Composition of Crude Oils

Main groups of compounds in crude oils

Saturated Hydrocarbons:
Usually the major group, except in
degraded heavy oils; Contain normal
plus isoalkanes (paraffins) and
cycloalkanes (naphthenes); Relative
abundance of paraffins and
naphthenes is rather comparable in
many crude oils, with the exception of
paraffinic and degraded heavy oils

Composition of Crude Oils

Aromatic Hydrocarbons:
Comprised of pure aromatics,
naphthenoauromatics (condensed aromatic
and saturated cycles) and benzothiophene
derivatives (containing heterocycles with
sulfur)
Resins and Asphaltenes:
These are high molecular weight polycyclic
molecules containing N, S, and O atoms.
There is strong positive correlation between
the concentrations of aromatics, resins plus
asphaltenes and the sulfur content

Classification of Crude Oil

&
Composition of Petroleum and Natural Gas

Composition of Crude Oils

Classification of crude oils is based on the content
of n + isoalkanes (paraffins), cycloalkanes
(naphthanes), and aromatic compounds (aromatic
hydrocarbons, resins, asphaltenes)
Main classes of crude oils:

Composition of Crude Oils

Composition of Crude Oils

Evolution & alteration change the composition of
crude oils
Process

Initial crude

Product

Thermal
evolution

Paraffinicnaphthenic oil

Paraffinic oil

Alteration
(Degradation)

Paraffinic &
Paraffinicnaphthenic oil

Aromatic- naphthenic
(<1% S)

Aromaticintermediate oils

Aromatic- asphaltic
oils (>1% S)

Composition of crude oils

Paraffin-base crudes constitute only a tiny
fraction of modern world crude supplies (by
1980, ~2%)
The standard is Pensylvania crude; this
and most other North American crudes are
Paleozoic in age (from Michigan, Ohio,
Oklahama)
Nearly most of the paraffinic crudes from
other continents are much younger:
Mesozoic in southern Chile, Brasil, Southern
Russia; even Tertiary in some African Basins,
Caucasus, Borneo, Chinese basins

Composition of crude oils

Crudes dominated by the naphthenic
components are called Asphalt-base oils, as
asphalts are closely associated with the
naphthenes and not with the paraffins. ~15%
of world crude supplies in 1980 were truly
naphthene -based; These are the black-oils
of Venezuela, Mexico, parts of California,
Gulf coast, and many Russian crudes
The great majority of crude oils are of mixed
base (naphthene paraffin); they include
nearly all Middle East, Mid-continent, and
North Sea oils

Composition of crude oils

Most crude oils contain minor quantities of
HC (pristane and phytane) belonging to
neither the paraffins nor the naphthene
series; occurrences of these in crude oil and
ancient sediments are believed to be
derivatives of chlorophyll, and they
constitute useful indicators of an oils origin
The ratio between pristane and phytane
content of a crude oil or rock extract
indicates the type of organic matter from
which the oil originated and/or the level of
thermal maturation of the source. The ratio is
therefore a vital finger-print for any crude
oil containing both molecules

Natural Gas
Natural gas consists of HC not condensable
at 20C (68F) and atmospheric pressure
These are the first four members of the
paraffin series (methane through n-butane)
Gas composed almost entirely of methane is
dry gas; if the proportion of ethane (C2H6) and
heavier molecules exceeds some arbitrary
value (conventionally 0.3 US gallons of
vapour / cubic feet of gas, or between 4 and
5%, in North America), the gas is called wet
gas

Natural Gas
Natural gases consisting largely or
wholly of methane may have any one of
three distinct origins
Petroleum gas: formed as a byproduct
of the generation of petroleum
Associated gas: accompanies oil
Non-associated gas: no longer accompanies
oil; formed by the thermocatalytic modification
of petroleum

Coal gas: formed by the modification of

coal, thermocatalytically or otherwise

Natural Gas
Bacterial gas: formed by the low-temperature
alteration of organic matter at or near the
earths surface
The amount of gas in solution increases with
increasing reservoir pressure, and exerts
great effect upon the oils physical
properties. This is also responsible for many
oil wells to flow their oil to the surface
without artificial assistance
If the gas content is sufficient to saturate the
oil under the existing conditions, the amount
unable to go into solution forms a free gas
cap above the oil

Non-HC constituents of oil

& natural gases
Common non-HC constituents:
Heterocompounds (S-N-O compounds)
and Organocompounds containing
certain heavy metals (principally V, Ni)
in crude oil
Natural gas may also contain N, H, He,
Ar

S and its compounds

Most important heterocompound
Few are wholly without it
Few contain >3% by weight
S content is higher in heavy oils (higher
MW, BP with more polar fractions i.e.,
resins and asphaltenes) than in light oils
Small proportion of S in crude oil is in the
form of elemental form in solution or of
H2S; the greater part is bonded with C in
organic combination

Non-HC constituents of oil & natural gases

Crude oils containing detectable amount of H2S Sour Crudes

S content as low as 0.1 0.2% Sweet Crudes (Algeria,
Angola, Nigeria)
Low sulfur crude < 0.6 % S
Intermediate crude: 0.6 1.7 % S
High sulfur crude > 1.7 % S
High S content are found in reservoirs of dolomite anhydrate
facies
Middle EastArabian heavy fields, Iran, Suez graben
2.8 4.9 % S
Athabasca tar sand in Alberta (very heavy degraded oil)
5.5 % S
Boscan in Venezuela 5.4 % S
In most of the major exporting countries (Middle East,
Mexico, Venezuela)
High S crudes are 5 10 times of sweet crude

H 2S
Gases high in H2S occur typically in carbonatesulfate reservoirs and also contain higher than
normal concentrations of N & CO2
H2S Concentrations exceeding 100 ppm in gas/oil
Dangerous as it is highly corrosive to drilling
equipment, particularly in deep well with high
temperature
North American Basins (the Permian Alberta,
Tampico, and Reforma Campeche basin and Texas
Panhandle); Permian of Ural Volga region; Jura
Cretaceous of Aquitaine Basin in France 15 16
% H2S
Deep Smackover in Southeastern USA (Jurassic)
30 % routine, 80-90%
Deep carbonate reservoirs of Rocky Mt. Foothills
60-65% below 4000 m

Nitrogen
Nitrogen in crude oil is primarily related to the
asphalt content
0.2 % N considered high (as in Los Angeles,
Maracaibo (Venezuela), Tampico (Illinois) basins)
High N gases occur especially in Paleozoic strata
Up to 80 % San Juan Basin of New Mexico (He 3.0
7.5 % in addition)
Up to 90 % Eastern part of Rotliegendes (Western
Poland) Basin
Pennsylvanian gases 19 %
South Alberta gases 8 85 %
Pakistani gas field 28 % N + high CO2
Orenburg (USSR) Sour gas in the Permian
Reservoir (5.8 % N + 28 ppm Ar + 4.5 % H2S)

Oxygen Compounds
Oxygen compounds of definite structure in
crude oils are acids (in many fields in
southern USSR) and phenols
Natural gases may contain considerable
quantities of CO2
Paradox Basin in Utah (Carboniferous to
Triassic reservoirs) Up to 90%
Wyoming (Ordovician & Mississippian
carbonates) 80 %
Northern Mexico, Pakistan (some fields) ~
50 %

Other elements in oil & gas

Natural gas may also contain H, He, or Ar
Hydrogen in no case exceeds 0.5 %;
usually < 0.1 %
Helium Occurs in some dry gases
particularly in those with high N content
Fields producing both oil & gas more
commonly contain 1 % or more He than dry
gas fields
In North America, most of the He-bearing
reservoirs are over large basement uplifts
Argon rarely exceed 0.1 % in natural gases
Ar in gases is enriched in 40Ar to the extent of
6 10 % (derived from the decay of 40K)
Radon occur in many crude oils

Organometallic compounds
Porphyrins are HC ring complexes containing N & a
metallic (V, Ni) nucleus
Porphyrin (traces 400 ppm in crude oils)

C numbers range from 25 36, mostly 30 32

V 30 300 ppm (high S); Venezuela 1100 ppm
Ni 20 85 ppm (low S)
V : Ni ratio is highest in Paleozoic oils (> 1)
Mesozoic & Cenozoic oils (< 1)

There is good correlation between metals, sulfur, &

asphaltene content
Degraded oils, enriched in asphaltenes, contain also
more metals than the nondegraded oils of similar
origin
Other metals, may be present are: Fe, Zn, Cu, Pb, As,
Md, Co, Mn, Cr, etc.

Correlation Index
Useful means of classifying oils on a
qualitative basis.
CI is a number whose magnitude indicates
certain characteristics of a crude oil
distillation
Paraffins: CI 0 (zero)
Benzene: CI 100
Lower the CI greater the concentration of
paraffins
Higher the CI greater the concentration of
naphthenic and aromatic HC