Chapter-3

LIQUID EXTRACTION
(Solvent Extraction)
Separation of components of
a liquid solution by contacting
with another insoluble liquid in
one of the feed components.
3
Separation of solution of acetic acid in water
with ethyl acetate.
in single stage, multistage countercurrent,
continuous contact with or without reflux.
Feed Solution to be extracted.
Solvent Liquid with which the feed is contacted.
Extract Solvent rich product of the operation.
Raffinate Residual liquid from which solute has
been removed.
More complicated processes may use two
solvents.
Ex: Separation of a mixture of p- and o-
nitrobenzoic acids using insoluble liquids
chloroform and water. Double-solvent or
fractional extraction

4
Fields of usefulness
a) In competition with other mass-transfer operations
- distillation, evaporation (direct separation methods)
- latent heat
- thermal decomposition (long chain fatty acids from
vegetable oils with propane)
- Tantalum and niobium
b) As a substitute for chemical methods
- disposal problems
- metal separations U-V, Hf-Zr, W-Mo
c) In separations not possible by other methods
- vapor pressures,
- separation of aromatic and paraffinic hydrocarbons
of nearly same mol wt by extraction with a number
of solvents. Extractive distillation liquid extraction.

5
Analogy between Distillation and Extraction
Distillation Extraction
Addition of heat Addition of solvent
Reboiler Solvent Mixer
Removal of heat Removal of solvent
Condenser Solvent separator
Mixture of liquid and vapor Two-phase liquid mixture
Relative volatility Selectivity
Distillate Extract product
Residue Raffinate
More volatile component Solute to be extracted
Less volatile component Carrier component from which
solute is to be extracted
6
Notation
A, B, C
Same letter for quantity of a solution
or mixture.
E, R, B mass per time
Solvent-free (B-free) quantities are
indicated by primed letters. Thus
x = weight fraction C in the solvent-
lean (A-rich), or raffinate , liquids
y = weight fraction C in the solvent-
rich (B-rich), or extract, liquids
7
E
'
E
'
x = x/(1-x) = mass C/ mass non-C in the raffinate
liquid.
y = y/(1-y) = mass C/ mass non-C in the extract
liquid.
X = weight fraction C in the raffinate liquids on a B-
free basis, mass of C/mass of (A + C)
Y = weight fraction C in the extract liquid on a B-
free basis, mass of C/mass of (C + A)
N = weight fraction B on a B-free basis, mass of
B/mass of (A + C)
= mass of B-free solution/time
E= /(1+ )

E
N
8
Coordinates of Ternary liquid
Equilibrium (TLE)
Equilateral triangular coordinates
Rectangular coordinates


9
R M
M E
x x
x x
RM
ME
E
R

= =
line
line
Equilateral Triangular Coordinates
10
Types of Liquid systems in
Extraction
1) Systems of three liquids with one
pair partially soluble.
2) Systems of three liquids with two
pairs partially soluble.
3) Systems of two partially soluble
liquids with one solid.

11
Systems of three liquids with one pair partially soluble
Ex: 1) Water-chloroform-acetone
2) Benzene-water-acetic acid
Binodal solubility curve
P plait point


y
*
/x = distribution coefficient
Solutropic
tie line
horizontal
12
Effect of temperature on solubility
Effect of pressure on liquid equilibrium is
very small.
13
Systems of three liquids with two pairs partially soluble
(A-B and B-C partially miscible)
Ex;1) Chlorobenzene(A)-Water(B)-Methylethylketone(C)
14
Effect of temperature
15
Systems of two partially soluble liquids with one solid
(A-B are partially miscible)
Ex; 1) Aniline(A)-Isooctane(B)-naphthalene (C)
16
To expand one concentration scale relative to
another.
Unequal scales can be used.
Other coordinates
17
Fig. 10.10 Rectangular
coordinates, solvent-free
basis, for a system of two
partly miscible liquid pairs
18
Ex: Distribution of formic and
acetic acids between partially
soluble water and CCl
4
.
Multicomponent systems
19
Choice of solvent
1. Selectivity


2. Distribution coefficient (y
*
/x, need not be
> 1)
3. Insolubility of solvent
4. Recoverability
5. Density
6. Interfacial tension (high for coalescence)
7. Chemical reactivity
8. Viscosity, vapor pressure, freezing point
9. Nontoxic, nonflammable, low cost.


20
21
EQUIPMENT AND FLOWSHEETS
STAGEWISE CONTACT
Single-stage Extraction

F + S
1
= M
1
= E
1
+ R
1
Fx
F
+ S
1
y
s
= M
1
x
M1
(10.6)
(10.7)

(10.8)
Min and Max -
solvent
1 1
1 1 1
1
1 1 1 1 1 1
1
1 1
) (
x y
x x M
E
x M x R y E
y x
x x
F
S
M
M
S M
M F

=
= +

=
22
Solvent-free basis
Balance for C and B
Figure 10.13: Single-stage extraction, solvent-free
coordinates.
) 1 (
) 1 (
) (
1
'
1 1
1
'
1 1
1 1
1 1
'
1
'
1
1
'
1 1
'
1 1
'
1
' '
1
'
1 1
'
1 1
'
1
' '
'
1
'
1
'
1
' '
R
E
M
R E M S F
M S F
N R R
N E E
X Y
X X M
E
N R N E N M N X N F
X R Y E X M Y S X F
R E M S F
+ =
+ =


=
+ = = +
+ = = +
+ = = +

(10.9)

(10.10)
(10.11)

(10.12)

(10.13)
23
If the solvent is pure B, N
S
= , these equations still apply, with the
simplification that S

= 0, Y
S
= 0, S

N
S
= B, and F

= M
1

. Minimum and
maximum amounts of solvent correspond to putting M
1
at D and K on the
figure, as before.
Equations (10.9) and (10.10) lead to

(10.14)
1 1
1 1
'
1
'
1
X X
X Y
E
R
M
M

=
Analogy with distillation?
If solvent is pure, operating line passes through the 45
o
line
at X
F
.
24
Multistage cross-current Extraction
25
Total balance : (10.15)
C Balance: (10.16)


For the solvent-free coordinates,
A + C balance : (10.17)
C balance : (10.18)
B balance : (10.19)
n n n n
n
R n E n M n S n R n
n n n n M n S n n n
n n n n n
n n n n Mn n S n n n
n n n n n
N R N E N M N S N R
X R Y E X M Y S X R
R E M S R
x R y E x M y S x R
R E M S R
' ' ' ' '
1
' ' ' '
1
'
1
' ' 1 ' '
1
1 1
1
1
+ = = +
+ = = +
+ = = +
+ = = +
+ = = +

For any stage n

26
Where x = x/(1-x) and y = y/(1-y)
Figure 10.16: Crosscurrent extraction with an insoluble
solvent
Insoluble liquids:
(10.20)
(10.21)

' '
1
' '
' ' ' '
1
n n
n S
n
n n n S n n
x x
y y
B
A
Ax y B y B Ax

=
+ = +

27
Countercurrent multistage extraction
material balance about the entire plant is
(10.22)
Point M can be located on line FS through a balance for substance C,
(10.23)
(10.24)
Equation(10.22) indicates that M must lie on line R
Np
E
1
, as shown.
Rearrangement of Eq. (10.22) provides
(10.25)
R N
S F
M
M N N S F
N
E F S R
S F
Sy Fx
x
Mx x R y E Sy Fx
M R E S F
P
P P
P
A = =
+
+
=
= + = +
= + = +
1
1 1
1
28
A material balance for stages s through N
p
is
(10.26)
(10.27)
R s s N
s N s
E R S R
E R S R
p
p
A = =
+ = +

1
1
29
Minimum solvent for countercurrent extraction
30
31


When the number of stages is very large
32
Insoluble liquids
When the liquids A and B are insoluble over the range of solute
concentrations encountered,
(10.35)
or (10.36)

Which is the equation of a straight line, the operating line, of slope A/B,
through points . For stages 1 through s, similarly
(10.37)
) , ( ), , (
' ' ' '
1
p
N S F
x y x y
' '
'
1
'
1
' '
' '
1
'
1
' ' '
s F
s
N F
S
N F S
x x
y y
B
A
x x
y y
B
A
By Ax Ax By
p
p

=
+ = +
+
33
For the special case where the equillibrium curve is of constant slope
Eq. (5.50) applies,


Where is the extraction factor. This can be used in
conjunction with Fig. 5.16, with as
ordinate and as parameter.
1 ) / (
/ ) / (
/
1
'
'
1
'
' ' '
' '

+
+
p
p
p
N
N
S F
N F
A B m
A B m A B m
m y x
x x
' ' '
/ x y m
-
=
A B m /
'
) / /( ) / (
' ' ' ' ' '
m y x m y x
S F S N
p

A B m /
'
34
Continuous counter-current extraction with reflux
Feed introduced at feed stage f (and not at one end of the
cascade).
Solvent removed from extract E
1
to produce solvent free
stream E

part of which is removed as product and part

returned as reflux.
35
Murphree Stage efficiency
For extract E
ME
=

For raffinate E
MR
=




The overall stage efficiency E
o
of the cascade is the ratio of number of
theoretical stages to the number of actual stages required to bring
about a given concentration change.
1
*
1
+
+

m m
m m
y y
y y
*
1
1
m m
m m
x x
x x

36
37
Solute Carrier Solvent
Acetic Acid Water Ethyl acetate
Acetic Acid Water Isopropyl acetate
Benzoic acid Water Benzene
Penicillin Broth Butyl acetate
Vanilla Oxidized liquors Toluene
Vitamin A Fish-liver oil Propane
Vitamin E Vegetable oil Propane
Representative Industrial Liquid-Liquid Extraction
38
Emulsions
Emulsion a mixture of two immiscible liquids.
Stability (or permanence) of the emulsion is of utmost
importance in extraction.
Stable emulsions the ones which do not coalesce and settle
rapidly - should be avoided.
An emulsion should break or separate into two phases;
sedimentation and coalescence of dispersed phase must occur.
The sedimentation is more rapid if the size of the droplets and
the density difference of the liquids are large and the viscosity of
the continuous phase (?) is small.
39
Stable emulsions which settle over long periods of time
should be avoided (droplets 1 to 1.5 m).
Higher the interfacial tension more rapid coalescence.
Higher mutual solubility leads to lower interfacial tension.
High viscosity of continuous phase reduces the rate at which the
residual film between the drops is removed hinders
coalescence.
Dust particles at the interface between two liquids also hinder
coalescence.

40
Staged-type extractors
Two major types
Single stage mixer-settlers and multistage cascades
constructed from them
Sieve tray multistage towers
Mixers two types
Flow mixers or line mixers
Mixing vessels
41

Gravity Settlers
a) Simple
b) & c) with
coalescer
42
Mixer-settler Cascades
Flow sheet of three-stage countercurrent mixer settler cascade
43
Kerr McGee uranium extractor
44
Box-type mixer settler cascade
45
Sieve-tray (perforated plate) towers
Very effective with respect to liquid-
handling capacity and extraction
efficiency, particularly for systems of
low interfacial tension (?).
46
pilot Khni column

There are several types of such columns
that are commercially available,
e.g. the Scheibel, Oldshue, Rushton,
Khni columns and the rotating-disk contactors.

47
Flow configuration (gravitational field)
Feed heavier (denser) Solvent heavier (denser)
Solvent lighter Feed lighter


Feed Solvent
Feed Solvent
Counterflow in centrifugal field.
48
Design (Differential or continuous-contact extractors)
One of the liquids can be pumped at any rate.
The maximum rate for the other liquid will depend, inter alia,
upon the density difference of the liquids.
At flow rates more than this, one of the liquids will be rejected
flooding.
Flooding velocities of extractors are much lower.
Large diameter and more open cross-section will ensure that
flooding velocities are not reached.
Internal structures will help in flooding.
49
Effect of axial mixing
Axial mixing severely reduces the extraction rates.
Pe = Ul/D
50
Towers filled with same random packings used
for used for gas-liquid contact , also used for
liquid extractors.
Packing serves to reduce axial mixing
somewhat.
The position of the interface can be adjusted by
a control valve for pressure in the bottom outlet
pipe.
Packed towers
Packed extraction tower, light
liquid dispersed
51
The nature of the liquid flow requires that the choice of
packing and arrangement of dispersed phase behavior
be given careful attention.
If the dispersed phase preferentially wets the packing, it will
pass as rivulets, and not as droplets, and the interfacial area
produced will be small.
For this reason, the packing material should be preferentially
wetted by the continuous phase.
Usually, ceramics are preferentially wet by aqueous liquids,
and carbon and plastics by organic liquids.

52
Mixco Lightnin CMContactor (Oldshue-
Rushton extractor)
53
Rotating disc contactor (RDC)
54
Scheibel extractor
55
Pulsed column
56
Centrifugal extractor
Useful for
Small density differences
Very short residence times
are essential e.g., extraction
of penicillin from nutrient
broth

57
Class of Equipment Advantages Disadvantages
Mixer settlers Good contacting
Handles wide flow
ratio
Low headroom
High efficiency
Many stages available
Reliable scale-up
Large Holdup
High power costs
High investment
Large floor space
Interstage pumping
may be required
Continuous,
counterflow
contactors (no
mechanical drive)
Low initial cost
Low operating cost
Simple construction
Limited throughput
with small density
difference
Cannot handle high
flow ratio
High headroom
Difficult scaleup
Advantages and Disadvantages of Different Extraction Equipment
58
Class of Equipment Advantages Disadvantages
Continuous,
counterflow contactors
(mechanical agitation)
Good dispersion
Reasonable cost
Many stages possible
Relatively easy scale-
up
Limited throughput
with small density
difference
Cannot handle
emulsifying systems
Cannot handle high
flow ratio
Centrifugal extractors Handles low density
difference between
phases
Low holdup volume
Short holdup volume
Low space
requirements
Small inventory of
solvent
High initial costs
High operating cost
High maintenance cost
Limited number of
stages in a single unit
59
Always 1 raffinate entry, extract exit
2 extract entry, raffinate exit

1
2
1
1
ln
2
1
) )( 1 (
) 1 (
) 1 (
) )( 1 (
) 1 (
) )( 1 (
) 1 (
1
2
1
2
1
2
1
2
x
x
x x
dx
x x x
dx x
N
x a k
R
a F
R
H
N H
x x x
dx x
H
x x x a F
dx x R
Z
x
x i
x
x i
iM
tR
iM R R
tR
tR tR
x
x i
iM
iR
x
x i R
iM

= =
=

=
} }
} }
60
Where x
i
= interface concentration of solute
F
R
, k
R
= transfer coefficients for raffinate phase
H
tR
= raffinate height of transfer unit
N
tR
= number of raffinate transfer units
(1-x)
iM
= logarithmic mean of 1-x and 1-x
i

The interface concentration corresponding to any bulk raffinate
concentration x if found through Eq. (5.21) adapted to the present
situation

(10.102)
R
E
F
F
i
i
y
y
x
x
|
|
.
|

\
|

1
1
1
1
61
)] 1 /( ) 1 ln[(
) 1 ( ) 1 (
) 1 (
)] 1 /( ) 1 ln[(
) 1 ( ) 1 (
) 1 (
1
1
ln
2
1
) )( 1 (
) 1 (
1
1
ln
2
1
) )( 1 (
) 1 (
) 1 (
) 1 (
2
1
1
2
1
2
1
2
1
2
1
2
-
-
-
-
-
-
- -
-
- -
-
-
-


=


=

= =

= =
= =
} }
} }
y y
y y
y
x x
x x
x
y
y
y y
dy
y y y
dy y
N
x
x
x x
dx
x x x
dx x
N
y a K
E
a F
E
H
x a K
R
a F
R
H
N H N H Z
M
M
y
y
y
y
M
tOE
x
x
x
x
M
tOR
M E OE
tOE
M R OE
tOR
tOE tOE tOR tOR
(10.103)
(10.104)
(10.105)

(10.106)

(10.107)

(10.108)

(10.109)
62
If x and y are expressed in weight fractions,
(10.110)

(10.111)

Where r is the ratio of molecular weights of non-solute to the
solute, for weight ratio concentrations,
(10.112)

(10.113)
'
2
'
1
' '
'
'
1
'
2
' '
'
2
1
2
1
1
2
1
2
1
1
ln
2
1
1
1
ln
2
1
1 ) 1 (
1 ) 1 (
ln
2
1
1
1
ln
2
1
1 ) 1 (
1 ) 1 (
ln
2
1
1
1
ln
2
1
'
1
'
2
'
1
'
2
1
2
1
2
ry
ry
y y
dy
N
rx
rx
x x
dx
N
r y
r y
y
y
y y
dy
N
r x
r x
x
x
x x
dx
N
y
y
tOE
x
x
tOR
y
y
tOE
x
x
tOR
+
+
+

=
+
+
+

=
+
+
+

=
+
+
+

=
}
}
}
}
-
-
-
-
63
Dilute solutions




(10.114), (10.116) and (10.117) can be used in terms of
weight fractions
R mE
R
mE
R
mE
mx y
mx y
N
mE R
mE
R
mE
R
m y x
m y x
N
y y aZ K x x aZ K y y E x x R
y y
y y
N
x x
x x
N
tOE
tOR
M E M R
M
tOE
M
tOR
/ 1
1 ln
/ 1
1
/
/
ln
) ( ) ( ) ( ) (
) (
,
) (
1 1
1 2
2 2
2 1
2 1 2 1
2 1 2 1

+
|
.
|

\
|

+
|
.
|

\
|

=
= = =

=
- -
- -
(10.114)
Equivalent expressions in terms of mass transfer coefficients are
(10.115)
In addition the equivalent of Henrys laws applies

(10.116)

(10.117)
64
Use of specialized fluids
For separation of complex mixtures into their components, it has been
necessary to develop fluids with highly selective characteristics.
Metallurgical, nuclear, biotechnology and food industries are major users
of this technique.
Supercritical fluids can be highly selective and their solvent power can be
controlled by the adjustment of the operating pressure.
With SCF such as CO
2
there is no residual contamination of the product as
the solvent evaporates completely at the end of operation.

65
Supercritical fluids
A substance that exists above its critical point (?).
Many materials dont decompose before reaching the supercritical region.
Two most popular and inexpensive fluids water, CO
2
nontoxic and
nonflammable.
Other SCFs ethane, ethylene, propane, ammonia.
Densities of these fluids change considerably with changes in T and P.
Therefore, density dependent property such as solubility can be
manipulated(?).
Advantages of SCFs viscosities are less than those of typical liquids and
diffusivities of solutes are closer to those of gases.
SCFs combine the advantages of gases (diffusivities) and liquids (solvent
power).
Commercial application decaffeination of tea and coffee.
Extraction of spices, flavors, range of natural products, including
pharmaceutical compounds, health supplements and fragrances.
66
Fractionation of coal by use of high
temperature solvent extraction
For separation of coal (corresponding to the refining of petroleum)
Solvent extraction method extracts coal using a flowing stream of
non-polar solvent such as tetralin or 1-methylnaphthalene under
10 MPa at temperatures lower than 350 C.
To increase the extraction yield strong polar solvents such as
pyridine
67
Design of optimal solvent for extraction of bio-
active ingredients from mulberry leaves

Recent studies on exploiting natural compounds for
medicine and cosmetics have drawn much attention to the
effective extraction of the desired bio-active ingredients
from natural products.
Typically, various solvents of water, alcohols, acetone and
ether, etc. are used to extract bio-active substances from
natural products due to their broad solubility propensity on
solvents.
Water is generally applied to extract high polar ingredients,
such as carbohydrates, glycosides, and amino acids, while
ether is used to extract low polar ingredients, such as
aromatic compounds.
Thereby, alcoholwater mixtures are used to extract out
various ingredients having broad range of solubility
propensity for the investigation of the specific functionality
of the molecular compounds from extracted ingredients.

68
To develop a method for determining the optimal solvent conditions and
designing a solvent for the optimal extraction of bio-active ingredients
from mulberry leaf known to contain the active ingredients for anti-
oxidation and anti-hyperpigmentation.
Since the extraction of specific ingredients from natural resources
depends on the polarity of the solvent, the extraction efficiency of the
solvent for bio-active ingredients is investigated, along with the variation
in the polarity of the solvent according to the species and composition of a
binary alcoholwater solvent.
Methanol, ethanol, n-propanol, and iso-propanol are used as the alcohol
species for the binary mixture. Plus, ethylene glycol and acetone are used
to design model solvents to confirm the relationship between the
extraction of bio-active ingredients and the solvent polarity.
Based on the extraction of mulberry leaf, activities of ingredients specific
to anti-oxidation and anti-hyperpigmentation are used as references to
evaluate the extraction efficiency of the solvent

69
Soxhlet extractor
It was originally designed for the extraction
of a lipid from a solid material.
However, a Soxhlet extractor is not limited
to the extraction of lipids.
Typically, a Soxhlet extraction is only
required where the desired compound has
only a limited solubility in a solvent, and the
impurity is insoluble in that solvent