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CHEMICAL COMPOSITION OF PETROLEUM

&
FRACTIONAL CATEGORIZATION
BY
Dr A.K. Mittal

Introduction
Petroleum is a form of bitumen composed principally of
hydrocarbons and existing in the gaseous or liquid state
in its natural reservoir.
The word petroleum originates from the Latin petra
(rock) and oleum (oil).
The main forms of petroleum are natural gas,
condensate, and crude oil, the liquid part of petroleum.

Condensates

Reservoir gases under very high pressure are able to dissolve large
amounts of liquid hydrocarbons. When such gases are produced, the liquid
condenses and is collected in a separator.

The condensate generally has an API gravity higher than 55o. Most
condensates are composed of saturated hydrocarbons in the light gasoline
range which causes the high API gravities.

A condensate is distinguished from a light oil in that the former usually, but
not always, has a gas-oil ratio greater than 5000 cubic feet of gas per barrel
of oil. In addition, by definition a condensate must exist in the gaseous state
in its reservoir.

Petroleum is composed almost entirely of the elements


hydrogen and carbon. Crude oil contains approximately
84-87 percent carbon and 11-13 percent hydrogen.
The minor elements sulfur, nitrogen, and oxygen
constitute less than 3% of most petroleum.
Traces of heavy metals such as vanadium and nickel
also are present.

The quantity of petroleum generated from kerogen


is determined mainly by the hydrogen content of the
kerogen. A high-hydrogen kerogen (7 to 10% H)
generates far more oil and gas than does a lowhydrogen kerogen (3 to 4%H).
Since hydrogen is a much lighter element than the
other elements, oils with a higher hydrogen content
have lower specific gravities.

The table below compares the elemental composition of gas, oil, asphalt, coal,
and the dispersed organic matter (kerogen) in sedimentary rocks.

Going across from gas to kerogen, there is a marked decrease in hydrogen and
a corresponding increase in sulfur, nitrogen, and oxygen relative to carbon.

The elements carbon and hydrogen are combined as hydrocarbons


that vary in both size and type of molecule in crude oil.
Differences in the physical and chemical properties are due to the
variations in the distribution of the different sizes and types of
hydrocarbons and the percentage of NSO compounds.
A crude oil becomes heavier and API gravity decreases as the
percentage of aromatic and naphthenic hydrocarbon increases
relative to paraffin and as the percentage of NSO compounds
increases.
The term light and heavy also are used in marketing crude oils.
Currently, light is greater than 31.1oAPI gravity; medium is 22.3 to
31.1oAPI; heavy is 10 to 22.3oAPI; and extra heavy is less than 10oAPI
gravity.
The API gravity is measured in degrees and is calculated using the
formula:
API Gravity=[141.5/(S. G. at 60oF)]-131.5

How Crude Oil Is Classified

The two most widely used criteria to determine the quality of crude oil are density and
sulfur content:

Density:

Crudes can be classified as light or heavy, a characteristic which refers to the oils
relative density based on the American Petroleum Institute (API) Gravity. This
measurement reflects how light or heavy a crude oil is compared to water. If an oils
API Gravity is greater than 10, it is lighter than water and will float on it. If an oils API
Gravity is less than 10, it is heavier than water and will sink.

Lighter crudes are easier and less expensive to produce. They generally have a
higher percentage of light hydrocarbons that can be recovered with simple distillation
at a refinery. A crude oil with lower density tends to yield higher levels of products.

Heavy crudes cant be produced, transported, and refined by conventional methods


because they have high concentrations of sulfur and several metals, particularly
nickel and vanadium. With simple distillation, these dense, heavier crude oils produce
a greater share of lower-valued products. Heavy crudes require extra refining to
produce more valuable and in-demand products.

How Crude Oil Is Classified

Sulfur content is another key determinant of crude oil quality. Sulfur is a


corrosive material that decreases the purity of a crude oil.

Crude oil with high sulfur content, which is known as sour, is much less
desirable than a crude oil with low sulfur content, known as sweet crude.

The New York Mercantile Exchange designates petroleum with less than
0.42% sulfur as "sweet".

"Light sweet crude oil" is the most sought-after version of crude oil as it
contains a disproportionately large fraction that is directly processed
(fractionation) into gasoline (naptha), kerosine, and high-quality diesel (gas
oil).

Molecular Size Variation


The smallest molecule in petroleum is methane (CH4), with a
molecular weight of 16.
The largest molecules are the asphaltenes, with molecular weights in
the tens of thousands.
Between these two extremes are thousands of compounds having
simple to very complex structures.
Hydrocarbons form homologous series, that is, families of molecules
whose members have similar properties and differ in size by the CH2
group.
As the molecular size increases, the individual members change from
gases to liquids to solids.
For the paraffin series with formula CnH2n+2, n equals 1 to 4 for gases,
5 to 16 for liquids, and above 16 for solids for the straight-chain
paraffins.
Petroleum is separated into its various molecular sizes by distillation.

Molecular Type Variation


Hydrocarbon molecules occur in different structural forms
with the following names:

Alkanes or paraffins are open-chain molecules with single


bonds between the carbon atoms;

cycloalkanes or naphthenes or cycloparaffins are alkane


rings;
alkenes or olefins contain one or more double bonds
between the carbon atoms;
and arenes or aromatics are hydrocarbons with one or more
benzene rings.

In discussing molecular structures, both conventional and shorthand


skeletal formulas are used as shown in the figure. In the skeletal
formulas shown on the right, a carbon atom with enough hydrogen
atoms to give a total of four bonds is implied at each corner or end of
the structures.

Paraffins (CnH2n+2)

The paraffin-type hydrocarbons are the second most common


constituent of crude oil next to naphthenes.

Paraffins dominate the gasoline fraction of crude oil, and they are the
principal hydrocarbons in the oldest, most deeply buried reservoirs.

The terms saturated and aliphatic hydrocarbons are also used for this
group.

Since a normal paraffin is defined as a straight chain, there are a limited


number of them in crude oil-usually fewer than eighty (n= 1 to 80). This
makes them the most easily identified compounds in petroleum. All other
molecular types contain hundreds of different molecules, so
identification is much more difficult.

The normal paraffins are relatively inert with strong acids, bases, and
oxidizing agents.

Plants began to synthesize paraffin waxes early in geologic history as


coatings of seeds, spores, leaves, and other cells that had to be
protected from weathering. As sediments undergo diagenesis, much of
the original organic matter is altered or destroyed, but the paraffin
coatings last unless the rock is subjected to high-temperature
metamorphism.

Paraffins (CnH2n+2) contd


Carbon atoms need not always bond together in a linear
arrangement. In addition to straight chains, the paraffins can
form branched-chain paraffins or isoparaffins.
Whereas only about eighty structures of straight chain nparaffins exist in petroleum, it is theoretically possible to have
more than a million branched-chain structures representing
different type of branching.
Among the most important branched hydrocarbons in organic
geochemistry are the isoprenoids. Regular isoprenoids consist
of a straight chain of carbon atoms with a methyl branch on
every fourth carbon.
Isoprenoids ranging in length from six to forty carbon atoms
have been found in petroleum and rocks.

This table lists the number of possible isomers representing different


kinds of branching, all containing the same number of carbon atoms
and corresponding to the formula CnH2n+2. Isomers are different
compounds with the same molecular formula.

Fortunately, since crude oil is derived from a finite number of structures


in living things, it is not as complex as the theoretical number of isomers
seems to indicate.

However, since a number of these isomers can form through the


cracking and rearrangement of organic structures over geologic time
and since there are an equally large number of isomers possible with
naphthenes and aromatics, it is obvious that the composition of
petroleum is very complex.

Naphthenes or Cycloparaffins
The cycloparaffins that are formed by joining the carbon atoms in a ring
are the most common molecular structures in petroleum.
Naphthene rings generally contain five or six carbon atoms.
A few cycloheptanes (C7 H14) have been identified in petroleum but no
rings smaller than C5 or larger than C7 have been found.
The average crude oil contains about 50% naphthenes, with the
quantities increasing in the heavier fractions and decreasing in the
lighter fractions.
In the heavier fractions, naphthenes tend to fuse into polycyclic rings;
that is, a group of rings in which two or more carbon atoms are shared
between the rings.
The most common naphthenes are methylcyclopentane and methyl
cyclohexane, which together represent 2% or more of the average crude.
A general chemical formula for cycloalkanes would be CnH2(n+1-g) where
n = number of C atoms and g = number of rings in the molecule.

Steranes and triterpanes which are important biomarkers are also cycloalkanes, basic
structures of which are given below.
Organic compounds whose carbon structure, or skeleton, is formed by living organism
and is sufficiently stable to be recognized in crude oil or the organic matter of ancient
sediments are called biomarkers. Typical markers are the porphyrins, pristane, phytane,
steranes, carotanes, and pentacyclic triterpanes.

Steroids are biological precursors of steranes and triterpenoids are biological precursors for triterpanes.
Steranes and triterpanes are useful in determining maturity, the type of organic matter and in interpretations
of depositional environments as well as in fingerprinting.

The naphthenes, normal and branched paraffins and isoprenoids are all
saturated hydrocarbons because all available carbon bonds are saturated
with hydrogen.

Olefin Hydrocarbons

Another important group of hydrocarbons is the unsaturates, which in


contrast are able to combine with additional hydrogen.

Many unsaturated compounds have carbon-carbon double bonds between


two or more carbon atoms; these compounds are called alkenes or olefins.
Examples are ethene (ethylene), propene and cyclohexene, etc. Due to
double bonds olefins become very reactive compared with the other
hydrocarbon types.

The unsaturated state of the olefin is much more unstable than that of the
aromatics. If hydrogen or other elements are not available to react with the
unsaturation, some olefin will react with themselves to form high molecular
weight polymers.

Many hydrocarbons formed by plants and animals are olefins. Ethylene


(C2H4) is the major gas formed by the ripening of fruits and vegetables.
Apples, pears, tomatoes, and corn all yield ethylene on ripening.

Peanut oil, olive oil, fishliver oil, and wheat germ oil all contain some
olefinic hydrocarbons. Squalene, a natural component of human tissues
that is an intermediate in the biosynthesis of cholesterol, is an olefin.
Vitamin A and many pigments, such as the orange of carrots and the red of
tomatoes, are olefins.

Olefin Hydrocarbons (contd)


Isoprene is an important olefin which is the basic building block
for many hydrocarbon structures in living things, including the
terpenes, rubber, most pigments, vitamin A, and the sterols. It is
the precursor of essential oils of flowers, fruits, seeds, and
leaves.
Of all the biological structures that have formed the
hydrocarbons of recent sediments, isoprene is undoubtedly the
most important.
Because olefins are highly reactive, they do not long persist in
geologic environments. A variety of reactions, including
hydrogenation, converts olefins to alkanes and cyclic compounds
during diagenesis.
Thus, although olefins are the most common hydrocarbons of
living things, they are uncommon in crude oils. Olefins are
formed in refinery processes, where they are major materials for
petrochemicals.

Skeletal formulas for some olefin hydrocarbons

Skeletal formulas for olefin hydrocarbons. Squalene, the precursor of sterols,


is formed from six isoprene units.

Aromatic Hydrocarbons
Aromatics form an extremely important class of unsaturated
hydrocarbons.
Although they are unsaturated, they do not add hydrogen easily.
Their stability permits aromatics to be important constituents of
oils and sediments.
Aromatics possess a system of alternating single and double
bonds within a cyclic structure. A simplified notation for drawing
these molecules permits us to represent the double-bond system
by a circle within a ring.
The circle indicates that the electrons in the double bonds are
delocalized; that is, they are free to move throughout the cyclic
system instead of being held between two particular carbon
atoms.
It is this delocalization of electrons which makes aromatic
compounds very stable.
All aromatic hydrocarbons have at least one benzene ring (C 6H6).

Aromatic Hydrocarbons, contd

The aromatics rarely amount to more than 15% of a total crude oil. They tend to be
concentrated in the heavy fractions of petroleum, such as gas oil, lubricating oil, and
residuum, in which the quantity often exceeds 50%.

Heavy fractions of petroleum contain polycyclic aromatic hydrocarbons having fused


ring structures. The extreme case is graphite, which is an almost endless sheet of
aromatic rings.

Some compounds (called naphthenoaromatics) contain both aromatic and naphthenic


rings. Many naphthenoaromatics are derived from steranes and triterpanes.

Toluene and metaxylene are the most common aromatic hydrocarbons in petroleum.

Aromatics have the highest octane ratings of the hydrocarbon types, so they are
valuable in gasoline blends. However, they are undesirable in the lubricating oil
range, because they have the highest change in viscosity with temperature of all the
hydrocarbons.

Polycyclic aromatic hydrocarbons in natural products are being studied more


intensively, because some of them, such as 3,4-benzpyrene, 3,4-benzphenanthrene,
and 1,2,3,4,-dibenzphenanthrene, are potent carcinogens. Besides being found in
coal tars and petroleum, they are a common constituent of the burning of most
organic material.

NONHYDROCARBONS-Nitrogen, Sulfur and Oxygen


compounds (asphaltics)

The fifth molecular type are the nonhydrocarbons.

Atoms other than hydrogen and carbon that occur in petroleum, bitumen
and kerogen are called heteroatoms; the compounds in which they occur
are called heterocompounds. They are also called NSO compounds,
because the most common heteroatoms are nitrogen, sulfur and oxygen.

Most crude oil residua contain a high percentage of nonhydrocarbon


compounds.

Fossil organic matter often contains a wide variety of heterocompounds,


of which some are biogenic and others are formed during diagenesis.

Fatty acids, derived from natural fats, oils, and waxes, were among the
first NSO compounds to be studied.

NONHYDROCARBONS-Nitrogen, Sulfur and Oxygen compounds


(asphaltics), contd
One of the most important classes of NSO compounds is the
porphyrins. These molecules are structurally related to, and in most
cases derived from, chlorophyll. Early work on porphyrins provided
important evidence about the organic origin of petroleum.
There are small amounts of nonhydrocarbons scattered through the
entire boiling range of crude oil and a few of them are listed in next
slide.
Sulfur compounds include thiols, sulfides, thiophenes, and
benzothiophenes.
Nitrogen compounds include pyrroles, indoles, pyridines, quinolines,
and carbazoles.
Oxygen compounds are mainly chain or ring acids.

R equals a straight or branched paraffin chain

Skeletal formulas for nitrogen, sulfur, and oxygen compounds.


Heterocyclics are common in the residuum of petroleum.

Chlorophyll is a green pigment found in cyanobacteria and


the chloroplasts of algae and plants.
Chlorophyll plays a crucial role in producing food for the
plant by synthesizing simple sugars (glucose) from
Sunlight + CO2 (Carbon dioxide) + H20 (Water) in the
process of photosynthesis. The by-product of photosynthesis is
Oxygen.
The reaction preformed by chlorophyll can be expressed as:
6CO2 + 6H20 + Sunlight => C6H12O6 (glucose) + 6O2

Many common NSO compounds are not directly related to biogenic


precursors.
Among the most important NSO compounds are the asphaltenes, which
are large, highly aromatic materials of varying structure.
They have many characteristics in common with kerogens, but asphaltene
molecules are smaller and more aromatic than most kerogens.

Distillation of crude oil

Petroleum is separated into its various molecular sizes by distillation.


Distillation is the principal method for separating crude oil into useful products. It is
done in a refinery.

A refinery tower will yield products from the smallest to the largest size, of molecule,
as follows: gas, gasoline, kerosene, light gas oil (diesel fuel), heavy gas oil, lubricating
oil, and residuum.

Some examples of the resulting fractions and their uses follow:


Refinery Gas - used to make Liquid Petroleum Gas (LPG)
Light Gasoline - used to make petrol
Naphtha - used to make petrol
Kerosene - used as central heating fuel or to make jet fuel
Gas Oil - used to make diesel fuel
Residue Fractions - used to make bitumen for roads.

A refinery tower is equivalent to a series of individual distillation flasks,


in which the distillate from the first flask is condensed in the second
flask and redistilled to produce a distillate for the third flask. Instead of
flasks, the tower has condensation plates.
The vapour distilled from one of the chambers rises to the chamber
above and passes through the condensed liquid of that chamber.
Each overlying chamber in the tower condenses successively lighter
and smaller molecules, until only the light gasoline escapes from the
top.
At the bottom of the tower are those molecules that are so large and
heavy that they can not penetrate as gases through the first plate and
so end up in the residuum.
The refining tower is run continuously by taking products out at various
levels in the tower while continuously introducing fresh crude oil.

Generally, the less processing or refining a crude oil must undergo,


the more valuable it is considered. Price differentials between crude
oils typically reflect the ease of refining.

The lighter the oil, the more of the desirable, in-demand products it
will produce through distillation at a range of temperatures. At the
lowest distillation temperatures, products produced include liquid
petroleum gases (LPG), naphtha, and so-called "straight run"
gasoline.

In the middle range of distillation temperatures, the refinery produces


jet fuel, home heating oil and diesel fuel for transportation vehicles as
well as construction and farm equipment.

At the highest distillation temperatures over 1,000 degrees


Fahrenheit the heaviest products are produced, including residuum
or residual fuel oil, which can be used for lubricants. To maximize
output of more-desirable products, refineries commonly reprocess
these heaviest products into lighter products.

A distillation tower. The boiling ranges for the various crude oil fractions shown are for a typical Gulf
Coast refinery. Refineries in other areas will show some variation in products and boiling ranges.

The composition of a typical 35oAPI gravity oil is given in Table

The average oil tends to have more paraffins in the gasoline fraction and more
aromatics and asphaltics in the residuum. However, a highly paraffinic oil will
have waxes predominating over asphaltic compounds in the residuum.

The density of an oil varies with both the size and types of molecules. Since the
element carbon is heavier than hydrogen, the density of hydrocarbons generally
increases with a decreasing ratio of hydrogen to carbon atoms. Thus in table below,
normal hexane, cyclohexane, and benzene have increasing density (decreasing
o
API) as the H/C ratio decreases.

Different molecular sizes have a larger effect on gravity than do different


molecular types. An oil with 50 percent gasoline is always lighter than one
with 50 percent lubricating oil and residuum, irrespective of molecular type
distribution. The greater density of the large molecules outweighs any type
differences.

Figure shows the distribution of various hydrocarbon types with boiling range (molecular size) in a
naphthenic crude oil. The light gasoline fraction of the oil is dominated by the normal, iso-, and
cycloparaffins because there are only two aromatics, benzene and toluene, that boil below 130 oC

Crude Oil, Volume Percent

Boiling ranges of crude oil fractions


Fraction

Boiling Range

Gasoline

About 15-200oC

Kerosine

About 200-260oC

Gas Oil

About 260-332oC

Lubricating Oil

About 332-421oC

Residuum

Gases

Gas at the well head usually consists of methane with decreasing amounts of the heavier
hydrocarbons, sometimes including traces as high as nonane (C 9H20).

The principal nonhydrocarbon gases in a natural gas are nitrogen, carbon dioxide, and
hydrogen sulfide. Small amounts of helium are also found in some gases.

Dry gas is predominantly methane, whereas wet gas may contain 50% or more of C 2+
hydrocarbons. Dry gas contains less than 0.1 gallon natural gas liquid vapors per 1000 ft 3
(1.3 liters per 100 m 3). In a wet gas, the natural gas liquid vapours amount to 4 liters or more
per 100 m3 (0.3 or more gallons per 1000 ft 3).

Normal butane usually predominates over isobutane in the older, more deeply buried gases.

Hydrogen sulfide is one of the most poisonous gases known. A 0.1 percent concentration in
air is fatal in less than 30 minutes. At the refinery, it is converted to sulfur as follows:
2H2S + 3O2 2SO2 + 2H2O
2H2S + SO2 3S + 2H2O
The sulfur is used to manufacture sulfuric acid and other sulfur products.

Liquefied natural gas (LNG) is primarily methane with a boiling point of -161 oC. Liquified
petroleum gas (LPG) is largely propane and butane. It can be liquefied under pressure at
room temperature.

Ethylene, propylene, and butylene are olefins, not present in natural gas but formed in the
refinery by cracking the gas oils and heavier hydrocarbons to make gasoline. Hightemperature (700-900oC), low-pressure (5 psi) vapor-phase cracking favors production of the
olefins.

Gasoline

Gasoline is composed of hydrocarbons mainly ranging from C5 to


C10.

Since crude oil contain only 10-40 percent gasoline, the cracking
process, which involved breaking large molecules into gasoline
sized ones at high temperatures, was developed.

Also, molecules smaller than the gasoline range were polymerized


to the larger gasoline size.

Combined cracking and polymerization would yield as much as 70


percent gasoline from a barrel of crude.

Later more processes were developed, such as cyclization of


paraffins to form naphthenes and dehydrogenation of naphthenes
to form aromatics. These processes reform the molecules.

Petrol is a complex mixture of at least 100 different compounds, mostly


hydrocarbons. Most of these are branched-chain alkanes, and some are aromatic
compounds.
THE INTERNAL COMBUSTION ENGINE
A number of things happen to the petrol in the internal combustion engine, including:
Petrol is vaporised
The vapour is mixed with air
The petrol-air mixture is compressed
The mixture is ignited by a spark from the spark plug and burned
The gases produced by the combustion reaction expand
Expansion causes the piston to move i.e. kinetic energy is produced.
PREMATURE IGNITION
The greater the extent to which gases are compressed the more they tend to heat up.
Sometimes this causes ignition before the spark is produced. This is intended in a
diesel engine, where there is no spark plug, but in a petrol engine the occurrence is
called auto-ignition or knocking or pinking. This is quite a problem as it can cause
loss of power, with obvious danger, or damage to the engine.
It can be prevented in two ways during petrol manufacture:
1. Use of additives
2. Use of a suitable mixture of high-octane compounds.

OCTANE RATING

The octane rating is a measure of the tendency of a fuel to auto-ignite. The lower the
octane rating the more likely it is that auto-ignition will occur. Clearly, high-octane
fuels are more desirable.

The scale is an arbitrary one. Two compounds were chosen, heptane (C 7H16) and
2,2,4-trimethylpentane (CH 3C(CH3)2CH2CH(CH3)CH3).

Heptane has a high tendency to auto-ignite, so it was given an octane number of 0.


On the other hand, 2,2,4-trimethylpentane has a low tendency to auto-ignite, so it was
given a rating of 100.

A mixture of these two compounds containing 95% of 2,2,4-trimethylpentane is said to


have an octane number of 95 (2,2,4-trimethylpentane was formerly known as isooctane, hence the terms octane number or octane rating).

A mixture of compounds with an identical tendency to auto-ignite, under the same


conditions of compression, would thus also be given an octane rating of 95. A
compound that is less likely to auto-ignite than pure 2,2,4-trimethylpentane would
have an octane rating of more than 100.

Refinery processes for rebuilding hydrocarbons


Today a refinery operation can be shifted to produce almost any molecular type and size range of
hydrocarbons from a single crude feedstock. Reforming hydrocarbon molecules is particularly
important to producing high-octane gasolines without the use of such additives as tetraethyl lead.
Today high-octane fuels are made by converting the long chain hydrocarbons into highly branched
chains and ring compounds by means of reforming processes

For gasoline, the knock characteristics of all hydrocarbons and fuels (in a spark ignition
engine) are rated relative to the n-heptane-iso-octane (2,2,4-trimethylpentane) scale.
The increase in oxidation temperature and octane number with increased branching of
the chain is apparent.
For the same molecular formula, as a straight chain becomes branched, the structure
becomes more compact and octane rating is raised.
The naphthenes and aromatics generally have higher octane numbers than paraffins,
because their rings are basically compact.

One of the most useful hydrocarbon in the gasoline range is benzene, which is a major
raw material for a host of petrochemicals. Benzene is produced by reforming methyl
cyclopentane, cyclohexane, and some hexanes over a platinum catalyst.

Kerosine
The kerosine fraction of crude oil (C11 to C13) is the first to show an
appreciable increase in the cyclic hydrocarbons that dominate the
heavier fractions of crudes.
The aromatics in kerosine range from 10 to 40 percent.
Condensed bicyclic naphthenes and aromatics, such as tetralin and
naphthalene, are common in this range.
Naphthenic acids, phenols, and thiophenes are among the
nonhydrocarbons of kerosine.
kerosene lamps and lanterns are widely used in rural area where
electrical distribution is not available or too costly for widespread use.
In countries such as India, kerosene is the fuel used for cooking,
especially by the poor, and kerosene stoves have replaced traditional
wood-based cooking appliances.
Today, kerosene is mainly used in fuel for jet engines in several
grades.

Gas Oil (C14-C25)

Light gas oils (C14 to C18) are used in both jet fuels and diesel fuels.

In a diesel engine (compression ignition engine), fuel requirements


for high thermodynamic efficiencies are exactly the opposite of the
gasoline engine.

Long chain paraffin hydrocarbons that knock badly in spark ignition


are the best fuels for the diesel engine.

Cetane, i.e., normal hexadecane (C16H34), is the standard for the


diesel engine just as iso-octane is for the gasoline engine.

The composition of gas oil is so complex that only a few


hydrocarbons have been identified in its total range (C14-C25).

Lubricating Oils and Waxes

Lubricating oil normally ranges from about C26-C40, but it can go as low as C20
and as high as C50, depending on the distillation process.

This range contains the normal paraffin waxes (C22-C40) and some asphaltics
(NSO compounds).
Highly paraffinic crude oils frequently have a high wax content in this range
and a correspondingly high pour point.
The paraffinicity of a crude and the volume of its +300oC fraction determines its
wax content.
Petroleum waxes are extracted from the lubricating oil fraction and residuum of
high wax crudes. Wax is predominantly n- paraffins and branched paraffins in
the range from C20 to about C60.

Residuum: Resins, Asphaltenes, and Waxes

The most complex and least understood fraction of petroleum is the residuum.
The principal constituents of residuum or asphalt are some of the very heavy oils,
resins, asphaltenes, and high molecular-weight waxes.
The wax fraction in most residua is about half that in the lube oil fraction.
The asphaltenes are dark brown to black amorphous solids.
The resins may be light to dark coloured, thick, viscous substances to amorphous
solids.

SUMMARY

Petroleum has an average composition of 85 percent carbon, 13 percent


hydrogen, and 2 percent sulfur, nitrogen, and oxygen.

Distillation separates petroleum into molecular groups of different sizes:


gas C1-C4, gasoline C5-C10, kerosine C11-C13, light gas oil (diesel fuel) C14-C18,
heavy gas oil C19-C25, lubricating oil C26-C40, residuum > C40. High oAPIgravity crudes have a high gasoline and low residuum content whereas low
oAPI-gravity oils are low in gasoline and high in residuum.

The different types of hydrocarbon molecules in crude oil are paraffins


(alkanes with single bonds between carbon atoms), naphthenes
(cycloalkanes, cycloparaffins with carbon rings), olefins (alkenes with one
or more double bonds between carbon atoms), and aromatics (arenes with
one or more benzene rings).

Olefins with one or more double bonds are found in refinery cracking
products but not normally in crude oil.

Lubricating oil and residua contain polycyclic ring hydrocarbons with


multiple aromatic or mixed naphthene-aromatic rings fused together, two
rings sharing one side in common.

SUMMARY

Nonhydrocarbons in petroleum are composed predominately of carbon and


hydrogen but also contain one or more of the elements nitrogen, sulfur, and
oxygen (NSO). Small amounts of NSO compounds occur throughout
petroleum, with the largest quantities in the lubricating oil and residuum.
Heterocyclic compounds containing N, S, or O in a ring are common in
residuum.

Less than 3% of the output of oil refineries is used to produce more than
two-thirds of the organic chemicals used for producing 7,000 end use
materials.

Petroleum waxes are extracted from the lubricating oil fraction and residuum
of high-wax crudes. Wax is predominately n-paraffins and branched
paraffins in the range from C20 to about C60.

Petroleum asphalts are either straight-run residues from distilling crude oils
or blown asphalts produced by air oxidation of crude residues. Asphalts
contain heavy oils, resins, asphaltenes, and high-molecular-weight waxes.

Asphaltenes are large organic molecules that are highly aromatic and often
relatively high in heteroatoms with molecular weights in the thousands. They
are apparently formed during diagenesis and catagenesis, as well as in oil
reservoirs as by-products of cracking.

ORIGIN OF PETROLEUM
There are mainly two theories of petroleum origin:
The Organic theory of petroleum origin is based on the accumulation of
hydrocarbons from living things plus the formation of hydrocarbons by the
action of heat on biologically formed organic matter.
The Inorganic theory assumes that oil forms from the reduction of primordial
carbon or its oxidized form at elevated temperature deep in the earth.
The overwhelming geological and geochemical evidence from both sediments
and petroleum studies of the past few decades, however, clearly showed that
most petroleum originated from organic matter buried with the sediments in
sedimentary basins.

The organic origin of petroleum follows two pathways from the living material:

Around 10 to 20% of the petroleum is formed directly from the hydrocarbons synthesized
by living organisms or from their molecules, which are readily converted to hydrocarbons
(the first pathway). Most of these early formed hydrocarbon molecules contain more than
15 carbon atoms, and they include easily recognized biological structures.

The second pathway involves the conversion of the lipids (fats), proteins and
carbohydrates of living material into the organic matter (kerogen) of sedimentary rocks.
When this kerogen is buried deeper at higher temperatures, it cracks to form bitumen that
breaks down further to form petroleum. Some hydrocarbons also form directly from
kerogen.

The first pathway from life simply represents an accumulation of the free hydrocarbons
from dead organisms, plus hydrocarbons formed by bacterial activity and low-temperature
chemical reactions in Recent unconsolidated sediments. These are the hydrocarbons that
can be extracted from the Recent sediments with organic solvents. In the second pathway,
there are no free hydrocarbons until the kerogen is heated to a high enough temperature
to crack it and release the hydrocarbons. From 80 to 90% of petroleum is formed along
this pathway.

If the petroleum is buried deeper at higher temperatures, it changes along two pathways,
one leading to increasingly smaller hydrogen-rich molecules and the other leading to
larger, hydrogen-deficient molecules. The end products are methane and graphite.

MAJOR STAGES OF PETROLEUM FORMATION


a) DIAGENESIS
The biological, physical and chemical alteration of the organic debris before a pronounced effect of
temperature is called Organic Diagenesis.
It covers the temperature range up to approximately 50 degree Celsius.
The quantity of petroleum generated is determined mainly by the quantity of hydrogen in the organic matter
(OM) in the sediment. It follows that strongly reducing environments such as stagnant lakes and silled basins
preserve and enhance the quantity and hydrogen content of OM, whereas oxidizing environments lower it.
The OM deposited in the sediments consists primarily of biopolymers from living things: carbohydrates,
proteins, lipids, lignin, and subgroups such as chitin, waxes, resins, glycosides, pigments, fats and essential
oils. Some of this material is consumed by burrowing organisms; some may be complexed with the mineral
matter; and some is attacked by microbes that use enzymes to degrade the biopolymer into the simple
monomers from which they were originally formed. Some degraded biomonomers undergo no further
reaction, but others condense to form complex high-molecular weight geopolymers, which, along with
undegraded biopolymers, become the precursors of kerogen.
During diagenesis under reducing conditions, this complex mixture of geo- and biopolymers and monomers
undergoes a whole series of low temperature biological and chemical reactions that result in the formation of
more hydrocarbon-like materials through the loss of oxygen, nitrogen and sulphur. The stronger the reducing
conditions are, the greater the hydrogen content of the resulting OM (called kerogen at the end of
diagenesis) will be.

b) CATAGENESIS
Organic matter is subjected to increasingly higher temperature with greater depth of
burial. Over time, these higher temperatures cause the thermal degradation of kerogen to
yield petroleum- range hydrocarbons under reducing conditions. These hydrocarbonforming reactions have been demonstrated many times in the laboratory and have been
observed in the natural environment.
KEROGEN BITUMEN OIL + GAS + RESIDUE
In this equation, the bitumen is defined as the nonvolatile organic matter soluble in
organic solvents that is formed in the shale during initial heating, whereas kerogen is the
insoluble organic matter. Further heating converts the bitumen to oil and gas. The residue
is the non-volatile portion of the kerogen and bitumen remaining after maximum heating
in the laboratory or under natural conditions.
The depth interval in which a petroleum source rock generates and expels most of its oil
is called the oil window. Most oil windows are in the temperature range from 60oC to
160oC.

c) METAGENESIS AND METAMORPHISM

Metagenesis is the last stage in the significant thermal alteration of organic matter.
Here methane generation diminishes and graphitic structures begin to form.
Metagenesis occurs in the temperature range of 200 to 250 C. At such
temperatures, the atomic H/C ratio of the kerogen falls to less than 0.4, typical of the
kerogen in a phyllite.

The bottom of the 9,583m well drilled in the Cambro-Ordovician Arbuckle Formation
in the Anadarko Basin of Oklahoma contained kerogen with an H/C ratio of about
0.25. That is equivalent to a C96H24 hydrocarbon structure containing 37 fused
aromatic rings. Such a structure could generate only trace amounts of methane
before becoming pure graphite.

Inorganic geochemists term mineralogic changes that can be attributed to the action
of heat and pressure at depth as Metamorphism. The low temperature end of the
metamorphic scale is about 200C to 300C. Consequently, the high-temperature end
of organic thermal alteration overlaps with the low temperature beginning of inorganic
thermal alteration.

MIGRATION OF OIL AND GAS

The process of migration has been divided mainly into two parts:
Primary and Secondary migration.

Primary Migration is defined as any movement of the petroleum within the


fine-grained portion of the mature source rock and out into a migration
conduit, and Secondary Migration is any movement of hydrocarbon from
source to the final accumulation in the trap through porous media called
carrier beds.

Tertiary Migration is the movement of a previously formed accumulation.

PETROLEUM GEOCHEMISTRY

Petroleum Geochemistry is the application of the chemical principles to


study of the origin, migration, accumulation and alteration of petroleum (Oil
and Gas) and the use of this knowledge in exploring and recovering of
petroleum.

Petroleum/organic geochemistry has now become a widely used tool in


hydrocarbon exploration conducted by many companies. These exploration
applications are the result of recent technical and philosophical advances
that have permitted direct utilization of geochemistry in evaluations of
basins, plays, and prospects.

There are a number of important questions that organic geochemistry can answer to help
solve the hydrocarbon exploration problem. These include the following:
What was the original hydrocarbon-source potential of a particular rock? Does it have any
remaining source potential at the present time?
What depositional environments are conducive to the formation of kerogens having high
hydrocarbon-source potentials? Can we predict their occurrence?
Which types of kerogen are converted to oil? to gas?
What factors influence oil gravity and composition?
What thermal conditions are required for hydrocarbon formation? Can we predict when and
where generation has occurred?
Can we correlate several samples with each other to decipher genetic relationship? Can
we distinguish biogenic methane from thermal methane?
Can we predict the direction, timing, and efficiency of hydrocarbon migration in a particular
area?
What conditions are required for hydrocarbons to be preserved against the destructive
forces of oxidation, cracking, and biodegradation? Can we predict where destruction will
occur?
Geochemical models form an important part of the overall geological model. Three main
type of geochemical models (organic facies, thermal maturity, and volumetric) exist at the
present time. In immaturely explored areas we have some data with which to test and refine
our early models. Use of models helps develop entirely new plays even in mature areas.

Source Rock
A petroleum source rock may be defined as a fine grained sediment
that has generated and released enough quantity of hydrocarbons to
form a commercial accumulation of an oil and gas.
The source rocks are clay or carbonates muds deposited under low
energy and reducing conditions. The shales and bituminous limestone
consolidated from muds and marls are generally regarded as source
rocks of petroleum and gas.
The mean TOC (Total Organic Carbon) content of fine grained rocks in
petroliferous areas is 1.37% for shales and 0.5 % for carbonates.
Some shales and carbonates with porous and permeable sections
within them can act as both source and reservoir.
The relative ability of the source rock to generate petroleum is defined
by the kerogens quantity (TOC), quality (HI) and state of maturation
(Tmax and Ro).

KEROGEN

The term kerogen is normally defined as that portion of the organic matter present
in sedimentary rocks that is insoluble in ordinary organic solvents.
The chemical and physical characteristics of a kerogen are strongly influenced by
the type of biogenic molecules from which the kerogen is formed and by
diagenetic transformations of those organic molecules.
The kerogen is the precursor of most oil and gas that we exploit as fossil fuels.
Diagenetic and catagenetic histories of a kerogen, as well as the nature of the
organic matter from which it was formed, strongly influence the ability of the
kerogen to generate oil and gas.
Coals are a subcategory of kerogen. Humic coals are best thought as kerogens
formed mainly from land plant material without codeposition of much mineral
matter.
Kerogen formed under reducing conditions will be composed of fragments of
many kinds of biogenic molecules.
Those kerogens formed under oxidizing conditions, in contrast, contain mainly the
most resistant types of biogenic molecules that were ignored by micro-organisms
during diagenesis.

CLASSIFICATION OF KEROGEN
Geoscientists at French Petroleum Institute identified three main types of kerogen (called
Types I, II, and III). Subsequent investigations have identified Type IV kerogen as well.
Type I kerogen is quite rare because it is derived principally from lacustrine algae. The
best known example is the Green River Shale, of middle Eocene age, from Wyoming,
Utah, and Colorado. Occurrences of Type I kerogens are limited to anoxic lakes and to a
few unusual marine environments. Type I kerogens have high generative capacities for
liquid hydrocarbons.
Type II kerogens arise from several very different sources, including marine algae, pollen
and spores, leaf waxes, fossil resin and contributions from bacterial cell lipids. Most Type
II kerogens are found in marine sediments deposited under reducing conditions. They all
have great capacities to generate liquid hydrocarbons.
Type III kerogens are composed of terrestrial organic matter that is lacking in fatty or
waxy components. Cellulose and lignin are major contributors. Type III kerogens have
much lower hydrocarbon-generative capacities than do Type II kerogens and, unless they
have small inclusions of Type II material, are normally considered to generate mainly gas.
Type IV kerogens contain mainly reworked organic debris and highly oxidized material of
various origins. They are generally considered to have essentially no hydrocarbon source
potential.

Kerogen are isolated from inorganic minerals by dissolving the inorganic


mineral with HCl and HF acids. They are brown to black powder resembling
coal dust.

The different kerogen and coal have different elemental composition.

Coal chemist refer to Liptinite as high in hydrogen content, Vitrinite as high in


oxygen content and Inertinite as high in carbon content and likewise the
amorphous kerogen is high in hydrogen and herbaceous and woody kerogen is
high in oxygen content and the H/C ratio decreases in following order:
Amorphous Herbaceous Woody Inertinite

And also the potential to form oil decreases in the same order. Thus, the main
key difference between oil generating, gas generating and non-generating
kerogen is the hydrogen content.

FIGURE Schematic structures of oil-generating and gas-generating kerogens.

SOME ANALYTICAL TECHNIQUES USED IN LABORATORY STUDIES OF ORGANIC MATERIALS


Organic geochemistry and petroleum geochemistry have always been analysis-based sciences.
Proper application of modern analytical technology has been critical to our ability to describe the
chemical composition of fossil fuels and kerogens, to predict source potential of sedimentary rocks, to
correlate samples with each other, and to understand transformation processes like biodegradation.
Bitumen and Oil Analysis
Extraction:
The first step in analyzing bitumen or crude oil is to obtain a sample of that material. Crude oils
generally arrive as a liquid in a sample bottle.
The presence of a water emulsion is the main problem that can occur. If the emulsion does not break
spontaneously upon standing, distillation may be necessary to remove the water.
In fine-grained rocks, bitumen is that portion of organic matter that is soluble in ordinary organic
solvents. Bitumen is universally accepted as the direct precursor of petroleum and, therefore,
compositions of oil and bitumen can be used in oil-source correlation studies.
The bitumen must be separated from the rock matrix and kerogen by some sort of extractive process.
The most commonly used apparatus is a Soxhlet extractor, which provides clean solvent continuously
by a redistillation process. Soxhlet extractions are normally carried out for a considerable length of
time (typically 24 hours). The extracting solvent is usually chloroform or dichloromethane.
Once the extraction is complete, solvent evaporation is carried out slowly at low temperatures.
Despite these precautions, virtually all of the extract molecules having fewer than ten carbon atoms
are evaporated with the solvent, and those between ten and fifteen carbon atoms will be partially
removed. For this reason the extract, or bitumen, is often referred to as the C 15+ extract.

Column Chromatography

The first step in the separation procedure is precipitation and removal of intractable asphaltenes
from bitumen or oil upon addition of a large excess of pentane. The asphaltenes are then filtered
off and the asphaltene-free bitumen or oil is recovered by evaporation of pentane. The technique
most commonly used to separate the asphaltene-free bitumen or crude oil into fractions is called
column chromatography.

In column chromatography a glass tube 20-50 cm in length is held in a vertical position and filled
with a slurry of silica gel or alumina suspended in a hydrocarbon solvent like n-hexane. A small
amount of bitumen or petroleum is added to the top of the column, and the solvent is allowed to
run through by gravity flow. The hydrocarbon solvent dissolves the saturated hydrocarbons and
carries them slowly along with it down the column. The other more polar components of the
bitumen (aromatics and NSO compounds) remain stationary or move much more slowly than the
saturates. Nonpolar molecules (saturates) move rapidly because they have little affinity for the
highly polar stationary phase (alumina or silica gel), but they are very compatible with the
nonpolar hexane.

n-Hexane is allowed to pass through the column until the saturated hydrocarbons have all been
eluted. The solvent and its dissolved hydrocarbons (saturates) are collected as the first columnchromatographic fraction.
Aromatic hydrocarbons (along with some sulfur-bearing heterocompounds) are then collected in
a second fraction eluted by a slightly more polar solvent, benzene.

A third fraction, containing mainly NSO compounds, is eluted with methanol or chloroform.

WHAT ARE POLAR AND NONPOLAR COMPOUNDS ?

Depending on the relative electronegativities of the two atoms sharing electrons, there may be partial transfer of
electron density from one atom to the other. When the electronegativities are not equal, electrons are not shared
equally and partial ionic charges develop.
The greater the electronegativity difference, the more ionic the bond is. Bonds that are partly ionic are called polar
covalent bonds.
Nonpolar covalent bonds, with equal sharing of the bond electrons, arise when the electronegativities of the two
atoms are equal.

Nonpolar Covalent Bond


A bond between 2 nonmetal atoms that have the same electronegativity and therefore have equal sharing of the bonding electron
pair
Example: In H-H each H atom has an electronegativity value of 2.1, therefore the covalent bond between them is considered
nonpolar
Polar Covalent Bond
A bond between 2 nonmetal atoms that have different electronegativities and therefore have unequal sharing of the bonding
electron pair
Example: In H-Cl, the electronegativity of the Cl atom is 3.0, while that of the H atom is 2.1
The result is a bond where the electron pair is displaced toward the more electronegative atom. This atom then obtains a partialnegative charge
while the less electronegative atom has a partial-positive charge. This separation of charge or bond dipole can be illustrated using
an arrow with the arrowhead directed toward the more electronegative atom.

The Greek letter delta indicates "partially".

Figure: Column-chromatographic separation of fractions of bitumens or crude oils.


Saturated hydrocarbons move fastest, followed by aromatics and then by NSOs.

Molecular Sieving/Urea Adduction

Molecular sieving and urea adduction are both used to separate n-alkanes from
branched and cyclic saturated hydrocarbons, including isoprenoids.
Both techniques are applied to the saturated hydrocarbon fraction obtained by
column chromatography.

In molecular sieving the saturated-hydrocarbon fraction is dissolved in a


solvent like cyclohexane and added to a batch of molecular sieves (synthetic
zeolites), which have crystalline structures that contain holes just large enough
for n-alkanes to fit into. Other saturated hydrocarbons and the solvent
molecules are excluded because of their greater size.

When the n-alkanes are all trapped in the holes in the crystals, the solvent
containing the branched and cyclic hydrocarbons is decanted.

The n-alkanes are then replaced in their holes by addition of an n-alkane


solvent, and both n-alkanes and branched-cyclic hydrocarbons are recovered
by evaporation of solvent from the two fractions.

Urea adduction functions in a similar manner. Both urea adduction and


molecular sieving are often used in conjunction with gas chromatography or
combined gas chromatography-mass spectrometry in order to simplify the
spectra and make interpretation easier.

Gas Chromatography

Gas-chromatographic analyses are usually carried out on the saturated-hydrocarbon


fraction of crude oils and bitumens.

Gas chromatography of saturated hydrocarbons is principally used to look at n-alkane and


isoprenoid distributions.

A gas chromatograph is an oven containing a long, thin, coiled column of metal or glass.

One end of the column is attached to a heated injection port, through which the sample to
be analyzed can be introduced onto the column.

The other end is attached to a detector that can monitor the passage of the compounds
out of the column after they have been separated.

The column itself can be either a packed column or a capillary; capillary columns are far
more common today.

Packed columns contain a porous solid support material coated with a non-volatile liquid
(organic polymer).

The much thinner capillary columns have no solid support; the polymer is coated directly on
the walls of the column.

At the beginning of an analysis the sample is injected with a syringe into the hot injection port.
The molecules in the sample are vaporized rapidly and swept onto the column by an inert gas
flowing continuously through the column.
The components of the injected mixture separate as a result of differences in vapour pressure
above the liquid phase and in solubility in the liquid phase.
The rate of movement of a particular molecule through the column therefore depends upon how
much time it spends in the vapour phase (in which it can be swept along) and how much time it
spends immobilized in the liquid phase.
Heavy molecules generally move more slowly than light ones, and polar molecules move more
slowly than nonpolar ones.
During the analysis the oven can be gradually heated to increase the volatility and mobility of the
heavier molecules.
This gradual increase in column temperature, which is called temperature programming, permits
both light and heavy components to pass through the column in a reasonable length of time.
As the compounds emerge from the column they are detected, and a signal proportional to their
concentration is recorded.
The trace representing all the emerging compounds is known as a gas chromatogram.
Identification of the compounds represented by the various peaks is carried out by comparison of
retention times (times required for components to emerge from the column) with authentic
standards.
Quantification is accomplished either by measuring peak heights (if all peaks in question are the
same shape) or, more correctly, by measuring the areas under the peaks using an automatic
integrator attached to the detector.

FIGURE Schematic diagram of a gas chromatograph. The white molecules are more volatile and thus
have a shorter retention time than the black molecules.

Gas Chromatography-Mass Spectometry

Combined gas chromatography-mass spectrometry requires a gas chromatograph


interfaced with a mass spectrometer. In such a system the gas chromatograph is
utilized only to separate the components before they enter the mass spectrometer
one by one.

The mass spectrometer is designed to characterize and identify chemical compounds


by breaking them up into electrically charged fragments (ions). Each compounds
fragmentation pattern, which is closely related to its chemical structure, provides a
unique fingerprint for that compound.

Fragmentation of a molecule is initiated by hitting the molecule with a large amount of


energy, thus knocking an electron out of the molecule. The molecular ion (M+)
produced by loss of this electron has the same mass as the original neutral molecule
but bears a single positive charge. Molecular ion also can break apart to form smaller
charged fragments.

These various molecular and fragment ions are accelerated in an arc by the magnetic
field within the evacuated mass-spectrometer chamber. The radius of the arc
depends upon both the mass/charge ratio (written as m/z or m/e) of the ion and the
strength of the magnetic field. For any given field strength only those ions with a
particular m/z value pass through the centre of the chamber and strike the detector.
The detector response tells us how many such ions were present.

As the field strength is varied rapidly during the analysis, ions with different m/z
values are allowed to strike the detector. The detector responses over the range of
field strengths employed are summed to yield a mass spectrum. The height of each
bar is proportional to the number of ions with that particular m/z value.

Mass spectra are mainly used to identify particular unknown compounds. What has
proven useful for petroleum geochemists seeking to apply gc/ms in exploration is the
knowledge that compounds with similar chemical structures have similar mass
spectra. Thus steranes all have a large m/z 217 peak. Similarly, most triterpanes
have a large m/z 191 peak. These fragment ions are among the most important ones
for most gc/ms work.

One of the tricks of modern electronics allows us to monitor selected m/z values
during the entire gas-chromatographic separation. The trace obtained by monitoring a
single m/z value during an entire gas-chromatographic run is called a mass
chromatogram or a mass fragmentogram.

Mass chromatograms can be used as fingerprints in correlating samples.


Alternatively, careful and detailed analyses of the individual compounds can be made
in order to learn about source, diagenesis, maturity, and biodegradation.

FIGURE Schematic diagram of a combined gas chromatograph/mass spectrometer showing the


detector response when the system is set to monitor m/z 217, a fragment ion derived mainly from
steranes.

Isotope Measurements

The most commonly measured isotopes are of carbon, followed by hydrogen and
sulfur, and more distantly by nitrogen. Isotope measurements are made on a mass
spectrometer specially designed and set up to look at a single chemical compound. In
principle, however, the instrument operates in a manner similar to the mass
spectrometer described earlier.

In all cases the material whose isotopic composition is to be measured is converted


completely to a single compound (for carbon, it is carbon dioxide; for hydrogen, it is
water which is subsequently converted to hydrogen gas; for sulfur, it is sulfur dioxide;
and for nitrogen, it is N2). This material is then introduced into a mass spectrometer,
where the molecules are gently ionized to form molecular ions. The only differences
among the ions are isotopic.

The relative amounts of each isotope are determined by comparing the amounts of
ions containing the heavy isotope with those containing the light isotope. For
example, 13CO2 has a mass of 45 amu, whereas 12CO2 is 44 amu. The quantities of
each type can be measured very accurately by the mass spectrometer.

Samples on which isotopic measurements are made are always compared directly
with reference samples, called standards. The value reported is thus always the
difference between the isotope ratios of the sample and the standard.

FIGURE The range in the carbon-13 content of carbon reservoirs (in parts per thousand relative to the Peedee belemnite standard)

Quantity of Organic Material


TOC ANALYSIS
For source rock evaluation, the fundamental parameter is the Total Organic Carbon
(TOC) of the Sedimentary rock sample under investigation. This simple, quick and
inexpensive analysis serves as the first and most important screening technique in
source-rock analysis. Analysis normally requires one gram of rock. The samples can be
conventional cores, sidewall cores or drilled cuttings of a well or outcrops. The samples
are analyzed after carbonate is removed by treatment with hydrochloric acid.
Virtually all TOC analyzers measure the CO2 formed when a sample of powdered,
carbonate-free rock is combusted at very high temperature in the presence of a large
excess of oxygen. All organic carbon is converted to carbon dioxide, which is trapped
within the instrument and then released into a detector when combustion is complete.
The amount of carbon dioxide produced is proportional to the organic-carbon content of
the rock. Carbonate is removed from the preweighed rock sample with hydrochloric acid
prior to combustion, because carbonate minerals would also decompose during
combustion to yield carbon dioxide.

Type of Organic Material


ROCK EVAL PYROLYSIS
Rock Eval Pyrolysis is used to evaluate the source rock and their characterization i.e. type and
maturity of organic matter and detection of petroleum potential in sediments. The water washed
samples are crushed and taken for Rock Eval analyses.
The Rock Eval (RE) pyrolysis method consists of a programmed temperature heating (in a pyrolysis
oven) in an inert atmosphere (Helium or Nitrogen) of a small sample (~100 mg) to quantitatively and
selectively determine
(1) The free hydrocarbons contained in the sample and
(2) The hydrocarbon- and oxygen-containing compounds (CO 2) that are volatilized during the
cracking of the unextractable organic matter in the sample.
For 3 min, the oven is kept isothermally at 300C and the free hydrocarbons are volatilized and
measured as the S1 peak. This detection is done by Flame IonizationDetector (FID). The
temperature is then increased from 300 to 550C at 25C/min. This is the phase of volatilization of
the very heavy hydrocarbons compounds (>C 40) as well as the cracking of nonvolatile organic matter.
The hydrocarbons released from this thermal cracking are measured as the S 2 peak (by FID). The
temperature at which S2 reaches its maximum depends on the nature and maturity of the kerogen and
is called Tmax. During the course of pyrolysis, carbon dioxide is also released from the kerogen. This
carbon dioxide is trapped during pyrolysis and then released into a second detector (TCD) after all the
hydrocarbon measurements are complete. The amount of carbon dioxide given off by the kerogen is
supposed to be related to the amount of oxygen in the kerogen. Because high oxygen contents are
related to either woody-cellulosic source material or to strong oxidation during diagenesis, high
oxygen content of a kerogen is a negative indicator of hydrocarbon-source potential.

Basic Parameters
S1 = the amount of free hydrocarbons (gas and oil) in the sample. If S1 >2 mg
HC/g rock in immature sediments, it may be indicative of migratory oil or oil
contaminants. S1 normally increases with depth. S1/TOC is high and the Tmax is
low if migrated hydrocarbons are present. S1/TOC = 0.1 to 0.2 for oil expulsion.
S2 = the amount of hydrocarbons generated through thermal cracking of
nonvolatile organic matter. S2 (mg HC/g rock) is an indication of the quantity of
hydrocarbons that the rock has the potential of producing should burial and
maturation continue. It is 2 for poor source rocks, 2-5 for fair, 5-10 for good,
and > 10 for very good source rocks. It is used to calculate the Hydrogen
Index.
S3 = the amount of CO2 (in milligrams CO2 per gram of rock) produced during
pyrolysis of kerogen. S3 is an indication of the amount of oxygen in the kerogen
and is used to calculate the Oxygen Index.
Tmax = the temperature at which the maximum release of hydrocarbons from
cracking of kerogen occurs during pyrolysis (top of S2 peak). Tmax is an indication
of the stage of maturation of the organic matter.

Quality of Source Rock (kerogen types I, II, or III)


HI = Hydrogen Index (mg HC/g TOC)
HI = (100 x S2) / TOC
HI is a parameter used to characterize the quality of organic matter.
HI typically ranges from ~100 to 900 in geological samples.
OI = Oxygen Index (mg CO2/g TOC)
OI = (100 x S3)/ TOC
OI is a parameter that correlates with the ratio of O to C, which is high for polysacharride-rich
remains of land plants and inert organic material sediments. OI values range from near 0 to ~150.
Hydrocarbon type index = S2 / S3
It is < 2 for gas and > 5 for Oil.
Maturation State
PI = Production Index
PI = S1 / (S1 + S2)
PI is used to characterize the evolution level of the organic matter and identifying the migratory
hydrocarbons accumulations.
Oil window = 0.08 0.4. Higher values are often due to migrating hydrocarbons or contaminants.
Tmax = S2 Peak Temperature
Oil window ~ 430C to 470C
Maturation of the organic matter can be estimated by Tmax range.
Reservoir Studies
Oil and gas recovery from sands has been monitored by S1 / S2 , with the best recoveries from
horizons with values greater than 5. It is normally used with mud logging and wireline logs. Also, the
S1 / TOC can be used.

FIGURE Modified van Krevelen diadram used for Rock-Eval pyrolysis data,
showing maturation pathways of Types I, II, and III kerogens.

Maturity of Organic Material

VITRINITE REFLECTANCE
Vitrinite Reflectance (VRo) is the most commonly used organic maturation indicator used
in the petroleum industry. This is mainly because it is accurate, quick, non-destructive
and inexpensive. Vitrinite is a coal maceral. It is not strongly prone to oil and gas
formation, and is common as a residue in source rocks.
As coal maturity increases, and the chemical composition of the Vitrinite correspondingly
changes, the vitrinite macerals become increasingly reflective. Therefore, the percentage
reflection of a beam of normal incident white light from the surface of polished vitrinite is a
function of the rank (maturity) of the macerals. Vitrinite includes telinite, the cell wall
material of land plants, and collinite the organic substance that fills the cell cavities.
Vitrinite is composed of clusters of condensed aromatic rings linked with chains and
stacked on top of one another.
With increasing maturity, the clusters fuse into larger, condensed aromatic ring
structures. Eventually they form sheets of condensed rings that assume an orderly
structure. Both the increase in the size of these sheets and their preferred orientation
cause greater reflectivity.

There are two techniques for preparing samples to measure reflectance.


The first involves concentrating the organic matter by removing the minerals matter with
hydrochloric and hydrofluoric acids. The organic matter is freeze-dried, mounted in epoxy, and
polished.
The second involves using whole rock polished pellet mounts or thin sections, rather than the
kerogen concentrates. A whole rock matrix has the advantage of showing the entire sample so
that the relationship of the vitrinite particles to the rock matrix background can be seen more
clearly.
Only ten to twenty measurements of the true relevant population need to be made by this
technique. Also, the mounts can be re-evaluated if anomalous results occur in a succession of
samples.
However, whole rock mounts require a very skilled, experienced petrologist; since the
determination of the relevant population is quite subjective.
The results are reported as Ro values, where the o indicates that the measurements were made
with the plug immersed in oil.
Reflectance values are normally plotted versus depth in a well. If the reflectance scale is linear,
the reflectance profile is curved. When we use a log scale for vitrinite reflectance, however, the
plot is a straight line.
Because extrapolation of a straight line is much easier, the log scale is preferable for reflectance
profiles.

CORRELATIONS

In order to identify source rocks and determine migration pathways, it is often important to
know whether two samples of organic material share a common origin.

Correlations are easiest between materials of the same type (two oils for example), but they are
also possible between dissimilar samples (oils with kerogens or bitumens, bitumens with
kerogens).

Two fundamentally different types of characteristics can be measured: bulk parameters and
specific parameters.

Bulk parameters refer to properties of the whole sample; sulfur content, API gravity, saturatedhydrocarbon content, and pour point are examples. Because they tend to be affected strongly by
processes such as migration, biodegradation, and cracking, bulk parameters have some
important limitations as correlation tools.

Specific parameters, in contrast, measure in detail one characteristic of a small fraction of the
sample; they include, for example, the many types of biomarker ratios. Specific parameters are
sometimes strongly affected by a small amount of contamination, biodegradation, or mixing.

Bulk parameters are better for detecting transformations that affect the whole sample but
generally are not sensitive enough to be reliable positive correlation tools without corroboration
by specific parameters. It is therefore important to utilize both bulk and specific parameters in
correlation studies.

BULK PARAMETERS

API gravity, reported in degrees API (oAPI). API gravity is a measure of


density (or specific gravity). Specific gravity and API gravity are related by
the following equation:
141.5
oAPI = ------------------- - 131.5
Specific gravity
The API gravity of pure water is 10o. Most normal oils have API gravities
from 25o to 45o. Oils having API gravities less than about 20o are usually
biodegraded, high in sulfur content, or both. Condensates typically have
gravities above 50o API (generally > 55oAPI).
Sulfur content, expressed as weight percent. Most oils are low sulfur,
containing less than 0.5% S. High sulfur oils are less common in general;
they are thought to be sourced mainly from nonclastic (carbonate), organic
rich source rocks. Most of the sulfur resides in the asphaltene fraction,
incorporated into the ring structures of large polycyclic aromatic molecules.
Sulfur content can be raised substantially during biodegradation.

Isotope ratios of bulk samples, measured by mass spectrometry and reported in


permil (parts per thousand deviation from the standard). Natural variations in isotope
ratios are great enough and measuring precision is good enough to permit utilization
of isotopes in correlation. On the average, oils are about 2 per mil () more negative
(lighter) than source kerogens in their carbon isotope ratios. Bitumens are also about
2 more negative than the kerogens from which they were extracted. If an oil is
isotopically heavier than the suspected source kerogen, the correlation is negative.

Oils and kerogens derived from highly reducing evaporates are often quite heavy
isotopically (values near -20 versus PDB), probably because they contain
exclusively algal material. Waxy oils, in contrast, are sometimes isotopically light,
having values more negative than -30 . The carbon isotope ratios of majority of oils
and kerogens fall in the range -24 to -28 .

The causes of variations of hydrogen isotopes in oils are poorly understood. One
useful generalization, however, is that the deuterium content of oils sourced from
carbonates is higher than for shale-sourced oils.

Sulfur-isotope ratios are occasionally useful in correlating oils, especially those that
are high in sulfur content.

Gas chromatography, measured on either the light hydrocarbons or on whole oil.


Hydrogen stripping method is used for removing and analyzing light hydrocarbons
from rock samples, thus permitting source rock-oil correlations.

Various ratios of light hydrocarbons have been used as correlation or maturity


parameters because formation of branched isomers increases as maturity increases.

Compound classes, as determined by column or thin-layer chromatographic


separation. The relative proportion of each compound class (saturated hydrocarbons,
aromatic hydrocarbons, resins, and asphaltenes) can give indications about both
source and maturity.

Low contents of hydrocarbons in an extract indicate immaturity. Large proportions of


hydrocarbons in an extract indicate either maturity, contamination by drilling fluid
additives, or presence of migrated oil.

Most oils will contain more than 75% hydrocarbons. Certain oils formed at low levels
of maturity from sulfur-rich kerogens can have large amounts of NSO compounds and
asphaltenes, however.

SPECIFIC PARAMETERS

Isotope profiles, measured on fractions obtained by column chromatography or on a


series of specific compounds, such as n-alkanes. 13C values of successively more
polar fractions become, in theory, increasingly more positive. The source kerogen
should therefore be slightly more positive than the asphaltene fraction of a related
bitumen or crude oil.

Sofer (1984) has used carbon-isotope measurements on two fractions (saturates and
aromatics) of a crude oil to classify it as high- or low-wax (interpreted by Sofer to be
terrestrially influenced or wholly marine). He employed following empirical equation to
make the distinction at about the 90% confidence level.

CV (Cannonical Variable) = -2.53 (13Csat) + 2.22 (13Carom) 11.65

Where if CV < 0.47 the oil is low-wax (wholly marine), and if CV > 0.47 the oil is highwax (terrestrially influenced).

Isoprenoid distributions, measured by the gas chromatography of the saturated


hydrocarbon fraction.
Most commonly used are pristine/phytane ratios which are believed to be sensitive to
diagenetic conditions.
Very high Pr/Ph ratios (> 3) are associated with terrestrially influenced sediments,
including coals.
Pr/Ph ratios substantially below 1.0 are taken as indicators of highly reducing
depositional environments.
Isoprenoid/n-alkane ratios, also obtained by gas chromatography.
Combining isoprenoid and n-alkane data provides valuable information on
biodegradation, maturity, and diagenetic conditions.
A good way to display these data is by plotting pristane/n-C17 versus phytane/n-C18.
With increasing maturity n-alkanes are generated faster than isoprenoids, resulting in a
derease in isoprenoid/n-alkane ratios and regression along the line toward the origin in
figure in the next slide.
Biodegradation, in contrast, removes n-alkanes faster, increasing isoprenoid/n-alkane
ratios away from the origin in figure.

Polycyclic-hydrocarbon biomarkers, measured by gc/ms of


saturate and aromatic-hydrocarbon fractions. These include
diterpanes, triterpanes, and steranes.

Triterpanes have proven very valuable as correlation parameters


because they are sensitive to diagenetic conditions, to
biodegradation, and in some cases, to the type of organisms from
which the organic matter is derived.

The ratio of C29 to C30 regular hopanes appears to be related to


depositional environment, with a predominance of C 29 possibly
indicating euxinic conditions.

Gammacerane and oleanane are thought to be associated with


lacustrine and certain deltaic sediments, respectively.

C-25 norhopanes are found only in severely biodegraded crudes.

Steranes are valuable correlation parameters because of the direct dependence of C 27, C28, and
C29 regular-sterane concentrations on their precursor C 27 to C29 sterols.
C27 sterols dominate in marine organisms, whereas C 29 sterols are more common in terrestrial
plants.
These relationships can be expressed in a triangular diagram, which allows one to estimate the
growth environment (paleoenvironment) of the contributing organic matter.
Steranes are of less value where biodegradation is extreme because the regular steranes are
destroyed completely in the late stages of biodegradation.

Oil-oil correlations
Oils in the Michigan Basin have been produced from Ordovician (Trenton), Silurian
(Niagara), and Devonian (Dundee and Lucas) reservoirs. On the basis of n-alkane and
isoprenoid distributions and carbon-isotope profiles for individual n-alkanes, it was
decided that the Ordovician and Devonian oils had a common source and that the
intervening Silurian oils had a different source, probably in lagoonal facies adjacent to the
reefs from which they are produced.

FIGURE n-alkane and isoprenoid distributions from gas chromatograms of saturated hydrocarbons
from typical Ordovician, Silurian, and Devonian oils from the Michigan Basin.

Source Rock-Oil Correlations

One example of oil-source


correlation in different basins of
California is given in the figure
using carbon isotopic ratios and
nickel and vanadium porphyrin
ratios.

Another example of oil-source correlation

Oils are produced from several fields in the Basin and Range province of Utah and Nevada. Two very different type of source rocks are identified
in the area. The chainman Shale of Mississippian age was deposited in a marine basin. The Sheep Pass and Elko formations , in contrast, are of
Paleogene age and represent lacustrine facies.
The most useful analytical techniques for correlating specific oils and source rocks were gas chromatography (fig. D) and gc/ms (fig. E) The Trap
Spring oil, for example, has a very similar gas chromatogram to that from a mature sample of Chainman shale (fig. D): Pr/Ph ratios are near 1.5,
and the samples are low in heavy n-alkanes. Oils from the Eagle Springs and Currant field, in contrast, have Pr/Ph ratios below 1.0, and contain
moderate to large amounts of heavy n-alkanes similar to the source rock extract from Sheep Pass formation.

FIGURE D Gas
chromatograms
of saturated
hydrocarbons
from three oils
(top) and three
source-rock
extracts
(bottom) from
the Basin and
Range province
of Utah and
Nevada. Each
oil correlates
with the extract
immediately
below it.

The most powerful arguments for the proposed source rock-oil correlations come from sterane
and triterpane distributions (fig. E).

The lacustrine rocks (Sheep Pass and Elko formations) all contain large amounts of
gammacerane (peak 7 in fig. E), an indicator of lacustrine origin.

Five of the oils analyzed, including the previously mentioned Eagle Springs and currant oils, also
contain large amounts of gammacerane and thus suggest their generation from lacustrine
source rocks.

These five oils correlate very well with the lacustrine source rocks in other respects as well. All
(White River Valley oil is an exception) have more of the 20R- than 20S- epimer of the C29
sterane (peaks D and A in fig. E), which indicates low maturity.

The remaining four oils shown in figure E correlate well with the Chainman shale extracts.
Gammacerane contents of all samples are low; maturities are high, as indicated by an excess of
the C29 20S-epimer over the 20R-epimer.

One implication of this study is that oil generation from the lacustrine source beds in the Basin
and Range province occurs at very low levels of maturity, probably as the result of the combined
effects of the great richness of the source rocks and high sulfur contents of the kerogens.

The knowledge thus derived from correlation studies in an area can be incorporated into future
exploration models for the area.

Biodegradation
The Lakes Entrance oil (16o API< 365-m depth, Tertiary reservoir) and West Sea Horse #1 oil (48 o
API, 1400-m depth, Cretaceous reservoir) from the Gippsland Basin of Australia have very different
chemical and physical properties. Gas chromatograms of the saturated hydrocarbon fractions are
shown in figure A. Mass chromatograms are presented in figures B an C. Could there be any
genetic relationship between these two oils?

From the gas chromatograms it is evident that the Lakes Entrance oil is heavily
biodegraded, with both n-alkanes and isoprenoids completely destroyed.
Biodegradation has even affected the steranes (fig. B), leading to a decrease in the
biologically produced sterane (peak 4). However, the biodegradation has not
reached the stage to affect the triterpanes (m/z 191 mass chromatogram, fig. C)

On the basis of gas chromatograms and sterane biomarker data it is not possible to state
with certainty that the Lakes Entrance and West Sea Horse #1 oils are related. The
triterpane mass chromatograms are rather similar and are therefore consistent with a
common origin.