SOLVENT EXTRACTION (LIQUID-LIQUID EXTRACTION)

Introduction

Solvent Extraction is the process where two immiscible or partly miscible liquids
are brought in contact with each other and soluble substance(s) in one liquid (raffinate
phase) passes into the other liquid (extract phase) by diffusion.

Commonly used for concentration of the soluble substance(s) or for purification

of the raffinate liquid.

Feed Solvent – major liquid component in the feed

Extraction Solvent – the immiscible liquid leaving the liquid-liquid extraction

nd
Raffinate – the liquid phase left from the feed after being contacted by the 2 phase

Extract – the extraction solvent phase leaving the liquid-liquid extractor

*Note: The fresh feed and the extraction solvent are immiscible with each other

1
Separation Processes
Engr. Rejie C. Magnaye
Distribution Coefficient vs, Partition Ratio

Distribution Coefficient (k) – DRE

𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐨𝐟 𝐬𝐨𝐥𝐮𝐭𝐞 𝐢𝐧 𝐫𝐚𝐟𝐟𝐢𝐧𝐚𝐭𝐞 𝐩𝐡𝐚𝐬𝐞 (𝐤𝐠 𝐦𝐨𝐥𝐞

𝐋 ),( 𝐋 )
k=
𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐨𝐟 𝐬𝐨𝐥𝐮𝐭𝐞 𝐢𝐧 𝐞𝐱𝐭𝐫𝐚𝐜𝐭 𝐩𝐡𝐚𝐬𝐞 (𝐤𝐠 𝐦𝐨𝐥𝐞
𝐋 ),( 𝐋 )

Partition Ratio (k) – PER

𝐦𝐚𝐬𝐬 𝐟𝐫𝐚𝐜𝐭𝐢𝐨𝐧 𝐨𝐟 𝐬𝐨𝐥𝐮𝐭𝐞 𝐢𝐧 𝐞𝐱𝐭𝐫𝐚𝐜𝐭 𝐩𝐡𝐚𝐬𝐞

k=
𝐦𝐚𝐬𝐬 𝐟𝐫𝐚𝐜𝐭𝐢𝐨𝐧 𝐨𝐟 𝐬𝐨𝐥𝐮𝐭𝐞 𝐢𝐧 𝐫𝐚𝐟𝐟𝐢𝐧𝐚𝐭𝐞 𝐩𝐡𝐚𝐬𝐞

𝐰𝐭 𝐨𝐟 𝐬𝐨𝐥𝐮𝐭𝐞
𝒚 𝐰𝐭 𝐨𝐟 𝐞𝐱𝐭𝐫𝐚𝐜𝐭𝐢𝐨𝐧 𝐬𝐨𝐥𝐯𝐞𝐧𝐭 + 𝐰𝐭 𝐨𝐟 𝐬𝐨𝐥𝐮𝐭𝐞
k=𝒙= 𝐰𝐭 𝐨𝐟 𝐬𝐨𝐥𝐮𝐭𝐞
𝐰𝐭 𝐨𝐟 𝐩𝐮𝐫𝐞 𝐬𝐨𝐥𝐯𝐞𝐧𝐭 + 𝐰𝐭 𝐨𝐟 𝐬𝐨𝐥𝐮𝐭𝐞

Partition ratio K is commonly defined for a given solute as the solute

concentration in the extract phase divided by that in the raffinate phase after equilibrium
is attained in a single stage of contacting. A variety of concentration units are used, so it
is important to determine how partition ratios have been defined in the literature for a
given application. The term partition ratio is preferred, but it also is referred to as the
distribution constant, distribution coefficient, or the K value. It is a measure of the
thermodynamic potential of a solvent for extracting a given solute and can be a strong
function of composition and temperature.

Factors affecting solvent extraction

1. Solubility (S), SE(Raffinate)

2. Viscosity (V),SE

3. Selectivity/Separation();  >1 for extraction to proceed

4. Temperature: T,SE

5. Axial Mixing: AM,SE

2
Separation Processes
Engr. Rejie C. Magnaye
Classification:
Single Solvent System

A. Stage-wise Contact:

1. Single Contact (analogous to Equilibrium Distillation)

2. Co-current Multiple Contact or Simple Multi-stage contact

3. Counter-Current Multi-stage or Multiple Contact

a) Without Reflux

b) With Reflux (analogous to Fractional Distillation)

B. Continuous Contact: (Differential Contact)

Counter-current Flow, N Equilibrium Stage Liquid-Liquid Extraction Cascade

Kremser Equation
𝑌𝑏−𝑌𝑏∗
ln ( )
𝑌𝑎−𝑌𝑎∗
N=
ln 𝐴′
Where:
Yb* = mxb
Ya* = mxa
A’ = L’/mV’
A’ = solute free
m = slope

3
Separation Processes
Engr. Rejie C. Magnaye
Solute Balance:
Laxa + Vbyb = Lbxb+VaYa
La(xa – xb) = Va(ya - yb)
𝐿𝑎 𝑥𝑎 − 𝑥𝑏 𝐿
= =
𝑉𝑎 𝑦𝑎 − 𝑦𝑏 𝑚𝑉

COUNTERCURRENT MULTISTAGE EXTRACTION

V2 Vn
Vn+1
V1 1 2 n-1 n
Ln
L0
L1  Ln-1

McCabe-Thiele Method
In this method of determining the number of theoretical equilibrium stages, the
operating line replaces the delta. This is specifically applicable when the two
components (b and c) are completely immiscible.

The operating line is given by the equation:

L' V ' Y1 − L' X 0

Yn+1 = Xn +
V' V'

In order to yield a straight operating line, the mass fraction is changed to mass
ratio. The variables are redefined as:

V’ = mass of solvent c, not including solute a

L’ = mass of unextracted component b, not including solute a

Y = mass of solute, a, per unit mass of solvent c, in extract phase

X = mass of solute a per unit mass of unextracted component, b in

raffinate phase

4
Separation Processes
Engr. Rejie C. Magnaye
Rearranging:

L' Yn +1 − Y1
=
V' Xn − X0

If 4 streams are given or 3 streams and the V/L ratio are given, the operating line can be
plotted with the equilibrium curve (replotted in mass ratio). The number of stages may
be determined by stepping-down in a “staircase” manner.

Equilibrium curve

XA1
YA1
YA mass ratio, mass A/mass C

XA2
YA2

XA3
YA3

XA4 Operating Line

YA4
YN+1

XN
XA0
XA mass ratio, mass A/massB

Minimum V/L Ratio

For processes with a component that is insoluble in the solvent, conditions are
that there is no solvent in the feed,𝑥𝑎0 = 0, and if the solvent is pure, 𝑥𝑠𝑛+1 = 1.

x1s xsn
P = (1 − Ln ) + Ln
1 − x1s 1 − x1s

where P = solvent to feed ratio, 𝑉𝑛+1 /𝐿0

minimum P occurs for 𝑥𝑠1 = 0

5
Separation Processes
Engr. Rejie C. Magnaye
PROBLEM-SOLVING ON LIQUID- LIQUID EXTRACTION

Problem #1
The concentration in mass fraction of the solute toluene in an extract solvent methyl
perfluro octanoate. If the concentration of the raffinate is 0.025 mass fraction toluene
and 0.975 mass fraction methyl cyclohexane @ 10degC is ____.

Extract 𝑀𝑃𝐹𝑂

Extractor

𝐹𝑒𝑒𝑑 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 (𝑀𝐶𝐻) Raffinate ( 0.025 & 0.975)

From the Table 15-5 (7th ed.) ; k = 0.1297

k = 0.1297 = E/R = xC7H8

0.025
-3
xC7H8 = 3.2425 x 10

Problem #2
There are 75 kg benzene in 250 kg of solvent n-hexane. The mass of the benzene that
can be extracted using 400 kg of ethylenediamine @ 20degC is _______.

Solution: PER using Table 15-5 ; k = 4.14

Extract (75-x); 400kg 400 kg EDA

Extractor

Benzene: 75 kg Raffinate: x – benzene unextracted

n-hexane: 250 kg 250 kg n-hexane

k = 4.14

(75 – x)kg / 400 +(75-x) kg

x / 250 + x
x = 8.8709 kg benzene unextracted
75-x = 66.1291 kg benzene extracted (mass of C6H6 in E)

6
Separation Processes
Engr. Rejie C. Magnaye
Problem #3
There are 30kg of solute in 100L of H2O, the weight of the solute that will remain in the
raffinate by 35L of ether if the distribution coefficient, k = 4, using a 3-stage
countercurrent extraction system is __________.

Solution: k=4

Extract (35L ether) 35𝐿 35𝐿 𝑉𝑛+1 = 35L ether

solute: 30 - z x-y y-z

1 2 3
Feed x y z=?
100L H2O 100L H2O 100L H2O 100L H2O
30kg solute

Using k = 4; DRE
@stage 1: @stage3:
k= 4 = x/100 @stage 2: k= 4 = z/100
30 – z/35 k= 4 = y/100 y– z/35
4(30 – z) = x x – y/35 400y = 435z
35 100 400x = 435y
12,000 – 400z = 35x

x = 32.1525 kg
y = 29.5655 kg
z = 27.1867 kg

7
Separation Processes
Engr. Rejie C. Magnaye
Problem # 4
It is desired to extract benzoic acid from toluene using water as the extraction
solvent.
Data: Analysis of the FEED: Benzoic acid 10%
Toluene : 90%
Rate of Feed: 120 gpm
Rate of solvent: 20 gpm
Assumptions:
1. All flows rates are steady
2. Toluene and water are immiscible
3. Feed concentration remains constant
4. two streams leaving each stage are in equilibrium with each other & k=0.125
The % of the extracted acid is ______.
a. with a single stage system
b. with a two-stage system

Solution: Basis: 1 minute operation

200 gal H2O

Acid ext. = 12-x 𝑉𝑛+1 = 20 gal H2O

a.) Extractor

𝐿𝑜 = 120 gal let x = unextracted benzoic acid

Benzoic acid: 12 gal Toluene: 108 gal

Toluene: 108 gal

𝑥𝜌
108
k = 0.125 = (12−𝑥)𝜌
20

x = 4.8358 gallons

12 – x = 7.1642 gallons
7.1642
% acid extracted = (100)
12

= 59.70% (% benzoic acid extracted)

8
Separation Processes
Engr. Rejie C. Magnaye
b.)

12 – y x-y
20 gal 20 gal 𝑉𝑛+1 = 20 gal

1 2
B acid: 12 gal x y = unextracted acid
Tol: 108 gal 108 gal 108 gal

@stage 1
x/108
0.125 =
(12−y)/20
20x + 13.5y = 162 ----------------------- equation 1

@stage 2
y/108
0.125 =
(x−y)/20
13.5x = 33.5y -----------------------------equation 2

Solving simultaneously: x = 6.3678; y = 2.5661

12−𝑦
% acid extracted = (100) = 78.62%
12

9
Separation Processes
Engr. Rejie C. Magnaye
 Problem # 5

A liquid mixture containing 35% solute and 65% water will be treated in a
countercurrent liquid extraction system. Pure solvent entering at a rate of 2750 kg/hr will
enter the last stage. The final raffinate will be limited to contain 2.5% solute. Assume
that the water and solvent are immiscible and that the distribution coefficient is 1.1965 in
terms of wt. ratio solute to solvent (Y) and wt. ratio to solute to water (X). If the final
extract rate is to be 4080 kg/hr, how many stages are needed and what feed rate may
be processed?

4080 kg/hr 2750 kg/hr

1 2 N

Feed
35% solute 2.5 % solute
65 % water

Basis: 1 hr operation
𝑌𝑏−𝑌𝑏∗
ln ( )
𝑌𝑎−𝑌𝑎∗
Solution: N=
ln 𝐴′
@Lo: @Ln:
Solute: 0.35 Lo Solute: 0.025Ln
Solvent: 0.65 Lo ------------------------------- Solvent: 0.975Ln

OMB: Lo + Vn+1 = Ln + V 1
Lo + 2750 = Ln + 4080
Lo - Ln = 1330 ----------- eqtn 1
0.65 Lo = 0.975 Ln ----------- eqtn 2

Solving simultaneously: Lo = 3990 kg ; Ln = 2660 kg

@Lo:
Solute: 0.35 Lo = 0.35(3990) = 1396.5 kg
Solvent: 0.65 Lo

@Ln:
Solute: 0.025Ln = 0.025(2660) = 66.5 kg

10
Separation Processes
Engr. Rejie C. Magnaye
Since L’ = solvent @Lo = Solvent@ Ln

L’ = 0.65Lo = 0.65(3990) = 2593.5

=0.975Ln = 0.975(2660) = 2593.5

A’ = L’ / mV’

Yb = 0
𝟎.𝟎𝟐𝟓
Yb* = mXb = 1.1965( ) = 0.0307
𝟎.𝟗𝟕𝟓

Ya = solute@Y1/ solvent@Y1

= 1396.5 – 66.5 / 2750 = 0.4836

𝟎.𝟑𝟓
Ya* = mXo = 1.1965 ( ) = 𝟎. 𝟔𝟒𝟒𝟑
𝟎.𝟔𝟓

𝑌𝑏−𝑌𝑏∗
ln ( )
𝑌𝑎−𝑌𝑎∗
N=
ln 𝐴′
0−0.0307
ln ( )
0.4836−0.6443
N= 2593.5
ln
1.1965(2750)

N = 6.9551 = 7 stages

11
Separation Processes
Engr. Rejie C. Magnaye
Problem # 7

The nicotine equilibrium relationship between water F & kerosene S, can be

expressed by the equilibrium relationship, y = 0.9167x where x is the mass ratio of
nicotine to water & y is the mass ratio of nicotine to kerosene. Water and kerosene is
essentially insoluble. Determine the

a). % extraction of nicotine of 100 lb m of feed solution containing 1% nicotine which is

processed of 150 lbm of kerosene containing 0.001% nicotine.

b) Repeat previous problem using 3 ideal co – current extraction of 50 lbm solvent for
each stage.

Solution:
a.
𝑛𝑖𝑐𝑜𝑡𝑖𝑛𝑒
y = 𝑘𝑒𝑟𝑜𝑠𝑒𝑛𝑒 kerosene: 150 lbm (0.001% nicotine)

Extractor
𝑛𝑖𝑐𝑜𝑡𝑖𝑛𝑒
Feed: 100 lbm x= 𝑤𝑎𝑡𝑒𝑟

Nicotine: 1%
Water: 99%

@𝐿0 : @𝑉𝑛+1 :
Nicotine: 1 lbm Nicotine: 0.00001(150) = 0.0015 lbm
Water: 99 lbm Kerosene: 150 – 0.0015 = 149.9985 lbm

@𝑉1:
Nicotine: (1+0.0015) – x
Kerosene: 149.9985 lbm

y = 0.9167x
1.0015−𝑥 𝑥
= 0.9167⌊ ⌋
149.9985 99
x = 0.4192 lbm

12
Separation Processes
Engr. Rejie C. Magnaye
 (1.0015−0.4192)= 0.5823
% nicotine extracted = (100) = 58.23%
1

50 lbm 50 lbm 50 lbm

b.

Feed 1 2 3
100 lbm
1% nicotine= 1 N: x N: y N: z
99% H2O = 99 W: 99 W: 99 W: 99

N: 1- x N: x - y N: y - z
W: 50 W: 50 W: 50

@stage 1: @stage 2: @stage 3:

y = 0.9167x y = 0.9167x y = 0.9167x

𝟏−𝒙 𝒙 𝒙−𝒚 𝒚 𝒚−𝒛 𝒛
= 0.9167 𝟗𝟗 = 0.9167 𝟗𝟗 = 0.9167 𝟗𝟗
𝟓𝟎 𝟓𝟎 𝟓𝟎

x = 0.6835 y = 0.4672 z = 0.3193

𝟏−𝒛 𝟏−𝟎.𝟑𝟏𝟗𝟑
% nicotine extracted = (100) = (100) = 68.07%
𝟏 𝟏

13
Separation Processes
Engr. Rejie C. Magnaye