Abstract:

As an important chemical raw material and deuterated intermediate, deuterated methanol (CD₃OD) has been widely used in nuclear magnetic resonance reagents, deuterated drug intermediates and photoelectric material modification, but its catalytic synthesis efficiency in CO-CO₂ system is still not sufficiently high. In this study, rare earth elements were doped into CuO/ZnO/Al₂O₃ (CZA) catalyst by impregnation method. The catalytic performance of CZA catalysts in CO-CO₂ system with D₂ was tested and the catalysts were characterized. The results showed that the rare earth elements were uniformly dispersed in the CZA catalyst. The incorporation of La and Ce could effectively increase the specific surface area and pore volume of the catalyst and the amount of CuO on the surface of the catalyst as well. But the activity of the catalyst was reduced with the incorporation of Pr. CZA-3%La catalyst had the largest specific surface area of 46.69m²/g and the largest pore volume of 0.26cm³/g, therefore, giving the best catalytic activity with a deuterated methanol space-time yield of 7.96 %, higher than that of CZA catalyst. The CZA catalyst doped with rare earth elements was of great significance to improve the deuterated methanol synthesis efficiency in CO-CO₂ system.

Key words: catalyst, synthesis, activity, deuterated methanol, rare earth element modification

摘要：

作为一种重要的化工原料和氘代中间体，氘代甲醇（CD₃OD）广泛用于核磁共振试剂、氘代药物中间体和光电材料改性，但其在CO-CO₂体系的催化合成效率仍有待提高。本研究采用浸渍法掺杂稀土元素对CuO/ZnO/Al₂O₃（CZA）催化剂进行改性，评价了其在CO-CO₂体系加D₂制氘代甲醇的催化性能，并表征了催化剂。结果表明，稀土元素成功掺杂并均匀分散于CZA催化剂中，La和Ce的掺入能有效提高催化剂的比表面积和孔容，增加表面CuO的数量；而Pr的掺入降低了催化剂活性。其中，CZA-3%La催化剂具有最大的比表面积（46.69m²/g）和最大的孔容（0.26cm³/g），催化活性最好，其氘代甲醇时空产率相比CZA催化剂提高了7.96%。稀土掺杂改性的CZA催化剂对提升CO-CO₂体系合成氘代甲醇的反应效率有重要意义。

关键词: 催化剂, 合成, 活性, 氘代甲醇, 稀土元素改性