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Unit 5 Fuels

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Unit 5 Fuels

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bulletaintshawty
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© © All Rights Reserved
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Unit 5 Fuels

Suggested Readings:
1.Engineering Chemistry by Vairam S, Kalyani P.
and Suba R.
2.Engineering Chemistry by Renu Bapna and
Renu Gupta.
Unit Objectives
At the end of the unit, you should be able to:

1.define fuel;
2.describe the properties of fuels;
3.Identify the classification of fuels;
4.discuss calorific value of fuels and its importance;
5.Differentiate solid, liquid and gaseous fuels from one to another.
Definition
Fuels are dense repositories of energy
that are consumed to provide energy
services such as heating, transportation
and electrical generation. Even though
most fuels ultimately get their energy
from the sun
A fuel is a combustible substance
containing carbon as the main constituent
which on proper burning gives large
amount of heat that can be used
economically for domestic and industrial
purposes.
Chemical fuel is a combustible
carbonaceous material which on proper
burning in air gives large amount of heat
that can be used economically for
domestic and industrial purposes
Ex. wood, charcoal, coal, kerosene,
petrol, diesel, producer gas, water gas,
natural gas, etc.
So, carbon compounds have been used for many
centuries as the source of heat and energy.

The main source of fuel is coal and petroleum. These


are stored fuels available in earth's crust and are
generally called fossil fuels because they were formed
from the fossilised remains of plants and animals.

During the process of combustion of a fuel, the atoms of


carbon, hydrogen, etc combine with oxygen with
simultaneous liberation of heat. The calorific value of a
fuel depends mainly on the two elements.
C + O2 → CO2 + 94 kcals.
2H2 + O2 → 2H2O + 68.5 kcals.
Properties

1. High calorific value.


2. Moderate ignition temperature.
3. Low moisture content
4. Low content of non-combustible matter.
5. In case of solid fuel, the ash content should be
less and the size
should be uniform.
6. Readily available in bulk at low cost.
7. Products of combustion should not be harmful.
8. Combustion should be easily controllable.
9. It should be safe, convenient and economical for
storage and 5

transport
Classification
A. On the basis of occurrence, fuels are
classified as
primary and secondary fuels
1. Primary fuels occur in nature and
are used
without processing.
2. Secondary fuels are obtained by
chemical
processing of primary fuels.
B. On the basis of physical state, fuels
are classified as solid, liquid and gaseous fuels6
7
8
Calorific Value
• Calorific value of a fuel is "the total quantity of heat
liberated, when a unit mass (or volume) of the fuel is
burnt completely."
Units of heat :
(1) 'Calorie' is the amount of heat required to raise the
temperature of one gram of water through one degree
Centigrade (15-16°C).
(2) "Kilocalorie" is equal to 1,000 calories. It may be
defined as 'the quantity of heat required to raise the
temperature of one kilogram of water through one degree
Centigrade. Thus: 1 kcal = 1,000 cal
(3) "British Thermal unit" (B.T.U.) is defined as "the
quantity of heat required to raise the temperature of one
pound of water through one degree Fahrenheit (60-61°F).
This is the English system unit.
1 B.T.U. = 252 cal = 0.252 kcal 1 kcal = 3.968 B.T.U.
9
Calorific Value
Higher or gross calorific value (HCV)
Higher calorific value (HCV) is "the total amount of heat produced,
when unit mass/volume of the fuel has been burnt completely and
the products of combustion have been cooled to room
temperature"(i.e., 15°C or 60°F ).

Lower or net calorific value (LCV)


⚫ In actual use of any fuel, the water vapour and moisture, etc., are
not condensed and escape as such along-with hot combustion
gases. Hence, a lesser amount of heat is available. So, net or lower
calorific value (LCV) is "the net heat produced, when unit mass
/volume of the fuel is burnt completely and the products are
permitted to escape".

Net calorific value= Gross calorific value - Latent heat of condensation


of water vapour produced
⚫ = GCV - Mass of hydrogen per unit weight of the
fuel burnt x 9 x Latent heat of condensation of water vapour
10
Calorific Value
• Dulong's formula for calorific value from the chemical
composition of fuel is :

HCV = 1/100 [8,080 C + 34,500 (H – O/8)+ 2,240 S] kcal/kg

where C, H, O, and S are the percentages of carbon, hydrogen,


oxygen and sulphur in the fuel respectively. In this formula,
oxygen is assumed to be present in combination with hydrogen
as water, and

LCV = [ HCV - 9H/100 x 587] kcal/kg = [HCV - 0.09 H x 587]


kcal/kg

This is based on the fact that 1 part of H by mass gives 9 parts of


H2O, and latent heat of steam is 587 kcal/kg.

11
Importance of CV

• The efficiency of fuel or food mainly depends


on the calorific value. If the value is high, its
efficiency will also be high. If the value is low,
its efficiency would also decrease.
• Fuel: Calorific Value Of Fuel(Approximately)
• Coal: 33000
• Diesel: 45000
• Methane: 50000

12
The higher heating value takes into account the
latent heat of vaporization of water in the
combustion products, and is useful in calculating
heating values for fuels where condensation of
the reaction products is practical (e.g., in a gas-
fired boiler used for space heat).
If the fuel has higher calorific value it will have
tendency to produce more power in the engine.
The fuels with less calorific value tend to burn
inefficiently thus causing lots of exhaust and air-
pollution.
MOST IMORTANT QUALITY INDICATOR OF A
FUEL

13
Solid Fuels

COAL
Coal is regarded as a fossil fuel produced from large
accumulations of vegetable debris due to partial decay
and alteration by the action of heat and pressure over
millions of years. Coal is a highly carbonaceous matter
that has been formed as a result of alteration of
vegetable matter (e.g., plants) under certain favourable
conditions. It is chiefly composed of C, H, N, and O,
besides non-combustible inorganic matter.

14
Solid Fuels
Classification of Coal
• Coals are classified on the basis of their rank. Rank is
defined as the degree or extent of maturation and is
therefore a qualitative measure of carbon contents. Peat,
lignite and sub-bituminous coals are referred as low rank
coals while bitu­minous coals and anthracites are classed
as high rank. In European terminology, the lignite and
sub-bituminous coals are called soft coals while
bituminous coals and anthracite coals are termed as hard
coals. In North American terminology, the coal series is
written as
Wood
peat
lignite
bituminous
anthracite.
15
Solid Fuels
Analysis of Coal

In order to assess the quality of coal the following two types


of analysis are made.

1.Proximate Analysis. it includes the determination of


moisture, volatile matter, ash and fixed carbon. This gives
quick and valuable information regarding com­mercial
classification and determination of suitability for a particular
industrial use.

2.Ultimate Analysis It includes the determination of


carbon, hydrogen, nitro­gen, sulfur and oxygen in coal.
Since it is used For the determination of elements present
in the coal, it is also called elemental analysis. This analysis
gives exact results and are useful in calculating the calorific
value of coal using Dulong's formula.
16
Solid Fuels
Importance of proximate analysis

Proximate analysis provides following valuable informations


in assessing the quality of coal:

(1) Moisture: Moisture lowers the effective calorific value of


coal. Moreover, it quenches the fire in the furnace. Hence,
lesser the moisture content, better the quality of coal as a
fuel. However, presence of moisture, up to 10%, produces
a more uniform fuel-bed and less of "fly-ash".

(2) Volatile matter: A high volatile matter containing coal


burns with a long flame, high smoke and has low calorific
value. Hence, lesser the volatile matter, better the rank of
the coal. Higher volatile content in coal is undesirable.
17
Solid Fuels
(3) Ash is a Importance
useless, non-combustible
of proximate analysis matter,
which reduces the calorific value of coal. Moreover,
ash causes the hindrance to the flow of air and
heat. Hence, lower the ash content, better the
quality of coal. The presence of ash also increases
transporting, handling and storage costs. The
presence of ash also causes early wear of furnace
walls, burning of apparatus and feeding
mechanism.

(4) Fixed carbon: Higher the percentage of fixed


carbon, greater is its calorific and better the quality
coal. Greater the percentage of fixed carbon,
smaller is the percentage of volatile matter. This
also represents the quantity of carbon (in coal) that
can be burnt by a primary current of air drawn
through the hot bed of a fuel.
18
Solid Fuels
Proximate analysis
⚫ Moisture: About 1 g of finely powered air-dried coal sample is
weighed in a crucible. The crucible is placed inside an electric
hot air-oven, maintained at 105° - 110°C. The crucible is
allowed to remain in oven for 1 hour and then taken out, cooled
in a desiccator and weighed. Loss in weight is reported as
moisture (on percentage-basis).

Percentage of moisture = Loss in weight x 100


Wt. of coal taken
⚫ Volatile matter: The dried sample of coal left in the crucible
in (1) is then covered with a lid and placed in an electric
furnace (muffle furnace), maintained at 925°± 20°C. The
crucible is taken out of the oven after 7 minutes of heating. The
crucible is cooled first in air, then inside a desiccator and
weighed again. Loss in weight is reported as volatile matter on
percentage-basis.
Percentage of volatile matter =
Loss in weight due to removal of volatile matter x 100 19
Wt. of coal sample taken
Solid Fuels
(3) Ash: The residual coal in the crucible in (2) is
then heated without lid in a muffle furnace at 700 ±
50° C for 1/2 hour. The crucible is then taken out,
cooled first in air, then in desiccator and weighed.

Heating, cooling and weighing is repeated, till a


constant weight is obtained. The residue is reported
as ash on percentage-basis.

Percentage of ash = Wt. of ash left x 100


Wt. of coal taken

(4) Fixed carbon: Percentage of fixed carbon = 100


- % of (moisture + volatile matter + ash) high
percentage of rued carbon is desirable.
20
Solid Fuels
Ultimate Analysis

Carbon and hydrogen: About 1-2 g of accurately weighed coal


sample is burnt in a current of oxygen in a combustion apparatus.
C and H of the coal are converted into CO2 and H2O respectively.
The gaseous products of combustion are absorbed respectively in
KOH and CaCl2 tubes of known weights. The increase in weights
of these are then determined.

Increase in weight of KOH tube x 12 x 100


Percentage of C = Weight of coal sample taken x 44

Increase in weight of CaCl2 tube x 2 x


100
Percentage of H = Weight of coal sample taken x 18

2
1
Solid Fuels

Significance of ultimate analysis

(1) Carbon and hydrogen: Greater the percentage of carbon and


hydrogen better is the coal in quality and calorific value. However,
hydrogen is mostly associated with the volatile matter and hence, it
affects the use to which the coal is put. Also higher percentage of
carbon in coal reduces the size of combustion chamber required. The
amount of carbon, the major combustible consti1fent of coal, depends
on the type of coal and its percentage increases with rank from lignite
to anthracite. Thus, percentage of carbon forms the basis of
classification of coal.

(2) Nitrogen has no calorific value and hence, its presence in coal is
undesirable; thus, a good quality coal should have very little nitrogen
content.

22
Solid Fuels

Nitrogen

About 1 g of accurately weighed powdered 'coal is heated with


concentrated H2SO4 along-with K2SO4(catalyst) in a long-necked
flask(called Kjeldahl's flask). After the solution becomes clear, it is
treated with excess of KOH and the liberated ammonia is distilled over
and absorbed in a known volume of standard acid solution. The unused
acid is then determined by back titration with standard NaOH solution.
From the volume of acid used by ammonia liberated, the percentage of
N in coal is calculated as follows:
Volume of acid used x Normality x 1.4
Percentage of N = Weight of coal taken

23
Solid Fuels
Sulfur is determined from the washings obtained from the known
mass of coal, used in a bomb calorimeter for determination of a
calorific value. During this determination, S is converted into
sulphate. The washings are treated with barium chloride solution,
when barium sulphate is precipitated. This precipitate is filtered,
washed and heated to constant weight.

Weight of BaSO4 obtained x 32 x 100


Percentage of S = Weight of coal sample taken in bomb x 233

Ash determination is carried out as in proximate analysis.


Oxygen: It is obtained by difference.
Percentage of O = 100 - Percentage of (C + H + S + N + ash)

24
Solid Fuels
(3) Sulphur, although contributes to the heating value of coal, yet on
combustion produces acids (SO2 and SO3), which have harmful effects
of corroding the equipments and also cause atmospheric pollution.

Presence of sulphur is highly undesirable in coal to be, used for making


coke for iron industry, since it is transferred to the iron metal and badly
affects the quality and properties of steel. Moreover, oxides of sulphur
(formed as combustion products) pollute the atmosphere and leads to
corrosion.

(4) Oxygen content decreases the calorific value of coal. High oxygen-
content coals are characterized by high inherent moisture, low calorific
value, and low coking power. An increase in 1% oxygen content
decreases the calorific value by about 1. 7% and hence, oxygen is
undesirable. Thus, a good quality coal should have low percentage of
oxygen

25
Liquid Fuels

The important liquid fuels are petroleum, petroleum


products, tar, alcohols. These are naturally found under the
sea surface. Liquid fuels are also obtained synthetically
from hydrogenation of coal.

Petroleum
Petroleum or crude oil is a dark greenish brown or black
coloured viscous oil found deep in earth's crust. The oil is
usually floating over a brine solution and above the oil,
natural gas is present. Crude oil containing mixture of
paraffinic, olefinic and aromatic hydrocarbons with minor
amounts of organic compounds like N, 0 and S. The
average composition of crude oil is C =80 - 87 %, H =11-
15%, S = 0.1 -3.5%, (N +O) =0.1- 0.5%.
26
Liquid Fuels
a) Classification of petroleum
Petroleum is classified into three types based on
variation of chemical nature of crude oil found in the earth.
i) Paraffinic-base type crude oil: It contains saturated
hydrocarbons from CH4 to C35H72 and little amount of
naphthalenes and aromatics.
ii) Asphaltic-base type crude oil: It contains mainly
cycloparaffins or naphthalenes with smaller amount of
paraffins and aromatic hydrocarbons.
iii) Mixed-base type crude oil : It contains both paraffinic
and asphaltic hydrocarbons and are generally in the form of
semi-solid waxes.

27
Liquid Fuels
Mining and Refining of Petroleum

Step - I: Separation of water (Cottrell's process)


The crude oil from the oil well is an extremely stable
emulsion of oil and salt water. The crude oil is allowed to
flow between two highly charged electrodes, where colloidal
water droplets coalesce to form large drops, which is then
separated out from the oil.

Step - II: Removal of harmful impurities


a) The presence of NaCl and MgCl in the crude oil can
corrode the refining equipment, hence these salts are
removed by electrical desalting and dehydration methods.
b) The sulfur compounds present in the crude oil is removed
by treating oil with copper oxide, which results in the
formation of copper sulfide (solid), which is then removed by
filtration.
28
Liquid Fuels
Fractional distillation
Step - III: Fractional distillation
The crude oil is then heated to about 400°C in an iron retort, whereby all
volatile substances (except asphalt or coke) are evaporated. The hot
vapors are then passed up a fractionating column, 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. (Figure )

When the vapours of the oil go up in the fractionating column, they


become gradually cooler and get condensed at different heights of
column. The fractions having higher boiling points condense at lower
trays whereas the fractions having lower boiling points condense at
higher trays. The gasoline obtained by the fractional distillation is called
straight --run gasoline. Various fractions obtained at different trays are
given in table.
29
Liquid Fuels

30
Fractional distillation of Crude oil
Liquid Fuels
Various fractions of crude oil and their composition and uses

Composition
Sn Boiling
Name of the fractions Of Uses
. range (OC)
Hydrocarbons.
As domestic and
1. Uncondensed gases Below 30°C C1 to C4 industrial fuel under
the name LPG
2. Petroleum ether 30 70 °C C5 to C7 As a solvent.
Gasoline (or) petrol. 40 - 120 °C As motor fuel, solvent
3. C5 to C9 and in dry cleaning.

Naphtha ( or}solvent spirit As solvent and in dry


4. 120. - 180 °C C9 to C10
. cleaning.
As fuel for jet engines
5. Kerosene oil. 180 - 250 °C C10 to CI6
and an illuminant.
6. Diesel oil (or) gas oil 250 320 °C C10 to CI8 As Diesel engine fuel.
Production of gasoline
7. Heavy oil. 320 - 400 °C C17 to C30 by cracking
process. 31
Liquid Fuels
Various fractions recovered from Heavy Oil
Compositio
n
Boiling Of
Sn. Name of the fractions Uses
range (OC) Hydrocarbo
ns
.

1. Lubricating oil - C17 to C20 Used as lubricants

Used in medicines
Petroleum jelly and cosmetics
2. - -
(Vaseline)

Paraffin wax - Used in candles,


3. C20 to C28 wax paper, boot
polish, etc

4. Grease - - Used as lubricants.

Used for making


C30 and roads, water
5. Asphalt or bitumen Above 400°C proof roofing,
above
etc 32
Liquid Fuels
Cracking

• The decomposition of bigger hydrocarbon molecules into simpler,


low boiling hydrocarbons of lower molecular weight is called
cracking.
• The gasoline obtained from the fractional distillation of petroleum,
has the highest demand as a motor fuel, but the yield of this
fractions is only 20-30% (Crude oil) and also quality as straight-run
gasoline which is not good an_ hence is used only after proper
blending. To overcome these difficulties, the higher boiling fractions
(e.g. fuel oil and gas oil) are converted into lower boiling fractions
gasoline (petrol) by cracking process.
• The cracked gasoline gives better engine performance i.e., they are
suitable for spark -ignition engines of automobiles. In cracking
process, higher saturated hydrocarbon molecules are converted into
simpler molecules such as paraffinic and olefinic hydrocarbons,
• There are two methods of cracking in use
1. Thermal cracking 2. Catalytic cracking
33
Liquid Fuels
Thermal cracking .
•In this process, the heavy oil is subjected to
high temperature and pressure, when the
bigger hydrocarbon molecules break down to
give smaller molecules of the paraffins,
olefins and hydrogen. The cracked products
are then separated by fractional distillation.
This process is carried out in liquid phase at a
temperature of 4 75 - 530° C and under
pressure of 100 kg/cm2 is called Liquid-
phase thermal cracking or at a
temperature of 600-650°C (heavy oil is
vapourised) and under a low pressure of 10-
20 kg/cm2, such process is called Vapour-
phase thermal cracking. 34
Liquid Fuels

Catalytic cracking

• In this process, cracking is carried out in


presence of a catalyst at lower temperature
(300° C to 450° C) and pressures (l to 5 kg/cm 2).
The catalyst like aluminum silicate [Al 2(SiO3)] or
alumina [A12O3] used in cracking gives higher
yield and better quality of gasoline.
.
35
Liquid Fuels
⚫The vapours produced are then passed through a
fractionating column, where heavy oil fractions condensed.
The vapours are then admitted into a cooler, where some of
the gaseous products are condensed along with gasoline
and uncondensed gases move on. The gasoline containing
some dissolved gases is then sent to a stabilizer, where the
dissolved gases are removed and pure gasoline is
obtained.

⚫When substantial amount of carbon is deposited on the


catalyst bed, during cracking, the catalyst stops functioning.
It is reactivated by burning off the deposited carbon in a
stream of hot air. During the reactivation of catalyst, the
vapours are diverted through another catalyst chamber.

36
Liquid Fuels
Knocking

• Knocking is a kind of explosion due to rapid pressure rise


occurring in an IC (Internal Combustion) engine.

• In a petrol engine, a mixture of gasoline vapour and air


at 1: 17 ratio is used as fuel. This mixture is compressed and
ignited by an electric spark. The products of oxidation
reaction (combustion) increases the pressure and pushes
the piston down the cylinder. If the combustion proceeds in a
regular way, there is no problem in knocking. But in some
cases, the rate of combustion (oxidation) will not be uniform
due to unwanted chemical constituents of gasoline. The rate of
ignition of the fuel gradually increases and the final portion of
the fuel-air mixture gets ignited instantaneously producing an
explosive sound known as "Knocking". Knocking property of
the fuel reduces the efficiency of engine. So a good
gasoline should resist knocking.
37
Liquid Fuels

Chemical structure and knocking


The knocking tendency of fuel hydrocarbons mainly
depends on their chemical structures. The knocking
tendency decreases in the following order.
Straight chain paraffins > Branched chain paraffins >
Cycloparaffins > Olefins > Aromatics.
SCP BCP CP O A

38
• Improvement of antiknock characteristics
• The octane number of fuel can be improved by
(i)blending petrol of high octane number with
petrol of low octane number, so that the
octane number of the latter can be improved.
(ii) the addition of anti-knock agents like Tetra-
Ethyl Lead (TEL).

39
Liquid Fuels
Anti-Knocking agent
LEADED PETROL (ANTI-KNOCK AGENT)

The anti-knock properties of a gasoline can be


improved by the addition of suitable additives.
Tetraethyl lead (TEL) or (C2H5)4Pb is an important
additive added to petrol. Thus the petrol containing
tetra ethyl lead is called leaded petrol.

TEL reduces the knocking tendency of hydrocarbon.


Knocking follows a free radical mechanism, leading
to a chain growth which results in an explosion. If the
chains are terminated before their growth, knocking
will cease. TEL decomposes thermally to form ethyl
free radicals which combine with the growing free
radicals of knocking process and thus the chain 40

growth is stopped.
Liquid Fuels

Disadvantages of using TEL


•When the leaded petrol is used as a fuel, the TEL is
converted to lead oxide and metallic lead. This lead deposits
on the spark plug and on cylinder walls which is harmful to
engine life. To avoid this, small amount of ethylene dibromide
is added along with TEL. This ethylene dibromide reacts with
Pb and PbO to give volatile lead bromide, which goes out
along with exhaust gases.
•But this creates atmospheric pollution. So nowadays aromatic
phosphates are used instead of TEL
•Nowadays aromatic phosphates are used as antiknock agent
because it avoids lead pollution.
41
Liquid Fuels
OCTANE NUMBER (or) OCTANE RATING
• Octane number is introduced to express the knocking
characteristics of petrol. It has been found that n-heptane
knocks very badly and hence, its anti-knock value has
been given zero. On the other hand, iso-octane gives very
little knocking and so, its anti-knock value has been
given 100.

• Thus octane number is defined as 'the percentage of iso-


octane present in a mixture of iso-octane and n-heptane.‘

42
Liquid Fuels
CETANE NUMBER (or) CETANE RATING

• Cetane number is introduced to express the knocking characteristics


of diesel. Cetane has a very short ignition lag and hence its cetane
number is taken as 100. On the other hand 2-methyl naphthalene has
a long ignition lag and hence its cetane number is taken
CH 3
as zero.
• CH3 – (CH2)14 – CH3
• n- cetane (hexa decane)
• cetane number = 100
2-methyl naphthalene (cetane number = 0)
• Thus the cetane number is defined as "the percentage of hexa decane
present in a mixture of hexa decane and 2-methyl napthalene, which has the
same ignition lag as the fuel under test".
• The cetane number decreases in the following order.
• n-alkanes > Cycloalkanes > alkenes >branched alkanes >aromatics
• The cetane number of a diesel oil can be increased by adding additives
called dopes.
• Important dopes: Ethyl nitrate, Iso-amyl nitrate.
43
Liquid Fuels
Power alcohol
• When ethyl alcohol is used as fuel in internal combustion engine, it is
called as "power alcohol". Generally ethyl alcohol is used as its 5-
25% mixture with petrol.
Advantages of power alcohol:
• Ethyl alcohol has good antiknocking property and its octane number
is 90, while the octane number of petrol is about is 65. Therefore,
addition of ethyl alcohol increases the octane number of petrol.
• Alcohol has property of absorbing any traces of water if present in
petrol.
• Ethyl alcohol contains 'O' atoms, which helps for complete
combustion of power alcohol and the polluting emissions of CO,
hydrocarbon, particulates are reduced largely.
• Use of ethyl alcohol in petrol reduces our dependence on foreign
countries for petrol and saves foreign considerably.
-Power alcohol is cheaper than petrol.

44
Liquid Fuels
Disadvantages of power alcohol

•Ethyl alcohol has calorific value 7000cal/gm much lower than


calorific value of petrol 11500cal/gm. Use of power alcohol
reduces power output upto 35%.

•Ethyl alcohol has high surface tension and its atomisation,


especially at lower temperature, is difficult causing starting
trouble.

•Ethyl alcohol may undergo oxidation reaction to form acetic


acid, which corrodes engine parts.

•As ethyl alcohol contains 'O' atoms, the amount of air require for
complete combustion of power alcohol is lesser and therefore
carburetor and engine need to be modified, when only ethyl
alcohol is used as fuel.

45
Liquid Fuels
Production of ethanol

• The basic steps for large scale production of ethanol are: microbial
(yeast) fermentation of sugars, distillation, dehydration and
denaturing. Prior to fermentation, some crops require
saccharification or hydrolysis of carbohydrates such as cellulose and
starch into sugars. Saccharification of cellulose is called cellulolysis .
Enzymes are used to convert starch into sugar.

Fermentation
Ethanol is produced by microbial fermentation of the sugar. Microbial
fermentation will currently only work directly with sugars. Two
major components of plants, starch and cellulose, are both made up
of sugars, and can in principle be converted to sugars for
fermentation. Currently, only the sugar (e.g. sugar cane) and starch
(e.g. corn) portions can be economically converted. There is much
activity in the area of cellulosic ethanol, where the cellulose part of a
plant is broken down to sugars and subsequently converted to
ethanol.
46
Liquid Fuels
Distillation

• For the ethanol to be usable as a fuel, the majority of the water must be
removed. Most of the water is removed by distillation, but the purity is
limited to 95–96% due to the formation of a low-boiling water-ethanol
azeotrope with maximum (95.6% m/m (96.5% v/v) ethanol and 4.4%
m/m (3.5% v/v) water). This mixture is called hydrous ethanol and can
be used as a fuel alone, but unlike anhydrous ethanol, hydrous ethanol
is not miscible in all ratios with gasoline, so the water fraction is typically
removed in further treatment in order to burn in combination with
gasoline.

47
Liquid Fuels
Dehydration
•There are basically three dehydration processes to remove the water
from an azeotropic ethanol/water mixture. The first process, used in
many early fuel ethanol plants, is called azeotropic distillation and
consists of adding benzene or cyclohexane to the mixture. When
these components are added to the mixture, it forms a heterogeneous
azeotropic mixture in vapor-liquid-liquid equilibrium, which when
distilled produces anhydrous ethanol in the column bottom, and a
vapor mixture of water, ethanol, and cyclohexane/benzene. When
condensed, this becomes a two-phase liquid mixture. The heavier
phase, poor in the entrainer (benzene or cyclohexane), is stripped of
the entrainer and recycled to the feed, while the lighter phase together
with condensate from the stripping is recycled to the second column.
Another early method, called extractive distillation, consists of adding
a ternary component which will increase ethanol's relative volatility.
When the ternary mixture is distilled, it will produce anhydrous ethanol
on the top stream of the column.

48
Liquid Fuels
• With increasing attention being paid to saving energy, many methods have
been proposed that avoid distillation altogether for dehydration. Of these
methods, a third method has emerged and has been adopted by the majority
of modern ethanol plants. This new process uses molecular sieves to
remove water from fuel ethanol.
• In this process, ethanol vapor under pressure passes through a bed of
molecular sieve beads. The bead's pores are sized to allow absorption of
water while excluding ethanol. After a period of time, the bed is regenerated
under vacuum or in the flow of inert atmosphere (e.g. N 2) to remove the
absorbed water. Two beds are often used so that one is available to absorb
water while the other is being regenerated. This dehydration technology can
account for energy saving of 3,000 BTU/gallon (840 kJ/L) compared to
earlier azeotropic distillation.

49
Liquid Fuels
Biodiesel
A fuel derived from organic oils, such as vegetable oil, rather than petroleum.
Biodiesel's use and production are increasing. It's typically used for aircraft,
vehicles and as heating oil.

Transesterification
Animal and plant fats and oils are composed of triglycerides, which are esters
containing three free fatty acids and the trihydric alcohol, glycerol. In the
transesterification process, the alcohol is deprotonated with a base to make it
a stronger nucleophile. Commonly, ethanol or methanol are used. As can be
seen, the reaction has no other inputs than the triglyceride and the alcohol.
Under normal conditions, this reaction will proceed either exceedingly slowly
or not at all, so heat, as well as catalysts (acid and/or base) are used to speed
the reaction. It is important to note that the acid or base are not consumed by
the transesterification reaction, thus they are not reactants, but catalysts.
Common catalysts for transesterification include sodium hydroxide,
potassium hydroxide, and sodium methoxide.

50
Liquid Fuels
• Almost all biodiesel is produced from virgin vegetable oils using the base-
catalyzed technique as it is the most economical process for treating virgin
vegetable oils, requiring only low temperatures and pressures and
producing over 98% conversion yield (provided the starting oil is low in
moisture and free fatty acids). However, biodiesel produced from other
sources or by other methods may require acid catalysis, which is much
slower.

51
Gaseous Fuels
COMPRESSED NATURAL GAS

•Natural Gas is obtained from wells dug in the oil bearing


regions. When natural gas occurs along with petroleum in
oil wells, it is called as ‘wet gas’ and contains gaseous
hydro carbons from C1 to C4. The wet gas is then suitably
treated to remove propane, propene, butane and butane,
which is used as LPG. When the natural gas is
compressed, it is called Compressed Natural Gas (CNG).
The primary component present in CNG is methane. It is
mainly derived from natural gas.
•The natural gas can either be stored in a tank of a vehicle
as compressed natural gas (CNG) at 3,000 or 3,600 psi
or as liquified natural gas (LNG) at typically 20-150 psi.
A suitably designed natural gas engine may have a higher
output compared with a petrol engine because the octane
number of natural gas is higher than that of petrol. 52
Gaseous Fuels
COMPRESSED NATURAL GAS

Compressed natural gas vehicles require a greater amount


of space for fuel storage than convention gasoline power
vehicles. Since it is a compressed gas, rather than a liquid
like gasoline, CNG takes up more space for each GGE
(Gallon of Gas Equivalent). This makes it difficult to design
smaller vehicles that look and operate like the vehicles that
people are accustomed to.

53
Gaseous Fuels
• CNG is often confused with liquefied natural gas (LNG). While both
are stored forms of natural gas, the key difference is that CNG is in
compressed form, while LNG is in liquefied form. CNG has a lower
cost of production and storage compared to LNG as it does not
require an expensive cooling process and cryogenic tanks. CNG
requires a much larger volume to store the same mass of natural
gas and the use of very high pressures (3000 to 4000 lbf/in², or 205
to 275 bar).

Properties
l. CNG is; the cheapest, cleanest and least environmentally impacting
alternative fuel.
2. Vehicles powered by CNG produce less carbon monoxide and
hydrocarbon (HC) emission.
3. It is less expensive than petrol and diesel.
4. The ignition temperature of CNG is about 550°C. CNG requires
more air for ignition.

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