FUEL TECHNOLOGY

Prepared By

NARAYAN GOUDA
 Fuel
 A fuel is a substance which gives heat energy on combustion.
 A fuel contains carbon and hydrogen as main combustible elements.
 fuel is any material that can be made to react with other substances so that it
releases chemical or nuclear energy as heat or to be used for work.
PETROLEUM PROCESSING AND FRACTIONS:
Petroleum or crude oil is dark greenish-brown, viscous oil found deep in earth
crust. It is composed mainly of various hydrocarbons (like straight-chain
paraffins, cycloparaffins or naphthalenes, olefins and aromatics), together with
small amounts of organic compounds containing oxygen, nitrogen and sulphur.
Mining of petroleum:
It is done by drilling holes in the earth’s crust and sinking pipes upto the oil-
bearing porous rocks.
Refining of crude oil:
The crude oil is separated into various useful fractions by fractional distillation
and finally converted into desired specific products. The process is called
‘refining of crude oil’ and the plants set up for the purpose, are called the oil
refineries.
The refining involves
Step 1: Separation of water (Cottrell’s process):
The crude oil from the oil well is an extremely stable emulsion of oil and salt
water. The process of freeing oil from water consists in allowing the crude to
flow between two highly charged electrodes. The colloidal water-droplets
coalesce to form large drops, which separate out from the oil.
Step 2: Removal of harmful sulphur compounds:
This involves in treating oil with copper oxide. A reaction occurs with sulphur
compounds, which results in the formation of copper sulphide (a solid), which is
then removed by filtration.

Step 3: Fractional distillation:

The crude oil is then heated to about 4000 C in an iron retort whereby all volatile
constituents, except the residue (asphalt or coke) are evaporated. The hot vapours
are then passed up a fractionating colum, which is a tall cylindrical tower
containing a number of horizontal stainless steel trays at short distances. Each
tray is provided with small chimney, covered with a loose cap. As the vapours go
up, they become gradually cooler and fractional condensation takes place at
different heights of column. Higher boiling fraction condenses first, while the
lower boiling fractions turn-by-turn.
 GASEOUS FUELS

WATER GAS:
It is essentially a mixture of CO and H2. Its calorific value is 2800 kcal/m3. The average composition of
water gas is H2 (51 %); CO (41 %); N 2 (4 %); CO2 (4 %).

Manufacture:
A water gas generator is a steel cylindrical vessel. At the top, it is provided with a hopper for adding
coke. Water gas outlet is provided near the top. At the bottom, it is provided with an arrangement of
taking out ash formed.
Water gas is obtained by the action of steam on a bed of coal heated to 1000°C.

Since the above reaction is endothermic, the

coal cools down after a few minutes and the
reaction proceeds in a different way to form
CO2 and H2, instead of water gas (CO + H2).
 Since the above reaction is endothermic, the
coal cools down after a few minutes and the
reaction proceeds in a different way to form
CO2 and H2, instead of water gas (CO + H2).

In order to avoid the above undesirable

reaction, the blow of air replaces the
blow of steam. The following reactions
now occur.
Uses: Water gas is used
1) As a source of hydrogen gas
2) In the manufacture of NH3 by Haber’s process.
3) As an illuminating gas.
4) As a fuel gas
5) For welding purposes
 PRODUCER GAS:
Producer gas is essentially a mixture of combustible gases (CO and H2) associated
with larger percentage of non combustible gases (N2 and CO2). The calorific value is
only 1800 k cal/m3. The average composition of producer gas is 50 % N2; 30 % CO; 10
% H2 and rest CO2 and CH4.
Manufacture:

The reactor (furnace used for the manufacture of producer gas is known as producer. It
consists of large airtight mild steel cylindrical towers lined inside with refractory bricks.
At the bottom, it is provided with pipe for blowing air and an arrangement for removing
air. Coal is added through a hopper at the top and producer gas comes out from an exit
near the top.
The formation of producer gas involves the following:

(a) Combustion or oxidation zone:

When a mixture of air and little steam is passed
through a bed of red hot coal, carbon (of the coal)
combines with oxygen (of the air) in the lower part of
the furnace to form CO2.

C + O2 → CO2 + 97 kcal.
 (b) Reduction zone:

Here, carbon dioxide and steam combines with the red hot coke and liberates free hydrogen
and carbon monoxide.

Nitrogen of the air remain unaffected throughout the process. Thus, a mixture of CO and N2
with traces of CO2 and hydrocarbons comes out through the exit at the upper side of the
producer.

Producer gas is a poisonous gas; insoluble in water and heavier than air.

Uses:

1. It is a cheap, clean and easily producible gas and is used for heating open hearth furnaces (in
steel and glass manufacture); muffle furnaces, retorts etc.,
2. As a reducing agent in metallurgical operations.
COMPRESSED NATURAL GAS (CNG)

CNG is natural gas compressed to a high pressure of about 1000 atmospheres. A

steel cylinder containing 15 kg of CNG contains about 2 x 104 L or 20 m3 of natural
gas at 1 atmospheric pressure. It is derived from natural gas and the main constituent of
CNG is methane.

Properties:

1) CNG is comparatively much less pollution causing fuel as it produces less CO,
ozone and hydrocarbons during combustion.
2) During it s combustion, no sulphur and nitrogen gases are evolved.
3) No carbon particles are ejected during combustion.
4) It is less expensive than petrol and diesel.
4) The ignition temperature of CNG is 5500C.
5) CNG is a better fuel than petrol/diesel for automobiles.
6) CNG requires more air for ignition.
Uses:
As CNG is the cheapest, cleanest and least environmentally impacting alternative fuel.
In Delhi, it is mandatory for all buses, taxis and auto to use CNG as a fuel.
LIQUIFIED PETROLEUM GAS (LPG)

LPG or bottled gas or refinery gas is obtained as a by-product during the cracking of heavy
oils or from natural gas. LPG is dehydrated, desulphurised and traces of odorous organic sulphides
(mercaptans) are added to give warning of gas leak. LPG is supplied under pressure in containers
under the trade name like Indane, Bharat gas, etc. Its calorific value is about 27,800 kcal/m3.
It consists of hydrocarbons of such volatility that they can exist as gas under atmospheric
pressure, but can be readily liquefied under pressure. The main constituents of LPG are n-butane,
isobutene, butylenes and propane, with little or no propylene and ethane.

Uses: Use as a domestic fuel and industrial fuel. Nowadays used as motor fuel.
knocking:
It is essential that combustion of the fuel in the cylinder of an internal combustion
engine should proceed in a regular way.
After the reaction initiated by a spark, a flame should spread rapidly and smoothly
through the gas mixture and the expanding gas drives the piston down the cylinder. In
certain cases, the rate of oxidation is so great that the mixture detonates and producing a
rattling sound called engine knock.

Premature instantaneous ignition of fuel-air mixture in an I.C. engine , leading to

production of an explosive violence, is known as knocking.

Knocking is caused due to the presence of some constituents in the gasoline fuel.
Consequences of knocking:
 Decreased power output
 Mechanical damage by over heating of the cylinder parts.

Mechanism of chemical reaction that lead to knocking:

Free radical chain reaction leading to the cracking and oxidation of the hydrocarbon is
probable mechanism of chemical reaction that lead to knocking.

Factors on which knocking depends:

i. Engine design
ii. Running condition
iii. Chemical structure of the fuel hydrocarbons

For example: Knocking tendency decreases in the order

n-alkanes(Straight chain parrafins)> mono-substituted alkanes (Branched chain
paraffins) > cyclo alkanes > alkenes > polysubstituted alkenes > aromatics.

For straight chain hydrocarbons, the tendency to knock increases with molecular
weight and boiling point
e.g: n-hexane > n-pentane > n-butane.

Aromatic hydrocarbons have higher antiknocking properties than paraffins and

Octane number:
 The resistance offered by gasoline to knocking is generally expressed on an arbitrary
scale, known as Octane rating (proposed by Graham Edgar in 1926)
 n-heptane knocks severely, so its octane number is 0 whereas isooctane is high resistance
to knocking. Its octane number is 100.

“The percentage of isooctane in the n-heptane and isooctane mixture which has the same
knocking characteristics as the gasoline sample, under the same set of conditions is
known as octane number.”
Additives for improving antiknock properties:
Tetra ethyl lead [(C2H5)4 Pb], diethyl telluride [(C2H5)2Te] are the most
commonly used additives to resist knocking.
TEL gives rise to Pb and PbO during combustion. These particles act as a
free radical chain inhibitors as they arrest the propagation of the explosive
chain reactions responsible for knocking.
Efficiency of TEL decreases in presence of sulphur hence desulphurised
gasoline is used.
Pb and PbO2 decrease engine life hence they must be remove along with the exhaust gases
by adding ethylene bromide
Pb, PbO2 + C2H4Br2 → PbBr2

PbBr2 is volatile and escapes into atmosphere. But pollution problem exists.

Thus unleaded petrol should be used.

Unleaded petrol
The petrol whose octane number is increased without the addition of lead compounds is
known as unleaded petrol.
The octane number of a fuel can be increased by:
i. Reforming: This process increases the contents of molecules having branched and
aromatic ring structures. Thus, by molecular reforming, the contents of isopentane,
isooctane, ethyl alcohol and isopropyl benzene increases in the given fuel.
ii. Methyl tertiary butyl ether can also be added to improve the octane rating of the fuel.
Advantages of using unleaded petrol:
i. Unleaded petrol is free from lead pollution
ii. It allows the use of a catalytic converter to be attached to the exhaust in the automobiles.
 Power Alcohol

 When ethyl alcohol is used as fuel for internal combustion engine, it is called as power
alcohol.
 Ethyl alcohol is not used directly. It is used an additive to motor fuels.
 Blends containing upto 25% of alcohol with petrol are used.
Manufacture of power alcohol:
In India, alcohol is manufactured from molasses( a viscous semi-solid material left after
the crystallisation of sugar from concentrated sugar-cane juice.) . It contains about 50-60%
sucrose plus invert sugar(glucose + fructose). The molasses are diluted with water to bring
its sugar concentration to 10-12%. Then some nutrients like ammonium sulphate and
ammonium phosphate and some sulphuric acid are added to bring its pH value between 4
and 5. Then proper quantity of yeast (an enzyme mixture) is added and the temperature is
maintained at about 30⁰C. The invertase of the yeast converts sucrose into glucose and
fructose, and the zymase of yeast converts glucose and fructose into ethyl alcohol and
carbon dioxide, the process is known as fermentation.
Biodiesel
 Biodiesel is an alternative fuel similar to conventional or ‘fossil’ diesel. Biodiesel
can be produced from straight vegetable oil, animal oil/fats, tallow and waste
cooking oil.
 The process used to convert these oils to Biodiesel is called transesterification.

Biodiesel Production:- As mentioned above biodiesel can be produced from straight

vegetable oil, animal oil/fats, tallow and waste oils.
There are three basic routes to biodiesel production from oils and fats:
 Base catalyzed transesterification of the oil.
 Direct acid catalyzed transesterification of the oil.
 Conversion of the oil to its fatty acids and then to biodiesel.
Almost all biodiesel is produced using base catalyzed transesterification as it is the
most economical process requiring only low temperatures and pressures and
producing a 98% conversion yield.
 The Transesterification process is the reaction of a triglyceride (fat/oil) with an
alcohol to form esters and glycerol. A triglyceride has a glycerine molecule as its
base with three long chain fatty acids attached..
 During the esterification process, the triglyceride is reacted with alcohol in the
presence of a catalyst, usually a strong alkali like sodium hydroxide. The alcohol
reacts with the fatty acids to form the mono-alkyl ester, or biodiesel and crude
glycerol. In most production methanol or ethanol is the alcohol used (methanol
produces methyl esters, ethanol produces ethyl esters) and is base catalysed by either
potassium or sodium hydroxide. Potassium hydroxide has been found to be more
suitable for the ethyl ester biodiesel production, either base can be used for the
methyl ester.
 The figure below shows the chemical process for methyl ester biodiesel. The
reaction between the fat or oil and the alcohol is a reversible reaction and so the
alcohol must be added in excess to drive the reaction towards the right and ensure
complete conversion
The engine combustion benefits of the transesterification of the oil are:
•Lowered viscosity
•Complete removal of the glycerides
•Lowered boiling point
•Lowered flash point
•Lowered pour point
 Catalytic Converter:

 A catalytic converter is an exhaust

emission control device that converts
toxic gases and pollutants in exhaust
gas from an internal combustion
engine to less toxic pollutants
by catalysing a redox reaction (an
oxidation and a reduction reaction).
 Catalytic converters are used with
internal combustion engines fueled
by either petrol (gasoline) or diesel
—including lean- burn engines as
well as kerosene heaters and stoves
Type of Catalytic Converter:
Two-way
A 2-way (or "oxidation", sometimes called an "oxi-cat") catalytic converter has two
simultaneous tasks:Oxidation of carbon monoxide to Carbon dioxide 2 CO + O2 → 2 CO2
Oxidation of hydrocarbons (unburnt and partially burned fuel) to carbon dioxide and water:
CxH2x+2 + [(3x+1)/2] O2 → x CO2 + (x+1) H2O (a combustion reaction)
This type of catalytic converter is widely used on diesel engine to reduce hydrocarbon and
carbon monoxide emissions. They were also used on gasoline engines in American- and
Canadian-market automobiles until 1981. Because of their inability to control oxides of
nitrogen, they were superseded by three-way converters.
Three-way
Three-way catalytic converters (TWC) have the additional advantage of controlling
the emission of nitric oxide and nitrogen dioxide (both together abbreviated
with NOx and not to be confused with nitrous oxide), which are precursors to acid
rain and smog.
Since 1981, "three-way" (oxidation-reduction) catalytic converters have been used
in vehicle emission control systems in the United States and Canada; many other
countries have also adopted. The reduction and oxidation catalysts are typically
contained in a common housing; however, in some instances, they may be housed
separately. A three-way catalytic converter has three simultaneous tasks:
Reduction of nitrogen oxides to nitrogen and oxygen: 2 NOx → x O2 + N2
Oxidation of carbon monoxide to carbon dioxide: 2 CO + O2 → 2 CO2
Oxidation of unburnt hydrocarbons (HC) to carbon dioxide and water: CxH2x+2 +
[(3x+1)/2] O2 → x CO2 + (x+1) H2O.
Since 1981, "three-way" (oxidation-reduction) catalytic converters have been used in
vehicle emission control systems in the United States and Canada; many other countries
have also adopted. The reduction and oxidation catalysts are typically contained in a
common housing; however, in some instances, they may be housed separately. A three-
way catalytic converter has three simultaneous tasks:
Reduction of nitrogen oxides to nitrogen and oxygen: 2 NOx → x O2 + N2
Oxidation of carbon monoxide to carbon dioxide: 2 CO + O2 → 2 CO2
Oxidation of unburnt hydrocarbons (HC) to carbon dioxide and water: CxH2x+2 + [(3x+1)/2]
O2 → x CO2 + (x+1) H2O.
Damage:
Catalyst poisoning occurs when the catalytic converter is exposed to exhaust
containing substances that coat the working surfaces, so that they cannot contact and
react with the exhaust. The most notable contaminant is lead, so vehicles equipped with
catalytic converters can run only on unleaded fuel. Other common catalyst poisons
include sulfur, manganese and silicon, which can enter the exhaust stream if the engine
has a leak that allows coolant into the combustion chamber. Phosphorus is another
catalyst contaminant. Although phosphorus is no longer used in gasoline, it (and zinc,
another low-level catalyst contaminant) was until recently widely used in engine
oil antiwear additives such as zinc dithiophosphate (ZDDP)
Photovoltaic cell (PV cell):

 Photovoltaics (PV) is a term which covers the conversion of light into electricity using semiconducting
materials that exhibit the photovoltaic effect.
 It is a device which converts directly the sunlight into electricity.
 It consists of an arrangement of several components, including solar panels to absorb and directly
convert sunlight into electricity, a solar inverter to change the electric current from DC to AC, as well as
mounting, cabling and other electrical accessories.
 It ranges from small, roof top mounted or building integrated systems with capacities from a few
to several tens of kilowatts, to large utility-scale power stations of hundreds of megawatts.
Basic principles
 Light, which is pure energy, enters a PV cell and imparts enough energy to some electrons (negatively
charged atomic particles) to free them. A built-in-potential barrier in the cell acts on these electrons to
produce a voltage (the so-called photovoltage), which can be used to drive a current through a circuit.
 The first PV cells were made of silicon combined, or doped, with other elements to affect the behaviour
of electrons or holes (electron absences within atoms). Other materials, such as copper indium diselenide
(CIS), cadmium telluride (CdTe), and gallium arsenide (GaAs), have been developed for use in PV cells.
Construction and working:
There are two basic types of semiconductor material, called positive
(or P type) and negative (or N type). In a PV cell, flat pieces of these
materials are placed together, and the physical boundary between them
is called the P-N junction. The device is constructed in such a way that
the junction can be exposed to visible light, IR, or UV. When such
radiation strikes the P-N junction, a voltage difference is produced
between the P type and N type materials. Electrodes connected to the
semiconductor layers allow current to be drawn from the device.
DETERMINATION OF CALORIFIC VALUE USING BOMB CALORIMETER
Construction of bomb calorimeter:
Bomb Calorimeter consists of a strong stainless steel bomb where the fuel sample is
burnt. The bomb has oxygen inlet valve and two stainless steel electrodes. A small ring is
attached to one of the electrodes. In this ring, a nickel or stainless steel crucible is placed.

The bomb is placed in a copper calorimeter containing a known weight of water sample.
The copper calorimeter is provided with a Beckmann’s thermometer and stirrer for
stirring water. The copper calorimeter is covered by an air jacket and water jacket.imes
Functioning:
A known weight of the fuel sample is taken into the crucible. The fine magnesium
wire is touching the fuel sample and then stretched across the electrodes. The bomb lid is
tightly closed with the help of screw. The bomb is filled with oxygen at 25 atmospheric
pressure.
The bomb is now placed in a copper calorimeter which containing known weight of
water. Initial temperature of the water in the calorimeter is noted (t1°C) after stirring. The
electrodes are connected to a battery (6 v). The current is now supplied to the fuel
sample which undergoes burning with the evolution of heat. The liberated heat increases
the temperature of water in the calorimeter. The maximum temperature of the water
during experiment is finally noted (t2°C). From the temperature difference, calorific
value of the fuel can be calculated
Calculation:
Weight of the fuel sample taken in the crucible = X g
Weight of the water taken in the calorimeter = W
Calculation
Weight of calorimeter and stirrer in terms of water equivalent = A g
Initial temperature of water in the calorimeter = t1 °C
Final temperature of water in the calorimeter = t2 °C
Heat absorbed by the water = W (t2 –t1) cal -------(1)
Heat absorbed by the calorimeter = A (t2 – t1) cal ---- (2)
Total heat absorbed by the water = W (t2 –t1) + A (t2 – t1) Cal---------- (3)
= (W + A) (t 2 – t1) Cal.
The relationship between heat liberated by the fuel and HCV is as follows:
Heat liberated by the fuel = X × HCV ---- (4)
Therefore, heat liberated by the fuel = Weight of fuel X Heat absorbed by the water and calorimeter
Comparing equation (3) and (4)
X × HCV = (W + A) (t 2 – t1)
(W + A) (t 2 – t1)
⇒ 𝐻𝐶𝑉 = Cal/g
X

The percentage of hydrogen in the fuel = H

9
Weight of water produced 1 g of the fuel = 𝐻 g = 0.09 g
100

Therefore, heat liberated during the condensation of steam = 0.09 H × 587 cal/g
Lower calorific value of the fuel = HCV – Latent heat of water liberated by the fuel
LCV = HCV – (0.09 H × 587 ) cal/g