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Lecture 8

Liquid – Liquid Extraction

Liquid – Liquid extraction (Sometimes abbreviated as LLE) is a mass transfer operation in which a
solution (called feed which is a mixture of a solute and a carrier liquid) is brought into intimate
contact with a second immiscible or slightly miscible liquid (called the solvent) in order to achieve
transfer of the solute(s) from the feed to the solvent

The two liquid phases that have different densities are then separated.

The solute rich phase i.e the solvent stream enriched with the solute is called extract.

The residual feed stream that may have a little solute left in it is called raffinate.

If the carrier in the feed and the solvent are partly miscible, the raffinate will also have a little
solvent dissolved in it, and the extract phase will contain a little dissolved carrier.

The solute is separated from the extract phase in an acceptably pure form, and the solvent
dissolved in the raffinate is recovered.

An extraction process generally involves four major steps –

 Bringing the feed and the solvent into intimate contact by dispersing one phase into the
other as droplets.
 Separation of the extract and the raffinate phase that have different densities.
 Removal and recovery of the solute from the extract phase in a relatively pure form (by
distillation, evaporation, crystallization, etc)
 Removal and recovery of the solvent from each phase, usually by distillation.

Some facts about extraction process –

• Extraction process requires at least one distillation column in addition to the extractor.
• Phase separation may not be rapid if the difference in densities of extract and raffinate is
small and the interfacial tension is low.
• Loss of solvent may also occur in some cases.

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Solvent extraction is a more elaborate process than distillation. In a typical liquid – liquid
extraction process, only about 15% of the capital cost goes towards the extractor and the remaining
85% goes toward the distillation columns and other equipments for solvent recovery and product
purification. 5% of the operating cost of the unit is required for the extractor and the remaining
95% goes towards solvent recovery. Despite these limitations, there are situations when the
technique of distillation either fails or become uneconomic.

Cases where solvent extraction is attractive –

a) The components to be separated have close boiling points. For example, aromatics are
extracted from paraffinic feedstocks in the refineries by using solvent like sulphur dioxide,
n- methyl pyrolidone, sulpholane, etc. The number of distillation trays becomes
prohibitively large if the relative volatility is close to unity (say less than 1.2).

b) Separation of heat sensitive materials such as antibiotics, vitamins etc. Penicillin is

recovered from the fermentation broth by using suitable solvent such as butyl acetate.

c) Recovery of non-volatile solutes, usually from aqueous solutions , in hydro metallurgy.

d) Recovery of a solute from a very dilute solution or present in small quantities – for
example, bioseparation (protiens, antibiotics, high value bioproducts)

e) Removal of organics from aqueous streams – for example, removal of phenol from aqueous
wastes

Fig.1: Product recovery and raffinate clean up arrangement, C; carrier, S: Solvent, A: Solute

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Species in brackets are present in low concentration.
*The recycled solvent may have a little dissolved carrier in it.
**The make up solvent is added to compensate for the loss of solvent in the operation.

Fig.2: Separation of Aromatics from a feedstock – The Sulpholane process.

Extraction of Aromatics

Solvent extraction is used as a separation technique in lube oil production in petroleum refineries.
Viscosity Index (V.I.) is an important parameter for lubricating oil. Undesirable compounds like
aromatics reduces the V.I. and have to be removed.

Aromatics like BTX must also be removed from kerosene and jet fuel. Solvent selective for
aromatics are sulphur, nitrogen and oxygenated compounds. Important solvents are furfural,
sulpholane (tetrahydrithiophene-1,1-dioxide), N-methyl pyrrolidone (NMP), diethylene Glycol,
tetraethylene glycol, methyl – ethyl ketone (MEK) and methyl – isobutyl- ketone (MIBK)

Phenol and sulphur dioxide are no longer used because of toxicity and other problems.

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The process involves extraction followed by distillation – stripping of both the raffinate (that
contains the purified lube and some solvent) and the extract (containing the aromatics and the
solvent).

Fig.3: Common Liquid – Liquid extraction cascade configuration; (a) Single section cascade (b)
Two – section cascade, (c) dual solvent with two section section cascade. SR; solvent S recovery;
TR: Solvent T recovery

The factors influencing extraction: -

1) Entering feed flow rate, composition, temperature and pressure.

2) Type of stage configuration (one – section or two – section)
3) Desired degree of recovery of one or more solutes for one section cascades
4) Degree of separation of the feed for two – section cascades.
5) Choice of liquid solvent(s)
6) Operating temperature
7) Operating pressure (greater than the bubble point of the system)
8) Minimum – solvent flow rate and actual solvent flow rate as a multiple of the minimum
rate of one section cascades or reflux rate and minimum reflux ratio for two – section
cascades.
9) Number of equilibrium stages
10) Emulsification and scum – formation tendency
11) Interfacial tension

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12) Phase density difference

13) Type of extractor
14) Extractor size and horsepower requirement

The Ideal solution has:

1) A high selectivity for the solute relative to the carrier, so as to minimize the need to recover
carrier from the solvent
2) A high capacity for dissolving the solute, so as to minimize the solvent –to- feed ratio
3) A minimal solubility in the carrier
4) A volatility sufficiently different from the solute that recovery of the solvent can be
achieved by distillation, but the vapour pressure should not be so high that a high extractor
pressure is needed or so low that a high temperature is needed if the solution is recovered
by distillation
5) Stability to maximize the solvent life and minimize the solvent make-up requirement.
6) Inertness to permit use of common materials of construction
7) A low viscosity to promote phase separation, minimize pressure drop, and provide a high
solute mass – transfer rate.
8) Nontoxic and nonflammable characteristic to facilitate its safe use.
9) Availability at a relative low cost.
10) A moderate interfacial tension to balance the ease of dispersion and the promotion of
phase separation.
11) A large difference in density relative to the carrier to achieve a high capacity in the
extracter.
12) Compatibility with the solute and carrier to avoid contamination
13) A lack of tendency to form a stable rag or scum layer at the phase interval.
14) Desirable wetting characteristic with respect to extractor internals.
Lecture 9

Counter current multiple contact operation may be either continuous or batch. Because of the
greater ease in handling liquid phases, continuous operation is more commonly used in liquid –

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liquid extraction than in solid –liquid extraction. In certain cases “Reflux” in counter current
operation may be advantageous.

Higher concentration of the solute in the extract layer is possible by taking a portion of the extract
layer from which some or all of the solvent has been removed and returning this to the system at
the same stage from which the extract layer leaves.

This type of operation has been termed “Enriching by Reflux” or “Extract Reflux”

Fig.4: Countercurrent multiple contact extraction with extract reflux, Stream L0

Reflux may be provided at the end of the system from which the raffinate layer leaves. Such an
operation is termed as “Exhausting by Reflux or “Raffinate Reflux” The use of Reflux is limited to
certain types of ternary systems

Fig.5: Countercurrent multiple contact extraction with Raffinate reflux, Stream Vn+1

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In Liquid – Liquid extraction, calculation of equilibrium stage depends on two principles

1) Material Balances
2) Equilibrium relationships

Energy balances are generally not made due to lack of data. Material balances are similar to solid –
liquid extraction.

Equilibrium relationship in ternary systems

A ternary system consisting of three components A, B and C may be regarded as composed of

three binary systems –

• A and B (Carrier and Solute)

• B and C (Solute and Solvent)
• A and C (Carrier and Solvent)

Fig. 6: Equilateral Phase diagram for diphenylhexane- docosane-furfural at 45 0C and 1 atm.

Most of the ternary system fall in one of the following categories

a) The carrier (A) and the solvent (C) are practically immiscible. The equilibrium in such a
system may be represented in the form of a “x – y” plot as in the case of distribution of a
solute between a carrier gas and a solvent. If the solute concentration is small, a Henry’s
law type linear distribution law applies

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Type – I ternary system. About 75% of ternary liquid system falls in this category.

Completely miscible
• A and B (Carrier and Solute)

Completely miscible
• B and C (Solute and Solvent)

Partially miscible
• A and C (Carrier and Solvent)

Type – II ternary system not encountered so often.

Completely miscible
• A and B (Carrier and Solute)

Partially miscible
• B and C (Solute and Solvent)

Partially miscible
• A and C (Carrier and Solvent)

Completely miscible
• Docosane and Diphenylhexane (A and B)

Completely miscible
• Diphenylhexane and Furfural (B and C)

Partially miscible
• Docosane and Furfural (A and C)

The equilibrium curve MPQ is called binodal because it has two arms MP and PQ representing
raffinate and extract sides. Diphenylhexane is distributed between two liquid phases – Docosane
and Furfural. Since Docosane and Furfural are partially miscible, all three components are present
in each phase.

Region (I) consist of mixtures which exist as single liquid.

Region (II) consist of mixtures of two liquid phases under equilibrium.
The curve MPQ is called the solubility curve and it separates region (I) from region (II). The pair
points H and I on the curve represent two liquid phases in equilibrium. H is rich in carrier

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(raffinate phase) and I is rich in the solvent (extract phase). Such line which connects two points
representing two phases in equilibrium is called a tie line.
• There are infinite numbers of tie line.
• Tie lines are normally not parallel to each other.
• The length of the tie line decreases as we move away from the sides AB.
• The last tie line reduces to a point P, corresponding to a tie line of zero length. Both liquid
phases in equilibrium have the same composition.
• The point P, demarcates the Raffinate and the Extract sides of the equilibrium line and is
called the Plait Point, or Critical point.
• There are infinite numbers of tie line.
• Tie lines are normally not parallel to each other.
• The length of the tie line decreases as we move away from the sides AB.
• The last tie line reduces to a point P, corresponding to a tie line of zero length. Both liquid
phases in equilibrium have the same composition.
• The point P, demarcates the Raffinate and the Extract sides of the equilibrium line and is
called the Plait Point, or Critical point.

Fig. 7: Equilateral Phase diagram for diphenylhexane-docosane-furfural at 45 0C , 80 0C, 115 0C, 140 0C, at 1 atm.

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Lecture 10

Type – II ternary system

(Methylcyclopentane – normal Hexane – Aniline)

Completely miscible
• A and B (n - Hexane and Methylcyclopentane)

Partially miscible
• B and C (Methylcyclopentane and Aniline)

Partially miscible
• A and C (n - Hexane and Aniline)

The phase diagram for Methylcyclopentane – normal Hexane – Aniline at 25 0C and I atm is
illustrated in Fig.8. In this case the solubility curve is not continuous but consists of two branch
MN and QR. This type is important as it allows the use of “Extract Reflux”. If the temperature is
increased to 45 0C, the phase diagram is similar to type (I)

Fig. 8: Equilateral Phase diagram for Methylcyclopentane – normal Hexane – Aniline at 25 0C at 1 atm.

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Fig. 9: Equilateral Phase diagram for Methylcyclopentane – normal Hexane – Aniline at 25 0C at 1 atm. And 45 0 C.

Selectivity is the preferential uptake of the solute by the solvent over the carrier. Selectivity or
Separation factor is defined as:

Selectivity of the solute varies with the compositions of the two phases in equilibrium and depends
upon the temperature. It is unity at the plait point because the compositions of the two phases
become the same.

Following the equality of the activities of the solute in the two phases at equilibrium

Where (γB)E and (γB)R are the activity coefficient of the solute in the extract and the raffinate
phases respectively, and K is the “Distribution coefficient” or “Partition Coefficient” of the solute
for the carrier-solvent pair. From equation (2) and (3) it appears that if the activity coefficient of
the solute is small in the extract phase, the distribution coefficient is large, and the solvent has a
better selectivity for the particular solute.

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Equilibrium plot on a solvent free basis.

The mass ratios of the solute X and Y in the two phases are plotted versus the corresponding mass
ratios z or Z of the solvent on “solvent free basis”
A: carrier;
B: Solvent;
C: Solute

Type – I, Ternary system.

(A – C) – miscible
(B – C) – miscible
(A – B) – partially miscible
A: carrier;
B: Solvent;
C: Solute
Type – II, Ternary system.
(A – C) – miscible
(B – C) – partially miscible
(A – B) – partially miscible
A: carrier;
B: Solvent;
C: Solute

xC xB
X ; z
x A  xC x A  xC

yC yB
Y ; Z
y A  yC y A  yC

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Here x is the mass fraction of a component in the raffinate, and y is that in the extract. The X – z
and Y – Z plots of LLE are similar to the enthalpy – concentration diagrams (x-HL and y – HV)
used in distillation calculation

Such plots (X – z) and (Y – Z) are called Malony – Schubert diagram or Janecke diagrams.

Example 1: Draw the Janecke diagram for a liquid - liquid system using the following equilibrium
data. Show the tie lines on the diagram

Raffinate Phase Extract Phase

xA xB xC yA yB yC
0.939 0.0601 0.0 0.06 0.94 0.0

0.7327 0.0654 0.0219 0.0520 0.918 0.03

0.4402 0.0732 0.4866 0.036 0.88 0.064

0.246 0.090 0.664 0.0185 0.851 0.1305

0.103 0.1047 0.7923 0.0069 0.8276 0.1655

0.0 0.1103 0.8897 0.0 0.8246 0.1754

Solution:
The X – z and Y – Z data are calculated from the above table

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Lecture 11

Extraction apparatus
Specifications

To transfer high amounts of active agent from the starting phase into the extract phase the extraction
apparatus has to fulfil following points:

 Production of a large phase boundary which is achieved in most cases by producing fine droplets
and dispersing these droplets in the continuous phase.
 High mass transfer coefficient which is achieved in most cases by high relative velocities between
the two phases
 No axial remixing
 Fast and complete phase separation after extraction

Extractor types

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Single step mixer - separator

This is the simplest extraction apparatus (see figure 1) which can be operated discontinuously or
continuously. The transfer of the active agent from one phase into the other takes place in the
mixer and the separation of the two phases is done in the separator by gravity forces.

Advantages: high efficiency per step, high operating area, low apparatus height, insensible for
suspended substances

Disadvantages: high ground area necessary, high solvent costs (because of high volumes), high
energy and regulating effort

Mixer – settler – cascade

Adding more mixer – settler units in series a cascade is obtained. These units can be operated in

counter current, current and cross flow.

2 types:

 · For the box type (see figure 2) mixing and settling zones are separated by plates.
 · For the tower type (see figure 3) the single steps are one above the other so that less
ground area is used.

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Design calculation for stage – wise extraction

While dealing with the problem of separation of a liquid mixture, a decision has to be taken first
about the separation process (such as distillation, extraction, crystallization, etc.) to be adopted. If
liquid – liquid extraction appears to be the choice, then the next job is to select the solvent to be
used.

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Pilot plant tests may have to be done if reliable design data collected from operating units handling
of a similar mixture are not available.

The important stage – wise pieces of contact equipment are:

(1) Mixer – settler
(2) Sieve tray column
(3) Schiebel column

Continuous contact takes place in equipment like:

(1) Rotating disk contactor (RDC)

(2) Graesser raining bucket contactor
(3) Podbielniak extractor
(4) Packed column
(5) Spray column,
(6) Kuhni extractor. Etc

Lecture 11

Single stage operation: A single stage equilibrium contact device is shown in Fig.11.

Fig.11: Schematic of single stage extraction unit

The feed enters the mixer at a rate F having a solute concentration x F. The solvent is supplied at a
rate of S; it has a solute concentration yS. The liquid – liquid dispersion attains equilibrium and
leaves the mixer at a rate M with an overall solute concentration xM. The raffinate (flow = R,

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solute concentration xR) and the extract (flow = E, solute concentration yE) phase leaves the settler
after phase separation.

Total material Balance

Total material balance : F  S  M  E  R - (4)

Solute material balance : Fx F  Sy S  MxM  Ey E  Rx R - (5)

Fx F  Sy S
 xM  - (6)
FS
-

Combining the equations (4) to (6), we get

Fx F  SyS  ( F  S ) xM
F xM  y S
 
S x F  xM - (7)

Fig. 12: Single stage liquid extraction calculation using the equilibrium plot

The composition of the feed and the solvent stream are located at points F and S on the diagram.
By Lever arm rule.
Rx R  Ey E  ( R  E ) xM
E xM  x R
  - (8)
R y E  xM -

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Point M lies on the line ER. Since the mixer acts as a “theoretical” or “equilibrium stage”, the
phases E and R are at equilibrium and must lie on the terminals of the tie line through the point M.

Thus the solute concentration in the extract and the raffinate phases (yE and XR) can be obtained by
drawing the tie line through the point M. The steps of the graphical procedure is given:

(1) Draw the ternary equilibrium curve on the equilateral triangular diagram. Locate the points
F and S.
(2) Calculate xM from the material balance equation (6) and locate the point M on the line FS.

(3) Draw the tie line ER through the point M. The terminals of the tie line give the extract and
raffinate concentration yE and xR. The amount of the extract and the raffinate phases E and
R and the percentage of the solute separated from the feed can now be calculated from
equation (4), (5) and (7).

If a required percentage separation of the solute is specified, the necessary solvent rate can be
calculated. However, this will involve a trail and error procedure.

Fig 13: Construction of conjugate line using tie line data (see 8.4.2 pg 440. BKD)

See solved problem 8.2 & 8.3 (examples) by B. K. Dutta

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Lecture 12

Multi step extraction with counter current flow

The feed and the solvent flow in counter current way through the apparatus. This is a continuous
process where feed and solvent enter the apparatus at opposite ends. While raffinate is contacted
with pure solvent the extract is contacted with the feed.

Stage 1 Stage 2 Stage m Stage n

figure 14: multi step extraction with counter current flow

CONSTRUCTION OF THE TRIANGLE DIAGRAM

Basic for the construction are the mass balances. It is obvious that the difference of the mass flows
∆ in a section between two steps is constant. The result is that the balance lines cross in one point,
the pole point P
total balance:
F – E 1 = Rn – L = ∆
balance for one step (e.g. m):
Rm- 1 – E m = Rm – E m+ 1 = ∆

With ∆ as a hypothetical amount of the pole point P result the amount F and the single raffinate as
mixing point of P with the corresponding extracts. If L is given and Rn is wanted with the
knowledge of the hypothetical pole point amount results:

Rn  P  L
PL
Rn  L
PRn

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figure 15: multi step extraction with counter current flow.

If Rn is given so L can be determined by the law of balance:

PRn
L  Rn
PL
The position of the pole point P results as crossing point of the lines FE 1 and Rn L . In most cases
not all four points F, E1, Rn and L are given. Normally F, the raffinate concentration Rn and either
the extract concentration E1 or the amount of solvent are given. With the help of the mixing point
the missing point can be determined.

Phases in equilibrium are combined by a connode and therefore after construction of the pole point
the raffinate R1 according to extract E1 can be determined. Combining this raffinate R 1 with the
pole point last in the extract E 2 of the next step. The line PR1E2 is a balance line. This construction
is repeated until the desired raffinate concentration is reached. By the numbers of raffinate points
the number of theoretical steps is determined.

DETERMINATION OF THE MINIMUM AMOUNT OF SOLVENT

In the same way as for other thermal processes the minimum amount of solvent is this amount of
solvent which is necessary to achieve a certain separation with maximum consumption (= infinite
number of steps).

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In general the minimum amount of solvent for the counter current extraction is determined
following:

All connodes are extended and crossing points with the line LRn are constructed. This crossing
point which is farest away from point A is the pole point for minimum amount of solvent (see
figure 16).

Figure 16: determination of minimum amount of solvent for counter current extraction

For the case that the pole point is on the other side the construction is the same as given in figure
17. A large amount of solvent is given (at M1 respectively P1). The amount of solvent is the ratio
between solvent flow and feed flow which can be determined from the triangle diagram:

L FM

FS ML

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Reducing the amount of solvent results in moving the mixing point M on the line FL in direction of
F. With this the extract point E 1 moves on the binodal line upwards so that the pole point P goes
farer away until it is infinite. For this case the mixing point is in the position that the lines FE1 and
Rn L are parallel. Further reducing of the amount of solvent brings the pole point to the other side
of the triangle diagram and the pole point comes closer.

figure 17: minimum amount of solvent with infinite pole point

The minimum solvent rate

To determine the minimum solvent rate Sm, the equilibrium curve is drawn on a suitable co-
ordinate and the points F, S and RN are located.

The points RN and S points are joined and produced. A tie line through the point F and a few other
points below it are drawn

All these tie line are extended to meet the line RNS produced at a number of Δ points. The meeting
point closest to S is Δm, if the tie lines are inclined towards the point S.

If the tie line slope away from the point S, then the extended tie lines intersect the line R NS
produced on the left side of the diagram. The Δm will correspond to the Δ point farthest from S.

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Once the minimum solvent rate is found, the actual solvent rate is chosen on the basis of economic
considerations. A higher solvent rate will no doubt reduce the fixed costs because less number of
stages are required, but the operating costs will be higher primarily because of (i) handling a larger
quantity of liquids, (ii) larger equipment size, and (iii) higher cost of separation of the solvent.

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