LI Di, SUN Weizhen, XI Zhenhao, et al. Alkylation kinetics of mixed butenes/isobutane by sulfuric acid[J]. CIESC Journal, 2015, (2): 584-590.DOI: 10.11949/j.issn.0438-1157.20141366.
The alkylation kinetics of isobutane with mixed butenes using sulfuric acid as catalyst was investigated by batch experiments at temperatures from 276.2 K to 285.2 K under the conditions of industrial interest. With the decrease of reaction temperature
both the production of main product trimethylpentanes (TMPs) and RON of alkylates increased
and byproducts dimethylhexanes (DMHs) changed a little
but heavy ends components (HEs) reduced significantly. By using the alkylation kinetics model based on the classic carbonium ion mechanism
the concentration profiles with time regarding three groups of key alkylates
including TMPs
DMHs
and HEs
were compared against experiments. The regression results showed that the kinetics model fitted experimental data very well. An anti-Arrhenius behavior was found in the chain initiation step of the addition reaction of H+ to isobutene
and the apparent activation energies of itself and the reverse reaction were 45.14 kJ·mol-1 and 41.44 kJ·mol-1. The calculation of reaction rates of the TMPs+ and DMHs+ forming steps was added
and most of the reaction rates of chain transfer and chain termination reactions remained the same as those in literature.