KIL 2008 / KKEK 2158

Separation Processes 1

11 – Liquid-liquid Extraction

Dr. Hanee Farzana Binti Hizaddin

Department of Chemical Engineering
University of Malaya

hanee@um.edu.my

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Learning outcomes
At the end of this class, you should be able to:
• Explain the mechanism of liquid-liquid extraction process
• Plot phase diagrams for ternary liquid-liquid systems in the form of
equilateral triangular diagram, right-angle triangular diagram and
rectangular diagram.
• Perform material balance calculation for single-stage countercurrent
extraction process

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Introduction to Extraction Process
Raffinate phase
Carrier • Rich in carrier
Solute

Extract phase
Solvent • Rich in solvent

• In distillation, the liquid is partially vaporized to create another phase, i.e. vapor.
• The separation of the components depends on the relative vapor pressures of the substances.
The vapor and liquid phases are similar chemically.
• In LLE, the two phases are chemically different, which leads to a separation of the
components according to physical and chemical properties.
• LLE can be used as alternative to distillation or evaporation.
• What is the separating agent in LLE? MSA or ESA?
• When would LLE be preferable to distillation?

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When is LLE preferred over distillation?
1. Dissolved or complexed inorganic substances in organic or aqueous solutions.
2. Removal of a contaminant present in small concentrations, such as a color former
in tallow or hormones in animal oil.
3. A high-boiling component present in relatively small quantities in an aqueous
waste stream, as in the recovery of acetic acid from cellulose acetate.
4. Recovery of heat-sensitive materials, where extraction may be less expensive
than vacuum distillation.
5. Separation of mixtures according to chemical type rather than relative volatility.
6. Separation of close-melting or close-boiling liquids, where solubility differences
can be exploited.
7. Separation of mixtures that form azeotropes.
Equilibrium relations in extraction
1. Phase rule
• Generally in a liquid-liquid system there are three components, e.g. A,
B, and C, and two phases in equilibrium.
• Gibbs phase rule: F=C-P+2. Thus, in ternary liquid-liquid system, the
number of degrees of freedom is 3.
• What are the 3 variables? T, P, and four concentrations. The four
concentrations i.e. two of the concentrations in a phase can be
specified. The third concentration can be obtained by a total of
mass/mole fraction equal to 1.

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Equilibrium relations in extraction
2. Triangular coordinates and equilibrium data
• how to read them?

https://demonstrations.wolfram.com/BasicTernaryPhaseDiagram/ 6
 Equilibrium relations in extraction
2. Triangular coordinates and equilibrium data

What information can be obtained from the diagram?

• In the diagram, components A and B are partially miscible.

• Liquid C dissolves completely in A or in B.
• Liquid A is only slightly soluble in B and B is slightly soluble in A.
• The two-phase region is included inside below the curved
envelope.
• An original mixture with composition will separate into two
phases and which are on the equilibrium tie line through point
.
• The two phases are identical at point , the Plait point.

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Equilibrium relations in extraction
3. Equilibrium data on rectangular coordinates
• Often times it’s more useful to use rectangular
coordinates to plot the phase diagrams.
• Example: acetic acid (A)-water (B)-isopropyl ether
(C).
• The solvent pair B and C are partially miscible.
• The concentration of A is plotted on the horizontal
axis and that of C on the vertical axis.
• The concentration of B is calculated from the
following equation
;

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How to plot the graph?

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Convert to mass percent to mass fraction
Water layer (wt./wt.) Isopropyl ether layer (wt./wt.)

acetic acid water isopropyl ether acetic acid water isopropyl ether
0 0.988 0.012 0 0.006 0.994
0.0069 0.981 0.012 0.0018 0.005 0.993
0.0141 0.971 0.015 0.0037 0.007 0.989
0.0289 0.955 0.016 0.0079 0.008 0.984
0.0642 0.917 0.019 0.0193 0.01 0.971
0.133 0.844 0.023 0.0482 0.019 0.933
0.255 0.711 0.034 0.114 0.039 0.847
0.367 0.589 0.044 0.216 0.069 0.715
0.443 0.451 0.106 0.311 0.108 0.581
0.464 0.371 0.165 0.362 0.151 0.487
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Equilibrium points in the extract
phase (ether layer)

Equilibrium points in the raffinate

phase (water layer)

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Tie lines

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Equilibrium relations in extraction
• Another common type of phase diagram
is shown here, where B and C pair and A
and C pair are partially miscible.

• Examples of such systems are

• Styrene (A)-ethylbenzene (B)-diethylene
glycol (C)
• Chlorobenzene (A)-methyl ethylketone (B)-
water (C)

• This is Type II phase diagram

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Phase splitting of ternary mixtures

components A and C mutually insoluble components A and C partially soluble

Ternary diagrams

Type I Type II
• Most common
• One immiscible pair of compounds • Less common
• Solute and solvent are miscible in all proportions • Two pairs of immiscible compounds
• Larger two-phase region between C-S means greater • Solute and solvent are only miscible
immiscibility between carrier and solvent in certain proportions
• Distance between the top of two phase region to the
apex A indicate the range of feed composition that
can be separated using the solvent S
Example 2: Material Balance for Equilibrium Layers
An original mixture weighing 100 kg and containing 30 kg of isopropyl ether (C), 10 kg of acetic acid
(A) and 60 kg of water (B) is equilibrated and the equilibrium phases separated. What are the
compositions of the two equilibrium phases?

At the extract phase (y-phase), yA=0.04,

yC=0.94. Thus yB=1-0.04-0.94=0.02

At the raffinate phase (x-phase), xA=0.12,

xC=0.02. Thus, xB=1-0.12-0.02=0.86
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 Single-stage Equilibrium Extraction:
Derivation of lever-arm rule for graphical addition.
• This is for use with the rectangular extraction-phase-
diagram charts.
• Fig a): two streams, L kg and V kg containing components
A, B and C are mixed to give a mixture stream M kg total
mass.
• Overall mass balance:
• Balance on A:
• Balance on C:

Derive: and

Obtain:; rearrange:

i.e. the points , , and must lie on a straight line.

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Single-stage Equilibrium Extraction:
Derivation of lever-arm rule for graphical addition.

• Using the properties of similar right

triangles,

Similarly,

The same equations hold for kmol, mol

fraction, lb-mole etc.

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Example 3: Amount of phases in solvent extraction

Use the compositions of the two equilibrium layers in Example 2. For an

original mixture containing 100 kg and , determine the amounts of and
by:

a) Material balance calculation

b) Lever rule method

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Single-stage Equilibrium Extraction
• Example: Separation of from a mixture of and
by a solvent in a single equilibrium stage.
• In Figure a), is solvent inlet, solvent outlet. is
the feed mixture inlet, the stream outlet.
• The exit streams and are in equilibrium.
• Let be the composition of the streams and the
streams.
• Material balance:

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Single-stage Equilibrium Extraction
• Since , an equation for B is not needed.
• To solve the three equations, the equilibrium phase
diagram shown in Figure b) is used.
• Given the amounts and compositions of and , we
can calculate , and .
• The points , , and can be plotted.
• The tie line is drawn through point by
approximation (trial and error or interpolation
between experimental tie lines).
• This locates the compositions of and .
• The amounts of and can be determined by material
balance or by lever arm rule.
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Example 4: Single-stage Equilibrium
Extraction
A mixture weighing 1000 kg contains 23.5
wt.% acetone and 76.5 wt% water and is to
be extracted by 500 kg methyl-isobutyl
ketone (MIK) in a single-stage extraction.

Determine the amounts and compositions

of the extract and raffinate phases.

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 1

0.9

0.8

0.7

0.6

xMIK, yMIK
0.5 distribution curve
V2
0.4 M
L0
0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

xAcetone, yAcetone
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