Unit-I

Fuels: Classification of Fuels, Calorific value, Determination of calorific value of a

solid and liquid fuel, Bomb & amp; Boy’s Gas Calorimeter, Carbonization, Beeheive
Oven Method, Otto-Hoffman’s Byproduct Method, Petroleum, Cracking- fluidized
catalytic cracking. Reformation of petrol, Knocking, Octane number, Cetane
number, Synthetic petrol, Bergius process and Fischer-Tropsch process.

Fuel:
 A fuel is a combustible substance which on proper burning in presence of oxygen or air
gives large amount of heat energy that can be used economically for domestic and
industrial purposes.
 The main elements of any fuel are carbon and hydrogen. During the process of
combustion of a fuel, these elements combine with oxygen to produce CO2 and H2O with
the liberation of heat.
 The energy released in combustion process is the difference in the energy of the reactants
and that of the products formed.

Fuel + O2 → Products (CO2 + H2O) + Heat

Classification of Fuel: Fuels are classified according to occurrence and state of aggregation.
(A) According to occurrence.

1. Primary fuels: Fuels which occur in nature as such are called primary fuels, e.g.,
coal, petroleum and natural gas.
2. Secondary fuels: Fuels which are derived from the primary fuels, e.g., coke.
petrol. diesel and water gas are called secondary fuels.

(B) According to state of aggregation

1. Solid fuels: e.g. wood, coke and coal.

2. Liquid fuels: e.g. petroleum, petrol and diesel.
3. Gaseous fuels: e.g. natural gas, producer gas and water gas.

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A good fuel should possess the following characteristics for its selection for a particular
purpose-

 High calorific value

 Moderate ignition temperature
 Low moisture content
 Low non-combustible matter content
 Moderate velocity of combustion
 Products of combustion should not be harmful
 Low cost
 Easy to transport
 Easy control of combustion
 Should not undergo spontaneous combustion
 Storage cost in bulk should be low
 Burn efficiently without smoke
 Uniform size in solid fuel for regular combustion.

Calorific value:
1. Higher or gross calorific value (HCV): Gross or 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 are cooled down to room temperature (i.e., 25°C).

2. Lower or net calorific value (NCV): The amount of heat liberated when a unit of fuel is
completely burnt and the combustion products are allowed to escape is called net calorific
value. Generally, during the combustion of a fuel, the water vapors escape as such along
with combustion products and are not condensed.

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Net calorific value (NCV) = HCV - Latent heat of water vapours formed
= HCV - Mass of hydrogen x a x Latent heat of steam

= HCV - Mass of hydrogen x 9 x Latent heat of steam

Since 1 part by mass of hydrogen produces ‘a’ part by mass of water.

Units of calorific value: The calorific value is expressed in either Calorie/gram (cal/g) or
Kilocalorie/kg (kcal/kg) or British Thermal unit/lb (B.T.U/lb) in case of solid and liquid fuel.
While in the case of gaseous fuels, the units are K.cal/m3 or B.T.U/ft3.

Determination of Calorific Value:

1. Bomb Calorimeter: The apparatus which is used to determine the calorific value of solid
and liquid fuels is known as Bomb Calorimeter.

Figure: Bomb Calorimeter

Construction:
 It consists of a strong cylindrical stainless-steel bomb in which the combustion of fuel is
made to take place.
 The bomb has a lid, which can be screwed to the body of bomb so as to make a perfect gas
tight seal.
 The lid is provided with two stainless steel electrodes and an oxygen inlet valve. To one of
the electrodes, a small ring is attached.
 In this ring, a nickel or stainless-steel crucible can be supported.

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  The bomb is placed in a copper calorimeter, supported by air-jacket and water-jacket to
prevent heat losses due to radiation.
 The calorimeter is provided with an electricity operated stirrer and Beckmann’s
thermometer, which can read accurately temperature difference upto 1/100 th of a degree.

Procedure:

 About 0.5 to 1.0 g of air-dried fuel is taken in the clean crucible which is supported over
the ring.
 A fine magnesium fuse wire is placed on the fuel sample and stretched across the
electrodes.
 About 10 ml of water is filled in the bomb to absorb any vapours.
 The bomb lid is tightly screwed and the bomb is filled with oxygen gas up to 25 atmosphere
pressure.
 The bomb is then lowered into the calorimeter containing a known mass of water.
 The stirrer is worked and initial temperature of the water is noted.
 The electrodes of the bomb are connected to a 6 volts battery and circuit is completed. The
fuel burns and heat are liberated.
 The temperature of water gradually increases with uniform stirring and attained maximum
temperature (final) is noted.
 A weighed mass of fuels placed in the crucible is allowed to burn in oxygen by electric
spark across the electrode
 Heat liberated is measured by principle of calorimetry i.e. taken by water and calorimeter
 Initial and final temperatures of calorimeter are noted.

Calculation:

m = mass of fuel pellet

W = mass of water in the calorimeter
w = water equivalent of calorimeter
t1 = initial temperature of calorimeter
t2 = final temperature of calorimeter
HCV = gross calorific value of calorimeter
(𝑊+𝑤) (𝑡2−𝑡1)
L= 𝐻𝐶𝑉 = 𝑐𝑎𝑙/𝑔
𝑚

Correction factors are used to get accurate results which include:

A. Fuse Wire Correction: Heat liberated during sparking should be subtracted from heat
liberated.
B. Acid Correction: Fuels containing sulphur and nitrogen if oxidized, the heat of formation
of H2SO4 and HNO3 should be subtracted (as the acid formations are exothermic reactions).

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 C. Cooling Correction: Rate of cooling of temperature from max. temperature to room
temperature is noted. From the rate of cooling and the actual time taken for cooling then
correction is called cooling correction and is added to the (t2-t1) term.

(𝑊 + 𝑤) (𝑡2 − 𝑡1 + 𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑜𝑛) − (𝐴𝑐𝑖𝑑 + 𝐹𝑢𝑠𝑒 𝑤𝑖𝑟𝑒 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑜𝑛)

𝐿= 𝑐𝑎𝑙/𝑔
𝑚

2. Boy’s Gas Calorimeter: This is the standard apparatus used for measuring the calorific
values of gaseous and liquid fuels (which get vaporized easily).

Construction:

 The apparatus consists of a suitable gas burner in which a known volume of gas at
a known pressure can be burnt at a uniform rate.
 Around the burner, there is a chimney or combustion chamber, which has a copper
tubing coiled inside as well as outside it.
 Water at a constant rate is passed through the coil. Water enters from the top of the
outer coil, moves to the bottom of the chimney and then goes up through the inner
coil to the exit at top.
 Separate thermometers are used to measure the incoming and outgoing water
temperatures (t1 and t2)
 During the process of down and up movement through coil, the flowing water takes
away practically whole of the heat of burner.
 Steam formed during combustion gets condensed as water, which can be collected.
 The whole assembly is enclosed in an insulated container.

Figure: Boy’s Gas Calorimeter

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Working:

 Circulation of water and burning of gaseous fuel are continued at constant rates for about
15 minutes for initial warming up period.
 The rates of fuel burning and water circulation are controlled so that the exit water leaves
the apparatus nearly at atmospheric pressure.
 When the steady conditions are established, then readings are taken simultaneously of:
(1) the volume of gas burnt at given temperature and pressure in a certain time period
(2) the quantity of water passing through the coil, during the same time;
(3) the steady rise in temperature, i.e., (t2-t1) and
(4) mass of water condensed during this time.

Calculation:
Let V = volume of gas burning
W = mass of cooling water used in time t
t1 and t2 = incoming and outgoing water temperatures respectively
m = mass of steam condensed in time t
Total heat liberated = V x HCV
Total heat absorbed = W x (t2 - t1)
𝐖 ×(𝐭𝟐 −𝐭𝟏)
So, we get 𝐇𝐂𝐕 =
𝐕
Also mass of water condensed per m3 of gas = m/V kg
𝑚 ×587
So latent heat of steam per m3 of gas = kcal
𝑉
𝐦 ×𝟓𝟖𝟕
So, 𝐍𝐂𝐕 = [𝐇𝐂𝐕 − ] Kcal/m3
𝐕

3. Dulong’s Formula (Theoretical calculation of Calorific Value): It is used for the

calculation of calorific value from the chemical composition of fuel.

i.e. HCV = sum of HCV’s of individual elemental constituents present in the fuel

Derivation:
Exothermic reactions during the process of combustion with their respective HCV values are:

C + O2 → CO2 + 8080 kcal/kg

H2+1/2O2 → H2O + 34500 kcal/kg
S+O2 → SO2 + 2240 kcal/kg

Oxygen present in the fuel is assumed to be present as water and which also prevents some part of
hydrogen available for combustion

H2+ 1/2O2 → H2O + 34500 kcal/kg

2g 16g 18g
1 8 9

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So, Available hydrogen for combustion = Total hydrogen – Fixed hydrogen in the form of H2O
= Total hydrogen – 1/8 (mass of oxygen in fuel)

So if C, H, O and S are percentages of carbon, hydrogen, oxygen and sulphur in the fuel
respectively. Then,
𝑪 𝟑𝟒𝟓𝟎𝟎 𝑶 𝑺
⇒ 𝑯𝑪𝑽 = [𝟖𝟎𝟖𝟎 × + (𝑯 − ) + 𝟐𝟐𝟒𝟎 × ] 𝒌𝒄𝒂𝒍/𝒌𝒈
𝟏𝟎𝟎 𝟏𝟎𝟎 𝟖 𝟏𝟎𝟎

1 O
or, HCV = [8080C + 34500 (H − ) + 2240S ] kcal/kg
100 8

𝑁𝐶𝑉/LCV = HCV − 0.09H × 587 kcal/kg

as 1 part of H by mass gives 9 parts of H2O, and latent heat of steam is 587 kcal/kg.

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Carbonization: The process of converting coal into coke is called carbonization, heated in
absence of air /O2.

1. Low-temperature carbonization: In this process, the heating of coal is carried out at 500
- 700°C. The yield of coke is about 75-80% and it contains about 5-15% volatile matter. It
is not mechanically strong, so it cannot be used as a metallurgical coke. However, it burns
easily giving practically a smokeless, hot and radiant fire. Hence, it is suitable for domestic
purposes. The by-product gas produced (about 130-150 m"/tonne) by this process is richer
in heating value (about 6500-9,500 kcal/m°) and is, therefore, a more valuable gaseous
fuel.

2. High-temperature carbonization is carried out at 900-1,200°C with the object of

producing coke of the right porosity, hardness, purity, strength, etc., so that it can be used
in metal21`lurgy. Nearly all the volatile matter of coal is driven off and the yield of coke
is about 65-75%, containing only 1-3% volatile matter. The by-product gas produced is
high in volume (about 300-390 m3/tonne), but its calorific value is low (about 5400-6,000
kcal/m3).

Difference between HTC and LTC:

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Beeheive Oven Method: The coke, for metallurgical purposes, is obtained by either of the
following processes-

Beeheive Oven:
 It is the earliest and cheapest process for manufacturing metallurgical coke.
 The oven (see Figure) is a dome-shaped structure of bricks, about 4 m wide and 2.5 m high.
 There are too openings, one at the top for the charging of coal and the other in one side for
air supply as well as for coke discharge. These openings can be opened or closed as desired.

Figure: Beeheive Oven Real image of Beeheive Oven

 Coal is charged through the top opening and levelled evenly to produce a layer, about 0.6
m deep.
 Some air is supplied in and the coal ignited.
 The volatile matter escapes or burns inside the partially closed side door.
 Combustion is allowed to proceed in a gradually diminishing supply of air so that slow
carbonization, from the top layer to the bottom, takes place, completion of which takes
about 3-4 days.
 When the carbonization is complete, the hot coke is quenched with water and raked out
through the side door; leaving the oven hot enough to start the carbonization next charge
batch.
 The yield of coke is about 80% of the coal charged and averages about 5 to 6 tonnes of
coke per firing.
 To make the process economical, many such ovens are worked in series, so that the waste
heat of the outgoing gases is utilized for heating purposes.

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Otto-Hoffmann’s Byproduct Method:
Otto-Hoffmann developed modern by-product coke oven unlike beehive oven in order to:
(i) increase the thermal efficiency of the carbotization process,
(ii) recover valuable by-product (like coal gas, ammonia, benzol oil, tar, etc.),
(iii) Moreover, the heating is done on the basis of "regenerative system of heat economy'", ie., utilizing
the waste flue gases for heating the checker-work of bricks.

Construction and Working Principle:

 It consists of number of narrow silica chambers. Each chamber is provided with a charging
hole at the top, a gas off- take and a refractory lined cast iron door at each end for
discharging coke.
 Coal is introduced into the chambers and the chambers are closed (to prevent access of air).
The ovens are heated to 1200°C by burning a gaseous fuel (producer gas) and usually
employs a regenerative principle to as economical heating.
 The flue gases produced during combustion are passed the regenerators chequer brickwork
that takes up the heat and gets heat to about 1000°C. The flow of heating gases is then
reversed so that the hot flue gases preheat the other chambers. The heating is continued till
the evolution of volatile matter ceases completely which is about 11 to 18 hours.
 When co is formed, a massive ram pushes the red-hot coke outside. It is subsequent
quenched by water spray (wet quenching). The coke can also be quenched by inert gases
like nitrogen (dry quenching). The coke obtained by dry quenching is drier, clean and
stronger than wet quenched coke.

Figure: Otto-Hoffman’s Byproduct Method

Recovery of by-products: The gas coming out from the oven is known as "coke oven gas and is
mainly composed of ammonia, H2S, naphthalene, benzene, tar, moisture, etc.

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 (i) Recovery of tar: The gas is first passed through a tower in which liquor ammonia is
sprayed. Here dust and tar get collected in a tank below, which is heated by steam coils
to recover back ammonia sprayed. The ammonia is used again.
(ii) Recovery of ammonia: The gases from the chamber are then passed through a tower
in which water is sprayed. Here ammonia goes into solution as NH4OH.
(iii) Recovery of naphthalene: The gases are then passed through another tower in which
water at very low temperature is sprayed. Here naphthalene gets condensed.
(iv) Recovery of benzene: The gases are then sprayed with petroleum, when benzene and
its homologues are removed.
(v) Recovery of H2S: The gases are then passed through a purifier, packed with moist
Fe2O3. Here H2S is retained.

Fe2O3 + 3H2S → Fe2S3+ 3H2O

After some time, when all Fe2O3 is changed into Fe2S3, the purifier is exposed to
atmosphere, when Fe2O3 is regenerated.

Fe2S3 + 4 O2 → 2 FeO + 3 S2O↑

4FeO + O2 → 2 Fe2O3

Figure: Otto-Hoffman’s Byproduct Method

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Petroleum:
 Petroleum (petra = rock; oleum = oil)
 Petroleum or crude oil is a dark greenish brown or black colored 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, O and S.

Classification of petroleum
Petroleum is classified into three types based on variation of chemical nature of crude oil found in
the earth.

• Paraffinic-base type crude oil: It contains saturated hydrocarbons from CH4 to C35H72 and
little amount of naphthalene and aromatics.

• Asphaltic-base type crude oil: It contains mainly cycloparaffins or naphthalene with

smaller amount of paraffins and aromatic hydrocarbons. Hydrocarbons from C 18H38 to
C35H72 are called waxes.
• Mixed-base type crude oil: It contains both paraffinic and asphaltic hydrocarbons and are
generally in the form of semi-solid waxes.

Origin of petroleum:
 Resulted from the partial decomposition of marine animals and vegetable organisms of pre-
historic forests
 These materials had buried by changes in earth (like earthquake, volcano etc.) andsubjected
to high pressure and temperature during the ages of time.
 Then influenced by either radioactive elements or bacterial decomposition under anaerobic
conditions to get converted to various hydrocarbons.

Mining of petroleum:
 Done by drilling holes in the earth crust and sinking pipes upto the oil-bearing porous rocks
 Oil usually gushes out itself due to hydrostatic pressure of natural gas.
 Then it may be mechanically pumped up by using either lift pump or air-lift pump.

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 Mining of crude oil and use of air-lift pump

Refining of petroleum:
 The crude oil obtained from the earth crust contains water, sulphur and some unwanted
impurities.
 After removal of water, sulphur and these impurities, the crude oil is separated into
various useful fractions by fractional distillation and finally converted into desired
specific products having different boiling points. The process is called "Refining of
Petroleum" and the refining plants are called "Oil refineries". The process of refining
involves the following steps.

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: The sulphur compounds present in the crude
oil is removed by treating oil with copper oxide, which results in the formation of copper
sulphide (solid), which is then removed by filtration.

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.
 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.

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 Figure: Fractional Distillation of Crude Petroleum
Fractional Distillation of Crude Petroleum:

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Fractional Distillation of Heavy Oil:

Cracking: The decomposition of bigger hydrocarbon molecules into simpler, low boiling
hydrocarbons of lower molecular weight is called Cracking.

There are two methods of cracking in use- 1. Thermal cracking 2. Catalytic cracking

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 475 - 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.
 Petrol obtained from vapor phase cracking has better anti-knock properties but poor
stability than petrol from liquid phase cracking.

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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/cm2). The catalyst like aluminum silicate [Al2(SiO3)] or alumina
[A12O3] used in cracking gives higher yield and better quality of gasoline.
Advantages
i. No external fuel is required. Heat required is derived from coal, embedded in the catalyst.
ii. Low pressure is required (1-5 kg/cm2)
iii. Product contain very less amount of Sulphur (major part escapes out as H2S gas)
iv. Catalytic cracking yields a higher quantity of branched-chain, unsaturated, aromatic
hydrocarbons as compared to thermal cracking and hence have better anti-knock
characteristics
There are two types of catalytic cracking in use
i) Fixed-bed catalytic cracking
ii) Fluid (Moving)-bed catalytic cracking

i) Fixed-bed catalytic cracking:

 The heavy oil is passed through the heater, where the oil is vaporized and heated to 400 to
500°C and then forced through a catalytic champers containing the catalyst of silica
alumina gel (SiO2, Al2O3) or bauxite, is mixed with clay and zirconium oxide maintained
at 400 to 500°C and 1.5 kg/cm2 pressure. During their passage through the tower, cracking
takes place about 30-40% of the charge is converted into gasoline and about 2- 4% carbon
is formed which gets deposited on the catalytic bed.
 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.

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 Figure: Fixed-bed catalytic cracking

ii) Fluid (Moving)-bed catalytic cracking:

 In this process, solid catalyst is finely powdered, so that it behaves almost as a fluid, which
can be circulated in gas stream.
 The vapours of cracking stock (gas oil, heavy oil, etc.,) mixed with fluidized catalyst is
forced up into a large reactor bed in which cracking of the heavier molecules into lighter
molecules occurs at a temperature of 530°C and pressure of about 3 to 5 kg/cm2.
 The top of the reactor, there is a centrifugal separator, which, allows the low boiling lighter
molecules move up to the top of the reactor and enter into the fractionating column but
retains all the catalyst powder in the reactor itself.
 The carbon deposited on the catalyst powder are burnt off in the regenerator and the
temperature rises to about 590°C or more.
 The cracked gases and gasoline are removed from the top of the fractionating column and
sent to a cooler, where gasoline is condensed. It is then sent to a stabilizer to recover pure
gasoline.
 The product contains a higher proportion of aromatics and iso-paraffins.

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 Figure: Fluid (Moving)-bed catalytic cracking

Synthetic Petrol: Synthetic petrol can be synthesized using these two methods-
(1) Fishcher-Tropsch method
(2) Bergius process

Fishcher-Tropsch method:

 In this process, water gas (CO + H2) is produced by the action of steam over red-hot coke.
 The gas is purified by passing through Fe2O3 (to remove H2S) and then into a mixture of
Fe2O3.Na2CO3 (to remove organic Sulphur compounds).
 The purified gas is compressed to 5 to 25 atm and then led through a converter. (containing
a catalyst, consisting of a mixture of 100 parts cobalt, 5 parts thoria, 8 parts magnesia and
200 parts kieselguhr earth) maintained at ~200-300°C.

 Reaction is exothermic, so outcoming hot mixture is led to a cooler, where a liquid is

resembling crude oil is obtained
 Crude oil then fractionated to get gasoline and high boiling point heavy oil.
 Heavy oil then recycled for cracking to get more gasoline

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 Figure: Fishcher-Tropsch method

Bergius Method:

 This method was developed by Bergius in Germany during the First World War.
 The low ash coal is finely powdered and made into a paste with heavy oil and then a catalyst
(composed of tin or nickel oleate) is incorporated.
 The whole is heated with hydrogen at 450°C and under a pressure 200-250 atm for about
1.5 hours, during which hydrogen combines with coal to form saturated hydrocarbons,
which decompose at prevailing high temperature and pressure to yield low-boiling liquid
hydrocarbons.
 The issuing gases (from the reaction vessel) are led to condenser, where a liquid resembling
crude oil is obtained, which is then fractionated to get: (i) gasoline, (ii) middle oil, and (iii)
heavy oil.
 The latter is used again for making paste with fresh coal dust. The middle oil is
hydrogenated in vapour-phase in presence of a solid catalyst to yields more gasoline. The
yields of gasoline in about 60% of the coal dust used.

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 Figure: Bergius process of hydrogenation of coal to gasoline

REFINING OF GASOLINE:

 Gasoline obtained from fractionation of crude petroleum contains some undesirable

unsaturated straight chain hydrocarbons and Sulphur compounds
 These hydrocarbons gets oxidized and polymerized to form gum and sludge on storing
 Also Sulphur compounds lead to corrosion of internal combustion engine
 The sulphur compounds are, generally, removed by treating gasoline with an alkaline
solution of sodium plumbite with controlled addition of S. This refining process (called
'sweetening') converts sulphur compounds into disulphides (Doctor's process).

 PbS is removed by filtration

 Disulphides are extracted with a suitable solvents
 After the refining of gasoline, some inhibitors are added. These retard the oxidation
reactions, thereby improving storing qualities of gasoline.

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  Reforming: Reforming is a process of bringing about structural modifications in the
components of straight run gasoline (prepared by the fractional distillation of the crude oil),
with the primary object of improving its anti-knock characteristics. It is carried out either
thermally or in the presence of a catalyst.
Example of catalytic reforming-
Dehydrogenation:

 Knocking: Knocking is a kind of explosion due to rapid pressure rise occurring in an IC

engine.
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.

 Anti-knocking Agent: An antiknock agent is a gasoline additive used to reduce engine

knocking and increase the fuel's octane rating by raising the temperature and pressure at
which auto-ignition occurs. e.g. Tetraethyllead

 Octane Number/Octane Rating: It has been found that n-heptane knocks very badly and
hence, it’s anti-knock value has arbitrarily been given zero. On the other hand, isooctane
(2,2,4-trimethyl pentane) is having very good anti-knocking properties. Thus, octane
number is given 100. Thus, octane number of gasoline (or any other combustion engine
fuels) is the percentage of isooctane in the mixture of isooctane and n-heptane, which
matches the fuel under test in knocking characteristics. In this way, “80-octane” fuel is one
which has the same combustion characteristics as a 80:20 mixture of isooctane and n-
heptane.
 Cetane Number: Cetane rating, also known as cetane number is a measurement of the
quality or performance of diesel fuel. The higher the number, the better the fuel
burns within the engine of a vehicle. n-hexadecane is given cetane number 100 and α-
methyl naphthalene is given cetane number zero. If the given fuel matches with in quality
with blend having 40/60 blend of hexadecane and α-methyl naphthalene. It is assigned a
cetane number 40.

A. Mishra
MCQ type question for Practice:
Q.1 A good fuel should possess:
(a) High ignition temperature (b) moderate ignition temperature (c) high calorific value
(d) both b and c
Q.2 Bomb calorimeter is used for determining the calorific value of
(a) Solid fuel (b) volatile liquid fuel (c) gaseous fuel (d) both a and b
Q.3 Iso-octane has an octane rating of:
(a) 100 (b) zero (c) 50 (d) above 100
Q.4 The process of splitting bigger hydrocarbons into smaller hydrocarbons is called:
(a) Pyrolysis (b) thermal decomposition (c) cracking (d) combustion
Q.5 which of the following possess zero octane number:
(a) iso-octane (b) petrol (c) n-heptane (d) LPG
Q.6 The cetane rating of n-hexadecane is
(a) 100 (b) zero (c) 50 (d) none of these
Q.7 If fuel contains 10% of hydrogen and HCV as 900 cal/gm than its LCV is (latent heat of
condensation of steam is 587 cal/gm)
(a) 371.7 cal/gm (b) 375.8 cal/gm (c) 275.9 cal/gm (d) 171.4cal/gm
Q.8 Octane number is related with the petroleum product:
(a) Diesel oil (b) kerosene oil (c) petrol (d) lubricating oil
Q.9 A gasoline with octane number 80 would contain how much percentage of isooctane by
volume:
(a) 20 (b) 80 (c) 100 (d) all
Q.10 Bergius process of synthetic petrol involve mainly
(a) Passing water gas over heated powdered coke under pressure (b) catalytic hydrogenation
of coal (c) heating coal alone under pressure (d) cracking of heavy oil
Q.11 Fischer - Tropsch process involve formation of gasoline from
(a) coal (b)crude oil (c) water gas (d) heavy oil
Q.12 The fuel selected is most suitable if it has calorific value:
(a) higher (b) lower (c) both (d) none
Q.13 Naphthalene will be recovered in Otto Hoffmann process by quenching with water at:
high temperature (b) low temperature (c) both (d) none
Q.14 Coal gas is:
(a) CO2 + H2 (b) CO + H2 (c) CO+ N2 (d) none
Q.15 Knocking decreases as complexity in fuel composition
(a) Remains constant (b) decrease (c) increase (d) none
Q.16 The calorific value of a coal sample is higher, if its:
(a) Moisture content is high (b) Ash content is high
(c) Volatile matter is high (d) Carbon content is high

A. Mishra