Fuels Liquid

Liquid fuels
All liquid fuels are generally products obtained

from petroleum refining
Crude Petroleum,
gasoline,
Diesel,
Biodiesel are examples
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more notes n updates
Mining of petroleum
Petroleum occurs at a depth ranging from a few
hundred meters to about 2-3 kilometers, hence very
expensive process.
The possible locations are first identified by aerial
surveys and ground tests (this is called oil
exploration).
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Holes are drilled into the earths crust and pipes are
inserted until the pipes reach the petroleum bearing
rocks (this is called oil drilling). These rocks are
surrounded by natural gas
The drill-hole from which crude oil are mined are

called oil-wells.
When pipes are lowered to slightly greater depths,

then the crude oil gushes out on its own due to high
internal pressure of natural gas. When the gas
pressure decreases, the crude oil is pumped out
with the help of pumps.
At some point there will be insufficient underground

pressure to force the oil to the surface.
Secondary recovery methods are applied which rely on

the supply of external energy into the reservoir in the form
of injecting fluids to increase reservoir pressure
The reservoir's pressure is increased by water injection,

natural gas reinjection, injection of compressed air,
carbon dioxide or some other gas into the bottom of an
active well
The crude oil from the oil field is taken to the refineries
with the help of underground
pipelines.
Cracking of Heavy Oils

Cracking is a process of converting heavy oil with
higher molecular weight hydrocarbons to the oil with
lower molecular weight hydrocarbon which is known
as gasoline. (C5-C9)
The lower molecular weight hydrocarbons have low
boiling points
Heavy oil is heated at a high temperature under
pressure or in the presence of catalyst to obtain
gasoline.
Why Cracking is done?

Higher hydrocarbons with high boiling points are
decomposed into a variety of lower hydrocarbons that
are more volatile (low boiling)
The Quality n quantity (20%) of the important fraction
-straight run gasoline/ petrol is not good from fractional
distillation of crude petroleum.
The middle and heavy surplus fractions are further
cracked to get petrol. This petrol is better for IC engines
.

The heavy oil is heated at high temperature under

pressure or in the presence of catalyst
C10H22 C5H12 (n-pentane) + C5H10
C16H34 C8H18 (n-octane) + C8H16
Thus, n-pentane or octane along with other lower
hydrocarbon is used as gasoline.
Generally, on cracking a mixture of hydrocarbon is
obtained which is allowed to undergo fractional
condensation to separate gasoline.

Types of Cracking
There are two methods for cracking.
i) Thermal cracking which may be
a) In liquid phase or
b) In vapour phase
ii) Catalytic cracking which may be
a) Fixed bed
b) Moving bed
Summary of All cracking processes

Comparison of Liquid n Vapour phase Cracking

Sr.
No
.
Characteristic
Liquid Phase Thermal

Cracking
Vapour Phase
Thermal
Cracking
1.
Cracking
temperature
Moderate i.e. 420C

550C
600C 650C
2.
Pressure
High 100 kg/cm2
3.
Yield percentages
50 60%
Low 10 20
kg/cm2
Higher
4.
Octane rating
65 70
> 70 (75 80)
5.
Pre-requirement
for process
Any type of heavy oil

can be used
Oil has to be
vaporised readily
6.
Time required
Comparatively more
Comparatively
less

10
Comparison of Fixed Bed n Moving Bed Catalytic

cracking
Sr. No
Characteristic
1.
Cracking
temperature
2.
Pressure
3.
Octane value
Fixed Bed
Catalytic
Cracking
Moving Bed or Fluidised

Bed Catalytic Cracking
i.e. 425C
450C
1.5 kg/cm2
Around 500C
Around 1 kg/cm2
80 85
85 90

11
Advantages of catalytic process over Thermal

process
i)
The cracking reaction can be carried out at lower temperature and

pressure.
ii)
Yield is high
iii)
No external fuel is required. Heat required for cracking is derived

from the coal embedded in the catalyst.
iv)
Better control of the reaction so better choice of product.
v)
The cracking is specific in nature and can give proper quality of

gasoline.
vi)
The octane value of gasoline is higher by catalytic process, hence

better for petrol engine.
12
Reforming
Reforming is the process of bringing about structural
modifications in the components of straight run gasoline
with the primary objective of improving its anti knock
characteristics.
Reforming or aromatisation involves the conversion of open
chain (aliphatic) hydrocarbons and/or cycloalkanes in the
presence of a catalyst, into aromatic hydrocarbons (arenes)
containing the same number of carbon atoms.
It is carried thermally (temp 500-6000C, pressure 85 atm) or
catalytically [Pt (0.75%) supported over Alumina (temp 4605300C, pressure 30-35 atm)].
13
Dehydrogenation
-3H2
cyclohexane
Benzene
Dehydrocyclasition
n Heptane
methyl cyclohexane
Toluene
Isomerisation

14
Knocking in IC Engines
Knocking related to the internal combustion
engine working on petrol.
In IC engine - gasoline vapours + air = fuel
Burning of a fuel is initiated by a spark in the
cylinder.
Due to combustion, gases are formed which
moves the piston down the cylinder.
The movement of the piston must be
even/uniform without any vibration.
15
But sometimes, the rate of combustion/

oxidation becomes so great that the fuel on
ignition, instantaneously produces sudden
increase in the gaseous volume which causes
uneven movement of the piston with rattling
noise in the engine.
It is called as knocking of the engine.
The knocking results in the loss of efficiency of
I.C. engine & damage to the piston and cylinder
16
The petrol is a mixture of various lower

hydrocarbons and the knocking of the engine
depends upon the structure of hydrocarbons,
present in the petrol.
Straight chain saturated hydrocarbons have
more knocking tendency than the straight chain
unsaturated hydrocarbons, as it burns with a
little difficulty.

17
Further, the cyclic compounds have less
tendency to knock than the straight chain

compounds. The presence of double bond and
aromaticity is also important.
The aromatic hydrocarbons burn uniformly, thus it
has a little tendency towards knocking.

Thus, tendency of gasoline to knock is in the
following order. Straight chain paraffins >

Branch chain paraffins > Olefins > Cyclo
paraffins > Aromatics.
18
Octane number
The knocking property of the fuel is expressed as Octane
number. It has been understood that the phenomenon of
knocking is related to the chemical composition of the fuel.
The fuel containing large number of straight chain
hydrocarbons possesses more knocking tendency, thereby
proving itself to be worst.
N-heptane knocks very badly, so its anti-knock value is
arbitrarily zero. Isooctane gives very little knocking, so its
anti-knock value is 100.

19
The octane number of a fuel may be defined as, the

percentage of iso-octane in a mixture of iso-octane and nheptane that matches the fuel under test in its knocking
character.
Aromatic hydrocarbons have octane numbers higher than 100,

while the straight-run gasoline has the octane number of 55.
Thus, the aromatic hydrocarbons prove better
20
Sr.
No.
Parts of
Iso-Octane
Parts of nheptane
Knocking
Octane
Number
1.
100
Zero
Minimum
100
2.
Zero
100
Maximum
Zero
3.
78
22
Moderate
78
4.
85
15
Less
85
Antiknocking Agents/Compounds :
Antiknocking agents are the compounds which help to
increase the octane number of the fuel or decreasing the
knocking. By the addition of these agents, the gasoline/
petrol can be improved in its quality. Some of the
compounds normally used are TEL, i.e. Tetra Ethyl Lead
[(C2 H5)4 Pb].
21
Diesel Engine
In diesel engine fuel is exploded not by spark, but by the
application of heat n pressure.
Diesel engine fuels should easily ignite below the
compression temperature n there should be as short an
induction lag as possible.
So essentially the hydrocarbons molecules in diesel
engine fuels should be as far as possible the straight
chain ones, with minimum admixture of aromatic n side
chain hydrocarbons.
22
Centane Number
In the diesel engines, the fuel with straight chain paraffin
is only used. The diesel fuels generally consists of the
fractions boiling between kerosene and heavier
lubricating oils.
The term centane number is introduced as the mixture
that was first studied was cetane (n-hexa-decane) and
-methyl naphthalene.
Centane has high ignition while 2-methyl naphthalene
has very low ignition quality.

23
Sr.
No
Parts of
Parts of Cetane C16H34 methyl
Naphthalene
Ignition Delay
Cetane Number
1.
100
Zero
Minimum
100
2.
Zero
100
Maximum
Zero
3.
55
45
Moderate
55
4.
45
55
Moderate
45

24
Centane number is defined as the percentage by

volume of cetane in a mixture of cetane and methyl naphthalene which exactly matches in its
ignition characteristics with the diesel under test.
The cetane value of the diesel can be improved by
adding substances (Dopes) like ethyl nitrite, iso-amyl
nitrite and acetone peroxide. The dopes are added upto
2%.

25

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Liquid fuels

All liquid fuels are generally products obtained

Visit www.gyandharaonline.com for

The drill-hole from which crude oil are mined are

When pipes are lowered to slightly greater depths,

At some point there will be insufficient underground

Secondary recovery methods are applied which rely on

The reservoir's pressure is increased by water injection,

Cracking of Heavy Oils

Why Cracking is done?

Visit www.gyandharaonline.com for

The heavy oil is heated at high temperature under

Visit www.gyandharaonline.com for

Summary of All cracking processes

Comparison of Liquid n Vapour phase Cracking

Liquid Phase Thermal

Moderate i.e. 420C

High 100 kg/cm2

> 70 (75 80)

Any type of heavy oil

Visit www.gyandharaonline.com for

Comparison of Fixed Bed n Moving Bed Catalytic

Moving Bed or Fluidised

Visit www.gyandharaonline.com for

Advantages of catalytic process over Thermal

The cracking reaction can be carried out at lower temperature and

No external fuel is required. Heat required for cracking is derived

Better control of the reaction so better choice of product.

The cracking is specific in nature and can give proper quality of

The octane value of gasoline is higher by catalytic process, hence

Visit www.gyandharaonline.com for

But sometimes, the rate of combustion/

The petrol is a mixture of various lower

Visit www.gyandharaonline.com for

Further, the cyclic compounds have less

tendency to knock than the straight chain

has a little tendency towards knocking.

following order. Straight chain paraffins >

Visit www.gyandharaonline.com for

The octane number of a fuel may be defined as, the

Aromatic hydrocarbons have octane numbers higher than 100,

Visit www.gyandharaonline.com for

Visit www.gyandharaonline.com for

Centane number is defined as the percentage by

Visit www.gyandharaonline.com for

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