Effect of adsorption-catalytic deformation and partial deactivation on the determination of the absolute activity of a liquid phase hydrogenation catalyst

• Published in: Tonkie himičeskie tehnologii (Online) Vol. 18; no. 4; pp. 341 - 354
• Main Authors: Afineevskii, A. V., Prozorov, D. A., Osadchaya, T. Yu, Gordina, N. E.
• Format: Journal Article
• Language: English
• Published: MIREA - Russian Technological University 08.10.2023
• Subjects: active sites; adsorption-catalytic deformation; bulk catalysts; catalyst deactivation; liquid-phase hydrogenation; nickel catalyst; tof
• ISSN: 2410-6593; 2686-7575
• DOI: 10.32362/2410-6593-2023-18-4-341-354

Objectives . To take into account the change in the number of active sites during the adsorptioncatalytic deformation and deactivation of a catalyst surface by means of a catalytic poison when calculating the turnover frequency (TOF) of a hydrogenation catalyst. Methods. The activity was determined by a static method, using a titanium reactor having a volume of 400 mL, an experimental temperature controlled using a liquid thermostat with an accuracy of 0.5 K, with a paddle stirrer rotation speed of 3600 rpm and system hydrogen pressure equal to atmospheric. The consumption of hydrogen used to reduce the model compound was taken into account via the volumetric method. The heats of hydrogen adsorption were determined using a reaction calorimeter with an operating mode close to that of a chemical reactor. After measuring the specific surface area using low temperature nitrogen adsorption, the results were processed using Brunauer–Emmett–Teller theory approximations. Deactivation was carried out by introducing dosed amounts of catalytic poison into the system in titration mode. Results. A kinetic experiment for the reduction of a multiple carbon bond in a sodium maleate molecule using aqueous solutions of sodium hydroxide with additions of monohydric aliphatic alcohols as solvents under conditions of partial deactivation of the catalyst was carried out. The obtained values of heats of hydrogen adsorption on skeletal nickel in the course of the experiment are given. The described approach is used to calculate TOF values taking into account changes in the number of active surface sites during the course of a catalytic reaction and upon the introduction of a deactivating agent. A refined equation for the correct calculation of TOF is proposed along with its mathematical justification. The results of TOF calculations under various assumptions for a number of catalytic systems are shown. Conclusions. When calculating absolute activity values, a change in the number of active sites has a significant effect on the obtained values. The physical meaning of a number of constants in the proposed equation relates the activity of the catalyst to the distribution of hydrogen on its surface in terms of heats of adsorption.