THE UNIVERSITY OF DODOMA

PETROLEUM REFINING AND

PETROCHEMICALS

PE 411

 Pre-requisites:
CH 105 PE 303 PE 306 PE 305 -

Organic chemistry I
Petroleum Production Engineering I
Petroleum Production Engineering II
Reservoir Engineering I

Mode of Delivery and Assessment:

Delivery:
3 hours Lecture + 1 hours tutorial per week
Assessment:
40% continuous assessment
60% University examination
Recommended books
1.
2.
3.
4.

Introduction to Petroleum Production-I & II, Dr. Skimmer.

Surface Operation in Petroleum Production, G.V. Chillingarian, J.O. Robertsin and S. Kumar.
Handbook of petroleum refining processes, by Robert A. Meyers, MaC-Graw Hill, 2003
Petroleum Refining: Technology and Economics by James H. Gary and Glenn E. Handwerk, CRC
Press, 4th Edition, 2001

Petroleum - Crude oil

Petroleum (L. petroleum, from Greek: (rock) + Latin: oleum (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.

 The name Petroleum covers both naturally occurring unprocessed crude oils and
petroleum products that are made up of refined crude oil.
Petroleum contains different hydrocarbons; the most commonly found molecules are
alkanes (linear or branched), cycloalkanes, aromatic hydrocarbons, or more
complicated chemicals like asphaltenes.
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.

COMPOSITION OF CRUDE OILS

Crude oil (petroleum) is a naturally occurring brown to black flammable liquid.

Crude oils are principally found in oil reservoirs associated with sedimentary rocks beneath the earths
surface. Although exactly how crude oils originated is not established, it is generally agreed that crude
oils derived from marine animal and plant debris subjected to high temperatures and pressures.
It is also suspected that the transformation may have been catalyzed by rock constituents.

 Regardless of their origins, all crude oils are mainly constituted of hydrocarbons
mixed with variable amounts of sulfur, nitrogen, and oxygen compounds.
Metals in the forms of inorganic salts or organometallic compounds are present in
the crude mixture in trace amounts.
The ratio of the different constituents in crude oils, however, 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.
Crude oils are refined to separate the mixture into simpler fractions that can be
used as fuels, lubricants, or as intermediate feedstock to the petrochemical
industries.
A general knowledge of this composite mixture is essential for establishing a
processing strategy.

CRUDE OIL
Composition
The hydrocarbons in crude oil are mostly alkanes (paraffins), cycloalkanes (naphthenes) and various
aromatic hydrocarbons
The other organic compounds contain nitrogen, oxygen and sulphur, and trace amounts of metals
such as iron, nickel, copper and vanadium.
The exact molecular composition varies widely from formation to formation but the proportion of
chemical elements vary over fairly narrow limits as follows:
Elemental 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%

Sulfur

0.05 to 6.0%

Metals

< 0.1%

CRUDE OIL CONITUNUES..

Four different types of hydrocarbon molecules appear in crude oil.

The relative percentage of each varies from oil to oil, determining the properties
of each oil.
Petroleum - Composition by weight

Hydrocarbon

Average

Range

Paraffins

30%

15 to 60%

Naphthenes

49%

30 to 60%

Aromatics

15%

3 to 30%

Asphaltics

6%

remainder

CRUDE OIL CONTINUES..

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.
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.

 In its strictest sense, petroleum includes only crude oil, but in common usage it includes all liquid,
gaseous, and solid hydrocarbons.
Under surface pressure and temperature conditions, lighter hydrocarbons methane, ethane, propane and
butane occur as gases, while pentane and heavier ones are in the form of liquids or solids.
However, in an underground oil reservoir the proportions of gas, liquid, and solid depend on subsurface
conditions and on the phase diagram of the petroleum mixture.
An oil well produces predominantly crude oil, with some natural gas dissolved in it. Because the pressure
is lower at the surface than underground, some of the gas will come out of solution and be recovered
(or burned) as associated gas or solution gas.
A gas well produces predominantly natural gas. However, because the underground temperature and
pressure are higher than at the surface, the gas may contain heavier hydrocarbons such as pentane,
hexane, and heptane in the gaseous state. At surface conditions these will condense out of the gas to
form natural gas condensate, often shortened to condensate.
Condensate resembles petrol in appearance and is similar in composition to some volatile light crude
oils.
The proportion of light hydrocarbons in the petroleum mixture varies greatly among different oil fields,
ranging from as much as 97 percent by weight in the lighter oils to as little as 50 percent in the
heavier oils and bitumens.

Crude oil
1.
2.
3.

mixture is composed of the following groups:

Hydrocarbon compounds(compounds made of carbon and hydrogen).
Non-hydrocarbon compounds.
Organometallic compounds and inorganic salts (metallic compounds).

The principal constituents of most crude oils are hydrocarbon compounds.

All hydrocarbon classes are present in the crude mixture, except alkenes and
alkynes.

Alkanes (Paraffins)
Alkanes are saturated hydrocarbons having the general formula
CnH2n+2
The simplest alkane, methane (CH4), is the principal constituent of
natural gas. Methane, ethane, propane, and butane are gaseous
hydrocarbons at ambient temperatures and atmospheric pressure.
They are usually found associated with crude oils in a dissolved
state.
Normal alkanes (n-alkanes, n-paraffins) are straight-chain
hydrocarbons having no branches.
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.
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 (C5 - C12)
has three isomers; hexane (C6H14) has five.
The following shows the isomers of hexane:

 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

CYCLOPARAFFINS (NAPHTHENES)

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 monosubstituted 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.

CYCLOALKANES / 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.
Cycloalkanes have similar properties to alkanes but have
higher boiling points.
The smallest cycloalkane is cyclopropane
Cycloalkanes are very similar to the alkanes in reactivity,
except for the very small ones - especially cyclopropane.
Cyclopropane is much more reactive than expected.
The reason has to do with the bond angles in the ring.
Normally, when carbon forms four single bonds, the bond
angles are about 109.5. In cyclopropane, they are 60.
With the electron pairs this close together, there is a lot
of repulsion between the bonding pairs joining the carbon
atoms. That makes the bonds easier to break.

AROMATIC COMPOUNDS

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.
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 constituents of heavy crudes and crude residues.
Asphaltenes are a complex mixture of aromatic and heterocyclic compounds.
The following are representative examples of some aromatic compounds found in crude oils:

SULPHUR COMPOUNDS

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

Hydrogen sulfide is the only important inorganic sulfur compound found in crude oil.
Its presence, however, is harmful because of its corrosive nature.
Organosulphur compounds may generally be classified as acidic and non-acidic.
Acidic sulfur compounds are the thiols (mercaptans).
Thiophene, sulfides, and disulfides are examples of non-acidic sulfur compounds found
in crude fractions.
Extensive research has been carried out to identify some sulfur compounds in a
narrow light petroleum fraction.
Examples of some sulfur compounds from the two types are:

NITROGEN COMPOUNDS

Organic nitrogen compounds occur in crude oils either in a simple heterocyclic form as in
pyridine (C5H5N) and pyrrole (C4H5N), or in a complex structure as in porphyrin.
The nitrogen content in most crudes is very low and does not exceed 0.1 wt%.
In some heavy crudes, however, the nitrogen content may reach up to 0.9 wt %.
Nitrogen compounds are more thermally stable than sulfur compounds and accordingly are
concentrated in heavier petroleum fractions and residues.
Light petroleum streams may contain trace amounts of nitrogen compounds, which should
be removed because they poison many processing catalysts.
During hydro treatment of petroleum fractions, nitrogen compounds are hydro
denitrogenated to ammonia and the corresponding hydrocarbon.
Nitrogen compounds in crudes may generally be classified into basic and non-basic
categories.
Basic nitrogen compounds are mainly those having a pyridine ring, and the non-basic
compounds have a pyrrole structure.
Both pyridine and pyrrole are stable compounds due to their aromatic nature

 Porphyrins are non-basic nitrogen compounds.

The porphyrin ring system is composed of four pyrrole rings joined by =CH- groups.
The entire ring system is aromatic. Many metal ions can replace the pyrrole hydrogens and
form chelates. The chelate is planar around the metal ion and resonance results in four
equivalent bonds from the nitrogen atoms to the metal.
Almost all crude oils and bitumens contain detectable amounts of vanadyl and nickel
porphyrins.

OXYGEN COMPOUNDS

Oxygen compounds in crude oils are more complex

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

METALLIC COMPOUNDS

Many metals occur in crude oils.

Some of the more abundant aresodium (Na), calcium (Ca), magnesium (Mg), aluminium
(Al), iron (Fe), vanadium (V), and nickel (Ni).
They are present either as inorganic salts, such as sodium and magnesium chlorides, or
in the form of organometallic compounds, such as those of Ni and V (as in porphyrins).
Calcium and magnesium can form salts or soaps with carboxylic acids. These compounds
act as emulsifiers, and their presence is undesirable.
Although metals in crudes are found in trace amounts, their presence is harmful and
should be removed. When crude oil is processed, sodium and magnesium chlorides
produce hydrochloric acid, which is very corrosive.
Desalting crude oils is a necessary step to reduce these salts.
Vanadium and nickel are poisons to many catalysts and should be reduced to very low
levels.
Most of the vanadium and nickel compounds are concentrated in the heavy residues.
Solvent extraction processes are used to reduce the concentration of heavy metals in
petroleum residues.

CRUDE OIL CLASSIFICATION

Appreciable property differences appear between crude oils as a result of the variable ratios of the crude
oil components.
Crude oils can be arbitrarily classified into three or four groups depending on the relative ratio of the
hydrocarbon classes that predominates in the mixture.
The following describes three types of crudes:
1. Paraffinic- the ratio of paraffinic hydrocarbons is high compared to aromatics and naphthenes.
2. Naphthenic- the ratios of naphthenic and aromatic hydrocarbons are relatively higher than in paraffinic
crudes.
3. Asphaltic- contain relatively a large amount of polynuclear aromatics, a high asphaltene content, and
relatively less paraffins than paraffinic crudes.
General characteristics
- Content of impurities: water, sediment, salts, metals, nitrogen
- Sulfur: 0.1 0.5 wt.% sweet / 0.5 0.8 wt.% semi-sweet / 0.8 5 wt.% sour
- Density: 38 45 oAPI light / 28 38 oAPI medium / 12 28 oAPI heavy
NOTE: API gravity, is a measure of how heavy or light a petroleum liquid is
compared to water. API gravity is greater than 10, it is lighter and floats on
water; if less than 10, it is heavier and sinks

EVALUATION OF CRUDE OIL

Crude oils differ appreciably in their properties according to origin and the ratio of
the different components in the mixture.
Lighter crudes generally yield more valuable light and middle distillates and are sold
at higher prices.
Evaluation of crude oil is important for refiner because it gives the following types
of information:
I. Base and general properties of the crude oil.
II. Presence of impurities such as sulfur, salt, and emulsions which cause general
difficulties in processing.
III. 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.

IV. 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
V. Curves of the properties of the fractions vs. percent distilled (mid percent
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.

Density, Specific Gravity and API Gravity

A more useful unit used by the petroleum industry is specific gravity, which is the ratio of the weight
of a given volume of a material to the weight of the same volume of water measured at the same
temperature.
Specific gravity is used to calculate the mass of crude oils and its products.
Usually, crude oils and their liquid products are first measured on a volume basis, then changed to
the corresponding masses using the specific gravity.
The API (American Petroleum Institute) gravity is another way to express the relative masses of crude
oils. The API gravity could be calculated mathematically using the following equation:

Specific gravities of crude oils roughly range from 0.82 for lighter crudes to over 1.0 for heavier
crudes (41 - 10 API scale).
Higher API , more paraffinic crude, higher yields of gasoline.
Lower API , more aromatic crude, lower yields of gasoline.

Sulfur Content
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.

Pour Point, (C)

The pour point of the crude oil, in For 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 D189).

Salt Content

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 Factor (Kw) and Correlation Index (CI)

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).

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 (CI) 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.
For petroleum fractions 10 < Kw < 15 (Watson characterization factor ranges)

contain
highly
aromatic
compounds

contain
highly
paraffinic
compounds

 For crude oil 10.5 < Kw < 12.9

highly

highly

naphthenic

paraffinic

crude

crude

For pure hydrocarbons

Kw = 13 for paraffins.
Kw = 12 for HC with equivalent chain and ring weights.
Kw = 11 for pure naphthenes.
Kw = 10 for pure 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.

Viscosity Index
This is 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

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.

ANALYSIS OF CRUDE PETROLEUM

1. Distillation Range (Curve)

The boiling point range is an alternate method

to represent the composition of petroleum and
its products.
It gives an indication of the quantities and
qualities of the various products present in
crude oil (i.e. naphtha, kerosene, diesel, gas oil,
residue, etc).
Can be used to determine the most desirable
processing sequence to obtain the required
products.
Can be used to determine whether the crude
is suitable for asphalt or lube oil manufacture.

 Types
1.
2.
3.

of distillation curves
TBP (True Boiling Point) distillation curve.
EFV (Equilibrium Flash Vaporization)
ASTM (D86/D1160) distillation curve.

1. TBP (True Boiling Point)

TBP is the most useful.
However, no standard test exists for measuring the TBP.
Most common TBP test is Hempel & D-285. (Neither specifies # of stages or reflex ratio
used).
Trend is toward 15/5 distillation (D-2892) to stand for TBP (assumed to be the same as
TBP).
An estimate of the composition of the butane and lighter components is frequently added
to the lowboiling end or the IBP of the TBP curve to compensate for the loss during
distillation.

2 Equilibrium or Flash Vaporization (EFV).

The feed material is heated as it flows continuously through a heating coil.

As vapor is formed it kept cohesively with liquid at some temperature and a
sudden release of pressure quickly flashes or separates the vapor from the
mixture without any rectification.
By successive flash evaporation like this the stock can be progressively distilled
at different increasing temperatures.
a curve of percentage vaporized vs. temperature may be plotted. travels along in
the tube with remaining liquid until separation is permitted in a vapor
separator or vaporizer.
By conducting the operation at a series of outlet temperature, a curve of
percentage vaporized vs. temperature may be plotted.

3 ASTM or no fractionating distillation: (no fractional , run on fractions) .

It is supposed to be like EFV, a non fractionating distillation system, distinguishing

itself as differential distillation. It is a simple distillation carried out with standard
ASTM flasks 100,200,500 ml flasks. The data obtained is similar to TBP data

Mid Percent Curves

The physical properties of an oil found to vary gradually throughout the
range of compounds that constitute the oil.
Distillation is a means of arranging of compounds these chemical compounds
in order of their boiling points.
The properties such as color, specific gravity, and viscosity are found to be
different for each drop or fraction of the material distilled.
The rate at which these properties change from drop to drop may plot as
mid per cent curves.

 In reality, the specific gravity or viscosity of a fraction is an average of the properties

of the many drops that constitute the fraction.
If each drop is equally different from the last drop and from the succeeding one, then
the drop that distills at exactly half of the fraction has the same property as the
average of all the drops.
This would be the condition for a mid per cent that is a straight line, but they are
substantially straight through any short range of percentage. For a short range of
percentage the average property is equal to the property at the mid-point of the
fraction.
The arithmetical average of the properties of these small fractions is the property of
the total or large fraction, or even the entire sample.
Integral- averaging by adding together the properties of a series of short fractions and
dividing by number of fractions can not be used on properties that are not additive.
Specific gravity (not API gravity) is an example of an additive property, e. g. 10
volumes of an oil of specific gravity 0.8 when mixed with an equal volume of 0.9
specific gravity oil yields a mixture that has a specific gravity 0.85

Additive Properties

Non additive Properties

Boiling Point (T.B.P)

API Gravity

Vapour Pressure

Viscosity

Specific Gravity

Colour

Aniline Point

Flash Point

Sulphur Content
Hydrogen/Carbon ratio