PET631 Origin of Oil and Gas

Where does petroleum

come from?
Why is it normally
found in huge pools
under ground?
Was it formed in a big
pool where we find it,
or did it gather there
due to outside natural
forces?

PET631 Origin of Oil and Gas

The oil pool is an end product to a 5-stage sequence
of events:
Raw materials,
Accumulation,
Transformation,
Migration and
Geologic time.
A better understanding of how accumulation and
transformation take place would help clarify the whole
process.
the elemental chemical analysis indicates 10-15%
hydrogen and 82-87% carbon by weight.

PET631 Origin of Oil and Gas

Any theory regarding the origin of
petroleum must explain two sets of
observations,
one geological and the other
chemical.
Geological observations are that major
accumulations:
occur in sedimentary rocks
occur in porous material totally
encapsulated from other porous material.
Traces Chemical observations are:
crude oil differs from recent
hydrocarbons formed in shallow
environments, and
crude has over 50% light hydrocarbons
while light hydrocarbons are rare or
absent in the recent variety.

Inorganic Hypothesis:
There are two theories of origin:
Organic (bionic) or Inorganic (abionic).
Early theories postulated an inorganic origin when it
became apparent that there were widespread deposits
of petroleum throughout the world.
Dmitri Mendele'ev (1877), a Russian and the father of
the periodic table of elements, reasoned that
metallic carbides deep within Earth reacted with water
at high temperatures to form acetylene (C2H2) which
subsequently condensed to form heavier
hydrocarbons.
This reaction is readily reproduced in the laboratory.

Other hypotheses (Inorganic)

(Berthelot, 1860, Mendele'ev, 1902) were a
modification of the acetylene theory.
They theorized that the mantle contained iron
carbide which would react with percolating
water to form methane:
FeC2 + 2H2O = CH4 + FeO2
The problem was and still is the lack of
evidence for the existence of iron carbide in the
mantle.
These theories are referred to as the deepseated terrestrial hypothesis.

Another inorganic hypothesis

Another inorganic hypothesis was suggested
by Sokoloff (1890) who proposed a cosmic
origin.
His theory was such as
hydrocarbons precipitated as rain from original
nebular matter from which the solar system
was formed and then ejected from earth's
interior onto surface rocks.
This theory and others like it are referred to as
the extraterrestrial hypothesis

Conclusion:
There are unquestioned instances of indigenous
magmatic oil. But the occurrences are rare and the
volumes of accumulated oil (pools) are infinitesimally
low.
Other problematic issues:
Commercial accumulations are restricted to
sedimentary basins, petroleum seeps and
accumulations are absent from igneous and
metamorphic rocks, and gas chromatography can
fingerprint the organic matter in shales that found in
the adjacent pool.
Thus current theory holds that most petroleum is
formed by the thermal maturation of organic matter An Organic Origin generated the vast reserves (pools)
of oil and gas.

Organic Hypothesis:
There are a number of compelling reasons that support an
organic development hypothesis.
First and foremost, is the carbon-hydrogen-organic matter
connection.
Carbon and Hydrogen are the primary constituents of
organic material, both plant and animal.
Moreover, carbon, hydrogen, and hydrocarbons are
continually produced by the life processes of plants and
animals.
A major breakthrough occurred when it was discovered
(Smith, 1952; Smith, 1954; Stevens, 1956; Hunt, 1957;
Meinschein, 1959; Erdman, 1961; Kvenvolden, 1964;
Silverman, 1965) that hydrocarbons and related
compounds occur in many living organisms and are
deposited in the sediments with little or no change.

Second observation
Second were observations dealing with the chemical
characteristics of petroleum reservoirs.
Nitrogen and porphyrins (chlorophyll derivatives in
plants, blood derivatives in animals) are found in all
organic matter; they are also found in many
petroleums.
Presence of porphyrins also mean that anaerobic
conditions must have developed early in the formation
process because porphyrins are easily and rapidly
oxidized and decompose under aerobic conditions.
Additionally, low Oxygen content also implies a
reducing environment.
Thus there is a high probability that petroleum
originates within an anaerobic and reducing
environment.

Third observation
Third were observations dealing with the physical
characteristics.
Nearly all petroleum occurs in sediments that are
primarily of marine origin.
Petroleum contained in non-marine sediments
probably migrated into these areas from marine source
materials located nearby.
Furthermore, temperatures in the deeper petroleum
reservoirs seldom exceed 300oF (141oC) . But
temperatures never exceeded 392oF (200oC) where
porphyrins are present because they are destroyed
above this temperature.
Therefore the origin of petroleum is most likely a lowtemperature phenomenon.

Organic Hypothesis - Summary.

The organic theory became the accepted
theory about the turn of the century as the
oil and gas industry began to fully develop
and geologists were exploring for new
deposits.
Simply stated, the organic theory holds that
the carbon and hydrogen necessary for the
formation of oil and gas were derived from
early marine life forms living on the Earth
during the geologic past -- primarily marine
plankton.

Coal Formation
Coal deposits come from many epochs, but the best
and most abundant are from the forests in the warm,
swampy river deltas of the Carboniferous period,
some 320 million years ago.

Formation of Hydrocarbon
All fossil fuels, whether solid, liquid, or gas, are the result of
organic material being covered by successive layers of
sediment over the course of millions of years.
Some deposits of coal can be found during the time of the
dinosaurs. For example, thin carbon layers can be found
during the late Cretaceous Period (65 million years ago) - the
time of Tyrannosaurus Rex. But the main deposits of fossil
fuels are from the Carboniferous Period.
Fossil fuels supply over 80% of the worlds energy needs.

Plankton and other forms of marine life

Although
plankton are microscopic, the
ocean contains so many of them
that over 95% of living matter in
the ocean is plankton.
The Sun's energy provides
energy for all living things
including plankton and other
forms of marine life (Fig.1)
As these early life forms died,
their remains were captured by
the processes of erosion and
sedimentation (Fig 2).

Porphyrin

.A

porphyrin is a heterocyclic macrocycle

derived from four pyrrole-like subunits
interconnected via their carbon atoms via
methine bridges (=CH-).

The macrocycle, therefore, is a highly

conjugated system, and is consequently
deeply colouredthe name porphyrin
comes from a Greek word for purple.
The macrocycle has 22 pi electrons.
The parent porphyrin is porphine, and
substituted porphines are called
porphyrins.
Many porphyrins occur in nature, such as in
green leaves and red blood cells, and in bioinspired synthetic catalysts and devices.

Structure of
porphine, the
simplest porphyrin

Space-filling model
of porphyrin

Organic-rich mud and silt

Successive layers of organic-rich mud and silt covered
preceding layers of organic rich sediments and over
time created layers on the sea floor rich in the fossil
remains of previous life (Fig. 3).
Thermal maturation processes (decay, heat, pressure)
slowly converted the organic matter into oil and gas.

Thermal maturation processes

Add additional geologic time (millions of years) and the organic
rich sediments were converted into layers of rocks.
Add more geologic time and the layers were deformed,
buckled, broken, and uplifted; the liquid petroleum flowed
upward through porous rock until it became trapped and could
flow no further forming the oil and gas that we explore for at
present (Fig. 4).

chemistry of the hydrocarbons

But the chemistry of the hydrocarbons found in
the end product (oil, gas) differ somewhat from
those we find in living things.
Thus changes, transformation, takes place
between the deposition of the organic remains
and the creation of the end product.
The basic formula for the creation of petroleum
(oil, gas) is:
Petroleum End Product = ([Raw Material +
Accumulation + Tranformation + Migration] +
Geologic Time)

Marine Ecosystems

Intertidal zone
Examples:
sandy beaches
rocks
estuaries
mangrove swamps
coral reefs
Some of these regions are quite productive.
Many of their inhabitants have adaptations that
enable them to survive periodic exposure to the
air and wave action.

Marine Ecosystems
Neritic zone
This is the relatively shallow ocean that extends to the
edge of the continental shelf. Primary productivity here
depends on planktonic algae growing as deep as the
light can reach.
Oceanic zone
Located over the ocean basins. Here, too, primary
productivity is pretty much limited to the depths that light
can reach. The producers are planktonic algae that
support secondary and higher consumers (e.g., fish) in
the nekton.
Despite its diversity of life, the
net productivity of the open ocean is little better than
that of a desert.

Photosynthesis.
The process of merging hydrogen and
carbon (from carbon dioxide and
water) is accomplished through
photosynthesis.
Organisms like diatoms, a one celled
plant, can start the process of creating
organic matter ("A" in the diagram).
As the carbon and hydrogen are
trapped in the food chain for
nourishment of other organisms, crude
oil is not produced immediately.
However, as the death of these
organisms and the burial of the
organic matter in sediments is
complete, crude oil will start to form
(black layers in "B")

HOW OIL AND GAS ARE CREATED

Crude is associated mainly with
sedimentary rocks deposited in
the marine environment.
These deposits indicate that
high productivity of organic
carbon is important and contain
many fossil microorganisms like
diatoms and radiolarians.

Crude oil, tar, and natural gas Composition

Element

crude % weigh

Carbon

82.2-87.1

80-85

65-80

Hydrogen 11.7-14.7

8.5-11

1-25

tar(asphalt)

natural gas

sulfur.

1-5.5

2-8

trace-.2

nitrogen.

1-1.5

0-2

1-15

oxygen.

1-4.5

Fermentation
Today, we can create methane gas from decaying
organic matter through bacterial fermentation.
Fermentation is a chemical transformation by bacteria
that chemically alters different substances.
It is likely that the environment for petroleum
production is without oxygen, as sediment covers the
organic matter.
This is called a reducing environment.
It has been shown in the laboratory that reducing
bacteria tend to convert organic matter into a
petroleum like substance.
Reducing bacteria are very slow, and maybe that is
why geologic time plays an important part.

Transformation of organic matter

Heat combined with increased pressure aids the
transformation of organic matter into petroleum
products. But too much heat or too much pressure can
prevent any oil from forming.
Many geologists use petroleum formation to guide
them on how much heat was in an area. For example,
if oil is found, the temperature never exceeded 200E C
or (392E F).
As oil is being produced in source rocks like
diatomite or limestone, the oil and gas will move into
reservoir rocks that can trap the oil as shown in the
diagram below

High productivity

Plate tectonics creates areas that are ideal for oil

accumulation. High productivity, especially along continental

Organic matter

The Carbon Cycle

During the carbon cycle, autotrophs acquire CO2 from the atmosphere by diffusion through leaf
stomata, incorporating it into their biomass. Some of this becomes a carbon source for
consumers and respiration returns CO2 to the atmosphere. Photosynthesis and cellular
respiration form a link between the atmosphere and terrestrial environments (fig. 49.10). Carbon
cycles in the environment very quickly. Plants have a high demand for CO2, yet CO2 is present in
the atmosphere at a low concentration (0.03%). Carbon loss by photosynthesis is balanced by
carbon release during respiration. Some carbon is diverted from cycling for longer periods of
time, as when it accumulates in wood or other durable organic material. Decomposition
eventually recycles this carbon to the atmosphere. However carbon can be diverted for millions of
years, such as in the formation of coal and petroleum.
The amount of atmospheric CO2 decreases in the Northern Hemisphere in summer due to
increased photosynthetic activity. Amounts increase in the winter when respiration exceeds
photosynthesis. Atmospheric CO2 is increased by combustion of fossil fuels by humans,
disturbing the balance. The ocean may act as a buffer to absorb excess CO2. In aquatic
environments photosynthesis and respiration are also important but carbon cycling is more
complex due to interaction of CO2 with water and limestone. Dissolved CO2 reacts with water to
form carbonic acid, which reacts with limestone to form bicarbonates and carbonate ions. As CO2
is used in photosynthesis, bicarbonates convert back to CO2; thus bicarbonates serve as a CO2
reservoir and some aquatic autotrophs can use dissolved bicarbonates directly as a carbon
source.
The ocean contains about 50 times the amount of carbon (in various inorganic forms) as is
available in the atmosphere

Biogeochemical Cycles

As a part of biogeochemical
cycles, certain elements
move through both living and
non-living components of the
Earth system. The living parts
of the Earth system comprise
the biosphere, while the nonliving parts of the Earth
include the hydrosphere,
atmosphere, cryosphere, and
geosphere. The same
individual elements are
recycled over and over in
different parts of the Earth
through biogeochemical
cycles.
The carbon cycle, one of Earth's biogeochemical cycles

The element carbon is a part of seawater, the atmosphere, rocks such as limestone and coal, soils, as well as all
living things. On our dynamic planet, carbon is able to move from one of these realms to another as a part of the
carbon cycle.
Carbon moves from the atmosphere to plants.
In the atmosphere, carbon is attached to oxygen in a gas called carbon dioxide (CO2). Through the process of
photosynthesis, carbon dioxide is pulled from the air to produce food made from carbon for plant growth.
Carbon moves from plants to animals.
Through food chains, the carbon that is in plants moves to the animals that eat them. Animals that eat other
animals get the carbon from their food too.
Carbon moves from plants and animals to soils.
When plants and animals die, their bodies, wood and leaves decays bringing the carbon into the ground. Some is
buried and will become fossil fuels in millions and millions of years.
Carbon moves from living things to the atmosphere.
Each time you exhale, you are releasing carbon dioxide gas (CO2) into the atmosphere. Animals and plants need
to get rid of carbon dioxide gas through a process called respiration.
Carbon moves from fossil fuels to the atmosphere when fuels are burned.
When humans burn fossil fuels to power factories, power plants, cars and trucks, most of the carbon quickly
enters the atmosphere as carbon dioxide gas. Each year, five and a half billion tons of carbon is released by
burning fossil fuels. Of this massive amount, 3.3 billion tons stays in the atmosphere. Most of the remainder
becomes dissolved in seawater.
Carbon moves from the atmosphere to the oceans.
The oceans, and other bodies of water, absorb some carbon from the atmosphere. The carbon is dissolved into
the water. Marine animals are able to use the carbon to build their skeletal material.

Microscopic marine life

Microscopic marine life, plankton, are considered to be the
primary source of all hydrocarbons. There are two types of
plankton:
Phytoplankton are the most important and comprise the bulk
of the marine plankton. The most abundant volumetrically,
are the Diatoms, siliceous unicellular plants. Diatoms contain
minute droplets of oil that accumulate in their cellular
structure late in the vegetative period.
The other type of plankton is Zooplankton. Foraminifera and
Radiolaria are the most widely represented fossils in young
oil-bearing strata.
Whatever the reason, the bulk of evidence favors planktonic
aquatic organisms, zooplankton and phytoplankton, as the
primary source material for the formation of oil and wet gas.
Plankton (Phytoplankton, Zooplankton) create the oil by synthesizing fatty
acids

The Carbon Cycle

Carbon is an element. It is part of oceans, air,
rocks, soil and all living things. Carbon
doesnt stay is one place. It is always on the
move!

 Carbon moves from the atmosphere to

plants.
In the atmosphere, carbon is attached to oxygen
in a gas called carbon dioxide (CO2). With the
help of the Sun, through the process of
photosynthesis, carbon dioxide is pulled from the
air to make plant food from carbon.
Carbon moves from plants to animals.
Through food chains, the carbon that is in plants
moves to the animals that eat them. Animals that
eat other animals get the carbon from their food
too.

Oil and Gas Generation and Yields:

Compositional Kinetics
Introduction
Compositional kinetic and yield analysis describes the rate at
which organic matter decomposes into oil and gas as well as
the yields of these compounds or compound-classes at
various levels of conversion or maturity. It is needed to
determine the yields and timing of generation of:
dry gas (C1, methane)
wet gas (C2-C4)
light oil (C5-C14)
normal oil (C15+)
explain the first oil formed and expelled from source rocks
predict GOR and gas wetness at varying temperatures or
maturities

 Bulk kinetic modeling, i.e., decomposition of kerogen into

hydrocarbons without description of products formed,
has supplanted empirically-based TTI modeling as the
latter does not take into account the variability in kerogen
decomposition rates. However, while improving our
estimates of the timing of hydrocarbon generation, bulk
kinetic data does not provide any description of the
products formed nor the timing of generation of the
hydrocarbon moities listed above. Furthermore, bulk
kinetics constrain all data to a single set of kinetic
parameters, which limits its capability to predict early oil
generation or the broad dry gas (methane) generation
window.

 Compositional kinetic data, which measures the rate of

kerogen decomposition into specific chemical moieties,
provides detailed kinetic parameters and hydrocarbon
yields for each of these fractions including dry and wet
gas as well as light and normal oil.
Further, these data show that the gas window varies
among and within kerogen types, as do the condensate
and oil windows. In addition these data explain the
formation of early oil, i.e., the oil present in low to early
oil window maturity source rocks.
Development of a breakthrough in trapping capability by
Humble Instruments has enabled the precise evaluation
of C1 through C40+ hydrocarbons using the MACT10
instrument.

MACT10
Multiple Automatic Cryogenic Trapping

This instrument features Humble

Instruments performance flow
programmable pyrolysis injector the TEPI,
multiple automatic cryogenic trapping,
Agilent 6890 gas chromatograph with
either flame ionization or mass
spectrometer detectors; provides data for
determining oil and gas compositional
kinetics for detailed modeling hydrocarbon
generation from petroleum source rocks.

MACT10
Multiple Automatic Cryogenic Trapping

This sophisticated instrument allows

effluent from Pyrolysis (or other process
effluents) to be trapped in up to 9 separate
cryogenically cooled (-200 C) traps at
specified times or temperatures. The
complete analysis cycle consisting of
trapping, desorbing, separation, detection
and quantitation is programmable and
automated under unattended computer
control.

MACT10
Multiple Automatic Cryogenic Trapping
Diagrammatic sketch of the MACT10 system: The
effluent from pyrolysis or other process effluents are
trapped automatically in up to nine separate cryogenic
traps at times or temperatures selected by the user.
Subsequent separation, detection, and quantitation is
completed automatically via software control.

MACT10
Multiple Automatic Cryogenic Trapping

MACT10 Plus System offers flexibility in

sample introduction, processing, and
detection techniques. These techniques
include open or closed system isothermal or nonisothermal pyrolysis,
qualitative or quantitative analysis, flame
ionization, mass spectrometer, or
compound-class specific detectors.

Sample Introduction Options

Sample Introduction Options

Humble Instruments TEPI featuring uniform temperature profile, insample temperature measurement and recording, and flow or
pressure programming is featured on the MACT10 Plus System.
The Humble TEPI is constructed of either stainless steel or quartz
and can be operated in isothermal and nonisothermal modes with 1
C precision. Nonisothermal pyrolysis can be completed with
programming rates up to 60 C/minute to final temperatures of 750
C.
The TEPI can be utilized for thermal extraction gas chromatography
which is useful for solvent free evaluation of volatile components
such as hydrocarbons, pollutants, contaminates, and other unknown
compounds in solid, semi-solid or liquid samples.

MACT10 interfaced to the Agilent

GCD system

MACT10 interfaced to the Agilent 6890 gas

chromatograph with FID and MSD 5973 detectors
coupled to the HISI pyrolysis inlet.

The MACT10 operating software makes complicated sequencing completely automatic

and trouble free.

Thermal Extraction Pyrolysis Inlet

(TEPI)
Thermal Extraction Pyrolysis Inlet (TEPI)
interfaced to a gas chromatograph with FID,
MSD, or other detectors plus data system,
provide an integrated solution to a wide range of
analytical needs. We offer the SR Analyzer-TEPI
as a standalone instrument for use with any GC
system or integrated workstations
(recommended) for utilization of fast, high
resolution GC analysis of volatile or pyrolyzed
products allowing results in minutes instead of
hours.

SR Analyzer-TEPI/Thermal Extraction
Advantages

SR Analyzer-TEPI/Thermal Extraction Advantages

Preservation of volatiles (more accurate analyses)
No solvents required (environmentally-sound)
No sample preparation (low cost operation)
Fast, high resolution GC compatible (quick results)
Easy to maintain and operate (high productivity)

Background
Kerogen, the organic matter that forms oil and
gas under increasing thermal stress, has two
reactive components (Cooles et al., 1985).
There is oil and gas prone organic matter as well
as an inert carbon residue (Figure 1). While
most bulk kinetic and basin modeling programs
only account for gas formation from oil cracking,
there is also significant gas formed directly from
kerogen depending on kerogen composition.

Figure 1. Diagrammatic illustration of kerogen composition, which leads to oil

and gas formation directly from kerogen cracking and gas from oil cracking

HISI Analytic Technologies

HISI Analytic Technologies' MACT10 was
developed for assessment of the oil and
the gas portions of kerogen (see Appendix
for analytical details). MACT10 data is
used to evaluate in chemical detail the
products formed from kerogen in terms of
both oil and gas formation. Of course, oil
cracking must also be accounted for in
assessing total gas yields.

Compositional yields of resolved hydrocarbons from

MACT10 experimental data.
The resulting data can be used to assess the yield of
various compound classes (Figure 2).

 These yield data for this lacustrine (Type I)

sample are not very surprising
demonstrating that a high yield of oil is
expected. However, for other samples the
yield results have sometimes been quite
surprising. For example, the Type II
kerogen shown in Figure 3 yields over
53% gas!

Figure 3.
Figure 3. A Type II kerogen,
which is about 20-30%
converted, has a very high
gas yield. This explains
overpressuring in this
formation and inherent
"sealing" of the source rock
inhibiting expulsion. Without
oil expulsion, oil cracking
will proceed.