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The basics
In a liquid-liquid extraction unit, a liquid stream (carrier)
containing the component(s) to be recovered (solute) is fed
into an extractor, where it contacts a solvent. The two liquids
must be immiscible or only slightly miscible; this allows
them to form a dispersion, with one liquid dispersed as droplets in the other.
Mass transfer occurs between the droplets (dispersed
phase) and the surrounding liquid (continuous phase). In
order for the two liquids to be subsequently separated, they
must have different densities. The droplets then accumulate
above or below the continuous phase, depending on the liq22
Feed
(Carrier A and
Solute C)
Solvent B
Mixing
and
Contacting
Section
Phase-Settling
and Coalescing
Section
Extract
(Solvent B and
Solute C with
some A)
Raffinate
(Carrier A with
some B and C)
p Figure 1. An extraction unit has two inlet streams (the liquid carrier
containing solute molecules, and the solvent) and two outlet streams (the
raffinate and the solute-rich extract).
Selecting a solvent
Solvents used in liquid-liquid extraction are chosen to
achieve maximum transfer of the solute from the carrier
into the solvent. They must not be completely miscible
with the carrier liquid and should have a high affinity for
the solute molecules.
An ideal solvent for liquid-liquid extraction will typically
have the following properties:
high solubility for the solute and low solubility for the
carrier liquid
density difference vs. the carrier liquid greater than
150 kg/m3
mid-level interfacial tension (530 dyne/cm)
high resistance to thermal degradation
nonreactive with other chemicals involved in the
extraction process
high boiling point (for ease of material handling)
low viscosity (for ease of handling)
nontoxic, nonflammable, and not corrosive to process
equipment (for ease of handling)
low cost.
Engineers usually choose several solvents for process
development. Often, the solvent candidates violate one or
more of the criteria for an ideal solvent, so a comparison
study is required to identify the best solvent for a particular
application.
Dispersed-phase droplet size
An extraction column can be designed with either
liquid as the dispersed phase: The solvent can be dispersed
as droplets in the carrier liquid, or the carrier liquid can be
dispersed as droplets in the solvent.
In packed columns, it is generally desirable to disperse
the inlet stream with the higher volumetric flowrate into
the continuous phase in order to maximize the interfacial
area for mass transfer. In agitated columns, the liquid phase
with the lower volumetric flowrate is typically dispersed,
Copyright 2015 American Institute of Chemical Engineers (AIChE)
(1)
Raffinate
A (some B + C)
Coalescer
Section
Feed
A+C
Solvent
B
Mass-Transfer
Section
Solvent
B
Coalescer
Section
Raffinate
A (some B + C)
Mass-Transfer
Section
Feed
A+C
Extract
B + C (some A)
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Axial mixing
Axial (longitudinal) mixing causes the extractor to
deviate from ideal plug-flow operation. As a result of axial
mixing, the dispersed phase and the continuous phase will
exhibit a range of residence times, which tends to reduce
the concentration driving force for mass transfer in the
column. Axial mixing can be a particular problem in largediameter extraction columns, because redistributors have
less profound effects in larger columns than they do in
small-diameter extractors.
Several mechanisms and conditions can lead to axial
mixing, including:
Vessel walls or other fixed components can exert
frictional drag on the liquids and cause turbulent mixing.
Nonuniform droplet size distribution in the contacting
section of the extractor can cause the extractor to deviate
from plug-flow operation.
Chaotic eddy patterns can form when fluids interact
Transfer of Solute Outward
Flooding
The maximum flowrate through an extraction column
is limited by flooding. Hydraulic flooding occurs when the
two liquid streams can no longer uniformly flow counterChaotic Flow Patterns
Vertical Barriers
Horizontal Barriers
p Figure 3. The solute can move either outward from the droplets to the
continuous solvent phase, or inward from the continuous phase into the
dispersed solvent. Left: The transfer of solute outward causes the droplets to
grow and can cause them to shatter into smaller droplets. Right: The transfer of
solute from the solvent into the droplets can create stable droplet surfaces.
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Efficiency
Capacity
Low to
Medium
High
Low
Mixer-Settler
Extractors
High
Low
High
Pulsed Static
Extractors
Medium
Medium
Medium
Stirred Extractors
High
Medium
Medium
Centrifugal Extractors
High
Low
High
Static Extractors
Costs
25
26
0.40
Equilibrium Line
(Shake Test)
NTS
0.30
0.20
Operating Line
(Pilot Trials)
0.10
0.00
0.00
0.10
Raffinate
Composition
0.20
0.30
0.40
0.50
0.60
Feed
Composition
0.70
p Figure 6. The data obtained from the shake test and the pilot-scale runs
are used to determine the NTS, and thus the column height.
p Figure 7. Many types of random packing, such as the rings shown here,
are available for static extraction columns.
Copyright 2015 American Institute of Chemical Engineers (AIChE)
Structured Packing
27
p Figure 11. Sieve trays are perforated plates with round holes.
p Figure 12. Left: In a simple one-pass sieve tray column with downcomers,
the light phase (orange) is dispersed and the heavy phase (yellow) flows through
the downcomers. Right: In a sieve-tray column with upcomers, the heavy phase
(yellow) is dispersed, and the light continuous phase (orange) flows through the
upcomers.
p Figure 14. The internals of the Khni column can be made of metal (left)
or corrosion-resistant materials (right).
by adding more upcomers or downcomers, and the hydraulic correlations developed for short flow-path lengths are
still applicable.
Each of these static extractors requires specialized distributors to introduce the dispersed and continuous phases
into the mass-transfer contacting device. Small extractors with
diameters less than 600 mm can use simple spargers, or T-pipe
or H-pipe distributors. Larger-diameter extractors are typically
designed with header pipes equipped with multiple arms.
Table 2 compares the various static extractor devices.
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wide range of operating conditions, and can have significantly higher separation performance at high throughput
than RDCs, simple spray columns, and pulsed sieve plate
columns (10).
The Khni column is also well-known for being adaptable; it can employ internals that handle high mass transfer
and cope with changing liquid physical properties (11). The
geometrical details of each compartment can be modified
to enable the column to compensate for varying conditions
over the height of the column and to produce a uniform
droplet size and hold-up profile, which is beneficial for column performance and reliable scale-up.
Figure 14 shows internal devices for a Khni column, which are available in metal or corrosion-resistant
internals.
Table 2. The internals of an extraction column facilitate the distribution of the dispersed and continuous phases
and the contact between the two fluids for mass transfer.
Extractor Device
Spray Columns
Random Packing
Benefits
High volumetric throughput
Simple vessel design (inexpensive)
29
Closing thoughts
Significant developments have pushed the state of
liquid-liquid extraction forward over the past 5060 years.
In the past, many extractors were simple spray columns
or RDC columns. In the 1950s, engineers began to study
extractor packing and trays, and there was a small number
of equipment suppliers that provided proprietary extractor
equipment.
The field of extraction has developed much differently
than the gas-liquid distillation field. Much of the progress
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Literature Cited
1. Frank, T. C., et al., Liquid-Liquid Extraction and Other LiquidLiquid Operations and Equipment, Section 15 in Green, D. W.,
and R. H. Perry, eds., Perrys Chemical Engineers Handbook,
8th ed., McGraw-Hill, New York, NY (2008).
2. de Ortiz, E. S. P., Marangoni Phenomena: Science and Practice
of Liquid-Liquid Extraction, Vol. 1, Thornton, J. D., ed.,
Clarendon Press, Oxford, U.K. (1992).
3. Treybal, R. E., Liquid Extraction, 2nd ed., McGraw-Hill,
New York, NY (1963).
4. Shiveler, G., Modern Sieve Trays for Liquid-Liquid Extraction, AIChE Annual Meeting, San Francisco, CA (Nov. 3, 2013).
5. de Villiers, W., et al., Tray Technology Enhances Extraction,
Petroleum Technology Quarterly (Q3-2007).
6. Thornton, J. D., Science and Practice of Liquid-Liquid
Extraction, Oxford University Press, New York, NY (1992).
7. Lo, T. C., et al., Handbook of Solvent Extraction, Krieger
Publishing Co., New York, NY (1983).
8. Godfrey, J. C., and M. J. Slater, eds., Liquid-Liquid Extraction
Equipment, Wiley, Hoboken, NJ (1995).
9. Aksamija, E., and M. Siebenhofer, Design and Operation
Characteristics of Liquid-Liquid Extractors with Disc Supported
Taylor-Couette-Flow, AIChE Annual Meeting, Atlanta, GA
(Nov. 19, 2014).
10. Kumar, A., and S. Hartland, Mass Transfer in a Khni Extraction Column, Industrial and Engineering Chemistry Research,
27 (7), pp. 11981203 (July 1988).
11. Bhlmann, U., Aromatics Extraction with the Khni Column,
An Application Requiring an Extreme Design Flexibility, in
Solvent Extraction in the Process Industries, Logsdail, D.H.,
and Slater, M.J., eds., Proceedings of ISEC 1993, York, PA (1993).