Chemical Process Industries 2

CPT150S
Petroleum Industry

Lecture 2

2020
 WHAT TO NOTE
•Definitions
•Processes involved: description & underlying
principles
•Significance: economics, internationally &
nationally, uses etc
•Interrelationships with other industries
•Environment & pollution
•What’s in the news
PETROLEUM INDUSTRY
• Crude oil is the term for ‘unprocessed’ oil. Complex
mixture of hydrocarbons of various molecular weights
& other liquid organic compounds.
•It is also known as petroleum.

• Crude oil is a fossil fuel - made naturally - decaying

plants and animals (organic material). Found in
geologic formations beneath the earth surface
• Crude oils vary in colour, from clear to tar-black
and in viscosity, from water to almost solid.
• Crude oils are a useful starting point for so many
different substances because they contain
hydrocarbons.
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 CONSTITUENTS OF PETROLEUM/CRUDE OIL
Hydrocarbons are molecules which contains hydrogen and carbon atoms and
come in various lengths and structures, from straight chains to branching chains
to rings.
On average, crude oils are made of the following elements or compounds:

Carbon 84%
Hydrogen 14 %
Sulphur 1 to 3 %
Nitrogen <1%
Oxygen <1%
Metals <1 % (nickel, iron, vanadium, copper, arsenic)

Salts < 1 % (sodium chloride, magnesium chloride, calcium chloride)

Typical Elemental Analysis of Crude Oil (Austin, 1986)

Elements C H S O N Traces of Metal
% 83 - 87 11 - 15 0-6 0 - 3,5 0 - 0,5 0
Elemental Analysis of Crude Oil (Kent, 1983)
Crude Oil Cuts Consumer Products

Gases Liquefied petroleum gas (LPG) , Fuel gas

Light/Heavy Naphtha Petrol , Jet fuel

Kerosene Jet fuel

Light gas oil Diesel , Commercial heating oil

Heavy gas oil Industrial heating oil , Lubricants

Residuals Bunker oil , Asphalt

There are two things that make hydrocarbons exciting to chemists:

•Hydrocarbons contain a lot of energy

•Hydrocarbons can take on many different forms. The smallest

hydrocarbon is methane (CH4) which is a gas lighter than air. Very
long chains are solids like wax or tar.
 Constituents of Petroleum

Aliphatic / Open chain Ring Compounds

•n - Paraffin / Alkanes Series
•Naphthene Series /
(CnH2n+2) cycloalkanes (CnH2n)
•Iso-paraffin or iso-alkane
series
(CnH2n+2)

•Aromatic or Benzenoid Series

•Olefin / Alkene series (CnH2n)
(CnH2n-6)
 Products of refining
Products Application
Natural Gasoline and natural gas (LPG)]
Light Distillates Motor gasoline
Solvent Napthas
Jet Fuel
Kerosene
Light heating oils

Intermediate distillates Heavy fuel oils

Diesel oils
Gas oils

Heavy distillates Heavy mineral oils (medicinal)

Heavy flotation oils
Lubricating oils
Waxes (candles, sealing,
insulating)
Residues Lubricating oils
Asphalts (tar)
Coke
SEPARATION PROCESSES
DISTILLATION
Distillation is a method of separating mixtures based on
differences in their volatilities in a boiling liquid mixture.
Distillation is a unit operation, or a physical separation
process, and not a chemical reaction
 Sorption
Sorption refers to the action of absorption (also desorption) or adsorption:
• Absorption is the incorporation of a substance in one state into another of
a different state (e.g. liquids being absorbed by a gas or gases being
absorbed by a liquid).
• Adsorption is the physical adherence or bonding of ions and molecules
onto the surface of another phase.

Gas absorption (also known as

scrubbing) is an operation in which a gas
mixture is contacted with a liquid for the
purpose of preferentially dissolving one
or more components of the gas mixture
and to provide a solution of them in the
liquid.

Therefore we can see that there is a mass transfer of the component of the
gas from the gas phase to the liquid phase. The solute so transferred is said to
be absorbed by the liquid.
In gas desorption (or stripping), the mass transfer is in the opposite direction,
i.e. from the liquid phase to the gas phase. The principles for both systems are
the same.
 Liquid-liquid extraction
• Liquid-liquid extraction, also known as solvent extraction and partitioning, is
a method to separate compounds based on their relative solubilities in two
different immiscible liquids, usually water and an organic solvent. It is an
extraction of a substance from one liquid phase into another liquid phase.

• If the two phases are immiscible liquids, the technique is called liquid-liquid
extraction. Usually, one phase is aqueous (hydrophilic) and the other is a
hydrophobic organic solvent. A sequence of extractions with various
solvents can be used to separate, with considerable efficiency, relatively
complex mixtures.
CONVERSION PROCESSES
 Isomerisation

• The alteration of the arrangement of the atoms in a

hydrocarbon molecule without changing the
number of atoms.
• Important for producing iso-butane.

300 ˚C
AlCl3

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 Alkylation (alteration)

Alkylation: light, gaseous hydrocarbons are combined to produce high-

octane components of gasoline. Various “pieces” are rearranged to make
desired hydrocarbons. An alkene & aromatic or alkane can be reacted to
produce a saturated branched chain in the presence of a sulfuric-acid or
hydrofluoric-acid catalyst/ pressure/ heat. A mixture of heavier hydrocarbons
is formed. Alkylation reactions are catalyzed by strong acids (i.e., sulfuric acid
[H2SO4] and hydrofluoric acid [HF])
 Catalytic Reforming (unifaction)

Reforming: Smaller hydrocarbons to make larger ones -- this process is called

unification. Alkanes are converted to produce products with higher number
of double bonds & aromatic rings (unsaturated hydrocarbons). Smaller pieces
are combined to make larger ones. The major unification process is called
catalytic reforming and uses a catalyst (platinum, platinum-rhenium mix) to
combine low weight naphtha into aromatics, which are used in making
chemicals and in blending gasoline.
 Esterification/Hydration

• This process involves the reaction between an

acid and an alcohol.

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 Cracking (catalytic or thermal)

Cracking: breaking large hydrocarbons into smaller pieces. Catalytic - uses a

catalyst to speed up the cracking reaction. Thermal - you heat large
hydrocarbons at high temperatures (sometimes high pressures as well) until
they break apart. steam - high temperature steam (816 degrees Celsius) is
used to break ethane, butane and naptha into ethylene and benzene,
which are used to manufacture chemicals.

After various hydrocarbons are cracked into smaller hydrocarbons, the

products go through another fractional distillation column to separate them.
 Hydrogenation

• The addition of hydrogen to an alkene.

• Helps in the overall upgrading of products.

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 Polymerisation

• The linking of similar molecules, such as the

joining of light alkenes

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An oil refinery is a combination of all of these processes.
 GENERAL AIMS OF DISTILLATION AND CHEMICAL
PROCESSING

•To improve colour

•To improve odour
•To remove sulphur
•To remove gums, resins and asphaltic
materials
•To improve stability of product to light and
air
QUALITY IMPROVEMENT PROCESSES
 TREATING AND BLENDING THE FRACTIONS
• Processed fractions are treated to remove impurities, such
as organic compounds containing sulphur, nitrogen,
oxygen, water, dissolved metals and inorganic salts.

• After the fractions have been treated, they are cooled and
then blended together to make various products.

1. Blending is the physical mixture of a number of different

liquid hydrocarbons to produce a finished product with
certain desired characteristics e.g.
AIMS
a. different mixtures of chains can create gasoline with
different octane ratings
b. for ease in handling and
c. to reduce the undesirable emissions produced when the
product is burned
2. Chemical Treatment
Additives incorporated during and/or after blending
to provide specific properties not inherent in
hydrocarbons.

Additives include
• octane enhancers
• anti-oxidants
• anti-knock agents
• gum and rust inhibitors
• detergents
 OCTANE NUMBER
• Octane number is a standard which determines the
knocking ability and quality of gasoline. The octane rating of
a fuel is a measure of its resistance to knock - the higher the
rating, the less will be the tendency of a fuel to cause knock.
• Knocking i.e. Auto ignition is the phenomenon whereby an
engine ignites before it is ignited by the spark plug. Knocking
is caused by the low octane number of gasoline.
• Engine knock is caused by the uncontrolled detonation of
the last part of the air-fuel mixture in the combustion
chamber and may damage the engine
Octane number can be increased by the following methods:
1.Blending
2.Chemical Treatment
3.Reforming
4.By adding TEL (tetraethyl lead) / TML (tetramethyllead
 OCTANE RATING IN DIFFERENT REGIONS

At the coast, the predominant demand will be for

higher octane fuel. Generally, the lower the altitude
the higher the octane requirement of a vehicle).

In RSA, "regular" unleaded fuel is 95 RON (Research

Octane Number) in coastal areas. Inland (higher
elevation) "regular" unleaded fuel is 93 RON

• At higher-elevation areas, a typical engine draws in

less air mass per cycle because of the reduced density
of the atmosphere.

• At higher elevations, since the air is "thinner" there is

less likelihood for pre-ignition at higher elevations, so a
lower octane fuel is sufficient.