CATALYTIC

CRACKING
 Mechanism of catalytic cracking

 Unlike thermal cracking (free radical reaction mechanism),

catalytic cracking proceeds through carbocation reactions over
acid sites of heterogeneous catalysts.

 The catalyst provides acidic sites (Lewis acid & Bronstead acid
sites) which promote carbocation formation at the surfaces.

Electron pair acceptor Proton donor

good acceptor for an electron pair, e.g., hydride H-
 Mechanism of Catalytic Cracking

• The initiation step involves generation of hydrocarbon carbocation.

• This may occur via two methods:

(i)thermal splitting (homolytic cleavage) of a hydrocarbon that loses a

proton to give olefins which are then protonated by the catalyst to
give carbocations.

(ii) Direct abstraction of a hydride ion from a hydrocarbon by the catalyst to

give a carbocation.
 Mechanism of Catalytic Cracking

 The next step is the interaction of these carbocations with other

hydrocarbons – they react by abstracting a hydride to afford
carbocations of the target molecules.
 Mechanism of Catalytic Alkylation

 Isobutane and butane/propene

 Initiation involves protonation of the alkene by the catalyst to form a secondary
carbocation, and this is followed by abstraction of a hydride from the isobutane (by
the carbocation) to form the more stable tertiary t-butyl carbocation.

 The t-butyl carbocation then attacks an alkene (i.e., propene) to give a

dimethylpentyl carbocation.

Carbocations can undergo a bewildering range of 1,2-methyl

shifts and 1,2-hydride shifts
 • PETROLEUM OVERVIEW
• CHEMISTRY OF PETROLEUM
• PETROLEUM REFINERY –
FRACTIONATION
• THERMAL CRACKING AND ITS
PETROLEUM MECHANISMS
CHEMISTRY • CATALYTIC CRACKING – FCC,
CATALYTIC REFORMATION,
ISOMERIZATION,
POLYMERIZATION,
ALKYLATION,
HYDROCRACKING
• MECHANISMS OF CATALYTIC
CRACKING
 • REFINERIES
• FRACTIONATION

PETROLEUM • CRACKING – THERMAL OR

CATALYTIC
CHEMISTRY • TREATMENT
 Petroleum Treating Processes

• Petroleum treating processes stabilize and upgrade the petroleum products by

separating them from less desirable products and by removing objectionable
elements.

 Hydrotreating employs a catalyst to react hydrogen, at high pressure and

temperature, with the sulfur, nitrogen or oxygen in the crude oil to form hydrogen
sulfide, ammonia and water, respectively.

 Chemical sweetening employs caustic and air to covert odorous mercaptans in the
petroleum to less odorous disulfides.

 Acid gas removal absorbs sulfur compounds into a solution in order to separate
them from the refinery fuel gas.
 Petroleum Treating Processes

 Deasphalting is used for separation of asphaltenes and resins from vacuum

distillation residues by extraction with a solvent such as refinery propane.

 Asphalt blowing is used for polymerizing and stabilizing asphalt in order to

improve its weathering characteristics. This is accomplished by heating the
asphalt in the presence of a flowing air stream.

 Dewaxing is used to remove any waxy hydrocarbon components from

lubricating oil base stocks. Dewaxing is done by either selective
hydrocracking over a zeolite catalyst or by solvent extraction.
 Hydrotreating

• A number of contaminants are found in crude oil. As fractions travel through

the refinery processing units, these impurities can damage the equipment, the
catalyst and the quality of the products.
• There are also legal limits on the contents of some impurities like sulphur in
the products.
• Hydrotreating is one way of removing many of the contaminants from many
of the intermediate or final products.
• In the hydrotreating process, the entering feedstock is mixed with hydrogen
and heated to 300-380°C.
 Hydrotreating

• The oil combined with the hydrogen then enters a reactor loaded with a catalyst
which promotes several reactions:

 Hydrogen combines with sulphur to form hyrogen sulphide (H2S)

 Nitrogen compounds are converted to ammonia
 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 and some cracking takes place, causing the creation of
some methane, ethane, propane and butane.
 Desulphurization

• The hydrogen sulphide created from hydrotreating is a toxic gas that needs
further treatment.

• The process involves :

 The removal of the hydrogen sulphide from the hydrocarbon stream (Acid
gas removal process).

 The conversion of the hydrogen sulphide to elemental sulphur, a non toxic

and useful chemical (the Claus process).
 Desulphurization: Gas Removal
Process
• Solvent extraction, using solution of diethanolamine (DEA) dissolved in
water, is applied to separate the hydrogen sulphide gas from the process
steam.
• The hydrocarbon gas steam containing the hydrogen sulphide is bubbled
through a solution of diethanolamine solution (DEA) under high pressure,
such that the hydrogen sulphide gas dissolves in the DEA.
• The DEA and hydrogen mixture is heated at a low temperature and the
dissolved hydrogen sulphide is released as a concentrated gas steam which is
sent to another plant for conversion into sulphur.
• Other solvents used are:
 Monoethanolamine (MEA)
 Methyl-Diethanolamine (MDEA)
 Diglycolamine (DGA)
 Hot potassium carbonate
 Desulphurization: The Claus process

• Conversion of the concentrated hydrogen sulphide gas into sulphur occurs

in 2 stages:
• Combustion of part of the H2S stream in a furnace, producing sulphur dioxide
(SO2), water and sulphur (S).
 2H2S + 3O2  2SO2 + 2H2O
• Reaction of the remainder of the H2S with the combustion products in the
presence of a catalyst. The H2S reacts with the SO2 to form sulphur
 2H2S + SO2  3S + 2H2O
• As the reaction products are cooled, the sulphur drops out of the reaction
vessel in a molten state.
• Sulphur can be stored and shipped in either a molten or solid state.
 • GASOLINE
• DIESEL
PRODUCTS OF • PETROLEUM WAX
PETROLEUM • LUBRICATING OIL
 Gasoline

 Gasoline produced by distillation of crude oil is called straight-run

gasoline.
 This mixture boils in the range 25-150°C.
 The major chemical components of straight-run gasoline are straight-chain
paraffins in the range of pentane to nonane (C5 to C9).
 Gasoline is the most important product of a petroleum refinery.
 A good quality old-deep crude oil may yield 20% straight-run gasoline
upon distillation. That is, every 100 barrels of crude oil distilled would
provide 20 barrels of gasoline.
 Gasoline

 Gasoline (also called petrol) is a petroleum-derived liquid mixture consisting

primarily of hydrocarbons and enhanced with benzenes to increase octane ratings,
used as fuel in internal combustion engines.
 Many Commonwealth countries use the term petrol (abbreviated from petroleum
spirit).
 The term gasoline is commonly used in North America.
 The word is commonly shortened in colloquial usage to "gas"
 The term mogas (motor gasoline) for use in cars is used to distinguish it from avgas
(aviation gasoline) used in aircraft.
 Gasoline

 Straight-run gasoline has an octane number (ON) of about 55. Most modern
automobile engines require gasolines with ON in the range of 87-97.
 Refiners’ priorities - increase the total amount of gasoline produced and ways to
increase the ON.
 Three options are available for improving the ON.
a) straight-chain paraffins can be converted to branched chain compounds
b) Ring-containing aromatic compounds can be blended into the gasoline, because many
aromatic compounds have very high octane numbers.
c) special anti-knock compounds can be added to the gasoline in small quantities.
 Gasoline

 The use of aromatic compounds in gasoline is reducing because of the Clean

Air Act Regulations: these compounds contribute much more than paraffins to
soot and smoke formation - air pollution from vehicle exhausts.

 Benzene, is thought to be responsible for causing leukemia in laboratory

animals and long-term exposure to gasoline vapors containing benzene can
potentially cause leukemia in humans.

 The use of tetraethyllead, anti-knock additive in gasoline is now almost

completely discontinued because of environmental concerns.
 Gasoline

 Lead compounds that are produced when tetraethyllead burns in the engine destroy
the effectiveness of the catalytic converters in the engine exhaust system.

 Most lead compounds are poisonous to humans and other animals.

 Thus the best strategy for improving the ON of gasoline is to convert straight-chain
paraffins to branched-chain compounds.
 Assignment – Gasoline

 Chemical characteristics of gasoline

 Production of gasoline
 Additives in gasoline
 Octane Number of gasoline
 How does automobile engine system work?
 What does it mean by knocking and anti-knocking in automobile engine?
 What is the relationship between knocking/anti-knocking and octane number
 Octane Number – Motor Octane Number and Research Octane Number
 How can octane number be measured - Cooperative Fuels Research (CFR)
engine and Calculation Method