Petroleum

properties

Dr. Hanoon H. Mashkoor &

Asst. Lect. Maryam J. Jaafar
What is Petroleum?
• 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.
This is any naturally-occurring flammable mixture of
hydrocarbons found in geological formations such as rock
strata.
• Technically, the term petroleum refers to describe any
solid, liquid or gaseous hydrocarbons. It’s also known as
‘crude oil’ or ‘mineral oil.’
Occurrence of Petroleum
• Petroleum occurs in the earth’s crust, in all possible states
and varies in color from light brown to dark brown or
black, exhibiting luminescence in some cases. It is a
mixture of various hydrocarbons, of homologous series
namely paraffins, napthenes and aromatics.
• The final result is a black viscous product of composition:
• Carbon 80 to 89%
• 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 (algae and planktons).
• 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 Basis Theory Or Metallic Theory
• This hypothesis of petroleum origin without biology was
first proposed in 16th century by Georg Agricola, then in
19th century by Alexander (Prussian geographer), Dmitri
(Russian chemist), Marceline (French chemist) and re-
defined in 20th century by Cornell University physicist,
Thomas Gold.
• The theory argued that petroleum originated from
limitless pools of liquid primordial hydrocarbons at great
depths in the earth.
• These carbon-bearing fluids migrated upward from the
mantle where they slowly replenish the reservoirs that
conventional oil drillers tap.
• The most important Iraqi oil fields
1. The Rumaila oil field
2. Majnoon oil field
3. Al-Zubair oil field
4. West Qurna oil field
5. Luhais (bpd)
6. Nahr Bin Omar
7. Nassiriya (bpd)
8. Gharraf (bpd)
9. East Missan fields (Buzurgan, Fakka, Abu Gharb)
10. Halfaya (bpd)
11. Badra
12. East Baghdad + Naft Khana
13. Eastern Kirkuk (Baba, Jambour, Khabbaz)
14. Western Kirkuk (Bai Hassan and Avana)
15. Qayarah
• Composition of Petroleum

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, exhibiting sometimes
bloom or fluorescence. The semi-solid or solid petroleum is
well known by the name pitch, usually black in color. Such
kind of deposits ate assumed to form after the evaporation
or migration of lighter fractions.
• 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%
• 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.
• Paraffins :
• CnH2n+2 is the general formula of paraffins. First three compounds are
gases while compounds upto C16 are liquids and beyond that, they
assume semisolid consistency. Well 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 up to 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.
• General properties of paraffins
• Paraffins are stable, not attacked by sulfuric acid or other oxidizing
agents. However, paraffins of higher order > C30 are prone to oxidation.
Even usual oxidizing agents like potassium permanganate can cause
good amount of oxidation. The aptitude to contribute the substituted
products with halogens has magnified the petrochemical industry. Higher
paraffins are very much insoluble in water ; though the lower ones are
soluble in ethers and alcohols. Paraffins up to 3 carbon atoms have
inclination to form hydrates such as [CH4.7H2O, C2H6. 7H2O] and
these hydrates offer clogging and corrosion difficulties. Hence drying is
essential before usage.
• 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, their stability is decreased because of excessive
strain (Bayer’s Strain, Theory). Naphthenes are isomeric with
olefins but differ profoundly 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. Usually, all the ring
structures are having branched chains, where the isomeric
character predominantly occurs, followed by positional
isomerism in rings
• 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
.Aromatics are usually having high boiling points, low pour
points (freezing points), high octane numbers, high viscosity and
low viscosity index and these bum characteristically with a red
flame with much soot. As these behave like saturates, they resist
oxidation. In petroleum fractions aromatics beyond 3-ring
structure (Anthracenes) are probably non-existent. Aromatics
usually extend their presence from a temperature of 80° C
onwards and well dominate, in lower middle cuts and heavy cuts.
Actually the light aromatics (BTX) do not exceed even 5% of
crudes of general nature. Bulk of the aromatics are with side
chains and naphthenes and exist in heavier portion of crudes.
• 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
weight stocks. Usually the sulfur content does not exceed 5%, however rare
exemptions are : Venezuela (5.25%), California (USA 5.21%), Qaiyarah (Iraq—
7%) etc. crudes.
• Sulfur in crude occurs in different forms (like free sulfur, hydrogen sulfide,
mercaptans and thiophenes etc. These are frequently occuring compounds in almost
all fractions of the crude though to a different degree. Heavier fractions contain
sulfides, polysulfide, sulfonates and sulfates.
• Sulfur occupies prominent position in refining due to its ominous problems of
corrosion and odor. Pollution problems and following cost of waste treatment is
punitive for all refiners with high sulfur-stocks. However, refiners habitually
remove more detrimental sulfur compounds and leave the less harmful ones into
the products, as seen in the case of sulfides converted to disulfides in gasolines.
Some of the sulfonates are regarded as good emulsifiers and detergents, hence
promptly extracted for use in cutting oils. Conspicuous effect of sulfur is reflected
in increasing the density of crude.
• A correlation presented by Obolentsev shows the influence of sulfur on gravity
• ρ at 20C =0.0087 (S%)2+0.0607(S%)+0.7857
• Different crudes are presented in following table. It clearly shows the effect of
sulfur on API gravity of crude and pour point of crude. All sulfur crudes
mysteriously exhibit low pour points.
• Further, sulfur containing residuum when cracked leaves cross
linked structures, resembling the phenomenon of vulcanization
of rubber and offer perennial problems in desulfurization. Its
presence in different fractions complicates the refining and
treatment methods. Yet another problem is, it desists the effects
of additives. Sulfur in gasoline inevitably depresses the effect
of lead and demands more amount of additive. When crude
contains more than 0.5% S, it is denoted as high sulfur crude.
A terse distinction, at this juncture between sour crudes and
sulfur crudes is desirable. Free hydrogen sulfide is available in
some crudes, which naturally fosters corrosion. Such crudes
are classified as sour crudes ; other sulfur bearing compounds
are not taken into this account. The crudes containing sulfur
compounds other than hydrogen sulfide and exceeding 0.5 %
are denoted as high sulfur crudes
• Oxygen
Oxygen and nitrogen do not occur in free state either in
crudes or in fractions. 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
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 are some of the offshoots of nitrogen.
Nitrogen is present in two forms, basic and non-basic. Basic nitrogen is
characterized by its titratability with perchloric acids, whereas nonbasic
nitrogen is not titratable hence no possibility of extraction. Most of the
nitrogen pigments impart color to crude and fractions. The most
interesting compounds of nitrogen are porphyrins. These are obtained
from living organisms and preserved in petroleum. It stands to reason
that anaerobic conditions were prevailing durring petroleum formation;
otherwise oxidation would have destroyed them. Chlorophyll is also a
complex of porphyrins, where central atom is magnesium instead of
nickel or vanadium or iron. Iron porphyrins are also known as heme, the
constituents of red cell in the blood. Porphyrins pigments are usually
associated in complex form with metals like, copper, iron, vanadium
and nickel. The proper understanding of these pigments may augment
the knowledge of origin and formation of petroleum.
• There are other compounds such as
• Organometalic Compounds.
• Insoluble Impurities.