Liquid-Liquid Extraction

Engr. Elisa G. Eleazar

CHE135-1P: SEPARATION PROCESSES 1

 Outline

Kremser-
Hunter-Nash
Single McCabe-Thiele Souders-Brown
General Design Graphical Cross-current
Mechanism Extraction Type Graphical Analytical
Considerations Equilibrium Extraction
Stage Method Analytical
Stage Model
Solution

Learning Objectives
1. Explain the mechanism of Liquid-Liquid Extraction
2. Enumerate the design considerations in Liquid-Liquid Extraction
3. Perform equilibrium and material balance calculations for Liquid-Liquid
Extraction
4. Perform single-stage and countercurrent multiple-contact stage liquid-
liquid extraction calculations
5. Perform cross-current extraction calculations

CHE135-1P: SEPARATION PROCESSES 2

 Mechanism

Solvent Extraction Liquid-Liquid Liquid feed in contact with a liquid

Extraction solvent
process for separating the
components of any matrix by Solid feed in contact with a liquid
Leaching solvent
contact with a liquid

Driving Force: differences in the chemical properties of the

C
feed components (e.g., polarity, hydrophilic/hydrophobic
character)
A + B
Applications:
Extraction of product from fermentation broth (e.g.,
A solute penicillin, lactic acid)
B carrier
Removal of contaminants from liquid
C separating agent (solvent)
Separation of aromatics from paraffins during refining

CHE135-1P: SEPARATION PROCESSES 3

 Mechanism

CHE135-1P: SEPARATION PROCESSES 4

 Mechanism
Applications of Extraction
1. In the case of dissolved or complexed inorganic substances in organic or aqueous solutions
2. The removal of a component present in small concentrations
3. When a high-boiling component is present in relatively small quantities in an aqueous waste stream
4. The recovery of heat-sensitive materials, where extraction may be less expensive than vacuum
distillation
5. The separation of a mixture according to chemical type rather than relative volatility
6. The separation of close-melting or close-boiling liquids, where solubility differences can be exploited
7. Mixtures that form azeotropes

CHE135-1P: SEPARATION PROCESSES 5

 General Design Considerations
Factors Affecting the Extraction Process Cascade Configurations
1. Entering feed flow rate, composition, temperature and pressure
2. Type of stage configuration
3. Desired degree of recovery of one or more solutes (for one-
section cascades)
4. Degree of separation of the feed (for two-section cascades)
5. Choice of liquid solvent
6. Operating temperature
7. Operating pressure
8. Minimum and actual solvent flow rate
9. Number of equilibrium stages
10.Emulsification and scum-formation tendency
11.Interfacial tension
12.Phase-density difference
13.Type of extractor
Single-stage Two-stage Dual Solvent with
14.Extractor size and horsepower requirement cascade Two-stage cascade
cascade

CHE135-1P: SEPARATION PROCESSES 6

 General Design Considerations
Properties of an Ideal Solvent
High selectivity for the solute relative to the carrier to minimize the need to recover carrier from the solvent
High capacity for dissolving the solute to minimize the solvent-to-feed ratio
Minimal solubility in the carrier
Volatility sufficiently different from the solute that recovery of the solvent can be achieved by distillation, but
the vapor pressure should not be so high that a high extractor pressure is needed or so low that a high
temperature is needed if the solvent is recovered by distillation
Stability to maximize the solvent life and minimize the solvent make-up requirement
Inertness to permit use of common materials of construction
Low viscosity to promote phase separation, minimize pressure drop and provide a high solute mass transfer
rate
Nontoxic and nonflammable characteristics to facilitate safe use
Availability at a relatively low cost
Moderate interfacial tension to balance the ease of dispersion and the promotion of phase separation
Large difference in density relative to the carrier to achieve a high capacity in the extractor
Compatibility with the solute and carrier to avoid contamination
Lack of tendency to form a stable rag or scum layer at the phase interphase
Desirable wetting characteristics with respect to the extractor internals
CHE135-1P: SEPARATION PROCESSES 7
 Single Extraction Stage
E S
1
F R

Material Balance Partition Ratio or Distribution Coefficient, K

+ =+ = () ()
=
() () ()
= +
Extraction Factor, EB
F Feed A Carrier
Solvent Solute ()
S B
1
E Extract C Solvent = ()
=
R Raffinate XA Ratio of moles (or mass)
1 +
of A to moles (or mass)
of other components
CHE135-1P: SEPARATION PROCESSES 8
 Single Extraction Stage
A feed of 13,500 kg/h consists of 8 wt% acetic acid in water. The removal of the acetic acid is to be
accomplished by liquid-liquid extraction at 25C with methyl isobutyl ketone solvent, because
distillation of the feed would require vaporization of large amounts of water. If the raffinate is to
contain only 1 wt% acetic acid, estimate the kilograms per hour of solvent required if a single
equilibrium stage is used. The distribution coefficient for this system is 0.657.

CHE135-1P: SEPARATION PROCESSES 9

 Single Extraction Stage
Equilateral Triangle Plot
Binodal Locus
line delineating the region where two liquid
phases form

Tie Line
connecting equilibrium compositions for each
phase

Plait Point
point on the binodal locus where both liquid
phases attain the same composition (leads to
infinite number of stages)

CHE135-1P: SEPARATION PROCESSES 10

 Single Extraction Stage
Equilateral Triangle Plot Equilibrium Miscibility Data
the sum of the lengths of Furfural Glycol Water
the perpendicular lines 95.0 0.0 5.0
drawn from any interior 90.3 5.2 4.5
point to the sides equals 86.1 10.0 3.9
the altitude of the 75.1 20.0 4.9
triangle 66.7 27.5 5.8
49.0 41.5 9.5
M 34.3 50.5 15.2
% water 19.8
27.5 52.5 20.0
% ethylene glycol 20.0
% furfural 61.0 13.9 47.5 38.6
11.0 40.0 49.0
9.7 30.0 60.3
8.4 15.0 76.6
7.7 0.0 92.3

CHE135-1P: SEPARATION PROCESSES 11

 Single Extraction Stage
Determine the composition of the equilibrium extract and raffinate phases produced when a 45% by
weight glycol 55% water solution is contacted with twice its weight of pure furfural solvent at 25C
and 101 kPa.

1. Locate F and S
2. Define M = F + S
3. Use the Inverse Lever Arm Rule
to determine the compositions

CHE135-1P: SEPARATION PROCESSES 12

 Single Extraction Stage
Right Triangle Plot

One-phase region
Two-phase region
Tie lines

Determine the composition of the

equilibrium extract and raffinate phases
produced when a 45% by weight glycol 55%
water solution is contacted with twice its
weight of pure furfural solvent at 25C and
101 kPa.

CHE135-1P: SEPARATION PROCESSES 13

 Hunter-Nash Graphical Equilibrium Stage Method

F Mass flow rate of feed

S Mass flow rate of solvent
EN Mass flow rate of extract
RN Mass flow rate of raffinate
yi,N Mass fraction of species i in
extract leaving stage n
xi,N Mass fraction of species i in
raffinate leaving stage n

CHE135-1P: SEPARATION PROCESSES 14

 Hunter-Nash Graphical Equilibrium Stage Method
Construction 1: Product Points Given the following feed and solvent
specifications, determine the extract and
1. Locate F and S raffinate flow rates and compositions. The
2. Define and locate M = F + S solute concentration in the raffinate is 0.025.
3. Plot RN
4. Extend RN through M to
Feed Solvent
locate E1
(F) (S)
5. Determine compositions and
flow rates Mass, kg 250 100
xA 0.76 0.00
xB 0.24 0.00
xC 0.00 1.00

CHE135-1P: SEPARATION PROCESSES 15

 Hunter-Nash Graphical Equilibrium Stage Method
Construction 2: Operating Point and Lines

Difference Point:
intersection between 1 and

CHE135-1P: SEPARATION PROCESSES 16

 Hunter-Nash Graphical Equilibrium Stage Method
Construction 3: Equilibrium Lines

Conjugate curves are used to

develop more tie lines.

CHE135-1P: SEPARATION PROCESSES 17

 Hunter-Nash Graphical Equilibrium Stage Method
Stepping off Stages

Tie Line
Operating Line

Determine the number of stages in SP4.

CHE135-1P: SEPARATION PROCESSES 18

 Hunter-Nash Graphical Equilibrium Stage Method
Minimum Solvent-to-Feed Flow Rate Ratios

Given F, S and RN;

Draw through and extended to the left and right of
the diagram
Assume each tie line to be a pinch point (extend the tie line
until it intersects
The pinch point corresponds to , which is located at
the greatest distance from
Draw an operating line through and extend to locate 1

Solve for using material balance:

() ()

= () ()

CHE135-1P: SEPARATION PROCESSES 19

 Hunter-Nash Graphical Equilibrium Stage Method
Using the given equilibrium data, use the Hunter-Nash method to determine: (a) minimum solvent
flow rate; (b) number of equilibrium stages for a solvent flow rate of 1.5 times the minimum; (c)
flow rate and composition of the leaving streams. The feed containing 30% solute A in carrier C
enters at 1,000 kg/h. The solute concentration in the raffinate is 10%.

CHE135-1P: SEPARATION PROCESSES 20

 Hunter-Nash Graphical Equilibrium Stage Method
One thousand kg per hour of a 45 wt% acetone in water solution is to be extracted in a continuous,
countercurrent system with pure 1,1,2-trichloroethane to obtain a raffinate containing 10 wt%
acetone. Using the following equilibrium data, determine with a right triangle diagram: (a) the
minimum solvent flow rate; (b) the number of stages required for a solvent rate equal to 1.5 times
the minimum; (c) the flow rate and composition of each stream leaving each stage.

Extract Raffinate Tie Line Data

Acetone, Water, Trichloroethane, Acetone, Water, Trichloroethane, Wt frac Wt frac
wt frac wt frac wt frac wt frac wt frac wt frac Acetone in Acetone in
0.60 0.13 0.27 0.55 0.35 0.10 Raffinate Extract

0.50 0.04 0.46 0.50 0.43 0.07 0.44 0.56

0.40 0.03 0.57 0.40 0.57 0.03 0.29 0.40

0.30 0.02 0.68 0.30 0.68 0.02 0.12 0.18

0.20 0.015 0.785 0.20 0.79 0.01

0.10 0.01 0.89 0.10 0.895 0.005

CHE135-1P: SEPARATION PROCESSES 21

 McCabe-Thiele Type Graphical Method

CHE135-1P: SEPARATION PROCESSES 22

 McCabe-Thiele Type Graphical Method
An inlet water solution of 100 kg/h containing 0.010 wt fraction nicotine in water is stripped with a
kerosene stream of 200 kg/h containing 0.0005 wt fraction nictotine in a countercurrent stage
tower. The water and kerosene are essentially immiscible in each other. I tis desired to reduce the
concentration of the exit water to 0.0010 wt fraction nicotine. Determine the theoretical number of
stages needed. The equilibrium data are as follows:
Wt frac Wt frac
Nicotine in Nicotine in
Water Kerosene
0.0010101 0.000806
0.0024600 0.001959
0.0050000 0.004540
0.0074600 0.006820
0.0098800 0.009040
0.0202000 0.018500

CHE135-1P: SEPARATION PROCESSES 23

 Kremser-Souders-Brown (KSB) Analytical Solution

1 1
ln 1 +
=



=
ln
N Number of theoretical stages Determine the number of stages
in SP8 using the KSB analytical
X Mass ratio solute to solvent
solution.
Ys Mass ratio solute to extraction solvent
E Extraction factor
m' Slope of equilibrium line
S Mass flow rate of extraction solvent (solute-free basis)
F Mass flow rate of feed solvent (solute-free basis)

CHE135-1P: SEPARATION PROCESSES 24

 Cross Current Extraction

ln

=
ln + 1

Equal amounts of solvent (S) are

used for each treatment.

CHE135-1P: SEPARATION PROCESSES 25

 Cross Current Extraction
It is desired to reduce the concentration of pyridine in 500 kg of aqueous solution from 20 wt% to 5
wt% in a single batch extraction using chlorobenzene as solvent. Equlibrium compositions
(endpoints of the tie line) in terms of wt% pyridine-water-chlorobenzene are (5, 95, 0) and (11, 0,
89). Determine the number of extraction stages for cross-current extraction where, into each stage,
100 kg of fresh (but presaturated) solvent is used?

CHE135-1P: SEPARATION PROCESSES 26

 Outline

Kremser-
Hunter-Nash
Single McCabe-Thiele Souders-Brown
General Design Graphical Cross-current
Mechanism Extraction Type Graphical Analytical
Considerations Equilibrium Extraction
Stage Method Analytical
Stage Model
Solution

Learning Objectives
1. Explain the mechanism of Liquid-Liquid Extraction
2. Enumerate the design considerations in Liquid-Liquid Extraction
3. Perform equilibrium and material balance calculations for Liquid-Liquid
Extraction
4. Perform single-stage and countercurrent multiple-contact stage liquid-
liquid extraction calculations
5. Perform cross-current extraction calculations

CHE135-1P: SEPARATION PROCESSES 27

 Liquid-Liquid Extraction
Engr. Elisa G. Eleazar

CHE135-1P: SEPARATION PROCESSES 28