High-Temperature Water as a Medium for Industrial Chemistry (TSE99-F)

高温水作为工业化学介质 (TSE99-F)

• 批准号: 9985456
• 负责人: Phillip Savage
• 金额: $ 23.73万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-02-15 至 2004-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9985456&HistoricalAwards=false
• 关键词: Temperature; Water; Medium; Industrial; Chemistry

Water near its critical point is an environmentally benign medium for organic chemical reactions. Additionally the properties of water (dielectric constant, density, viscosity, etc.) near its critical point (called high temperature water - HTW) are strong functions of temperature and pressure, which offers the possibility of manipulating these variables to optimize the properties of this reaction medium for a given chemical transformation. The use of HTW as a medium for organic chemical synthesis, rather than organic solvents, is thus one approach to pollution prevention. The PI's long-range goal is to determine reaction mechanisms and quantitative kinetics in HTW to assess the economic feasibility of doing chemical synthesis is HTW.The key objectives of this project are to determine the reaction networks for two different organic chemical reaction systems in HTW, to obtain quantitative reaction rate laws for each reaction network, and to identify reaction mechanisms consistent with the kinetics. The systems chosen for investigation are the reactions of cyclohexanol and the partial oxidation of xylenes. Cyclohaxonol and its reaction products can undergo different reactions (dehydration, dehydrogenation, rearrangement and oxidation) in HTW, so the results would be generally relevant to a broad range of potential chemistries in HTW. The catalytic partial oxidation of xylenes to the corresponding carboxylic acids is done on a very large scale (billions of pounds annually) commercially to produce terephthalic acid and phthalic anhydride, which are important intermediates in the plastics industry. Commercial processes for terephthalic acid production currently use high-pressure, high-temperature acetic acid, which is corrosive, as the reaction medium. The kinetics in HTW are needed to assess economic feasibility of this alternative solvent.

接近临界点的水是有机化学反应的环境友好介质。 此外，水的性质（介电常数、密度、粘度等）在其临界点附近（称为高温水- HTW）是温度和压力的强函数，这提供了操纵这些变量以优化该反应介质对于给定化学转化的性质的可能性。因此，使用HTW而不是有机溶剂作为有机化学合成的介质是预防污染的一种方法。 PI的长期目标是确定HTW中的反应机理和定量动力学，以评估化学合成的经济可行性。本项目的主要目标是确定HTW中两种不同有机化学反应体系的反应网络，获得每个反应网络的定量反应速率定律，并确定与动力学一致的反应机理。 选择环己醇反应和二甲苯部分氧化反应作为研究体系。 环己醇及其反应产物在HTW中可以经历不同的反应（脱水、脱氢、重排和氧化），因此结果通常与HTW中的广泛潜在化学相关。 二甲苯催化部分氧化成相应的羧酸在商业上以非常大的规模（每年数十亿磅）进行，以生产对苯二甲酸和邻苯二甲酸酐，它们是塑料工业中的重要中间体。 对苯二甲酸生产的商业方法目前使用腐蚀性的高压高温乙酸作为反应介质。 需要HTW中的动力学来评估这种替代溶剂的经济可行性。