PgDip/MSc Oil and Gas Engineering/Petroleum Technology 1 Topic 7: Nature of Petroleum

Topic 7: Nature of Petroleum

Review

In this topic the student is introduced to hydrocarbon chemistry and

occurrence of petroleum in nature.

Content
Nature of Petroleum

Petroleum consists of a mixture of various classes of chemical compounds. The relative

amounts of these compounds determine the properties of petroleum. Each compound is
made up of atoms joined together according to a number of bonds. The commonest
elements are carbon (symbol C; 4 bonds) and hydrogen (Symbol H; 1 bond) - hence
hydrocarbons. Other minor elements include: oxygen (O; 2 bonds); nitrogen (N; 3
bonds) and sulphur (S; 2 bonds).
The compounds can be described based upon:
• a systematic naming based on structure;
• formulae giving the elements present and relative numbers of each;
• as pictorial representations.

What is an Organic Compound ?

Even though organic chemistry focuses on compounds that contain carbon and
hydrogen, more than 95% of the compounds that have been isolated from natural
sources or synthesized in the laboratory are organic. The special role of carbon in the
chemistry of the elements is the result of a combination of factors including, the number
of valence electrons on a neutral carbon atom, the electronegativity of carbon, and the
atomic radius of carbon atoms.
Carbon forms covalent bonds with a large number of other elements, including the
hydrogen, nitrogen, oxygen, phosphorus, and sulfur found in living systems. Because
they are relatively small, carbon atoms can come close enough together to form strong
C-C single bonds, C=C double bonds or even C C triple bonds. Carbon also forms
strong double and triple bonds to nitrogen and oxygen. It can even form double bonds to
elements such as phosphorus or sulfur that do not form double bonds to themselves.
The chemical and physical properties of carbon provide for an almost infinite variety of
potential structures for organic compounds, and provide the basis for all life on planet
Earth.

The Saturated Hydrocarbons, or Alkanes

Compounds that contain only carbon and hydrogen are known as hydrocarbons. Those
that contain as many hydrogen atoms as possible are said to be saturated. The
saturated hydrocarbons are also known as alkanes.
The simplest alkane is methane: CH4. The Lewis structure of methane can be
generated by combining the four electrons in the valence shell of a neutral carbon atom
with four hydrogen atoms to form a compound in which the carbon atom shares a total
of eight valence electrons with the four hydrogen atoms.

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PgDip/MSc Oil and Gas Engineering/Petroleum Technology 1 Topic 7: Nature of Petroleum

Methane is an example of a general rule that carbon is tetravalent; it forms a total of four
bonds in almost all of its compounds. To minimize the repulsion between pairs of
electrons in the four C H bonds, the geometry around the carbon atom is tetrahedral
(Figure 1). The angle between the bonds is 109.5˚
Figure 1. Tetrahadral Structure of Carbon Bonding in Methane

The naming sequence continues, ethane (C2H6), propane (C3H8), and butane (C4H10) for
alkanes containing two, three and four carbon atoms respectively.
The names, formulas, and physical properties for a variety of alkanes with the generic
formula CnH2n+2 are given in Table 1. The boiling points of the alkanes gradually
increase with the molecular weight of these compounds. At room temperature, the
lighter alkanes are gases; the midweight alkanes are liquids; and the heavier alkanes
are solids, or tars.
Table 1. Some Alkanes in Series.
Molecular Melting Point Boiling Point State at
Name Formula ( C) ( C) STP
methane CH4 -182.5 -164 gas
ethane C2H6 -183.3 -88.6 gas
propane C3H8 -189.7 -42.1 gas
butane C4H10 -138.4 -0.5 gas
pentane C5H12 -129.7 36.1 liquid
hexane C6H14 -95 68.9 liquid
heptane C7H16 -90.6 98.4 liquid
octane C8H18 -56.8 124.7 liquid
eicosane C20H42 36.8 343 solid
triacontane C30H62 65.8 449.7 solid

The alkanes above are all straight-chain hydrocarbons, in which the carbon atoms form
a chain that runs from one end of the molecule to the other. The generic formula for
these compounds can be understood by assuming that they contain chains of CH2
groups with an additional hydrogen atom capping either end of the chain. Thus, for
every n carbon atoms there must be 2n + 2 hydrogen atoms: CnH2n+2.
Because two points define a line, the carbon skeleton of the ethane molecule is linear
(Figure 2, left). Because the bond angle in a tetrahedron is 109.5 , alkane molecules that
contain three or four carbon atoms can no longer be thought of as linear (Figure 2,

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PgDip/MSc Oil and Gas Engineering/Petroleum Technology 1 Topic 7: Nature of Petroleum

centre and right) although they are still straight chained as there is no branching or
joining of the chain.
Figure 2. Ethane, Propane and Butane Molecules

In addition to the straight-chain examples considered so far, alkanes also form branched
structures. The smallest hydrocarbon in which a branch can occur has four carbon
atoms. This compound has the same formula as butane (C4H10), but a different
structure. Compounds with the same formula and different structures are known as
isomers (from the Greek isos, "equal," and meros, "parts"). When it was first discovered,
the branched isomer with the formula C4H10 was therefore given the name isobutane
(Figure 4)
Figure 4. Isobutane.

Butane and isobutane are called constitutional isomers because they literally differ in
their constitution. One contains two CH3 groups and two CH2 groups; the other contains
three CH3 groups and one CH group.
There are three constitutional isomers of pentane, C5H12 (Figure 5). The first is
"normal" pentane, or n-pentane. A branched isomer is also possible, which was
originally named isopentane. When a more highly branched isomer was discovered, it
was named neopentane (the new isomer of pentane).
Figure 5. Isomers of Pentane.

There are two constitutional isomers with the formula C4H10, three isomers of C5H12, and
five isomers of C6H14. The number of isomers of a compound increases rapidly with
additional carbon atoms. There are over 4 billion isomers for C30H62, for example.

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PgDip/MSc Oil and Gas Engineering/Petroleum Technology 1 Topic 7: Nature of Petroleum

The Unsaturated Hydrocarbons: Alkenes and Alkynes

Alkenes

Carbon not only forms the strong C C single bonds found in alkanes, it also forms
strong C=C double bonds. Compounds that contain C=C double bonds were once
known as olefins (literally, "to make an oil") because they were hard to crystallize. (They
tend to remain oily liquids when cooled.) These compounds are now called alkenes. The
simplest alkene has the formula C2H4.
Because an alkene can be thought of as a derivative of an alkane from which an H2
molecule has been removed, the generic formula for an alkene with one C=C double
bond is CnH2n. The series continues ethene, propene, butene.

Alkynes

Compounds that contain C C triple bonds are called alkynes. These compounds have
four less hydrogen atoms than the parent alkanes, so the generic formula for an alkyne
with a single C C triple bond is CnH2n-2. The simplest alkyne has the formula C2H2 and
is known by the common name acetylene. Again the series follows the same pattern of
naming.

The alkanes, alkenes and alkynes are generally grouped together as a class of organic
compounds known as the Aliphatics, often termed paraffins.

For all paraffins : if n < 5 they are gaseous at STP;

5 < n< 15 they are liquid;
n > 15 they are solid.

The Cycloalkane or Napthene Compounds

If the carbon chain that forms the backbone of a straight-chain hydrocarbon is long
enough, we can envision the two ends coming together to form a cycloalkane. One
hydrogen atom has to be removed from each end of the hydrocarbon chain to form the
C C bond that closes the ring. Cycloalkanes therefore have two less hydrogen atoms
than the parent alkane and a generic formula of CnH2n.
The smallest alkane that can form a ring is cyclopropane, C3H6, in which the three
carbon atoms lie in the same plane (Figure 6, left). Following connvention, cyclohexane
is a six carbon atom ringed alkane (Figure 6, right)
Figure 6.Cyclopropane and Cyclohexane Rings.

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PgDip/MSc Oil and Gas Engineering/Petroleum Technology 1 Topic 7: Nature of Petroleum

The Aromatic Compounds

The aromatic hydrocarbons include benzene and the alkyl derivatives of benzene, a six
sided unsaturated ring. There is no general formula. Toluene is the most common
aromatic compound of crude oil, followed by xylenes and benzene itself. Any compound
with the benzene ring is an aromatic compound.

Heteroatomic Compounds

Heteroatomic compounds refer to all the other elements found in hydrocarbons except
for hydrogen and carbon. These include: oxygen; nitrogen and sulphur.

Metallic Compounds

Metallic compounds also occur in hydrocarbons. Vanadium, copper and nickel all form
oil soluble complexes.

Oil Composition

Composition of oils from around the globe will vary from field to field and region to
region. Figure 8 shows one example of how oils can be classified based on their
hydrocarbon compound content.
Figure 8. Classification of Oils on Hydrocarbon Content (after Tissot & Welte, 1978).

The variation of hydrocarbons found in petroleum will be examined in greater detail in

Unit 3 of this Module.

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PgDip/MSc Oil and Gas Engineering/Petroleum Technology 1 Topic 7: Nature of Petroleum

Occurrence of Petroleum

Surface Occurrences

These can be seen as “live” occurrences or “dead” occurrences. Live occurrences refer
to seepages, often associated with springs and mud volcanoes. Dead occurrences refer
to bitumen laden sediments or dikes and cavities filled with solid bitumen.
Seepages occur through bedding planes, fractures and interconnected porous
openings. They indicate the possible presence of much larger accumulations nearby.
Early drilling in the Nineteenth Century was based on seepages. Oil escaping in water is
easily seen as oil floats on water to form an iridescent film at the surface. Gas seepages
are often clearly seen as the gas bubbles out through the water. They may be unnoticed
in land areas.
Mud Volcanoes are intrusions of plastic clay, mud and high-pressure gas water mix.
The active volcanoes carry mud, sand, rock, gas and very occasionally oil to the surface
driven by the high pressures. Gas can escape constantly or intermittently. The
volcanoes indicate the presence of gas below.
Solid petroleum is found at the surface disseminated in pore spaces as a matrix or
bounding material in the rock or as dike like deposits filling cracks and cavities. These
‘inspissated’ deposits were once pools of petroleum at the surface that have ‘dried up’ in
situ as the lighter fractions of oil have escaped. They indicate the presence of source
rocks in the vicinity.
Examples of surface occurrences are the La Brea tar pits in Los Angeles, California,
and bitumen pools in Monketown (also referred known as La Brea, confusingly),
Trinidad. In the latter case the pools are formed by seepage from the underlying
Miocene tar sands, which are themselves fed from an Upper Cretaceous source rock.
These pools were used by 17th Century buccaneers to caulk their ships. Tar sands also
occur in Alberta (Canada), Olenik (Russia), Orinoco (Venezuela) and in Malagasy.

Subsurface Occurrences

Underground occurrences can be as minor showings or commercial finds. As before

they can be “live” if, for example, gas bubbles out of a core, or “dead” if, for example, the
core reveals an asphaltene stain. Minor showings are important as they may indicate the
presence of commercial deposits nearby.
A Pool is the simplest commercial occurrence. A hydrocarbon body in a single,
separate reservoir.
A field is a combination of separate Pools that are all related to a geological feature.
This feature can be a structural or stratigraphical feature. In the Niger Delta we find roll-
over anticlinal structures produced by growth faults that contain pairs of reservoirs on
the down and upthrown sides of the faults (Figure 9). Individually these reservoirs would
be pools. Collectively they represent a field. Other features include: salt plugs; folds;
faults.
A petroleum province is a region containing several fields occurring in a related
environment. The Niger delta, the Gulf of Mexico and the North Sea are examples.
Distinct entities within provinces can be called Sub-provinces. The Northern North Sea
and the Southern North Sea are both sub-provinces of the North Sea province.

Geographic Occurrence

Petroleum deposits are unevenly distributed throughout the World. They are generally
restricted to sedimentary basins (Figure 10). There are two main oil poles to be aware
of. The Middle East and the Gulf of Mexico produce over 60% of the World’s petroleum.
Other important regions include: Nigeria; Libya; North Sea; Alaskan Slope; Russia;
Indonesia; Australia; Malaysia.

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PgDip/MSc Oil and Gas Engineering/Petroleum Technology 1 Topic 7: Nature of Petroleum

Figure 9. Faults and Pools in the Niger Delta (after Weber & Daukoru, 1975).

Figure 10. Oil Bearing Sedimentary Basins in Relation to Present Plate Boundaries
(Holmgren et al, 1975).

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PgDip/MSc Oil and Gas Engineering/Petroleum Technology 1 Topic 7: Nature of Petroleum

Geological Occurrence

Pools, provinces, fields are classified according to the age of their reservoir formation.
58% of the World’s petroleum is found in reservoirs of Tertiary age. 17% of Cretaceous
age, 13% of Jurassic-Triassic age, ~11% of Palaeozoic age and less than 1% of
Precambrian age.
Minor commercial deposits are found in ancient Precambrian deposits because they are
usually highly metamorphosed which destroys porosity and permeability. They are
largely composed of ancient shield and craton areas of Basement Rock - considered to
be the lower limit of exploratory drilling.

Minor commercial deposits are found in recent Pleistocene deposits as not enough time
has elapsed for the formation and accumulation of oil and gas to occur.
Petroleum deposits are dominant in the Tertiary age rocks due to a combination of
factors: we find thick sequences of unmetamorphosed sedimentary rocks; we have
frequent lateral variations in permeabilities in reservoir rocks and we find adequate
covers, traps and source rocks.

Types of Petroleum

Hydrocarbons are a physically diverse group ranging from gases to liquids to solids.

Natural Gas

Natural gas is a mixture of Hydrocarbon and Non-hydrocarbon gases. They can occur
subsurface as dissolved (in solution in oil under subsurface pressures); as associated
gas (as a gas cap) or as non-associated gas (a commercial gas deposit in its own right –
no oil present). Gas dissolved in oil will act like a “coke bottle”. Under pressure gas will
be in solution but as oil migrates upwards the pressure will decrease and the gas will
bubble out of the oil and form a cap.

Hydrocarbon gases are predominantly from the paraffin group: methane, ethane,
propane, butane. Non-hydrocarbon gases include: carbon dioxide; nitrogen; helium. Dry
gas refers to gas with no liquid vapour content (methane). Wet gas has liquid vapour
content (ethane, propane, butane). Sour gas indicates the presence of hydrogen
sulphide.

Non hydrocarbon gases are sometimes present in large quantities and are sometimes of
commercial value in their own right. Helium enriched gases can form up to 8% of the
weight in some areas. Economically significant amounts are found in Texas, Alberta,
Poland and Queensland. Nitrogen enriched gases are found in the North Sea and the
Gulf of Mexico. 14% by weight of the Groningen field gas in the Dutch sector is nitrogen.
Argon, radon, carbon dioxide and hydrogen sulphides are also found. The latter is
particularly nasty.

Gas Hydrates

Hydrates are compounds of frozen water containing gas molecules. The gas may
include methane, ethane or carbon dioxide. They occur only in highly specific
temperature/pressure regimes. Hydrates are only stable at high pressures and low
temperatures. They occur in shallow arctic sediments and deep oceanic deposits. They
have also been found in active permafrost zones in Alaska and Siberia. They are
potentially an important energy source as ice molecules can hold up to 6 times as much
gas as the normal open pore system found in reservoirs.

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PgDip/MSc Oil and Gas Engineering/Petroleum Technology 1 Topic 7: Nature of Petroleum

Condensates

Condensates are gaseous at subsurface pressures but liquify as pressures decrease at

the surface.

Crude Oil

Crudes vary widely in composition, density, colour (from green, yellow, brown, black)
and viscosity. They are defined, and the price of crude is largely fixed, on the density of
the crude as specified by the American Petroleum Institute (API). The API specify the
scale of crude density in degrees according to the following empirical equation:
Equation 1: API = 141.5 − 131.5
SG
Where SG is the specific gravity of the oil at 60° F as compared to that of water at 60° F.

Light oils have high densities (> 50). Heavy crudes have low densities (< 15). The
majority of oils have densities between 20-40 API.

Generally the following apply:

• young-shallow oils are heavy, viscous and low in paraffins;
• young-deep oils are less viscous, have high API values and are lighter with more
paraffins;
• old-shallow oils are also less viscous, have high API and are lighter with more
paraffins;
• old-deep oils are more viscous and are heavy with low API values.

Solid/Plastic Hydrocarbons

Asphalts and resins are semi-solid to solid materials with melting points of approximately
150-200° F. They are fairly soluble, soft, tarry and will flow when heated.

Asphaltenes are hard, brittle solids with higher melting points of over 300° F. They are
denser and less soluble than the asphalts and contain large amounts of oxygen and
sulphur.

Bitumens are the most dense They swell and explosively decompose when their melting
point is reached. They are insoluble.

Formation Brines

Oil is always found in contact with water. This water is the remains of the formation
water that originally filled the pores of the reservoir rock before being displaced by
hydrocarbons. Brines are named according to, their relative position to the oil bearing
strata: top, intermediate, bottom, edge, or, their history.
Meteoric waters are relatively dilute containing carbonate and have recently been in
atmospheric circulation. Connate waters are those derived directly from the original
water in which the sediments were deposited. Interstitial or formation water refers to
water in place at the time of drilling. Diagenetic waters are waters that have been altered
during the diagenesis process.

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