HYDROCARBONS

A hydrocarbon is an organic compound composed of two elements, hydrogen and carbon. A large part
of the composition of petroleum is made up of hydrocarbons of varying lengths. The smallest
hydrocarbon, methane, is composed of a single carbon atom and four hydrogen atoms. However,
hydrocarbons can literally consist of hundreds or thousands of individual atoms that are linked together
in any number of ways, including chains, circles, and other complex shapes.

Hydrocarbons are carbon containing organic compounds that provide a source of energy and raw
materials. Real world relation: If you are driven in a car, bus, jet or truck, you have used hydrocarbons.
The gasoline and diesel fuel that we used in cars, jets and buses, are hydrocarbons.

Organic compounds.

These are carbon containing compounds with the primary exception of carbon oxides, carbide, and
carbonated, which are considered inorganic. In organic compounds, carbon atoms are bonded to
hydrogen atoms or atoms of other elements that are near carbon in the periodic table, especially nitrogen
oxygen sulphur phosphorous and the halogens.

The simplest organic compounds are hydrocarbons. Which contain only elements of carbon and
hydrogen. Thousands types of hydrocarbons are known each containing only the elements carbon and
hydrogen. The simplest hydrocarbon molecule, CH4, consists of a carbon atom bonded to four hydrogen
atoms. This substance called methane. It’s is an excellent fuel and it’s the main component of natural
gas.

Petroleum is a naturally occurring flammable liquid consisting of a complex mixture of hydrocarbons of

various molecular weights and other liquid organic compounds that are found in geologic formations
beneath the Earth's surface.

Properties

Because the structure of different hydrocarbons can vary so drastically, the properties of each class of
molecule vary greatly as well. In order to help categorize the properties of hydrocarbons, they are
broken up into several basic types.

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Alkanes – These are referred to as saturated hydrocarbons. Saturated has a specific definition in terms
of carbon-based molecules. Carbon can form up to four separate bonds with four separate other atoms.
However, it is also possible for carbon to form multiple bonds with a single atom, even another carbon
atom. When two carbon atoms in a hydrocarbon are linked together by two or more bonds rather than
one, the molecule is termed unsaturated. All alkanes are saturated, which means they only contain single
bonds between all carbon atoms. Alkanes are the basis of petroleum fuels and are found in linear and
branched forms.

Unsaturated Hydrocarbons – Those hydrocarbons that have one or more double bonds between
carbon atoms are called alkenes. Those with one or more triple bonds between carbon atoms are called
alkynes. These are mixed with alkanes in petroleum and contribute more carbon dioxide per pound than
do saturated hydrocarbons.

Cycloalkanes – Any hydrocarbon containing one or more ring structures. These are generally used for
the same functions as the non-cyclic alkanes, though they have additional uses in creating certain
plastics and in pharmaceutical bases.

Aromatic Hydrocarbons – This class of molecules has specialized ring structures where bonds
between carbon atoms are an intermediate between single and double bonds. Molecules in this class
include the industrial solvent benzene.

The structure, hydrogen to carbon ratio, and the length of a particular hydrocarbon determine its
properties. In general, small linear hydrocarbons will be gases while medium sized linear hydrocarbons
will be liquids. Branched hydrocarbons of intermediate size tend to be waxes with low melting points.
Long hydrocarbons tend to be semi-solid or solid. Unsaturated hydrocarbons are more likely to be solid
than their saturated counterparts as are cyclic hydrocarbons.

Hydrocarbons in Fuel

Hydrocarbons containing between six and 10 carbon molecules are the top components of most fuels,
regardless of whether they are alkanes, alkenes, or cyclic. In general, these molecules are burned to
produce energy.

Burning hydrocarbons requires oxygen. The hydrocarbon and oxygen combine, in a process called
combustion, to produce water, carbon dioxide, and energy. Of course, these molecules are not the only

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products of the combustion of hydrocarbon. Hydrocarbons that are contaminated with atoms such as
sulfur and nitrogen will also produce nitrogen dioxide and sulfur dioxide.

Because hydrocarbons are composed purely of carbon and hydrogen, their combustion with oxygen can
only produce water as a result of the combination between hydrogen and oxygen and carbon dioxide as a
result of the combination of carbon and oxygen. The energy produced by burning a hydrocarbon comes
from breaking both carbon-hydrogen and carbon-carbon bonds and recombining them into carbon-
oxygen and hydrogen-oxygen bonds.

Because an unsaturated hydrocarbon has fewer hydrogen carbon bonds, it has less hydrogen per
molecule than a similar unsaturated hydrocarbon and will produce more carbon dioxide. This also means
unsaturated hydrocarbons produce less energy when burned than do saturated hydrocarbons. In order to
gain the same amount of energy, a greater quantity of unsaturated hydrocarbon must be burned and as a
result more carbon dioxide is created in the process. Thus, unsaturated hydrocarbons are less
environmentally friendly than saturated hydrocarbons.

Beyond the release of carbon dioxide, burning hydrocarbons also releases other contaminants into the
atmosphere. Because refining hydrocarbons is not perfect process, all fuels will contain some level of
contaminants. During combustion, sulfur combines with oxygen to produce sulfur dioxide. Sulfur
dioxide later combines with hydrogen in the atmosphere to produce the weak sulfurous acid as well as
the strong sulfuric acid. Both of these contribute to acid rain. In addition to sulfur, nitrogen is also a
common contaminant in hydrocarbons. Nitrogen dioxide can react with hydrogen in the atmosphere to
produce nitric acid, which also contributes to acid rain.

How Hydrocarbons burn

Ideal Reaction

Under ideal settings, where only hydrocarbon and oxygen are present, the chemical reaction commonly
called combustion or burning produces only water, carbon dioxide, and energy as the following basic
equation shows.

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In the above ideal reaction, the energy gained from the reaction is greater than the energy put into the
reaction. It is common knowledge that a spark is needed to make a hydrocarbon burn. The spark
represents the energy need to break the carbon-carbon and carbon-hydrogen bonds of the hydrocarbon
molecule as well as the oxygen-oxygen bond of the oxygen molecule. The typical C-C bond requires
350 kJ/mol to break, the typical C-H bond requires 413 kJ/mol, and the O-O bond requires about 498
kJ/mol.

We know, however, the energy is released from these reactions and it is released when new bonds are
formed. The H-O bonds of water release about 464 kJ/mol of energy when formed and the C=O bonds
of CO2 release about 800 kJ/mol when formed. The net outcome is the release of energy in the form of
heat.

Oxygen as Limiting Factor

The atmosphere is not pure oxygen. It contains a number of other gases including nitrogen (78%), argon,
hydrogen, iodine, and other trace compounds. The effect of these other compounds is two-fold. First,
they act as contaminants in the reaction, which is discussed in this section. They also act to effectively
limit the concentration of oxygen. Rather than 100% oxygen, reactions that occur under atmospheric
conditions are subject to only 21% oxygen.

When oxygen is a limiting factor, it is not possible to pair every carbon atom with two oxygen atoms
during a combustion reaction. Thus, some carbon atoms end up with only one oxygen atom. This
produces carbon monoxide. When a combustion reaction produces CO, it is referred to as incomplete
combustion.

Atmospheric combustion would then be more closely modeled by the equation that follows (note this is
not a balanced equation).

Atmospheric Contaminants

Contamination can come from the petroleum refining process or from the atmosphere itself. The most
common atmospheric contaminant (for purposes of combustion) is nitrogen in the form of N2. When
nitrogen is burned at high temperatures in the presence of oxygen, it produces nitrogen oxide and

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nitrogen dioxide. These two compounds represent about 1% of the output of a common hydrocarbon
combustion reaction under atmospheric conditions. Thus, the equation can be rewritten to reflect this
new addition.

Both nitrogen compounds can participate in the formation of nitric acid (HNO3), which is a component
of acid rain. The reactions are as follows:

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Common Hydrocarbons and Their Uses

Name Number of Uses

Carbon Atoms

Methane 1 Fuel in electrical generation. Produces least about of

carbon dioxide.

Ethane 2 Used in the production of ethylene, which is utilized in

various chemical applications.

Propane 3 Generally used for heating and cooking

Butane 4 Generally used in lighters and in aerosol cans

Pentane 5 Can be used as solvents in the laboratory and in the

production of polystyrene.

Hexane 6 Used to produce in glue for shoes, leather products, and

in roofing

Heptane 7 The major component of gasoline

Octane 8 An additive to gasoline that reduces knock, particularly

in its branched forms

Nonane 9 The component of fuel, particularly diesel

Decane 10 A component of gasoline, but generally more important

in jet fuel and diesel

Hydrocarbons longer than 10 carbon atoms in length are generally broken down through the process
known as “cracking” to yield molecules with lengths of 10 atoms or less.

Original Hydrocarbons in Place

Knowing the hydrocarbon saturation from the resistivity logs and the porosity from the suite of porosity
logs, engineers can begin to approximate the amount of hydrocarbons that have been discovered. With

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these parameters, input from the geologists, and volumetric formulas, engineers calculate the amount of
hydrocarbons in the formation before production begins.
For oil,
N= (1- Sw) x porosity x A x h x Bo x 7,758
and for gas,
G = (1- Sw) x porosity x A x h x (1/Bg) x 43,560
Where
N is the total oil in place (in barrels)
G is the total gas in place (in cubic feet)
A is the drainage area (in acres)
h is the net pay thickness (the thickness of the formation corrected for any shale or nonporous layers)
• Bo is the oil shrinkage factor (a measure of how much oil shrinks as it reaches surface temperature and
pressure,
1/Bg is the gas formation volume factor (a measure of how much gas expands when it reaches surface
temperature and pressure.
7,758 is a constant to convert acre-feet into barrels
• 43,560 is a constant to convert acres into square feet
For example, suppose an oil-bearing formation has been discovered. The parameters required in order to
calculate the amount of oil discovered and their sources are as follows:
Water saturation, SW> is 15% determined by examination of the resistivity from induction logs.
Porosity is 25% (0.25) determined by examination of cores and/or a combination of density, neutron, or
sonic logs. The drainage area (the productive area), obtained from the geologist's maps, equals 250
acres. The net pay thickness found on the gamma ray or SP logs is 27feet.
The oil shrinkage factor is assumed, on the basis of experience and laboratory work with oils common to
the area, to be 0.6.
The solution becomes
N= (1- 0.15) x 0.25 x 250 x 27 x 0.6 x 7,758
N= 0.85 x 7,894,975
N= 6,676,729 barrels
In a similar fashion, the volume of gas discovered can be calculated. The calculation gives an estimate
of the total amount of hydrocarbons in the reservoir. But that is not the amount the engineers expect to

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be able to produce. That requires another set of assumptions, which result in a recovery factor. In simple
terms, the recovery factor is the amount of oil to be recovered (produced) as compared to (divided by)
the total oil in the reservoir (N in the above equation). In most cases, the volume produced (the ultimate
recovery) is less than 50% of the total hydrocarbons in the reservoir; often it is on the order of 30%,
especially in oil reservoirs.
COMPOSITION OF PETROLEUM
The hydrocarbons in petroleum are mostly alkanes, cycloalkanes and various aromatic hydrocarbons
while the other organic compounds contain nitrogen, oxygen and sulfur, and trace amounts of metals
such as iron, nickel, copper and vanadium. The exact molecular composition varies widely from
formation to formation. Other compounds such as Sulphur, nitrogen and oxygen combined with carbon
and hydrogen are also found.
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, vary appreciably from one reservoir to
another. Normally, crude oils are not used directly as fuels or as feedstocks for the production of
chemicals. This is due to the complex nature of the crude oil mixture and the presence of some
impurities that are corrosive or poisonous to processing catalysts.
The exact molecular composition varies widely from formation to formation but the proportion of
chemical elements vary over fairly narrow limits as follows:
Composition by weight

Element Percent range

Carbon 83 to 87%

Hydrogen 10 to 14%

Nitrogen 0.1 to 2%

Oxygen 0.05 to 1.5%

Sulphur 0.05 to 6.0%

Metals < 0.1%

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Four different types of hydrocarbon molecules appear in petroleum.
The relative percentage of each varies 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%
Asphaltic 6% remainder
Petroleum is used mostly, by volume, for producing fuel oil and petrol, both important "primary
energy" sources. 84 vol. % of the hydrocarbons present in petroleum is converted into energy-rich fuels
(petroleum-based fuels), including petrol, diesel, jet, heating, and other fuel oils, and liquefied petroleum
gas.
Properties of petroleum
1) API gravity
API (American Petroleum Institute) gravity of petroleum fractions is a measure of density of the stream.
Usually measured at 60 oF, the API gravity is expressed as API = 141.5/specific gravity – 131.5 where
specific gravity is measured at 60 oF.
According to the above expression, 10 oAPI gravity indicates a specific gravity of 1 (equivalent to water
specific gravity). In other words, higher values of API gravity indicate lower specific gravity and
therefore lighter crude oils or refinery products and vice-versa. As far as crude oil is concerned, lighter
API gravity value is desired as more amount of gas fraction, naphtha and gas oils can be produced from
the lighter crude oil than with the heavier crude oil. Therefore, crude oil with high values of API gravity
are expensive to procure due to their quality.
2) Watson characterization factor.
The K factor or characterization factor is a systematic way of classifying a crude oil according to
its paraffinic, naphthenic, intermediate or aromatic nature. 12.5 Or higher indicate a crude oil of
predominantly paraffinic constituents, while 10 or lower indicate a crude of more aromatic nature. The
K factor is also referred to as the UOP K factor or just UOPK.

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The Watson characterization factor, KW (Wauquier, 1995; Nelson, 1978), is probably the oldest of such
factors and it is defined as:

In which Tb is the boiling temperature (in kelvins) and S is the standard

specific gravity (15.6°/15.6° C). This characterization factor, which was initially introduced by the
research personnel of the Universal Oil Products Company (UOP), is based on the observation that
specific gravities of hydrocarbons are related to their H/C ratio (hydrogen-to-carbon ratio of the
molecule) and as a result to their chemical character, and that their boiling points are linked to the
carbon number of their molecules. Therefore, KW of the pure components was defined using only their
densities and boiling points in the form of Equation (1). In Table 1 the range of values of this factor for
three families of hydrocarbons, namely paraffinic, naphthenic and aromatic, are reported.
The Watson characterization factor is usually expressed as Kw = (Tb)1/3/specific gravity.
Where Tb is the average boiling point in degrees R taken from five temperatures corresponding to 10,
30, 50, 70 and 90 volume % vaporized.
Typically Watson characterization factor varies between 10.5 and 13 for various crude streams. A
highly paraffinic crude typically possesses a K factor of 13. On the other hand, a highly naphthenic
crude possesses a K factor of 10.5. Therefore, Watson characterization factor can be used to judge upon
the quality of the crude oil in terms of the dominance of the paraffinic or naphthenic components

As it can be observed in this table

there is an overlap between the ranges of this factor for various hydrocarbon families. As a result, the
use of this factor will not allow us to identify every hydrocarbon uniquely by a number.
3) Sulphur content
Since crude oil is obtained from petroleum reservoirs, sulphur is present in the crude oil. Usually, crude
oil has both organic and inorganic sulphur in which the inorganic sulphur dominates the composition.

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Typically, crude oils with high sulphur content are termed as sour crude. On the other hand, crude oils
with low sulphur content are termed as sweet crude. Typically, crude oil sulphur content consists of 0.5
– 5 wt % of sulphur. Crudes with sulphur content lower than 0.5 wt % are termed as sweet crudes. It is
estimated that about 80 % of world crude oil reserves are sour.
4) TBP/ASTM distillation curves
The most important characterization properties of the Crude/intermediate/product streams are the
TBP/ASTM distillation curves. Both these distillation curves are measured at 1 atm pressure. In both
these cases, the boiling points of various volume fractions are being measured. However, the basic
difference between TBP curve and ASTM distillation curve is that while TBP curve is measured using
batch distillation apparatus consisting of no less than 100 trays and very high reflux ratio, the ASTM
distillation is measured in a single stage apparatus without any reflux. Therefore, the ASTM does not
indicate a good separation of various components and indicates the operation of the laboratory setup far
away from the equilibrium.
5) Viscosity
Viscosity is a measure of the flow properties of the refinery stream. Typically in the refining industry,
viscosity is measured in terms of centistokes (termed as cst) or saybolt seconds or redwood seconds.
Usually, the viscosity measurements are carried out at 100 oF and 210 oF. Viscosity is a very important
property for the heavy products obtained from the crude oil. The viscosity acts as an important
characterization property in the blending units associated to heavy products such as bunker fuel.
Typically, viscosity of these products is specified to be within a specified range and this is achieved by
adjusting the viscosities of the streams entering the blending unit.
6) Flash and fire point
Flash and fire point are important properties that are relevant to the safety and transmission of refinery
products. Flash point is the temperature above which the product flashes forming a mixture capable of
inducing ignition with air. Fire point is the temperature well above the flash point where the product
could catch fire. These two important properties are always taken care in the day to day operation of a
refinery.
7) Pour point
When a petroleum product is cooled, first a cloudy appearance of the product occurs at a certain
temperature. This temperature is termed as the cloud point. Upon further cooling, the product will
ceases to flow at a temperature. This temperature is termed as the pour point. Both pour and cloud

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points are important properties of the product streams as far as heavier products are concerned. For
heavier products, they are specified in a desired range and this is achieved by blending appropriate
amounts of lighter intermediate products.
8) Octane number
Though irrelevant to the crude oil stream, the octane number is an important property for many
intermediate streams that undergo blending later on to produce automotive gasoline, diesel etc.
Typically gasoline tends to knock the engines. The knocking tendency of the gasoline is defined in
terms of the maximum compression ratio of the engine at which the knock occurs. Therefore, high
quality gasoline will tend to knock at higher compression ratios and vice versa.

However, for comparative purpose, still one needs to have a pure component whose compression ratio is
known for knocking. Iso-octane is eventually considered as the barometer for octane number
comparison. While iso-octane was given an octane number of 100, nheptane is given a scale of 0.
Therefore, the octane number of a fuel is equivalent to a mixture of a iso-octane and n-heptane that
provides the same compression ratio in a fuel engine. Thus an octane number of 80 indicates that the
fuel is equivalent to the performance characteristics in a fuel engine fed with 80 vol % of isooctane and
20 % of n-heptane.
Octane numbers are very relevant in the reforming, isomerisation and alkylation processes of the
refining industry. These processes enable the successful reactive transformations to yield long side
chain paraffins and aromatics that possess higher octane numbers than the feed constituents which do
not consist of higher quantities of constituents possessing straight chain paraffins and non-aromatics
(naphthenes).
Dry gas is a natural gas stream that consists almost entirely of methane, with possibly a few percent
ethane and propane.
Wet gas is a natural gas stream that consists of a high percentage of methane (80-90%), plus natural gas
liquids, ethane, propane, butane, and natural gasoline, and small amounts of other constituents.
Condensate is a very light crude oil-type hydrocarbon that comes from a well producing predominantly
natural gas (a gas well). Condensate generally has some natural gas liquids in it. Light crude oil
probably has a few percent natural gas liquids. Heavy crude has little or no natural gas liquids and a high
percentage of the heavy hydrocarbons. Sometimes the heaviest of the heavy crudes have to be heated to
make them fluid enough to pump out of the ground and through a pipeline.

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Bitumen is a composition of heavy hydrocarbons, including the very complex asphaltenes. Together,
they form solids at ambient temperatures. Bitumen is a hard substance to handle. In the reservoir,
bitnmen is a thick, sluggish fluid like road asphalt and has to be extracted from the ground with much
heat and effort and hauled away to a facility that can upgrade it to a useful product.

DIESEL
Diesel fuel is any liquid fuel used in diesel engines, originally obtained from crude-oil distillation (petro
diesel), but alternatives are increasingly being developed for partial or total substitution of petro diesel,
such as biodiesel (from vegetal oils), and synthetic diesel (usually from a gas fuel coming from coal
reforming or biomass, also named gas to liquid fuels, GTL). In all cases, diesel nowadays must be free
of sulphur.
Diesel types.
Type A for road vehicles, B for industries (agriculture, fishing; same properties as type A, but red-
coloured for different taxation), C for heating (not for engines; blue-coloured).
Properties
i. Density
=830 kg/m3 (780-860 kg/m3 at 40 ºC). Thermal expansion coefficient=800⋅10-6 K-1. 880 kg/m3 for
biodiesel (860-900 kg/m3 at 40 ºC).
ii. Boiling and freezing points. Not well defined because they are mixtures. In general, these fuels
remain liquid down to −30 ºC (some antifreeze additives may be added to guarantee that).
iii. Viscosity=3⋅10-6 m2/s (2.0⋅10-6-4.0⋅10-6 m2/s at 40 ºC) for diesel; 4.0⋅10-6-6.0⋅10-6 m2/s for
biodiesel.
iv. Vapour pressure=1-10 kPa at 38 ºC for diesel and JP-4, 0.5-5 kPa at 38 ºC for kerosene.
v. Cetane number =45 (between 40-55); 60-65 for biodiesel. This is a measure of a fuel's ignition
delay; the time period between the start of injection and start of combustion (ignition) of the fuel,
with larger cetane numbers having lower ignition delays. This is only of interest in compression-
ignition engines, and only valid for light distillate fuels (because of the test engine; for heavy
fuel oil, a different burning-quality index is used, calculated from the fuel density and viscosity).
vi. Flash-point=50 ºC typical (40 ºC minimum). In the range 310-340 K (370-430 K for biodiesel).
vii. Heating value. HHV=47 MJ/kg, LHV=43 MJ/kg (HHV=40 MJ/kg for biodiesel).

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Composition. All natural fuels are mixtures (and most synthetic fuels too). The analysis can be ultimate
(i.e. mass fraction of chemical elements), or structural (mass fraction of identified molecules). The
ultimate analysis of desulfurized kerosenes (<0.2% S), by weight, may yield some 84-86% C, some 13-
15% H, and 1% impurities and additives.

The structural analysis shows, by volume, some 66% of saturated hydrocarbons (linear and cycle
chains), 30% aromatics (benzene derivatives), and 4% olefins (unsaturated hydrocarbons). From the
ultimate analysis one may establish a reduced molecular formula (per unit carbon atom) of CH n with
n=1.8-2 (e.g. for 86% C and 14% H, n=(14/1)/(86/12=1.95). If the structural analysis is also considered,
a mean molecular formula can be found (i.e., with whole number of atoms and typical carbon-
chainlength, as C11H21, or C12H23, or C12H26, or C13H26, or C14H30; dodecene and tridecene are the most
usual surrogates). Composition of biodiesel, by weight, may be: 77% C, 12% H, 11% O, 0.01% S.
PARAFFINS
Paraffin hydrocarbon, also called alkane, any of the saturated hydrocarbons having the general formula
CnH2n+2, C being a carbon atom, H a hydrogen atom, and n an integer. Paraffin wax, colourless or white,
somewhat translucent, hard wax consisting of a mixture of solid straight-chain hydrocarbons ranging
in melting point from about 48° to 66° C (120° to 150° F). Paraffin wax is obtained from petroleum by
dewaxing light lubricating oil stocks. It is used in candles, wax paper, polishes, cosmetics, and electrical
insulators. It assists in extracting perfumes from flowers, forms a base for medical ointments, and
supplies a waterproof coating for wood. In wood and paper matches, it helps to ignite the matchstick by
supplying an easily vaporized hydrocarbon fuel.
The paraffins are major constituents of natural gas and petroleum. All paraffins are colorless. Alkanes
such as methane, ethane, propane, n and iso butane, n and iso pentane. These compounds are primarily
obtained as a gas fraction from the crude distillation unit. The simplest alkane, methane (CH4), is the
principal constituent of natural gas. Alkanes (paraffins), are saturated hydrocarbons with straight
(normal) or branched (iso) chains which contain only carbon and hydrogen and have the general formula
CnH2n+2.

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They generally have from 5 to 40 carbon atoms per molecule, although trace amounts of shorter or
longer molecules may be present in the mixture.
- the alkanes from pentane (C5H12) to octane (C8H18) are refined into petrol, the ones from
nonane (C9H20) to hexadecane (C16H34) into diesel fuel, kerosene and jet fuel.
- alkanes with more than 16 carbon atoms can be refined into fuel oil and lubricating oil.
- at the heavier end of the range, paraffin wax is an alkane with approximately 25 carbon atoms,
while asphalt has 35 and up, although these are usually cracked by modern refineries into more valuable
products.
- the shortest molecules, those with four or fewer carbon atoms, are in a gaseous state at room
temperature. They are the petroleum gases.
- Depending on demand and the cost of recovery, these gases are either flared off, sold as liquefied
petroleum gas under pressure, or used to power the refinery's own burners.
- During the winter, butane (C4H10), is blended into the petrol pool at high rates, because its high vapor
pressure assists with cold starts. Heavier petroleum fractions such as kerosene and gas oil may contain
two or more cyclohexane rings fused through two vicinal carbons.

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. Branched alkanes
are saturated hydrocarbons with an alkyl substituent or a side branch from the main chain.

A branched alkane with the same number of carbons and hydrogens as an n-alkane is called an isomer.

15
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. The following shows the isomers of hexane:
C5 - C17 / liquids
C16 – C78 / solids
Crude oils contain many short, medium, and long-chain normal and branched paraffins.
A naphtha fraction (obtained as a light liquid stream from crude fractionation) with a narrow boiling
range may contain a limited but still large number of isomers.

Properties of Paraffins
i. Substitution reactions
One or more hydrogen atoms of alkanes can be replaced by halogens, nitro group and sulphonic acid
group. Halogenation takes place either at higher temperature (573-773 K) or in the presence of diffused
sunlight or ultraviolet light. Lower alkanes do not undergo nitration and sulphonation reactions. These
reactions in which hydrogen atoms of alkanes are substituted are known as substitution reactions.
ii. Combustion
Alkanes on heating in the presence of air or dioxygen are completely oxidized to carbon dioxide and
water with the evolution of large amount of heat.
iii. Controlled oxidation
Alkanes on heating with a regulated supply of dioxygen or air at high pressure and in the presence of
suitable catalysts give a variety of oxidation products.
iv. Isomerisation ;n-Alkanes on heating in the presence of anhydrous aluminium chloride and
hydrogen chloride gas isomerise to branched chain alkanes. Major products are given below.
Some minor products are also possible which you can think over. Minor products are generally
not reported in organic reactions.
v. Pyrolysis
Higher alkanes on heating to higher temperature decompose into lower alkanes, alkenes etc. Such a
decomposition reaction into smaller fragments by the application of heat is called pyrolysis or cracking.

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 vi. Aromatization; n-Alkanes having six or more carbon atoms on heating to 773K at 10-20
atmospheric pressure in the presence of oxides of vanadium, molybdenum or chromium
supported over alumina get dehydrogenated and cyclised to benzene and its homologues. This
reaction is known as aromatization or reforming.
vii. Reaction with steam
Methane reacts with steam at 1273 K in the presence of nickel catalyst to form carbon monoxide and
dihydrogen. This method is used for industrial preparation of dihydrogen gas.

CYCLOPARAFFINS (NAPHTHENES)
The cycloalkanes (naphthenes), are saturated hydrocarbons which have one or more carbon rings to
which hydrogen atoms are attached according to the formula CnH2n. Naphthenes or cycloalkanes such as
cyclopropane, methyl cyclohexane are also present in the crude oil. These compounds are not aromatic
and hence do not contribute much to the octane number. Therefore, in the reforming reaction, these
compounds are targeted to generate aromatics which have higher octane numbers than the naphthenes.
Cycloalkanes have two fewer hydrogen atoms than alkanes, because another carbon-carbon bond is
needed to form the ring. Cycloalkanes are drawn as simple polygons in which the sides represent the
carbon-carbon bonds. It is understood that each corner of the polygon is a carbon atom bonded to two
hydrogen atoms.

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Cycloalkanes have similar properties to alkanes but have higher boiling points.
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.

AROMATICS
Aromatics, so called because of their distinctive perfumed smell, are substances derived from crude oil
and, in small quantities, from coal. Aromatics are hydrocarbons, organic compounds that consist
exclusively of the elements carbon and hydrogen – without which life would not be possible on Earth.
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. Aromatic
hydrocarbons, also called arenes, are a unique class of carbon molecules in which carbon atoms are
connected by alternating double and single bonds.

They tend to burn with a sooty flame, and many have a sweet aroma. Some are carcinogenic. Aromatics
such as benzene, toluene o/m/p-xylene are also available in the crude oil. These contribute towards
higher octane number products and the target is to maximize their quantity in a refinery process. 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.

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How are aromatics produced?
Benzene, toluene, and xylenes can be made by various processes. However, most BTX production is
based on the recovery of aromatics derived from the catalytic reforming of naphtha in a petroleum
refinery. ... The BTX aromatics can be extracted from catalytic reformate or from pyrolysis gasoline by
many different methods

Separating BTX aromatics from crude oil distillates is not feasible because they are present in low
concentrations. Enriching a naphtha fraction with these aromatics is possible through a catalytic
reforming process.
Binuclear aromatic hydrocarbons are found in heavier fractions than naphtha. Trinuclear and
polynuclear aromatic hydrocarbons, in combination with heterocyclic compounds, are major

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constituents of heavy crudes and crude residues. Asphaltenes are a complex mixture of aromatic and
heterocyclic compounds.

Benzene (C6H6)

The structure of benzene can be drawn in two ways. In the first, the double bond character is explicitly
drawn. In the shorthand version, a circle is simply drawn inside the ring to demonstrate the structure.
Each carbon atom in benzene has a single hydrogen attached to it. In the diagram, the hydrogen have
been omitted for clarity.

Basic Properties

Like other hydrocarbons, benzene is a natural component of petroleum. It is a colorless, flammable,

sweet-smelling liquid at room temperature and is a component of most gasoline mixes as it has a high
octane number. Benzene is also highly carcinogenic and is well-known to cause bone marrow failure
and bone cancer. Of course, its carcinogenicity was not well known when it was being used as an
additive in after shave and other cosmetics due to its “pleasant aroma.”

Cancer

What makes benzene carcinogenic is its interaction with DNA. It breaks the bonds between subunits of
DNA in the body, which in turn causes cells to either die or reproduce without normal controls (cancer).
It is general consensus that no amount of benzene is safe, but this has not stopped its use in many
industrial and laboratory applications where is properties have yet to be supplanted by another
substance. Toluene is used where possible as a less carcinogenic and less toxic alternative to benzene.

Currently, the largest exposures to benzene occur through smoking as it is a byproduct of burning the tar
found in cigarettes. The second largest exposure is in gasoline service stations, which, when combined

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with industrial emissions and the emissions from car exhaust, accounts for 20% of all atmospheric
benzene.

Uses

The largest use of benzene (50%) is in the product of styrene and polystyren plastics. It is also converted
to a molecule known as cyclohexane, which is important in the production of Nylon. About 15% of
benzene is used to produce cyclohexane. Smaller amounts are used in everything from pesticides to
rubber to pharmaceuticals.

Impurities
All sorts of cats and dogs can turn up in a hydrocarbon reservoir, whether it contains oil or gas or both.
Along with natural gas and its natural gas liquid constituents, other gases can present themselves (table
3-1). Carbon dioxide (C02), oxygen (02), nitrogen (N2), and hydrogen sulfide (H2S) are the most
common. Not only is hydrogen sulfide a lethal gas in very small concentrations, but burning has it
created a pollutant. That gives two good reasons why environmental laws and safety considerations
require it be removed. Excess carbon dioxide has to be eliminated because it can cause corrosion of
transportation and processing equipment.

A gas stream can contain minor amounts of the rare gases-argon, helium, neon, and xenon. Sometimes
they are in sufficient quantities to make separation and recovery commercially attractive.
Crude oils can have the same contaminant problems. Most serious for crude oil is the presence of sulfur
and metals. Sulfur can reside in crude oil in the form of dissolved hydrogen sulfide, or it can be sulfur
atoms chemically attached to the hydrocarbon molecules like thiophene (CsHsS).

Depending on the country, environmental regulations require almost all the sulfur be removed from
refined products before they can be sold. Special units in refineries are required in order to remove it,
and as a result, the more sulfur there is in the crude, the lower will be its value to refiners. Metals, such
as vanadium, nickel, and copper, can damage the catalysts used to process a crude oil in refineries and
can also cause debits to the values of crude oils so contaminated.

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Petroleum Contaminants

Though sulfur is not a major component of the atmosphere, it is often found in petroleum. In fact, sour
versus sweet petroleum is determined by the sulfur content where sour petroleum contains more than
0.5% sulfur. Sulfur, when burned during hydrocarbon combustion produces sulfur dioxide, which acts as
a precursor to sulfuric acid. Like nitric acid, this contributes to acid rain. We can once again update our
hydrocarbon combustion reaction to reflect this new contaminant (reaction not balanced and H2S is not
the only sulfur contaminant. Others include COS, CS2, SO2 and more).

The reaction that produces sulfuric acid from sulfur dioxide is more complicated than that which
governs nitric oxide production. In general, the reaction proceeds as follows (note that a dot indicates an
extra electron on a compound, making it a radical in chemistry lingo).

Soot and Smoke

Soot and smoke both refer to particulate matter that gets trapped in gases during combustion. The
visible, dark black component of smoke is carbon that has incompletely burned and, rather than forming
CO2, has formed solid carbon compounds known as amorphous carbon. These carbon compounds are
collectively referred to as soot. Diesel exhaust accounts for 25% of all smoke and soot in the
atmosphere. This is generally the result of the lower quality of fuel (less refined) that constitutes diesel
fuel. Soot, in particular, contains large amounts of polycyclic aromatic hydrocarbons, which are well-
known mutagens and carcinogens. Diesel exhaust is considered the most carcinogenic of fossil fuels
used in transportation.

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