Chapter 1: Introduction to

Petrochemistry

1
 Learning outcomes

• Students should be able to:

1. Identify the bases for petrochemicals
industries
2. Describe the properties of raw material
3. Explain the petroleum refining process

2
 What is..?
▪ Petrochemistry - a branch of chemistry that studies
the transformation of crude oil (petroleum) and
natural gas into useful products or raw materials.
▪ Petroleum industry ??

✓ The petroleum industry includes the global

processes of exploration, extraction, refining,
transporting (often by oil tankers and
pipelines), and marketing petroleum products.
✓ The largest volume products of the industry are
fuel oil and gasoline (petrol).
3
 What is..?
Petrochemicals are chemicals made from petroleum
(crude oil) and natural gas.

Some of the petrochemical products used in our daily lives. 4

 Petrochemical Industry

• The primary raw materials for the production of

petrochemicals are natural gas and crude oil.
• The petrochemical industry is mainly based on three
types of intermediates:
➢ the C2-C4 olefins,
➢ the C6-C8 aromatic hydrocarbons,
➢ and synthesis gas (an H2/CO2 mixture).

5
Produced from ‘syngas’

Olefins – steam cracking of

natural gas

Aromatics – catalytic
reforming of naphtha

6
7
8
World oil reserves, 2009

At 27th place -
693,700 bbl/day
(0.82%), 2009

9
 Petrochemical Supply-Chain Dynamics
Consumers Retail
Converters

Energy Petrochemicals
Derivatives

10
 Petrochemicals Industries in
Malaysia
• Malaysia holds the world's 23rd largest crude oil
reserves and the world’s 14th largest natural gas
reserves with a capacity of 84.1 trillion cubic feet in
2009 (MIDA report).
• In 2008, the Petrochemical Industry is one of the
leading industrial sectors with total investments of
RM 58 billion - with PETRONAS being the major
investor (RM 37.8 billion - 65%).
• Besides Petronas, Shell and ExxonMobil also a giant
players in petroleum industry.
11
• A competitive feedstock prices have made Malaysia a
viable petrochemical hub in the ASEAN region.
• Major petrochemical industry players – eg., BP, Dow
Chemical, ConocoPhilips, Toray, Dairen, Mitsui,
Idemitsu, Titan, Thirumalai.
• The major petrochemical zones with 29
petrochemical plants are in:
➢ Kertih, Terengganu (Petronas Petrochemical
Integrated Complex (PPIC))
➢ Gebeng, Pahang – hub for BASF, Amoco, Kaneka,
Eastman and Polyplastics.
➢ Pasir Gudang – Tanjung Langsat, Johor
➢ Bintulu, Sarawak – major LNG producer
12
• Each zone is an integrated complex with crackers,
syngas and aromatics facilities to produce basic
feedstocks for downstream products.
• In addition, there are also petrochemical plants
located in other parts of Malaysia such as:
➢ the ammonia/urea plants in Gurun, Kedah and
Bintulu, Sarawak,
➢ the acrylonitrile butadiene styrene (ABS) plant in
Penang,
➢ the methanol plant in Labuan
➢ the nitrilebutadiene rubber (NBR) plant in Kluang
and Pasir Gudang, Johor.
13
 14
List of products manufactured in petrochemical plants in Malaysia
 Petroleum and Natural Gas
• The word petroleum (literally “rock oil” from the Latin
petra, “rock” or “stone,” and oleum, “oil”) – black
gold.
• It is a complex mixture of hydrocarbons – occur in the
earth in liquid, gaseous, or solid forms.
Liquid = crude oil
Gaseous = natural gas Petroleum
Viscous solid = bitumen

Liquid dark and thick 15

Petroleum & Natural Gas
Formation

Can you explain ??

 Petroleum Composition

Element Percent range

Carbon 83 to 87 wt%
Hydrogen 10 to 14 wt%
Nitrogen 0.1 to 2 wt%
Oxygen 0.05 to 1.5 wt%
Metals < 0.1 wt%

1. Source of energy ( ≈ 90%)

• as fuel
2. Raw material for chemical products (≈ 10%) -
synthetic organic compounds
 Distillation
Process
• Chemical
components of
crude oil is
separated by the
process distillation
(fractional
distillation) 18
 Petroleum Refining
Petroleum refining processes are those chemical
engineering processes used in petroleum refineries to
transform crude oil into useful products such as
liquefied petroleum gas (LPG), gasoline or petrol,
kerosene, jet fuel, diesel oil and fuel oils.
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. 19
 Thermal
cracking
Catalytic
cracking
CRACKING

CATALYTIC
Hydro-
REFORMING
cracking

ISOMERIZATION

ALKYLATION CONVERSION
PROCESS
Petroleum POLYMERIZATION
Refinery
 Cracking
• Cracking is the process of breaking down of a large
alkane into smaller, more useful alkanes and alkenes.
• Purposes:
- making HC that have carbon
atoms between 5~12.
- conversion of saturated HC to
non-saturated HC.
 Thermal Cracking

• 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.
 Thermal Cracking
• Gasoline produced has a higher octane number than
that by straight distillation.
• Octane number- a measure of tendency of fuels to
knock/ping when used in high-compression, internal-
combustion engines.
• The higher octane number, the less knock.

eg: C15H32 2C2H4 + C3H6 + C8H18

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.
Schematic representation of the thermal cracking process.
 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:

Propane 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.
 Step 1: Initiation step

• C-C bond in an alkane molecule is split into two alkyl

free radicals by homolytic bond fission.
• The red dots represent the unpaired electron on the
free radical.

• Free radicals are highly reactive species with an

unpaired electron and tend to form a new bond as
soon as is possible, in this case by:
✓ abstracting a hydrogen from another molecule e.g.
steps (2) to (6) or

✓ pairing up with another radical e.g. steps (7) and (8).

 Step 2: Chain Propagation step

• Step 2 to 6 chain propagation steps - because as well

as a product, a free radical is also produced to
continue the chain reaction and lead to a variety of
other products.
 Step 3: Chain Termination step

• Steps (7) and (8) are two possible chain termination

steps via:
➢ recombination, where the two radicals combine to
form one larger molecule (eg. Step 8).

➢ disproportionation, where one radical transfers a

hydrogen atom to the other, giving an alkene and an
alkane (eg. Step 7).
 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.
A schematic flow diagram of a Fluid Catalytic Cracking unit as used in petroleum refineries
 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:

ethene and propene are

important materials for
making plastics
octane is one of the
(petrochemicals)
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 - 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.
 Catalytic Reforming
Four major catalytic reforming reactions:
1. The dehydrogenation of naphtha to aromatics.

2. The isomerization of n-paraffins to isoparaffins.

3. The dehydrogenation and aromatization of paraffins
to aromatics (commonly called dehydrocyclization).

4. The hydrocracking of paraffins into smaller

molecules.
Process flow scheme of catalytic naphtha reforming
 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 performance of the petrol.
Example 1:
[cat]
CH2=CH2 + (CH3)2CHCH3 (CH3)2CHCH(CH3)2
ethylene isobutane 2,3-dimethylbutane
 Example 2:

• Isobutene is used to alkylate a branched-chain

hydrocarbon, isobutane in the presence of Friedel-
Crafts Catalyst H2SO4 or HF – to produce 2,2,4-
trimethylpentane (isooctane).
• Mechanism – carbenium ion attack (carbocation chain
process).

isobutane isobutene Isooctane (octane number = 100)

 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 C8 alkene dimer.
 CH3 CH3 CH3
2 C=CH2 C=CH C CH3
CH3 CH3 CH3
isobutylene C8 alkene dimer

• Polymerization may be accomplished thermally or in

the presence of a catalyst (eg: solid phosphoric acid)
at lower temperatures.
Typical process scheme of a polymerization unit.
 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.
C5/C6 paraffins isomerization reaction
Typical process scheme of an isomerization unit.
 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:

→ When hydrotreating is done for sulfur removal

→ process is called hydrodesulfurization (HDS)H2
– combines with S to from H2S
– Cat used: Co/Al2O3 and MoOx/Al2O3
→ to reduce the nitrogen content of a petroleum
stream → hydrodenitrogenation (HDN) process
– Nitrogen compounds are converted to
ammonia.
– Cat used: Ni-Mo/Al2O3

• 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 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).
 Pre- Conversion/
treatment Separation Treatment Products

Summary:
 Petrochemical Process
Technology
• A chemical plant is an industrial process plant that
manufactures (or otherwise processes) chemicals,
usually on a large scale – use special equipment,
units, and technology in the processes.
• Petrochemical plants are usually located adjacent to
an oil refinery to minimize transportation costs for the
feedstocks produced by the refinery.
• A chemical plant usually has large vessels or sections
called units that are interconnected by piping or other
material-moving equipment which can carry streams
of material.
Petronas
Petrochemical
plant at Kertih,
Terengganu

62
 Chemical Process
UNIT OPERATION

Input/feed Chemical
stock Product
Process

• Chemical processes may be run in continuous or

batch operation.

63
 Batch vs. Continuous Process

Assuming that it takes 1 min per car at If we build them one at a time in a one-
each stage, the expected results: piece continuous flow process, the
Time to build first car: 21 min expected results:
Time to build first batch of ten: 30 min Time to build first car: 3 min
Time to build first batch of ten: 12 min
Continuous process shows an improvement of 18 min over the batch process64
 Batch Process
• In batch operation, production occurs in time-sequential
steps in batches.
• Process sequences:
1. a batch of feedstock is fed into a process/unit,
2. chemical process takes place,
3. the product and any other outputs are removed.
• The production may be repeated over again and again
with new batches of feedstock.
• Batch operation is commonly used in smaller scale plants
such as pharmaceutical, food, beverages or specialty
chemicals production. 65
 Example: The production of slime

Compounding the batch → QC check → adjustment is

needed (if any) → stored for filling → packed for sell. 66
 Continuous Process
• In continuous operation, all steps are ongoing
continuously in time.
• Meaning the feeding and product removal are
ongoing streams of moving material (together with
the process itself) – all take place simultaneously and
continuously.
• Continuous operation is more efficient in many large
scale operations like petroleum refineries – for
practical and economic reasons.
• Chemical plants or units in continuous operation are
usually in a steady state.
67
 Continuous Process
• Steady state means that quantities related to the process
(i.e, stream flow rates, heating or cooling rates,
temperatures, pressures, and chemical compositions) do
not change as time passes during operation.
• The amount of primary feedstock or product per unit of
time which a plant or unit can process is referred to as
the capacity of that plant or unit.
• Example: the capacity of an oil refinery may be given in
terms of barrels of crude oil refined per day.
• Production workers in continuous production commonly
work in rotating shifts.
68
 Example : Ammonia production (Haber Process).

• The raw materials are fed

continuously into the
reactor.
• The process is carefully
designed so that the
ammonia is extracted
from the gas stream and
leftover nitrogen and
hydrogen are fed back to
the beginning without the
process stopping.
69
 Chemical Reactor
• Chemical reactors are vessels designed to contain
chemical reactions.
• Vessel can be (i) tank or (ii) pipe/tubular reactor
• Chemical engineers design reactors to maximize net
present value for the given reaction, by ensuring that;
✓ the reaction proceeds with the highest efficiency
towards the desired output,
✓ producing the highest yield of product, and
✓ in the most cost effective way (i.e., minimize the
operating expenses).
70
 Chemical Reactor

• There are three main basic models of chemical

reactors:
I. batch reactor model (batch),
II. continuous stirred-tank reactor model
(CSTR),
III. plug flow reactor model (PFR) (sometimes
called continuous tubular reactor, CTR, or
piston flow reactors)

71
I II

III

72
73
• Reactors are designed based on features like mode
of operation or types of phases present or the
geometry of reactors.

74
 Chemical Reactor
• They are thus called:
✓ Batch or Continuous - depending on the mode of
operation.
✓ Homogeneous or Heterogeneous - depending
upon the phases present.
• They may also be classified as (reactor geometry) :
✓ Stirred Tank Reactor, or
✓ Tubular Reactor, or
✓ Packed Bed Reactor, or
✓ Fluidized Bed Reactor
75
 Chemical Reactor
• Batch process - a process in
which all the reactants are
added together at the
beginning of the process and
products removed at the
termination of the reaction .
– all the reagents are added
at the commencement and
no addition or withdrawal is
made while the reaction is
progressing .
76
 Chemical Reactor
• Continuous process - a process in which the
reactants are fed to the reactor and the products
or byproducts are withdrawn in between while
the reaction is still progressing.

77
 Chemical Reactor
• Semi batch process - is operated with both continuous
and batch inputs and outputs.
• Example : in industrial fermentation process, a
fermenter is loaded with a batch, which constantly
produces carbon dioxide, which has to be removed
continuously.

78
• In semi-batch reactors, some of the reactants may be added
or some of the products withdrawn as the reaction proceeds.
• A semi-continuous process can also be one which is
interrupted periodically for some specific purpose – example
for the regeneration of catalyst etc.

79
Example : semi batch process - chlorination of liquid
 Chemical Reactor
• Catalytic process – chemical reactions that proceed in
the presence of catalysts.
I. Homogeneous reaction – in liquid or gaseous
phase.
→ Tubular (Pipe line) reactors – for homogeneous
gas phase reaction.
→ Batch or continuous reactors – for
homogeneous liquid phase reaction.

80
 Chemical Reactor
II. Heterogeneous reaction
→ Two or more phases (liquid-gas-solid)
→ Most solid catalytic processes employ fixed beds,
but some use fluidized beds.

A Continuous Feed Fixed Bed Reactor The fluidized bed reactor 81

82
 Chemical Reactor
Reactor Geometry
• The reactors used for established processes are
usually complex and unique designs – to suit the
requirements of the process.

A. Stirred Tank Reactors :

– Stirred tank agitated reactors consist of a tank
fitted with a mechanical agitator and a cooling
jacket or coils.
– They are operated as batch reactors or
continuous reactors.
83
84
 Chemical Reactor
B. Tubular Reactors :
– always used in a continuous flow mode with
reagents flowing in and products being removed.
– generally used for gaseous reactions, but are also
suitable for some liquid phase reactions.
– Tubular reactors are often referred to by other
names:
– Example: Pipe reactors, Packed-bed reactors,
Trickle-bed reactors, Bubble-column reactors
or Ebulating-bed reactors.
85
86
 Chemical Reactor

C. Packed Bed Reactors :

– These reactors are tubular and are filled with
solid catalyst particles.
– The chemical reaction takes place on the surface
of the catalyst.
– Normally used for gas and gas-liquid reactions,
but most often used to catalyze gas reactions.

87
Tubular fixed bed Reactor

88
 Chemical Reactor
D. Fluidized Bed Reactors :
– A fluidized-bed reactor is a combination of the two
most common, packed-bed and stirred tank,
continuous flow reactors.
– The essential features of a fluidized bed reactor is that
the solids are held in suspension by the upward flow of
the reacting fluid - promotes high mass and heat
transfer rates and good mixing.
– Fluidization can only be used with relatively small sized
particles, that is less than 300μm.
89
fluidized bed reactors arrangement for the
fluid catalytic cracking process for HC

90