Understanding shape selectivity effects of hydroisomerization using a reaction equilibrium model

• Published in: The Journal of chemical physics 2024-06, Vol.160 (21)
• Main Authors: Sharma, Shrinjay, Rigutto, Marcello S., Zuidema, Erik, Agarwal, Umang, Baur, Richard, Dubbeldam, David, Vlugt, Thijs J. H.
• Format: Article
• Language: English
• Subjects: Alkanes; Chemical reactions; Dilution; Equilibrium; Equilibrium conditions; Hydrocarbons; Isomers; Monte Carlo simulation; Phase equilibria; Reaction products; Shape effects; Vapor phases; Zeolites
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0209210

We study important aspects of shape selectivity effects of zeolites for hydroisomerization of linear alkanes, which produces a myriad of isomers, particularly for long chain hydrocarbons. To investigate the conditions for achieving an optimal yield of branched hydrocarbons, it is important to understand the role of chemical equilibrium in these reversible reactions. We conduct an extensive analysis of shape selectivity effects of different zeolites for the hydroisomerization of C7 and C8 isomers at chemical reaction equilibrium conditions. The reaction ensemble Monte Carlo method, coupled with grand-canonical Monte Carlo simulations, is commonly used for computing reaction equilibrium of heterogeneous reactions. The computational demands become prohibitive for a large number of reactions. We used a faster alternative in which reaction equilibrium is obtained by imposing chemical equilibrium in the gas phase and phase equilibrium between the gas phase components and the adsorbed phase counterparts. This effectively mimics the chemical equilibrium distribution in the adsorbed phase. Using Henry’s law at infinite dilution and mixture adsorption isotherm models at elevated pressures, we calculate the adsorbed loadings in the zeolites. This study shows that zeolites with cage or channel-like structures exhibit significant differences in selectivity for alkane isomers. We also observe a minimal impact of pressure on the gas-phase equilibrium of these reactions at typical experimental reaction temperatures 400 − 700 K . This study marks initial strides in understanding the reaction product distribution for long-chain alkanes.