Advances in modeling hydrocarbon cracking kinetic predictions by quantum chemical theory: A review

Abstract

Summary In the modeling of hydrocarbon thermal cracking processes, complicated reaction networks of multicomponent reactants make kinetic parameter predictions very challenging. To solve this problem, the additivity method and Evans‐Polanyi equation were proposed for the prediction of kinetic factors. As the calculation of kinetic parameters using quantum chemical theory was used for higher accuracy, new additivity methods at the quantum theory level were developed for the prediction of thermodynamic kinetic parameters. At the same time, a reaction class transition state theory RC‐TST, analogous to the Evans‐Polanyi equation, was proposed by considering quantum factors for kinetic constant evaluation. Quantum calculation methods promoted mechanistic studies of electronic effects to accurately reveal the kinetic constant rules with different structural factors. Under these circumstances, kinetic parameter predictions by different quantum chemical computation methods were firstly introduced and reviewed. Meanwhile, development of the new additivity method and RC‐TST theory at the quantum chemistry level were summarized, and the new outlook on electronic effects with an appropriate quantum chemical computational method into the new additivity method was conducted to develop more perspicuous and accuracy in a simplified method for the calculation of complicated thermal cracking reaction.

Thermal Cracking of Hydrocarbons for the Production of Light Olefins; A Review on Optimal Process Design, Operation, and Control

“…The modeling and simulation of olefin plants is discussed in the previous review of the authors, including (1) mechanisms and kinetic models, (2) computational fluid dynamics (CFD) simulations, (3) rigorous models, and (4) abstract models. The mechanisms and kinetic models include models for the main reactions , and kinetic models for coke deposition and removal. , The kinetic models for the thermal cracking of hydrocarbons can be classified into three major types of empirical, , molecular, and mechanistic , (free-radical) models. The kinetic models are the most important integral parts of the CFD simulations and the rigorous and abstract models.…”

Formation Mechanism of Monocyclic Aromatic Hydrocarbons during Pyrolysis of Styrene Butadiene Rubber in Waste Passenger Car Tires

“…Computer simulation has always played an indispensable role in the fields of materials and chemical engineering, especially for complex systems or processes that are difficult to carry out in experiment. , The calculation work related to the pyrolysis process and reaction mechanism of the waste tire system has reported in recent years, and most of the work is reactive force field (ReaxFF) molecular dynamics (MD) simulation. − The ReaxFF MD can efficiently study the product distribution of the pyrolysis process under different reaction conditions and provide theoretical guidance on the experiment . However, due to the lack of a set of dedicated ReaxFF parameters for the waste tire system, it is difficult to use this method to effectively study the reaction pathway of specific products.…”

On-The-Fly Kinetics of the Hydrogen Abstraction by Hydroperoxyl Radical: An Application of the Reaction Class Transition State Theory

“…The crucial initialization step of the combustion of hydrocarbons is the H abstraction (Walker and Morley, 1997;Handford-Styring and Walker, 2002;Scott and Walker, 2002;Aguilera-Iparraguirre et al, 2008;Battin-Leclerc et al, 2013;Shi, 2018;Curran, 2019;Hashemi et al, 2019). Metatheses by atoms (i.e., •O, •H) (Saeys et al, 2003(Saeys et al, , 2006Battin-Leclerc et al, 2013;Hou and You, 2017;Hashemi et al, 2019) and simple radicals (i.e., •OH (Chen et al, 2004;Battin-Leclerc et al, 2013;Edwards et al, 2014;Semenikhin et al, 2017;Frenklach et al, 2018;Gao et al, 2018;Wang et al, 2019), CH 3 (Battin-Leclerc et al, 2013;Li et al, 2015;Mai et al, 2018),•OOH (Handford-Styring andCarstensen and Dean, 2005;Battin-Leclerc et al, 2013;De Oliveira et al, 2016;Curran, 2019) are especially known to be the most significant channels for petrol depletion, thus mathematical combustion models are strongly sensitive to their rate constants (Semenikhin et al, 2017).…”