Liquid-liquid extraction

RGhosh/ChemEng/McMaster/3M04/2010-11

1. Introduction

Liquid-liquid extraction processes take advantage of the partitioning of a solute (either solid or
liquid) between two immiscible or partially miscible liquids. For example citric acid is more
soluble in methyl amyl ketone than in water at pH 5.0 and this phenomenon can be utilised to
separate citric acid from an aqueous product stream containing other material, and thus enrich it.
When the solute to be extracted is a liquid, extraction processes are used primarily when
distillation is impractical or too costly to use. Some of the situations where liquid-liquid
extraction has obvious advantages over distillation are:

a) When the solute and solvent have close boiling points (e.g. petroleum products)
b) When the solute is temperature sensitive (e.g. bioproducts)
c) When solute and solvent form azeotropic mixture
d) When concentration of solute is very low

Applications of liquid-liquid extraction include:

a. Separation of aromatics from hydrocarbons

b. Purification of antibiotics
c. Purification of aromatics such as benzene, xylene and toluene
d. Protein purification using aqueous two-phase systems
e. Purification of natural products
f. Purification of dyes and pigments
g. Metallurgical purifications

2. Solvent systems and principles of extraction

Generally speaking, two types of solvent extraction systems are utilised in the chemical process
industry:

a. Aqueous/non-aqueous solvent system (also called aqueous/organic system)

b. Aqueous two-phase systems

Most solvent systems encountered in solvent extraction processes are of the aqueous/non-aqueous
type. Aqueous two-phase systems can be created by dissolving a high molecular weight polymer
(e.g. PEG) and an appropriate salt (e.g. sodium phosphate) in water. This generates two aqueous
phases, one rich in the salt and the other rich in the polymer. Biological macromolecules are
separated by aqueous two-phase extraction.

The addition of a second solvent to a binary (solute-solvent) mixture may lead to several
possibilities:

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 a) A homogeneous three-component solution may be formed
b) The new solvent may be completely immiscible with the initial solvent and thus two
phases, each having two components may be formed
c) The new solvent may be partially miscible with the initial solvent resulting in the
formation of a pair of partially miscible liquids

Possibility (a) is not suitable for extraction. Possibility (b) is the ideal scenario. Possibility (c)
could be used for extraction under appropriate conditions.

When the two solvents are immiscible, the partitioning of solute is conveniently summarised as a
partition coefficient K

Ky (1)
x

y is the equilibrium solute concentration in the extracting solvent L, and x is the equilibrium
solute concentration in the initial solvent H. The value of K is often a constant, independent of
solute concentration (though in some cases it might not be so) and is experimentally determined.
Once equilibrium distribution is reached, the chemical potential of the solute in the two phases
must be equal.

 ( H )   ( L) (2)

Therefore

 0 ( H )  RT ln x   0 ( L)  RT ln y (3)

The 0 s are the chemical potentials in standard reference states.

Therefore

  0 ( H )   0 ( L) 
Ky  exp   (4)
x
 RT 

From equation (4) it is evident that the greater the difference between the chemical potentials in
standard reference states, the better the extraction. After extraction, the solute rich phase is called
the extract phase while the solute poor or spent phase is called the raffinate phase.

With totally immiscible solvents, the representation of concentration terms is pretty straight
forward. The concentration of the solute could be expressed in different ways:

a. Mass of solute per unit solution weight or volumes

b. Mass of solute per unit solvent weight or volume
c. Molar concentration
d. Mole fraction
e. Mass fraction

If the “amount” of solute is small compared with amounts of solvent (i.e. for dilute solutions), a, b
and c are the preferred units.

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For partially miscible solvent systems, the concentration terms are represented by triangular
diagrams. For such systems, mole fraction and mass fractions are the units used. Triangular phase
diagrams make use of the fact that for any point within a triangle, the sum of the perpendiculars
dropped on to the three sides is a constant.

Fig. 1 shows the phase diagram for acetone (A) - water (B) - methyl isobutyl ketone (C) system.
Here acetone is the solute, which is completely miscible with the two solvents, water and MIBK.
Water and MIBK are only partially miscible with each other. A mixture indicated by point H on
the diagram has the three components A, B and C in the ratio of the perpendiculars HL, HJ and
HK. The area under the curve line NPFQM that is called the binodal solubility curve) represents a
two-phase region, which will split up into two layers in equilibrium with each other. The
composition of the two-phase are represented by points P and Q which are obtained from the
points of intersection of the binodal solubility curve with the “tie line” PQ. The “tie lines” are
straight lines, which connect together the compositions of the two phases, which are in
equilibrium with each other. These are experimentally determined. The point F on the binodal
distribution curve represents a single phase, which does not split into two phases and is known as
the plait point. The distance BN represents the solubility of MIBK in water while the distance MC
represents the solubility of water in MIBK. The area above the binodal solubility curve represents
the single-phase region.

Fig. 2 shows a phase diagram where the mutually miscible condition exists in between conditions
where two-phase systems exist. Fig. 3 shows a phase diagram where the two-phase system exists
in between mutually miscible conditions.

Fig. 1. Equilibrium distribution of acetone between water and MIBK

A, Acetone

F
K
J
P
H Q

C, MIBK
Water, B

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 Fig. 2. Phase diagrams Fig. 3. Phase diagram
A A

B C B C

Liquid-liquid extraction involves transfer of material from one liquid phase to another. These
processes can be carried out in different ways. Three basic steps are common to all liquid-liquid
extraction processes:

1. Mixing or contacting
Transfer of solute between two partially or completely immiscible liquid phases requires
intimate contact of the two phases. This is usually achieved by dispersing one phase (the
dispersed phase) as tiny droplets in the other phase (i.e. the continuous phase). Material
transport rate is critically dependent on the interfacial mass-transfer coefficient (which
depends on hydrodynamic conditions) and on the contact area. Vigorous agitation can
achieve both these requirements.

2. Phase separation or settling

Once the desired material transport has been achieved, the next step is to allow the dispersed
phase droplets to coalesce. This eventually leads to separation of the two phases (the extract
and the raffinate) into distinct layers due to density difference. In liquid-liquid extraction
processes, it is important that the two phases should have sufficient density difference to
allow phase segregation.

3. Collection of phases
After settling (or phase separation), the extract and raffinate phases have to be collected as
separate streams.

3. Batch extraction

This is the simplest mode of operation for extraction. In a batch extraction process, a solution
containing the solute of interest is mixed with the extracting solvent. The solute distributes
between the two phases depending on the partition coefficient. Once equilibrium is reached, the
extract and raffinate phases are allowed to separate. The separation funnel (see Fig. 4) is the
simplest batch extraction equipment for small-scale extraction. For larger scale batch extraction, a
variety of devices are used. All of these allow the fluids to be mixed and separated. The basic
principle is also illustrated in Fig. 4.

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 Fig. 4. Batch extraction equipment

Feed Extracting solvent

Mixer

Extract

Settler

Separating funnel
Raffinate

Mixer-settler unit

4. Analytical solution for batch extraction using immiscible solvents

H litres of initial solution (also called feed) having a solute concentration of x0 moles/litre is
mixed with L litres of extracting solvent. The equilibrium concentration distribution between the
two phases is given by:

y  Kx (5)

y is the solute concentration in the extract phase while x is the solute concentration in the raffinate
phase.

From solute material balance:

Hx0  Hx  Ly (6)

We define the term extraction factor E as:

KL
E (7)
H

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From (5), (6) and (7)

Kx0
y (8)
1 E

x0
x (9)
1 E

The fraction extracted p is given by:

Ly E
p  (10)
Hx0 1  E

5. Graphical solution for batch extraction using immiscible solvents

This method is more useful when the equilibrium relationship between extract and raffinate
concentration is non-linear. The graphical method is based drawing the equilibrium line and the
operating line as shown in Fig. 5. Equilibrium line is given by:

y  f (x) (11)

The operating line is obtained from material balance:

H
y   x0  x  (12)
L

Hx0/L + y0

Equilibrium line

y Slope = -H/L

Operating line
x

Fig. 5. Graphical solution for batch extraction

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The point of intersection of these two lines gives the equilibrium concentrations in the extract and
raffinate phases.

6. Single-stage continuous extraction with immiscible solvents

The single-stage continuous extraction process is merely an extension of the batch process.
Continuous steams of feed and extracting solvent enter a mixing unit. The mixed liquid is fed into
a settling unit from which continuous raffinate and extract streams are taken out. The analytical
solution of the single unit continuous process is analogous to that of batch extraction. The
analysis shown here is based on totally immiscible solvent system. The basic assumptions are:

1. The exit streams from the extractor are in equilibrium

2. The is negligible entrainment of the other phase with each exit stream

Kx0
y (13)
1 E

x0
x (14)
1 E

Where

KQL
E (15)
QH

QL and QH being the flow rates of the extracting solvent (= flow rate of extract phase) and the
feed (= flow rate of raffinate phase) respectively.

The graphical solution is similarly analogous. The operating line is given by:

Q 
y   H x0  x  (16)
 QL 

7. Batch extraction using partially miscible solvents

A graphical solution (see Fig. 6) is usually required for solving batch extraction using partially
miscible solvents. In the analysis shown in this section all concentration terms are in mass
fraction or mole fraction. A feed solution having composition F is brought into contact with pure
extracting solvent (composition S). The overall composition is represented by M and its position
is such that the distance ratio (FM/SM) = (L/H). L is the amount (in mass or total moles) of
extracting solvent and H is the amount (in mass or total moles) of the feed. Using the tie line
passing through M, the solute concentration in the raffinate and extract can be determined. In Fig.
6, these are represented by R1 and E1 respectively.

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If further solute needs to be extracted from the same raffinate using fresh extracting solvent, R1
and S are joined by a straight line. The new overall composition represented by N depends on the
relative amounts of raffinate and fresh solvent. The tie line passing through N can be used to
obtain the raffinate and extract concentration of the second step. In Fig. 6 these are represented by
R2 and E2 respectively.

Fig. 6. Extraction with partially miscible solvents

F M
R1
E1

R2 E2

B S

8. Cross –current continuous extraction using immiscible solvents

An extraction process is limited by the equilibrium constant. In order to recover residual solutes
from the raffinate stream it could be sent to one or several subsequent stages for extraction. The
multi-stage extraction scheme shown in Fig. 7 is referred to as cross-current extraction. Fresh
extracting solvent is generally fed into each stage. Such a system is usually solved in stages, i.e.
starting with the first forward substituting the values. Some of the basic assumptions are:

1. The raffinate and extract streams from each phase are in equilibrium
2. There is negligible entrainment of the other phase with each exit stream
3. The same equilibrium relationship holds good for all the stages, i.e. the value of K is
independent of concentration

For i = 1 to n:

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 Kxi 1
yi  (17)
1  Ei

xi 1
xi  (18)
1  Ei

Where

KQL ,i
Ei  (19)
QH

Fig. 7. Cross-current extraction

y1 y2 yn-1 yn

1 2 n-1 n
QH QH
x0 xn

QL,1 QL,2 QL,n-1 QL,n

The major disadvantage of using cross-current extraction is the diminishing concentration driving
force in the stages. The efficiency is low and hence such processes are suitable only for very high
value products.

7. Staged counter-current extraction

The drawback of diminishing concentration driving force is eliminated using staged counter-
current extraction. This refers to repeated extraction in the form of a chain of counter-current
cascades. As with cross-current extraction the individual elements are referred to as stages. Fig. 8
shows an idealised staged counter-current scheme. The feed stream enters the nth stage and the
solvent stream enters the 1st stage. The raffinate phase is collected from the 1st stage while the
extract phase is collected from the nth stage. Using this scheme the concentration driving force is
maintained more uniform in all the stages. The apparatus used for staged counter-current
extraction varies widely. Fig. 9 shows a counter-current extraction set-up having three stages.

Some of the basic assumptions are:

1. The raffinate and extract streams from each phase are in equilibrium
2. There is negligible entrainment of the other phase with each exit stream

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 3. The same equilibrium relationship holds good for all the stages, i.e. the value of K is
independent of concentration

Fig. 8. Idealised staged counter-current extraction

yn-2 y2
QL yn yn-1 y1 QL, y0 = 0

n n-1 2 1

QH x0 xn QH x1
x2
xn-1 x3

Fig. 9. Staged counter-current unit having three stages

Feed
Extracting
solvent

Extract
Raffinate

8. Analytical solution for staged countercurrent extraction using immiscible solvents

If the equilibrium relationship between the extract phase and raffinate phase leaving each stage is
assumed to be linear:

yi  Kxi i = 1 to n (20)

From a solute material balance over the first stage:

QH x2  QH x1  QL y1 (21)

From (20) and (21)

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x2  E  1x1 (22)

Where

E = K QL/QH

Similarly from a solute material balance over second stage:


x3  1  E  E 2 x1  (23)

For the nth stage:

 E n 1  1 
xn 1  2 n

 1  E  E       E x1  

 x1 (24)
 E 1 

The fraction extracted is given by:

p
QL y n Q x  QH x1 E E n  1
 H n 1  n1
  (25)
QH xn1 QH xn1 E 1

9. Graphical solution for staged countercurrent extraction using immiscible solvents

The graphical method, which can be used to determine the number of stages, is once again
dependent on drawing the equilibrium line and operating line. If we assume the equilibrium
relationship to of the form:

y i   ( xi ) i = 1 to n (26)

And from an overall solute material balance:

QH
yn  xn1  x1  (27)
QL

Fig. 10 shows a plot of the equilibrium line and operating line. The number of stages can be
calculated as shown in the Figure.

10. Differential extraction

Differential extraction is an extraction process in which the feed and extracting solvents
continuously flow past one another. This is carried out in equipment having tubular geometry in
which the two phases usually enter from opposite directions. Within the equipment arrangement
is made to ensure intimate mixing of the two phases. The flow of one liquid past the other and
subsequent collection of separate phases will depend on the density difference. Using a

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differential extractor, the contacting-settling-stream separating scheme seen with staged
operations is avoided. When the overall process is considered, differential extraction is a “non-
equilibrium” process. However, at any point within the extraction unit the extract and raffinate
streams could be in local equilibrium. Different types of equipment used for differential
extraction are shown in Figs. 11 to 14.

Fig. 10. Graphical solution for staged counter-current extraction

Equilibrium
line y3

Operating line
y2

y
y1
x3

x2 x4

x1
x

Fig. 11. Baffle plate extractor

Extract

Feed

Extracting
solvent

Raffinate

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 Fig. 12. Agitated baffle plate extractor

Extract
Feed

Extracting
solvent

Raffinate

Fig. 13. Reciprocating disk extractor

Extract

Feed

Extracting
Raffinate solvent

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 Fig. 14. Spray tower

Extract

Feed

Extracting solvent

Raffinate

The efficiency of solute transfer depends on the interfacial area generated within the extractor as
well as on the local mass transfer coefficients. The solute transfer takes place across interfacial
stagnant films on the raffinate side and on the extract side as shown in Fig. 15.

Fig. 15. Solute transport in extraction

yi Concentration
profile
y
Raffinate
Extract
x

xi

Raffinate side Extract side

film film
Interface

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The local solute flux is given by:

N S  k H ( x  xi )  k L ( yi  y) (28)

If local equilibrium exists, and if the equilibrium relationship is linear

yi  Kxi (29)

The overall separation process in a differential extraction is depicted in Fig. 16. Considering
solute transfer on the raffinate side:

QH dx  k H ( x  xi ) a dz (30)

a is the interfacial area per unit length of extractor. Rearranging and integrating

k a
x0
dx
 xx
x i
  H  z
 QH 
(31)

Fig. 16. Overall differential extraction process

QL y QH x0

z

QL y0 QH x

The integral in equation (31) is the number of film transfer units on the raffinate side and is
denoted by NTUH. The term (QH/ kH a) is the height of film transfer unit on the raffinate side and
is denoted by hH. Therefore

z  NTU H hH (32)

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Similarly
z  NTU L h L (33)

The overall height of a transfer unit based on raffinate concentration is given by

 Q 
hOH  hH   H hL (34)
 KQL 

Similarly, the overall height of a transfer unit based on extract concentration is given by

 KQL 
hOL  hL   hH (35)
 QH 

References

Coulson and Richardson’s Chemical Engineering Volume 2 (4th edition), J.M. Coulson etal.
(1991) Butterworth-Heinemann, Oxford.

Bioseparations: Downstream Processing for Biotechnology, P.A. Belter etal. (1988) John Wiley
and Sons, New York.

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