 Petroleum: its chemical composition and fractional

distillation;
 Cracking of heavy oil residues – thermal and catalytic
cracking; Knocking and chemical structure, octane
number;
 Synthesis and applications of bio-fuels, Photovoltaic cell

2
 Petroleum

Petroleum is a naturally occurring complex mixture made up

predominantly of organic carbon and hydrogen compounds.
It contains significant amounts of nitrogen, sulfur and oxygen
together with smaller quantities of nickel, vanadium and other
elements. It occurs in the sedimentary rocks in the form of gases
(natural gas), liquids (crude oil), semisolids (bitumen), or solids
(wax or asphaltite).

An underground reservoir that contains hydrocarbons is called

petroleum reservoir and its hydrocarbon contents that can be
recovered through a producing well is called reservoir fluid.

3
 Petroleum Components
Paraffins

Generally, hydrocarbons in petroleum are divided into four groups:

paraffins, olefins, naphthenes and aromatics.
Paraffins are also called alkanes and have the general formula of
CnH2n+2, where n is the number of carbon atoms.
Paraffins from C1 to C40 usually appear in crude oil and represent up to
20% of crude by volume.
Since paraffins are fully saturated (no double bond), they are stable
and remain unchanged over long periods of geological time.

4
 Petroleum Components
Olefins

Olefins are another series of noncyclic hydrocarbons but they are

unsaturated and have at least one double bond between carbon-carbon
atoms. Compounds with one double bond are called monoolefins or
alkenes. Monoolefins have a general formula of CnH2n.

Olefins are uncommon in crude oils due to their reactivity with hydrogen
that makes them saturated; however, they can be produced in refineries
through cracking reactions.

5
 Petroleum Components
Aromatics
Aromatics are an important series of hydrocarbons found in almost
every petroleum mixture.

Aromatics are cyclic but unsaturated hydrocarbons that begin with

benzene molecule (C6H6) and contain carbon-carbon double bonds.

Some of the common aromatics found in petroleum and crude oils are
benzene and its derivatives with attached methyl, ethyl, propyl, or
higher alkyl groups. This series of aromatics is called alkylbenzenes
and have a general formula of CnH2n-6 (where n ≥ 6).

6
 Petroleum Components
Naphthenes

Naphthenes or cycloalkanes are ring or cyclic saturated hydrocarbons with

the general formula of CnH2n. Cyclopentane (C5H10), cyclohexane (C6H12),
and their derivatives such as n-alkylcyclopentanes are normally found in
crude oils.
Thermodynamic studies show that naphthene rings with five and six carbon
atoms are the most stable naphthenic hydrocarbons. The content of
cycloparaffins in petroleum may vary up to 60%.

7
 Petroleum Components
Sulfur

Sulfur is the most important heteroatom in petroleum and it can be found

in cyclic as well as noncyclic compounds such as mercaptanes (R-S-H)
and sulfides (R-S-R’), where R and R’ are alkyl groups.

Sulfur in natural gas is usually found in the form of hydrogen sulfide

(H2S). Some natural gas contain H2S as high as 30% by volume. The
amount of sulfur in a crude may vary from 0.05 to 6% by weight.

8
 Fractional distillation

Fractional distillation is the process by which oil refineries

separate crude oil into different, more useful hydrocarbon products based
on their relative molecular weights in a distillation tower.
This is the first step in the processing of crude oil, and it is considered to
be the main separation process as it performs the initial rough separation
of the different fuels.
The different components that are separated out during this process are
known as fractions.
Fractions that are separated out include gasoline, diesel, kerosene,
and bitumen.
Fractional distillation allows a lot of useful products to be made from
crude oil, with many environmental consequences for the use of those
useful products!
9
 Fractional distillation

BOILING RANGE # CARBON ATOMS

• Refinery Gas <25 oC 3
• Gasoline 40-150 oC 4-10
• Naptha 150-200 oC 10-12
• Kerosene 200-300 oC 12-16
• Diesel Fuel 300-400 oC 16-25
• Residual Oil >400 oC >25

10
 Fractional distillation Process

 First, the crude oil is heated to vapourize it and is fed into the
bottom of a distillation tower.
 The resulting vapour then rises through the vertical column.
 As the gases rise through the tower, the temperature decreases.
 As the temperature decreases, certain hydrocarbons begin to
condense and run off at different levels.
 Each fraction that condenses off at a certain level contains
hydrocarbon molecules with a similar number of carbon atoms.
 These boiling point 'cuts' allow several hydrocarbons to be
separated out in a single process.
 It is this cooling with the height of the tower that allows for the
separation.

11
Fractional distillation Tower

12
 Petroleum: its chemical composition and fractional
distillation;
 Cracking of heavy oil residues – thermal and
catalytic cracking; Knocking and chemical structure,
octane number;
 Synthesis and applications of bio-fuels, Photovoltaic cell

2
 Petroleum Cracking

Crude oil often contains too many large hydrocarbon molecules and not
enough small hydrocarbon molecules.
There is more demand for shorter alkane molecules and alkenes than for
many of the longer chains formed during fractional distillation.
Cracking allows large hydrocarbon molecules to be broken down into
smaller, more useful hydrocarbon molecules.
Fractions containing large hydrocarbon molecules are heated to vaporise
them.
Cracking produces a mixture of smaller alkanes and alkenes.
This helps to meet the demand for the more useful fractions and to
increase profit.

3
 Petroleum Cracking
Cracking, in petroleum refining, the process by which
heavy hydrocarbon molecules are broken up into lighter molecules
by means of heat and usually pressure and sometimes catalysts.
Cracking is the most important process for the commercial
production of gasoline and diesel fuel.

4
 Petroleum Cracking

Cracking involves the breaking of C-C bonds in alkanes

It converts heavy fractions into higher value products

THERMAL
Proceeds via a free radical mechanism

CATALYTIC
Proceeds via a carbocation (carbonium ion) mechanism

5
 THERMAL CRACKING

 High Pressure ... 7000 kPa

 High Temperature ... 400°C to 900°C
 Free Radical Mechanism
 Homolytic fission
 Produces mostly alkenes ...e.g. ethene for making polymers
and ethanol
 Produces Hydrogen ... used in margarine manufacture
 Bonds can be broken anywhere in the molecule by C-C bond
fission or C-H bond fission

6
THERMAL CRACKING

7
 CATALYTIC CRACKING

 Slight pressure
 High Temperature
 Use catalyst to speed up the cracking reaction.
 Catalysts include zeolite, aluminium hydrosilicate,
bauxite and silica alumina.
 Carbocation Mechanism
 Heterolytic fission
 Produces branched and cyclic alkanes, aromatic
hydrocarbons used for motor fuels

8
 CATALYTIC CRACKING

Catalytic cracking is similar to thermal cracking except that catalysts

facilitate the conversion of the heavier molecules into lighter products.
Use of a catalyst (a material that assists a chemical reaction but does
not take part in it) in the cracking reaction increases the yield of
improved-quality products under much less severe operating conditions
than in thermal cracking.
Typical temperatures are from 450-510 °C at much lower pressures of
10-20 psi.
The catalysts used in refinery cracking units are typically solid materials
(zeolite, aluminum hydrosilicate, treated bentonite clay, fuller's earth,
bauxite, and silica-alumina) that come in the form of powders, beads,
pellets or shaped materials called extrudates.

9
 STEPS IN CATALYTIC CRACKING

There are three basic steps in the catalytic cracking process:

I. Reaction: Feedstock reacts with catalyst and cracks into different
hydrocarbons;
II. Regeneration: Catalyst is reactivated by burning off coke;
III. Fractionation: Cracked hydrocarbon stream is separated into various
products.

10
11
 Knocking

 Knocking, in an internal-combustion engine, sharp

sounds caused by premature combustion of part of the
compressed air-fuel mixture in the cylinder.

 Reason
 In certain circumstances, the rate of oxidation becomes so
great that the last portion of the fuel-air mixture gets ignited
instantaneously, producing an explosive violence, known as
“knocking”.

 Knocking is also known as “Pinking” or “Pinging”.

 Knocking results in loss of efficiency

12
The main causes of knocking are:

 Poor quality of fuel (nature and composition)

 Poor conditions of engine such as:

 Poor design of engine
 Poor mechanical condition of engine

 Poor operational manners of engine such as:

 Incorrect combustion process
 Improper cooling of engine
 Improper exhaust gas re-circulation

13
Knocking can be prevented by –

 Using good quality fuel with higher octane rating

 Adding anti-knocking agents
 Increasing the amount of fuel injected or lowering the air to fuel ratio
 Reducing the cylinder pressure
 Improving the combustion chamber design
 Correct ignition timings are necessary for better engine
performance and fuel efficiency.
 Now-a-days, modern automotives have sensors that can detect
knock and retard ignition (spark plug firing) to reduce knocking and
protect the engine

14
 Chemical structure, octane number

in 1933 by the general use of a single-cylinder test engine,

which allowed comparisons of the antiknock characteristics of
gasoline to be made in terms of octane numbers.
The octane numbers formed a scale ranging from 0 to 100: the
higher the number, the greater the antiknock characteristics.

Quality of gasoline – Octane number

Quality of diesel – Cetane number

15
 Octane number
Two different types of Octane numbers are obtained in two different test
procedures;
Motor octane numbers or MON (indicative of high speed performance).
The motor octane number (MON) describes the behavior of the fuel in
the engine at high temperatures and speeds – a full-throttle range,
comparable to driving fast on a highway
Research octane numbers or RON (indicative of normal road
performance)
The research octane number (RON) describes the behavior of the fuel in
the engine at lower temperatures and speeds

Anti-Knock Index (AKI) = (RON+MON)/2

16
What affects the number of octane?

 Octane number decreases with an increase in the carbon chain

length
 Normal paraffins have low octane numbers and these become
lower as the molecular weight increases.
 Octane number increases with carbon chain branching.
 Iso-paraffins have higher octane numbers than the
corresponding normal paraffins

17
In the test methods used to determine the antiknock properties of
gasoline, comparisons are made with blends of two pure hydrocarbons,
n- heptane and iso-octane (2,2,4-trimethyl- pentane).
Iso-octane has an octane number of 100 and is high in its resistance
to knocking ; n- heptane is quite low (with an octane number of 0) in
its resistance to knocking.

18
How octane number of a fuel can be increased ?
1. By putting special additives into the fuel which discourage
auto ignition.
2. By blending high-octane fuels in with the ordinary petrol.

19
 Anti-knocking additives

Anti-knocking additives are substances which reduce the tendency

of a fuel to auto-ignite, and so increase the octane number.
Small amounts of lead compounds have been used as economical
and effective anti-knock additives. E.g., Tetraethyl lead (TEL)
But it damage the environment.

Tetraethyl lead (TEL)

[Link] 20
 Cetane number
Cetane number: Indicates the cold starting ability of diesel fuel
Most automakers recommend a cetane rating of about 45 High
cetane rating means the fuel will ignite easily from heat and
pressure and burn quickly

21
 Petroleum: its chemical composition and fractional
distillation;
 Cracking of heavy oil residues – thermal and catalytic
cracking; Knocking and chemical structure, octane
number;
 Synthesis and applications of bio-fuels, Photovoltaic
cell

2
 Bio-fuels

• Biofuel: Any fuel that is derived from biomass—that is,

plant or algae material or animal waste. Since such
feedstock material can be replenished readily.
• A biofuel is a renewable energy source, unlike other
natural resources such as petroleum, coal, and nuclear
fuels.

3
 Bio-fuels
Like coal and petroleum, biomass is a form of stored solar
energy. The energy of the sun is "captured" through the
process of photosynthesis in growing plants.

One of the major advantages of biofuel over most other fuel

types is that it is biodegradable, and so relatively harmless to
the environment if spilled.

4
Classification of Bio-fuels

5
 Bioalcohol/Bioethanol

• Bioethanol is ethanol fuel (ethyl alcohol) made from plant matter (as
with most ethanol).
• Currently most of it is made from corn, but cheaper organic material
such as grass and various plant waste can also be used as source.
• It can be used as a fuel similar to gasoline, but is commonly used as
a gasoline additive to minimize emissions.
• It can also be used as a total gasoline replacement to power our cars
with only minor modifications to a standard gasoline engine.

6
 Bioalcohol/Bioethanol
Bioethanol production includes three processes (1) pretreatment to
separate hemicellulose and lignin from cellulose (2) hydrolysis of
cellulose to obtain fermentable sugars and (3) fermentation to
convert sugars into ethanol, followed by distillation to separate and
purify the ethanol

7
 Bio-diesel
• Bio-diesel is a form of diesel fuel manufactured from vegetable oils, animal
fats, or recycled restaurant greases. It is safe, biodegradable, and produces
less air pollutants than petroleum-based diesel.
• Bio-diesel is meant to be used in standard diesel engines and is thus distinct
from the vegetable and waste oils used to fuel converted diesel engines. Bio-
diesel can be used alone, or blended with petro diesel.
• Bio-diesel can also be used as a low carbon alternative to heating oil.

Almost all biodiesel is produced from vegetable oils using the base-catalyzed
transesterification technique

8
Bio-diesel Preparation

9
 Bio-gas
Biogas is the mixture of gases produced by the breakdown of organic
matter in the absence of oxygen, primarily consisting of methane and
carbon dioxide. Biogas can be produced from raw materials such as
agricultural waste, manure, municipal waste, plant material, sewage, green
waste or food waste.

10
 Photovoltaic cell/Solar cell

Solar Photovoltaic (PV) cells generate electricity by absorbing

sunlight and using that light energy to create an electrical current.
There are many PV cells within a single solar panel, and the
current created by all of the cells together adds up to enough
electricity to help power home and offices.

[Link] 11
 Construction/Working Principle
Solar cells are composed of two different types of semiconductors—a p-type
and an n-type joined together to create a p-n junction.
• By joining these two types of
semiconductors, an electric field is
formed in the region of the junction
as electrons move to the positive p-
side and holes move to the negative n-
side.
• This field causes negatively charged
particles to move in one direction and
positively charged particles in the other
direction.
• When light of a suitable wavelength is
incident on these cells, energy from
the photon is transferred to an electron
of the semiconducting material,
causing it to jump to a higher energy
state known as the conduction band. The photovoltaic effect is a process that
these electrons are free to move generates voltage or electric current in
through the material and create an
electric current in the cell.
a photovoltaic cell when it is exposed
to sunlight. 12
Construction/Working Principle

13
Photovoltaic cell Uses

14