Origin of Petroleum (H/C)

There are two origin for Petroleum, which are:

1. Inorganic
2. Organic
1. Inorganic Origin

In late 19th Century, when hydrocarbon first recognized the following

proposal put forwarded:

 Alexander von Humboldt, 1804 was the first to propose an

inorganic hypothesis, he observed petroleum springs in the Bay of
Cumaux (Cumaná) on the northeast coast of Venezuela and quoted
“petroleum is the product of a distillation from great depth and
issues from the primitive rocks beneath which the forces of all
volcanic action lie”.
 Dmitri Mendeleev, a Russian scientist, father of the periodic table,
proposed: when mettalic carbide deep within the earth reacted at
high temperature to water to form acetylene (C2H2) on condensation
form heavier hydrocarbon.

 Abraham Gottlob Werner in the 18th century believed basaltic sills

to be solidified oils or bitumen.

 In the mid-19th century. The prolific French chemist Marcelin-

Pierre Berthelot described in 1860 experiments where n-alkanes
formed during the acid dissolution of steels.

 W. Sokoloff, 1890, proposed a cosmic origin for petroleum, it was

precipitated as a rain from original nebular matter, that presently
ejected form the earth.
 Russian geochemists proposed that telluric currents deep in the
Earth’s crust combine water, graphite, iron and sulfur as a giant
battery that were “cooked” into hydrocarbons. V.B. Porfirev (1974)
even postulated that all known oilfields were formed in this way
during the Neogene.

 Another hypothesis was formulated by T. Gold. In his view, the

components of the early atmosphere are still stored in and slowly
degassed from the Earth’s mantle, mostly in the wake of
earthquakes.
 Objection to Inorganic Theories

 Optical rotatory power is a characteristics of Organic Matter

 Petroleum has homologue series of H/C, hardly to be formed by

inorganic agencies.

 The lack of association with volcanism, also is a great objection

because 8-10% found in igneous and metamorphic and this is due
to migration.

 If petroleum were to be cosmic origin then would have been

distributed uniformly in earth crust. So relatively the
Precambrian/Cambrian rocks contains less petroleum as compared
to younger rocks.
 2. Organic Origin

There following are compelling reasons favor the organic origin of

Petroelum (and are basis for Current theory):
1. Availability of Carbon and Hydrogen: A vast complex variety of
hydrocarbon containing carbon and hydrogen found in the
sediments can also be found in remains of animals and plants.
2. Presence of Porphyrin Pigments: Many oils found, contains
pigment name Porphyrin (C20H12N4): a pigment formed from red
colouring blood (hemin) and green colouring chlorophyll in plants,
which is the strong evidence for organic origin.
3. Presence of Nitrogen: found in petroleum indicating organic
source.
4. Optical Activity: Petroleum shows rotation in plane of polarization
of the light, which is due to the presence of chelostrol (C26H45OH)
and can be found in both vegetable and animal matter.
 Characteristics of Petroleum (H/C)

a. Nearly all petroleum occurs in marine sediments, from

Precambrian to Pleistocene.
b. Petroleum contains complex hydrocarbons, which chiefly
composed of 11-15% hydrogen and 82-87% carbon by weight.
c. The formation of petroleum is low temperature, anaerobic
(reducing environment) phenomena and temperature never
exceeds 200 degree Celsius, as indicated by a compound
“Porphyrine (C20H12N4)”.
d. The fluctuation of condition (P and T) within reservoir is
secondary phenomena due to erosion or deformation of area.
e. The oil pool indicate that some petroleum has migrated from its
place while other has not.
f. The time required for the formation and concentration is less than
1 million years.
 Composition of Petroleum

 Petroleum is mixture of Hydrocarbons, Hydrogen and Carbon are

an essential components.

 The Hydrocarbon on the basis of their structure can occur in nature

as:
Hydrocarbons
(H/C)

Aliphatic Aromatic
Compounds Compounds

Alkanes Cycloalkane
Alkenes Alkyne
(Paraffin) (Nephthene)
 But the principle series occur in the petroleum are, Alkane
(Paraffin) and Cycloalkane (Nephthane).

Aliphatic Compounds
The compounds that have no benzene or similar ring in its structure,
and have the following two principle compounds within petroleum:
1. Alkanes (Paraffin)
2. Cycloalkanes (Nephthenes)

1. Alkanes (Paraffins)
 (Methane Series) are saturated Hydrocarbons, having general
formula: CnH2n+2

 Compound starts from methane and through homologue series with

each heavier molecule than the one above it by adding CH2.
The Series
Methane CH4
Ethane C2H6
Propane C3H8
Butane C4H10
Pentane C5H12
Hexane C6H14
…….and so on

 At STP; the first four are gaseous in nature.

 First liquid is n-pentane (C5H12)

 First solid is n-hexadecane (C16H34)

 From 16th onward are high molecular weight hydrocarbon called as

“Solid Paraffin Waxes”.
2. Cycloalkane (Nephthene)
 (Cycloparaffin) are cyclic chain saturated Hydrocarbons, having
general formula: CnH2n

 Ring cannot posses fever than three carbon.

 At STP; cyclopropane (C3H6) and cyclobutane (C4H8) are gaseous

 Cyclopentane (C5H10) and cyclohexane (C6H12) are in liquid in

most of the crude oil.
Note: by combining above two main series within petroleum, we can
divide Aliphatic compounds into three types based on ratio between
Alkanes and Cycloalkanes as:

A. Paraffin based Aliphatic Compounds: ratio of paraffin greater than

cycloparaffin (when fractioned leaves wax as residuum)

B. Cycloparaffin based Aliphatic Compounds: ratio of cycloparaffin

greater than paraffin (when fractioned leaves asphalt as residuum)

C. Mixed Aliphatic Compounds: if ratio between paraffin and

cycloparaffin are equal.
 Besides, Alkane and Cycloalkane we have important petrochemical
compounds: those which are formed during fractional distillation of
crude oil (they are manufactured). They never exceeds in crude oil
more than trace amount. They are unstable and highly reactive.
They are very common in living matter (many natural oils, vitamins
A, pigments, rubber, sterols, etc.). These compounds are:

3. Alkenes (Olefins)
 These are isomers of cycloparaffins (Cycloalkanes) are unsaturated
Hydrocarbons, having general formula: CnH2n

 First three members are ethene (C2H4), propene (C3H6), butene

(C4H8). Methene is not possible due to single carbon.

4. Alkynes
 Unsaturated hydrocarbons, having general formula CnH2n-2
Aromatic Compounds
 The compounds that have benzene or similar ring in its structure,
and have formula CnH2n-6

 They may range in crude oil 1-10%.

 The density of a compound depends on Aromacity: the ratio

between aromatic carbon to total carbon (A=Aromatic C/Total C).

 High aromacity means low in density and vice versa.

 Aromacity low in lubricating oil while high in gasoline, toulene.

Geochemical Fossils
 Some crude oil do not contain paraffins and asphalts, instead
contains branching saturated hydrocarbons called as geochemical
fossils, produced by action of certain organism.

 These are helpful in locating the source on the basis of structure.

These come from animals and plants.

 High molecular weight having formula CnH2n-x, ratio between C and

H < 2.

Types of Geochemical Fossils

1. Long Chain Geochemical Fossils: derived from waxes of higher
plants

2. Complex Ring Alcohols: based on cyclohexane, and are derived

from plants and animals
3. Triterpentinoid Alcohols:
 are aromatic compounds based on Terpene: organic compound
having basic structure (C10H16) or multiple of (C10H16) e.g., steroid
having formula (C30H50OH) as an alcohol.

4. Acyclic Isoprenoids:
 compounds based on isoprene, chemical composition (C5H8), a
compound may have multiple of isoprene.

 Isoprenoids form long branched and saturated molecule, branching

is every 4th carbon having methyl group attached.

 Occurs in sediments with abundant derivatives from chlorophyll

from plants and hemin from animals.
 They are useful indicators of oil origin. Ratio of Pristane: Phytene,
measured chromatographically. Indicates type of organic matter
from which oil is derived and also measured maturity of source.

 Pristane (2,4,6,10,14 Tetra Methyl Pentadecane; having nineteen

carbon)

 Phytene (Tetra Methyl Hexadecane; having twenty carbon)

 If ratio is high, indicates organic matter derived from continent.

Therefore ratio is a vital finger prints for crude oil.
 Natural Gas
 Natural gas consists of Hydrocarbons not condensed at STP.

 First four member of Paraffin are in gaseous form

Classification of Natural Gas (Composition)

1. Dry gas: entirely composed of methane
2. Wet gas: a gas contains ethane with other molecule between 4-5%

Classification of Natural Gas due to Origin

1. Petroleum Gas: Formed as a by product of Petroleum, if present
with oil in reservior called associated gas, if not called non-
associated gas

2. Coal Gas: formed by modification of coal thermochemically,

world most comercial gas.
3. Bacterial Gas: formed in low temperature near surface, no relation
with petroleum e.g., marsh gas.

Other type of natural gas is:

4. Mineral Gas: totally unrelated with petroleum, formed during

volcanic activity

GOR (Gas Oil Ratio)

Volume of gas within reservoir in relation to the volume of oil

 Gas dissolved within oil in reservoir under great pressure and

temperature, and gas increases with increase in pressure and effect
the property of oil within reservoir.

 The pressure is also responsible oil to flow to the surface without

any effort.
 If the gas content is sufficient (saturate the oil) within reservoir it
cap the oil as “free gas cap”.

Distillation Process/Fractionization
 About 70-80% crude oil contains heavy Hydrocarbon higher than
C10 , The gasoline, kerosine, diesel and heavy oil are middle
fractionate, the remaining are residuum.
Natural-Gas Liquid (NGL)
Hydrocarbon that occurs naturally in gaseous or solution within oil in
reservoir and are recoverable through fractionation.

Forms of NGL
1. Condensate
2. Liquified Petroleum Gases (LPG)

1. Condensate
 A liquid hydrocarbon of wet gas at STP
 Includes pentanes and higher, called as pentane-plus, 10-40%
butane may include.
 Color pale yellow, API gravity above 60o.

2. Liquified Petroleum Gas (LPG)

 Hydrocarbon which are gaseous at STP, but compressed through
distillation process.
 Used as motor car fuel and mostly (propane and butane)
 Non-Hydrocarbon Constituents of Crude oil and Natural Gas
 Sulphur, nitrogen and oxygen and its compounds along with some
heavy metals like vanadium and nickel are non-hydrocarbon
constituents and are as;

1. Sulphur
2. Nitrogen
3. Oxygen
4. Other element
5. Metals

1. Sulphur and its compounds

 Range from 0-3%, found in heavy oil

 Some found in elemental form or as compound (H2S) the rest

attached in petroleum compounds e.g., Mercaptons or Thioalcohol
(C2H5SH), disulphides (as diethyl disulphide: C2H5SSC2H5) and
cyclic aromatic sulphides (as Thiophene: CnH2n-y S).
Classification of Crude oil on basis of Sulphur
1. Sour Crude Oil: contains detectable amount H2S
2. Sweet Crude Oil: S (wt.) = 0.1-0.2%
3. Low Sulphur Crude Oil: S (wt.) = 0.3-0.5%
4. Intermediate Sulphur Crude Oil: S (wt.) = 0.6-1.7%
5. High Sulphur Crude Oil: S (wt.) = > 1.7%

2. Nitrogen and its Compounds

 Amount ranges from 0.1-1.5%, generally 0.2% and present all type
of oil
 Its compounds are Pyridine (C5H5N) and Quinoline (C9H7N).

Classification of Crude oil on basis of Nitrogen

1. Low Content “N” Crude oil: N (wt.) = 0.2%
2. High Content “N” Crude oil: N (wt.) = 0.5%
3. Oxygen and its Compounds
 Ranges from 0.1-4.5% by weight.
 It may be present as free state, very beginning of organic decay
(anaerobically) or Phenol as OH in aromatics. It is also present at
some amount in CO2

4. Other Element in Crude oil and gas

 Are in trace amounts and are;

a. In Gas: H (wt.) = 0.1-0.5%, He= 5ppm (in dry gas or high in

nitrogen base gas and Ar (wt.) = 0.1%.

b. In crude oil: Radon = 0.1-0.4% PCi g-1, Thoron etc.

5. Metals in crude oil (like Nickel and Vanadium)

 Can be found in residuum, with heigh molecular weight 50 carbon
or greater atom.
 Compounds include: Asphaltene and Porphyrins
 Asphaltene: composition variable, in polymertic sheets having
aliphatic side chain and S-N-O, and metals which binds molecule of
porphyrins.

 Porphyrins: hydrocarbon ring complexes containing N and metallic

nucleus, metal in invariable either, Vanadium = 30-300 ppm or
Nickel= 20-85 ppm (in oily part of bitumen)
 Oilfield Water
The water associated with oil and gas pools are known as oilfield
waters.

Classification of Oilfield waters

1. Genetic Classification
2. Classification on the basis of occurrences

1. Genetic Classification
 Classified into three groups;

A: Meteoric Water
 The water, as a rain, which percolate from surface to subsurface.
 Water of this type contains combined oxygen, carbon dioxide in
form of carbonates, bicarbonates and sulphates.
B: Connate Water
 The water in which the sediments were deposited, mainly sea water.
 There chemistry is the same as sea water, may some time little high
in concetration w.r.t various minerals

C: Mixed Water
 The water which has both the affinity of meteoric or connate.
 Water and has chlorite, sulphate, carbonate and bicarbonates,
suggesting multiple origin.

2. Classification on the basis of occurrences

A. Free Water
B. Interstitial (attached) Water

A. Free Water
 A water which is ready to flow at any point of pressure release.
 They found in the aquifer in their inter connected pore spaces as a
continuous body.
B. Interstitial Water
 A water which is present at pore spaces of rock.

 May coexists with the oil and gas of every pool, and believed to be
present at time of rock is being formed and did not escape from
their because of capillary action.

 They found in oil and gas is less than 10% to 50% or more in pore
spaces.