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)
• can be single stage (mixer-settler) or multistage (cascade)
 Extraction equipment
Batch: Continuous:

single-stage: column:

separatory funnel

mixer-settler
rotating-disk contacter
a. agitator; b. stator disk
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. It consists of a number of
stages installed one on top of the other, each hydraulically separated, and
each with a mixing and settling zone (see below). This design enables the
elimination of some of the main disadvantages of conventional mixer-
settlers, whilst maintaining stage-wise phase contact.
The mechanical design of the mixer-settler-column is comparable to the
agitated ECR Kühni column.
Key characteristics
For long residence times: >15 min
Extraction controlled by residence time
Reactive extraction systems
Long phase separation
For extraction controlled by pH (stage-wise pH adjustment)
For batch extraction
Stage-wise phase contact
 Mixer-settlers operate with a purely stage-
wise contact. After every mixer there is a
settler. Mixer-settlers can be operated in a
multistage, co- or countercurrent fashion.

In extraction with high mass transfer and/or

changing physical properties, this is the
column of choice. The geometry of the
agitated compartments can be adapted for
changing hydrodynamic conditions. Other
main features are the special mixing turbines
and the perforated partition plates.
Mixer-settler column
In general, liquid-liquid extraction is applied where alternative separation technologies such as
distillation are uneconomical, or even unsuitable. Typical examples:
Simultaneous separation of various components with widely differing boiling points
Separation of high-boiling products or pollutants that are present in only low
concentrations
Separation of components with similar boiling points or components forming
azeotropes
Separation of mixtures with thermally sensitive components
Selective separation of single components out of a complex mixture
Our portfolio includes a complete range of liquid-liquid-extraction equipment, enabling us to
provide you with the most appropriate solution for your requirements. In addition to agitated
columns, it includes mixer-settlers and packed columns.
Design
The agitated Kühni column has a simple and robust design. The drive unit and the shaft are
supported at the top of the column, allowing you to use all common types of shaft seals
(stuffing box, mechanical seals). In special cases, the seal can be replaced by a magnetic drive.
Only radial slide-bearings are necessary inside the column, which are accessible through hand
or man holes. The sturdy design, the selected materials, and the low rotational speed of
industrial columns (typically 10-100 rpm) allow a practically maintenance-free operation.
Agitated column
Packed extraction column

The ECP packed column is based on c

Packing
The special Sulzer extraction packing
Liquid distributors
In order to create an even liquid flow
Main benefits
High specific throughput fac
Small column diameters
Revamp of existing columns
Use in cases of difficult phy
Low density difference < 50
Low interfacial tension: < 2
Tendency to form emulsion
Reliable scale-up
 Stream labeling
feed raffinate
mixture
solvent extract E, yA,1 F, xA,0
mixer settler
1
Feed (F) contains solute A (xA) dissolved in
diluent D (xD = 1 – xA). S≠E F≠R
solvent flow rate diluent flow rate
Solvent (S) extracts A (yA), creating the product = FS = constant = FD = constant
extract stream (E). The depleted feed becomes
the product raffinate stream (R).

Equilibrium (no longer VLE!) is defined by the N

distribution ratio, Kd:
S, yA,N+1 R, xA,N
Kd = yA/xA
Note that yA does not refer to gas composition. 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:
FD FD
Y= X + (Y1 - X )
FS FS 0
•X0
(analogous to operating line for
stripper column).
(FD/FS)max gives FS,min for N = ∞. 1• •(X0,Y1)

For dilute solutions, 2• •

R R
y = x + (y1 - x0 )
E E
3• •
Can also use Kremser eqns, if solutions
are dilute and equil. line is straight. N=3
éæ mE ö æ y N+1 - y 0 ö mE ù •(XN,YN+1)
ln êç 1- ÷ ç ÷ + ú
ê è R ø è y - y ø R úû
N= ë
1 0

ln R( mE )
 Cross-flow cascade
From mass balance around stage j:
R R
y j = - xi + (y j,in + x j -1)
Ej Ej

Figure 13-8 Cross-flow cascade

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

(ISBN: 0131382276) Copyright © 2012 Pearson Education, Inc. All rights reserved. N=3

• Increase overall efficiency by introducing

fresh extracting solvent at each stage. (x1,y1) •

• Each stage has its own mass balance and

operating line (x2,y2)
•
• Uses much more solvent than counter- (x3,y3)•
current cascade (requires much more
solvent recovery) •(x2,y3,in)•(x1,y2,in) •(x0,y1,in)
• A mixer-settler is just one cross-flow stage. •
x3
 Dilute fractional extraction
A common situation:
extract solvent 2
yA,1 xA,0 = 0
the feed contains two important yB,1 xB,0 = 0
solutes (A, B), and we want to
1
separate them from each other.

absorbing
section
E R
Choose two solvents: F
zA
A prefers solvent 1 (“extract”) zB

stripping
section
E R
B prefers solvent 2 (“raffinate”)
N
Kd,A = yA/xA > 1 solvent 1 raffinate
yA,N+1 = 0 xA,N
Kd,B = yB/xB < 1 yB,N+1 = 0 xB,N
 McCabe-Thiele analysis: dilute fractional extraction
Operating lines intersect at feed
One operating line for each solute i, in composition (not shown, may be
each section of the column (i.e., 4 total). very large).
Top operating lines (absorbing section):
• • N = 4,
R R F
yi = xi + (yi,1 - xi,0 ) feed stage
E E
3
Bottom operating lines (stripping section): • •
R R •5 •
y i = xi + (y i,1 - xi,0 )
E E •
2
•
Equilibrium data is different for each
solute (use separate McCabe-Thiele 1 • •
yA,1• •6
diagrams!)

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

known, use M-T diagram to obtain N, then xA,N
use trial-and-error to find xB,0 and xB,N+1
If yA,1 and xB,N are specified, vary NF (trial-and-error)
until N is the same for both solutes.
 Center-cut extraction
When there are 3 solutes: A, B and C,
solvent 1 solvent 2 solvent 3 solvent 2
+A +B
and B is desired
(A and C may be > 1 component each)

Requires two columns:

• column 1 separates A from B+C F
• column 2 separates B from C zA, zB, zC

Requires three extracting solvents:

A prefers solvent 1 over solvent 2

B, C prefer solvent 2 over solvent 1 solvent 1 solvent 2
+B+C solvent 3 solvent 2
B prefers solvent 3 over solvent 2 +C
C prefers solvent 2 over solvent 3
 Partially miscible solvents
• There are two liquid phases

• Each phase is a ternary (3-component)

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) Figure 13-14 Effect of temperature on equilibrium of
methylcyclohexane-toluene-ammonia system from
• Each axis is bounded 0 ≤ x ≤ 1 Fenske et al., AIChE Journal, 1,335 (1955), ©1955, AIChE

• Miscibility boundary = equilibrium line From Separation Process Engineering, Third Edition by Phillip C. Wankat
(ISBN: 0131382276) © 2012 Pearson Education, Inc. All rights reserved.
(depends on T, P)
 Reading ternary phase diagrams
Consider the point M: •
water content (xA) is ? 0.19
ethylene glycol content (xB) is ? 0.20
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
R) are given by the tie-line through M. region of partial miscibility A-C
The compositions of E and R converge at the plait point, P (i.e., no 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 (otherwise – single phase).
 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 right-triangle phase

diagram, which is easy to plot and read.

• raffinate compositions are

represented by coordinates (xA, xB) Figure 13-12 Equilibrium for water-chloroform-acetone at 25°C and 1 atm
From Separation Process Engineering, Third Edition by Phillip C. Wankat
• extract compositions are (ISBN: 0131382276) Copyright © 2012 Pearson Education, Inc. All rights
reserved.
represented by coordinates (yA, yB)
Vertical axis corresponds to both xA and yA.
More tie-lines can be obtained by trial-and-
Horizontal axis corresponds to both xB and yB
error, using the conjugate line.
Q: Where does pure C appear on this diagram? Ex.: find the tie-line that passes through M.
 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 mixer-settler
F R
M
S E

mixer settler Why does F appear on or

near the hypotenuse?
Flow rates of E and R are related
Why does S appear at or
by mass balance. coord.: near the origin?
Compositions of E and R are also (yD,yA)
related by equilibrium.

Overview of solution using RT mixing line

diagram: •F
1. Plot F and S and join with a coord.:
E
line. • (xD,xA)
2. Find mixing point, M, which •
M •
is co-linear with F and S. R
3. Find tie-line through M; find
E and R at either end (co- tie-line
linear with M). •S
4. Find flow rates of E and R.
 Co-linearity
F
M
S Why are F, S and M co-linear on the Hunter-Nash diagram?
mixer
solve for coordinates of M: (xA,M, xD,M)
TMB: F+S=M FxA,F + SxA,S
xA,M =
CMBA: FxA,F + SxA,S = MxA,M = (F + S)xA,M F +S
CMBD: FxD,F + SxD,S = MxD,M = (F + S)xD,M FxD,F + SxD,S
xD,M =
F +S
F xA,M - xA,S xD,M - xD,S xA,M - xA,S xA,F - xA,M
= = rearrange =
S xA,F - xA,M xD,F - xD,M xD,M - xD,S xD,F - xD,M

CMBA CMBD
• F (xD,F, xA,F) slope from slope from
M to S F to M
•
M (xD,M, xA,M) Therefore F, S and M are co-linear. To locate
M on the FS line: calculate either xA,M or xD,M.
• S (xD,S ,xA,S)
 The lever-arm rule

Another way to locate M: To calculate flow rates E and R:

F E
MF • • EM
M
• M
MS • MR
S similar triangles similar triangles R
• •

FxA,F + SxA,S = MxA,M M=R+E

FxA,F + (M – F)xA,S = MxA,M R xA,M - y A,E ME

= =
M xA,R - y A,E RE
F(xA,F - xA,S) = M(xA,M - xA,S)

F xA,M - xA,S MS
= =
M xA,F - xA,S FS Your choice! Use mass balances, or
measure distances and use lever-arm rule.
 Hunter-Nash analysis of cross-flow cascade

S1 S2

F = R0 R1 R2
1 2

E1 E1

F
•
Treat each stage as a mixer-settler. E1
•
• each Ri, Si pair creates a mixing line •
M1
• find each Ei, Ri pair using a tie-line •
R1
E2
• •
M2 •
R2

•
S
 Hunter-Nash analysis of counter-current cascade
F R1
M
S EN

mixer separator
(column)

E and R are both points on the

equilibrium line. But they are not
related by the same tie-line.
•F
mixing line
Overview of solution using RT
diagram: EN
1. Plot F and S and join with a line. •
•
2. Find mixing point, M, which is co- xA,1 M
linear with F and S. • •
3. Plot specified xA,1 on raffinate NOT a R1
tie-line
side of equilibrium line to find R1.
4. Extrapolate R1M line to find EN.
•S
5. Find flow rates of E and R.
 Stage-by-stage analysis

stage 1 TMB: E 0 + R2 = E 1 + R1
R1 S = E0
xA,1 yA,0
E0 – R1 = E1 – R2 = E2 – R3 etc.
1
R2 E1
constant difference in flow rates of passing streams
= Ej – Rj+1 = constant

stage 1 CMBA: E0yA,0 + R2xA,2 = E1yA,1 + R1xA,1

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

F = RN+1 EN
xA,N+1 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 (xA, , xD, ):
E0 y A,0 - R1xA,1 E0 y D,0 - R1xD,1
xA,D = xD,D =
D D

 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 tie-line);
• 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 E0-R1,

and EN-RN+1, to find at the
intersection point.
last mixing line

F = RN+1

EN •
•
•
M •
R1
first mixing line

•
S = E0 4. All intermediate mixing lines
must pass through .
 Stepping off stages on the H-N diagram
Procedure:

N=3 1. Use R1 and conjugate line to find E1

2. Use E1 and D-point to find R2

3. Use R2 and conjugate line to find E2

4. Use E2 and D-point to find R3

3. Use R3 and conjugate line to find E3

EN
• F = RN+1
E2 •
• •
• R3 
E1 M • 
• R2
•
R1
•
S = E0 Stop when you reach or pass EN.
 Using McCabe-Thiele diagram instead of Hunter-Nash
• M-T diagram can be used with much greater accuracy than H-N 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 streams

1 • extract composition represented by yA
• raffinate composition represented by xA
extract
Each (xA, yA) pair is a point on the M-T equilibrium line
compositions
A
P raffinate
1 P
yA • • compositions
• • •
xA • • equilibrium line ends at P
•
• yA •
0 • •
0 1 •
D
•
0•
0 xA 1
 Obtaining the M-T operating line
R1 S = E0 Mixing lines represent passing streams.
xA,1 yA,0 All mixing lines lie between the limits:
A (x1, y0) and (xN+1, yN)
1
yN EN RN+1
xN+1 • •
•
x1 M •R
1 WAIT! In general, operating line is
y0•
E0 not straight.
D
Plot arbitrary intermediate mixing
lines to obtain more points.

N 1 P
EN •
F = RN+1 •
xA,N+1 yA,N+1 •(xN+1, yN)
yA •
•
•
•
Note: passing streams are (xj+1, yj) instead of •
(xj, yj+1) as in distillation, simply due to our 0• •
labeling convention (feed enters at stage N). 0 (x1, y0) xA 1
 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
• Smin achieves the desired separation with N = ∞

• as M moves towards S, (S/F) increases

(lever-arm rule)
• when M reaches the equilibrium line, all
A feed dissolves in extracting solvent (Mmax)
F
•
M• • • as M moves towards F, (S/F) decreases
Mmin
• • before reaching the equilibrium line, there is
•
S D usually a pinch point (Mmin)
Mmax

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, Dmin (corresponding to Mmin) occurs when a mixing
line and a tie-line coincide.
 Minimum solvent flow rate
On H-N diagram whose tie-lines have negative slopes: 1. Plot S = E0, F = RN+1, R1
2. Join S and F
3. Extend SR1 mixing line
4. Locate several tie-lines
5. Extend tie-lines to the SR1
mixing line
6. Tie-line with furthest intersection
from S locates Dmin
E
7. Mixing line from Dmin through F
N,min
• locates EN,min
8. Connecting R1 and EN,min
F
• completes the mass balance
• 9. Mmin is located at the intersection
M of SF and R1EN,min
min
•
• D
min
R
1

• 10. (S/F)min = (FMmin)/(SMmin)

S

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

 Minimum solvent flow rate
On H-N diagram whose tie-lines have positive slopes:
Strategy:
1. Plot S = E0, F = RN+1, R1
2. Join S and F
3. Extend SR1 mixing line •F
4. Locate several tie-lines
5. Extend tie-lines to SR1
mixing line
6. Find tie-line which gives
closest intersection to S;
this locates Dmin E •
7. Draw mixing line from Dmin
N,min •
M •
min
R
through F to locate EN,min 1

8. Connect R1 and EN,min to

complete mass balance
•
S

•
9. Mmin is at the intersection of SF and R1EN,min
D
min 10. (S/F)min = (FMmin)/(SMmin)
 Two feed counter-current column

S
R1 E0 = S F1 R1
M
F2 FT EN
1
mixer 1 mixer 2 separator
R E
F2 Feed balance: F1 + F2 = FT

R E Overall balance:
• hypothetical mixed feedstream FT is co-linear with F1, F2
N
Stage-by-stage analysis:
• mass balance changes where F2 enters the column
F1 = RN+1 EN • upper and lower sections have different sets of operating
lines ➙ different D-points
 Hunter-Nash analysis of 2-feed column

Overall balance:

1. Plot F1 and F2. Locate FT (co-

linear with F1 and F2).

2. Plot S . Locate M (co-linear with

F1 S and FT).
•
FT 3. Plot R1. Locate EN (co-linear with
EN •
• F2 R1 and M).
•
•
M • 1. Calculate flow rates R1 and EN.
R1

•
S = E0
 Stage-by-stage analysis
Balance around top of column:
R1 – E0 = Rj+1 – Ej = D1 ➙ R1, E0, D1 are co-
linear
R1 E0 = S
Balance around bottom of column:
EN – RN+1 = Ek – Rk+1 = D2 ➙ RN+1, EN, D2 are co-linear
1
j Overall balance:
R E F2 + RN+1 + E0 = EN + R1
F2 F2 = (EN – RN+1) + (R1 – E0) = D1 + D2

k ➙ F2, D1, D2 are co-linear “feed-line”

R E D2 is located at the intersection of two mixing lines:

RN+1, EN, D2 and F2 , D 1 , D 2
N
Need another line to locate D1:
TMB: FT = F1 + F2 = EN + (R1 – E0) = EN + D1
F1 = RN+1 EN ➙ FT, EN, D1 are co-linear
D1 is located at the intersection of two mixing lines:
R1, E0, D1 and FT, EN, D2
Note: D1 and D2 may be on different sides of the phase diagram.
 Using the feed-line
1. Locate D1 at intersection of R1E0
and ENFT

2. Locate D2 at intersection of F2D1

and ENRN+1

3. Step off stages, initially using D1 to

generate the first mixing lines
•
EN 4. Identify the optimum feed stage
when the mixing line crosses the feed
F1
• line, F2D1D2
FT
•
M
•
E2 • F2
• feed line
• •
E1 • •
R2 D1 •
R1 D2
• 5. When the tie-line crosses the feed
S
line, the next mixing line will be
generated using D2
 Countercurrent liquid-liquid extraction with reflux
makeup solvent
R1 E0 = S How to increase yA,N?
need to increase xA,N+1 R1 E0
1 make RN+1 an reflux stream
1

“extract reflux” R E
R E (no benefit to raffinate reflux)
F

Turning extract into raffinate : R E

• extract is mostly solvent
N • raffinate is mostly diluent recovered
We need to remove solvent, N solvent
F1 = RN+1 EN SR
e.g., distillation, stripping
xA,N+1 yA,N
RN+1 EN
In a conventional liquid-liquid extraction column: reflux solvent
yA,N is related by equilibrium to xA,N separator
xA,N depends on xA,N+1
Q
dilute feed gives dilute extract PE
highest yA,N obtained with S ≈ Smin , but this requires very large N product extract
 Analogy to distillation reflux
V1
recovered
1 N solvent
L0 D SR
RN+1 EN
reflux solvent
Saturated liquid reflux stream is separator
obtained by condensing V1 (vapor
Q
stream rich in A) to give L0 (liquid PE
stream rich in A) product extract

External reflux ratio = L0/D Extract reflux stream is obtained by removing

solvent from EN (extract stream rich in A and
Internal reflux ratio = L/V solvent) to give RN+1 (raffinate stream rich in A
and depleted in solvent)

External reflux ratio = RN+1/PE

Internal reflux ratio = RN+1/EN

 Stage-by-stage balances
Similar to 2-feed liq-liq extraction column:
- two D-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 sat’d 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 ➙ can’t locate FT (or EN) because we don’t know RN+1

 Mass balance: solvent separator
SR
EN solvent
EN = Q + SR
separator = RN+1 + PE + SR
RN+1 Q
PE A PE, Q, RN+1
• F
EN is co-linear with Q and SR. •
EN also lies on sat’d extract line. EN
• •
Obtain EN/SR from lever-arm rule. SR • R1
•
We will also need RN+1/SR: E0 D

EN RN+1 PE
= + +1
SR SR SR don’t know
æ RN+1 ö
+1
EN SR RN+1 S SR çè PE ÷ø R E P
´ = + 1+ R = ➙ N+1 = N - E - 1
SR PE PE PE PE æ EN ö SR SR SR
çè S ÷ø - 1
R
 Finding the D-points
D2 = EN - RN+1
D2xA,D2 = ENyA,N - RN+1xA,N+1
EN y A,N - RN+1xA,N+1
xA,D 2 =
EN - RN+1

We don’t know the individual

flow rates EN, RN+1, but we know PE, Q, RN+1
•
EN/SR and RN+1/SR. We can
calculate xA,D2 and thereby locate F
D2 on the ENRN+1 line. •
••
Locate D1 at the intersection SREN
of two mixing lines: D2 •
• R1
D1 = E0 - R1 •
E0•
F = D1 + D2 D1

Proceed to step off stages.