Thermal Cracking:

Thermal cracking is a process in which hydrocarbons such as crude oil is subjected to high
heat in order to extract usable components during the cracking process.
Thermal cracking occurs when heavy residues is heated under severe thermal condition.
Thermal cracking gives mixtures of products containing high proportions of hydrocarbons
with double bonds - alkenes.

THERMAL CONVERSION PROCESSES:

Thermal cracking process designed to handle heavy residues with high asphaltene and metal
contents. These residues contain impurities which deactivate and poison the catalysts.
Thermal Cracking Reactions:

1. Decane -----> Pentyl radicals

2. Pentyl radicals------> Propyl radical + Ethene
 3. Propyl radical --------> Hexane
4. C10H2----------> 2C5H11 (radicals)
5. C5H11 (radical) ------------> C3H7 (radical) + C2H4
6. 2C3H7 (radical) ----------> C6H14
Conditions for Thermal Cracking:

High Pressure ... 7000 kPa

High Temperature ... 450C to 750C

Free Radical Mechanism: (Homolytic fission)

Produces mostly alkenes ... e.g. ethene for making polymers and ethanol

Produces Hydrogen ... used in the Haber Process and in margarine manufacture

Bonds can be broken anywhere in the molecule by C-C bond fission or C-H bond fission

Free Radical Mechanism:

A free radical is a species containing one or more unpaired electrons. Free radicals are
electron-deficient species, but they are usually uncharged, so their chemistry is very different from
the chemistry of even-electron electron-deficient species such as carbocations and carbenes.
The alkyl radical OCR3) is a seven-electron, electron-deficient species. The geometry of the alkyl
radical is a shallow pyramid, somewhere between sp2 and sp3 hybridization, and the energy
required to invert the pyramid is very small. In practice, one can usually think of alkyl radicals as
if they were sp2-hybridized

Fluid catalytic cracking

Oil is cracked in the presence of a finely divided catalyst, which is maintained in an aerated
or fluidized state by the oil vapors'.
Process employs a catalyst in the form of very fine particles [average particle size about 70
micrometers (microns)]
The fluid cracker consists of a catalyst section and a fractionating section that operate
together as an integrated processing unit.
The catalyst section contains the reactor and regenerator, which, with the standpipe and
riser, form the catalyst circulation unit. The fluid catalyst is continuously circulated
between the reactor and the regenerator using air, oil vapors, and steam as the conveying
media.
Preheated feed is mixed with hot, regenerated catalyst in the riser and combined with a
recycle stream, vaporized, and raised to reactor temperature (485-540C) by the hot
catalyst.
 As the mixture travels up the riser, the charge is cracked at 0.7-2 bar.
In modern FCC units, all cracking takes place in the riser and the "reactor" merely serves
as a holding vessel for the cyclones. Cracked product is then charged to a fractionating
column where it is separated into fractions, and some of the heavy oil is recycled to the
riser.
Spent catalyst is regenerated to get rid of coke that collects on the catalyst during the
process.
Spent catalyst flows through the catalyst stripper to the regenerator, where most of the coke
deposits burn off at the bottom where preheated air and spent catalyst are mixed.
Fresh catalyst is added and worn-out catalyst removed to optimize the cracking process.
Flow diagram of Fluid Catalytic Cracking

Alkylation:
Alkylation is the process of producing gasoline range material (alkylates)
from olefins such as propylene, butylenes and amylene.
Form a longer chain highly branched iso paraffin by reacting an alkyl group
(almost exclusively isobutane) with a light olefin (predominately butylene)
High octane hydrocarbons are needed to help prevent auto ignition of gasoline
(knocking) in an engine and to meet recommended engine octane ratings.
Alkylation is an important refining process to produce alkylates, a high-octane
gasoline blending component
Alkylate product is a mixture of branched hydrocarbons of gasoline boiling range.
Alkylate has a motor octane (MON) of 90-95 and a research octane (RON) of 93-
98. Because of its high octane and low vapor pressure, alkylate is considered an
excellent blending component for gasoline.
Isomerization:
Catalytic cracking is like thermal cracking except that catalyst facilitate the
conversion of heavier molecules into the lighter products.
Use of catalyst (a material that assist a chemical reaction but does not take part
in it) in cracking reaction increase the yield of improved-quality products under
much less severe operating conditions than in thermal cracking.
Catalyst used in are typically solid material (zeolite, aluminum, hydro silicate,
bauxite, silica-alumina) that come in form of powder, beads, pellets or shaped
material called extrudites.