Example Referring to the 3-component diagram
in Figure 9.6 on Page 55, if 30,000 kg/h of ter-
nary mixture of 40 wt% of A, 20% of B, and
40% of C was fed into a decanter (a mixer and
settler) operating at 25 oC, what would the flow
rates of two liquid streams leaving the decanter
be?
R kg/h
A = ?%
B = ?%
C = ?%
30,000 kg/h
A = 40%
B = 20%
C = 40%
E kg/h
A = ?? %
B = ?? %
C = ?? %
64
By employing the diagram, Point M, with
the composition of z A = 0.40 , z B = 0.20 , and
zC = 0.40 is located
B
0.0 1.0 Given overall
0.1 component
0.9
0.2 0.8
0.3 0.7
0.4 0.6
Raffinate Extract
0.5 0.5
Phase Phase
0.6 0.4
0.7 0.3
0.8 0.2
0.9 0.1
1.0
A 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 C
65
Raffinate Phase Extract Phase
A = 78% (x A = 0.78) A = 17% (yA = 0.17 )
B = 13% (x B = 0.13) B = 24% (yB = 0.24)
C = 9% (xC = 0.09) C = 59% (yC = 0.59)
Basis 1 h of operation
Overall Balance
30,000 = R + E (9.34)
66
Solving Eqs. 9.34 and 9.35 simultaneously
gives
E = 19,091 kg
R = 10,909 kg
67
Note that the trial & error technique is com-
monly employed to solve an extraction problem,
especially for a single-stage extraction
68
Consider the counter-current liquid-liquid
extraction cascade with N equilibrium stages in
Figure 9.7
69
The raffinate stream leaves stage j with the
flow rate of Rj and the solute concentration of
x A , and, finally, exits the system with the flow
j
yA
N +1
70
yD
N +1
xA
N
yA
1
yD
1
(9.37)
yD S + x D F = yD E1 + x D RN
N +1 o 1 N
(9.38)
71
Since we have 5 unknowns, but we have only
3 independent equations, we need another 2
equations
(9.40)
yD S + x D F = z D M = yD E1 + x D RN
N +1 o M 1 N
(9.41)
73
Since x i and yi are known (normally given
o N +1
computed as follows
yA S + x A F yA S + x A F
zA = N +1 o
= N +1 o
M
M S +F
(9.42)
yD S + x D F yD S + x D F
zD = N +1 o
= N +1 o
M
M S +F
(9.43)
Hence,
the composition of the feed can be speci-
fied (Point F – see Figure 9.8)
the composition of the solvent can be
specified (Point S – see Figure 9.8)
74
Point M can be located (since z A and
M
and 9.43)
75
From the explanation above and from Eqs.
9.39-9.41, we obtain the facts that
Points E1 and RN must be on the extract-
phase curve and the raffinate-phase curve,
respectively
A straight line E1RN must pass through
Point M
the diagram)
77
In Figure 9.7 (on Page 69),
streams E2 and R1 passes through each
other
streams E 3 and R2 passes through each
other
streams S and RN passes through each
other
78
The difference of F - E1 (or D ) can be illus-
trated graphically by drawing a line passing
through Points E1 and F
The difference of RN - S (= F - E1 = D)
can be also depicted by drawing a line that
passes through Points S and RN
79
F = E1 + P (9.47)
80
These two lines are the operating lines, and
the meeting point (Point P) is called the opera-
ting point
81
In Figure 9.9, Point E1 is not on a tie-line;
however, we can draw the tie-line that passes
through Point E1 by interpolating from the
nearest two tie-lines
82
Figure 9.10: The determination of equilibrium
stages for a partially miscible extraction system
(from “Separation Process Principles” by Henley, Seader, and Roper, 2011)
83
We then use Points P and R2 to get Point
E 3 on the extract-phase curve
84
æS ö
the solvent-to-feed çç ÷÷÷ ratio is higher
çè F ÷ø
S
The minimum ratio leads to the infinity
F
S
(¥) number of stages, while the maximum F
ratio results in the fact that no raffinate phase is
formed (will be explained in detail later)
85
In the distillation, gas absorption, and strip-
L
ping operations, minimum (or minimum reflux
V
L
ratio: in the distillation operation) occurs when
D
the operating line touches or intersects with the
equilibrium line
86
E1
S
Figure 9.11: Determination of the minimum
F
ratio
(from “Separation Process Principles” by Henley, Seader, and Roper, 2011)
87
Accordingly, the line P1F is the operating line
S
used for determining the minimum ratio
F
z A (S + F ) = yA S min + x A F (9.50)
M S F
88
The readings from Figure 9.11 are:
x A = 0.28 (28%)
F
yA = 0 (0%)
S
z A = 0.22 (22%)
M
S min
which yields the ratio of
F
S min 0.28 - 0.22
= = 0.27
F 0.22 - 0
S min
The calculation for the ratio is similar to
F
the case when the slope of the tie-line is downward
toward the raffinate side
S
For the maximum ratio, consider Figure
F
9.8 (on Page 75)
S max
=
xA - zA
F
( ) M max
(9.52)
F (z )
AM
max
- yA
S
S S min
The operating must be between and
F F
S max S
; normally, the optimal is approximately
F F
æS ö
1.5 ççç min ÷÷÷
çè F ÷ø
91
Example Acetone is to be extracted from a
mixture of 30 wt% acetone + 70% ethyl acetate
at 30 oC using pure water as a solvent
The final raffinate contains no higher than 5%
of acetone on the water-free basis
S
Determine the minimum and maximum
F
ratios, as well as the number of equilibrium stages
S
required for two intermediate ratios between
F
S
the minimum and maximum ratios
F
92
Figure A
(from “Separation Process Principles” by Henley, Seader, and Roper, 2011)
93
Figure B
(from “Separation Process Principles” by Henley, Seader, and Roper, 2011)
94
The final raffinate contains 5% of acetone
on the water-free basis, which is Point B
on the line AC (at Point B, the concentra-
tion of acetone is 5% and the concentration
of water is 0%–water-free ), which corres-
ponds to Point RN of 4% (or 0.04 mole
fraction) [i.e. Point B ¢ in Figures A and B]
S
The minimum ratio takes place when the
F
tie-line that starts from Point F is extended to
the point on the extended SB ¢ line that is closest
to Point S , and Point E1 on the extract-phase
¢ in Figure B)
curve is then obtained (= Point Dmin
95
¢ B ¢ (or
Subsequently, the lines SF and Dmin
E1RN ) can be drawn, and Point M min is obtained;
at this point, z A is read as 19% (or 0.19 mole
M
fraction)
S
Accordingly, the minimum ratio can be com-
F
puted as follows
S min xA - zA 0.30 - 0.19
= F M
= = 0.58
F z A - yA 0.19 - 0
M S
S
The maximum ratio is obtained when Point
F
M reaches the extract-phase curve, which gives
S max
( )
the value of z A
M max
of 4% or 0.04, and the
F
can then be calculated as follows
96
S max
=
xA - zA
F
( ) M max
=
0.3 - 0.03
F (z )AM
max
- yA
S
0.03 - 0
S max
= 9.0
F
S
Hence, the operating ratio must be between
F
0.58-9.0
S
Choose the ratio of 1.75 (or S = 1.75F ) as
F
S
the operating ratio, which results in Point M
F
with the concentration of acetone (solute) of
yA S + x A F yA S + x A F
zA = S F
= S F
M
M S +F
(0)(1.75F ) + (0.3)(F ) 0.3F
zA = = = 0.11
M
(1.75F ) + (F ) 2.75F
97
and the concentration of ethyl acetate (diluent)
of
yD S + x D F yD S + x D F
zD = S F
= S F
M
M S +F
(0)(1.75F ) + (0.7)(F ) 0.7F
zD = = = 0.25
M
(1.75F ) + (F ) 2.75F
98
When Point E1 (or Point D ¢ is located) the
line FE1 (or FD ¢ ) and the line SRN (or SB ¢ )
can then be drawn and extended to the LHS of
the diagram; these 2 lines meet at Point P
99
Performing this iteration (ทําซ้ําไป-มาแบบนี้)
until we reach Point RN , and the number of
equilibrium stages is eventually obtained
S
For the case of the ratio of 1.75, the num-
F
ber of stages was found to be 4
S
Try doing it yourself for the ratio of 3.0
F
(the number of stages is 2)
100