Abstract: CuOZnOZrO2 catalyst was modified by combustion method, using Al2O3, CeO2, NiO metal oxides as promoters. The effects of Al2O3, CeO2, NiO on phase composition and catalyst structure were illuminated by using Xraydiffraction (XRD), temperatureprogrammed reduction ofhydrogen(H2TPR), temperatureprogrammed desorption of hydrogen (H2TPD) and carbon dioxide (CO2TPD) techniques. And the effects of the three chosen promoters on catalytic performance for CO2 hydrogenation to methanol were studied in a fixedbed plug flow reactor. The results indicated that the three promotes of Al2O3, CeO2, NiO all contributed to improving theactivity of catalysts and CeO2modified catalyst had best catalytic performance. Moreover, the three promotes all could inhibit CuO crystal grain growth and improve the dispersion of CuO, which could benefit the reduction of catalysts and H2 adsorptiondissociation. Besides that, the three metal oxides could modulate the intensity amount of basic sites on the catalyst surface in different degrees. Comparing with NiOmodified catalyst, CeO2modified catalyst and Al2O3 modified catalyst both possessed higher basic intensity and more basia sites, which led to CO2 adsorptionactivation easily.

Key words: CO2 hydrogenation, Methanol, Combustion method, CuO-ZnO-ZrO2 catalyst, Promoter

摘要： 采用燃烧法制备了Al₂O₃、CeO₂、NiO 金属氧化物改性的CuO-ZnO-ZrO₂ 催化剂,通过X 射线衍射(XRD)、H2-程序升温还原(H2-TPR)、H2-程序升温脱附(H2-TPD)、CO₂-程序升温脱附(CO₂-TPD)表征手段,探讨Al₂O₃、CeO₂、NiO 助剂对催化剂物相组成及微观结构的影响,且在固定床连续流动反应装置上考察了添加3种不同助剂对CO₂ 加氢合成甲醇性能的影响。结果表明,Al₂O₃、CeO₂、NiO 助剂均有助于提高CuO-ZnO-ZrO₂ 催化剂的活性,且添加适量CeO₂ 的催化剂催化效果最好;3种助剂都可以抑制CuO 晶粒的生长和提高CuO 的分散度,从而更利于催化剂的还原和H2 的吸附解离;3种金属氧化物助剂均可不同程度地调变催化剂表面碱强度和碱性位数目,较之NiO 改性的催化剂,Al₂O₃ 和CeO₂ 改性的催化剂表面碱强度更强,碱性位数目也更多,从而更利于CO₂ 的吸附活化。

关键词: 二氧化碳加氢, 甲醇, 燃烧法, CuO-ZnO-ZrO₂ 催化剂, 助剂