LIQUID LIQUID EXTRACTION

1
OBJECTIVES
• Explain the basic theory and
principle of liquid-liquid extraction.
• Demonstrate the liquid-liquid
extraction under batch and
continuous mode.
• Analyze the number of theoretical
stages and height equivalent a
theoretical stage using theory as
well as graphical methods.
• Discuss industrial liquid extraction
equipment.

2
WHAT
is A method which a
compound (solute) is
LLE? pulled from Solvent A to
Solvent B, where Solvent A
and B are not miscible.
@Liquid extraction
@Solvent extraction

3
 EASY
PHYSICAL
SEPARATIONS

EVAPORATION

SEPARATION DIFFICULTY
DISTILLATION

EXTRACTION

ADSORPTION

CRYSTALLIZATION

MEMBRANES
4
WHEN LLE is used?
Distillation column is inappropriate
Targeted compound is due to BOILLING POINTS of
TEMPERATURE SENSITIVE or components are CLOSE to each
NONVOLATILE (e.g metal salts) other OR formed azeotropes OR
similar volatilities

Complex process sequences are

High operating cost/investment
involved

5
 SIMILAR VOTALITIES

Example Extracting solvent

Acetic Acid (BP: 119 Deg C) Methyl tert-butyl ether (BP

Water (BP: 100 Deg C) 55.2 Deg C) (MTBE) or Ethyl
Acetate (BP 77.1 Deg C)
1,3-butadiene (-4.4 Deg C) N-methylpyrrolidone (NMP)
Butenes (-6.3 Deg C)

6
 FORMING AZEOTROPES

Example Extracting solvent

Formic Acid Tetrahydrofuran

Water

Pyridin ??
Water
An azeotrope (constant boiling point mixture) is a
mixture of two or more liquids whose proportions
cannot be altered or changed by simple distillation.
This happens because when an azeotrope is boiled,
the vapour has the same proportions of constituents
as the unboiled mixture

7
 HOW?
Extracting
solvent

Feed carrier (C) +

(to allow
Targeted
molecules to
compound (A)
mic) 8
9
 TERMS & DEFINITIONS Residual feed solvent
that contains less
A liquid that targeted solute
contains our
targeted solute (A)
with the carrier (C)
FEED SOLVENT RAFFINATE
*Feed solvent Extracting solvent
and extracting that contains high
solvent are not EXTRACTOR targeted solute
miscible to
each other
EXTRACTING EXTRACT
The added liquid that SOLVENT
will be used to extract Distribution Coefficient
the targeted solute High KD or
from the feed Low KD is 𝑇𝑎𝑟𝑔𝑒𝑡𝑒𝑑 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛𝑒𝑥𝑡𝑟𝑎𝑐𝑡
𝐾 𝐷=
solvent. better? 𝑇𝑎𝑟𝑔𝑒𝑡𝑒𝑑 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛𝑟𝑎𝑓𝑓𝑖𝑛𝑎𝑡𝑒

10
 Large density Must be
difference selective to a
How to between the
phase
targeted
solute

choose the
correct
Big interfacial
tension between Low cost
the two phase

extracting Low solubility

solvent? Good
recoverability
of the solvent
in the feed
solvent

Noncorrosive

11
 CROSS FLOW EXTRACTION

E1 E2 E3
FEED R1 R2 R3

Types of SOLVENT SOLVENT SOLVENT

FLOWS in
LLE COUNTERCURRENT FLOW EXTRACTION
FEED R1 R2 R3

E3 E2 E1 SOLVENT

12
 CO-CURRENT FLOW EXTRACTION
FEED R1 R2 R3

SOLVENT E1 E2 E3
Types of
FLOWS in
LLE

13
Batch system

Rest to allowed
Mixing the mass Separation
settled down
14
Continuous system

15
 &C
vertex

fA
KEY:

o
re
C

xtu
Mi
M
vertex

ixt
vertex

u
Ternary Phase

re
ofB
Diagram

&C
- The vertices of the triangle
represent PURE component A
- The bases (sides) of the
triangle (connecting two Mixture of _____ B
vertices) represents binary
mixture of the components
indicated at the vertices of
that particular base. 16
 vertex
KEY:

vertex vertex
Ternary Phase

0%
of
Diagram

of A
0%
- The bases represents ZERO
(0%) composition lines for the A
components on the opposite
vertex 0% of _______ B

17
 vertex
KEY:

vertex vertex
Ternary Phase

B
of
Diagram

0%
- The bases represents ZERO
(0%) composition lines for the A
components on the opposite
vertex
B

B
B
B

of
of
of

of

%
%
%

80
60
20

40
18
 vertex

KEY:

20%
C

of A
40%
of
vertex vertex

A
60
%o

0%
80%
Ternary Phase

fA

of
A
of A
Diagram

- The bases represents ZERO

(0%) composition lines for the A
components on the opposite
vertex
B

19
 vertex

KEY:

C
vertex vertex

Ternary Phase
Diagram

Do it by yourself.

1. What is composition of M?
A:______
B:______
A
C:______ B
2. Plot point X to represent
70% B, 20%A and 10% C
20
 A MIXTURE SPLITS into EXTRACT
TWO IMMISCIBLE LIQUID ALL three COMPONENTS
PHASES are DISSOLVED into a
SINGLE liquid PHASE
Single
Phase
Ternary Phase TIE LINE: connect Region MISCIBILITY BOUNDARY :
liquid-liquid equilibrium
Diagram equilibrium points line
on the miscibility
boundary
Two Phase
Region

RAFFINATE SOLVENT

21
 a mixture of M in the two phases
region will ALWAYS SPLIT into TWO
phase with composition L for phase P1
and N for phase P2 on the miscibility
boundary following the tie lines

Ternary
Phase
Diagram
EXTRACT
E
AT
IN
FF
RA

22
LEVER ARM RULE

- Acetone is to be extracted from

water using TCE.
- A stream of F with composition, xf
is to be extracted using pure solvent,
S
- Points S and F define the mix line,
the mixture point M is found with the
inverse-lever arm rule as follows:

- Where S and F are mass flowrates;

SM and MF are LENGTHS of line
segments as indicated
Mass balance: S + F = M
Geometry: MF + SM = SF

23
- To find the composition of the two
phases that result from mixture, M,
we follow the tie line to the
miscibility boundary
- The composition of the raffinate, c1
and the extract, c2 can be read from
the diagram
- The mass flowrates will be
calculated from mass balance or with
lever arm rule as follows:

- Where E and R are mass flowrates;

EM and MR are LENGTHS of line
segments as indicated
Mass balance: E + R = M
Geometry: EM + MR = ER

24
Single-stage LLE
EXTRACT, E SOLVENT, S

FEED, F RAFFINATE, R

Overall mass balance

F+S=M=R+E
Component balance (one for each component, example, component i, xi)
F(xi)F + S (xi)S = M (xi)M = R(xi)R + E (xi)E
25
 Example
Consider a 100kg mixture (F) of 55% water
and 45% of ethylene glycol. The aim is to use
200kg pure furfural as a solvent (S) to extract
ethylene glycol from water.

Step 1: Find location of point F

Step 2: Find location of point S
Step 3: Connect point F and S (point M will
lies anywhere on this connecting line). To
find M,
(a) use mass balance equation.
Total mass balance:
M = F + S = 100 + 200 = 300
Composition of water (c), (xc)M:
(0.183
Composition of ethylene glycol (A), (xA)M: 26
 Example
Consider a 100kg mixture (F) of 55% water
and 45% of ethylene glycol. The aim is to use
200kg pure furfural as a solvent (S) to extract
ethylene glycol from water.

Step 1: Find location of point F

Step 2: Find location of point S
Step 3: Connect point F and S (point M will
lies anywhere on this connecting line).
Total mass balance:
M = F + S = 100 + 200 = 300
Composition of furfural (S), (xs)M:
(0.667

27
 Example
Consider a 100kg mixture (F) of 55% water and
45% of ethylene glycol. The aim is to use 200kg
pure furfural as a solvent (S) to extract ethylene
glycol from water.

Step 1: Find location of point F

Step 2: Find location of point S
Step 3: Connect point F and S (point M will lies
anywhere on this connecting line).
(b) Alternatively, we could use inverse-lever-arm
rule
M = F + S = 300 kg
8.75 units = 300kg

Therefore, . Then, x = 2.917 28

 Example
Consider a 100kg mixture (F) of 55% water
and 45% of ethylene glycol. The aim is to use
200kg pure furfural as a solvent (S) to extract
ethylene glycol from water.

Step 1: Find location of point F

Step 2: Find location of point S
Step 3: Connect point F and S (point M will
lies anywhere on this connecting line).
(b) Alternatively, we could use inverse-lever-
arm rule
The resulting mixture, M will split into two
phases E1 and R1 along the tie line. From
the ternary diagram,
(xs)E = 0.88 ; (xA)E = 0.09; (xc)E = 0.03
(xs)R = 0.1; (xA)R = 0.34; (xc)R = 0.56
How about the mass of each E and R? 29
 Example
Consider a 100kg mixture (F) of 55% water
and 45% of ethylene glycol. The aim is to use
200kg pure furfural as a solvent (S) to extract
ethylene glycol from water.
Step 1: Find location of point F
Step 2: Find location of point S
Step 3: Connect point F and S (point M will
lies anywhere on this connecting line).
(b) How about the mass of each E and R?
M = R1 + E1 = 300 kg

Therefore, , R1= 82.15kg

30
 Example
Consider a 100kg mixture (F) of 55% water
and 45% of ethylene glycol. The aim is to use
200kg pure furfural as a solvent (S) to extract
ethylene glycol from water.
Step 1: Find location of point F
Step 2: Find location of point S
Step 3: Connect point F and S (point M will
lies anywhere on this connecting line).
(b) How about the mass of each E and R?
M = R1 + E1 = 300 kg

Therefore, , R1= 82.15kg

31
 Example
Consider a 100kg mixture (F) of 55% water
and 45% of ethylene glycol. The aim is to use
200kg pure furfural as a solvent (S) to extract
ethylene glycol from water.
Step 1: Find location of point F
Step 2: Find location of point S
Step 3: Connect point F and S (point M will
lies anywhere on this connecting line).
(b) How about the mass of each E and R?
M = R1 + E1 = 300 kg

Let’s try on the other side to find E1.

32
 Example
Consider a 100kg mixture (F) of 55% water
and 45% of ethylene glycol. The aim is to use
200kg pure furfural as a solvent (S) to extract
ethylene glycol from water.

Step 1: Find location of point F

Step 2: Find location of point S
Step 3: Connect point F and S (point M will
lies anywhere on this connecting line).
The value of each composition also can be
calculated from the mass balance: LETS TRY

33
 Example
Consider a 100kg mixture (F) of 55% water
and 45% of ethylene glycol. The aim is to use
200kg pure furfural as a solvent (S) to extract
ethylene glycol from water.

Step 1: Find location of point F

Step 2: Find location of point S
Step 3: Connect point F and S (point M will
lies anywhere on this connecting line).
The value of each composition also can be
calculated from the mass balance: LETS TRY

34
Hunter-Nash
Method
A feed of 40 wt.% isopropyl alcohol
(IPA), 55 wt% diisopropyl ether
(ether) and 5 wt.% water is mixed
with pure water as a solvent. The
solvent, in a LLE cascade to recover
the ether. The solvent enters the
top and feed enters the bottom, so
as to produce an ether containing
less than 3 wt.% alcohol and an
extracted alcohol of at least 20 wt.
%. The system will operate at 1 atm
and 25 Deg C. How many stages
are required for this extraction?

35
 Extract the info!

xa xe xw
Hunter-Nash
Feed (F) 0.4 0.55 0.05
Solvent (S) 0 0 1.0 Method
Raffinate (R) 0.03 ? ?
Extract (E) 0.2 ? ? A feed of 40 wt.% isopropyl alcohol
(IPA), 55 wt% diisopropyl ether
(ether) and 5 wt.% water is mixed
FEED, F
R1 R2 Rn RN with pure water as a solvent. The
solvent, in a LLE cascade to recover
1 2 n N the ether. The solvent enters the
E3 E2 En EN SOLVENT, S top and feed enters the bottom, so
as to produce an ether containing
less than 3 wt.% alcohol and an
FIND number of stages. extracted alcohol of at least 20 wt.
Assumptions? %. The system will operate at 1 atm
and 25 Deg C. How many stages
Approach: PLOT F,S,R and E on the ternary phase diagram to locate location are required for this extraction?
of M
36
 xa xe xw
Feed (F) 0.4 0.55 0.05
Solvent (S) 0 0 1.0 1. Find location of F
2. Find location of S
Raffinate (R) 0.03 ? ?
3. Locate Extract position
Extract (E) 0.2 ? ? • We know that Extract POINT
must be lie on the miscibility
boundary and closed to the
extract vertex. (X)
4. Locate Raffinate position
• We know that RAFFINATE
POINT must be lie on the
miscibility boundary and
closed to the carrier feed
vertex. (X)
5. We could determine the
position of M if we have flow rates
of F and S

37
 xa xe xw
FEED, F
Feed (F) 0.4 0.55 0.05 R2 Rn RN
R1
Solvent (S) 0 0 1.0
Raffinate (R) 0.03 ? ? 1 2 n N
Extract (E) 0.2 ? ? SOLVENT
E1 E2 En EN
,S
From the mass balance equation;

F + S = M = E 1 + RN

• We can connect a line between F

to S, and E1 to RN to get M.
• From M, we can get the ratio of S
to F
6. Locate the Operating Point (P)

P = F – E 1 = RN - S

38
FEED, F
R1 R2 Rn RN

1 2 n N

En EN SOLVENT
E1 E2
,S

Step 1: Draw a line from E1 to R1

following the tie line

R1

E1

39
FEED, F
R1 R2 Rn RN

1 2 n N

En EN SOLVENT
E1 E2
,S

Step 1: Draw a line from E1 to R1

following the tie line

Step 2: Draw a line from R1 to point

P

R1

E1

40
FEED, F
R1 R2 Rn RN

1 2 n N

En EN SOLVENT
E1 E2
,S

Step 1: Draw a line from E1 to R1

following the tie line

Step 2: Draw a line from R1 to point

P
- Intersection point between the
draw line with the miscibility R1
boundary named as E2

E1
E2

41
FEED, F
R1 R2 Rn RN

1 2 n N

En EN SOLVENT
E1 E2
,S

Step 1: Draw a line from E1 to R1 following the tie

line

Step 2: Draw a line from R1 to point P

- Intersection point between the draw line with
the miscibility boundary named as E2
R1
Step 3: Draw a line from E2 to another side of R2
curve which represent R2.
E1
E2
Step 4 : Repeat until reach RN

42