Structure–activity relationships and reaction mechanisms for future fuel components: Dialkyl ethers, oxymethylene ethers, and furanes

未来燃料成分的结构-活性关系和反应机制：二烷基醚、甲醛醚和呋喃

• 批准号: 427458221
• 负责人: Professor Dr. Uwe Riedel
• 金额: --
• 依托单位: Institut für Verbrennungstechnik
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/427458221?language=en
• 关键词: Structure; activity; relationships; reaction; mechanisms

Linear and cyclic ethers, as fuel components that can be produced from biomass or electrochemically, will play an important role in future combustion systems. Despite their importance, the understanding of their decomposition and combustion chemistry is insufficient. This important knowledge gap should be closed in this project by experimental and theoretical chemical kinetics investigations of dialkyl ethers, oxymethylene ethers (OMEs), and furanes under combustion-relevant conditions, i.e. at temperatures above 1000 K.For detailed modeling of combustion processes, hydrogen abstraction reactions represent a class of crucial importance. Therefore, the first part of this project aims at determining rate coefficients for H abstractions by OH radicals and H atoms for a series of selected linear, branched, and cyclic ethers by shock-tube experiments in combination with spectrometric techniques and interpretations by ab initio transition state theory (TST) calculations. Following the concept of group additivity, the combination of experimental and theoretical results aims to derive rate rules that enable the calculation of H-abstraction rate coefficients for all ether compounds. In the second part of the project, the pyrolysis of representative molecules of this substance class will be investigated in shock-tube experiments. On the one hand, shock tube experiments coupled with gas chromatography (GC/MS) and time-of-flight mass-spectrometry (TOF-MS), and on the other hand, flow reactor experiments coupled with GC/MS will be carried out to determine the composition of reaction products obtained during pyrolysis. As a result, the required kinetics information of the initial unimolecular reactions can be determined and important secondary reactions can be identified. With the help of experimental results and the Reaction Mechanism Generator (RMG) code developed by MIT, reaction models are being developed and optimized. An important contribution to this is provided by the rate rule expressions for the description of H-abstraction reactions.In this project, the complementary expertise of the Institute for Combustion and Gas Dynamics (IVG) of the University of Duisburg-Essen and the Institute of Combustion Technology (DLR Stuttgart) will be brought together. The experimental work on H abstraction by OH radicals, the time-resolved measurements by mass spectrometry, the flow reactor measurements, and the ab initio TST calculations are assigned to the IVG, while the experiments on H abstraction by H atoms in isotope-labeled components, the measurement of product compositions by shock-tube-experiments with GC/MS and the development of reaction mechanisms are assigned to the DLR Stuttgart.

直链醚和环醚作为可由生物质或电化学生产的燃料组分，将在未来的燃烧系统中发挥重要作用。尽管其重要性，但对其分解和燃烧化学的理解是不够的。这一重要的知识差距应关闭在这个项目中的实验和理论化学动力学研究的二烷基醚，甲醛醚（OME），和呋喃在燃烧相关的条件下，即在1000 K以上的温度。对于燃烧过程的详细建模，氢提取反应是一类至关重要的。因此，本项目的第一部分旨在确定一系列选定的线性，支化和环状醚的OH自由基和H原子的H提取率系数的激波管实验结合光谱技术和从头算过渡态理论（TST）计算的解释。根据基团加和性的概念，结合实验和理论结果，旨在推导出速率规则，使所有醚类化合物的H-提取速率系数的计算。在该项目的第二部分，将在激波管实验中研究这类物质的代表性分子的热解。一方面，激波管实验结合气相色谱（GC/MS）和飞行时间质谱（TOF-MS），另一方面，流动反应器实验结合GC/MS将进行，以确定在热解过程中得到的反应产物的组成。结果，可以确定初始单分子反应所需的动力学信息，并且可以识别重要的次级反应。在实验结果和MIT开发的反应机理生成器（RMG）代码的帮助下，正在开发和优化反应模型。在这个项目中，杜伊斯堡-埃森大学燃烧和气体动力学研究所（IVG）和斯图加特燃烧技术研究所（DLR Stuttgart）的互补专业知识将汇集在一起。H抽象的OH自由基，时间分辨测量质谱，流动反应器的测量，和从头TST计算的实验工作被分配到IVG，而H抽象的H原子的同位素标记的组件，测量的产品组合物的激波管实验与GC/MS和反应机理的发展的实验被分配到德国航天中心斯图加特。