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Introduction

Liquid extraction (or solvent extraction) refers to an operation in which

the components of a liquid mixture are separated by contacting it with a
suitable insoluble liquid solvent which preferentially dissolves one or
more components.  In this operation, the separation of the

components depends upon the unequal distribution of the components

between the immiscible liquids.  The feed solution represents one phase
and the solvent to be used to effect separation represents the second
phase.  The mass transfer of the solute liquid takes place from the feed
solution to the solvent phase.

Both the distillation and liquid-liquid extraction are used for the
separation of the constituents of a liquid mixture.  In order to achieve a
separation by distillation, as well as by liquid-liquid extraction, it is
necessary to have two phases.  In distillation it is necessary to have
liquid and vapor phases and heat is used to produce the vapor.  In liquid-
liquid extraction it is necessary to have two liquid phases and the solvent is used to produce another
liquid phase.  The solvent used in liquid-liquid extraction is analogous to the heat used in the distillation.

Distillation and extraction both are used for the separation of the constituents of any liquid mixture based
on the economics evaluation of the individual methods.

Table 1: Comparing Extraction and Distillation

Extraction Distillation
1. Extraction is an operation in which 1. Constituents of the liquid mixture are
constituents of the liquid mixture are separated separated by using thermal energy
by using an insoluble liquid solvent

2. Extraction utilizes the differences in 2. Utilizes the differences in vapor pressures of

solubilities of the components to effect the components to effect separation
separation

3. Selectivity is used as a measure of degree of 3. Relative volatility is used as a measure of

separation degree of separation
4. A new insoluble liquid phase is created by 4. A new phase is created by addition of heat
addition of solvent to the original mixture
5. Phases are hard to mix and harder to 5. Mixing and separation of phases is easy and
separate rapid
6. Extraction does not give pure product and 6. Gives almost pure products
needs further processing
7. Offers more flexibility in choice of operating 7. Less flexibility in choice of operating
conditions conditions
 8. Requires mechanical energy for mixing and 8. Requires thermal energy
separation
9. Does not need heating and cooling 9. Requires heating and cooling provisions
provisions
10. Often a secondary choice for separation of 10. Usually the primary choice for separation of
components of liquid mixture components of liquid mixture

Whenever separation by both distillation and extraction is possible the choice is usually distillation,
irrespective of heating and cooling requirements. When extraction is used, the solvent should be
recovered for reuse and hence extraction is usually followed by distillation for the recovery of solvent.
The combined operation is more complicated and more expensive than ordinary distillation. However,
when the separation of the components via distillation is
difficult, extraction can be an attractive alternative.

Typical liquid-liquid extraction operations utilize the

differences in the solubilities of the components of a liquid
mixture. The basic steps involved include:

1.       Contacting the feed with the extraction solvent.

2.       Separation of the resulting phases, and
3.       Removal/recovery of solvent from each phase.

The liquid mixture to be treated and a suitable, insoluble

solvent are contacted intimately. 

The constituents of liquid mixtures are distributed between the

two phases resulting in some degree of separation (which can
be improved by a multistage contact) and the phases are
separated from one another based on the density differences
of the liquid phases. For example, acetone may be
preferentially extracted from a solution in water with the help
of chloroform. The resulting chloroform phase contains a
large part of acetone, but little water.

The solution to be extracted is called the feed. The liquid extraction liquid is called the solvent. The
residual liquid solution from which the solute is removed is called the raffinate. The extracted solvent rich
product is called the extract. The extract phase contains the desired product in a larger proportion.

Thus, if a solution of acetic acid in water is contacted with a solvent such as ethyl acetate then two
phases will results. The extract (ester/organic layer) will contain most of acetic acid in ethyl acetate with a
small amount water. The raffinate (aqueous layer) will contain a weak acetic acid solution with a small
amount of ethyl acetate. The amount of water in the extract and ethyl acetate in the raffinate depends
upon their solubilties in one another.

The Distribution Coefficient

In dilute solutions at equilibrium, the concentration of the solute in the two phases is called the distribution
coefficient or distribution constant ‘K’.
K= CE/CR
Where the CE and CR are the concentrations of the solute in the extract and the raffinate phases
respectively. The distribution coefficient can also be given as the weight fraction of the solute in the two
phases in equilibrium contact:
K’ = y*/x
Where y* is the weight fraction of the solute in the extract and x is the weight fraction of the solute in the
raffinate.
In liquid-liquid extraction, the liquid-liquid equilibrium must be considered. This is best represented by
equating the chemical potential of both liquid phases:

This relationship reduces to an expression, which is dependent only on the liquid mole fractions and their
respective activity coefficients:

Activity coefficient models, such as UNIFAC, UNIQUAC (universal quasichemical), and NRTL can be
used to determine the mole fractions. All three models above are applicable to liquid-liquid equilibrium,
the choice of which model to use depends on which properties are available. For a multi-component
system, the UNIQUAC equation for the liquid-phase activity coefficient is:

The combinatorial and residual activities are based on the statistical mechanical theory which describes
how local compositions result from the size and energy differences between the molecules in the mixture.

When to Chose Liquid-Liquid Extraction

 When large volumes of water must be removed to complete a separation. The large latent heat
of vaporization of water can make this an energy intensive process.
 When two or more liquids form a close boiling azeotrope, the desired final concentration may not
be possible via distillation.
 When one or more of the components are considered thermally sensitive or unstable, distillation
may not be a feasible option.

In such cases, extraction is attractive and often preferred. The separation of acetic acid from dilute
solutions of water is usually more economical via extraction followed by distillation. Distillation would be
feasible for this separation, but by using extraction first, the amount of water that must be vaporized is
reduced significantly.

Modes of Operation: Cross-Current

Cross-current mode is mostly used in batch operation.  Batch extractors

have traditionally been used in low capacity,

multi-product plants typically found in the pharmaceutical and

agrochemical industries.   For washing and neutralization operations that
require very few stages, cross-current operation is particularly practical
and economical and offers a great deal of flexibility.  The extraction
equipment usually includes an agitated tank that may also be used for
the reaction steps.  In these tanks, the solvent is first added to the feed,
the contents are mixed, settled, and then separated.   Single stage
extraction is used when the extraction is fairly simple and can be
achieved without a high amount of solvent.  If more than one stage is
required, multiple solvent-washes will be required.
Though operation in cross-current mode a great deal of flexibility, it must be examined carefully due to the
high solvent volume requirements and low extraction yields.  The following illustration gives a quick
method to calculate solvent requirements for cross-current extraction.

A single-stage extractor can be represented as:

F = Feed quantity / rate, mass

R = Raffinate quantity / rate, mass
S = Solvent quantity / rate, mass
E = Extract quantity / rate, mass
 
Xf , X r, Y s, and Ye are the weight fractions of solute in the feed, raffinate, solvent and extract, respectively.
Partition coefficient ‘m’ is defined as the ratio of Y e to Xr at equilibrium conditions
The flows and concentrations are represented in solute-free basis as such a representation leads to
simplification of equations. 
For example, for a 100 kg/hr feed containing 10% weight acetic acid, F = 100-10 = 90 kg/hr, X r = 0.1/(1-
0.1) = 0.111
 
The component mass balance can be represented as:
 F Xf + S Ys = R Xr + E Ye
Assuming (i) immiscibility of feed and solvent and (ii) the initial solvent is free of solute, i.e., F = R, S = E
and Ys = 0 and using the equilibrium relation of Ye = m Xr, this equation simplifies to
 S = F/m (Xf /Xr–1)
Or
Reduction ratio, Xf /Xr = 1+ m S/F
For multi-stage crosscurrent operation:

Assuming that the partition coefficient (m) is constant over the concentration range and the solvent
quantity in each of the ‘n’ stages is the same, i.e., S1 = S2 =…..=S n = S/n,
Solvent Requirement is
 S = n * F/m [(Xf /Xr)1/n - 1]
Or
Reduction ratio Xf /Xr = (1+mS/nF)n
It can be proved mathematically that the total solvent quantity would be minimum if the solvent were
distributed equally between washes.
 
Reference: Optimize Liquid-Liquid Extraction, R. Madhaven, Cheresources.com
 
Modes of Operation: Counter-Current

As described above, the cross-current operation is mostly used in low capacity, multi-product, batch
plants.  For larger volume operations, a counter-current configuration is often used. Counter-current
patterns are capable of more efficient use of the solvent. Counter-current mixer-settlers or columns are
usually employed.  Countercurrent operation conserves the mass transfer driving force thus they typically
yield optimal performance.

Equations for countercurrent extraction get more complicated with increasing number of stages.  It can be
shown that for a ‘n’ stage operation, the raffinate concentration would be
 Xr = Xf * (mS/F – 1)/ ( [mS/F] n+1 -1)
The solvent requirement for any raffinate concentration X r could be determined by iteration from the
above equation.

For mS/F = 1, the equation takes the form of Xr = Xf / (n + 1)

Reference: Optimize Liquid-Liquid Extraction, R. Madhaven, Cheresources.com

The dimensionless term mS/F, included in all the above equations, is called the extraction factor (E), and
is an important parameter in the design of extraction processes.  For a given number of stages, the higher
the E factor, the higher the reduction ratio thus a better extraction.  Systems with E of less than 1.3 are
not likely to be commercially feasible.

Operational Conditions

The following are typically key operational parameters for an extraction

process:

Operating Temperature

Operating Pressure

Residence Time

Feed Flow Rate

Composition

Temperature of entering stream

Pressure of entering stream

As in many separation processes, the pressure and temperature play a large role in the effectiveness of
the separation. In order for a good split of the feed stream, vaporization must be prohibited. The process
will be adversely affected if one or more of the components are allowed to vaporize. In addition, the
temperature should be high enough that the components are all soluble with one another. Moderate
temperatures can facilitate the selection of a suitable solvent. With these rules in mind, most extraction
processes can proceed at or near ambient temperature and pressure which is a key advantage of
extraction.

Temperature can also be used as a variable to alter selectivity.  Elevated temperatures are sometimes
used to keep viscosity low minimizing mass-transfer resistances.  Other parameters to be considered are
selectivity, mutual solubility, precipitation of solids, and vapor pressure.

In many applications, a “gently” separation process is needed as an high temperatures could destroy the
desired product (pharmaceutical industry). For these applications, extraction is ideal since the only
temperature requirement is that dictated by the solubility. The challenge in these cases is to find a
suitable solvent for the extraction.

Operating pressure has a negligible affect on extraction performance and therefore most extractions take
place at atmospheric pressure unless governed by vapor pressure considerations.

Residence time is an important parameter in reactive extraction processes (e.g., metals separations,
formaldehyde extraction from aqueous streams) and in processes involving sensitive components (e.g.,
antibiotics & vitamins).

Selecting a Solvent

Any liquid to be used as a solvent will not posses all the properties considered desirable for extraction
and hence compromise is usually necessary for selecting the best solvent. While selecting a solvent for
extraction, qualities such as selectivity, recoverability, distribution coefficients, and density should be
given careful consideration.

 Selectivity – The ratio of the concentration of solute to feed solvent in the extract phase to that in
raffinate phase is called the selectivity or separation factor. It is a measure of the effectiveness of
the extraction solvent for separating the constituents of feed. Selectivity should be greater than 1
for all extraction operations. If it is equal to 1, then separation by extraction is not possible.
 Recoverability - As the solvent must be recovered for reuse (usually by distillation), the formation
of an azeotrope with the extracted solute is not desirable. To minimize recovery costs, the
relative volatility should be high. The latent heat of vaporization of the solvent should be as small
as possible whenever the solvent is to be vaporized.
 Density – A difference in the densities of saturated liquid phases should be as large as possible
for physical separation of the phases.
 Interfacial Tension – The interfacial tension should be higher for the coalescence of droplets to
occur more readily.
 The solvent should be inexpensive, non-toxic, and non-flammable if possible. The solvent should
have a low viscosity, freezing point, and vapor pressure, for ease in handling and storage. The
solvent should be chemically stable and inert to the other components.
 Extraction Equipment
 Industrial extraction equipments can
 be classified as stage type extractors or differential/continuous
contact extractors. In stage type extractors, the two phases are
allowed to mix together so as to reach equilibrium, then they are
incrementally separated while being passed counter-current to
one other. The advantages of stage type contactors include
simplicity of design, no axial mixing, and high stage efficiency.
These units are large and bulky due to separation performed
after each stage. In differential extractors, the two phases are
always in continuous contact. Differential extractors are
compact and required minimal floor space.

 Mixer-Settler
 Mixer-settlers may be used
in batch mode (a single unit)
or in continuous mode by
staging multiple units. A
mixer-settler consists of a
vertical tank incorporating a
turbine or a propeller
agitator. Charging nozzles
are located at the top and
discharge connection with a
sight glass at the bottom.
The feed solution to be
extracted is charged into the
vessel and the necessary
amount of solvent is added.
The vessel is agitated for a
predetermined amount of
time and at the end of mixing
cycle, agitation is stopped and the phases are allowed to settle. Finally, the raffinate and extract
phases are withdrawn from a separate receiver vessel.
 The main disadvantage of the mixer-settler is that it requires a large vessel with high liquid
volume demands. Advantages include the high stage efficiency, flexibility, ability to handle high
viscosity liquids, and its high capacity.
 Contacting Columns
 Contacting columns are practical for most liquid-liquid extraction systems. The packing, trays, or
sprays typically used increase the surface area in which the two liquid phases contact. This also
allows for a longer flow path. In the selection of packing, it is necessary to select a material that
is wetted by the continuous phase. In column extractors, the phase with the lower viscosity
(lower flow resistance) is generally chosen as the continuous phase.  Also note that the phase
with the higher flow rate can be dispersed to create more interfacial area and turbulence.   This is
accomplished by selecting an appropriate material of construction with the desired wetting
characteristics.  In general, aqueous phases wet metal surfaces and organic phases wet non-
metallic surfaces.  Changes in flows and physical properties along the length of extractor should
also be considered.
 Tray Columns
 Tray columns are multi-staged, counter-current
contactors where the axial mixing of the
continuous phase is confined to the region
between trays, and dispersion occurs at each
tray resulting into effective mass transfer. Tray
columns are very effective, especially for
systems of low-interfacial tension, with respect
to their liquid handling capacity and extraction
efficiency. The perforations in the plates are
about 1.5 to 4.5 mm in diameter and the
plate/tray spacings are usually 150-600 mm.
 Generally the arrangement of plates and down
comers is the same as that used for gas-liquid
contact, except that no weir is needed. The
light liquid is introduced at the bottom, passes
through the perforation in the plate in the form
of the fine droplets. The fine droplets rise
through the heavy continuous phase (being fed
into the top) and coalesce into a layer beneath
the plate and then are again dispersed through
the plate above. Heavy continuous phase
liquid is introduced at the top, passes across
the each plate and flows downward from a plate above to the plate below via downcomer.
Principle interface is maintained at the top, light liquid is removed from the top and the heavy
liquid from the bottom.
 Spray Columns
 Spray columns consists of an empty tower with
inlet and outlet connection at the top and
bottom, for introducing and removing the heavy
and light liquid phases. Since the spray column
is essentially an empty vessel, there will be
axial mixing making it difficult to obtain the
equivalent of more than one or two theoretical
stages.
 Spray towers are operated in one of two distinct
ways: either the light phase or the heavy phase
may be dispersed. When the light phase is
dispersed, it is introduced through the bottom
nozzle, droplets rise through the heavy phase
and finally coalesce to form a liquid-liquid
interface at the top. When the heavy phase is
dispersed, it is introduced from the top, and the
principle interface will be at the bottom.
 Advantages of the spray column include
construction simplicity and a high throughput
per unit area. Disadvantages include its low efficiency due to axial mixing in the continuous
phase and the need for a tall tower to achieve the degree of separation needed. Spray tower
performance is generally considered poor because of its considerable recirculation of the
continuous phase with little turbulence.
 Packed Towers
  The packed tower is arranged such that the light
phase is dispersed. The tower is a cylindrical shell
filled with packing which is rested on support plates.
The heavy liquid is fed from the top and light liquid is
fed from the bottom. A large portion of the void space
in the packing is filled with the continuous phase
which flows downward. The remainder of the void
space is filled with drops of light liquid which rise
through the continuous phase and finally coalesce to
form a liquid-liquid interface at the top. The packing
material should be such that it is wetted by the
continuous phase.
 Packing provide large interfacial areas for the phase
contacting. This causes the drops to coalesce and
reform. The mass transfer rates in packed towers are
higher and than those that can be obtained with spray
towers because the packing lowers the recirculation
of the continuous phase. Packed towers, however,
are not appropriate for dirty liquids, suspensions, or
highly viscose liquids.

 High capacity:  20-30 M3/M2
 Poor efficiency due to backmixing and wetting
 Limited turndown flexibility
 Affected by changes in wetting characteristics
 Limited as to which phase can be dispersed

 Rotating Disc Contactor
 The rotating disc contactor is a mechanically agitated, counter-current extractor. Agitation is
supplied by a rotating disc, which usually runs at much higher speeds than a turbine type
impeller. The disc contactor consists of a cylindrical column that is divided into number of
compartments formed by a series of stator rings. Each compartment contains a centrally located,
horizontal rotor disk that creates a high degree of turbulence inside the column. The diameter of
the rotor disk is slightly less than the opening in the stationary stator rings. Typically, the disk
diameter is 33-66 % of the column diameter. The disk disperses the liquid and forces it outward
toward the wall where the stator rings create quite zones where the two phases can separate.
Shown below is a Scheibel column which is classified as a type of rotating disc contactor.

Advantages of the rotating disc contactor include a reasonable capacity, low operating costs, and high
efficiency. The main disadvantage is that corrosive liquids can damage the internal moving parts.
Characteristics

 Reasonable capacity: 20-30 M3/M2-hr

 Limited efficiency due to axial backmixing
 Suitable for viscous materials
 Suitable for fouling materials
 Sensitive to emulsions due to high shear mixing
 Reasonable turndown (40%)

 Pulse Column
 A reciprocating pump is a common mechanical,
pulsating device that pulses the entire contains of
the column at frequent intervals. The rapid
reciprocating motion, of relatively small
amplitude, is superimposed on the usual flow of
the liquid phases. Bellows, diaphragms made of
Teflon-coated steel, or any other reciprocating,
pulsating mechanism can be used.
 A pulsed, sieve plate column is a vertical column
with a large number of sieve plates lacking down
comers. The perforations in the plates of such
columns are smaller than non-pulsating column
(1.5-3.0 mm in diameter). A pulse amplitude of 5-
25 mm is generally recommended with a
frequency of 100-260 cycles per minute. The
pulsation causes the light liquid to be dispersed
into the heavy phase on the upward stroke and
heavy liquid phase to jet into the light phase on
the downward stroke. The column has no
moving parts, low axial mixing, and a high
extraction efficiency.
  A pulse column typically requires less than a third the number of theoretical stages as compared
to a non-pulsating column. A pulse column may contain ordinary packing or sieve plates without
down comers. A special type of reciprocating mechanism is used in a Karr Column which is
shown below.
 Pulse columns increase both the turbulence and interfacial areas when compared to other types
of columns.  This type of column is used extensively for the processing of radioactive solutions.

Characteristics

 Reasonable capacity: 20-30 M3/M2-hr

 Best suited for nuclear applications due to lack of seal
 Also suited for corrosive applications since can be constructed out or non-metals
 Limited stages due to backmixing
 Limited diameter/height due to pulse energy required

 Centrifugal Contactors
 Centrifugal contactors are high-speed, rotary machines with the advantage of a very low
residence time.  The number of stages in a centrifugal device is usually one, but recently devices
with multiple stages are becoming more common.  These extractors are mainly used in the
pharmaceutical industry. These are ideal for systems in which the density difference is less than
4%. Additionally, this type of system should be utilized if the process requires many equilibrium
stages. Centrifugal contactors utilize mechanical devices to agitate the mixture to increase the
interfacial area and decrease the mass transfer resistance.
 The following table shows the advantages and disadvantages for each type of centrifugal
contactor:


 Factors Affecting the Selection of Extraction Equipment
 When selecting a type of extractor, the following factors should be considered: stage
requirements, fluid properties, and operational considerations. The following table outlines the
capabilities and characteristics of different types of extractors:


Reference: Optimize Liquid-Liquid Extraction, R. Madhaven, Cheresources.com
  The Karr reciprocating plate extractor can effectively handle low interfacial tension systems. 
Other factors governing extractor selection include the presence of solids and safety and
maintenance requirements.

Design Criteria

The basic function of extraction equipment is to mix two phases, form and maintain droplets of dispersed
phase, and subsequently separate the phases.  The following section outlines some of the factors that
need to be considered while designing and optimizing extraction equipment.

Mixing

The amount of mixing required is determined by the fluid physical

properties such as viscosity, interfacial tension, and

the density differences between the two phases.  It is important to

provide just the right amount of mixing.  Less mixing causes the
formation of large droplets and decreases interfacial area (interfacial
area varies with the square of the droplet diameter).   This reduces mass
transfer and decreases stage efficiency.  Higher agitation (more mixing)
minimizes mass transfer resistance during reactions and extraction but
contributes to the formation of small droplets or emulsions which are
difficult to settle.

In agitated batch extractors, the agitator design is often optimized for a

reaction and heat transfer, not extraction, as these are generally multi-
purpose vessels.

The agitator imparts maximum energy at the tip where the velocity is highest and minimum energy at the
center.   This creates non-uniform droplet sizes, with the smallest being formed at the agitator tip.
Extraction equilibrium is controlled by the largest droplet size and the smallest droplet controls the settling
time.  Therefore, excessive agitation sometimes causes difficulties in phase separation.  Usually a
redesign in terms of configuration or a change in agitation speed helps in optimizing batch time.

Static extraction columns rely completely on the packings or internals and the fluid flow velocities past the
internals to create turbulence and droplets.  Therefore, these are restricted by minimum flow requirement
of at least one of the phases. Agitated columns have more operating flexibility as the specific energy
input can be varied in most designs.

Axial mixing (along the column length) in column contactors reduces stage efficiencies.  Baffles or similar
devices are used to minimize axial mixing in static as well as agitated columns.   It is also important to
avoid temperature gradients in columns to prevent thermal currents contributing to axial mixing.

Settling

The settling characteristics depend on the fluid properties (density difference, interfacial tension, and
continuous phase viscosity) and the amount of mixing.  Stopping the agitator causes settling in agitated
batch vessels.  In continuous columns, a settling section is provided either as a part of the extractor or as
a separate piece of equipment downstream of the extractor.

Emulsions are usually formed due to over agitation and in such cases, settling needs to be carried out
over an extended period.  Emulsions can also form due to the inherent nature of the chemical compounds
involved or due to contaminants that substantially lower the interfacial tension.  Sometimes coagulants
are added to prevent or minimize emulsification.  Passing the emulsion layer through a coalescer can
break some of these emulsions.  In continuous extractors, the creation of emulsions is less severe as
good droplet size distribution can be attained at lower agitation speeds.  Also, columns such as the Karr
reciprocating plate extractor impart uniform energy throughout the radius as a result of the reciprocating
motion and this creates a much narrower droplet distribution.

A phenomenon similar to emulsions is the formation of a ‘rag layer’.  This is a layer containing loose solid
substances that float at the interface.  These solid substances are generally foreign impurities that exist in
the feed streams or those that precipitate from the system during extraction.  In continuous extraction, the
liquid interface containing the rag layer can be continuously withdrawn, filtered and sent back to the
extractor.

Theory - The Ternary Phase Diagram

Ternary phase diagrams act as map for liquid extraction applications. Ternary phase diagrams are
unique in that they show all three components of a reaction system on one plot. The following general
principles govern ternary phase diagrams:

 Sum of the perpendicular distances from any point within the triangle to the three sides equals the
altitude of the triangle.
 Each apex of the triangle represents one of the pure components.
 Any point of a side of the triangle represents a binary mixture.
 Lines may be drawn parallel to the sides of the equilateral triangle for the plotting of the
compositions.
 Phase Diagram for a Three-Component System

The ternary phase diagram may be constructed directly from experimental data. The saturation curve
(miscibility boundary), represented by JDPEK in the figure above, can be obtained experimentally by a
cloud point titration. For example, a solution containing components A & C with some composition is
made, and then component B is added until the onset of cloudiness due to the formation of a second
phase. Then the composition is known for the mixture of the three components and can plotted onto the
ternary phase diagram.

Tie lines are lines that connect points on the miscibility boundary. The tie lines may also be presented on
the ternary phase diagram from an experiment. A mixture may be prepared with composition shown by
point H (40% A, 40% C, 20% B) from above figure. If allowed to equilibrate, then a chemical analysis of
the final extract (E) phase and the raffinate (R) phase can be conducted. Point F is a feed composition
into the extractor while point S is the solvent feed to the extractor. Point H represents the composition of
the two feeds at equilibrium. This point is determined by summing the feed (F) and solvent (S)
compositions for each component. Points R and E are the compositions of the raffinate and extract from
the unit, respectively, and the line between them forms the tie line. The tie lines move above and below
this line based on the relationship between the raffinate and the extract. Point P represents the plait
point. At this point, only one liquid phase exists and the compositions of the two effluents are equal.
When C is added to the two phase mixture of A and B, C gets distributed between the phases (layers)
and the compositions of the phases follow the raffinate and extract phase solubility curves. Curved line
KGEP indicates the composition of the saturated B layer extract phase and the curved line JRDP
indicated the composition of the saturated A phase/layer raffinate. The curve represented by JRDPEK is
the equilibrium between all three components. The area under the curve is the region where two liquid
phases will exist. Above the curve, there will only be one liquid phase. If a line is drawn from F to E or
from S to R, this will represent the operating line.
 

In addition to these considerations, equilibrium constraints must be satisfied.

This implies that:

(1)

Where AE is the activity coefficient for the solute A in the extract and AR is the activity coefficient of A in
the raffinate. This condition is one of the most important aspects of liquid-liquid extraction since it allows
for calculations and assumptions based on equilibrium systems (e.g. the ternary phase diagram).

Another consideration is the separation factor. The goal is to have a separation factor as far from unity as
possible. This leads to a better separation in the extraction process. The separation factor is represented
as follows:

(2)

One of the last essential points to the theory behind liquid-liquid extraction is mass transfer. The driving
force for this mass transfer arises from the concentration difference between the solute in each of the
solvents. In general, it is assumed that the system is at an equilibrium state when mass transfer is
occurring. Solute fluxes in the raffinate and extract can be expressed as:

(3)

(4)

Where KE and KR are the overall mass transfer coefficients, A is the cross-sectional area, X E and XR are
the concentrations of solute in the extract and raffinate respectively, and X Ei and XRi are the concentrations
of solute in each phase at the liquid-liquid interface.

The following General Flowchart can be utilized for almost any process. The figure below illustrates a
general ternary diagram for a desired solute (C), an extracting solvent (B), and a carrier solvent (A). In
this process, it is assumed that the feed (F) contains components A and C. A solvent (S) is introduced in
such a way that it will extract C from the feed. The raffinate composition (R) is specified with respect to
the recovery of C that is needed.
 

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Process Conceptualization
Liquid-liquid extraction is a powerful separation technique that falls right behind distillation in the
hierarchy of separation methods (see figure on the right).

REASONS TO USE EXTRACTION

 Separation not feasible by distillation

 Break azeotropes
 Energy requirements of distillation are prohibitive
 A complex distillation sequence is required
 The material is heat sensitive
 The material is non-volatile

The general rule: If a separation can be made economically by distillation, there is no reason to consider
extraction. However, in situations where distillation is not feasible for reasons such as a complex process
sequence, high investment or operating costs, heat sensitive materials, or low volatility, extraction is often
the best technology to use.

Extraction frequently involves additional steps to recover and recycle the solvent. A typical extraction
process is shown below. Since most investment and operating costs are associated with the solvent recovery
steps, it is very important to consider and study this aspect when designing the entire process.

In a typical extraction process about 3% of the operating cost is in the extractor, with the remaining 97% in
solvent recovery. Therefore, it is extremely important to consider the solvent recovery aspects early in the
project since they play such an important role in overall process economics.
Liquid-liquid Extraction Applications by Industry

Chemical
     o Washing of acids/bases, polar compounds from organics

Pharmaceuticals
     o Recovery of active materials from fermentation broths
     o Purification of vitamin products

Effluent Treatment
     o Recovery of phenol, DMF, DMAC
     o Recovery of acetic acid from dilute solutions

Polymer Processing
     o Recovery of caprolactam for nylon manufacture
     o Separation of catalyst from reaction products

Petroleum
     o Lube oil quality improvement
     o Separation of aromatics/aliphatics (BTX)

Petrochemicals
     o Separation of olefins/parafins
     o Separation of structural isomers

Food Industry
     o Decaffeination of coffee and tea
     o Separation of essential oils (flavors and fragrances)

Metals Industry
     o Copper production
     o Recovery of rare earth elements

Inorganic Chemicals
     o Purification of phosphoric acid

Nuclear Industry
     o Purification of uranium

Process Development
Most projects involve a pilot test to provide the basis for commercial plant design.
Unlike distillation, which can often be designed by simulations alone, liquid-liquid
extraction usually has many unknown factors such as stage efficiency, rates of
diffusion, flood point, emulsion formation, interface behavior, entrainment
tendency and capacity data. Small trace impurities can have a significant impact
on all of the above. For this reason, only actual plant feed and solvent materials are
best used for these tests.

Before pilot testing begins bench scale tests are performed to generate the liquid-
liquid equilibrium data. Besides supplying the equilibrium data, these tests can
reveal information on emulsions or entrainment that help guide extractor selection.

Information from Testing

 Bench Scale Tests Provide

- Equilibrium data
- Mixing characteristics
- Settling times
- Extractor type selection for pilot test
 Pilot Scale Tests Provide
- Data for scale-up -> stage efficiency, throughput, agitation
speed
- Demonstration of the entire process
- Process optimization
- Basis for performance guarantee

We select the appropriate extractor based on our review of each

application. Pilot tests are then run to demonstrate the process
performance as well as provide data for scale-up. These pilot tests
are performed in the same type of extractor planned for the
commercial scale. In some cases, more than one type of extractor
will be tested to compare performance.

Extractor Design
During the pilot plant tests, the extractor separation performance is measured over a range of flow rates,
solvent to feed ratios and effective heights. If the extractor selected is agitated then the agitation speed is
also varied. At each flow rate, the agitation is increased until the flood point is reached. From this data, the
conditions that give the optimum volumetric efficiency are determined.
 Next comes scaleup to commercial size. Any scaleup procedure must
determine (1) how diameter varies with throughput and (2) how
stage efficiency varies with diameter. For the agitated columns, there
is an additional parameter to be determined, namely (3) how the
power input varies with column size.

Finally the extractor is sized with the active zone height, together
with the top and bottom settler zones and instrumentation for control
of the column interface.

KMPS has a wide range of extractors to choose from, both static and agitated columns.
Click on the column types below for more information on each.

 Static Columns
- Sieve Trays
- Random Packing
- Structured (SMVP) Packing

 Agitated Columns
- KARR® Column
- SCHEIBEL® Column
- Rotating Disc Contactor (RDC)
- Pulsed Column
- Special Designs
 In addition to the extractor, an extremely important aspect of any extraction application is th
system to recover and recycle the solvent. In most cases, these additional steps are accompl
distillation, and when necessary, are also studied during the pilot tests.

At KMPS, we often supply the extraction and distillation components as a complete m

Typical examples are illustrated on this page.

Our team of experienced engineers is available to work together with you on your nex
extraction application, from conceptualization through start-up.

 ADVANTAGES OF MODULAR CONSTRUCTION:

 Lower cost/lump sum bid

 Schedule compression
 Minimal plant site interruption
 Construction proceeds while waiting for permits
 Single source responsibility
 Progress of work is not affected by weather conditions

Definition & Purpose:

Flash distillation (sometimes called "equilibrium distillation") is a single stage separation
technique. A liquid mixture feed is pumped through a heater to raise the temperature and
enthalpy of the mixture. It then flows through a valve and the pressure is reduced, causing the
liquid to partially vaporize. Once the mixture enters a big enough volume (the "flash drum"), the
liquid and vapor separate. Because the vapor and liquid are in such close contact up until the
"flash" occurs, the product liquid and vapor phases approach equilibrium.

Simple flash separations are very common in industry, particularly petroleum refining. Even
when some other method of separation is to be used, it is not uncommon to use a "pre-flash" to
reduce the load on the separation itself.

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