LIQUID-LIQUID

EXTRACTION
ENGR. CRIZALDY V. TUGADE
DEPARTMENT OF CHEMICAL ENGINEERING
TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES - MANILA
Liquid-Liquid Extraction

It is a process of transferring a solute from one liquid phase to another

immiscible or partially miscible liquid in contact with the first. The two
phases are chemically quite different, which leads to a separation of the
components according to their distribution or partition between the
two phases, normally one organic and one water.

This is different from distillation, in which the liquid is partially

vaporized to create another (vapor) phase, but the two phases are
similar chemically.
Liquid-Liquid Extraction

Liquid-Liquid Extraction a.k.a. Solvent Extraction is the process of

extracting a Solute from a Feed by use of a Solvent to produce an
Extract and a Raffinate. In its simplest form, it may take the guise of a
single stage mixing and separation unit analogous to a single stage flash
in distillation.
 Liquid-Liquid Extraction

Extract - This is the exit stream from the process being substantially Solvent material into which the Solute has
transferred.
Feed - This is the inlet stream to the unit in which the substance to be extracted is originally dissolved.
Liquid-Liquid Extraction- This is the unit operation by which a substance or substances may be substantially
passed from solution in one liquid to solution in another by the contacting of the liquids. This process is also known
as Solvent Extraction.
Raffinate -This is the exit stream from the process being substantially Feed material from which the Solute has been
transferred.
Solute - This is the substance or substances which are to be transferred from the Feed.
Solvent - This is the second liquid phase fed to the process into which the Solute is transferred. The Solvent should
be substantially immiscible with the Feed.
 Liquid-Liquid Extraction
Where or Why do we use LLE?

Where? Why?
• Bioseparations • Temperature sensitive products
• Nuclear (uranium recovery) • High purity requirements
• Mining: nickel/cobalt; copper/iron • High-boiling point species in low quantity
• Perfumes, fragrances and essential oils • Need to separate by species type (rather than
• Fine and specialty chemicals relative
• Oil sands: extract bitumen away from • volatility)
water • Close-boiling points, but high solubility
dierence
• Azeotrope-forming mixtures
Liquid-Liquid Extraction
Choice of Extraction Solvent

The choice of Solvent is critical in effecting a Liquid-Liquid Extraction. Factors

affecting the choice are summarized later; it is usually necessary to compromise in
one area or another.

Schweitzer: “The choice of solvent for a LLE process can often have a more significant
impact on the process economics than any other design decision that has to be made".
Liquid-Liquid Extraction
Choice of Extraction Solvent
The choice of Solvent is influenced by many factors some of which are listed below:

(a) High Selectivity:  The ability of a Solvent to extract a component or class of

components in preference to others. This factor will determine the number of extraction
stages required.
(b) Distribution or Partition Coefficient:
 The ratio of the solubility of the Solute in the Solvent compared to the Feed. This factor
will affect the selectivity and the amount of Solvent phase required.

(c) Density:
 The greater the density difference between the Feed and the Solvent the easier it will be to
obtain phase separation.
Liquid-Liquid Extraction
Choice of Extraction Solvent
(d) Viscosity:  A high viscosity will inhibit both mass transfer and separation of the phases.
A low viscosity (say less than 10 cP) is desirable.

(e) Interfacial Tension: This affects the settling, coalescence and mass transfer coefficient
of a system. Coalescence and settling are generally aided by high interfacial tension whilst
mass transfer is hindered.

(f) Volatility:  The Solvent is likely to need to be separated from the Solute and/or the
Feed. If this is to be done by distillation the volatility should, where possible, be chosen to
allow this separation to be easily effected
  
(g) Stability:  The Solvent should be stable at process conditions in order to minimize
losses by degradation and generation of further impurities.
Liquid-Liquid Extraction
Choice of Extraction Solvent

(h) Corrosivity:  If possible, there is a strong incentive to use a component that is already
in the process, such as a reactant feed stream, as the Solvent. This may avoid additional
materials handling, environmental and corrosion penalties later in the process.

(j) Toxicity:  The advantages of a non-toxic Solvent are self evident in considering
inherent process safety and capital cost. Some solvents now appear on the "Environmental
Red List" and should be avoided.

(k) Cost:  The extraction process may only be a small part in the overall process and
solvent losses should not greatly affect process economics.
 Liquid-Liquid Extraction
Distribution or Partition Coefficient

Solvent Extraction depends on a favorable distribution of the Solute between the Solvent
and Feed streams. The two important parameters which fix the number of extraction stages
and the Solvent usage are the distribution coefficient and the selectivity factor.

The distribution or partition coefficient, K, is defined as:

𝐶𝐸
𝐾=
𝐶𝑅
where C refers to the composition of a component in any consistent convenient units and the subscripts E and R refer to the
Extract and Raffinate phase respectively.
Liquid-Liquid Extraction
Distribution or Partition Coefficient

The separation or selectivity factor, S, is defined as:

𝐾1
𝑆=
𝐾2

where the subscript1 refers to the component to be preferentially extracted and subscript 2 refers to the component to
be preferentially retained.

The separability of component 1 from component 2 increases with increasing

separation factor. A high value of S indicates the potential for a high degree of
separation in a small number of extraction stages.
Liquid-Liquid Extraction
Sample Problem

1. Calculate the partition coefficient of caffeine in water/methylene chloride from the following data: 10.3
g/100 mL for methylene chloride and 2.04 g/100 mL for water.

𝐶𝐸
𝐾=
𝐶𝑅
Extraction solvent is methylene chloride (organic), carrying solvent is water (aqueous)
10.3 𝑔 𝑐𝑎𝑓𝑓𝑒𝑖𝑛𝑒
100 𝑚𝐿 𝑜𝑓 𝑚𝑒𝑡h𝑦𝑙𝑒𝑛𝑒 𝑐h𝑙𝑜𝑟𝑖𝑑𝑒
𝐾=
2.04 𝑔 𝑐𝑎𝑓𝑓𝑒𝑖𝑛𝑒
100 𝑚𝐿 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

𝐾 =5.05
 Liquid-Liquid Extraction
Sample Problem

2. Imagine that a nearly saturated solution of 0.50 g of hyoscyamine in 150mL water is to be extracted into
150mL of diethyl ether. What is the percent recovery of solute?

Given:

150 𝑚𝐿𝑤𝑎𝑡𝑒𝑟 150 𝑚𝐿𝑤𝑎𝑡𝑒𝑟

𝐹 LLE Extractor 𝑅
0.5 − 𝑋𝑔 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
0.50 𝑔 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
150 𝑚𝐿 𝑑𝑖𝑒𝑡h𝑦𝑙 𝑒𝑡h𝑒𝑟  
𝐸 𝑋𝑔h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
Liquid-Liquid Extraction
Sample Problem # 2
𝐶𝐸
𝐾=
𝐶𝑅

1.44 𝑔 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
100 𝑚𝐿 𝑜𝑓 𝑑𝑖𝑒𝑡h𝑦𝑙 𝑒𝑡h𝑒𝑟
𝐾=
0.35 4 𝑔 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
100 𝑚𝐿 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

𝐾 =4.07
Liquid-Liquid Extraction
Sample Problem # 2
𝐾 =4.07
𝑋𝑔h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
150 𝑚𝐿𝑜𝑓 𝑑𝑖𝑒𝑡h𝑦𝑙 𝑒𝑡h𝑒𝑟
4.07=
0.50 − 𝑋𝑔 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
15 0 𝑚𝐿𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

𝑋=0.40 𝑔𝑜𝑓 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒𝑖𝑛 𝐸

0.50 − 𝑋 =0.1 𝑔𝑜𝑓 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒𝑖𝑛 𝑅
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝐸𝑥𝑡𝑟𝑎𝑐𝑡
% 𝑅𝑒𝑐𝑜𝑣𝑒𝑟𝑦 = (100 %)
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑡h𝑒 𝐹𝑒𝑒𝑑

0.40
% 𝑅𝑒𝑐𝑜𝑣𝑒𝑟𝑦 = ( 100 % )=80 %
0.50
 Liquid-Liquid Extraction
Sample Problem

3. Same problem as in #2, but instead of using a single stage extraction using 150mL of diethyl ether, you
use 50mL of the solvent in three stages extraction. What is the percent recovery of solute?

Given:

150 𝑚𝐿𝑤𝑎𝑡𝑒𝑟 𝑅3
𝑅1 𝑅2
𝐹 Extractor 1 Extractor 2 Extractor 3
0.50 𝑔 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
𝐸1 𝐸2 𝐸3
Liquid-Liquid Extraction
Sample Problem # 3
𝐾 =4.07
Consider the 1st stage:
0.50 − 𝑋 1 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
50 𝑚𝐿𝑜𝑓 𝑑𝑖𝑒𝑡h𝑦𝑙 𝑒𝑡h𝑒𝑟
4.07=
𝑋 1 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
5 0 𝑚𝐿𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

𝑋 1=0.21 𝑔𝑜𝑓 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒 𝑖𝑛 𝑅1

0.50 − 𝑋 1=0.29 𝑔 𝑜𝑓 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒 𝑖𝑛 𝐸1
Liquid-Liquid Extraction
Sample Problem # 3
𝐾 =4.07
Consider the 2nd stage:

0. 21− 𝑋 2 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
50 𝑚𝐿𝑜𝑓 𝑑𝑖𝑒𝑡h𝑦𝑙 𝑒𝑡h𝑒𝑟
4.07=
𝑋 2 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
5 0 𝑚𝐿𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

𝑋 2=0.09 𝑔 𝑜𝑓 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒 𝑖𝑛 𝑅 2
0.021 − 𝑋 2=0.12 𝑔𝑜𝑓 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒 𝑖𝑛 𝐸 2
Liquid-Liquid Extraction
Sample Problem # 3
𝐾 =4.07
Consider the 3rd stage:
0. 09 − 𝑋 3 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
50 𝑚𝐿𝑜𝑓 𝑑𝑖𝑒𝑡h𝑦𝑙 𝑒𝑡h𝑒𝑟
4.07=
𝑋 3 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒
5 0 𝑚𝐿𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

𝑋 3=0.04 6 𝑔 𝑜𝑓 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒𝑖𝑛 𝑅 2
0.09 − 𝑋 3 =0.05 𝑔 𝑜𝑓 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒 𝑖𝑛 𝐸 2
Liquid-Liquid Extraction
Sample Problem # 3

𝑋 3=0.04 𝑔 𝑜𝑓 h𝑦𝑜𝑠𝑐𝑦𝑎𝑚𝑖𝑛𝑒 𝑖𝑛 𝑅 3
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝐸𝑥𝑡𝑟𝑎𝑐𝑡 𝑆𝑡𝑟𝑒𝑎𝑚
% 𝑅𝑒𝑐𝑜𝑣𝑒𝑟𝑦 = (100 %)
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑡h𝑒 𝐹𝑒𝑒𝑑

0.50 − 0.046
% 𝑅𝑒𝑐𝑜𝑣𝑒𝑟𝑦 = ( 100 % ) =92 %
0.50
Liquid-Liquid Extraction

What is the limitation of using the Partition Ratio or

Distribution Coefficient in determining the E and R Based on
the Sample Problems?
The carrying solvent (the solvent in the feed)and the
extraction solvent are immiscible with one another.
Liquid-Liquid Extraction

What if the carrying solvent and the extraction solvent is

partially miscible with one another?

Use of Ternary Phase Diagram in solving E and R.

Liquid-Liquid Extraction
Ternary Phase Diagram
A common phase diagram is shown below,
where a pair of components A and B are
partially miscible, and liquid C dissolves
completely in A or B. The two phase region
is included inside below the curved
envelope. An original mixture of
composition M will be separate into two
conjugate phases a and b which are on
equilibrium tie line through point M. Other
tie lines are also plotted. The two phases are
identical in point P, which is called the Plait
point.
Liquid-Liquid Extraction
Ternary Phase Diagram

https://www.youtube.com/watch?v=gGYHXhcKM5s
Liquid-Liquid Extraction
Ternary Phase Diagram
Liquid-Liquid Extraction
Ternary Phase Diagram
Liquid-Liquid Extraction
Sample Problem #1

Determine the what is the composition of mixture, M?

Liquid-Liquid Extraction
Sample Problem #1
Liquid-Liquid Extraction
Sample Problem #1

Remember that:
 Liquid-Liquid Extraction
Sample Problem #1

𝑆𝐹=63𝑚𝑚

Remember that:
Liquid-Liquid Extraction
Sample Problem #1

Remember that:

Answer:
Liquid-Liquid Extraction
Sample Problem #2

Determine the composition of E and R in sample #1.

Liquid-Liquid Extraction
Sample Problem #2

Please note that for the consistency of calculation, we are to use

OMB and CB in terms of A to solve for the streams.
Liquid-Liquid Extraction
Sample Problem #3

Determine the composition of E and R.

Liquid-Liquid Extraction
Sample Problem #3

Determine 1st point F and point S.

Liquid-Liquid Extraction
Sample Problem #3

Determine point M to determine E and R.

Liquid-Liquid Extraction
Sample Problem #3

Remember that:
Liquid-Liquid Extraction
Sample Problem #3

Remember that:
Liquid-Liquid Extraction
Sample Problem #3

Use tie-line to know points E and R

Liquid-Liquid Extraction
Sample Problem #3

Remember that
Liquid-Liquid Extraction
For Countercurrent Arrangement
Liquid-Liquid Extraction
Sample Problem #4
Consider a system for which you
have been given the ternary
diagram. A = solute, S = solvent
(100% pure), C = carrier. The feed,
F enters at 112 kg/hr with
composition of 25 wt% solute and
75 wt% carrier.

Show the construction on the ternary

diagram for the number of
equilibrium stages to achieve xRN =
0.025, given a solvent flow of 28
kg/hr and countercurrent
arrangement.
Liquid-Liquid Extraction
Sample Problem #4

𝑥𝑅 , 𝑁 = 0.25
Liquid-Liquid Extraction
Sample Problem #4
𝐷𝑒𝑡𝑒𝑟𝑚𝑖𝑛𝑒 𝑝𝑜𝑖𝑛𝑡 𝐹 𝑎𝑛𝑑 𝑆.

Remember that:

𝐷𝑒𝑡𝑒𝑟𝑚𝑖𝑛𝑒 𝑝𝑜𝑖𝑛𝑡 𝑀 .
Liquid-Liquid Extraction
Sample Problem #4
𝐷𝑒𝑡𝑒𝑟𝑚𝑖𝑛𝑒 𝑝𝑜𝑖𝑛𝑡 𝑅𝑁 .
Connect point RN
to M and extend
the line until it hit
the equilibrium
curve.

𝑇h𝑎𝑡 𝑖𝑠 𝑝𝑜𝑖𝑛𝑡 𝐸1
Liquid-Liquid Extraction
Sample Problem #4
𝐷𝑒𝑡𝑒𝑟𝑚𝑖𝑛𝑒 𝑝𝑜𝑖𝑛𝑡 𝑅𝑁 .
Connect point RN
to M and extend
the line until it hit
the equilibrium
curve.

𝑇h𝑎𝑡 𝑖𝑠 𝑝𝑜𝑖𝑛𝑡 𝐸1
Liquid-Liquid Extraction
Sample Problem #4
𝐶𝑜𝑛𝑛𝑒𝑐𝑡 𝑝𝑜𝑖𝑛𝑡𝑠 𝐸1∧ 𝐹
𝐶𝑜𝑛𝑛𝑒𝑐𝑡 𝑝𝑜𝑖𝑛𝑡𝑠 𝑆∧𝑅𝑁

Intersect these lines from and

𝑇h𝑎𝑡 𝑖𝑠 𝑝𝑜𝑖𝑛𝑡 𝑃
Liquid-Liquid Extraction
Sample Problem #4

Use tie-line from point to

carrier (aqueous) rich section

𝑇h𝑎𝑡 𝑖𝑠 𝑝𝑜𝑖𝑛𝑡 𝑅1
Liquid-Liquid Extraction
Sample Problem #4

Connect point P to point

extend the line to the solvent
rich section

𝑇h𝑎𝑡 𝑖𝑠 𝑝𝑜𝑖𝑛𝑡 𝐸2

Use tie-line from point to

carrier (aqueous) rich section

𝑇h𝑎𝑡 𝑖𝑠 𝑝𝑜𝑖𝑛𝑡 𝑅2
Liquid-Liquid Extraction
Sample Problem #4

Repeat the step until Rx ≤ Rn

6 theoretical stages