Liquid-liquid extraction

(LLE)
Introduction
LLE vs Distillation
Equipment for LLE
Principle of LLE

Introduction
Liquid-liquid extraction (LLE) is a
separation technique in which a solute of a
liquid solution is separated out of the
Before
theanother liquid.
solution by contact
with
contact, the
When this solution

The constituent
we want to
extract is called
solute or
component A.

solute
originally exists
as a liquid
solution with an
original
solvent B or
diluent

C is known as
an extracting
solvent.

(containing A in B)
is mixed with a
different liquid C,
a portion of A will
cross to form a
new solution in C.

This separation
technique is called
extraction since C has
extracted (pulled away)
some of A from B.

B A
B A
A
A
B
B
B
B
B
A
A
B
A
A
Original
solvent (B)
containing
A

B A
B A
A
A
B
B
B
B
B
A
A
B
A
A

Shake/stir to
allow
molecules to
partition

Extracting
solvent (C)

A = solute
B = original solvent
C = extracting
solvent

A A
A

B
B
B

B
B

A portion of A
will cross to
form a new
solution in C.

 A partially miscible solvent will

extract
mostly
the
desired
component
A
and
some
of
component B.
The resulting solution is a ternary
solution.

Ternary solution

A solution
that consists
of more than
two
components

Consists of 3 components

Solute A
example

Original
solvent B

Extracting
solvent C

Comparison
Liquid-liquid extraction

Distillation

Depends on solubility
1. The constituents of liquid
solution have relatively
volatility near unity
2. The constituents of a liquid
solution have close boiling
points
3. The constituents of liquid
solution form an azeotropic
mixture

Depends on relative volatility

between the components in the
solution

No heat input required for the

process
1. The component involved is
sensitive to heat.

Required heat upon distillation

process

Driven by chemical differences

Vapor pressure differences

Equipment for Liquid-Liquid

Extraction
Introduction and Equipment
Types
As in the separation processes of distillation, the two phases in
liquid-liquid extraction must be brought into intimate contact
with a high degree of turbulence in order to obtain high masstransfer rates.
Distillation:
difference in

Rapid and easy because of the large

density (Vapor-Liquid).
Liquid extraction:
Density difference between the two
phases is not
large and separation is more difficult.
Liquid extraction equipment

Mixing by mechanical
agitation
Mixing by fluid flow
themselves
6

Mixer-Settles for Extraction

Separate mixer-settler

Combined mixer-settler

Plate and Agitated Tower Contactors for Extraction

Perforated plate
tower

Agitated extraction tower

Packed and Spray Extraction Towers

Spray-type extraction tower

Packed extraction tower

Principle of liquid-liquid
extraction
As the solution (A+B) is mixed and agitated
with the solvent C, an intermediate solution
will form at which a lighter liquid bubbles
through a heavy liquid.
The intermediate will settle into two distinct
layers:
Solvent-rich (extract) layer : mainly C, extracted
A and any dissolved B
Diluent-rich (raffinate) layer : rich with B,
leftover A and tiny fraction of dissolved C

Solvent selection
Distribution Coefficients
y/x at equilibrium; large values preferable. (The distribution
coefficient (m) or partition coefficient for a component (A) is
defined as the ratio of concentration of a A in extract phase to
that in raffinate phase.
Selectivity
can be defined as the ability of the solvent to pick up the
desired component in the feed as compared to other
components
Insolubility
solvent should not be soluble in carrier liquid
Recoverability
consider constraints (i.e. azeotropes)
Interfacial Tension
if too high, liquids will be difficult to mix

Density
must be different so that phases can be separated by settling
Chemical Reactivity
solvent should be inert and stable
Viscosity, Vapor Pressure, Freezing Point
low values make storage easier
Safety
toxicity, flammability
Cost

Ternary phase equilibrium

diagram

Equilibrium relationship can be presented

in triangular diagram
Two types of triangular diagrams
1. Right-angle triangular diagram
2. Equilateral triangular diagram

Ternary equilateral triangular Phase

Diagram
Acetone

TernaryPhaseDiagram
Solvent:TCE
Solute:Acetone
Carrier:Water

TCE

Water

Ternary Single-Stage
Solute
Acetone
Acetone

A point where the

composition of the extract is
the same as the composition
of the raffinate
PlaitPoint
P

Extract

F Feed
Mixingpoint

Raffinate

Tielines

Solvent S
TCE
TCE

Water
Water

Carrier

Right-angle triangular diagram

Single-stage LLE

In single-stage LLE, the solvent and solution are in

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

solutio
n

Normally the solution

is a binary solution
containing solute A
dissolved in an initial
solvent B (diluent)

solven
t

The extracting solvent

can be either
Pure solvent C or
Recycled solvent
that may contain a
little A

raffina
te

Resulting liquid phase

formed at equilibrium
that contains:
Mostly B
Residual A and
Little C that may have
dissolved

extrac
t

Resulting liquid phase

formed at equilibrium
consists of:
Mainly C
Extracted A (molecules
A that has transferred
from B)
Little B that have
dissolved

 In most single-stage extraction, we

are interested to determine the
equilibrium composition (y of A in E
and x of A in R) and masses of
raffinate (R) and extract (E) phases.
These can be easily determined by
means or ternary phase diagram and
simple material balances.

How to determine the equilibrium compositions

and masses of a typical single-stage extraction
F, Feed
solution
xF
S, extracting
solvent
yS

Single-stage
LLE

M,
Intermediate
xM

E, Extract
phase
y
E

R, Raffinate
phase
x
R

Where
F : mass of feed solution in kg or lbm
S : mass of extracting solvent in kg or lbm
E : mass of extract phase in kg or lbm
R : mass of raffinate phase in kg or lbm
M : mass of an intermediate in kg or lbm
xF : mass fraction of solute A in solution with B
yS : mass fraction of solute A in solution with extracting solvent C
xM : mass fraction of solute A in intermediate phase
xR : equilibrium mass fraction of solute A in raffinate phase
y : equilibrium mass fraction of solute A in extract phase

Step 1
Calculate the
mass of
intermediate M
using total
material
balance
F+S=M

Step 2
Do component
material
balance to find
xM
xF(F) + yS(S) =
xM(M)

Step 3

Step 4

On ternary
diagram:
Locate point F
and S
Draw straight
line from F to
S
Using the
calculated
value of xM,
locate point M
on the FS line
Draw a new
tie line that
pass through
point M
From the new
tie line, locate
point E and
point R and
hence can
determine

Determine the
masses of E and
R using material
balance
Total material
balance:
F+S=R+E
Material
balance for
solute A
xF(F) + yS(S) =
xR(R) + yE(E)

Example 1
100 kg of a solution containing 0.4
mass fraction ethylene glycol (EG) in
water is to be extracted with equal
mass of furfural at 25oC and 101 kPa.
Using the ternary phase equilibrium
diagram method, determine:
i) The composition of raffinate and extract
phases
ii) The mass of extract and raffinate
iii) The percent glycol extracted

Answer: i) 0.075, 0.26; ii) 135.3 kg and 64.9 kg;

Example 2
A mixture containing 33 wt% acetic
acid, 2 wt% isopropyl ether and 65 wt
% water is treated with equal weight of
recycled solvent which contains 3 wt%
acetic acid in a simple one stage batch
extraction.
a) Determine the compositions and mass
fraction of the raffinate and extract, xR
and yE.
b) Calculate the percent extraction of

Multi-stage continuously
countercurrent LLE
In multi-stage continuously countercurrent LLE, the solvent
and solution come into contact MORE THAN ONCE and thus
the raffinate and extract reach equilibrium more than once.
F kg/h feed
solution
xF
A

S kg/h extracting
solvent
yS A

E kg/h final extract

Stage
Stage
1
2
Stage
3
Stage
4

yE
A

Stage n2
Stage n-1
Stage
n
Stage
n+1
Stage
n+2

R kg/h final
raffinate
xR

example

Minimum solvent flow rate

Minimum solvent flow rate is the
lowest rate/amount at which solvent
could be theoretically used for a
specified extraction.
Point M is dependant upon the
solvent flow rate.
The larger the rate, the closer is point M
to point S on FS line.
The smaller the flow rate, the closer in
point M to point F on FS line

Step by step guidelines to determine

minimum solvent flow rate (Smin)
Step 1
Find the
positions of
point F and
S on a
triangular
ternary
diagram

Step 2

Step 3

Draw the
Draw a
best tie line
straight line
that
from point
Emin to point
originate
from F.
R.
The
The
intersection
intersection
of this line
of this line
with extract
with FS
half-dome is
gives point
point Emin
Mmin
(minimum
From point
extract flow
Mmin can

Step 4
Using the
xmin, use
material
balance to
calculate
Smin.

Overall efficiency of a multi-stage

extraction column
% Overall efficiency of extraction
column =
Number of ideal stages x 100
number of real stages

Example 3
5000 kg/h of a solution containing 25 wt% ethylene
glycol in water is to be reduced to 5% (solvent-free)
by continuous extraction in a countercurrent
column using furfural as the extracting solvent.
a) Determine the minimum solvent flow rate for the
extraction.
b) If the solvent enters at twice the minimum
solvent rate, how many ideal stages are
required?
c) Determine the number of real stages if the
overall efficiency of the column is 60%
solution