高效稳定的铜镍催化剂在草酸二甲酯加氢中的应用

doi:10.11949/j.issn.0438-1157.20170010

摘要/Abstract

摘要：

为了探索高效、稳定的草酸二甲酯（DMO）加氢制乙醇酸甲酯（MG）催化剂，采用水热合成法制备Cu-Ni/SiO₂催化剂，探索了不同Cu：Ni摩尔比对于催化剂活性的影响。通过XRD、TEM和XPS等表征，结果表明：利用二氧化硅微球作载体，铜镍物种的分散更加均匀。并且调变不同的Cu：Ni摩尔比，对Cu⁺在催化剂中的比例有一定的影响，从而影响乙醇酸甲酯的收率。在氢酯比为150、反应压力2 MPa、反应温度200℃和液时空速为0.5 h^-1的反应条件下，Cu：Ni摩尔比为1：1时的催化剂Cu₁Ni₁/SiO₂表现出了最好的催化性能，草酸二甲酯的转化率达到90%，乙醇酸甲酯的选择性达到了80%，催化剂能稳定运行100 h。上述结果可为研制催化活性高、选择性强、寿命长、易于生产乙醇酸甲酯的催化剂提供一定的参考。

关键词: 催化剂, 加氢, 载体, 草酸二甲酯, 乙醇酸甲酯

Abstract:

In order to explore the efficient and stable catalysts hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG), the Cu-Ni/SiO₂ catalysts was prepared by hydrothermal synthesis method. The effect of different Cu and Ni mole ratio on catalytic activity was studied. By XRD, TEM and XPS characterization, the results show that the dispersion of copper and nickel species is more uniform by using silica microspheres as carriers. The ratio of Cu⁺ in the catalysts has certain influence on the yield of methyl glycolate. The reaction conditions are as follows: the hydrogen ester mole ratio 150, reaction pressure 2 MPa, reaction temperature 200℃ and the liquid space velocity 0.5 h^-1. The Cu₁Ni₁/SiO₂ catalyst showed the best catalytic performance, the conversion of dimethyl oxalate reached 90%, and the selectivity of methyl glycolate reached 80%, which has stable operation for 100 h. Above results can provide some references for the development of high catalytic activity, high selectivity, long service life and easy production of methyl glycolate.

Key words: catalyst, hydrogenation, support, dimethyl oxalate, methyl glycolate

中图分类号:

王登豪, 张传彩, 朱明远, 于锋, 代斌. 高效稳定的铜镍催化剂在草酸二甲酯加氢中的应用[J]. 化工学报, 2017, 68(7): 2739-2745.

WANG Denghao, ZHANG Chuancai, ZHU Mingyuan, YU Feng, DAI Bin. Efficient and stable hydrogenation of dimethyl oxalate via copper-nickel catalysts[J]. CIESC Journal, 2017, 68(7): 2739-2745.

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