NSF/EPA: Nearcritical Water for Environmentally Benign Chemical Processing

NSF/EPA：用于环境友好的化学加工的近临界水

• 批准号: 9613063
• 负责人: Charles Eckert
• 金额: $ 18万
• 依托单位: Georgia Tech Research Corporation
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1996
• 资助国家: 美国
• 起止时间: 1996-09-15 至 1999-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9613063&HistoricalAwards=false
• 关键词: NSF; EPA; Nearcritical; Water; Environmentally

9613063 Eckert Nearcritical water (NCW) is an environmentally-benign solvent that offers tremendous opportunities for pollution prevention for a wide variety of manufacturing processes in the chemical, petrochemical, pharmaceutical, and plastics industries. In the range 250-350C, NCW has a density and dielectric constant similar to that of ambient acetone, permitting the dissolution and reaction of both organic and ionic species, as well as the swelling of polymers. Unlike supercritical water, which is used for complete oxidation (usually 400C), the more moderate temperatures permit a wider range of useful reactions. Finally, NCW has an ionization constant which is three orders of magnitude greater than water at ambient temperatures and pressures. This latter property should facilitate promotion of acid- and base- catalyzed reactions in the absence of added mineral acids and bases. This investigation proposed first to gather, evaluate critically, expand, and model the database of thermodynamic data (primarily solubilities) for organics in NCW. Next kinetic data will be obtained for a variety of important reactions which are of industrial interest. Such information will facilitate the commercialization of this technology by industry, especially by the active collaborator on this proposal, DuPont. The reactions that will be run will be: o Friedel-Crafts alkylation reactions o Friedel-Crafts acylation reactions o Oxidation of alkyl aromatics o Hydrolytic depolymerization of condensation polymers o Isomerization reactions o Hydrolysis of cellulose We already have preliminary kinetic data that demonstrate that one alkylation reaction can be run successfully without any added acid catalyst, and that an acylation reaction can be run with only traces of a catalyst in place of the 2-3 fold molar excess of AlCl 3 usually used. As a result of these investigations, new processes will be available using "green chemistry" for sustainable development. NCW will replace ma ny less desirable solvents, such as aromatic hydrocarbons and chlorinated compounds, it will avoid the use of polluting mineral acids and hazardous catalysts, it will permit the minimization of even the elimination of unwanted byproducts, it will provide better control of reactions which can be run homogeneously instead of heterogeneously, and it will facilitate closed processes by reuse of waste material. ***

9613063埃克特 近临界水（NCW）是一种环境友好型溶剂，为化学、石化、制药和塑料行业的各种制造工艺提供了巨大的污染预防机会。 在250- 350 C范围内，NCW的密度和介电常数与环境丙酮相似，允许有机物质和离子物质的溶解和反应，以及聚合物的溶胀。 与用于完全氧化的超临界水（通常 400 ℃），更温和的温度允许更广泛的有用反应。 最后，NCW的电离常数在环境温度和压力下比水大三个数量级。 后一种性质应有助于在不存在添加的无机酸和碱的情况下促进酸和碱催化的反应。 这项调查建议首先收集，批判性地评估，扩展和模拟NCW中有机物的热力学数据（主要是溶解度）的数据库。 接下来将获得工业上感兴趣的各种重要反应的动力学数据。 这些信息将促进工业界，特别是这项建议的积极合作者杜邦公司将这项技术商业化。 将运行的反应为： 〇 Friedel-Crafts烷基化反应 〇 Friedel-Crafts酰化反应 o烷基芳烃的氧化 〇缩聚物的水解解聚 o异构化反应 o纤维素的水解 我们已经有了初步的动力学数据，表明一个烷基化反应可以在不添加任何酸催化剂的情况下成功地进行，并且酰化反应可以在仅使用痕量催化剂代替通常使用的2-3倍摩尔过量的AlCl 3的情况下进行。 由于这些调查，新的工艺将使用“绿色化学”可持续发展。 NCW将取代许多不太理想的溶剂，如芳烃和氯化化合物，它将避免使用污染性无机酸和危险催化剂，它将允许最小化甚至消除不需要的副产物，它将提供对反应的更好控制，该反应可以均匀地而不是非均匀地进行，并且它将通过再利用废料来促进封闭过程。 ***