Incremental identification of kinetic models for homogeneous reaction systems
Incremental identification of kinetic models for homogeneous reaction systems
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DOI：
10.1016/j.ces.2006.04.028
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发表时间：
2006-08-01
影响因子：
4.7
通讯作者：
Marquardt, Wolfgang
中科院分区：
文献类型：
--
作者：
Brendel, Marc;Bonvin, Dominique;Marquardt, Wolfgang
本文提出了一种用于复杂均相反应体系的化学计量学和动力学鉴定的增量方法。将识别问题分解为一系列子问题。首先，根据平衡方程和来自等温实验的浓度测量，估计了各种物质的反应通量。这个任务代表了一个需要适当正则化的病态逆问题。利用目标因子分析，可以确定合适的反应化学计量。在进一步的步骤中，无需假设动力学结构就可以估计反应速率。最后，通过从一组候选模型中选择最佳模型结构，构建反应速率随浓度变化的动力学规律。对于利用可用的过程知识，这种增量方法既有效又灵活。该方法以工业上相关的吡咯与二烯酮的乙酰化为例进行了说明。(c) 2006 Elsevier Ltd.版权所有。
An incremental approach for the identification of stoichiometries and kinetics of complex homogeneous reaction systems is presented in this paper. The identification problem is decomposed into a sequence of subproblems. First, the reaction fluxes for the various species are estimated on the basis of balance equations and concentration measurements stemming from isothermal experiments. This task represents an ill-posed inverse problem that requires appropriate regularization. Using target factor analysis, suitable reaction stoichiometries can then be identified. In a further step, the reaction rates are estimated without postulating a kinetic structure. Finally, the kinetic laws, i.e., the dependencies of the reaction rates on concentrations, are constructed by selecting the best model structure from a set of model candidates. This incremental approach is shown to be both efficient and flexible for utilizing the available process knowledge. The methodology is illustrated on the industrially relevant acetoacetylation of pyrrole with diketene. (c) 2006 Elsevier Ltd. All rights reserved.