OGU 07102:PETROLEUM CHEMISTY

Course Instructor: Daniel Rukonu

 CHEMISTRY OF PETROLEUM

• Petroleum deposits are naturally occurring mixtures of

organic compounds found within the strata of the earth.
• The exact origin of petroleum is not known, but scientific
opinion is in favour of origin from the transformation of
plant, animal, and marine organisms after marine deposition
within finely divided muds.
• Consensus holds that, after being formed, petroleum was
transferred from its source beds to the rock strata where it is
now found (reservoir)
• Petroleum is found to occur in local accumulations within
the strata of the earth where conditions for accumulation
and storage are favorable.
• Petroleum deposits vary widely in chemical composition
and those obtained from different localities may have
entirely different physical and chemical properties.
• The bulk of the chemical compounds found in petroleum
are hydrocarbons.
• A hydrocarbon is a compound consisting of carbon and
hydrogen only.
 What is Petroleum?
• Petroleum (Latin Petroleum derived from Greek (Latin petra) -
rock + (Latin oleum) - oil) or
• Crude oil is a naturally occurring liquid found in formations in the
Earth consisting of a complex mixture of hydrocarbons (mostly
alkanes) of various lengths.
• Crude oil, or petroleum, is an organic substance derived from the
remains of prehistoric plant and animal matter.
• It is a mixture of hydrocarbons, i.e. molecules containing hydrogen
and carbon, which exist sometimes in liquid form (crude oil) and
sometimes as a vapor (natural gas).
• Petroleum reservoir fluids are multicomponent mixtures
consisting primarily of hydrocarbons.
ØMethane (CH4) is the simplest of all hydrocarbons, and also
the most common component in petroleum reservoir fluids.
• Because methane contains one carbon atom, it is often referred
to as C1.
ØHydrocarbons with seven and more carbon atoms are called
C7+ components, and the entity of all C7+ components is called
the C7+ fraction.
ØPetroleum reservoir fluids may contain hydrocarbons as heavy
as C 200.
 𝑪𝟕! Components
• A particular C7+ component will belong to one of the following component classes:
Paraffins:
• A paraffinic compound consists of hydrocarbon segments of the type C, CH, CH 2, or CH 3.
The carbon atoms are connected by single bonds.
• Paraffins are also sometimes referred to as alkanes.
Napthenes:
• These compounds are similar to paraffins in the sense that they are built of the same types
of hydrocarbon segments, but they differ from paraffins by containing one or more cyclic
structures.
• Naphthenes are also called cycloalkanes.
Aromatics:
Similar to naphthenes, aromatics contain one or more cyclic structures, but the carbon atoms
in an aromatic compound are connected by aromatic double bonds.
• The percentage contents of paraffinic (P), naphthenic (N), and aromatic (A) components in
a reservoir fluid is often referred to as the PNA distribution.
 Molecular Structures

Molecular Structures of Some

Petroleum Reservoir Fluid
Constituents
 Non HC Components
• Petroleum reservoir fluids may also contain inorganic compounds, of
which
• Nitrogen (𝑁! ),
• Carbon dioxide (𝐶𝑂! ), and
• Hydrogen sulfide (𝐻! 𝑆)
• Are the most common.
• Water (𝐻! 𝑂) is another important reservoir fluid constituent.
• As water has limited miscibility with hydrocarbons, most of the
water in a reservoir is usually found in a separate water zone located
beneath the gas and oil zones.
 Chemical Composition of Petroleum
• Petroleum is a mixture of hundreds of hydrocarbons of all type with:
• water, salts, sulfur and nitrogen containing compounds and some metal
complexes.
• The elementary composition of crude oil usually falls within the following ranges.
How OIL and Gas is Formed?

Source: EIA
 GENERATION OF PETROLEUM
• Petroleum generation takes place in source rocks, which may be
defined as organic rich, fine grained sediments deposited under
low energy, reducing conditions.
• Most commonly, petroleum source rocks containing a minimum
of 0.3% to 0.5% by weight of organic matter.
• Preservation of the organic matter is the key to the development
of potential source rocks.
• The environment of source rock deposition is therefore
characterised by a relatively deep, unagitated (low energy) body
of water with an oxygen starved bottom but abundant life at the
surface.
CONVERSION OF KEROGEN TO OIL AND GAS.
• Anaerobic bacteria convert lipids (fat, oil and waxes) into a waxy
substance called kerogen.
• During burial of sediments, the increase in temperature results in a
progressive change in the composition of kerogen.
• Three successive stages are distinguished and referred as diagenesis,
catagenesis and metagenesis.
• The main trend is a continuous increase in the carbon content of
kerogen.
• Thus Kerogen is referred as a fossilized mixture of insoluble organic
material that,when heated,break down into petroleum and natural gas.
 DIAGENESIS

• Diagenesis of kerogen is characterised by an important

decrease of oxygen and a corresponding increase of
carbon content with increasing depth.
• CO2, H2O and some heavy N, S, O compounds are
released.
• Source rocks are considered as immature at this stage.
 CATAGENESIS

•A significant decrease in hydrogen content and in

the H/C ratio takes place due to the generation
and release of hydrocarbons.
•This is the main zone of oil generation and the
beginning of the cracking phase which produces
wet gas with a rapidly increasing proportion of
methane.
 METAGENESIS
• Begins at temperature exceeding 175 degree Centigrade.
• During this stage, a rearrangement of the aromatic sheets
occurs.
• The stacks of aromatic layers, previously distributed at
random in kerogen, now gather to form larger clusters.
• At this stage, only dry gas is generated.
• The color of kerogen changes as it matures
COLOR OF KEROGEN CHANGE
 SEPARATION/REFINERY

NATURAL GAS OIL

Natural Gas
NATURAL GAS SEPARATION OR TREATMENT
 Why Ga s Treatment?
• Separation aim to removel the following hamfulm gases,

*H2S is a poisonous and corrosive

*CO2 reduce the heat value of the fuel and solidifies under
transportation conditions ( high presssure and low temperature)

The removal of this harmful gases is necessary.

WATER REMOVAL
ALTERNATIVE WAYS INSTEAD OF GLYCOLS

1. Injection of Methanol:
Lowering of the hydrate formation temperature below
ambiet.

2 .Employing of solid adsorbents as molecular sieves.

Typical Composition of Natural Gas Products
 COMPRESSED NATURAL GAS
• Compressed Natural Gas (CNG) is an alternative fuel for gas and diesel
engines, is stored in tanks similar to acetylene.
• It is easily stored in pressurized tanks and in cooking, transportation.
• Also a by-product of oil refining.
• Burns cleaner than gasoline or diesel.
CONDESABLE HYDROCARBON RECOVERY
• C2- C7 hydrocarbons ( valuable fuels )
• It can be recovered by weak oil extraction.
• By cooling the treated gas by exchange with liquid propane. The
cooled gas is then washed with a cold hydrocarbon liquid, which
dissolves most of the condensable hydrocarbons.
• The uncondensed gas is dry natural gas and is composed mainly
of methane with small amounts of ethane and heavier
hydrocarbons.
• The condensed hydrocarbons or natural gas liquids (NGL) are
stripped from the rich solvent, which is recycled.
 NATURAL GAS LIQUID (NGL)
• Natural gas liquids (condensable hydrocarbons): heavier than
methane in the natural gas.
• High in associated gas.
• Fractionated to separate them into:
1. An ethane-rich stream, which is used for producing ethylene.
2. Liquefied petroleum gas (LPG), which is a propane-butane
mixture.
3. Natural gasoline (NG) is mainly constituted of C5 +
hydrocarbons and is added to gasoline to raise its vapor
pressure.
 ANOTHER WAY TO RECOVER. NGL
Another way to recover NGL is through cryogenic cooling to very low
temperatures (–150 to –180°F), by adiabatic expansion of the inlet gas.

First, remove water and acid gases, then cooled via heat exchange and
refrigeration.
Further cooling of the gas is accomplished through turbo expanders,
and the gas is sent to a demethanizer to separate methane from NGL.
Improved NGL recovery could be achieved through better control
strategies and use of on-line gas chromatographic analysis.
 LIQUEFIED PETROLEUM GAS (LPG)
• LP gas, any of several liquid mixtures of the volatile
hyrocarbons propene, propane ,buteene and butane.

• It was used as early as 1860 for a portable fuel source, and

its production and consumption for both domestic and
industrial use have expanded ever since.
• A typical commercial mixture may also
contain ethane and ethylene, as well as a volatile mercaptan,
an odorant added as a safety precaution.
 LP -GAS
• Liquefied petroleum gas (LPG) is recovered from
“wet” natural gas (gas with condensable
heavy petroleum compounds) by absorption.
• The recovered product has a low boiling point and must be
distilled to remove the lighter fractions and then be treated to
remove hydrogen sulfide, carbon dioxide, and water.
• The finished product is transported by pipelineand by
specially built seagoing tankers.
 LP –GAS USES
• LPG reaches the domestic consumer in cylinders under
relatively low pressures.
• The largest part of the LPG produced is used in central
heating systems, and the next largest as raw material
for chemical plants.
• LPG commonly is used as fuel for gas barbecue grills
and gas cooktops and ovens, for gas fireplaces, and in
portable heaters
 NATURAL GASOLINE
• A complex mixture of petroleum hydrocarbons separated as a
liquid from natural gas and/or natural gas liquids from which
methane, ethane, propane, butane, and possibly pentane have
been extracted.
• It consists of hydrocarbons with carbon numbers
predominantly in the range C5 to C8.
• It is a liquid at atmospheric temperature and pressure.
 LIQUEFIED NATURAL GAS (LNG)
• After the recovery of Natural Gas Liquid (NGL),sweet dry
natural gas may be liquefied for transportation through
cryogenic tankers.

• Further treatment may be required to reduce the water

vapour below 10 ppm and carbon dioxide and hydrogen
sulfide to less than 100 and 500 ppm,respectively.
METHODS USED TO LIQUEFY NATURAL GAS

• Two methods are generally used to liquefy natural gas :

1.The expander cycle and
2. Mechanical refrigeration.

In the expander cycle,part of the gas is expanded from a high

transmission pressure to a lower pressure. This lower the
temperature of the gas.Through heat exchange,the cold gas cools
the incoming gas which is a similar way cools more incoming gas
untill the liquefaction temperature of methane is reached.
METHODS USED TO LIQUEFY NATURAL GAS

• In mechanical refrigeration,a multicomponent refrigerant

consisting of nitrogen,methane,ethane ,and propane is used
through a cascade cycle.
• When these liquids evaporate,the heat required is obatined
from natural gas,which losses energy / temperature till is
liquefied.
• The refrigerant gases are recompressed and recycled.
 PROPERTIES OF NATURAL GAS
• Treated natural gas consists mainly of methane;the properties
of both gases (natural gas and methane) are neraly similar.

• However,natural gas are not pure methane and its properties

are modified by the presence of impurities,such as N2 and
CO2 and small amounts of unrecovered heavier
hydrocarbons.
Important properties of representative
liquefied natural gas mixture.
• An important property of natural gas is its heating
value.
• Relatively high amounts of nitogen and / or carbon
dioxide reduce the heating value of the gas.
• Pure ethane has a heating value of 1,009 Btu/ft3.This
value is reduced to approximately 900 Btu/ft3 if the
gas contain about 10 % N2 and CO2.(The heating
value of either nitrogen or carbon dioxide is zero)
• On the other hand, the heating value of natural gas
could exceed methane’s due to the presence of higher-
molecular weight hydrocarbons, which have higher
heating values.
• For example, ethane’s heating value is 1,800 Btu/ft3,
compared to 1,009 Btu/ft3 for methane.

• Natural gas is usually sold according to its heating

values. The heating value of a product gas is a function
of the constituents present in the mixture.
• In the natural gas trade, a heating value of one million
Btu is approximately equivalent to 1,000 ft3 of natural
gas.
• Since it is colorless and odorless, a scent is added to it for
safety purposes – called a “mercaptan” – giving it a sulfur-
based, rotten-egg type smell that cannot be removed.
 CRUDE OILS
• Crude oils are mainly constitutes of hydrocrbons mixed
with variable amounts of sulfur ,nitrogen ,and oxygen
compounds.
• Metals in the forms of inorganic salts or organometallic
sompounds are present in the crude mixture in trace
amounts.The ratio of the difference constituents in crude
oils,however,vary appreciably from one reservior to
another.
 CRUDE OILS
• 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 seprate the mixture into simpler
fractions that can be used as fuels,lubricants,or as
intermediate feedstocks to the petrochemicals industries.
Chemical Composition of Crude Oils
• The crude oil mixture is composed of the following group:
1.Hydrocarbon compounds(Compound made of carbon and hydrogen)
ØParaffins
ØNaphthenes
ØAromatics
2. Non-hydrocarbons compounds
3.Organomettalic compounds and inorganic salts (metallic compounds)

• The relative proportions of these compounds determine the physical

properties (density ,viscosity,pour point,etc) of petroleum.
PARAFFINS
NAPHTHENES
 AROMATICS
• The basic building block of
these hydrocarbons is the
benzene ring.
• The aromatic structure occurs
especially in the high
molecular weight fraction
of petroleum.
NON - HYDROCARBONS
CRUDE OIL REFINERY (SEPARATION
AND TREATMENT)

Most easily done by boiling point, into a large number

of consumer products, from gasoline and kerosene to
asphalt and chemical reagents used to make plastics
and pharmaceuticals..
FRACTION DISTILLATION
Where do Product come out of Still?
FRACTION THAT COME FROM THE DISTILLATION PROCESS