Open AccessCatalytic Conversion of Alkenes on Acidic Zeolites: Automated Generation of Reaction Mechanisms and Lumping Technique
Author(s) -
Elsa Koninckx,
Joseph G. Colin,
Linda J. Broadbelt,
Sergio Vernuccio
Publication year - 2022
Publication title -
acs engineering au
Language(s) - English
Resource type - Journals
ISSN - 2694-2488
DOI - 10.1021/acsengineeringau.2c00004
Subject(s) - chemistry , protonation , catalysis , aromatization , brønsted–lowry acid–base theory , hydrocarbon , alkylation , propene , reaction intermediate , carbon fibers , computer science , biochemical engineering , computational chemistry , combinatorial chemistry , organic chemistry , ion , algorithm , composite number , engineering
Acid-catalyzed hydrocarbon transformations are essential for industrial processes, including oligomerization, cracking, alkylation, and aromatization. However, these chemistries are extremely complex, and computational (automatic) reaction network generation is required to capture these intricacies. The approach relies on the concept that underlying mechanisms for the transformations can be described by a limited number of reaction families applied to various species, with both gaseous and protonated intermediate species tracked. Detailed reaction networks can then be tailored to each industrially relevant process for better understanding or for application in kinetic modeling, which is demonstrated here. However, we show that these networks can grow very large (thousands of species) when they are bound by typical carbon number and rank criteria, and lumping strategies are required to decrease computational expense. For acid-catalyzed hydrocarbon transformations, we propose lumping isomers based on carbon number, branch number, and ion position to reach high carbon limits while maintaining the high resolution of species. Two case studies on propene oligomerization verified the lumping technique in matching a fully detailed model as well as experimental data.