Azeotrope

152
AZEOTROPE
 An azeotrope is a liquid mixture which when vaporized,
produces the same composition as the liquid, in which its
composition cannot be changed by simple distillation.

 This is because when an azeotrope is boiled, the resulting

vapor has the same ratio of constituents as the original
mixture of liquids.

 As the composition is unchanged by boiling, azeotropes are

also known as constant boiling mixtures.

153
Two Types of Azeotropes:-
(i) Positive Azetropes
 Positive azeotropes are also called minimum boiling
mixtures or pressure maximum azeotropes.

 A well-known example of a positive azeotrope is

95.6% ethanol and 4.4% water (by weight).

 Ethanol boils at 78.4 °C, water boils at 100 °C, but the
azeotrope boils at 78.2 °C, which is lower than either of its
constituents.

 In general, a positive azeotrope boils at a lower temperature

than any other ratio of its constituents.

154
 Pure water
boiling point

Pure ethanol
boiling point

Figure 46. Minimum boiling

azeotropic system

Figure 45. Minimum boiling azeotrope

155
(ii) Negative Azetropes

 Negative azeotropes are also called maximum boiling

mixtures or pressure minimum azeotropes.

 An example of a negative azeotrope is hydrochloric acid at a

concentration of 20.2% and 79.8% water (by weight).

 Hydrogen chloride boils at −84 °C and water at 100 °C, but the
azeotrope boils at 110 °C, which is higher than either of its
constituents.

 In general, a negative azeotrope boils at a higher temperature

than any other ratio of its constituents.

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 Pure water
boiling point

Pure hydrogen
chloride boiling
point

Figure 48. Maximum boiling azeotrope

Figure 47. Maximum boiling azeotrope system

157
Table 1. Azeotropic compostions associated with some liquid mixtures

Mixture Azeotrope (weight%)

Water/ethanol 4.4/95.6
Water/i-propanol 12.2/87.8
Water/t-butanol 11.8/88.2
Water/tetrahydrofuran 5.9/94.1
Water/dioxan 18.4/81.6
Methanol/acetone 12.0/88.0
Ethanol/hexane 21.0/79.0
n-propanol/cyclohexane 20.0/80.0

158
Examples to separate the benezene and cyclohexane azeotropic
mixture:

 Benzene boiling point

80.1oC

 Cyclohexane boiling point

80.7oC

 Benzene and cyclohexane

form azeotrope at 45 vol%
Figure 49. Benzene and cyclohexane cyclohexane
structures

Chemical structures of benzene (top) and cyclohexane (bottom).

Benzene has a planar structure with six equal C–C bonds and
bond angles. Cyclohexane posses a chair conformation.
159
Conventional Separation Processes for Benzene/Cyclohexane (Bz/CH):
(i) Hybrid Process Consisting of Azeotropic Distillation and Extraction

Figure 50. Azeotropic

distillation-extraction
hybrid process

The process consists of a first distillation stage to remove lower

boiling fraction with the aid of an entrainer/auxiliary agent. The
entrainer is then water washed from the distillate and recovered in
a second distillation process. 160
(ii) Extractive Distillation

Figure 51. Extractive

distillation

Separation of benzene/cyclohexane by extractive distillation.

An entrainer/auxiliary agent is added to shift the vapor–liquid
equilibrium curve. Cyclohexane is distilled overhead.
Benzene/entrainer is treated in a secondary distillation
process. 161
Disadvantages of the Conventional Process:-

 high capital and operating cost

 complexity of the process

 need for a secondary distillation of the entrainer/auxiliary

agent

 limited range of feed concentration

162
Introduction to Pervaporation (PV)

Pervaporation = Permeation + Evaporation

Figure 52. Schematic diagram of the pervaporation process

163
Figure 53. Schematic diagram of the pervaporation process:
(a) Vacuum pervaporation, (b) purge gas pervaporation

164
 Circulation pump

Circulation pump
Membrane
cell
Heating
Feed tape
tank

Temperature
Pressure controller
gauge

Vacuum pump
Control valve

Cold traps
with dewar
flaks

Figure 54. Schematic representation of pervaporation

apparatus
165
 the liquid mixture to be separated (feed) is placed in contact
with one side of a membrane and the permeated product
(permeate) is removed as low-pressure vapor from the other
side
 the driving force can be created by applying either a vacuum
pump or an inert purge (normally air or steam) on the
permeate side to maintain the permeate vapor pressure lower
than the partial pressure of the feed liquid
 downstream pressure 1-3 mmHg
 removing all the molecules migrating to the membrane face,
thus rendering a concentration difference across the membrane

166
Pervaporation survives the challenge of phase change by two
features:-

(1) to separate (or better remove) a small amount of liquid (<10

wt.%) from a liquid mixture

(2) good to separate azeotropic composition and closed boiling

mixtures, where distillation is not effective

167
 2 Different Types of Pervaporation-Distillation Hybrid Processes:-
(i) Pervaporation as the final step of a process which achieves
the required concentration of retentate and/or permeate

Figure 55. Ethanol production: Pervaporation-distillation hybrid process with a

pervaporation unit as final step
168
(ii) Pervaporation as a primary process combined with other
steps within a process that then achieves the required
concentration of retentate and/or permeate

Figure 56. Dimethyl carbonate (DMC) production: PV-distillation

hybrid process with PV in front of distillation
169
Advantages of the pervaporation-distillation hybrid process:-

 more cost-effective for separation of azeotropic miscible

liquids

 no entrainers required to affect separation of miscible

mixtures

 significant capital cost and operating cost savings over

conventional systems

 Pervaporation rarely used as a stand alone process unit

 Pervaporation-based hybrid processes are more economically

compared to the conventional separation processes, or
pervaporation alone
170
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