Pira International LTD

Advances in Bioethanol
Pratima Bajpai
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Pira International Ltd 2007
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Contents
List of tables v
List of figures vi
Introduction 1
Background 1
Scope of the report 8
Methodology 9
Glossary 9
Ethanol: an overview 13
Key drivers 13
Trends 14
Chemistry 15
Types of ethanol 16
Sources 16
The energy balance of ethanol 19
Future of bioethanol 21
Production of bioethanol 23
Production of alcohol from corn 24
Dry milling 27
Wet milling 28
New technologies 28
Co-products 28
Production of ethanol from lignocellulosic
biomass 29
Pre-treatment 30
Hemicellulose hydrolysis 31
Cellulose hydrolysis 33
Fermentation 37
Product recovery 39
Recycling of process stream 40
Page iii
Copyright Pira International Ltd 2007
Promising developments in the

production of ethanol from
cellulose 41
Estimates of production costs of bioethanol
from different raw materials 47
Markets for bioethanol 49

Oxygenated and reformulated fuels 50
E5 51
E10 (gasohol) 51
E15 52
E20 52
E85 52
E95 54
E100 54
Niche markets 55
Fuel cells 55
E diesel 55
Aviation 56
Snowmobiles 56
Boats/marine 56
Small-engine equipment 57
6
7
Characteristics of ethanol 59
Using ethanol in engines 62
Fuel economy 64
Benefits of bioethanol 65
Environmental benefits 67
Carbon dioxide 67
Carbon monoxide 68
Contents
Nitrous oxide 68
Other octane additives 68
Ozone 68
Particulate matter 69
Lead 69
Environmental behaviour 69
Health effects 70
Summary 71
Problems with ethanol/ethanol

blends 73
Storage 73
Transportation 73
Corrosion 73
Solvent effect 73
Separation of layer 74
Combustion 74
Effect on other vehicle parts 74
Scale of operation 74
Environment 75
Page iv
Bioethanol worldwide 77
EU 77
France 80
Germany 80
Spain 80
Sweden 81
Poland 81
Austria 82
Italy 82
UK 82
Australia 83
China 83
US 84
Brazil 88
Canada 91
India 91
Thailand 92
Japan 92
References 95
List of tables
1.1Biofuels summary 1
1.2Pros and cons of ethanol fuel 3
1.3Reductions in per-mile GHG
emissions by ethanol blend to
displace an energy-equivalent
amount of gasoline 5
1.4GHG emission reduction per
gallon of ethanol to displace an
energy-equivalent amount of
gasoline 5
1.5World ethanol production in 2006 7
1.6Ethanol production in the US,
19802006 7
2.1Properties of bioethanol 16
2.2Feedstocks for bioethanol
production 17
2.3Typical composition of lignocellulosic
biomass 18
2.4Ethanols net energy value:
a summary of major studies,
19952005 20
3.1First- and second-generation raw
materials for ethanol production 23
3.2Composition of corn 27
3.3Comparison of various pre-treatment
options 33
Page
3.4Comparison of the different cellulose

hydrolysis processes 37
4.1Companies developing biofuel
technologies 44
6.1Properties of fuel ethanol 59
6.2Ethanol emissions compared to
gasoline 60
6.3Comparison of fuel properties 60
6.4Volumetric energy density of ethanol
compared to gasoline and other
fuels 61
9.1EU bioethanol fuel production,
200406 78
9.2EU: leading ethanol producers 79
9.3Ethanol industry expansion in the
US, 200007 84
9.4US ethanol statistics, 200506 85
9.5Ethanol imports in the US, 2006 85
9.6Top ten ethanol producers by
capacity in the US, 2006 85
9.7Flexi-fuel cars sold in Brazil,
200306 89
9.8Ethanol production costs in different
countries 89
List of figures
1.1The carbon cycle 3

1.2World ethanol production,
19802006 6
3.1Ethanol production from corn by the
wet milling process 25
3.2Ethanol production from corn by the
dry milling process 26
3.3Distillers grains from US ethanol
refineries 29
3.4Biomass to ethanol process 30
Page vi
3.5SHF with separate pentose and

hexose sugars and combined sugar
fermentation 35
3.6SSF with combined sugars (pentoses
and hexoses) 35
4.1Iogens cellulose ethanol process 41
4.2Celunol process for production of
ethanol from biomass 43
9.1EU: bioethanol fuel production,
19932006 79
9.2Ethanol production in Brazil,
19822006 88
Introduction
Background
The 1970 energy crisis stimulated research into alternative fuels, with an objective
to reduce the dependency on oil in the strategic sector of transport (Wyman and
Hinman, 1990; Lynd and Wang, 2004; Herrera, 2004; Tanaka, 2006; Dien et al., 2006; Sun
and Cheng, 2004; Yacobucci and Womach, 2003; Chandel et al., 2007; Gray et al., 2006;
Kheshgi et al., 2000). At present, one of the main reasons for the interest in renewable
biofuels is the possibility of obtaining a considerable reduction of noxious exhaust
emissions from combustion, particularly as statutory limits are becoming more stringent
and more exhaust components are regulated. Table 1.1 summarises the developments.
TABLE 1.1 Biofuels summary
What are biofuels?
General definition: Biofuel is a generic term
for any liquid fuel produced from sources other
than mineral reserves such as oil, coal and
gas. In general, biofuels can be used as a
substitute for, or additive to, petrol and diesel
in most transport and non-transport
applications
Biomass means any plant-derived organic
matter available on a renewable basis

Examples: ethanol, methanol, Fischer-Tropsch
diesel, gaseous fuels such as hydrogen and
methane

The most popular biofuels are ethanol
and biodiesel

Benefits of biofuels
Reduced dependency on fossil fuel
Reductions in GHG (greenhouse gas) emissions

(biofuels recycle carbon dioxide that is extracted
from the atmosphere in producing biomass).
Ethanol produced from corn can achieve moderate
reductions in GHG emissions whereas ethanol
produced from cellulosic plants can achieve much
greater energy and GHG benefits
Reductions in air pollution
No new logistics and infrastructure required
Supportive of local agriculture
Source: Pira International Ltd
Wider use of a chemically simple fuel such as bioethanol will mean that there are less
harmful effects on life and ecosystems. In particular, people living in urban areas may
in future appreciate the use of improved low-emission vehicles that do not smell, are
smokeless and are propelled either by reformulated bioethanol, by bioethanol blended
with gasoline or by neat biofuels. How the air quality can be improved is something that
is increasingly worth investigating for the sake of people and the environment.
Large-scale, sustainable, worldwide production and use of bioethanol from biomass
resources will produce tangible significant benefits for our growing and fast-evolving
society and also for the earths climate. The following list summarises the factors
favouring bioethanol.

Bioethanol
is a proven global transport fuel, presently supplying 1.2% of the worlds
petrol.

It
can be produced from virtually any organic material which means that it is a secure
form of energy and in the long run will be relatively cheap.

Page
Introduction
Bioethanol contains more useful energy than is required to produce it.
Bioethanol
reduces emissions of greenhouse gases, of carcinogens such as benzene and
of other harmful emissions such as particulates. It is biodegradable in water and soil.

Biofuel
industries provide economic development and employment in rural areas. The
World Bank reports that biofuel industries require about 100 times more workers per
unit of energy produced than the fossil fuel industry.

Bioethanol
enhances competitiveness through the development of new and efficient
technologies. Above all, it offers the prospect of converting lignocellulose into

fuel. This will, at a stroke, further improve energy security, reduce greenhouse gas
emissions and broaden economic development and employment opportunities.

Even
with subsidies, the economic savings with bioethanol from avoided oil imports
are considerable.

Bioethanol
has the potential to be used in compression engines as well as spark
ignition engines.

Bioethanol
is unique amongst todays sustainable transport fuel options in that it
can be used in internal combustion engines but is also a perfect fuel source for the
hydrogen fuel cell. So its development now offers a seamless transition into the
hydrogen energy system of the future.

Important environmental benefits could be achieved in the socio-economic development

of large rural populations and the diversification of energy supply, in particular for the
strategically vital sector of transport (Turkenberg, 2000). A life-cycle analysis of ethanol
production from field to the car by the US Department of Agriculture found that
ethanol has a large and positive energy balance. Ethanol yields 134% of the energy used
to grow and harvest the corn and process it into ethanol. By comparison gasoline yields
only 80% of the energy used to produce it. Bioethanol does not add to global CO2 levels
because it only recycles CO2 already present in the atmosphere. See Figure 1.1.
Page
Introduction
FIGURE 1.1 The carbon cycle

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More specifically, CO2 is removed from the atmosphere through photosynthesis when
crops intended for conversion to bioethanol are grown. CO2 is then released into the
atmosphere during combustion. In contrast, burning a fossil fuel such as petrol adds
to global CO2 because it releases new amounts of CO2 that were previously trapped
underground for millions of years. Finally, unlike oil, bioethanol is a renewable fuel, which
inherently helps the environment by allowing us to conserve other energy resources. The
pros and cons of ethanol fuel are detailed in Table 1.2.
TABLE 1.2 Pros and cons of ethanol fuel
Pros
Positive net energy balance
Reduced air pollution
Carbon cycle maintains a balance of carbon
dioxide in the atmosphere when ethanol is
used as a fuel source
Reduced dependence on foreign oil

Page
Cons
Reduced fuel economy
Gas cost for consumer initially similar
Many modern cars cannot run ethanol
concentrations higher than E10 gasohol
under warranty
Ethanol-powered vehicles will have trouble
starting at low temperatures
Introduction
TABLE 1.2 (Continued)

Pros
Smooth transition from gasoline through
alcohol mixtures
Will slow global warming
Greater production at refineries
Cons
Vehicles need alteration to run on ethanol
It is harder to transport
Ethanol is already commonly used in a 10% ethanol/90% gasoline blend. Adapted

internal combustion engine vehicles (ICEVs) can use a blend of 85% ethanol/15%
gasoline (E85) or even 95% ethanol (E95). Addition of ethanol increases octane and
reduces CO, volatile organic compounds (VOCs) and particulate emissions of gasoline.
And, via on-board reforming to hydrogen, ethanol is also suitable for use in future fuel
cell vehicles (FCVs). Those vehicles are supposed to have about double the current ICEV
fuel efficiency (Lynd, 1996). Beginning with the model year 1999, an increasing number of
vehicles in the world are manufactured with engines which can run on any gasoline from
0% ethanol up to 85% ethanol without modification. Many light trucks are designed to
be dual fuel or flexible fuel vehicles, since they can automatically detect the type of fuel
and change the engines behaviour, principally the air-to-fuel ratio and ignition timing, to
compensate for the different octane levels of the fuel in the engine cylinders.
Ethanol has three major uses: as a renewable fuel, as a beverage and for industrial
purposes. Of the three grades of ethanol, fuel grade ethanol is driving record ethanol
production in many countries. About 95% of all ethanol is derived from sugar or
starch crops by fermentation; the rest is produced synthetically. The synthesis route
involves dehydration of hydrocarbons (e.g. ethylene) or by reaction with sulphuric
acid, to produce ethyl sulphate, followed by hydrolysis. The production routes from
biomass are based on fermentation or hydrolysis. According to FO Licht (Berg 2004),
synthetic alcohol production is concentrated in the hands of a few, mostly multinational,
companies such as:

Sasol, with operations in South Africa and Germany
SADAF of Saudi Arabia
A 50:50 joint venture between Shell of the UK and the Netherlands
The Saudi Arabian Basic Industries Corporation
BP of the UK
Equistar in the US.
Fermentation ethanol is mainly produced for fuel, though a small share is used by
the beverage industry and the industrial industry. The bulk of the production and
consumption is located in Brazil and the US. Fermentation technologies for sugar and
starch crops are very well developed but have certain limits these crops have a high
value for food application, and their sugar yield per hectare is very low compared with the
Page
Introduction
most prevalent forms of sugar in nature (cellulose and hemicellulose). Suitable processes
for lignocellulosic biomass therefore have room for further development:

A bigger crop variety can be employed
A larger portion of these crops can be converted.
Hence larger scales and lower costs are possible. There is a copious amount of
lignocellulosic biomass worldwide that can be exploited for fuel ethanol production.
According to the US Department of Energy, cellulosic ethanol reduces greenhouse gas
emissions by 85% over reformulated gasoline.
TABLE 1.3 Reductions in per-mile GHG emissions by ethanol blend to displace an
energy-equivalent amount of gasoline
Ethanol blends
E10 GV: DM
Corn ethanol
E10 GV: WM
Corn ethanol
E10 GV:
Cellulosic ethanol
E85 FFV: DM
Corn ethanol
E85 FFV: WM
Corn ethanol
E85 FFV:
Cellulosic ethanol
Reduction (%)
2
2
6
23
17
64
Note: GV = gasoline vehicle; FFV = flexible fuel vehicle; DM = dry milling; WM = wet milling
Source: Based on data from Wang (2005)
TABLE 1.4 GHG emission reduction per gallon of ethanol to displace an
energy-equivalent amount of gasoline
Ethanol blends
E10 GV: DM
Corn ethanol
E10 GV: WM
Corn ethanol
E10 GV:
Cellulosic ethanol
E85 FFV: DM
Corn ethanol
E85 FFV: WM
Corn ethanol
E85 FFV:
Cellulosic ethanol
Reduction (%)
26
18
85
29
21
86
Note: GV = gasoline vehicle; FFV = flexible fuel vehicle; DM = dry milling; WM = wet milling
Source: Based on data from Wang (2005)
Page
Introduction
By contrast, sugar-fermented ethanol reduces greenhouse gas emissions by 1819%

compared with gasoline. Dan Sperling, UCD professor and director of the Institute of
Transportation Studies has commented that ethanol from cellulose is a great energy
strategy because for every gallon of ethanol, a small amount of fossil material is used. It
is much better from an energy perspective as a dramatic reduction in greenhouse gases is
observed. Ethanol-blended fuels reduced CO2-equivalent GHG emissions by approximately
7.8 million tonnes in 2005 which is equivalent to removing the annual GHG emissions
of 1.18 million cars from the road (RFA, 2006a). Beyond added environmental benefits,
cellulose-based ethanol could offer additional revenue streams to farmers for the
collection and sale of currently unused corn stover (leaves, stalks and cobs) or straw, for
example.
Close analysis of the current production and future expansion of ethanol production
in the US, Brazil and worldwide reveals that the generation of ethanol can hardly be
identified as a trend anymore: it is a well-defined and planned expansion programme
(Berg, 2004; Paszner, 2006). Most major oil-consuming or agricultural exporting countries
either have or are considering public policies to introduce ethanol as a blend agent into
their gasoline supplies. Many are encouraging ethanol production (BP, 2006). Total world
ethanol production increased substantially in 2006 totalling 13.5 billion gallons, with 70%
of this total produced by the US and Brazil. Other significant producers are China, India
and the EU (RFA, 2007a).
FIGURE 1.2 World ethanol production, 19802006 (million gallons)

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Source: Based on data from RFA (2006a, 2007a); www.earth-policy.org/Updates/2005/Update49_data.htm
Page

Introduction
TABLE 1.5 World ethanol production in 2006 (%)

US
Brazil
China
India
Others
39.1
33.3
7.5
3.7
16.4
Source: Based on data from RFA, 2007a

TABLE 1.6 Ethanol production in the US, 19802006
Year
1980
1981
1982
1983
1984
1985
1986
1987
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
Million gallons
175
215
350
375
430
610
710
830
845
870
900
950
1,100
1,200
1,350
1,400
1,100
1,300
1,400
1,470
1,630
1,770
2,130
2,810
3,410
3,900
4,900
Source: Based on data from RFA, 2006c, 2007a
Fuel ethanol production has been on the rise in the US since 1980, though production has
increased dramatically since 2001. US ethanol production is expected to grow from 4.9
billion gallons/yr in 2006 to 7.5 billion gallons/yr by 2013 (Jessel, 2006). The production
and use of nearly 5 billion gallons of domestic ethanol in the US reduced CO2-equivalent
GHG emissions by approximately 8 million tonnes in 2006. That would be the equivalent
of removing 1.21 million cars from US roads.
In Europe and other parts of the world, high gasoline prices and an urgency to find
cleaner fuel additives has increased the interest in ethanol production as well. However,
Page
Introduction
the quantity of production still lags far behind Brazil and the US. The primary reason
for this is said to be a lack of a single biomass source that would help standardise the
industry, although other economic hurdles also still exist. Asias three main countries
involved in the development of ethanol production are China, Thailand and India. China
has built the worlds biggest ethanol plant and is planning another just as big.

The technology on the whole has risen ever since the modest inception of a sizeable
ethanol industry, thus developing lower-cost methods of producing greater quantities of

fuel ethanol which are simultaneously more efficient in their use of fossil fuel inputs. These
combined effects have helped the production of ethanol fuel to increase in the US by more
than 225% between 2001 and 2005 (RFA, 2006a). Ethanol has also been used outside the
US, most notably in Brazil which started a programme of government-mandated ethanol
production in 1975 and has since encouraged production of flex-fuel vehicles (FFVs)
and cars fuelled entirely by ethanol (Luhnow and Samor, 2006). Due to its geographic
advantage in growing sugar cane (an ideal ethanol feedstock), Brazil is one of the biggest
producers of ethanol. Brazil is so efficient that it can produce a gallon of ethanol for
about 0.73 (Luhnow and Samor, 2006). The Brazilian ethanol market, which was once
dependent on governmental regulation and subsidies, has blossomed into a system that
thrives even without regulation. Fuel ethanol production in the US caught up with that
in Brazil for the first time, growing by 15% in 2005, as both remained the dominant
producers (REN21, 2006). Although there are cultural and institutional differences between
the US and Brazil, the general pattern of ethanol production and consumption under a
regulatory environment in the US could closely mirror what has happened in Brazil. Their
policy effectiveness can be used as a benchmark for the US market.
Scope of the report
This report covers bioethanol that is predominantly produced from biomass, including
living organisms or their metabolic by-products. Bioethanol produced from traditional
biomass, for example fuel wood and charcoal, etc. as used in developing countries, falls
outside the scope of this report. This report provides a general background and looks at
the key drivers and the recent trends, chemistry, types of ethanol, sources and production
of the first- and second-generation bioethanol. For first-generation bioethanol, the
production technologies have already been developed and can be implemented directly.
For second-generation bioethanol, the production technologies need to be developed
further before their production is possible on a large scale.
This report also discusses the advantages, biotechnology breakthroughs and
promising developments in the production of cellulosic ethanol. Furthermore, it addresses

the end-use application of bioethanol as a transportation fuel and the smaller niche
markets such as fuel-cell applications, E diesel, aviation, etc. where ethanol can be
utilised. It also presents information about the benefits, problems, environmental effects
and characteristics of fuel ethanol. Finally, the report provides detailed information about
the use of ethanol in different parts of the world and also highlights the challenges and
future of ethanol.
Page
Introduction
Methodology
Information has been collected from scientific literature, reports from international
and national agencies, websites, conference presentations, patent literature, statistics
databases, small and medium-sized biotechnology companies and university research
groups.
Glossary
Alcohol: The family name of a group of organic chemical compounds composed of carbon,
hydrogen and oxygen. The molecules in the series vary in chain length and are composed
of a hydrocarbon plus a hydroxyl group. Examples are methanol, ethanol, etc.
Anhydrous ethanol: This is water free or absolute. The 95% pure product is dehydrated
using a molecular sieve or azeotropic processes to remove the water, resulting in 99%
pure ethanol. Anhydrous ethanol is normally blended with 1025% petrol for use in most
unmodified or slightly modified engines or as a 3% blend in diesel.
Bacteria: Single-celled micro-organisms which can exist either as independent organisms

or as parasites that break down the wastes and bodies of dead organisms, making their
components available for reuse by other organisms.
Bagasse: The fibrous material left after the extraction of juice from the sugar cane. It is
often burned by sugar mills as a source of energy.
Biodiesel: Biodiesel is a general name for methyl esters from organic feedstock. Biodiesel
can be made from a wide range of vegetable oils, including rapeseed, and competitor
oils such as sunflower, palm oil and soy. It can also be derived from animal fats, grease
and tallow. Rapeseed is one of the main oil-seed crops grown in Europe and is the most
common feedstock used for biodiesel production. The oil undergoes a chemical process
(esterification) to make a methyl ester which has similar fuel specifications to fossil diesel.
Bioenergy: Energy (fuel, electricity, heat) produced from biomass.
Bioethanol: Ethanol produced from biomass feedstocks. This includes ethanol produced
from the fermentation of crops such as corn, as well as cellulosic ethanol produced from
woody plants or grasses. E5 contains 5% ethanol and 95% gasoline; E10 contains 10%
ethanol and 90% gasoline; E15 contains 15% ethanol and 85% gasoline; E20 contains
20% ethanol and 80% gasoline; E25 contains 25% ethanol and 75% gasoline; E85
contains 85% ethanol and 15% gasoline; E95 contains only 5% gasoline and 95% ethanol
and E100 is straight ethanol, which is most widely used in Brazil and Argentina.
Biofuel: Liquid or gaseous fuel for transport, produced from biomass.
Page
Introduction
Biomass: Organic matter available on a renewable basis. Biomass includes forest and mill
residues, agricultural crops and waste, wood and wood waste, animal waste, livestock
operation residues, aquatic plants, fast-growing trees and plants, municipal and industrial
waste, etc.
Biorefinery: A facility that processes and converts biomass into value-added products.
These products can range from biomaterials to fuels such as ethanol or important
feedstocks for the production of chemicals and other materials. Biorefineries can be
based on a number of processing platforms using mechanical, thermal, chemical and
biochemical processes.
Cellulase: Cellulase is an enzyme that hydrolyses cellulose to its constituent

monosaccharide (glucose) and disaccharide (cellobiose) units.
Cellulosic biomass: Biomass composed primarily of inedible plant fibres having cellulose
as a prominent component. These fibres may be hydrolysed to yield a variety of sugars
that can subsequently be fermented by micro-organisms. Examples of cellulosic biomass
include grass, wood and cellulose-rich residues resulting from agriculture of forest
products.
E diesel: Blends containing up to 15% ethanol, blended with standard diesel and a
proprietary additive, are called E diesel.
Emissions: Waste substances released into the air or water.
Energy crops: Crops grown specifically for their fuel value. These include food crops
such as corn and sugar cane, and non-food crops such as poplar trees and switchgrass.
Currently, two energy crops are under development: short-rotation woody crops, which are
fast-growing hardwood trees harvested in 58 years, and herbaceous energy crops, such
as perennial grasses, which are harvested annually after taking 23 years to reach full
productivity.
Enzyme: Protein that acts as a catalyst, or biocatalyst, in living organisms.
Ethyl tertiary butyl ether (ETBE): This is produced from bioethanol. This is used as a fuel
additive to increase the octane rating and reduce knocking.
Ethanol: Also known as ethyl alcohol, alcohol or grain-spirit. This is a clear, colourless,
flammable oxygenated hydrocarbon with a boiling point of 78.5C in the anhydrous state.
In transportation, ethanol is used as a vehicle fuel by itself (E100 100% ethanol by
Page 10
Introduction
volume), blended with gasoline (E85 85% ethanol by volume), or as a gasoline octane
enhancer and oxygenater (10% by volume). It is produced by fermenting biomass high
in carbohydrates. Most ethanol is made using sugars and starches, but researchers are
working to more efficiently make alcohol from cellulose and other polymers in plants.
Ethanol made from cellulosic biomass is called cellulosic ethanol.

Feedstock: The source of carbon for production of organic fuels and chemicals via
industrial processes.
Fermentation: Conversion of carbon-containing compounds by micro-organisms for

production of fuels and chemicals such as alcohols, acids or energy-rich gases.
Flexible fuel vehicle (FFV): Vehicles whose engines can be operated with petrol as well as
with E85 or any interim products.
Fossil fuel: Solid, liquid or gaseous fuels formed in the ground after millions of years by
chemical and physical changes in plant and animal residues under high temperature and
pressure. Oil, natural gas and coal are fossil fuels.
Fuel cell: A device that converts the energy of a fuel directly to electricity and heat
without combustion.
Fuel ethanol: A liquid transportation fuel, which accounts for roughly two-thirds of world
ethyl alcohol. Most fuel ethanol is made from sugar cane, corn and other starch crops.
Fungi: Superficially this resembles a plant, but it does not have leaves and roots, and it
lacks chlorophyll, so that it must obtain its nutrients from other organisms by living either
as a parasite on living organisms or as a saprophyte on dead organic matter.
Gasoline: A liquid fuel for use in internal combustion engines where the fuelair mixture
is ignited by a spark. It consists of a mixture of volatile hydrocarbon derived from the
distillation and cracking of petroleum. It normally contains additives such as lead
compounds or benzene to improve performance (the prevention of premature ignition) or
rust inhibitors. It is also called gas (in the US) or petrol.
Greenhouse effect: The effect of certain gases in the Earths atmosphere that traps heat
from the sun.
Greenhouse gases: Gases that trap the heat of the sun in the Earths atmosphere,
producing the greenhouse effect. The two major greenhouse gases are water vapour and
Page 11
Introduction
carbon dioxide. Other greenhouse gases include methane, ozone, chlorofluorocarbons and
nitrous oxide.

Hemicellulase: An enzyme that breaks down hemicellulose, which is not as complex as

cellulose and is easier to break down.
Hemicellulose: A type of polysaccharide found in plant cell walls, which is broken down
more easily than cellulose, the main component of the cell walls.
Hydrous ethanol: This can be used as a pure form of fuel in specially modified vehicles. It
has a purity of about 95% plus 5% water. Brazil is the only country that produces vehicles
that run on this form of ethanol.
Lignin: The structural constituent of wood and (to a lesser extent) other plant tissues,
which encrusts the cell walls and cements the cells together. It is not fermentable.
Mannanase: This is an enzyme that breaks down mannans. Mannans are mannosecontaining polysaccharides found in plants as storage material, in association with
cellulose (as hemicellulose).
Methyl tertiary butyl ether (MTBE): This is methyl tertiary butyl ether produced from
methanol and it is used as a fuel additive to increase the octane rating and reduce
knocking. It does not biodegrade and can contaminate groundwater.
Starch: Starch is a polymer made from thousands of glucose units.
Sustainable: An ecosystem condition in which biodiversity, renewability and resource

productivity are maintained over time.
Synthetic ethanol: Ethanol produced from ethylene, a petroleum by-product.
Xylanase: An enzyme that digests xylans and xylose, components of the plant cell wall.
These are used in animal feed and added to cereal-based diets to aid the efficiency of
carbohydrate breakdown. It is also used in the pulp and paper industry to cut and remove
hemicelluloses from fibres.
Yeast: A general term including single-celled, usually rounded fungi that produce
by budding. Some yeasts transform to a mycelial stage under certain environmental
conditions, while others remain single celled. They ferment carbohydrates.
Page 12
Ethanol: an overview
This chapter considers the key drivers, trends, chemistry, types, sources, energy balance
and future of bioethanol.
Key drivers
The forces pushing for ethanol fuel vary considerably, but there are some common
features (Rosillo-Calle and Walter, 2006; FAO, 2006; Hazell and Pachauri, 2006;
Bergstrom, 2007):
Environmental:
around the world concern with clean air is a social and political
priority. For example, the necessity to reduce pollutant emissions and achieve targets
defined by the Kyoto Protocol.

Energy
security: increasing dependency on imported energy supply, especially in a
context of rising oil prices, is also a general concern, particularly in the US and EU.

Social
and economic pressures: for example, the desire to support rural development
and to generate jobs.

In recent years, there has been growing interest regarding the use of renewable biofuels
in the transport sector, ethanol and biodiesel being the best short-term alternatives. More
than 30 countries have introduced or are interested in introducing programmes for fuel
ethanol (Rosillo-Calle and Walter, 2006). Other countries have done the same regarding
biodiesel, but to a lesser extent. Thus, the ethanol experience is so far much more
important than with biodiesel, excluding Europe where the prospects for biodiesel use are
much better than fuel ethanol due to the availability of feedstock.
Developing countries have a reasonably good potential for biofuels production due to
the availability of land, better weather conditions and the availability of a cheaper labour
force. Another important issue to be taken into account is that it is imperative for these
countries to strengthen their rural economies. Obviously each country is different, and a
careful analysis is required to assess the pros and cons of large-scale biofuels production,
particularly with regard to competition for land and water for food production and
potential pressures on food prices (Hazell and von Braun, 2006).

Another important driving force for ethanol production is the generation of a huge
amount of new employment. The ethanol industry in Brazil is responsible for about one
million direct jobs, approximately 50% of them being in sugar cane production. Indirect
jobs are estimated at 2.53 million. However, it should be mentioned that this high
employment is partly due to the low level of mechanisation of agricultural activities, as
well as poor automation at the industrial site.

From an environmental perspective, first the benefits of phasing out lead from
gasoline should be highlighted, as lead has adverse neurological effects. Hydrated ethanol
has a higher level of octanes than regular gasoline (Joseph, 2005), and its use in blends
allows the phasing out of lead at a low cost. This would be a very important advantage of
ethanol use in countries where lead is still in use, as is the case of many African and some
Asian and Latin American countries.

In order to protect the environment, developing countries need to change over to
clean and renewable fuel from crude oil-based fuels. Large-scale use of biofuels is one
Page 13
of the main strategies for the reduction of GHG emissions (IPCC, 2001). Despite the fact
that developing countries currently do not have binding GHG reduction targets under the
Kyoto Protocol, two main aspects should be considered:

U
nder
the clean development mechanism (CDM), developing countries can sell credits
to those with reduction commitments. Considering a typical Brazilian figure of 2.7kg

of CO2 equivalent avoided per litre of anhydrous ethanol, biofuels use could represent
additional income of $0.02$0.05 (0.01460.0365) per litre (on credits in the
range $7$20 per tonne of CO2 equivalent), value that should be compared with
production costs in the $0.23$0.28 per litre range (Nastari; Nastari et al., 2005).

Climate change effects are supposed to be worst in developing countries so it is

important to take action.
Trends
The international market in fuel ethanol is in its initial stage and its full development will
require:
T
he
diversification of production in terms of both feedstocks and the number of
Technological development in the manufacturing field;
Favourable policies to induce market competitiveness;
Sustainable development.
(Rosillo-Calle F and Walter A, 2006).
producing countries;
Bioethanol production based on lignocellulosic biomass is the technology of the
future. Lignocellulosic ethanol is made from a wide variety of plant materials, including
wood wastes, crop residues and grasses, some of which can be grown on marginal lands
not suitable for food production (Ghosh and Ghose, 2003). Lignocellulosic raw materials
minimise the potential conflict between land use for food and feed production and energy
feedstock production. The raw material is less expensive than conventional agricultural
feedstock and can be produced with lower input of fertilisers, pesticides and energy.
Biofuels from lignocellulose generate low net GHG emissions, reducing environmental
impacts, particularly climate change (Hahn et. al, 2006).

Global ethanol production more than doubled between 2000 and 2005, while
production of biodiesel, starting from a much smaller base, expanded nearly fourfold. In
contrast, oil production increased by only 7% over this period. In 2005, ethanol comprised
about 1.2% of the worlds gasoline supply by volume and about 0.8% by transport distance
travelled (due to its lower energy content). From 2002 to 2004, world oil demand increased
by 5.3%. Chinas consumption alone increased by 26.4%, while consumption in the US
increased by 4.9%; Canada 10.2%; and the UK 6.3%. Demand in Germany and Japan,
meanwhile, reduced by 1% and 2.6% respectively. The World Bank reports that biofuel
industries require about 100 times more workers per unit of energy produced than the fossil
fuel industry. The ethanol industry is credited with providing more than 200,000 jobs
Page 14
in the US and half a million direct jobs in Brazil. Transportation, including emissions from
the production of transport fuels, is responsible for about one-quarter of energy-related
greenhouse gas (GHG) emissions, and that share is rising.

The GHG balance of biofuels varies dramatically depending on such factors as
feedstock choice, associated land use changes, feedstock production systems and the type
of processing energy used. In general, most currently produced biofuels have a solidly
positive GHG balance. The greatest GHG benefits will be achieved with cellulosic inputs as
mentioned above. Energy crops have the potential to reduce GHG emissions by more than
100% (relative to petroleum fuels) because such crops can also sequester carbon in the
soil as they grow. The estimated GHG reductions for different feedstock are:

Fibres (switchgrass, poplar): 70110%
Wastes (waste oil, harvest residues, sewage): 65100%
Sugars (sugar cane, sugar beet): 4090%
Vegetable oils (rapeseed, sunflower seed, soya beans): 4575%
S
tarches
Major research challenges in the field of bioethanol production based on lignocellulosic
(corn, wheat): 1540%.
biomass are:

Improving the enzymatic hydrolysis with efficient enzymes.
Reduced enzyme production cost and novel technology for high solids handling.
D
eveloping
robust fermenting organisms which are more tolerant of inhibitors
and ferment all sugars in the raw material in concentrated hydrolysates at high
productivity and with high concentration of ethanol.

E
xtending
process integration to reduce the number of process steps and the energy
demand and to reuse process streams for eliminating the use of fresh water and to
reduce the amount of waste streams.

(Hahn et al., 2006).
Ethanol is a clear, colourless, volatile, flammable liquid that is the intoxicating agent in
Chemistry
liquors and is also used as a fuel or solvent. Ethanol is also called ethyl alcohol or grain
alcohol. Ethanol is the most important member of a large group of organic compounds
that are called alcohol. It may be shown as:
H H
| |
HCCOH
| |
H H

or
CH3CH2OH
In its pure form, ethanol is a colourless clear liquid with a mild characteristic odour.
Ethanol melts at 114.1C, boils at 78.5C and has a density of 0.789g/ml at 20C.
Page 15
TABLE 2.1 Properties of bioethanol

Physical properties
Specific gravity
Vapour pressure (38C)
Boiling temperature
Dielectric constant
Solubility in water
Chemical properties
Formula
Molecular weight
Carbon (wt)
Hydrogen (wt)
Oxygen (wt)
C/H ratio
Stechiometric ratio (AIR/ETOH)
Thermal properties
Lower heating value
Ignition temperature
Specific heat (Kcal/Kg C)
Melting point
0.79g/cm3
50mmHg
78.5C
24.3
C2H5OH
46.1
52.1%
13.1%
34.7%
4
9.0
6,400Kcal/kg
35C
0.60
115C
Source: Based on data from EUBIA (2006)
Ethanols low freezing point has made it useful as the fluid in thermometers for
temperatures below 40C, the freezing point of mercury, and for other low-temperature
purposes, such as for antifreeze in automobile radiators. The molecular weight is 46.07.
One gallon of 190 proof ethanol weighs 6.8lb. Ethanol has no basic or acidic properties.
When burned, ethanol produces a pale blue flame with no residue and considerable
energy, making it an ideal fuel. Ethanol mixes readily with water and with most organic
solvents. It is also useful as a solvent and as an ingredient when making many other
substances including perfumes, paints, lacquer and explosives.
Types of ethanol
Ethanol can be produced in two forms:

H
ydrous
ethanol: it can be used as a pure form of fuel in specially modified vehicles.
It has a purity of about 95% plus 5% water. Brazil is the only country that produces
vehicles that run on this form of ethanol.

Anhydrous ethanol: it is water free or absolute. A second-stage process is required

to produce high purity ethanol for use in petrol blends. The 95% pure product is
dehydrated using a molecular sieve or azeotropic processes to remove the water,
resulting in 99% pure ethanol. Anhydrous ethanol is normally blended with 1025%
volume in petrol for use in most unmodified or slightly modified engines or as a 3%
blend in diesel.
Sources
Ethanol can be produced from a variety of organic materials. These can be classified in to
three groups (see Table 2.2).
Page 16
TABLE 2.2 Feedstocks for bioethanol production

Sugar-based: Sugar cane, molasses, sugar beet, sweet sorghum, fruits
Starch-based: Cereal grains, potato, sweet potato, corn, cassava
Cellulose-based: Agricultural plant waste, forest residue, municipal solid waste, energy crops
Source: Based on data from Kim and Dale, 2004b; US DOE (2006a)
Agricultural waste available for ethanol conversion includes crop residues such as wheat
straw, corn stover (leaves, stalks and cobs), rice straw, and bagasse (sugar cane waste).
Forestry waste includes underutilised wood and logging residues; rough, rotten and
salvable dead wood; and excess saplings and small trees. Municiple solid waste contains
some cellulosic materials such as paper. Energy crops, developed and grown specifically
for fuel, include fast-growing trees, shrubs and grasses such as hybrid poplars, willows and
switchgrass (US DOE, 1996a). Switchgrass is one source likely to be tapped for ethanol
production because of its potential for high fuel yields, hardiness and the ability to be
grown in diverse areas. Trials show current average yields to be about five dry tonnes
per acre. However, crop experts say that progressively applied breeding techniques could
more than double that yield. Switchgrasss long root system actually a fifty-fifty split
above ground and below helps to keep carbon in the ground, improving soil quality. It is
drought tolerant, grows well even on marginal land and does not require heavy fertilising.
Other varieties including big blue stem and Indian grass are also possible cellulose sources
for ethanol production. Researchers estimate that ethanol yield from switchgrass is in the
range of 60140 gallons per tonne; some say 8090 gallons per tonne is a typical figure.
It is estimated that the energy output/energy input ratio for fuel ethanol made from
switchgrass is about 4.4 (Iowa State University, 2006). The US Department of Agriculture
estimates that by 2030 approximately 129 million acres of excess cropland could be used
for energy crops. If 40 million of these acres were utilised for energy crops for biofuels
such as ethanol, it would provide a transportation fuel equivalent to 550 million barrels
of oil per year (US DOE, 1996b). Sugar cane bagasse, the residue generated during the
milling process, is another potential feedstock for cellulosic ethanol. Research shows that
one tonne of sugar cane bagasse can generate 112 gallons of ethanol.
Lignocellulosic feedstock is composed of cellulose, hemicellulose, lignin and extractives
and ash. The cellulose and hemicellulose, which typically comprise two-thirds of the dry
mass, are polysaccharides that can be hydrolysed to sugars and eventually fermented to
ethanol. The combination of hemicellulose and lignin provides a protective sheath around
the cellulose, which must be modified or removed before efficient hydrolysis of cellulose
can occur, and the crystalline structure of cellulose makes it highly insoluble and resistant
to attack. Therefore, to hydrolyse hemicellulose and cellulose economically, more advanced
pre-treatment technologies are required than those used in processing sugar or starch
crops (Eggeman and Elander, 2005). After the cellulose and hemicellulose have been
saccharified, the remainder of the ethanol production process is similar to grain ethanol.
However, the different sugars require different enzymes for fermentation.
Page 17
Lignocellulosic crops are promising feedstock for ethanol production because of high
yields, low costs, good suitability for low-quality land and low environmental impact. Most
ethanol conversion systems that are written about are based on a single feedstock. But
considering the hydrolysis fermentation process, it is possible to use multiple feedstock types.
TABLE 2.3 Typical composition of lignocellulosic biomass (%, dry basis)
Feedstock

Cellulose
Glucan 6C
Hemicellulose
Xylan 5C
Arbinan 5C
Glactan 6C
Mannan 6C
Lignin
Ash
Acids
Extractives
Heating values
(GJHHV/tonnedry)
Black
locust
41.61
41.61
17.66
13.86
0.94
0.93
1.92
26.70
2.15
4.57
7.31
19.50
Hardwood
Hybrid
Eucalyptus
poplar
44.70
49.50
44.70
49.50
18.55
13.07
14.56
10.73
0.82
0.31
0.97
0.76
2.20
1.27
26.44
27.71
1.71
1.26
1.48
4.19
7.12
4.27
19.60
19.50
Softwood
Pine
Grass
Switchgrass
44.55
44.55
21.90
6.30
1.60
2.56
11.43
27.67
0.32
2.67
2.88
19.60
31.98
31.98
25.19
21.09
2.84
0.95
0.30
18.13
5.95
1.21
17.54
18.60
Note: totals may not add up due to rounding

Source: Based on data from Hamelinck (2003)
Table 2.3 presents biochemical compositions for several suitable feedstock. Pine has the
highest combined sugar content, implying the highest potential ethanol production. The
lignin content for most feedstock is about 27%, but grasses contain significantly less and
will probably co-produce less electricity.
Cellulosic resources are in general very widespread and abundant. For example, forests
comprise about 80% of the worlds biomass. Being abundant and outside the human food
chain makes cellulosic materials relatively inexpensive feedstocks for ethanol production.
Brazil uses sugar cane as primary feedstock whereas in the US more than 90% of the
ethanol produced comes from corn. Other feedstocks such as beverage waste, brewery
waste and cheese whey are also being utilised. In the EU, most of the ethanol is produced
from sugar beet and wheat. Crops with higher yields of energy, such as switchgrass
and sugar cane, are more effective in producing ethanol than corn. Ethanol can also be
produced from sweet sorghum, a dry-land crop that uses much less water than sugar cane,
does not require a tropical climate and produces food and fodder in addition to fuel. In
terms of gallons of fuel per acre, the best farm crop for ethanol production is sugar beet,
with the lowest water requirements to grow the crop. The beet plant drives a central tap
root deep into the soil and the entire beet is underground, minimimising evaporation.

One result of increased use of ethanol is increased demand for the feedstocks.
Large-scale production of agricultural alcohol may require substantial amounts of
Page 18
cultivable land with fertile soils and water. This may lead to environmental damage such
as deforestation or decline of soil fertility due to reduction of organic matter.

In 2003, about 5% of the ethanol produced in the world was actually a petroleum
product. It is made by the catalytic hydration of ethylene with sulphuric acid as the
catalyst. It can also be obtained via ethylene or acetylene, from calcium carbide, coal,
oil, gas and other sources. Two million tonnes of petroleum-derived ethanol are produced
annually. The principal suppliers are plants in the US, Europe and South Africa. Petroleumderived ethanol (synthetic ethanol) is chemically identical to bioethanol and can be
differentiated only by radiocarbon dating.
The energy balance One of the most controversial issues relating to ethanol is the question of net energy of

of ethanol ethanol production. The definition of net energy value (NEV) is the difference between the
energy in the fuel product (output energy) and the energy needed to produce the product
(input energy). While the topic has been hotly debated for years, the current prevailing
opinion is that ethanol has a net positive energy balance. It takes less than 35,000BTU of
energy to turn corn into ethanol, while the ethanol offers at least 77,000BTU of energy,
which shows that ethanols energy balance is clearly positive (Shapouri et al., 1995, 2002,
2003; Lorenz and Morris, 1995; Wang et al., 1999; Kim and Dale, 2004a; Farrell et al.,
2006) and an extremely high petroleum/fossil energy displacement ratio.

Since 1979, David Pimentel, of Cornell University has consistently argued in more
than 20 published articles that the amount of fossil fuel energy needed to produce
ethanol is greater than the energy contained in the ethanol. According to Pimentel and
his colleague Tad Patzek of the University of California, Berkeley, there is just no energy
benefit in using plant biomass for liquid fuel (Pimentel, 2003; Patzek, 2003; Ferguson,
2003). Their research used fundamentally flawed, decades old data that is not valid
considering todays efficiencies in agriculture and in ethanol production. Now the advances
in the farming community as well as technological advances in the production of ethanol
have led to positive returns in the energy balance of ethanol. Studies have shown that
the ethanol energy balance is improving by the year (Wang, 2005b; Shapouri et al., 1995,
2002, 2003; Lorenz and Morris, 1995; Wang et al., 1999; Morris, 1995). These studies show
that the energy output to energy input ratio for converting irrigated corn to ethanol is now
1.67:1. In a July 1995 US Department of Agriculture (USDA) Economic Research Service
report entitled Estimating the Net Energy Balance of Corn Ethanol, it was concluded that
the ethanol energy balance had a gain of 24%. That same report was revisited the next
year, in a presentation entitled Energy Balance of Corn Ethanol Revisited the authors
concluded that the ratio had risen to 34%. This number is reinforced by a 2002 report, The
Energy Balance of Corn Ethanol: An Update published by the USDAs Office of the Chief
Economist and Office of Energy Policy and New Uses. The report concluded that ethanol
production is energy efficient because it yields 34% more energy than is used. In June
2004, the USDA looked at this issue again and determined that ethanol continues to be
more efficient and now provides the aforementioned 1.67:1 gain in energy.
Page 19
Many advances have led to the surge in ethanol production efficiency. One key issue
is the ability to produce more gallons of ethanol per bushel of corn. In the early 1990s,
plants were able to produce about 2.5 gallons of ethanol per bushel. That number has
since increased to between 2.7 and 2.8 gallons per bushel.

Crops with a higher sugar content than corn, such as sugar beet, would result in
production with a much higher positive net energy balance. If corn farmers use
state-of-the-art, energy-efficient farming techniques, and ethanol plants use state-of-the-art
production processes, then the amount of energy contained in a gallon of ethanol and the
other co-products is more than twice the energy used to grow the corn and convert it into
ethanol. Studies indicated an industry average net energy gain of 1.38:1. The industry-best
existing production net energy ratio was 2.09:1. If farmers and industry were to use all of
the best technologies and practices, the net energy ratio would be 2.51:1. In other words,
the production of ethanol would result in more than two-and-a-half times the available
energy than it took to produce it.

A 1999 study by Argonne National Laboratory found the energy balance of cellulosic
ethanol to be in excess of 60,000BTU per gallon (Wang, 1999). Given that feedstocks
for cellulosic ethanol are essentially waste products like corn stover, rice bagasse, forest
thinnings or even municipal waste, there are relatively few chemical and energy inputs
that go into the farming of feedstocks for cellulosic ethanol. A secondary factor, although
to a much lesser extent, is the fact that cellulosic ethanol plants will presumably produce
extra energy that can be fed into the power grid. Doing so will effectively displace the use
of electricity produced in power plants, which for the most part rely upon fossil fuels.

Table 2.4 shows ethanols net energy value as published by different researchers.
TABLE 2.4 Ethanols net energy value: a summary of major studies, 19952005
Authors and date

Shapouri et al. (1995) USDA
Lorenz and Morris (1995) Institute for Local Self-Reliance
Agri. and Agri-Food, Canada (1999)
Wang et al. (1999) Argonne National Laboratory
Pimentel (2002) Cornell University
Shapouri et al., update (2002) USDA
Kim and Dale (2002) Michigan State University
Graboski (2002) Colorado School of Mines
Pimentel (2003) Cornell University
Shapouri et al. (2003) Argonne National Laboratory/USDA
Shapouri et al., update (2004) USDA
Pimentel and Patzek (2005) Cornell/UC-Berkeley
NEV (BTU)
+20,436 (HHV)
+30,589 (HHV)
+29,826 (LHV)
+22,500 (LHV)
33,562 (LHV)
+21,105 (HHV)
+23,866 to +35,463 (LHV)
+17,508
22,300
+21,105
+30,258 (LHV)
22,300
Note: HHV = higher heating value; LHV = lower heating value

The energy balance of corn ethanol revisited (2003) by Shapouri et al. included a new energy credit for
the co-product distillers dried grains with solubles (DDGS)
The 2001 net energy balance of corn-ethanol (2004) by Shapouri et al. included a revised energy credit
for DDGS
Source: Based on data from White (2006)
Page 20
Future of bioethanol
The future of bioethanol appears to be bright as the need for renewable energy sources
to replace dependence on foreign oil is growing. With many nations seeking to reduce
petroleum imports, boost rural economies and improve air quality, world ethanol
production rose to 13.5 billion gallons in 2006. The success of domestic ethanol industries
in the US and Brazil has sparked tremendous interest in countries around the globe
where nations have created ethanol programmes seeking to reduce their dependence
on imported energy, provide economic boosts to their rural economies and improve the
environment. As concerns over greenhouse gas emissions grow and supplies of world oil
are depleted, Europe and countries like China, India, Australia and some south-east Asian
nations are rapidly expanding their production and use of biofuels.
A lot of research is being done including turning biomass (materials from plants) into
ethanol using special biotechnological methods. Biomass ethanol is the future of ethanol
production because biomass feedstocks, like wheat straw or switchgrass, require less fossil
fuels to grow, harvest and produce. It also allows more marginal land, such as grasslands,
to be utilised rather than precious acreage devoted to food crops like corn or soya beans.
In this way, ethanol production from biomass does not negatively affect the livestock
and food industry. The biorefinery, analogous to todays oil refineries, could economically
convert lignocellulose to an array of fuels and chemicals not just ethanol by
integrating bio- and thermo-chemical conversion (Fernando, 2006). Fundamental research
and partnerships with the emerging bioenergy industry are critical for the success.

There has been continued research to improve the energy output of ethanol and
improvements should continue. Currently, E85 stations are popping up everywhere and
more products, from generators to power tools and lawnmowers, will all start to use
alternative fuels. There are already engines that can run on 100% pure ethanol, and
improvements will help migrate these engines to other areas. Big auto manufacturers like
Nissan, Ford and Honda have all invested money into E85 models. Portable generators,
stand-by and emergency generators should all start using ethanol as a fuel source.

The emergence of carbon trading programmes in response to many countries
ratification of the Kyoto Protocol will also enhance the affordability of ethanol fuels in
comparison to gasoline and diesel. Because ethanol fuels offer a substantial reduction
in carbon dioxide emissions, users can obtain carbon credits that can be sold to heavy
polluters, again reducing ethanol costs while increasing that of fossil fuels. The EU
recently developed a carbon trading programme. Japan has conducted several scenario
simulations and hopes to initiate its own nationwide trading system. As Russia considers
ratification of the Kyoto Protocol, which would bring the agreement into effect, it seems
likely that similar carbon trading schemes will continue to emerge around the world.

A combination of well-reasoned government policies and technological advancements
in ethanol fuels could guide a smooth transition away from fossil fuels in the
Page 21
transportation sector. As environmental factors continue to be incorporated into policy

and the fledgling industry emerges, ethanol fuels are likely to become an increasingly
attractive fuel alternative in the foreseeable future. Looking into the future, the ethanol
industry envisions a time when ethanol may be used as a fuel to produce hydrogen for
fuel-cell vehicle applications.
Page 22
Production of bioethanol
Production of bioethanol requires fermentation of the sugar (mono- and polysaccharides)

in nearly all kinds of biomass (Olsson et al., 2005). Today there are primarily two types
of process technology called first- and second-generation technology. First generation
produces bioethanol from sugars (a dimer of the monosaccharides glucose and fructose)
and starch-rich (polysaccharides of glucose) crops such as grain and corn.
Sugars can be converted to ethanol directly, but starches must first be hydrolysed to
fermentable sugars by the action of enzymes from malt or moulds. The technology is well
known, but high prices of the raw material and the ethics about using food products for
fuel are two major problems. This is not an issue with the second-generation production of
bioethanol instead a new technology is required. The raw material in second-generation
process technology is lignocellulosic material such as straw, wood and agricultural residue,
which is often available as waste.
TABLE 3.1 First- and second-generation raw materials for ethanol production
First generation
Sugar cane
Corn
Wheat
Rye
Sorghum
Cassava
Second generation
Agricultural waste
Leftover crop material, such as stalks, leaves and husks of corn plants
Forestry waste
Wood chips and sawdust from lumber mills, dead trees and tree branches
Energy crops
Fast-growing trees and grasses such as switchgrass
Municipal solid waste
Household garbage and paper products
Food processing and other industrial waste
Black liquor, a paper manufacturing by-product
Source: Based on data from Hamelinck (2003); US DOE (2006a)
These kinds of materials are cheap but the process technology is more advanced than
converting sugar and starch. The major cause is the lignin which binds together pectin,
protein and the two types of polysaccharides, cellulose and hemicellulose, in lignocellulosic
biomass. Lignin resists microbial attack and adds strength to the plant. Pre-treatment
is therefore used to open the biomass by degrading the lignocellulosic structure and
releasing the polysaccharides. Pre-treatment is followed by treatment with enzymes which
hydrolyse cellulose and hemicellulose respectively. The cellulose fraction releases glucose
(C6 monosaccharide sugar with six carbon atoms) and the hemicellulose fraction
releases pentoses (C5 monosaccharide sugar with five carbon atoms) such as xylose. Out
of carbohydrate monomers in lignocellulosic materials, xylose is the second most abundant
Page 23
after glucose. Glucose is easily fermented into ethanol, but another fermentation process is
required for xylose for example using special micro-organisms.

The second-generation technology holds great advantages for the fermentation of
biomass in the form of agricultural waste materials. The first-generation technology is

based on much more costly raw material and there are some ethical questions. This is not
an issue with the second-generation technology instead there are some challenges such
as efficient pre-treatment and fermentation technologies together with environmentally
friendly process technology (for example the reuse of the process water).
Production of Ethanol is produced from corn by using one of two standard processes: wet milling or dry
alcohol from corn milling (Yacobucci and Womach, 2003).
Page 24
FIGURE 3.1 Ethanol production from corn by the wet milling process
$PSO
8FUNJMMJOH
$MFBOJOH
4UFFQJOH
4UFFQXBUFS
(SJOEJOH
$PSOPJM
(FSNTFQBSBUJPO
(FSNNFBM
(SJOEJOH
'JCSF
'JMUSBUJPOXBTIJOH
(MVUFO
(MVUFOTFQBSBUJPO
4ZSVQ
4UBSDI
4XFFUFOFS
-JRVFGBDUJPO
4BDDIBSJGJDBUJPO
$0
'FSNFOUBUJPO
:FBTU
:FBTUSFDZDMJOH
%JTUJMMBUJPO
8BTUFXBUFS
-JWFTUPDLBOE
QPVMUSZGFFET
%FIZESBUJPO
"MDPIPM
%FOBUVSJOH
'VFM
Source: Source: Based on RFA (2007d)
Page 25
FIGURE 3.2 Ethanol production from corn by the dry milling process
$PSO
%SZNJMMJOH
$MFBOJOH
.JMMJOH
-JRVFGBDUJPO
4BDDIBSJGJDBUJPO
$0
'FSNFOUBUJPO
%JTUJMMBUJPO
%FIZESBUJPO
$FOUSJGVHBUJPO
"MDPIPM
%FOBUVSJOH
%SZJOH
&WBQPSBUPST
%JTUJMMFEHSBJOT
BOETPMVCMFT
4ZSVQ
'VFM
Source: Based on RFA (2007d)
The main difference between the two processes is in the initial treatment of the grain.
Dry milling plants cost less to build and produce higher yields of ethanol (2.7 gallons per
bushel of corn), but the value of the co-products is less. The value of corn as a feedstock
for ethanol production is due to the large amount of carbohydrates, specifically starch,
present in corn.
Page 26
TABLE 3.2 Composition of corn

Component
Carbohydrates (total)
Starch
Fibre (NDF)
Simple sugars
Protein
Oil
Minerals
Other
Dry matter (%)

84.1
72.0
9.5
2.6
9.5
4.3
1.4
0.7
Dry milling
In the US, most of the ethanol plants utilise a dry milling process. The major steps of dry
milling are outlined below:
1 Milling: after the corn (or other grain or biomass) is cleaned, it passes first through
hammer mills which grind it into a fine powder.
2 Liquefaction: the meal is then mixed with water and an enzyme (alpha amylase), and
passes through cookers where the starch is liquefied. A pH of 7 is maintained by adding
sulphuric acid or sodium hydroxide. Heat is applied to enable liquefaction. Cookers with
a high temperature stage (120150C) and a lower temperature holding period (95C)
are used. The high temperatures reduce bacteria levels in the mash.
3 Saccharification: the mash from the cookers is cooled and the enzyme glucoamylase is
4 Fermentation: yeast is added to the mash to ferment the sugars to ethanol and
added to convert starch molecules to fermentable sugars (dextrose).

carbon dioxide. Using a continuous process, the fermenting mash flows through
several fermenters until the mash is fully fermented and leaves the tank. In a batch
fermentation process, the mash stays in one fermenter for about 48 hours.

5 Distillation: the fermented mash, now called beer, contains about 10% alcohol, as well
as all of the non-fermentable solids from the corn and the yeast cells. The mash is then
pumped to the continuous flow, multi-column distillation system where the alcohol
is removed from the solids and water. The alcohol leaves the top of the final column
at about 96% strength, and the residue mash, called stillage, is transferred from the
base of the column to the co-product processing area. The stillage is sent through a
centrifuge that separates the coarse grain from the solubles. The solubles are then
concentrated to about 30% solids by evaporation, resulting in Condensed Distillers
Solubles (CDS) or syrup. The coarse grain and the syrup are then dried together
to produce dried distillers grains with solubles (DDGS), a high-quality, nutritious
livestock feed. The CO2 released during fermentation is captured and sold for use in
carbonating soft drinks and beverages and the manufacture of dry ice. Drying the
distillers grain accounts for about one-third of the plants energy usage (Bryan and
Bryan Inc., 2001).
Page 27
6 Dehydration: the alcohol then passes through a dehydration system where the
remaining water is removed. Most plants use a molecular sieve to capture the last bit of
water in the ethanol. The alcohol at this stage is called anhydrous (pure, without water)
ethanol and is approximately 200 proof.
7 Denaturing: ethanol that is used for fuel is then denatured with a small amount (25%)
of some product, like gasoline, to make it unfit for human consumption.
Wet milling
The wet milling operation is more elaborate because the grain must be separated into its
components. After milling, the corn is heated in a solution of water and sulphur dioxide
for 2448 hours to loosen the germ and the hull fibre. The germ is then removed from the
kernel, and corn oil is extracted from the germ. The remaining germ meal is added to the
hulls and fibre to form corn gluten feed. A high-protein portion of the kernel called gluten
is separated and becomes corn gluten meal which is used for animal feed. In wet milling,
only the starch is fermented, unlike dry milling, when the entire mash is fermented.
New technologies
The production of ethanol is an example of how science, technology, agriculture, and

allied industries must work in harmony to change a farm product into a fuel. Ethanol
plants receive the large quantities of corn that they need by lorry, rail or barge. The corn
is cleaned, ground and blown into large tanks where it is mixed into a slurry of corn meal
and water. Enzymes are added and exact acidity levels and temperatures are maintained,
causing the starch in the corn to break down first into complex sugars and then into
simple sugars.
New technologies have changed the fermentation process. In the beginning it took
several days for the yeast to work in each batch. A new, faster and less costly method of
continuous fermentation has been developed. Plant scientists and geneticists are also
involved. They have been successful in developing strains of yeast that can convert greater
percentages of starch to ethanol. Scientists are also developing enzymes that will convert
the complex sugars in biomass materials to ethanol. Cornstalks, wheat and rice straw,
forestry wastes and switchgrass all show promise as future sources of ethanol.
Co-products
Each bushel of corn can produce 2.52.7 gallons of ethanol, depending on which milling
process is used. Only the starch from the corn is used to make ethanol. Most of the
substance of the corn kernel remains, leaving the protein and valuable co-products to
be used in the production of food for people, livestock feed and various chemicals. The
volume of co-products has increased dramatically with the growth in ethanol production.
In the US in 2006, ethanol dry mills produced a record 12 million tonnes of distillers grains.
Page 28
FIGURE 3.3 Distillers grains from US ethanol refineries, 19992006

5POOFT

Of this, approximately 7580% is fed to ruminants (dairy and cattle), 1820% to swine
and 35% to poultry. Some estimate that production of distillers grains will reach more
than 20 million metric tonnes by the time the renewable fuel standard (RFS) is fully
implemented in 2012. This level of output will make it necessary to find new markets and
uses for co-products. New uses being considered include food, fertiliser and cat litter.
While the majority of feed is dried and sold as distillers dried grains with solubles (DDGS),
approximately 2025% is fed wet locally, reducing energy costs associated with drying as
well as transportation costs. Ethanol wet mills produced approximately 430,000 tonnes of
corn gluten meal, 2.4 million tonnes of corn gluten feed and germ meal, and 565 million
pounds of corn oil.
Production of
ethanol from
lignocellulosic
biomass
Lignocellulosic biomass can be converted to ethanol by hydrolysis and subsequent

fermentation (Fan et al. 1987; Badger, 2002). Also thermo-chemical processes can be used
to produce ethanol: gasification followed either by fermentation or by a catalysed reaction.
Hydrolysis fermentation of lignocellulose is much more complicated than just fermentation
of sugar. In hydrolysis, the cellulosic part of the biomass is converted to sugars, and
fermentation converts these sugars to ethanol. To increase the yield of hydrolysis, a
pre-treatment step is needed that softens the biomass and breaks down cell structures
to a large extent. The pre-treatment and hydrolysis sections allow for many process
configurations. Present pre-treatment processes are primarily chemically catalysed, but both
Page 29
economic and environmental arguments drive the development of physical pre-treatments.

The pre-treatment technology chosen affects the yield of both pre-treatment and
subsequent process steps. Acid hydrolysis processes have been used for many decades, but
have environmental consequences. Enzymatic processes under development are supposed
to have roughly equal costs to conventional processes today, but are more environmentally
sound, and these costs can be reduced further. Therefore, most studies focus on enzymatic
hydrolysis (Lynd, 1996; Ogier et al., 1999; Yu and Zhang, 2004; Sheehan, 2001). The
fermentation step, on its turn, does not yet convert all sugars with equal success. Future
overall performance depends strongly on development of cheaper and more efficient
micro-organisms and enzymes for fermentation. Newer micro-organisms may also allow for
combining more process steps in one vessel, such as fermentation of different sugars and
enzyme production (Lynd, 1996). Lastly, the biomass composition in hemicellulose, cellulose
and sugar influences the ethanol yield.

A simplified generic configuration of the hydrolysis fermentation process is shown in
Figure 3.4.
FIGURE 3.4 Biomass to ethanol process
#JPNBTT
1SFUSFBUNFOU
)ZESPMZTJT
4UFBN
1PXFS
HFOFSBUJPO
'FSNFOUBUJPO
1VSJGJDBUJPO
4PMJE
SFTJEVBMT
&MFDUSJDJUZ
8BTUF
8BUFS
&UIBOPM
Source: Based on RFA (2007d); Ladisch (2003); Wyman et al. (2005)
Pre-treatment
Pre-treatment is required to alter the biomass macroscopic and microscopic size and
structure as well as its submicroscopic chemical composition and structure so that
hydrolysis of carbohydrate fraction to monomeric sugars can be achieved more rapidly
and with greater yields (Sun and Cheng, 2004; Mosier et al., 2005; Wyman et al., 2005a).
Page 30
Pre-treatment affects the structure of biomass by solubilising hemicellulose, reducing

crystallinity and increasing the available surface area and pore volume of the substrate.
Pre-treatment has been considered as one of the most expensive processing steps in
biomass to fermentable sugar conversion (Mosier et al., 2005).

Each type of feedstock requires a particular pre-treatment method to minimise the
degradation of the substrate and to maximise the sugar yield. There is huge scope in
lowering the cost of pre-treatment processes through extensive R&D approaches.
Pre-treatment of cellulosic biomass in a cost-effective manner is a major challenge of
cellulose to ethanol technology research and development.

Native lignocellulosic biomass is extremely recalcitrant to enzymatic digestion.
Therefore, a number of thermochemical pre-treatment methods have been developed

to improve digestibility (Wyman et al., 2005a). Recent studies have clearly proved that
there is a direct correlation between the removal of lignin and hemicellulose on cellulose
digestibility (Kim and Holtzapple, 2006). Thermochemical processing options appear
more promising than biological options for the conversion of lignin fraction of cellulosic
biomass, which can have a detrimental effect on enzyme hydrolysis. It can also serve as
a source of process energy and potential co-products that have important benefits in a
life-cycle context (Sheehan et al., 2003). Pre-treatment can be carried out in different ways
such as mechanical combination (Cadoche and Lopez, 1989), steam explosion (Gregg and
Saddler, 1996), ammonia fibre explosion (Kim et al., 2003), acid or alkaline pre-treatment
(Damaso et al., 2004; Kuhad et al., 1997) and biological treatment (Keller et al., 2003).
Each technology has advantages and disadvantages in terms of costs, yields, material
degradation, downstream processing and generation of process wastes.
Hemicellulose In order to make the cellulose feedstock more digestible by enzymes, the surrounding
hydrolysis hemicellulose and/or lignin is removed, and the cellulose microfibre structure is modified.
Chemical, physical or biological treatment are employed to solubilise the lignin and
hemicellulose. Subsequently, when water or steam is added, the free hemicellulose polymer
is hydrolysed to monomeric and oligomeric sugars. During hydrolysis, hemicellulose
sugars may be degraded to weak acids, furan derivates and phenolics. These compounds
inhibit the later fermentation, leading to reduced ethanol yields. The production of these
inhibitors increases when hydrolysis takes place at higher temperatures and higher acid
concentrations. In order to remove the inhibitors and increase the hydrolysate fermentability,
several chemicals and biological methods have been used (Martinez et al., 2000; Nilvebrant,
2001; Martin et al., 2002; Lopez et al., 2004). The detoxification of acid hydrolysates has
been shown to improve their fermentability. However, the cost is often greater than the
benefits achieved (Palmqvist and Hahn-Hagerdal, 2000; von Sivers et al., 1994).
Common chemical pre-treatment methods use dilute acid, alkaline, ammonia, organic
solvent, sulphur dioxide, carbon dioxide or other chemicals. The most important methods
are the use of acid and alkali. Acid catalysed hydrolysis uses dilute sulphuric, hydrochloric
Page 31
or nitric acids. Of all chemical pre-treatments, dilute sulphuric acid (0.51.5%, temperature
above 160C) has been most favoured for industrial application because it achieves
reasonably high sugar yields from hemicellulose: xylose yields of at least 7590% (Sun
and Cheng, 2002). The acid will have to be removed/neutralised before fermentation,
yielding a large amount of gypsum. This is usually done after the cellulose hydrolysis. A
concentrated acid-based process also exists but is ranked to be very expensive. Alkaline
pre-treatment uses sodium hydroxide or calcium hydroxide. All lignin and part of the
hemicellulose is removed, and the reactivity of cellulose for later hydrolysis is sufficiently
increased. Reactor costs are lower than those for acid technologies. However, the use of
these more expensive salts in high concentrations raises environmental concerns and may
lead to prohibitive recycling, waste-water treatment and residual handling costs. Alkalinebased methods are generally more effective at solubilising a greater fraction of lignin while
leaving behind much of the hemicellulose in an insoluble, polymeric form (US DOE, 2003).

Other pre-treatment methods use steam explosion or liquid hot water. Steam
explosion is one of the most promising methods to make biomass more accessible to
cellulase attack (Szengyel, 2000). The material is heated using high-pressure steam
(2050 bar, 210290C) for a few minutes. These reactions are then stopped by
sudden decompression to atmospheric pressure. Most steam treatments yield high
hemicellulose solubility and low lignin solubility. Studies conducted without added
catalyst report xylose-sugars recovery between 45% and 65%. The addition of sulphur
dioxide during steam explosion has been shown to improve carbohydrate survival,
decrease the production of inhibitory compounds and to effect more complete removal
of hemicellulose. The major advantages of this method are that it produces a material
that is quite susceptible to enzymatic hydrolysis, its energy requirements are considerably
less than mechanical processes and it does not have the recycling or environmental
costs associated with predominantly chemical treatments. The liquid hot water process
uses compressed, hot liquid water at pressure above saturation point to hydrolyse the
hemicellulose. Xylose recovery is high (8898%) and no acid or chemical catalyst is
required in this process, which makes it economically interesting and environmentally
attractive. This process is still at the laboratory stage.

Biological pre-treatment methods use fungi to solubilise the lignin (Graf and Koehler,
2000). These methods have the advantages of low energy use and mild environmental
conditions. However, the hydrolysis rate is very low. Sometimes biological treatments are
used in combination with chemical treatments (Graf and Koehler, 2000).

Combinations of physical and chemical treatments are also used. Use of dilute acid in
steam explosion has been found to improve enzymatic hydrolysis, reduce the production of
inhibitory compounds, and lead to more complete removal of hemicellulose. It is possible
to recover around 70% of xylose as monomer. Acid catalysed steam explosion is one of
the most cost-effective processes for hardwood and agricultural residues, but it is not as
effective for softwoods. Limitations include incomplete disruption of the biomass structure,
Page 32
destruction of a portion of the xylan fraction and generation of compounds that may
inhibit micro-organism uses in downstream processes. The necessary water wash reduces
the overall sugar yields (Sun and Cheng, 2002). Ammonia fibre explosion involves the use
of liquid ammonia and steam explosion. This process enhances hydrolysis of hemicellulose
and cellulose from grass. However, the effect on biomass that contains more lignin (soft
and hardwood) is not much (Sun and Cheng, 2002). CO2 explosion is similar to steam and
ammonia explosion. The glucose yields in the later enzymatic hydrolysis are low (75%)
compared to steam and ammonia explosion. Overall, CO2 explosion is more cost effective
than ammonia explosion and does not cause the formation of inhibitors as in the case of
steam explosion (Sun and Cheng, 2002).

Table 3.3 compares the different pre-treatment methods.
TABLE 3.3 Comparison of various pre-treatment options

Pre-treatment
Chemicals Temperature/ Reaction time
Xylose
method
Pressure yield (%)
Dilute acid hydrolysis
Acid
>160C
210 minutes
7590
Alkaline hydrolysis
Base
6075
Uncatalysed

160260C
2 minutes
4565
steam explosion
Acid catalysed
Acid
160220C
steam explosion
Liquid hot water
None
190230C
45 seconds
8898
to 4 minutes

p > psat
Ammonia fibre
Ammonia
90C
30 minutes
explosion
CO2 explosion
CO2
56.2 bar
Downstream
enzymatic effect
<85%
55%
90%
Available
Now
Now
25 years
88%
25 years
>90%
510 years
5090% (2 steps)
75% (2 steps)
Of the promising pre-treatment options, dilute acid is as yet the most developed. Xylose
yields are 7590%, which is much higher than when using steam-explosion (4565%).
Dilute acid pre-treatment also produces less fermentation inhibitors and significantly
increases the later cellulose hydrolysis. However, the acid consumption is an expensive
part of the method, it gives a gypsum waste disposal problem and requires the use of
expensive corrosion-resistant materials (Klinke et al., 2004). This may eventually tip the
balance in favour of the less effective, but also less problematic and environmentally
friendly steam explosion. Also additional research may lead to higher yields. The costs
associated with steam explosion are as yet uncertain. The liquid hot water (LHW) process
is still at the laboratory stage.
Cellulose hydrolysis
Cellulose hydrolysis is considered the major hydrolysis step. Cellulose is hydrolysed to

glucose by acid or enzymes (cellulase) (Ghose and Bisaria, 1979; Kuhad et al., 1997;
Itoh et al., 2003; Tucker et al., 2003). Hydrolysis without prior pre-treatment yields typically
less than 20%, whereas after pre-treatment yield often exceeds 90%. Both bacteria and
Page 33
fungi are good sources for the production of cellulases and hemicellulases that could
be used for the hydrolysis of pre-treated lignocellulosics but fungi get the most research
attention because of their aerobic growth conditions and fair production rate (Sun and
Cheng, 2002). The enzymatic cocktails are usually mixtures of several hydrolytic enzymes
comprising of cellulases, xylanases, hemicellulases and mannanases. Since the mid-1990s,
new cellulases and hemicellulases from bacterial and fungal sources have been isolated and
regular efforts have been made for the improved production of enzymatic titres (Aro et al.,
2005; Foreman et al., 2003). Genetic engineering is used to produce super strains, which are
capable of hydrolysing cellulose and xylan along with fermentation of glucose and xylose to
ethanol (Aristidou and Penttil, 2000; Tanaka, 2006).

Acid hydrolysis is only applied in so-called two-stage acid processes, following acid
pre-treatment. There are two types of acid hydrolysis process commonly used dilute and
concentrated acid hydrolysis.

The dilute acid process is conducted under high temperature and pressure and has
a reaction time in the range of seconds or minutes. The concentrated acid process uses
relatively mild temperatures, but a high concentration of sulphuric acid and minimum
pressure. Reaction times are typically much longer than for dilute acid processes.

The dilute acid process is the oldest technology for converting cellulose biomass to
ethanol. The first stage is essentially the hemicellulose hydrolysis as discussed above. If the
reaction is extended, the sugars produced are converted into other chemicals typically
furfural. The sugar degradation not only reduces the sugar yield, but the furfural and other
by-products can also inhibit the fermentation process. Therefore, the first stage is conducted
under mild process conditions (e.g. 0.7% sulphuric acid, 190C) to recover the five-carbon
sugars, while in the second stage only the remaining solids with the more resistant cellulose
undergo harsher conditions (215C, but a milder 0.4% acid) to recover the six-carbon
sugars. Both stages have a three-minute residence time. Yields are 89% for mannose, 82%
for galactose, but only 50% for glucose. The hydrolysed solutions are recovered from both
stages and fermented to alcohol (US DOE, 2003; Graf and Koehler, 2000).

The primary advantage of the concentrated acid process is the potential for high
sugar recovery efficiency; about 90% of both hemicellulose and cellulose fraction gets
depolymerised into their monomeric fractions. The acid and sugar syrup are separated via
ion exchange and then acid is reconcentrated through multiple effect evaporators. The
remaining lignin-rich solids are collected and optionally pelletised for fuel generation.
This process can also handle different types of feedstock. However, environmental and
corrosion problems and the high cost of acid consumption and recovery present major
barriers to economic success.

Enzymatic hydrolysis is highly specific and can produce high yields of relatively pure
glucose syrups without the generation of glucose degradation products. Utility costs are
low as the hydrolysis occurs under mild reaction conditions. The process is compatible with
many pre-treatment options, although purely physical methods are typically not adequate
(Graf and Koehler, 2000; Sun and Cheng, 2002).
Page 34
Many experts see enzymatic hydrolysis as key to cost-effective ethanol production
in the long run (US DOE, 2003). Although acid processes are technically more mature,
enzymatic processes have comparable projected costs and the potential for cost reductions
as technology improves (Lynd et al., 1999).

Enzymatic hydrolysis performed separately from the fermentation step is known as
separate hydrolysis and fermentation (SHF) (Wingren et al., 2003; Soderstrom, 2005).
The separation of hydrolysis and fermentation offers various processing advantages
and opportunities. It enables enzymes to operate at higher temperatures for increased
performance, and fermentation organisms to operate at moderate temperatures,
optimising the utilisation of sugars.
FIGURE 3.5 SHF with separate pentose and hexose sugars and combined sugar fermentation
1FOUPTF
TVHBST
#JPNBTT
%FUPYJGJDBUJPO
$FMMVMPTJD
GSBDUJPO
%FMJHOJGJDBUJPO
XJUIBMLBMJ
3FDPWFSZPG
FUIBOPM
'FSNFOUBUJPO
&O[ZNBUJD
TBDDIBSJGJDBUJPO
&O[ZNBUJD
TBDDIBSJGJDBUJPO
)FYPTF
TVHBST
.JYUVSFPG
IFYPTF
QFOUPTFTVHBST
'FSNFOUBUJPO
Source: Based on Chandel (2007)
The most important process improvement made for the enzymatic hydrolysis of biomass is
the introduction of simultaneous saccharification and fermentation (SSF), which has been
improved to include the co-fermentation of multiple sugar substrates.
FIGURE 3.6 SSF with combined sugars (pentoses and hexoses)
#JPNBTT
%FMJHOJGJDBUJPO
XJUIBMLBMJ
NJDSPPSHBOJTNT
%FMJHOJGJFE
TVCTUSBUF
&O[ZNBUJDTBDDIBSJGJDBUJPO
XJUIDFMMVMPMZUJDFO[ZNFT
FUIBOPMGFSNFOUBUJPOPG
$$TVHBST
3FDPWFSZPG
FUIBOPM
Source: Based on Chandel (2007)
Page 35
This approach combines the cellulase enzymes and fermenting microbes in one vessel. This
enables a one-step process of sugar production and fermentation into ethanol.
Simultaneous saccharification of both carbon polymer (cellulose to glucose; and
hemicellulose to xylose and arabinose) and fermentation is carried out by recombinant

yeast or the organism which has the ability to utilise both C5 and C6 sugars. According
to Alkasrawi et al. (2006) the mode of preparation of yeast must be carefully considered
in SSF designing. A more robust strain will give substantial process advantages in terms
of higher solid loading and the possibility to recirculate the process stream, which results
in increased energy demand and reduced fresh-water utilisation demand in process.
Adaptation of yeast to the inhibitors present in the medium is an important factor for
consideration in the design of SSF process.

SSF combines enzymatic hydrolysis with ethanol fermentation to keep the
concentration of glucose low. The accumulation of ethanol in the fermenter does not inhibit
cellulase action as much as high concentrations of glucose; so SSF is a good strategy for
increasing the overall rate of cellulose to ethanol conversion (Tanaka, 2006; Krishna et al.,
2001; Kroumov et al., 2006). SSF gives higher ethanol yield while requiring lower amounts
of enzyme because end-product inhibition from cellobiose and glucose formed during
enzymatic hydrolysis is relieved by the yeast fermentation (Banat et al., 1998). However, it
is not feasible for SSF to meet all of the challenges at industrial level due to its low rate
of cellulose hydrolysis and most micro-organisms employed for ethanol fermentation can
not utilise all sugars derived after hydrolysis. To overcome this problem, the cellulolytic
enzyme cocktail should be more stable in a wide range of pHs and temperatures. Also, the
fermenting micro-organisms should be able to ferment a wide range of C5 and C6 sugars.

Recently, some promising ethanol-producing bacteria, namely recombinant E. coli
K011, Klebsiella oxytoca and Zymomonas mobilis, have been identified for industrial
exploitation (Chandel et al., 2007). The SSF process has now improved after including
the co-fermentation of multiple sugar substrates present in the hydrolysate. This new
variant of SSF is known as simultaneous saccharification and co-fermentation (SSCF)
(Wyman et al., 2005a). SSF and SSCF are preferred over SHF, since both operations
can be performed in the same tank resulting in lower cost, higher ethanol yield and
shorter processing time. The most upgraded form of biomass to ethanol conversion is
consolidated bioprocessing (CBP) featuring cellulose production, cellulose hydrolysis and
fermentation in one step. It is a highly integrated approach with outstanding potential
(Lynd et al., 2005). It has the potential to provide the lowest-cost route for biological
conversion of cellulosic biomass to ethanol with high productivity and desired yields.

Direct microbial conversion is a method of converting cellulosic biomass to ethanol
in which both ethanol and all of the required enzymes are produced by a single
micro-organism. The potential advantage of direct microbial conversion is that a dedicated
process step for the production of cellulase enzyme is not necessary. Cellulase enzyme
production (or procurement) contributes significantly to the cost involved in the enzymatic
Page 36
hydrolysis process. However, direct microbial conversion is not considered the leading
process alternative. This is because there is no robust organism available that can produce
cellulases or other cell-wall degrading enzymes in conjunction with ethanol with a high
yield. Singh and Kumar (1991) found that several strains of Fusarium oxysporum have the
potential for converting not only D-xylose, but also cellulose to ethanol in a one-step
process. Distinguishing features of F. oxysporum for ethanol production in comparison to
other organisms have been identified. These include the advantage of in situ cellulase
production and cellulose fermentation, pentose fermentation, and the tolerance of
sugars and ethanol. The main disadvantage of F. oxysporum is its slow conversion rate
of sugars to ethanol as compared to yeast.
TABLE 3.4 Comparison of the different cellulose hydrolysis processes

Dilute acid
Concentrated acid
Enzymatic
Consumables
<1% H2SO4
3070% H2SO4
Cellulase
Temperature
215C
40C
70C
Time
3 minutes
26 hours
1.5 days
Glucose yield
5070%
90%
7095%
Available
Now
Now
Now2020
A comparison of the process conditions and performance of the different cellulose

hydrolysis process is shown in Table 3.5. The dilute acid process has a low sugar yield
(5070% of the theoretical maximum). The enzymatic hydrolysis has currently high yields
(7085%) and improvements are still projected. Moreover, refraining from using acid may
be economically better (cheaper construction materials, cutting operational costs) and
better for the environment (no gypsum disposal).
Fermentation
The sugar syrup obtained after cellulosic hydrolysis is used for ethanol fermentation.
A variety of micro-organisms bacteria, yeast or fungi ferment sugars to ethanol
under oxygen-free conditions. They do so to obtain energy and to grow. According to the
reactions, the theoretical maximum yield is 0.51kg ethanol and 0.49kg carbon dioxide per
kilogram of sugar:
3C5H10O5 5C2H5OH + 5CO2 [Equation 1]
C6H12O6 2C2H5OH + 2CO2 [Equation 2]
Methods for C6 sugar fermentation were already known. The ability to ferment pentoses
along with hexoses is not widespread among micro-organisms. S. cereviseae is capable
of converting only hexose sugars to ethanol. The most promising yeasts that have
the ability to use both C5 and C6 sugars are Pichia stipitis, Candida shehatae and
Pachysolan tannophilus. However, ethanol production from sugars derived from starch
and sucrose has been commercially dominated by the yeast S. cereviseae (Tanaka, 2006).
Thermotolerant yeast could be more suitable for ethanol production at industrial level.
In high-temperature processes, energy savings can be achieved through a reduction
Page 37
in cooling costs. Considering this approach, Sree et al. (1999) developed a solid state
fermentation system for ethanol production from sweet sorghum and potato employing a
thermotolerant S. cereviseae strain.

Currently research is focusing on developing recombinant yeast, which can greatly
improve the ethanol production yield by metabolising all form of sugars and reduce
the cost of operation. Two approaches have been used. The first approach has been to
genetically modify the yeast and other natural ethanologens additional pentose metabolic
pathways. The second approach is to improve ethanol yields by genetic engineering in
micro-organisms that have the ability to ferment both hexoses and pentoses (Jeffries and
Jin, 2000; Dien et al., 2003). Jeffries and Jin (2000) compiled the recent developments in
the genetic engineering of yeast metabolism and concluded that strain selection through
mutagenesis, adaptive evolution using quantitative metabolism models may help to
further improve their ethanol production rates with increased productivities.

Piskur et al. (2006) showed the recent developments in comparative genomics and
bioinformatics to elucidate the high ethanol production mechanism from Saccharomyces sp.
Though new technologies have greatly improved bioethanol production, there are still a lot
of problems to be solved. The major problems include:

Maintaining
a stable performance of genetically engineered yeast in commercial-scale
fermentation operation (Ho et al., 1998, 1999);

Developing more efficient pre-treatment technologies for lignocellulosic biomass;
Integrating
optimal components into economic ethanol production systems
(Dien et al., 2000).

Fermentation can be performed as a batch, fed batch or continuous process. The choice
of the most suitable process will depend upon the kinetic properties of micro-organisms
and the type of lignocellulosic hydrolysate in addition to process economics aspects.
Traditionally, ethanol has been produced in batch mode. At present, nearly all of the
fermentation ethanol industry uses the batch mode. In batch fermentation, the
micro-organism works in high substrate concentration initially and a high product
concentration finally (Olsson and Hahn-Hagerdal, 1996). The batch process is a
multi-vessel process and allows flexible operation and easy control over the process.
Generally batch fermentation is characterised by low productivity and intensive labour.
For batch fermentation, elaborate preparatory procedures are needed, and because of
the discontinuous start-up and shut-down operations, high labour costs are incurred.
This inherent disadvantage and the low productivity offered by the batch process have
led many commercial operators to consider the other fermentation methods like fed batch
fermentation, continuous fermentation, immobilised cells, etc.
In fed batch fermentation the micro-organism works at low substrate concentration
with an increasing ethanol concentration during the course of fermentation process. Fed
batch cultures often provide better yield and productivity than batch cultures for the
production of microbial metabolites. For practical reasons, therefore, some continuous
operations have been replaced by fed batch process. Keeping the low feed rate of
Page 38
substrate solution containing high concentration of fermentation inhibitors such as

furfural, hydroxymethyl furfural and phenolics, the inhibitory effect of these compounds to
yeast can be reduced. Complete fermentation of an acid hydrolysate of spruce, which was
strongly inhibiting in batch fermentation, has been achieved without any detoxification
treatment (Taherjadeh, 1999). The productivity in fed batch fermentation is limited by the
feed rate which, in turn, is limited by the cell mass concentration. The specific ethanol
productivity has also been reported to decrease with increasing cell mass concentration
(Palmqvist et al., 1996). Ideally, the cell density should be kept at a level providing
maximum ethanol productivity and yield.

Continuous fermentation can be performed in different kinds of bioreactors stirred
tank reactors (single or series) or plug flow reactors. Continuous fermentation often
gives higher productivity than batch fermentation, but at low dilution rates which
offers the highest productivities. Continuous operation offers ease of control and is less
labour intensive than batch operation. However, contamination is more serious in this
operation. Since the process must be interrupted, all of the equipment must be cleaned,
and the operation started again with the growth of new inoculum. The continuous
process eliminates much of the unproductive time associated with cleaning, recharging,
adjustment of media and sterilisation. A high cell density of microbes in the continuous
fermenter is locked in the exponential phase, which allows high productivity and overall
short processing of 46 hours as compared to the conventional batch fermentation
(2460 hours). This results in substantial savings in labour and minimises investment
costs by achieving a given production level with a much smaller plant.

A limitation to continuous fermentation is the difficulty of maintaining high cell
concentration in the fermenter. The use of immobilised cells circumvents this difficulty.
Immobilisation by adhesion to a surface (electrostatic or covalent), entrapment in
polymeric matrices or retention by membranes has been successful for ethanol production
from hexoses (Godia et al., 1987).

The applications of immobilised cells have made significant progress in fuel ethanol
production technology (Najafpour, 1990; Abbi et al. 1996; Sree et al., 2000; Yamada,
2002). Immobilised cells offer rapid fermentation rates with high productivity that is,
large fermenter volumes of mash put through per day, without the risk of cell washout.
In continuous fermentation, the direct immobilisation of intact cells helps to retain cells
during transfer of broth into collecting vessels. Moreover, the loss of intracellular enzyme
activity can be kept to a minimum level by avoiding the removal of cells from downstream
products. Immobilisation of microbial cells for fermentation has been developed to
eliminate inhibition caused by high concentration of substrate and product and also to
enhance ethanol productivity and yield.
Product recovery
The product stream from fermentation, also called beer, is a mixture of ethanol, cell mass
and water. In this flow, ethanol from cellulosic biomass has lower product concentrations
(5wt%) than in ethanol from corn. The maximum concentration of ethanol tolerated by
Page 39
the micro-organisms is about 10wt% at 30C but decreases with increasing temperature.
To maximise cellulase activity, the operation is rather at maximum temperature (37C),
since the cost impact of cellulase production is high relative to distillation (Lynd, 1996).
On the processing side, slurries become difficult to handle when they contain over 15wt%
solids, which also corresponds to 5% ethanol (two-thirds carbohydrates, and <50wt%
conversion) (Lynd, 1996). The first step is to recover the ethanol in a distillation or beer
column, where most of the water remains with the solids part. The product (37% ethanol)
is then concentrated in a rectifying column to a concentration just below the azeotrope
(95%) (Wooley et al., 1999). Hydrated ethanol can be employed in E95 ICEVs
(Wyman et al., 1993) or in FCVs (requires onboard reforming), but for mixtures with
gasoline, water-free (anhydrous) ethanol is required. It is possible to further distillate
in the presence of an entrainer (e.g. benzene), dry by desiccants (e.g. corn grits), or
use pervaporation or membranes (Lynd, 1996). By recycling between distillation and
dehydration, eventually 99.9% of the ethanol in the beer is retained in the dry product
(Wooley et al., 1999).

The main solid residual from the process is lignin. Its amount and quality differs
with feedstock and the applied process. Production of co-products from lignin, such
as high-octane hydrocarbon fuel additives, may be important to the competitiveness
of the process (US DOE, 2003). Lignin can replace phenol in the widely used phenol
formaldehyde resins. Both production costs and market value of these products are
complex. In corn-based ethanol plants, the stillage (20% protein) is valuable as animal
feed.
Recycling of The water consumption is reduced by recirculating process streams for use in the
process stream washing and hydrolysis steps (Palmqvist and Hahn-Hagerdal, 2000). Recirculating part
of the dilute ethanol stream from the fermenter can increase the ethanol concentration
in the feed to the distillation stage. However, computer simulations have shown that
recirculation of streams leads to the accumulation of non-volatile inhibitory compounds
(Galbe and Zacchi, 1992; Palmqvist et al., 1996). To increase the ethanol productivity,
cell recycling has been employed by several workers while retaining the simplicity of the
batch process. Cell recycling generally does not increase the sugar consumption or ethanol
production, but the time required for fermentation can be reduced by 6070%. Schneider
(1989) observed a reduction in ethanol production after third cell cycle and suggested
that the decrease in ethanol production was due to the limitations of oxygen and sugar as
a result of an increase in cell density.
Page 40
Promising developments in the

production of ethanol from
cellulose

In 2004, Iogen corporation became the first company to begin commercial production of
ethanol from cellulose. Using biotech enzymes that convert wheat straw to clean-burning
ethanol, Iogens pilot plant in Ottawa, Canada has an annual capacity of 800,000 gallons
(Tolan, 2006, 2007). Ethanol from the plant is sold at a nearby Shell petrol station. In
January 2006, Iogen and Shell announced plans to explore ethanol production from
cellulose in Germany, and Iogen is seeking government assistance to construct the first
commercial-scale cellulosic biorefinery in the US. EcoEthanol is the patented name of
Iogens cellulose ethanol process.
FIGURE 4.1 Iogens cellulose ethanol process
&O[ZNF
1MBOUGJCSF
1SFUSFBUNFOU
&O[ZNBUJD
IZESPMZTJT
4FQBSBUJPO
&UIBOPM
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HFOFSBUJPO
&MFDUSJDJUZ
$FMMVMPTF
FUIBOPM
Source: Based on Tolan (2007)
The yield of cellulose ethanol is more than 340 litres per tonne of fibre. The lignin in
the plant fibre is used to drive the process by generating steam and electricity, thus
eliminating the need for fossil CO2 sources such as coal or natural gas.
Iogen has developed an efficient pre-treatment method to increase the surface
area and accessibility of the plant fibre to enzymes. This was achieved through their
modified steam explosion process which improves ethanol yield, increases pre-treatment
efficiency and reduces overall cost. It has a highly potent and efficient cellulase enzyme
system tailored to the specific pre-treated feedstock and has developed reactor systems
that feature high productivity and high conversion of cellulose to glucose (accomplished
through separate hydrolysis and fermentation using a multi-stage hydrolysis process).
Advanced micro-organisms and fermentation systems are used that convert both C6 and
C5 sugars into ethanol. The so-called beer produced by fermentation is then distilled
using conventional technology to produce cellulose ethanol for fuel-grade applications.
Large-scale process designs include energy efficient heat integration, water recycling and
co-product production that make the overall process efficient and economical.

Sweden has two federal plants that create ethanol from cellulose. In the US there
are plants in Kansas and California producing cellulosic ethanol. Japan currently has the
Page 41
Promising developments in the production of ethanol from cellulose
first plant that uses Californian technology to produce ethanol from cellulose, largely
attributed to NEDO commitment to sustainable development through biomass resource
(there are plans for a second plant using rice straw in the works).

Another company which appears to be nearing commercialisation of cellulosic
ethanol is Spains Abengoa Bioenergy (Mielgo et al., 2005). Abengoa is investing

heavily in the necessary technology to bring cellulosic ethanol to the market. They are
constructing a 5 million gallon cellulosic ethanol facility in Spain and have recently
entered into an R&D agreement with Dyadic International Inc. to create better enzyme
mixtures that may be used to improve both the efficiencies and the cost of producing
cellulosic ethanol. Two other companies, Genencor and Novozymes, have received US
Department of Energy funding for research into reducing the cost of cellulase, which is a
key enzyme in the production of cellulosic ethanol by enzymatic hydrolysis.

Biotech
companies Genencor and Novozymes have a DOE contract to improve
cellulase enzyme.

In
late 2004, Genencor announced that it had achieved an estimated cellulase cost
in the range of $0.10$0.20 (0.0730.146) per gallon of ethanol in the National

Renewable Energy Laboratory (NREL) cost model this represented an approximate
30-fold improvement in enzyme cost in that model.

In
2005, Novozymes and NREL were able to reduce the cost of the enzyme part of
biomass-to-ethanol conversion from above $5 per gallon to below $0.30 per gallon of
ethanol.

Other enzyme companies, such as Dyadic International Inc. are developing genetically
engineered fungi which would produce large volumes of cellulase, xylanase and
hemicellulase enzymes which can be utilised to convert agricultural residues such as corn
stover, distiller grains, wheat straw and sugar cane bagasse and energy crops such as
switchgrass into fermentable sugars which may be used to produce cellulosic ethanol.
Ceres Inc., a plant biotechnology company in California that uses genomics to create
unique plant varieties for conversion to biofuels, is collaborating with The Samuel Roberts
Noble Foundation to develop and commercialise new and advanced biomass crops
for ethanol production. Diversa, a San Diego-based enzyme company, has joined with
Syngenta to develop enzyme cocktails that can rapidly hydrolyse the cellulosic material
in corn and corn stover. Also looking for enzymes in the guts of termites in an attempt
to capitalise on the insects ability to convert wood to energy, Celunol Corporation of
Dedham, MA, has genetically engineered micro-organisms which are able to ferment
the whole range of sugars resulting from the hydrolysis, thus significantly increasing the
efficiency of ethanol production. Celunol has purchased the technology from SunOpta.

SunOpta has four cellulosic ethanol projects which are or will be operational using
SunOptas technology and equipment to produce ethanol from cellulosic biomass. This
company built the first cellulosic ethanol plant in the 1980s in France. SunOpta provided
its systems and technology to China Resources Alcohol Corporation in September 2006
Page 42
and the plant started production of ethanol from local corn stover in October 2006.
Recently, key components of SunOptas equipment and technology have been shipped to
Spain for the start-up of the Abengoa wheat straw to ethanol facility which is located in
Salamanca, Spain. This project will start in the summer of 2007. SunOptas equipment
and technology will also be used in a new Celunol facility being built in Jennings, LA,
to produce ethanol from sugar cane bagasse and wood. This will be the first commercial
production of cellulosic ethanol plant in the US and is scheduled to start up in the
summer of 2007.
FIGURE 4.2 Celunol process for production of ethanol from biomass
4VHBSDBOF
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TPMJE

4PMJEDFMMVMPTFMJHOJO
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$FMMVMPTF
IZESPMZTJT
GPSSFMFBTFPG
HMVDPTF
GSPNDFMMVMPTF
9ZMPTF
GFSNFOUBUJPO
UPGFSNFOUYZMPTF
UPFUIBOPM
%JTUJMMBUJPO
UPSFDPWFS
FUIBOPM
(MVDPTF
GFSNFOUBUJPO
(MVDPTFTVHBS
TPMJEMJHOJO
-JHOJOGPSCPJMFS
UPGFSNFOUHMVDPTF
UPFUIBOPM
Source: Based on Celunol (2006)
The Celunol process is depicted in Figure 4.2. In this process, the hemicellulose in
the biomass is first broken into xylose sugar. Then the xylose is separated from the
remaining cellulose. The xylose is fermented with E. coli, and the cellulose is broken
down into normal glucose which is fermented in the normal way. Finally all the ethanol
is distilled (the water and lignin by-products are removed). The lignin is burned in the
stills boilers.
The joint venture of SunOpta with GreenField Ethanol Inc., Canadas largest producer
of ethanol, has been announced. The idea of this joint venture is to design, build, jointly
own and operate plants producing ethanol from wood chips.
Page 43
Flambeau River Biorefinery project in Park Falls, WI, will be the first modern
US-based pulp mill biorefinery to produce cellulosic ethanol from spent pulping liquor.
The production of ethanol is expected to begin as early as 2009. BRI Energy developed
a process that uses gasification, fermentation and distillation to produce ethanol and
electricity from a wide range of carbon-based wastes. BlueFire Plans to use the Arkenol
Technology for creating cellulosic ethanol. Arkenol Technology has been used in Izumi,
Japan since 2002.

Broin Companies are collaborating with DuPont and Novozymes in the research and
development of cellulosic ethanol technology. In 2004, Broin and Novozymes teamed up

to develop raw starch hydrolysing enzymes for the BPX process (a raw starch hydrolysis
process; patent pending) that converts starch to sugar, which then ferments to ethanol
without heat. This innovative technology eliminates the cooking process which has been
part of ethanol production for several years. The technology was taken to commercial
scale after four years of extensive research and development work. There are several
benefits of this technology which include:

Higher ethanol yields
Increased nutrient quality and flowability in distillers dry grain soluble (DDGS)
Reduction in plant emissions
Energy costs reduced by up to 15%.
During the developmental phase, Broin obtained from Novozymes a sample of acid fungal
amylase enzyme that ultimately became specific to the BPX process. The BPX process,
when combined with Broins fractionation technology (BFrac), is expected to provide the
foundation for the biorefinery of the future. Broin plans to expand their Emmetsburg, IA,
facility to include cellulosic ethanol production. The completion of this project is expected
in 2009. Besides these companies, many other biofuel technology companies have been
established to compete in the huge transportation fuels market (Table 4.1).
TABLE 4.1 Companies developing biofuel technologies
Company
Abengoa Bioenergy Corp.
Agrivida Inc.
Altra Inc.
American Biodiesel LLC
Amyris Biotechnologies Inc.
Archer Daniels Midland
Aventine Renewable Energy Inc.
Badger State Ethanol LLC
BioEnergy International LLC
Bioengineering Resources Inc.
Bixby Energy System Inc.
BRI Energy
Blue Fire
Broin
Celunol Corp.
Page 44
Business/products offered
Cellulosic and corn (using entire kernel) ethanol refineries
Optimised corn varieties for cellulosic ethanol production
Ethanol and biodiesel production
Biodiesel production
Synthetic biology for high-performance biofuels
Corn ethanol production from corn kernel
Corn ethanol production
Thermal gasification of waste for co-production of electricity, biofuels
Thermal gasification of waste for co-production of electricity, biofuels
Biomass combustion products for industrial and residential heating
Ethanol production
Cellulosic ethanol production from Arkenol technology process
Cellulosic ethanol production
Ethanol from agricultural waste and other cellulosic biomass

Company
Ceres Inc.
ClearFuels Technology Inc.
Codexis Inc.
Colusa
Diversa Corp.
Dogwood Energy LLC
Dupont
Dyadic International Inc.
Ethanol Boosting Systems LLC
Galveston Bay Biodiesel LP
Globex

Green star product
Hawkeye Renewables
Iogen Corp.
Iroquois Bio-Energy Co., LLC
Kergy
Lignol Energy Corp.
Mascoma Corp.
Methanotech Inc.
NatureWorks, LLC
Novozymes Inc.
ORYXE Energy Intl Inc.
Seattle Biodiesel
SunOpta
Pacific Ethanol Inc.
Synthetic Genomics Inc.
VeraSun Energy Corp.
Virgin Fuels
White Energy Ltd
Xethanol
Business/products offered
Optimised plant varieties for cellulosic ethanol production
Fuels (ethanol, methanol, hydrogen) from agricultural crop waste
Biological catalysts enzymes or fermentation strains
Ethanol production from rice straw
Enzymes and small molecules with agricultural applications
Small- and industrial-scale ethanol and biodiesel production
Enzymes to convert biomass into biofuels
Ethanol fuel-injection system to boost engine efficiency
Biodiesel fuel for off-road or on-road diesel engines
Developing super-critical fluid (SCF) used in cellulosic ethanol
production
Improved enzymes, microbes, and processes for cellulosic ethanol
Methanol production from biomass
Polymers from renewable resources rather than petroleum materials
Enzymes for making ethanol from corn stover
Biodiesel and petroleum additives
Biodiesel production
Corn ethanol production and saleable by-products
Optimised micro-organisms for ethanol and hydrogen production
Source: Based on data from PCAST (2006)
Dr Lonnie Ingram, Director of the Florida Center for Renewable Chemicals and Fuels,
has developed genetically engineered E. coli bacteria that is capable of converting all
types of sugar found in plant cell walls into fuel ethanol (Newswise, 2005). The bacteria
produces a high yield of ethanol from different types of biomass such as sugar cane
residues, rice hulls, forestry and wood wastes and other organic materials. Dr Ingram
genetically engineered the E. coli organisms by cloning the unique genes needed to direct
the digestion of sugars into ethanol, the same pathway found in yeast and higher plants.
With the ethanol genes, he says that bacteria produce ethanol from biomass sugars
with 9095% efficiency. He has developed a microbe that serves as a biocatalyst for
the conversion of glucose, and all other five-carbon and six-carbon sugars contained in
biomass, to fuel ethanol. He began research in this area in 1985. Dr Nancy Ho of
Purdue University has also made considerable progress in engineering yeasts to use
Page 45
in this process. Reducing the cost and improving the efficiency of converting cellulosic
materials into fermentable sugars is one of the keys to progress.

The Department of Energys National Renewable Energy Laboratory (NREL) has
partnered with private biotech companies to make significant advances in this area.
Ingrams University of Florida technology has become Landmark Patent No. 5,000,000
through the US Department of Commerce. It is being commercialised with assistance
from the Department of Energy, and BC International Corp. (based in Dedham, MA) holds
exclusive rights to use and license the engineered bacteria.

NREL and its partners say that the research conducted in this area is an important
step towards realising the potential of biorefineries. Biorefineries, analogous to todays

oil refineries, will use plant and waste materials to produce an array of fuels and
chemicals not just ethanol. Biorefineries will extend the value-added chain beyond the
production of renewable fuel only. Progress towards a commercially viable biorefinery
depends on the development of real-world processes for biomass conversion. With these
new technologies for the production of cellulosic ethanol, its promise comes closer to
reality with each passing day.

In his State of the Union address on 23 January 2007, President Bush announced a
proposed mandate for 35 billion gallons of ethanol by 2017. The maximum production of
ethanol from corn starch is 15 billion gallons per year, implying a mandated production
of some 20 billion gallons per year of cellulosic ethanol by 2017. Bushs plan includes
massive funding ($2 billion) for cellulosic ethanol plants, with an additional $1.6 billion
announced by the USDA on 27 January 2007.

On 28 February 2007, the Department of Energy announced that six
companies Abengoa Bioenergy Biomass of Kansas, LLC ALICO Inc., BlueFire Ethanol
Inc., Broin Companies, Iogen Biorefinery Partners LLC and Range Fuels will be awarded
cellulosic ethanol grants to help with the construction of cellulosic ethanol biorefineries
(RFA, 2007b). The release of these grants is a major step forwards for the cellulosic
ethanol industry as many ethanol producers were waiting for this announcement to move
ahead with their plans. These grants are critical to bringing cellulosic ethanol to the
commercial market and underscore the important partnership that the federal government
must have with the US ethanol industry to achieve both the short-term and long-term
energy goals. These grants will help ethanol producers with the up-front capital costs
associated with the construction of the cellulosic ethanol biorefineries. The DOE goal is
to prove the feasibility of cellulosic ethanol technology. Recipients are entitled to up to
$100 million and must show a 60% industry/40% government cost share. In addition,
the DOE is working on a loan guarantee programme for cellulosic ethanol biorefineries as
authorised in the 2005 energy bill. This programme has seen considerably slower progress
but is important to helping companies build cellulosic ethanol facilities often costing
about 45 times more than the traditional corn ethanol biorefineries.
Page 46

Estimates of

production costs

of bioethanol
from different raw

materials
A study by Goldemberg (2007) estimated the production costs of bioethanol as follows:
EUBIA (2004) estimated the production costs of bioethanol as follows:
From sugar beet: 17.90/GJ
From wheat: 16.70/GJ
From sugarcane (Brazil): 5.20/GJ
From maize: 13.60/GJ.
A study by Ecofys (2003) estimated the production costs of bioethanol as follows:
From straw: 26/GJ
From wheat: 29.80/GJ.
From sugar cane (Brazil): 7.30/GJ
From sugar cane (US and UK): 12.30/GJ
From maize: 9.30/GJ
From cellulose: 20.30/GJ.
Another study by AEA (2003) estimated the production costs of bioethanol as follows:
From EU straw or beet pulp: 29.30/GJ
From EU sugar beet: 24.20/GJ
From EU wheat: 21.3o/GJ
From US maize: 11.20/GJ
From Brazilian sugar cane in Brazil: 9/GJ
From Brazilian sugar cane in the UK: 31.10/GJ.
Page 47
Markets for bioethanol
Alcohols have been used as fuels since the inception of the automobile. The term alcohol
has often been used to represent either ethanol or methanol as a fuel. Ethanol became
established as an alternative fuel with the oil crises of the 1970s. Countries like the US
and Brazil have long promoted domestic ethanol production. Ethanol/gasoline blends
were promoted as an environmentally driven practice in the US initially as an octane
enhancer to replace lead. Ethanol is also used as an oxygenate in clean-burning gasoline
to reduce vehicle exhaust emissions. In the US ethanol supplies currently account for
about 1% of the highway motor vehicle fuel market, in the form of a gasoline blending
component. At present, most of this ethanol is used in a 10% blend with gasoline which is
commonly referred to as gasohol, a term which is being replaced with ethanol/gasoline
blends or E10. In some areas, lower percentage blends, containing 5.7% or 7.7% ethanol,
are also being used to match to air quality regulations affecting the oxygen content of
reformulated gasoline. The 5.7% blend is Californias formulation used to meet a 2% by
weight federal oxygenate requirement in Phase II gasoline. A 5% bioethanol blend does
not require any engine modification and is covered by vehicle warranties. Combined with
gasoline, ethanol increases octane levels while also promoting more complete fuel burning
that reduces harmful exhaust emissions such as carbon monoxide and hydrocarbons.
In addition to ethanol/gasoline blend markets, ethanol has other motor fuel
applications including:

Use as E85, 85% ethanol and 15% gasoline;
Use as E100, 100% ethanol with or without a fuel additive;
Use
in oxydiesel, typically a blend of 80% diesel fuel, 10% ethanol and 10% additives
and blending agents.

There are also smaller niche markets such as fuel-cell applications, E diesel (a cleanerburning diesel fuel containing up to 15% ethanol), aviation, etc. where ethanol can be
utilised (Launder, 1999). Ethanol is used in the chemical industry to make a variety of basic
and intermediate chemicals. Bioethanol could be of great economic and environmental
interest in developing countries especially for cooking and lighting as a substitute for LPG
(particularly for remote locations). The power and heat segment may be a much larger
market than transport for bioethanol. Below is a summary of markets for bioethanol.
Transport
market: in transportation, ethanol is used as a vehicle fuel by itself
(E100 100% ethanol by volume), blended with gasoline, (E95 95% ethanol
and 5% gasoline; E85 85% ethanol and 15% gasoline; E20 20% ethanol and
80% gasoline; E15 15% ethanol and 85% gasoline; E10 10% ethanol and 90%
gasoline and E5 5% ethanol and 95% gasoline). Bioethanol is also used as an
oxygenate in the clean burning of gasoline and as an economical octane enhancer.

Niche
markets: there are also smaller niche markets such as fuel-cell applications,
E diesel (a cleaner-burning diesel fuel containing up to 15% ethanol), aviation

(AGE aviation grade ethanol), snowmobile, boats/marine, small-engine equipment
like lawnmowers, chainsaws and strimmers, etc. where ethanol can be utilised.
Page 49
Chemicals
market: ethanol is used in the chemical industry to make a variety of
chemicals which include ethylene, glycol ethers, ethyl acrylate, acetic acid, ethyl
amines, ethyl acetate, acetaldehyde, ethyl ether, ethyl + chlorine (DDT). Ethylene is
also used as an intermediate chemical in surfactants, adhesives, cosmetics, and
fatty-acid, carbon-black and rubber manufacturing industries.

Power
and heat markets: the power and heat segment may be a much larger market
than transport for bioethanol. In fossil-fuel plants, abatement of NOx is obtained by

reburning other fuels (such as natural gas) in a secondary zone of the combustion
chamber. An oxygenated fuel like bioethanol could be a good reburning fuel for
steam injection gas turbines (aero derivative) to satisfy peak-load requirements.

Domestic
market: bioethanol could be of great economic and environmental interest
in developing countries especially for cooking and lighting as a substitute for

LPG (particularly in remote locations). For cooking, the average annual amount of
bioethanol needed is estimated at around 80100l per person.
Oxygenated and
reformulated fuels
Ethanol has been added to gasoline since the late 1970s. Until the late 1980s ethanols
main role in the fuels market was that of an octane enhancer and it was viewed as an
environmentally sound alternative to the use of lead in gasoline. Ethanol continues to be
one of the most economic octane enhancers available to the refiner or fuel blender with
its 112.5 blending octane value (R+M)/2. In the late 1980s, some states in the US began
to use ethanol and other oxygenates in mandatory oxygenated fuel programmes to reduce
automobile exhaust emissions of carbon monoxide. Fuel oxygenates, such as ethanol, add
chemical oxygen to the fuel, which promotes more complete combustion thereby reducing
carbon monoxide emissions. Hydrocarbon exhaust emissions are also often reduced, but to
a lesser extent.
The US Clean Air Act (1990) amendments also mandated the use of reformulated
gasoline (RFG) in areas with severe ozone pollution, and oxy fuels during winter months
and in areas with high carbon monoxide pollution. Alcohols, such as ethanol, were
designated as the fuels to be used in reformulated and oxygenated gasoline (CFDC,
1999). Carbon monoxide emission violations were reduced by 90% in the first year of
the Oxygenated Fuel Program. The compounds creating ozone pollution or smog reduced
by about 17% and air toxic pollution reduced by more than 25% (CFDC, 1999) through
the Reformulated Gasoline Program. While ethanol has been blended at the 5.7% and
7.7% level, it is more frequently blended at the 10% (by volume) level to take maximum
advantage of available tax credits. At the 10% (by volume) level, ethanol would add
approximately 3.5% oxygen (by weight) to the blend which is the highest level allowed
under Environmental Protection Agency (EPA) regulations.

The Energy Policy Act of 2005 (Public Law 109-58) established a Renewable Fuels
Standard (RFS). This standard requires the use of 4.0 billion gallons of renewable fuels
in 2006, increasing each year to 7.5 billion gallons in 2012. Most of this requirement is
Page 50
expected to be met with ethanol. In the US, approximately 3.4 billion gallons of ethanol
were consumed in 2004. Thus, the RFS will probably lead to a doubling of the US ethanol
market by 2012.

Ethanol can be used as a replacement for methyl tertiary butyl ester (MTBE) in light
of water contamination and health concerns. Unlike ethanol, MTBE is highly soluble in
water and travels easily and swiftly to ground and surface water supplies. Even a small
amount of methanol either swallowed or absorbed through the skin is very harmful. It can
cause blindness, permanent neurological damage and death. The potential health hazards
from the use of MTBE were also documented in a report from the University of CaliforniaDavis titled Health and Environmental Assessment of MTBE which concluded that there
are significant risks and costs associated with water contamination due to the use of
MTBE. Researchers also found MTBE in over 10,000 groundwater sites in California. The
report supports the use of ethanol in place of MTBE stating that the use of ethanol as an
oxygenate would result in much lower risk to water supplies, lower water treatment costs
in the event of a spill, and lower monitoring costs. In 1999, an EPA panel recommended
that MTBE usage be reduced, with some members of the panel recommending that it
be phased out entirely. As of early 2006, MTBE was banned in 17 states in the US. The
elimination of MTBE has created a large market opportunity for ethanol, since ethanol is
much less toxic than MTBE and creates no known water quality threat.
E5
The standard applicable throughout Europe for petrol allows the addition of up to
5% (by volume) of bioethanol as a direct petrol additive. E5 fuel blends can be used for
the conventional petrol engine and can also be distributed through the existing petrol
station network. In the EU, E5 fuel blends are becoming increasingly important. These
fuels have been available in Sweden, Germany, the UK and Poland for some years now.
An increase of the additive level to 10% is being supported by the German automobile
industry trade association and is currently under investigation by the manufacturers.
In Sweden, it is quite extensively used. In the UK, the Tesco chain of supermarkets have
started selling an E5 brand of gasoline marketed as 99 RON super-unleaded. It is cheaper
than the other two forms of high-octane unleaded on the market, Shells Optimax
(98 RON) and BPs Ultimate (97 RON). E5 blends are also being used in Australia and the
US but not in Japan. No evidence has been found of any problems with the use of
E5 blends, but to date, the fuel has only achieved a relatively low market penetration.
India has also trialled E5 extensively with no reported problems.
E10 (gasohol)
E10 is a fuel mixture of 10% ethanol and 90% gasoline. It is sometimes called gasohol.
All car manufacturers now endorse the use of ethanol blends of 10% or less for all of
their vehicles. E10 can be used in all gasoline fuelled vehicles without any special engine
modifications. In the US, certain states like Minnesota support more widespread use of E10
through state-imposed mandates. As of spring 2006, due to the phasing out of MTBE as a
Page 51
gasoline additive, E10 has become very common throughout the US. Approximately 99%
of ethanol consumed in the US is gasohol or E10 blends. Ethanol comprises about 3.5% of
total US gas consumption (140 billion gallons annually). One way to measure alternative
fuels in the US is the gasoline-equivalent gallons (GEG). In 2002, in the US, an amount of
ethanol equal to 137petajoules (PJ), the energy of 1.13 billion US gallons (4,280,000m3) of
gasoline, was used. This was less than 1% of the total fuel used that year.

Many petrol stations throughout Australia are now also selling E10, typically at a
few cents cheaper per litre than regular unleaded. It is more commonly found throughout
Queensland due to its large sugar cane farming regions. The use of E10 is also subsidised
by the Queensland government.

For blend levels above E10, some engine modifications may be necessary. The exact
level at which modifications are required varies with local conditions such as climate,
altitude and driver performance criteria (EAIP, 2001). In Brazil, cars with electronic fuel
injection (including imported cars with minor modifications) have operated satisfactorily
on a 2025% ethanol blend since 1994. There have been few complaints about drivability
or corrosion (Moreira, 2005).

According to analysis by Smog Reyes, the use of 10% ethanol blends lowers exhaust
fine particulate matter (PM) emissions by 50%, carbon monoxide emissions by 30%, toxics
content by mass by up to 13%, and toxics content by potency by up to 21%. Ethanol blends
also reduce secondary PM formation by diluting aromatic content in gasoline (IEA, 2004;
RFA, 2006a; Niven, 2005).
E15
E15 contains 15% ethanol and 85% gasoline. This is generally the greatest ratio of ethanol
to gas that is recommended by auto manufacturers that sell vehicles in the US, though
it is possible that many vehicles can handle higher-ratio mixtures without any problem.
Flexible fuel vehicles are designed to take higher concentrations, up to 96% by volume
ethanol (and no gasoline).
E20
E20 contains 20% ethanol and 80% gasoline. This fuel is not yet widely used in the
US but will be mandated by Minnesota by 2013. Since February 2006, this has been the
standard ethanol-gasoline mixture sold in Brazil, where concerns with the alcohol supply
resulted in a drop in the ethanol percentage which was previously 25%. Flexible fuel cars
are set up to run with gasoline in such a concentration range and few will work properly
with lower concentrations of ethanol.
E85
E85 is a mixture of 85% ethanol and 15% gasoline. Currently, in the US approximately
50 million gallons of ethanol are made into E85. E85 is available at 1,000 locations in the
US (both public and private). The National Ethanol Vehicle Coalition estimates that there
are approximately 6 million flexible fuel vehicles (FFVs) on US roads today as compared to
approximately 230 million gasoline- and diesel-fuelled vehicles. Most E85-capable vehicles
Page 52
are FFVs (RFA, 2001). This mixture has an octane rating of about 105. This is significantly
lower than that of pure ethanol but still much higher than normal gasoline. The addition
of a small amount of gasoline helps a conventional engine to start when using this fuel
under cold conditions. E85 does not always contain exactly 85% ethanol. In winter,
particularly in colder climates, additional gasoline is added to facilitate cold start.

E85 has been similar in cost to gasoline, but with the large oil price rises of 2005,
it is being sold for as much as $0.70 (0.51) less per gallon than gasoline which makes
it highly attractive to the small but growing number of motorists with cars capable of
burning it. Gasoline contains more energy, gallon for gallon, than ethanol. One gallon of
gasoline contains approximately 114,132BTU and ethanol contains 76,000BTU. Therefore
E85 contains approximately 27% less BTU than 100% gasoline. However, when factoring
in the fuel efficiency of gasoline and ethanol (which is more fuel efficient), it was found
that with E85 the number of miles per gallon reduced by only about 1015% instead of
the 27% based strictly on energy content.

E85 is environmentally friendly (Niven, 2005). It has the highest oxygen content of
any fuel available today, making it burn cleaner than ordinary gasoline. The use of E85
reduces pollutants such as ozone and carbon monoxide and air toxins like benzene. E85
cars perform well with significant reductions in emissions when compared to vehicles using
ordinary unleaded gasoline. Reductions in two particularly troublesome pollutants carbon
monoxide and hydrocarbons are reduced significantly. Ethanol is one of only two liquid
fuels available that combats global warming because of its raw-material source. As corn
grows, it converts carbon dioxide into oxygen.

Auto makers are offering more flexible fuel vehicles. The purchase price of these
vehicles has been comparable to the base price of gasoline models. Since E85 is a
cleaner-burning fuel, it is expected that the life of a flexible fuel vehicle will be somewhat
longer than that of a comparable gasoline vehicle.

Flexible fuel vehicles can use any mixture of ethanol and gasoline up to E85.
Examples of FFVs are the Ford Taurus, Ford Ranger2 pick-up truck, the Chevrolet S-10 and
Chryslers Voyager minivan. Because E85 cannot be used in all vehicles, it is mainly used
in fleets of vehicles, which use centralised refuelling stations.

Vehicles are not modified to run on E85, they are specially manufactured as FFVs.
A special diesel-fuel mixture of 15% ethanol and 85% diesel fuel made with the help
of an additive can be used to fuel diesel engines. E85 compatible vehicles have special
hoses, valves, fuel lines and fuel tanks that resist alcohol corrosion.

The vehicles also have a fuel sensor to detect the amount of ethanol in the fuel
tank, and a larger tank to compensate for the mileage decrease when using ethanol.
The mileage decrease which occurs when operating a vehicle on E85 has been debated.
Ford reports an average of 16mpg for an E85 Taurus (based on city and motorway driving)
and 22mpg for gasoline (Ford Motor Company, 1998). DaimlerChrysler reports a 27%
range reduction when using E85 in their minivans (Chrysler Corporation, 1997).
Page 53
E85 vehicles were first manufactured by General Motors. In 1992, General Motors
produced approximately 500 E85 Chevrolet Luminas (NEVC, 2001). In 1996, Ford released
a flexible-fuelled Taurus and introduced a Ranger truck in model year 1999. In the first
year of production, Ford manufactured 100,000 of the E85 flexible fuel Rangers. In 1998,
Chrysler manufactured over 153,000 E85 vehicles when they introduced three types of
flexible fuel minivans the Plymouth, Grand Voyager and Chrysler Town and Country. All
recently manufactured E85 vehicles can run on E85, gasoline, or any combination of both.

Recently sales of FFVs have increased globally. Leading the way are Brazil, the US
and Sweden. In 2005, approximately six million vehicles with flexible fuel technology were
registered in the US. In Brazil, meanwhile, the market share of FFVs in the car registrations
sector has reached over 75%. On Swedish roads by the end of 2005, there were some
23,000 FFVs. In Germany, so far only Ford and Saab have introduced vehicles which
are able to run on E85. More car manufacturers have announced that they will also be
offering FFVs for the European market, e.g. Renault, which will introduce a Mgane FFV
onto the German market in 2007.

On 22 April 2000, the US President issued an Executive Order to use bio-based
motor vehicle products when feasible (RFA, 2000b). In some cities in the US, incentives
are given to encourage the refuelling of E85 vehicles with ethanol. Illinois has placed
coupons in state E85 vehicles for drivers to receive a free beverage at E85 stations. The
coupons not only encourage drivers to refuel at E85 stations, they also make them aware
of where the stations are located for future refuelling. In June 1999, Ford introduced a
similar programme to encourage the use of E85 in their flexible fuel vehicles. Consumers
in Chicago, Minneapolis and the St Paul area in the US who purchase Ford E85 pick-up
trucks and live within 15 miles of an E85 station would be mailed eight coupons for $5 off
the purchase of E85 fuel and maps with the location of all the current E85 stations (RFA,
1999). The number of E85 fuelling stations is growing rapidly in the US. As of February
2006, there were 556 fuel stations with E85, as compared to roughly 120,000 gasoline
stations across the country. Further, 362 of these stations are located in the five states that
produce most ethanol, which are: Minnesota, Illinois, Iowa, South Dakota and Nebraska
(Yacobucci, 2006).
E95
E95 contains only 5% gasoline and is used in some diesel engines where high
compression is used to ignite the fuel, as opposed to the operation of gasoline engines
where spark plugs are used.
E100
E100 is straight ethanol, which is most widely used in Brazil and Argentina. Operation in
ambient temperatures below 15C causes problems with pure, or so-called neat, ethanol
for starting engines. The most common cold-weather solution is to add a small gasoline
reservoir to increase the gasoline content momentarily to permit starting of the engine.
Once started, the engine is switched back to neat ethanol. The ethanol used as fuel in
Page 54
Brazil is the azeotrope, the highest concentration of ethanol that can be achieved via
distillation, and contains 4% water. Hydrated ethanol is usually labelled E100, which
indicates that it does not contain gasoline. Gasoline itself is sold as E20 up to E25, in
accordance with the current legislation (since February 2006, the concentration has ranged
from 19% to 21%), but in extreme cases the ethanol concentration could increase to 40%.
Niche markets With ethanol production expanding at a record pace, the industry continues to pursue
new and expanded uses for ethanol. Opportunities exist as ethanol-blended diesel fuel, as
a hydrogen source for fuel cells, as an aviation fuel, for snowmobiles and other off-road
vehicles, for boats and other personal watercraft, and for small engine equipment (RFA
2004, 2005a).
Fuel cells Fuel cells create electricity by combining hydrogen and oxygen. Fuel cells are more energy
efficient than the internal combustion engine. They could operate on hydrogen from a
number of sources including ethanol, methanol, gasoline and, perhaps at some point,
even water.
Ethanol is expected to play an important role as a fuel-cell fuel supplying the
hydrogen for fuel-cell operation (RFA, 2005a). Ethanol is a clean, renewable, hydrogen
source that provides huge benefits in reducing the greenhouse gases that contribute to
climate change (Fuel cells, 2000).

Nuvera Fuel Cells, formerly Epyx, has developed a fuel-cell processor capable of
converting ethanol, methanol and gasoline to hydrogen. They have found that Ethanol
provides higher efficiencies, fewer emissions and better performance than other fuel
sources, including gasoline. Ethanol is also much less corrosive then methanol.

Ethanol use in fuel cells is a great opportunity for consumers, the environment and
the ethanol industry (RFA, 2000a). The RFA has a Fuel Cell Task Force that continues to
follow fuel-cell developments and to position ethanol for a role in fuel cells. President
Bushs Hydrogen Fuel Initiative supports research and commercialisation of fuel cells
for automobiles and power generation. The first commercial demonstration of ethanols
potential to produce hydrogen to power a fuel cell is underway at Aventine Renewable
Energy Inc.s Pekin (IL) ethanol plant. The 13kW stationary fuel-cell system is generating
power for the plants visitor centre and additional energy for the plant. The project is a
partnership with the US Department of Energy, Caterpillar Inc., Nuvera Fuel Cells, the
State of Illinois, Renewable Fuels Association and the Illinois Corn Growers Association.
E diesel
Another market for ethanol is the use in diesel fuel. Presently E diesel fuels are considered
experimental and are being developed by many companies. Blends containing up to 15%
ethanol, blended with standard diesel and a proprietary additive, are called E diesel fuels.
A number of fleet demonstrations have been completed with favourable results and some
controlled testing has also been completed. Results show that E diesel blends reduce
Page 55
certain exhaust emissions, especially particulates, in certain diesel applications and duty
cycles. However, additional testing is needed to assess compatibility of E diesel blends
with various fuel system parts and also to determine the long-range effects on engine
durability. Additional emissions tests are also needed to more accurately quantify the
emissions profile of various E diesel blend levels. The RFA is working closely with industry
to address the research needs (RFA, 2005a). Most E diesel blends have properties similar
to standard diesel fuel, or can be modified to be similar through the use of additives. One
of the important difference is the lower flash point of E diesel blends. E diesel blends are
designated as Class I whereas diesel fuel is designated as a Class II flammable liquid.
Aviation Another niche market for ethanol is aviation (Caddet, 1997; Higdon, 1997; Bender, 2000).
Research on the use of ethanol in aviation started in the 1980s. In March 2000, FAA
certified AGE85 (aviation grade ethanol) which is a high-performance fuel that may be
used in any piston engine aircraft. It contains approximately 85% ethanol, along with
light hydrocarbons and biodiesel fuel. AGE85 is specifically blended for cold starting and
good mixture balance. AGE is unleaded, burns cleaner, has lower exhaust emissions and
is more environmentally friendly than traditional aviation fuels. The ethanol in AGE85
prevents carburettor and fuel line icing and provides excellent detonation margins.
Presently, ethanol is used in some small-engine crafts and by experimental aircraft
pilots. The largest general aviation market in the world is the US and the second-largest
is Brazil. Pressure is being put on the aviation sector by the EPA to take the lead out
of their fuel. It appears likely that Avgas (the leaded aviation standard fuel) will need
to be replaced with an unleaded fuel in the near future and that ethanol could be the
replacement fuel.
Snowmobiles The snowmobile manufacturers approve the use of ethanol blends of up to 10%. The
use of ethanol in snowmobiles greatly reduces emissions. In the US, several million
snowmobiles are registered. This is a significant factor to consider as a snowmobile with a
conventional two-stroke engine emits 36 times more carbon monoxide and 98 times more
hydrocarbons than an automobile. In fact, snowmobiles can create serious environmental
and health risks and many national parks are considering limiting or banning the use of
snowmobiles within the parks. Using a blend of 10% ethanol also eliminates the need for
the use of gas-line antifreeze and removes and prevents deposit build-up in the fuel tank.
Boats/marine
Ethanol has been shown to be a viable alternative to gasoline for use in recreational
boat engines due to better environmental performance as a fuel than gasoline. Many
marine/boat manufacturers approve the use of ethanol blends of up to 10%. A study
conducted by Dambach et al. (2004) proved the ability to retrofit an engine with minimal
modifications and little loss of performance. The use of alcohol-based fuels in older boats
may cause some problems as the boats may not have alcohol-compatible parts and
therefore certain parts could be degraded with the use of ethanol-blended fuels.
Page 56
Small-engine
equipment
Ethanol blends can also be used in small engines such as lawnmowers, chainsaws and
weed trimmers. The benefits of using ethanol would again be decreased emissions. The
Portable Power Equipment Manufacturers Association has conducted reformulated fuel
research for chainsaws, weed trimmers and other hand-held equipment and observed no
operating problems with equipment when using reformulated gasoline. A study conducted
by the California Environmental Protection Agency has shown that a gasoline-powered
lawnmower run for an hour produces about the same amount of smog-forming emissions
as 40 new automobiles run for an hour. They also found that a chainsaw operated for
two hours is able to generate the same amount of emissions as ten automobiles driven
250 miles.
Page 57
Characteristics of ethanol
The use of ethanol as a fuel has increased since the late 1970s (Morris, 1993). Ethanol is
an important viable alternative to unleaded gasoline fuel. It is used as an automotive fuel
and can be used in specially designed engines alone or blended with gasoline and used
without any engine modifications. Motorboats, motorcycles, lawnmowers, chainsaws, etc.
can all use the ethanol fuel. Most importantly, the millions of automobiles on the road
today can use this improved fuel without any performance problems. Some adjustments
may be required for air intake.
Ethanol is a high-octane fuel (2.53 points above the octane of the blending
gasoline) with high oxygen content (35% oxygen by weight). Therefore, it allows the
engine to burn the fuel more completely, which results in fewer emissions. Since ethanol
is produced from plants that harness the power of the sun, ethanol is also considered
a renewable fuel. Therefore, ethanol has several advantages as an automotive fuel.
The carbon monoxide emissions are also reduced with ethanol blends. When used in a
correctly formulated fuel, ethanol can reduce vehicle emissions which contribute to the
formation of smog.

Ethanol is a water-free alcohol and therefore it can withstand cooler temperatures. Its
low freezing point has made it useful as the fluid in thermometers for temperatures below
40C, the freezing point of mercury, and for other low-temperature purposes, such as for
antifreeze in automobile radiators. The properties of ethanol fuel are detailed in Table 6.1.
TABLE 6.1 Properties of fuel ethanol
Property
Comment
Vapour density
Ethanol vapour, like gasoline vapour, is denser than air and tends to settle in

low areas. However, ethanol vapour disperses rapidly
Solubility in water
Fuel ethanol will mix with water, but at high enough concentrations of water,

the ethanol will separate from the gasoline
Flame visibility
A fuel ethanol flame is less bright than a gasoline flame but is easily visible

in daylight
Specific gravity
Pure ethanol and ethanol blends are heavier than gasoline
Conductivity
Ethanol and ethanol blends conduct electricity. Gasoline, by contrast, is an

electrical insulator
Toxicity
Ethanol is less toxic than gasoline or methanol. Carcinogenic compounds are

not present in pure ethanol. However, because gasoline is used in the blend,

E85 is considered to be potentially carcinogenic
Flammability At low temperatures E85 vapour is more flammable than gasoline vapour.
However, at normal temperatures, E85 vapour is less flammable than gasoline
because of the higher auto ignition temperature of E85
Source: Based on data from US DOE (2006b)
The Energy Policy Act of 2005 (PL 10958) established a renewable fuels standard (RFS)
which mandates the use of ethanol and other renewable fuels in gasoline. Most of the
fuel ethanol consumed in the US is E10. A blend of 85% ethanol and 15% unleaded
gasoline (E85) is also being used. Currently, there are thousands of E85 vehicles on
the roads in the US, driving millions of miles every year. E85 vehicles are flexible fuel
Page 59
vehicles, meaning they will run on whatever is in the tank, from 100% gasoline to 85%
ethanol, but they run best on E85. The small percentage of unleaded gasoline in E85 fuels
enhances starting in extremely cold weather. E85 lowers most vehicle exhaust emissions
(Table 6.2) but can slightly increase ethanol and acetaldehyde emissions.
TABLE 6.2 Ethanol emissions compared to gasoline
Emissions
Carbon monoxide
Carbon dioxide
Particulate matter
Nitrogen oxide
Volatile organic compounds (VOCs)
Sulphur dioxide
Aldehydes

Aromatics (benzene and butadiene)
E10
2530%
10%
Some reduction
5%
7%
Some reduction
3050% increase but negligible
due to catalytic converter
Some reduction
E85
40%
14102%
20%
10%
30%
Up to 80%
Insufficient data
More than 50%
Source: Based on data from EPA fact sheet EPA420- F- 00-035.
E85 vehicles have been designed for versatility. The main component in a variable-fuel
vehicle is a sensor that determines the percentage of ethanol in the fuel. With the help of
a computer, the vehicle automatically adjusts for best performance and emissions.
Chrysler began offering E85 minivans in the 1998 model year and Ford offered the
Taurus and added Windstar and Ranger to the E85 flexible fuel vehicles in the 1999
model year. Ford, GMC, Chevrolet and Daimler-Chrysler are now offering E85 variable-fuel
vehicles.

Ethanol is a flammable, colourless liquid (E100 is clear like water) with a faint alcohol
odour. The colour of ethanol fuel blends depends on the colour of the gasoline in the
blend. Blends may also have a gasoline-like odour.

Science shows that a gallon of E85 contains 27% less energy than regular gasoline.
However, experience has shown that a motor vehicle will experience only a 512% decline
in fuel mileage. The energy content of a gallon of ethanol is equal to 76,000BTU as
compared to about 115,000BTU for a gallon of conventional gasoline. It follows that to
replace the energy equivalent of a gallon of gasoline, approximately 1.5 gallons of ethanol
would be needed, or, to put it another way, a gallon of ethanol can contribute the energy
equivalence of 0.66 gallons of gasoline. Table 6.3 shows the properties of E85 compared
to those of methanol, ethanol and gasoline.
TABLE 6.3 Comparison of fuel properties
Property
Chemical formula
Main constituents
(% by weight)
Octane (R+M)/2
Methanol
CH3OH
38 C,12 H, 50 O
Ethanol
C2H5OH
52 C,13 H, 35 O
Gasoline (87 octane)

C4 to C12 chains
8588 C,1215 H
E85
*
57 C,13 H, 30 O
100
98100
8694
96
Page 60

Property
Methanol
Ethanol
Gasoline (87 octane)
Lower heating value
8,570
11,500
18,00019,000
(BTU/lb)
Gallon equivalent
1.8
1.5
1
Miles per gallon
55%
70%

compared to gasoline
Relative tank size to yield
Tank is 1.8 times larger
1
(driving range
equivalent to gasoline)
Reid vapour pressure (psi)
4.6
2.3
815
Ignition point
Fuel in air (%)
736
319
18
Temperature (approx.) (F)
800
850
495
Specific gravity (60/65F)
0.796
0.794
0.720.78
Cold-weather starting
poor
poor
good
Vehicle power
4% power increase
5% power increase
Standard
Stoichiometric air/
6.45
9
14.7
fuel ratio (by weight)
E85
12,500
1.4
72%
612
*
*
0.78
good
35% power increase
10
*Depends on the percentage and type of the hydrocarbon fraction

Source: Based on data from US DOE (2006b)
The volumetric energy density of ethanol compared to gasoline and other fuels is shown
in Table 6.4.
TABLE 6.4 Volumetric energy density of ethanol compared to gasoline and other fuels
Fuel type
mJ/l
BTU/
BTU/

imperial gallon
US gallon
Ethanol
19.59
101,360
84,400
Gasoline
32.0
150,000
125,000
LPG
22.16
114,660
95,475
Methanol
14.57
75,420
62,800
E10 gasohol
28.06
145,200
120,900
Diesel
40.9
176,000
147,000

Research Octane
Number (RON)
129
9198
115
123
9394
25 (not used in
gasoline engines)
Source: Based on data from Banks et al. (2006)
According to the US Federal Highway Administration, the average vehicle on the road
today releases more than 600lb of pollution into the air each year. These harmful
emissions include carbon monoxide, volatile organic compounds, particulate matter, oxides
of nitrogen, and carbon dioxide. These emissions have significant health implications
because they contribute to the amount of smog and carbon monoxide in the air. Carbon
monoxide emissions have also been implicated in global warming. One of the benefits of
using E85 vehicles is a reduction in the amount of pollutants emitted into the air (Niven,
2005). In general, the type of emissions from vehicles using E85 will be similar to those
from gasoline-powered vehicles, but the amount of emissions will be less. The amount of
Page 61
pollutants released depends on how well the vehicles emissions control system captures
and burns emissions and how well the engine is designed and tuned for using fuel
ethanol. The emissions control systems found on ethanol-powered vehicles manufactured
today have been engineered to meet or exceed all federal and state emissions control
regulations.

Two types of emissions are released by E85 vehicles exhaust and evaporative.
Although compliance with federal and state regulations has already resulted in a decrease
in exhaust emissions from gasoline-powered vehicles, ethanol-fuelled vehicles can further
reduce pollution from emissions by a modest but meaningful amount. Compared with
gasoline-fuelled vehicles, most ethanol-fuelled vehicles produce lower carbon monoxide and
carbon dioxide emissions and the same or lower levels of hydrocarbon and non-methane
hydrocarbon emissions (Niven, 2005). Nitrogen oxide emissions are about the same for
ethanol and gasoline vehicles. Emissions resulting from fuel evaporation are a potential
problem for any vehicle regardless of the fuel. More emissions can leak from a vehicle
when it is not being used than when it is operating. The build up of heat in the engine
compartment, and sometimes even the heat reflected from the pavement onto the fuel
tank, can cause the most volatile parts of the fuel to boil off and leak into the air, causing
pollution. Compared to gasoline, E85 has fewer highly volatile components and so has
fewer emissions resulting from evaporation.

Brazil has used ethanol blends since 1939. High oil prices in the 1970s prompted a
government mandate in Brazil to produce vehicles fuelled by pure ethanol in order to

reduce dependence on foreign oil and provide value-added markets for its sugar cane
producers. There are several million ethanol-powered vehicles in Brazil today that consume
more than 4 billion gallons of ethanol annually.

Requirements in the Clean Air Act to make cleaner-burning reformulated gasoline
(RFG) with lower volatility and fewer toxic components have increased interest in
ethanol-based ethers such as ethyl tertiary butyl ether (ETBE). ETBE is a chemical
compound produced by reacting ethanol and isobutylene which is a petroleum-derived
by-product of the refining process. Compared to other ethers, ETBE has superior physical
and combustion characteristics. They are:

Low volatility
Lower carbon monoxide and hydrocarbon emissions
High octane value
Superior driveability.
Ethanol and ETBE are among the oxygenates used in reformulated gasoline that is
required in certain ozone non-attainment areas in the US.
Using ethanol For environmental reasons, all manufacturers approve the use of ethanol. A study revealed
in engines that nine out of ten car dealers use ethanol-blended gasoline in their personal vehicles.
Several benefits were reported that included: reduced knocking and pinging, improved
gas mileage, better acceleration and improved starting qualities. A study conducted in
Page 62
Iowa showed that nine out of ten technicians used ethanol in their personal vehicles and
reported the same benefits as the car dealers.

E10 unleaded (10% ethanol/90% gasoline) is approved under the warranties of all
domestic and foreign automobile manufacturers marketing vehicles in the US. The top
three automakers in the US Daimler-Chrysler, Ford and General Motors recommend
the use of oxygenated fuels such as ethanol blends because of their performance qualities
and clean air benefits.

Ethanol is a good cleaning agent. It helps keep the engine clean in newer vehicles. In
older vehicles, it can sometimes loosen contaminants and residues that have already been
deposited in a vehicles fuel delivery system. Occasionally, these loosened materials collect
in the fuel filter, and can then be removed simply by changing the fuel filter. All alcohols
have the ability to absorb water. Condensation of water in the fuel system is absorbed
and does not have the opportunity to collect and freeze. Since ethanol blends contain
at least 10% ethanol, they are able to absorb water and eliminate the need for adding a
fuel-line antifreeze in winter.

Ethanol is a fuel for old and new engine technology. Automotive engines older than
1969 with non-hardened valve seats may need a lead substitute added to gasoline or
ethanol blends to prevent premature valve seat wear. Valve burning is decreased when
ethanol blends are used because ethanol burns cooler than ordinary unleaded gasoline.
Many high-performance racing engines use pure alcohol for that reason.

Modern computerised vehicles perform better than non-computer equipped vehicles
when operating correctly. The improvement in performance is due to the vehicles

computerised fuel system being able to make adjustments and changes in operating
conditions or fuel type.

Some of the chemicals used to manufacture gasoline, such as olefins, have been
identified as a cause of deposits on port fuel injectors. Todays gasolines contain

detergent additives that are designed to prevent fuel injector and valve deposits.

The quality of fuel used in any motor vehicle engine is very important to its long life
and proper operation. Driveability will suffer if the fuel is not right for the air temperature
or if fuel changes to vapour incorrectly. Gasoline is a complex mixture of approximately
300 various ingredients, mainly hydrocarbons, refined from crude petroleum oil for use
as fuel in engines. Refiners must meet gasoline standards set by the American Society
for Testing and Materials (ASTM), the Environmental Protection Agency (EPA), state
regulatory agencies and their own company.

Methyl tertiary butyl ether (MTBE) is a popular oxygenate that competes with
ethanol for market share as an additive. It is the most widely used fuel additive to make
reformulated gasoline (RFG), however it cannot be used as the leading ingredient in a
fuel. MTBE is highly corrosive, more volatile than ethanol and more damaging to plastic
and rubber fuel system components known as elastomers. Both MTBE and ethyl tertiary
butyl ether (ETBE) are high octane, low volatility, oxygenated fuel components made by
reacting alcohol with isobutlylene. MTBE is permitted in unleaded gasoline up to a level
Page 63
of 15%, whereas ETBE can be added to gasoline up to a level of about 17%. Many car
company warranties do not cover the use of methanol-based fuels, while all auto makers
approve of the use of ethanol-blended gasoline. MTBE has been found to contaminate
ground water and a ban on MTBE has been implemented in half of the states in the
US with a reasonable possibility of the ban spreading to the remaining 25 states in the
near future. As long as a reformulated fuel mandate stays in place, ethanol is virtually
guaranteed an expanded market. If the MTBE ban passes, then ethanol production
capacity will be insufficient to immediately meet the excess demand caused by the ban.
Therefore, more ethanol infrastructure would need to be built to accommodate the extra
demand. A more gradual phase out would help the ethanol industry to adapt to the
growing need for its product.

Fuel economy
For vehicles with current design flexible-fuel engines, fuel economy is directly proportional
to energy content. Fuel economy is measured in miles per gallon or litres per 100km.
Ethanol contains approximately 34% less energy per gallon than gasoline, so it results
in a 34% reduction in miles per gallon. The effect is approximately 3% for a 10%
ethanol and 90% gasoline blend when compared to conventional gasoline, and 12%
when compared to oxygenated and reformulated blends. However, for 85% ethanol and
15% gasoline blends, the effect becomes significant. E85 will produce approximately
27% lower mileage than gasoline, and will require more frequent refuelling. Actual
performance varies depending on the vehicle. This reduced fuel economy should be taken
in to consideration when making price comparisons. For example, if regular gasoline costs
2.19 per gallon and E85 costs 1.59 per gallon, the prices are essentially equivalent. If
the discount for E85 is less than 27%, it actually costs more per mile to use.
Research is being conducted to increase fuel efficiency by optimising engines
for ethanol-based fuels. Ethanols higher octane allows an increase of an engines

compression ratio for increased thermal efficiency. In one study, complex engine controls
and increased exhaust gas recirculation allowed a compression ratio of 19:5 with fuels
ranging from neat ethanol to E50. Thermal efficiency up to approximately that for a diesel
was achieved. This would result in the miles per gallon of a dedicated ethanol vehicle to
be about the same as one burning gasoline. There are currently no commercially available
vehicles that make significant use of ethanol-optimising technologies, but this is expected
to change in the future.
Page 64
Benefits of bioethanol
Ethanol provides several economic, social and environmental benefits to the producing
regions. Ethanol is easily biodegraded in the environment and produces fewer airborne
pollutants in internal combustion engines than petroleum fuels (RFA, 2000c; Green fuels,
1998a, 1998b). It has low toxicity and is miscible with water. Convincing evidence can be
shown on the pollution prevention characteristics of ethanol-gasoline blends, especially
for E85 formulations (85% ethanol/15% gasoline). Many car manufacturers are producing
more vehicles with tolerances to burn high percentage ethanol fuels more efficiently.
Therefore, the risk posed by ethanol to the environment is considerably lower than that of
fuels produced from petroleum and the demand for ethanol is expected to increase with
time as these automobile improvements take place.
Ethanol is miscible with gasoline in any proportion, but is found most commonly as
10% ethanol (E10) and 85% ethanol (E85). Flexible fuel vehicles can operate on blends
of ethanol and gasoline anywhere between 0% and 85% ethanol. Benefits of ethanol
include:

Higher performance
Cleaner-burning fuel
Positive energy balance
Currently cheaper than gasoline (after considering subsidies).
An important fact is that fuel ethanol is versatile and can mainly be used in two
capacities: a fuel additive (E10) and an almost stand-alone fuel (E85). Different issues
surround each type of fuel. Any internal combustion engine, including small engines
such as those in lawnmowers, can use a blend up to 10% ethanol. Ethanol has a higher
octane rating than most gasolines, which means that engines burning ethanol are less
likely to knock. Knocking can cause damage to the engine. Pure ethanol has an octane
number of 112 while E85 is about 105 octane. Such a high octane rating means that even
high-performance engines can use ethanol fuels. In fact ethanol will soon be fuelling the
legendary IndyCar Series! Like the cars themselves, the transition will be quick (Ethanol
360, 2006). Ethanol is a good racing fuel because it combusts at a lower temperature
than gasoline, thus requiring less cooling power from the radiator. This can help stop
everyday cars from overheating.
Ethanol is a cleaner-burning fuel. It contains more oxygen than gasoline and
therefore undergoes more complete combustion. In its use as an additive, it produces

cleaner-burning gasoline by adding oxygen from a source other than the air. Gasoline
is made up of different kinds of hydrocarbons which partially combust in the engine in
a chemical reaction with the air to form carbon dioxide, water, nitrogen oxides, sulphur
dioxide, carbon monoxide, benzene and uncombusted fuel, also known as volatile organic
compounds. By adding oxygen to the combustion chamber via ethanol, more of the
hydrocarbons are able to produce carbon dioxide and water, and less uncombusted fuel is
passed through the exhaust. Fewer nitrogen oxides are formed because the ethanol fuel
mixture burns at a lower temperature.
Page 65
Because ethanol is produced from plants, the next generation of ethanol-producing
plants will absorb carbon dioxide in the atmosphere during photosynthesis and at the
same time compensate for the emissions of carbon dioxide produced by combustion of
the previous generations ethanol. In this way, there is a sink (a natural removal process
such as dissolution in rain or oxidation by atmospheric gases) for some of the emissions
that fossil fuel sources leave to accumulate in the atmosphere (Baird, 1999). Moreover,
the carbon dioxide that is produced when ethanol combusts is offset by an amount of
carbon dioxide required for the feedstock to grow. Since the simplified version of a plants
metabolic process involves absorbing carbon dioxide and releasing oxygen, fuel ethanol
produces less atmospheric carbon dioxide than its fossil fuel substitutes during their
respective lifecycles. All of these benefits result in less pollution as a result of burning
ethanol-blended fuel.

Ethanol as a fuel has a positive energy balance. This means that combustion of one
unit of ethanol produces more energy than the total energy required to produce the
inputs that make up that unit (Shapouri et al., 2002, 2003). It follows that ethanol is more
advantageous for the environment than using only petroleum-based fuels. These inputs
include, but are not limited to:

Fertiliser
Planting
Harvest
Irrigation
Transportation
Chemical conversion
Electricity.
In this sense, it does not take more energy to make ethanol than it is worth, and ethanol
offers a fuel alternative that is relatively better for the environment.
Due to population growth and industrial activity, there is a growing concentration
of greenhouse gases in the atmosphere that contribute to the greenhouse effect. These
gases include carbon dioxide, methane and nitrous oxide. The term greenhouse effect
relates to the effect of certain gases in the Earths atmosphere in trapping heat from the
sun. This results in a net increase in global temperature. Global warming is the term
used to describe the increasing average global temperature. The term climate change
relates to a wide range of changes in weather patterns that result from global warming.
A substantial increase in the Earths average temperature could result in a change in
agricultural patterns and the melting of polar ice caps, which would raise sea levels and
cause flooding in low-lying coastal areas. The Earths climate is already adjusting to past
greenhouse gas emissions, and the average global temperature is expected to rise by
13.5C by 2100. This increase in average temperature is greater than that which has been
experienced over the past 10,000 years! The average sea level is expected to rise by about
50cm by 2100. These phenomena could have severe effects on the natural and physical
Page 66
environment and human health. The need for green fuels is quickly becoming a necessity
with the threat of global warming and energy crises in todays environment.

According to the US Environmental Protection Agency (EPA), ozone is the most
widespread air pollution problem. To fight this problem, ethanol is extensively used in
reformulated gasolines to help urban cities meet public health standards for ozone.

Because ethanol is produced from renewable resources, it is the only transportation
fuel that reduces greenhouse gas emissions from cars. Fossil fuels release into the air
carbon that is trapped in the soil. There it reacts with oxygen to form carbon dioxide
which is a greenhouse gas that traps the Earths heat, contributing to global warming.

Ethanol is produced from agricultural crops which absorb carbon dioxide and give
off oxygen. This maintains the balance of carbon dioxide in the atmosphere. More
use of ethanol will help counter the pollution and global warming effects of burning
gasoline. Hu et al. (2004) have reported that the use of ethanol-blended fuels as E85 can
reduce the net emissions of greenhouse gases by as much as 3036% and can further
contribute by decreasing fossil energy use by 4248%. Ethanol-blended fuel as E10
reduces greenhouse gases by 2.42.9% and fossil energy use by 3.33.9%. The E10 blend
reductions are lower because a smaller fraction of the blend is ethanol. With improved
technologies and the use of ethanol made from cellulose, these reductions in emissions
are expected to increase.

The Canadian government estimates that if 35% of gasoline in Canada contained
10% ethanol, GHG emissions would be reduced by 1.8 million tonnes per year, which is the
equivalent of removing more than 400,000 vehicles from the roads.
Environmental
benefits
Carbon dioxide
Carbon dioxide from the burning of fossil fuels is the largest single source of greenhouse
gases from human activities. This represents about half of all greenhouse gas emissions.
The US EPA has stated that the US is responsible for about one-fifth of the worldwide
greenhouse gas emissions that cause global warming (US EPA, 2001). Use of 10% ethanolblended fuels results in a 610% carbon dioxide reduction and higher levels of ethanol
can further reduce the net quantity of carbon dioxide released into the atmosphere.
More carbon dioxide is absorbed by crop growth than is released by producing and using
ethanol. The carbon dioxide produced during ethanol production and gasoline combustion
is removed from the atmosphere by plants for starch and sugar formation during
photosynthesis. It is absorbed by the crop in its roots, stalks and leaves, which usually
return to the soil to maintain organic matter, or to the grain, the portion currently used to
produce ethanol. Only about 40% or less of the organic matter is actually removed from
farm fields for ethanol production. The remainder is returned to the soil as organic matter,
increasing fertility and reducing soil erosion. With modern conservation farming practices,
this organic matter will build up, representing a net removal of carbon dioxide from the
atmosphere. An increase of only 1% in the soil organic matter level means an atmospheric
reduction of over 40 tonnes of carbon dioxide per hectare of farmland. Ethanol use in
gasoline has great potential for a net reduction in atmospheric carbon dioxide levels.
Page 67
Carbon monoxide
Carbon monoxide, formed by the incomplete combustion of fuels, is produced most

readily from petroleum fuels, which contain minimal oxygen in their molecular structure.
Because ethanol and other oxygenated compounds contain oxygen, their combustion
in automobile engines is more complete. The result is a significant reduction in carbon
monoxide emissions. Research shows that reductions range up to 30% depending on
the type and age of the automobile, the automobile emission system used and the
atmospheric conditions in which the automobile operates.
Because of health concerns over carbon monoxide (high levels of carbon monoxide
can cause nausea, headaches and other serious health problems), the 1990 amendments
to the US Clean Air Act mandate the use of oxygenated gasolines in many major urban
centres during the winter (when atmospheric carbon monoxide levels are highest) to
reduce this pollution. In the US, the Department of Energy has stated that 82% of carbon
monoxide emissions are due to transportation (CFDC, 1999). The EPA found that carbon
monoxide violations were reduced by 90% during the first year of the Oxygenated Fuel
programme. A study conducted by the University of Colorado showed carbon monoxide
emission reductions in automobiles of up to 30% when 10% ethanol blends were used
(US NREL, 1999). The use of 10% ethanol blends has also been shown to reduce carbon
monoxide emissions when used in snowmobiles. These reductions are particularly
important for snowmobiles as they release almost 40 times more carbon monoxide than
a car (Barry, 2001). Because of snowmobiles high emissions, there is a debate about
whether or not they should be restricted or banned in US national parks.

Reductions in carbon monoxide emissions may also be achieved through the use of
oxygenated diesel fuel. Oxygenated diesel, which consists of ethanol blends of 7.715%, is
being tested in buses and heavy-duty lorries. Results showed carbon monoxide reductions
of approximately 27% when using 15% ethanol blends. Twenty per cent reductions were
experienced with 10% ethanol blends. An additional benefit of using 715% ethanol
blends in diesel is that no engine modifications are required.
Nitrous oxide
The use of E85 reduces vehicle nitrogen oxide emissions by 10% (State of Michigan, 1996).
Nitrogen oxides contribute to ground-level ozone, global warming and acid rain. Acid rain
causes an estimated 1.462.19 billion-worth of damage to agricultural crops in the
US each year (EIA, 1999). Approximately 57% of nitrogen oxide emissions in US cities are
from transportation vehicles (CFDC, 1999).
Other octane additives
Because of its high octane rating, adding ethanol to gasoline can permit the reduction
or removal of aromatic hydrocarbons such as benzene and other hazardous high-octane
additives commonly used to replace tetra-ethyl lead in gasoline.
Ozone
The American Lung Association of Metropolitan Chicago credits ethanol-blended

reformulated gasoline with reducing smog-forming emissions by 25% since 1990. Smog
can result in eye irritation, coughing and shortness of breath. Ground-level ozone is the
Page 68
main cause of smog. The EPA reports that exposure to ozone has been linked to increased
hospital admissions for respiratory aliments such as asthma and that repeated exposure
can make people more susceptible to respiratory infection and lung inflammation
(EPA, 1997). It can also cause significant damage to plants, reducing crop yields. Over 30%
of ozone emissions can be attributed to motor vehicles. The Renewable Fuels Association
(RFA) equated these reductions to taking 16 million vehicles off the road each year
(Vaughn, 2000) . To decrease emissions the Clean Air Act Amendments of 1990 mandated
the use of reformulated fuels in the most serious ozone non-attainment areas. The EPA has
reported significant reductions in ozone-forming emissions due to RFG. Although ethanol
can be used for reformulated gasoline to achieve the required reduction in ozone-forming
emissions, methyl tertiary butyl ester (MTBE) has been used most often as the additive for
reformulated gasoline (RFG). As previously discussed, the use of MTBE is currently being
curtailed due to water contamination issues, and many states have even banned its use.
Therefore, it is expected that ethanol will now be used in areas mandated for RFG.
Particulate matter
Particulate matter is a result of the incomplete combustion of fuel. It can affect breathing,
exacerbate existing respiratory and cardiovascular problems and cause other serious
health problems. Studies have shown that ethanol reduces particulate matter emissions
by more than 25%. By using even small amounts of ethanol-blended fuel, such as in RFG,
particulate matter can be reduced by almost 10% (CFDC, 1999).
Lead
The 1978 Clean Air Act Amendment resulted in the EPA adding lead to its list of criteria
pollutants. This resulted in eliminating lead as an additive for octane enhancement in
gasoline. This has opened up the market to new octane-enhancement products, including
ethanol. The National Corn Growers Association estimated in 1990 that ethanol displaces
the octane equivalent of 4 billion grams of harmful lead components in gasoline
(NCGA, 1990).
The aviation sector was given a temporary waiver for the elimination of lead in
aviation fuel. Today many are calling for the industry to finally remove lead from aviation
fuel. One unleaded aviation fuel alternative is AGE85, which contains 85% ethanol.
AGE85 has been certified for use in several models of piston-engine aircraft.
Environmental
behaviour
Recent reviews of the environmental behaviour of gasoline oxygenates generally report

that ethanol is not likely to accumulate or persist for long in the environment
(RFA, 2000c). According to the Interagency Assessment of Oxygenated Fuels, ethanol is
expected to be rapidly degraded in groundwater and is not expected to persist beyond
source areas. Ethanol in surface water is also expected to undergo rapid biodegradation,
as long as it is not present in concentrations directly toxic to micro-organisms.
The half-life of ethanol in surface water is reported to range from 6.5 to 26 hours.
Atmospheric degradation is also predicted to be rapid.
Page 69
Health effects
Ethanol, the active ingredient of alcoholic beverages, has been part of the human
diet and the human environment for thousands of years. It is found at low levels in
the blood and breath of persons who do not drink alcohol. Ethanol is widely ingested in
alcoholic beverages, usually with only mild effects. However, at sufficiently high doses,
ethanol can cause toxic effects in humans. The toxic effects can be both short term and
long term. The short-term effect is inebriation and the long-term effect is cirrhosis of the
liver. If ethanol becomes a common fuel additive, there may be possibilities for exposure
by inhalation. For example, ethanol vapours might be inhaled at gasoline stations or in
automobiles. Thus, concern has been raised about the possible health consequences of
using ethanol for this purpose.
Scientist Sarah R Armstrong has reported that it is highly unlikely that exposure to
airborne ethanol associated with gasoline use could produce toxic effects (RFA, 2007c).
The reasons for this are:

The
tiny doses that might be received, which might not be observable in light of
endogenous levels of ethanol in blood;

The
The bodys rapid elimination of ethanol;

relatively large doses of ethanol and high blood levels of ethanol associated with
toxic effects in people.

No data in the literature supports the hypothesis that chronic exposure to non-irritating
levels of ethanol in air could cause a significant increase of blood ethanol concentrations
(unless exposed individuals are exercising at the time), or that there would be a risk
of cancer or birth defects. A study regarding the inhalation toxicity of ethanol by the
Swedish Institute for Environmental Medicine reached similar conclusions, namely that a
high blood concentration of ethanol is needed for the development of adverse effects and
ethanol at low air concentrations should not constitute a risk for the general population.
There are some environmental barriers for the use of ethanol with respect to aldehyde
emissions and volatility. Oxygenated gasoline including that made with ethanol has
higher aldehyde emissions than regular unleaded gasoline. The main component of
aldehyde emissions from ethanol is acetaldehyde which is found to be toxic and possibly
a carcinogen. However, with improved exhaust systems, vehicles manufactured after 1987
reduce the emissions to approximately that of gasoline. The Royal Society of Canada said
the possibility of negative health effects from the emissions were remote (Green Fuels,
1998a, 1998b). Another problem with the use of ethanol blends in gasoline is that it
increases evaporative volatile organic compounds (VOCs). A 10% ethanol blend increases
the Reid vapour pressure by 1lb. By themselves, VOCs are not a problem. However, when
combined with carbon monoxide and other chemicals they can form ozone. Although
lower volatility gasoline can be produced to offset this increase in VOCs, petroleum
companies have argued that it will cost much more to produce (Morris, 1999). A study
by the Institute for Local Self-Reliance shows that petroleum companies are hesitant to
produce low volatility gasoline, especially if they only need to produce it for a few areas.
Page 70
The Institute also reported that although ethanol may increase evaporative VOCs, it
reduces exhaust pipe VOCs, which are more toxic. The study also showed that reductions
in carbon monoxide emissions from ethanol blends offset any increases in VOCs emissions
(Morris and Jack, 2000).
Summary
The following list summarises the various benefits (environmental, economic, social) of
bioethanol:
Ethanol
is a renewable fuel produced from plants, unlike petroleum-based fossil fuels
that have a limited supply.

Ethanol
is non-toxic, biodegradable and water soluble, and it is a higher octane fuel
than gasoline.

Ethanol
has a much higher latent heat of vaporisation (855MJ/kg) compared to
petrol (293kJ/kg). As a result, the fuel mixture entering the cylinder is much cooler
and denser and hence requires less cooling energy to radiators.

Ethanol
has a higher octane number (99) than petrol (80100) which inhibits
pre-ignition. The higher octane rating of ethanol allows the compression ratio of the
engines to be increased; this results in increased production of power.

Ethanol
is much less likely to catch fire and explode in cases of fuel leakage,
e.g. when an accident occurs.

Ethanol
adds oxygen to gasoline which improves combustion efficiency and reduces
toxic exhaust emissions. Ethanol/ethanol blends reduce exhaust carbon monoxide

emissions by as much as 30%, exhaust volatile organic compounds emissions by
12%, toxic emissions by 30%, particulate matter emissions by more than 25% and
greenhouse gas emissions by 1219% compared to conventional gasoline.

Bioethanol
Bioethanol
can be produced in large volumes from grain, and potentially in much
larger quantities from lignocellulose, thereby reducing dependency on oil.

vehicles have been in use for many years in North and South America,
where they have proved to be cost efficient and technically fit for large-scale
deployment.

Bioethanol
production will create work in a range of sectors including agriculture,
industry and services.
Page 71
Problems with ethanol/ethanol

blends
Ethanol/ethanol blends create problems during storage, transportation and combustion

(Orbital Engine Company 2002a, 2002b, 2003). The main drawback of using ethanol with
gasoline is phase separation because it is immiscible with diesel fuel over a wide range
of temperatures (Lapuerta et al., 2007; Bhattacharya and Mishra, 2003). Some of the
problems associated with ethanol/ethanol fuel blends are as follows.
Storage
One of the most challenging issues relating to ethanol fuel blends involves the stability of
mixtures. The shelf life of ethanol fuel blends is much shorter due to its water-absorbing
and corrosive qualities. It does not store longer than 23 months unless a stabiliser is
added (US DOE, 2006b). Even so, ethanol stored in fibreglass or plastic tanks will make
the fibreglass soft and mushy, leading to tank failure and engine failure, because the
plastic or fibreglass dissolves into the gas (Wisconsin, 2005).
Transportation
Ethanol cannot travel in pipelines along with gasoline because it picks up excess water
and impurities. As a result, ethanol needs to be transported by lorries, trains or barges,
which is more expensive and complicated than sending it down a pipeline. It would be an
expensive affair to build a completely new pipeline network specifically for ethanol.
Corrosion
Some of the soft metals such as zinc, brass, lead, aluminium and copper are not compatible
with ethanol and can suffer corrosion and pitting if exposed to it for extended periods
(US DOE, 2006b). Furthermore, ethanol dissolves in water and is more electrically
conductive than petrol. The presence of water can facilitate corrosion and the conductivity
facilitates the possibility of galvanic corrosion. Some non-metallic materials (such as natural
rubber; polyurethane; adhesives (used in older fibreglass piping); certain polymers used
in flex piping, bushings, gaskets, meters and filters; and materials made of cork) may also
degrade when these materials come in contact with ethanol (Ternz, 2006). The copper and/
or plastic in air eliminator floats may lack compatibility with ethanol. Ethanol can accelerate
corrosion in steel and degradation in non-metal tank systems by scouring or loosening
deposits on the internal surfaces of the tanks and piping (Orbital Engine Company, 2003).
Solvent effect
Ethanol has a solvent effect and will loosen gums and other deposits in fuel systems that
have been operating on mineral petrol for a long time. In extreme cases this can clog fuel
filters and cause the engine to run poorly. Degradation of fuel system components can
potentially occur because the materials used for hoses, seals, O-rings, membranes and
gaskets are not compatible with ethanol. The typical mechanism is that the ethanol is
absorbed into the material and breaks down the molecular bonds within it. This can lead to
swelling of the material, softening or embitterment and eventually failure of the component.
With older motorcycles and marine applications, there is a potential problem with fibreglass
fuel tanks. In this case the ethanol may react with the resins in the matrix. In the event of
fuel spillages, the solvent effect of ethanol is more likely to cause damage to car paintwork
than conventional petrol. However, the aromatics used in unleaded petrol to boost the
Page 73
Problems with ethanol/ethanol blends
octane level also have a corrosive effect on paintwork. Modern paint systems are more
resistant to this form of damage, but in all cases petrol spillages should be washed off as
soon as possible. Because ethanol is water-soluble it is easier to wash off (Ali et al., 2004).
Separation of layer
Ethanol blend fuels have an ability to absorb much more water, very quickly, than
conventional non-alcohol gasoline (ethanol gasoline blends can absorb 50 times more
water than conventional non-alcoholic gasoline). Some water can be dissolved in
ethanol-petrol blends and will pass through the fuel system with no effect. However,
if the amount of water present is too great, the blend will separate into an upper petrol
layer and a lower water/ethanol layer (phase separation happens in ethanol gasoline
blends, when ~0.5% water is absorbed by the fuel). Generally fuel is drawn from the
bottom of the tank so the water/ethanol layer will be drawn into the engine first and the
engine will not run (Lapuerta et al., 2007; Bhattacharya and Mishra, 2003).
Combustion
The ethanol molecule contains oxygen while the main components of petrol do not. The
effect of this is that less oxygen from air is required to achieve complete combustion and
so if the air/fuel mixture is not adjusted, the mixture is leaner than it would be in pure
petrol. This can lead to engine operability problems such as hesitancy at full throttle
and/or higher exhaust temperatures (Orbital Engine Company, 2002a). The volatility
characteristics of an ethanol/petrol blend differ from those of the unblended petrol on
its own. These differences in volatility can impact on engine operability. In particular the
higher latent heat of vaporisation can lead to cold-starting difficulties, while higher vapour
pressures can result in vapour-lock problems when the engine is hot. Poor ignitability of
ethanol-blended fuel results in a higher rate of pressure rise at high engine loads and
unstable and incomplete combustion at lower engine loads. Ethanol has only 66% of the
energy content of gasoline (in terms of lower heating value with units of BTU/US gallon).
So to match the detonation characteristics of gasoline at high-power settings, ethanolbased fuels require fuel-flow volume increases of nearly 40%. The same car will get more
miles per gallon of gasoline than miles per gallon of ethanol (Ali et al., 2004).
Effect on other Ethanol fuel blends are not compatible with some vehicle parts like capacitance fuel level
vehicle parts gauging indicators as they give erroneous fuel quantity indications in vehicles. The use of
ethanol-based fuels can negatively affect electric fuel pumps by increasing internal wear
and undesirable spark generation.
Scale of operation
Small-scale production of ethanol requires a significant input of equipment and labour.

There is added cost to process the alcohol to the required 200 proof for blending with
gasoline for unmodified engines. To be most effective, the ethanol should be used in
modified engines. There are various costs associated with modifying a gasoline engine,
depending on the engine.
Page 74
Problems with ethanol/ethanol blends
Environment
An ethanol and gasoline mixture can cause damage to the environment during
transportation, storage and consumption. Once the mixture is leaked or spilled into surface
or ground water, ethanol will hamper degradation of other toxic components in gasoline.
Ethanol also increases water solubility of gasoline, leading to larger contamination areas.
Moreover, improvement of air quality is still uncertain. While an ethanol and gasoline
mixture has lower sulphuric oxide and carbon dioxide emissions, it has higher nitrogen
oxide and VOC emissions, which causes ozone depletion. When ethanol is blended with
gasoline, it has the potential to increase the volatility of gasoline. High volatility gasoline
has higher emissions that contribute to increased smog formation. It is the gasoline
emissions that are creating the smog; however, it is ethanol that raises the volatility of the
gasoline blend. In Canada, gasoline volatility is closely regulated. Commercial blends of
ethanol and gasoline cannot have higher volatility than unblended gasoline. Therefore,
there is no increase in smog-forming emissions due to ethanol-blended fuel in Canada.
The E10-fuelled motorcycle engine has been found to produce more ethylene, acetaldehyde
and ethanol emissions than unleaded gasoline engine (Jia et al., 2005).
Page 75
Bioethanol worldwide
Ethanol production and use has spread to every corner of the world. As concerns over
petroleum supplies and global warming continue to grow, more nations are looking to
ethanol and renewable fuels as a way to counter oil dependency and environmental
impacts.
Global ethanol production reached an all time high of nearly 13.5 billion gallons in
2006. The US was the leading producer closely followed by Brazil. China, India and a
number of other nations are rapidly expanding their own domestic ethanol industries.

In 2006, Brazil and the US were responsible for more than 70% of the world ethanol
production (all grades) (RFA, 2007a). Brazil is the biggest exporter and has abundant land
to boost production. In 2005, the US and Brazil had almost identical production, whereas
in 2004 Brazil produced about 13% more than the US (EPI, 2005; Rodrigues, 2006). Now
the two countries appear ready to team up on further development of the renewable
fuel. Brazilian ethanol is made from sugar which is significantly cheaper than production
of fuel from corn, the raw material in the US. The production of ethanol for fuel use in
2005 was roughly equivalent to 17.6 metric tonnes of oil equivalent (Mtoe) (0.74EJ), or
approximately 2% of global gasoline consumption (IEA, 2006).

While the vast majority of ethanol is used in the country in which it is produced,
some nations are finding it more advantageous to export ethanol to countries like the US
and Japan. High spot-market prices for ethanol and the rapid exclusion of methyl tertiary
butyl ether (MTBE) by gasoline refiners led to record imports into the US in 2006. More
than 500 million gallons of ethanol entered through US ports, paid the necessary duties
and competed effectively in the marketplace. The increased trade of ethanol around the
world is helping to open up new markets for all sources of ethanol (Rosillo-Calle and
Walter, 2006).

EU
Below is a description about bioethanol programmes worldwide:
The European Commission is supporting biofuels with an objective to reduce greenhouse

gas emissions, boost the decarbonisation of transport fuels, expand fuel supply sources,
offer new income opportunities in rural areas and develop long-term replacements for
fossil fuel. In 2003, two EU directives on the promotion of biofuels for the traffic sector
were promulgated:
Page 77
The
Biofuels Directive (2003/30/EC): Member States are to ensure that the
proportion of biofuels in overall vehicle fuel consumption in the EU measured in

terms of energy content reaches 5.75% by 2010.

The
Energy Tax Directive (2003/96/EC): this empowers/enables Member States to
However, the average biofuel contribution has been minimal, e.g. 0.5%, 0.6% and 1%
free biofuels from up to 100% of the mineral-oil or energy tax.

in 2003, 2004 and 2005 respectively, and from 2003 to 2005, ten countries did not
use either biodiesel or bioethanol as a substitute (Rosillo-Calle and Walter, 2006). Also,
the Biofuels Directive has left individual Member States to decide on the policies and
measures needed to reach the target as well as biofuels mix strategies most beneficial to
each country. The EU Directive stipulates that the energy-based share of biofuels should
be 2% by the end of 2005, increasing 0.75% per year until it reaches 5.75% by the end
of 2010 (EBIO, 2006). In its recent Energy Policy Document, the EU has adopted a more
conservative estimate for 2020 of 10% based on current trends rather than the 20%
suggested in previous documents.

In the EU, ethanol is mainly produced from sugar beet and wheat. Sugar beet has
proved to be a good feedstock for European bioethanol production. Because sugar beet
has a much larger yield per hectare than wheat, the EU currently produces 2 million more
tonnes of sugar beet than wheat on 20 million less hectares of land. Additionally, sugar
beet produces more ethanol per hectare: a hectare of sugar beet can produce
30 hectolitres more ethanol, on average, than wheat. Also, sugar beet ethanol is shown to
have a more energy-efficient production process than wheat ethanol.
TABLE 9.1 EU bioethanol fuel production, 200406 (million litres)
Country
Czech Republic
Finland
France
Germany
Hungary
Italy
Latvia
Lithuania
Netherlands
Poland
Spain
Sweden
Total
2004
0
3
101
25
0
0
12
0
14
48
254
71
528
2005
0
13
144
165
35
8
12
8
8
64
303
153
913
2006
15
0
250
431
34
128
12
18
15
120
402
140
1565
Source: Based on data from EBIO (2006a)
Currently, the most important bioethanol producers are France, Spain, Germany, Sweden,
Poland and Italy, and their combined production accounted for about 6% of the world
production (all grades) in 2005 (2.7Gl) (EAIP, 2006). Regarding fuel ethanol, the main
Page 78
players in Europe are Spain, Germany, Sweden and France, and in 2005 they produced
84% of the 913Ml as fuel ethanol (EBIO, 2006). However, total consumption in 2005
was close to 1,200 million litres. Sweden, Germany and the UK consumed much more
than they produced and they are therefore strong import markets, while Spain is a strong
exporter (EBIO, 2006).

In comparison with the US and Brazil, EU ethanol for fuel production is still very
modest. The leading ethanol producers in the EU are shown in Table 9.2. In 2006, the
EU produced 1,565 million litres of fuel ethanol.
TABLE 9.2 EU: leading ethanol producers
Abengoa Bioenergy
Saint-Louis Sucre
Agroethanol AB
Svensk Ethanolkemi
Sudzucker
Spain
France
Sweden
Sweden
Germany
Source: AEBTP (2006)

circa.europa.eu/.../rtd/biofrac/library?l=/public_1/documentation/background_documentd
FIGURE 9.1 EU: bioethanol fuel production, 1993 and 19992006

.JMMJPOMJUSFT

Source: Based on data from EBIO (2006a)
In Europe, except for Sweden, and unlike the US or Brazil, ethanol is not incorporated
directly, it is transformed into ethyl tertiary butyl ether (ETBE) (obtained by reacting
isobutene, a liquefied petroleum gas, with ethanol) before being blended with gasoline.
One reason for this regional particularity is the obligation to properly account for
motor-fuel properties such as volatility, since pure ethanol makes ethanol/gasoline blends
more volatile. Another advantage of this practice is that it avoids separation of the
alcohol and gasoline phases in the presence of traces of water.
Page 79
France
Since the mid 1990s, France has led Europe both in bioethanol and biodiesel production.
France produces both bioethanol and biodiesel in significant quantities. A clear
government strategy and early participation of stakeholders from agriculture and industry
ensured support for biofuel production facilities throughout France. Lower tax rates are
also applied to biofuels and these have encouraged the continuous growth of the sector.
Biodiesel is blended at 5% with conventional diesel for private cars and higher blends are
used in the public sector.
France is one of the biggest fuel ethanol producers in the EU. In 2006, it produced
250 million litres of fuel ethanol (EBIO, 2006a). Since 2005, in France 15% of ETBE
(from bioethanol) and 5% of pure ethanol can be blended to gasoline. The target for
2015 is that on average 10% of biofuels (for energy) could be added to conventional
transportation fuels. The French government is offering tax exemption to foster ETBE and
ethanol use, but in 2005 just 5% of the maximum volume of fuel ethanol was used, while
ETBE consumption reached 85% of its maximum (France, 2006).
Germany
Currently, Germany is the biggest fuel ethanol producer in the EU. In 2006, it produced
431 million litres of fuel ethanol (EBIO, 2006). Biodiesel plays a much more important
role than ethanol. The current law provides for full de-taxation for biofuels until 2009. All
biofuels pure, blended or in processed form such as ETBE are exempt from the tax on
mineral oil products. Biofuels are also not subject to the ecology tax established in 1999,
which is added to the taxes levied on petroleum products. In the autumn of 2006, the
federal government passed legislation according to which the blending of 1.2% (energy
equivalent) of bioethanol to petrol would be mandatory in Germany from 1 January
2007. In following years, the share of bioethanol is to be increased by 0.8% annually, so
that 2% will be added in 2008 and 2.8% in 2009. In 2010, 3.6% of bioethanol will be
blended. If bioethanol is used as a fuel extender, the exemption from the mineral oil tax
or the future energy tax is to be discontinued. Fuels regarded as particularly worthy of
promotion, such as E85 (consisting of about 85% ethanol to which approximately 15% of
petrol is blended), will in contrast remain untaxed until the end of 2015.
Spain
Spain was the biggest producer of ethanol in 2004 and 2005 (EBIO, 2006). However, in
2006, Germany became the biggest producer. The success of ethanol production in Spain
can be explained by the fact that the government does not collect any tax on ethanol.
In addition there is an increasing number of plant projects and new plants are currently
being built. In Spain, ethanol has been used as ETBE and in 2005 it was estimated to
account for 1.5% (energy basis) of the total gasoline consumption (Spain, 2006). A limited
volume of ethanol is eligible for a full exemption from the mineral oil tax of 37 per
hectolitre (hl). This tax incentive ends in 2012. In its Renewable Energy Plan for 200510,
the Spanish government has allocated 2.85 billion of sales tax breaks for bioethanol
and biodiesel producers over the five-year period in order to reach a total share of 5.83%
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of biodiesel and bioethanol in the total consumption of diesel and petrol in Spain by
2010. As a result the use of biofuels will more than quadruple by 2010 when it will reach
2.2 million tonnes of oil equivalent against 500,000 tonnes at present.
Sweden
The bioethanol industry in Sweden is developing fast (Sweden, 2006; EBIO, 2006) and
has strong government support. It also imports ethanol from Brazil and Spain.
Feedstocks used for ethanol production are cereals and waste sulphite liquor. Sweden
is also developing new technologies for the production of ethanol from lignocellulosic raw
materials. Both the weak acid hydrolysis and enzymatic hydrolysis approaches are being
studied. Sweden produces about 60 million litres of fuel grade ethanol from cereals, etc.
and the remaining (about 100 million litres) is produced from wine alcohol. Sweden is the
only EU country that has achieved the 2005 target of 2% with bioethanol only and is now
blending up to 5% bioethanol in petrol. Unsurprisingly Sweden and Spain have submitted
a request to the EU Council of Ministers to raise the blending level to up to 10%.

It is the only EU country where a strong market is developing for so-called
flexi-fuel or E85 cars (15% of new cars are flexi cars) that can run on either conventional
fuel or an 85% bioethanol blend that reduces emissions by 70%. At present there are
several thousand flexible fuel vehicles on Swedens roads. They are given special parking
privileges, there is no congestion charge for urban flexi-fuel drivers and the taxes are lower.

Sweden applies both low and high blending. E5 accounts for approximately 85% of
total fuel ethanol use and E85 accounts for approximately 15% of total fuel ethanol use.
There is a tax exemption of 100%, enabling petrol stations to offer ethanol-blended fuel
at the same price as pure petrol. This exemption is due to end in 2009 but is likely to be
extended till 2013. Presently, all the petrol stations offer E5 blends, and several stations
are also selling E85 blends.
Poland
Poland has developed the bioethanol sector in a significant way (EBIO, 2006). This is
probably due to the law that was made in November 2003 regarding tax exemption for
the production of ethanol mixed with petrol. The definitive percentages and the size of
this exemption are determined on a yearly basis after approval of the annual budget.
Fuel ethanol is mainly added to petrol in the form of ETBE. In Poland only limited
amounts of biodiesel are currently produced. The first industrial-scale biodiesel plant, with
a capacity to produce 110 million litres a year, came online in December 2004 in Trzebinia
(southern Poland). Most of its output is exported to Germany. However, since May 2005,
part of the biodiesel produced is being sold on the Polish market as B20 (a blend of
20% biodiesel and 80% conventional diesel). The 20% biodiesel blend benefits from a
full excise tax exemption. According to the National Statistical Office, the share of liquid
biofuels in the transportation sector (in calorific values) amounted to only 0.3% in 2004.
This share increased to 0.5% in 2005 and 1.5% in 2006.
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Austria
Austria is currently producing small volumes of fuel ethanol. The sugar company Agrana
plans to build a 190 million litre plant in Pischelsdorf that will use cereals (mainly wheat)
and sugar beet as feedstocks. This plant is scheduled to start production from 2008.
Recently the Austrian biodiesel sector has increased rapidly. In June 2006, the largest
Austrian biodiesel plant with an annual capacity of more than 100 million litres, started
production. Since 1 October 2005, transportation fuel distributors in the country have been
obliged to blend in 2.5% of biofuels. The national target for the share of biofuels in the
transport sector was 2.5% by October 2005, rising to 4.3% by October 2007 and to 5.75%
by October 2008. The oil industry has started to offer diesel with a 5% biodiesel content.
Total sales of diesel in Austria in 2004 were almost 6 million tonnes while sales of petrol
reached only 2.1 million tonnes.
Italy
In 2006, the production of fuel ethanol in Italy was about 128 million litres (EBIO, 2006).
By contrast, Italy is the third-biggest producer of biodiesel in the EU. In 2004, it produced
approximately 360 million litres, which was a 17% increase on 2003. More than 90% of
this production was intended for the fuels market, with the rest being destined for other
applications.
As in the case of fuel ethanol, a limited amount of biodiesel is eligible for a mineral
oil tax reduction each year. In contrast to France and Germany, the biodiesel situation
deteriorated in Italy in 2005 because the volume of biodiesel benefiting from the tax
incentive decreased by 110 million litres to 220 million litres in 2005. This decrease in
quotas was due to the introduction of tax break quotas for ethanol in 2005. The decision
was justified by the fact that biodiesel is produced using mainly imported vegetal oils
while Italy possesses a sizeable capacity for producing its own alcohol of cereal and wine
origin.
UK
In the UK, fuel ethanol requirements are exclusively being met by imports from Brazil. In
the first three quarters of 2005, total Brazilian ethanol imports into the UK amounted to
92.2 million litres compared with negligible amounts in 2004.
The UK is a long way behind Sweden and Brazil in terms of government support
for the biofuel industry. The UK government currently allows a fuel duty rebate of
0.29 per litre on bioethanol and a 14.87 reduction in Vehicle Excise Duty (VED) for
environmentally friendly cars like E85 vehicles. The expansion of the UK biofuel industry
could be greatly accelerated if government backing included the necessary tax breaks
and legislation to make it commercially viable. Already government support of the biofuel
industry in other countries around the world has shown how successful this alternative
fuel can be. There are currently two flexi-fuel vehicles (the Saab 9-5 Biopower and the
Ford Focus) available in the UK that can run on bioethanol E85.
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Australia
The Australian government has supported ethanol since 2000 with a range of tax
exemptions and production subsidies, aiming to produce 92 million gallons of biofuel
by 2010, which is enough to replace 1% of total fuel supply. In 2006, production of
ethanol stood at 39.4 million gallons. In view of low consumer confidence in ethanol,
the government launched a campaign in September 2005 to encourage greater use of
fuel ethanol. There is additional support at regional level in certain states including
Queensland, e.g. for biofuel marketing, the development of blending and distribution
facilities and technical support for biofuel use.
In Australia, bioethanol is produced from sugar cane molasses and grains. Currently
Australia only produces small amounts of biodiesel. However, several industrial-scale

plants are on the drawing board or in the construction phase.

The fuel ethanol industry is still waiting for the big breakthrough, but political
support for the industry is growing. Australia is a net importer of crude oil, and biofuels
are considered to be increasingly important in view of rising and falling world oil prices.
Advocates of ethanol production also cite benefits for the ailing domestic sugar cane
industry.
China
China is the focus of attention due to its high economic growth rates in recent years,
and currently it is the third-largest producer of fuel ethanol in the world. It is the worlds
second-largest consumer of oil and currently imports 120 million tonnes of crude oil
annually which is roughly 40% of its consumption. Increasingly more vehicles are being
bought (Rosillo-Calle and Walter, 2006).
China has four official ethanol plants (although numerous others are operating
and contributing to the ethanol supply), but these facilities can only replace a small
percentage of the annual oil consumption. Plans have been announced to increase
Chinas annual ethanol production from the current 1 billion gallons to 1.7 billion gallons
by 2010. At current corn production levels, this would require 11% of Chinas 5.1 billion
bushel corn crop. In total, ethanol and other biofuels are expected to replace 2 million
tonnes of crude oil by 2010, with a further increase to 10 million tonnes by 2020. The
challenge will be to produce enough crop material to feed biofuel production, as corn
stocks have been declining. China presently imports 100,000 tonnes of corn each year
and its Cereals and Oils Association estimates that an additional 10 million tonnes could
be needed by 2010. Recently, China has built the largest ethanol production plant in the
world. The plant produces ethanol from corn. Liu (2006) reports the construction of three
new plants that will have a capacity equal to 1.5Gl/year of fuel ethanol production.

So far, the Chinese government has made compulsory the use of E10 in nine provinces
in central and northern China that account for about one-sixth of that countrys vehicles.
Officials say that this mandate aims to reduce the oil demand (40% of which is currently
imported) and also aims to improve air quality in big cities. However, Chinese authorities
also frequently highlight the targets of helping to stabilise grain prices and increase
farmers income.
Page 83
In China, more than 80% of ethanol is produced from grains, about 10% from sugar
cane, 6% from paper pulp waste residue and the rest is produced synthetically. So far, no
significant amounts of biodiesel have been produced in China. There are no
industrial-scale biodiesel plants in the country. Fuel ethanol is exempt from consumption
tax (5%) and value-added tax (17%).

Under Chinas Renewable Energy Plan, the government set a target of 11 million
tonnes of biofuels (bioethanol and biodiesel) production by 2020. According to Tsinghua

University in Beijing, total transport fuel (petrol and diesel) consumption is expected
to reach 228 million tonnes in 2020, so that a production level of 11 million tonnes of
biofuels would mean an average share of 5% of renewable fuels in 2020. Fuel ethanol
demand will continue to expand in China as more provinces introduce the compulsory use
of ethanol-blended petrol.

Due to limited land resources and low crop yields, the Chinese government is trying
to diversify feedstocks and technologies of ethanol production. Attempts are being made
to develop technology for ethanol production from cellulosic material. A pilot plant with
the capacity to produce 750kl/year using acid and enzymatic hydrolysis of sawdust and
rice straw is in operation in Shanghai, and another plant with a capacity of 3.8Ml/year of
fuel ethanol production from the stalks of sweet sorghum has been built in Helongjiang
(Zhenhong, 2006).
US
The US has the worlds fastest-growing and largest fuel ethanol market. There has been
a two-fold increase in its production capacity in just three years between 2004 and 2007
and almost a four-fold increase in seven years 200007. As a result of the implementation
of the Renewable Fuels Standard (RFS), increased octane demand and other market
forces, the US ethanol industry produced a record ~4.9 billion gallons of ethanol from 110
biorefineries located in 19 states across the country in 2006.
TABLE 9.3 Ethanol industry expansion in the US, 200007

January 2000
January 2001
January 2002
January 2003
January 2004
January 2005
January 2006
January 2007
Biorefineries online
54
56
61
68
72
81
95
110
Capacity (million gallons/year)

1,748.7
1,921.9
2,347.3
2,706.8
3,100.8
3,643.7
4,336.4
5,493.4
Source: Based on data from RFA, 2006b, 2007a
Production in 2006 exceeded the previous years production by a record 1 billion gallons,
which is more than 25%. Since 2000, ethanol production in the US has increased more
than 300%. Similarly, demand for ethanol also increased. According to the Renewable
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Fuels Association (RFA), demand for ethanol reached 5.4 billion gallons, an average of
350,000 barrels per day.
TABLE 9.4 US ethanol statistics, 200506
2005
>3.90 billion gallons of production
>4.05 billion gallons of demand
>133.6 million gallons of imports

2006
>4.86 billion gallons of production
>5.4 billion gallons of demand
>653 million gallons of imports, some
434 million directly from Brazil
Source: Based on data from RFA (2007c)
No fewer than 15 new biorefineries came online in 2006, making it a record year for
construction. The addition of these biorefineries, including the completion of expansion
projects, added 1.051 billion gallons of new production capacity for the year. Also, 2006
closed with no fewer than 73 biorefineries under construction and eight expanding that
will add 6 billion gallons of new production capacity by 2009. High-spot market prices for
ethanol and the rapid exclusion of MTBE by gasoline refiners led to record imports into
the US in 2006.
TABLE 9.5 Ethanol imports in the US, 2006
Country imported from
Brazil
Jamaica
China
Costa Rica
El Salvador
Trinidad and Tobago
Canada
Pakistan
Netherlands
Amount imported (000 gallons)

418,465
58,250
37,497
34,464
30,124
22,595
7,073
5,678
1,508
More than 500 million gallons of ethanol entered through US ports, paid the necessary
duties and competed effectively in the marketplace. The main producers are the states of
Iowa, Nebraska, Illinois, South Dakota and Minnesota, with 80% of the online production
capacity in early 2006 (16.2Gl/year) and 76.4% of the total production capacity in the
near future (RFA, 2007a). Table 9.7 shows the top ten ethanol producers by capacity.
There is a sharp political focus in the US on increasing the share of bioethanol, partly with
a view to reducing dependence on oil.
TABLE 9.6 Top ten ethanol producers by capacity in the US, 2006
(million gallons per year)
Abengoa Bioenergy Corp.
Archer Daniels Midland (ADM)
AS Alliances Biofuels
Page 85
198
1,070
200

Aventine Renewable Energy
Cargill
Hawkeye Renewables
Midwest Grain Processors
New Energy Corp.
US Bio Energy Corp.
VeraSun Energy Corp.
All others
Total
207
120
200
152
102
145
230
3,658
6,282
Source: Based on data from RFA (2006b); Yacobucci and Womach, (2003)
Since 2006, fuel ethanol has been used across the country and blended in 30% of
the gasoline consumed in the US (RFA, 2007a). Previously, ethanol was used in niche
markets in the mid-west, where production is still concentrated. It is expected that fuel
ethanol would be blended in 40% of the gasoline consumed. Ethanol is sold in most
states as an octane enhancer or oxygenate blended with petrol, and currently accounts
for nearly 3% of gasoline demand in the US. In recent years, fuel ethanol demand has
been stimulated by the phasing out of methyl tertiary butyl ether (MTBE) as an octane
enhancer that was banished in 23 states by the end of 2005. A major concern with MTBE
is water contamination and its health effects. With the discontinued production of MTBE
in May 2006, a market as large as 11.413.2Gl was filled by fuel ethanol. Demand has also
increased due to concerns over oil prices and external oil dependency.
The cost of production of fuel ethanol from corn in the US in 2006 was estimated to
be in the 0.330.50/l range compared with 0.210.29/l for production from sugar
cane in Brazil (Worldwatch Institute, 2006). The energy balance of ethanol production
from corn is also much less favourable (1.34, according to Shapouri, 1995) than in Brazil
(8.310, according to Macedo et al. 2004). In the long term, the competitiveness of
ethanol production from corn will depend on large improvements along all stages of the
production chain (i.e. reducing energy consumption, diversifying energy supply, developing
new co-products, improving refinery efficiency, etc.). It is estimated that production costs
can be reduced by 815% (Worldwatch Institute, 2006).

The US EPA regulates the use of 10% ethanol blends via the Substantially similar
rule to make sure that the use of oxygenates does not contribute to emission control
system failure. The regulation prohibits the introduction or increase in concentration
of a fuel or fuel additive which is not substantially similar to any fuel or fuel additive
already utilised. The Substantially similar rule recognises that the use of certain types
of oxygenates have no undesirable effects below a specified oxygen content. The US EPA
regulations also create a process by which a waiver can be granted for an oxygenated
recipe that is demonstrated not to cause/contribute to the failure of any emission
control device or system. Under this regulation, the US EPA has granted waivers for
Page 86
concentrations of ethanol in petrol up to 10%. The finished product must match to

gasoline specified by ASTM D 4814-88, and US original equipment manufacturer (OEM)
vehicle warranties specify that petrol must not contain more than 10% ethanol. Therefore,
the use of blends greater than 10% in OEM vehicles could result in vehicle warranties
becoming void.

In August 2005, the US government brought into force the Energy Policy Act of
2005, creating a national Renewable Fuels Standard (RFS) which set targets of 28.4Gl of
renewable fuel to be used in the transport sector by 2012, the vast majority fuel ethanol.
As a result, ethanol production capacity should almost double between 2006 and 2012.
During 2006, the US Congress debated measures to increase mandate levels in 2010 and
in 2020 that will push demand even higher.

Under its Clean Cities Program, the US Department of Energy and the National
Corn Growers Association are cooperating to promote the development of refuelling

infrastructure for E85 and to encourage fleet operators to choose ethanol to meet the
alternatively fuelled vehicles requirements of the Energy Policy Act. As previously stated,
E85 blends require flexible fuel technology (FFT). The potential phase-out of MTBE and
an increasing emphasis on domestic energy supply and energy security are likely to favour
increased use of fuel ethanol in the US.

In spite of the strong interests of corn producers, the long-term sustainability of fuel
ethanol production in the US will ultimately depend on the use of new feedstocks and
so there is a strong commitment to develop new routes of liquid fuels production from
cellulosic material. However, the EIA (2006) believes that by 2030 more than 93% of
ethanol production should be based on corn and less than 7% on cellulose feedstocks.
This evaluation has been strongly criticised by the Biotechnology Industry Organization,
as the EIA failed to take into account recent developments in the ethanol industry that
will ramp up production of ethanol from cellulose (BIO, 2006). In fact, the EIA projects
slow growth in production of ethanol from cellulose, reaching less than 4Gl/year by
2030, when the target under the Renewable Fuels Standard is to reach almost 1Gl/year
in 2013.

A study conducted by the Natural Resources Defense Council in July 2005 found that
the US could produce the equivalent of 7.9 million barrels of oil per day by 2050, more
than 50% of their current total oil use for transportation (RFA, 2006a). Biofuels could:

Almost abolish the demand for gasoline by 2050;
Be
cheaper than gasoline and diesel, saving about $20 billion (14.6 billion) per year
on fuel costs by 2050;

Increase farmers profits by more than $5 billion per year by 2025;
Reduce
greenhouse gas emissions by 1.7 billion tonnes per year, which is equal to
more than 80% of their transportation-related emissions in 2002.
Page 87
Brazil
For decades, Brazil has been the worlds largest producer and consumer of fuel ethanol,
but it was overtaken by the US in 2006. Production amounted to 4,227 million gallons in
2005 and 4,491 million gallons in 2006, which was slightly lower than the US. Brazil is
the worlds top exporter. In 2006, it exported 3.43 billion litres of ethanol, up 350% from
2003. Its exports in 2005 totalled 2.59 billion litres. In Brazil, ethanol consumption has
seen three key periods:
Growth
between 1975 and 1990 led by the governmental alcohol incentive
programme;

Relative
stagnation between 1990 and the early 2000s;
Renewed
growth from the early 2000s to the present in connection with the rising
price of oil in international markets and, more locally, with the introduction of
flexi-fuel vehicles (FFVs).

It is important to emphasise that the introduction of FFVs in the early 2000s had a
decisive effect on the consumption of ethanol motor fuels. A number of projects are
underway to build infrastructure, including port terminals and pipelines. The main target
market is Japan, whose government is considering enforcing the use of 310% ethanol in
gasoline products and whose production capacity is very limited. The US and Europe are
also potential export markets.
FIGURE 9.2 Ethanol production in Brazil, 19822006

.JMMJPOHBMMPOT

Source: Based on data from EPI (2005)
Page 88

In March 2007, Brazil and the US signed a broad agreement to work together to advance
biofuels technology and set common standards for the ethanol trade. Brazil plans
to double its ethanol production to 9.2 billion gallons per year and triple its ethanol
exports to 2.6 billion gallons per year between 2007 and 2014, and it will require about
$13.4 billion in investments to meet that goal. The production increase will require the
construction of 89 new ethanol production plants. The National Ethanol Programme
in Brazil, initiated in 1975, reduced crude oil imports by 59%. Brazil no longer offers
subsidies to ethanol producers, the industry generates sustainable profit. Ethanol, on
average, costs $0.50 less per gallon than imported gasoline. Brazil, the US, Latin America
and the Caribbean become the Saudi Arabia of ethanol.
In Brazil, 45% of the total fuel used in cars is bioethanol. Flexi-fuel vehicles which
allow the use of high percentage blends of bioethanol have proved very popular and it is
predicted that by 2010 all new cars bought in Brazil will be flexi-fuel models. Statistical
data from ANFAVEA (2006), the Brazilian Motor Manufacturers Association, shows strong
growth in the sales of flexi-fuel cars capable of running on high blends of bioethanol,
unleaded petrol or any mixture of the two.
TABLE 9.7 Flexi-fuel cars sold in Brazil, 200306 (cumulative sales)
2003
2004
2005
2006
43,200
37,600
1.2 million
2 million+
Source: Based on data from ANFAVEA (2006)
In 2004, over 350,000 flexi-fuel cars were sold in Brazil (ANFAVEA, 2006). This amounted
to 16.1% of the market, a 500% increase from 2003. In 2005, flexi-fuel car sales jumped
again to approximately 800,000, or 38% of the cars sold.
Brazils ethanol industry has been encouraged by government support. A mandate
requires all Brazilian gasoline to contain 25% ethanol and the government helped to fund
the establishment of the ethanol supply infrastructure. Brazils current very strong position
regarding fuel ethanol can mainly be explained by the early introduction of a large ethanol
support programme in 1975, favourable feedstock production conditions and the widespread
use of flexi-fuel cars. Current support instruments include blending provisions, minor mineral
oil tax reductions for fuels containing ethanol, and motor vehicle tax reductions for ethanolpowered cars. Fuel ethanol prices have been very competitive compared to petrol prices.
TABLE 9.8 Ethanol production costs in different countries ($ per litre)
Australia (sugar cane)
Brazil (sugar cane)
EU (cereals)
Thailand (sugar cane)
US (corn)
Source: Based on data from Salomao (2005)
Page 89
0.32
0.20
0.97
0.29
0.47
Ethanol production costs are lowest in Brazil (see Table 9.9). Energy balances for the
production of bioethanol in Brazil are quite impressive. This is due to the low requirement
for mineral fertilisers in the cultivation of sugar cane and the energy surplus in the
conversion process which results from the use of bagasse as an energy source. Therefore,
greenhouse gas emissions per litre of bioethanol are much lower than in Europe. The
greenhouse gas abatement attained by the substitution of bioethanol for traditional
gasoline ranges between 2kg and 2.8kg CO2-equivalent per litre of bioethanol.
Some 85% of Brazils sugar cane production is concentrated in the centre-south
region, especially in the states of So Paulo and Paran. The rest is produced in the
north-eastern part of Brazil but under less favourable conditions. Presently, the cultivation
of sugar cane is only responsible for a relatively small part of the total farmland. Brazil
has 320 million hectares of arable farmland of which 53 million are currently in use. Only
5.6 million hectares are used for the production of sugar cane. Currently, about half of
the sugar cane is allocated to the production of sugar, the other half to the production of
bioethanol. The crop yield in 2003 was 350 million tonnes. Great fluctuations in the yields
are mainly due to weather conditions.

The blending of bioethanol into gasoline started with the Prolcool programme
after the first oil crisis in 1975. Today, there is no ethanol-free gasoline on the Brazilian
fuel market. All gasoline is marketed with a 25% share of bioethanol (E25, also called
gasohol). Actual ethanol content varies as it is adapted yearly according to the market
situation. Pure bioethanol (E100) is on the market as well. In 2005, about 14 million cubic
metres of bioethanol were sold on the domestic market as E100 or E25. For these two
types of fuels there are three different types of automobiles on the market:

To
use the so-called gasohol, ordinary gasoline engines need some minor
modification. Automobiles on the market in Brazil experience no problems using E25.

On the contrary, the blending of bioethanol improves the engine performance.

There
are automobiles that use pure bioethanol (E100) which need more modification.
Since
2003, so-called flexible fuel vehicles (FFVs) have been on the market. They can
be run on E25 as well as E100. This type of vehicle has been a major success.

In 2004, FFVs already accounted for 30% of the newly registered vehicles. In mid-2006,
FFVs reached 80% of sales of new vehicles. In comparison with neat ethanol vehicles, the
main advantage of the FFVs is that these engines can operate with any fuel mix between
gasoline (in Brazil, E20E25) and pure hydrated ethanol (E100). In 2010, the FFVs are
expected to account for 25% of the entire Brazilian fleet.
Brazil is the only country in the world with the right conditions to considerably
expand its capacity of ethanol production in the short to mid term, for example land
availability, technology, workforce, investment capacity, etc. Currently 335 units are in
operation and some 80 new industrial units are in different stages of construction
(Unica, 2006). It is expected that ethanol production capacity will more than double from
2006 to 2015 (Carvalho, 2006). Potentially, Brazil could expand its ethanol production
Page 90
capacity 810 times in the next 2030 years. Ethanol production in Brazil is so far
concentrated in the state of So Paulo, which was responsible for 72% of the production
in 2006 (Carvalho, 2006). Once the planned expansion production is completed,
production will be better distributed countrywide.
Canada
A number of major initiatives are underway to increase production significantly. Canada

currently produces relatively low volumes of fuel ethanol. In 2006, total fuel ethanol
production amounted to about 150 million gallons. Production is expected to increase
significantly by 2010 if current and announced biofuels programmes are implemented.
To meet Kyoto Protocol commitments, the country aims to replace 35% of its gasoline use
with E10 blends, requiring production of 350 million gallons of ethanol. Seven new plants
with a total capacity of 200 million gallons are planned under the Ethanol Expansion
Program. Ontario, Saskatchewan and Manitoba are already promoting ethanol through
production subsidies, tax breaks and blending requirements.
In Canada, ethanol is produced almost entirely from cereals. Iogen Corp. maintains a
demonstration plant in Ottawa for producing ethanol from cellulose, but this plant produces
demonstration, not commercial, quantities of cellulose ethanol (Tolan, 2006, 2007).

Ethanol-blended gasoline is now available at over 700 petrol stations across Canada
from Quebec to the Pacific, including the Yukon Territory. In many regions, ethanol blends
are available for bulk delivery for farm and fleet use. The federal government and several
provinces offer tax incentives based on environmental, economic development and/or
energy diversity benefits, for the production and/or marketing of ethanol-blended gasoline
to encourage development of an alternative fuel industry. Also, Environment Canada has
designated ethanol-blended gasoline, which meets their specifications, as an Environmental
Choice product on the basis of reduced toxic emissions, reduced use of non-renewable
resources and reduced carbon dioxide emissions. However, a firm and broad-based
commitment to procurement and incentives for ethanol in the near term is essential to
ensure the successful establishment of this fledgling renewable energy industry.
India
India is the second-largest producer of ethanol in Asia and is one of the worlds largest
sugar producers. Traditionally most of the Indian ethanol production is directed to
industrial consumption (Rosillo-Calle and Walter, 2006). Recently, mainly due to economic
and strategic reasons, the Indian government has seriously considered fuel ethanol
production and a mandate for E10 blends is currently effective in 13 states. Up to 2010, the
mandate for E10 will be effective in the whole country. In addition, the Indian Institute of
Petroleum has conducted experiments using a 10% ethanol blend in gasoline and
15% ethanol in biodiesel (DSD, 2005).
The Indian vehicle fleet is dominated by domestically produced models. Some 70%
of the fleet are motorcycles, 11% are scooters and only 19% are cars. Indian-produced cars
are typically local variants of international models produced by the major automotive
manufacturers, such as Suzuki, Ford, Toyota and Mitsubishi. In the past, Indian-produced
Page 91
vehicles were often based on older models. For example, the Hindustan Ambassador,
which is still produced, is based on a 1950s Morris Oxford although it has been
modernised. In spite of this preponderance of old-technology vehicles, there are no reports
of any problems with E5 use in India.

In addition to the federal moves, several Indian states have also attempted to support
local ethanol production through the use of additional fiscal measures. The government
plans to achieve a countrywide ethanol-petrol blending rate of 5% in the near future,
which would require 500 million litres of ethanol. Later on, it plans to increase the ethanol
content in petrol to 10% and to blend conventional diesel with 5% ethanol. The countrys
Planning Commission proposes increasing the proportion of biofuels used in India from
5% to 20% by 2012.

India has the potential to be a large-scale fuel ethanol producer from sugar cane
and its dependency on foreign oil supplies justifies this. However, land availability will
be a matter of concern in India. Also, sugar cane is produced by many small farmers and
cost reductions due to scale of production will be more difficult. India is currently Brazils
largest customer for ethanol exports, just ahead of the US (Lynch, 2006).
Thailand
Low oil reserves force Thailand to import 90% of its oil consumption (Potash Corp., 2006).
This is equivalent to 13% of the countrys GDP, making Thailand desperate to reduce its
reliance on foreign oil.
The Thai government is pursuing a policy of increasing consumption of biodiesel and
ethanol produced domestically from cassava. One of its initial steps has been to replace
the octane-enhancing additive MTBE in gasoline with ethanol, immediately driving its
ethanol requirement from an insignificant level in 2003 to 90 million gallons per year by
the end of 2006.

Large-scale production of fuel ethanol production has started with molasses, but
cassava was officially designated the prime raw material. Thailand is a large producer of
cassava and, depending on rainfall, it is possible to grow up to three crops per year. In
addition, low-fertility land can be utilised even with minimal inputs of fertilisers. As the
domestic price of sugar is high, it does not seem worth producing ethanol from sugar cane.

According to the Thai government policy, by the end of 2009 there will be at least
24 ethanol plants in operation, totalling a production capacity of 1.7Gl. Production

capacity will reach 1.8Gl by the end of 2011. By early 2006, the demand for fuel ethanol
had already increased, but domestic production was able to cover only 30% of the total
demand. In Thailand all premium gasoline will be replaced by E10.
Japan
Japan is one of the main consumers of motor gasoline in the world and is heavily
dependent on imported oil. The country has considered large-scale use of fuel ethanol,
or ETBE, aiming at improving its energy security and at reducing GHG emissions, in this
case in order to accomplish its Kyoto obligations. Since 2005, the use of E3 (ethanol 3%,
gasoline 97%) has not been mandatory in Japan and now ethanol blends are used in
Page 92
some regions. The Japanese government intends to define a mandate for E3 valid for
the whole country and to expand this mandate to E10 by 2010. However, there is some
resistance due to the low number of large-scale ethanol suppliers and also due to the
interests of oil companies that prefer gasoline blends with ETBE rather than with fuel
ethanol (Piacente, 2006).

During 2006, it was announced by the Environment Ministry that a new policy would
require all new cars to be able to run on a blend of 10% ethanol by 2006. The same
ministry has set the goal to have all cars in Japan capable of running on the new fuel by
2030. These vehicles will probably be flexi-fuel models (Ethanol News, 2006). In 2005,
Japan was the second-largest importer of ethanol (more than 500Ml) that was mostly
used as fuel ethanol. If a mandate for fuel ethanol blends is decided, or even ETBE blends,
Japan will be one of the main markets for fuel ethanol in the world.
Page 93
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The facts set out in this publication

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Promising developments in the

Markets for bioethanol 49

Problems with ethanol/ethanol

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3.4Comparison of the different cellulose

1.1The carbon cycle 3

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3.5SHF with separate pentose and

Reductions in GHG (greenhouse gas) emissions

Source: Pira International Ltd

Large-scale, sustainable, worldwide production and use of bioethanol from biomass

is a proven global transport fuel, presently supplying 1.2% of the worlds

form of energy and in the long run will be relatively cheap.

Copyright Pira International Ltd 2007

Bioethanol contains more useful energy than is required to produce it.

reduces emissions of greenhouse gases, of carcinogens such as benzene and

of other harmful emissions such as particulates. It is biodegradable in water and soil.

industries provide economic development and employment in rural areas. The

enhances competitiveness through the development of new and efficient

technologies. Above all, it offers the prospect of converting lignocellulose into

has the potential to be used in compression engines as well as spark

is unique amongst todays sustainable transport fuel options in that it

Important environmental benefits could be achieved in the socio-economic development

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FIGURE 1.1 The carbon cycle

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TABLE 1.2 (Continued)

Source: Pira International Ltd

Ethanol is already commonly used in a 10% ethanol/90% gasoline blend. Adapted

Sasol, with operations in South Africa and Germany

SADAF of Saudi Arabia

A 50:50 joint venture between Shell of the UK and the Netherlands

The Saudi Arabian Basic Industries Corporation

Equistar in the US.

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A bigger crop variety can be employed

A larger portion of these crops can be converted.

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By contrast, sugar-fermented ethanol reduces greenhouse gas emissions by 1819%

Source: Based on data from RFA (2006a, 2007a); www.earth-policy.org/Updates/2005/Update49_data.htm

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TABLE 1.5 World ethanol production in 2006 (%)

Source: Based on data from RFA, 2007a

Source: Based on data from RFA, 2006c, 2007a

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ethanol industry, thus developing lower-cost methods of producing greater quantities of

This report also discusses the advantages, biotechnology breakthroughs and

promising developments in the production of cellulosic ethanol. Furthermore, it addresses

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Bacteria: Single-celled micro-organisms which can exist either as independent organisms

Bioenergy: Energy (fuel, electricity, heat) produced from biomass.

Biofuel: Liquid or gaseous fuel for transport, produced from biomass.

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Cellulase: Cellulase is an enzyme that hydrolyses cellulose to its constituent

Emissions: Waste substances released into the air or water.

Enzyme: Protein that acts as a catalyst, or biocatalyst, in living organisms.

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3.4Comparison of the different cellulose

1.1The carbon cycle 3

3.5SHF with separate pentose and

Climate change effects are supposed to be worst in developing countries so it is

Anhydrous ethanol: it is water free or absolute. A second-stage process is required