CHAPTER 2

PETROLEUM BASED CHEMICALS

Learning outcomes:

At the end of the lesson, student

should:

1. Know the definition of petroleum,

its origin and compositions.
2. Explain the petroleum refining
processes.
3. Describe the process of
petrochemicals production and
application.
 Can be gaseous (natural
gas), liquid (crude oil, crude
petroleum), solid (asphalt,
tar, bitumen)

Petroleum is called a
nonrenewable energy Product: gasoline,
sources because it naphtha (by
takes millions of years refining process)
to form. We cannot
make new petroleum What is
reserves. Petroleum

A dark oil
consisting
mainly of
hydrocarbon
Fossil fuel –formed from
remains of tiny sea plants
and animal that died
millions of year ago
1. Source of energy (90%)
• as fuel
2. Raw material for chemical products (10%) - synthetic
organic compounds
 Petroleum & Natural Gas
Formation

https://www.youtube.com/watch?v=8YHsxXEVB1M
 Crude Oil Pretreatment
• Crude oil often contains water, inorganic salts,
suspended solids, and water-soluble trace metals –
that need to be removed to avoid or to reduce
corrosion, plugging, and fouling of equipment and
to prevent poisoning the catalysts in processing
units (refining).
• Cleanup takes place in two ways:
✓ Field separation
✓ Crude desalting
• Field separation:

– remove the gases, water and dirt that accompany

crude oil coming from the ground.
– Apply gravity separation based on three phases:
gases, crude oil and water (with entrained dirt).
– The gases are withdrawn from the top – piped to a
natural gas processing plant or pumped back into
the oil well.
– The crude oil – middle layer – is pumped to the
refinery or storage for transportation
– Water is withdrawn from the bottom – disposed.
Field separation process:

foam in oil gas separator

• Crude desalting:

– The salts that are most frequently present in crude

oil are calcium, sodium and magnesium chlorides.
If these compounds are not removed from the oil
several problems arise in the refining process.
– Water-washing operation performed at the
refinery to get additional crude oil cleanup.
– The crude oil coming from field separators will
continue to have some water and dirt.
– Water washing removes much of the water-soluble
minerals and entrained solids.
 Petroleum Refining
• Petroleum refining refers to the process of
converting crude oil into useful products,
• Crude oil is composed of hundreds of different
HC molecules, which are separated through
the process of refining.
• The process is divided into three basic steps:
i. Separation (Distillation)
ii. Conversion (Cracking, Reforming, Alkylation,
Polymerization and Isomerization)
iii. Treatment/Treating (Hydrotreating)
Distillation
Process
 Fractional Distillation Process
• The various components of crude oil have
different sizes, weights and boiling
temperatures – so, the first step is to
separate these components.
• Because they have different boiling
temperatures, they can be separated easily
by a process called fractional distillation.
• The steps of fractional distillation are as
follows:
https://www.youtube.com/watch?v=PYMWUz7TC3A&t=153s
• Fractional distillation is useful for separating a mixture of
substances with narrow differences in boiling points, and is the
most important step in the refining process.
 Petroleum Refining Process

The aims of petroleum refining are:

1) To produce as many high-octane compounds in
the gasoline as possible.
2) To change hydrocarbon larger than C10 or smaller
than C4 into chemical substances in the range of
C4 – C10.
https://www.youtube.com/watch?v=vD0kbdIS6kE
 Cracking
• Cracking is the process of breaking down of a large
alkane into smaller, more useful alkanes and alkenes.
• In other word, HC cracking is the
process of breaking long-chain
hydrocarbons into short ones.
• Purposes:
- making HC that have carbon
atoms between 5~12.
- conversion of saturated HC to
non-saturated HC.
 Thermal Cracking
• Useful to convert saturated →non-saturated HCs.
• Also known as steam cracking.
• Uses heat (~800°C) and pressure (~700 kPa) to ‘crack’
heavy hydrocarbon molecules →light hydrocarbon
molecules.
• Mainly used to produce alkenes/olefin.
• Cracking unit consist of one or more tall, thick
walled, bullet-shaped reactors and a network of
furnaces, heat exchangers and other vessels.
• Increases the quantity and quality of gasoline made
by straight distillation.
 Thermal Cracking
• Gasoline produced has a higher-octane number than
that by straight distillation.
• Octane number - Measure of the ignition quality of
gas (gasoline or petrol). Higher this number, the less
susceptible is the gas to 'knocking' (explosion caused
by its premature burning in the combustion
chamber) when burnt in a standard (spark-ignition
internal combustion) engine.
• No catalyst involved.
eg: C15H32 2C2H4 + C3H6 + C8H18
ethene propene octane
 C15H32

heat

ethene propene octane

 Thermal Cracking
(The process)
• The HC feedstock is vaporised and
mixed with steam.
• The mixture passed thru tubes (~an
inch in diameter) through furnace.
• The residence time is short ~30-100
msec to minimized coking.
• Product gases obtained at about
800oC.
• Different fractions of product are
collected by distillation.
• The products of steam cracking
depends on the feedstock and the
reaction conditions.
 Thermal Cracking
(Mechanism)

• Is a free radical reaction.

Carbon-carbon bonds are

broken, so that each carbon
atom ends up with a single
electron (free radical formed).
Example: Thermal cracking of propane (C3H8)
CH3CH2CH3 CH4, CH2=CH2, CH3CH3, CH2=CHCH3, H2
(*The equation is not meant to be balanced, but just to show the variety of possible
products.)

• Balanced equations e.g:

Propene methane + ethene
CH3CH2CH3 CH4 + CH2=CH2

Propane propene + hydrogen

CH3CH2CH3 CH2=CHCH3 + H2

When alkane hydrocarbons are heated to a high temperature (450-900oC,

with/without superheated steam) they are thermally decomposed or
'cracked' to form mainly alkanes of lower C number, alkenes of equal or
smaller C number and hydrogen.
 Catalytic Cracking
• Breaking of bonds and dehydrogenation to produce
unsaturated gasoline.
• Purpose → to break the heavy naphtha fraction and
gas oil into products of mainly branched alkanes such
as isoalkane petro, iso-olefin, cycloalkanes and
aromatics.
• Occurs at low temperature and low pressure by using
strong acid catalyst such as crystal aluminosilicates,
such as zeolite.
• Produces more gasoline of even higher octane
numbers than thermal cracking process.
 Catalytic Cracking
(The process)
• Catalytic Cracking takes place
at 500oC.
• At atmospheric pressure/or
slight above.
• The reaction is carried out in a
fluidized-bed reactor.
• The fine catalyst is maintained
in fluid state by stream of
steam - and easily removed
from the reactor in its fluid
state and regenerated.
• Residence time is 1-3 sec. The
products are rapidly quenched
to prevent decomposition.
 Catalytic Cracking
(Mechanism)
• The HC molecules are broken up in a fairly random
way to produce mixtures of smaller HC, some of
which have C-C double bonds.
• One possible reaction involving the hydrocarbon
C15H32 might be:
• The ethene and propene are important materials for
making plastics or producing other organic chemicals.
The octane is one of the molecules found in petrol
(gasoline).
• Hydrocarbons used in petrol (gasoline) are given an
octane rating which relates to how effectively they
perform in the engine. A hydrocarbon with a high-
octane rating burns more smoothly than one with a
low octane rating.
• Octane ratings are based on a scale on which heptane
is given a rating of 0, and 2,2,4-trimethylpentane (an
isomer of octane) a rating of 100.
• To raise the octane rating of
the molecules found in petrol
(gasoline) and so make the
petrol burn better in modern
engines, the oil industry
rearranges straight chain
molecules into their isomers
with branched chains.

One process uses a platinum catalyst on a zeolite base at a temperature of about

250°C and a pressure of 13 - 30 atmospheres. It is used particularly to change
straight chains containing 5 or 6 carbon atoms into their branched isomers.
 Hydrocracking
• Hydrocracking is a two-stage process combining
catalytic cracking and hydrogenation.
• Heavier feedstock are cracked in the presence of
hydrogen to produce more desirable products.
• Also, a treating process because the hydrogen
combines with contaminants (sulphur and nitrogen),
eg. H2S, NH3 and H2O – allowing them to be removed.
• The process employs high pressure, high temperature,
a catalyst, and hydrogen.
A two-stage Hydrocracking unit.
 Catalytic Reforming
• The process re-arranges or re-structures the
hydrocarbon molecules in the naphtha feedstocks as
well as breaking some of the molecules into smaller
molecules.
• Mainly used for converting straight chain hydrocarbons
and cyclic aliphatic to aromatic (BTX) with a high octane
number through dehydrogenation.
• Catalysts: Pt-alumina, Rh-alumina, Pt-ZSM-5
• Feedstock : naphtha
• Temperature: 400-550oC and pressure 25-35 bar
• Products: benzene, toluene (major) and xylene.
Process flow scheme of catalytic naphtha reforming
 Catalytic Reforming
Four major catalytic reforming reactions:
1. The dehydrogenation of naphtha to aromatics.
File:Methylcyclohexanetotoluene.svg

2. The isomerization of normal paraffins to

isoparaffins.
File:Paraffintoisoparaffin.svg
3. The dehydrogenation and aromatization of paraffins
to aromatics (commonly called dehydrocyclization).
File:CatReformerEq2.png

4. The hydrocracking of paraffins into smaller

molecules.
 Alkylation
• In the petroleum chemistry,
it referred to the reaction of
olefins (ethylene/isobutene)
with isoparaffin (isobutane)
to produce more branched
chain molecules in the
presence of Friedel-Crafts
Catalyst.
• Catalyst: H2SO4and HF (the
preferred catalyst).
• Purpose → to produce a
branched compound that can
be blended with gasoline to
increase octane number up
to 85~95 as well as the Alkylation unit in a refinery
performance of the petrol.
 Alkylation
• Example: CH2=CH2 + (CH3)2CHCH3 [cat] (CH3)2CHCH(CH3)2
ethylene isobutane 2,3-dimethylbutane
Octane number : 90

Octane number = 93

isobutane isobutene Isooctane (octane number = 100)

2,2,4-trimethylpentane
• Isobutene is used to alkylate a branched-chain hydrocarbon, isobutane in
the presence of Friedel-Crafts Catalyst H2SO4 or HF - produce 2,2,4-
trimethylpentane (isooctane), but 2,3,4- and 2,3,3-trimethylpentanes are
also formed.

isooctane

Octane number of some selected HCs

 Polymerization
• Polymerization in petroleum refining is the process of
converting light olefin gases including ethylene,
propylene, and butylene into hydrocarbons of higher
molecular weight and higher octane number that can
be used as gasoline blending stocks.
• In polymerization, an alkene can react with another
alkene to generate dimers, trimers, and tetramers of
the alkene.
• As an example, isobutylene (C 4 ) reacts to give a
highly branched C 8 alkene dimer.
 CH3 CH3 CH3
2 C=CH2 C=CH C CH3
CH3 CH3 CH3
C8 alkene dimer
isobutylene 2,4,4-trimethyl-1-pentene

Typical polymerization reactions.

• Polymerization may be accomplished thermally or in the

presence of a catalyst (eg: solid phosphoric acid) at
lower temperatures.
 Isomerization
• Referred to the restructuring/reforming of n-paraffin
molecules to its branched isomer that use for
alkylation process.
• The paraffin often used are n-butane, n-pentane and
n-hexane and the catalyst used is AlCl3
• Purposes:
→to create extra isobutane feed for alkylation.
→to improve the octane number of straight run
pentanes and hexanes - better petrol blending
components - improve petrol quality.
 62 92.3

25 74 76
2-MP 3-MP

25 92
92.8
2,2-DMB 2,3-DMB

C5/C6 paraffins isomerization reaction

 Treatment
• The finishing touches occur during the final
treatment –petroleum contains impurities – these
impurities can damage the equipment, the catalysts
and the quality of the products.
• Purpose:
→to improve the petrol
→to remove the unwanted materials or heavy
materials, such as sulphur, wax and sludge
• There are two types of treatment:
→ Hydrotreating
→ Sulfur recovery
 Hydrotreating
• The entering petrol is mixed with hydrogen and heated to
300~380oC, then enters a reactor loaded with a catalyst which
promotes several reactions:
→ H2 combines with S to from H2S.
- When hydrotreating is done for sulfur removal → process
is called hydrodesulfurization
- Cat used: Co/Al2O3 and MoOx/Al2O3

→ Nitrogen compounds are converted to ammonia.

- For nitrogen removal → process denitrogenation @
hydrodenitrogenation
- Cat used: Ni-Mo/Al2O3
 Hydrotreating

→ Any metals contained in

the oil are deposited on the
catalyst.
→ Some of the olefins,
aromatics or naphthenes
become saturated with
hydrogen to become
paraffins.
→ Some cracking takes
place - the creation of Hydrodesulfurization unit (HDS)
some methane, ethane,
propane and butanes.
 Sulfur Recovery
• Purpose:
→To treat the H2S, which is a toxic gas produced from
hyrotreating.
• Process:
→The removal of the H2S gas from the hydrocarbon
stream.
→The conversion of H2S to elemental sulfur, which is a
non-toxic and useful chemical – most widely used
recovery system is the Claus process.
• The solvent used to treat H2S is diethanolamine (DEA).
 Claus process
• The Claus process is the most significant gas desulfurizing process,
recovering elemental sulfur from gaseous hydrogen sulfide.
• Hydrogen sulfide produced, for example, in the hydro-desulfurization of
refinery naphthas and other petroleum oils, is converted to sulfur in Claus
plants. The reaction proceeds in two steps:

2 H2S +3 O2 → 2 SO2 + 2 H2O

4 H2S +2 SO2 → 3 S2 + 4 H2O

• Catalyst - typically alumina based and

often made up of aluminium oxide
mixed with other substances, such as
titanium oxide.
• The latest modern designs can
achieve up to 99.8% conversion –
Piles of sulfur produced in Alberta by the Claus
producing 99% saleable bright yellow process awaiting shipment at docks in Vancouver,
sulfur. Canada.
 Pre- Conversion/
treatment Separation Treatment Products
 Petroleum Based Chemicals

PETROCHEMICALS
▪ Petrochemicals are
chemicals made from
petroleum (crude oil) and
natural gas and used for a
variety of commercial
purposes.
▪ Can be divided into two
groups:
1. Primary Petrochemical
2. Intermediates and
derivatives
PETROCHEMICALS
• Petrochemical intermediates are generally produced by
chemical conversion of primary petrochemicals to form
more complicated derivative products.
• Petrochemical derivative products can be made in a
variety of ways:
1. directly from primary petrochemicals
2. through intermediate products which still contain only
carbon and hydrogen; and,
3. through intermediates which incorporate chlorine,
nitrogen or oxygen in the finished derivative.
• The most important process in petrochemicals
production is polymerization.
PETROCHEMICALS

Produced from ‘syngas’

Olefins – steam cracking of

natural gas

Aromatics – catalytic
reforming of naphtha

63
PETROCHEMICALS
• Some typical petrochemical intermediates are:
1. vinyl acetate - paint, paper and textile coatings
2. vinyl chloride - polyvinyl chloride (PVC)
3. resin manufacture
4. ethylene glycol - polyester - textile fibers
5. styrene - rubber and plastic manufacturing
PETROCHEMICALS

The Petrochemical Products

PETROCHEMICALS
Methanol
• Methanol is one of the most heavily traded
chemical commodities in the world, with an
estimated global demand of around 27 to 29
million metric tons.

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PETROCHEMICALS

Methanol
• Methanol is mainly
produced from synthesis
gas, which in turn is
produced by the steam
reforming or partial
oxidation of hydrocarbons
or a combination of both
processes
• MeOH also can be made
from renewable sources,
such as renewable natural
gas, biomass and green
hydrogen combined with
recycled carbon dioxide –
biomethanol.
PETROCHEMICALS
Methanol Production
Production of Methanol from syngas
• Today, the most widely used catalyst is a mixture of
copper, zinc oxide, and alumina first used by ICI in
1966.
• At 5–10 MPa (50–100 atm) and 250 °C, it can catalyze
the production of methanol from carbon monoxide
and hydrogen with high selectivity (>99.8%).

CO + 2 H2 → CH3OH
70
PETROCHEMICALS

Feedstock for methanol production

• Steam methane reforming - methane reacts with
steam on a nickel catalyst to produce syngas:

CH4 + H2O → CO + 3 H2
• The production of synthesis gas from methane
produces three moles of hydrogen gas for every mole
of carbon monoxide, while the methanol synthesis
consumes only two moles of hydrogen gas per mole
of carbon monoxide.
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PETROCHEMICALS

• One way of dealing with the excess hydrogen is to

inject carbon dioxide into the methanol synthesis
reactor, where it reacts to form methanol according
to the equation:

CO2 + 3 H2 → CH3OH + H2O

• Where as, the H2O byproduct is recycled via the
water-gas shift reaction (WGS):

CO + H2O → CO2 + H2
72
PETROCHEMICALS

• This gives an overall reaction:

CO + 2 H2 → CH3OH

Schematic diagram of methanol production - Johnson Matthey

73