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11 Liquid-liquid Extraction

11.1 Introduction

A liquid mixture (e. g. A+B) is treated

with a solvent S (extractant) in which
one or more of the desired components is
preferentially soluble.
The separation of compounds is based on
differences in solubilities
[distribution of components between
(partially) immiscible liquid phases].

11.1.1 Extraction processes

Requirement for the solvent in physical

extractions:
(1) the solvent S and liquid-mixture are at
least partially if not completely
immiscible;
(2) its solubilities for components are
different.
A+B
S
A

depends on the solubilities

in two (partially) immiscible liquids

physical operation

chemical operation
chemical reaction occurs,
with higher selectivity

A single stage batch extraction:

solvent S
feed F
(solute A +
diluent B )

extract E
(S+A+B)
yA, yB

yA
x
> A
yB
xB

raffinate R
(B+A+S)
xA, xB

Subsequent separation process:

distillation, crystallization, reextraction,

Extraction is preferable in the following

cases:
(1) when the relative volatility is near unity,
or when the azeotrope is formed;
(2) when the concentration of less volatile
components is low;
(3) when heating must be avoided; and
(4) when the components to be separated
are quite different in nature.

Factors to be considered for selecting

solvent:
(1) solubility
(2) selectivity
(3) subsequent separations

11.2 Equilibrium of Ternary Systems and

Principle of Extraction
11.2.1 Triangular diagram
1. Triangular diagram A
xA = 0.4
0.8

11.1.2 Contact between two phases

differential contacting equipment

xB = 0.3
xS = 0.3
xA + xB + x S = 1

e. g., packed columns, pulsed columns,

spray towers.

stagewise equipment

x mass fraction

e. g., mixer-settler units

0.2
xS
0.4

0.6
0.4

xA

0.6

0.8
xB
0.2 0.4 0.6 0.8 S

0.2
B

Lever rule:
(1) M, E, and R are along the same line;
(2) the mass ratio of mixtures equals to the
A
length ratio of
line segments.

2. Lever rule
A

Two liquid mixtures

R kg (xA, xB, xS ) and
E kg (yA, yB , yS ) are
mixed to form a
mixture
M kg (zA, zB, zS ).

yA
zA
xA
B

E
MR
=
R
ME

E
M
R
S

xS zS yS

When the solvent S is mixed with the

binary mixture F (A+B) , point M must be
on line SF, and its position is determined by
the lever rule.
S
MF
=
F
MS

(11-26)

On the line SF, the mass

ratio of A and B is the same.

M
S

E
MR
=
,
M
RE

R ME
=
M RE

yA
zA
xA
B

E
M
R
xS zS yS

11.2.2 Equilibrium of partially miscible

systems
Liquid mixture: solute A + solvent B
New solvent S
Types of ternary mixture:
(1) S may be completely immiscible with
the original solvent B.
(2) S may be partially miscible with B.
(3) S and B, S and A form two partially
miscible liquids.

II

1. Solubility curve, tie line, and plait point

Solubility curve:

solubility curve

A
homogeneous
phase

Extract on the RHS of pint P

(11-9)
ys = (yA )

Raffinate on the LHS of pint P

(11-10)
xs = (xA )

tie line

plait point P
conjugate phases

E1

R1

E and R are
connected by the
tie line.

M1

BR
0

P
E0 S

two-phase region

BR
0

E0 S

2. Distribution coefficient and

distribution curve

11.2.3 Phase equilibrium and extraction

operation

Distribution coefficient

1. Single-stage extraction process

kA = mass fraction of A in extract .

mass fraction of A in raffinate
yA
y
= A
(11-6)
xA
Distribution curve
yA = f (xA )
(11-8)

solvent S
E

xA

extract E

R R
B

raffinate R
M

purified extract
E, yA
solvent
recovery
purified raffinate
R, xA

E
S

y oA =

x oA
1 + ( 1) x oA

(11-13)

y /y
k
= A B = A
x A / x B kB

(11-11)

y oA / y Bo
x oA / x Bo

When y oA = x oA , = 1, separation by
A
extraction is impossible.

(11-12)

Note:
distribution coefficient k E
F
phase equilibrium
R
selectivity ratio
B
separability by extraction

Binary systems:

x
y =
1 + ( 1) x oA
o
A

feed F

y= x

2. Selectivity ratio of solvent

or

o
A

(11-13)

E
S

3. Effect of miscibility of original solvent B

and extractant S
small miscibility
larger two-phase region
, better result of separation

lower temperature
miscibility
, surface tension .

Rm1, xm1, A, xm1, S

11.3 Calculation for an Extraction Process

11.3.1 Mathematical description
1. Material balance
Stage m:
Rm1, xm1, A, xm1, S

Rm , xm, A, xm, S
m

Em , ym, A, ym, S

Em+1, ym+1, A, ym+1, S

Rm , xm, A, xm, S

2. Equilibrium stage and stage efficiency

m
Em , ym, A, ym, S

Em+1, ym+1, A, ym+1, S

Total material balance:

Rm1 + Em+1 = Rm + Em

Material balance for solute A:

Rm1xm1, A + Em+1ym+1, A = Rm xm, A + Em ym, A

Material balance for solvent S:

Rm1xm1, S + Em+1ym+1, S = Rm xm, S + Em ym, S

A problem of extraction may be

considered from two aspects:

equilibrium stage
it is independent of equipment and
may be calculated first.
stage efficiency
it depends on the equipment, determined
experimentally.

actual number of stages

= equilibrium stage/efficiency

Equilibrium stage:
The compositions of the two streams
leaving the stage are in equilibrium,
no mater what composition they have
when they enter the stage.
Rm1, xm1, A, xm1, S

Rm , xm, A, xm, S
m

Em , ym, A, ym, S

Em+1, ym+1, A, ym+1, S

11.3.2 Single-stage extraction

F, xFA

R, xA, xS

S, zA, zS

E, yA, yS

For design:
given: F, xFA
specify: xA
select: zA, zS
calculate: S, E, yA, yS,
R, xS.

For operation:
given: F, xFA
S, zA, zS
calculate: E, yA, yS,
R, xA, xS.

1. Analytical method
Six unknowns are solved from 6
equations.

Total material balance:

F+S=R+E=M
Material balance for solute A:
xFA+SzA = RxA+EyA = MxMA
Material balance for solvent S:
SzS = RxS+EyS

Phase equilibrium relationship:

yA = f (xA )
(11-8)
ys = (yA )
(11-9)
(11-10)
xs = (xA )

2. Graphical method
(1) Draw the solubility
curve.
(2) Locate points F and
S, and the mixture
M is on the line FS.

Find the tie line RE:

MR
RE

R=ME

(11-22)

(a) By estimation;
F
xA
B

?
E

(b) By auxiliary
curve.

R
M
S

(4) Determine the flowrates of streams

by material balance and lever rule

E=M

(11-21)

(3) Locate point R by xA,

find the tie line RE by interpolation,
M is the intersection of lines RE and FS.

S MF
=
F MS
Total material balance:
M=F+S

(11-20)

xA
B

E3

E2

E?
E1

(5) Find the composition in the extract yA

and yS , and the concentration of solvent
in the raffinate xS.
E = F

R3
R2
R1

E
R
M
S

RF
R E

R = F E
are the amount of
purified extract and
raffinate, respectively.

A
E
F
R yA R
xA
B xS

E
M
yS

3. Range of separation in a single-stage

extraction and the limit in the amount of
extractant
Point c:
the maximum amount
A
of solvent Smax .

Or: the flowrates of streams may be

obtained by material balance only,
S=F

xFA xMA
xMA zA

E=M

xMA xA
yA xA

Correspondingly,

in which xFA is given, xA is specified, zA is

selected, and xMA and yA are found from the
phase diagram.

Point d:
the minimum amount of solvent Smin .
The amount of
solvent used for
operation:
Smin < S < Smax
In general,
S = (1.1 2.0)Smin

x oA,min

d
R

Bx
A,min

E
M

o
A ,min

Draw a line tangent

to the solubility curve
through point S, we
obtain the maximum
concentration in the
purified extract,

F
xF,A

in raffinate: xA, min

in purified raffinate: x

c
S

11.3.3 Multi-stage crosscurrent extraction

The calculation is the repeat of that
for single-stage extraction,
F
but the amount of liquid
mixture in each stage is
S
E1
1
usually different.
R1
Features:
S
E2
2
the concentration of solute
R2
is low in the raffinate, and
S
E3
3
the amount of solvent is
R3
large.

o
A,max

F
xF,A
o
A ,min

E
R

Bx
A,min

A
y oA,max

F
xF,A

o
A ,min

d
R

B xA,min

E
M

c
S

11.3.4 Multistage countercurrent extraction

Higher extract rate may be obtained with
less extractant.
Calculation:
amount of solvent, number of equilibrium
stages, amount and concentration of
streams leaving each stage.
Method of stage-to-stage:
analytical or graphical

11.3.5 Calculation for extraction with

completely immiscible solvents
1. Representation of composition and phase
equilibrium
X mass ratio in raffinate
(kg solute/kg diluent )
Y mass ratio in extract
(kg solute/kg solvent )

Equilibrium relationship:

2. Single-stage extraction

Equilibrium relationship:

feed B, XF

extract S, Y

solvent S, Z

raffinate B, X

B amount of original solvent

S amount of pure solvent
Z mass ratio of A in extractant
Material balance for solute A:
S(Y Z) = B(XF X)
(11-36)

Y = KX
(11-35)
K distribution coefficient, generally
dependent upon concentration.

Y = KX
Material balance for solute A:
S(Y Z) = B(XF X)

(11-35)
(11-36)

For given B, XF and Z, specify one variable

among S, Y and X, other two may be
calculated.
3. Multistage crosscurrent extraction and
countercurrent extraction

11.3.6 Extraction with reflux

High purity may be achieved.
11.3.7 Differential contacting
countercurrent extraction
The diameter of column depends on the
flowrates and velocities of two phases.
The height of column may be obtained by
calculating the number of transfer unit or
HETS.

Exercises: 11 1, 3, 5

11.4.1 Types of extraction equipment

stagewise contactors
differential contactors
11.4 Extraction Equipment
Requirement:
bringing the feed mixture and the solvent
into intimate contact
separation of the resulting two phases

Differential contactors:
1. spray tower
2. packed column
3. pulsed packed column
pulsed sieve column
4. vibrational sieve plate column
5. rotary disc column
6. centrifugal extractor

11.4.3 Rate of mass transfer in extraction

equipment
Factors affecting mass transfer:
(1) drop size and size distribution of
dispersed phase
(2) circulation inside drops and interfacial
disturbance
(3) axial mixing in the equipment

Both may be with or without the addition

of external energy.
Stagewise contactors:
mixer-settler unit
sieve-plate column

11.4.2 Flooding in extraction equipment

and limit of velocity
The performance of equipment is mainly
determined by:
allowable flowrates of two phases ( D)
rate of mass transfer
( H)
The superficial velocities of two phases at
which the flooding occurs are the limit for
the velocities.

11.4.4 Selection of extraction equipment

Following factors are to be considered:
the number of stages required
production capacity
properties of the materials
residence time

Supercritical fluid:
p

11.5 Supercritical Fluid Extraction and

Liquid Membrane Extraction
11.5.1 Supercritical fluid extraction
1. Principle
It is an extraction process in which a
supercritical fluid is used as the solvent.

SF
critical
point

viscosity that of gas

density and solubility

G
t

those of liquid

diffusivity >> that in liquid

2. A process of supercritical extraction

CO2 is compressed as a supercritical
fluid, and used as an extractant.
feed

reducing valve

extract

raffinate

11.5.2 Liquid membrane extraction

( separation )

compressor
extraction
product

SF

(a) make an emulsion by dispersing

aqueous drops (in m) into an organic
phase (W/O);
liquid
external
(b) disperse the
emulsion into the
aqueous phase
(in 0.11 mm)
(W/O/W).

membrane

Or: with O/W/O system.

phase

A
B
internal
phase

The extraction and reverse extraction

are carried out simultaneously.

Extraction with supported membrane:

The liquid
membrane phase
is retained in a
porous medium.

recovery
phase

original
liquid

A
liquid
membrane
lyophilic
porous
membrane