含氨高温液态水中苯乙腈水解反应动力学研究.pdfVIP

含氨高温液态水中苯乙腈水解反应动力学 任浩明，吕秀阳* （浙江大学化学工程与生物工程学系，浙江杭州310027） 摘 要: 高温液态水环境友好的反应介质吸引了研究者的注意，但很多反应存在选择性差、反应速度慢等问题，限制了高温液态水的 应用。为了充分利用高温液态水的独特性质，为其工业化做准备，必须解决高温水中大多数有机合成反应速度偏慢的问题。本文介 绍的高温液态水体系中加入少量氨水从而提高碱催化反应。在高温液态水中苯乙腈无催化水解制备苯乙酸反应的研究基础上，本文 研究了含氨高温液态水体系中的苯乙腈水解反应。系统地测定了433.15K～493.15K 以及不同氨含量下苯乙腈及其分解的中间产物苯 乙酰胺的水解反应动力学数据，结果表明苯乙腈水解反应中由于氨的引入提高了反应速度，并且增加了中间产物苯乙酰胺的产率。 同时由于氨的引入，串联反应的第一步苯乙腈水解反应级数也发生改变，通过对实验数据进行拟合计算，得到了苯乙腈和苯乙酰胺 水解反应活化能分别为57.2 kJ·mol-1 和67.7kJ·mol-1 。并用理论计算了反应条件下介质的pOH 值，讨论了反应的机理。 关键词: 含氨高温液态水；苯乙腈；苯乙酰胺；苯乙酸；反应动力学 Kinetics of hydrolysis of phenylacetonitrile in NH -enriched high 3 temperature liquid water REN Haoming, Lü Xiuyang * (Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027, China) Abstract: High temperature liquid water (HTLW) has drawn increasing attention as an environmentally benign medium for organic chemical reactions, especially acid/base catalysis without added acid or base. However, problems such as slow reaction rate and poor selectivity exist for these organic syntheses in HTLW, which greatly hinder the applications of the attractive technique in industrially interesting processes. We developed a novel solvent system to accelerate base-catalyzed reactions by the addition of NH3 to HTLW. Hydrolysis of phenylacetonitrile in NH3-Enriched HTLW was investigated under the condition of 8 MPa, 433.15K to 493.15K . Addition of ammonia could enhance the reaction rate greatly and increase the yield of phenylacetamide as an intermediate product,. The effects of NH3 concentration and temperature on the reactions were also investigated. Int