Thermal Cracking Reactions
المؤلف:
sami matar & Lewis. F. Hatch
المصدر:
Chemistry of PETROCHEMICAL PROCESSES
الجزء والصفحة:
p57
9-5-2016
1459
Thermal Cracking Reactions
The first step in cracking is the thermal decomposition of hydrocarbon molecules to two free radical fragments. This initiation step can occur by a homolytic carbon-carbon bond scission at any position along the hydrocarbon chain. The following represents the initiation reaction:
The radicals may further crack, yielding an olefin and a new free radical. Cracking usually occurs at a bond beta to the carbon carrying the unpaired electron.
Further β bond scission of the new free radical R˙ can continue to produce ethylene until the radical is terminated.
Free radicals may also react with a hydrocarbon molecule from the feed by abstracting a hydrogen atom. In this case the attacking radical is terminated, and a new free radical is formed. Abstraction of a hydrogen atom can occur at any position along the chain. However, the rate of hydrogen abstraction is faster from a tertiary position than from a secondary, which is faster than from a primary position.
The secondary free radical
can crack on either side of the carbon carrying the unpaired electron according to the beta scission rule, and a terminal olefin is produced.
Free radicals, unlike carbocations, do not normally undergo isomerization by methyl or hydrogen migration. However, hydrogen transfer (chain transfer) occurs when a free radical reacts with other hydrocarbons. There are two major commercial thermal cracking processes, delayed coking and fluid coking. Flexicoking is a fluid coking process in which the coke is gasified with air and steam. The resulting gas mixture partially provides process heat.
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