3.

The octane number of a fuel The octane scale was established in 1927 using

is a measure of its quality. The a standard test engine and two pure
compounds: n-heptane and isooctane (2,2,4-
higher the octane number, the
trimethylpentane).
lesser the tendency of the fuel
n-Heptane, which causes a great deal of
to knock.
knocking on combustion, was assigned an

It can be caused either by an octane rating of 0, whereas isooctane, a very

engine malfunction or by a fuel smooth-burning fuel, was assigned an octane

that burns too fast. In either case, rating of 100.

the gasoline-air mixture detonates Chemists assign octane ratings to different

at the wrong point in the engine blends of gasoline by burning a sample of each

cycle, which reduces the power in a test engine and comparing the observed

output and can damage valves, knocking with the amount of knocking caused

pistons, bearings, and other by specific mixtures of n-heptane and

engine components. isooctane.

1
 CH3

2-methylnaphtalene
Cetane no. 0

2
For example, the octane rating of a blend of 89% isooctane and 11% n-heptane is simply
the average of the octane ratings of the components weighted by the relative amounts
of each in the blend. Converting percentages to decimals, we obtain the octane rating of
the mixture:
0.89(100)+0.11(0)= 89

Anti-Knocking Compounds
About octane enhancers: Lead tetraacetate, methyl t-butyl ether (MTBE), ethanol 3
 Isooctane
CH3

2-methylnaphtalene
Cetane no. 0

4
4. Light gasoline has octane no of 65 and naphtha (40). Bothe are unsuitable as
fuel.

5. It is chemically modified by a process called “catalytic reforming” which

converts alkanes and cycloalkanes into aromatic hydrocarbons (catalytic
reformate) having octane number of 95-100.

6. Fuel is made by appropriate blending of gasoline (less) and heavy oils (more).

Q. More examples of Catalytic reformates

5
 ………………………….gasoline (less) and heavy oils/catalytic reformate (more).

The need for catalytic cracking: the above process lead to imbalance of out put of fuel
products. Long chain molecules are “cracked” in the presence of strongly acidic catalyst at
500 oC.
What happens: Molecular weight reduction
occurs to produce gasoline with an octane
number of about 90 together with a high boiling
fraction and “catalytic cracker gas”.

Composition of Catalytic cracker gases

wt (%)
H2 0.6
H2S 3.4
Methane 10.3
Ethylene 3.4
Ethane 7.5
Propylene 13.8
Propane 12.1
Butenes 18.4
Butane 30.5
6
 The basic building block processes

Large proportion of petrochemical manufacture is based on intermediates made by

three basic building block process
1. Thermal cracking or steam cracking: Used for the manufacture of ethylene using
feedstock's such as ethane, propane, naphtha and gas oil.

2. Catalytic reforming: Used for the manufacture of benzene, toluene, xylenes etc
using naphtha

3. Steam reforming: Produces initially a mixture of CO and H2 (Syn gas), which may
be subsequently used or the manufacture of a variety of chemicals

7
 Classification of Petrochemicals:
1. First Generation Petrochemicals
2. Second Generation Petrochemicals
3. Third Generation Petrochemicals

First Generation Petrochemicals

Chemicals directly available from “petroleum crude” or
“natural gas” either by fractionation or isomerization or cracking.

Represent the basic petrochemicals, which are the building blocks for
various chemical synthesis.

8
 Examples of First Generation

• Alkanes: Methane, ethane, propane

• Alkenes/alkynes: Ethylene, propylene, butene, butadiene,

acetylene.

• Aromatics: Benzene, toluene, xylenes.

• These can be sub-grouped as aliphatic, olefins, acetylene, diene,

naphthenic and aromatics.

Further examples/details will be discussed later

9
 Second Generation Petrochemicals

• Not present as such as in petroleum or crude oil.

• Cannot be obtained by simple operations such as reforming,

cracking or hydrocracking.

• Derivatives of first-generation petrochemicals.

• Second-generation petrochemicals constitute the

intermediate chemicals that constitute as the raw materials
for consumer products like plastic, rubbers, fibers, dyes etc.

10
 Examples of Second Generation Petrochemicals

• Ethylene glycol (derived from ethylene)

• Acrylonitrile (derived from propylene)

• Vinyl chloride monomer (derived from acetylene)

• Dimethyl Terephthalate (derived from p-xylene)

• Styrene (derived from benzene and ethylene).

11
• Intermediates and Derivatives:

Petrochemical intermediates are generally produced by chemical

conversion of primary petrochemicals to other useful chemicals.

• Petrochemical derivative products can be made in a variety

of ways:

Directly from primary petrochemicals;

Through intermediate:
(i) which still contain only carbon and hydrogen; and
(ii) through intermediates which incorporate chlorine, nitrogen or oxygen
in the finished derivative.

In some cases, they are finished products; in others, more steps are
needed to arrive at the desired composition.

12
 Third Generation Petrochemicals
• Consumer commodities derived from second generation petrochemicals.

• Represent most important commercial products such as Plastics, Rubbers, Fibers,

Detergents etc.

• Some of these may be directly synthesized from first generation petrochemicals.

• For instance, polybutadiene rubber is obtained by polymerizing butadiene which is a

basic petrochemicals.

13
Examples of Third Generation Petrochemicals
• Polystyrene (from styrene)
• Polyvinyl chloride (from vinyl chloride monomer)
• DDT (from chlorobenzene)
• Azo dyes (from aniline)
• Most of the plastics or rubbers are derived from second
generation petrochemicals.
• Polybutadiene rubber is regarded as a third generation
petrochemical. The classification can, therefore, be said to be
a bit arbitrary.

14
 Is ‘Asprin’ a Petrochemical?

Petrochemicals

• Likely? that same C-atoms and H-atoms comes from

petroleum/natural gas.

• Yet, it is not a petrochemicals.

• Phenol and acetic anhydride are petrochemicals. However, aspirin
is not petrochemicals despite it is prepared from them.
• Petrochemicals are made on large scale.
15
 From where do we get petrochemicals?

Natural gas and petroleum are the main sources of

petrochemicals.

16
Fractions from Distillation of crude oil

Petrol is also called

Light gasoline

Fraction between 250-

350 is called
Gas Oil

Cracking is a process
of manufacturing
ethylene using
ethane, propane,
naptha and gas oil

17
 From where do we get petrochemicals?

• Several important chemical buildings blocks are obtained from

them.
• These are ethylene (C2), propylene (C3), the C4 olefins (butenes and
butadiene), benzene, toluene, the xylenes (ortho, meta and para),
and methane.

• The olefins – ethylene, propylene, butadiene and butenes are

derived from both natural gas and petroleum.

• The aromatics – benzene, toluene, and xylenes – are derived from

petroleum and to a small extent from coal.

• Methane comes from natural gas.

18
 Whether natural gas fractions or petroleum is used for
olefins (ethylene or propylene)?
• It varies throughout the world depending on the availability of natural gas
and the demand of gasoline.
• Both light and heavy naphthas are petroleum fractions that can be cracked
to olefins. Of course, they can be used for gasoline also.
• In the US demand for gasoline is higher than for other petroleum fractions.
• Consequently, the price of naphtha has traditionally been high and the
chemical industry preferred to extract ethane and propane from natural gas
for cracking to olefins.
• This is dictated by linear programming techniques that define the
appropriate mix of feeds to maximize profitability in the flexible crackers.
Why zero octane fuel is used at all??

19
 Petrochemical Process Technology

1. Continuous processing: is one in

which the raw materials are
constantly fed into the plant, reacting
as they move through the equipment
to give a continuous flow of product.
Advantages: for large scale
manufacture, easier to automate,
better energy conversion, shorter
reaction time.
Disadvantages: high capital cost to
built plant, not cost effective when
running below capacity.

20
1. Excess benzene is used to reduce
polyalkylation.
2. Ethylbenzene is separated and
dehydrogenated.
3. The yield refer to the raw material used
21
2. Batch processing: is one in which the reactants
are placed into a vessel and allowed to react.
When the reaction is complete, the product is
removed for purification, and the process is
repeated for a fresh batch of materials.
eg - Pharma Industries use this mostly

Advantages: cost-effective for small quantities,

a range of products can be made in the same
vessel.
Disadvantages: risk of cross-contamination,
requirement of more work-force

22
 The basic building block processes

A large proportion of petrochemical manufacture is based on intermediates made

by three basic building block process
1. Thermal cracking or steam cracking: Used for the manufacture of ethylene
using feedstocks such as ethane, propane, naphtha and gas oil.

2. Catalytic reforming: Used for the manufacture of benzene, toluene, xylenes

etc using naphtha.

3. Steam reforming: Produces initially a mixture of CO and H2, which may be

subsequently used for the manufacture of a variety of chemicals

23
Steam cracking without a catalyst is typically done at >800 ∘C and is
generally used to produce very short alkenes in large quantities. This form of
cracking is often called thermal cracking, because we rely entirely on the
high temperature to drive the reaction.

Catalytic cracking is typically done at 500 ∘C–700 ∘C, reducing the amount of
energy needed to heat the reaction mixture. Catalytic cracking is generally
used for converting crude oil fractions into lighter, more profitable ones.

The two applications of cracking are:

(i) production of alkenes and the
(ii) conversion of heavier fractions of crude oil into lighter ones.

24
1. THERMAL CONVERSION PROCESSES
Coking Processes: Coking is a severe thermal cracking process. Products from coking
processes vary considerably with feed type and are characterized by a high percentage
of unsaturation.

Thermal Cracking Reactions

• The first step in cracking is the thermal decomposition of hydrocarbon
molecules to two free radical fragments.
• This initiation step can occur by a homolytic carbon-carbon bond scission at
any position along the hydrocarbon chain.

25
The radicals may further crack, yielding an olefin and a new free radical.
Cracking usually occurs at a bond beta () to the carbon carrying the unpaired
electron.

Further β-bond scission of the new free radical R˙ can continue to produce
ethylene until the radical is terminated.

Free radicals may also react with a hydrocarbon molecule from the feed by
abstracting a hydrogen atom. In this case the attacking radical is terminated,
and a new free radical is formed.

Intermolecular and intramolecular

26
Abstraction of a hydrogen atom can occur at any position along the chain.
However, the rate of intermolecular hydrogen abstraction is:
tertiary > secondary > primary position.

The secondary free radical can crack on either side of the carbon carrying the
unpaired electron according to the beta scission rule, and a terminal olefin is
produced.

27
Ethane Cracking

β- bond scission

28
Propane Cracking

Since CC bonds are much weaker than C-H bond, most primary
propyl radicals undergo later reaction

29
30
31
Example 3: Identifying the Property That Increases for Hydrocarbons
That Undergo Cracking in a Set of Properties

In which of the following properties is an increase observed when

hydrocarbon fuels undergo cracking?
A. Melting point
B. Volatility
C. Viscosity
D. Molecular size
E. Ignition temperature

32
 Work out the naptha and gas oil cracking (straight chain and branched chain)
cracking: Understand the difference between C-C beta session and C-H beta
session.

Nonane C-9
The radical thus formed can undergo further β- bond scission

If there is no other interference it will continue until it leave either an

methyl radical or an ethyl radical 33
The ethyl radical can undergo CH -session, though this is much more
slower than the CC -session

Secondary radical: But most homolysisreactionsndos not start their reaction

by undergoing homolysis, but rather by suffering hydrogen atom abstraction
from the –CH2- position. In this process, a secondary hydrogen radical will
be generated

The CC -session of this radical will give an alkene other than ethylene
and a small primary radical

H .
.
. -H

-session 34
Primary radical: The generated primary radical can undergo a series of
-session reactions, each of which will give rise to a molecule of ethylene.

Composition of Catalytic cracker gases

The hydrogen atom or small radical formed at wt (%)
the end of this series of reactions can continue H2 0.6
by abstracting a hydrogen atom from a further H2S 3.4
molecule of nonane. Methane 10.3
Ethylene 3.4
Ethane 7.5
Propylene 13.8
Propane 12.1
Butenes 18.4
Butane 30.5

35
How reducing pressure help production of ethylene.
For maximum ethylene production there should be maximum -session and
minimum chain termination and chain transfer reactions.

Since both the termination and chain transfer are bimolecular and the rate may be
reduced relative to the rate of the unimolecular -session by reducing the pressure.
But it is technically inconvenient to operate at reduced absolute pressure, so the
steam is used as a diluent maintaining the same pressure.

Temperature: The -session and hemolysis of alkene requires higher activation

energies than the chain transfer and termination reaction. Thus higher temperature
increases ethylene yield.

36
Branched Chain alkanes
Usually branched chain alkanes gives lower yield of ethylene than their linear chain

37
Cycloalkanes
Usually cycloalkane will give lower yields of ethylene than the corresponding straight
chain alkanes. They tend to give dienes along with other products.

Aromatic Hydrocarbons
Aromatic ring is essentially stable under cracking condition, and is the main cracking
occurs only in the side chain.
38
39
Secondary Reactions
The alkanes formed in the primary cracking reactions can undergo further secondary
reactions. Many of which are not very well understood.
Carbon is a undesirable outcome of secondary reactions. Since it coats the wall the
cracking and transfer line exchange tube and impeded heat transfer and, ultimately
leads to blockages. Steam helps improving the ethylene because it dilutes the
chamber (minimize bimolecular reactions) it reacts to give synthesis gas.

40