CHE 1014
P ETROLEUM T ECHNOLOGY
THERMAL CRACKING
Intro
• Cracking is a petroleum refining process in which heavy-molecular weight
hydrocarbons are broken up into light hydrocarbon molecules by the
application of heat and pressure, with or without the use of catalysts, to
derive a variety of fuel products.
• Cracking is one of the principal ways in which crude oil is converted into
useful fuels such as motor gasoline, jet fuel, and home heating oil.
• The term cracking is used to describe any type of splitting of molecules
under the influence of heat, catalysts and solvents, such as in processes of
destructive distillation or pyrolysis.
• C16H34 C5H12 + C11H22
• C16H34 -> C8H18 + C8H16
Application
• Cracking processes allow the production of "light" products such as LPG
and gasoline from heavier crude oil distillation fractions such as gas oils
and residues.
• Thermal cracking is used to "upgrade" very heavy fractions or to produce
light fractions or distillates, burner fuel and/or petroleum coke.
• Two extremes of the thermal cracking
high-temperature process ( 750 °C to 900 °C or more)
- produces ethylene and other feedstocks for the
petrochemical industry,
milder-temperature delayed coking ( 500 °C)
- under the right conditions, valuable needle coke, a highly
crystalline petroleum coke used in the production of
electrodes for metal industries.
Thermal Cracking
• Thermal cracking is a refining process in which heat (~800°C) and
pressure (~700kPa) are used to break down, rearrange, or combine
hydrocarbon molecules.
• The first thermal cracking process was developed around 1913.
• However, this method produced large amounts of solid, unwanted coke.
• Distillate fuels and heavy oils were heated under pressure in large drums
until they cracked into smaller molecules with better antiknock
characteristics.
What is Knocking?
• The sound of abnormal combustion.
• Light Knocking won’t harm an engine.
• Heavy or prolonged can result in engine damage.
Thermal Cracking
• Heat sensitive high molecular weight paraffins fragment when temperature
exceeds 400 degree C.
• A molecule of Cn H2n+2 where ‘n’ ranges from and above 25 easily splits in to two,
almost at the middle, resulting in one saturated molecule and other unsaturated
molecule.
• All cracking reactions ultimately give rise to coke and hydrogen.
Cn H2n+2 Cn/2 Hn+ 2 + Cn/2 Hn
• The above rcn is foremost and conclusive at moderate temperatures around 400
deg C. , But fragmentation continues with increasing temperature, giving rise to
often simple products and occasionally complex molecules.
• A paraffin of lesser molecular order, cracking can be illustrated as
C12 C6 + C6
C6 C4 + C2 / C3 + C3
Thermal cracking operations
Cracking Temperature Nature of Operation Products
(degree C)
425-460 Visbreaking Fuel oil
460- 520 Thermal Cracking Gas, Gasoline. Tar oils,
Circulating oils
520-600 Low Temperature Coking Gas, Gasoline soft coke.
600-800 Gas Production Gas and unsaturated
800-1000 High Temperature Coking Gas, Heavy aromatics pitch or
coke
Above 1000 Decomposition H2, Gas, Carbon-black
