Chemical Industry Digest.

September 2012
CMYK
Ethanol
AUTHORS
Introduction
I
n a distillery unit, sugar in molasses is fermented to pro-
duce ethanol. Figure 1 shows the typical process flow
diagram in a distillery. Fermentation process will pro-
duce an aqueous solution with alcohol content lesser than
12 to 15% since the fermenting yeast is destroyed at these
alcohol concentrations. To produce ethanol of higher con-
centration, the aqueous solution must be distilled. Using
multi pressure distillation, the aqueous solution produces
mixtures that are progressively closer to the azeotropic ra-
tio of 95.5/4.5%.
We all know ethanol water forms a positive azeotrope
having 95.63% ethanol and 4.37% water (by weight). Etha-
nol boils at 78.4
o
C, water boils at 100
o
C, but the azeotrope
boils at 78.2
o
C, which is lower than either of its constitu-
ents. Indeed 78.2
o
C is the minimum temperature at which
any ethanol-water solution can boil at atmospheric pressure.
No number of distillations, however, will ever result in a dis-
tillate that exceeds the azeotropic ratio. The further purifi-
cation of ethanol up to 99.80% is done by dehydration us-
ing molecular sieve dehydration technology.
This technology was introduced more than two decades
ago to dehydrate ethanol. Earlier systems used for this pur-
pose operated in liquid phase and used thermal swing re-
generation process, which made them very energy consum-
ing. Further development in the adsorbents saw introduc-
tion of vapour phase operation with pressure swing regen-
eration system. This proved to be highly energy-efficient. The
molecular sieve has proved to be the ideal solution to bring
down energy consumption and ensure high level of dryness
in the final ethanol product.
Molecular Sieve Dehydration Technology
for Ethanol Dehydration
Nilesh Patil, Dr V S Patil
Today many European countries are
using 10-15% blend of anhydrous
ethanol in petroleum. Molecular sieve
dehydration technology, an adsorption
phenomenon, is the technology used to
produce anhydrous ethanol. The
technology was first used in ethanol
drying in the early 80s.
The very precise pore size of molecular
sieves enables them to select and sieve
molecules of specific size and polarity.
In adsorption, molecules diffuse from
the bulk of the fluid to the surface of the
solid adsorbent forming a distinct
adsorbed phase. These adsorbed
molecules adhere to the surface of
adsorbents due to weak cohesive forces
called van der Waals forces. Separation
by adsorption relies on one component
being more readily adsorbed than the
other. For e.g. in an ethanol water
mixture, water is more readily adsorbed
on zeolite than ethanol.
The article elaborates the recent ad-
vances of this technology along with all
the improvements for the production of
anhydrous alcohol from ethanol.
Nilesh P Patil is Senior Engineer - Process Design, Praj
Industries Ltd. He has 4 years of experience in functional
areas of process design, process development, trouble-
shooting of distillation columns, mass transfer operations
etc. He is an Associate Member of the Institution of
Engineers, Indian Institute of Chemical Engineers, and
the National Foundation of Indian Engineers.
Dr Vilas S Patil is Reader - Chemical Engi-
neering, Department of Chemical Technol-
ogy, North Maharashtra University, Jalgaon.
He has 25 years of experience in mass trans-
fer operations, waste water treatment, corro-
sion engineering, transport phenomena etc.
He is a Life Member Institution of Engineers.
52
Chemical Industry Digest. September 2012
CMYK
Ethanol
A molecular sieve
is a synthetic adsor-
bent. The vapour
phase pressure swing
regeneration system
employs molecular
sieve beds which act
as an adsorbent.
These beds are made
of zeolite with an effec-
tive pore size opening
of about 3. In the
ethanol dehydration
process, the rectified
spirit (hydrated etha-
nol) vapours are al-
lowed to pass through
a column packed with
freshly activated mo-
lecular sieve bed. As
the rectified spirit
vapour enters the
sieve bed, water is dif-
fused and adsorbed
within the pores of the
adsorbent structure in
a thin layer. As more
alcohol enters the col-
umn, it passes
through this layer to a
slightly lower level
where another incremental amount of water is adsorbed.
This continues until a point is reached where all possible
water adsorption from this slug of alcohol is accom-
plished or till the molecular sieve is saturated.
Transfer of water from the vapour of rectified spirit to
the molecular sieve occurs through a zone where water
(adsorbate) content is reduced from its inlet to its outlet
concentration. This finite length of bed, where the adsor-
bate transfer occurs, is known as a
mass transfer zone. Two beds are pro-
vided in order to make the process con-
tinuous. Whilst the active bed is under
pressure carrying out dehydration, the
second bed is under regeneration and
is under vacuum. The swing of opera-
tion from one bed to another is con-
trolled with the help of control valves
and automation.
Principle of Operation
The very precise pore size of mo-
lecular sieves enables
them to select and remove
molecules of particular
size from a bulk mixture
containing molecules
with large sizes and low
polarity.
Fig 2 shows that a mo-
lecular sieve has a porous
structure containing uni-
form cavities of a specific
size. The selection of mo-
lecular sieves depends
mainly on the size of the
molecules to be removed from the mixture of other mol-
ecules. As shown in the figure the water (H
2
O) molecule
having size 3 is easily getting adsorbed in the cavities
present in the molecular sieves, whereas the ethanol
(C
2
H
5
OH) molecule being larger in size than the water
molecule cannot enter the cavities present in the molecu-
lar sieves.
Molecular sieves:
> Separate molecules by size and polarity
> Have very strong affinity for water
> Dehydrate under pressure, regenerate under vacuum.
Fig 2. Cavities in a molecular sieve
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Cyclohexane
Rectified
Spirit
Steam
Dehydration
Column
Absolute Alcohol
Steam
Decanter
CWR
CWS
Alcohol
Recovery
Column
Spent Lees
Fig 3. Process flow diagram for azeotropic distillation
Molasses
Fermentation
Distillation
Rectified Spirit
Dehydration
Anhydrous Alcohol
(96.50% V/V)
(99.80% V/V)
Fig 1. Process flow diagram in a
distillery
Detail Process in a Distillery
Production of Fuel-Ethanol from
Molasses
The water (H
2
O) molecule
having size 3 is easily
getting adsorbed in the
cavities present in the
molecular sieves, whereas
the ethanol (C
2
H
5
OH)
molecule being larger in
size than the water mol-
ecule cannot enter the
cavities present in the
molecular sieves.
53
Chemical Industry Digest. September 2012
CMYK
Ethanol
Comparison of various processes to purify ethanol
Further purification of ethanol to produce anhydrous
alcohol is done by using:
> Azeotropic distillation
> Extractive distillation
> Membrane separation
> Molecular sieve dehydration.
Azeotropic Distillation
Process flow dia-
gram for azeotropic dis-
tillation is shown in Fig
3. Some of the reasons
that make azeotropic
distillation unfeasible
include:
Use of carcinogens
High energy require-
ment
Traces of entrainer
Complex installa-
tion process.
Extractive
Distillation
Fig 4 outlines the
process of extractive
distillation. Extractive
distillation is more ex-
pensive and unfeasible
for use due to:
Uses chemical com-
pounds like glycol
to extract moisture
Requires high pres-
sure steam
Operating cost is
lower than azeotropic distillation but is
still higher than molecular sieve dehy-
dration technology.
Membrane Separation
Membrane separation is more expen-
sive and unfeasible for use due to:
Unavailability of membranes of par
ticular size
Requires high pressure source to pass
the fluid through membrane
Membranes do not have the ability to
separate the selective size molecules.
Molecular Sieve Dehydration
Following points make molecular sieve the most at-
tractive option:
Lower operating costs
No external chemicals required
Highly automated plant
High alcohol recovery.
Fig 5 shows that rectification in addition to water ad-
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Solvent
Rectified
Spirit
Steam
Extractive
Column
Absolute
Alcohol
Spent Lees
Steam
Solvent Recycle
Recovery
Column
CWS
CWR
Fig 4. Process flow diagram for extractive distillation
Adsorption
50
60
80
Rectification

88 90 92 94 96 98
4. 5
4
3. 5
3
2. 5
2
1. 5
1
H
e
a
t
i
n
g

s
t
e
a
m

c
o
n
s
u
m
p
t
i
o
n
,

k
g

p
e
r

k
i
l
o
g
r
a
m

o
f

s
e
p
a
r
a
t
e
d

w
a
t
e
r
Ethanol concentration, % vol
Fig 5. Energy consumption in rectification and water adsorption process
Number of Plates in
Rectification Section
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54
Chemical Industry Digest. September 2012
CMYK
Ethanol
sorption can achieve significant energy savings. The plot
diagram of heating steam consumption vs. ethanol con-
centration (% V/V) of end products from 88 to 96.5%
has been developed on the basis of data collected from
several authors.
From the graph it is clear that as the alcohol concen-
tration in a rectified spirit increases beyond 95%, the en-
ergy consumption grows rapidly, approaching the infi-
nite consumption at azeotrope alcohol concentration. In
contrast, the energy consumption of water adsorption is
independent of the alcohol concentration. The graph also
shows that the energy consumption of alcohol dehydra-
tion solution upto 95% concentration is less in rectifica-
tion process, whereas above this concentration, the en-
ergy consumption is more in rectification process than
in water adsorption.
It can be concluded that significant reduction in en-
ergy consumption of bioethanol technology can be
achieved by reconciling (congruenting) rectification of al-
cohol to water adsorption. The graph also shows that the
potential energy savings can be obtained by combining
rectification of alcohol with water adsorption. In the clas-
sic dehydration bioethanol technology, in which rectify-
ing achieves 96.5% alcohol concentration, one kilogram
of water separation consumes 4.0 kg heating steam. If the
congruent technology relationship between the rectifica-
tion and adsorption of
water be set so that upto
90% concentrations,
rectification is used,
while for further con-
centration water ad-
sorption is used, then
the heating steam con-
sumption will be only
1.8 kg per kilogram of
separated water, that is,
about 55% less.
If 15% energy sav-
ings are added from the
waste water recircula-
tion between the mo-
lecular sieves and the
rectification column, the
used congruent
bioethanol dehydration
technology can bring
significant energy sav-
ings. This technology
not only saves energy
but also simplifies the
equipment design. It is
known that greater is the rectified alcohol concentration,
greater is the number of stages (plates) required in the tra-
ditional rectification column. This, in turn, increases the
tower height. Figure 5 shows that for 95% (V/V) alcohol
concentration, the column requires 50 plates, while for
96.5% (V/V) alcohol concentration reach, the column re-
quires 80 plates.
Conclusion
Molecular sieve technology reduces energy require-
ment and leads to significant savings. This new technol-
ogy allows rectification and significantly reduces the num-
ber of plates in the rectification column and hence the
height of the column. This new technology brings about
technological ease in the design of the process and pro-
cess equipments.
References
1. Lyons T. P., Kelsall D. R., Murtagh J. E. The Alcohol Text-
book Nottingham: University Press, 1995, Page 259.
2. Bremers G., Birzietis G., Blija A., Skele A., Danilevics A.
Bioethanol Congruent Dehydration. Proceedings of 8th In-
ternational Scientific Conference Engineering for Rural De-
velopment, Jelgava, 2009, Page 131-134.
3. Handbook of alcohol production: equipment, means of mechani-
zation and Automation 1983, Page 480.
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Water to Recycle
Purge Revap
Product
98.8%
EtOH
Product
Tank
1/2 Ballast
Two
Units
Condenser
Wire Mesh
Support Screen
1/2 Ballast
1/4Ballast
Purge
Vac for
regeneration
Feed
Super Heater
Sequencing: Adsorption cycle ends,
bed is depressurized & flow is
diverted to the next bottle set for
adsorption. Heat & pressure are
transferred to the next bottle & not
lost.
Distillation/
Rectification
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Fig 6. Process flow diagram for combined bioethanol dehydration technology
57