Department of Chemical and Biological Engineering, Northwestern University, Evanston, IL 60208, USA.
Annu Rev Chem Biomol Eng. 2012;3:29-54. doi: 10.1146/annurev-chembioeng-062011-081108. Epub 2012 Jan 13.
Many natural and industrial processes involve a complex set of competing reactions that include several different species. Detailed kinetic modeling of such systems can shed light on the important pathways involved in various transformations and therefore can be used to optimize the process conditions for the desired product composition and properties. This review focuses on elucidating the various components involved in modeling the kinetics of pyrolysis and oxidation of polymers. The elementary free radical steps that constitute the chain reaction mechanism of gas-phase/nonpolar liquid-phase processes are outlined. Specification of the rate coefficients of the various reaction families, which is central to the theme of kinetics, is described. Construction of the reaction network on the basis of the types of end groups and reactive moieties in a polymer chain is discussed. Modeling frameworks based on the method of moments and kinetic Monte Carlo are evaluated using illustrations. Finally, the prospects and challenges in modeling biomass conversion are addressed.
许多自然和工业过程涉及一组复杂的竞争反应，其中包括几种不同的物质。对这类系统进行详细的动力学建模可以揭示各种转化过程中涉及的重要途径，因此可以用于优化所需产物组成和性质的工艺条件。本综述的重点是阐明聚合物热解和氧化动力学建模中涉及的各种成分。概述了构成气相/非极性液相过程链式反应机制的基本自由基步骤。描述了动力学主题的核心——各种反应族的速率系数的指定。基于聚合物链中端基和反应部分的类型构建反应网络进行了讨论。使用实例评估了基于矩方法和动力学蒙特卡罗方法的建模框架。最后，讨论了在生物质转化建模方面的前景和挑战。
