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