26.02.

2012

SEPARATION PROCESSES

LIQUID-LIQUID EXTRACTION PROCESSES

Equilibrium Relations in LL Extraction

Transport Processes and Separation Process Principles CHRISTIE J.

GEANKOPLIS

Unit operations in chemical engineering by Mccabe, Smith and Harriot

PRINCIPLES AND MODERN APPLICATIONS OF MASS TRANSFER
OPERATIONS by Jaime Benitez
Separation process principles by Seader and Henley
Separation processes by King
Chemical Engineering by Coulson and Richardson

LIQUID-LIQUID EXTRACTION PROCESSES

removing one constituent from a liquid by means of an other liquid

solvent
When separation by distillation is ineffective or very difficult (close-boiling
mixtures or substances / or heat sensitive mixtures), liquid extraction is one
of the main alternatives to consider
recovery of penicillin from the fermentation broth by extraction with a
solvent such as butyl acetate
recovery acetic acid from dilute aqueous solutions

26.02.2012

Equilibrium Relations in LL Extraction

Equilateral triangular coordinates are often used to represent the equilibrium
data of a three-component system, since there are three axes
A, B, or C : a pure component
point M a mixture of A, B, and C
the perpendicular distance from the
point M to
the base AB : the mass fraction xc of
C in the mixture at M,
to base CB the mass fraction xA of A,
to base AC the mass fraction xB of B

xA + xB + xc = 0.40 + 0.20 + 0.40 = 1.0

C dissolves completely in A or in B.
A is only slightly soluble in B and B slightly soluble in A.
The two-phase region is included inside below the curved envelope.
An original mixture of composition M will separate into two phases a and b
which are on the equilibrium tie line through point M.
Other tie lines are also shown. The two phases are identical at point P, the Plait
point.

Liquid-liquid phase diagram where components A and B are partially

miscible

26.02.2012

Phase diagram where the solvent pairs bc and a-c are partially miscible.

26.02.2012

A: acetic acid, B: water, C: isopropyl ether solvent

The solvent pair B and C are partially miscible.
The concentration of the component C is plotted on the vertical axis and that
of A on the horizontal axis.
The concentration of component B is obtained by difference from

inside the envelope: two phase

Outside: one-phase region
A tie line g-i connecting the raffinate and extract layers
raffinate layer : water-rich layer
extract layer : ether-rich solvent layer g,
The raffinate composition is designated by x and the extract by y

26.02.2012

the mass fraction of C in the extract layer : yc

the mass fraction of C in the raffinate layer and as xc
To construct the tie line gi using the equilibrium yA xA plot below the phase
diagram, vertical lines to g and i are drawn.

26.02.2012

Equilibrium: System Water-Chloroform-Acetone

Equilibrium extraction data for the system
water-chloroform-acetone at 298 K and 1 atm are given in Table. Plot these
data on a right-triangular diagram, including in the diagram a conjugate or
auxiliary line that will allow graphical construction of tie lines.

26.02.2012

Chloroform as solvent (B), water as diluent (A), and

acetone as solute (C).
This system exhibits a type I equilibrium behavior. The
graphical construction to generate the conjugate line
from the tie-line data given (e.g., line RE) is shown, as
well as the use of the conjugate line to generate other
tie lines not included in the original data. Line LRP is
the saturated raffinate line, while line PEK is the
saturated extract line.

Single-Stage Equilibrium Extraction

Derivation of lever-arm rule for graphical addition.
two streams, L kg and V kg, containing components A, B, and C, are mixed
(added) to give a resulting mixture stream M kg total mass.
overall mass balance and a balance on A,

Graphical addition and lever-arm rule : (a) process flow, (b) graphical addition

26.02.2012

An original mixture weighing 100 kg and containing isopropyl ether (C), acetic
acid (A), and water (B) is equilibrated and the equilibrium phases separated The
compositions of the two equilibrium layers are for the extract layer (V) yA = 0.04,
yB = 0.02, and yc = 0.94, and for the raffinate layer (L) xA =0.12, xB = 0.86, and
xc = 0.02. The original mixture contained 100 kg and xAM = 0.10. Determine the
amounts of V and L.

26.02.2012

M = 100 kg and xAM= 0.10

L = 75.0 and V = 25.0

L = 72.5 kg and V = 27.5 kg

Single-stage equilibrium extraction

separation of A from a mixture of A and B by a solvent C in a single equilibrium
stage.
the solvent, as stream V2 and the stream L0 enter

The streams are mixed and equilibrated and

the exit streams L1 and V1 leave in equilibrium with each other.

26.02.2012

Single-Stage Extraction
Pure chloroform is used to extract acetone from a feed containing 60 wt%
acetone and 40 wt% water in a co-current extractor. The feed rate is 50 kglh,
and the solvent rate is also 50 kg/h. Operation is at 298 K and 1 atm. Find the
extract and raffinate flow rates and compositions when one equilibrium stage
is used for the separation. (assume water and chloroform do not mix)

10

26.02.2012

V= C, Solvent, chloroform, ya1=0, yC1=1.0

L= Liquid mixture, A: acetone, B=water
xA1=0.60, xB1=0.40

V1

A: acetone

L1

V2

yA2

L1

L2
xA2
V1

B: water
V1+L1=V2+L2=M
V1yA1+L1xA1=V2yA2+L2xA2=MxAM
V1yB1+L1xB1=V2yB2+L2xB2=MxBM
V1yC1+L1xC1=V2yC2+L2xC2=MxCM

V1+L1=V2+L2=M
V1yA1+L1xA1=V2yA2+L2xA2=MxAM

C: chloroform

V= C, Solvent, chloroform, ya1=0, yC1=1.0

L= Liquid mixture, A: acetone, B=water
xA1=0.60, xB1=0.40

L1

yA2

xA2
V1

Tie line is constructed through by trial and error, using conjugate line extract
(V2, yA2) and rafinate (L2, xA2) locations are obtained. The concentrations
yA2=0.334, xA2=0.189

11

26.02.2012

L1

yA2

xA2

V1

Continuous Multistage Countercurrent Extraction

12

26.02.2012

Material Balance for Countercurrent Stage Process Pure solvent isopropyl

ether at the rate of VN+1= 600 kg/h is being used to extract an aqueous
solution of L0 = 200 kg/h containing 30 wt % acetic acid (A) by countercurrent
multistage extraction. The desired exit acetic acid concentration in the
aqueous phase is 4%. Calculate the compositions and amounts of the ether
extract V1 and the aqueous raffinate LN.

13

26.02.2012

L0xA0+VN+1yAN+1=LNxAN+V1yA1=MxAM
Pure solvent isopropyl ether (C)
VN+1= 600 kg/h yAN+1=0

yCN+1=1.0

B: aqueous solution of L0 = 200 kg/h containing 30 wt % acetic acid (A) exit

acetic acid concentration in the aqueous phase is 4%.
xA0= 0.30, xB0=0.70, xC0=0, xAN=0.04

VN+1= 600 kg/h yAN+1=0 yCN+1=1.0

L0 = 200 kg/h

xA0= 0.30, xB0=0.70, xC0=0, xAN=0.04

14

26.02.2012

, yCN+1, yAN+1
yC1, yA1

xC0, xA0

xCN, xAN

L0xA0+VN+1yAN+1=LNxAN+V1yA1=MxAM
VN+1= 600 kg/h yAN+1=0 yCN+1=1.0
L0 = 200 kg/h
xA0= 0.30
xB0=0.70, xC0=0, xAN=0.04
xCM=0.75, xAM= 0.075
VN+1 and L0 are plotted
LN is on phase boundary
It can be plotted at xAN=0.04
For the mixture point M
xCM=0.075, xAM=0.75
Draw a line from the point of
LN and M at equilibrium of
extract phase gives V1,
yA1=0.08 and
yC1=0.90

VN+1= 600 kg/h yAN+1=0 yCN+1=1.0

L0 = 200 kg/h
xA0= 0.30
xB0=0.70, xC0=0, xAN=0.04
xCM=0.75, xAM= 0.075
yA1=0.08 and
yC1=0.90

LN= 136 kg/h

V1= 664 kg/h

15

26.02.2012

Stage-to-stage calculations for countercurrent extraction

stage by stage to determine the concentrations at each stage and the total
number of stages N needed to reach LN

total balance on stage 1

total balance on stage n

Assumption: D (kg/h) is constant for all stages

16

26.02.2012

balance on component A, B, or C.

17

26.02.2012

Number of Stages in Countercurrent Extraction

Pure isopropyl ether (C) of 450 kg/h is being used to extract an aqueous solution of
150 kg/h with 30 wt % acetic acid (A) by countercurrent multistage extraction. The
exit acid concentration in the aqueous phase (B) is 10 wt %. Calculate the number
of stages required.

VN+1=450, yAN+1=0, yCN+1=1.0

L0=150, xA0=0.30, xB0=0.70, xC0=0, xAN=0.10

(150 x0) (450 x1.0)

0.75
150 450

(150 0.30) (450 0)

0.075
150 450

VN+1=450, yAN+1=0, yCN+1=1.0

L0=150, xA0=0.30, xB0=0.70, xC0=0, xAN=0.10

18

26.02.2012

Countercurrent-Stage Extraction with Immiscible Liquids

If the solvent stream VN+l contains components A(solute) and C(solvent) and
the feed stream L0 contains A (solute) and B(feed solvent) and components
B and C are relatively immiscible in each other, the stage calculations are
made more easily.
The solute A is relatively dilute and is being transferred from L 0 to VN+1

where L = kg inert B/h, V = kg inert C/h, y = mass fraction A in V stream, and x = mass fraction A in L
stream
Slope of the operating line is L / V (if y and x are dilute)

19

26.02.2012

EXAMPLE Extraction of Nicotine with Immiscible Liquids. An inlet water solution of

100 kg/h containing 0.010 wt fraction nicotine (A) in water is stripped with a
kerosene stream of 200 kg/h containing 0.0005 wt fraction nicotine in a
countercurrent stage tower. The water and kerosene are essentially immiscible in
each other. It is desired to reduce the concentration of the exit water to 0.0010 wt
fraction nicotine. Determine the theoretical number of stages needed. The
equilibrium data are as follows (C5), with x the weight fraction of nicotine in the
water solution and y in the kerosene.

20

26.02.2012

L0=100 kg/h,
x0=0.010
VN+1= 200 kg/h, yN+1= 0.0005, xN=0,0010

L=L(1-x)=L0(1-x0)=100(1-0.010)=99.0 kg water/h
V=V(1-y)=VN+1(1-yN+1)=200(1-0.0005)=199.9 kg kerosen/h

y1
0.010
0.0005
0.0010
99.0

199.9
99.0
199.9
1

0.010
1

0.0005
1

0.0010

1 y 1
y1=0.00497

L0=100 kg/h,
x0=0.010
VN+1= 200 kg/h, yN+1= 0.0005, xN=0,0010

y1=0.00497

N=3.8 theoretical plate

21

26.02.2012

Minimum Solvent and Countercurrent Extraction of Acetone. An aqueous

feed solution of 1000 kg/h containing 23.5 wt % acetone and 76.5 wt % water is
being extracted in a countercurrent multistage extraction system using pure
methyl isobutyl ketone solvent at 298-299 K. The outlet water raffinate will
contain 2.5 wt % acetone. Use equilibrium data from Appendix A.3.
a) Calculate the minimum solvent that can be used. [Hint: In this case the tie
line through the feed L0 represents the condition for minimum solvent flow rate.
This gives V1 min . Then draw lines LN V1 min and L0 VN+1 to give the mixture point
Mmin and the coordinate xAMmin, find VN+ 1 min the minimum value of the solvent
flow rate VN+ 1]
b) Using a solvent flow rate of 1.5 times the minimum, calculate the number of
theoretical stages.

22

26.02.2012

VN+1=? kg/h
yAN+1=0
yCN+1=1.0
L0=1000 kg/h
xA0=0.235
xC0=0

xAN=0.025
Tie line on L0(xA0), V1(y1)min
C

A:Acetone
C:MIK

VN+1

V1 min y1 min

Tie line
yA

Mmin

xAmin=0.175

LN,
xAN=0.025
L0, xA0

A
y1min

Dmin

x AM min

L0 x A0 VN 1min y AN 1
L0 VN 1min

xA0

0.175

xA

1000(0.235) VN 1min (0)

1000 VN 1min

VN 1min 340kg / h

VN+1=1.5(VN+1 min)=1.5(340)=510kg/k

xAM

L0=1000 kg/h
xA0=0.235
xC0=0

yAN+1=0
yCN+1=1.0

L0 x A0 VN 1 y AN 1 1000(0.235) 510(0)

L0 VN 1
1000 510

xAM 0.156
xCM

L0 xC 0 VN 1 yCN 1 1000(0) 510(1.0)

L0 VN 1
1000 510

xCM 0.337

23

26.02.2012

M(xAM and xCM)

M(0.156, 0.337)

xAN=0.025 given
LN-M line gives V1, y1
yA1=0.290, yC1=0.645
xCN=0.020 from graph

x AM

Lo+VN+1=LN+V1=M
1000+510=LN+V1
V1=1510-LN

LN x AN V1 y A1
LN V 1

0.156

LN (0.025) (1510 LN )(0.290)

1510

LN=763, V1=747

To calculate D point

xDC

L0 xC 0 V1 yC1 1000(0) 747(0.645)

L0 V1
1000 747

xDC 1.91
xDA

L0 x A0 V1 y A1 1000(0.235) 747(0.290)

L0 V1
1000 747

xDC 0.073

24

26.02.2012

VN+1

yA
C

V3, y3
V2 , y2

y2

V1 , y1

y1
x1

x2

xA

M
L1

Draw tie line y1 (V1), x1(L1)

Draw L1D,
Draw tie line y2 (V2), x2(L2)
Draw L2D
Draw tie line y3 (V3), x3(L3)

LN, xAN
L0, xA0

A
L2

Repeat steps to LN
N= 5 stage

Countercurrent Extraction of Acetic Acid and Minimum Solvent. An

aqueous feed solution of 1000 kg/h of acetic acid-water solution contains 30.0 wt
% acetic acid and is to be extracted in a countercurrent multistage process with
pure isopropyl ether to reduce the acid concentration to 2.0 wt % acid in the final
raffinate. (a) Calculate the minimum solvent flow rate that can be used.
(b) If 2500 kg/h of ether solvent is used, determine the number of theoretical
stages required. (Note: It may be necessary to replot on an expanded scale the
concentrations at the dilute end.)

25

26.02.2012

Extraction with Immiscible Solvents. A water solution of 1000 kg/h containing

1.5 wt % nicotine in water is stripped with a kerosene stream of 2000 kg/h
containing 0.05 wt % nicotine in a countercurrent stage tower. The exit water is to
contain only 10% of the original nicotine, i.e., 90% is removed. Calculate the
number of theoretical stages needed.

26

26.02.2012

27