Petroleum Refining And Petrochemicals

Reference book-
Origin of Petroleum

Several theories were put forward to explain the formation of petroleum,

only three widely accepted ones are given below.
Carbide theory-
According to this theory, hydrocarbons present in petroleum are formed by
the action of water on inorganic carbides.

Inorganic carbides, are formed by the reaction of metal and carbon under
high temperature & pressure conditions inside the earth.
High temp & pressure
Ca + 2C CaC2
Calcium carbide
High temp & pressure
4Al + 3C Al4C3
Aluminum carbide
CaC2+ 2H2O Ca (OH) + C2H2
acetylene
Al4C3+12H2O 4AI (OH)3 + 3CH4
methane
These lower hydrocarbon then undergo hydrogenation and
polymerization to give various types of hydrocarbons (paraffins,
aromatic & cycloparaffins).

H2
C2H2 +H2 C2H4 C2H6
acetylene ethylene ethane
Polymerization
3C2H2 C6H6
benzene
This theory fails to explain the following facts:
Presence of nitrogen and Sulphur compounds.
Presence of chlorophyll
Presence of optically active compounds.
Engler Theory-
According to Engler, petroleum is of animal origin.

Engler suggested that petroleum is formed by the decay and

decomposition of marine animals under high pressure and
temperature.

Experimental destructive decomposition of fish oil & other animal

fats under high pressure &temperature gives a product similar to
natural petroleum.
This theory fails to account for the
Presence of chlorophyll (green-colouring matter of plants) in
petroleum.
Presence of coal deposits in the vicinity of the oil fields.
Modern Theory-
According to modern views, petroleum is believed to be formed by
the decay & decomposition of marine animals as well as that of
vegetable organism of the pre-historic forests.
Due to action of prolonged action of high temperature & pressure in
the interior of earth for ages, the biological matter decomposed into
petroleum.
This modern theory explains the presence of brine on the basis of
animal origin while the presence of coal is explained by plant origin.

Composition of Petroleum-

A typical composition (by weight %) of petroleum is given below:

Carbon = 84-87%, Hydrogen = 11-15%, Sulphur = 0.1-3%, Nitrogen

= 0.1-1.5%, Oxygen = 0.3-1.8%

 Sulphur compounds found in petroleum are hydrogen sulphide,

thiophenes, mercaptans.

Oxygen occurs in combined form in alcohols, phenols, resins and

organic acids present in petroleum.
Nitrogen compound include pyridines, quinolines, pyroles etc.
Inorganic compounds present in petroleum are salt, clay and sand
etc.
Detection of Petroleum Deposit
Petroleum deposits are detected by visual, geophysical, geological
and drilling methods.

Visual method includes oil seepages at the surface of the earth.

Geophysical method includes the measurement of density, elasticity,

magnetic, seismic & electrical properties of the rock in the crust of
the earth from which the inference are drawn whether the petroleum
deposit occurs there or not.

The seismic method of oil and gas exploration involves generation

of a series of shock waves in the subsurface and picking up the
reflected waves by sensitive geophones which are laid along a line
on the surface. The time taken for the return signifies the velocities
through the subsurface rocks and these can be interpreted to assess
the nature of rocks and their angle of dip.

Geological method includes the measurement of age and nature of

rocks inside the earth's crust which gives an idea of oil deposit. In
Mesozoic era (50%),Cenozoic era (40%) and Paleozoic era (10%)
oil produced.

Drilling in the crust of earth is the final test when the petroleum
deposits have been proved by either of the earlier methods.
Exploration/Production of Crude Oil

For digging an oil well, the rotary drilling system, utilizes the principle of
torsional grinding or cutting.

The drilling rig consists of four main parts, viz.

a) derrick—a tall steel structure equipped with hoisting gear for raising and
lowering the drilling equipment

b) drill column or stem - this consists of a main section of steel pipes (drill
pipe) with at its lower end some extra heavy pipe to which the bit is
attached;

(c) rotating mechanism at the upper end of the drill column,

d) mud circulation system — at the top of the Kelly is the so-called swivel
through which a thin mud (drilling fluid) passes from a flexible hose;
The hoisting system is controlled from a working platform built
within the derrick above the ground level.

The mud is pumped through the holes of the bit

The main boring is of 20 to 30 cm diameter and its depth may vary

from 1.5 to 4.5 km. Wells of more than 7.5 km have also been
drilled while quite shallow wells also exist. The entire well is
provided with a casing of steel pipes right upto the productive work
layer. This prevents the collapse of the bore walls and ensures that
other extraneous fluids do not enter the well. Steel casing is
provided with control valves and outlet pipe at the wall head.
The source of the pressure may be a body of compressed gas above
the oil or a mass of water underlying the oil. These pressures cause
the oil to flow towards the foot of the well and then drive it up the
tubing to the surface.

When oil pressure is low or it falls, lifting is done by sending a high

pressure gas through the annulus between the casing and the tubing
or by providing a suitable pumping device at the lower end of the
tubing.

The total production from each well is piped to the gathering station.
The gas is separated by directing the fluid against baffles in
cylindrical pressure vessels.
The water and solids are separated either by sealing out in tanks or
by centrifuging.

The gas is called wet natural gas. It is processed for the recovery of
natural gasoline and the crude is sent to the refinery.
True Boiling Point Distillation(TBP)
Distillation characteristics of crude are assessed by performing
preliminary distillation called ‘True Boiling Point’ analysis (TBP).

This pulse test enlightens the refiners with all possible information
regarding the percentage quantum of fractions, base of crude and
possible difficulties beset during treatment operation etc.

This type of distillation is commonly used due to the accuracy of the

results obtained by this method which is very close to that obtained
via real distillation or industrial distillation.

In this distillation, there is a fractionation column located between

the condenser and the flask.
In general, this type of distillation is carried out by two steps:
firstly, under atmospheric pressure until 300°C (1% distilled very 2
min), secondly under vacuum pressure (to prevent cracking process
and to reduce the boiling point) at 40mmHg (1% distilled every 3-5
min).

For boiling points below 340◦ C (644◦F) the distillation is

performed at atmospheric pressure. The residue is distilled under
vacuum (1to10 mm Hg).
The distillation apparatus has 15 to 18 theoretical plates with a high
reflux ratio.
The boiling points under vacuum are converted to normal boiling
points.
ASTM Distillation
The distillation of petroleum cuts is done in a simple distillation
apparatus which does not have a fractionation column located
between the condenser and the flask.

For light cuts (gasoline, kerosene, diesel and heating oil) the
distillation is run at atmospheric pressure under ASTM D86 test. For
heavier fractions an ASTM D1160 test at reduced pressure is
employed.

ASTM distillation is measured in a single stage apparatus without

any reflux. Hence The ASTM does not indicate good separation of
various components.
Some examples of ASTM International standards utilizing distillation
are

D86 Test Method for Distillation of Petroleum Products at

Atmospheric Pressure

ASTM D20-03(2014) Standard Test Method for Distillation of

Road Tars

D1160 Test Method for Distillation of Petroleum Products at

Reduced Pressure
It indicate the operation of laboratory set up far away from the
equilibrium.
Equilibrium Flash Vaporization (EFV):
It is a single stage separation technique. A liquid mixture feed is
pumped through a heater to raise the temperature and enthalpy of the
mixture.

It then flows through a valve and the pressure is reduced, causing the
liquid to partially vaporize. Because the vapor and liquid are in such
close contact up until the "flash" occurs, the product liquid and vapor
phases approach equilibrium.
Indian Crude Oil and Refineries

The major oil fields in India are in Assam (Naharkatiya) and

Gujarat (Cambay and Ankleswar). Besides, Bombay high is
producing good amount of crud oil.

The Naharkatiya crudes have a relative density of 0.857, sulphur

0.17% &e high wax content (7.8%) and contain very little water &
salt.

The Cambay crude has been found to be associated with substantial

amounts of water, has a relative density of 0.863 ,sulphur content of
0.16%, wax content 10.6% and gives somewhat low yields of
lighter distillates.
The Ankleswar crude has relative density of 0.803, sulphur 0.14%
and wax 7%.

The Ankleswar crude is a light oil containing high amounts of

lighter & middle boiling fractions and only negligible amount of
water. In these respects, it differs very much from the Cambay oil
though both are paraffinic base crudes.

The crudes from the Gujarat oil fields give gasolinewith much
smaller content of aromatic hydrocarbons (3-5%). These are very
highly Paraffinic and wax-bearing.
Exploration for oil in all prospective sedimentary basins of India is
continuing. The areas which are still under survey are : Kutch
regions of Gujarat, Brahmaputra valley, place of Punjab, Uttar
Pradesh & Bihar and the adjoining Himalayan foot hills, Rajastan,
Cauveri, Mahanadi & Godavari deltas, the Andaman & Nicobar
Islands and off'Cambay, Kutch & Madras coast.

Exploration of oil in India is done by Oil and Natural gas

Corporation Ltd (ONGC),Oil India Limited (OIL)
Q.1 List the different types of theories that are accepted for
the formation of petroleum

Q.2 How the detection of petroleum product done?

Q.3 WHY TBP,ASTM and EFV used?

Q.4 Which are the main parts of exploration or production

of crude oil?