www.iitk.ac.

in/erl

Lecture 3

Analysis of Fossil-Fuels, and

Petroleum Refining Processes

Course Instructor
Dr. Avinash Kumar Agarwal
Professor
Department of Mechanical Engineering
IIT Kanpur Indian Institute of Technology Kanpur, Kanpur
 Introduction

Lecture-3 2 Alternate Fuels and Advances in I.C. Engines

 History of Crude Oil
3000 BC Sumerians use asphalt as an adhesive; Egyptians use pitch to grease chariot wheels;
Mesopotamians use bitumen to seal boats
600 BC Confucius writes about drilling a 100 feet gas well and using bamboo for pipes
1500 AD Chinese dig oil wells >2000 feet deep
1847 First “rock oil” refinery in England
1849 Canada distills kerosene from crude oil
1856 World’s first refinery in Romania
1857 Flat-wick kerosene lamp invented
1859 Pennsylvania oil boom begins with 69 feet oil well producing 35 bpd
1860-61 Refineries built in Pennsylvania and Arkansas
1870 US Largest oil exporter; oil was US 2nd biggest export
1878 Thomas Edison invents light bulb
1901 Spindle top, Texas producing 100,000 bpd kicks off modern era of oil refining
1908 Model T’s sell for $950/T
1913 Gulf Oil opens first drive-in filling station
1942 First Fluidized Catalytic Cracker (FCC) commercialized
1970 First Earth Day; EPA passes Clean Air Act
2005 US Refining capacity is 17,042,000 bpd, 23% of World’s capacity
Lecture-3 3 Alternate Fuels and Advances in I.C. Engines
 Crude Oil: Formation and Exploration
Formation– Dead marine animals and plant matter accumulated over
millions of years, transformed into oil in sedimentary rocks due to heat
and pressure.
Deposits found beneath the crust, have a water body below and
pressurized natural gas above.

Thick and dense rock layer seals off the deposit, ensuring no leakage.

Conventional
Petroleum Drilling
Drilling through the rock layer causes pressure release, pushing oil and Advanced Petroleum
gas to surface. When pressure is attenuated, oil can be pumped up. Drilling
Lecture-3 4 Alternate Fuels and Advances in I.C. Engines
 Sources of Petroleum and Drilling Arrangement

Lecture-3 5 Alternate Fuels and Advances in I.C. Engines

 Crude Oil
Modern technological society relies heavily on fossil fuels (crude oil) as an important source of
energy
Crude oil (known as black gold) is a thick, dark brown or greenish flammable liquid, which
is found in the upper strata of some regions of the Earth's crust.
It is a complex mixture of various hydrocarbons along with traces of other chemicals and
compounds.

Lecture-3 6 Alternate Fuels and Advances in I.C. Engines

 Crude Oil Products

Petroleum products are produced from the

processing of crude oil at petroleum refineries
and the extraction of liquid hydrocarbons at
natural gas processing plants.
Petroleum is a broad category that includes
both crude oil and other petroleum products.
The main goal of petroleum refining is to take
the undesirable components of the crude oil
and convert them into more valuable products.
Petroleum refining: Greater output than the
input because of changes in the overall density
of refined products w.r.t. that of the input oils.
Gasoline, diesel, and jet fuel are among the
most valuable products, whereas fuel oils and
lubricants are sometimes sold at a loss.
Petroleum Products and their use

Lecture-3 7 Alternate Fuels and Advances in I.C. Engines

 Petroleum based liquid fuels
Crude petroleum is a mixture of large number of hydrocarbon compounds differing widely in:-
Molecular structure
Sulphur, oxygen, nitrogen content
Impurities

For purpose of comparison, it is convenient to arrange these hydrocarbon compounds into

families based on the hydrogen and carbon arrangement within the molecules.
Primary hydrocarbons families in petroleum
Molecular
Family General Formula
Arrangement
Paraffins CnH2n+2 Chain
Olefins CnH2n Chain
Diolefins CnH2n-2 Chain
Napthalene CnH2n Ring
Aromatics CnH2n-6 Ring

Lecture-3 8 Alternate Fuels and Advances in I.C. Engines

 Petroleum based liquid fuels
Paraffins consist of hydrocarbons with straight chain (open chain) molecular structure.
Straight chain paraffins are termed as saturated compounds and are characteristically very
stable.

Another variation of the paraffin family consists of an open chain structure with an attached
branch, and is usually termed branch chain paraffins. Example - Isobutane.
The branch chain paraffins have good antiknock qualities when used as SI engine fuels.
Olefins are chain compounds similar to paraffins, but are unsaturated because they contain
one double carbon-to-carbon bond. Example – Butene.

Olefins are not as stable as the single bond paraffins due to presence of a reactive double bond.
Crude oil does not contain olefins and these result from certain refinery processes.

Lecture-3 9 Alternate Fuels and Advances in I.C. Engines

 Petroleum based liquid fuels
Diolefins are olefins with two double bonds. They are unsaturated and rather unstable.
Example – Butadiene.

Butadiene

Naphthenes have same general formula as olefins but have ring structure. Example –
Cyclopentane.

Cyclopentane

Aromatics are ring structure compounds based on the benzene ring. A double bond indicates
unsaturation. Example – Benzene.

Benzene

Lecture-3 10 Alternate Fuels and Advances in I.C. Engines

 Characteristics of Hydrocarbon families in Petroleum
The anti-knock quality of a fuel when used in a SI engine appears to be poorest in the normal
paraffins and improves generally in the order:
Paraffins, Olefins, Diolefins, Naphthenes, Aromatics

The suitability of these fuels for CI engine is in the inverse order of their suitability for SI
engine.
For CI engine, normal paraffins are better fuels and aromatics are the least desirable.

In general, as number of atoms in molecular structure increases, the boiling point temperature
rises.
Fewer the number of atoms in molecule, more volatile the compound tends to be.

As proportion of H-atoms to C-atoms in a molecule increases, heating value generally increases.

Paraffins have the greatest heating value and aromatic the least.

Lecture-3 11 Alternate Fuels and Advances in I.C. Engines

 Fractional Distillation

Lecture-3 12 Alternate Fuels and Advances in I.C. Engines

 Petroleum Refining
Crude petroleum is rarely used as fuel for internal combustion engines.
Petroleum is purified and separated into different usable components before various
applications.
Refining- Process of separating petroleum into useful fractions & removal of undesirable
impurities.
Although modern refinery is a complex chemical processing plant, it’s based on a simple
principle: The constituents of crude petroleum have boiling points varying roughly with their
molecular weights
Steps in Petroleum Refining
Before the crude oil is subjected to refining, it is passed under high pressure into cylindrical
tanks to remove gas, oil and sand particles.
It is then washed with acid and alkali solutions one after the other to remove basic and acidic
impurities respectively.
It then undergoes the refining process through the process of fractional distillation.
This process works on the variation of boiling points of different components of crude oil.

Lecture-3 13 Alternate Fuels and Advances in I.C. Engines

 Petroleum Refining

Lecture-3 14 Alternate Fuels and Advances in I.C. Engines

 Petroleum Refining
Fractional distillation
Fractional distillation utilizes a fractionating tower, through which the vaporized petroleum is passed.
Components having higher boiling points separate out at lower levels & those with lower boiling.
points are removed at higher levels. The condensed fractions in each tray are tapped off continuously.
Each of these fractions covers a certain boiling point range, and each may be further refined by another
separate fractionating within a narrow range of boiling points.
The various fractions obtained by the fractional distillation of crude petroleum oil are:
Asphalt, lubricating oil, paraffin wax, fuel oil, diesel, kerosene, petrol & petroleum gas
Except for asphalt, lubricating oil and paraffin wax, all other fractions readily burn producing heat.
The yield of some of the petroleum products from the fractional distillation process does not always
coincide with the commercial demand for such products. Economic necessity usually dictates need for
conversion of some of the products in small demand into products for which demand is greater.
To respond to such necessities, various processes are used to convert some of these fractions to more
valuable compounds.

Lecture-3 15 Alternate Fuels and Advances in I.C. Engines

 Oil Refinery

Lecture-3 16 Alternate Fuels and Advances in I.C. Engines

 Crude Oil Refining Stages
Detailed crude oil refining can be divided into following three categories:
1. Separation Units
2.Finishing Units
3.Conversion Units

Lecture-3 17 Alternate Fuels and Advances in I.C. Engines

 Oil Refinery
A refinery is a complex chemical processing plant that utilizes different techniques to take a very rough
feedstock, crude oil, and converts it into desirable products, such as gasoline, diesel etc.
The first large oil refinery was built in Romania in 1856 using the abundant oil available in Romania.
Oil firms invest huge capitals into these refineries in hopes of making large profits. The largest oil
refinery is Reliance Jamnagar Refinery (Gujarat, India) which processes 1.24M barrels of oil per day.
In fact, most of the oil industry’s largest refineries are in Asia and South America.
A total of 636 refineries operated on the 31st December 2014 for a total capacity of 87.75M barrels.

Lecture-3 18 Alternate Fuels and Advances in I.C. Engines

 Petroleum Refining Process
A petroleum refinery is a chemical plant that processes crude oil and produces several valuable
products. A refinery contains different types of units that perform a variety of different operations.
The main goal is to take the undesirable components of the crude oil and upgrade them into more
valuable products.

At the top of the At the bottom of the

distillation column distillation column

Short carbon chains Long carbon chains

Light molecules Heavy molecules

Low boiling points High boiling points

Gases & very runny Thick, viscous liquids

liquids

Very volatile Low volatility

Light colour Dark colour

Highly flammable Not very flammable

Lecture-3 19 Alternate Fuels and Advances in I.C. Engines

 Processes used in Oil Refineries
Cracking consists of breaking down large and complex molecules into lighter and simpler
compounds with lower boiling points. These are of two types:

Thermal cracking subjects the heavy hydrocarbons to high temperatures and pressures.

Catalytic cracking is accomplished at somewhat lower temperatures and pressures, but in

the presence of a catalyst and generally produces a fuel with higher anti-knock qualities.

Hydrogenation involves addition of hydrogen atoms to certain hydrocarbons, under high

pressure and temperature, to produce more stable and desirable compounds.

Polymerization brings together light, unsaturated gases of one family, in the presence of a
catalyst, to produce a liquid.

Alkylation combines light gases of different families in the presence of a catalyst. Generally an
olefin is combined with paraffin in this process to give branch chain paraffins.

Lecture-3 20 Alternate Fuels and Advances in I.C. Engines

 Processes used in Oil Refineries
Isomerization changes the relative position of the atoms within the molecules of a hydrocar-
bon without changing its molecular formula. It produces isomers of the original hydrocarbon.

Cyclization essentially joins together the ends of straight chain molecules to form a ring
compound of the naphthene family.

Aromatization is a process similar to cyclization except that the product is an aromatic

compound.

Reforming is a type of cracking process in which naphtha or straight gasoline is converted into
gasoline of higher octane rating.

Blending is a process of mixing refinery products to obtain a commercial product of desired

quality.

Lecture-3 21 Alternate Fuels and Advances in I.C. Engines

 Refined Petroleum Products
Products refined from the liquid fractions of crude oil can be placed into ten main categories.
These main products are further refined to create materials more valuable in everyday life.
The ten main products of petroleum are:
1. Asphalt
2. Diesel
3. Fuel Oil
4. Gasoline
5. Kerosene
6. Liquefied Petroleum Gas (LPG)
7. Lubricating Oil
8. Paraffin Wax
9. Bitumen
10. Petrochemicals

In all above mentioned products, gasoline and diesel are the major constituent. Both of them
are mainly used for automotive applications.
Jet fuel is the other major faction used for used for aviation application.
Lecture-3 22 Alternate Fuels and Advances in I.C. Engines
 Refinery Products

Lecture-3 23 Alternate Fuels and Advances in I.C. Engines

 Refined Petroleum Products
Asphalt
It is a colloid of asphaltenes and maltenes that is extracted from crude oil by fractional distillation.
Asphalt is usually stored and transported at around 140o C and commonly used to make roads.
Diesel
Diesel is any fuel that can be used in a compression ignition engine.
Diesel is produced by fractional distillation between 200 and 350oC.
Diesel has a higher density than gasoline and is simpler to refine from crude oil.
It is most commonly used in transportation.
Fuel Oil
Fuel oil is any liquid petroleum product that is burned in a furnace to generate heat.
Fuel oil is also the heaviest commercial fuel that is produced from crude oil.
The six classes of fuel oil are:
Distillate fuel oil, Diesel fuel oil, Light fuel oil, Gasoil, Residual fuel oil, Heavy fuel oil
Residual fuel oil and heavy fuel oil are commonly known as navy special fuel oil and bunker fuel; both
of these are also often called furnace fuel oil.

Lecture-3 24 Alternate Fuels and Advances in I.C. Engines

 Refined Petroleum Products
Gasoline
Almost half of all crude oil refined, is made into gasoline. It is used as fuel in SI engines.
Gasoline is a mixture of paraffins, naphthenes, and olefins, although the specific ratios of these parts
depend on the refinery where the crude oil is processed.
Gasoline is known as petrol, petroleum spirit, gas, petro-gasoline, and mo-gas around the globe.
Kerosene
Kerosene is collected through fractional distillation at temperatures between 140o C and 270o C.
It is a combustible liquid that is thin and clear; most commonly used as a jet fuel and as heating fuel.
Kerosene is used as fuel in portable stoves, kerosene space heaters, and in liquid pesticides.
Liquefied Petroleum Gas (LPG)
LPG is a mixture of gases that is used in heating appliances, aerosol propellants, and refrigerants.
Different gases present in the liquefied petroleum gas are: propane and butane.
At normal atmospheric pressure, it evaporates, so it needs to be stored in pressurized steel bottles.
Lubricating Oil
Lubricating oils consist of base oils and additives.
Different lubricating oils are classified as paraffinic, naphthenic, or aromatic.
The most common lubricating oil is motor oil, which protects moving parts inside an IC engine.

Lecture-3 25 Alternate Fuels and Advances in I.C. Engines

 Refined Petroleum Products
Paraffin Wax
Paraffin wax is a white, odorless, tasteless, waxy solid at room temperature.
The melting point of paraffin wax is between 117°F and 147°F, depending on various factors.
It is an excellent electrical insulator, second only to Teflon, a specialized product of petroleum.
Paraffin wax is used in drywall to insulate buildings.
Bitumen
Bitumen, commonly known as tar, is a thick, black, sticky material.
Refined bitumen is the bottom fraction obtained by the fractional distillation of crude oil.
Bitumen is used in paving roads and waterproofing roofs and boats.
Bitumen is also made into thin plates & used to soundproof dishwashers & hard drives in computers.
Petrochemicals
Petrochemicals are the chemical products made from the raw materials of petroleum.
These chemicals include:
ethylene, used to make anesthetics, antifreeze, and detergents
propylene, used to produce acetone and phenol
benzene, used to make other chemicals and explosives
toluene, used as a solvent and in refined gasoline
xylene is used as a solvent and cleaning agent

Lecture-3 26 Alternate Fuels and Advances in I.C. Engines

 Refined Petroleum Products

Number of Boiling Point

Name Uses
Carbon Atoms (°C)

Refinery Gas 3 or 4 below 30 Bottled gas (propane or butane).

Gasoline 7 to 9 100 to 150 Fuel for car engines.

Naphtha 6 to 11 70 to 200 Solvents and used in gasoline.

Kerosene (paraffin) 11 to 18 200 to 300 Fuel for aircraft and stoves.

Diesel Oil 11 to 18 200 to 300 Fuel for road vehicles and trains.

Lubricating Oil 18 to 25 300 to 400 Lubricant for engines and machines.

Fuel Oil 20 to 27 350 to 450 Fuel for ships and heating.

Greases and Wax 25 to 30 400 to 500 Lubricants and candles.

Bitumen above 35 above 500 Road surface and roofing.

Lecture-3 27 Alternate Fuels and Advances in I.C. Engines

Lecture-3 28 Alternate Fuels and Advances in I.C. Engines