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Theories of origin of

petroleum
Even though believer of organic origin of petroleum
agrees on its origin, they differ on the issues related to
The process of formation and the primary organic
constituents, i.e., marine / continental origin?
Quantity of present day petroleum as directly obtained from
hydrocarbon of living organisms or by the transformation of
hydrocarbon compounds into petroleum?
Nature of energy involved in the transformation? Viz.
biochemical action, heat and pressure, radioactivity,
catalytic phenomena, etc.

As far as the occurrence of petroleum is concerned, two


schools of thought prevails:
All petroleum was formed in place, either at or adjacent to
the position of the present pools
Petroleum has migrated from areas of origin to trap areas
i.e., source area doesnt necessarily coincide with the
accumulation area.

Theories of origin of
petroleum

Cosmic theory

Bertheiot (1865), Mendaleef (1877) suggested the


formation of petroleum in the earths interior by the
action of water on metallic carbides such as those of Ca
and Fe. Another proposed mechanism involved the
interaction of alkali metals with CO 2 and water
Metallic Carbide + H2O vapor = CH4 + metallic hydroxide
Free alkali + CO2 + H2O vapor = CH4 + alkali hydroxide
Mantle theory/ Golds earthquake out gassing theory
(Gold,1979; Sugisaki et al, 1983; Gold and Held,1987).
Enriched 13C of methane from the hot spots of red sea,
Lake Kivu (East Africa), and East Pacific rise depicts an
abiogenic origin (Mac Donald, 1983).

Theories of origin of
petroleum

Reasons favouring organic origin of proto-petroleum:


The vast amount of organic matter and hydrocarbons
now found are in the sediments of the earth; and carbon
and hydrogen predominate in the remains of both plant
and animal organic matter
Petroleum crude is a complex mixture of hydrocarbon
compounds belonging to a number of homologous
series which, with no stretch of imagination, can be
synthesized from elemental stage
Many crudes have been found to contain porphyrin
pigments an essential component of all forms of life

Theories of origin of
petroleum

Most of the crudes contain nitrogen an essential


component of amino acids [CH2(NH2)COOH] a basic
constituent of life
All forms of crude posses the property of rotating the
plane polarized light which is possessed by cholesterol
(C26H45OH) again an essential component of both plant
and animal life. Only inorganic substances which
possess this property are cinnabar (HgS) and quartz
(SiO2)
The intimate relation of organic matter with the
petroleum in the sediments leaves little doubt that
organic matter was the original source of the petroleum

Theories of origin of
petroleum

Duplex origin of petroleum

Duplex origin of petroleum


CO2 and Hydrogen are passed over a catalyst of
haematite and magnetite at temperature in excess of
500C
Robinson (1963) suggested this process could
produce methane and liquid petroleum in nature.
Szatmari (1986, 1989) discussed this process in the
light of plate tectonics. According to him,
hydrocarbon could be generated by F T process at
convergent plate boundaries where sedimentary
rocks and oceanic crust undergo subduction. Carbon
dioxide could be produced by the metamorphism of
carbonates, and hydrogen by the serpentinization of
ophiolites. The latter would provide the iron oxides
necessary to catalyse the reaction

Origin of petroleum
Criteria for a sedimentary rock to be effective oil
source rock
TOC content > 0.4%
Elemental carbon: 75 90% (< 75% - immature;
> 90% due to advanced catagenesis)
Bitumen : TOC > 0.05
Kerogen should be of amorphous or oil prone type
rather than of structured or gas prone type
Vitrinite reflectance (RO) > 0.6 and < 1.3
H : C and O : C atomic ratios of kerogen residues
should be favourable. Principle phase of oil
formation occurs at an H : C between 0.84 and 0.69.

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 (pristine 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

Physical properties of Oils


Chemical compositions of crude oils
are the principal determinants of their
physical properties

Specific Gravity of oil


Range 0.73 slightly above 1.0
Paraffin-base oils light
Asphalt-base oils invariably heavy
Earlier, gravity was expressed in degrees of the
European Beaum scale, read directly on a
hydrometer at 15.6C (60F); degree goes up as the
density decreases
i.e., A high gravity oil is not a heavy oil but a light oil
B = (140 / ) 130

Specific Gravity of oil


Later, B has been replaced by API scale
API value = (141.5 / ) 131.5
So that water under STP conditions becomes
10 API
Relation between API & B
API value = (1.01071 x B) 0.10714
Presently, the measured quantity is
Density Relative to Water Kgdm-3

Specific Gravity of oil


Relation between API gravity & relative density

Specific Gravity of oil


By general convention
Oils with API gravities > 30 light
30 - 22 medium
< 22 heavy
< 10 extra-heavy
Worldwide average value is ~33.3 API
Most favoured grade of crude oil is ~37 API
Oils heavier than 12 API difficult to be
distinguished on the basis of gravity;
viscosity provides a more useful
discriminant
Oils lighter than ~50 API not really oils but
rather condensates / distillates

Specific Gravity of oil

Specific Gravity of oil


~37 API Middle East, Mid-continent, Appalachian
provinces (USA), Alberta, Libya, North Sea, etc.
crudes
>40 API large quantities in Algeria, south-eastern
Australia, Indonesia, Andes, etc. crudes
Very heavy crudes California, Mexico, Venezuela,
Sicily, etc.
<6 API + ~8 % S some crudes from fractured
Miocene reservoir rocks in California (Santa Maria
Basin)

Viscosity of oil
Viscosity is the internal friction of a fluid, causing its
resistance to change of form. It is the ratio of stress to
shear per unit time; shear in liquid is not constant, but
is proportional to time
Viscosity = Force x Distance / Area x Velocity
MLT-2L / L2 LT-1 = ML-1T-1
CGS Unit Poise
Conventional Unit centipoise
[1 cP = 10-2 Poise, viscosity of water at 20C (68F)]
SI Unit mPas [1 cP 1 mPas]

Viscosity of oil
Saybolt Universal Second (SUS) number of
seconds needed for a steel ball to roll through a
standard volume of the fluid
SUS = viscosity in cP x 4.635 / relative density
Typical oil viscosities measured in SUS at STP are
from ~1000 to 50

Viscosity of oil
Viscosity vary directly with densities
Hence, viscosities of oil are a function of the number
of C atoms and of the amount of gas dissolved in
the oil

Viscosity of oil
Viscosities of light oils < 30 mPas
Typical values between 5.0 & 0.6 (gasoline) mPas
Heavy asphaltic oils 50,000 mPas (Miocene oil in the
Bolivar coastal field in western Venezuela)
Very heavy oil ~1,00,000 mPas (Cold Lake, Alberta)
>106 mPas (Athabasca)
HC having viscosities > 10,000 mPas are known as natural
tars

Pour Point
A useful indicator of viscosity of crude oils; the lowest temperature
at which the crude flows under prescribed, controlled conditions
Pour points > 40C (more than 100F) are relatively common among
crudes having high contents of paraffin wax
Middle eastern and African crudes flow at ~ - 36C
Oils with high pour points because of high wax contents have a
shiny appearance & are associated with formation waters with low
salinity
When oils with high pour point rise in the traps, their temperatures
are lowered and the waxes crystalise out, forming a residue of high
molecular weight paraffins & oil becomes lighter
Prolific basins in which the original oils were paraffinic and derived
oils, in younger strata are asphaltic include the Carpathian Basin
(Romania), & Niger delta basin (off Africa)

Pour Point
Both paraffinic & asphaltic crudes may undergo
prolific volatilization through surface or near
surface alteration that they become totally
dried-up, so viscous that they effectively solids.
The drying-up process is INSPISSATION.

Pour Point
Very waxy crudes
Uinta Basin (Western USA), Anaco trend (Eastern
Venezuela) Reconcavo Basin (Brasil), Mendoza Basin
(Argentina), Beatrice field (off Eastern Scottland),
Mangyshlak field (east of the Caspian Sea), several
fields in the Sirte Basin (Libya & Sudan); Remarkable
proportion of the fields in young sandstone reservoirs
in Eastern Asia & Australia, (many oils from West India
& Upper Assam Basin of North Eastern India contain 10
15 % wax), most crudes from China, Sumatra, and the
Gippsland off-shore basin in Australia.

Colours & RI of oils


Paraffinic oils are commonly light in colour yellow
to brown by transmitted light, & green (of automobile
engine oil) by reflected light
Asphalt-base oils are commonly brown to black;
RI of oils vary with the relative density, between 1.42
and 1.48for most of the oils
Lighter oils Lower indices
At lower temperature Lower indices
Within any one molecular weight range
RI increase from paraffins through naphthenes,
to aromatics

Volume
Oil in reservoir contains dissolved gas, and the volume
of the solution depends upon the
formation gas-oil ratio
reservoir pressure
The gas that may be dissolved in oil under increasing
pressure increases the volume of the solution until the
saturation pressure (bubble point) is reached after
which the volume decreases with increased pressure

Volume
0.5 0.8 barrel of gas-free oil on the ground (stock
tank oil) may represent 1 barrel of oil in the
reservoir at the saturation pressure
The volume of liquid petroleum at constant pressure
increases with increasing temperature, but at a
much lower rate than gases
The solubility of gas in oil increases linearly with
pressure in accordance with Henrys law.
Heavy crudes have much less capacity to hold gas

Fluorescence
Fluorescence is observed under UV radiation (2537
3650 )
All oils exhibit more or less fluorescence (bloom)
Aromatic oils most fluorescent
Fluorescent colours of crudes range continuously from
yellow through green to blue
Fluorescence is used in the logging of wells to locate
oil showings in the cores, cuttings, and drilling mud
Fluorescence rapidly reduces by aging; this helps in
differentiating fresh oil from oil previously caught in the
drilling mud

Optical Activity
Most crudes have optical activity (the power to
rotate the plane of polarization of polarized light
Optical activity pertains to the presence of
cholesterin (cholesterol), an alcohol (C26H45OH)
Measured by a polariscope in degrees/mm
Average range 0 1.2 degrees
Plane rotated to the right dextrorotary
left levorotary

Odor
Paraffins, naphthenes, aromatics, S, H2S,
N-compounds have characteristics odor

Flash & Burning Point


These are the measurements of the hazard
involved in handling and storing petroleum and
petroleum products
Flash point Temperature at which the
vapours rising off the surface of the heated oil
ignites with a flash
Burning point At higher temperature ignition
and burning with a steady flame at the surface

Coefficient of expansion
For an increase in temperature of 1F for crude
oils, the coefficient of expansion varies between
0.00036 0.00096
For most crude oils 0.00040 to 0.00065
Average coefficient of expansion
Pennsylvania crude oils 0.000840
Baku crude oils 0.000817
Heavier crude oils (lower API) lower
coefficient & vice-versa

Calorific value

Calorific value of the crude oil decreases as


the specific gravity increases