Development of Support Tools for Next-generation Combustion Engineering using Reaction Knowledgebase

详细的动力学建模已被认为是发展下一代燃烧技术不可或缺的，如均匀装药压缩点火。在这项研究中，开发了一种燃烧工程工具，可以自动生成任何饱和烃混合物的详细模型。详细的模型，包括成千上万的基本反应，是一个简单的数据库方法无法达到的，只能通过基于类似反应的知识的经验规则的结构良好的知识库来实现。这些知识来自以往和现在的实验结果以及本研究中进行的量子化学计算的结果。量子化学计算是不可避免的，特别是对烷基过氧自由基的异构化和离解过程的竞争，这在点火中起着至关重要的作用。对所开发的自动生成工具进行了如下验证：1)首先，对该工具生成的模型进行了验证，以再现辛烷值的主要参考燃料正庚烷和异辛烷的点火延迟时间。2)其次，需要验证不同种类和不同结构燃料的模型是否能再现燃烧特性的变化趋势。这是通过计算50种烷烃零维点火的临界压缩比来完成的，这些烷烃的实验ron（研究辛烷值）已经报道过。通过本研究中开发的工具生成的详细动力学模型计算出的临界压缩比与ron之间存在良好的相关性。这些结果表明，本研究所建立的模型至少可以半定量地再现许多碳氢化合物的自燃趋势。此外，在单个燃料分子的点火特性中发现了一些新的特征，这些特征不能用现有的评级（如RON）来描述。少

The detailed kinetic modeling has been claimed to be indispensable for development of next-generation combustion technology, such as homogeneous charge compression ignition. In this study, a tool for combustion engineering, which automatically generates the detailed model for the mixture of any saturated hydrocarbons, has been developed.Detailed models, including thousands to tens of thousands elementary reactions, are beyond the reach of a simple database approach, and can only be achieved by a well-structured knowledgebase of empirical rules based on the knowledge on the similar reactions. The knowledge has been acquired from the previous and present experimental results as well as the results of quantum chemical calculations performed in this study. The quantum chemical calculations were inevitable, particularly for the competition of isomerization and dissociation processes of alkylperoxy radicals, which play essential role in the ignition.The auto-generation tool developed has bee … More n validated as follows :1)First, the models generated by the tool were confirmed to reproduce the ignition delay time for n-heptane and iso-octane, the primary reference fuels for the octane number.2)Second, it was necessary to validate that the models for fuels of various kinds and structures reproduce the trends of the ignition properties. This was done by calculating the critical compression ratio for the zero-dimensional ignition for 50 alkanes, for which the experimental RONs (research octane numbers) have been reported. A good correlation was found between RONs and critical compression ratios calculated by the detailed kinetic models generated by the tool developed in the present study.These results indicate that the models generated in the present study can reproduce the trends of auto-ignition, at least semi-quantitatively for many hydrocarbons. Also several new features have been found in the ignition properties of individual fuel molecules, which cannot be described by the existing rating such as RON. Less