Liquid-Liquid Extraction (LLX)

Extraction is a liquid-liquid operation. It is a process of

transferring a solute from one
liquid phase to another immiscible
or partially miscible liquid in
contact with the first. The two
phases are chemically quite
different, which leads to a
separation of the components
according to their distribution or
partition between the two phases,
normally one organic and one
water. This is different from
distillation, in which the liquid is
partially vaporized to create
another (vapor) phase, but the two
phases are similar chemically.

Equilibrium Relations in Extraction

1. Phase rule.
In a liquid-liquid system, the minimum number of
components is three and we have two phases in
equilibrium. For a ternary system, the number of degrees
of freedom is three, as calculated by the phase rule (F = C
- P + 2 = 3 - 2 + 2 = 3). We have six variables:
temperature, pressure, and four concentrations. If the
pressure and temperature are specified, then setting one
concentration will fix the system. The other three
concentrations must be calculated from the phase
equilibrium.
2. Triangular coordinates and equilibrium data.
Since we have three components, the equilibrium data are
often expressed in equilateral triangular coordinates. This
is shown in the following figure.

Figure 1. Coordinates for a triangular diagram.

146

147

The three corners represent three pure components, A, B

and C. The point M is a mixture. The perpendicular
distance from the point M to any base line is the mass
fraction of the component at the corner opposite to that
base line. For example, the distance from M to base AB
is the mass fraction of C (xC = 0.40).

A com
mmon phase
p
d
diagram
m is Typ
ype I sy
ystem and
a shown in
Fig 2, wheree a paiir of coomponeents A and B are parrtially
nd liquid C ddissolvees com
mpletelyy in A or B.
miscible, an
wo phaase regiion is include
i
d insid
de below
w the curved
c
The tw
envellope. An
A oriiginal m
mixturee of co
omposiition M will
separate into
o 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,
which
h 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
experrimentss. If com
mponennts B
and S are partiallly miscible,
we can
c
ch
hoose any bbinary
mixtu
ure liqu
uid of B and S
S, say
point D in
n Fig. 3.
This
ed into
ure is separat
s
o two
mixtu
equiliibrium liquid
d phasees, P
Fig.3. Experrimentaal solub
and Q.
Q
bility.
148

149

Under constant temperature, if we add component A into

this binary mixture drop by drop, the composition of the
ternary mixture will change along line DA. The ratio of
B/S is constant while the amount of A is changing. When
the amount of A is just to make the mixture from two
phases to one single homogeneous phase, the composition
is represented by the point D. By repeating this
procedure for other binary mixtures with compositions of
E, F, G, we obtain the points E, F, G. The curve links
the points PDEFGQ is the equilibrium solubility curve.
If B and S are completely immiscible, the two end points
P and Q on the solubility curve will superimpose to the
top points B and S, respectively.

Conjugate line. As far as some equilibrium tie lines are

available, other tie lines can be obtained by interpolation
with the help of conjugate curve. Assuming the tie lines
E1R1, E2R2, E3R3, E4R4 are known, we draw a vertical line
which
from
E1 ,
intersects
the
horizontal line from
R1 at point F.
Similary, the vertical
lines from E2, E3, E4,
intersects
the
horizontal lines from
R2, R3, R4 at points G,
H and J. The curve
joining FGHJ and the
plait point P is called
the conjugate line.
150

Example E1: Ternary acetic acid-benzene-water mixture.

The liquid-liquid equilibrium data at 25oC is given in the
following table. In the right-angled triangle, illustrate
(1) Solubility curve
(2) Tie lines for experiments of Nos. 2, 3, 4, 6, 8
(3) Plait point and conjugate line
Benzene phase (mass %) Water phase (mass %)
No.
acetic benzene water acetic benzene water
acid
acid
1
0.15
99.85
0.001 4.56
0.04
95.4
2
1.4
98.56
0.04
17.7
0.20
82.1
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
5
15.0
84.5
0.5
59.2
4.0
36.8
6
19.9
79.4
0.7
63.9
6.5
29.6
7
22.8
76.35
0.85
64.8
7.7
27.5
8
31.0
67.1
1.9
65.8
18.1
16.1
9
35.3
62.2
2.5
64.5
21.1
14.4
10
37.8
59.2
3.0
63.4
23.4
13.2
11
44.7
50.7
4.6
59.3
30.0
10.7
12
52.3
40.5
7.2
52.3
40.5
7.2
(1)The data points are plotted in the right-angled triangle
coordinates, joining the points gives the solubility curve.
(2) The experiments of Nos. 2, 3, 4, 6, 8 are shown as
points R1, E1, R2, E2, R3, E3, R4, E4, R5, E5. The tie lines
are the straight lines R1E1, R2E2, R3E3, R4E4, R5E5.

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).

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.

Figure 4. Acetic acid (A)-Water (B)-Isopropyl ether (C)

o
liquid-liquid phase diagram at 293 K (20 C).

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.

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

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.

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.

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

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:

(a) process flow diagram, (b) phase diagram.
Material balances:
(1)
Overall: L 0 + V2 = L1 + V1 = M
L 0 x A 0 + V2 y A 2 = L1x A1 + V1y A1 = Mx AM (2)
(A):
L 0 x C 0 + V2 y C2 = L1x C1 + V1y C1 = Mx CM (3)
(C):
Since xA + xB + xC = 1 , an equation for B is not needed.
because L0 and V2 are known, values of M, xAM, and xCM,
can be found from Eqs. (1) to (3). L1 and V1 are obtained
by drawing a tie line through point M.

158

(b)

Figure 7. Graphical addition and lever-arm rule:

(a) process flow, (b) graphical addition.
By doing material balances, we have
Overall: V + L = M
(4)
Lx A + Vy A == Mx AM
(5)
(A):
Lx C + Vy C == Mx CM
(6)
(C):
Combining Eqs. (4) & (5), and (4) & (6), we have
L x AM y A
=
(7)
V x A x AM
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
159

points L, M, and V must be on a straight line. The leverarm rule is

L VM
L VM
&
(10)
=
=
V LM
M LV

Countercurrent Multistage Extraction

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
hg 4.2
L
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
The overall balance on all N stages is
L 0 + VN +1 = L N + V1 = M
(11)
where M is the total mass (kg/h) and is a constant, L0 the
inlet feed flow rate (kg/h), VN+1 the inlet solvent flow rate
(kg/h), V1 the exit extract stream, and LN the exit raffinate
stream. Material balance on C gives
L 0 x C 0 + VN +1y C, N +1 = L N x C, N + V1y C1 = Mx CM
(12)
xCM is obtained By solving Eqs. (11) & (12)
L x + VN +1y C, N +1 L N x CN + V1y C1
x CM = 0 C 0
=
(13)
L 0 + VN +1
L N + V1
A similar balance on component A gives
L x + VN +1y A, N +1 L N x AN + V1y A1
=
x AM = 0 A 0
(14)
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

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.
Water phase
(mass fraction)
acetic Water
acid
(xB)
(xA)
6.9e-3 0.9810
0.0141 0.9710
0.0289 0.9550
0.0642 0.9170
0.1330 0.8440
0.2550 0.7110
0.3670 0.5890
0.4430 0.4510
0.4640 0.3710

isopropyl ether phase

(mass fraction)
isopropyl acetic Water isopropyl
ether (xC) acid
ether
(yB)
(yA)
(yC)
0.0120
1.8e-3 5.0e-3 0.9930
0.0150
3.7e-3 7.0e-3 0.9890
0.0160
7.9e-3 8.0e-3 0.9840
0.0190
0.0193 0.0100 0.9710
0.0230
0.0482 0.0190 0.9330
0.0340
0.1140 0.0390 0.8470
0.0440
0.2160 0.0690 0.7150
0.1060
0.3110 0.1080 0.5810
0.1650
0.3620 0.1510 0.4870

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
concentrations at each stage and the total number of
stages N needed to reach LN in the process.

Solution:

The given values are

Pure solvent inlet:
VN+1 = 600, yA,N+1 = yB,N+1 = 0, yC,N+1 = 1,
Feed:
L0 = 200, xA0 = 0.3, xB0 = 0.7, xC0 = 0,
Raffinate:
xAN = 0.04.
VN+1 and L0 are located by the compositions.
Since LN is on the phase boundary of the raffinate phase,
it can be plotted at xAN = 0.04 & we find xCN = 0.017.
164

Making a total balance on stage 1 and then on stage n,

L0 + V2 = L1 + V1
(15)
Ln 1 + Vn +1 = Ln + Vn
(16)
The above equations can be rearranged as

L0 V1 = L1 V2 = ... = Ln Vn +1 = LN VN +1 =

(17)
The value of is constant for all stages. The coordinates
of the operating point can be obtained by material
balances on A, B or C:
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
=
(20)
L N VN +1
L 0 V1
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
phase boundary at V1.
(5) draw an equilibrium tie line through V1 to locate L1.
(6) draw a line L1 to give V2 at the phase boundary.
(7) a tie line from V2 gives L2. This is continued until
the desired LN is reached.
x A =

166

Alternately, the point can firstly be located using Eq.

(20). Then we start at L0 and draw a line L0 to locate V1.
Then an equilibrium tie line through V1 locates L1. Line
L1 is drawn to give V2. A tie line from V2 gives L2.
This is continued until the desired LN is reached.

167

Example E6: Number of stages in countercurrent extraction

1.0

Solution: draw a diagram,

C (isopropyl ether)
V1

0.8

0.6

xC, yC

Pure isopropyl ether (C) of 450 kg/h is being used to

extract an aqueous solution of 150 kg/h with 30 wt %
acetic acid (A) and 70 wt % water (B) by countercurrent
multistage extraction. The exit acid concentration in the
aqueous phase is 10 wt %. Calculate the number of
stages required.

VN+1

0.4

0.2

Known values:
Pure solvent from N+1:
VN+1 = 450 kg/h
yA,N+1 = yB,N+1 = 0
yC,N+1 = 1.0,
Feed:
L0 = 150 kg/h
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

B 0.0
(water) 0.0

A (acetic acid)
0.1LN

0.2

0.3

xA, yA

L0

0.4

0.5

The mixture points are found by Eqs. (13) & (14), xCM =
0.75, xAM = 0.075. The point V1 is located as the
intersection of line LNM with the phase boundary in the
extract phase, yA1 = 0.072, yC1 = 0.895.

169

Then lines L0V1, and LNVN+1 is drawn to locate the point

.
1.4

1.2

Starting at L0 we draw a line L0 to locate V1. Then an

equilibrium tie line through V1 locates L1. Line L1 is
drawn to give V2. A tie line from V2 gives L2. A final tie
line gives L3, which is beyond the desired LN. Hence,
about 2.5 theoretical stages are needed.

VN+1 C (isopropyl ether)

1.0

V1

xC, yC

0.8

0.6

0.4

0.2

LN

A (acetic acid)

0.0
-0.1

0.0

B
(water)

0.1

L
0.3 0

0.2

0.4

0.5

x A, y A

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

If a solvent rate VN+1 is selected at too low a value, a
limiting case will be reached with an operating line
through and a tie line being the same. Then an infinite
number of stages will be needed to reach the desired
separation. The minimum amount of solvent is reached.
For actual operation a greater amount of solvent must be
used.
The procedure to obtain
this minimum solvent rate
is as follows and shown in
the right figure. Firstly
line LNVN+1 is extended,
then all tie lines between
L0 and LN are drawn to
intersect the extended line
LNVN+1. The intersection
farthest from VN+1 (if is
in the LN side, which is the
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

This is proved as below.

If is in the LN side,
LN - VN+1 =
LN = VN+1 +
According to lever arms
rule:
VN VN LN LN
=( LN - VN+1) LN
= LN LN - VN+1 LN

LN LN
LN LN

VN
=V

VN
LN

LN
LN

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

maximum when the length of LN is at its maximum.

177

If is in the VN+1 side,

VN
VN

VN

LN LN
VN

= LN 1

LN LN

LN VN
VN
LN
VN
LN VN
VN

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

maximum when the length of VN is at its minimum.

178