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Chapter 8 - Extraction and

Leaching
ChE 221 / ChE 516
Mass Transfer Operations
Main references: McCabe, 7
th
Ed, Ch 23; Seader, 3
rd
Ed, Ch 8 & 16
Professor San Ping J iang
Part I: Liquid-Liquid Extraction
Based on equilateral triangular diagram
Liquid-liquid extraction
The method to remove one constituent from a solid or liquid
by means of a liquid solvent
Liquid extraction to recover a valuable product from a
multicomponent solution by contact with an immiscible solvent that
has a high affinity for the product
When separation by distillation is ineffective or very difficult,
liquid-liquid extraction (or solvent extraction) is one of the
main alternatives to consider.
Close-boiling mixtures or substances that cannot withstand
the temperature of distillation, even under a vacuum, may
often be separated from impurities by extraction, which
utilises chemical differences instead of vapour pressure
differences.

3
An industrial example
4
Acetic acid: b.p.=118.1
o
C
Water: b.p.=100
o
C
Ethyl-acetate: b.p.=77.1
o
C
The feed of 30260 1b/h of
22wt% acetic acid in water is in
contact with 71100 1b/h of
ethyl-acetate solvent in a single-
section extraction column. The
low-density, solvent rich extract
exits from top of the extractor
with 99.8% acetic acid in the
feed. The high density, carrier-
rich raffinate exiting from
bottom contains only 0.05wt%
acetic acid.
4 major steps in an extraction process
Bringing the feed and the solvent into intimate contact by
dispersing one phase into the other as droplets
Separation of the extract and the raffinate phases that have
different densities
The extract is the layer of solvent plus extracted solute
The raffinate is the layer from which solute has been removed.
Removal and recovery of the solute from the extract
phase in a relatively pure form (by distillation, evaporation,
crystallization, etc)
Removal and recovery of the solvent from each phase,
usually by distillation
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Extraction preferred over distillation for
Dissolved or complexed inorganic substances in organic or
aqueous solutions
Removal of a contaminant present in small concentration
A high-boiling component present in relatively small quantities
in an aqueous waste steam
Recovery of heat-sensitive materials, where extraction may be
less expensive than vacuum distillation
Separation of mixtures according to chemical type rather than
relative volatility
Separation of close-melting or close-boiling liquids, where
solubility differences can be exploited
Separation of mixtures that form azeotropes
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Industrial liquid-liquid leaching process
Solute Carrier Solvent
Acetic acid Water Ethyl acetate
Ammonia Butenes Water
Aromatics Paraffins Furfural
Aromatics Kerosene Sulfur dioxide
Benzoic acid Water Benzene
Fatty acids Oil Propane
Acetic acid Water Methyl isobutyl ketone
Formic acid Water Tetrahydrofuran
Penicillin Broth Butyl acetate
Vanilla Oxidized liquors Toluene
Vitamin A Fish-liver oil Propane
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Principles of Extraction
Since most continuous extraction methods use
countercurrent contacts between two phases, many
of the fundamentals of countercurrent gas absorption
and of distillation carry over into the study of liquid
extraction.
Thus questions about ideal stages, stage efficiency,
minimum ratio between the two streams, and size of
equipment have the same importance in extraction as
in distillation.
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Design Considerations
Some factors influencing extraction:
Types of stage configuration
Min solvent flow rate and actual flow as multiple of
min flow rate (or reflux for more than one stage
system)
Operating conditions
Emulsification and scum formation tendencies
Phase density difference
Interfacial tension
Types of extractor
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Desirable properties of a solvent
Some characteristics of an ideal solvent:
High selectivity for solute / low for carrier
High capacity for dissolving solute
Volatility difference with solute - recoverability
Large density difference with carrier
Lack tendency to form scum layer at interface
Low viscosity promote phase separation
Stable minimise make-up solvent
Availability and low cost
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Types of extractor Mixer-settlers
For batchwise extraction the mixer
and settler may be the same unit.
For continuous flow the mixer and
settler are usually separate pieces of
equipment.
The mixer may be a small agitated tank
provided with inlets and drawoff line
and baffles to prevent short-circuiting,
or it may be other flow mixer;
The settler is often a simple continuous
gravity decanter
The extract may be lighter or
heavier than the raffinate, and so the
extract may come from the top or
the bottom of the equipment
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Perforated-plate towers
The perforations are typically 1 to 4 mm in diameter and
plate spacings range from 150 to 600 mm;
Usually the light liquid is the dispersed phase, and
downcomers carry the heavy continuous phase from one plate
to the next;
Depending on gravity flow both for mixing and for separation.
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Perforations in
horizontal plates Cascade weir tray with
mixing and settling zones
Agitated tower extractors
Mechanical energy is
provided by internal
turbines or other
agitators, mounted on a
central rotating shaft.
13
Rotating-disk unit York-Scheibel extractor
Types of configuration
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(a) Single-section cascade; (b) two-section cascade; (c) dual solvent with two-
section cascade.
15
The equilateral triangular diagram
16
Ternary phase diagram
The basis of the technique of presentation of equilibrium data on an
equilateral triangular graph paper is that the sum of the distances of a point
within an equilateral triangle from the three sides is equal to the height of
the triangle;
On the equilateral triangle ABC, each apex is a pure component of the
mixture, A, B and C, respectively;
Each edge is a mixture of the two pure components at the terminal apexes
of the side, A-B, B-C and C-A, respectively.
Consider the point M, for example: MN
1
+MN
2
+MN
3
= CT; M represents
mixture of 16%A, 24%B and 60%C [100-(16+24)=60%].
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The equilateral triangular diagram
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Exercise:
73.27%A, 6.54%B, 20.19%C
(Raffinate phase, x, rich in A)

5.2%A, 91.8%B, 3.0%C
(Extract phase, y, rich in B)

A: Carrier
B: Solvent
C: Solute

A B
C
20.19% C
10%
0%
100%
0%
10%
100%
73.27% A
(Print this slide in full size.)
Construct ternary phase diagram
Point Furfural Glycol Water
A 95.0 0.0 5.0
B 90.3 5.2 4.5
C 86.1 10.0 3.9
D 75.1 20.0 4.9
E 66.7 27.5 5.8
F 49.0 41.5 9.5
G 34.3 50.5 15.2
H 27.5 52.5 20.0
I 13.9 47.5 39.6
J 11.0 40.0 49.0
K 9.7 30.0 60.3
L 8.4 15.0 76.6
M 7.7 0.0 92.3
Point Glycol in
water
layer, wt%
Glycol in
furfural
layer, wt%
P 41.5 41.5
1 52.5 27.5
2 51.5 20.0
3 47.5 15.0
4 40.0 10.0
5 30.0 7.5
6 20.0 6.2
7 7.3 2.5
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Equilibrium miscibility data Mutual equilibrium (tie-line) data
Water-ethylene glycol-furfural system at 25
o
C, 101 kPa.
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Ethylene Glycol (B)
Furfural (C)
0.1 0.9
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.4
0.5
0.6
0.7
0.8
Print this slide in full size
for Class Problem - 1
0.2
0.3
0.1
0.9 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0.1
Water (A)
Water-EG-Furfural phase diagram
Water-EG and furfural-
EG are completely
miscible pairs
Furfural-water is a
partially miscible pair
At plait point, P, the two
liquid phases have
identical compositions
Miscibility limit for the
furfural-water binary
system are D and G
Thus, furfural can be
used as solvent to
remove EG from water
Furfural-rich phase is
the extract and water-
rich phase is raffinate
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A single-stage extraction
What is composition of
mixture represented by
point M?
What is the composition
of extract phase and
raffinate phase?
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solvent
carrier
solute
Mixture, M: 20% EG;
19% Water;
61% Furfural.
H
2
O =0.19
EG =0.2
Extract, E: 10% EG;
4% Water;
86% Furfural.
Raffinate, R: 40% EG;
49% Water;
11% Furfural.
Ternary systems comprising a
carrier A, a solvent B and a solute
C. Three binary mixtures can be
formed out of these components,
A-B, B-C, and C-A. The mutual
miscibility behaviour of the
components in each of these
binaries determines the nature of
the equilibrium diagram for the
ternary system.
Here, the solute C is miscible with
A and B in all proportions, but the
carrier and the solvent are only
partially miscible. The curve RPS is
the equilibrium diagram in the
equilateral triangular coordinate
system.
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Liquid-liquid equilibria (LLE)
Solute C
Carrier A Solvent B
Equilibrium or
binodal curve

Plait point, P
Separation range
The larger the two-phase
region on line R-S, the
greater the immiscibility of
carrier and solvent.
The closer the top of the
two-phase region is to apex
A, the greater the range of
feed composition, along the
line R-C, that can be
separated with solvent S.
Limiting cases.
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Solute C
Carrier A Solvent B
F
1

F
2

M
D

Feed
composition
range to be
separated
LLEcontinue
The point R on the line AB represents the solubility of the
solvent B in the carrier A; the point S represents that of
the carrier A in the solvent B.
The pair of points G
1
and H
1
on the curve represents two
liquid phases in equilibrium: G
1
is rich in the carrier
(raffinate phase) and H
1
is rich in the solvent (extract
phase). The line G
1
H
1
is called tie line. Usually they are not
parallel. The point P, that demarcates the raffinate and the
extract sides of the equilibrium curve is called the plait
point. The type of equilibrium RPS is called binodal because
it has two arms RP and PS, representing the raffinate and
the extract sides.
25
Phase splitting of ternary mixtures
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Solvent S
Component B
Feed F
Component A, C
Extract E
Component B, C
Raffinate R
Component A, C
(a) Components A and B mutually insoluble.
Solvent S
Component B
Feed F
Component A, C
Extract E
Component A, B, C
Raffinate R
Component A, B, C
(b) Components A and B partially soluble.
Reverse-level-arm rule
Level rule or mixing rule for ternary
liquid systems asserts that the
composition that results when two
liquid solutions are mixed lies on a
straight line connecting their
compositions. Thus, if R kg of a
mixture represented by point R is
combined with E kg of a solution
located at point E, the resulting
composition M will lie on a straight
line connecting points R and E.
Furthermore, the location of M will
be such that line segments it defines
stand in the ratio of the weights of the
parent solutions:
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C
A
B


R
The mixing rule in a triangular diagram
E
M
S
L
P
F N K



RM
EM
E
R
= (8.1)

Validation of reverse-level-arm rule
First we have: (8.2)
M is mass of mixture, and for the component mass balance

Combine eq. (8.2) and (8.3) yields

Re-arrange eq.(8.4)

Because

Thus
Because triangle MPR is similar to triangle ESM, consequently
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CM CE CR
Mx Ex Rx = +
CM CE CR
x E R Ex Rx ) ( + = +
CM CE
CR CM
CE CM
CM CR
x x
x x
x x
x x
R
E

=
RF x EK x MN x
CR CE CM
= = = ; ;
ES
SL
MN EK
RF MN
R
E
=

=
EM
MR
ES
SL
R
E
= =
M E R = +
(8.3)
(8.4)
(8.5)
(8.6)
(8.1)
Type I - Acetone-water-MIK system
The solute and solvent are
miscible in all compositions.
Partial miscibility of the
solvent (methyl isobutyl
ketone, MIK) and the carrier
(water): one immiscible pair
The tie lines slope up to the
left and the extract is richer
in acetone than the raffinate
phase.
The most common type.
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solvent
solute
carrier
Type II - Aniline-n-heptane-MCH system
The solvent (aniline) is only
partially miscible with both the
solute (methylcyclohexane,
MCH) and carrier n-heptane:
two immiscible pairs.
The tie lines slope up to the
right more solvent would
be required since the final
extract would not be as rich
in the desired component.
In Type II system, there is no
plait point.
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solvent carrier
solute
Single stage extraction
Locate the feed and solvent
compositions at points F and S,
respectively.
Define mixing point M as M = F + S = E
+ R.
Apply the inverse-level-arm rule. Let w
i
(E)

be the species I in the extract, w
i
(R)
be
the species I in the raffinate, and w
i
(M)
be
the species I in the feed+solvent phase.
For solvent C


Obtain R and E phase compositions.
The inverse-level-arm rule applies to
obtain weight fractions of R and E
phases.
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Feed F
Solvent S
Extract E
Raffinate R
Solute
B
Carrier A C Solvent
F
A
C
B
M
E
R

S
S
c
F
c
M
c
Sw Fw w S F + = + ) (
MF
SM
S
F
=




Multistage cross-flow extraction
Feed goes through stages in series and
to each stage, fresh solvent is added. This
process is an extension of single-stage
extraction.
For multistage with cross-flow, raffinate
from each stage is contacted with
following stage with pure solvent.
Extracts are withdrawn from each stage.
The concentration of solute (B) in
raffinate and extract decreases from
stage to stage.
Apply material balance and inverse-level-
arm rules, similar to single-stage
extraction calculation procedures.
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Feed F
Solvent S
1

Extract E
1

Raffinate R
1

Solute
B
Carrier A C Solvent
F
A
C
B
M
1

E
1

R
1


S




Solvent S
2

R
2

Extract E
2




E
2

R
2

M
2

Right-triangle diagrams
Ternary, countercurrent extraction
calculations can also be made on a
right-triangle diagram.
A right-triangle diagram can be
developed from an equilateral-
triangle diagram. Rectangular
coordinate are in mass or mole
fractions, x
A
and x
C
, where A is the
solute and C the carrier.
The advantage of the right-triangle
diagram is that ordinary,
rectangular-coordinate graph
paper can be used and either one
of the coordinates can be
expanded.
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Right-triangle diagrams
34
L
L
Point L: Furfural-8.4%; EG-15% (water=100-8.4-15=76.6)
0.15
0.84
Distribution diagram
Plots of solute weight fraction in two phases against each other two phase
behaviour.
Plait point is located on the 45
o
diagonal equality of phase concentrations
Compositions that lie above the diagonal are richer in solute content than those of
the companion phase, while points below it denote a depletion in solute.
Distribution coefficient is defined as the solute mole-fraction ratio in two phases,:
m = x
CB
/x
CA

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Part II: Solid-Liquid Extraction
Solid-liquid extraction or leaching
Leaching involves the removal of a soluble fraction (the
solute or leachant) of a solid material by a liquid solvent
Effluents from a leaching stage are essentially solid-free liquid, called the
overflow, and wet solids, the underflow. To reduce the concentration of
solute in the liquid portion of the underflow, leaching is often
accompanied by countercurrent-flow washing stages.
The combined process produces a final overflow, called extract, and a
final underflow, the extracted or leaching solids.
Ideally, the soluble solids are perfectly separated from the
insoluble solids, but solvent is distributed to both
products
Additional processing of extract and leaching solids is necessary to
recover solvent for recycle.
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Industrial applications of leaching
Inorganic and organic materials
Metal processing industries e.g. removal as soluble salts
Removal of copper from ore using sulfuric acid
Recovery of gold from ore using sodium-cyanide solution
Biological substances
Biological and food industries
Extraction of sugar from sugar beets using hot water as solvent
Removal of caffeine from green coffee beans using supercritical CO
2

Vegetable oils from nuts and seeds using organic solvents (hexane,
acetone, ether)
Pharmaceutical products from plant roots, leaves, stems

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An industrial example
Soybeans contain highest percentage of edible oil
For soybeans, whose oil content is typically less than 0.3 1b per 1b of dry and oil-
free solids, leaching is more desirable than expression.
The ideal solvent for commercial leaching of soybeans should have a high oil
solubility; a high volatility; nonflammability; low cost; chemical stability; low toxicity.
Nonflammable trichloroethylene is an ideal solvent, but is classified as a hazardous,
toxic chemical.
The favoured solvent is the commercial n-hexane, which presents fire hazard but
has a low toxicity.
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Soybean flakes
(10.67%moisture,
0.2675g oil/dry flake):
6.375 1b/h
Leached solid
contains 0.0151 g
oil/dry oil, free flake
Extract of 7.313 1b/h
contains 15.35% oil
after 11 h operation
Solvent flow: 10.844 1b/h
Kennedy extractor
Espresso machine
A batch-leaching machine
In the machine, 7-9 grams of coffee
beans are ground to a powder of
particle size of 250-750 m
Water is pumped to a pressure of 9-
15 atm and heated to 88-92
o
C. The
high pressure is required for pressure
infusion of hot water through the bed
of coffee powder, so extraction can
proceed rapidly
During a period of 20-30 s, hot water
is percolated through the coffee
powder to produce a 45 mL shot.
Maximise extraction of the flavour-
and-aroma chemicals and minimise
extraction of the chemicals associated
with bitterness such as quinine and
caffeine.
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Moving-bed leaching: Bollman extractor
Buckets are loaded with flaky seeds and
beans such as soybeans and are sprayed
with intermediate solvent, half miscella.
As solids and solvent flow concurrently
down the right-hand side of the machine,
the solvent extracts more oil from the
beans.
As the partially extracted beans rise
through the left side of the machine, a
stream of pure solvent percolates
countercurrently through them.
Fully extracted beans are dumped at the
top of the elevator.
Each basket contains ~350kg of solids and
~200,000 kg of solids can be extracted per
day
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Moving-bed leaching: Rotocel extractor
A horizontal basket is divided into
walled compartments with floor
that is permeable to the liquid.
Solids are admitted to each
compartment at the feed point;
the compartments then
successively pass a number of
solvent sprays, a drainage section,
and a discharge point at which the
floor of the compartment opens
to discharge the extracted solids.
To give countercurrent extraction,
fresh solvent is fed only to the last
compartment before discharge
point.
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Rotocel extractors are typically 3.4-11.3 m in
diameter, 6.4-7.3m in height, and with bed
depths of 1.8-3.0m.
Continuous, perforated-belt extractor
Used to process sugar cane, sugar
beets, oil seeds and apples (for apply
juice)
The feed solids are fed from a hopper
to a slow-moving, continuous and
nonpartitioned perforated belt. Below
the belt are compartments for
collecting solvent
Fresh solvent is sprayed over solids
and above the compartments in a
countercurrent fashion, starting from
the discharge end of the belt.
Units from 7 to 37m long with belts
from 0.5 to 9.5m wide and 0.8 to
2.6m deep can process as much as
7,000,000 kg/day of sugar cane or
sugar beets.
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Factors influencing leaching processes
Stages involved in leaching: (1) dissolution of solute in the
solvent; (2) diffusion of the solute through the solvent; (3)
transfer of the solute from the solution in contact with
the particles to the bulk of the solution.
Particle size, nature of the solvent used, temperature and
agitation are the important factors that influence
extraction rates.
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Countercurrent leaching cascade
S = mass flow rate of inert solid and is constant from stage to stage
V = mass flow rate of entering solvent or overflow liquid (solvent + solute),
which varies from stage to stage.
L = mass flow rate of underflow liquid (solvent + solute) which varies from stage
to stage.
y = mass fraction of solute in the overflow liquid
x = mass fraction of solute in the underflow liquid
Alternatively, V and L can refer to mass flow rate of solvent on solute-free basis and
symbols Y and X can be used as mass ratios of solute to solvent in overflow and
underflow liquids, respectively.
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overflow
underflow
y
N+1
y
L

x
N

x
L

Equilibrium-stage model
Overflow contains no solid; solvent is not vaporised, adsorbed,
or crystallised
Any entering solid solute is completely dissolved into liquid in
the stage; composition of liquid in the stage is uniform
Solute is not adsorbed on the surface of inert solid; inert solid
leaving in underflow from each stage are wet with liquid, such
that mass ratio of solvent in that liquid to inert solid is
constant from stage to stage
Concentration of solute in the overflow is equal to that in the liquid
portion of solute in the underflow. This is equivalent to an
equilibrium assumption


46

Equilibrium-stage model
For the continuous, countercurrent system of ideal
leaching stages, solute and total-liquid material balances
can be used to solve problems:
Determination of ideal stages required to achieve a specified
degree of washing
Determination of the effect of washing for a specified degree
of washing with a certain number of ideal stages
For most problems, it is best to consider the leaching
stage separately from the washing stage
Depending on the problem, either an algebraic or a
graphic method (e.g., McCabe-Thiele method) can be
used.
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Ideal leaching stage
In an ideal leaching stage, all of
the solute is dissolved by the
solvent, whereas the solid is
not dissolved. Also the
composition of the retained
liquid phase in the underflow
slurry is identical to the
composition of the liquid
overflow, and that overflow
is free of solids.
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Mixer-settler
Overflow
Liquid (B,C)
Liquid (B,C)
Solid (A)
underflow
Solid feed, F
Insoluble A
Soluble B
Liquid
solvent, S
Leaching and washing
When leaching is very rapid, it is common to countercurrently
wash the solids to reduce the solute concentration in the
liquid adhering to the solids. This can be accomplished in a
series of gravity thickeners or centrifugal thickeners, called
hydroclones.
The arrangement ensures that a clear overflow is obtained.
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Strong solution
Operating lines for washing stages
Material balances for the portion of the cascade consisting of the N units
are as follows:
Total solution: L
L
+ V
N+1
= L
N
+ V
1
(8.7)
Solute: L
L
x
L
+ V
N+1
y
N+1
= L
N
x
N
+ V
1
y
1
(8.8)
Solving for y
N+1
gives the operating line equation:



As usual, the operating line passes through the two end points (X
L
, Y
1
) and
(X
N
, Y
N+1
), and if the flow rates are constant, the slope is L/V.
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1
1 1
1
1
+ +
+

+ =
N
L L
N
N
N
N
V
x L y V
x
V
L
y
(8.9)
McCabe-Smith algebraic method
McCabe and Smith derived an algebraic method based on Kremser equation
for the calculation of number of ideal stages, N


The term log(L/V) can be written in terms of end points


Combining eq(8.10) and (8.11) gives




When V and L are liquid flows of solute-free solvent, x and y in (8.10) and
(8.11) are replaced by X and Y solute mass ratios.
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( ) V L
y y
y x
N
L L
N N
/ log
log
1

=
+
N L
N
N L
N
x y
y y
x x
y y
V
L

=
+ + 1 1 1 1
(8.10)
(8.11)

=
+
+
N L
N
L L
N N
x y
y y
y y
y x
N
1 1
1
log
log
(8.12)
Tutorial 9
Study questions
When a binary feed is contacted with a solvent to form
two equilibrium liquid phases, which is the extract and
which is the raffinate?
What are the characteristics of triangular diagrams? On
such a diagram, what are the miscibility boundary, plait
point, and tie lines?
What are the conditions for an ideal, equilibrium leaching
stage?
What are the similarities and differences between
extraction and distillation?
What is inverse-level-arm rule and its application in
extraction?

52
Class problem - 1
Construction of equilateral triangular diagram for
Furfural-Ethylene Glycol-Water system at 25
o
C and 101
kPa.
53
Class problem - 2
A mixture containing 40wt% acetone and 60wt% water is
contacted with an equal amount of MIK
(a) What fraction of the acetone can be extracted in a single-
stage process?
(b) What fraction of the acetone could be extracted if the
fresh solvent were divided into two parts and two successive
extractions used?
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Answers: (a) fraction of acetone extracted = 78.9%;
(b) Fraction of acetone extracted = 86.3%.
Class problem - 3
4000 1b per day of waxed paper containing 25wt% soluble wax and 75wt%
insoluble pulp are to be dewaxed by leaching with kerosene in the
continuous, countercurrent system. The wax is completely dissolved by
kerosene in the leaching stage, L. Subsequent washing stages reduce the
wax content in the liquid adhering to the pulp leaving the last stage, N, to
0.2 1b wax/100 1b pulp. Kerosene entering the system is recycled from a
solvent-recovery system and contains 0.05 1b wax/100 1b kerosene. The
final extract is to contain 5 1b wax/100 1b kerosene. Experiments show
that underflow from each stage contains 2 1b kerosene/1b insoluble pulp.
Determine the required washing stage using McCabe-Thiele graphic method.
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Y
N+1
, X
N

Y
1
, X
L

Answers: three washing stages are required.