碳氢燃料燃烧模型中C0-C4核心机理的发展与实验验证

The development of the combustion kinetic models will help to find solutions to burn fuels more efficiently, while the kinetic mechanism for small fuels which include H2, CO and C1-C4 hydrocarbons (i.e. C0-C4 Core Mechanism) serves as the kinetic foundation for practical fossil fuels. Not a single C0-C4 core mechanism around the world is accepted as a universal model with accurate predictive capabilities. To solve this problem, we will use the advanced synchrotron VUV photoionization mass spectrometry combined with flow reactor, jet stirred reactor, and burner-stabilized premixed flame to study the pyrolysis, low temperature and high temperature oxidation for all the C0-C4 foundation fuels at variable pressures. An experimental database including both the literature and current experimental results over extended ranges of temperature, pressure, and stoichiometry will be built for model validation. Along with these efforts, ab initio electronic structure calculations, reaction rate theory calculations, kinetic modeling and uncertainty quantification will be performed to build a unified, predictive and well-validated C0-C4 core mechanism. This research will provide the detailed chemical structures like species profiles for all these foundation fuels which are seriously scare during the validation for the previous C0-C4 core mechanisms; at the same time the pressure effect on the core C0-C4 mechanism will be revealed. The new core mechanism will provide the theoretical supports for the predictive model development for the practical transportation fuels and for the device optimized design for internal combustion engines or gas turbines.

燃烧反应动力学模型的发展将有助于燃料高效清洁燃烧的实现，而包含H2/CO/C1-4等基础燃料的反应动力学机理（即C0-C4核心机理）是构建化石燃料燃烧模型的重要基础。本课题围绕解决世界范围内核心机理在适用性和准确性存在严重不足的问题，拟利用同步辐射光电离质谱技术对C0-C4碳氢燃料的燃烧开展流动反应器热解、射流搅拌器低温氧化、层流预混火焰高温氧化在变压力条件下的系统研究，构建包含广泛的温度、压力范围和不同当量比条件的较为完备的验证实验数据库；在此基础上，借助高精度量化计算、速率常数计算、动力学模型发展及不确定性分析等手段，构建一个经过广泛验证的适用性更强的全新核心机理。研究结果将解决前人核心机理的实验验证中微观燃烧化学结构数据严重缺乏的问题，同时揭示压力效应对燃料模型的影响。新的核心机理将为实用运输燃料的燃烧模型发展等基础燃烧研究和内燃机、燃气轮机等实用动力设备的优化设计提供理论支持。

燃烧反应动力学模型的发展有助于燃料高效清洁燃烧的实现，而包含H2/CO/C1-4等基础燃料的反应动力学机理（即C0-C4核心机理）是构建化石燃料燃烧模型的重要基础。本课题围绕着解决世界范围内核心机理在适用性和准确性存在严重不足的问题，改进了同步辐射真空紫外光燃烧诊断方法，对C0-C4碳氢燃料的燃烧开展了流动反应器热解、射流搅拌器低温氧化、层流预混火焰高温氧化在变压力条件下的系统研究，定量测量到火焰中及其活泼的H、O、OH及ROO自由基；构建了C0-C4核心机理数据库，包括小分子组份相关的热力学和基元反应速率常数及基础燃烧实验数据；在此基础上，借助高精度量化计算、速率常数计算、动力学模型发展及不确定性分析等手段，构建了经过广泛验证、全新的C0-C4小分子核心机理，并应用于实际燃料的动力学模型中；发展了新的经过广泛实验验证的天然气燃烧反应动力学模型；提出了基于人工神经网络的全局灵敏性熵的方法用于实验设计。同时，基于该项目，课题组在燃烧领域著名期刊发表SCI论文21篇，中文期刊2篇，培养了8名博士研究生，7名硕士研究生。