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Liquid-liquid

extrac/on

Basic principles
In liquid-liquid extrac/on, a soluble component (the solute) moves
from one liquid phase to another. The two liquid phases must be
either immiscible, or par/ally 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 dicult to achieve good contact between poorly
miscible liquids (low stage eciency)
extrac/ng solvent is usually recycled, oEen by dis/lla/on
(expensive and energy-intensive)
can be single stage (mixer-seFler) or mul/stage (cascade)

Extrac/on equipment
Batch:

Con/nuous:
single-stage:

column:

separatory funnel

mixer-seFler
rota/ng-disk contacter
a. agitator; b. stator disk

Stream labeling
feed
solvent

ranate

mixture

extract

E, yA,1

seFler

mixer

F, xA,0
1

Feed (F) contains solute A (xA) dissolved in


diluent D (xD = 1 xA).

S E
solvent ow rate
Solvent (S) extracts A (yA), crea/ng the product = FS = constant

F R
diluent ow rate
= FD = constant

extract stream (E). The depleted feed becomes


the product ranate stream (R).
Equilibrium (no longer VLE!) is dened by the
distribu/on ra/o, Kd:

Kd = yA/xA

Note that yA does not refer to gas composi/on.


N
S, yA,N+1

R, xA,N

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

McCabe-Thiele analysis:
Counter-current extrac/on with immiscible liquids
Equa/on of the opera/ng line:
FD
FD
Y =
X + (Y1
X )
FS
FS 0

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

For dilute solu/ons,



R
R
y = x + (y1 x0 )
E
E
Can also use Kremser eqns, if solu/ons
are dilute and equil. line is straight.

mE y N+1 y 0 mE
ln 1
+

R
y

y
R

1
0
N=
ln R
mE

(X0,Y1)

X0

(analogous to opera/ng line for


stripper column).

2

3


N = 3

(XN,YN+1)
X

Cross-ow cascade
From mass balance around stage j:

R
R
y j = xi + (y j ,in +
x j 1)
Ej
Ej

Figure 13-8 Cross-ow cascade


From Separa0on Process Engineering, Third Edi0on by Phillip C. Wankat
(ISBN: 0131382276) Copyright 2012 Pearson Educa/on, Inc. All rights reserved.

N = 3

Each stage has its own mass balance and


opera/ng line
Uses much more solvent than counter-
current cascade (requires much more
solvent recovery)
A mixer-seFler is just one cross-ow stage.

(x1,y1 )

Increase overall eciency by introducing


fresh extrac/ng solvent at each stage.

(x2,y2)

(x3,y3 )

x3

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

(x0,y1,in)

Dilute frac/onal extrac/on

F
zA
zB

A prefers solvent 1 (extract)

B prefers solvent 2 (ranate)

Kd,A = yA/xA > 1

Kd,B = yB/xB < 1

solvent 1
yA,N+1 = 0
yB,N+1 = 0

N
ranate
xA,N
xB,N

absorbing
sec/on

the feed contains two important


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

Choose two solvents:

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

extract
yA,1
yB,1

stripping
sec/on

A common situa/on:

McCabe-Thiele analysis: dilute frac/onal extrac/on


Opera/ng lines intersect at feed
composi/on (not shown, may be
very large).

One opera/ng line for each solute i, in


each sec/on of the column (i.e., 4 total).
Top opera/ng lines (absorbing sec/on):

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

R
R
y i = xi + (y i,1 xi,0 )
E
E

Equilibrium data is dierent for each


solute (use separate McCabe-Thiele
diagrams!)
If yA,1 and xA,N are specied, and NF is
known, use M-T diagram to obtain N, then
use trial-and-error to nd xB,0 and xB,N+1


yA,1

1
6

BoFom opera/ng lines (stripping sec/on):

N = 4,
F
feed stage

xA,N

If yA,1 and xB,N are specied, vary NF (trial-and-error)


un/l N is the same for both solutes.

Center-cut extrac/on
When there are 3 solutes: A, B and C,

and B is desired
(A and C may be > 1 component each)

Requires two columns:
column 1 separates A from B+C
column 2 separates B from C
Requires three extrac/ng solvents:

A prefers solvent 1 over solvent 2
B, C prefer solvent 2 over solvent 1

B prefers solvent 3 over solvent 2
C prefers solvent 2 over solvent 3

solvent 1
+ A

solvent 2

solvent 3
+ B

solvent 2

solvent 3

solvent 2
+ C

F
zA, zB, zC

solvent 1

solvent 2
+ B + C

Par/ally 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 frac/ons 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 Eect of temperature on equilibrium of


methylcyclohexane-toluene-ammonia system from
Fenske et al., AIChE Journal, 1,335 (1955), 1955, AIChE
From Separa0on Process Engineering, Third Edi0on by Phillip C. Wankat
(ISBN: 0131382276) 2012 Pearson Educa/on, Inc. All rights reserved.

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 frac/on 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 composi/ons (E and
R) are given by the /e-line through M.
region of par0al miscibility A-C
The composi/ons of E and R converge at the plait point, P (i.e., no separa/on).
A 2-component mixture of furfural and water is par/ally miscible over the composi/on
range from about 8 % furfural to 95 % furfural. Separa/on by extrac/on requires a
furfural/water ra/o in this range (otherwise single phase).

Right-triangle phase diagrams


Ranate (diluent-rich): xA + xB + xC = 1
Extract (solvent-rich): yA + yB + yC = 1

We need to specify only two of the
composi/ons 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.
ranate composi/ons are
represented by coordinates (xA, xB)

Figure 13-12 Equilibrium for water-chloroform-acetone at 25C and 1 atm

extract composi/ons are


represented by coordinates (yA, yB)
axis corresponds to both xA and yA.
Ver/cal

From Separa0on Process Engineering, Third Edi0on by Phillip C. Wankat


(ISBN: 0131382276) Copyright 2012 Pearson Educa/on, Inc. All rights
reserved.

Horizontal axis corresponds to both xB and yB


More /e-lines can be obtained by trial-and-


error, using the conjugate line.

Q: Where does pure C appear on this diagram?

Ex.: nd the /e-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 ranate side of the
equilibrium line

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

Hunter-Nash analysis of mixer-seFler


F
S

R
E

M
mixer

Why does F appear on or


near the hypotenuse?

seFler

Flow rates of E and R are related


by mass balance.
Composi0ons of E and R are also
related by equilibrium.
Overview of solu/on 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 /e-line through M; nd
E and R at either end (co-
linear with M).
4. Find ow rates of E and R.

Why does S appear at or


near the origin?

coord.:
(yD,yA)
mixing line

F
E


M
/e-line

coord.:
(xD,xA)

R

Co-linearity
F
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
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

rearrange

CMBD

CMBA

F (xD,F, xA,F)

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

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

slope from slope 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

MF

similar triangles

To calculate ow rates E and R:

EM

similar triangles

M
MR

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-ow cascade


S2

S1
F = R0

1
E1

R1

R2

E1

Treat each stage as a mixer-seFler.



each Ri, Si pair creates a mixing line
nd each Ei, Ri pair using a /e-line

E1

E2

F


M1

M2


R1

R2

Hunter-Nash analysis of counter-current cascade


F

R1
EN

S
mixer

separator
(column)

E and R are both points on the


equilibrium line. But they are not
related by the same /e-line.
Overview of solu/on 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 specied xA,1 on ranate
side of equilibrium line to nd R1.
4. Extrapolate R1M line to nd EN.
5. Find ow rates of E and R.

mixing line
EN

xA,1


M
NOT a
/e-line


R1

Stage-by-stage analysis
R1
xA,1

S = E0
yA,0
1
E1

R2

N
F = RN+1
xA,N+1

EN
yA,N+1

stage 1 TMB: E0 + R2 = E1 + R1




E0 R1 = E1 R2 = E2 R3 etc.

constant dierence in ow rates of passing streams



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




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

constant dierence in composi/ons of passing streams
net ow of A: xA, = EjyA,j Rj+1xA,j+1
net ow of D: xD, = EjyD,j Rj+1xD,j+1

The dierence point


Dene a dierence point, , with coordinates (xA, , xD, ):



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 o stages on Hunter-Nash diagram:
using the specied loca/on of R1 (as xA,1), can nd E1 (use /e-line);
given the loca/on of E1, can nd R2 (use );
given the loca/on of R2, can nd E2 (use /e-line);
given the loca/on of E2, can nd R3 (use );
and so on, un/l desired separa/on 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.

last mixing line

F = RN+1

EN


M


S = E0

3. Extend the lines joining E0-R1,


and EN-RN+1, to nd at the
intersec/on point.


R1

rst mixing line

4. All intermediate mixing lines


must pass through .

Stepping o stages on the H-N diagram


Procedure:

1. Use R1 and conjugate line to nd E1

N = 3

2. Use E1 and -point to nd R2


3. Use R2 and conjugate line to nd E2
4. Use E2 and -point to nd R3
EN

E2

E1


S = E0

3. Use R3 and conjugate line to nd E3

F = RN+1


R3
R2



R1
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 opera/ng line
Transferring equilibrium data from RT diagram
Each /e-line represents a pair of equilibrium streams
extract composi/on represented by yA
ranate composi/on represented by xA
Each (xA, yA) pair is a point on the M-T equilibrium line

1
extract
composi/ons

A
yA
xA

0
0

ranate
composi/ons

equilibrium line ends at P

yA



0
0

xA

Obtaining the M-T opera/ng line


R1
xA,1

Mixing lines represent passing streams.


All mixing lines lie between the limits:
(x1, y0) and (xN+1, yN)

S = E0
yA,0
A

yN

xN+1
x1
y0
E0

EN

RN+1


M
R1

WAIT! In general, opera/ng 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 dis/lla/on, simply due to our
labeling conven/on (feed enters at stage N).

yA

P

(xN+1, yN)

0

0 (x1, y0) x
A

Choice of extrac/ng solvent ow rate


As S increases, separa/on improves, but extract becomes more dilute
As S decreases, N must increase to maintain desired separa/on
Smin achieves the desired separa/on with N =

A
M

M

S

min


Mmax

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


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

It is not easy to locate this pinch point on a McCabe-Thiele diagram, since the
opera0ng line curvature changes as S changes.
On a Hunter-Nash diagram, min (corresponding to Mmin) occurs when a mixing
line and a 0e-line coincide.

Minimum solvent ow rate


On H-N diagram whose /e-lines have nega/ve slopes:
Acetone-water-trichloroethane at 25 C and 1 atm
1
0.9
0.8

6. Tie-line with furthest intersec/on


from S locates min
7. Mixing line from min through F
locates EN,min

0.6 E

N,min

8. Connec/ng R1 and EN,min


completes the mass balance
9. Mmin is located at the intersec/on
of SF and R1EN,min

0.3

min

0.2

0.1

0
S0

0.4

weight fraction acetone

0.7

0.5

1. Plot S = E0, F = RN+1, R1


2. Join S and F
3. Extend SR1 mixing line
4. Locate several /e-lines
5. Extend /e-lines to the SR1
mixing line

min

10. (S/F)min = (FMmin)/(SMmin)


0.1

0.2

0.3

0.4

0.5

0.6

weight fraction water

0.7

0.8

0.9

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

Minimum solvent ow rate

Portion of right triangle phase diagram


for water-acetic acid-isopropyl ether at 20 C, 1 atm
0.5

On H-N diagram whose /e-lines have posi/ve slopes:

0.3

0.2

N,min

0.1

0.1

0.2

0.3

weight fraction acetic acid

0.4

Strategy:
1. Plot S = E0, F = RN+1, R1
2. Join S and F
3. Extend SR1 mixing line
4. Locate several /e-lines
5. Extend /e-lines to SR1
mixing line
6. Find /e-line which gives
closest intersec/on 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 balance

min

0.4

0.5

0.6

0.7

0.8

0.9

weight fraction water

min

9. Mmin is at the intersec/on of SF and R1EN,min


10. (S/F)min = (FMmin)/(SMmin)

Two feed counter-current column


E0 = S

R1

R1

FT
mixer 1

mixer 2

EN
separator

F2

Feed balance: F1 + F2 = FT
E

F1
F2

F1 = RN+1

N
EN

Overall balance:
hypothe/cal mixed feedstream FT is co-linear with F1, F2

Stage-by-stage analysis:
mass balance changes where F2 enters the column
upper and lower sec/ons have dierent sets of opera/ng
lines dierent -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


M


S = E0

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


S and FT).
FT

F2


R1

3. Plot R1. Locate EN (co-linear with


R1 and M).

4. Calculate ow rates R1 and EN.

Stage-by-stage analysis
Balance around top of column:
R1 E0 = Rj+1 Ej = 1 R1, E0, 1 are co-linear
E0 = S

R1
1
R

F1 = RN+1

F2, 1, 2 are co-linear

feed-line

2 is located at the intersec/on of two mixing lines:




RN+1, EN, 2 and
F2, 1, 2

Balance around boFom 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

EN

Need another line to locate 1:


TMB:
FT = F1 + F2 = EN + (R1 E0) = EN + 1


FT, EN, 1 are co-linear
1 is located at the intersec/on of two mixing lines:


R1, E0, 1

and
FT, EN, 2

Note: 1 and 2 may be on dierent sides of the phase diagram.

Using the feed-line


1. Locate 1 at intersec/on of R1E0
and ENFT

2. Locate at intersec/on of F
2
2 1
and ENRN+1

Acetone-water-trichloroethane at 25 C and 1 atm


1
0.9
0.8

3. Step o stages, ini/ally using 1 to


generate the rst mixing lines

0.6

4. Iden/fy the op/mum feed stage


when the mixing line crosses the feed
line, F212

EN

F1

E2
0.2
E1

FT


R2 R
0.1

0.2

0.3

0.4

0.5

0.6

weight fraction water

0.7

0.8

0.1

0
S0

feed line

F2

0.3

0.9

0.4

0.5

weight fraction acetone

0.7

5. When the /e-line crosses the feed


line, the next mixing line will be
generated using 2

Countercurrent liquid-liquid extrac/on with reux


E0 = S

R1
1

makeup solvent

How to increase yA,N?


need to increase xA,N+1
make RN+1 an reux stream

extract reux

N
F1 = RN+1
xA,N+1

EN
yA,N

E0

R1

(no benet to ranate reux)

F
Turning extract into ranate :
extract is mostly solvent
ranate is mostly diluent
We need to remove solvent,

e.g., dis0lla0on, stripping

RN+1

In a conven/onal liquid-liquid extrac/on column:


reux
yA,N is related by equilibrium to xA,N
xA,N depends on xA,N+1
dilute feed gives dilute extract
highest EN obtained with S Smin, but requires very large N

recovered
solvent

SR
EN

solvent
separator

PE

product extract

Analogy to dis/lla/on reux


V1
1

recovered
solvent

N
L0

SR

D
RN+1

Saturated liquid reux stream is


obtained by condensing V1 (vapor
stream rich in A) to give L0 (liquid
stream rich in A)

External reux ra/o = L/D

Internal reux ra/o = L/V

reux

EN

solvent
separator

PE

product extract

Extract reux stream is obtained by removing


solvent from EN (extract stream rich in A and
solvent) to give RN+1 (ranate stream rich in A
and depleted in solvent)

External reux ra/o = RN+1/PE

Internal reux ra/o = RN+1/EN

Stage-by-stage balances
Similar to 2-feed liq-liq extrac/on column:
- two -points (mass balance above and below feed stage)
- if F, E0, R1 and RN+1 are specied, same stage-by-stage analysis
But RN+1 is an internal stream, usually not specied.

Usually specied:
F, xA,F, xD,F plot F
yA,0, yD,0 plot E0
xA,1 plot R1 on satd ranate curve
xA,PE, xD,PE plot PE (same loca/on as RN+1 and Q, dierent ow 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 + SR
= R + P + S
N+1
E
R

solvent
separator

PE

EN is co-linear with Q and SR.


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

dont know

EN SR RN+1
S

=
+ 1+ R
SR PE
PE
PE

EN

SR

E0

RN+1
+1
PE
SR
=
EN
PE
S 1
R

PE, Q, RN+1
F


R1
D

RN+1 EN PE
=

1
SR
SR SR

Finding the -points


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

1
0.9

EN y A,N RN+1xA,N+1

0.8

EN RN+1

We dont know the individual


ow rates EN, RN+1, but we know
EN/SR and RN+1/SR. We can
calculate xA,2 and thereby locate
2 on the ENRN+1 line.
Locate 1 at the intersec/on
2
of two mixing lines:


1 = E0 - R1
F = 1 + 2
1

0.7

weight fraction acetone

xA, 2 =

Acetone-water-trichloroethane at 25 C and 1 atm

0.5

0.4
0.3


S RE N

R1

0.2
E0
0.1
0

Proceed to step o stages.

PE, Q, RN+1

0.6

0.1

0.2

0.3

0.4

0.5

0.6

weight fraction water

0.7

0.8

0.9