CATALYTIC CRACKING

ASSOC PROF DR SIM SIONG FONG

 Overview of Catalytic Cracking

u Catalytic cracking breaks complex hydrocarbons into simpler

molecules with the aims:
u To increase the quality and quantity of lighter fraction
u To increase more desirable products
u To decrease the amount of residuals

u This process rearranges the molecular structure of hydrocarbon

compounds to convert heavy hydrocarbon feedstock into lighter
fractions.
u Catalytic cracking is similar to thermal cracking, except that catalysts
facilitate the conversion of the heavier molecules into lighter products
(the operating conditions is less severe than in thermal cracking).
 Overview of Catalytic Cracking

• Catalytic cracking process involves contacting a gas oil faction

with an active catalyst under suitable conditions of
temperature, pressure, and residence time, so that a substantial
part (> 50%) of the gas oil is converted into gasoline and
lower-boiling products, usually in a single-pass operation.

• During the cracking reaction, carbonaceous material is

deposited on the catalyst reduces its activity. Thus, removal of
the deposit is necessary.
 Overview of Catalytic Cracking

• This is usually accomplished by burning the catalyst in the

presence of air, until catalyst activity is re-established.

• The catalyst - may be an activated natural or synthetic material,

is employed in bead, pellet, or microspherical form and can be used
as a fixed bed, moving bed, or fluid bed.

• Process:
• Cracking
• Regeneration
• Fractionation
Catalytic Cracking

u Fluid Catalytic Cracking

u Moving Bed Catalytic Cracking
u Thermofor Catalytic Cracking C6H12 ® C6H6 + 3H2
u Hydrocracking
u Alkylation
u Catalytic Reformation
u Polymerisation CH3
CH3 CH3 CH3

u Isomerisation CH3 C CH2

+ CH3 C CH3 CH3 C CH2 CH CH3

H CH3

Isobutylene Isobutane 2,2,4 - trimethylpentane (isooctane)

 Catalysts

• The term “catalysis” was introduced by Berzelius in 1836. He found

that catalysts posses special powers that can influence the affinity of
chemical compounds.

• After many years in 1895 Ostwald proposed the definition of catalysts:

“a catalyst accelerates a chemical reaction without affecting the
position of the equilibrium”.

• It was assumed that the catalyst remained unchanged in the course of

the reaction.
 Catalysts

u The catalysis is a cyclic process with the following

steps:
1. the reactants are bound to one form of the catalyst,
2. the intermediate catalysts-reactant complexes are
formed (usually the intermediate catalyst
complexes are highly reactive and difficult to
detect),
3. the reaction takes place,
4. the products are released from another form of
catalyst, regenerating its initial state.
 Catalysts

• The suitability of a catalyst for an industrial process depends mainly on the

following properties:
1. activity
2. selectivity
3. stability

u These properties are related to a series of physical, chemical and mechanical

properties which are used to characterize the catalyst.
 Catalysts

u Physical properties: texture (specific surface area, porosity, pore size

distribution), morphology (form and size of the catalyst grain, and its
granulometric distribution) and thermal characteristics (conductivity and
specific heat).
u Chemical properties: elemental chemical composition and the nature and
structure of the chemical compounds (crystalline state, crystal size, and
surface functional groups).
u Mechanical properties: crushing strength, resistance to attrition and abrasion
u Industrial priority: selectivity > stability > activity.
 Catalysts classification

Catalyst in the
Catalyst in the same
different phase as
phase as the
the reactants
reactants
Mechanism of catalytic cracking

u Unlike thermal cracking (free radical reaction mechanism),

catalytic cracking proceeds through carbocation reactions over
acid sites of heterogeneous catalysts.
u Carbocations are longer lived and accordingly more selective
than free radicals.
u Acid catalysts such as amorphous silica-alumina and crystalline
zeolites promote the formation of carbocations.
 Mechanism of Catalytic Cracking

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

Electron pair acceptor Proton donor

• 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.
 Mechanism of Catalytic Cracking

(ii) Direct abstraction of a hydride ion from a hydrocarbon

by the catalyst to give a carbocation.

u 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.
u Note that secondary carbocations are formed predominantly – they
are much more stable than primary carbocations.
 Mechanism of Catalytic Cracking

• A feature of these long chain carbocations is that they readily

undergo scission by a β-cleavage mechanism – generating
terminal olefins and new primary carbocations.

u Primary carbocations isomerise by 1,2-hydride shifts to give the

more stable secondary carbocations, which can then undergo
further β-cleavages.
 Mechanism of Catalytic Cracking

u Other (secondary) mechanisms involved in catalytic cracking are:

(i) The migration of terminal double bonds, which can be envisaged to occur
by successive protonation and deprotonation steps;

(ii) The cleavage of alkylbenzenes

(iii) The dehydrogenation of cyclohexanes

Mechanism of catalytic cracking

u The mechanism of catalytic cracking of hydrocarbons is ionic e.g.

zeolite type catalyst.
u Zeolite is a synthetic aluminosilicate with formula:
Me2/nO·Al2O3·nSiO2·pH2O
u n=1, Me: Na, K, Ag, H,...
u n=2, Me: Mg, Ca, Ba,...).
u Depending on which reaction (β-splitting or isomerization) dominates
the main products are different.
u In case of β-splitting domination the products contain mainly alkenes
(propene, butane).
u In case of isomerization domination branched hydrocarbons arise.
Differences between free radicals and
carbocations:

u Both carbocation and free radical are electron deficient, but they are
different:
1. Carbocation (e.g., RCH2+) is positively charged, while free radical
(e.g., RCH2•) is neutral.
2. Structure rearrangement in reactions of radicals and carbocations.

Ø In most reactions of free radicals, the radicals initially formed will retain
its basic carbon framework throughout the subsequent reactions.
Ø In contrast, a carbocation will undergo a rearrangement of the carbon
skeleton to form a more stable carbocation. For example, a 2° carbocation
may rearrange to form a 3°carbocation.
 Zeolite

u Two kinds of Zeolites: Natural and Synthetic

u Synthetic and natural zeolites are hydrated aluminosilicates with
symmetrically stacked alumina and silica tetrahedras (AlO4 and SiO4),
attaining an open and stable three dimensional honey comb structure.

u Over 150 zeolite structural types have been identified.

u The basic structure of a zeolite crystal - silicon dioxide (SiO2)

tetrahedra, in which some Si4+ are substituted by Al3+.
 Zeolite

u Thus, in order to be a zeolite the ratio (Si +Al)/O must equal ½, and the
resulting alumino-silicate structure is negatively charged.

u The negative charge within the pores can be neutralized by positively

charged ions (cations) such as sodium (Na+).

u The simplest synthetic zeolite is the zeolite A with a molecular ratio of

one silica to one alumina to one sodium cation (Na3Al3Si3O12).
 Zeolite

u The acidity of zeolites comes from the

surface (internal or external surface)
oxygen atoms could bear hydrogen
atoms.
u First, the structure has the potential of
forming a strong Bronsted acid by self-
rearrangement of the bonding of the –
OH groups.
u Second, the structure has the potential
of forming a strong Lewis acid on the
sites of Al atoms (with only three pairs
of electrons) which is the good acceptor
for an electron pair, e.g., hydride H-).
 Zeolite

• Bronsted acid sites in HY-zeolites mainly originate from protons that

neutralize the alumina tetrahedra.
• When HY-zeolite (X- and Y-zeolites are cracking catalysts ) is heated
to temperatures in the range of 400–500°C, Lewis acid sites are
formed.
Zeolite
 Zeolite

u Highly selective due to its smaller pores, which allow diffusion of only smaller
molecules through their pores, and to the higher rate of hydrogen transfer
reactions. However, the silica-alumina matrix has the ability to crack larger
molecules.

u Deactivation of zeolite catalysts occurs due to coke formation and to poisoning

by heavy metals. Deactivation may be reversible or irreversible.

u Reversible deactivation occurs due to coke deposition. This is reversed by

burning coke in the regenerator.

u Irreversible deactivation results as a combination of four separate but interrelated

mechanisms: zeolite dealumination, zeolite decomposition, matrix surface
collapse and contamination by metals such as vanadium and sodium.
 Aromatization reaction

u Dehydrocyclization reaction. Olefinic compounds formed by

the beta scission can form a carbocation intermediate with the
configuration conducive to cyclization.
 Aromatization Reaction

Once cyclization has occurred, the formed carbocation can lose a

proton,and a cyclohexene derivative is obtained. This reaction is
aided by the presence of an olefin in the vicinity (R–CH=CH2).
 Mechanism of Catalytic Alkylation

§ Alkylation is a chain reaction; 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.
 Mechanism of Catalytic Alkylation

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

give a dimethylpentyl carbocation.
 Mechanism of Catalytic Alkylation

§ At this point , carbocations can undergo a bewildering range of 1,2-

methyl shifts and 1,2-hydride shifts – generating a large number of
intermediate ions, for example:
 Mechanism of Catalytic Alkylation

§ The end comes when the C7 carbocations finally quench themselves

by abstracting a hydride from isobutane giving the corresponding
C7 hydrocarbon and regenerating a t-butyl carbocation (which goes
on to react with another alkene an so on).