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It is important to note that, in many applications, the downstream process that separates
solvent from the solute(s) is usually more expensive than the extraction operation itself
The raffinate phase exits the extraction system with the concentration of the solute of x N ,
while the extract phase leaves the system with
the concentration of y1
9.1 McCabe-Thiele Diagram for Dilute
Extraction Systems
In order to be able to use the McCabeThiele 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
(9.1)
Re-arranging Eq. 9.1 to obtain the operating equation for the extraction process yields
y j +1
R
R
= x j + y1 - x o
E
E
(9.2)
R
the slope for the operating line i.e. is
constant
The operating line can be plotted on the
McCabe-Thiele diagram, in which
x represents the concentration in the
raffinate phase
y represents the concentration in the
extract phase
11
yA
xA
or
yA = Kd x A
(9.3)
12
Kd
desired
13
Kd
Kd
desired
undesired
and
14
Example A feed of 100 kg/min of 1.2 wt% mixture 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 contercurrently 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)
The solvent is pure butanol; thus, yN +1 = 0
The flow chart for this operation is as follows
16
75
The concentration of the exiting extractphase stream can be computed using operatingline equation (Eq. 9.2) as follows
y j +1
yN +1
R
R
= x j + y1 - x o
E
E
R
R
= x N + y1 - x o
E
E
17
100
100
0=
0.001) + y1 -
0.012
(
(
)
75
75
y1 = 0.015
Thus, the co-ordinates for the operating line
are
(
) (
)
(x , y ) = (0.012, 0.015)
x N , yN +1 = 0.001, 0
o
The next thing to do is to establish the equilibrium relationship between acetic acid in
water (x ) and acetic acid in 1-butanol (y )
From literature [e.g., Table 13-3 (Page 506)
in Separation Process Engineering (3nd ed.) by
P.C. Wankat], Kd for acetic-water-1-butanol at
26.7 oC is 1.613
18
y = 1.613x
(9.4)
19
0.025
yacetic acid
0.020
0.015
0.010
0.005
0.000
0.000
0.002
0.004
0.006
0.008
xacetic acid
20
0.010
0.012
0.014
(9.5)
y j = - x j + x j -1 + y j , in
Ej
E j
22
(9.6)
Since each stage is (assumed to be) an equilibrium stage, x j and y j are in equilibrium with
each other
(x , y )
j
23
) (
The McCabe-Thiele diagram for the crossflow extraction can be depicted as Figure 9.5
24
25
26
= 0.12
27
or
1-
Rx N
Rx o
28
xN
xo
29
x
= 0.12
y
(9.7)
30
x
y=
= 8.33x
0.12
(9.8)
31
Unknowns:
xF
xz
y1, out
xz
xF
Eq. 9.6:
y j = - x j + x j -1 + y j , in
Ej
E j
(9.6)
y1, out
= - x z + x F + y in
E1
E1
(9.9)
20
20
y1, out = - x z + x F + 0
10
10
y1, out = -2x z + 2x F
or
y = -2x + 2x F
From Eq. 9.10, when
y = 0, x = xF
x = 0 , y = 2x F
33
(9.10)
(x
(x , y ) in this Example
z
1, out
8.33x = -2x + 2x F
Solving Eq. 9.11 for x yields
34
(9.11)
8.33x + 2x = 2x F
10.33x = 2x F
x = x z = 0.194x F
y = -2x + 2x F
(9.10)
xz
xF
= 1-
0.194x F
xF
35
= 0.806
36
y2, out
= - x 2 + x z + y in
E2
E2
(9.12)
20
20
= - x 2 + x z + 0
10
10
(9.13)
y = -2x + 0.388x F
(9.14)
(9.15)
8.33x + 2x = 0.388x F
10.33x = 0.388x F
x = x 2 = 0.0376x F
Substituting x = 0.0376x F into Eq. 9.14 and
solving for y yields
y = y2, out = 0.313x F
= 0.0376x F
Accordingly, the total recovery fraction of
alcohol dehydrogenase in the dextran solvent
phase is
1-
x2
xF
= 1-
0.0376x F
xF
39
= 0.962
FD = R )
the flow rate of the solvent can be used
for the flow rate of the extract phase, or
vice versa (i.e. FS = E ); in other words,
the flow rate of the extract phase is
constant
40
However, when the concentration of the solute is large (i.e. cannot be ignored), the flow
rates of the raffinate and extract phases are no
longer constant, as
the solute is removed from the raffinate
phase, which makes the flow rate of the
raffinate phase decrease
the solute of extracted into the extract
phase, which results in an increase in the
flow rate of the extract phase
41
Xi =
Yi =
xi
(9.16)
1 - xi
yi
(9.17)
1 - yi
(9.18)
FD X j -1 + FS Yj , in = FD X j + FS Yj
j
(9.19)
and
Yj +1
F
X j + Y1 - D Xo
=
FS
FS
FD
(9.20)
43
FD
FS
FD
Yj = Xj +
X j -1 + Yj , in
F
FS
S
j
j
FD
(9.21)
(note that the slope for the operating line is -
FD
FS
44
45
46
yA = 0.40
yB = 0.30
Locate the exact point of this mixture in a treecomponent diagram
In the 3-component diagram, the summit or
the tip () of each corner represents a 1.0 mass
(or mole) fraction (or 100%) of each substance
or species
The edge or side () opposite to the tip
represents a 0 mass (or mole) fraction (0%) of
the substance
47
In this example, species A has a mass fraction of 0.40 and species B has a mass fraction of
0.30, which can be depicted by the solid and
dotted lines, respectively, in the equilateral 3component diagram on the next Page
B
0.0 1.0
0.1
0.9
0.2
0.8
0.3
0.7
0.4
0.6
0.5
0.6
0.7
0.5
0.8
0.9
0.4
yB =
0.2 0.30
0.3
0.1
1.0
0.0
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
The right-triangle 3-component diagram can
also be used to locate Point A as shown on the
next Page
49
B
0.9
0.8
0.7
0.6
0.5
0.4
yB =
0.30
0.3
0.2
0.1
0.6
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
A+B
A+B+C
53
Chloroform phase
(Raffinate phase)
(Extract phase)
xD
xS
xA
yD
yS
yA
Water
Chloroform
acetone
Water
Chloroform
acetone
99.2
0.8
0.5
99.5
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
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
0.3
0.8
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
Tie line
Composition in the
Composition in the
raffinate phase
extract phase
Overall composition
of the mixture
56
For example, if the mixture has the composition of z A = 0.42, z B = 0.18, and zC = 0.40
(i.e. Point M), which is within the solubilitycurve envelope, it will be divided into 2 phases:
The raffinate phase with the composition
of x A = 0.80, x B = 0.10, and xC = 0.10
The extract phase with the composition
of yA = 0.15, yB = 0.21, and yC = 0.64
57
If the composition is NOT within the solubility-curve envelope (i.e. outside the solubilitycurve envelope), the system will be a single
phase
58
Since M is divided into 2 phases, the raffinate phase (R ) and the extract phase (E )
Thus,
R +E = M
(9.22)
59
x B R + yB E = z B M
(9.23)
x AR + yAE = z AM
(9.24)
zB =
x B R + yB E
M
x B R + yB E
R +E
(9.25)
zA =
x AR + yAE
M
x AR + yAE
R +E
(9.26)
x B R + yB E = z B (R + E )
(9.27)
x AR + yAE = z A (R + E )
(9.28)
(9.29)
R (yA - z A )
=
E
(z A - x A )
(9.30)
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
=
E
RM
(9.31)
(9.32)
E
RM
=
M
RE
(9.33)
62
63
30,000 kg/h
A = 40%
B = 20%
C = 40%
E kg/h
A = ?? %
B = ?? %
C = ?? %
64
zC = 0.40 is located
B
0.0 1.0
Given overall
component
0.1
0.9
0.2
0.8
0.3
0.7
0.4
Raffinate
Phase
0.6
0.5
0.5
0.6
0.4
0.7
0.3
0.8
0.2
0.9
Extract
Phase
0.1
1.0
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
Raffinate Phase
Extract Phase
A = 78% (x A = 0.78)
B = 13% (x B = 0.13)
C = 9% (xC = 0.09)
Basis 1 h of operation
Overall Balance
30,000 = R + E
(9.34)
Species B balance
66
(9.35)
67
Note that the trial & error technique is commonly employed to solve an extraction problem,
especially for a single-stage extraction
68
yA
N +1
69
yA
N +1
70
yD
N +1
xA
yA
yD
(9.36)
yA S + x A F = yA E1 + x A RN
N +1
(9.37)
yD S + x D F = yD E1 + x D RN
N +1
(9.38)
71
(9.39)
yA S + x A F = z A M = yA E1 + x A RN
N +1
(9.40)
yD S + x D F = z D M = yD E1 + x D RN
N +1
(9.41)
73
Since x i and yi
N +1
computed as follows
zA =
yA S + x A F
N +1
yA S + x A F
N +1
S +F
(9.42)
zD =
M
yD S + x D F
N +1
yD S + x D F
N +1
S +F
(9.43)
Hence,
the composition of the feed can be specified (Point F see Figure 9.8)
the composition of the solvent can be
specified (Point S see Figure 9.8)
74
and 9.43)
the diagram)
Once Point RN can be located, and we have
already had Point M, Point E1 can then be
specified, as illustrated in Figure 9.8
76
(9.44)
(9.45)
77
(9.46)
streams
78
F = E1 + P
(9.47)
(9.48)
(9.22)
80
Drawing a tie-line from Point E1 to the raffinate-phase curve yields Point R1 , as illustrated
in Figure 9.10
82
84
S
the solvent-to-feed ratio is higher
F
S
the
ratio is lower than the maximum
F
ratio
S
ratio leads to the infinity
F
S
() number of stages, while the maximum F
ratio results in the fact that no raffinate phase is
The minimum
85
L
ping operations, minimum
(or minimum reflux
V
L
in the distillation operation) occurs when
ratio:
D
the operating line touches or intersects with the
equilibrium line
S
minimum
takes place when the operating line
F
coincides () with the tie-line, which
is the equilibrium line for the LLE operation
E1
S
F
ratio
(from Separation Process Principles by Henley, Seader, and Roper, 2011)
S
used for determining the minimum
ratio
F
The line P1F is extended to the extract-phase
curve and reaches the curve at Point E1
As per Figure 9.8, the intersection of the lines
E1RN and SF is Point M, at which the material
(9.49)
z A M = yA S min + x A F
M
z A (S + F ) = yA S min + x A F
M
(9.50)
S min
F
xA - zA
F
z A - yA
M
88
(9.51)
yA = 0 (0%)
S
z A = 0.22 (22%)
M
S min
ratio of
F
S min
0.28 - 0.22
=
= 0.27
F
0.22 - 0
diagram
89
S
the minimum
ratio (or Point P1 ) is the point
F
that is closest to Point S
S min
ratio is similar to
F
the case when the slope of the tie-line is downward
S
For the maximum
ratio, consider Figure
F
9.8 (on Page 75)
According to the lever-arm rule, if the amount
of solvent (S ) increases, the distance FM becomes
longer, which means that Point M moves toward
Point S
90
S
The maximum
ratio occurs when Point M
F
S max
reaches the extract-phase curve, and the
F
ratio can be computed as follows
S max
F
( )
xA - zA
F
(z )
AM
max
max
- yA
(9.52)
S
required for two intermediate
ratios between
F
S
ratios
the minimum and maximum
F
The flow chart of this extraction operation
and the 3-component diagram for this operation
is as shown in the Figure A
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)
be specified
94
B (or
Subsequently, the lines SF and Dmin
E1RN ) can be drawn, and Point M min is obtained;
fraction)
S
Accordingly, the minimum ratio can be comF
puted as follows
S min
F
xA - zA
F
z A - yA
M
0.30 - 0.19
=
= 0.58
0.19 - 0
S
ratio is obtained when Point
The maximum
F
M reaches the extract-phase curve, which gives
( )
the value of z A
max
S max
F
S max
F
( )
xA - zA
F
(z )
AM
max
max
- yA
0.3 - 0.03
=
0.03 - 0
S max
F
= 9.0
S
ratio must be between
Hence, the operating
F
0.58-9.0
S
Choose the
ratio of 1.75 (or S = 1.75F ) as
F
S
ratio, which results in Point M
the operating
F
with the concentration of acetone (solute) of
zA =
M
zA
yA S + x A F
S
yA S + x A F
S
S +F
= 0.11
yD S + x D F
S
M
S +F
(0)(1.75F ) + (0.7)(F ) 0.7F
=
=
= 0.25
2.75F
(1.75F ) + (F )
M
zD
yD S + x D F
Drawing a line Point E1 (or D ), using a tieline, until reaching the raffinate-phase curve,
Point R1 (or L1 ) is specified
Draw the line L1P and Point E 2 can be specified on the extract-phase curve, and by using
Point E 2 and the corresponding tie-line, Point
R2 is subsequently located
99
S
For the case of the
ratio of 1.75, the numF
ber of stages was found to be 4
S
ratio of 3.0
Try doing it yourself for the
F
(the number of stages is 2)
100