1.

2 Biomass and Its Products

Biomass is formed from living species like plants and animals—that is, anything that
is now alive or was a short time ago. Unlike fossil fuel, biomass does not take
millions of years to develop. Fossil fuels do not reproduce whereas biomass does,
and, for that reason, is considered renewable. Every year, a vast amount of biomass
grows through photosynthesis by absorbing CO2 from the atmosphere.

1.2.1 Products of Biomass

Three types of primary fuel are produced from biomass:

(a) Liquid (ethanol, biodiesel, methanol, vegetable oil, and pyrolysis oil)

(b) Gaseous (biogas (CH4, CO2), producer gas (CO, H2, CH4, CO2 , H2), syngas
(CO, H2), substitute natural gas (CH4))

(c) Solid (charcoal, torrefied biomass).

From these come four major categories of product:

 Chemicals such as methanol, fertilizer, and synthetic fiber
 Energy such as heat
 Electricity
 Transportation fuel such as gasoline and diesel

Utilization of Liquid Fuels from Biomass

The use of ethanol and biodiesel as transport fuels reduces the emission of CO2 per
unit of energy production. It also lessens dependence on fossil fuel. Thus, biomass-
based energy not only is renewable but is also clean from a greenhouse gas (GHG)
emission standpoint, and so it can take the center stage on the global energy scene.

Fine Chemicals from Biomass

1
Most chemicals produced from petroleum or natural gas can be produced from
biomass. The two principal platforms for chemical production are sugar based and
syngas based. The former involves sugars like glucose, fructose, xylose, arabinose,
lactose, sucrose, and starch.

Energy from Biomass

Biomass was probably the first on-demand source of energy that humans exploited.
However, less than 22% of our primary energy demand is currently met by biomass
or biomass-derived fuels. The position of biomass as a primary source of energy
varies widely depending on the geographical and socioeconomic conditions.

Transport Fuel from Biomass

Diesel and gasoline from crude petro-oil are widely used in modern transportation
industries. Biomass can help substitute these petro-derived transport fuels. Ethanol,
produced generally from sugarcane and corn, is used in gasoline (spark-ignition)
engines, while biodiesel, produced from vegetable oils such as rape seed, is used in
diesel (compression-ignition) engines.
Pyrolysis, fermentation, and mechanical extraction are three major ways to produce
transport fuel from biomass.

1.3 Biomass Conversion

1.3.1 Biochemical Conversion

2
In biochemical conversion, biomass molecules are broken down into smaller
molecules by bacteria or enzymes. This process is much slower than
thermochemical conversion, but does not require much external energy. The three
principal routes for biochemical conversion are:

 Digestion (anaerobic and aerobic)

 Fermentation
 Enzymatic or acid hydrolysis
Digestion (anaerobic and aerobic)
The main products of anaerobic digestion are methane and carbon dioxide in
addition to a solid residue. Bacteria access oxygen from the biomass itself instead of
from ambient air.

Aerobic digestion, or composting, is also a biochemical breakdown of biomass,

except that it takes place in the presence of oxygen. It uses different types of
microorganisms that access oxygen from the air, producing carbon dioxide, heat,
and a solid digestate.

Fermentation
In fermentation, part of the biomass is converted into sugars using acid or enzymes.
The sugar is then converted into ethanol or other chemicals with the help of yeasts.
The lignin is not converted and is left either for combustion or for thermochemical
conversion into chemicals. Unlike in anaerobic digestion, the product of fermentation
is liquid.

Fermentation of starch and sugar-based feedstock (i.e., corn and sugarcane) into
ethanol is fully commercial, but this is not the case with cellulosic biomass because
of the expense and difficulty in breaking down (hydrolyzing) the materials into
fermentable sugars. Ligno-cellulosic feedstock, like wood, requires hydrolysis
pretreatment (acid, enzymatic, or hydrothermal) to break down the cellulose and
hemicellulose into simple sugars needed by the yeast and bacteria for the
fermentation process. Acid hydrolysis technology is more mature than enzymatic
hydrolysis technology, though the latter could have a significant cost advantage.
Figure 1.6 shows the schemes for fermentation (of sugar) and acid hydrolysis (of
cellulose) routes.

1.3.2 T hermochemical Conversion

In thermochemical conversion, the entire biomass is converted into gases, which are
then synthesized into the desired chemicals or used directly (Figure 1.7). The
Fischer-Tropsch synthesis of syngas into liquid transport fuels is an example of
thermochemical conversion. Production of thermal energy is the main driver for this
conversion route that has four broad pathways:

 Combustion
 Pyrolysis
 Gasification

3
 Liquefaction

Combustion
Chemically, combustion is an exothermic reaction between oxygen and the
hydrocarbon in biomass. Here, the biomass is converted into two major stable
compounds: H2O and CO2. The reaction heat released is presently the largest
source of human energy consumption, accounting for more than 90% of the energy
from biomass.

Heat and electricity are two principal forms of energy derived from biomass. Biomass
still provides heat for cooking and warmth, especially in rural areas. District or
industrial heating is also produced by steam generated in biomass fired boilers.

Pyrolysis

4
Unlike combustion, pyrolysis takes place in the total absence of oxygen, except in
cases where partial combustion is allowed to provide the thermal energy needed for
this process. Pyrolysis is a thermal decomposition of the biomass into gas, liquid,
and solid. It has three variations:

 Torrefaction, or mild pyrolysis

 Slow pyrolysis
 Fast pyrolysis
 Flash Pyrolysis
In pyrolysis, large hydrocarbon molecules of biomass are broken down into smaller
hydrocarbon molecules. Fast pyrolysis produces mainly liquid fuel, known as bio-oil;
slow pyrolysis produces some gas and solid charcoal (one of the most ancient fuels,
used for heating and metal extraction before the discovery of coal). Pyrolysis is
promising for conversion of waste biomass into useful liquid fuels. Unlike
combustion, it is not exothermic.

Torrefaction, which is currently being considered for effective biomass utilization, is

also a form of pyrolysis. In this process (named for the French word for roasting), the
biomass is heated to 230 to 300 °C without contact with oxygen. The chemical
structure of the wood is altered, which produces carbon dioxide, carbon monoxide,
water, acetic acid, and methanol.

Gasification
Gasification converts fossil or nonfossil fuels (solid, liquid, or gaseous) into useful
gases and chemicals. It requires a medium for reaction, which can be gas or
supercritical water (not to be confused with ordinary water at subcritical condition).
Gaseous mediums include air, oxygen, subcritical steam, or a mixture of these.

5
Gasification is carried out generally in one of the three major types of gasifiers:

 Moving bed (also called fixed bed)

 Fluidized bed
 Entrained flow
Downdraft and updraft are two common types of moving-bed gasifier.

Liquefaction

Liquefaction of solid biomass into liquid fuel can be done through pyrolysis,
gasification as well as through hydrothermal process. In the latter process, biomass
is converted into an oily liquid by contacting the biomass with water at elevated
temperatures (300–350 °C) with high (12–20 MPa) for a period of time.

Refuse-derived fuel (RDF) is a fuel produced from various types of waste such as municipal
solid waste (MSW), industrial waste or commercial waste.

1.6.1 Pyrolysis
The solid carbon as well as the condensed liquid enters the gasification reaction with
carbon dioxide, oxygen, or steam to produce combustible or synthetic gas. To
illustrate the different reactions we take simple carbon as the feedstock.

6
1.6.2 Combustion of Carbon
When 1 kmol of carbon is burnt completely in adequate air or oxygen, it produces
394 MJ heat and carbon dioxide. This is a combustion reaction. The positive sign on
the right side (+Q kJ/kmol) implies that heat is absorbed in the reaction. A negative
sign (−Q kJ/kmol) means that heat is released in the reaction i.e. exothermic.

2.2 What Is Biomass?

Biomass refers to any organic materials that are derived from plants or animals.

Common sources of biomass are:

 Agricultural: food grain, bagasse (crushed sugarcane), corn stalks, straw,
seed hulls, nutshells, and manure from cattle, poultry, and hogs
 Forest: trees, wood waste, wood or bark, sawdust, timber slash, and mill
scrap
 Municipal: sewage sludge, refuse-derived fuel (RDF), food waste, waste
paper, and yard clippings
 Energy: poplars, willows, switchgrass, alfalfa, prairie bluestem, corn, and
soybean, canola, and other plant oils
 Biological: animal waste, aquatic species, biological waste.
2.2.1 Biomass Formation

Botanical biomass is formed through conversion of carbon dioxide (CO2) in the

atmosphere into carbohydrate by the sun’s energy in the presence of chlorophyll and
water. Biological species grow by consuming botanical or other biological species.
Plants absorb solar energy in a process called photosynthesis (Figure 2.1).

7
Aerobic digestion: This process takes place in the presence of air and so does not
produce fuel gas. Here, the leachate is removed from the bottom layer of the landfill
and pumped back into the landfill, where it flows over the waste repeatedly. Air
added to the landfill enables microorganisms to work faster to degrade the wastes
into compost, carbon dioxide, and water.

Anaerobic digestion: This process does not use air and hence produces the fuel
gas methane. In the absence of oxygen, the waste is broken down into methane,
carbon dioxide, and digestate (or solid residues). Methanogenesis bacteria like
thermophiles (45–65 °C), mesophiles (20–45 °C), and psychophiles (0–20 °C)
facilitate this process (Probstein and Hicks, 2006). These biodegradation reactions
are mildly exothermic.

8
Carbohydrates are mainly cellulose or hemicellulose fibers, which impart strength to
the plant structure; the lignin holds the fibers together. These constituents vary with
plant type. Some plants, such as corn, soybeans, and potatoes, also store starch
(another carbohydrate polymer) and fats as sources of energy, mainly in seeds and
roots.
Ash: The inorganic component of the biomass.

2.4 General C lassification of Fuels

2.4.1 Atomic Ratio

Classification based on the atomic ratio helps us to understand the heating value of
a fuel, among other things. For example, the higher heating value (HHV) of a
biomass correlates well with the oxygen-to-carbon (O/C) ratio, reducing from 38 to
about 15 MJ/kg while the O/C ratio increases from 0.1 to 0.7. When the hydrogen-to-
carbon (H/C) ratio increases, the effective heating value of the fuel reduces. The
atomic ratio is based on the hydrogen, oxygen, and carbon content of the fuel.

9
Figure 2.10 plots the atomic ratios (H/C) against (O/C) on a dry ashfree basis for all
fuels, from carbon-rich anthracite to carbon-deficient woody biomass. This plot,
known as van Krevelen diagram, shows that biomass has much higher ratios of H/C
and O/C than fossil fuel. For a large range of biomass, the H/C ratio might be
expressed as a linear function of the (O/C) ratio (Jones et al., 2006).

2.5 Properties of Biomass

The following three primary properties describe its composition and energy content:
(1) ultimate analysis, (2) proximate analysis, and (3) heating values.

2.6.1 Ultimate A nalysis

Here, the composition of the hydrocarbon fuel is expressed in terms of its basic
elements except for its moisture, M, and inorganic constituents. A typical ultimate
analysis is
C H O N S ASH M 100%

Here, C, H, O, N, and S are the weight percentages of carbon, hydrogen, oxygen,

nitrogen, and sulfur, respectively, in the fuel.

2.6.2 Proximate A nalysis

Proximate analysis gives the composition of the biomass in terms of gross

components such as moisture (M), volatile matter (VM), ash (ASH), and fixed carbon
(FC).

10
Volatile Matter

The volatile matter of a fuel is the condensable and noncondensable vapour

released when the fuel is heated. Its amount depends on the rate of heating and the
temperature to which it is heated.

Ash

Ash is the inorganic solid residue left after the fuel is completely burned. Its primary
ingredients are silica, aluminum, iron, and calcium; small amounts of magnesium,
titanium, sodium, and potassium may also be present.
Moisture

11
High moisture is a major characteristic of biomass. The root of a plant biomass
absorbs moisture from the ground and pushes it into the sapwood. The moisture
travels to the leaves through the capillary passages.

The moisture in biomass can remain in two forms: (1) free, or external; and (2)
inherent, or equilibrium.

Moisture Basis

Biomass moisture is often expressed on a dry basis. For example, if Wwet kg of wet
biomass becomes Wdry after drying, its dry basis (Mdry) is expressed as

Fixed Carbon

Fixed carbon (FC) in a fuel is determined from the following equation, where
M, VM, and ASH stand for moisture, volatile matter, and ash, respectively.
FC = 1 - M - VM - ASH (2.23).

12
Char

Char, though a carbon residue of pyrolysis or devolatilization, is not pure

carbon; it is not the fixed carbon of the biomass. Known as pyrolytic char, it
contains some volatiles and ash in addition to fixed carbon. Biomass char is
very reactive. It is highly porous and does not cake. This noncaking property
makes it easy to handle.

2.6.4 Bases of Expressing Biomass C omposition

The composition of a fuel is often expressed on different bases depending on the

situation. The following four bases of analysis are commonly used:

 As received
 Air dry
 Total dry
 Dry and ash-free
A comparison of these is shown in Figure 2.14.
As-Received Basis
When using the as-received basis, the results of ultimate and proximate analyses
may be written as follows:
Ultimate:C + H + O + N + S + ASH + M = 100%
Proximate:VM + FC + M + ASH = 100%

where VM, FC, M, and ASH represent the weight percentages of volatile matter,
fixed carbon, moisture, and ash, respectively, measured by proximate analysis; and
C, H, O, N, and S represent the weight percentages of carbon, hydrogen,

Higher Heating Value

Higher heating value (HHV) is defined as the amount of heat released by the unit
mass or volume of fuel (initially at 25 °C) once it is combusted and the products have
returned to a temperature of 25 °C. It includes the latent heat of vaporization of
water.

Lower Heating Value

The lower heating value (LHV), also known as the net calorific value (NCV), is
defined as the amount of heat released by fully combusting a specified quantity less
the heat of vaporization of the water in the combustion product.

3.2.1 Pyrolysis Products

13
As mentioned earlier, pyrolysis involves a breakdown of large complex molecules
into several smaller molecules. Its product is classified into three principal types:
 Solid (mostly char or carbon)
 Liquid (tars, heavier hydrocarbons, and water)
 Gas (CO2, H2O, CO, C2H2, C2H4, C2H6, C6H6, etc.)

3.2.2 Types of Pyrolysis

Based on heating rate, pyrolysis may be broadly classified as slow and fast. It is
considered slow if the time, t heating ,required to heat the fuel to the pyrolysis
temperature is much longer than the characteristic pyrolysis reaction time, t r
and vice versa. That is:

 Slow pyrolysis: t heating ≫ t r

 Fast pyrolysis: t heating ≪ t r

These criteria may be expressed in terms of heating rate as well, assuming a simple
linear heating rate (T pyr /t heating , K/s). The characteristic reaction time, t r, for a single
reaction is taken as the reciprocal of the rate constant, k,
evaluated at the pyrolysis temperature.

Types of burners

Burner Working & Types

Burners are mechanical devises which are used to control the air and fuel mixture so
that if the mixture is burnt then the flame is also sustained for as much time as
required for a task. Combustion is a high temperature exothermic redox reaction

14
carried between a fuel and an oxidant to produce gaseous products along with heat
and light energy. Essentially burners are devices which are used to sustain
combustion reactions for the purpose of heating fluids or carrying out endothermic
chemical reactions or converting liquids into vapours etc.

The burners which are used commonly in labs are called Bunsen burners. It is simply
a tube which is connected to a supply of fuel. The fuel is gaseous in nature. The flow
of fuel supply is regulated by a valve, usually a needle valve. When the valve is
opened, the gas flows through the tube. The gas leaving out of the tube can be
ignited, once ignited a flame appears at the top because the gas starts burning. The
gas burns only at the top portion of the tube and not in inside the tube because
sufficient oxygen is only available at the top portion of the tube. It is a handy and
simple device used for heating, sterilization and combustion tasks at lab scale
processes.

Industrial burners are much more large and complex in nature. Some of the types
are:

Burner Types

 Air Staged Burners

 Regenerative Burners
 Self-Recuperative Burners
 Radiant Tube Burners

Air Staged Burners

All the fuel is mixed with some quantity of air through inner air jet and then as
required by the combustion process, air is supplied from outer air jets in stages.

Regenerative Burners
They use a pair of burners which operate together in order to increase thermal
efficiency of the system. The exhaust gas from one burner is used to heat the air
which is about to be fired in the other burner and vice versa. Thus they operate in an
alternate cycle.

Self-Recuperative Burners
This burner has a recuperating action installed. The exhaust gases are pulled back
through an educator and the air is which is incoming is heated using the exhaust
gases.

Radiant Tube Burners

All the previous burners had the fuel and air mixture burning in presence with the
load, the raw material. In radiant tube burners, the process of combustion happens in
a tube, the tube serves as a boundary which separates fuel air mix and the load. The
heat is transferred to the load via radiation.

Burner types

There are five basic types of fuel burning home heating appliances:

15
 gas and diesel burners
Gas and diesel burners are generally boilers or gas fires that run on LPG or diesel.
So long as they have a rated output of 40kW or less, they are allowed to be used
anywhere, with no age restriction.
 ultra-low emission burners
Ultra-low emission burners are any solid fuel burners, including pellet burners, that
achieve a stringent real-life emission standard – they are the cleanest solid fuel
burners and are allowed anywhere with no age restriction.
 low emission burners
Low emission burners are the most common burners in Canterbury and have been
around since the early 2000s. These burners burn wood or pellets and will generally
have only one air flow control and will not be able to be banked down overnight. You
can use these burners in most areas, but in some Clean Air Zones they are being
phased out. Fitting an approved secondary emission reduction device to a National
Environmental Standard compliant low emission burner may extend its use.
 older-style burners
Older-style burners are generally only common outside of Christchurch, Kaiapoi,
Rangiora and Ashburton. They may have two air flow controls, a grate and an ash
pan and may be multi-fuel burners. They can be banked down overnight. These
burners are being phased out in all Clean Air Zones and in Christchurch they can no
longer be used. Fitting an approved secondary emission reduction device to a
National Environmental Standard compliant older-style burner may extend its use.
 open fires
Open fires are any fire places that are not enclosed and in which air flow cannot be
controlled. These burners are being phased out in all Clean Air Zones and in
Rangiora, Kaiapoi, Christchurch, Ashburton and Timaru they can no longer be used.

Fission and Fusion

Introduction

Protons and neutrons make up a nucleus, which is the foundation of nuclear science.
Fission and fusion involves the dispersal and combination of elemental nucleus and
isotopes, and part of nuclear science is to understand the process behind this
phenomenon. Adding up the individual masses of each of these subatomic particles
of any given element will always give you a greater mass than the mass of the
nucleus as a whole. The missing idea in this observation is the concept called
nuclear binding energy. Nuclear binding energy is the energy required to keep the
protons and neutrons of a nucleus intact, and the energy that is released during a
nuclear fission or fusion is nuclear power. There are some things to consider
however. The mass of an element's nucleus as a whole is less than the total mass of
its individual protons and neutrons. The difference in mass can be attributed to the
nuclear binding energy. Basically, nuclear binding energy is considered as mass,
and that mass becomes "missing". This missing mass is called mass defect, which is
the nuclear energy, also known as the mass released from the reaction as neutrons,

16
photons, or any other trajectories. In short, mass defect and nuclear binding energy
are interchangeable terms.

Nuclear Power Plant

(1) It uses nuclear energy to generate power

(2) Nuclear fuels used in power industry are principally Uranium and thorium.

(3) One kg of Uranium can produce the energy equivalent to burning of about 4×10 6
kg of high grade of coal.

Advantages:

(1) Nuclear power plants high initial cost but has low operating cost compared to
conventional thermal power plants.
(2) These plants become more economical if built in large capacities.
(3) It reduces the demand on depleting resources of energy i.e. coal, oil and natural
gas.
(4) The problem of transportation of conventional fuels is avoided since requirement
of nuclear fuel for nuclear power station is negligible.
(5) Large storage facilities of fuel are not needed.

Disadvantages:

(1) Waste of nuclear fuels difficulty to dispose as it constantly releases hazardous

radioactive radiations to environment that may be harmful.

Nuclear Binding Energy

Nuclei are made up of protons and neutron, but the mass of a nucleus is always less
than the sum of the individual masses of the protons and neutrons which constitute
it. The difference is a measure of the nuclear binding energy which holds the nucleus
together.

Mass Defect & Binding Energy

According to nuclear particle experiments, the total mass of a nucleus ( mnuc) is less
than the sum of the masses of its constituent nucleons (protons and neutrons). For a
nucleus with Z protons and mass number A, the mass difference or mass defect is
given by,

∆ m=Z m p+ ( A−Z ) mn −mnuc (1)

Where Z m pthe total mass of the protons is,( A−Z ) mn is the total mass of the
neutrons, and mnuc is the mass of the nucleus. According to Einstein’s special theory
of relativity, mass is a measure of the total energy of a system (E=mc 2 ). The energy
equivalent to mass defect is called the binding energy B or ∆ E of the nucleus. Thus,

17
 2
B=[∆ m]c (2)

Equivalent of 1 gm mass defect is

2
∆ E=1 ×10 × ( 3 × 10 ) =9× 10 MJ
−3 8 7

Similarly, energy equivalent to 1 amu (1.66 × 10-27 kg)

2
× ( 3 ×10 ) =931 MeV (Mega electron volt)
−27 8
∆ E=1.66 ×10

Nuclear fission is the splitting of a heavy nucleus into two lighter ones with releases
of a large amount of energy:
238 1 239 141 92 1
92 U + 0n → 92→ 56 Ba + 36 Kr +3 0n +200 MeV

Nuclear fusion is the process in which two lighter nuclei are combined to be found
together to form a heavier and stable nucleus, is the opposite of nuclear fission.

For example, in a typical fusion reaction, two deuterium atoms combine to produce
helium-3, a process known as deuterium–deuterium fusion (D–D fusion):
2 3 1
3 1 H → 2 He + 0n

In another reaction, a deuterium atom and a tritium atom fuse to produce helium-4, a
process known as deuterium–tritium fusion (D–T fusion):

2 3 4 1
1 H + 1 H → 2He + 0n

18
E= Energy (Joules), c= speed of light (meters/second), m= mass of kg.
Elements of Nuclear power plant:
(1) Nuclear Reactor (2) Coolant and Coolant pump (3) Heat Exchanger (4)
Steam Turbine, Condenser and generator.
(1) Fuel Rod:
The fuel rod is fabricated in various shapes like rods, plates, fins, pallets,
etc.
(2) Moderators
In any chain reaction, the neutrons produced are fast moving neutrons. This is done
by making these neutrons collide with lighter nuclei of other materials, which does
not absorb these neutrons but simply scatter them. Each collision causes loss of
energy and thus the speed of neutrons is reduced. Such a material is called a
Moderator. The neutrons thus slowed down are easily captured by the fuel element
at the chain reaction proceeds slowly.

(3) Control Rods

It is used to control the chain reaction by absorbing required neutrons and materials
used are boron and cadmium.

(4) Reflector
It is desirable that the neutrons are not allowed to escape the reactor core. Hence a
reflector surrounding is provided.

(5) Coolant
The main purpose of the coolant in the reactor is to transfer the heat produced inside
the reactor. The same heat carried by the coolant is used in the heat exchanger for
further utilization in the power generation. The water, heavy water, gas (He, CO2), a
metal in liquid form (Na) and an organic liquid are used as coolants.

(6) Shielding
During Nuclear fission α , β an d γ particles and neutrons are also produced. They are
harmful to human life. Therefore it is necessary to shield the reactor with thick layers
of lead, or concrete to protect both the operating personnel as well as environment
from radiation hazards.

(7) Steam generator

The steam generator is fed with feed water which is converted into steam by the heat
of the hot coolant. Ordinary water or heavy water is a common coolant.

(8) Turbine
The steam produced in the steam generator is passed to the turbine and
work is done by the expansion of steam in the turbine.

(9) Coolant pump and Feed pump

19
The steam from the turbine flows to the condenser where cooling water is
circulated. Coolant pump and feed pump are provided to maintain the flow of
coolant and feed water respectively.

Type of Nuclear Reactor Power Plants

(a) Thermal Reactor and (b) Fast Breeder Reactor

(a) Thermal Reactor
(1) Pressurized Water Reactor (PWR)
(2) Boiling Water Reactor (BWR)
(3) The gas cooled Reactor (GCR)
(4) High Temperature gas cooled Reactor (HTGR)
(5) Pressurized Heavy water Reactor (PHWR)
(6) CANDU Reactor (Canadian Deutorium Uranium)
(B) Fast Breeder Reactor
(1) Liquid metal fast breeder reactor (LMFBR)
(2) Gas cooled fast breeder reactor (GCFBR)

20
21