Liquid-Liquid Extraction
CHOICE OF SOLVENT
Choosing the best solvent is the most critical aspect of developing a
liquid-liquid extraction process. The solvent should have a high
selectivity for the extracted solute. The selectivity of a solvent is similar
to relative volatility and is given by
x1S / x 2S
R R
x1 / x 2
x1S = weight fraction of component 1 (solute) in the solvent phase
x2S = weight fraction of component 2 in the solvent phase
x1R = weight fraction of component 1 (solute) in the raffinate phase
x2R = weight fraction of component 2 in the raffinate phase
Liquid-Liquid Extraction
SINGLE-STAGE CALCULATIONS
In one-stage liquid-liquid extractor as shown in the next Figure, Component 1 is
the solute, component 2 is the other component in the feed that we are trying to
separate from component 1, and component 3 is the solvent.
Feed Raffinate phase
F, z1, z2 , z3 Stage R1, x1R1, x2R1 , x3R1
Fresh solvent solvent phase
So, x1So, x2So , x3So S1, x1S1, x2S1 , x3S1
In the normal situation, the process feed contains no solvent, so that z3 = 0. We
need to specify only two weight fractions in this ternary system.
If the solvent is essentially pure, as is often the case, x3So = 1, x1So = 0, x2So = 0
Liquid-Liquid Extraction
The total mass balance at this stage is
(4)
A component balance on the jth component yields
(5)
Now we define the parameter
(6)
Where the point M must lie on the straight line joining F and So. It also
must lie on a straight line joining S1 and R1
Liquid-Liquid Extraction
(7)
(8)
(9)
Since the two liquid phases leaving the system
are in phase equilibrium, the points R1 and S1
must be connected by an LLE tie-line.
the procedure for determining the
compositions and flow rates of the two liquid
streams leaving the system is as follows:
1. Calculate M from equation (7).
2. Calculate x1M and x3M from equations (8) and (9).
3. Locate the point M using x1M and x3M .
4. Find the LLE tie-line that passes through the
point M.
Liquid-Liquid Extraction
5. The points at the two ends of the LLE tie-line give the compositions of the two
phases leaving the system: the raffinate-rich phase with composition x1R1 and x3R1
and the solvent-rich phase with composition x1S1 and x3S1
6. Calculate the flow rates S1 and R1 by solving equations (4) and (5)
simultaneously:
Splitting the mixture of F and So into raffinate-rich
phase R1 and solvent-rich phase S1 at ends of a tie-line.
Liquid-Liquid Extraction
Example: An organic stream, with composition 30 weight percent acetone
and 70 weight percent methyl isobutyl ketone and flow rate 10,000 kg/h,
is mixed with a pure water solvent with flow rate 5,000 kg/h. What are the
compositions and flow rates of the two liquid phases leaving a single-
stage liquid-liquid extractor operating at 25oC.
Solution:
Feed= 10000 Raffinate phase
z1 = 0.3 x1So = 0
So =
z1=0.3 z2= 0.7, z3=0 Stage R1, x1R1, x2R1 , x3R1
z2 =0.7 x2 0
Fresh solvent=5000 solvent phase
z3 = 0 x3So= 1.0 x1So,=0 x2So =0, x3So=1.0 S1, x1S1, x2S1 , x3S1
Liquid-Liquid Extraction
Fz1 S 0 x1S0
M
x
1
M
Fz 3 S 0 x3S0
x M
3
M
Liquid-Liquid Extraction
The point M is thus located at (0.333,0.20), as shown in Figure
Note that M lies on the straight line connecting the points F and So
Liquid-Liquid Extraction
The LLE conjugate line is used to determine the other end of the LLE
tie-line on the solvent phase solubility curve. If the tie-line goes through
the point M, the compositions of the water solvent phase and organic
raffinate phase have been found. We have:
Liquid-Liquid Extraction
MULTIPLE STAGES WITH CROSSFLOW OF SOLVENT
If the process liquid stream from the first stages fed into a second
extractor and mixed with more fresh solvent, as shown in the Figure, we
have what is called cross-flow extraction.
The process can be described the same as for a single stage .it is simply
repeated again for each stage, using the raffinate phase from the
upstream stage as the feed to each stage.
Liquid-Liquid Extraction
Mix points for cross-flow extractor.
Liquid-Liquid Extraction
MULTISTAGE COUNTERCURRENT EXTRACTION
Multistage countercurrent extraction is the most commonly encountered
liquid-liquid extraction process. The raffinate and solvent streams travel
countercurrent to each other through N stages. The flow rate of the
raffinate leaving the last stage (tray N) is RN.
Mass and component balances around the entire cascade give
F S 0 RN S1 (10)
z1 F x1S0 S 0 x1RN RN x1S1 S1 (11)
z3 F x3S0 S 0 x3RN RN x3S1 S1 (12)
Liquid-Liquid Extraction
We next define a pseudo flow rate M and pseudo compositions x1M and x3M :
M F S0 (13)
x1M M z1 F x1S0 S 0 (14)
x3M M z3 F x3S0 S 0 (15)
Liquid-Liquid Extraction
If the fresh solvent flow rate So
and composition are given
along with the feed flow rate F
and composition, we can
locate the point M on the
straight line connecting the
points F and So.
From equations (10) through
(12), it is clear that M must
also lie on the straight line
connecting S1 and RN, as
shown in the figure.
Liquid-Liquid Extraction
In the typical design problem, you will be given:
The point RN will be given, i.e., the concentration of the raffinate phase
leaving the final stage will be specified so as to recover the desired
amount of the solute from the feed.
Note: in any real system we cannot recover all of the solute from the feed
Since the points RN and M are known, a straight line can be drawn
to the solubility curve to determine the composition of the x1S1 and
x3S1 of the S1 stream.
Equations (10) and (11) can be used to solve for the flow rates RN
and S1.
Liquid-Liquid Extraction
Since S1 and R1 are in phase
equilibrium, we can use an LLE tie-
line to determine the point R1 on the
solubility curve.
Liquid-Liquid Extraction
Component and mass balances around the first stage can then be used to
calculate the flow rate S2 and compositions x1S2 and x3S2 of the solvent entering
stage 1 from stage 2:
F S 2 R1 S1 (16)
z1 F x1S2 S 2 x1R1 R1 x1S1 S1 (17)
z3 F x3S2 S 2 x3R1 R1 x3S1 S1 (18)
Once S2 is known, R2 can be found at the other end of the LLE tie-line.
This computational procedure can be repeated from stage to stage until enough
stages have been used to produce a process stream that meets or exceeds the
specifications on RN (the final raffinate phase leaving the unit).
Liquid-Liquid Extraction
Graphical procedure
First, define another pseudo flow rate and pseudo compositions x1 and x3
This fictitious stream serves the same purpose as the operating lines did in
binary distillation. We can calculate the compositions of "passing" streams in the
column. It provides a graphical way to solve the three mass balances that
describe this ternary system simultaneously:
RN S 0 (19)
x1 x1RN RN x1S0 S 0 (20)
x3 x3RN RN x3S0 S 0 (21)
Liquid-Liquid Extraction
The pseudo composition xj is entirely fictitious and, therefore, can be
less than zero or greater than unity.
Using equations (10) and (19), we see that
RN S 0 F S1 (22)
Therefore, the point must lie on two straight lines, one through the
points RN and S0 and the other through the points F and S1.
Liquid-Liquid Extraction
can lie either to the left or to
the right of the phase diagram
Liquid-Liquid Equilibrium
The mass balances for the first stage (equations (16) through (18), the
definition of (equations (19) through (21), and equation(22) can be
combined to give
RN S 0 F S1 R1 S 2 (23)
The two streams R1 and S2 that pass each other between the first and
second stages are related to each other by the point. Hence, if we
know R1 we can determine S2 by using the straight line that connects
R1 and .
Liquid-Liquid Extraction
Liquid-Liquid Extraction
Example: A liquid-liquid ternary phase diagram for isopropyl alcohol (IPA), toluene, and
water at 25oC. Feed flow rate is 100 kg/hr, and feed compositions 40 weight
percent IPA and 60 weight percent toluene. Fresh solvent is pure water at a flow
rate of 100 kghr. Determine the number of equilibrium stages required to produce
a raffinate stream that contains 3 weight percent IPA.
