Journal of Petrochemical Universities

Journal of Petrochemical Universities ›› 2016, Vol. 29 ›› Issue (3): 12-17.DOI: 10.3969/j.issn.1006-396X.2016.03.003

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Effect of Promoters on Performance of CuOZnOZrO2 Catalyst Prepared for CO2 Hydrogenation to Methanol

Li Peipei, Qin Yucai, Li Qiang, Mo Zhousheng, Zhang Yuanyuan, Song Lijuan   

  1. (Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning Shihua University, Fushun Liaoning 113001, China)
  • Received:2016-03-05 Revised:2016-05-09 Published:2016-06-25 Online:2016-07-01

助剂对CuO-ZnO-ZrO2 催化剂CO2 加氢制甲醇性能的影响

李培培,秦玉才,李 强,莫周胜,张媛媛,宋丽娟   

  1. (辽宁石油化工大学 辽宁省石油化工催化科学与技术重点实验室,辽宁 抚顺 113001)
  • 通讯作者: 宋丽娟(1962-),女,博士,教授,博士生导师,从事新型催化材料与工艺方向的研究;E-mail:lsong56@263.com。
  • 作者简介:李培培(1989-),女,硕士研究生,从事清洁燃料生产新工艺方向的研究;E-mail:912750330@qq.com。
  • 基金资助:
    国家自然科学基金项目(21076100)

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

Cite this article

Li Peipei, Qin Yucai, Li Qiang, Mo Zhousheng, Zhang Yuanyuan, Song Lijuan. Effect of Promoters on Performance of CuOZnOZrO2 Catalyst Prepared for CO2 Hydrogenation to Methanol[J]. Journal of Petrochemical Universities, 2016, 29(3): 12-17.

李培培,秦玉才,李 强,莫周胜,张媛媛,宋丽娟. 助剂对CuO-ZnO-ZrO2 催化剂CO2 加氢制甲醇性能的影响[J]. 石油化工高等学校学报, 2016, 29(3): 12-17.