Module 3

Liquid Fuels: The importance of liquid fuels is the fact

that almost all combustion engines run on them.
The largest source of liquid fuels is petroleum. The
calorific value of petroleum is about 40000 kJ/kg.
There are other supplements of liquid fuels such as coal
tar, crude benzol, synthetic liquid fuel made from coal etc.
Petroleum: The term petroleum means rock oil. It is also
called mineral oil.
Petroleum is a complex mixture of paraffinic, olefinic and
aromatic hydrocarbons with small quantities of organic
compounds containing oxygen, nitrogen and sulphur.
 Oil was formed from the remains of
animals and plants that lived millions
of years ago in a marine (water)
environment.

 Over the years, the remains were

covered by layers of earth.

 Heat and pressure from these layers

helped the remains turn into what we
today call crude oil .
The world's top five crude oil-producing
countries are:

◦ Saudi Arabia
◦ Russia
◦ United States
◦ Iran
◦ China
Composition:

Element Carbon Hydrogen Sulphur Oxygen Nitrogen

Percentage 80-87 11.1-15 0.1-3.5 0.1-0.9 0.4-0.9

Crude oil is a mixture of straight chain paraffins and
aromatic hydrocarbons e.g., benzene, toluene,
naphthalenes etc.
Sulphur is present in the form of derivatives of
hydrocarbons such as alkylsulphides, aromatic
sulphides etc.
Nitrogen is present in the form of pyridine, quinoline
derivatives, pyrrole etc.
Oxygen is present as carboxylic acids, ketones and
phenols.
Classification of Crude Petroleum

Residue obtained Name Contents

after distillation
Paraffin wax Paraffin Straight chain
base hydrocarbons and small
amounts naphthenes and
aromatic hydrocarbons
Asphaltic Aromatic and
Asphalt naphthenic
base
hydrocarbons
Paraffins, naphthenes
Paraffin wax and Mixed base and aromatic
asphalt hydrocarbons
Processing of Crude Petroleum:
Petroleum is found deep below the earth crust. The oil
is found floating over salt water or brine. Generally,
accumulation of natural gas occurs above the oil.

Pumping of oil
 Desalting and Dewatering
 Distillation
 Cracking
 Reforming
 Alkylation
 Isomerisation
 Polymerisation
 Hydrotreating
Refining of Petroleum
Crude oil reaching the surface, generally consists of a mixture
of solid, liquid and gaseous hydrocarbons containing sand and
water.
After the removal of dirt, water and much of the associated
natural gas, the crude oil is separated into a no. of useful
fractions by fractional distillation.
The resultant fractions are then subjected to purification known
as refining of petroleum.
Steps involved in refining of petroleum:
(i) Demulsification: The crude oil coming out from the well, is
in the form of stable emulsion of oil and salt water, which is
yellow to dark brown in colour.
The demulsification is achieved by Cottrell’s process, in which
the water is removed from the oil by electrical process. The
crude oil is subjected to an electrical field, when droplets of
colloidal water coalesce to form large drops which separate
out from the oil.

(ii) Removal of harmful impurities: Excessive salt content

such as NaCl and MgCl2 can corrode the refining equipment.
These are removed by washing with water.
The objectionable sulphur compound are removed by treating
the oil with copper oxide. The copper sulphide so formed is
separated by filtration.
(iii) Fractional Distillation: It is done in tall fractionating
tower or column made up of steel.
In continuous process, the crude oil is preheated to 350-
380 oC in specially designed tubular furnace known as
pipe still.

video
Fractional distillation of crude petroleum

Video
The hot vapours from the crude are passed through a tall
fractionating column, called bubble tower.
Bubble tower consists of horizontal trays provided with a no
of small chimneys, through which vapours rise.
These chimneys are covered with loose caps, known as
bubble caps. These bubble caps help to provide an intimate
contact between the escaping vapours and down coming
liquid.
The temperature in the fractionating tower decreases
gradually on moving upwards.
As the vapours of the crude oil go up, they become gradually
cooler and fractional condensation takes place at different
heights of column.
Atmospheric distillation Unit
Vacuum distillation Unit
The residue from the bottom of the fractionating tower
is vacuum distilled to recover various fractions

Vacuum distillation of residual oil

There is yet another type of fractional distillation
called Top-flashing.

Top Flashing
In top flashing, there is better control of product
composition, but requires more pumps and
instruments and hence is an expensive process.
 Cracking processes break down heavier
hydrocarbon molecules (high boiling point
oils) into lighter products such as petrol
and diesel.
 These processes include:
1. catalytic cracking
2. thermal cracking
3. hydrocracking
Cracking:
• Gasoline is the most important fraction of crude oil.
• The yield of this fraction is only 20% of the crude oil.
• The yield of heavier petroleum fraction is quite high.
Therefore, heavier fractions are converted into more
useful fraction.
This is achieved by a technique called cracking.
Cracking is the process by which heavier fractions are
converted into lighter fractions by the application of heat, with
or without catalyst. Cracking involves the rupture of C-C and
C-H bonds in the chains of high molecular weight
hydrocarbons.
 C H Cracking C H
 C H
10 22 5 12 5 10
Decane n - pentane pentene
B.Pt 174ο C B.Pt  36ο C

C H Cracking
  C H C H
8 18 5 12 3 6
Nearly 50% of today’s gasoline is obtained by cracking.
The gasoline obtained by cracking is far more superior
than straight run gasoline.
The process of cracking involves full chemical changes:
• Higher hydrocarbons are converted to lower hydrocarbons
by C-C cleavage. The product obtained on cracking have
low boiling points than initial reactant.
• Formation of branched chain hydrocarbons takes place
from straight chain alkanes.
• Unsaturated hydrocarbons are obtained from saturated
hydrocarbons.
• Cyclization may takes place.
Cracking can also be used for the production of olefins from
naphtha, oil gas from kerosene.
Cracking can be carried out by two methods:
Thermal Cracking: It takes place simply by the application of
heat and pressure.
The heavy oils are subjected to high temperature and pressure,
when the bigger hydrocarbons break down to give smaller
molecules of paraffins, olefins etc. The thermal stability among
the constituents of petroleum fractions increases as
Paraffins < naphthenes < aromatics
(a) Liquid Phase thermal cracking: The charge is kept in
the liquid form by applying high pressures of the range 30-100
kg/cm2 at a suitable temperature of 476-530 °C. The cracked
products are separated in a fractionating column.
The important fractions are: Cracked gasoline (30-35%),
Cracking gases (10-45%); Cracked fuel oil (50-55%).
(b) Vapor phase thermal cracking: By this method, only
those oils which vaporize at low temperatures can be cracked.
The petroleum fractions of low boiling range like kerosene oil,
are heated at a temp of 670-720 oC under low pressure.
Mechanism of thermal cracking: It follows free radical
mechanism.

Initiation
CH (CH ) CH Heat  H C
  CH (CH ) C  H (CH ) CH
3 27 3 3 23 2 2 22 3
Propagation
The free radical formed are thermally unstable and undergo
fission to yield a new radical and an olefin.

CH 3  CH 2CH 2  CH 2  C H 2  CH 3  CH 2  CH 2

Catalytic cracking: Cracking is carried out in the

presence of a catalyst at much lower temperatures and
pressures. The catalyst used is mainly a mixture of silica and
alumina. Most recent catalyst used is zeolite. The quality
and yield of gasoline is greatly improved by this method.
Visbreaking
Visbreaking is a mild thermal cracking
process utilized in the refinery to
reduce the viscosity and/or improve
the pour point of a heavy oil, mainly
residues, AR and VR both.
29
Hydrocracking is an operation in which
low-value gas oil with a high
percentage of polynuclear aromatics is
simultaneously cracked and
hydrogenated to produce low-boiling
and mid-boiling distillates which are of
high value.
Advantages of catalytic cracking over thermal
cracking:
• High temp and pressure are not required in the presence of a
catalyst.
• The use of catalyst not only accelerates the cracking
reactions but also introduces new reactions which
considerably modify the yield and the nature of the products.
• The yield of the gasoline is higher.
• No external fuel is required for cracking.
• The process can be better controlled so desired products can
be obtained.
• The product contains a very little amount of undesirable
sulphur because a major portion of it escapes out as H2S
gas, during cracking.
• It yields less coke, less gas and more liquid products.
• The evolution of by-product gas can be further minimized,
thereby increasing t he yield of desired product.
• Catalysts are selective in action and hence cracking of only
high boiling fractions takes place.
• Coke forming materials are absorbed by the catalysts as
soon as they are formed.

Hydrocracking video
Reforming
• It is a refinery process which is used to upgrade low
octane naphtha to high octane motor fuel.

• The hydrocarbons content of naptha are paraffins,

naphthenes and aromatics in C5 to C12 range. This
process involves the reconstruction of naphtha
constituent of hydrocarbon molecules without changing
the boiling range.

• Reforming is accomplished by processing the naphtha

feed at elevated temperature (450-5200C) and
moderate pressure (4-30 bar) in presence of hydrogen.

• Catalyst used is mainly platinum based. The chloride

treated alumina is used as support to improve acidic
sites of the catalyst.
• Reforming unit practiced in the refinery are of two
types
1. Semi regenerative type
2. Continuous type

Reaction chemistry of reforming:

• Dehydrogenation of naphthenes
• Isomerization of naphthenes and paraffins
• Dehydrocyclization of paraffins
• Hydrocracking of paraffins
Continuous Catalytic Regenaration Reforming
 Storage and handling of liquid fuels
• It is important to use only the original containers or safe, UL-approved
containers to store fuels. It is dangerous to store fuels in unapproved
containers because they can become damaged easily and leak or spill.

• Containers that are UL-approved are red for gasoline, blue for kerosene,
and yellow for diesel

• A container should be clearly labeled to identify its contents, and it also

should be fitted with a spout or some other device to allow pouring
without spilling

• Periodically check for leaks from storage containers and fuel-powered

devices, especially if they haven’t been used for some time.

• Small leaks can add up over time. Always recycle or safely dispose of fuel
containers and unused fuel.

• To avoid fuel vapors, which are a health hazard and a fire danger, keep
fuel containers and fuel-powered devices in a secure, well-ventilated
place
 Storage and handling of liquid fuels

• Storage in an unattached shed or garage is safer than storage in the

basement or in a garage attached to your home.

• Store containers off the floor and keep them out of the reach of children.
Make sure lids are on tight to prevent easy access.

Tank Location
• With both underground and aboveground storage tanks, location is very
important.

• Recommends a minimum distance of 150 feet between your fuel tank and
nearby wells, but the greater the distance, the better.

• Fuel tanks are safer when located downslope (downhill) from drinking water
sources and surface water.
 Leak protection
• With underground tanks, knowing the age of the tank is vital. Tanks more
than 15 years old have a dramatically higher chance of leaking.

• Corrosion protection helps keep steel tanks from leaking, but most older
tanks do not have this protection and are at high risk for leaks.

• New underground tanks should have a safeguard against corrosion, such as

an interior tank liner, a protective coating on the tank exterior, or cathodic
protection.

• Fiberglass tanks do not corrode but are vulnerable to other problems, such
as puncture by sharp objects.

• The pipes, hoses, valves, and fittings connected to a storage tank also can
be a major source of leaks, and age is again a factor.
 Leak detection

• Detecting leaks is more complicated with underground

storage tanks and is critical for underground tanks
more than 15 years old.

• Set up a regular schedule to inspect all tanks for leaks

and damage, including heating-oil tanks in your
basement. Some testing for leaks can be costly, but an
inexpensive way to check for leaks is to monitor the
fuel level over time.
 Avoiding spills

• Overfilling is the most common cause of spills.

• Automatic shutoff devices are available to prevent

spills, but they are not suitable for every tank. Spills
caused by overfilling basement tanks can be reduced
by installing a vent whistle or fill-level indicator.

• For aboveground storage tanks, boxlike containment

structures can prevent leaks and spills from
spreading.
 Protection of tanks
• Tanks can become damaged if they are not well
supported and protected from impact.

• Aboveground tanks should be placed on a solid, stable

base or on footings make of brick, cinder block, or
concrete.

• Do not store anything around, over, or under a heating

oil tank in your basement.

• Heavy objects can damage pipes, so all tanks located

in a garage or outdoors
 Knocking and Anti-knocking
In a spark-ignition petrol engine, a phenomenon that occurs when
unburned fuel-air mixture explodes in the combustion chamber
before being ignited by the spark. The resulting shock waves
produce a metallic knocking sound.
Loss of power occurs, which can be prevented by reducing the
compression ratio, re-designing the geometry of the combustion
chamber, or increasing the octane number of the petrol.(formerly by
the use of tetraethyl lead anti-knock additives, but now increasingly
by MTBE – methyl tertiary butyl ether in unleaded petrol).
An antiknock agent is a gasoline additive used to reduce engine
knocking and increase the fuel's octane rating.
The typical antiknock agents in use are:
Tetra-ethyl lead (phased out), Methyl cyclo pentadienyl manganese
tricarbonyl (MMT), Ferrocene, Iron pentacarbonyl, Toluene,
Isooctane
Octane rating of a spark ignition engine fuel is a
measure of the resistance to detonation or knocking
compared to a mixture of iso -octane (2,2,4-tri methyl
pentane, an isomer of octane) and n- heptane. It is a
numerical representation of the antiknock properties of
motor fuel, compared with a standard reference fuel,
such as isooctane, which has an octane number of 100.
Octane rating does not relate to the energy content of
the fuel .It is only a measure of the fuel's tendency to
burn in a controlled manner, rather than exploding in an
uncontrolled manner.
Octane number: is defined as the percentage of iso octane
present in a mixture of iso-octane and n-heptane, which has the
same knocking characteristics as that of fuel under
examination, under same set of conditions.
Thus a gasoline with an octane no of 80, would give the same
knocking as a mixture of iso octane and n-heptane containing
80% of iso octane by volume. Greater the octane number,
greater is the antiknock property of the fuel.
Cetane Rating: Fuels required for diesel engine are in contrast
to petrol engine fuels, hence a separate scale is used to grade
the diesel oils as they cannot be graded on octane number
scale.
The cetane number of a diesel oil is defined as the percentage
of cetane in a mixture of cetane and a-methyl naphthalene
which will have the same ignition characteristics as the fuel
under test, under same set of conditions.
Cetane is n-hexadecane
The cetane rating of a fuel depend upon the nature and
composition of hydrocarbon. The straight chain hydrocarbons
ignite quite readily while aromatics do not ignite easily. Ignition
quality order among the constituents of diesel engine fuels in
order of decreasing cetane no, is as follows:
n-alkanes> naphthenes > alkenes > branched alkanes >
aromatics
This is an approximate measure of the aromatic content of
a hydrocarbon fuel.
It is defined as the lowest temperature at which a fuel oil is
completely miscible with an equal volume of aniline.
Aniline is an aromatic compound and aromatics are more
miscible in aniline than are paraffins.
Hence, the lower the aniline point, the higher the
aromatics content in the fuel oil.
The higher the aromatics content, the lower the cetane
number of the fuel.
The aniline point can thus be used to indicate the
probable ignition behavior of a diesel fuel.
 The Diesel Index indicates the ignition quality of the
fuel. It is found to correlate, approximately, to the
cetane number of commercial fuels. It is obtained
by the following equation

Diesel Index 
  
aniline po int o F x Degrees API gravity 60 o F 
100
In API (American Petroleum Institute) scale, water
at 600F has a 0API Of 10.
Diesel Index and cetane number are usually about
50. Lower values will result in smoky exhaust
XGXKX-T6FQT