Introduction to Petroleum Refining and

Crude Oil Composition

1. Introduction
 Petroleum has been defined as Gaseous, liquid and solid mixture of
hydrocarbon and non-hydrocarbon components which are derivatives that
occur naturally in the earth.

Gaseous hydrocarbon is composed of lighter fractions, of which the more

common is methane ( CH4 ) that refer to as natural gas. Liquid petroleum
consists of the liquid hydrocarbon but also contain varying proportion of
dissolved gases and bituminous materials, it is most commonly called crude
oil. Solid and semisolid petroleum is consists of heavier fraction from
hydrocarbon and bituminous materials and had been refer to as bituminous or
asphalt.

Petroleum is a mixture of hydrocarbon compounds and relatively small

quantities of other materials such as oxygen, nitrogen, sulphur, salt , water,
dissolved gases such as hydrogen sulphide ( H2S ) and trace amounts of
metals such as .iron, nickel, copper and vanadium.

Figure 1.1 shows a typical distribution of products from a barrel of crude oil in
a U.S. refinery. Distillation process separates the crude oil into boiling point
fractions. The liquefied petroleum gas (LPG) constitutes the lowest boiling
point (most volatile) product from a refinery and higher boiling fractions lead to
most desirable distillate liquids, such as gasoline, jet fuel, diesel fuel, and fuel
oil in the increasing order of boiling points, while asphalt is made from the
residual fraction remaining after distillation.
Figure 1.1: A typical distribution of products made from crude oil in a U.S. refinery.

2. Chemical composition of crude oil

The proportion of hydrocarbons in the mixture is highly variable and ranges
from as much as 97% by weight in the lighter oils to as little as 50% in the
heavier oils and bitumen.
The exact molecular composition varies widely from formation to formation but
the proportion of chemical elements vary over fairly narrow limits as follows:
Element Wt %

C ( Carbon ) 83 - 88
H2 ( Hydrogen ) 11 – 14
S ( Sulphur ) 0.05 – 8
N2 ( Nitrogen ) 1–2
O2 ( Oxygen ) 0.05 – 1.5
Metals ( Fe , Ni , Cu , V , < 0.03
….. )
The hydrocarbons in crude oil are mostly paraffin, naphthene, olefin 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 as follows:
Paraffins
The paraffin series of hydrocarbons is characterized by the rule that the
carbon atoms are connected by a single bond and the other bonds are
saturated with hydrogen atoms. The general formula for paraffins is CnH2n+2.
The simplest paraffin is methane, CH4, followed by the homologous series of
ethane, propane, normal and isobutane, normal, iso-, and neopentane, etc.
Naphthenes or cycloparaffins
Cycloparaffin hydrocarbons in which all of the available bonds of the carbon
atoms are saturated with hydrogen are called naphthenes. Typical examples
of these are cyclopentane, cyclohexane, etc.

Aromatics
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 below.
Olefins
Olefins do not naturally occur in crude oils. However, they are formed during
its processing. They are very similar to paraffins, but they exhibit double
bonds, usually one per molecule, although some di-olefins (two double bonds
in the same molecule, can be found.
Heteroatom compounds
Sulfur compounds might be present in inorganic and organic forms. In crude
oils sulfur concentration can range from 0.1 to more than 8 weight percent.
Such as dibenzylthiophene (2 benzene rings separated by 1 S atom) – is
most difficult to relase the Sulfur Oxygen compounds are responsible for
petroleum acidity in particular. Carboxylic (OH-C=O bonded to a benzene
ring) Phenolic (OH bonded to a benzene ring) Nitrogen compounds carbazole
(2 benzene rings separated by 1 N atom) – neutral Quinoline (2 benzene rings
with 1 N atom on 1 ring) - basic
Metal Compounds
o Porphyrins contain Ni, V, or Fe

Physical properties of feedstocks and products

Crude petroleum is very complex and, except for the low-boiling components,
no attempt is made by the refiner to analyze for the pure components
contained in the crude oil. Relatively simple analytical tests are run on the
crude and the results of these are used with empirical correlations to evaluate
the crude oils as feedstocks for the particular refinery. Each crude is
compared with the other feedstocks available and, based upon the operating
cost and product realization, is assigned a value. The more useful properties
are discussed.

API Gravity
The density of petroleum oils is expressed in the United States in terms of API
gravity rather than specific gravity; it is related to specific gravity in such a
fashion that an increase in API gravity corresponds to a decrease in specific
gravity. The units of API gravity are °API and can be calculated from specific
gravity by the following:
In equation (1), specific gravity and API gravity refer to the weight per unit
volume at 60°F as compared to water at 60°F. Crude oil gravity may range
from less than 10°API to over 50°API but most crudes fall in the 20 to 45°API
range. API gravity always refers to the liquid sample at 60°F (15.6°C). API
gravities are not linear and, therefore, cannot be averaged. For example, a
gallon of 30°API gravity hydrocarbons when mixed with a gallon of 40°API
hydrocarbons will not yield two gallons of 35°API hydrocarbons, but will give
two gallons of hydrocarbons with an API gravity different from 35°API.
Specific gravities can be averaged.
Viscosity
Resistance to flow, usually measured @ 100oF in centistokes (kinematic
viscosity)
Sulfur Content, wt%
Sulfur content and API gravity are two properties which have had the greatest
influence on the value of crude oil, although nitrogen and metals contents are
increasing in importance. The sulfur content is expressed as percent sulfur by
weight and varies from less than 0.1% to greater than 5%. Crudes with
greater than 0.5% sulfur generally require more extensive processing than
those with lower sulfur content. Although the term ‘‘sour’’ crude initially had
reference to those crudes containing dissolved hydrogen sulfide independent
of total sulfur content, it has come to mean any crude oil with a sulfur content
high enough to require special processing. There is no sharp dividing line
between sour and sweet crudes, but 0.5% sulfur content is frequently used as
the criterion.

Pour Point, °F (°C)

The pour point of the crude oil, in °F or °C, is a rough indicator of the relative
paraffinicity and aromaticity of the crude. The lower the pour point, the lower
the paraffin content and the greater the content of aromatics.

Carbon Residue, wt%

Carbon residue is determined by distillation to a coke residue in the absence
of air. The carbon residue is roughly related to the asphalt content of the
crude and to the quantity of the lubricating oil fraction that can be recovered.
In most cases =the lower the carbon residue, the more valuable the crude.
This is expressed in terms of the weight percent carbon residue by either the
Ramsbottom (RCR) or Conradson (CCR) ASTM test procedures (D-524 and
D-189).
Salt Content, lb/1000 bbl
If the salt content of the crude, when expressed as NaCl, is greater than 10
lb/1000 bbl, it is generally necessary to desalt the crude before processing. If
the salt is not removed, severe corrosion problems may be encountered. If
residua are processed catalytically, desalting is desirable at even lower salt
contents of the crude. Although it is not possible to have an accurate
conversion unit between lb/1000 bbl and ppm by weight because of the
different densities of crude oils,1 lb/1000 bbl is approximately 3 ppm.

Characterization Factors
There are several correlations between yield and the aromaticity and
paraffinicity of crude oils, but the two most widely used are the UOP or
Watson ‘‘characterization factor’’ (KW) and the U.S. Bureau of Mines
‘‘correlation index’’ (CI).

where
TB _ mean average boiling point, °R
G _ specific gravity at 60°F.
The Watson characterization factor ranges from less than 10 for highly
aromatic materials to almost 15 for highly paraffinic compounds. Crude oils
show a narrower range of KW and vary from 10.5 for a highly naphthenic
crude to 12.9 for a paraffinic base crude.

The correlation index is useful in evaluating individual fractions from crude 

oils. The CI scale is based upon straight-chain paraffins having a CI value of 0
and benzene having a CI value of 100. The CI values are not quantitative, but
the lower the CI value, the greater the concentrations of paraffin hydrocarbons
in the fraction; and the higher the CI value, the greater the concentrations of
naphthenes and aromatics.

Nitrogen Content, wt%

A high nitrogen content is undesirable in crude oils because organic nitrogen
compounds cause severe poisoning of catalysts used in processing and
cause corrosion problems such as hydrogen blistering. Crudes containing
nitrogen in amounts above 0.25% by weight require special processing to
remove the nitrogen.
Distillation Range

The boiling range of the crude gives an indication of the quantities of the
various products present. The most useful type of distillation is known as a
true boiling point (TBP) distillation and generally refers to a distillation
performed in equipment that accomplishes a reasonable degree of
fractionation. There is no specific test procedure called a TBP distillation, but
the U.S. Bureau of Mines Hempel and ASTM D-285 distillations are the tests
most commonly used. Neither of these specify either the number of theoretical
plates or the reflux ratio used and, as a result, there is a trend toward using
the results of a 15:5 distillation (D-2892) rather than the TBP. The 15:5
distillation is carried out using 15 theoretical plates at a reflux ratio of 5:1. The
crude distillation range also has to be correlated with ASTM distillations
because product specifications are generally based on the simple ASTM
distillation tests D-86 and D-1160. The TBP cut point for various fractions can
be approximated by use of Figure bellow. A more detailed procedure for
correlation of ASTM and TBP distillations is given in the API Technical Data
Book—Petroleum Refining published by the American Petroleum Institute,
Washington, DC.

Cut Points
Using a crude TBP curve, cut points are defined as the temperatures that
represent the limits of a distillate fraction, as illustrated in Figure 4.11. For
example, for kerosene, fraction Ta represents the lower cut point, and Tb
represents the upper cut point in Figure below:
Boiling ranges between the cut points represent distillate products, such as
naphtha, kerosene, light gas oil, etc. The difference between the cumulative
volume percent at upper and lower cut points is reported as the yield (in
volume %) for the particular distillate fraction. For example, for the crude
represented in Figure 4.11, the kerosene yield can be calculated as 40%(at
Tb) -20% (Ta) = 20% by volume. Table 4.1 shows the TBP cut points for
crude oil distillate fractions.
Refractive Index Of Petroleum Fractions
The refractive index of a petroleum fraction can be predicted from its mean
average boiling point, molecular weight, and relative density using the API
databook procedure.19
The method may be used to predict refractive index for a petroleum fraction
with normal boiling point up to 1100 Kelvins
Metals Content, ppm
The metals content of crude oils can vary from a few parts per million to more
than 1000 ppm and, in spite of their relatively low concentrations, are of
considerable importance. Minute quantities of some of these metals (nickel,
vanadium, and copper) can severely affect the activities of catalysts and result
in a lowervalue product distribution. Vanadium concentrations above 2 ppm in
fuel oils can lead to severe corrosion to turbine blades and deterioration of
refractory furnace linings and stacks.

Distillation concentrates the metallic constituents of crude in the residues, but

some of the organometallic compounds are actually volatilized at refinery
distillation temperatures and appear in the higher-boiling distillates.

The metallic content may be reduced by solvent extraction with propane or

similar solvents as the organometallic compounds are precipitated with the
asphaltenes and resins.

Classification of Crude Oil

Classifying crude oils is necessary to provide a guide to the quality, and
hence value, of the oil. In the very early days, the kerosene fraction used for
lighting purposes was the most valuable product. With the introduction of the
internal combustion engines, gasoline became the most valuable fraction in
the crude oil. The specific gravity of the crude oil provided a rough measure of
the amount of the lighter fractions present; the lower the specific gravity (or
the higher the API gravity, which is an inverse scale) the greater is the yield of
light fractions obtained by simple distillation, and hence, the higher the price
of the crude oil. With the introduction of refining procedures, the rough guide
provided by specific gravity was insufficient to classify the crude petroleum
oils. Moreover, further information on the nature of the oil and some
indications of the chemical composition of both the crude oil and the various
fractions which could be produced from it are necessary.

1- Classification According to the Base of a Crude Oil

The first attempt to provide such information was the use of the "base"
concept of a crude oil. Crude oils were classified as paraffinic base, asphaltic
base, and mixed base types. Paraffinic base crude oils are assumed to have
gasoline of low knocking quality, good burning kerosene, high viscosity index
lube oil, high wax content, and no asphalt. On the other hand, asphaltic crude
oils are assumed to have gasoline of high knocking quality, kerosene of poor
burning characteristics, lubricating oil of low viscosity index and asphalt
suitable for commercial.uses. The mixed base crudes are those which on
distillation yielded residues containing both paraffin waxes and asphaltic
material. This scheme was later enlarged to accommodate a fourth group of
crudes, namely, a "hybrid base" group whose residue on atmospheric
distillation contains asphaltic material with small amounts of paraffin wax.
These were described as "naphthenic" crudes. Later on, it has been shown
that this type of classification is not good enough to comprise all types of
crude oils.

2- Classification According to the Wax Content of the Distillation

Residue (Mallison classification)

Mallison (1927) suggested a classification system based on the wax

considered to be asphaltic if the distillation residue contains less than 2%
wax. On the other hand, a crude oil is considered paraffinic if it contains more
than 5% wax.

3- Classification According to the U.S. Bureau of Mines

The U.S. Bureau of Mines has developed a system which classifies the crude
according to two key fractions obtained in distillation: No. 1 from 482  to 527°F
(250 to 275°C) at atmospheric pressure and No. 2 from 527 to 572°F (275 to
300°C) at 40 mmHg pressure. The gravity of these two fractions is used to
classify crude oils into types as shown below.
The paraffinic and asphailic classifications in common use are based on the
properties of the residuum left from nondestructive distillation and are more
descriptive to the refiner because they convey the nature of the products to be
expected and the processing necessary.

4- Ternary Classification of Crude Oils

5- Classification according to Viscosity Gravity Constant

Another parameter defined in the early years of petroleum characterization is

the viscosity gravity constant (VGC). This parameter is defined based on an
empirical relation developed between Saybolt viscosity (SUS) and specific
gravity through a constant. VGC is defined at two reference temperatures of
38°C (100°F) and 99°C (210°F):
Viscosity gravity constant for light oils:
Viscosity gravity constant for heavy oils:

Where:
V38 = viscosity at 38°C (100°F) in SUS (Saybolt Universal Seconds)
V99 = Saylbolt viscosity (SUS) at 99°C (210°F)
VGC varies for different hydrocarbons as follow:
Paraffinic hydrocarbons between 0.74 - 0.75
Naphthenic between 0.89 - 0.94
Aromatics between 0.95 - 1.13
Evaluation of Crude Oil
Evaluation of crude oil is important for refiner because it gives the following
types of information:
1. Base and general properties of the crude oil.
2. Presence of impurities such as sulfur, salt, and emulsions which cause
general difficulties in processing.
3. Operating or design data. Primarily this necessitates curves of temperature
and gravity vs. per cent distilled.
a. Fractionating or true boiling point distillation curve.
b. Equilibrium or flash-vaporization curve.
c. API or specific gravity curve of each fraction distilled.
4. Curves of the properties of the fractions vs. percent distilled (mid per cent
curves) or the average properties of a series of fractions vs. Percentage yield
(yield curve) by which common realization of yields can by prepared. Among
property curves are
a. Viscosity of lubricating-oil fractions
b. Octane number of gasoline fractions.
c. Aniline point of solvents, kerosene, or diesel fractions.
d. Percentage of asphaltic residues.
e. Viscosity of distillation residues.
5. Finished products. Having established the general properties and yield by
means of distillation and property curves and exploring the economy of the
various break-ups of the crude oil.

Example 2
Estimate average boiling point of crude oil that has the following data.
Cumulative vol% 10 20 50 70 80
TBP F 110 170 360 470 680
Solution
MeABP: Mean average boiling point = 363 F
VABP: Volume-average boiling points = 400 F
MABP: Molar-average boiling point = 334 F
Example 2
Estimate the characterization factor for the crude oil in example 1 if the API of
the crude 20.
Answer: Kw = 10.2