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SOLVENT EXTRACTION

(LIQUID-LIQUID
EXTRACTION)

Perrys Chemical
Engineers Handbook
8th Edition

7th Edition

Section 15
Pages 15-6 to 15-21
Pages 15-58 to 15-92

Section 15
Pages 15-4 to 15-47

Table 15-1 Selected


Partition Ratio Data

Table 15-5 Selected List of


Ternary Systems

Solvent Extraction (LiquidLiquid Extraction)


The process where two immiscible or partly miscible
liquids are brought in contact with each other and
soluble substance(s) in one liquid (raffinate phase)
passes into the other liquid (extract phase) by
diffusion.
Commonly used for concentration of the soluble
substance(s) or for purification of the raffinate liquid.

CLASSIFICATION:
Single Solvent System

A. Stage-wise Contact:
1. Single Contact (analogous to Equilibrium
Distillation)
2. Co-current Multiple Contact or Simple Multistage contact
3. Counter-Current Multi-stage or Multiple
Contact
a. Without Reflux
b. With Reflux (analogous to Fractional Distillation)

B. Continuous Contact: (Differential Contact)

Counter-current Flow, N Equilibrium Stage


Liquid-Liquid Extraction Cascade

Liquid-Liquid Extraction with Reflux: (a) with Extract and


Raffinate Reflux; (b) with Extract Reflux only

k = distribution coefficient

concentration of solute in raffinate phase


k
concentration of solute in extract phase
k = partition ratio

mass fraction solute in extract phase


k
mass fraction of solute in raffinate phase
A = feed solvent, B = solute,
S = extraction solvent
Feed solvent, A and extraction solvent, S
are immiscible with each other

Partition ratio K is commonly defined for a given


solute as the solute concentration in the extract phase
divided by that in the raffinate phase after equilibrium
is attained in a single stage of contacting. A variety of
concentration units are used, so it is important to
determine how partition ratios have been defined in
the literature for a given application. The term
partition ratio is preferred, but it also is referred to as
the distribution constant, distribution coefficient,
or the K value. It is a measure of the thermodynamic
potential of a solvent for extracting a given solute and
can be a strong function of composition and
temperature.

Extraction factor E is a process variable that


characterizes the capacity of the extract phase to carry
solute relative to the feed phase. Its value largely
determines the number of theoretical stages required
to transfer solute from the feed to the extract. The
extraction factor is analogous to the stripping factor in
distillation and is the ratio of the slope of the
equilibrium line to the slope of the operating line in a
McCabe-Thiele type of stage-wise graphical
calculation.

Desirable Solvent Properties


1. Loading capacity - This property refers to the maximum
concentration of solute the extract phase can hold before
two liquid phases can no longer coexist or solute
precipitates as a separate phase.
2. Partition ratio Ki = Yi/Xi - Partition ratios on the order of
Ki = 10 or higher are desired for an economical process
because they allow operation with minimal amounts of
solvent (more specifically, with a minimal solvent-to-feed
ratio) and production of higher solute concentrations in
the extractunless the solute concentration in the feed
already is high and a limitation in the solvents loading
capacity determines the required solvent-to-feed ratio.

3. Solute selectivity -In certain applications, it is


important not only to recover a desired solute from the
feed, but also to separate it from other solutes present
in the feed and thereby achieve a degree of solute
purification. The selectivity of a given solvent for
solute i compared to solute j is characterized by the
separation factor i,j = Ki/Kj. Values must be greater
than i,j = 1.0 to achieve an increase in solute purity
(on a solvent-free basis). When solvent blends are used
in a commercial process, often it is because the blend
provides higher selectivity, and often at the expense of
a somewhat lower partition ratio.

4. Mutual solubility - Low liquid-liquid mutual


solubility between feed and solvent phases is desirable
because it reduces the separation requirements for
removing solvents from the extract and raffinate
streams.
5. Stability - The solvent should have little tendency to
react with the product solute and form unwanted byproducts, causing a loss in yield.
6. Density difference - As a general rule, a difference in
density between solvent and feed phases on the order
of 0.1 to 0.3 g/mL is preferred. A value that is too low
makes for poor or slow liquid-liquid phase separation
and may require use of a centrifuge.

7. Viscosity -Low viscosity is preferred since higher


viscosity generally increases mass-transfer resistance
and liquid-liquid phase separation difficulty.
8. Interfacial tension - Preferred values for interfacial
tension between the feed phase and the extraction
solvent phase generally are in the range of 5 to 25
dyn/cm (1 dyn/cm is equivalent to 103 N/m).
Systems with lower values easily emulsify.
9. Recoverability - The economical recovery of solvent
from the extract and raffinate is critical to commercial
success. Solvent physical properties should facilitate
low-cost options for solvent recovery, recycle,
and storage.

10. Freezing point - Solvents that are liquids at all


anticipated ambient temperatures are desirable since
they avoid the need for freeze protection and/or
thawing of frozen solvent prior to use.
11. Safety - Solvents with low potential for fire and
reactive chemistry hazards are preferred as inherently
safe solvents. In all cases, solvents must be used with a
full awareness of potential hazards and in a manner
consistent with measures needed to avoid hazards.
12. Industrial hygiene - Solvents with low mammalian
toxicity and good warning properties are desired. Low
toxicity and low dermal absorption rate reduce the
potential for injury through acute exposure.

13. Environmental requirements - The solvent must


have physical or chemical properties that allow
effective control of emissions from vents and other
discharge streams. Preferred properties include low
aquatic toxicity and low potential for fugitive
emissions from leaks or spills.
14. Multiple uses - It is desirable to use as the extraction
solvent a material that can serve a number of purposes
in the manufacturing plant. This avoids the cost of
storing and handling multiple solvents. It may be
possible to use a single solvent for a number of
different extraction processes practiced in the same
facility, either in different equipment operated at the
same time or by using the same equipment in a series
of product campaigns.

15. Materials of construction - It is desirable for a


solvent to allow the use of common, relatively
inexpensive materials of construction at moderate
temperatures and pressures.
16. Availability and cost - The solvent should be
readily available at a reasonable cost. Considerations
include the initial fill cost, the investment costs
associated with maintaining a solvent inventory in
the plant (particularly when expensive extractants are
used), as well as the cost of makeup solvent.

DESIGN DIAGRAMS. (Diluent and Solvent Partially


Miscible)
Triangular Coordinates. (Equilateral triangle diagram)
S

extract branch
plait point
raffinate branch
AB

A
B
Type I

extract

raffinate

B
A

A
B
Type II

Rectangular Coordinates:
Right Triangle diagram (weight basis)
S
xs

BA

Xs
orny s
Ys

s vs y (extract)
plait point

A B S
AB

S
s
B A S

s vs x (raffinate)
AB

x AB or y AB
Type I
X Bor YB

B
B A S

S
xs
or

extract

ys
ate
n
i
f
f
a
r

AB

B
A

x AB or y AB
Type II

Janecke or Ponchon Diagram. (weight ratio


solvent-free basis)

extract branch
s'
plait point
raffinate
X, Y
Type I
S
A
s'
A B

X or Y

B
B A

s' vs Y
extract
s'
s' vs X
raffinate
X, Y
Type II

Equilibrium Data for the system Acetic Acid


water isopropyl ether at 20C.
Water Layer
(Raffinate)

Isopropyl Ether Layer


(Extract)

Wt. %
acetic acid
100%

Water

Isopropyl
ether

Acetic acid
100%

Water

Isopropyl
ether

0.69
1.41
2.89
6.42
13.30
25.50
36.70
44.30
46.40

98.1
97.1
95.5
91.7
84.4
71.1
58.9
45.1
37.1

1.2
1.5
1.6
1.9
2.3
3.4
4.4
10.6
16.5

0.18
0.37
0.79
1.93
4.82
11.40
21.60
31.10
36.20

0.5
0.7
0.8
1.0
1.9
3.9
6.9
10.8
15.1

99.3
98.9
98.4
97.1
93.3
84.7
71.5
58.1
48.7

Most Common Classes of Ternary Systems:

(a) Type I, one immiscible pair; (b) Type II, two immiscible
pairs

Effect of Solubility on Range of Feed


Composition that can be Extracted

Location of Product Points

Location of Operating Point

Determination of the Number of


Equilibrium Stages

Determination of Minimum Solvent to


Feed Ratio

Construction of Equilibrium Stages on Janecke Diagram

Limiting conditions on a Janecke Diagram: (a) minimum number


of stages at total reflux; (b) minimum reflux determined by a tie
line through the feed point; (c) minimum reflux determined by a
tie line to the right of the feed point

Commercial Extractors with Mechanically Assisted Agitation


(a),(b),(c) Scheibel Column (d) Oldshue Rushton (Mixco) Column

Scheme for Selecting Extractors

Common Liquid-Liquid Extraction Cascade Configurations


(a) single section cascade; (b) two section cascade;
(c) dual solvent with two section cascade

Mixer Settler Extraction System

System Acetone-MIK-Water at 25C

System Aniline-n-Heptane-MCH at 25C

Countercurrent Extraction with Reflux

Sulfolane Extraction Process

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