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Example text

In the first case (bimolecular initiation), by applying the theorem of stationary states, the order 2 is obtained. In the second case (interruption by the  collision of two radicals R1 ), the  order 1/2 is obtained and in the third case (interruption by the collision of the R3 radicals) the order 3/2 is obtained [66]. Of great interest is the application of the general scheme for ethane and propane, which are important feeds for commercial pyrolysis.

For radicals of higher molecular mass the isomerization reaction must also be taken into account [40]. 10 lists the kinetic parameters, recommended for calculations on the basis of these studies [35]. In commercial pyrolysis, it is of great interest to predict the ratio of ethene to propene produced, as a function of the ratio n-/i-alkanes in the feed. 35 This calculation proves that the ethene/propene ratio diminishes strongly with the degree of branching of the alkane feedstock. The pyrolysis of heavy petroleum fractions (atmospheric and vacuum gas oils) has prompted studies [107,108], aiming at the understanding of the mechanism of the thermal decomposition of the C13 – C14 n- and i-alkanes.

0 35 1 À C6 H13 ! 3 35 2 À C6 H13 ! 0 35 3 À C6 H13 ! 3 35         10 11 Copyright © 2003 by Taylor & Francis Group, LLC For the methyl and ethyl radicals, at temperatures of 600–9008C, the life is of the order of 10–3 s. It decreases as the temperature and the molecular mass of the radicals increase. Since the ethyl and sec-propyl radicals possess only C – H bonds in position, these will be the ones cracked. 4, the thermal effect for the reaction:   C 2 H5 ! C 2 H4 þ H is 165 kJ/mole; while for the reaction:   C2 H5 !

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