Al-doped Cu/SBA-15 catalysts for the hydrogenation of dimethyl adipate to 1,6-hexanediol

doi:10.16085/j.issn.1000-6613.2022-0584

Abstract

Abstract:

The industrial production of 1,6-hexanediol (HDO) is by the hydrogenation of dimethyl adipate (DMA). The rational design and development of the Cu-based catalysts is of great importance to improve the yield of HDO. In this work, a series of CuAl _x /SBA-15 catalysts on Al-doped mesoporous molecular sieve SBA-15 were prepared. The catalytic performance and mechanism of the catalysts were investigated, and the reaction conditions were also optimized. The results showed that the CuAl₅/SBA-15 catalyst increased the amount of Lewis acid in the catalyst matrix and improved the Cu⁺/Cu⁰ ratio, thus enhancing the selectivity of the DMA hydrogenation reaction. Besides, the doping of Al reduced the agglomeration of Cu active species, and therefore, improved the stability of the catalyst. The yield of HDO reached the maximum of 87.05% under the reaction conditions of 240℃, 6MPa, and 6h. After the CuAl₅/SBA-15 catalyst was recycled for 36h, the yield of HDO maintained at about 86.01%, implying great stability of catalyst. In summary, the results of this study provided reference for the design of Cu-based catalysts for ester hydrogenation reactions.

Key words: catalyst, molecular sieves, hydrogenation, reaction, optimization

摘要：

作为一种重要的有机合成原料，1,6-己二醇（HDO）的工业化生产主要通过己二酸二甲酯（DMA）加氢反应来实现，而理性设计开发相应的Cu基催化剂是提高HDO产率的关键。本文采用Al掺杂的介孔分子筛SBA-15为载体制备得到了一系列CuAl _x /SBA-15催化剂，探究了使用该催化剂用于DMA加氢反应合成HDO的催化性能和催化机理，并对反应条件进行了优化。研究结果表明：CuAl₅/SBA-15催化剂能够增加催化剂的路易斯酸酸量，提高Cu⁺/Cu⁰的比例，从而提升DMA加氢反应的选择性，同时Al的掺杂也能减少Cu活性组分的团聚，从而增强催化剂的稳定性。当反应温度为240℃、反应压力为6MPa、反应时间为6h时，HDO的反应产率达到最大，为87.05%；重复使用CuAl₅/SBA-15催化剂36h后，HDO的反应产率能够维持在86.01%左右。本文的研究结果对设计Cu基催化剂用于酯加氢反应具有一定的借鉴意义。

关键词: 催化剂, 分子筛, 加氢, 反应, 优化

CLC Number:

TQ225.2

LIU Shulin, YANG Na, ZHANG Longfei, SUN Yongli, JIANG Bin, XIAO Xiaoming, TANTAI Xiaowei, ZHANG Lyuhong. Al-doped Cu/SBA-15 catalysts for the hydrogenation of dimethyl adipate to 1,6-hexanediol[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 289-296.

刘书林, 杨娜, 张龙飞, 孙永利, 姜斌, 肖晓明, 澹台晓伟, 张吕鸿. Al掺杂的Cu/SBA-15催化剂用于己二酸二甲酯加氢合成1,6-己二醇[J]. 化工进展, 2023, 42(1): 289-296.

Figures/Tables 13

References 21

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催化剂名称	Cu质量分数/%	Al质量分数/%	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
Cu/SBA-15	24.18	0	450.91	0.51	4.35
CuAl_2.5/SBA-15	24.48	2.57	423.01	0.50	4.26
CuAl₅/SBA-15	24.76	4.86	399.12	0.42	3.87
CuAl_7.5/SBA-15	24.53	7.48	391.00	0.43	4.35

催化剂名称	Cu质量分数/%	Al质量分数/%	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
Cu/SBA-15	24.18	0	450.91	0.51	4.35
CuAl_2.5/SBA-15	24.48	2.57	423.01	0.50	4.26
CuAl₅/SBA-15	24.76	4.86	399.12	0.42	3.87
CuAl_7.5/SBA-15	24.53	7.48	391.00	0.43	4.35

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