Course: Chemical Technology (Organic) Module V

Lecture 2
Ethanol As Biofuel And
Chemical Feed Stock




165

LECTURE 2
ETHANOL AS BIOFUEL AND CHEMICAL FEED
STOCK
INTRODUCTION
Alcohol is a key feedstock for the manufacture of basic chemicals. Alcohol based chemical
industry occupies an important place in the Indian chemical industry and is a key contributor to
the growth of the sector. The current size of alcohol based chemical industry is $1.1 billion
(Rs.4850 crores) [Indian chemical industry Five year plan 2012-17, Indian Chemical Industry-
XII Five Year plan, Govt of India]

INDIAN ALCOHOL INDUSTRY
There are 340 distilleries in the country with a capacity of 3,500 million litres. However, the
capacity utilization is low mainly due to non-availability of sufficient molasses. The past
production of alcohol from the ten major producing states viz. Andra Pradesh, Gujarat,
Karnataka, Maharashtra, Tamil Nadu, Uttar Pradesh , Uttaranchal, Bihar, Haryana, and Punjab as
shown in chart. Production has been steadily decreasing from 2,500 million litres in FY07 to
1830 million litres in FY10 registering a negative growth of 10percent PA. Demand and
production of alcohol in India is shown in Figure M-V 2.1 and Figure M-V 2.2.
In India alcohol is mainly produced by the sugar and distillery industries as a byproduct of
molasses fermentation Technologies for producing ethanol from cellulosic biomass through
fermentation and chemical hydrolysis have been developed from lab to commercial scale.
Ethanol thus produced can be a promising chemical feedstock as well as biofuel

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Figure M-V 2.1: Alcohol Production in India


Figure M-V 2.2: Alcohol Demand in India
Source- Working group report on alcohol

ETHANOL AS BIOFUEL
India is now going an unprecedented energy crisis due to dwindling energy resources. The
present import of crudes which is around 180 million tones per annum, is expected to exceed 240
million tones per annum in the next 5 years, if the GDP growth of around 6 to 7percent were to
be sustained [Venkataraman, 2012]. India is also importing 80 million tones per annum of coal.
1,194
1,670
2,503
2,483
2,265
1,830
2004-05 2005-06 2006-07 2007-08 2008-09 2009-10
Alcohol production, India (mn litres)
33%
32%
35%
5% EBP 1,040
Industrial use
1,000
Potable Use 1,100
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Global crude oil prices are also surging unbated as global crude oil is finite and depleting, there
is continuously searching all over the world to go for alternative energy sources. World demand
for energy is expected to double by 2050 and this demand cannot be satisfied with conventional
fuel resources like, crude oil, natural gas and coal [Tuli & Gupta, 2010]. In order to meet the
rising demand of energy and increasing population, alternate energy resources will play a
important role and biofuels based on ethanol are expected to grow rapidly. Biofuels
developments are primarily driven by three fundamental policy considerations: rural
development, energy independence, reduced carbon footprint.
Alcohol has been globally accepted as an alternative to gasoline and alcohol blend gasoline are
being used in many countries in varying proportion ranging from 5-20percent as ethanol. Brazil
which is one of the major sugar producing industry introduced commercial gasoline with ethanol
content of about 25percent. Even ethanol is being sold in Brazil pure ethanol as E-100 fuel.
Ethanol accounts for about 40percent of the fuel consumed by passenger vehicles [Sehagal,
2006]. Brazil and U.S. together account for about 70percent of worlds ethanol production.
Blending characteristics of fuel oxygenates are presented in Table M-V 2.1 [Brockwell et al.,
1991]. US the largest user of gasoline introduced gasoline with 10percent ethanol content.
Similar trend has been observed in several countries [Tuli& Gupta, 2010].
Table M-V 2.1: Blending Characteristics of Fuel Oxygenates
Boiling
Point
(
o
C)
Blending
RVP
(Kg/cm
2
)
Average
Octane
(R+M)/2
Oxygen
content
(wt.%)
Blending limits
(Percentage)
O
2

(vol.%)
O
2

(wt.%)
Ethers
MTBE
ETBE
TAME

131
161
187

8
4
1

110
111
106

18
16
16

15
16
17

2.7
2.0
2.0
Alcohols
Methanol
Ethanol
MeOH
Blend
GTBA

148
173
145/180

181

60
18
31

12

120
115
108

100

50
35
35

21

-
10
9.5

16


3.7
3.7

3.7
Source: Brockwell, H.L., P.R. Sarathy, R. Trotta, Synthesize ethers, Hydrocarbon Processing, Volume
70, No. 7, 1991, p. 133.
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India is currently has a mandate for 5% blending of ethanol in petrol and is being implemented
Through the nationwide Ethanol Blending Program (EBP). About 3.5 billion liters of ethanol are
being produced in about 320 distilleries in India which is enough to cater to the 800 million liters
requirement for 5% blending. However, the national average blending in 2008-09 was only about
2% [Sarangi, 2011].
Gashol is new ecofriendly fuel containing blend of gasoline with 5-10% ethanol from molasses.
Gashol can be also made by blending gasoline and methanol. gashol has higher octaneor
antiknock properties than gasoline and burns more slwly, cooly and completely resulting in
reduced emission [Lawson, 2004]. The octane number of gasoline increases with blending of
5% ethanol by 1.3-3.4 times. blending of ethanol increases the reid vapour pressure and vapour
lock index. ethanol increases the oxygen content of the blend [Raje et al. 2002]

ETHANOL AS CHEMICAL FEED STOCK
Chemical industry utilizes a wide variety of raw materials like petroleum product derived from
crude oil and natural gas, ethanol, coke oven by products like coal tar and other inorganic
constituent. However, ethanol and coal play important role during developing stage of
petrochemical industry by providing feedstock for manufacture of large number of organic
chemical which is now being produced by petroleum route.
India is amongst the top sugar producing industry in the world and produces ethanol from the
byproduct molasses. Between 1960s and 1980s numerous alcohol based plants came in different
part of country manufacturing organic chemicals like ethanol, ethylene, ethylene oxide and
MEG, acetaldehyde acetic acid, acetic anhydride, butanol, ethoxylate, pyridine , picolin
butadiene, synthetic rubber, polymers like polyethylene, PVC etc. Indian glycol, VAM organics
now J ubilant Organosys, Synthetic chemicals and rubber barely, Somaiya chemicals, SD
chemicals, Kanoria chemicals and larger number of plants based on ethanol were started in India.
Selected downstream products of molasses and alcohol is given in Table M-V 2.2. India first
stated ethylene through ethanol route by ICI in Rishra W.B. Product profile of ethanol is given in
Figure M-V 2.3. Bioetahnol based plants has been also started in other part of the world. In
Brazil ethylene derived from ethanol is being used production of polyethylenes.

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Figure M-V 2.3: Product Profile of Ethanol
Source: Mall, 1995, 2007

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Table M-V 2.2: Selected Downstream Products of Alco-Chemicals

Sr.
No.
Alco-chemical Downstream Product
Major application of
downstream product
A. Plastics, Resins, Elastomers
1 Styrene ABS Resins ABS Products
2 Styrene SAN Resins SAN Products
3 Styrene Ion-Exchange Resins
Water Treatment, Effluent
Treatment.
4 Ethylene LDPE LDPE Products
5 MEG Polyester Films Packaging
6 Vinyl Acetate EVA/VAE Polymer
7 Styrene SBR
Tyres, Footwear, Belts and
Rubber Goods
8 Acetic Anhydride/Acid Cellulose Acetate
Bangles, Films, Spectacle
Frames
9 Styrene Poly-Styrene PS Products
10 Styrene PS Foam Packaging
11 Vinyl Acetate Emulsions Adhesives
B. Chemicals
12 Styrene Styrenated Phenol Rubber Chemical
13 Acetic Acid PTA Polyester Feedstock
14 Acetic Acid Di-methyl-Acetamide
Solvent for Acrylic Fibre
Industry
15 Acetic Acid Aceto Acetates
Pharmaceutical & Pesticide
Intermediate
16 Acetic Acid Aceto Acetanilide Dyestuff Intermediate
17 Acetic Acid AcetoAcetanides
18 Acetic Anhydride Paracetamol Pharmaceuticals
19 Acetic Anhydride Aspirin - do -
20 Acetaldehyde Vinyl Sulphone Dyestuff Intermediate
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21 Acetic Anhydride Acetanilide Dyestuff Intermediate

22 Pentaerithritol Emulsions/Dispersions Paint Industry
23 Pentaerithritol PETN Explosives Industry
24 Glyoxal Pharma Drugs & Pharmaceutical
25 Glyoxal Textiles
26 Ethyl Acrylate Emulsions/Dispersions Paint Industry
27 Ethyl Vanillin Flavouring- Formulations Food Processing Industry
28 DDT Formulations Pesticide
29 2,4-D Formulations Pesticide
30 Ethylene Oxide Condensates Various Industries
C. Synthetic Fibres
31 MEG Polyester Fibres
Textiles, Tyre Cord/ Yarn,
Industrial Yarn
32 Chloro Acetic Acid CMC
33 Acetic Acid/ Anhydride Vinyl Acetate Adhesives/Polymers
34 Acetanilide Sulpha Drugs Drugs & Pharmaceuticals
35 Acetanilide Intermediate Dyestuffs
Sources: Alcohol based industry marching into the 21
st
century, Ashok Kadakia, Chemical Business,
J anuary 2000, p.39., Chemical Industry News, match 2003, p.69


INTEGRATION OF SUGAR, PAPER, DISTILLERY AND
CHEMICAL PLANT
Integration of paper-sugar-distillery-Chemical industries with introduction of minor process
modification/intensification could revitalize these interdependent industries. Integration of sugar,
distillery and paper manufacturing, chemical manufacture and waste utilization is given in Figure
M-V 2.4 [Mall, 2012].


172

Figure M-V 2.4: Integration of Sugar, Distillery and paper Manufacturing
and Waste Utilization



173

REFERENCES

1. Brockwell, H.L., Sarathy, P.R. , Trotta, R., Synthesize ethers, Hydrocarbon Processing,
Vol. 70, No. 7, 1991, p. 133.
2. Indian chemical industry Five year plan 2012-17, Indian Chemical Industry-XII Five Year
plan, Govt of India
3. Kadakia A., Alcohol based industry marching into the 21
st
century, Chemical Business,
J anuary 2000, p.39.
4. Lawson,B. Gashol again Oil and gas journal J an19,2004,p.15
5. Mall I.D. Waste utilization and management in sugar and distillery plants, Chemical
Engineering World vol. 30 (1)1995 pp. 51.
6. Mall, I.D Waste management in sugar and distillery plant for Resource generation SGAT
bulletin Volume 13, No.2 December, 2012, p.25
7. Raje, N.R. Indian experiences with the use of ethanol gasoline and ethanol diesel blend
ISAF XIV Technical papers 2002-GS-02
8. Sarangi, S.K. Feb 17-19, 2011 Compendium 16
th
Refinery technology Meet organized by
Centre for high technology & Indian oil corporation, p.161
9. Sehagal, J . M. Emergence of ethanol as global alternative to gasoline, Chemical Weekly
September 26, 2006, and p.193

10. Tuli, D.K., Gupta, R.P. Indian oil alternate and renewable Energy initiatives for sustainable
development, Chemical industry digest August 2010, p.83
11. Venkataraman N.S., Algae biofuel could be India savior, Chemical News, J uly 2012, p.40.