NATIONAL INSTITUTE OF TECHNOLOGY,ROURKELA

ASSIGNMENT-1
COMPOSITION AND CLASSIFICATION OF PETROLEUM

SESSION:-2012-2013

DATE-28.01.2013

GUIDED BY SUBMITTED BY

Proff SUJIT SEN GANGADHAR HOTA

(Department of chemical engg.) 110CH0445

INTRODUCTION:
Petroleum or crude oil 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. A fossil fuel, it is formed when large quantities of dead
organisms, usually zooplankton and algae, are buried underneath sedimentary
rock and undergo intense heat and pressure.
Petroleum is recovered mostly through oil drilling. This comes after the studies of
structural geology (at the reservoir scale), sedimentary basin analysis, reservoir
characterization (mainly in terms of porosity and permeable structures). It is
refined and separated, most easily by boiling point, into a large number of
consumer products, from petrol (or gasoline) and kerosene to asphalt and
chemical reagents used to make plastics and pharmaceuticals. Petroleum is used
in manufacturing a wide variety of materials, and it is estimated that the world
consumes about 88 million barrels each day.
The use of fossil fuels such as petroleum can have a negative impact on earth's
biosphere, releasing pollutants and greenhouse gases into the air and damaging
ecosystems through events such as oil spills. Concern over the depletion of the
earth's finite reserves of oil, and the effect this would have on a society dependent
on it, is a field known as peak oil.

Crude oil varies greatly in appearance depending on its composition. It is usually

black or dark brown (although it may be yellowish, reddish, or even greenish). In
the reservoir it is usually found in association with natural gas, which being
lighter forms a gas cap over the petroleum, and saline water which, being heavier
than most forms of crude oil, generally sinks beneath it. Crude oil may also be
found in semi-solid form mixed with sand and water, as in the athabasca oil
sands in canada, where it is usually referred to as crude bitumen. In canada,
bitumen is considered a sticky, black, tar-like form of crude oil which is so thick
and heavy that it must be heated or diluted before it will flow. Venezuela also has
large amounts of oil in the orinoco oil sands, although the hydrocarbons trapped
in them are more fluid than in canada and are usually called extra heavy oil.
These oil sands resources are called unconventional oil to distinguish them from
oil which can be extracted using traditional oil well methods. Between them,
canada and venezuela contain an estimated 3.6 trillion barrels (570×109 m3) of
bitumen and extra-heavy oil, about twice the volume of the world's reserves of
conventional 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
 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%

APPLICATIONS:

Petroleum is used mostly, by volume, for producing fuel oil and petrol, both
important "primary energy" sources. 84 per cent by volume 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 liquified petroleum
gas. The lighter grades of crude oil produce the best yields of these products, but
as the world's reserves of light and medium oil are depleted, oil refineries are
increasingly having to process heavy oil and bitumen, and use more complex
and expensive methods to produce the products required. Because heavier crude
oils have too much carbon and not enough hydrogen, these processes generally
involve removing carbon from or adding hydrogen to the molecules, and
using fluid catalytic cracking to convert the longer, more complex molecules in
the oil to the shorter, simpler ones in the fuels.
Due to its high energy density, easy transportability and relative abundance, oil
has become the world's most important source of energy since the mid-1950s.
Petroleum is also the raw material for many chemical products,
including pharmaceuticals, solvents, fertilizers, pesticides, and plastics; the 16
per cent not used for energy production is converted into these other materials.
Petroleum is found in porous rock formations in the upper strata of some areas of
the Earth's crust. There is also petroleum in oil sands (tar sands). Known oil
reserves are typically estimated at around 190 km3 (1.2 trillion (short
scale) barrels) without oil sands, or 595 km3 (3.74 trillion barrels) with oil
sands. Consumption is currently around 84 million barrels (13.4×106 m3) per day,
or 4.9 km3 per year. Which in turn yields a remaining oil supply of only about 120
years, if current demand remain static.

FORMATION

[STRUCTURE OF A VANADIUM PORPHYRIN COMPOUND (LEFT) EXTRACTED FROM PETROLEUM

BY ALFRED E. TREIBS, FATHER OF ORGANIC GEOCHEMISTRY. TREIBS NOTED THE CLOSE
STRUCTURAL SIMILARITY OF THIS MOLECULE AND CHLOROPHYLL A(RIGHT). ]

Petroleum is a fossil fuel derived from ancient fossilized organic materials, such
as zooplankton and algae. Vast quantities of these remains settled to sea or lake
bottoms, mixing with sediments and being buried under anoxic conditions. As further
layers settled to the sea or lake bed, intense heat and pressure built up in the lower
regions. This process caused the organic matter to change, first into a waxy material
known as kerogen, which is found in various oil shales around the world, and then with
more heat into liquid and gaseous hydrocarbons via a process known as catagenesis.
Formation of petroleum occurs from hydrocarbon pyrolysis in a variety of
mainly endothermic reactions at high temperature and/or pressure
There were certain warm nutrient-rich environments such as the Gulf of Mexico and
the ancient Tethys Sea where the large amounts of organic material falling to the ocean
floor exceeded the rate at which it could decompose. This resulted in large masses of
organic material being buried under subsequent deposits such as shale formed from
mud. This massive organic deposit later became heated and transformed under pressure
into oil.
Geologists often refer to the temperature range in which oil forms as an "oil
window"—below the minimum temperature oil remains trapped in the form of kerogen,
and above the maximum temperature the oil is converted to natural gas through the
process of thermal cracking. Sometimes, oil formed at extreme depths may migrate and
become trapped at a much shallower level. The Athabasca Oil Sands are one example of
this.

COMPOSITION:
Petroleum is a mixture of a very large number of different hydrocarbons; the most
commonly found molecules are alkanes (linear or branched),cycloalkanes, aromatic
hydrocarbons, or more complicated chemicals like asphaltenes. Each petroleum variety
has a unique mix of molecules, which define its physical and chemical properties, like
color and viscosity.
The alkanes, also known as paraffins, are saturated hydrocarbons with straight or
branched chains which contain only carbon and hydrogen and have the general
formula CnH2n+2. 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 liquified 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. Liquified
under pressure slightly above atmospheric, it is best known for powering cigarette
lighters, but it is also a main fuel source for many developing countries. Propane can be
liquified under modest pressure, and is consumed for just about every application
relying on petroleum for energy, from cooking to heating to transportation.
The cycloalkanes, also known as naphthenes, are saturated hydrocarbons which have
one or more carbon rings to which hydrogen atoms are attached according to the
formula CnH2n. Cycloalkanes have similar properties to alkanes but have higher
boiling points.
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.
These different molecules are separated by fractional distillation at an oil refinery to
produce petrol, jet fuel, kerosene, and other hydrocarbons. For example, 2,2,4-
trimethylpentane (isooctane), widely used in petrol, has a chemical formula of
C8H18 and it reacts with oxygen exothermically:

2 C8H18(l) + 25 O2(g) → 16 CO2(g) + 18 H2O(g) (ΔH = −10.86 MJ/mol of octane

The amount of various molecules in an oil sample can be determined in laboratory.

The molecules are typically extracted in a solvent, then separated in a gas
chromatograph, and finally determined with a suitable detector, such as a flame
ionization detector or a mass spectrometer. Due to the large number of co-eluted
hydrocarbons within oil, many cannot be resolved by traditional gas
chromatography and typically appear as a hump in the chromatogram.
This unresolved complex mixture (UCM) of hydrocarbons is particularly apparent
when analysing weathered oils and extracts from tissues of organisms exposed to
oil.
Incomplete combustion of petroleum or petrol results in production of toxic
byproducts. Too little oxygen results in carbon monoxide. Due to the high
temperatures and high pressures involved, exhaust gases from petrol combustion in
car engines usually include nitrogen oxides which are responsible for creation
of photochemical smog.
CLASSIFICATIONS :
Generally ,oil with an API gravity between 40 and 45 commands the highest
prices. Above 45 degrees the molecular chains become shorter and less
valuable to refineries.
Crude oil is classified as light, medium or heavy, according to its measured
API gravity.
 Light crude oil is defined as having an API gravity higher than 31.1 °API
(less than 870 kg/m3)
 Medium oil is defined as having an API gravity between 22.3 °API and
31.1 °API (870 to 920 kg/m3)
 Heavy crude oil is defined as having an API gravity below 22.3 °API (920
to 1000 kg/m3)
 Extra heavy oil is defined with API gravity below 10.0 °API (greater than
1000 kg/m3)
Not all parties use the same grading.The United States Geological Survey uses
slightly different definitions.
Crude oil with API gravity less than 10 °API is referred to as extra heavy
oil or bitumen. Bitumen derived from the oil sands deposits in the Alberta,
Canada area has an API gravity of around 8 °API. It is "upgraded" to an API
gravity of 31 °API to 33 °API, and the upgraded oil is known as synthetic
crude.

POUR POINT

The pour point of a liquid is the lowest temperature at which it becomes semi solid and
loses its flow characteristics. In crude oil a high pour point is generally associated with
a high paraffincontent, typically found in crude deriving from a larger proportion of
plant material. That type of crude oil is mainly derived from a kerogen Type II.

ANILINE POINT

The aniline point of an oil is defined as the minimum temperature at which equal
volumes of aniline (C6H5NH2) and the oil are miscible, i.e. form a single phase upon
mixing.
The value gives an approximation for the content of aromatic compounds in the oil,
since the miscibility of aniline, which is also an aromatic compound suggests the
presence of similar (i.e. aromatic) compounds in the oil. The lower the aniline point, the
greater is the content of aromatic compounds in the oil as obviously a lower
temperature is needed to ensure miscibility.
The aniline point serves as a reasonable proxy of the aromatic content as petrochemical
oils largely consist of saturated hydrocarbons (i.e. alkanes, paraffins) or unsaturated
compounds (mostly aromatics) only.

FLASH POINT

The flash point of a volatile material is the lowest temperature at which it can vaporize
to form an ignitable mixture in air. Measuring a flash point requires an ignition source.
At the flash point, the vapor may cease to burn when the source of ignition is removed.
The flash point is not to be confused with the autoignition temperature, which does not
require an ignition source, or the fire point, the temperature at which the vapor
continues to burn after being ignited. Neither the flash point nor the fire point is
dependent on the temperature of the ignition source, which is much higher.
The flash point is often used as a descriptive characteristic of liquid fuel, and it is also
used to help characterize the fire hazards of liquids. “Flash point” refers to
both flammable liquids andcombustible liquids. There are various standards for
defining each term. Liquids with a flash point less than 60.5 or 37.8 °C (141 or
100 °F)—depending upon the standard being applied—are considered flammable,
while liquids with a flash point above those temperatures are considered combustible.

Gasoline (petrol) is a fuel for use in a spark-ignition engine. The fuel is mixed with air
within its flammable limits and heated above its flash point, then ignited by the spark
plug. In order to avoid preignition by the residual heat of a hot combustion chamber,
the fuel must have a low flash point and a high autoignition temperature.
Diesel fuel flash points vary between 52 and 96 °C (126 and 205 °F). Diesel is suitable
for use in a compression-ignition engine. Air is compressed until it has been heated
above the autoignition temperature of the fuel, which is then injected as a high-pressure
spray, keeping the fuel-air mix within flammable limits. In a diesel-fueled engine, there
is no ignition source (such as the spark plugs in a gasoline engine). Consequently,
diesel fuel must have a high flash point and a low autoignition temperature.
Jet fuel flash points also vary. Both Jet A and Jet A-1 have flash points between 38 and
66 °C (100 and 151 °F), close to that of off-the-shelf kerosene. Yet both Jet B and JP-4
have flash points between -23 and -1 °C (-9 and 30 °F).

TOTAL ACID NUMBER

The total acid number (TAN) is a measurement of acidity that is determined by the
amount of potassium hydroxide in milligrams that is needed to neutralize the acids in
one gram of oil. It is an important quality measurement of crude oil. The TAN value
indicates to the crude oil refinery the potential of corrosion problems. It is usually
the naphthenic acids in the crude oil that causes corrosion problems. This type of
corrosion is referred to as naphthenic acid corrosion (NAC).

FIRE POINT

The fire point of a fuel is the temperature at which it will continue to burn for at least 5
seconds after ignition by an open flame. At the flash point, a lower temperature, a
substance will ignite briefly, but vapor might not be produced at a rate to sustain the
fire. Most tables of material properties will only list material flash points, but in general
the fire points can be assumed to be about 10 °C higher than the flash points. However,
this is no substitute for testing if the fire point is safety critical.
SULPHUR CONENT:

Sulphur is the heteroatom most commonly found in crude oil and the total sulphur is
usually in the range 0.1% to 5% depending on the crude and seldom falls outside the
range 0.05-6.0%. It is also the least desirable heteroatom from a transportation fuel
perspective. The distribution of sulphur compounds is not equal over the distillation
range and the sulphur content generally increases with boiling point (Table 1).

Table 1. Distribution of sulphur compounds over the

distillation range of a 1.2% sulphur containing crude oil.
Distillation Sulphur Sulphur compound distribution
(%)
range (°C) content (%) Thiols Sulphides Thiophenes Other †
70-180 0.02 50 50 trace -
160-240 0.2 25 25 35 15
230-350 0.9 15 15 35 35
350-550 1.8 5 5 30 60
>550 2.9 trace trace 10 90

(† = Benzothiophenes and heavy sulphides.)

The sulphur can be present in an inorganic form g as elemental sulphur,

carbonyl
sulphide (COS) or hydrogen sulphide (H2S), or it can be present in an
organic form. The organic classes most often encountered are sulphides,
thiols (mercaptans) and thiophenes.
NITROGEN CONTENT:

Nitrogen containing compounds are mostly found in crude oil fractions

boiling above 250°C. The nitrogen content depends on the crude origin, but is
generally less than 0.5%, although it may be as high as 2%.(4) Basic, neutral
and acidic nitrogen compounds are present, with the main nitrogen
containing compound classes being amines, amides, pyrroles and pyridines.l,(2)
The basic nitrogen containing compounds reduce the acidity of refining
catalysts and are especially undesirable. Nitrogen compounds may also
contribute to gum formation in products such as domestic fuel oil.(4)
Amines are basic nitrogen compounds and are found as primary (R-NH2),
secondary (R-NH-R′) and tertiary (R-NR′R″) amines.
Amides are acidic nitrogen compounds containing the -(C=O)-N functional
group and are found as both aliphatic and aromatic compounds.
Pyrroles are aromatic compounds containing nitrogen as part of a 5-
membered ring structure and may be present as pyrrole, indole, carbazole
and even heavier derivatives of pyrrole (Figure 5). These are all neutral
compounds, despite the presence of the N-H functionality.m
Pyridine and its derivatives like quinoline, isoquinoline and acridine (Figure 6) are
basic nitrogen compounds, with the nitrogen forming part of a 6-membered aromatic
ring.
These compounds and their heavier derivatives occur throughout the distillation range

METAL CONTENT:

The main metal impurities in crude oil are nickel, vanadium and to a lesser
extent iron too.These metals are generally found in the heaviest fractions
and end up as deposits in the residue processing units of a refinery. Some
of the metals are trapped in molecules of the porphyrine family (Figure 7),
which act as efficient chelating agents for ions like Ni2+ and VO+. The metal
content is very crude dependent and may vary from less than 1 μg·g-1 to more
than 1000 μg·g-1. However, it should be noted that not all Ni and V are
contained in porphyrine structures.

Metals are also introduced in the form of salts of sodium, magnesium and
calcium, usually as the chlorides (NaCl, MgCl2 and CaCl2), but calcium
can also be present as the sulphate or carbonate (CaSO4 and CaCO3).The salt
levels vary, with most crudes having a salt level of between 25-350 μg·g-1 of
NaCl equivalent. The major portion of salt is found in the residues, causing
problems in the refinery, like fouling of burners and deterioration of product
quality. Furthermore, magnesium and calcium chlorides start to hydrolyse at
120°C , a reaction that proceeds quite readily at higher temperatures and that
can lead to severe corrosion in the presence of water.

MgCl2 + 2 H2O → Mg(OH)2 + 2 HCl

There are other metal impurities too, which can be present at low
concentrations, like mercury and arsenic. Impurities like Si, Cu, Pb and P
may also be introduced during refining and recycling of petroleum wastes.
Organometallic soaps of Zn, Ti. Ca and Mg may also be present as surface-
active compounds in the oil-water interface.
Correlation Index:

An early classification methodology based itself on the quantum of distillation residue.

If the residue contained less than 2 % wax than it was classified as asphaltic. If residue
contained more than 5 % wax than it was called paraffinic. Another methodology,
suggested division according to the chemical composition of the 250 to 300° C fraction
(refer table below). But this method created a difficulty, since, in the fractions boiling
above 200° C the molecules can no longer be placed in one group because most of them
are of a typically mixed nature. Purely napthenic or aromatic molecules occur very
seldom; cyclic compounds generally contain paraffinic side-chains & often even
aromatic & napthenic rings side by side. More direct chemical information is often
desirable & can be supplied by means of the correlation index.

This index, developed by the U. S. Bureau of Mines, is based on the plot of specific
gravity at 60/60° F versus the reciprocal of the boiling point in degrees Kelvin for pure
hydrocarbons on which the line described by the constants of the individual members of
the normal paraffin series is given a value of CI = 0, & a parallel line passing through
the point for the values of benzene is given as CI = 100. From this plot, the following
empirical equation is derived:

CI = 473.7d – 456.8 + (48640/K)

Where K is the average boiling point, determined by the Bureau of Mines standard
distillation method & d is the specific gravity.
The values of the index between 0 & 15 indicate a predominance of paraffinic
hydrocarbons in the fraction; values from 15 to 50 indicate a predominance either of
napthenes or of mixtures of paraffins, napthenes, & aromatics; values above 50 indicate
the predominant aromatic character.
 Cloud Pt Vacuum
75 Distillate; Indicates wax
content
50
25
0
0 Carbon Residue in
percent of Residuum,
5 indicates Asphalt
content
10

15
20
100
0 20 30 40 50 60 70

High Paraffins and Napthenes High Aromatics

It is also possible to describe a crude oil by an expression of its chemical composition on

the basis of the correlation index figures for its middle portions. The above figure is
constructed based on this principle. The horizontal axis represents a progression from
paraffinic oils to aromatic oils with 0 representing n-paraffins & 100 representing
benzene. The position of a crude on this scale is determined by the avg. correlation
index for its fractions boiling between 200° C at atmospheric pressure & 275° C at 40
mm Hg, & the paraffinic, or cyclic nature of the fractions, & thereby, the nature of the
bulk of the crude, are expressed directly. The height of the vertical bar above the
horizontal indicates the wax content of the heavy gas oil & light lubricating fractions of
that crude &, hence, the crystalline wax content of the crude can be assessed. The
length of the vertical bar below the horizontal is a measure of the carbon residue
(Conradson) of the undistilled residuum &, thereby the content of each crude. By
combining these indicative properties with results of distillation, the petroleum can be
classified in terms of composition & application.
THE UNIVERSAL OIL PRODUCTS (UOP) CHARACTERIZATION
FACTOR:

This factor is perhaps one of the more widely used of the derived characterization or
classification factors & is defined by the formula:

K = ( TB )1/3 / d
Where “TB” is the average boiling point in degrees Rankine & “d” is the specific gravity
60° / 60° F. This factor has been shown to be additive on a weight basis. It was
originally devised to show the thermal cracking characteristics of heavy oils; thus,
highly paraffinic oils have K~ 12.5 to 13.0 while cyclic (napthenic) oils have K~ 10.5 to
12.5.

BY CARBON DISTRIBUTION:
The distribution according to volatility of the various fractions of petroleum is
considered the main property for classification & any fractionating column with
sufficient number of theoretical trays may be used for generating a curve in which the
boiling point of each fraction is plotted against percentage by weight.

A method known as the n-d-M method (n: refractive index, d: density, M: molecular
weight)
Is used for characterization of various fractions of petroleum. This method enables
determination of carbon distribution &, thus, indicates the percentage of carbon in
aromatic structure (%CA), the percentage of carbon in napthenic structure (%CN), & the
percentage of carbon in paraffinic structure (%CP).The yield over the various boiling
ranges can be estimated &, for example, in the lubricating oil fractions the percentage
of carbon in paraffinic structure can be divided into two parts, giving the percentage of
carbon in paraffinic side-chains. The percentage of normal paraffins present in
lubricating oil fractions can be calculated from the percentage of normal paraffinic
carbon (%CnP) by multiplication by a factor that depends on the hydrogen content of the
fractions. It may also be possible to extrapolate the carbon distribution to the gasoline
range on one hand & to the residue on the other hand; a high value of %C A at 500° C
boiling point indicates a high content of asphaltenes in the residue, whereas a high
value of %CnP at 500° C boiling point usually indicates a waxy residue.

BOILING POINT RANGES:

Coefficients for paraffin content in petroleum fractions.

Boiling-point range Paraffin (vol.%)

A B C D AAD

Light Naphtha 311.146 -771.335 230.841 66.462 2.63

Heavy Naphtha 364.311 -829.319 278.982 15.137 4.96

Kerosene 543.314 -1560.493486.345 257.665 3.68

Diesel 274.530 -712.356 367.453 -14.736 4.01

VGO 237.773 -550.796 206.779 80.058 3.41