KINETICS OF PROPYLENE EPOXIDATION WITH CUMENE HYDROPEROXIDE CONTAINED IN INDUSTRIALLY OXIDIZED CUMENE
Rubrics: 1. CHEMISTRY
Authors:
1.
Kazan National Research Technological University
2.
KNITU
3.
KNITU
4.
KNITU
5.
KNITU
6.
KNITU
7.
KNITU; KNRTU
8.
Kazan National Research Technological University
Russian Federation
Russian Federation
9.
KNITU
10.
KNITU
Type:
Article
Pages:
from 21
to 26
Status:
Published
Received:
01.02.2026
Accepted:
15.03.2026
Published:
05.04.2026
Language:
Russian
Keywords:
SENSITIVITY ANALYSIS, CUMENE HYDROPEROXIDE, KINETIC MODEL, MOLYBDENUM CATALYST, INVERSE KINETIC PROBLEM, EPOXIDATION OF PROPYLENE
Funding:
Rabota vypolnena za schet granta, predostavlennogo Akademiey nauk Respubliki Tatarstan obrazovatel'nym organizaciyam vysshego obrazovaniya, nauchnym i inym organizaciyam na podderzhku planov razvitiya kadrovogo potenciala v chasti stimulirovaniya ih nauchnyh i nauchno-pedagogicheskih rabotnikov k zaschite doktorskih dissertaciy i vypolneniyu nauchno-issledovatel'skih rabot (Soglashenie №10/2025-PD-KNITU ot 22.12.2025).
Abstract:
The article is devoted to the development and sensitivity analysis of a kinetic model for the epoxidation of propylene with cumene hydroperoxide in the presence of a molybdenum catalyst with respect to variations in its parameters. The relevance of this research is due to the prospects for creating a joint production facility for propylene oxide, phenol, and acetone in Russia based on existing enterprises, which requires a deep understanding of the kinetic regularities for the subsequent development of a digital twin of the process. Experimental kinetic studies were carried out in a wide temperature range (323-393 K) using commercially oxidized cumene containing cumene hydroperoxide, as well as metallic molybdenum as a catalyst. The composition of the reaction mixture was analyzed using iodometric titration and gas chromatography methods. Based on literature data and chromatographic-mass spectrometric analysis of the reaction mixture, a detailed kinetic scheme comprising 17 non-catalytic reactions (including initiation, chain propagation, and chain termination reactions, as well as molecular reactions) was compiled, and 17 catalytic reactions were matched to them. The kinetic model was written according to the law of mass action based on the obtained kinetic scheme in the form of a system of nonlinear differential equations describing the rates of change in the concentrations of all substances in the reaction mixture. The reaction rate constants in the model were defined as functions of temperature according to the Arrhenius equation. The parameters of the Arrhenius equation (pre-exponential factors and activation energies) for all reactions were determined by solving the inverse kinetic problem using the zero-order direct search method. A sensitivity analysis of the kinetic model was performed, based on estimating the uncertainty intervals of its parameters. The sensitivity analysis of the kinetic model for the epoxidation of propylene with cumene hydroperoxide in the presence of a molybdenum catalyst to changes in its parameters showed that the reaction kinetics are influenced by the catalytic chain initiation reactions from cumene hydroperoxide, the catalytic chain propagation reactions from cumyloxyl and cumylperoxyl radicals, non-catalytic chain termination reactions, and certain non-catalytic and catalytic molecular reactions. The non-catalytic and catalytic chain propagation reactions from the hydroperoxyl radical are included in the scheme as the sole reactions by which this radical is consumed.
The article is devoted to the development and sensitivity analysis of a kinetic model for the epoxidation of propylene with cumene hydroperoxide in the presence of a molybdenum catalyst with respect to variations in its parameters. The relevance of this research is due to the prospects for creating a joint production facility for propylene oxide, phenol, and acetone in Russia based on existing enterprises, which requires a deep understanding of the kinetic regularities for the subsequent development of a digital twin of the process. Experimental kinetic studies were carried out in a wide temperature range (323-393 K) using commercially oxidized cumene containing cumene hydroperoxide, as well as metallic molybdenum as a catalyst. The composition of the reaction mixture was analyzed using iodometric titration and gas chromatography methods. Based on literature data and chromatographic-mass spectrometric analysis of the reaction mixture, a detailed kinetic scheme comprising 17 non-catalytic reactions (including initiation, chain propagation, and chain termination reactions, as well as molecular reactions) was compiled, and 17 catalytic reactions were matched to them. The kinetic model was written according to the law of mass action based on the obtained kinetic scheme in the form of a system of nonlinear differential equations describing the rates of change in the concentrations of all substances in the reaction mixture. The reaction rate constants in the model were defined as functions of temperature according to the Arrhenius equation. The parameters of the Arrhenius equation (pre-exponential factors and activation energies) for all reactions were determined by solving the inverse kinetic problem using the zero-order direct search method. A sensitivity analysis of the kinetic model was performed, based on estimating the uncertainty intervals of its parameters. The sensitivity analysis of the kinetic model for the epoxidation of propylene with cumene hydroperoxide in the presence of a molybdenum catalyst to changes in its parameters showed that the reaction kinetics are influenced by the catalytic chain initiation reactions from cumene hydroperoxide, the catalytic chain propagation reactions from cumyloxyl and cumylperoxyl radicals, non-catalytic chain termination reactions, and certain non-catalytic and catalytic molecular reactions. The non-catalytic and catalytic chain propagation reactions from the hydroperoxyl radical are included in the scheme as the sole reactions by which this radical is consumed.
Keywords:
SENSITIVITY ANALYSIS, CUMENE HYDROPEROXIDE, KINETIC MODEL, MOLYBDENUM CATALYST, INVERSE KINETIC PROBLEM, EPOXIDATION OF PROPYLENE
SENSITIVITY ANALYSIS, CUMENE HYDROPEROXIDE, KINETIC MODEL, MOLYBDENUM CATALYST, INVERSE KINETIC PROBLEM, EPOXIDATION OF PROPYLENE
