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CHAPTER 2: LIQUID

LIQUID EXTRACTION

CHAPTER / CONTENT
Definition & Application
Solvent selectivity
LLE for Partially Miscible Solvent

LLE for Immiscible Solvent


Liquid liquid extraction equipment

Definition & Application

The separation of constituents (solutes) of a liquid solution by contact with


another insoluble liquid.
Solutes are separated based on their different solubilities in different liquid.
The separation process of the components of a liquid mixture by treatment
with a solvent in which one or more desired components is soluble.
There are two requirements for liquid liquid extraction to be feasible:
component (s) to be removed from the feed must preferentially
distribute in the solvent.
the feed and solvent phases must be substantially immiscible

Definition & Application


The simplest LLE involves only a ternary (i.e 3 component system)
Important terms you need to know:
Feed

The solution which is to be extracted


(denoted by component A)

Solvent

The liquid with which the feed is contacted


(denoted by component C)

Diluent

Carrier liquid
(denoted by component B)

Extract

The solvent rich product of the operation

Raffinate -

The residual liquid from which solutes has been


removed.

Definition & Application


In some operations, the solutes are the desired product, hence the extract
stream is the desirable stream. In other applications, the solutes my be
contaminants that need to be removed, and in this instance the raffinate is the
desirable product stream.
Extraction processes are well suited to the petroleum industry because of
the need to separate heat sensitive liquid feeds according to chemical type
(e.g aromatic, naphthenic) rather than by molecular weight or vapor pressure.
Application:
Major applications exist in the biochemical or pharmaceutical industry,
where emphasis is on the separation of antibiotics and protein recovery.
In the inorganic chemical industry, they are used to recover high
boiling components such as phosphoric acid, boric acid and sodium
hydroxide from aqueous solution.

Definition & Application


Examples:
Extraction of nitrobenzene after reaction of HNO3 with toluene in
H2SO4
Extraction of
perchlorethylene

methylacrylate

from

organic

solution

with

Extraction of benzylalcohol from a salt solution with toluene.


Removing of H2S from LPG with MDEA
Extraction of caprolactam from ammonium sulfate solution with
benzene
Extraction of acrylic acid from wastewater with butanol
Removing residual alkalis from dichlorohydrazobenzene with water

Definition & Application

Examples:
Extraction of methanol from LPG with water
Extraction of chloroacetic acid from methylchloroacetate with water.
The difference between LLE and distillation process in the separation of
liquid mixtures:
LLE depends on solubilities between the liquid components and
produces new solution which in turn has to be separated again,
whereas;

Distillation depends on the differences in relative volatilities / vapor


pressures of substances. Furthermore, it requires heat addition.

Definition & Application


Advantages of LLE over distillation process:
Where distillation requires excessive amount of heat
Presence of azeotropes or low relative volatilities are involved (
value near unity and distillation cannot be used)
Dissolved or complex inorganic substances in organic or aqueous
solution
Removal of a component present in small concentrations, e.g
hormones in animal oil.
Recovery of a high boiling point component present in small
quantities in waste stream, e.g acetic acid from cellulose acetate.
Recovery of heat sensitive materials (e.g food) where low to
moderate processing temperatures are needed. Thermal decomposition
might occur.
Solvent recovery is easy and energy savings can be realized.

Solvent selectivity
The solvent is the key to a successful separation by LLE. The several criteria:
Distribution Coefficient.
This is the ratio (at equilibrium) of the concentration of solute in the
extract and raffinate phases. It gives a measure of the affinity of the solute
for the two phases.
A distribution coefficient other than unity implies that the solute must
have different affinity in the two phases. If only one solute is involved
(such as in the recovery of an impurity from an effluent stream), only the
distribution coefficient need to be considered, and it is desirable for this to
be as large as possible.

Solvent selectivity
Selectivity (Separation factor).
If there are more than one solutes (sat two solutes A and B), then
consideration should be given to the selectivity of the solvent for solutes A
against B.
The selectivity between two solutes A and B is defined as the ratio of
the distribution coefficient of A to the distribution coefficient of B. For all
useful extraction operation the selectivity must exceed unity. If the
selectivity is unity, no separation is possible.
Insolubility of Solvent.
The solvent should have low solubility in the feed solution, otherwise
the separation is not clean. For example, if there is significant solubility
of solvent in the raffinate stream, an additional separation step is required
to recover the solvent.

Solvent selectivity
Recoverability.
It is always necessary to recover the solvent for re-use, and this must
ordinarily be done by other means, e.g distillation. If distillation is to be
used, the solvent should form no azeotrope with the extracted solute and
mixtures should show high relative volatility. The solvent should also be
thermally stable under the distillation temperature.

Density.
A large difference in density between extract and raffinate phases
permits high capacities in equipment. This is especially important for
extraction devices utilizing gravity for phase separation.

Solvent selectivity
Interfacial tension.
The larger the interfacial tension, the more readily coalescence of
emulsions will occur but the more difficult the dispersion of one liquid in
the other will be. The more readily coalesces the emulsions the easier
phase separation will be.
Low interfacial tension aids dispersion and thus improves contacting
mass transfer efficiency. Coalescence is usually of greater importance, and
interfacial tension should therefore high.
Chemical Reactivity.
The solvent should be stable chemically and inert toward the other
components of the system and toward the common materials of
construction.

Solvent selectivity
Viscosity, Vapor pressure, Freezing Point.
These should be low for ease in handling and storage, for example, a
high viscosity leads to difficulties with pumping, dispersion and mass
transfer rate.
Availability and Cost.
An excellent solvent may not commercially available. Or it may
represent a large initial cost for charging the system, and a heavy
continuing expense for replacing inevitable operating losses.
Other Criteria.
Toxicity and flammability of the solvent are important occupational
health and safety consideration.
Stability of the solvent (i.e resistance to breakdown), particularly in the
recovery steps, is significant, especially if the breakdown products might
contaminate the products of the main separation.

LLE for Partially Miscible Solvent

SINGLE STAGE CALCULATIONS

MULTISTAGE COUNTER CURRENT SYSTEM

Single stage calculations


Solvent and the solution are in contact with each other only once and thus
the raffinate and extract are in equilibrium only once.

The solution normally binary solution containing solute (A) dissolved in a


diluent or carrier (B). The extracting solvent can be either pure solvent C or
may content little A. Raffinate (R) is the exiting phase rich in carrier (B) while
extract is exiting phase rich in solvent (C).

When liquid solution mixed with solvent (C), an intermediate phase M


momentarily forms as the light liquid moves through the heavy liquid in the
form of bubbles. These bubbles provide a large surface area for contact
between the solution and the solvent that speed up mass transfer process.

The raffinate and extract are in equilibrium with each other.

Single stage calculations

Liquid-Liquid Extraction
Extracting Solvent, S
Intermediate, M

ys (A)

Feed Solution, F

xM (A)
Raffinate phase, R
x* (A)

xF (A)

F
E
M
yS
x*

Mass of feed solution


Mass of extract phase
Mass of intermediate
Mass fraction of A in S
Equilibrium mass fraction
of A in R

Extract phase, E
y* (A)

S
R
xF
xM
y*

Mass of extracting solvent


Mass of raffinate phase
Mass fraction of A in F
Mass fraction of A in M
Equilibrium mass fraction of A in E

Note: Intermediate shown just for purpose of demonstration. Dont have to draw it when
answering the question

Single stage calculations


In most single extraction, we are interested to determine the equilibrium
composition and masses of raffinate and extract phases by using ternary phase
diagram and simple material balances.
Using material balance,
Calculate the mass of intermediate M using total material balance:
FS M

Eq. (1)

Determine mass fraction of solute A in intermediate M using material balance


for solute A :
xF F y S S xM M

Use both Eq. 1 and 2 to find xM value

Eq. (2)

Single stage calculations


On a right angle triangular diagram or equilateral triangular diagram for
A-B-C system:
Locate point F (xF) and S (yS)
Draw a straight line from F to S

Using the calculated value of xM, locate point M (xM) on the FS line. Note that
point M must be on FS line.
Draw a new tie line that pass through point M. This new tie line must take shape
of the nearest given tie lines.
From the new tie line, you can locate point E and R and hence you can
determine the composition of raffinate, R and extract, E that are in equilibrium.

Single stage calculations


Once you have determine composition of R and E, you can determine the
masses of E and R using the material balance as follows:
Using the total material balance:

FS RE

Eq. (3)

Using the material balance for solute A:


x F F y S S x * R y * E

Eq. (4)

Solve those Eq 3 and 4 to determine the masses of E and R

Single stage calculations


Example 1
100 kg of a solution containing 0.4 mass fraction of ethylene glycol (EG) in water is
to be extracted with equal mass of furfural 250C and 101 kPa. Using the ternary
phase equilibrium diagram method, determine the followings:

the composition of raffinate and extract phases


the mass of extract and raffinate
the percent glycol extracted
Furfural rich layer

Water rich layer

% EG

% water

% furfural

% EG

% water

% furfural

0.0

5.0

95.0

0.0

92.0

8.0

8.5

4.5

87.0

2.0

89.6

8.4

14.5

4.5

81.0

5.5

86.0

8.5

21.0

6.0

73.0

7.0

84.4

8.6

29.0

7.0

64.0

8.0

83.3

8.7

42.0

8.5

49.5

14.0

77.2

8.8

50.0

14.0

36.0

31.0

60.0

9.0

51.0

33.0

16.0

51.0

33.0

16.0

Use the following


equilibrium tie line
to
construct
the
ternary
phase
diagram

Single stage calculations


Solution 1
F = 100 kg

S = 100 kg

xF=0.4

yS=0

Calculate the mass of intermediate M using total material balance

FS M

100 100 M

M 200 kg

Determine mass fraction of solute A in intermediate M using material


balance for solute A:
xF F y S S xM M

0.4 100 0 100 x M 200

x M 0.2

Locate point F & S, draw line FS. Locate point xM on FS line. Draw new tie
line that pass through point xM. From that tie line, locate point E and R hence
you can determine the composition of R (x*) and E (y*) which is in equilibrium.
From the graph, y* = 0.26, x* = 0.075 (Solution for point 1)

Single stage calculations


Right angle method

F
M
R

Single stage calculations


Equilateral method

F
E

M
R

Single stage calculations


Solution 1 (cont)
Using the total material balance
FS RE

100 100 R E

R 200 E

Eq. (i)

Using the material balance for solute A:


x F F y S S x * R y * E

0.4 100 0 100 0.075 R 0.26 E

Insert eq (i) into eq above


0.075 200 E 0.26E 40
15 0.075E 0.26E 40
0.185E 25
E 135 .14kg
R 200 E 200 135 .14
R 64.86kg

Solution for point 2

% of EG extracted = (Mass of EG in extract /


Mass of EG in feed) x 100%
% of EG extracted =
y * E
0.26 135.14
100%
x100% 87.8%
xF F
0.40 100

Solution for point 3

Multi stage counter current system


Solvent and solution which flow opposite (countercurrent) to each other,
come into contact more than once and mix on stages inside the reactor.

Normally numbering of the stages begin at the top down to the bottom.
Thus the top most stage is named as stage 1, stage directly below stage 1 is
stage 2 and so on.
Final extract, E

Feed solution, F
xF (A)
1

yE (A)

2
3
n
N-1

Extracting solvent, S
yS (A)

Final raffinate, R
XR (A)

Multi stage counter current system

The analysis of multistage extraction can be performed using right angle


or equilateral triangular diagram to determine the number of ideal stages
required for a specified separation.
Using material balance,
Calculate the mass of intermediate M using total material balance:
FS M

Eq. (1)

Determine mass fraction of solute A in intermediate M using material balance


for solute A :
xF F y S S xM M

Use both Eq. 1 and 2 to find xM value

Eq. (2)

Multi stage counter current system


On a right angle triangular diagram or equilateral triangular diagram for
A-B-C system:
Locate point F (xF) and S (yS)
Draw a straight line from F to S
Using the calculated value of xM, locate point M (xM) on the FS line. Note that
point M must be on FS line.
Locate point E1 (Point M must be on E1RN line).
Operating Points and Lines.
Locate the Operating Point by finding the intersection of operating
lines for the left most and right most stage.
Draw a line through E1 and F.
Draw a line through S and RN.
Locate the intersection P. This point is the operating point P.

Multi stage counter current system

Solute

Plait Point
E1

Feed
Operating Point
P

M
RN
S
Carrier

Multi stage counter current system


Operating Lines and Tie Lines: Stepping Off Stages:

Locate point R1 from the tie line intersecting E1


Draw a line from the operating point P through R1 to the extract side of
the equilibrium curve. The intersection locates E2

Locate point R2 from a tie line.


Repeat Steps 2 and 3 until RN is obtained
Summary: E1 R1 : Tie line, R1 E2 : Operating line. Stop until E
value is slightly below RN value

Multi stage counter current system

Solute

Plait Point

E1
E2
E3

E4

Feed
M

Operating Point
P

R1

E5
E6

RN
Carrier

Solvent C

Multi stage counter current system


Minimum solvent amount / minimum solvent flow rate
Minimum solvent flow rate is the lowest rate / amount at which solvent could be
theoretically used for a specified extraction.

Occurs when operating line touches the equilibrium curve at which the
separation requires infinite number of ideal stages.

Point M is dependent upon the solvent flow rate / amount. The larger the rate /
amount, the closer is point M to point S on the FS line.

Multi stage counter current system


On a right angle triangular diagram or equilateral triangular diagram for A-BC system:
Locate point F (xF) and S (yS)
Draw a best tie line that originate from F. The intersection of this line with
extract half dome is point Emin (minimum extract flow rate / amount).
Draw a straight line from Emin to point R. The intersection of this line with
FS gives point Mmin. From point Mmin you can read the value of xmin.
Use the value of xmin and material balance to calculate the Smin .
% Overall efficiency of multi stage extraction column:
% Overall efficiency = (number of ideal stage / number of real stage) x 100%

Multi stage counter current system


Example 2
5300 kg/h of a solution containing 30% by weight of ethylene glycol (EG) in water
is to be reduced to 4.5% (solvent free) by a continuous extraction in a
countercurrent column using recycled furfural that contains 1.5% EG as the
extracting solvent:
Determine the minimum solvent flow rate for the extraction above
If the solvent enters at 1.25 times the minimum solvent rate, how many ideal
stages are required?
Determine the number of real stages if the overall efficiency of the column
is 60%

Multi stage counter current system


Solution 2
F = 5300 kg/hr

xF = 0.30

RSF = 0.045

Emin

F
Mmin
RSF
S

yS = 0.015

Multi stage counter current system


From the graph above, XMmin = 0.25
From material balance:
Solution for point 1
F S min Mmin
0.3 5300 0.015S min 0.25Mmin

5300 S min Mmin


x F F y s S min x Mmin Mmin

S = 1.25 x Smin=1.25 x 1127.66 kg/h

Smin=1127.66 kg/h

S = 1409.58 kg/h

Calculate the mass of intermediate M using total material balance :

FS M

5300 1409.58 M

M 6409.58 kg

Determine mass fraction of solute A in intermediate M using material


balance for solute A:
From material balance:

Multi stage counter current system


xF F y S S xM M

xM 0.24

0.3 5300 0.015 1409.58 xM 6709.58

Solution for point 2


E1
E2

From figure above, no


of ideal stages = 5

E3

E4
E5

RSF

Number of real stages = 5 / 0.60 = 8.33 = 9 stages.

Solution for point 3

LLE for Immiscible Solvent

Sometimes extraction use a solvent C that is only slightly soluble in B or the


solvent C used is in range where the solubility in B is so low that for all practice
purpose, it can be assumed to be completely insoluble / immiscible in B and vice
versa.

Bancroft weight fractions or mass ratio, x and y are defined as follows:

x (in raffinate phase) = mass of solute A / mass of diluent B


y (in extract phase) = mass of solute A / mass of solvent C

LLE for Immiscible Solvent

SINGLE STAGE CALCULATIONS

MULTISTAGE COUNTER CURRENT SYSTEM

Single stage calculations


Feed solution
M kg A in feed

B kg diluent B in Raffinate
x kg A/kg diluent B

Solvent
N kg A in feed

S kg solvent C in Extract
y kg A/kg solvent C

Solvent C is used in such a range that it is considered insoluble in B.

Material balance of the solute (A) are:


M N y' S x' B

y'

B
MN
x'
S
S

Eq. (3)

Single stage calculations


Example 3
An aqueous solution of acetic acid is to be extracted in a single extractor with
isopropyl ether. The solution contains 24.6 kg of acetic acid and 80 kg of water.
If 100 kg of isopropyl ether is added to the solution, what weight of acetic acid
will be extracted by isopropyl ether if equilibrium is attained?
Water and isopropyl ether may be considered as completely immiscible under
the condition of extraction. The equilibrium data as follows:
x (kg acid/kg water)

0.030

0.046

0.063

0.070

0.078

0.086

0.106

y (kg acid/kg isopropyl ether)

0.10

0.15

0.20

0.22

0.24

0.26

0.30

Single stage calculations


Solution 3
A = Acetic Acid

B = Water

C = Isopropyl ether

Feed solution
24.6 kg A

80 kg diluent B in Raffinate
x kg A/kg diluent B

Solvent
0 kg A in feed

100 kg solvent C in Extract


y kg A/kg solvent C

From mass balance,


M N y' S x' B

24.6 0 y'100 80 x'

y' 0.80x' 0.246

The equilibrium data and equation above is plotted in figure next page.
From the intersection of lines, x = 0.062, y = 0.195

Amount of acetic acid extracted = 19.5 kg

Single stage calculations


Solution 3
x' - y' diagram for system acetic acid-water-isopropyl ether
0.35
0.3
0.25

y'

0.2
0.15
0.1
0.05
0
0

0.02

0.04

0.06

0.08
x'

0.1

0.12

0.14

Multi stage counter current system


The principle is quite same with the partially miscible solvent, but in this case
the extraction process involved the immiscible solvent.

B kg/h pure diluent B in feed solution

S kg/h pure solvent in extract phase

x2 kg A/kg pure B
1

y2 kg A/kg pure solvent

2
3
n
N-1
N

S kg/h pure solvent C

B kg/h pure diluent B in raffinate

yn+1 kg A/kg pure solvent

xn kg A/kg pure B

Multi stage counter current system


For immiscible solvents, analysis of the extraction process become much simpler
since the flow rate of pure solvents (extracting solvent and feed solvent (diluent) )
are constants).

The operating line equation for multi stage liquid liquid extraction:
y'

y' S x' 2 B
B
x' 2
S
S

Form of y = mx + c

The operating line gives a relationship between mass fraction of A (xn) in


raffinate phase coming out of the nth stage, with mass fraction of A (yn+1) in extract
phase entering the nth stage.
The operating line can be plotted by locating points (x1,y1) and (x2,y2) and
draw a straight line through these points.

Using the method similar to Mc Cabe Thiele diagram, the number of ideal
stages can be determined by drawing the triangular steps connecting equilibrium
line and the operating line.

Multi stage counter current system


Example 4
8000 kg/h of an acetic acid-water solution containing 20% acid by mass is to be
counter currently extracted with isopropyl ether to reduce the concentration of acid
to 2% in the solvent-free raffinate product.
Determine the number of theoretical stages if 20,000 kg/h solvent is used.
Use the following equilibrium data:
x (kg acid/kg
water)

0.000

0.025

0.050

0.100

0.150

0.200

0.220

0.240

0.260

0.300

y (kg acid/kg
isopropyl ether)

0.000

0.005

0.013

0.030

0.046

0.063

0.070

0.078

0.086

0.106

Multi stage counter current system


Solution 4
Since acid is to be extracted, acid is the absorbable component A, while water is
component B and isopropyl ether is component C.

0.8(8000) kg/h of water in

20,000 kg/h isopropyl ether (C) in extract phase

x2

y2
TOP (2)

0.8(8000) kg/h of water (B) in raffinate


0.02 kg A/kg (solvent free)
x1

BOTTOM (1)
20,000 kg/h isopropyl ether (C) in
y1

Multi stage counter current system


Solution 4
F = 8000 kg/h

xF = 0.20

xBF = 0.80

S = 20,000 kg/h

From the definition:


x (in raffinate phase) = mass of solute A / mass of diluent B
y (in extract phase) = mass of solute A / mass of solvent C
For location 1,
Solvent feed

Raffinate phase

Mass of solute A = 0 kg/h

Solvent-free composition of A = 0.02, B = 0.98

Mass of solvent C = 20,000 kg/h.

x'1

Coordinates for (x1,y1) = (0.0204, 0)

A
A
B
A
A B 0.02

0.0204
B A B A B A B
B
0.98

y '1

0
0
20000

Multi stage counter current system


Solution 4
For location 2,
Feed
Mass of solute A = 0.20 x 8000 = 1600 kg/h
Mass of diluent B = 0.80 x 8000 = 6400 kg/h.

Extract
Mass of solute A = Mass of acid in Mass of acid in raffinate
Mass of solute A = 1600 - x1x B = 1600 0.0204 x 6400= 1469.44 kg/h
Mass of solvent C = 20 000 kg/h

Multi stage counter current system


Solution 4
For location 2,
Extract
x'2

1600
0.250
6400

y'2

1469 .44
0.0735
20000

Coordinates for (x2,y2) = (0.250, 0.0735)


The points for operating line are (0.0204, 0) and (0.250, 0.0735).
No. of theoretical stages = 14 stages

Multi stage counter current system


Solution 4

Multi stage counter current system


Minimum solvent amount / flow rate: immiscible solvent
Minimum solvent flow rate, Smin is defined as the flow rate of solvent at which
the number of stages approaches infinity.
Smin can be determined graphically by drawing a straight line originating from
the bottom (x1,y1) until it becomes tangential to the equilibrium curve. The slope
of this line corresponds to minimum slope (mmin):
m min

B
S min

S min

B
m min

Example 5
Determine the minimum flow rate of isopropyl ether for the problem in
Example 4.

Multi stage counter current system


Solution 5
The line tangential to the equilibrium curve and originates from (x1,y1)
which is (0.0204, 0) is drawn in figure below:

The slope of the tangential line = 0.343

S min

B
0.8 8000
= 18 658.89 kg/h.

m min
0.343

Liquid liquid extraction equipment

Two main classes of solvent extraction equipment:


1)

Vessels in which mechanical agitation is provided for mixing

2)

Vessels in which the mixing is done by the flow of the fluid themselves.

The extraction equipment can be operated batch or continuous.

Liquid liquid extraction equipment


Mixer Settlers for Extraction
A mechanical mixer is often used to provide intimate contact between the
two liquid phases to provide efficient mass transfer.
One phase is usually dispersed into the other in the form of small droplet.
In figure 12.6 1(a) for typical mixer settler, mixer or agitator is entirely
separate from the settler. The feed of aqueous phase and organic phase are
mixed in the mixer, and then the mixed phases are separated in the settler.

In figure 12.6 1(b) for combined mixer settler, sometimes used in extraction
of uranium salts or copper salts from aqueous solution.

Liquid liquid extraction equipment


Spray Extraction Towers
In Figure 12.6 2 the heavy liquid enters at
the top of the spray tower, fills the tower as
the continuous phase, and flows out through
the bottom.
The light liquid enters through a nozzle
distributor at the bottom, which disperses or
sprays the droplets upward.
The light liquid coalesces at the top and
flows out.
In some cases the heavy liquid is sprayed
downward into a rising, light continuous
phase.

Liquid liquid extraction equipment


Packed Extraction Towers
More effective tower made
by packing the column with
random packing such as
Raschig rings, Berl saddles,
Pall rings and so on

Packings cause the droplets to


coalesce and redisperse at
frequent intervals through the
tower.
Packed tower is more efficient
than spray tower.
Table 12.6 1 shows typical
performance for several types
of
commercial
extraction
towers.