COMPOSITION OF PETROLEUM (CRUDE OIL)

Petroleum Definition: (L. petroleum, from Latin: Petra rock + oleum oil)

Petroleum (also called crude oil) is a naturally mixture of hydrocarbons, generally in the liquid
state, that may also include compounds of sulfur, nitrogen, oxygen, and metals and other
elements. Inorganic sediment and water may also be present.
Regardless of their origins, all crude oils are mainly constituted of hydrocarbons mixed with
variable amounts of sulfur, nitrogen, and oxygen compounds.
Metals in the forms of inorganic salts or organometallic compounds are present in the crude
mixture in trace amounts.

The ratio of the different constituents in crude oils, however, varies appreciably from one
reservoir to another. The exact molecular composition varies widely from formation to formation
but the proportion of chemical elements varies over fairly narrow limits as follows:

Element Percent range

Carbon 83 to 87%
Hydrogen 10 to 14%
Nitrogen 0.1 to 2%
Oxygen 0.05 to 1.5%
Sulfur 0.05 to 6.0%
Metals < 0.1%

The crude oil mixture is composed of the following groups:

1. Hydrocarbon compounds (compounds made of carbon and hydrogen).

2. Non-hydrocarbon compounds.
3. Organometallic compounds and inorganic salts (metallic compounds).

Hydrocarbon Compounds
The principal constituents of most crude oils are hydrocarbon compounds.
All hydrocarbon classes are present in the crude mixture, except alkenes and alkynes.
This may indicate that crude oils originated under a reducing atmosphere. Four different types of
hydrocarbon molecules appear in crude oil. The relative percentages of each vary from oil to oil,
determining the properties of each oil.

Composition by weight

Hydrocarbon Average Range

Paraffins 30% 15 to 60%

Naphthenes 49% 30 to 60%
Aromatics 15% 3 to 30%
Asphaltics 6% remainder
ALKANES (PARAFFINS)

Alkanes are saturated hydrocarbons having the general formula CnH2n+2.

The simplest alkane, methane (CH4), is the principal constituent of natural gas.
Methane, ethane, propane, and butane are gaseous hydrocarbons at ambient temperatures
and atmospheric pressure. They are usually found associated with crude oils in a dissolved state.
Normal alkanes (n-alkanes, n-paraffins) are straight-chain hydrocarbons having no branches.

Paraffins are very stable and show no reaction at room temperature with fuming sulfuric acid,
conc. Alkali, nitric acid and chromic acid. They react slowly with chlorine under sunlight and
react rapidly when catalyst is added. Only substitution reactions occur in paraffins with hydrogen
being substituted with an element or a chemical group.

The concentration of lower paraffins in crude oil is very low but higher members of paraffin
series are present in most of the crude oils. The boiling point of paraffins increases as the number
of carbon atoms increased.

C1 to C4 gases PETROLEUM GASES

C5 to C8 pentane (C5H12) to octane (C8H18) PETROL
C9 to C16 (C9H20) to hexadecane (C16H34) DIESEL, KEROSENE, JET FUEL
>C16 FUEL OIL, LUBRICATING OILS
C25 to C40 PARAFFIN WAX
C40 and above ASPHALT

ISO PARAFFINS

When the number of carbon atoms in the molecule is greater than three, several hydrocarbons
may exist which contain the same number of carbon and hydrogen atoms but have different
structures. This is because carbon is capable not only of chain formation, but also of forming
single- or double-branched chains which give rise to isomers that have significantly different
properties.

A branched alkane with the same number of carbons and hydrogens as an n-alkane is called an
isomer. For example, butane (C4H10) has two isomers, n-butane and 2-methyl propane
(isobutane). As the molecular weight of the hydrocarbon increases, the number of isomers also
increases. Pentane (C5C12) has three isomers; hexane (C6H14) has five. Crude oils contain many
short, medium, and long-chain normal and branched paraffins.

Number of Carbon atoms Number of Isomers

6 5
8 18
12 355
25 36,797,588
40 > 62 x 10 12
For example, the motor octane number of n-octane is -17 and that of iso-octane (2, 2, 4 trimethyl
pentane) is 100.
NAPHTHENES (CYCLOPARAFFINS)

Saturated cyclic hydrocarbons, normally known as naphthenes, are also part of the hydrocarbon
constituents of crude oils. Their ratio, however, depends on the crude type.
The lower members of naphthenes are cyclopentane, cyclohexane, and their mono-substituted
compounds.
They are normally present in the light and the heavy naphtha fractions. Cyclohexanes,
substituted cyclopentanes, and substituted cyclohexanes are important precursors for aromatic
hydrocarbons.

The examples shown here are for three naphthenes of special importance.
If a naphtha fraction contains these compounds, the first two can be converted to benzene, and
the last compound can dehydrogenate to toluene during processing. Dimethylcyclohexanes are
also important precursors for xylenes. Heavier petroleum fractions such as kerosene and gas oil
may contain two or more cyclohexane rings fused through two vicinal carbons.
Cycloalkanes (naphthenes) have similar properties to alkanes but have higher boiling points.
OLEFINS

Olefins do not naturally occur in crude oils but are formed during the processing. They are very
similar in structure to paraffins but at least two of the carbon atoms are joined by double bonds.
The general formula is CnH2n. Olefins are generally undesirable in finished products because;
double bonds are reactive and the compounds are more easily oxidized and polymerized to form
gums and varnishes.
In gasoline boiling-range fractions, some olefins are desirable because olefins have higher
research octane numbers than paraffin compounds with the same number of carbon atoms.
Olefins containing five carbon atoms have high reaction rates with compounds in the atmosphere
that form pollutants and, even though they have high research octane numbers, are considered
generally undesirable.
Some diolefins (containing two double bonds) are also formed during processing, but they react
very rapidly with olefins to form high-molecular-weight polymers consisting of many simple
unsaturated molecules joined together. Diolefins are very undesirable in products because they
are so reactive they polymerize and form filter and equipment plugging compounds.
AROMATICS

The aromatic hydrocarbons are unsaturated hydrocarbons which have one or more planar six-
carbon rings called benzene rings, to which hydrogen atoms are attached with the formula CnHn.
They tend to burn with a sooty flame, and many have a sweet aroma. Some are carcinogenic.

The aromatic series of hydrocarbons is chemically and physically very different from the
paraffins and cycloparaffins (naphthenes). Aromatic hydrocarbons contain a benzene ring which
is unsaturated but very stable and frequently behaves as a saturated compound. Some typical
aromatic compounds are shown in Figure 4.

Lower members of aromatic compounds are present in small amounts in crude oils and light
petroleum fractions.
The simplest mononuclear aromatic compound is benzene (C6H6). Toluene (C7H8) and Xylene
(C8H10) are also mononuclear aromatic compounds found in variable amounts in crude oils.
Benzene, toluene, and xylenes (BTX) are important petrochemical intermediates as well as
valuable gasoline components.

Binuclear aromatic hydrocarbons are found in heavier fractions than naphtha. Trinuclear and
polynuclear aromatic hydrocarbons, in combination with heterocyclic compounds, are major
constituents of heavy crudes and crude residues. Asphaltenes are a complex mixture of aromatic
and heterocyclic compounds.

The cyclic hydrocarbons, both naphthenic and aromatic, can add paraffin side chains in place of
some of the hydrogen attached to the ring carbons and form a mixed structure.
These mixed types have many of the chemical and physical characteristics of both of the parent
compounds, but generally are classified according to the parent cyclic compound.

The following are representative examples of some aromatic compounds found in crude oils:
SULFUR COMPOUNDS

Sulfur in crude oils is mainly present in the form of organosulfur compounds.

Hydrogen sulfide is the only important inorganic sulfur compound found in crude oil. Its
presence, however, is harmful because of its corrosive nature.
Organosulfur compounds may generally be classified as acidic and non-acidic.
Acidic sulfur compounds are the thiols (mercaptans). Thiophene, sulfides, and disulfides are
examples of non-acidic sulfur compounds found in crude fractions.

Examples of some sulfur compounds from the two types are:

Sour crudes contain a high percentage of hydrogen sulfide.

Because many organic sulfur compounds are not thermally stable, hydrogen sulfide is often
produced during crude processing. High-sulfur crudes are less desirable because treating the
different refinery streams for acidic hydrogen sulfide increases production costs.
Most sulfur compounds can be removed from petroleum streams through hydrotreatment
processes, where hydrogen sulfide is produced and the corresponding hydrocarbon released.
Hydrogen sulfide is then absorbed in a suitable absorbent and recovered as sulfur.

Effect of sulphur compounds

•Great environmental concern, contribute to particulate matter, emission of obnoxious odoured
sulphur oxide gases
•Receding sulphur level in all petroleum products
•Refining & Technology Focus shifted to sulphur removal from hydrocarbons

NITROGEN COMPOUNDS

Crude oils contain very low amounts of nitrogen compounds. In general, the more asphaltic the
oil, the higher its nitrogen content.
Organic nitrogen compounds occur in crude oils either in a simple heterocyclic form as in
pyridine (C5H5N) and pyrrole (C4H5N), or in a complex structure as in porphyrin.
The nitrogen content in most crudes is very low and does not exceed 0.1 wt%.
In some heavy crudes, however, the nitrogen content may reach up to 0.9 wt %.

Nitrogen compounds are more stable than sulphur compounds and therefore are harder to
remove. and accordingly are concentrated in heavier petroleum fractions and residues.
Light petroleum streams may contain trace amounts of nitrogen compounds, which should be
removed because they poison many processing catalysts.

During hydrotreatment of petroleum fractions, nitrogen compounds are hydrodenitrogenated to

ammonia and the corresponding hydrocarbon.
For example, pyridine is denitrogenated to ammonia and pentane:

Even though they are present at very low concentrations, nitrogen compounds have great
significance in refinery operations. They can be responsible for the poisoning of a cracking
catalyst, and they also contribute to gum formation in finished products.

Nitrogen compounds in crudes may generally be classified into basic and non-basic categories.
Basic nitrogen compounds are mainly those having a pyridine ring, and the non-basic
compounds have a pyrrole structure.
Pyrrole Pyridine
Indole Quinoline
Carbozole Indoline
Benzocarbozole Benzoquinoline

Effects of Nitrogen Compounds:

Catalysts poison & Nitrogen oxide emission
Both pyridine and pyrrole are stable compounds due to their aromatic nature.

OXYGEN COMPOUNDS
Oxygen compounds in crude oils are more complex than the sulfur types. However, their
presence in petroleum streams is not poisonous to processing catalysts.
Many of the oxygen compounds found in crude oils are weakly acidic. They are carboxylic
acids, cresylic acid, phenol, and naphthenic acid. Naphthenic acids are mainly cyclopentane
and cyclohexane derivatives having a carboxyalkyl side chain.
Naphthenic acids in the naphtha fraction have a special commercial importance and can be
extracted by using dilute caustic solutions. The total acid content of most crudes is
generally low, but may reach as much as 3%.
Non-acidic oxygen compounds such as esters, ketones, and amides are less abundant than acidic
compounds. They are of no commercial value.
METALLIC COMPOUNDS

Many metals occur in crude oils.

Some of the more abundant are sodium (Na), calcium (Ca), magnesium (Mg), aluminum (Al),
iron (Fe), vanadium (V), and nickel (Ni).

They are present either as inorganic salts, such as sodium and magnesium chlorides, or in
the form of organometallic compounds, such as those of Ni and V (as in porphyrins).

Metallic compounds exist in all crude oil types in very small amounts. Their concentration must
be reduced to avoid operational problems and to prevent them from contaminating the products.
Metals affect many upgrading processes. They cause poisoning to the catalysts used for hydro
processing and cracking. Even minute amounts of metals (iron, nickel and vanadium) in the
feedstock to the catalytic cracker affect the activity of the catalyst and result in increased gas and
coke formation and reduced gasoline yields.
Part of the metallic constituents of crude oils exists as inorganic water-soluble salts, mainly as
chlorides and sulphates of sodium, potassium, magnesium and calcium. These are removed in
desalting operations .More important are metals which are present in form of oil-soluble
organometallic compounds. Zinc, titanium, calcium and magnesium appear in the form of
organometallic soaps. However, vanadium, nickel, copper and iron are present as oil-soluble
compounds, capable of complexing with pyrrole compounds.

Calcium and magnesium can form salts or soaps with carboxylic acids. These compounds act
as emulsifiers, and their presence is undesirable.

Most of the vanadium and nickel compounds are concentrated in the heavy residues.
Vanadium and nickel are poisons to many catalysts and should be reduced to very low levels.
For high-temperature power generators, the presence of vanadium in the fuel may lead to ash
deposits on turbine blades and cause severe corrosion, and the deterioration of refractory furnace
linings. Solvent extraction processes are used to reduce the concentration of heavy metals in
petroleum residues.

WATER, SALT AND SEDIMENT

Considerable importance is attached to the presence of water or sediment in petroleum because

they lead to difficulties in the refinery, for example, corrosion of equipment, uneven running on
the distillation unit, blockages in heat exchangers, and adverse effects on product quality in heat
exchangers, and adverse effects on product quality.

Most of the salts are dissolved in the water, and the remainder is present in the oil as fine
crystals. Chlorides of magnesium, calcium and sodium are the most common salts. The presence
of salts causes problems in processing, such as corrosion, erosion and plugging of equipment,
and catalyst deactivation.

CLASSIFICATION

The petroleum industry generally classifies crude oil by:

1. The geographic location it is produced in(e.g. West Texas Intermediate, Brent, or Oman),
2. Its API gravity (an oil industry measure of density), and
3. Its sulfur content.
4. According to the type of Hydrocarbons present.

The geographic location is important because it affects transportation costs to the refinery.

Crude oil may be considered light if it has low density or heavy if it has high density; and it may
be referred to as sweet if it contains relatively little sulfur or sour if it contains substantial
amounts of sulfur.

Sour crude oil is defined as a crude oil containing larger amounts of the impurity sulfur, an
extremely corrosive element that is difficult to process, and deadly when released (hydrogen
sulfide gas). When the total sulfur level in the oil is over 0.5 % the oil is called sour; lower sulfur
oils are sweet.
Light crude oil is more desirable than heavy oil since it produces a higher yield of petrol, while
sweet oil commands a higher price than sour oil because it has fewer environmental problems
and requires less refining to meet sulfur standards imposed on fuels in consuming countries.
Each crude oil has unique molecular characteristics which are understood by the use of crude oil
assay analysis in petroleum laboratories.

Crude oil may be classified into three different groups according to the nature of the
hydrocarbons they contain, Paraffinic, Intermediate and Naphthene.

Paraffin-Base Crude Oils

These contain higher molecular weight paraffins which are solid at room temperature, but little
or no asphaltic (bituminous) matter. They can produce high-grade lubricating oils. Paraffin base
contained more than 5% wax.

Paraffinic base: Waxy, less asphaltic, low sulphur, High pour

Asphaltic-Base or Naphthene Base Crude Oils

Contain large proportions of asphaltic matter, and little or no paraffin. Some are predominantly
naphthenes so yield lubricating oil that is more sensitive to temperature changes than the paraffin-base
crudes.

Asphalt base - distillation residue contained less than 2% wax.

Naphthenic base: less wax, less asphaltic, low pour point

Asphaltic base: High sulphur, nitrogen, suitable for Base oils

Mixed-Base or Intermediate base Crude Oils

The "gray area" between the two types above. Both paraffins and naphthenes are present, as well as
aromatic hydrocarbons. Most crude fit this category.
1. CORRELATION INDEX

𝟒𝟖,𝟔𝟒𝟎
CI = 473.7 d – 456.8 +
𝑲

K - petroleum fraction is the average boiling point determined by the standard Bureau of Mines
distillation method
d - specific gravity

OR
𝟖𝟕,𝟓𝟓𝟐
CI = + 473.7G – 456.8
𝑻𝑩

TB - mean average boiling point, °R

G - specific gravity at 60°F

CI = 0 - straight-chain paraffins
CI = 100 - benzene

Values for the Correlation Index:

 0-15 : predominance of paraffin hydrocarbons in the fraction.
 15-50 : predominance of either naphthenes or of mixtures of paraffins, naphthenes, and
aromatics.
 more than 50 : predominance of aromatic species.

2. DENSITY

 Light: less than 870 kg/m3 (greater than 31.1°API)

 Medium: 870 to 920 kg/m3 (31.1°API to 22.3°API)
 Heavy: 920 to 1000 kg/m3 (22.3°API to 10°API)
 Extra-heavy: greater than 1000 kg/m3 (less than 10° API)

3. API GRAVITY

The formula to calculate API gravity from Specific Gravity (SG) is:

141.5
API GRAVITY = − 131.5
𝑆𝐺

SG – specific gravity at 60°F

The API values for each “weight” are as follows:
 Light – API > 31.1
 Medium – API between 22.3 and 31.1
 Heavy – API < 22.3
 Extra Heavy – API < 10.0
 Heavy oils were considered those petroleum-type materials that had gravity somewhat
less than 20° API
 Tar sand bitumen falling into the 5° to 10° API range

The higher the API gravity, the lighter the compound. If the API gravity is greater than 10, the
oil is lighter and floats on water; if less than 10, it is heavier and sinks. Light crudes generally
exceed 38 degrees API and heavy crudes are commonly below 22 degrees. Intermediate crudes
fall between 22 and 38 degrees. Oils are extra-heavy below 10; the API gravity of bitumen
approaches zero.

4. VISCOSITY

 Briefly, materials having viscosity less than 10,000 centipoises (cp) are conventional
petroleum and heavy oil
 Tar sand bitumen has a viscosity greater than 10,000 cp

5. CARBON DISTRIBUTION

 A high value of %CA at 500°C (930°F) boiling point usually indicates a high content of
asphaltenes in the residue

 A high value of %CNP at 500°C (930°F) boiling point usually indicates a waxy residue.

6. VISCOSITY–GRAVITY CONSTANT

For oil types:

1.0752 log(𝜐−38)
VGC = 10 d -
(10−(𝜐−38 ))

d is the specific gravity at 60° F

v is the Saybolt viscosity at 39°C (100°F).

For heavy oil (viscous crude oil):

0.022 log(𝜐−35.5)
VGC = d – 0.24 -
0.755

The lower the index number, the more paraffin the feedstock
7. UOP (Watson) CHARACTERIZATION FACTOR

K = (TB)1/3/d
Where:

TB is the average boiling point in degrees Rankine (° F + 460)

d is the specific gravity at 60° F

 Highly paraffin oils have K in the range 12.5 to 13.0

 Cyclic (naphthene) oils have K in the range 10.5 to 12.5
 Aromatics: 9.0- 10.5

8. POUR POINT

Pour Point is the temperature at which a liquid hydrocarbon ceases to flow or pour.

 When the reservoir temperature exceeds the pour point, the oil is fluid in the reservoir
and therefore mobile.
 When the reservoir temperature is lower than the pour point, this indicates that the
bitumen is solid within the deposit and therefore immobile.

Hydrocarbon Viscosity Viscosity Index Pour Point

Paraffin Low High High

Naphthene Medium Low Low

Aromatic High Low Low