University of Technology Properties of Petroleum Fuels Lecturer: Basheer Ahmed

Chemical Engineering Dept. 2nd Class/1st Semester 2019-2020

Petroleum Analysis:
The word petroleum originated from the latin words, petra, meaning rock and oleum,
meaning oil. Literally it means ‘rock oil,’ and can also be defined as a non-renewable
fossil fuel or oil that is found underground.
Technically, the term petroleum refers to describe any solid, liquid or gaseous
hydrocarbons. It’s also known as ‘crude oil’ or ‘mineral oil.’
Various theories have been advanced over the years as to the origin of petroleum
proposing an animal vegetable, mineral and even meteoric origin. Today, however,
most scientists believe that oil and gas originated in plant and animal matter that
accumulated in fine grained sediments at the bottom of ancient seas many millions of
years ago. This theory suggests that oil originated as the remains of countless
organisms that either lived in the sea or were deposited there with mud and silt from
prehistoric rivers and streams. The remains of these ancient plants and animals were
transformed into oil and gas by bacterial action with heat and pressure resulting from
deep burial beneath other sediments.
The term crude oil refers to oil in its "crude" or unrefined state; that is to say oil as it
comes out of the ground. This crude oil must be transported to a refinery to be
separated into constituents such as gasoline, aviation fuel, fuel oil, etc. before it can be
used by the consumer.
Conventional crude oil ranges from green to brown or black in color depending on the
petroleum type and the mineral matter present and is composed of a heterogeneous
mixture of liquids, solids, and gases. Some components of the crude oil are dissolved
and some are a separate phase. Water may occur with the petroleum produced as a
readily separated phase or as an emulsion

Differences Between Crude Oil, Petroleum Products And Petroleum

Crude oil- Mixture of hydrocarbons existing as liquid in natural underground

reservoirs and remain liquid during extraction.

Petroleum products- Produced from the processing of crude oil at petroleum

refineries and extraction of liquid hydrocarbons at natural gas processing plants.

Petroleum- is a naturally occurring mixture of hydrocarbons, generally in a liquid

state, which may also include compounds of sulfur, nitrogen, oxygen,
metals, and other elements.

Elemental analyses of petroleum show that it contains mainly carbon and

hydrogen. Nitrogen, oxygen, and sulfur are present in smaller amounts, and trace
elements such as vanadium, nickel, etc, are also present. The mixture of hydrocarbons
is highly complex. Paraffinic, naphthenic, and aromatic structures can occur in the
same molecule, and the complexity increases with boiling range. The attempted
classification of crude oils in terms of these three main structural types has proved
inadequate.

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University of Technology Properties of Petroleum Fuels Lecturer: Basheer Ahmed
Chemical Engineering Dept. 2nd Class/1st Semester 2019-2020

The final result is a black viscous

product of composition:
Carbon 80 to89%
Hydrogen 12 to 14%
Nitrogen 0.3 to 1 %
Sulphur 0.3 to 3%
Oxygen 2 to 3%
Petroleum Formation
There are basically two theories explaining the origin of oil,
1- Organic Theory (Biotic Theory)
Oil developed millions of years from organic material remains of dead plants and
animals. The dead organisms sank to the bottom of water bodies (seas and lakes), where
the environment tends to be anaerobic. They accumulated in the mud on the beds of the
water bodies, partially decomposed.
Sediment deposition on the bed of the water body, burying and compressing the organic
matter under its weight. Increase in temperatures (100-160°c) and pressures resulted due
to continued sediment deposition. With time the conditions broke down the organic
compounds into shorter hydrocarbon chains, forming oil and natural gas.
Oil and natural gas flowed from the source rock, accumulating in thicker more porous
rock called a reservoir rock. Earth movements (faulting, folding ) trapped the oil and
natural gas in the reservoir rock between layers of impermeable rock or cap rock also
called an oil trap.

2- Inorganic Theory
Proposed by Dmitri Mendeleev, he postulated that metallic carbides deep
within the earth reacted with water at high temps, forming acetylene which
condenses to heavier hydrocarbons.
CaC2(s)+2H20 ------> Ca(OH)2(s)+C2H2(g)

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University of Technology Properties of Petroleum Fuels Lecturer: Basheer Ahmed
Chemical Engineering Dept. 2nd Class/1st Semester 2019-2020

Classification as a Hydrocarbon Resource

The inclusion of coal and oil shale kerogen in the category hydrocarbon resources is
due to the fact that these two natural resources (coal and oil shale kerogen) will
produce hydrocarbons on high-temperature processing. Therefore, if coal and oil shale
kerogen are to be included in the term hydrocarbon resources, it is more appropriate
that they be classed as hydrocarbon-producing resources under the general
classification of organic sediments

FIGURE 2.2 Classification of the earth’s organic sediments according to

hydrocarbon occurrence and production.

Production of Petroleum
• Petroleum almost always occurs along with gas called natural gas. After drilling
in the crust of earth both natural gas and oil flow up through pipe under
pressure initially. When the oil pressure decreases, then the residual oil is
either sucked by a pump or pressure is created by injecting compressed gas or
high pressure water through a pipe bored by the side of oil delivery pipe so
that it can flow out.
• When the oil well contains both oil and gas it is called (wet well) and if it
contains only gas then it is called a (dry well).
• A sketch of typical oil pool formation inside the crust of earth is given in Fig.1.
Hard cap rock and hard rock at the bottom, both are impermeable to oil and
gas. Geological studies indicate that petroleum was not formed in the pools
where it is found today.

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University of Technology Properties of Petroleum Fuels Lecturer: Basheer Ahmed
Chemical Engineering Dept. 2nd Class/1st Semester 2019-2020

Fig.1. Typical oil-pool formations. In the centre, pool water has forced the petroleum
and gas up into a dome, or anticline, in the porous oil rock layer. Hard cap rock
prevents the escape of the oil. A fault, at the left, or a stratigraphic.

Pre-Treatment of Oil at Oil Field before Refining

Oil and gas when they come out of oil field are separated. The natural gas is
compressed to liquefy it which is used for heating of domestic and industrial ovens.
Petroleum oil is made free of:

• Water,
• Sediments and
• Salts present in it.

It is then made free of some dissolved gases into it by the process called
'stabilisation'. It is then sent to oil refinery _ for separation into various petroleum
products by distillation mainly and auxiliary operations.

Crude oil as it comes out of well may contain up to (25%) water, salts (MgC1 2,-
CaC12, NaCI etc.) up to 2000-5000 (mg/litre) and sediments up to (1-1.5%). For
refining crude oil, the salt content in it should be < 50 mg/litre and Water < 03%.
Excessive water in crude requires extra heat for its distillation, increases its cost of
transportation, forms emulsion which absorb materials like resin (hence emulsion
breakers are to be used).

Composition of Crude Oils

Petroleum occurs in nature in all three possible states solid, liquid and gas. The liquid
petroleum is usually colored from dark brown to bluish black or black, The semi-solid
or solid petroleum is well known by the name PITCH, usually black in color. The
gaseous deposits of petroleum are known as natural gas deposits, where sometimes
gasolines are also accompanied. Gas from condensate reservoirs contains a good
portion of lighter fractions of a boiling point upto 30° C.

The average ultimate composition of petroleum is mainly given in terms of

constituents of hydrocarbons, namely carbon and hydrogen as follows :
Carbon 84—86%
Hydrogen 11—14%

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University of Technology Properties of Petroleum Fuels Lecturer: Basheer Ahmed
Chemical Engineering Dept. 2nd Class/1st Semester 2019-2020

The other major elements of importance are Sulfur, Oxygen and Nitrogen.
These elements in hydrocarbons are usually treated as impurities because of their
inherent properties like odor, color corrosiveness etc

Generally
these three elements combined, do not exceed 5% on an average.
The bulk of petroleum is made up of hydrocarbons, of saturated compounds like
Paraffins, Naphthenes and unsaturated cyclic compounds Aromatics. The highest
carbon atom present in the crude is C70.
The general properties of these homologous series are discussed below :

Paraffins
CnH2n+2 is the general formula of paraffin. First three compounds are gases while
compounds upto C16 are liquids and beyond that, they assume semisolid consistency.
beyond C30 assume shape of solid blocks, sometimes even crystalline forms. There are
number of isomeric compounds for each compound, profoundly differing in
properties. For example upto C3 no isomers are possible, C4 exhibits only two isomers,
as shown here And C5 exhibits three isomers. The number of isomers increases as the
number of carbon atoms increase C13H28 exhibits 802 isomeric forms

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University of Technology Properties of Petroleum Fuels Lecturer: Basheer Ahmed
Chemical Engineering Dept. 2nd Class/1st Semester 2019-2020

Naphthenes

These are saturated ring compounds bearing the general formula CnH2n. The
prominence of ring structure starts with five carbon atoms. Although C3 and C4 ring
structures, are in existence, Naphthenes are isomeric with olefins but differ in
properties.. Naphthenes exhibit both the properties of saturated paraffins and
unsaturated aromatics, the result of which, all the properties like sp. gravity,
viscosity, pour point, thermal characteristics lie in between the two mentioned
homologues.

Aromatics

The first and smallest of the aromatics is benzene; other simple aromatics to follow are
toluene, xylene, cumene etc. Even though benzene is unsaturated, yet it follows the
principles of substitution with halogens rather than addition. This is mainly due to
symmetric grouping of closed ring structure and resonance

Inorganics

Sulfur compounds: Sulfur is found in most of the crudes in variable amounts.

Generally sulfur compounds are present in more quantities in higher molecular
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University of Technology Properties of Petroleum Fuels Lecturer: Basheer Ahmed
Chemical Engineering Dept. 2nd Class/1st Semester 2019-2020

weight stocks. Usually the sulfur content does not exceed 5%, Sulfur in crude
occurs in different forms like free sulfur, hydrogen sulfide, mercaptans and
thiophenes etc.
Nitrogen presence in free form is well known in natural gas only. Oxygen occurs as
oxygenated compounds like phenols, cresols, naphthenic acids, sulphonates, sulfates
and sulfoxides. Nitrogen exists in the form of indoles, pyridines, quinolines and
amines, usually well below 2%.
Nitrogen compounds exasperate problems in processing and stability of products.
Catalyst deactivation or poisoning, gum formation. Nitrogen is present in two forms,
basic and non- basic

Asphalts, Resins and Bitumens

Asphalts are high molecular weight complex molecules, black in color, soluble
preferably in aromatic solvents and carbon disulphide.
Resins are mostly compounds of highly condensed ring structures, containing
oxygen, sulfur and nitrogen, sometimes inorganic too.
bitumen is a manufactured product, it is essentially made up of three components,
asphalts, resins and mineral oil.
These three components comprise a colloidal system; asphalts are suspended in oil
and resins contribute to the stability of the system

Petroleum suitability for refining (to produce a slate of predetermined products)

(Table 2.2) is determined by application of a series of analytical methods, that
provide information that is sufficient to assess the potential quality of the petroleum
as a feedstock

Table 2.2. General Summary of Product Types and Distillation Range