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Reactions and Separations

Design Principles for


Liquid-Liquid Extraction
Joerg Koch
Glenn Shiveler
Sulzer

Many factors must be evaluated when


developing a liquid-liquid extraction process.
Here are some of the important parameters
to consider as you go from laboratory testing
to commercial-scale operation.

iquid-liquid extraction is an important separation


technology for a wide range of applications in the
chemical process industries (CPI). Unlike distillation, which is based on boiling point differences, extraction
separates components based on their relative solubilities in
two immiscible liquids. Extraction is typically chosen over
distillation for separation applications that would not be
cost-effective, or even possible, with distillation.
This article discusses the basics of liquid-liquid extraction and provides guidance on how to select the appropriate solvent and extraction equipment. It introduces key
concepts associated with designing a liquid-liquid extraction process. The article also touches on unit design and
the importance of placing temperature, pressure, and level
control devices in the correct location.

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

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uids relative densities. The boundary between the continuous


phase and the droplet dispersion is referred to as the interface,
and can be at the top or bottom of the extraction column.
Figure 1 illustrates the general concept of liquid-liquid
extraction. More fundamental information about liquidliquid extraction can be found in engineering textbooks as
well as in Perrys Handbook (1).
Extraction is typically carried out in continuous, staged
units, which can be operated in either of two modes: with
co-current mixing or with counter-current mixing. The
co-current mixing mode is generally limited to one theoretical stage per extraction unit, whereas counter-current

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).

Copyright 2015 American Institute of Chemical Engineers (AIChE)

mixing is amenable to multiple stages per unit. For this


reason, counter-current mixing is usually preferred over
co-current mixing.
Counter-current extractors can be arranged in one of two
ways (Figure 2), the choice of which depends on the density
of the solvent relative to that of the solute carrier. If the
solvent is less-dense than the carrier liquid, the solvent is fed
into the bottom of the column, the solute is carried upward
to the top of the extractor, and the carrier liquid is removed
from the bottom of the unit (Figure 2, left). If the solvent is
more-dense than the carrier liquid, the solvent is fed into the
top of the column, the solute is carried downward to the bottom of the extractor, and the carrier stream is removed from
the top (Figure 2, right).

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)

so that both phases (dispersed and continuous) have similar


residence times. It is generally desirable to disperse the
liquid containing the solute in the extracting solvent, so
that the direction of mass transfer is out of the dispersed
droplets and into the continuous phase.
The dispersion in the extraction unit is unstable, so
the droplets will eventually separate into a bulk phase.
Droplet size is a critical parameter in determining the rate
at which that occurs. The maximum stable size of droplets
in the contacting section of static (nonagitated) extractors
depends on the internal energy and physical properties
of the fluids, and can be determined through statistical
measurements taken during extraction tests. Droplets in
mechanically agitated extractors will be smaller than those
in static extractors. The maximum stable droplet diameter
(DM) for static extractors can be calculated by:
DM = c

(1)

where c is the proportionality constant, P is the interfacial


tension, is the difference between the two fluids densities, and g is the gravitational constant.
The direction of mass transfer can influence the
behavior of liquid-liquid dispersions, thereby affecting the
proportionality constant in Eq. 1. The Marangoni effect (2)
explains how mass transfer of solute from one phase to the
other creates interfacial tension gradients on the surface
Extract
B + C (some A)

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)

p Figure 2. Counter-current extraction units can be set up in one of two


ways. Left: When the solvent is lighter than the carrier liquid, the solvent is
introduced at the bottom of the column and the solute is carried up toward
the top of the extractor. Right: When the solvent is heavier than the carrier,
the solvent is introduced at the top of the column and the solute is carried
downward by the solvent toward the bottom of the column. The red dots
represent the region in which the solute is transferred to the solvent.

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23

Reactions and Separations

of the dispersed phase. Transfer of solute from the droplet


outward into the continuous phase tends to create larger
droplets and higher interfacial area of contact between the
two phases, and is represented by a larger proportionality
constant. Transfer of solute from the continuous phase into
the droplets tends to form smaller droplets and the proportionality constant is smaller. The mass-transfer rate across
the droplet surface can also influence droplet behavior,
with high flux rates causing the droplets to shatter. Figure 3
illustrates these effects.
Mechanically agitated extractors add energy to the system to influence the droplet size and thereby generate sufficient interfacial area of contact between the two phases.
The high shear rate produced by turbulent agitation breaks
the droplets into smaller droplets and distorts their shape.
Equations have been developed to calculate the maximum
drop size for agitated liquid-liquid extraction (1).

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

with fixed components of the extractor.


Wake shedding can occur when small droplets flow
in the wake of larger droplets. Wake shedding can become
a problem at extremely high or extremely low volumetric
phase ratios.
Extractors can be designed to minimize axial mixing.
This is done by dividing the mass-transfer section into
smaller compartments to minimize deviations from plugflow operation. Sieve plates, for example, act as horizontal
barriers that the liquid must pass through, establishing a
uniform velocity profile downstream of each sieve plate.
Structures can also be added to the extractor to divide it into
vertical compartments restricting horizontal movement.
Figure 4 illustrates hydraulic axial mixing and the use of
horizontal and vertical compartments to control this effect.

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

Transfer of Solute Inward

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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p Figure 4. Top: Several mechanisms can cause axial mixing, including


chaotic flow patterns that develop in the mass-transfer contacting section.
Axial mixing can be controlled by adding devices that divide the column
into vertical segments (center) or into horizontal segments (bottom).
Copyright 2015 American Institute of Chemical Engineers (AIChE)

currently past one another. It is the point at which stable


counter-current extraction is no longer possible.
Several circumstances can cause flooding, including:
excessive hold-up of the dispersed-phase droplets; the presence of very small droplets, which significantly increases
the mass-transfer-contacting surface area; and excessive
axial mixing.
Dispersed-phase hold-up can indicate the presence and
degree of flooding. During counter-current extractor operation, dispersed-phase droplets are held up by the continuous
phase that is flowing in the opposite direction. The pressure
drop over an extractor is essentially the hydrostatic head
of the dispersed and continuous phases. Information from
differential-pressure indicators (DPIs) can provide the average fluid densities between two DPI taps. Knowledge of the
dispersed and continuous fluid densities can then be used to
estimate the dispersed-phase hold-up.
The velocity of the dispersed-phase droplets relative to
the continuous phase is related to the volumetric flowrate
of the dispersed and continuous phases. Those relative
velocities and flowrates are published in various textbooks
and references (e.g., Ref. 1) and are not repeated here.

Equipment selection guidelines


Extraction equipment falls into three general categories:
units with static internals, units with pulsation, and units with
mechanical agitation. Table 1 compares the relative efficiencies, capacities, and costs of the various types of extractors.
Static internals. Extractors with static internals (packing or trays) generally require liquids with a density difference that exceeds 50 kg/m3 and difference in interfacial
tension that exceeds 5 dyne/cm in order to effectively
disperse one liquid in the other. Static devices are typically
selected for applications that require a low number of theoretical stages (NTSs), generally five or fewer. The investment and operating costs for static devices are typically
lower than those for mechanical agitation.
Pulsation. Energy in the form of pulses can be added
to one of the liquid streams in an extractor with static
Table 1. When choosing a type of extractor,
consider efficiency, capacity, and costs.
Type

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

Copyright 2015 American Institute of Chemical Engineers (AIChE)

internals to improve liquid-liquid contact. The energy can


be supplied in several ways, including the use of bellows.
Mechanical agitation. Mechanical agitation improves
liquid-liquid contact. Extractors with mechanical agitators
generally have higher mass-transfer efficiency in smaller
vessel sizes than static units. Although agitation can be
beneficial, it increases operating and investment costs. For
applications that require a high NTS or wide flexibility,
the benefits of mechanical agitation often justify the added
expenditure.

Phase equilibrium, pilot plant trials, and scale-up


The thermodynamic basis for liquid-liquid extraction
is phase equilibrium. Determining mechanical equilibrium
and thermal equilibrium are straightforward and linked to
process parameters pressure (mechanical) and temperature (thermal). On the other hand, chemical equilibrium
(chemical potential), which is the most important parameter
in designing extraction units, is not easy to determine.
Chemical potential is difficult to ascertain because it
cannot be directly measured. Existing models describing
chemical equilibrium (e.g., NRTL or UNIQUAC) are not
appropriate for extraction, because extraction involves at
least three components and the equilibrium is established
between two immiscible liquid phases.
Liquid-liquid equilibrium is very sensitive to the presence of trace components and surfactants. Such molecules
can accumulate at the liquid-liquid interface and significantly impact chemical equilibrium. Models cannot typically predict the effects of impurities, because the effects
are so dependent on the type of impurity. Laboratory and
pilot-scale testing is, therefore, mandatory for developing
new liquid-liquid extraction processes.
A common mixing test known as the shake test can be
performed in a laboratory to determine the chemical equilibrium of the liquids to be used in the extraction process. In a
shake test, the carrier liquid containing the solute is mixed
with the solvent in a stirred flask for a specified amount of
time. After the mixing stops, the two phases separate by
gravity settling and can be subsequently analyzed.
The solute concentration in both liquids is the most
important parameter to measure after the test is completed. However, the concentrations of each liquid within
the other liquid are also important, as they relate to the
mutual solubility of the carrier and the solvent. The measured composition of each phase represents the chemical
equilibrium for the temperature and pressure at which the
test was performed. Because the test is conducted with the
actual carrier liquid, solute, and solvent, the measured data
account for the effects of trace impurities.
The shake test should be repeated for several solute
concentrations to cover the entire concentration range that
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Reactions and Separations

p Figure 5. Pilot-scale extraction columns should operate with the same


droplet size as the commercial-scale unit. The diameter of pilot units is
typically 4050 mm.

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0.40

Extract Load, kg/kg

will be present during the separation.


The data obtained from the experiments are used to create an equilibrium diagram, which shows miscibility gaps
(i.e., compositions where the constituents are not miscible)
and is the basis for a ternary diagram. The ternary diagram
summarizes the entire liquid-liquid equilibrium and is the
basis for process design.
The chemical equilibrium data are then used to determine parameters of the thermodynamic models that simulate
the concentrations of the key components in each phase.
Typically, however, not all components of the system can be
analyzed and fit to available models. Thus, pilot-scale testing
is required.
The size of a pilot-scale column is dictated by droplet size.
Droplet size is a crucial parameter to control during scale-up
because mass transfer in extraction columns takes place at the
liquid-liquid interface (i.e., the surface of the droplet). The
droplet size should be the same in the pilot-scale column and
the future commercial column. The size of the droplet dictates
the minimum diameter of the pilot-scale column. To generate reliable data for scaling up to a 45-m-dia. static extractor column or to a 3-m-dia. mechanically agitated column, a
pilot column needs to have a diameter of 4050 mm. Figure 5
shows several pilot columns.
The pilot trials are conducted under operating conditions similar to those that will be used in the industrial plant,
with the same feed materials and solvents. Because the pilot
experiments are run under conditions as close to those of
the commercial unit as possible, the measured separation
performance and flooding point will closely represent the
operation of the commercial facility thereby minimizing
technical risks of scale-up.
The data obtained in the shake test and the pilot experiments are used to graphically determine the number of

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

Raffinate Load, kg/kg

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.

theoretical stages needed for the extraction unit (Figure 6).


The shake test data provide a measure of the thermodynamic
chemical equilibrium, while data from the pilot experiments
provide the real equilibrium, or operating line. Stepping
between the equilibrium line and the operating line reveals
the NTS, which will be the basis for scaling up the column
height (1). The flooding point is the basis for determining the
column diameter.

Static extractor equipment


Static extraction units are appropriate for simple extraction applications, for which the volumetric flowrate of the
fluids and the fluid properties (e.g., density, viscosity, and
interfacial tension) do not vary by more than 5% across the
height of the column. Several static extractors are available
with different relative capacities and efficiencies.
Spray columns are the simplest and oldest extractors.
They are equipped with header pipes that introduce the
carrier stream and the solvent stream at opposite ends of
the vessel. Dispersed-phase droplets rise (or fall) through
the continuous phase. Spray columns can operate in the
presence of suspended solids and components that react
to produce a precipitated solid; they are also amenable to
applications that experience fouling. However, these units

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)

are susceptible to axial mixing, which generally prevents


them from achieving more than 1 NTS of separation.
Static mixers are fixed devices installed in a pipe to
continuously blend the two immiscible fluids. This type of
internal device is typically used for co-current extractors or
for a battery of mixer-settlers. Co-current extractors include
a settler downstream of the mixing section to separate the
two liquids.
Random packing (Figure 7) in the extractor contacting section helps to control axial mixing. The movement
of droplets across the packing surfaces induces turbulence
inside and outside of the droplets, which accelerates mass
transfer. The phase ratio (ratio of the volumetric flowrate
of the dispersed phase to that of the continuous phase) in
water wash and treater columns with random packing can
be 0.58, while in chemical plant extraction applications,
the phase ratio is typically 0.55.
Random packing is commonly used to remove contaminants (H2S or CO2) and other chemicals (amines or methanol) from natural gas liquid (NGL) and liquidified petroleum
gas (LPG) streams.

In general, beds of random packing are limited to a


maximum depth of 2.43 m, and they require remixing
with a disperser or support plates to minimize the effects of
axial mixing.
Structured packing (Figures 810, sidebar), which
is geometrically organized, and random packing (which
is loose), perform the same function. Both minimize the
effects of axial mixing by preventing side-to-side flow and
promoting vertical flow in the contacting section.
Sieve trays are simple metal plates uniformly perforated
with round holes (Figure 11) that remix and redistribute
the dispersed phase, as shown in Figure 12. The dispersed
droplets coalesce when they reach the sieve tray deck, and
droplets form as the dispersed phase flows through the
holes. Sieve hole diameters are 38 mm for most applications, although trays with holes up to 12 mm in diameter
are available for applications susceptible to fouling. Reliable tray efficiencies can be achieved for liquids with an
interfacial tension of 545 dynes/cm.
Sieve trays can handle phase ratios of 0.530; trays
with specialized downcomers can handle phase ratios up

Structured Packing

everal manufacturers supply structured packings, which


are typically proprietary. These Sulzer packings are
described for illustrative purposes.
SMV structured packing (Figure 8) consists of corrugated
sheets that polarize the direction of flow within each layer. It
is usually supplied with a smooth surface and can be made
of metal or plastic. The periphery of the packing elements is
equipped with a wiper band to reduce wall effects. Surface
areas range from 125 m2/m3 to 350 m2/m3. A higher surface
area is generally selected for chemical plant services, while
lower surface areas are selected for applications with fouling

tp Figure 8. Unlike loose random


packings, structured packings such as
these are geometrically organized.

Copyright 2015 American Institute of Chemical Engineers (AIChE)

potential or that require plastic packing. Distributors provide


uniform distribution of the dispersed and continuous phases.
SMVP structured packing (Figures 910) is equipped with
perforated plates between the packing layers to significantly
improve the mass-transfer efficiency. The plates provide
remixing and redistribution between each layer of packing,
and can eliminate the need for separate disperser plates.
The operating phase ratio range for this structured packing is
generally between 0.5 and 10.

p Figure 9. Perforated plates in


this structured packing provide
remixing and redistribution between
the packing layers.

p Figure 10. An extraction test


demonstrates how structured
packing mixes the two immiscible
fluids and enables droplets to form.

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Reactions and Separations

p Figure 11. Sieve trays are perforated plates with round holes.

p Figure 13. The Shell HiFi tray features multiple downcomers or


upcomers with short flow-path lengths.

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.

to 70. The tray spacing is generally 400610 mm for


simple one-pass sieve trays. Single-pass trays are limited
to small extractors with diameters up to 23 m; multipass
sieve trays are recommended for larger-diameter extractors.
For many years, sieve tray extractors have been
designed using generalized tray-efficiency calculation
methods such as the Treybal correlation (3), or based on
experience with previous similar applications. Reference 4
discusses design considerations for sieve tray extractors.
Disc-and-donut and side-by-side baffle trays. Baffle
trays are used for applications with a high risk of fouling:
disc-and-donut trays for small-diameter extractors, and
side-by-side baffle trays for larger extractors. Baffle trays
have lower tray efficiencies than standard sieve extractor
trays. If a baffle tray has holes, the hole diameter is typically 1020 mm depending on the severity of fouling.
High-performance sieve trays. High-performance sieve
trays have been developed to address the shortcomings of
conventional sieve trays in large-diameter columns (5). The
Shell HiFi* extractor tray (Figure 13) has multiple downcomer buckets (or upcomers) with short flow-path lengths
that provide local control of the extractor hydraulics across
the perforated decks to minimize the effects of crossflowinduced backmixing. This allows for reliable scale-up,
since the short flow-path length can be maintained simply

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.

Pulsation extraction equipment


Pulsation can be added to extraction units to improve
mass transfer. Columns are equipped with static internals,
such as structured packing with perforated plates between
the packing layers or with fixed dual-flow plates. Bellows or a pulsation pump provides oscillating pulses to
the continuous phase. Typical applications include those
involving highly corrosive materials or radioactive liquids.
The drawbacks of pulsation are higher capital and operating costs.

* HiFi tray is a trademark of Shell Global Solutions.

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Copyright 2015 American Institute of Chemical Engineers (AIChE)

Mechanically agitated extraction equipment


Alternatively, energy can be added to the extraction
unit through mechanical agitation. References 68 provide
general overviews of agitated extraction columns.
Mechanically agitated extractors operate in a similar
way to a rotating disc contactor (RDC). The column is
divided into compartments; each compartment has a mixing element, all of which are mounted on a common shaft.
In the RDC column, the mixing element is a disc and the
power of the shaft is transferred, via frictional forces, from
the surface of the turning discs to the fluids. This has a
very low efficiency. Moreover, to avoid the formation of a
dead zone in the center of the column, the diameter of the
shaft on which the rotating discs are mounted is limited to
certain sizes.
Research is ongoing to improve the efficiency of RDC
columns, with developments such as a modified shaft design,
for example (9).
Modern agitated columns provide more design flexibility and achieve higher separation performance than the
first agitated columns (i.e., the so called RDC columns) (4).
For example, the agitated Khni column can be used for a

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.

General extractor design


Once the mass-transfer device has been chosen, the
rest of the extraction unit must be designed. An important
consideration is controlling the location of the interface
between the dispersed and continuous phases, especially
in the phase-separation section, where the dispersed phase

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)

Susceptible to axial mixing, which can lower the


mass-transfer efficiency

Can handle severe fouling

Generally limited to one NTS

Excellent for 2 < NTS < 5

Can have poor efficiency for phase ratios greater


than 8

High performance when used with multiple beds


and dispersers
Structured Packing

Possible Risks and Limitations

Some have high volumetric throughput and can


handle moderate fouling
Some can achieve excellent stage efficiency

Generally limited to fewer than 5 NTS


Some can have poor efficiency for phase ratios
greater than 8 and are generally limited to fewer
than 5 NTS
Some are susceptible to fouling

One-Pass Sieve Trays

Good for 2 < NTS < 8

Flow-path length restricts the extractor diameter

Good hydraulics for phase ratios less than 70

Limitations for multipass design

Sieve trays with extruded holes can handle fouling


Disc-and-Donut and
Side-by-Side Baffle Trays
Shell HiFi Extractor Trays

Can handle fouling

Can have poor tray efficiency

Can be designed for large-diameter extractors


Higher capacity than simple sieve trays
High tray efficiency due to minimal hold-up and
crossflow mixing

Higher capital costs than conventional one-pass


sieve trays and large side-by-side baffle trays

Can be easily scaled up with multipass buckets


Khni Column

Mechanical agitation can provide a significant


improvement in capacity and efficiency

Higher capital costs than most other static


extractors

Can reliably provide NTS > 20 for many applications


Pilot-plant testing is very representative of full-scale
operation of this column

Copyright 2015 American Institute of Chemical Engineers (AIChE)

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Reactions and Separations

coalesces. The phase-separation section is located at the


end of the vessel opposite the carrier stream inlet. The vessel height is specified to include the mass-transfer section,
as well as the height for the feed section and the coalescer
section. Typically, the feed nozzle is located 300500 mm
from the mass-transfer section.
Fluctuations in the location of the interface should be
controlled so that the coalescing section is always in the zone
where the raffinate phase (the carrier liquid without the solute)
is located. The liquid volume in the coalescer section should
be large enough to provide sufficient time for the droplets to
settle from the product stream. Typical coalescers are designed
for residence times of 35 minutes.
During the design phase, the location of the temperature, pressure, and interface-level controls must be carefully
considered. Temperature transmitters are generally placed
in the inlet lines upstream of the vessel and near the outlet
lines, or in the top and bottom of the vessel. In applications
with fluctuating temperatures in the mass-transfer section,
temperature transmitters can also be installed inside the
mass-transfer section.
The interface-level controller is located at the interface between the mass-transfer section and the coalescing
section, with the bridles located above the high-interface
level and below the low-interface level marks. A pressure
transmitter is usually located above the high-interface level.
A differential-pressure indicator is located across the masstransfer section, to monitor the dispersed-phase hold-up
during operation. Often, a ratio control system is used to
regulate the solvent inlet flowrate as a function of the carrier
fluid flowrate. The interface-level controller controls the
flowrate of one of the outlet steams, and the pressure transmitter controls the flowrate of the other outlet stream.
It is important to avoid placing any differential pressure drop bridles between the high and low interface levels.
Placing bridles in that region can significantly impact DPI
readings. The purpose of the DPI is to record the differential pressure drop, which provides information about the
hold-up of the dispersed phase in the mass-transfer section;
thus, it is important to place the bridles across the masstransfer section.

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
30

www.aiche.org/cep November 2015 CEP

made in distillation has stemmed from work coming out of


independent research organizations, such as Fractionation
Research, Inc. An equivalent organization does not exist
for liquid-liquid extraction. As a consequence, extraction
technology has been developed by the equipment companies that provide proprietary extractor technologies. Many
modern extractors are developed through collaboration
between clients and the proprietors under nondisclosure
agreements, and those designs are generally not dissemiCEP
nated in the public literature.
JOERG KOCH, DR.-ING., is the technology manager of liquid-liquid
extraction at Sulzer and is based in Allschwil, Switzerland (Phone:
+41 61 486 37 37; Email: joerg.koch@sulzer.com). He has worked
for more than 15 years in the process industry, focusing on thermal
separation processes. He has presented papers at several conferences, and has several publications. He holds a Dr.-Ing. in process
technology with focus on liquid-liquid extraction from the Technical
Univ. of Clausthal, Germany.
GLENN SHIVELER is an applications specialist at Sulzer in Tulsa, OK
(Phone: (918) 447-7623; Email: glenn.shiveler@sulzer.com). He has
worked for 30 years in the chemical and gas processing industries
designing mass-transfer equipment. He has coauthored several
papers on mass-transfer equipment for CEP, including a 1995 article
on heavy-duty trays. He has a bachelors degree in chemical engineering from Rutgers Univ. He is a member of AIChE, ACS, and ISA.

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).

Copyright 2015 American Institute of Chemical Engineers (AIChE)

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