LIQUID LIQUID EXTRACTION

-SINGLE STAGE PROCESS

Ir Syafiza Abd Hashib

 Phase rule
EQUILIBRIUM
RELATIONS IN
EXTRACTION
Triangular
coordinates and
equilibrium data
 (a)

PHASE
DIAGRAMS
(b)

(a) Phase diagram where the solvent pairs B-C and A-C
are partially miscible
(b) Liquid-liquid phase diagram where components A and
B are partially miscible
 SINGLE STAGE EQUILIBRIUM
EXTRACTION

• Considering two streams : L kg & V kg, containing components A,B and C

(mixed)
• Resulting mixture stream , M kg total mass

The overall and component A balance --- Eq (1)

XAM = mass fraction of A in the M stream.
Eq (2)

Component C mass balance : Eq (3)

 SINGLE STAGE EQUILIBRIUM
EXTRACTION

Combining equation (1) and (2) :

Eq (4)

Combining equation (1) and (3) : Eq (5)

Combining equation (4) and (5) :

Eq (6)
 SINGLE STAGE EQUILIBRIUM
EXTRACTION

Point L, M and V must lie on a straight line.

Eq (7)
L/kg V is equal to length of line VM/length of
line LM

These equations also hold for kg mol frac, lbm

Eq (8)
etc.
GRAPHICAL
ADDITION
LEVER-ARM
RULE

(a) Process flow

(b) Graphical edition
Ternary /triangular
diagram

Single stage LLE

Ternary Phase Equilibrium Diagram
Liquid-liquid system :
A (Solute), B (Carrier) and C
1) Right-angle triangular diagram (Solvent)
2) Equilateral triangular diagram
Phases in equilibrium:
1) Extract 2) Raffinate

Example:
• Benzene (A) – Water (B) – Acetic
Acid (C)
• Acetic Acid (A) – Water (B) –
Isopropyl ether (C)
• Acetone (A) – Water (B) –
Trichloroethylene (C)
• Acetone (A) – Water (B) –
Methyl isobutyl ketone (C)
Right-angle triangular
diagram
1. The solvent pair B and C are partially miscible
2. The concentration of component C is plotted
on the vertical axis and component A is plotted
on horizontal axis
3. The two phase region is inside the envelope
and one phase region is outside the envelope
4. A tie line ‘gi’ connecting the extract layer
(solvent rich) with raffinate layer (diluent rich)
5. The solute-solvent rich layer, ‘g’ is called
extract layer and designated by ‘y’
6. The diluent rich layer, ‘i’ is called raffinate
layer and designated by ‘x’
7. For example: the mass fraction
(concentration) of C is designated as yC in
the extract layer and as xC in the raffinate layer
Single – stage Counter-
current Extraction
1. Raffinate and extract are in
equilibrium only once.
2. Binary solution containing solute (A)
dissolved in a diluent or carrier (B).
3. The extracting solvent can be either
pure solvent C or may content little A.
4. Raffinate (R) is the exiting phase rich
in carrier (B)
5. Extract is exiting phase rich in solvent
(C).
 MASS BALANCE

Liquid-Liquid Extraction
Extracting Solvent, S
Extract phase, E
ys (A) Intermediate, M y* (A)
Feed Solution, xM (A)
F Raffinate phase, R
xF (A)
x* (A)

F Mass of feed solution S Mass of extracting solvent

E Mass of extract phase
M Mass of intermediate
yS Mass fraction of A in S
x* Equilibrium mass fraction
of A in R
R Mass of raffinate phase
xF Mass fraction of A in F
xM Mass fraction of A in M
y* Equilibrium mass fraction of A in E
Counter current single stage LLE
Extract, V1 Solvent, V2

yA1, yC1 yA2, yC2

Feed, Lo
Raffinate, L1

xA0 , xC0 xA1 , xC1

L0 Mass of feed solution V2 Mass of extracting solvent

V1 Mass of extract phase L1 Mass of raffinate phase
M Mass of intermediate xAM Mass fraction of A in intermediate
xA0 Mass fraction of A in feed
yA1 Mass fraction of A in extract xC0 Mass fraction of C in feed
yC1 Mass fraction of C in extract xA1 Mass fraction of A in raffinate
yA2 Mass fraction of A in solvent xC1 Mass fraction of C in raffinate
yC2 Mass fraction of C in solvent
Counter current single stage LLE
Objectives:
Calculate equilibrium composition and masses of raffinate
and extract phases

Mass of intermediate M using is calculated from mass balance:

L0 + V2 = L1 + V1 = M Eq. (1)
(A): L0xA0 +V2yA2 = L1xA1 + V1yA1 = MxAM Eq. (2)
(C): L0xC0 +V2yC2 = L1xC1 +V1yC1 = MxCM Eq. (3)

Extract, V1 Solvent, V2

yA1, yC1 yA2, yC2

Feed, Lo
Raffinate, L1

xA0 , xC0 xA1 , xC1

 Counter current single
stage LLE
• Plot point M at xAM and xCM on graph
• Plot point V2 at yA2 and yC2 Plot point L0 at xA0 and xC0
• L1 and V1 are obtained by drawing a tie line through Tie
point M line
Raffinate layer
• To draw a tie line, simply from any point at extract
layer move vertically downwards through 45°line, them
move horizontally to the equilibrium line.
• Finally, move vertically to point at raffinate layer. A
line connecting the points (at extract & raffinate layer) is
the tie line
• In order to determine tie line, the trial and error
technique should be used. This is done by drawing as
much as possible tie lines that cross through point M until
the right tie line is obtained.
• Hence,the extract and raffinate compositions for the
mixture (M) is at point ‘g’ and ‘i’, respectively.
Example 12.5.1
An original mixture weighing 100 kg and
containing 30 kg of isopropyl ether ( C ),
10 kg of acetic acid (A) and 60 kg water
(B) is equilibrated and the equilibrium
phases separated . What are the
compositions of two equilibrium
phases?
Try Problem
12-5-1 & 12-5-2
from textbook
 SINGLE STAGE EQUILIBRIUM

1. Raffinate and extract are in equilibrium only once.

2. Binary solution containing solute (A) dissolved in a
diluent or carrier (B).
3. The extracting solvent can be either pure solvent C
or may content little A.
4. Raffinate (R) is the exiting phase rich in carrier (B)
5. Extract is exiting phase rich in solvent (C).
 MASS BALANCE

Liquid-Liquid Extraction
Extracting Solvent, S
Extract phase, E
ys (A) Intermediate, M y* (A)
Feed Solution, xM (A)
F Raffinate phase, R
xF (A)
x* (A)

F Mass of feed solution S Mass of extracting solvent

E Mass of extract phase
M Mass of intermediate
yS Mass fraction of A in S
x* Equilibrium mass fraction
of A in R
R Mass of raffinate phase
xF Mass fraction of A in F
xM Mass fraction of A in M
y* Equilibrium mass fraction of A in E
 SINGLE – STAGE CALCULATIONS

Objectives:
Calculate equilibrium composition and masses of raffinate and extract
phases

From material balance:

Mass of intermediate M using is calculated:
F+S =M Eq. (1)

Determine mass fraction of solute A in intermediate M using material

balance for solute A :
xF ⋅ F + yS ⋅ S = xM ⋅ M Eq. (2)

Use both Eq. 1 and 2 to find xM value .

 COORDINATES
IN TRIANGULAR
DIAGRAM
EQUILATERAL TRIANGULAR DIAGRAM

a
b
RIGHT ANGLE DIAGRAM EG-WATER-FURFURAL SYSTEM
EG-water-furfural system
EG (A)

1.0

0.9

0.8

0.7

0.6
P
0.5

0.4

0.3

0.2

0.1 a
b
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Furfural (C)
 SINGLE – STAGE CALCULATIONS

Using the total material balance:

F+S = R+E 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
 Example 1 - Single stage LLE calculations

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 ternary phase equilibrium diagram method, determine the

followings:

a) the composition of raffinate and extract phases

b) the mass of extract and raffinate

c) the percent glycol extracted

 Example 1 - Plotting ternary phase diagram

Use the following equilibrium tie – line to construct the ternary phase diagram

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
 EG-FURFURAL- WATER TERNARY PHASE DIAGRAM
EG

EG WATER

FURFURAL WATER

FURFURAL
 SINGLE – STAGE LLE CALCULATIONS

(a) Determine the composition of raffinate and extract phases :

F = 100 kg S = 100 kg xF=0.4 yS=0

Calculate the mass of intermediate M using total material balance
F+S =M 100 + 100 = M M = 200 kg

Determine mass fraction of solute A in intermediate M using material

balance for solute A:

𝑥𝑥𝐹𝐹 ⋅ 𝐹𝐹 + 𝑦𝑦𝑆𝑆 ⋅ 𝑆𝑆 = 𝑥𝑥𝑀𝑀 ⋅ 𝑀𝑀, 0.4 × 100 + 0 × 100 = 𝑥𝑥𝑀𝑀 × 200, 𝑥𝑥𝑀𝑀 = 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

 SINGLE – STAGE LLE CALCULATIONS

Right angle method

M E

R
S
SINGLE – STAGE LLE CALCULATIONS

E
M

R
S
 SINGLE – STAGE GRAPHICAL STEPS

1. Locate point F (xF) and S (yS)

2. Draw a straight line from F to S

3. Using the calculated value of xM, locate point M (xM) on the FS

line. Note that point M must be on FS line.

4. Draw a new tie line that pass through point M. This new tie line
must take shape of the nearest given tie lines.

5. From the new tie line, you can locate point E and R and hence
the composition of raffinate, R and extract, E that are in
equilibrium, can be determined.
 SINGLE – STAGE LLE CALCULATIONS

(b) - Calculate the mass of extract and raffinate

Using the total material balance

F+S = R+E 100 + 100 = R + E
R = 200 − E Eq. (1)
Using the material balance for solute A:
𝑥𝑥𝐹𝐹 ⋅ 𝐹𝐹 + 𝑦𝑦𝑆𝑆 ⋅ 𝑆𝑆 = 𝑥𝑥 ∗⋅ 𝑅𝑅 + 𝑦𝑦 ∗⋅ 𝐸𝐸
0.4 × 100 + 0 × 100 = 0.075 × 𝑅𝑅 + 0.26 × 𝐸𝐸 Eq. (2)
Insert eq (1) into eq (2)
0.075 200 − 𝐸𝐸 + 0.26𝐸𝐸 = 40
15 − 0.075𝐸𝐸 + 0.26𝐸𝐸 = 40
0.185𝐸𝐸 = 25
𝑬𝑬 = 𝟏𝟏𝟏𝟏𝟏𝟏. 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏

𝑅𝑅 = 200 − 𝐸𝐸 = 200 − 135.14

𝑹𝑹 = 𝟔𝟔𝟔𝟔. 𝟖𝟖𝟖𝟖𝟖𝟖𝟖𝟖
 SINGLE – STAGE LLE CALCULATIONS

( C ) - calculate the the percent glycol extracted

% of EG extracted = (Mass of EG in extract / Mass of EG in feed) x 100%

𝑦𝑦 ∗ 𝐸𝐸
% of EG extracted = × 100%
𝑥𝑥𝐹𝐹 𝐹𝐹
0.26 × 135.14
= 𝑥𝑥𝑥𝑥𝑥𝑥
0.40 × 100
= 87.8%
 THANK YOU

“Success doesn’t come to you,You go to it.” – Marva Collins