Chapter 11

Biomass and biofuels

11.1 Introduction
The material of plants and animals, including their wastes and residues,
is called biomass. It is organic, carbon-based, material that reacts with
oxygen in combustion and natural metabolic processes to release heat.
Such heat, especially if at temperatures >400  C, may be used to generate
work and electricity. The initial material may be transformed by chemical
and biological processes to produce biofuels, i.e. biomass processed into
a more convenient form, particularly liquid fuels for transport. Examples
of biofuels include methane gas, liquid ethanol, methyl esters, oils and
solid charcoal. The term bioenergy is sometimes used to cover biomass and
biofuels together.
The initial energy of the biomass-oxygen system is captured from solar
radiation in photosynthesis, as described in Chapter 10. When released in
combustion the biofuel energy is dissipated, but the elements of the material
should be available for recycling in natural ecological or agricultural pro-
cesses, as described in Chapter 1 and Figure 11.1. Thus the use of industrial
biofuels, when linked carefully to natural ecological cycles, may be non-
polluting and sustainable. Such systems are called agro-industries, of which
the most established are the sugarcane and forest products industries; how-
ever, there are increasing examples of commercial products for energy and
materials made from crops as a means of both diversifying and integrating
agriculture.
The dry matter mass of biological material cycling in the biosphere is
about 250 × 109 t y−1 incorporating about 100 × 109 t y−1 of carbon. The
associated energy bound in photosynthesis is 2 × 1021 J y−1
=07 × 1014 W.
Of this, about 0.5% by weight is biomass as crops for human food. Biomass
production varies with local conditions, and is about twice as great per unit
surface area on land than at sea.
Biomass provides about 13% of mankind’s energy consumption, includ-
ing much for domestic use in developing countries but also significant
amounts in mature economies; this percentage is comparable to that of
fossil gas. The domestic use of biofuel as wood, dung and plant residues
352 Biomass and biofuels

Solar radiation
Biomass energy
store

Photosynthesis Natural Domestic and

industrial
biofuels

CO2 Energy
nutrients humus release

Figure 11.1 Natural and managed biomass systems.

for cooking is of prime importance for about 50% of the world’s pop-
ulation. The industrial use of biomass energy is currently comparatively
small for most countries, except in a few sugarcane-producing countries
where crop residues (bagasse) burnt for process heat may be as much as
40% of national commercial supply. Nevertheless, in some industrialised
countries, the increasing use of biomass and wastes for heat and electricity
generation is becoming significant, e.g. USA (about 2% of all electricity at
11 GWe capacity); Germany (at 05 GWe capacity) and in several countries
for co-firing with coal.
If biomass is to be considered renewable, growth must at least keep pace
with use. It is disastrous for local ecology and global climate control that
firewood consumption and forest clearing is significantly outpacing tree
growth in ever increasing areas of the world.
The carbon in biomass is obtained from CO2 in the atmosphere via
photosynthesis, and not from fossil sources. When biomass is burnt or
digested, the emitted CO2 is recycled into the atmosphere, so not adding
to atmospheric CO2 concentration over the lifetime of the biomass growth.
Energy from biomass is therefore ‘carbon neutral’. This contrasts with the
use of fossil fuels, from which extra CO2 is added to the atmosphere. The
use of biomass in place of fossil fuels leaves the fossil fuel underground and
harmless; the use of biomass ‘abates’ the extra CO2 otherwise emitted. Thus
use of renewable biofuels, on a large scale, is an important component of
most medium- to long-term policies for reducing greenhouse gas emissions.
The energy storage of sunshine as biomass and biofuels is of fundamental
importance. All of the many processes described in this chapter have
the aim of producing convenient fuels, at economical prices, for a full
range of end-uses, including liquid fuel for transport. The heat energy
available in combustion, equivalent in practice to the enthalpy or the net
−1
energy density, ranges from about 8 MJ kg (undried ‘green’ wood) and
 11.1 Introduction 353

−1 −1 −1
15 MJ kg (dry wood), to about 40 MJ kg (fats and oils) and 56 MJ kg
(methane). Biomass is, however, mostly carbohydrate material with a
−1
heat of combustion of about 20 MJ kg dry matter; refer to Table B.6,
Appendix B for detail.
The success of biomass systems is regulated by principles that are often
not appreciated:

1 Every biomass activity produces a wide range of products and services.

For instance where sugar is made from cane, many commercial products
can be obtained from the otherwise waste molasses and fibre. If the
fibre is burnt, then any excess process heat can be used to generate
electricity. Washings and ash can be returned to the soil as fertilizer.
2 Some high-value fuel products may require more low-value energy to
manufacture than they produce, e.g. ethanol from starch crops, hydro-
gen. Despite the energy ratio being >1, such an energy deficiency need
not be an economic handicap provided that process energy can be avail-
able cheaply by consuming otherwise waste material, e .g. straw, crop
fibre, forest trimmings.
3 The full economic benefit of agro-industries is likely to be widespread
and yet difficult to assess. One of many possible benefits is an increase
in local ‘cash flow’ by trade and employment.
4 Biofuel production is only likely to be economic if the production
process uses materials already concentrated, probably as a by-product
and so available at low cost or as extra income for the treatment and
removal of waste. Thus there has to be a supply of biomass already
passing near the proposed place of production, just as hydro-power
depends on a natural flow of water already concentrated by a
catchment. Examples are the wastes from animal enclosures, offcuts
and trimmings from sawmills, municipal sewage, husks and shells
from coconuts and straw from cereal grains. It is extremely important
to identify and quantify these flows of biomass in a national or
local economy before specifying likely biomass developments. If no
such concentrated biomass already exists as a previously established
system, then the cost of biomass collection is usually too great and too
complex for economic development. Some short-rotation crops may be
grown primarily for energy production as part of intensive agriculture;
however, within the widespread practice of agricultural subsidies it is
difficult to evaluate fundamental cost-effectiveness.
5 The main dangers of extensive biomass fuel use are deforestation, soil
erosion and the displacement of food crops by fuel crops.
6 Biofuels are organic materials, so there is always the alternative of
using these materials as chemical feedstock or structural materials. For
instance, palm oil is an important component of soaps; many plastic and
354 Biomass and biofuels

pharmaceutical goods are made from natural products; and much build-
ing board is made from plant fibres constructed as composite materials.
7 Poorly controlled biomass processing or combustion can certainly pro-
duce unwanted pollution, especially from relatively low temperature
combustion, wet fuels and lack of oxygen supply to the combustion
regions. Modern biomass processes require considerable care and
expertise.
8 The use of sustainable biofuels in place of fossil fuels abates the
emission of fossil-CO2 and so reduces the forcing of climate change.
Recognition of this is a key aspect of climate change policies.

Section 11.2 sets out a classification of biofuels, while the sections following
it consider the different types one by one. The concluding section brings
together the social, economic and environmental considerations that are
vital if biofuels are to contribute positively, and not negatively, to sustain-
able development.

11.2 Biofuel classification

Biomass is largely composed of organic material and water. However, signif-
icant quantities of soil, shell or other extraneous material may be present in
commercial supplies. It is essential that biomass is clearly assessed as either
wet or dry matter mass, and the exact moisture content should be given.
If m is the total mass of the material as it is and m0 is the mass when
completely dried, the dry basis moisture content is w =
m − m0 /m0 and
the wet basis moisture content is w =
m − m0 /m. The moisture content is
in the form of extracellular and intracellular water, and so drying processes
may be necessary, see Section 6.3. When harvested, the wet basis moisture
content of plants is commonly 50%, and may be as large as 90% in aquatic
algae including seaweed (kelps). The material is considered ‘dry’ when
it reaches long-term equilibrium with the environment, usually at about
10–15% water content by mass.
Carbon-based fuels may be classified by their reduction level,
Section 10.4. When biomass is converted to CO2 and H2 O, the energy
made available is about 460 kJ per mole of carbon (38 MJ per kg of carbon;
∼16 MJ per kg of dry biomass), per unit of reduction level R. This is not an
exact quantity because of other energy changes. Thus sugars
R = 1 have
a heat of combustion of about 450 kJ per 12 g of carbon content. Fully
reduced material, e.g. methane CH4
R = 2, has a heat of combustion of
about 890 kJ per 12 g of carbon (i.e. per 16 g of methane).
The presence of moisture in biomass fuel usually leads to a significant loss
−1
in useful thermal output because (i) evaporation uses 23 MJ kg of water
and (ii) the subsequently reduced combustion temperature increases smoke
 11.2 Biofuel classification 355

Oxygen Combustion
Solar Process heat
of fuels for: Transport
energy Direct Power
Photosynthesis combustion supply etc.

Biomass Thermo- Gases

production chemical Pyrolysis Liquids
Oils
Gasification Charcoal
Residues Further Gases
processes Liquids

Alcoholic
fermentation Ethanol
Bio-
chemical
Anaerobic Biogas/
digestion methane

Land fill
gas

Biophotolysis Hydrogen

Agrochemical Fuel extraction Liqiuds

Oils

Organic
humus
and nutrients
recycled

Figure 11.2 Biofuel production processes.

and air pollution. With condensing boilers, much of such latent heat can be
recovered by condensing water vapour in the emission and so pre-heating
incoming cold water. Nevertheless, the task of clean combustion remains.
The density of biomass, and the bulk density of stacked fibrous biomass,
is important. In general three to four times the volume of dry biological
material has to be accumulated to provide the same energy as coal. Thus
transport and fuel handling become difficult and expensive, especially if the
biofuels are not utilised at source.
We have identified three classifications and nine general types of biomass
energy process for fuller discussion in the later sections. These are as follows
(Figure 11.2).

11.2.1 Thermochemical, heat

1 Direct combustion for immediate heat. Dry homogeneous input is
preferred.
2 Pyrolysis. Biomass is heated either in the absence of air or by the partial
combustion of some of the biomass in a restricted air or oxygen supply.
356 Biomass and biofuels

The products are extremely varied, consisting of gases, vapours, liquids

and oils, and solid char and ash. The output depends on temperature,
type of input material and treatment process. In some processes the
presence of water is necessary and therefore the material need not be
dry. If output of combustible gas is the main product, the process is
called gasification.
3 Other thermochemical processes. A wide range of pre-treatment and
process operations are possible. These normally involve sophisticated
chemical control and industrial scale of manufacture; methanol pro-
duction is such a process, e.g. for liquid fuel. Of particular importance
are processes that break down cellulose and starches into sugars, for
subsequent fermentation.

11.2.2 Biochemical
4 Aerobic digestion. In the presence of air, microbial aerobic metabolism
of biomass generates heat with the emission of CO2 , but not methane.
This process is of great significance for the biological carbon cycle,
e.g. decay of forest litter, but is not used significantly for commercial
bioenergy.
5 Anaerobic digestion. In the absence of free oxygen, certain micro-
organisms can obtain their own energy supply by reacting with carbon
compounds of medium reduction level (see Section 10.4) to produce
both CO2 and fully reduced carbon as CH4 . The process (the oldest
biological ‘decay’ mechanism) may also be called ‘fermentation’, but is
usually called ‘digestion’ because of the similar process that occurs in
the digestive tracts of ruminant animals. The evolved mix of CO2  CH4
and trace gases is called biogas as a general term, but may be named
sewage gas or landfill-gas as appropriate.
6 Alcoholic fermentation. Ethanol is a volatile liquid fuel that may be
used in place of refined petroleum. It is manufactured by the action of
micro-organisms and is therefore a fermentation process. Conventional
fermentation has sugars as feedstock.
7 Biophotolysis. Photolysis is the splitting of water into hydrogen and
oxygen by the action of light. Recombination occurs when hydrogen
is burnt or exploded as a fuel in air. Certain biological organisms
produce, or can be made to produce, hydrogen in biophotolysis. Similar
results can be obtained chemically, without living organisms, under
laboratory conditions. Commercial exploitation of these effects has not
yet occurred, see Section 10.7.2.
 11.3 Biomass production for energy farming 357

11.2.3 Agrochemical
8 Fuel extraction. Occasionally, liquid or solid fuels may be obtained
directly from living or freshly cut plants. The materials are called exu-
dates and are obtained by cutting into (tapping) the stems or trunks
of the living plants or by crushing freshly harvested material. A well-
known similar process is the production of natural rubber latex. Related
plants to the rubber plant Herea, such as species of Euphorbia, produce
hydrocarbons of less molecular weight than rubber, which may be used
as petroleum substitutes and turpentine.
9 Biodiesel and esterification. Concentrated vegetable oils from plants
may be used directly as fuel in diesel engines; indeed Rudolph Diesel
designed his original 1892 engine to run on a variety of fuels, including
natural plant oils. However, difficulties arise with direct use of plant
oil due to the high viscosity and combustion deposits as compared with
standard diesel-fuel mineral oil, especially at low ambient temperature

≤∼5  C. Both difficulties are overcome by converting the vegetable
oil to the corresponding ester, which is arguably a fuel better suited to
diesel engines than conventional (petroleum-based) diesel oil.

11.3 Biomass production for energy farming

This section links the discussion of photosynthesis in Chapter 10 to
the production of crops. Of particular importance are the efficiencies of
photosynthesis and biomass production, Sections 10.2 and 10.6.6.

11.3.1 Energy farming

We use this term in the very broadest sense to mean the production of fuels
or energy as a main or subsidiary product of agriculture (fields), silviculture
(forests), aquaculture (fresh and sea water), and also of industrial or social
activities that produce organic waste residues, e.g. food processing, urban
refuse. Table 11.1 gives some examples from an almost endless range of
opportunities. The main purpose of the activity may be to produce energy
(as with wood lots), but more commonly it is found best to integrate
the energy and biofuel production with crop or other biomass material
products.
An outstanding and established example of energy farming is the sug-
arcane industry (Figure 11.3). The process depends upon the combustion
of the crushed cane residue (bagasse) for powering the mill and factory
operations. With efficient machinery there should be excess energy for the
production and sale of by-products, e.g. molasses, chemicals, animal feed,
ethanol, fibre board and electricity. Commonly the ethanol becomes a com-
ponent of transport fuel and the excess electricity is sold to the local grid.
Table 11.1 Biomass supply and conversion examples

Biomass source or fuel Biofuel Conversion technology Approx. Energy required Approx. range of energy
produced conversion in conversion: from biofuel/MJ
efficiency/% (n) necessary,
(o) optional

Forest logging (Heat) Combustion 70 Drying (o) 16–20 kg wood −1

⎡
Wood from timber mill residues either (a) (Heat) Combustion 70 Drying (o) 16–20 kg wood −1
∗
⎢ Gas 40 kg gas −1
⎣
Wood from fuel lot cropping or (b) Oil Pyrolysis 85 Drying (o) 40 kg oil −1
Char 20 kg char −1
Grain crops Straw Combustion 70 Drying (o) 14–16 kg dry straw −1
Sugarcane pressed juice Ethanol Fermentation 80 Heat (n) 3–6 kg fresh cane −1
Sugarcane pressed residue Bagasse Combustion 65 Drying (o) 5–8 kg fresh cane −1
Sugarcane total – – – – 8–14 kg fresh cane −1
Animal wastes (tropical) Biogas Anaerobic digestion 50 – 4–8 kg dry input −1
†
Animal wastes (temperate) Biogas Anaerobic digestion 50 Heat (o) 2–4 kg dry input −1
Sewage gas Biogas Anaerobic digestion 50 – 2–4 kg dry input −1
−1
Landfill gas (from MSW†† ) Biogas Anaerobic digestion 40 – 2–4 kg dry compostable
Urban refuse (MSW)†† (Heat) Combustion 50 – 5–16 kg dry input −1

Notes
∗
Nitrogen removed.
†
This value is net, having deducted the biogas fed back to heat the boiler.
††
Municipal Solid Waste.
Figure 11.3 (a) Sugar cane agro-industry; process flow diagram. Bagasse is plant fibre
residue: molasses is sugar-rich residue. (b) A 30 MWe co-generation plant
in Queensland (Australia) fuelled by bagasse and wood waste from nearby
industry. Sugar cane is growing in the foreground; wood waste and bagasse
are stockpiled in the open. [Photo by courtesy of Stanwell Corporation.]
360 Biomass and biofuels

Table 11.2 Advantages and dangers of energy farming

Advantages Dangers and difficulties

Large potential supply May lead to soil infertility and erosion

Variety of crops May compete with food production
Variety of uses (including transport fuel
and electricity generation)
Efficient use of by-products, residues, Bulky biomass material handicaps
wastes transport to the processing factory
Link with established agriculture and May encourage genetic engineering of
forestry uncontrollable organisms
Encourages integrated farming practice
Establishes agro-industry that may
include full range of technical
processes, with the need for skilled
and trained personnel
Environmental improvement by utilising Pollutant emissions from poorly controlled
wastes processes
Fully integrated and efficient systems Poorly designed and incompletely
need have little water and air pollution integrated systems may pollute water
(e.g. sulphur content low) and air
Encourages rural development Large-scale agro-industry may be socially
disruptive
Diversifies the economy with respect to
product, location and employee skill
Greatest potential is in tropical countries, Foreign capital may not be in sympathy
frequently of the Third World with local or national benefit

The variety of opportunities for energy farming has distinct advantages

and disadvantages (Table 11.2). A major disadvantage is that energy crops
may substitute for necessary food production. For example, the grain farms
of the United States grow about 10% of the world’s cereal crops, and
export about one-third of this. A sudden change to producing biofuels, e.g.
ethanol from corn, on a large scale would therefore decrease world food
supplies before alternatives could be established. A second major danger
is that intensive energy farming would be a further pressure towards soil
infertility and erosion. The obvious strategy to avoid these excesses is (a) to
always grow plants that can supply both human foods (e.g. grain) and
energy (e.g. straw), (b) to decrease dramatically the feeding of animals from
crops; and (c) to use all resources more efficiently.

11.3.2 Geographical distribution

Perhaps the greatest potential for energy farming occurs in tropical countries,
especially those with adequate rainfall and soil condition. Table 11.3 gives esti-
mates of the potential bioenergy production of various regions of the world.
 11.3 Biomass production for energy farming 361

Table 11.3 Potential bioenergy by region EJ y−1 = 1018 J y−1 = 32 GW

Region A: Recoverable residues B: Potential A+B /

Biomass (national
Crops Forests and Dung Total plantations energy use)
see note: [a] woodland [b] [c] [d]

Industrialised
US+Canada 1.7 3.8 0.4 5.9 19 0.3
Europe 1.3 2 0.5 3.8 6 0.1
Aust.+NZ 0.3 0.2 0.2 0.6 10 2.8
Former USSR 0.9 2 0.4 3.3 25 0.5
Developing
Latin America 2.4 1.2 0.9 4.5 27 1.8
Africa 0.7 1.2 0.7 2.6 28 3.3
China 1.9 0.9 0.6 3.4 9 0.5
other Asia 3.2 2.2 1.4 6.8 18 0.9
world 12.5 13.6 5.2 31.2 142 0.5

Source: After Hall et al. (1993), based on country estimates by Biomass Uses Network.
Notes:
[a] 25% of residues from cereals, vegetables and sugar cane.
[b] 75% of mill wastes +25% of forestry residues.
[c] 12% of dung from farm animals.
[d] 8 dry tonnes per hectare per year on 10% of land now in forest or cropland or pasture.

The assumptions used are generally optimistic about what is ‘recoverable’,

how much land is available for plantations and the possible biomass yields
on that land (see notes on Table 11.3). Thus, present fuelwood use appears
to be only about half of the ‘forest’ residue potential, although assessment is
difficult, since most use is non-commercial. Moreover, it would be negligent
not to leave significant amounts of rotting wood for ecological sustainabil-
ity. Dung from cattle is often more valuable as fertiliser than as fuel and only
where animals are penned is it easily collected for biogas production. Never-
theless, only by establishing extensive sustainable biomass plantations with
the associated post-harvest mechanisms and markets can biomass become a
significant proportion of commercial energy supply.

11.3.3 Crop yield

It is not possible to predict crop yields without detailed knowledge of mete-
orological conditions, soil type, farming practice, fertiliser use, irrigation,
etc. Comparison between different crops is made even more difficult by dif-
ferences in growing seasons and harvesting methods. Some arable crops are
planted annually, e.g. cereal grains, and may be cropped more than once,
e.g. grasses. Others are planted every few years and harvested annually,
e.g. sugarcane, or may grow for long periods before harvesting, e.g. more
362 Biomass and biofuels

than ten months for some varieties of cassava. Trees may grow for many
years and be totally harvested (timber logging); other tree crops may grow
from the continuing roots and be harvested as coppice every few years,
e.g. willow, hazel and some eucalyptus. Table 11.4 is a summary of data to
estimate the maximum biofuel potential of crops in terms of heat of com-
bustion and continuing energy supply. The data for aquatic crops assume
abundant nutrients. Grasses are assumed to have frequent harvesting in the
growing season. We emphasise the considerable uncertainty of such data
and the rule that such generalisations should never be applied for actual
developments without site-specific testing.

11.3.4 Energy and greenhouse gas analysis

Crop growth requires two forms of energy: (1) solar irradiance and
(2) energy expended in labour, fuel for tractors, and manufacturing
machines and fertiliser, etc. The total of the second form of energy is the
gross energy requirement (GER), also called the embedded energy, and is
the total of all forms of energy other than incident solar energy sequestered
(used up) in producing the crop. It is best to explain the technique of
energy analysis by an example. Note, however, that such energy analysis
neglects the thermodynamic ‘quality’ of the energy involved, i.e. it neglects
the proportion of the energy that can be transformed to work; such analysis
involves the thermodynamic functions of Free Energy and Exergy and will
not be pursued here.
The GER analysis of Table 11.5 lists the energy sequestered for all the
market inputs to make ethanol from various crop substrates; solar energy
is not considered in the analysis here as an input, since it arrives as a free
input. The total GER is given per kg of ethanol (row 7 of the table). Note
that in most instances the energy obtainable from the final product (ethanol
−1
at 30 MJ kg ) is less than the GER, which gives the impression of a useless
fuel manufacturing process, with negative net energy production (row 8).
However, the greatest amount of energy in production is associated with
process heat and factory machines (rows 3, 4 and 5). Frequently all, or a
large part, of this energy is available at very low cost within the factory
from the combustion or pyrolysis of otherwise waste material (bagasse from
sugarcane, trimmings and other waste from timber, part of the straw from
cereal crops). Thus such energy supplies can be treated as low cost gains
rather like solar radiation. Row 10 gives the net energy production (the ‘gain’)
without the components of rows 3, 4 and 5, showing the dramatic change
produced if otherwise waste material is used as a free (i.e. no cost) energy gain.
Another important parameter is the energy ratio (ER), being the ratio
of the heat of combustion (strictly the enthalpy) of the crop to the Gross
Energy Requirement. Published values much depend on what is included in
GER, how the analysis is performed and what crop yields are assumed. For
Table 11.4 Maximum practical biomass yields. Total plant mass, not just the grain; ‘R’
indicates the mass is coppiced, with the roots remaining in the soil. The data
are from a variety of sources and summarised by the authors. Accuracy of no
more than ±25% is claimed. The majority of plants and crops yield much less
than these maxima, with yields much dependent on soil, climate, fertilisers
and farming practice

Biomass yield

t ha−1 y−1
Crop
Energy density Energy from dried yield
(Assume one crop per year Wet Dry
−1
unless indicated otherwise) (a) basis basis MJ kg dry GJ ha−1 y−1

Natural
Grassland 7 3
Forest, temperate C3 14 7 18 130
Forest, tropical C3 22 11 18 200
Forage
Sorghum (3crops) R, C4 200 50 17 850
Sudangrass (6 crops) R, C4 160 40 15 600
Alfalfa C3 40 25
Rye grass, temperate C3 30 20
Napier grass C4 120 80
Food
Cassava (60% tubers) 50 25
Maize (corn) (35% grain) C4 30 25 18 77 b
Wheat (35% grain) C3 30 22
Rice (60% grain) C3 20
Sugarbeet C3 45
Sugarcane R, C4 100 30 18 150 b
Soya beans C3 20 c
Rapeseed C3 30 c
Plantation
Oil palm R, C3 50 40
Combustion energy
Eucalyptus R, C3 55 20 19 380
Sycamore R, C3 20 10 19 190
Populus R, C3 18 29 19 380
Willow (salix) R, C3 25 15 19 350
Miscanthus R, C4 21 18 18 330
Water hyacinth C3 300 36 19 680
Kelp (macro-algae) C3 250 54 21 1100
Algae (micro-algae) C3 230 45 23 1000
Tree exudates
Good output 1 1 40 40

Notes
(a) C3 , C4 : photosynthesis type (see Section 10.6).
R: harvested above the root (coppiced).
(b) As ethanol.
(c) As biodiesel.
364 Biomass and biofuels

Table 11.5 Ethanol production: energy analysis from various crop substrates. Data refer
to the gross energy requirement for the crop input and each component
of manufacture: unit MJ kg−1 of anhydrous ethanol produced. The heat of
combustion of the output ethanol is Ho = 30 MJ kg−1 . Rows 1 to 7 are from
Slesser and Lewis (1979). Rows 8, 9 and 10 show the importance of using
free waste products in such processes, which, as with solar radiation, need
not be accounted to the process as are purchased products. Many of these
processes have improved since 1980 – see text

Sugarcane Cassava Timber Timber (acid Straw

(enzyme hydrolysis)
hydrolysis)

(1) Substrate 73 192 127 200 44

(2) Chemicals 06 09 47 64 47
(3) Water pumping 03 04 08 03 08
(4) Electricity 70 105 176 78 167
(5) Fuel oil 80 29 42 62 42
(6) Machinery and buildings 05 12 33 06 33
(7) Total (1)–(6) MJ kg−1 24 61 239 98 222
(8) Net energy: #= Ho − 7 $ +8 −31 −209 −68 −192
If inputs (3), (4), (5) from waste:
(9) Total # 1 + 2 + 6 $ 84 21 21 27 12
(10) Net energy #= Ho − 9 $ +21 +9 +9 +3 +18
(11) Energy ratio#= Ho / 9 $ 36 14 14 11 25

instance, post-2000 data from process and cultivation improvements for

bioethanol from sugar cane in Brazil, beyond those assumed in Table 11.5,
give an increased value of ER of about 6. However, data for ethanol pro-
duction from corn (maize) in the USA gives an ER of only about 1.3 because
no use is made of the crop residues (Keshgi et al. 2000). Improved processes
for ethanol from lignocellulose may have ER > 4, although this has yet to
be confirmed in commercial practice (see Section 11.7.1(4)). Energy ratio
is a useful indicator for food and energy crops since the values can relate
to the farming practice, e.g. ‘organic’ or ‘intensive’. Best practice in energy
crop production may give ER of about 18 (hybrid poplar), 16 (sorghum)
and 11 (switchgrass) (Hall et al. 1993).
Other concerns regarding the energy characteristics of fuels are:

a Why are inputs for non-sustainable sources (fossil and nuclear fuels)
usually neglected, but included for sustainable, renewable, resources?
b Why treat all energy inputs and outputs purely in terms of Enthalpy
(which neglects ‘quality’), and not as the more thermodynamically com-
prehensive parameters of Free Energy or Exergy (which enumerate
‘quality’)? Good quality energy supplies, e.g. electricity and methane,
are much more valuable than those of poor quality energy, e.g. brown
coal, wet wood or warm water.
 11.4 Direct combustion for heat 365

In practice the energy analysis and subsequent economic analysis of biomass

agro-industries is much more complicated than this simplistic approach.
However, the crucial factor remains that use of cheap biomass residues for
process heat and electricity production can be of overriding importance.
Energy analysis is a useful tool in assessing energy-consuming and energy-
producing systems, since it emphasises the technical aspects and choices of
the processes. For instance, from Table 11.5 it would seem obvious that
ethanol production from sugarcane is most reasonable. Nevertheless, the
final choice must involve other factors, such as the market for non-fossil
fuel supplies, the value of the alternative products and by-products, and
government polices and incentives.
By enumerating the CO2 emissions associated with the energy use in each
step of a process, energy analysis can readily be turned into analysis of the
associated greenhouse gas emissions. Such analyses distinguish ‘automati-
cally’ between (i) the use of biomass residues for process energy (zero net
CO2 emissions, since the residues would have decayed naturally anyway)
and (ii) the use of fossil fuel energy inputs (see Keshgi et al. 2000).

11.4 Direct combustion for heat

Biomass is burnt to provide heat for cooking, comfort heat (space heat),
crop drying, factory processes and raising steam for electricity production
and transport. Traditional use of biomass combustion includes (a) cooking
with firewood, with the latter supplying about 10–20% of global energy use
(a proportion extremely difficult to assess) and (b) commercial and indus-
trial use for heat and power, e.g. for sugarcane milling, tea or copra drying,
oil palm processing and paper making. Efficiency and minimum pollution
is aided by having dry fuel and controlled, high temperature combustion.
Table B.6 gives the heat of combustion for a range of energy crops, residues,
derivative fuels and organic products, assuming dry material. Such data are
important for the industrial use of biomass fuel.

11.4.1 Domestic cooking and heating

A significant proportion of the world’s population depends on fuelwood
or other biomass for cooking, heating and other domestic uses. Average
daily consumption of fuel is about 0.5–1 kg of dry biomass per person,
−1
i.e. 10–20 MJ d ≈ 150 W. Multiplied by, say, 2 × 109 people, this repre-
sents energy usage at the very substantial rate of 300 GW. Most domestic
fuelwood use, but certainly not all, is in developing countries, with the
majority not included in commercial energy statistics. Here we assume the
fuel has dried thoroughly, since this is an essential first step for biomass
combustion, see Sections 6.4 and 11.4.2; using wet or damp fuel should be
avoided.
366 Biomass and biofuels

An average consumption of 150 W ‘continuous’, solely for cooking,

may seem surprisingly large. Such a large consumption arises from the
widespread use of inefficient cooking methods, the most common of which
is still an open fire. This ‘device’ has a thermal efficiency of only about
5%. That is, only about 5% of the heat that could be released by complete
combustion of the wood reaches the interior of the cooking pot. The rest
is lost by incomplete combustion of the wood, by wind and light breezes
carrying heat away from the fire, and by radiation losses, etc. resulting from
the mismatch of fire and pot size. Considerable energy is also wasted in
evaporation from uncovered pots and from wet fuel. Smoke (i.e. unburnt
carbon and tars) from a fire is evidence of incomplete combustion, and
there may be little control over the rate at which wood is burnt. More-
over, the smoke is a health hazard to the cook unless there is an efficient
extraction chimney. However, a reason for allowing internal smoke may be
to deter vermin and pests from the roof, and to cure (‘smoke’) dried food.
Efficiently burnt dry wood, in which the initially produced unburnt gases
and tars burn in a secondary reaction, emits only CO2 and H2 O with fully
combusted ash.
Cooking efficiency and facilities can be improved by

1 Using dry fuel.

2 Introducing alternative foods and cooking methods, e.g. steam cookers.
3 Decreasing heat losses using enclosed burners or stoves, and well-fitting
pots with lids.
4 Facilitating the secondary combustion of unburnt flue gases.
5 Introducing stove controls that are robust and easy to use.
6 Explanation, training and management.

With these improvements, the best cooking stoves using fuelwood and nat-
ural air circulation can place more than 20% of the combustion energy into
the cooking pots. Designs using forced and actively controlled ventilation,
say with an electric fan, can be more than 80% efficient. There are many
scientifically based programs to improve cooking stoves, yet full market
acceptability is not always reached, especially if cultural and gender factors
are not considered adequately. A major difficulty of ‘efficient’ stoves may
be the difficulty of obtaining rapid heat.
The combustion of firewood is a complex and varying process. Much
depends on the type of wood and its moisture content. Initial combustion
releases CO, which itself should burn in surplus air. At temperatures greater
than 370  C, calcium oxalate in the wood breaks down with the release
of some oxygen, so improving combustion and reducing particulate and
combustible emissions. Good design ensures that high temperature com-
bustion is restricted to a ‘white-hot’ small volume and that pyrolytic gases
 11.4 Direct combustion for heat 367

are themselves burnt in a secondary combustion region where further air

enters.
If space heating is needed, then the seemingly wasted heat from cook-
ing becomes useful. If space heat alone is needed, then closed stoves with
controlled combustion can be 80–90% efficient.
A parallel method for reducing domestic fuelwood demand is to encour-
age alternative renewable energy supplies, such as biogas (methane with
CO2 ), see Section 11.6 fuel from crop wastes and small-scale hydro-power,
Section 8.5. The need for such improvements is overwhelming when forests
are dwindling and deserts increasing.
Figure 11.4 shows two types of wood burning stoves, designed to make
better use of wood as a cooking fuel. Both designs are cheap enough to
allow widespread use in developing countries. More expensive stoves (often
called ranges) for both cooking and water-heating are luxury items in many
kitchens of northern European and North American homes, where some
designs allow wood burning.
In the stove shown in Figure 11.4(a), the fire is completely enclosed in
the firebox at the left. The iron (dark coloured) door is removed only when
fuel is inserted. Air enters through a hole of adjustable size beneath the
door (fully shut in the photo). Thus the rate of combustion can be closely
controlled to match the type of cooking being done. Hot gases from the
fire are led through a narrow channel underneath the cooking pots, which
are sized to fit closely in holes on the top. At this stage air can enter
through further channels for secondary combustion. The fully burnt gases
and vapours pass to the outside environment through the chimney at the far
end of the stove; this prevents pollution in the cooking place and encourages
air flow.
The stove shown in Figure 11.4(b) is simpler and cheaper, but has less
control and less flexibility. Nevertheless its small mass means that it is
transportable and little heat is used in heating the stove as distinct from
the pot, which is an advantage for quick cooking. Air reaches the fuel from
below, through a grate. Since the fire is contained and the heat is channelled
towards the pot, the efficiency is high. This stove is well suited for use with
charcoal as a fuel, since charcoal burns cleanly without smoke.
Many of these remarks on cooking apply also to the use of biofuels for
comfort (space) heat in buildings. It is important to have a controlled fire
with good secondary combustion. In some systems air for combustion is
introduced directly to the stove from outside the building. This decreases
air circulation and heat losses in the room. Some very sophisticated and
efficient wood-burners for heating are in wide use, especially in some wood-
rich industrialised countries (e.g. Norway, Canada and New Zealand) and
countries encouraging markets in fuelwood chips and pellets from otherwise
waste biomass residues (e.g. Northern Europe). For the latter, sophisticated
 (a)

(b) (c)

Figure 11.4 Improved efficiency cooking stoves. (a) A large stove designed by the Fiji
Ministry of Energy. It is a modification of the Indian (Hyderabad) chula, and
is constructed mainly from concrete mouldings. Its operation is described in
the text. (b) The ‘Thai bucket’ stove (sketch). (c) Vertical section through
same (units millimetres).
 11.4 Direct combustion for heat 369

stoves, usually with automatic input of fuel, are manufactured to ensure

ease of use, fuel efficiency and minimum pollution.

11.4.2 Crop drying

The drying of crops (e.g. fruit, copra, cocoa, coffee, tea), for storage and
subsequent sale, is commonly accomplished by burning wood and the crop
residues, or by using the waste heat from electricity generation. The material
to be dried may be placed directly in the flue exhaust gases, but there is a
danger of fire and contamination of food products. More commonly air is
heated in a gas/air heat exchanger before passing through the crop. Drying
theory is discussed in Section 6.4.
Combustion of residues for crop drying is a rational use of biofuel, since
the fuel is close to where it is needed. Combustion in an efficient furnace
yields a stream of hot clean exhaust gas
CO2 + H2 O + excess air at about
1000  C, which can be diluted with cold air to the required temperature. In
almost all cases, the flow of biomass exceeds that required for crop drying,
leaving an excess of the residues for other purposes, such as producing
industrial steam.

11.4.3 Process heat and electricity

Steam process heat is commonly obtained for factories by burning wood or
other biomass residues in boilers, perhaps operating with fluidized beds. It
is physically sensible to use the steam first to generate electricity before the
heat degrades to a lower useful temperature. The efficiency of electricity
generation from the biomass may be only about 20–25% due to low tem-
perature combustion, so 75–80% of the energy remains as process heat and
a useful final temperature is maintained. Frequently the optimum operation
of such processes treats electricity as a by-product of process heat genera-
tion, with excess electricity being sold to the local electricity supply agency,
as in modern sugarcane mills (Figure 11.3(b)).
Perhaps the easiest way to use energy crops and biomass residues is
co-firing in coal-burning power stations. The combustion method is adapted
for the known mixture of coal and biomass. Such substitution (abatement)
of coal may be one of the most effective ways for biomass to reduce green-
house gas emissions.

11.4.4 Wood resource

Wood is a renewable energy resource only if it is grown as fast as it is
consumed. Moreover there are ecological imperatives for the preservation
of natural woodland and forests. The world’s wood resource is consumed
370 Biomass and biofuels

not just for firewood, but for sawn timber, paper making and other indus-
trial uses. In addition, much forest is cleared for agriculture with its tim-
ber just burnt as ‘waste’. Approximate estimates of present and potential
biomass energy resources are given in Table 11.3, including forests and
woodland, but the accuracy in most countries is no better than a factor of
two, partly because of different definitions of exactly what are ‘forests’ and
‘woodlands’.
In many countries, firewood consumption exceeds replacement growth,
so that fuelwood is a depleting resource. In India, for example, present
consumption of fuelwood is estimated to be around 200 Mt y−1 , of which
only about 20 Mt y−1 constitutes sustainable availability from forests. About
100 Mt y−1 is derived from non-forest sources such as from village woodlots,
trees or shrubs on the edge of fields and roads, etc. The balance represents
non-sustainable extraction from forests plus miscellaneous gathering of
woody material. Moreover, the populations of firewood-using countries are
increasing at 2–3% per year, thus tending to increase the demand for cheap
cooking fuels. Fuelwood collection for household consumption, usually a
task for women and children, is becoming more burdensome as fuelwood
becomes scarcer. The proportion of rural women affected by fuelwood
scarcity is around 60% in Africa, 80% in Asia and 40% in Latin America.
Moreover, gathering firewood may require 1–5 hours per day. Alleviating
these difficulties requires both intensive reforestation and a switch to more
efficient cooking methods.
Regeneration may occur in natural forest or in man-made planta-
tions (which usually grow faster and are to be encouraged). Plantations
grown especially for energy supply need different management (silviculture)
techniques than plantations grown primarily for timber (Sims 2002). Com-
bustible wood need not be grown in long straight lengths, and can therefore
be harvested much more often (at 3–5 years rather than ∼30 years). Cop-
picing (i.e. leaving the roots in the ground and cropping only the branches)
is successful with many tree species; it reduces (costly) labour for plant-
ing and weeding, and also reduces soil erosion compared with repeated
replanting.

11.5 Pyrolysis (destructive distillation)

Pyrolysis is a general term for all processes whereby organic material is
heated or partially combusted to produce secondary fuels and chemical
products. The input may be wood, biomass residues, municipal waste or
indeed coal. The products are gases, condensed vapours as liquids, tars
and oils, and solid residue as char (charcoal) and ash. Traditional charcoal
making is pyrolysis with the vapours and gases not collected. Gasification is
pyrolysis adapted to produce a maximum amount of secondary fuel gases.
 11.5 Pyrolysis (destructive distillation) 371

Figure 11.5 Pyrolysis systems. (a) Small-scale pyrolysis unit. (b) Traditional charcoal kiln.

Various pyrolysis units are shown in Figure 11.5. Vertical top-loading

devices are usually considered the best. The fuel products are more con-
venient, clean and transportable than the original biomass. The chemical
products are important as chemical feedstock for further processes or as
directly marketable goods. Partial combustion devices, which are designed
to maximise the amount of combustible gas rather than char or volatiles,
are usually called gasifiers. The process is essentially pyrolysis, but may not
be described as such.
Efficiency is measured as the heat of combustion of the secondary fuels
produced divided by the heat of combustion of the input biomass as used.
Large efficiencies of 80–90% can be reached. For instance gasifiers from
wood can produce 80% of the initial energy in the form of combustible
gas (predominantly H2 and CO – producer gas), suitable for operation
in converted petroleum–fuelled engines. In this way the overall efficiency
of electricity generation (say 80% of 30% = 24%) could be greater than
that obtained with a steam boiler. Such gasifiers are potentially useful for
small-scale power generation
<150 kW.
372 Biomass and biofuels

The chemical processes in pyrolysis are much related to similar distilla-

tions of coal to produce synthetic gases, tars, oils and coke. For instance the
large-scale use of piped town gas
H2 + CO in Europe, before the change to
fossil ‘natural’ gas (mainly CH4 ), was possible from the reaction of water
on heated coal with reduced air supply:

H2 O + C → H2 + CO
C + O2 → CO2  CO2 + C → 2CO (11.1)

The following is given as a summary of the wide range of conditions and

products of pyrolysis. The input material needs to be graded to remove
excessive non-combustible material (e.g. soil, metal), dried if necessary
(usually completely dry material is avoided with gasifiers, unlike boilers),
chopped or shredded, and then stored for use. The air/fuel ratio during
combustion is a critical parameter affecting both the temperature and the
type of product. Pyrolysis units are most easily operated at temperatures
less than 600  C. Increased temperatures of 600–1000  C need more sophis-
tication, but more hydrogen will be produced in the gas. At less than 600  C
there are generally four stages in the distillation process:

1 ∼100–120  C. The input material dries with moisture passing up

through the bed.
2 ∼275  C. The output gases are mainly N2 , CO and CO2 ; acetic acid
and methanol distil off.
3 ∼280–350  C. Exothermic reactions occur, driving off complex mix-
tures of chemicals (ketones, aldehydes, phenols, esters), CO2 , CO, CH4 ,
C2 H6 and H2 . Certain catalysts, e.g. ZnCl2 , enable these reactions to
occur at smaller temperature.
4 >350  C. All volatiles are driven off, a larger proportion of H2 is
formed with CO, and carbon remains as charcoal with ash residues.

The condensed liquids, called tars and pyroligneous acid, may be separated
and treated to give identifiable chemical products (e.g. methanol, CH3 OH,
a liquid fuel). Table 11.6 gives examples and further detail.
The secondary fuels from pyrolysis have less total energy of combustion
than the original biomass, but are far more convenient to use. Some of the
−1
products have significantly greater energy density (e.g. CH4 at 55 MJ kg )
than the average input. Convenience includes easier handling and transport,
piped delivery as gas, better control of combustion, greater variety of end-
use devices and less air pollution at point of use. The following comments
consider the solid, liquid and gaseous products respectively.
 11.5 Pyrolysis (destructive distillation) 373

Table 11.6 Pyrolysis yields from dry wood

Approximate yields per 1000 kg (tonne) dry wood

Charcoal ∼300 kg
Gas (combustion 104 MJ m−3 ) ∼140 m3 (NTP)
Methyl alcohol ∼14 litre
Acetic acid ∼53 litre
Esters ∼8 litre
Acetone ∼3 litre
Wood oil and light tar ∼76 litre
Creosote oil ∼12 litre
Pitch ∼30 kg

11.5.1 Solid charcoal (mass yield 25–35% maximum)

Modern charcoal retorts operating at about 600  C produce 25–35% of the
dry matter biomass as charcoal. Traditional earthen kilns usually give yields
closer to 10%, since there is less control. Charcoal is 75–85% carbon, unless
great care is taken to improve quality (as for chemical grade charcoal),
−1
and the heat of combustion is about 30 MJ kg . Thus if charcoal alone
is produced from wood, between 15 and 50% of the original chemical
energy of combustion remains. Charcoal is useful as a clean controllable
fuel. Chemical grade charcoal has many uses in laboratory and industrial
chemical processes. Charcoal is superior to coal products for making high
quality steel.

11.5.2 Liquids (condensed vapours, mass yield ∼30%

maximum)
These divide between (1) a sticky phenolic tar (creosote) and (2) an aqueous
liquid, pyroligneous acid, of mainly acetic acid, methanol (maximum 2%)
and acetone. The liquids may be either separated or used together as a
crude, potentially polluting and carcinogenic fuel with a heat of combustion
−1
of about 22 MJ kg . The maximum yield corresponds to about 400 litres of
combustible liquid per tonne of dry biomass. The liquids may be better used
as a source of chemicals, but this requires larger-scale and sophisticated
operation.

11.5.3 Gases (mass yield ∼80% maximum in gasifiers)

The mixed gas output with nitrogen is known as wood gas, synthesis
gas, producer gas or water gas, and has a heat of combustion in air of
−1
5–10 MJ kg (4–8 MJ m−3 at STP). It may be used directly in diesel cycle or
spark ignition engines with adjustment of the fuel injector or carburettor,
374 Biomass and biofuels

but extreme care has to be taken to avoid intake of ash and condensable
vapours. The gas is mainly N2 , H2 and CO, with perhaps small amounts
of CH4 and CO2 . The gas may be stored in gas holders near atmospheric
pressure, but is not conveniently compressed. A much cleaner and more
uniform gas may be obtained by gasification of wet charcoal rather than
wood, since the majority of the tars from the original wood have already
been removed.

11.6 Further thermochemical processes

In the previous sections, biomass has been used directly after preliminary
sorting and cutting for combustion or pyrolysis. However, the biomass
may be treated chemically (1) to produce material suitable for alcoholic
fermentation, Section 11.7, or (2) to produce secondary or improved fuels.
Consider the following few important examples from the great number
of possibilities.

11.6.1 Hydrogen reduction

Dispersed, shredded or digested biomass, e.g. manure, is heated in hydrogen
to about 600  C under pressure of about 50 atmospheres. Combustible
gases, mostly methane and ethane, are produced, which may be burnt to
−1
give about 6 MJ kg of initial dry material.

11.6.2 Hydrogenation with CO and steam

The process is as above, but heating is within an enclosure with CO and
steam to about 400  C and 50 atmospheres. A synthetic oil is extracted
from the resulting products that may be used as a fuel. A catalyst is needed
to produce reactions of the following form:

CO + H2 O → CO2 + H2
(11.2)
Cn
H2 On +
n + 1H2 → nH2 O + H
CH2 n H

where the latter reaction implies the conversion of carbohydrate material

to hydrocarbon oils. The energy conversion efficiency is about 65%.

11.6.3 Acid and enzyme hydrolysis

Cellulose is the major constituent (30–50%) of plant dry biomass and is
very resistant to hydrolysis and hence to fermentation by micro-organisms
(see Section 11.7.1(4)). Conversion to sugars, which can be fermented, is
possible by heating in sulphuric acid or by the action of enzymes (cellulases)
of certain micro-organisms. The products may also be used as cattle feed.
 11.7 Alcoholic fermentation 375

11.6.4 Methanol liquid fuel

Methanol, a toxic liquid, is made from the catalytic reaction of H2 and CO
at 330  C and at 150 atmosphere pressure:

2H2 + CO → CH3 OH (11.3)

The gases are the components of synthesis gas, Section 11.5.3, and may
be obtained from gasification of biomass. Methanol may be used as a
liquid fuel in petroleum spark-ignition engines with an energy density of
−1
23 MJ kg . It is also used as an ‘anti-knock’ fuel additive to enhance the
octane rating, and is potentially a major fuel for fuel cells, Section 16.6.

11.7 Alcoholic fermentation

11.7.1 Alcohol production methods

Ethanol, C2 H5 OH, is produced naturally by certain micro-organisms from
sugars under acidic conditions, i.e. pH 4 to 5. This alcoholic fermentation
process is used worldwide to produce alcoholic drinks. The most com-
mon micro-organism, the yeast Saccharomyces cerevisiae, is poisoned by
C2 H5 OH concentration greater than 10%, and so stronger concentrations
up to 95% are produced by distilling and fractionating (Figure 11.6). When
distilled, the remaining constant boiling point mixture is 95% ethanol and
5% water. Anhydrous ethanol is produced commercially with azeotropic

Natural sugars:
cane Crush Residue
beet Process heat, byproducts
fruit

Starches: Hydrolysis Yeast fermentation

grain (e.g. barley) (easy) Sugar
to 10% ethanol
roots (e.g. cassava)

General
Distillation to
combustion
95% ethanol
fuel
Cellulose Hydrolysis
wood (difficult)
Purification to Petroleum
anhydrous alcohol additive or
substitute

Figure 11.6 Ethanol production.

376 Biomass and biofuels

removal of water by co-distillation with solvents such as benzene. Only

about 0.5% of the energy potential of the sugars is lost during fermentation,
but significant amounts of process heat are required for the concentration
and separation processes, see Table 11.5. This process heat may be provided
from the combustion or gasification of otherwise waste biomass and from
waste heat recovery.
The sugars may be obtained by the following routes, listed in order of
increasing difficulty.

1 Directly from sugarcane. Usually commercial sucrose is removed

from the cane juices, and the remaining molasses used for the alcohol
production process (Figure 11.3(a)). These molasses themselves have
about 55% sugar content. But if the molasses have little commercial
value, then ethanol production from molasses has favourable commer-
cial possibilities, especially if the cane residue (bagasse) is available to
provide process heat. In this case the major reaction is the conversion
of sucrose to ethanol:
yeast
C12 H22 O11 + H2 O −→ 4C2 H5 OH + 4CO2 (11.4)

In practice the yield is limited by other reactions and the increase in

mass of yeast. Commercial yields are about 80% of those predicted
by (11.4). The fermentation reactions for other sugars, e.g. glucose,
C6 H12 O6 , are very similar.
2 From sugar beet. Sugar beet is a mid-latitude root crop for obtaining
major supplies of sugar. The sugar can be fermented, but obtaining
process heat from the crop residues is, in practice, not as straightforward
as with cane sugar, so ethanol production is more expensive.
3 From starch crops. Starch crops, e.g. grain and cassava, can be
hydrolyzed to sugars. Starch is the main energy storage carbohydrate
of plants, and is composed of two large molecular weight components,
amylose and amylopectin. These relatively large molecules are essen-
tially linear, but have branched chains of glucose molecules linked by
distinctive carbon bonds. These links can be broken by enzymes from
malts associated with specific crops, e.g. barley or corn, or by enzymes
from certain moulds (fungi). Such methods are common in whisky dis-
tilleries, corn syrup manufacture and ethanol production from cassava
roots. The links can also be broken by acid treatment at pH 1.5 and
at 2 atmospheres pressure, but yields are small and the process more
expensive than enzyme alternatives. An important by-product of the
enzyme process is the residue used for cattle feed or soil conditioning.
4 From cellulose. Cellulose comprises about 40% of all biomass dry
matter. Apart from its combustion as part of wood, cellulose is poten-
tially a primary material for ethanol production on a large scale. It has
 11.7 Alcoholic fermentation 377

a polymer structure of linked glucose molecules, and forms the main

mechanical-structure component of the woody parts of plants. These
links are considerably more resistant to breakdown into sugars under
hydrolysis than the equivalent links in starch. Cellulose is found in
close association with lignin in plants, which discourages hydrolysis to
sugars. Acid hydrolysis is possible as with starch, but the process is
expensive and energy intensive. Hydrolysis is less expensive, and less
energy input is needed if enzymes of natural, wood-rotting fungi are
used, but the process is slow. Prototype commercial processes have used
pulped wood or, more preferably, old newspaper as input. The ini-
tial physical breakdown of woody material is a difficult and expensive
stage, usually requiring much electricity for the rolling and hammering
machines. Substantial R&D in the USA and Scandinavia led to processes
with improved yields and potentially cheaper production, key features
of which are acid-catalysed hydrolysis of hemicellulose, more effective
enzymes to breakdown cellulose, and genetically engineered bacteria
that ferment all biomass sugars (including 5-carbon sugars, which resist
standard yeasts) to ethanol with high yields. Although not yet generally
applied commercially, these processes may allow ethanol from biomass
to compete commercially with fossil petroleum (Wyman 1999).

11.7.2 Ethanol fuel use

Liquid fuels are of great importance because of their ease of handling and
controllable combustion in engines. Anhydrous ethanol is a liquid between
−117 and +78  C, with a flash point of 130  C and an ignition temperature of
423  C, and so has the characteristics of a commercial liquid fuel, being used
as a direct substitute or additive for petrol (gasoline), and is used in three ways:

1 As 95% (hydrous) ethanol, used directly in modified and dedicated

spark-ignition engines;
2 Mixed with the fossil petroleum in dry conditions to produce gasohol,
as used in unmodified spark-ignition engines, perhaps retuned;
3 as an emulsion with diesel fuel for diesel compression engines (this may
be called diesohol, but is not common).

In general such bioethanol fuel has the proportion of ethanol indicated

as EX, where X is the percentage of ethanol, e.g. E10 has 10% ethanol and
90% fossil petroleum. Gasohol for unmodified engines is usually between
E10 and E15, and larger proportions of ethanol require engine modification
to some extent. Note that water does not mix with petrol, and so water is
often present as an undissolved sludge in the bottom of petroleum vehicle
fuel tanks, as in cars, without causing difficulty. If gasohol is added to such
a tank, the fuel will be spoilt and may not be suitable for an unmodified
378 Biomass and biofuels

engine. With the ethanol mostly from sugarcane, gasohol is now standard
in Brazil, e.g. as E22, and in countries of southern Africa. In USA, gasohol
is also common, but with the ethanol likely to be from corn grain.
The ethanol additive has antiknock properties and is preferable to the
more common tetraethyl lead, which produces serious air pollution. The
excellent combustion properties of ethanol enable an engine to produce
up to 20% more power with ethanol than with petroleum. The mass den-
sity and calorific value of ethanol are both less than those of petroleum,
so the energy per unit volume of ethanol
24 GJ m−3  is 40% less than
for petroleum
39 GJ m−3 , see Table B.6. However, the better combustion
properties of ethanol almost compensate when measured as volume per
unit distance, e.g. litre/100 km. Fuel consumption by volume in similar cars
using petrol, gasohol or pure ethanol is in the ratio 1:1:1.2, i.e. pure ethanol
is only 20% inferior by this criteria. We note, however, that the custom
of measuring liquid fuel consumption per unit volume is deceptive, since
measurement per unit mass relates better to the enthalpy of the fuel.
Production costs of ethanol fuels depend greatly on local conditions and
demand relates to the prices paid for alternative products. Government
policy and taxation are extremely important in determining the market sales
and hence the scale of production, see Section 11.11.

11.7.3 Ethanol production from crops

Table 11.7 gives outline data of ethanol production and crop yield. Commer-
cial operations relate to many other factors, including energy analysis (see
Section 11.3.4 and Table 11.5) and economic analysis. We emphasise that the
use of otherwise waste biomass residues for electricity production and factory
process heat is crucial in these analyses. As a benchmark, global production
of ethanol for fuel was over 20 billion litres in 2003 – a year of considerable
political uncertainty affecting the international price of fossil oil.

Table 11.7 Approximate yields of ethanol from various crops,

based on average yields in Brazil (except for corn,
which is based on US yields). Two crops a year are
possible in some areas. Actual yields depend greatly
on agricultural practice, soil and weather

Litres of ethanol Litres of ethanol per

per tonne of crop hectare per year

Sugarcane 70 5200
Cassava 180 2160
Sweet sorghum 86 3010
Sweet potato 125 1875
Corn (maize) 370 2800
Wood 160 3200
 11.8 Anaerobic digestion for biogas 379

11.8 Anaerobic digestion for biogas

11.8.1 Introduction
Decaying biomass and animal wastes are broken down naturally to elemen-
tary nutrients and soil humus by decomposer organisms, fungi and bacteria.
The processes are favoured by wet, warm and dark conditions. The final
stages are accomplished by many different species of bacteria classified as
either aerobic or anaerobic.
Aerobic bacteria are favoured in the presence of oxygen with the biomass
carbon being fully oxidised to CO2 . This composting process releases some
heat slowly and locally, but is not a useful process for energy supply. To
be aerobic, air has to permeate, so a loose ‘heap’ of biomass is essential.
Domestic composting is greatly helped by having layers of rumpled news-
paper and cardboard, which allows air pockets and introduces beneficial
carbon from the carbohydrate material. Such aerobic digestion has minimal
emission of methane, CH4 , which, per additional molecule, is about eight
times more potent as a greenhouse gas than CO2 , see Section 4.6.2.
In closed conditions, with no oxygen available from the environment,
anaerobic bacteria exist by breaking down carbohydrate material. The
carbon may be ultimately divided between fully oxidised CO2 and fully
reduced CH4 , see (10.8). Nutrients such as soluble nitrogen compounds
remain available in solution, so providing excellent fertilizer and humus.
Being accomplished by micro-organisms, the reactions are all classed as
fermentations, but in anaerobic conditions the term ‘digestion’ is preferred.
It is emphasised that both aerobic and anaerobic decompositions are a
fundamental processes of natural ecology that affect all biomass irrespective
of human involvement. As with all other forms of renewable energy, we are
able to interface with the natural process and channel energy and resources
for our economy. The decomposed waste should then be released for natural
ecological processes to continue.
Biogas is the CH4 /CO2 gaseous mix evolved from digesters, including
waste and sewage pits; to utilise this gas, the digesters are constructed and
controlled to favour methane production and extraction (Figure 11.7). The
energy available from the combustion of biogas is between 60 and 90%
of the dry matter heat of combustion of the input material. However, the
gas is obtainable from slurries of up to 95% water, so in practice the
biogas energy is often available where none would otherwise have been
obtained. Another, perhaps dominant, benefit is that the digested effluent
forms significantly less of a health hazard than the input material. Note,
however, that not all parasites and pathogens are destroyed in the digestion.
The economics and general benefit of biogas are always most favourable
when the digester is placed in a flow of waste material already present.
Examples are sewage systems, piggery washings, cattle shed slurries, abat-
toir wastes, food processing residues, sewage and municipal refuse landfill
 Gas
Material pipe Removable cover
inlet
(c)
Outlet

Gas storage tank

Separating
wall

Anaerobic
digestion

Figure 11.7 Biogas digesters. (a) Simple oil drum batch digester, with cow to scale
(b) Indian ‘gobar gas’ digester. (c) Chinese ‘dome’ for small-scale use
[adapted from Van Burren]. (d) Accelerated rate farm digester with
heating, for use in middle latitudes [adapted from Meynell]. (e) A large
system near Aalborg in Denmark, which produces 10 000 m3 of biogas
per day. The biogas store is in the foreground, with the digester tanks
visible behind it. The lorry (truck) in front of the white shed indicates
the scale. [Photo by courtesy of NIRAS als].
 11.8 Anaerobic digestion for biogas 381

(d) Stirrer

Output

fields

Holding tank Heat exchanger Setting (overflow)

tank

Digester
Gas burner

Water sealed gas holder Gas takeoff

(e)

Figure 11.7 (Continued).

dumps. The economic benefits are that input material does not have to be
specially collected, administrative supervision is present, waste disposal is
improved, and uses are likely to be available for the biogas and nutrient-rich
effluent. However, in high and middle latitudes, tank digesters have to be
heated for fast digestion (especially in the winter); usually such heat would
come from burning the output gas, hence reducing net yield significantly.
Slow digestion does not require such heating. Obviously obtaining biogas
from, say, urban landfill waste is a different engineering task than from
382 Biomass and biofuels

cattle slurries. Nevertheless the biochemistry is similar. Most of the follow-

ing refers to tank digesters, but principles apply to other biogas systems.
Biogas generation is suitable for small- to large-scale operation. Several
million household-scale systems have been installed in developing countries,
especially in China and India, with the gas used for cooking and lighting.
However, successful long-term operation requires (a) trained maintenance
and repair technicians, (b) the users to perceive benefits and (c) alternative
fuels, e.g. kerosene, not to be subsidised.
Biogas systems may be particularly attractive as part of integrated farm-
ing, where the aim is to emulate a full ecological cycle on a single farm.
Thus plant and animal wastes are digested with the collection of the biogas
as a fuel, with the effluent passing for further aerobic digestion in open
tanks, before dispersal. The biogas is used for lighting, machines, vehicles,
generators, and domestic and process heat. Algae may be grown on the
open air tanks and removed for cattle feed. From the aerobic digestion, the
treated effluent passes through reed beds, perhaps then to fish tanks and
duck ponds before finally being passed to the fields as fertilizer. Success for
such schemes depends ultimately on total integrated design, good standards
of construction, and the enthusiasm and commitment of the operator, not
least for the regular maintenance required.

11.8.2 Basic processes and energetics

The general equation for anaerobic digestion is

Cx Hy Oz +
x − y/4 − z/2H2 O
(11.5)
→
x/2 − y/8 + z/4CO2 +
x/2 + y/8 − z/4CH4

For cellulose this becomes

C6 H10 O5 n + nH2 O → 3nCO2 + 3nCH4 (11.6)

Some organic material, e.g. lignin, and all inorganic inclusions do not digest
in the process. These add to the bulk of the material, form a scum and can
easily clog the system. In general 95% of the mass of the material is water.
The reactions are slightly exothermic, with typical heat of reaction being
−1
about 15 MJ kg dry digestible material, equal to about 250 kJ per mole
of C6 H10 O5 . This is not sufficient to significantly affect the temperature of
the bulk material, but does indicate that most enthalpy of reaction is passed
to the product gas.
If the input material had been dried and burnt, the heat of combustion
−1
would have been about 16 MJ kg . Only about 10% of the potential heat
of combustion need be lost in the digestion process. This is 90% conversion
efficiency. Moreover very wet input has been processed to give the con-
venient and controllable gaseous fuel, whereas drying 95% aqueous input
 11.8 Anaerobic digestion for biogas 383

−1
would have required much energy (about 40 MJ kg of solid input). In
practice, digestion is seldom allowed to go to completion because of the
long time involved, so 60% conversion is common. Gas yield is about 0.2
to 04 m3 per kg of dry digestible input at STP, with throughput of about
5 kg dry digestible solid per cubic metre of liquid.
It is generally considered that three ranges of temperature favour particu-
lar types of bacteria. Digestion at higher temperature proceeds more rapidly
than at lower temperature, with gas yield rates doubling at about every
5  C of increase. The temperature ranges are (1) psicrophilic, about 20  C,
(2) mesophilic, about 35  C, and (3) thermophilic, about 55  C. In tropical
countries, unheated digesters are likely to be at average ground tempera-
ture between 20 and 30  C. Consequently the digestion is psicrophilic, with
retention times being at least 14 days. In colder climates, the psicrophilic
process is significantly slower, so it may be decided to heat the digesters,
probably by using part of the biogas output; a temperature of about 35  C is
likely to be chosen for mesophilic digestion. Few digesters operate at 55  C
unless the purpose is to digest material rather than produce excess biogas.
In general, the greater is the temperature, the faster is the process time.
The biochemical processes occur in three stages, each facilitated by
distinct sets of anaerobic bacteria:

1 Insoluble biodegradable materials, e.g. cellulose, polysaccharides and

fats, are broken down to soluble carbohydrates and fatty acids (hydro-
genesis). This occurs in about a day at 25  C in an active digester.
2 Acid forming bacteria produce mainly acetic and propionic acid
(acidogenesis). This stage likewise takes about one day at 25  C.
3 Methane forming bacteria slowly, in about 14 days at 25  C, complete
the digestion to a maximum ∼70%CH4 and minimum ∼30%CO2
with trace amounts of H2 and perhaps H2 S (methanogenesis). H2 may
play an essential role, and indeed some bacteria, e.g. Clostridium, are
distinctive in producing H2 as the final product.

The methane forming bacteria are sensitive to pH, and conditions should
be mildly acidic (pH 6.6–7.0) but not more acidic than pH 6.2. Nitrogen
should be present at 10% by mass of dry input and phosphorus at 2%.
A golden rule for successful digester operation is to maintain constant
conditions of temperature and suitable input material. As a result a suitable
population of bacteria is able to become established to suit these conditions.

11.8.3 Digester sizing

The energy available from a biogas digester is given by:

E = Hb Vb (11.7)
384 Biomass and biofuels

where  is the combustion efficiency of burners, boilers, etc. (∼60%). Hb is

the heat of combustion per unit volume biogas (20 MJ m−3 at 10 cm water
gauge pressure, 0.01 atmosphere) and Vb is the volume of biogas. Note that
some of the heat of combustion of the methane goes to heating the CO2
present in the biogas, and is therefore unavailable for other purposes. The
net effect is to decrease the efficiency.
Alternatively:

E = Hm fm Vb (11.8)
−1
where Hm is the heat of combustion of methane (56 MJ kg , 28 MJ m−3 at
STP) and fm is the fraction of methane in the biogas. As from the digester, fm
should be between 0.5 and 0.7, but it is not difficult to pass the gas through
a counterflow of water to dissolve the CO2 and increase fm to nearly 1.0.
The volume of biogas is given by

Vb = cm0 (11.9)
−1
where c is the biogas yield per unit dry mass of whole input
02–04 m3 kg 
and m0 is the mass of dry input.
The volume of fluid in the digester is given by

Vf = m0 /m (11.10)
−3
where m is the density of dry matter in the fluid (∼50 kg m ).
The volume of the digester is given by

Vd = V̇f tr (11.11)

where V̇f is the flow rate of the digester fluid and tr is the retention time in
the digester (∼8–20 days).
Typical parameters for animal waste are given in Table 11.8.

Table 11.8 Typical manure output from farm animals; note the large proportion of
liquid in the manure that favours biogas production rather than drying
and combustion

Animal Total wet manure Of which, total Moisture

per animal solids per kg mass content
per day/kg per wet mass

Dairy cow ∼500 kg 35 4.5 87%

Beef steer ∼300 kg 25 3.2 87%
Fattening pig ∼60 kg 3.3 0.3 91%
Laying hen 0.12 0.03 75%