CRUDE OIL SELECTION

Adeel ur Rehman, PhD

Assistant Professor
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Department of Chemical Engineering
University of Karachi
Evaluation of Crude Oil

The basic raw material for

refineries is:

Petroleum or crude oil,

Synthetic crude oils from other

sources (Gilsonite, tar sands, etc.)

Natural gas liquids (condansate)

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 Composition of Crude Oil

The elementary composition of crude oil usually falls

within the following ranges.
Element % wt.
Carbon 84-87
Hydrogen 11-14
Sulfur 0-3
Nitrogen 0-0.6

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Evaluation of Crude Oil
Evaluation of
crude oil

Base and
Operating or Mid percent Finished
general Impurities
design data curves products
properties.

Viscosity of
TBP curve lubricating-oil
fractions

flash-vaporizat
Octane.
ion curve

Aniline point
API curve
of solvents.

Residues %age.

Viscosity of
distillation
residues. 4
Evaluation of Crude Oil
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.

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Base of crude oil

► Crude oils are classified as;

► paraffin base,
► naphthene base,
► asphalt base,
► or mixed base.

There are some crude oils in the Far East which have up to 80% aromatic
content, and these are known as aromatic-base oils.

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Mallison
Classification
❑ Crude oil is classified
based on residuum Residue
(the material left after
Compositi Crude Oil Base
distillation).
on
❑ The classification > 50% Paraffinic Base – High wax
depends on the
Paraffins content, good for lubricants.
paraffin content in the
residue. Asphaltic Base – High in
< 20%
asphaltenes, used for
Paraffins
bitumen production.
Mixed Base – Contains both
20-50%
paraffinic and asphaltic
Paraffins
characteristics.

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 ► Paraffinic Bases:
1. Pennsylvania Base – High paraffin content, high
API gravity, excellent lubricating properties.
2. California Base – High paraffin, but with some
heavier fractions.
3. Gulf Coast Base – Medium paraffin content,
commonly found in Gulf of Mexico crude.
► Naphthenic Bases:
U.S. Bureau 4. Louisiana Base – High naphthene content, lower
paraffin, suitable for fuel production.
of Mines 5. Texas Base – Naphthenic-rich crude, commonly
found in Texas oil fields.
Classification 6. Arkansas Base – Another variant of naphthenic
crude, less paraffinic.
► Intermediate Bases:
7. Oklahoma Base – A mix of paraffinic and
naphthenic properties, intermediate API gravity.
8. Mixed Base – A combination of paraffinic and naphthenic
components, not fitting strictly into other categories.

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Evaluation of Crude Oil
3) Specific Gravity and 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:

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).

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Evaluation of Crude Oil
4 & 5) Characterization Factor
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).

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Evaluation of Crude Oil
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 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

C.I for Paraffin =0

C.I for Benzene =100
C.I =0-15 Paraffin
C.I =15-50 either Naphtenes or mix (Paraffin + Naphtenes)
C.I = above 50 Aromatic

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Evaluation of Crude Oil
6) Viscosity Index
A series of numbers ranging from 0-100 which indicate the rate of
change of viscosity with temperature.

Paraffinic base C.O V.I =100

Naphthenic base C.O V.I = 40
Some Naphthenic base C.O V.I =0

7) 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.
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Evaluation of Crude Oil
Impurities in the crude oil

► Sulfur Content, wt%

Difficulties with oils that contain sulfur compounds arise in only two
main ways: corrosion and odor

At elevated temperature the rate of corrosion increases on the

presence of sulfur.

The main bulk of the corrosive sulfur compounds can by removed by

treatment with alkalis or the sweetening treatments.

In presence of air and moisture the sulfur gases produced during the
burning of oil may cause corrosion, as in steel stacks, ducts, and
engine exhaust pipes and mufflers.
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Evaluation of Crude Oil
Odor is most obnoxious with low boiling or gaseous sulfur compounds,
as H2S or SO2 in flue gases, mercaptans up to even six carbons atoms
(B.P. of about 400 0F), sulfides up to 8 carbons atoms (about 350 0F),
and among disulfides only methyl disulfide (B.P. 243 0F) . This odor is
not obnoxious in sweetened products except in certain extremely
high- sulfur gasoline.

The sulfur content is expressed as percent sulfur by weight and varies

from less than 0.1% to greater than 5%.

Although the term ‘‘sour’’ crude initially had reference to those

crudes containing dissolved hydrogen sulfide independent of total
sulfur content.

There is no sharp dividing line between sour and sweet crudes, but
0.5% sulfur content is frequently used as the criterion.
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Evaluation of Crude Oil
► Salt Contents
Salt carried into the plant in brine associated with crude oils is a major cause of
the plugging of exchangers and coking of pipe still tubes.

If salt content expressed as NaCl , is greater than 10 lb/1000 bbl, it is generally

necessary to desalt the crude before processing.

If residua are processed catalytically, desalting is desirable at even lower salt

contents of crude oil.

Carbon Residue, wt%

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).
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Evaluation of Crude Oil
► 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.

► Metals Content, ppm

The metals content of crude oils can vary from a few parts per million to more than 1000 ppm.
Minute quantities of some of these metals (nickel, vanadium, and copper) can severely affect the
activities of catalysts and result in a lower value 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.
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Evaluation of Crude Oil
COMPOSITION OF PETROLEUM
Crude oils and high-boiling crude oil fractions are composed of many
members of a relatively few homologous series of hydrocarbons [6].

The composition of the total mixture, in terms of elementary composition,

does not vary a great deal, but small differences in composition can greatly
affect the physical properties and the processing required to produce
salable products.

The hydrocarbons present in crude petroleum are classified into three

general types:
► paraffins,
► naphthenes,
► and aromatics.
► olefins, that is formed during processing by the dehydrogenation of
paraffins and naphthenes.
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Evaluation of Crude Oil
► Paraffin
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 number of possible isomers increases in geometric progression as the

number of carbon atoms increases.

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.

For example, the motor octane number of n-octane is -17 and that of
isooctane (2,2,4-trimethyl pentane) is 100.
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Evaluation of Crude Oil

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Evaluation of Crude Oil
► Naphthenes (Cycloparaffins)
Cycloparaffin hydrocarbons in which all of the available bonds of the
carbon atoms are saturated with hydrogen are called naphthenes.

They are classified according to boiling range and their properties

determined with the help of correlation factors such as the KW factor
or CI.

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Evaluation of Crude Oil
► Aromatics
Aromatic hydrocarbons contain a benzene ring which is unsaturated
but very stable and frequently behaves as a saturated compound.

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.

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Evaluation of Crude Oil
► 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.

Olefins are generally undesirable in finished products because the

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.
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Evaluation of Crude Oil
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.

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Evaluation of Crude Oil

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Evaluation of Crude Oil
CRUDES SUITABLE FOR ASPHALT MANUFACTURE

It is not possible to predict with 100% accuracy whether or

not a particular crude will produce specification asphalts
without actually separating the asphalts from the crude
and running the tests.

► If the crude oil contains a residue [750°F (399°C)] mean

average boiling point having a Watson characterization
factor of less than 11.8 and the gravity is below 35°API,
it is usually suitable for asphalt manufacture [7].

► If, however, the difference between the

characterization factors for the 750°F and 550°F
fraction is greater than 0.15, the residue may contain
too much wax to meet most asphalt specifications.
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Evaluation of Crude Oil

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Analysis of Crude
Petroleum
► Distillation Curves :
► a) ASTM or no fractionating distillation:
► b) True-boiling-point (T.B.P):
► c) Equilibrium or Flash Vaporization (EFV).

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