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Cyclohexene esterification–hydrogenation for efficient production of cyclohexanol
Green Chemistry ( IF 9.3 ) Pub Date : 2020-11-19 , DOI: 10.1039/d0gc03020a Yunfeng Zhu 1, 2, 3, 4, 5 , Liang Gao 1, 2, 3, 4, 5 , Langyou Wen 1, 2, 3, 4, 5 , Baoning Zong 1, 2, 3, 4, 5 , Hao Wang 5, 6, 7, 8 , Minghua Qiao 5, 6, 7, 8
Green Chemistry ( IF 9.3 ) Pub Date : 2020-11-19 , DOI: 10.1039/d0gc03020a Yunfeng Zhu 1, 2, 3, 4, 5 , Liang Gao 1, 2, 3, 4, 5 , Langyou Wen 1, 2, 3, 4, 5 , Baoning Zong 1, 2, 3, 4, 5 , Hao Wang 5, 6, 7, 8 , Minghua Qiao 5, 6, 7, 8
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A novel process based on cyclohexene esterification–hydrogenation for the production of cyclohexanol, the key intermediate in the production of ε-caprolactam, was devised and validated for the first time. In this process, cyclohexene obtained from the partial hydrogenation of benzene is esterified with acetic acid to cyclohexyl acetate, followed by hydrogenation to cyclohexanol. The experimentally determined equilibrium conversion of cyclohexene for cyclohexene esterification at the stoichiometric ratio is always ≥68% in the temperature range of 333–373 K over the commercial Amberlyst 15 catalyst, which is substantially higher than that of cyclohexene hydration. The apparent activation energy (Ea) for the esterification of cyclohexene with acetic acid is 60.0 kJ mol−1, which is lower than that of cyclohexene hydration. In the hydrogenation of cyclohexyl acetate to cyclohexanol, high conversion of 99.5% and high selectivity of 99.7% are obtained on the La-promoted Cu/ZnO/SiO2 catalyst prepared by the co-precipitation method. This process shows both a high overall atom economy of 99.4% comparable to that of the cyclohexene hydration process and a much higher catalytic efficiency than the phenol hydrogenation process. On the basis of the above fundamental works, a pilot-scale demonstration unit with a capacity of 8000 tonnes per annum was developed and operated smoothly for more than 1000 h with no indication of deactivation.
中文翻译：
环己烯酯化-氢化可有效生产环己醇
首次设计并验证了一种基于环己烯酯化-氢化的新型生产环己醇的方法，环己醇是生产ε-己内酰胺的关键中间体。在该方法中，将由苯的部分氢化得到的环己烯用乙酸酯化为乙酸环己酯，然后氢化为环己醇。根据实验确定，在化学计量比下，环己烯在333-373 K的温度范围内，相对于商业Amberlyst 15催化剂而言，环己烯酯化的平衡转化率始终≥68％，这大大高于环己烯水合的转化率。环己烯与乙酸酯化的表观活化能（E a）为60.0 kJ mol -1，这比环己烯水合的低。在通过共沉淀法制备的La促进的Cu / ZnO / SiO 2催化剂上，乙酸环己酯加氢成环己醇的过程中，高转化率达到99.5％，高选择性达到99.7％。该方法显示出与环己烯水合方法相当的99.4％的高总体原子经济性和比苯酚加氢方法高得多的催化效率。在上述基础工作的基础上，开发了一个年产8000吨的中试规模的示范装置，并平稳运行了1000多个小时，没有任何失活迹象。
更新日期：2020-12-17
中文翻译：
环己烯酯化-氢化可有效生产环己醇
首次设计并验证了一种基于环己烯酯化-氢化的新型生产环己醇的方法，环己醇是生产ε-己内酰胺的关键中间体。在该方法中，将由苯的部分氢化得到的环己烯用乙酸酯化为乙酸环己酯，然后氢化为环己醇。根据实验确定，在化学计量比下，环己烯在333-373 K的温度范围内，相对于商业Amberlyst 15催化剂而言，环己烯酯化的平衡转化率始终≥68％，这大大高于环己烯水合的转化率。环己烯与乙酸酯化的表观活化能（E a）为60.0 kJ mol -1，这比环己烯水合的低。在通过共沉淀法制备的La促进的Cu / ZnO / SiO 2催化剂上，乙酸环己酯加氢成环己醇的过程中，高转化率达到99.5％，高选择性达到99.7％。该方法显示出与环己烯水合方法相当的99.4％的高总体原子经济性和比苯酚加氢方法高得多的催化效率。在上述基础工作的基础上，开发了一个年产8000吨的中试规模的示范装置，并平稳运行了1000多个小时，没有任何失活迹象。
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