Compact Combustion Mechanisms of Typical n-Alkanes Developed by the Minimized Reaction Network Method.

The existing combustion kinetic modeling method which aims at developing phenomenological combustion mechanisms characterized by multiple reactions confronts several challenges, including the conflicts between computing resources and mechanism scales during numerical simulation, etc. In order to address these issues, the minimized reaction network method for complex combustion system modeling based on the principle of simultaneous chemical equilibrium is proposed, which is aimed to develop combustion mechanisms with minimal reaction steps under a limited number of species. The concept of mechanism resolution is proposed in this method, and the reaction network with minimal reaction steps under a given mechanism resolution is constructed so that the scale of mechanisms is compressed greatly. Meanwhile, distinguishing from other mechanisms, the reversible form of elementary reactions is adopted and the classical two-parameter (A, Ea) Arrhenius equation fits the rate constants. Typical n-alkanes including n-butane, n-heptane, n-octane, n-decane, n-dodecane and n-hexadecane were taken as examples to indicate the development process of mechanisms and systematic kinetic validations were carried out. Results show that this method leads to very compact mechanisms with satisfactory accuracy, and it eliminates the process of mechanism reduction and is beneficial for mechanism optimization. This method and the derived kinetic mechanisms are hoped to contribute to combustion engineering applications.

High-Pressure-Limit and Pressure-Dependent Rate Rules for Unimolecular Reactions Related to Hydroperoxy Alkyl Radicals in Normal Alkyl Cyclohexane Combustion. 1. Concerted HO2 Elimination Reaction Class and ß-Scission Reaction Class.

The reactions of the concerted HO2 elimination from alkyl peroxy radicals and the ß-scission of the C-OOH bond from hydroperoxy alkyl radicals, which lead to the formation of olefins and HO2 radicals, are two important reaction classes that compete with the second O2 addition step of hydroperoxy alkyl radicals, which are responsible for the chain branching in the low-temperature oxidation of normal alkyl cycloalkanes. These two reaction classes are also believed to be responsible for the negative temperature coefficient behavior due to the formation of the relatively unreactive HO2 radical, which has the potential to inhibit ignition of normal alkyl cycloalkanes. In this work, the kinetics of the above two reaction classes in normal alkyl cycloalkanes are studied, where reactions in the concerted elimination class are divided into subclasses depending upon the types of carbons from which the H atom is eliminated and the positions of the reaction center (on the alkyl side chain or on the cycle), and the reactions in the ß-scission reaction class are divided into subclasses depending upon the types of the carbons on which the radical is located and the positions of the reaction center. Energy barriers by using quantum chemical methods at the CBS-QB3 level, high-pressure-limit rate constants by using canonical transition state theory, and pressure-dependent rate constants at pressures from 0.01 to 100 atm by using Rice-Ramsberger-Kassel-Marcus/Master Equation theory are calculated for a representative set of reactions from methyl cyclohexane to n-butyl cyclohexane in each subclass, from which high-pressure-limit rate rules and pressure-dependent rate rules for each subclass are derived from the average rate constants of reactions within each subclass. A comparison of the rate constants for the reactions in the two reaction classes calculated in this work is made with the rate constants of the same reactions from available mechanisms published in the literature, where most of the rate constants are approximately estimated from analogous reactions in alkanes or small alkyl cyclohexanes, and it is found that a large difference may exist between them, indicating that the present work, which provides more accurate kinetic parameters and reasonable rate rules for these reaction classes, can be helpful to construct higher-accuracy mechanism models for normal alkyl cyclohexane combustion.

High-Pressure-Limit and Pressure-Dependent Rate Rules for Unimolecular Reactions Related to Hydroperoxy Alkyl Radicals in Normal-Alkyl Cyclohexane Combustion. 2. Cyclization Reaction Class.

The hydroperoxy alkyl radicals are important intermediates in the low-temperature combustion for normal-alkyl cycloalkanes, and the cyclization reactions of hydroperoxy alkyl radicals to form cyclic ethers are responsible for a major fraction of the OH formation, which has the potential to promote ignition. In most of the previous modeling studies for normal-alkyl cycloalkane combustion, the kinetic data of the cyclization reactions in the detailed combustion mechanism were mainly taken from the analogous reactions in cyclohexane, methyl cyclohexane, and alkanes in published literature studies. In this work, the kinetics of the cyclization reaction class of hydroperoxy alkyl radicals in normal-alkyl cycloalkanes is studied, where the reaction class is divided into subclasses depending upon the ring size of the transition states, the types of the carbons on which the -OOH site is located and the types of the carbons on which the radical site is located, and the positions of the cyclization (on the alkyl side chain, on the cycle, or between the alkyl side chain and the cycle). Energy barriers and high-pressure-limit site rate constants and pressure-dependent rates for reactions in all subclasses are calculated, and rate rules for all subclasses are developed. The high-pressure-limit rate constants are determined from CBS-QB3 electronic structure calculations combined with canonical transition-state theory calculations, and pressure-dependent rate constants are calculated by using the Rice-Ramsberger-Kassel-Marcus/Master Equation theory at pressures varying from 0.01 to 100 atm. Comparisons of the rate constants for cyclization reactions of hydroperoxy alkyl cyclohexylperoxy radicals calculated in this work with the values of the corresponding reactions in some of the popular combustion mechanisms show that it is unreasonable to use the kinetic data of analogous reactions in alkanes, cyclohexanes, or smaller normal-alkyl cyclohexanes. Therefore, the accurate kinetic calculations and the construction of rate rules for normal-alkyl cycloalkanes are necessary and significant for the reliable modeling of the low-temperature combustion of normal-alkyl cyclohexanes.