Petroleum is a naturally occurring, yellow-to-black liquid found in geological

formations beneath the Earth’s surface, which is commonly refined into various
types of fuels.

Figure: Oil and Gas found in sedimentary rock formation in the Earth’s
crust

Petroleumor crude oil was formed when large quantities of dead organisms,
usually zooplankton and algae, were buried underneath sedimentary rock and
subjected to intense heat and pressure, for a long time.

Petroleum and natural gas deposits are recovered mostly through drilling and
stored.Crude oil is refined and separated, most easily by distillation, into a large
number of consumer products, from gasoline (petrol) and kerosene to asphalt and
chemical reagents used to make plastics and pharmaceuticals. Petroleum is used in
manufacturing a wide variety of materials, and it is estimated that the world
consumes about 90 million barrels each day.

COMPOSITION

In its strictest sense, petroleum includes only crude oil, but in common usage it
includes all liquid, gaseous, and solid hydrocarbons. Under surface pressure and
temperature conditions, lighter hydrocarbons methane, ethane, propane and butane
occur as gases, while pentane and heavier ones are in the form of liquids or solids.
However, in an underground oil reservoir the proportions of gas, liquid, and solid
depend on subsurface conditions and on the phase diagram of the petroleum
mixture.

The proportion of light hydrocarbons in the petroleum mixture varies greatly among
different oil fields, ranging from as much as 97 percent by weight in the lighter oils
to as little as 50 percent in the heavier oils and bitumens.
 The hydrocarbons in crude oil are mostly alkanes, cycloalkanes and various aromatic
hydrocarbons while the other organic compounds contain nitrogen, oxygen and
sulfur, and trace amounts of metals such as iron, nickel, copper and vanadium. Many
oil reservoirs contain live bacteria. The exact molecular composition varies widely
from formation to formation but the proportion of chemical elements vary over fairly
narrow limits as follows:

Composition by weight

Element Percent range

Carbon 83 to 85%

Hydrogen 10 to 14%

Nitrogen 0.1 to 2%

Oxygen 0.05 to 1.5%

Sulfur 0.05 to 6.0%

Metals < 0.1%

Four different types of hydrocarbon molecules appear in crude oil. The relative
percentage of each varies from oil to oil, determining the properties of each oil.

Composition by weight

Hydrocarbon Average Range

Alkanes (paraffins) 30% 15 to 60%

Naphthenes 49% 30 to 60%

Aromatics 15% 3 to 30%

Asphaltics 6% remainder

PETROLEUM OIL FORMATION

 Petroleum is a fossil fuel derived from ancient fossilized organic materials, such as
zooplankton and algae. Vast quantities of these remains settled to sea or lake
bottoms, mixing with sediments and being buried under anoxic conditions. As further
layers settled to the sea or lake bed, intense heat and pressure build up in the lower
regions. This process caused the organic matter to change, first into a waxy material
known as kerogen, which is found in various oil shales around the world, and then
with more heat into liquid and gaseous hydrocarbons via a process known as
catagenesis. Formation of petroleum occurs from hydrocarbon pyrolysis in a variety
of mainly endothermic reactions at high temperature and/or pressure.

Crude Oil Reservoirs

Three conditions must be present for oil reservoirs to form: a source rock rich in
hydrocarbon material buried deep enough for subterranean heat to cook it into oil, a
porous and permeable reservoir rock for it to accumulate in, and a cap rock (seal) or
other mechanism that prevents it from escaping to the surface. Within these
reservoirs, fluids will typically organize themselves like a three-layer cake with a
layer of water below the oil layer and a layer of gas above it, although the different
layers vary in size between reservoirs. Because most hydrocarbons are less dense
than rock or water, they often migrate upward through adjacent rock layers until
either reaching the surface or becoming trapped within porous rocks (known as
reservoirs) by impermeable rocks above.

Refining crude oil

 How crude oil is refined into petroleum products
Petroleum refineries change crude oil into petroleum products for use as fuels for
transportation, heating, paving roads, and generating electricity and
as feedstocks for making chemicals.

Refining breaks crude oil down into its various components, which are then
selectively reconfigured into new products. Petroleum refineries are complex and
expensive industrial facilities. All refineries have three basic steps:
 Separation
 Conversion
 Treatment

Separation
Modern separation involves piping crude oil through hot furnaces. The resulting
liquids and vapours are discharged into distillation units. All refineries have
atmospheric distillation units, while more complex refineries may have vacuum
distillation units.
Inside the distillation units, the liquids and vapors separate into petroleum
components called fractions according to their boiling points. Heavy fractions are on
the bottom and light fractions are on the top.

The lightest fractions, including gasoline and liquefied refinery gases, vaporize and
rise to the top of the distillation tower, where they condense back to liquids.

Medium weight liquids, including kerosene and distillates, stay in the middle of the
distillation tower.

Heavier liquids, called gas oils, separate lower down in the distillation tower, while
the heaviest fractions with the highest boiling points settle at the bottom of the
tower.

Conversion
After distillation, heavy, lower-value distillation fractions can be processed further
into lighter, higher-value products such as gasoline. This is where fractions from the
distillation units are transformed into streams (intermediate components) that
eventually become finished products.

The most widely used conversion method is called cracking because it uses heat,
pressure, catalysts, and sometimes hydrogen to crack heavy hydrocarbon molecules
into lighter ones. A cracking unit consists of one or more tall, thick-walled, rocket-
shaped reactors and a network of furnaces, heat exchangers, and other vessels.
Complex refineries may have one or more types of crackers, including fluid catalytic
cracking units and hydrocracking/hydrocracker units.
Cracking is not the only form of crude oil conversion. Other refinery processes
rearrange molecules to add value rather than splitting molecules.

Figure:Fluid catalytic cracking distillation unit

Refining workers overlooking a refinery

Alkylation, for example, makes gasoline components by combining some of the

gaseous byproducts of cracking. The process, which essentially is cracking in
reverse, takes place in a series of large, horizontal vessels and tall, skinny towers.

Reforming uses heat, moderate pressure, and catalysts to turn naphtha, a light,
relatively low-value fraction, into high-octane gasoline components.

Treatment
The finishing touches occur during the final treatment. To make gasoline, refinery
technicians carefully combine a variety of streams from the processing units. Octane
level, vapor pressure ratings, and other special considerations determine the
gasoline blend.
Storage
Both incoming crude oil and the outgoing final products are stored temporarily in
large tanks on a tank farm near the refinery. Pipelines, trains, and trucks carry the
final products from the storage tanks to other locations across the country.

Cracking of petroleum
Definition of cracking

There are two possible definitions of cracking.The thermal decomposition of alkanes

in the absence of air is called cracking.

The process of decomposition of less volatile higher hydrocarbons into more volatile
lower hydrocarbons with the application of heat and catalyst is also called cracking
or pyrolysis.

Fig. Process of cracking

Importance of cracking
The fractional distillation of petroleum only gives us 20 % gasoline. This is a very
small fraction of the total gasoline used by the world. The higher demand of the
present civilization can be carried out by cracking of higher alkanes.

These higher alkanes mostly consist of kerosene oil. In fact, approximately 50% of
gasoline is now prepared through this method.
Examples of cracking
1. Cracking of methane
In order to illustrate the process of cracking and pyrolysis, let us try to understand
the process by cracking methane.

In this reaction carbon black, which is produced is used as a filler in the manufacture
of tires and hydrogen produced is sold in the other industries. Carbon black also
makes shoe polish and is a pigment for black paint.

2. Cracking of ethane

This reaction provides one of the ways to get ethene from ethane.

Similarly, the pyrolysis of propane and butane gives us a variety of products.

3. Cracking of propane and butane

4. Cracking of higher hydrocarbons

Greater the number of carbon and hydrogen atoms in alkane greater the variety of
products. A higher hydrocarbon C16H34 is cracked according to the following reaction.

Nature of the products in cracking

The nature of products from the given compound depend upon the following factors.

1. Structure of hydrocarbons
2. Temperature and pressure used in cracking
3. Nature of catalyst used in cracking

Types of cracking
Cracking is of three types.

1. Thermal cracking
2. Catalytical cracking
3. Steam cracking

Thermal cracking
This cracking is carried out by the application of heat and pressure. The products
after cracking are passed through the fractionating tower. In this way the gasoline
can be separated from the fractions. Thermal cracking is done both in liquid and
vapor phase.

In the liquid phase, the craking temperature of 470-530 °C is maintained along with
the pressure of 7-70 atmosphere.

In a vapor-phase cracking, the temperature is 600 °C and the pressure is 3.5-10.5

atmosphere.

Catalytical cracking
This cracking is done in the presence of catalyst. The temperature and pressure are
comparatively low.
Catalysts used for cracking
Typical catalyst used for this purpose is the mixture of silica (SiO2) and alumina
(Al2O3). The mixture of these two substances give us aluminum silicates. Catalytical
cracking produces gasoline of higher-octane number. In this way the gasoline of
better quality is obtained.

Steam cracking
Higher hydrocarbons are converted to vapors and mixed with steam. This mixture is
heated for a short time to about 900 °C. It is then cooled rapidly. This process is
suitable for obtaining lower unsaturated hydrocarbons.

Applications of cracking
Following are some important applications of the cracking.

1. Preparation of gasoline ( Petrol for cars)

More then 50 % petrol is produced by cracking. It gives better quality of petrol in
term of anti-knocking property.

2. Preparation of oil gas

Oil gas is a mixture of methane, ethane, propane, butane, and very small fractions
of other hydrocarbons along with hydrogen.

Oil gas is obtained by the cracking kerosene oil by dropping it over red hot iron
retort.

3. Preparation of petrol gas

Petrol gas is prepared by the cracking of petrol by passing it through electrically
heated coils.

4. Polymerization
Simple alkene which are produced in the pyrolysis are used to prepare polymers.

The simple hydrocarbons like ethane, propene, butane and benzene are used for the
manufacturing of following.

 Drugs
 Plastic
 Detergents
 Synthetic fiber
 Fertilizers
 Weed killer
 Chemicals like ethanol, phenols, and acetone