Liquid-liquid extraction

Basic principles
In liquid-liquid extraction, a soluble component (the
solute) moves from one liquid phase to another. The
two liquid phases must be either immiscible, or
partially miscible.
usually isothermal and isobaric
can be done at low temperature (good for
thermally fragile
solutes, such as large organic
molecules or biomolecules)
can be very difficult to achieve good contact
between poorly
miscible liquids (low stage
efficiency)
extracting solvent is usually recycled, often by
distillation
(expensive and energy-intensive)

Extraction equipment
Batch:

Continuous:
single-stage:

column:

separatory funnel

mixer-settler

rotating-disk contacter
a. agitator; b. stator dis

Design

Mixer-settlers, both as stand-alone

and as in-column type, are offered for
special applications. As implied by the
name, the mixer-settler-column is a
series of mixer-settlers in the form of
a column.
Mixer-settlers operate
with aIt consists of a number of
stages installed
urely stage-wise contact.
After one on top of the
each hydraulically separated,
very mixer there isother,
a settler.
and
each withina mixing and settling
Mixer-settlers can be
operated
multistage, co- or zone (see below). This design enables
the elimination of some of the main
ountercurrent fashion.
disadvantages of conventional mixersettlers, whilst maintaining stagewise phase contact.
The mechanical design of the mixersettler-column is comparable to the
agitated ECR Khni column.
Key characteristics
For long residence times: >15
min
Extraction controlled by
residence time
Reactive extraction systems

Mixer-settler column

various components with widely

differing boiling points
Separation of high-boiling
products or pollutants that are
present in only low concentrations
Separation of components
raction with high mass
with similar boiling points or
fer and/or changing physical
components forming azeotropes
erties, this is the column of
Separation of mixtures with
e. The geometry of the
thermally sensitive components
ted compartments can be
Selective separation of single
ed for changing
components out of a complex mixture
odynamic conditions. Other
Our portfolio includes a complete
features are the special
range of liquid-liquid-extraction
g turbines and the
equipment, enabling us to provide
rated partition plates.
you with the most appropriate
solution for your requirements. In
addition to agitated columns, it
includes mixer-settlers and packed
columns.
Design
The agitated Khni column has a
simple and robust design. The drive
unit and the shaft are supported at
the top of the column, allowing you to

Agitated column

Packed extraction column

The ECP packed column is based

Packing
The special Sulzer extraction pa
perforated plates can be inserte
Liquid distributors
In order to create an even liquid
operated without external energ
Main benefits
High specific throughpu
Small column diameters
Revamp of existing colu
Use in cases of difficult
Low density difference <
Low interfacial tension:
Tendency to form emuls
Reliable scale-up

Stream labeling
feed
solvent

mixer

mixture

raffinate
E, yA,1

extract

settler

Feed (F) contains solute A (xA)

dissolved in diluent D (xD = 1 xA).
Solvent (S) extracts A (yA), creating
the product extract stream (E). The
depleted feed becomes the product
raffinate stream (R).

1
SE
solvent flow rate
= FS = constant

Equilibrium (no longer VLE!) is defined

by the distribution ratio, Kd:
Kd = yA/xA

F, xA,0

FR
diluent flow rat
= FD = consta

N
S, yA,N+1

R, xA,N

Usually specified:
yA,N+1, xA,0, FD/FS and xA,N.

McCabe-Thiele analysis:
Counter-current extraction with immiscible liquids

Equation of the operating line:

Eq
.l

in
e

FD
FD
Y
X (Y1
X )
FS
FS 0

X0

)m
S

/F
D

(F
Y

FD/FS)max gives FS,min for N = .

ax

(analogous to operating line

for stripper column).

For dilute solutions,

R
R
y x (y1 x0 )
E
E
Can also use Kremser eqns, if
solutions are dilute and equil.
line is straight.

mE y y mE

y1 y0
R
ln R
mE

ln 1
R


N

N1

(X0,Y1)

N=
3

(XN,YN+1)
X

Cross-flow cascade
From mass balance around
stage j: R
R

Ej

xi (y j,in

Ej

Wankat
(ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All
rights reserved.

Eq
.l

in

Figure 13-8 Cross-flow

From Separation
Process Engineering, Third Edition by Phillip C.
cascade

N=
3

(x1,y1)

/E 1
-R

/E 3
-R

(x3,y3)

(x2,y2)

pe
slo

/E 2
-R

Increase overall efficiency by introducing

fresh extracting solvent at each stage.
Each stage has its own mass balance
and operating line
Uses much more solvent than countercurrent cascade (requires much more
solvent recovery)
A mixer-settler is just one cross-flow
stage.

xj1)

yj

(x2,y3,in)(x1,y2,in)
X

(x0,y1,in)

Dilute fractional extraction

F
zA
zB

Choose two solvents:

A prefers solvent 1
(extract)

Kd,A = yA/xA > 1

K

= y /x < 1

solvent
yA,N+1 =
yB,N+1 =

1
0
0

N
raffinate
xA,N
xB,N

absorbing
section

the feed contains two

important solutes (A, B),
and we want to separate
them from each other.

B prefers solvent 2
(raffinate)

solvent 2
xA,0 = 0
xB,0 = 0

extract
yA,1
yB,1

stripping
section

A common situation:

ttom operating lines (stripping section):

R
R
yi xi (yi,1 xi,0 )
E
E

Equilibrium data is different for

each solute (use separate
McCabe-Thiele diagrams!)

yA,1

1
6

fo
r

Operating lines intersect

at feed composition (not
shown, may be very
large).

eq
ui
l.

One operating line for each solute

i, in each section of the column
(i.e., 4 total).
p operating lines (absorbing section):
R
R
yi xi (yi,1 xi,0 )
E
E

McCabe-Thiele analysis: dilute fractional

extraction

NF = 4,
feed
stage

If yA,1 and xA,N are specified, and NF

xA,N
X
is known, use M-T diagram to
obtain N, then use trial-and-error
If yA,1 and xB,N are specified, vary NF (trialto find xB,0 and xB,N+1
and-error) until N is the same for both

Center-cut extraction
When there are 3 solutes: A, B and
solvent 1
C,
+A

solvent 2 solvent 3
+B

solvent 2

and B is desired
(A and C may be > 1 component
each)
Requires two columns:
F
column 1 separates A
zA , zB, zC
from B+C
column 2 separates B
from
C three extracting
Requires

solvents:
A prefers solvent 1 over
solvent 1
solvent 2
B
over
B,prefers
C prefersolvent
solvent3 2
oversolvent 2
C prefers
solvent
2 over solvent 3
solvent
1

solvent 2
+ B + C solvent 3

solvent 2
+C

Partially miscible solvents

There are two liquid phases
Each phase is a ternary (3component) mixture of solute
A, diluent D and solvent S
Ternary equilibrium diagrams
have 3 axes: usually, mole or
mass fractions of A, D, and S
Literature data is commonly
presently on an equilateral
triangle diagram (note NO
origin)
Each axis is bounded 0 x 1
Miscibility boundary =
equilibrium line (depends on T,
P)

Figure 13-14 Effect of temperature on

equilibrium of methylcyclohexane-tolueneammonia system from Fenske et al., AIChE
Journal, 1,335 (1955), 1955, AIChE
From Separation Process Engineering, Third Edition by
Phillip C. Wankat
(ISBN: 0131382276) 2012 Pearson Education, Inc. All
rights reserved.

Reading ternary phase diagrams

Consider the point M:
water content (xA) is ?
0.19
ethylene glycol content (x0.20
B) is ?
furfural content (xC) is ? 0.61
check: xA + xB + xC = 1

Read the mole/mass fraction of each

component on the axis for that
component, using the lines parallel to
the edge opposite the corner
corresponding to the pure component.
The mixture M lies inside the

miscibility boundary, and will

spontaneously separate into two
phases. Their compositions (E and
region of partial miscibility A-C
R) are
given by the
The
compositions
oftie-line
E and Rthrough
converge at the plait point, P (i.e., no
M.
separation).
A 2-component mixture of furfural and water is partially miscible over
the composition range from about 8 % furfural to 95 % furfural.
Separation by extraction requires a furfural/water ratio in this range

Right-triangle phase diagrams

Raffinate (diluent-rich): xA + xB + xC =
1
Extract (solvent-rich): yA + yB + yC =
1
We need to specify only two of the
compositions in order to describe
each liquid phase completely .

This can be shown on a righttriangle phase diagram, which is

easy to plot and read.
raffinate compositions are
represented by coordinates (xA, xB)
extract compositions are
represented by coordinates (yA, yB)

Figure 13-12 Equilibrium for water-chloroform-acetone at 25

From1Separation
Process Engineering, Third Edition by Phillip
and
atm
C. Wankat
(ISBN: 0131382276) Copyright 2012 Pearson Education, Inc
All rights reserved.

Vertical axis corresponds to both xA and yA.

Horizontal axis corresponds to both xB and yB
Q: Where does pure C appear on this
diagram?

More tie-lines can be obtained by

trial-and-error, using the conjugate
line.

Obtaining the conjugate line

Each point on the conjugate line is
composed of
- one coordinate from the extract side
of the equilibrium line
- one coordinate from the raffinate
side of the equilibrium line

On this graph, which component is the diluent? which is the solute?

Hunter-Nash analysis of mixersettler

F
S

mixer

R
E

M
settler

Flow rates of E and R are

related by mass balance.
Compositions of E and R
are also related by
equilibrium.
Overview of solution
using RT diagram:
1. Plot F and S and join
with a line.
2. Find mixing point, M,
which is co-linear with
F and S.
3. Find tie-line through M;
find E and R at either
end (co-linear with M).

coord.:
(yD,yA)

Why does F appear

on or near the
hypotenuse?
Why does S appear
at or near the origin?

mixing line
F

coord.:
(xD,xA)

M
tie-line

Co-linearity
F
S

Why are F, S and M co-linear on the Hunter-Nash

diagram?

mixer
TMB:

solve for coordinates of M: (xA,M, xD,M)

F+S=M

CMBA: FxA,F + SxA,S = MxA,M = (F + S)xA,M

CMBD: FxD,F + SxD,S = MxD,M = (F + S)xD,M

F xA,M xA,S xD,M xD,S

S xA,F xA,M xD,F xD,M

rearrang
e

FxA,F SxA,S

xA,M

F S

xD,M
xA,M xA,S
xD,M xD,S

FxD,F SxD,S
F S
xA,F xA,M

xD,F xD,M

CMBD

CMBA

F (xD,F, xA,F)

M (xD,M, xA,M)
S (xD,S ,xA,S)

slope fromslope from

M to S
F to M
Therefore F, S and M are co-linear. To locate
M on the FS line: calculate either xA,M or xD,M.

The lever-arm rule

Another way to locate M:

MS
S

MF F

similar triangles

FxA,F + SxA,S = MxA,M

FxA,F + (M F)xA,S = MxA,M
F(xA,F - xA,S) = M(xA,M - xA,S)
F xA,M xA,S MS

M xA,F xA,S FS

To calculate flow rates E and R:

EM

M MR
similar triangles

M=R+E
R xA,M yA,E ME

M xA,R yA,E RE

Your choice! Use mass balances, or

measure distances and use lever-

Hunter-Nash analysis of cross-flow

cascade
S2

S1
F = R0

1
E1

R1

R2

E1

eat each stage as a mixer-settler.

E1

each Ri, Si pair creates a mixing line

find each Ei, Ri pair using a tie-line
E2

M1

M2

R1

R2

Hunter-Nash analysis of counter-current

cascade
F
S

mixer

R1
EN
separator
(column)

E and R are both points on

the equilibrium line. But they
are not related by the same
tie-line.
Overview of solution using RT
diagram:
1. Plot F and S and join with a
line.
2. Find mixing point, M, which
is co-linear with F and S.
3. Plot specified xA,1 on
raffinate side of
equilibrium line to find R1.
4. Extrapolate R M line to find

mixing line

xA,1

EN

M
NOT
a tieline

R1

Stage-by-stage analysis
R1
xA,1

S = E0
yA,0

stage 1 TMB: E0 + R2 = E1 + R1
E0 R1 = E1 R2 = E2 R3 etc.

1
E1

R2

constant difference in flow rates of passing

streams
= Ej Rj+1 = constant

stage 1 CMBA:

E0yA,0 R1xA,1 = E1yA,1 R2xA,2 = etc.

N
F = RN+1
xA,N+1

E0yA,0 + R2xA,2 = E1yA,1 + R1xA,1

EN
yA,N+1

constant difference in compositions of passing

streams
net flow of A: xA, = EjyA,j Rj+1xA,j+1
net flow of D: xD, = EjyD,j Rj+1xD,j+1

The difference point

Define a difference point, with coordinates
xAxD
E y R x
E y R x
xA,

A,0

1 A,1

xD,

D,0

1 D,1

does not necessarily lie inside the RT graph.

All pairs of passing streams Ej, Rj+1 are co-linear with .
Using the -point to step off stages on Hunter-Nash diagram:
using the specified location of R1 (as xA,1), can find E1 (use tieline);
given the location of E1, can find R2 (use ;
given the location of R2, can find E2 (use tie-line);
given the location of E2, can find R3 (use );
and so on, until desired separation is achieved.
First, need to locate . It may be on either side of the Hunter-Nash
diagram.

Finding the -point

Procedure:
1. Plot F (= RN+1), S = (E0).
Locate M.
2. Plot R1 and locate EN.
3. Extend the lines joining E0last mixing line R1, and EN-RN+1, to find at
the intersection point.

F = RN+1

EN

S = E0

R1

first mixing line

4. All intermediate mixing

lines must pass through

Stepping off stages on the H-N

diagram
Procedure:
1. Use R1 and conjugate line to
find E1
2. Use E1 and -point to find R2

N=3

3. Use R2 and conjugate line to find

4. Use E2 and -point to find R3
3. Use R3 and conjugate line to find

EN

E2

E1

S = E0

F = RN+1

R3

R2

R1
Stop when you reach or pass
E N.

Using McCabe-Thiele diagram instead of Hunter-Nash

M-T diagram can be used with much greater accuracy than HN diagram
Need to transfer ternary equilibrium data from RT diagram
Need to obtain the operating line

Transferring equilibrium data from RT diagram

Each tie-line represents a pair of equilibrium stream

extract composition represented by yA
raffinate composition represented by xA
Each (xA, yA) pair is a point on the M-T equilibrium li

1
extract
compositio
ns

A
yA
xA

0
0

raffinate
compositio
ns

P
equilibrium line ends at P

yA

0
0

xA

Obtaining the M-T operating

line

R1
xA,1

S = E0
yA,0
1

Mixing lines represent passing

streams.
All mixing lines lie between the
limits:
(x1, y0) and (xN+1,
y N)

A
yN

xN+1
x1
y0
E0

M
D

RN+1

WAIT! In general, operating

line is not straight.
Plot arbitrary intermediate
mixing lines to obtain more
points.

N
F = RN+1
xA,N+1

1
EN
yA,N+1

Note: passing streams are (xj+1, yj)

instead of (xj, yj+1) as in distillation,
simply due to our labeling convention

yA

P
(xN+1, yN)

0 (x1, y0) x
A

Choice of extracting solvent flow rate

As S increases, separation improves, but extract becomes
more dilute
As S decreases, N must increase to maintain desired
separation
asseparation
M moves towards
with N =S,(S/F)
Smin achieves the desired
increases (lever-arm rule)
when M reaches the equilibrium
A
line, all feed dissolves in extracting
F
solvent (Mmax)

M
as M moves towards F, (S/F)
Mmin
decreases

before reaching the equilibrium line,

S
D
Mmax
there is usually a pinch point (Mmin)
It is not easy to locate this pinch point on a McCabe-Thiele
diagram, since the operating line curvature changes as S
changes.
On a Hunter-Nash diagram, min (corresponding to Mmin) occurs

Minimum solvent flow rate

weight fraction acetone

1. Plot S = E0, F = RN+1,

n H-N diagram whose tie-lines have negative slopes:
Acetone-water-trichloroethane at 25 C and 1 atm
R1
1
3.
SR1Fmixing line
2. Extend
Join S and
4. Locate several tie0.9
lines
5. Extend tie-lines to the
0.8
SR1Tie-line with furthest
6.
0.7
intersection
mixing line
from S locates min
0.6 E
N,min
7. Mixing line from min
0.5
F R1 and EN,min
8. through
Connecting
locates
EN,min
completes
the mass
F
0.4
9. Mmin is located at the
balance
0.3
intersection
M
min
of SF and R1EN,min

0.2

0.1

0
S0

0.1

0.2

0.3

0.4

0.5

0.6

weight fraction water

0.7

0.8

min

0.9

Rule-of-thumb: (S/F)act ~ 1.5

Minimum solvent flow

rate

P o r ti o n o f r i g h t t r i a n g l e p h a s e d i a g r a m
f o r w a t e r - a c e ti c a c i d - i s o p r o p y l e t h e r a t 2 0 C , 1 a tm
0 .5

H-N diagram whose tie-lines have positive slopes:

0 .2

N,min

0 .1

0 .1

0 .2

0 .3

w e ig h t f r a c tio n a c e t ic a c id

0 .3

min

0 .4

Strategy:
1. Plot S = E0, F = RN+1,
R1
2. Join S and F
3. Extend SR1 mixing
line
4. Locate several tielines
5. Extend tie-lines to SR1
mixing line
6. Find tie-line which
gives closest
intersection to S; this
locates min
7. Draw mixing line from
min through F to
locate EN,min
8. Connect R1 and
EN,min

to complete mass

min

0 .4

0 .5

0 .6

0 .7

0 .8

0 .9

w e ig h t fr a c tio n w a te r

9. Mmin is at the intersection of SF and

R1EN,min

Two feed counter-current column

E0 = S

R1

F1
F2

mixer 1

FT

mixer 2

R1

EN
separator

F2

Feed balance: F1 + F2 = FT

F1 = RN+1

N
EN

Overall balance:
hypothetical mixed feedstream FT is co-linear
with F1, F2
Stage-by-stage analysis:
mass balance changes where F2 enters the
column
upper and lower sections have different sets of
operating lines different -points

Hunter-Nash analysis of 2-feed column

Overall balance:
1. Plot F1 and F2. Locate FT
(co-linear with F1 and F2).

F1

EN

S = E0

2. Plot S . Locate M (co-linear

with S and FT).
FT
F
2

3. Plot R1. Locate EN (colinear with R1 and M).

R1

4. Calculate flow rates R1 and

E N.

Stage-by-stage analysis
E0 = S

R1
1
j
R

F2
k

F1 = RN+1

EN

Balance around top of column:

R1 E0 = Rj+1 Ej = 1
are co-linear

R1, E0, 1

Balance around bottom of column:

EN RN+1 = Ek Rk+1 = 2
RN+1, EN, 2
are co-linear
Overall balance:
F2 + RN+1 + E0 = EN + R1
F2 = (EN RN+1) + (R1 E0) = 1 + 2

F2, 1, 2 are co-linear feed2 is located at the intersection of two mixing

line
lines:
R , EN, 2 and
F2, 1, 2
Need another N+1
line to locate 1:
TMB:
FT = F1 + F2 = EN + (R1 E0) = EN +
1
1 is located
at the
of two mixing
FT,intersection
EN, 1 are co-linear
lines:
Note: 1 and 2 may R
be
on different sides
and of the phase
FT, Ediagr
1, E0, 1
N,

Using the feed-line

1. Locate 1 at intersection of
R1E0
and ENFT

A c e t o n e - w a t e r - tr i c h l o r o e t h a n e a t 2 5 C a n d 1 a t m
1

2. Locate 2 at intersection of
F21
and ENRN+1

0 .9
0 .8

3. Step off stages, initially using

1 to generate the first mixing
lines

0 .6

4. Identify the optimum feed

stage when the mixing line
crosses the feed line, F212

EN

0 .4

F1

R2 R 1
0 .1

0 .2

0 .3

0 .4

0 .5

0 .6

w e ig h t f r a c tio n w a te r

0 .7

0 .8

0 .1

0
S0

feed line

F2

E2
0 .2
E1

FT

0 .3

0 .9

0 .5

w e ig h t fr a c tio n a c e to n e

0 .7

5. When the tie-line crosses

the feed line, the next mixing
line will be generated using 2

Countercurrent liquid-liquid extraction with reflux

How to increase yA,N?
need to increase xA,N+1
R1
make RN+1 an reflux stream

E0 = S

R1
1

extract reflux
R

makeup
solvent

(no benefit to raffinate

reflux)

E0
1

Turning extract into

E
R
raffinate :
recovered
N
extract is mostly
solvent
N
We need
to remove
solvent
F1 = RN+1
EN
SR

solvent,
raffinate
is mostly
xA,N+1
yA,N
e.g., distillation,
diluent stripping
RN+1
EN
solvent
conventional liquid-liquid extraction column:
reflux
separator
yA,N is related by equilibrium to xA,N
xA,N depends on xA,N+1
Q
PE
dilute feed gives dilute extract
highest y obtained with S S , but this requires very large Nproduct extract

Analogy to distillation reflux

V1
1

recovered
solvent

N
L0

SR

D
RN+1

Saturated liquid reflux stream

is obtained by condensing V1
(vapor stream rich in A) to
give L0 (liquid stream rich in
A)
External reflux ratio = L0/D
Internal reflux ratio = L/V

reflux

EN

solvent
separator

PE

product extract

Extract reflux stream is obtained by

removing solvent from EN (extract
stream rich in A and solvent) to give
RN+1 (raffinate stream rich in A and
depleted in solvent)
External reflux ratio = RN+1/PE

Stage-by-stage balances
Similar to 2-feed liq-liq extraction column:
- two -points (mass balance above and below feed stage)
- if F, E0, R1 and RN+1 are specified, same stage-by-stage analysis
But RN+1 is an internal stream, usually not specified.
Usually specified:
F, xA,F, xD,F plot F
yA,0, yD,0 plot E0
xA,1 plot R1 on satd raffinate curve
xA,PE, xD,PE
plot PE (same location as RN+1 and Q, different flow
rates)
yA,SR, yD,SR plot SR
RN+1/PE
FT = F + RN+1

cant locate FT (or EN) because we dont know RN+1

Mass balance: solvent separator

SR
EN
RN+1

EN = Q + S R

solvent
separator

= RN+1 + PE + SR

Q
PE

EN is co-linear with Q and

SR.
Obtain
from
lever-arm
N/SR
EN also E
lies
on
satd
extract
rule.
line.
We will also need RN+1/SR:
E N RN1 PE

1
SR
SR SRdont know
E N SR RN1
S

1 R
SR PE
PE
PE

PE, Q, RN+1
F

EN
SR

E0

RN1

R1
D

1
PE
SR

EN
PE
1

SR

RN1 E N PE

1
SR
SR S R

Finding the -points

2 = EN - RN+1
2xA,2 = ENyA,N - RN+1xA,N+1

1
0 .9

E N yA,N RN1xA,N1

0 .8

E N RN1

We dont know the

individual flow rates EN,
RN+1, but we know EN/SR
and RN+1/SR. We can
calculate xA,2 and thereby
locate
Locate2 on
at the
the ENRN+1 line.

0 .7
w e ig h t fr a c t io n a c e to n e

xA, 2

A c e t o n e - w a t e r - tr i c h l o r o e t h a n e a t 2 5 C a n d 1 a t m

0 .6
0 .5

0 .4
0 .3

2
intersection of two

mixing lines:

1 = E0 - R1 1
F = 1 + 2
Proceed to step off stages.

PE, Q, RN+1

E
SR N

R1

0 .2

E0
0 .1

0 .1

0 .2

0 .3

0 .4

0 .5

0 .6

w e ig h t f r a c t io n w a te r

0 .7

0 .8

0 .9