Biomass and biofuels

Introduction
• The material of plants and animals, including their
wastes and residues,is called biomass.

• It is organic, carbon-based, material that reacts

withoxygen 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
 Bioenergy
• Biomass may be transformed by chemical and biological processes to produce
biofuels, i.e.Biomas s 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 biomas - oxygen system is captured from solar
radiation in photosynthesis.
• 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 processes

• Thus the use of industrial biofuels, when linked carefully to natural

 Carban neutral
• 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’
• 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.
 Energy Density
The heat energy available in combustion, equivalent
in practice to the enthalpy or
The net energy density
• 8MJkg−1 (un dried ‘green’ wood)
• 15MJkg−1 (dry wood)
• 40MJkg−1 (fats and oils)
• 56MJkg−1 (methane).
• Biomass is, however, mostly carbohydrate material
with a heat of combustion of about 20MJkg−1 dry
matter

Energy density is the amount of energy stored in a

given system or region of space per unit mass.
 Biofuel classification
Biomass is largely composed of organic material
and water. However, significant 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.
Three classifications and nine general
types of biomass energy process

• Thermochemical,
heat
• Biochemical
• Agrochemical
 Thermochemical, heat
• Direct combustion for immediate heat.
Dry homogeneous input is preferred.
• 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
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
• If output of combustible gas is the main
product,
the process is called gasification
 Biochemical

• 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.
• Anaerobic digestion
In the absence of free oxygen, certain microorganisms
can obtain their own energy supply by reacting with carbon
compounds of medium reduction level to produce both CO2
and fully reduced carbon as CH4.
 Agrochemical
• Fuel extraction.
Occasionally, liquid or solid fuels may be obtained
directly from living or freshly cut plants. The materials
are called exudates 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.
 Continue..
• 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 ≤∼5C.

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.
Sugar cane agro industry
 Biofuels from
Microorganisms
More recently, research has focused on whether microbial
systems can be exploited for the biosynthesis of a wide
range of liquid biofuels.
Initially, this focus was on ethanol, however, with increased
knowledge in the properties required for ideal biofuel
molecules, scientists agree that ethanol might not be the
best option.
Higher-chain alcohols, for example offer several
advantages compared with ethanol, such as higher
energy densities and lower water solubility.

In addition, the corrosive nature of ethanol prevents it from

being used as a pure biofuel in current engines, but rather it
must be used as a blend of less than 10% with gasoline.
Furthermore, ethanol can cause corrosion to the pipelines
used for its
transportation.
 Production of Ethanol
• Ethanol, C2H5OH, is produced naturally by
certain micro-organisms from sugars under
acidic conditions, i.e. pH 4 to 5.
 Directly from
• Usually commercial sucrose is removed from the cane
sugarcane
juices, and the remaining molasses used for the alcohol
production process (These molasses themselves have
about 55% sugar content. But if the molasses have little
commercial value, then ethanol production from molasses
has favourable commercial 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:

• In practice the yield is limited by other reactions and the

increase in mass of yeast. Commercial yields are about
80% of those predicted . The fermentation reactions for
other sugars,
e.g. glucose, C6H12O6, are very similar.
 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+78C, 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).
 Biomethane
• Methane produced from biomass is referred to as
Bio-Methane, Green Gas, Bio-Substitute Natural
Gas (Bio-SNG) or Bio-CNG when it is used as a
transport fuel.
• Biomass energy is expected to make a major
contribution to the replacement of fossil fuels.
The future world-wide available amount of
biomass for energy is estimated to be 200 to
500 EJ per year
CO2 balance for Natural gas and Bio-Methane produced
from woody biomass
 Biodiesel
Concentrated vegetable oils may be used directly as fuel in
diesel engines, but difficulties arise from the high viscosity and
from the combustion deposits, as compared with conventional
(fossil) petroleum-based diesel oil, especially at low ambient
temperature (≤5C).
Both difficulties are overcome by reacting the extracted
vegetable oil with ethanol or methanol to form the equivalent
ester.

Such esters, called biodiesel, have technical characteristics

as fuels that are better suited to diesel-engines than petroleum
based diesel oil. The reaction yields the equivalent ester and
glycerine (also called ‘glycerol’). The process usually uses KOH
as a catalyst. Glycerol is
also a useful and saleable product.

The process used to convert these oils to Biodiesel is

called transesterification
The energy density of biodiesel as an ester varies with
composition and is typically about 38MJkg−1, which is
greater than for the raw oil and near to
petroleum-based diesel fuel at about 46MJkg−1

Nevertheless, in practice fuel consumption per unit

volume of a diesel-engine vehicle running on biodiesel
is little different from that of fossil diesel. Quality
standards
have been established for the compatibility of biodiesel
with most vehicles. A minor benefit of using biodiesel is
that the exhaust smell is reminiscent of cooking, e.g. of
popcorn
 Biodiesel Production
• Base catalyzed transesterification of the oil.
• Direct acid catalyzed transesterification of the oil.
• Conversion of the oil to its fatty acids and then to biodiesel
Almost all biodiesel is produced using base catalyzed transesterification as it is the
most economical process requiring only low temperatures and pressures and
producing a 98% conversion yield.
The esterification process uses methanol and a catalyst, either caustic soda
(NaOH) or potassium hydroxide (KOH), to produce sodium or potassium
methoxide which reacts with the vegetable oil or fat. Methyl or ethyl esters, which
take the name of the feedstock; Rape methyl Ester, Soybean Methyl; Ester etc.
and glycerine are produced

Vegetable oils and animal fats contain mostly triglycerides

 Social and environmental aspects
Bioenergy in relation to agriculture and forestry
Production should be ecologically sustainable, i.e. that the resource
be used in a renewable manner, with
(re-)growth keeping pace with use. Moreover, for ethical reasons,
it is vital that biomass production for energy is not at the
expense of growing enough food to feed people.

Nevertheless, in the European Union and the USA, a major issue in

agriculture is over-production of food, as encouraged by agricultural
subsidies. Such subsidies increase general taxation and the
consequent surpluses of agricultural products distort world trade to
the disadvantage of developing countries.

Utilizing waste biomass increases the productivity of agriculture

and forestry. This is especially so for the acceptable disposal of
otherwise undesirable outputs, e.g. biodigestion of manure from
intensive piggeries, so the integrated system brings both
economic and environmental benefits.
Biofuel production utilizes already concentrated flows of biomass, such
as offcuts and sawdust from sawmilling, straw from crops, manure from
penned animals and sewage from municipal works. Biofuel processes
that depend first upon transporting and then upon concentrating diffuse
biomass resources are unlikely to be viable.

Energy developments utilizing local crops and established skills are most
likely to be socially acceptable. Thus the form of biomass most likely to
be viable as an energy source will vary from region to region.

Moreover, as with any crop, sustainable agriculture and forestry is

required, for instance extensive monocultures are vulnerable to disease
and pests and unfriendly to native fauna. Note, too, that greenhouse
gas benefits only occur when the biomass is used to replace fossil fuel
use, so leaving the abated fossil fuel underground

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.
 Food versus fuel
Production of liquid biofuels has been based historically on
biomass from grain, sugar and oil crops, all of which are
essential food crops, generally grown on the best agricultural
land available.

Despite crop production surpluses in the USA and Europe, the

increasing worldwide demand for food indicates that these crops
will not be diverted significantly from food to energy. Therefore,
biofuel production as a major contribution to world energy
supplies requires other feedstock and land than for food and
other strategies.

For instance, there is a need for cheaper, more energy-efficient

processes for producing ethanol from widely available
lignocellulosic
materials, e.g. corn-stalks, straw and wood, especially sawdust
and other woody residues, rather than from food-related crops.
 Greenhouse gas impacts: bioenergy and carbon sinks

When a plant grows, carbon is extracted from the air as CO2 is

absorbed in photosynthesis, so becoming ‘locked into’ carbohydrate
material both
above and below ground. Significant amounts of CO2 are released in
plant
metabolism, but the net carbon flow is into the plant. Such removal of
the greenhouse gas CO2 from the atmosphere is called a ‘carbon
sink’.

The Kyoto Protocol is an international treaty which aims to mitigate

climate change induced by greenhouse gas emissions; amongst other
things
it encourages countries to plant new forests. However, as explained
above,
such carbon sinks are only temporary because when the forest is
harvested
all its above-ground carbon will be returned relatively quickly to the
atmosphere: within months if used for paper, years if used for
construction. Thus only a new and thereafter continuing forest can be
a carbon sink, albeit ‘once only’.
 Other chemical impacts

Every country has regulations concerning the allowed and the

forbidden emissions of gases, vapours, liquids and solids. This is a
huge and complex subject within environmental studies.

The most vital aspect for the optimum combustion of any fuel is to
control temperature and input of oxygen, usually as air. The aim with
biomass and biofuel combustion, as with all fuels, is to have emissions
with minimum particulates (unburnt and partially burnt material), with
fully oxidised carbon to CO2 and not CO or CH4, and with minimum
oxides of nitrogen which usually result from excessive temperature of
the air.

Although the natural carbon cycle of plant growth fully renews the
carbon in a crop or plantation, there may be a net loss of nitrogen and
possibly other nutrients when the biomass is burnt or otherwise
processed. That is, nitrogen is not returned sufficiently to the soil
‘automatically’ and has to be put back as a chemical input, possibly in
the form of manure or by rotation
 Hydrogen from biomass
Production of hydrogen from renewable biomass
has several advantages compared to that of fossil
fuels
Process routes of hydrogen-production

Table 1 gives an overview of biological hydrogen production processes, that

are being explored in fundamental and applied research
 Biophotolysis
• Microalgae and cyanobacteria split water into hydrogen and
oxygen with the aid of absorbed light energy.
• Enzyme responsible for hydrogen production
(hydrogenase) is inhibited by the oxygen produced.
• Thereforphotochemical efficiency of this process is thus far
much lower (<1% on solar light).

Photofermentation
• Organic compounds, like acetic acid, are converted into
hydrogen and CO2 with sunlight by bacteria.
• This process takes place under anaerobic conditions.
• Scaling-up of the system is required.
• A large surface area is needed to collect light.
• Construction of a photobioreactor with a large
surface/volume ratio for direct absorption of sunlight is
expensive.
 The water-gas shift (WGS) reaction

The water-gas shift (WGS) reaction (CO + H2O = CO2 + H2) is used in
industrial hydrogen production

Its purpose is to produce hydrogen and to reduce the level of CO for

final cleanup by preferential oxidation.

The reaction of carbon dioxide with steam to make more hydrogen is

called the water gas shift reaction since it ‚shifts‛ hydrogen atoms from water to
gaseous hydrogen. Hydrogen must be separated from the shifted gas containing
CO2, CO, and other trace contaminants, and polished (cleaned further) to meet
the requirements for various end-uses (e.g., fuel cell vehicles).
VALUE ADDED CHEMICALS AND POLYMERS

Biogas Platform
Syngas Platform
Plant-based Oil Platform

Lignin Platform
Role of nanotechnology in Biofuels
• Recently, structurally ordered nanoparticles have attracted attention because of
their tailored porosity and surface chemistry; high specific surface area; large
pore volume; and high thermal, chemical, and mechanical stabilities.
• For example, ordered mesoporous catalytic solid (MCS) nanoparticles can be
used as a heterogeneous catalyst to enable cleaner biodiesel production.
• They aim is to selectively isolate fuel-relevant hydrocarbons from live
microalgae by using mesoporous material, to convert microalgae-based
hydrocarbons and waste oils to biodiesel in a single step using a mesoporous
mixed metal-oxide catalyst.
• This is expected to increase the extraction efficiency of fuel- relevant
hydrocarbons from feedstock and the establishment of extraction conditions
appropriate for a large oil-production scale.
Fuel Additives:

Nanoparticles have been shown to increase the fuel

efficiency of diesel by approximately 5%