Liquid-Liquid Extraction (LLX) Equilibrium Relations in Extraction

1. Phase rule.
Extraction is a liquid-liquid operation. It is a process of In a liquid-liquid system, the minimum number of
transferring a solute from one components is three and we have two phases in
liquid phase to another immiscible equilibrium. For a ternary system, the number of degrees
or partially miscible liquid in of freedom is three, as calculated by the phase rule (F = C
contact with the first. The two - P + 2 = 3 - 2 + 2 = 3). We have six variables:
phases are chemically quite temperature, pressure, and four concentrations. If the
different, which leads to a pressure and temperature are specified, then setting one
separation of the components concentration will fix the system. The other three
according to their distribution or concentrations must be calculated from the phase
partition between the two phases, equilibrium.
normally one organic and one
water. This is different from 2. Triangular coordinates and equilibrium data.
distillation, in which the liquid is Since we have three components, the equilibrium data are
partially vaporized to create often expressed in equilateral triangular coordinates. This
another (vapor) phase, but the two is shown in the following figure.
phases are similar chemically.

Figure 1. Coordinates for a triangular diagram.

146 147
The three corners represent three pure components, A, B A commmon phase
p d
diagram m is Typ
ype I syystem and
a shown in
and C. The point M is a mixture. The perpendicular Fig 2, wheree a paiir of coomponeents A and B are parrtially
distance from the point M to any base line is the mass miscible, annd liquid C ddissolvees com mpletelyy in A or B.
fraction of the component at the corner opposite to that The twwo phaase regiion is include
i d insid
de beloww the curved
c
base line. For example, the distance from M to base AB envellope. An A oriiginal m mixturee of coomposiition M will
is the mass fraction of C (xC = 0.40). separate intoo two conjuga
c ate phaases a and
a b which
w a on
are
equiliibrium tie linee throuugh poiint M. Other tie linees are
also plotted
p d. Thee two pphases are id denticall at point P,
whichh is callled thee Plait point. Outsiide the envelo ope is
one phase
p reegion.

Figurre 2. Liiquid-liiquid phase

p diiagram
m wheree
co
omponeents A aand B aare parrtially miscible
m e.

The equiliibrium soluubility

curvee is obtaineed thrrough
mponennts B
experrimentss. If com
and S are partiallly miscible,
we can
c hoose any bbinary
ch
mixtuure liqu
uid of B and SS, say
point D in n Fig. 3. This
mixtuure is separat
s ed into
o two
equiliibrium liquidd phasees, P
and Q.
Q Fig.3. Experrimentaal solub
bility.

148 149
Under constant temperature, if we add component A into
this binary mixture drop by drop, the composition of the Example E1: Ternary acetic acid-benzene-water mixture.
ternary mixture will change along line DA. The ratio of The liquid-liquid equilibrium data at 25oC is given in the
B/S is constant while the amount of A is changing. When following table. In the right-angled triangle, illustrate
the amount of A is just to make the mixture from two (1) Solubility curve
phases to one single homogeneous phase, the composition (2) Tie lines for experiments of Nos. 2, 3, 4, 6, 8
is represented by the point D. By repeating this (3) Plait point and conjugate line
procedure for other binary mixtures with compositions of Benzene phase (mass %) Water phase (mass %)
No.
E, F, G, we obtain the points E, F, G. The curve links acetic benzene water acetic benzene water
the points PDEFGQ is the equilibrium solubility curve. acid acid
If B and S are completely immiscible, the two end points 1 0.15 99.85 0.001 4.56 0.04 95.4
P and Q on the solubility curve will superimpose to the 2 1.4 98.56 0.04 17.7 0.20 82.1
top points B and S, respectively. 3 3.27 96.62 0.11 29.0 0.40 70.6
4 13.3 86.3 0.4 56.9 3.3 39.8
Conjugate line. As far as some equilibrium tie lines are 5 15.0 84.5 0.5 59.2 4.0 36.8
available, other tie lines can be obtained by interpolation 6 19.9 79.4 0.7 63.9 6.5 29.6
with the help of conjugate curve. Assuming the tie lines 7 22.8 76.35 0.85 64.8 7.7 27.5
E1R1, E2R2, E3R3, E4R4 are known, we draw a vertical line 8 31.0 67.1 1.9 65.8 18.1 16.1
from E1 , which 9 35.3 62.2 2.5 64.5 21.1 14.4
intersects the 10 37.8 59.2 3.0 63.4 23.4 13.2
horizontal line from 11 44.7 50.7 4.6 59.3 30.0 10.7
R1 at point F. 12 52.3 40.5 7.2 52.3 40.5 7.2
Similary, the vertical
lines from E2, E3, E4, (1)The data points are plotted in the right-angled triangle
intersects the coordinates, joining the points gives the solubility curve.
horizontal lines from
R2, R3, R4 at points G, (2) The experiments of Nos. 2, 3, 4, 6, 8 are shown as
H and J. The curve points R1, E1, R2, E2, R3, E3, R4, E4, R5, E5. The tie lines
joining FGHJ and the are the straight lines R1E1, R2E2, R3E3, R4E4, R5E5.
plait point P is called
the conjugate line.
150 151
 Example E2: For the ternary system of example E1 at
25oC, a mixture is separated into two liquid phases after
settling. One phase contains 15% acetic acid, 0.5% water
and the rest being benzene (all mass %). Use the
conjugate line in example E1 to determine the
composition of the other conjugate liquid phase and draw
the tie line.

Solution: The solubility and conjugate curves are given.

1. Find the composition of 15% acetic acid, 0.5% water
as point R.
2. Draw a horizontal line from R to intersect the
conjugate line at Q.
3. Draw a vertical line from Q to intersect the
solubility curve at E, which is the composition of the
other conjugate phase, 59% acetic acid, 37% water,
4% benzene.
4. Join RE to obtain the tie line.

(3) The last set of data have the same composition in the
two phases, which is the plait point. The auxiliary curve
is obtained by drawing vertical lines from E1, E2, E3, E4,
E5, which intersect the horizontal lines from R1, R2, R3,
R4, R5 at points G, H, I, J, L. Joining GHIJLP gives the
conjugate line.

152 153
3. Equilibrium data on rectangular coordinates.
Because of the special coordinates, the triangular diagram
is not convenient. The liquid-liquid phase equilibrium is
more often presented in rectangular coordinates, which is
shown in Fig. 4 for acetic acid (A) - water (B) - isopropyl
ether solvent (C).
Figure 4. Acetic acid (A)-Water (B)-Isopropyl ether (C)
o
liquid-liquid phase diagram at 293 K (20 C).
The solvent pair B and C are partially miscible. The
concentration of A is plotted on the horizontal axis and
that of C on the vertical axis. The concentration of B is
calculated from the following equation
154
x B = 1.0 x A x C y B = 1.0 y A y C
A tie line gi is shown connecting the water-rich layer i,
called the raffinate layer, and the ether-rich solvent layer
g, called the extract layer. The raffinate composition is
designated by x, and the extract by y. Hence, the mass
fraction of C is designated as yC in the extract laywer and
as xC in the raffinate layer. To construct the tie line gi
using the equilibrium yA-xA plot below the phase diagram,
vertical lines to g and i are drawn.
Example E3: Material balance for equilibrium layers
An original mixture weighing 100 kg and containing 30
kg of isopropyl ether (C), 10 kg of acetic acid (A), and 60
kg water (B) is equilibrated and the equilibrium phases
separated. What are the compositions of the two
equilibrium phases.
Solution: The composition of the original mixture is
xC = 0.30, xA = 0.10, xB = 0.60
This composition is plotted as point h on Fig. 4. The tie
line gi is obtained through point h by trial and error. The
composition of the extract (ether) layer at g is yA = 0.04,
yC = 0.94, and yB = 1 0.04 0.94 = 0.02 mass fraction.
The raffinate (water) layer composition at i is xA = 0.12,
xC = 0.02, and xB = 1 0.12 0.02 = 0.86 mass fraction.
155
In the above system (Fig. 4) the solvent pair B and C are
partially miscible, while A is totally soluble in B or C. It
is also common for some other systems that both pairs, A
and C, and B and C are partially miscible. This is Type II
system and shown in figure 5.
Figure 5. Liquid-liquid phase diagram where the
solvent pairs A-C and B-C are partially miscible.
Examples are the systems of Styrene (A) -Ethylbene (B) -
Diethylene Glycol (C), and Chlorobenzene (A) -
Methylethyl Ketone (B) -Water (C).
156
Single-Stage Equilibrium Extraction
In an extraction process we have two entering streams (L
kg and V kg) which are NOT in equilibrium, as shown in
Fig. 6. The solvent, as stream V2, enters and the stream
L0 enters from the other side. The two entering streams
are mixed and equilibrated and then exit as streams L1
and V1, which are in equilibrium with each other. To find
the final product compositions in the two phases, it is
required to know the mixture total mass and composition
(point M). This can be obtained by material balances.
After the point M is identified, the product composition
can be found by the equilibrium tie line.
157
 Derivation of lever-arm rule for graphical addition.
In Figure 7 we have two streams (L & V) mixed to give a
resulting mixture stream M kg total mass.
((b)

Figure 6. Single-stage Liquid-liquid extraction: (b)

(a) process flow diagram, (b) phase diagram.
Figure 7. Graphical addition and lever-arm rule:
Material balances: (a) process flow, (b) graphical addition.
Overall: L 0 + V2 = L1 + V1 = M (1)
By doing material balances, we have
(A): L 0 x A 0 + V2 y A 2 = L1x A1 + V1y A1 = Mx AM (2)
Overall: V + L = M (4)
(C): L 0 x C 0 + V2 y C2 = L1x C1 + V1y C1 = Mx CM (3) (A): Lx A + Vy A == Mx AM (5)
(C): Lx C + Vy C == Mx CM (6)
Since xA + xB + xC = 1 , an equation for B is not needed.
Combining Eqs. (4) & (5), and (4) & (6), we have
because L0 and V2 are known, values of M, xAM, and xCM, L x AM y A
can be found from Eqs. (1) to (3). L1 and V1 are obtained = (7)
V x A x AM
by drawing a tie line through point M. L x CM y C
= (8)
V x C x CM
Equating Eqs. (7) & (8) and rearranging,
x C x CM x CM y C
= (9)
x A x AM x AM y A
The left side is the slope of line LM and the right side is
the slope of line MV. Because the two slopes are the
same and the two lines have a common point M, the three
158 159
points L, M, and V must be on a straight line. The lever- Countercurrent Multistage Extraction
arm rule is
L VM L VM
= & = (10)
V LM M LV

Example E4: Amount of phases in solvent extraction

The compositions of the two equilibrium layers in
example E1 are:
for the extract layer (V),
yA = 0.04, yB = 0.02, yC = 0.94
for the raffinate layer (L),
xA = 0.12, xB = 0.86, xC = 0.02
The original mixture contained 100 kg and xAM = 0.10.
Determine the amounts of V and L.

Solution: The overall material balance is

V + L = M = 100 kg
The material balance of A is
V(0.04) + L(0.12) = 100(0.10)
Hence,
V = 75 kg, L = 25 kg

Alternatively, using the lever-arm rule, the distance hg in

Fig. 4 is measured as 4.2 units and gi as 5.8 units. Then
L L hg 4.2
M 100 g 5.8
Solving, L = 72.5 kg and V = 27.5 kg, which is in
reasonable close agreement with the material balance
method.

160 161
1. Countercurrent process and overall balances
A countercurrent multistage process is shown in Fig. 8.
Figure 8. Countercurrent multistage extraction process
flow diagram
Example E5: Pure solvent isopropyl ether (C) at the rate
of VN+1 = 600 kg/h is being used to extract an aqueous
solution of L0 = 200 kg/h containing 30 wt % acetic acid
(A) and 70 wt % water (B) by countercurrent multistage
extraction. The desired exit acetic acid concentration in
the aqueous phase is 4%. Calculate the compositions and
amounts of the ether extract V1 and the aqueous raffinate
LN. The equilibrium data at 20oC, 1 atm, are given and
plotted below.

The overall balance on all N stages is Water phase isopropyl ether phase
L 0 + VN +1 = L N + V1 = M (11) (mass fraction) (mass fraction)
where M is the total mass (kg/h) and is a constant, L0 the acetic Water isopropyl acetic Water isopropyl
inlet feed flow rate (kg/h), VN+1 the inlet solvent flow rate acid (xB) ether (xC) acid (yB) ether
(xA) (yA) (yC)
(kg/h), V1 the exit extract stream, and LN the exit raffinate
6.9e-3 0.9810 0.0120 1.8e-3 5.0e-3 0.9930
stream. Material balance on C gives
0.0141 0.9710 0.0150 3.7e-3 7.0e-3 0.9890
L 0 x C 0 + VN +1y C, N +1 = L N x C, N + V1y C1 = Mx CM (12)
0.0289 0.9550 0.0160 7.9e-3 8.0e-3 0.9840
xCM is obtained By solving Eqs. (11) & (12) 0.0642 0.9170 0.0190 0.0193 0.0100 0.9710
L x + VN +1y C, N +1 L N x CN + V1y C1 0.1330 0.8440 0.0230 0.0482 0.0190 0.9330
x CM = 0 C 0 = (13)
L 0 + VN +1 L N + V1 0.2550 0.7110 0.0340 0.1140 0.0390 0.8470
A similar balance on component A gives 0.3670 0.5890 0.0440 0.2160 0.0690 0.7150
L x + VN +1y A, N +1 L N x AN + V1y A1 0.4430 0.4510 0.1060 0.3110 0.1080 0.5810
x AM = 0 A 0 = (14) 0.4640 0.3710 0.1650 0.3620 0.1510 0.4870
L 0 + VN +1 L N + V1
So the point M, which ties together the two entering
streams (usually known) and the two exit streams, can be
located. The desired exit composition xAN is often set,
which is on the equilibrium curve (phase boundary). Then
the line LNM is extended to intersect the phase boundary
of the extract phase to give V1 composition.
162 163
 The composition of the mixture, xCM and xAM, are
calculated by Eqs. (13) & (14) as 0.75 & 0.075 and used
to plot point M. V1 is located by drawing a line from LN
through M & extending it until it intersects the phase
boundary in the extract phase. This gives yA1 = 0.08 &
yC1 = 0.90.

By solving Eqs. (11) & (12), LN = 136 kg/h & V1 = 664

kg/h.

2.Stage-to-stage calculation for countercurrent extraction

The next step is to go stage by stage to determine the
Solution: concentrations at each stage and the total number of
stages N needed to reach LN in the process.

The given values are

Pure solvent inlet: Making a total balance on stage 1 and then on stage n,
VN+1 = 600, yA,N+1 = yB,N+1 = 0, yC,N+1 = 1,
L0 + V2 = L1 + V1 (15)
Feed:
L0 = 200, xA0 = 0.3, xB0 = 0.7, xC0 = 0,
Ln 1 + Vn +1 = Ln + Vn (16)
The above equations can be rearranged as
Raffinate:
xAN = 0.04. L0 V1 = L1 V2 = ... = Ln Vn +1 = LN VN +1 =
VN+1 and L0 are located by the compositions. (17)
Since LN is on the phase boundary of the raffinate phase, The value of is constant for all stages. The coordinates
of the operating point can be obtained by material
it can be plotted at xAN = 0.04 & we find xCN = 0.017.
balances on A, B or C:

164 165
L 0 x A 0 V1y A1 = ... = L N x AN VN +1y A, N +1 = x A (18)
L 0 x C 0 V1y C1 = ... = L N x CN VN +1y C, N +1 = x C (19)
L 0 x A 0 V1y A1 L N x AN VN +1y A, N +1
x A = = (20)
L 0 V1 L N VN +1
Similar Eqs. for xB & xC can be obtained. This point
is located either by its coordinates as calculated by Eq.
(20) or graphically as the intersection of lines L0V1 and
LNVN+1. The method to locate V1 has been discussed in
example E5. All the operating lines (L0V1, L1V2,
LnVn+1, ... , LNVN+1) must pass through the common point
.
To graphically determine the number of stages, follow the
procedures below.
(1) locate L0, VN+1 and LN by their compositions.
(2) draw a line L0VN+1, and locate the mixture point M
by Eq. (13) or (14).
(3) draw a line from LN through M & extend it until it
intersects the phase boundary, where is V1.
(3) extend lines L0V1, and LNVN+1, which will intersect
at the common operating point .
(4) start at L0 and draw a line L0 which intersects the Alternately, the point can firstly be located using Eq.
phase boundary at V1. (20). Then we start at L0 and draw a line L0 to locate V1.
(5) draw an equilibrium tie line through V1 to locate L1. Then an equilibrium tie line through V1 locates L1. Line
(6) draw a line L1 to give V2 at the phase boundary. L1 is drawn to give V2. A tie line from V2 gives L2.
(7) a tie line from V2 gives L2. This is continued until This is continued until the desired LN is reached.
the desired LN is reached.

166 167
Example E6: Number of stages in countercurrent extraction VN+1
Pure isopropyl ether (C) of 450 kg/h is being used to 1.0
C (isopropyl ether)
extract an aqueous solution of 150 kg/h with 30 wt % V1
acetic acid (A) and 70 wt % water (B) by countercurrent
multistage extraction. The exit acid concentration in the 0.8

aqueous phase is 10 wt %. Calculate the number of

stages required. 0.6

xC, yC
Solution: draw a diagram, 0.4

0.2

A (acetic acid)
B 0.0
Known values: (water) 0.0 0.1LN 0.2 0.3 L0 0.4 0.5
Pure solvent from N+1: xA, yA
VN+1 = 450 kg/h
The mixture points are found by Eqs. (13) & (14), xCM =
yA,N+1 = yB,N+1 = 0
0.75, xAM = 0.075. The point V1 is located as the
yC,N+1 = 1.0,
intersection of line LNM with the phase boundary in the
Feed:
L0 = 150 kg/h extract phase, yA1 = 0.072, yC1 = 0.895.
xA0 = 0.3
xB0 = 0.7
xC0 = 0
Exit in water phase:
xAN = 0.1.
LN must be in the raffinate solubility line.
The points VN+1, L0, and LN are plotted.

168 169
Then lines L0V1, and LNVN+1 is drawn to locate the point Starting at L0 we draw a line L0 to locate V1. Then an
. equilibrium tie line through V1 locates L1. Line L1 is
1.4 drawn to give V2. A tie line from V2 gives L2. A final tie
line gives L3, which is beyond the desired LN. Hence,

1.2
about 2.5 theoretical stages are needed.

VN+1 C (isopropyl ether)

1.0
V1

0.8
xC, yC

0.6

0.4

0.2

LN
A (acetic acid)
0.0
-0.1 0.0 0.1 0.2
L
0.3 0 0.4 0.5
B x A, y A
(water)

170 171
3. McCabe-Thiele method
Stepping off many stages on a triangular diagram can be
difficult and inaccurate. More accurate calculations can
be done with a McCabe-Thiele diagram. Here we focus
on the concentration of solute in the extract and raffinate
phases. The diagram does not show the concentration of
the diluents in the extract or the concentration of solvent
in the raffinate. These minor components of both phases
are accounted for in determining the total flow of extract
and raffinate, which affects the position of the operating
line.

In the McCabe-Thiele diagram, the equilibrium data are

shown on a rectangular graph, where the mass fraction of
solute in the extract (V) phase, yA, is plotted as the
ordinate and the mass fraction of solute in the raffinate (L)
phase, xA, as the abscissa. The conversion of equilibrium
tie line in the triangle diagram to the y-x digram is shown
below.

172 173
Since the total flow rates are not constant, the triangular
diagram and the point are used to plot a curved
operating line on the McCabe-Thiele diagram. This
construction is illustrated in the following figure for a
single point.

The two end points of the operating line are already given
in example E6. (xAN = 0.1, yA,N+1 = 0), and (xA0 = 0.3, yA1
= 0.072).

For any arbitrary operating line (must go through ), the

values of the extract and raffinate concentrations of A are
determined from the phase diagram using the common
point and transferred to the y-x diagram, as shown in
the following figure.

The number of stages is then calculated by stepping off

the triangles with the operating and equilibrium lines,
which is about 2 in this case.

174 175
4. Minimum solvent rate This is proved as below.
If a solvent rate VN+1 is selected at too low a value, a
limiting case will be reached with an operating line If is in the LN side,
through and a tie line being the same. Then an infinite LN - VN+1 =
number of stages will be needed to reach the desired LN = VN+1 +
separation. The minimum amount of solvent is reached. According to lever arms
For actual operation a greater amount of solvent must be rule:
used. VN VN LN LN
=( LN - VN+1) LN
The procedure to obtain
this minimum solvent rate = LN LN - VN+1 LN
is as follows and shown in
the right figure. Firstly LN LN
line LNVN+1 is extended, VN
VN LN LN
then all tie lines between
L0 and LN are drawn to LN
=V LN
intersect the extended line N
LN
LNVN+1. The intersection
farthest from VN+1 (if is Since LN and VN LN are constant, VN+1 will achieve its
in the LN side, which is the maximum when the length of LN is at its maximum.
case in the figure) or
nearest VN+1 (if is on
the VN+1 side) is the min
point for minimum solvent. Minimum solvent for
The actual position of countercurrent extraction.
must be farther from VN+1
(if on the LN side) or nearer to VN+1 (if on the VN+1 side)
for a finite number of stages. The larger the amount of
solvent, the fewer the number of stages.

176 177
If is in the VN+1 side,

VN VN LN LN
LN LN LN VN VN
VN LN
VN VN
LN VN
= LN 1
VN

Since LN and VN LN are constant, VN+1 will achieve its

maximum when the length of VN is at its minimum.

178