13 Chapter3

Chapter 3
CONVENTIONAL FUELS AND ALTERNATIVE FUELS
Fossil fuels are formed by natural resources such as anaerobic decomposition of

buried dead organisms. The age of the organisms and their resulting fossil fuels is
typically millions of years, and sometimes exceeds 650 million years. The fossil fuels
include coal, petroleum, and natural gas which contain high percentages of carbon.
Fossil fuels range from volatile materials with low carbon:hydrogen ratio like
methane, liquid petroleum and nonvolatile materials composed of almost pure carbon like
anthracite coal. Methane can be found in hydrocarbon fields as alone, associated with oil,
or in the form of methane clathrates. It is generally accepted that they formed from the
fossilized remains of dead plants and animals by exposure to heat and pressure in the
Earth's crust over millions of years.
3.1 Fuel & Oxidizer
Chemically, the fuel can be defined as one, which donates electrons. In contrast,
an oxidizer can be defined as one, which accepts electrons. This property of elements to
accept or donate electrons is known as electronegativity, which dictates whether an
element can be classified as fuel or an oxidizer. This word electronegativity is defined as
the power of an atom in a molecule to attract electrons towards it. The electronegativity
values for various elements are given in Table 3.1 below.
Table 3.1 Electronegativity of various elements [25].
Elements Electronegativity
O 3.5
N, Cl 3.0
C, S, I 2.5
H, P 2.1
B 2.0
Be, Al 1.5
Mg 1.2
28
Chapter 3 - CONVENTIONAL FUELS AND ALTERNATIVE FUELS
Oxygen has the second highest electronegativity. Although, it is available

abundantly in nature, it is mostly accompanied with nitrogen which, being an inert gas,
reduces the actual capability of oxygen. The fuels such as carbon, hydrogen, aluminium,
magnesium, etc. have lower electronegativity in comparison to oxygen. In combustion
studies, air is a very common oxidizer used most of the times in which the fuel elements
such as carbon, hydrogen, aluminium, boron, etc oxidized easily by oxygen. The most
common fuels that we use in our day-to-day life are basically hydrocarbons. Of course,
hydrogen is emerging as the next generation fuel being the least pollutant fuel. Metals are
used as additives in some special fuels particularly in rocket engine.
3.1.1. Gaseous Fuel and Oxidizer
Recently, gaseous fuels are preferred most over liquid and solid fuels as it is easier
to control emissions from gaseous fuel operated combustion devices as they do not
contain any mineral impurities and are easier to burn for achieving higher efficiency.
Besides this, a gas handling system is least expensive to establish and operate among all
others forms of fuels. The most common gaseous fuels that we use profusely are natural
gas and liquefied petroleum gas. Apart from these two fuels, other gases such as biogas,
producer gas, coke oven gas, acetylene, methane, propane and hydrogen are being used as
fuels. Table 3.2 summarizes several commonly used gaseous fuels along with their
applications.
Natural gas is generally found in porous rocks, which is believed to be formed by

anaerobic (bacteria-assisted) decomposition of organic matter under heat and pressure,
million years ago. It contains mainly methane (CH4) ranging from 75 to 99% by volume
and other gases such as CO, CO2, N2, C2H6 etc as shown in Table 3.3. It must be kept in
mind that natural gases like coal and coke oven gas has regional variations. Recently,
liquefied natural gas is being produced by condensing dry natural gas at -102ºC causing
cryogenic refrigeration systems.
29
Table 3.2 Types of gaseous fuel and oxidizer.
Fuel Oxidizer Application

1. Liquefied Petroleum Gas (LPG) Air/O2 Domestic, burner, furnace.
2. Natural Gas (NG) Air/O2 IC engines, furnace
3. Producer Gas Air/O2 IC engine
4. CH4, C3H8, H2 Air/O2 IC engine
5. Biogas Air/O2 Engine, burner
6. Acetylene Air/O2 Gas welding, cutting
Liquidfied Petroleum Gas mainly consists of propane and butane. The typical
composition of LPG is shown in Table 3.3. Propane and butane are generally produced by
atmospheric fractional distillation of crude oil. Interestingly, LPG can be stored as liquid
in tank at around pressure of 0.8 MPa at normal atmospheric temperature (around 35ºC).
But it becomes gas when it is released to ambient pressure (0.1MPa), because butane has
a boiling point of -0.5ºC while propane has boiling point of -42.1ºC at ambient pressure.
Table 3.3 Typical compositions of gaseous fuels [26].
Type CO2 O2 N2 CO H2 CH4 C2H6 C3H8 C4H10 SG Heating value

% % % % % % % % % (kJ/m3)
Gross Net
Natural … … 5.0 … … 90.0 5.0 … … 0.60 37300 33680
Gas
Biogas 33 … 1 … 1 65 … … … 0.80 28890 25700
Propane … … … … … … 2.2 97.3 0.5 1.55 95290 87840
Butane … … … … … … … 6.0 94.0 2.04 119580 110300
Coal Gas 2.1 0.4 4.4 13.5 51.9 24.3 … … … 0.42 19370 17360
Coke oven 2.2 0.8 8.1 6.3 46.5 32.1 … … … 0.44 21200 18960
Gas
Producer 8.0 0.1 50 23.2 17.7 1.0 … … … 0.86 5330 4950
Gas
Blast 11.5 … 60 27.5 1.0 … … … … 1.02 3430 3430
furnace
LPG … … … … … … … 70.0 30.0 1697 102577 64878
30
Biogas is gaining popularity as a renewable source of energy in Third World

countries, which can be easily produced by anaerobic digestion of biomass. In India, the
cattle dung is the main constituent through which biogas is produced in a digester. It
mainly contains methane and carbon dioxide. Typical compositions of biogas can be
found in Table 3.3. It finds application both in direct burning (cooking stove) and power
producing devices mainly in IC engines.
Producer gas can be generated by gasifying biomass, coal, etc. It finds

applications both in direct heating and power producing devices. A typical producer gas is
given in Table 3.3. It can be noted that primary fuels are carbon monoxide and hydrogen.
The other constituents of this gas are nitrogen (around 40%) and carbon dioxide which
make it a low calorific value fuel. However, using oxygen instead of air for gasifying the
solid fuel enhances the heating content of this gas.
In recent times, hydrogen is contemplated as the future green fuel as it produces

least emission. Hydrogen can be easily produced by reforming natural gas, partial
oxidation of liquid fuels and gasification of coal or biomass. Acetylene can be produced
by hydration of calcium carbide, which is being very much used in gas welding shops in
India.
Gaseous fuels can be characterized by their composition, density and heating

value. The compositions of various gaseous fuels are already shown in Table 3.3. The
heating value of a fuel can be defined as the amount of heat released per unit volume
when it undergoes oxidation at normal pressure and temperature (0.1 MPa and 298 K).
The Higher Heating Value (HHV) corresponds to the heating value of fuel when water is
condensed. In contrast, Lower Heating Value (LHV) of a fuel is referred as amount of
heat released by burning of 1 kg of fuel assuming that latent heat of vaporization in the
reaction products is not recovered. The following expression can relate both these two
heating values:
LHV  HHV  (mH 2 O / m fuel )  H v (3.1)
Where ∆Hv is the latent heat of vaporization of water at 298.15 K.

31
3.1.2 Liquid Fuel and Oxidizer
Liquid fuel is one of the major energy sources, particularly in transport sector.
Some of the common and special liquid fuels and oxidizers are listed in Table 3.4, along
with their respective applications.
Liquid fuels are mainly obtained from the crude oil. Besides this, liquid fuels can
also be obtained from biomass, coal tar, sand and oil shale, etc. Basically, typical crude
oil is a mixture of alkanes (propane, butane etc.), alkenes, aromatics like benzene,
toluene, etc.) and cycloalkanes (napthene) of organic compounds containing C, H, O, N
and S elements.
Table 3.4 Types of liquid fuels and oxidizers .
Fuel Oxidizer Application

1. Gasoline Air SI engine, aircraft
piston engine
2. HSD Air CI engine
3. Furnace oil Air Furnaces
4. Kerosene Air Aircraft, gas turbine,
ramjet, domestic
5. Alcohols Air IC engine
6. Hydrazine, Unsymmetric Di-Methyl Liquid O2, Red Ramjet/scramjet,
Hydrazine (UDMH), Mono-Methyl Fuming Nitric liquid propellant
Hydrazine (MMH), Liquid hydrogen, Acid (RFNA), rocket
triethyl amine N2O4
The crude oil from Assam, India contains on an average, 40% paraffin, higher
alkanes, 25% napthene and cycloalkanes and 35% aromatics. The ultimate analysis of a
crude oil indicates that, on an average, it contains 84% of carbon, up to 0.5% of nitrogen
and 0.5% of sulphur.
32
Table 3.5 Fuel properties of certain common liquid fuels [27,28].
Fuel type Automotive Diesel Methanol Kerosene Aviation

Gasoline Fuel Turbine
Fuel
Specific gravity 0.72-0.78 0.85 0.796 0.82 0.71
Kinematics viscosity 0.8  10-6 2.5  10-6 0.75  10-6 3.626  10-6
At 293 K (m2/s)
Boiling point range 303-576 483-508 338 423-473 442
(K) at STP
Flash point (K) 230 325 284 311 325
Auto-ignition 643 527 737 483
Temperature (K)
Stoichiometric air/fuel 14.7 14.7 6.45 15 15.1
by weight
Heat of vaporization 380 375 1185 298.5 --
(kJ/kg)
Lower heating value 43.5 45 20.1 45.2 43.3
(MJ/kg)
3.1.3 Solid Fuel and Oxidizer
Wood, coal, charcoal, soft coke, agricultural waste (biomass), animal dung are
some of the widely used solid fuels, which are derived basically from fuels available
naturally. Biomass contains plant products such as wood, leaves, bark, branches,
agricultural residues like rice husk, rice straw, wheat straw, groundnut shell, etc. Biomass
as a fuel has been in use since time immemorial. It is well known that coal has been
produced from biomass millions years ago due to natural calamities while entrapped
under high pressure and temperature conditions. Coals can be mined either from open or
deep underground mines. Municipal waste and industrial refuse can also be used as solid
fuels. Besides these, several special fuels using polymers are being devised in last fifty
years to meet the demand of solid fuels in the chemical rocket engines. Several
applications of certain solid fuels are given in Table 3.6.
33
Table 3.6 Types of solid fuels and oxidizers.
Solid fuel Oxidizer Applications

1. Biomass (wood, sawdust, Air, O2 Domestic, IC engine
etc.) with producer gas
2. Coal, coke Air, O2 Domestic, IC engine
3. Special fuels Nitro Cellulose Nitroglycerine, Solid propellant rocket,
(NC), Hydroxyl Terminated Ammonium hybrid rocket
Poly-Butadiene (HTPB), percolate,
Carboxyl Terminated Poly- Ammonium nitrate,
Butadiene (CTPB) Nitrogen tetra oxide
3.2 Conventional Fuels
Most of the road vehicles today operate on Petroleum derived Gasoline and Diesel
fuels. Between 30 to 70% of the Petroleum crude throughout the oil refineries is
converted to automotive fuels thus controlling the refinery economics. Since the first
internal combustion engine and the automobile were developed more than 100 years ago,
the properties of engine fuel have been changing. A number of factors have been
responsible for evolution of modern fuels. Crude oil prices, progress in refinery
processing technology, developments in engine and vehicle technology, vehicle
performance and durability requirements, and more recently the environmental
regulations besides the geo-political considerations are the important factors that have
brought changes in fuel quality.
In early days, the main objective of engine designers was to improve power out
put and reliability. The one obvious route to improve performance of the spark ignition
engine was to increase engine compression ratio. With increase in engine compression
ratio however, knocking combustion was encountered in SI engines demanding high
octane number fuels to suppress engine knock. In the pursuit to increase knock resistance
of Gasoline, tetra-ethyl lead (TEL), an anti-knock additive was discovered in 1921 by
Thomas Midgley of General Motors Research Laboratory and was introduced for use in
[29]
Gasoline on February 1, 1923 . The principal requirements of automotive fuels are
given in Table 3.7.
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Table 3.7 Principal Quality Requirements of Automotive fuels.
Fuel Quality Relationship with engine and vehicle performance

Combustion Better ignition and combustion qualities result in better fuel economy
Quality and reduction in emissions of pollutants. High octane number for SI
engines and cetane number for CI engines are necessary for good
combustion.
High heat of A smaller mass of fuel is to be carried on board of vehicle for the
combustion same operation range.
High volumetric A smaller fuel tank and lower vehicle space is necessary, improving
energy content vehicle packaging. Liquid fuels being sold on volume basis, it results
in better economics for the operators.
Low temperature A significant fraction of fuel should vaporize at low engine
performance temperatures for a better engine cold start and warm-up, good low-
temperature drivability, fuel economy and emissions.
High temperature For ease of hot starting, reduced vapour lock and evaporative
performance emissions, fuels are blended appropriately to meet the needs of
seasonal and geographical variations in ambient temperature.
Oxidation Good low temperature oxidation stability reduces fuel deterioration
Stability during storage and deposit formation in the fuel system.
Deposit formation Helps in maintaining the engine performance, fuel economy and
control emissions close to the designed level by keeping the fuel and
combustion systems clean. Deposit control additives are low cost
products and now widely used for minimizing deposit formation.
Material Material compatibility is essential to prevent corrosion of metallic
compatibility and deterioration of rubber and elastomeric components of the fuel
system.
Flow Fuel has to be in fluid condition at low temperature and is important
characteristics particularly for diesel fuels. Also appropriate diesel fuel viscosity is
essential for flow as well as good injection characteristics.
35
High octane number fuels could be produced at a low cost with the use of TEL. It
led to increase in engine compression ratio to 10.5-11.0: 1 during late 1950s and 1960s in
the USA and Europe. However, since 1970 reduction of engine emissions has become an
over-riding requirement for the engine designers and fuel engineers. TEL was widely
used in Gasoline until 1975 when the Gasoline vehicles for the first time employed
catalytic converters for emission control. Since then, TEL has been gradually phased-out
from Gasoline and today Gasoline is almost totally lead-free all over the world. Besides
the environmental considerations, there are several other requirements that are to be met
by the engine fuels.
3.2.1 Motor Gasoline
Gasoline is a mixture of nearly 400 different types of hydrocarbons [30]. The types
of hydrocarbons present in Gasoline are normal-paraffins, iso-paraffins, olefins, aromatics
and to a smaller extent cyclo-paraffins. It has hydrogen to carbon ratio varying from 1.7
to 2.0 and is typically characterized by the molecular formula C8H16. The Gasoline is
liquid at room temperature with boiling range approximately of 35 – 315º C. The
principal properties of Gasoline that are specified in the fuel standards are:
 Distillation, ºC
 Reid vapour pressure
 Specific gravity
 Research Octane Number (RON)
 Motor Octane Number (MON)
 Oxidation stability
 Gum content, mg/100 ml
 Lead content, g/l
 Sulfur, wt %
 Benzene, vol. %
36
Octane Quality
High antiknock quality of Gasoline is needed to prevent or minimize knocking

combustion in high compression ratio SI engines. Knocking combustion in SI engines can
cause engine overheating, loss in efficiency and increase in emissions. Persistent
knocking can lead to mechanical damage to engine under high load operation.
Earlier lead antiknocks, tetra-ethyl lead and tetra-methyl lead were used to boost
octane number of Gasoline. Now however, due to catalyst poisoning and lead being a
health hazard by itself, Gasoline world over has become almost lead-free. The lead-free
Gasoline is blended with high-octane fuel components like aromatics, iso-parrafins,
alcohols and methyl tertiary butyl ether (MTBE) to improve anti-knock quality. The
regular grade Gasoline in Europe has a minimum of 91 RON and 82.5 MON. Due to
refinery economic reasons, the octane quality of premium unleaded Gasoline however, is
now kept at 95 RON and 85 MON as compared to 98 RON and 87 MON for the leaded
premium Gasoline earlier [31].
Volatility
The volatility of Gasoline is experimentally evaluated by its distillation range and

Reid vapour pressure (RVP). RVP measured by American Society for testing and
Materials (ASTM) is an important parameter of Gasoline front-end volatility. It has good
correlation with the evaporative losses during refueling, from tank vent and carburetor
when vehicle is running or during heat soaking after vehicle is stopped. Some other
parameter derived from the distillation characteristics and RVP are also used to evaluate
drivability performance of Gasoline. For hot weather drivability performance, vapour
lock index (VLI) is widely used in Europe and other countries.
Oxidation Stability
The fuel stays in the storage and transportation systems for several weeks after
production before it is consumed in vehicles or engines. During this period, the fuel
undergoes slow oxidation under the prevailing ambient conditions. Oxidation stability of
Gasoline is a measure of its suitability for long-term storage and its tendency to form
deposits in the engine especially the fuel system. The most commonly used methods are
induction period and existent gum test.
37
To improve oxidation stability of Gasoline anti-oxidants are usually added. The

type and amount of antioxidants depends on the Gasoline composition and storage
demands. These additives are based on aromatic diamine, alkyl phenol and amino-phenol
compounds. Additives called as metal deactivators are also used to nullify the catalytic
oxidation effect of some metals like copper present in the Gasoline.
Oxygenate Content
Various oxygenates, mainly ethers and alcohols are blended in unleaded Gasoline
to boost octane number of Gasoline. After the use of lead antiknocks has been banned,
use of ethers and alcohols for improving octane quality provides a relatively low cost
option to the fuel refiners. The main types of alcohols and ethers that have been used are
given in Table 3.8.
Table 3.8 Oxygenates used in Gasoline.
Alcohols Ethers
Methanol Methyl tertiary butyl ether (MTBE)
Ethanol Tertiary amyl methyl ether (TAME)
Isopropyl alcohol Ethyl tertiary butyl ether (ETBE)
Isobutyl alcohol
Tertiary butyl alcohol (TBA)
The amount of oxygenates added to Gasoline is limited for use in the vehicles
designed to operate on the conventional hydrocarbon fuels mainly due to two reasons.
One is mixture leaning effect due to presence of oxygen in the fuel and another reason is
their adverse effect on the fuel system materials. In addition, the use of oxygenates
particularly alcohols increases fuel volatility and may lead to hot weather drivability
problems caused by vapour lock. Also, increase in RVP would increase evaporative
emissions, resulting in further environmental pollution caused by unburned fuel
emissions. Increase in aldehydes emissions with the use of oxygenates containing
Gasoline, particularly in the non-catalyst equipped cars is another concern.
38
3.2.2 Diesel Fuels
Diesel fuels are mixtures of a large number of hydrocarbons, which generally boil
within the temperature range of 150 to 390º C. Earlier, diesel fuels were produced mostly
by blending a number of refinery streams from the atmospheric distillation unit. However,
to meet the increasing demand of the diesel fuels, products of secondary refinery
conversion processes like thermal and catalytic cracking, hydro-cracking etc are also
blended in the current diesel fuels. The quality of the final product depends on the
characteristics of the crude oil processed and the characteristics of the various streams
blended in the product. The key properties of the diesel fuel, which affect engine
performance and emissions, are:
 Ignition quality
 Distillation (volatility) characteristics
 Density
 Viscosity
 Hydrocarbon composition
 Sulphur content, and
 Stability and injection system cleanliness
Other significant properties include cold flow characteristics at low ambient

temperatures, water and sediment content, carbon residue etc.
Ignition Quality
Ignition quality of diesel fuel is an expression of the ease of self-ignition of diesel

injection spray in the hot compressed air inside the engine cylinder. Cetane number is the
most widely used and accepted measure of ignition quality of the diesel fuels.
A higher cetane number is being specified now for the diesel fuels as it results in
improved cold starting, warm-up, reduced combustion noise, lower fuel consumption and
exhaust emissions. Cetane or ignition improvers are used to improve ignition quality of
the diesel fuels, which do not naturally meet the specification limits. In premium quality
diesel fuels, oil companies use cetane improvers to produce diesel fuels even above the
specification limits in certain countries. Most commonly used cetane improving additives
39
are nitrates and peroxides like iso-propyl nitrate, cycle-hexyl nitrates, ethyl-hexyl nitrate
(EHN) and di-tertiaryl-butyl peroxide. These compounds decompose readily at high
compression temperatures in the engine, produce free radicals that accelerate
precombustion reactions in the fuel-air mixture and thereby reduce ignition delay. The
response of cetane improvers depends on the cetane number and hydrocarbon
composition of the base fuel.
Distillation Range
Higher the volatility of the fuel more readily it vaporizes, mixes with air and burns
in the combustion chamber. The low volatility components boiling above 350º C may not
burn completely forming engine deposits and producing high exhaust smoke emissions.
The mid boiling point often is taken as an overall representation of the fuel volatility and
has been observed to affect smoke emissions [32,33]. The volatility is also correlated to the
other physio-chemical properties of the fuel like, density, viscosity and ignition quality.
Density
The specific gravity of diesel fuel varies generally in the range 0.81-0.88. It is
interrelated to volatility, cetane number, viscosity and heat of combustion etc. In general,
an increase of 10% in density decreases heat of combustion by about 4% and, thus the
[32]
volumetric energy density of the fuel increases by approximately 6% . The fuel
injection pump calibration being on volume basis, the fuel density influences engine
power, fuel economy and smoke emissions.
Viscosity
The viscosity of diesel fuel affects injection characteristics, fuel atomization, drop
size distribution, spray cone angle and penetration. An increase in viscosity reduces spray
cone angle, increase droplet size and spray penetration. Viscosity of fuel affects fluidity
of fuel at low temperatures. High viscosity can reduce fuel flow rates to the injection
system resulting in an inadequate fuelling of the engine. Low viscosity on the other hand,
results in an increase in leakage of fuel past the pumping elements. If the fuel viscosity is
too low, at high temperatures it could result in total fuel leakage. Thus, the fuel viscosity
influences metering characteristics of the injection system. Viscosity of fuel is important
for lubrication and protection of the injection equipment from wear. Therefore, for a
40
given engine application the fuel viscosity range is specifies. Most specification limits
kinematic viscosity of diesel fuel in the range of 2 to 5 centistokes.
Stability
Resistance of fuel to degradation during storage before it is consumed is an

important requirement. More cracked products are being blended in diesel fuels to
increase its yield from the same crude barrel. Heavy residues from the atmospheric
distillation units are catalytically cracked to produce distillate fuels. During long-term
storage of diesel fuels particularly those containing thermally and catalytically cracked
stocks, high amounts of sediments are formed due to slow oxidation occurring at
atmospheric temperature conditions. The distillate products from cracking processes
consist of higher amount of olefins and also nitrogen and sulphur containing compounds
than those from the atmospheric distillation units. The olefins are more prone to oxidation
and the oxidation process is further enhanced by nitrogen containing compounds, such as
pyrolles and indoles. The oxidation products in the fuel are polymerized finally to high
molecular weight compounds called ‘gums’. The gums are of two kinds, ‘soluble gum’
that remains dissolved in the fuel and the ‘insoluble gum’, which gets precipitated out in
the fuel. The insoluble gum is also referred as ‘sediments’, which causes a number of
problems in the engine. The gums cause plugging of fuel filters, the problem being more
severe for the paper element micro-filters.
Chemical Composition
Aromatic content is of great concern as it increases particulate and poly-aromatic

hydrocarbons (PAH’s) emissions. The diesel fuels specifications in most of the countries
now limit aromatic content to 10% maximum. Also limits on the PAH’s are being
specified. One side effect of reduction in aromatic content is reduction in lubricity
characteristics of the diesel fuels resulting in high wear rates of the injection pump
elements and injector needles. Detergent additives are used in fuel to solve injector
cleanliness problems. Small dosage of additives can keep injectors clean while high
dosages of these additives can partially clean the heavily clogged injector holes [34].
Sulphur Content
Sulphur containing compounds naturally occur in the fuel and diesel fuels have
significantly higher sulphur content than Gasoline. Sulphur on combustion produces
41
sulphur dioxide (SO2), most of which is exhausted into atmosphere. A small fraction of
SO2 about 1 to 3% is oxidized in the oxygen rich diesel exhaust to sulphur trioxide (SO3)
[35]
and to sulphates found in particulate emissions . The sulphur trioxide on combining
with water forms sulphuric acid that causes wear of metallic components. It is well
known that high sulphur levels of diesel fuel increases wear of piston rings and cylinder
liners, the wear rates being higher at lower coolant temperatures. In addition, sulphur
increases deposit formation in the combustion chamber and the deposits become harder in
presence of sulphur. Sulphuric acid aerosols adsorbed on the foot particles and are
emitted as particulate emission. Depending on sulphur content, its contribution can be
significantly large to particulate emissions. This is why, sulphur content of diesel fuels is
being reduced to very low levels (< 500 ppm and even down to 50 ppm) as more and
more stringent emission standards are being implemented [31].
Lubricity
The diesel fuel itself provides lubrication of diesel pumping and injection
elements. The heavier, high viscosity hydrocarbons and polar compounds are believed to
be the lubricating compounds providing natural lubricity to the diesel fuel. The polar
compounds get adsorbed on the injection systems surfaces and act as anti-friction layer.
Hydro-treating refining processes are used to remove sulphur from the diesel fuels. In the
process, polar compounds are also removed. As the sulphur content of diesel fuel
decreases, the lubricity of diesel fuel goes down. Low lubricity can result in excessive
injection pump wear and in some cases in total mechanical failure.
3.3 Alternative Fuels
More and more stringent environmental regulations being enacted in the USA and
Europe have lead to research and development activities on clean alternative fuels.
Energy security has been another important consideration. A number of liquid and
gaseous fuels are among the potential fuel alternatives. Most important among them are,
alcohols, ethanol and methanol, natural gas, liquefied Petroleum gas (LPG), hydrogen,
ethers like di-methyl ether (DME), vegetable oil esters commonly called as ‘biodiesel’,
bio gas etc. The US Clean Air Act Amendments (CAAA) besides most of these
alternative fuels lists reformulated Gasoline, electricity and any other fuels that permit
attaining the legislated emission standards as the ‘clean alternative fuels’ [31].
42
Some of the important properties of different alternative fuels are compared in

Table 3.9 with those of typical Gasoline and diesel fuels.
Table 3.9 Properties of various fuels for vehicles [39,40].
Property Gasoline Diesel Methanol Ethanol Natural Propane DME RME Hydrogen
gas
Mol. wt 110 170 32.04 46.07 18.7 44.10 46.1 2.015
Density 0.72- 0.82- 0.796 0.794 0.72 0.51 0.67 0.882 0.090
0.78 0.88 (liquefied) (liquid)
Lower heating 44.0 42.5 19.9 26.8 50.0 46.3 28.4 37.7 120
value MJ/kg
Heat of 305 250 1110 904 509 426 410 at
vaporization, 20º C
kJ/kg
Boiling point, 30-215 180- 65 78 -160 -43 -24.9 330- -253
ºC 370 340
Octane 90-98 - 112 111 120-130 112 - - 106
number,
research
Octane 80-90 - 91 92 120-130 97 - - -
number, motor
Cetane number - 45-55 - - - - >55 51-52 -
Stoichiometric 14.7 15.0 6.43 8.94 17.12 15.58 9.0 11.2 34.13
A/F ratio, mass
Vapour 0.6-8.0 0.6- 5.5-26 3.5-15 5-15 9-9.5 3.4- - 4-75
flammability 7.5 18.6
limits, (vol. %)
Stoichiometric 71.9 69.0 71.2 54.9 64.5 69.0 0
CO2 emissions,
g/MJ fuel
Adiabatic 2266 2151 2197 2227 2268 2383
flame
temperature
(K)
High Petroleum crude prices generated a lot of interest in ethyl alcohol produced
from agricultural products during 1980s notably in Brazil. On the other end, during the
same period environmental considerations were foremost in the USA for vigorous
technological development activities related to methanol. At that time, methanol was
considered a more convenient and economically attractive carrier of natural gas across the
43
continents for import of cheaper energy available in the form of natural gas. Methanol
being liquid it was better suited than natural gas for storage on-board of vehicles. Interest
in methanol however, has almost more or less died down it being otherwise highly toxic
to living beings and its corrosive nature for many materials used in fuel handling and
engine fuel systems. Presently, natural gas and biodiesel have attracted an increasing
interest of the governments, vehicle manufacturers and fuel suppliers. Hydrogen is also
considered a long-term potential alternative.
According to an estimate, the reserves will last for 218 years for coal, 41 years for
oil, and 63 years for natural gas, under a business-as-usual scenario [36,37,38].
3.3.1 Alcohols
Alcohol is made from renewable resources like biomass from locally grown crops
and even waste products such as waste paper, grass and tree trimmings etc. Alcohol is an
alternative transportation fuel since it has properties, which would allow its use in
existing engines with minor hardware modifications. Alcohols have higher octane number
than Gasoline. A fuel with a higher octane number can endure higher compression ratios
before engine starts knocking, thus giving engine an ability to deliver more power
efficiently and economically. Alcohol burns cleaner than regular Gasoline and produces
lesser carbon monoxide, hydro carbons and oxides of nitrogen [41,42,43]. Alcohol has higher
heat of vaporization, therefore it reduces the peak temperature inside the combustion
chamber leading to lower NOx emissions and increased engine power. However, the
aldehyde emissions go up significantly. Aldehydes play an important role in formation of
photochemical smog.
Methanol (CH3OH) is a simple compound. It does not contain sulfur or complex

organic compounds. The organic emissions (ozone precursors) from methanol
combustion will have lower reactivity than Gasoline fuels hence lower ozone forming
potential. If pure methanol is used then the emission of benzene and PAH’s are very
low [42]. Methanol gives higher engine efficiency and is less flammable than Gasoline but
the range of the methanol-fuelled vehicle is as much as half less because of lower density
and calorific value, so larger fuel tank is required. It has invisible flames and it is
explosive in enclosed tanks. The cost of methanol is higher than Gasoline. Methanol is
toxic, and has corrosive characteristics, emits ozone creative formaldehyde. Methanol
44
poses an environmental hazard in case of spill, as it is totally soluble with water. Ethanol
is similar to methanol, but it is considerably cleaner, less toxic and less corrosive. It gives
greater engine efficiency. Ethanol is a grain alcohol, and can be produced from
agricultural crops e.g. sugar cane, corn etc. Ethanol is more expensive to produce, has
lower range, having cold starting problems and requires large harvest of these crops.
Higher energy input is required in ethanol production compared to other energy crops and
it leads to environmental degradation problems such as soil degradation [24].
Methanol and ethanol can be produced from renewable sources as well as from
fossil fuels. Methanol is mainly produced from natural gas. Coal and cellulose containing
biomass like wood etc. may also be used to produce methanol. Ethanol is produced
almost entirely from the renewable sources from fermentation of carbohydrate containing
biomass like sugar, grains, tapioca etc. Neat ethanol (95% ethanol + 5% water) and
anhydrous ethanol blended up to 20% in Gasoline have been widely used in Brazil during
1980s. In the USA, use of ethanol initially started in the agricultural surplus states like
Nebraska for blending in the reformulated Gasoline as oxygenate. Now, ethanol is the
preferred oxygenate replacing methyl tertiary butyl ether (MTBE). The 10% ethanol-
Gasoline blends used in the USA are commonly referred as ‘Gasohol’. Germany,
Sweden, New Zealand and California focused mainly on methanol as an automotive fuel
due to its potential near the natural gas field and it being liquid can be more easily
handled and transported compared to natural gas.
Physical and chemical characteristics of alcohols make alcohols as excellent fuels

for the SI engines. The ignition quality of alcohols being poor, these cannot replace diesel
fuels directly and a source of ignition is to be provided for their combustion in the diesel
engine cylinder. Gasoline at least in 15% v/v amount was added to alcohols to increases
visibility of flame from the fire safety considerations.
Alcohols are not suitable fuels for compression ignition as they have very poor
ignition quality. Cetane number of methanol and ethanol is 5 and 8, respectively. Further,
the alcohols are not easily soluble in the diesel fuels. To prepare alcohol-diesel blends
high amounts of additives (emulsifiers/solublizers) are required and ignition improvers
[44,45]
are to be used to compensate for loss in ignition quality . The following three
approaches have been largely considered practically feasible for total or part replacement
of diesel fuels by alcohols:
45
(i) Improving ignition quality of alcohols by use of ignition improvers.
(ii) Use of glow or spark plugs as a positive source of ignition.
(iii) Dual-fuel operation, using pilot diesel injection as an ignition source for
alcohol-air mixtures [46,47].
Widespread use of alcohols as motor fuels so far has not established. Firstly
significant cost benefits did not exist and also emission benefits compared to Petroleum
fuels have not been attractive. In addition, there are some negative factors and undesirable
effects on engines relative to conventional fuels. The main advantages and disadvantages
of alcohols with respect to conventional Gasoline and Diesel fuels are summarized in
Table 3.10 & Table 3.11.
Table 3.10 Advantages of alcohol motor fuels compared to Gasoline and Diesel.
Property/Performance Compared to Advantages

Parameter Gasoline and
Diesel fuels
Octane number Higher A higher engine compression ratio in
SI engines can be used resulting in
higher thermal efficiency
Latent heat of vaporization Higher Lower intake temperature may be
used to increase charge density and
higher volumetric efficiency
Adiabatic flame Lower Potentially lower NOx emissions and
temperature lower heat losses
Flame luminosity Lower Lower heat losses from combustion
PM emissions Lower Due to clean burning characteristics
PM emissions are even lower than the
Gasoline engines
Toxic emissions - Lower benzene and 1,3 butadiene
emissions
Nature of sources Renewable esp. of Sources more widespread around the
ethanol world, hence better energy security.
Lower net CO2 emissions
46
Table 3.11 Disadvantages of alcohol motor fuels compared to Gasoline and Diesel.
Property/Performance Compared to Disadvantages

Parameter Gasoline and
Diesel fuels
Volumetric energy Much lower Higher volumetric fuel consumption
content hence larger fuel storage space and
weight
Cetane number Much lower Cannot be directly used in compression
ignition engines. Needs a source of
ignition increasing complexity of
engine/fuel system
Vapour pressure Lower Poor cold starting and warm up
performance, higher unburned fuel
emissions during starting/warm up phase
CO and NOx Emissions Similar No definite trend is observed, So, no
advantage over Petroleum fuels have been
noted
Aldehyde emission Higher Formaldehyde and acetaldehyde emission
are higher
Material Higher Methanol and a lesser degree ethanol are
corrosion/adverse effects more corrosive to metals, elastomers and
plastic components. Needs selection of
suitable materials for the fuel system.
Engine wear Higher Washes away lubricants film during cold
starting, resulting in higher cylinder and
piston ring wear
Flame Luminosity Almost invisible Neat alcohols present fire safety hazards.
Addition of Gasoline or other material
required to increase flame luminosity
47
3.3.2 Natural Gas
Natural gas has been used now for more than 50 years as fuel for stationary
engines for power generation, gas compression and agricultural machinery. Presently, a
large number of natural gas vehicles (NGVs) are in operation throughout the world in
Argentina, Australia, Canada, Italy, India, New Zealand, countries of former Soviet
Union and a number of other Asian and European countries. Natural gas is finding favour
as an alternative fuel due to its large-scale availability and potentially high environmental
benefits. In the USA, stringent particulate emission standards for the urban buses
implemented in the year 1994 and later, provided impetus to the development of natural
gas fuelled urban buses. Table 3.12 gives the number of NGVs annual gas consumption
and number of natural gas filling station in operation in different regions worldwide for
the year 2010 and Table 3.13 represents natural gas vehicle growth since 2000.
Table 3.12 Worldwide Population of NGVs in 2010 [48].
Country Natural Gas Monthly Sales Average Refuelling

3
Vehicles N/m Stations
Iran 2,070,930 330,000,000 1490
Argentina 1,901,116 207,305,000 1878
Brazil 1,646,955 165,812,800 1782
India 1,100,000 NA 596
Italy 676,850 62,030,000 770
China 500,000 NA 1652
Colombia 320,036 45,000,000 614
Thailand 211,402 95,600,000 423
Bangladesh 200,000 91,550,000 500
Egypt 139,804 38,000,000 129
USA 110,000 105,000,000 1100
Russia 100,052 27,710,000 249
Germany 85,000 14,600,000 863
Korea 28,324 81,680,000 166
Sweden 23,125 6,770,000 134
Switzerland 9,279 1,320,000 15
48
Table 3.13 Natural gas vehicle growth since 2000 [48].
Region Average % NGV growth since 2000

Asia 52.50%
Europe 15.40%
North America 0.40%
South America 25.90%
Africa 19.30%
Total 29.80%
The principal constituent of natural gas is methane (80 to 95% by volume). The
balance is composed of small and varying amounts of other hydrocarbons such as ethane,
propane, butane and heavier hydrocarbons and non – hydrocarbon gases carbon dioxide,
nitrogen, water, hydrogen sulphide and other trace gases. Typical composition is given in
Table 3.14. The natural gas before transportation or use is upgraded by removing water,
hydrogen sulphide and condensable higher hydrocarbons. It helps in prevention of
condensation of these compounds in pipeline and also valuable by-products are obtained.
Natural gas, once flared-off as an un-needed byproduct of petroleum production, is now
considered a very valuable resource [49].
Table 3.14 Composition of CNG.
Constituents % Volume
Methane 93.20
Ethane 04.27
Propane 01.38
i-Butane 00.18
n-Butane 00.20
i-Pentane 00.04
n-pentane 00.03
Carbon dioxide 00.27
Nitrogen 00.43
Moisture content 2.0 ppm
49
In a nationwide survey across the USA reported in 1992, variations in

composition of natural gas could result in variations of 14% in density, 20% in Wobbe
[50]
index and 25% in stoichiometric air-fuel ratio . The Wobbe index is defined as
W=H/√ρ, where H is volumetric heating value and ρ is specific gravity. It has an almost a
linear relation with air-fuel equivalence ratio. Reasonably small variations in Wobbe
index have little effect on emissions using modern engines with three way catalysts and
closed loop feedback control. However, large variations in gas composition can have
significant effects on engine performance and emissions, especially if the engine
performance and emissions are optimized on a fixed gas composition and engine is not
equipped with means of adjusting to other composition can also affect the composition
and reactivity of the exhaust HC emissions.
Oil wells are primary source and refineries are a secondary source of natural gas
where the dissolved gases in the Petroleum crude are released during the refining process,
but in lesser volumes. CNG is a safe fuel. Being lighter than air, it diffuses easily into the
atmosphere and does not form a sufficiently rich mixture for combustion to take place. In
this respect, CNG is superior to other fuel. Storage of propane on vehicles is not as
cumbersome as CNG, but the cost of propane is higher than that of CNG. CNG represents
a more cost effective emission reduction measure than quite a few other options that have
been the subject of serious debate in recent years.
International Standards Organization (ISO) 15403-2000 provides specifications

[51]
for the natural gas delivered to the vehicle and not to the pipeline gas . These
specifications also include parameters like water content, sulphur content, condensate and
free oil that may come from the natural gas compressor.
Natural gas liquefies at -161ºC at atmospheric pressure. To use liquefied natural

gas (LNG) as automotive fuel cryogenic systems are required. There are other problems
too with the use of LNG. Liquid phase in the fuel tank should not become enriched with
other higher hydrocarbons during refilling cycles. Leakage of even small amounts of
LNG in an enclosed space may form explosive mixtures and risk of fire hazards increases
by manifold. Therefore, in most of the NGVs today, natural gas is stored on board in
high-pressure cylinders at a pressure of 200 to 300 bars as CNG, storage of natural gas at
high pressure on board provides an acceptable range of vehicle operation.
50
High antiknock quality of natural gas makes it a fuel that is better suited for SI
engines. The natural gas engine operation may be broadly classified in the following
types:
(i) Bi-fuel Operation: The conventional Gasoline vehicles are converted to

operate either on Gasoline or natural gas, as the operator prefers.
(ii) Dedicated or Mono-fuel Operation: Vehicle operating only on gas using a

positive source of ignition such as spark plug or hot surface ignition like glow
plug.
(iii) Dual-Fuel Operation: When the diesel injection constitutes 10% or less of
the total fuel, the diesel injection system particularly the injectors are replaced
by the new ones of a different calibration. These engines are known as ‘pilot-
injection’ engines and do not have the dual-fuel flexibility of operation on
diesel alone. In a new development of ‘pilot injection’ engine high-pressure
natural gas is directly injected in the combustion chamber and ignited by the
pilot diesel spray.
As natural gas has a very high antiknock quality, dedicated natural gas engines
can be built with much higher compression ratio than the Gasoline engines resulting in
significant improvements in fuel efficiency and lower carbon dioxide emissions. This is
particularly useful for heavy-duty vehicle application. Lean burn spark or low plug-
ignited, high compression ratio engines can be built to give very low particulate emissions
and high-energy efficiency. The stoichiometric SI engines can utilize the three-way
catalyst (TWC) emission technology and therefore, it provides the greatest emission
reduction potential. Problems with thermal stresses and low power density have favoured
the use of lean-burn combustion system over TWC in heavy-duty application.
3.3.2.1 Effect of Natural Gas on Emissions
With natural gas operation, large reductions in engine-out emissions compared to

either Gasoline or diesel fuel operation can be achieved. It could be mentioned that most
light-duty SI natural gas engines are stoichiometric similar to their Gasoline-fuelled
counterparts. With natural gas, mixture enrichment during cold starting is not required
unlike the Gasoline operation. Hence, use of natural gas results in lower unburned fuel
emissions during cold staring and warm-up phase.
51
CNG buses without after-treatment have high emissions of formaldehyde, which

is considered a possible human carcinogen. The formaldehyde emissions can be reduced
with an oxidation catalyst but not to the low level of a diesel bus equipped with catalytic
regeneration particulate trap (CRT). In addition to emissions benefits, NGV has other
differences from the vehicles operating on the conventional Petroleum fuels as below:
(i) The natural gas is stored in high-pressure cylinders. It results in weight penalty of
the vehicles and for heavy-duty vehicle it may increase weight of the vehicle by
600 to 1000 kg to provide an acceptable range of operation. Low weight cylinders
of composite material are available that reduce the cylinder weight by more than
half. These cylinders have a liner made of steel, aluminium or non-metal, which is
over-wrapped by hoop or fully wound carbon/fiberglass filament in a resin matrix.
These composite material cylinders however, are more expensive than the
conventional steel cylinders and the cost may be higher by a factor of 3 or 4.
(ii) Compared to Petroleum fuels, emissions of carbon dioxide, a green house gas are
lower in the dedicated natural gas engines as a higher engine compression ratio
can be used.
(iii)Low emissions of non-methane hydrocarbons from natural gas vehicles result in

low photochemical reactivity and ozone forming potential of the exhaust gases.
Emissions of air toxics such as benzene and 1-3, butadiene are very low.
3.3.3 Liquefied Petroleum Gas
LPG is commonly known as propane (C3H8), a combustible hydrocarbon based

fuel. It comes from the refining of crude oil and natural gas. There are currently three
grades of propane available, HD5 for ICEs, commercial propane and commercial
propane-butane mixture for other uses. The commercial grade of propane for automotive
use is known as HD5 and composition is shown in Fig. 3.1. The exact composition of
propane varies slightly between different parts of the country and different refineries.
Compared to Gasoline the energy content of LPG is 74%.
52
Composition of LPG
100
80
% Amount
60
40
20
0
Propane Propylene Butane Iso-butane Methane
Series1 90 5 2 1.5 1.5
Constituents
Fig 3.1 Composition of LPG.
In the USA, LPG contains more than 85% propane while in Europe and Asia,
propane constitutes just about half of LPG, the balance being largely the butane. It
remains in gaseous state at normal ambient temperatures and pressures (the boiling point
of propane and butane at atmospheric pressure is about -45º C and -2º C, respectively).
The pressure inside storage tank keeps LPG liquid, and it becomes gas when released
from the tank. The liquid form has an energy density 270 times greater than the gaseous
form, making it efficient for storage and transportation. The benefits of LPG as a clean
burning motor fuel results in practice largely from its ability to change between the liquid
and gaseous phase much more readily compared to natural gas.
In Europe, LPG motor fuel was first used in 1950s, especially in Italy and the
Netherlands who offered tax incentives making it economically more attractive. In 2003,
worldwide population of LPG vehicles stood at 9.5 millions consuming annually about
[48]
16.5 million tons of LPG . Population of LPG vehicles in some countries in the year
2003 is given in Table 3.15.
South Korea had the largest LPG passenger car fleet that stood at 1.7 million
units, ahead of Italy (1.2 million), Poland (1.1 million) and Turkey (1 million). The use of
LPG as motor fuel would help diversify the transport energy supply while exploiting local
resources that may be present in abundance in several countries.
53
Table 3.15 LPG Vehicle Fleet Worldwide in 2003 [48].
Country Number of Motor Consumption of LPG

Vehicles (thousands) (thousand tons)
Australia 492 1,213
Czech Republic 145 68
France 180 166
Italy 1,220 1,202
Japan 290 1,528
Mexico 700 1,200
Netherlands 290 435
Poland 1,100 1,700
Russia 550 780
South Korea 1,723 3,740
Turkey 1,000 1,260
United States 190 730
Worldwide 9,416 16,445
Most LPG vehicles employ bi-fuel systems for operation either on Gasoline or
LPG. It provides flexibility to vehicle operation, which is important as the number of
LPG filling stations is usually small. One drawback with a bi-fuel system is that neither
fuel can achieve optimum performance. Optimization of engine for LPG operation is
possible only for the dedicated gas engines. However, variation in propane/butane ratio in
LPG possess a problem as the octane number of the two main constituents, propane
(RON is 112) and butane (RON is 94) is quite different. When more stringent emission
standards like Euro IV are to be met, the bi-fuel vehicles may require a major technology
upgradation. For bi-fuel vehicles like conventional motor fuels, specific technological
development will be necessary to ensure compliance with the stringent emission
standards.
The advantages and disadvantages of LPG as a motor fuel are similar to those for
natural gas. The main advantages and disadvantages of LPG compared to Gasoline are
given below:
54
(i) Good cold start and warm-up characteristics due to its gaseous state
(ii) Higher antiknock quality of LPG provides an opportunity for use of a higher
compression ratio and improvement of engine performance and thermal
efficiency
(iii) Emissions are substantially lower compared to Gasoline vehicles. LPG has
disadvantage compared to natural gas in respect of non-methane hydro carbon
(NMHC) emissions as these consists of higher amounts of reactive olefinic
hydrocarbons. The ozone forming potential of LPG with Gasoline, Diesel and
CNG is compared in Fig.3.2. LPG has significantly lower smog formation
potential compared to Gasoline and Diesel fuels.
(iv) LPG operation results in negligible PM emissions compared to Diesel.
(v) LPG is relatively a low sulphur fuel.
(vi) Lower energy content results in higher volumetric fuel consumption
(vii) As the fuel on board is at a higher pressure, additional safety regulations are to
be implemented. As LPG is heavier than air, restrictions on vehicle parking in
confined space are also to be applied.
Ozone Forming Potential, mg/km
400
350
300
250
200
150
100
50
0
CNG LPG Gasoline Diesel
Fig 3.2 Comparison of ozone forming potential of different fuels for cars, during
summer [36].
Introduction of gaseous fuels in the intake manifold decreases the air partial
pressure notably compared to Gasoline. This reduction in power is inherent in the
structure of gaseous fuels.
55
 One way to compensate this loss is to use supercharger or turbocharger in order to

increase air flow rate. Superchargers and turbochargers provide more power from
the engine by compressing the inducted air higher density than ambient.
Volumetric efficiency goes up with turbochargers and superchargers along with
better bsfc. Turbocharger has a turbine and compressor in a common shaft.
Turbine is driven by the exhaust gas. Using of exhaust gas provides the recovery
of waste energy which leads to increase in the overall efficiency. An intercooler or
aftercooler is applied in order to provide further increase in the combustion air
density. Supercharger is operated on the same principle with turbocharger. But the
driven of compressor is achieved by engine's crankshaft. Turbo lag which
indicates the delay between boost and throttle response. This can be a problem in
SI engines. However this is not noticeable in large diesel engines. The drawback
with supercharger appears in cruise conditions. Because supercharger can not
adjust itself to this condition due to direct connection to crankshaft as easily as
turbocharger can. An electric clutch that turn the supercharger on and off and a
by-pass application which takes air from the supercharger output and introduce it
in the intake are the current methods for the solution.
 Another approach that has been considered is to enrich the oxygen content of the
intake air by using a membrane gas separator. The oxygen enrichment approach is
under research at the present time and is not available on purchased vehicle.
The second reason which causes power loss is related to the intake manifold air
density. The heat of vaporization of Gasoline helps to decrease the temperature of
mixture, producing the dense mixtures. Although propane and methane have higher heat
of vaporization value, they are already in gaseous state when inducted into the intake
manifold and they do not provide this cooling effect. Development of liquid fuel injection
systems for LPG engines should provide better performance and efficiency. Beside this
liquid fuel injection provides better A/F ratio control. Back-fire is almost eliminated due
to introducing less volume of explosive gases in the inlet system. Cooling effect of
endothermic expansion of the liquid increases the resistance to pre-ignition and knock.
This leads higher compression ratio which means higher power output.
56
Higher compression ratio improves thermal efficiency and provides more power
that can be produced by the engine. Higher octane rating of propane compared to
Gasoline allows higher compression ratio for the engine.
Natural gas and propane are generally considered to reduce engine maintenance
and wear in SI engines. The most commonly cited benefits are extended oil change
intervals, increased spark plug life, and extended engine life. Natural gas and propane
both exhibit reduced soot formation over Gasoline. Reduced soot concentration in the
engine oil is believed to reduce abrasiveness and chemical degradation of the oil.
Gasoline fuelled engines particularly carbureted engines require very rich operation
during cold starting and warm up. Some of the excess fuel collects on the cylinder walls,
"washing" lubricating oil off walls and contributing to accelerated wear during engine
warm up. Gaseous fuels do not interfere with cylinder lubrication.
Engines powered by gaseous fuels are generally considered easier to start than
Gasoline engines in cold weather. Because gaseous fuel are already vaporized before
inducted into engine. However, under very cold temperatures, cold-start difficulty occurs
for propane and natural gas. This is probably due to ignition failure caused by very
difficult ionization conditions, sluggishness of mechanical components.
Hot starting can cause difficulties for gaseous fuelled vehicles, especially in warm
weathers. After an engine is shut down, the engine coolant continues to draw heat from
the engine, raising its temperature. If the vehicle is restarted within a critical period after
shutdown, (long enough for the coolant temperature to rise, but before the entire system
cools), the elevated coolant temperature will heat the gas more than normal, lowering its
volumetric heating value and density. This would cause mixture enleanment.
Gasoline shows very little change over the normal temperature or pressure range.
Propane, however, is gas at ambient conditions. Its physical properties depend mainly on
the temperature and pressure at which they are being stored. There must be space left in a
propane fuel tank. As the temperature rises, the volume of liquid increases significantly.
Due to this, propane system has some kind of safety fill stop device to prevent tank fills to
not more than 80 to 85%. This provides room for liquid expansion if the temperature
increases after the tank is filled. Due to low viscosity of propane and its storage under
57
pressure, it may leak through small cracks, pumps, seals and gaskets more readily than
Gasoline.
3.3.4 Biodiesel
Use of vegetable oils as diesel engine fuel is almost as old as the diesel engine
itself. In a 1912 speech, Rudolf Diesel said, “the use of vegetable oils for engine fuels
may seem insignificant today, but such oils may become, in the course of time, as
important as Petroleum and the coal – tar products of the present time” [52]. However, due
to availability of cheaper Petroleum crude, interest in fuels derived from vegetable oils
diminished. The revival of biodiesel production started with farm co-operatives in the
1980s in Austria and in 1991, the first industrial-scale plant started biodiesel production
with a capacity in excess of 10,000 m3 per year. Through 1990s, plants were established
in many European countries, including the Czech Republic, France, Germany and
Sweden. In 1998, the Austrian Biofuels Institute identified 21 countries with commercial
biodiesel projects. In the 1990s, France launched the production of biodiesel obtained
from rapeseed oil. The European Directive 2003/30/EC proposed to promote the use of
biofuels or other renewable fuels for transport to reach 2% share of the total automotive
fuel market by December 31, 2005 and 5.75% by December 2010. Of this, biodiesel is
expected to constitute the major part [53].
Biodiesel is a renewable fuel that is produced from a variety of edible and non-
edible vegetable oils and animal fats. The term “biodiesel” is commonly used for methyl
or ethyl esters of the fatty acids in natural oils and fats that meet the specifications for
their use in the CI engines. Straight vegetable oils are not considered as biodiesel
although attempts have been made to use these as well in the CI engine. Biodiesel is
typically produced by a reaction of vegetable oils or animal fats with an alcohol such as
methanol or ethanol in the presence of a catalyst to yield mono-alkyl esters. Glycerin is
obtained as a by-product, which is removed. The straight mineral oils have very high
viscosity that makes flow of fuel difficult even at room temperatures and presence of
glycerin in the vegetable oil causes formation of heavy carbon deposits on the injector
nozzle holes.
58
A variety of vegetable oils such as those from soybean, rapeseed, sunflower,

jatropha – carcass, palm, and cottonseed etc. have been widely investigated for
production of biodiesel. Rapeseed oil and some other vegetable oils when transformed to
their methyl esters have many characteristics such as density, viscosity, energy content,
and cetane number close to that of diesel. The more widely used are Rapeseed Methyl
Ester (RME) in Europe and Soybean Methyl Esters (SME) in the US. They are
collectively known as Fatty Acid Methyl Esters (FAME). Recently non-edible oil
produced from jatropha-curcass seeds has gained interest as this plant can be easily grown
on wastelands.
The vegetable oil esters are practically free of sulphur and have a high cetane
number generally in the range 46 to 60 depending upon the feedstock. The cetane number
[54]
of methyl esters tends to be slightly lower than of ethyl or higher esters . Biodiesel
from saturated feed stocks such as animal fat and recycled restaurant cooking fats will
generally have a higher cetane number than the esters of oils high in poly-unsaturates
such as soybean oil. Due to presence of oxygen, biodiesel have a lower calorific value
than the diesel fuels.
The emission studies [55] show that the use of biodiesel results in reduction of CO,
HC and PM, but slight increase in NOx emissions. Reduction in CO emission could
probably be attributed to presence of oxygen in the fuel molecule. Decomposition of
biodiesel produces a variety of oxygenated hydrocarbons in addition to hydrocarbons.
Response of the standard HC measurement technique, the heated flame ionization
[56]
detector is different for the methyl esters than HC emission and this could be partly
responsible for the difference in HC emissions between the normal diesel fuels and
biodiesel. The methyl esters have a lower compressibility, which results in advance of
dynamic injection timing with biodiesel compared to diesel. Change in injection timing
and differences in cetane number and combustion characteristics and particulate
emissions are observed to be significantly lower with biodiesel compare to diesel fuels.
Volumetric fuel consumption with biodiesel is higher than diesel due to its lower
heating value. An increase of 10-11% in fuel consumption compared to diesel may be
expected when comparing their heating values.
59
As biodiesel is produced from vegetable oils or animal fats, its use has been
promoted as a means for reducing greenhouse gas CO2 emissions that would otherwise be
produced from the combustion of Petroleum-based fuels. The total impact that biodiesel
could have on global warming would be a function not just of its combustion products but
also of the emissions associated with the full biodiesel production and consumption
lifecycle. On an average the carbon content on mass basis of plant-based biodiesel is
77.8% and of animal fat based biodiesel is 76.1% compared to 86.7% for the Petroleum
based diesel.
Since biodiesel is free from sulfur hence less sulfate emissions and particulate
reduction is reported in the exhaust. Due to near absence of sulfur in biodiesel, it helps
reduce the problem of acid rain due to transportation fuels [57].
Higher thermal efficiency, lower BSFC and higher exhaust temperatures are
reported for all blends of biodiesel compared to mineral diesel [58].
Biodiesel is oxygenated fuel (hence more complete combustion) and causes lesser
particulate formation and emission. This is also due to oxygenated nature of biodiesel
where more oxygen is available for burning and reducing hydrocarbon emissions in the
exhaust [59,60,61].
The biodiesel have a slightly higher carbon content per unit energy (2.068
kg/100MJ) than the conventional diesel (2.042 kg/100MJ) and thus may be expected to
give higher CO2 emissions on combustion. The measured data however, suggest that the
combustion generated CO2 from biodiesel and conventional diesel are substantially
similar [62].
The cost of producing methyl or ethyl esters from edible oils is currently much
more expensive than hydrocarbon based diesel fuel. Due to the relatively high costs of
vegetable oils (about 1.5 to 2 times the cost of diesel), methyl esters produced from it
cannot compete economically with hydrocarbon-based diesel fuels unless granted
protection from considerable tax levies applied to the latter. In absence of tax relief, there
is a need to explore alternate feedstock for production of biodiesel.
The cost of biodiesel can be reduced if we consider non-edible oils and used-
frying oils instead of edible oils. Non-edible oils such as mahua, karanja, babassu,
60
jatropha, neem etc., are easily available in many parts of the world, and are cheaper
compared to edible oils. Most of these non edible oils are not used to their potential and in
fact produced in surplus quantities. Several countries including Netherlands, Germany,
Belgium, Austria, USA, Japan and India discard used frying oils. With the mushrooming
of fast food centers and restaurants in the world, it is expected that considerable amounts
of used-frying oils will be discarded. This oil can be used for making biodiesel, thus
helping to reduce the cost of water treatment in the sewerage system and in the recycling
of resources [24].
3.3.5 GAS-TO-LIQUID (GTL) FUELS:
GTL conversion is a broad term for a group of technologies that are used to
produce synthetic liquid hydrocarbon fuels from a variety of feed stocks. These fuels have
characteristics similar to those of Petroleum fuels and would form a more convenient
substitute for them. The synthetic gas, a mixture of carbon monoxide and hydrogen is
produced from a variety of feed stocks like coal, natural gas and biomass, and is
converted to a mixture of hydrocarbons of different molecular weights and structures. The
chemical conversion process was first developed by Petroleum deficient but coal rich
Germany during 1920s and is known as Fischer-Tropsch (F-T) process after the name of
its inventors. Therefore, GTL diesel is also known as F-T diesel. The basic process
consists of two steps.
1. Production of synthesis gas, and
2. F-T synthesis.
Synthesis gas is produced by steam reforming of natural gas, coal or biomass or

by partial oxidation of hydrocarbons like natural gas. Steam reforming reactions are:
CH y  H 2O  (1  0.5 y ) H 2  CO (3.2)
The value of n depends on the type of feedstock. For example, for typical
hydrocarbon feed stocks y = 2.2 to 4 as they have high content of hydrogen and for coal
y<<1. The partial oxidation reaction for natural gas to generate synthesis gas proceeds as
below;
2CH 4  O2  4 H 2  2CO (3.3)

61
The steam reforming and partial oxidation reactions are endothermic in nature and
the energy needed is supplied by the combustion of the feedstock itself with oxygen.
Fischer-Tropsch synthesis in generic form is described by the reaction.
nCO  2nH 2  n(CH 2 )  nH 2O (3.4)

(-CH2-) is the basic building block of paraffin hydrocarbons. The product is
primarily straight chain hydrocarbons with small quantities of isoparaffins and olefins.
Therefore, the F-T fuel has a high cetane number and is best suited as fuel for the diesel
engines. The F-T synthesis takes place over cobalt based catalyst at temperatures between
180° to 250° C and pressures ranging from 20 to 40 bar. As the catalyst gets poisoned by
sulphur the synthesis gas is made sulphur free before F-T synthesis. Commercial plants
are in operation in South Africa (Sasol) that uses coal and natural gas, and in Malaysia
and Qatar based on natural gas.
The properties of GTL fuels depend on the pressure, temperature and the catalyst
used for synthesis. The Table 3.16 gives the properties of GTL fuel and the range in
which these are generally obtained. The GTL fuel when compared to conventional diesel
has,
 High hydrogen content
 Similar heat of combustion
 Lower density and hence, lower energy content per unit volume
 Higher cetane number
 Ultra-low sulphur
 Near zero or very low aromatic content
The GTL diesel is composed of hydrocarbons like Petroleum derived diesel fuels.
Hence its effect on engine performance would so the trends similar to those obtained with
change in properties of the conventional diesel fuels. Use of GTL diesel alone as well in
blends with conventional diesel has been investigated on light and heavy duty Euro III
and Euro IV diesel engines. Reduction in emissions with 100% GTL fuel are significant
particularly the particulate, unburned HC and CO emissions. The soot emissions are low
with GTL fuels as these have negligible aromatic content. Combustion with GTL fuels
62
results in reduced HC and CO emissions due to higher cetane numbers and lower
densities. The NOx emissions are found to reduce slightly or similar to conventional
diesel fuels. The specific fuel consumption is also similar although, some studies have
reported 2 to 3% improvements in fuel efficiency. However, due to lower densities, the
volumetric fuel consumption is nearly 5% higher.
Table 3.16 Properties of GTL Diesel Fuels [63,64,65].
Properties Range
Density @ 20° C 0.765-0.800
Kinematic viscosity at 40° C, mm2/s 1.97-2.50
Cetane number 64-75
Distillation -
Initial boiling point, ºC 187-210
95% evaporation point 320-363
Sulphur, ppm by mass <1
Total aromatics,% mass 0.14-0.15
H/C atomic ratio 2.10-2.14
Lower heat of combustion, MJ/kg 43.49-43.84
3.3.6 Di-methyl Ether (DME)
During 1990s interest began to be focused in di-methyl ether (DME) as a potential

diesel engine fuel. DME can be produced from dehydration of methanol. Haldor Topsoe
[66]
developed a process for direct production of DME from synthesis gas . The synthesis
gas (CO+H2) can be produced from a variety of raw materials e.g., natural gas, coal,
biomass etc. The DME produced from biomass can be categorized as a renewable fuel,
while DME produced from natural gas can act as an energy carrier in liquid form which is
much easier to transport across continents than the natural gas.
DME is the simplest ether and has chemical formula CH3-O-CH3. It has vapour
pressure of 5.1 bar at 20º C and can be stored, transported and dispensed like LPG. It is
environmentally benign, is not harmful to ozone layer and it readily degrades in
troposphere to carbon dioxide and water. DME is considered non-toxic and is not
classified as a carcinogen, teratogen or mutagen. It is non-corrosive and burns with
63
visible blue flame. Important properties of DME are listed in Table 3.9. Its calorific value
is 33% lower than the conventional diesel but it has a high cetane number making it a
suitable fuel for CI engines. DME has no carbon-carbon bonds and oxygen constitutes
35% of its weight. These factors contribute to an almost smoke free combustion.
Density of DME is about 80% of diesel fuel and calorific value is just about two-
third of diesel. Therefore, compared to diesel twice the volume of DME should be
injected to get the same engine power. Moreover, it has a high compressibility and, low
viscosity and lubricity compared to diesel. Thus, the fuel injection system designed for
diesel fuel cannot be used for DME [67].
[68]
Gray and Webster studied emissions of a 5.9 liter Cummins engine equipped
with oxidation catalyst with DME and diesel fuel. Table 3.17 summarizes the overall
average regulated exhaust emissions with the engine operating on DME and diesel fuel.
Table 3.17 Emissions Results with DME and Diesel Fuel on a 5.9 liter Cummins engine
with Oxidation Catalyst, g/hp-h [69].
Fuel CO CO2 NOx HC PM

DME 0.253 544.7 3.33 0.427 0.02
Diesel 0.443 588.5 3.54 0.180 0.08
Emission operation on DME reduced CO emissions by 43% and PM emissions by

75% compared to diesel. NOx emissions were only slightly lower. However, the HC
emissions more than doubled, but most HC emissions were unburned DME that is
environmentally benign. Use of exhaust catalysts may be beneficial in reducing unburned
DME and methane emissions.
DME provides good engine cold starting. DME although is non corrosive to
metals but some rubber and elastomer components may not be compatible with it.
Therefore, material of seals has to be carefully selected. DME has a poor lubricity
requiring use of additives to protect injection equipment against excessive wear. It burns
with visible blue flame and the flame luminosity is quite good. This is important from fire
safety angle. It being gas at room temperature and atmospheric pressure, precautions to
prevent its leakage need to be taken as it could form explosive mixtures with air.
64
3.3.7 Hydrogen
Interest in hydrogen as a potential alternative automotive fuel has grown due to

need of reducing dependence on fossil fuels and to minimize air pollution. Hydrogen can
be produced from a variety of fossil and non-fossil sources. Presently the most economic
process to manufacture hydrogen is from hydrocarbon like natural gas or naphtha by
steam reforming. Coal gasification is another method. In these processes however, carbon
dioxide is also produced. Production of hydrogen by electrolysis of water is used in some
industrial plants but it is very expensive due to high consumption of electricity. Use of the
solar energy to produce hydrogen by photo-electrolysis is another potential route.
Hydrogen is a colorless, odourless and nontoxic gas. It burns with an invisible and
smokeless flame. The combustion products of hydrogen consist of mainly water and some
nitrogen oxides. The major hurdles in the use of hydrogen as a fuel are lack of production,
distribution and storage infrastructure. On board storage of hydrogen is a major challenge.
Hydrogen has very low boiling point (-253ºC) and a very low volumetric energy density.
The following methods of on-board storage of hydrogen are under consideration and
some of them are being used in demonstration vehicles:
(i) Compressed H2 in high-pressure cylinders at 20-70 MPa: It results in high

weight penalty and safety risks.
(ii) As a metal hydride: Hydrogen can be stored as a metal hydride like iron-
titanium metal hydride (FeTiH2), magnesium hydride, and magnesium-nickel
hydride or adsorbed on carbon. Metal hydrides release hydrogen on heating by
a heat source like vehicle exhaust gas. The main problems of hydride storage
system are limited storage capacity, contamination of storage materials by the
impurities in hydrogen, and high cost.
(iii) Storage of liquid hydrogen in cryogenic tanks: Liquefaction of hydrogen is

highly energy intensive. Energy spent in liquefaction of hydrogen to 20 K is
nearly equal to the energy content of the liquid hydrogen. Thermal insulation
of the cryogenic tanks at 20 K is also very challenging.
(iv) Chemical hydrogen carriers: Hydrogen can be stored as a constituent of a

chemical compound like methyl-cyclohexanol, sodium boro-hydride (NaBH4)
65
etc. A catalyst is required to dehydrogenate the chemical compound at high

temperature e.g. 500º C for hydrogenous methyl-cyclohexanol [70].
Volumetric energy density of compressed hydrogen is just one-third energy

density of natural gas. Liquid hydrogen also has a very low volumetric energy density,
which is about one-fourth of Gasoline. The liquid, hydride and compressed hydrogen
storage methods are compared in Table 3.18 for storing 5-gallon (19 liter) Gasoline
equivalent of energy storage. Hydrogen storage space required is at least 10 to 12 times
that for Gasoline. Storage and fuel weight for hydrides is 27 times and for compressed H2
is 4 to 5 times of Gasoline.
Table 3.18 Comparison of hydrogen storage methods [71].
Gasoline Liquid H2 Hydride Compressed

Fe-Ti H2 (70MPa)
(1.2%)
Energy stored, MJ 6.64  102 6.64  10 2
6.64  102 6.64  102
Fuel mass, kg 14 5 5 5
Tank mass, kg 6.5 19 550 85
Total Fuel System mass, kg 20.5 24 555 90
Volume, l 19 178 190 227
Hydrogen fuel-cell vehicles are expected to have more commercial potential in

long run. Though it is believed that significant production volumes for customers will not
be available until 2010-2020 time frame, automotive manufacturers world over like
Toyota, Honda, General Motors, Ford, Chrysler, BMW are going ahead with limited
production and field trials of fuel cell powered cars and buses. Hydrogen fuelled ICE
vehicles are however, regarded as transition or ‘bridging’ strategy to stimulate building of
hydrogen infrastructure and related hydrogen infrastructure and related technologies.
Hydrogen has significantly different combustion characteristics than Gasoline.

Octane rating of hydrogen is 106 RON, making it more suitable for SI engines. The
laminar flame speed of hydrogen is 3 m/s, about 10 times that of Gasoline and methane.
Hydrogen has very wide flammability limits ranging from 5-75% by volume (φ= 0.07-9),
which may lead to pre-ignition and backfiring problems. Its adiabatic flame temperature
is higher by about 110º C than for Gasoline (Table 3.9). If inducted along with intake air,
the volume of hydrogen is nearly 30% of the stoichiometric mixture, decreasing the
66
volumetric efficiency and engine power considerable. Another option is direct injection of
liquid hydrogen into the engine cylinder that provides some advantages like cooling of
charge, higher volumetric efficiency and no danger of backfiring.
Hydrogen on combustion produces water and there are no emissions of carbon

containing pollutants such as HC, CO and CO2 and air toxics benzene, PAH, 1-3
butadiene and aldehydes. Trace amounts of HC, CO, and CO2 originating from burning of
lubricating oil however, may be emitted. NOx is the only pollutant of concern from
hydrogen engines. Very low NOx emissions are obtained with extremely lean engine
[70]
operation (φ<0.05) . Injection of water into intake manifold or exhaust gas
recirculation which in this case consists primarily water vapour, can further suppress
formation of nitrogen oxides. In addition, water injection provides charge cooling and
control of pre-ignition and backfiring in the engines using external mixture preparation.
The direct fuel injection in the cylinder mitigates some of the problems faced by the
engines with external mixture preparation.
Hydrogen fuelled engines produces almost no CO2 and its global warming
potential is insignificant. Considering the total well-to-wheel energy analysis however,
when hydrogen is produced from fossil resources hydrogen fuelled vehicles provide no
overall reduction in greenhouse gas emissions and in some cases even worse than the
vehicles fuelled by the conventional Gasoline and diesel fuels.
Also the addition of H2 to other traditional slower burning fuels with narrow
operational mixture range such as those of methane and bio-gases, can accelerate
significantly the flame propagation rates, extend greatly the lean operational mixture
range while reducing the emissions of CO2 [72,73].
3.4 Vehicle Emissions and Air Pollution
Since, 1970 more and more stringent vehicle emission regulations have been
implemented in the developed countries like USA, Europe and Japan, but still vehicles
contribute significantly to the urban air pollution [74].
Combustion of various fossil fuels leads to emission of several pollutants, which

are categorized as regulated and unregulated pollutants. Regulated pollutants are ones,
whose limits have been prescribed by environmental legislations (such as USEPA, EURO
and Bharat norms) whereas there are some pollutants for which no legislative limits have
67
been prescribed. These are categorized as unregulated pollutants. Regulated pollutants

include NOx, CO, HC, particulate matter (PM) and unregulated pollutants include
formaldehyde, benzene, toluene, xylene (BTX), aldehydes, SO2, CO2, methane
etc.,[75,76,77].
These regulated as well as unregulated pollutants contribute to several harmful

effects on human health, which are further categorized as short-term and long-term health
effects. The short-term health effects are caused by CO, nitrogen oxides, PM,
formaldehyde (primarily regulated pollutants) etc., while long-term health effects are
caused mainly PAHs, BTX, formaldehyde (primarily unregulated pollutants) etc. CO is
fatal in large dosage, aggravates heart disorders, affects central nervous system, and
impairs oxygen-carrying capacity of blood by forming carboxy-hemoglobin. Nitrogen
oxides cause irritation in respiratory tract. HC cause drowsiness, eye irritation, and
coughing [78,79,80].
These pollutants also contribute towards several regional and global

environmental effects. Regional environmental effects such as summer smog are because
of aldehydes, carbon monoxides, nitrogen oxides etc. Winter smog is because of
particulate. Acidification is caused by nitrogen oxides, sulphuric oxides etc. Several
global effects like ozone layer depletion, global warming etc. are caused by CO2, CO,
methane, non-methane hydrocarbons, nitrogen oxides etc [81,82].
According to a report of Central Pollution Control Board (CPCB), out of the total
pollution load, 65% of CO, 22% of HC and 12% of Nitrogen oxides are due to Gasoline
and diesel vehicles [83].
Since CNG fuel is in gaseous form, it does not need to be vaporized. Therefore, no
fuel enrichment process is needed during cold starting or in transient conditions. This
contributes in the reduction of CO emission. In addition, due to higher H/C ratio, CNG
combustion produces 25% less carbon dioxide than Gasoline or diesel at the same engine
efficiency [84].
The main problem that all researchers and manufacturers are facing now is the
low power output of CNG engine due to loses in volumetric efficiency, low flame speed
and absence of fuel evaporation [85].
68
One major step towards emission control was introduction of exhaust oxidation
catalysts on passenger cars in the US and Japan in 1975. since then, high level of
advancements in engine technology including ‘death of carburettor’ in the US in 1990
and its replacement by multi-port fuel injection (MPFI), multi-valves per cylinder,
electronically controlled variable valve lift and timing, Gasoline direct injection (GDI)
engine have taken place [74].
Exhaust catalytic conversion being one of the mainstay of emission control, it has
seen many improvements like three-way catalytic control of HC, CO and NOx
simultaneously, electrically heated catalyst for emission reduction during engine
reduction during engine start-up, NOx storage catalysts to function under lean engine
operation such as in GDI engines etc [74].
The vehicles primarily emit the harmful gases CO, unburned fuel/hydrocarbons
also called as volatile organic compounds (VOC) and NOx. Among the mobile source,
diesel vehicles are the main contributors to smoke and particulate matter (PM) emissions.
Vehicles also emit sulphur di and tri-oxides (SOx), their amount depending upon the
sulphur content of the engine fuel. Some of the vehicle emissions in the atmosphere
produce other harmful chemicals, the secondary pollutants. The main secondary
pollutants are: oxidants like ozone, nitrogen dioxide (NO2) and total suspended
particulates (TSP) including host of other organic compounds like peroxy-acetyl nitrate
(PAN) etc. Carbon dioxide is not a pollutant for local environment but it being a green
house gas its contribution to global warming is causing an increasing concern. It is
estimated that CO2 is responsible for about 50% of the global greenhouse effect.
The adverse morbidity and mortality effect of air pollutants like suspended
particulate matter (SPM), respirable suspended particulate matter (RSPM or PM10), sulfur
dioxide (SO2), carbon monoxide (CO) and Ozone (O3) are well documented. In the case
of Delhi, the situation deteriorated in the 1990s as vehicles growth outpaced population
growth and economic development, vehicle had risen to nearly 3.6 million by 2001.
During the period, Delhi’s population increased from 9.5 to 13.8 million and road-length
from 22,000 to 25,000 km. The World Bank estimated that a person was dying every 70
minute in Delhi in 1995 from air pollution [86]. The Supreme Court (SC) of India ruled in
1998 that all the public transport should move away from diesel to CNG by 31st March,
2001 and by 1st December, 2002 all the buses were converted to CNG.
69
The United States, with less than 5% of the world’s total population, consumes
25% of the world’s current energy production and generates about 25% of the world’s
carbon emissions [87].
The emission norms and year of implementation for India are shown in Table 3.19
and Table 3.20.
Table 3.19 Emission norms for India – for heavy duty vehicles > 3.5 Tones (g/kWh) [88].
1992 1996 2000 2001 2005 2010

PRE EURO - 0 EURO - 1 EURO - 2 EURO - 3 EURO - 4
NOx 18.00 14.40 8.00 7.00 < 5.00 < 3.00
CO 14.00 11.20 4.50 4.00 2.50 1.00
HC 3.50 2.40 1.10 1.10 0.66 0.50
PM N.A N.A 0.36 0.15 < 0.15 < 0.10
Table 3.20 Emission norms and year of implementation.
Norms Year of Implementation

1996 (Euro 0) 1996
1998 ( Catalytic Converter Norms) 1998
Bharat Stage I (Euro I) 1999
Bharat Stage II (Euro II) 2000/2001
Bharat Stage III (Euro III) April, 2005
Bharat Stage IV (Euro IV) April, 2010
3.4.1 Carbon Monoxide (CO)
Carbon monoxide is formed due to deficiency of oxygen during combustion. It is

an odorless gas but is highly toxic. On inhalation it is rapidly absorbed by lungs and
combines with hemoglobin in the blood forming carboxy-hemoglobin. CO has 200 to 240
[89]
times greater affinity than oxygen to combine with hemoglobin . The CO-hemoglobin
complex is far more stable than oxy-hemoglobin. This exposure to CO reduces oxygen
carrying capacity of the blood to body tissues. The decrease in release of oxygen due to
70
CO intoxication damages tissue and cells and adverse effects are higher and more rapid to
the brain and nervous system as these have a higher oxygen demand. The toxic effects of
CO depend both on the exposure time and concentration as shown in Fig. 3.3.
The early signs of CO poisoning are shortness of breath, rapid breathing,

headache, dizziness, impaired judgment i.e., confusion and lack of motor coordination.
These signs and symptoms results due to reduced supply of oxygen to brain tissues, a
condition called hypoxia. Nausea, vomiting and diarrhea may appear later. Exposure to
high CO concentrations or for a longer period may lead to cardiac arrest, pulmonary
edema, loss of consciousness and eventually to death. If the concentration of CO in the
inhaled air is high enough, loss of consciousness and death may occur within a short time.
Treatment of CO intoxication includes remove of affected person from exposure to the air
having high CO and administration of 100% oxygen to accelerate dissociation of
carboxy-hemoglobin to hemoglobin. Hemoglobin then can combine with oxygen and
correct the tissue hypoxia [89].
Fig. 3.3 Toxicity of carbon monoxide [90].
3.4.2 Nitrogen Oxides
Oxides of nitrogen NO and NO2 are formed during combustion at high

temperatures. During combustion in IC engines, the principal oxide of nitrogen formed is
71
NO. The concentration of NO2 is small in SI engine emissions (less than 2% of total
nitrogen oxides), but is high in diesel engines ranging from about 10 to 20%. NO2 is a
strong oxidant and in the presence of ultraviolet radiations leads to formation of ozone via
NO2 - photolysis as below:
UV
NO2  hv  NO  O (3.5)
O  O2  M  O3  M (3.6)
Where M is a third body needed to absorb the energy of reaction.
NO2 is a reddish brown gas. It has an irritating odour and low solubility. Hence, it
reaches deep in lungs causing irritation. In low concentrations, NO2 may produce mild
irritation in upper respiratory tract. In asthmatic persons, such exposure may cause
asthmatic attacks. When nitrogen oxides get dissolved in aqueous medium of mucous in
the nose and throat lining, they produce nitrous and nitric acids. In acute exposure, these
acids cause immediate irritation to the mucous of the respiratory tract. Similar symptoms
may appear as eye irritation. In the lungs, reactions include cough and bronchospasm. If a
sufficient quantity of gas reaches lungs, it may cause acute bronchitis, pulmonary edema
and even death. Several weeks later of the acute pulmonary reaction, a chronic
inflammation of lungs may result leading to lung fibrosis. Such a progressive process may
lead to respiratory failure.
[89]
Nitrogen oxides too like CO react with blood hemoglobin . A variety of
nitrogen containing substances reacts with hemoglobin oxidizing iron to its ferric state
(Fe+3). This chemical state of iron may form methemoglobin, a black pigment like
substance. Methemoglobin does not combine reversibly with oxygen thus, reducing
oxygen carrying capacity of the blood to tissues. It also results in destruction of red blood
cells. When the concentration of methemoglobin exceeds 10% of the total hemoglobin
level, bluish coloration of skin (cyanosis) is caused in the affected person due to lack of
oxygen. At higher concentrations, symptoms like shortness of breath, weakness and
headache may occur. The symptoms on exposure to nitrogen oxides develop in a slow but
harmful way. The major signs of exposure include development of bluish skin
particularly of lips, fingers and toes.
72
3.4.3 Photochemical Smog
Photochemical smog, initially known, as ‘Los Angeles Smog’ is a brownish-grey

haze caused by reactions between hydrocarbons and nitrogen oxide in atmosphere in
presence of solar ultraviolet radiations. It consists of a variety organic compounds, ozone
and nitrogen oxides trapped above the ground level due to temperature inversion. The
photochemical smog is characterized by an unpleasant odour due to some gaseous
pollutants.
The VOCs other than methane, which include hydrocarbons and their derivatives,
undergo several chemical reactions with nitrogen oxides in presence of sunlight to form
photochemical smog. A simplified model of photochemical smog formation includes NO2
photolytic cycle.
The harmful constituents of photochemical smog are NO2, O3, PAN and
aldehydes. PAN and aldehydes in high enough concentration can cause eye irritation and
plant damage. Ozone concentrations close to roads are generally small. Movements in
atmospheric air carry the gaseous emissions away and as the air takes along the reacting
species, reactions continue to take place for several hours. The impact of photochemical
smog may therefore be felt several kilometers away from the source of emissions.
3.4.4 Ozone
Ozone is a colourless gas with pungent odour like chlorine. It is soluble in cold
water and alkalis. Ozone is a strong oxidant used in bleaching and sterilizing water. In the
stratosphere, it forms a life saving ozone layer, which acts as a shield for ultraviolet rays.
However, at ground level ozone due to its highly oxidizing properties is harmful. The
odour threshold of ozone depending upon individuals is about 0.01 to 0.05 ppm. It causes
irritation of mucous membranes of airways and lungs. Ozone like other irritants such as
sulphur dioxide, chlorine etc., causes marked reduction in airflow to lungs and ventilation
(bronchoconsrtiction). Exposure to low level of ozone (0.3 to 0.9 ppm) produces
[89]
symptoms like cough, dryness of throat and chest discomfort . These effects will
subside when exposure is discontinued. Eye irritation may also be caused by exposure to
ozone. Exposure to 0.2 ppm of ozone for three hours produces vision disorders like visual
acuity, decreases night vision and disturbs balance of muscles controlling position of
73
[91]
eye . The adverse effects of ozone increase substantially in presence sulphur dioxide
and are much more than the effect of either pollutant separately.
3.4.5 Particulates
Particulates are fine solid or liquid particles suspended in air. Particulate matter
emitted by the vehicles also, may be in solid or liquid phase. Solid particles emitted by
vehicles are largely made of carbonaceous matter (soot) consisting a small fraction of
inorganic substance. Different type of liquid phase substances and other materials are also
either adsorbed or absorbed on these particles. During engine start up and warming
particularly in cold weather, the heavy hydrocarbons in the exhaust gas may condense to
form ‘white smoke’. Among ICEs, diesel engines operating at light loads and small two
stroke SI engines employing total loss lubrication system are the main sources of liquid
phase particulate emissions. When lead antiknocks were used in fuel, the Gasoline-fuelled
engines emitted solid lead containing particles. The SI engines may also emit the carbon
particles when operating on over-rich mixtures. However, lead antiknocks have been
phased out of Gasoline in most countries due to toxicity of lead and poisoning of the
catalytic converters being employed for emission control on Gasoline vehicles. Use of
unleaded Gasoline results in very low particulate emission just about 20 mg/km in the
vehicles without catalytic converters [92].
One of the principal sources of solid carbon particles (soot) emitted in air is the
diesel engine. The particulate emission from diesel engines consists of unburned soot,
soluble organics from fuel and lubricating oil, ash particles coming form oil additives and
wear particles. The major source of particulate emission in diesel engines is
heterogeneous mode of combustion where fine soot particles are generated. These fine
soot particles grow and agglomerate as the combustion progresses. Later, during
expansion and in the exhaust system heavy hydrocarbons from fuel and oil, sulphates
produced form combustion of fuel sulphur and water is absorbed on the soot core of
particles.
Particles smaller than 2.5 µm constitute more than 90% of total mass of
particulates emitted by diesel engines. According to Stoke’ law, settling time is inversely
proportional to the square of particle diameter. The rate at which the fine particles settle
down is very low and these remain airborne for several days. The particles of less than 2.5
74
µm are of main concern as they take long time to settle, remain airborne for days and
reach the respiratory system of the human beings. Particles particularly smaller than 1
µm, are too small to be trapped in the upper portion of lungs and penetrate deep into
lungs. The particles larger than 2.5 µm settle down fast and are also filtered by the
respiratory system, and hence are not a serous health hazard. Adverse effects of various
pollutants originating from vehicles are summarized in Table 3.21.
Table 3.21 Adverse Effects of Principal Pollutants [91,93].
Pollutants Short-term health effects Long-term health effects

Oxidants Difficulty in breathing, chest Impaired lung function, increased
tightness, eye irritation susceptibility to respiratory function
Ozone Soreness, coughing , chest Development of emphysema,
discomfort, eye irritation pulmonary edema
Total Increased susceptibility to Many constituents especially poly-
suspended other pollutants organic matter are toxic and
particulate carcinogenic, contribute to silicosis,
/Respirable brown lung
suspended
particulate
Sulphates Increased asthma attacks Reduced lung function when oxidants
are present
Nitrogen Similar to those of ozone but Development of cyanosis especially at
Dioxide at a higher concentration lips, fingers and tows, adverse changes
in cell structure of lung wall
Carbon Headache, shortness of Effects on brain and central nervous
monoxide breath, dizziness, impaired system, nausea, vomiting, cardiac and
judgment, lack of motor pulmonary functional changes, loss of
coordination consciousness and death.
75
Particulates pose health hazard due to two reasons:
(i) They can penetrate deep into lungs and deposit there affecting performance of
lungs adversely, and
(ii) These can have synergistic effect with other pollutants present in air. Sulphur
oxides and water combining together produce sulphuric acid that may be
adsorbed on soot particles and carried to lungs. Carcinogens like PAHs when
adsorbed on soot particles can be carried to lungs and cause cancer.
3.4.6 Noise
Noise is a well known environmental problem associated with major cities world
wide. A great deal of effort has been devoted to extensive noise surveys and modeling
studies in various cities of the world. In most of the surveys, vehicular traffic has been
identified as a major factor contributing to urban noise. The impact of traffic noise
exposure on human beings in terms of annoyance has been examined by using various
statistical noise indices in a number of studies. Most of the studies pertain to outdoor
noise measurements. A limited number of studies have been carried out on the noise
levels and its spectral distribution inside vehicles [94].
CNG run vehicles also have quieter operation, less vibrations and less odour than
equivalent diesel engines. However, high vehicle cost, shorter driving range, heavy fuel
tank, expensive distribution and storage network and potential performance and
operational problems compared to liquid fuels are some of the drawbacks of CNG [95].
The fact that CNG driven vehicles have new body structure would have also
certainly contributed to a reduction in interior noise. It is found that the decision to run
public transport on CNG fuel in Delhi has a positive impact on the noise environment in
buses, auto-rickshaws and taxis [96].

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Chapter 3

CONVENTIONAL FUELS AND ALTERNATIVE FUELS

Fossil fuels are formed by natural resources such as anaerobic decomposition of

3.1 Fuel & Oxidizer

Table 3.1 Electronegativity of various elements [25].

Oxygen has the second highest electronegativity. Although, it is available

3.1.1. Gaseous Fuel and Oxidizer

Natural gas is generally found in porous rocks, which is believed to be formed by

Table 3.2 Types of gaseous fuel and oxidizer.

Fuel Oxidizer Application

Table 3.3 Typical compositions of gaseous fuels [26].

Type CO2 O2 N2 CO H2 CH4 C2H6 C3H8 C4H10 SG Heating value

Biogas is gaining popularity as a renewable source of energy in Third World

Producer gas can be generated by gasifying biomass, coal, etc. It finds

In recent times, hydrogen is contemplated as the future green fuel as it produces

Gaseous fuels can be characterized by their composition, density and heating

LHV  HHV  (mH 2 O / m fuel )  H v (3.1)

Where ∆Hv is the latent heat of vaporization of water at 298.15 K.

3.1.2 Liquid Fuel and Oxidizer

Table 3.4 Types of liquid fuels and oxidizers .

Fuel Oxidizer Application

Table 3.5 Fuel properties of certain common liquid fuels [27,28].

Fuel type Automotive Diesel Methanol Kerosene Aviation

3.1.3 Solid Fuel and Oxidizer

Table 3.6 Types of solid fuels and oxidizers.

Solid fuel Oxidizer Applications

3.2 Conventional Fuels

Table 3.7 Principal Quality Requirements of Automotive fuels.

Fuel Quality Relationship with engine and vehicle performance

3.2.1 Motor Gasoline

 Reid vapour pressure

 Research Octane Number (RON)

 Motor Octane Number (MON)

 Gum content, mg/100 ml

 Lead content, g/l

High antiknock quality of Gasoline is needed to prevent or minimize knocking

The volatility of Gasoline is experimentally evaluated by its distillation range and

To improve oxidation stability of Gasoline anti-oxidants are usually added. The

Table 3.8 Oxygenates used in Gasoline.

3.2.2 Diesel Fuels

 Distillation (volatility) characteristics

 Sulphur content, and

 Stability and injection system cleanliness

Other significant properties include cold flow characteristics at low ambient

Ignition quality of diesel fuel is an expression of the ease of self-ignition of diesel

Resistance of fuel to degradation during storage before it is consumed is an

Aromatic content is of great concern as it increases particulate and poly-aromatic

3.3 Alternative Fuels

Some of the important properties of different alternative fuels are compared in

Table 3.9 Properties of various fuels for vehicles [39,40].

Methanol (CH3OH) is a simple compound. It does not contain sulfur or complex

Physical and chemical characteristics of alcohols make alcohols as excellent fuels

(i) Improving ignition quality of alcohols by use of ignition improvers.

(ii) Use of glow or spark plugs as a positive source of ignition.

Property/Performance Compared to Advantages

Property/Performance Compared to Disadvantages

3.3.2 Natural Gas

Table 3.12 Worldwide Population of NGVs in 2010 [48].

Country Natural Gas Monthly Sales Average Refuelling

Table 3.13 Natural gas vehicle growth since 2000 [48].

Region Average % NGV growth since 2000

Table 3.14 Composition of CNG.

In a nationwide survey across the USA reported in 1992, variations in