CALCULATION OF THERMODYNAMIC AND KINETIC PARAMETERS OF CATALYTIC CRACKING REACTIONS ON LEWIS AND BRØNSTED ACID SITES

Link for citation: Nazarova G.Y., Ivashkina E.N., Maltsev V.V. Calculation of thermodynamic and kinetic parameters of catalytic cracking reactions on Lewis and Brønsted acid sites. Bulletin of the Tomsk Polytechnic University. Geo Аssets Engineering, 2023, vol. 334, no. 7, рр. 214-225. In Rus. The relevance of the research is caused by the emerging necessity of developing a mathematical model to optimize the heterogeneous process of catalytic cracking. This tools should take into account both the chemical transformations of a wide range of hydrocarbon groups (different feedstock types), as well as the stages of adsorption, reactants diffusion, conversion of hydrocarbons on the catalyst surface, acid characteristics and pore size of the catalysts. The study of the hydrocarbon conversion patterns on Lewis or Brønsted acid sites using quantum-chemical modeling methods allow us to quantify the thermodynamic parameters of reactants adsorption, the kinetic parameters of carbocations formation and cracking on acid sites. These results are necessary to develop a mathematical model based on the of heterogeneous catalytic reaction mechanism. The aim of this work is to identify the level of quantum chemical theory and to determine the thermodynamic and kinetic parameters of reactants adsorption, carbenium ions formationand hydrocarbons cracking on Lewis and Brønsted acid sites. Methods: quantum-chemical modeling methods to optimize the molecular geometry of reactants and products of catalytic cracking reactions, calculate vibrational frequencies, thermodynamic parameters of adsorption and catalytic cracking of hydrocarbons and heteroatomic compounds with the participation of Bronsted and Lewis acid sites. Results. The chosen level of quantum-chemical theory allowed obtaining the results that are consistent with the laws of the process and the experimental reactivity of hydrocarbons in cracking reactions on acid catalysts. The thermodynamic parameters of the adsorption of C6–C16 hydrocarbons and thiophenes on Lewis and Brønsted acid sites were identified. We found that during the cracking of n-hexane on the Lewis acid site, the reaction is limited by the carbenium ion formation stage.The activation energy of this stage was 281,3 kJ/mol whereas the value for the cracking stage was 277,2 kJ/mol. Further study shows that the activation energy of carbenium ion formation from izohexane and C8–C10 alkanes with normal structure on the Lewis acid site was 257,6 and 279,2…277,9 kJ/mol. The most energetically favorable is the formation of carbocation from hexene at Brønsted acid sites (76,59 kJ/mol). The results of the work will be used to create a mathematical model of a heterogeneous process based on the Langmuir–Hinshelwood equations