The mechanism of catalytic cracking of n‐alkenes on ZSM‐5 zeolite

The catalytic cracking of n‐alkenes on ZSM‐5 zeolite at 405°C can occur both by a monomolecular mechanism and a bimolecular process. In the latter, cracking is preceeded by dimerization. We show that pentenes are cracked exclusively by the bimolecular process. The dominant cracking mechanism for n‐hexenes also requires initial dimerization, although a small proportion (<19%) of the total cracking may proceed by a monomolecular process. Cracking of n‐heptenes is predominantly monomolecular, with only 13% of the total occurring via an initial dimer formation. The cracking of n‐octenes and n‐nonenes can be interpreted by assuming a monomolecular mechanism only. Thus it appears that at 405°C olefins smaller than C6 are stable with respect to direct cracking and must dimerize before a species is formed which is unstable enough to crack. No molecular hydrogen was produced in any of the cracking reactions reported here in the range of conversions studied.