热稳定性增强的铈改性Cu/SiO<sub>2</sub>催化剂及在草酸酯加氢制乙二醇反应中的应用

摘要

采用蒸氨法制备了一系列铈改性的Cu/SiO₂催化剂,并对该催化剂在草酸二甲酯(DMO)加氢制乙二醇反应中的催化活性及热稳定性进行了考察.研究发现铈的加入对于催化剂表面铜物种的分布有显著的影响,而Cu⁺的含量是影响加氢活性的主要因素,铈通过影响催化剂中Cu⁺的含量而影响催化剂的反应活性.此外,催化剂表征结果表明铈可以提高铜物种与载体间的相互作用,同时4价铈的氧化性阻碍了Cu⁺的进一步还原,从而使得催化剂表面大部分的Cu⁺在热冲击以及还原后得以保留.因此,相比于铜硅催化剂,铈改性催化剂(Cu-1.0Ce/SiO₂)在草酸酯加氢制乙二醇反应中表现出较强的热稳定性.

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	耿尧辰
	赵玉军
	王胜平
	马新宾

关键词：铜基催化剂；铈改性；加氢；草酸二甲酯；热稳定性

Abstract：

A series of ceria-modified Cu/SiO₂ catalysts were prepared by ammonia evaporation method and their catalytic activity and thermal stability for the hydrogenation of dimethyl oxalate (DMO) to ethylene glycol (EG) were investigated. The cerium had a remarkable influence on the distribution of copper species by two kinds of interaction form and the amount of Cu⁺ was found to be the determining factor for the hydrogenation activity. Moreover, the characterization results suggested that the addition of ceria could enhance the interaction between copper and support, and reserve most of the cuprous species on the catalyst surface upon thermal-shock by hindering the further reduction of Cu⁺ due to the oxidability of Ce⁴⁺. Hence, the ceria-modified catalyst (Cu-1.0Ce/SiO₂) showed a much better thermal stability than Ce-free catalyst in hydrogenation of DMO to EG.

Keywords： copper-based catalyst； ceria-modified； hydrogenation； dimethyl oxalate； thermal stability

Received 2014-05-13;

Fund:

天津市自然科学基金(13JCZDJC33000),国家自然科学基金(21276186),中国石油科技创新基金(2012D-5006-0503).

Corresponding Authors: 赵玉军,E-mail: yujunzhao@tju.edu.cn. Email: yujunzhao@tju.edu.cn

About author: 耿尧辰(1988-),男,硕士研究生,研究方向为合成气制乙二醇/乙醇.

引用本文:

耿尧辰, 赵玉军, 王胜平, 马新宾.热稳定性增强的铈改性Cu/SiO₂催化剂及在草酸酯加氢制乙二醇反应中的应用[J]. 化学工业与工程, 2015,32(6): 1-6,12

Geng Yaochen, Zhao Yujun, Wang Shengping, Ma Xinbin.Ceria-Modified Cu/SiO₂ Catalyst with Enhanced Thermal Stability and Its Application in Hydrogenation of Dimethyl Oxalate to Ethylene Glycol[J]. Chemcial Industry and Engineering, 2015,32(6): 1-6,12

[1] Hui S, Zhang B, Zhang S, et al. In situ IR study of dimethyl oxalate hydrogenation to ethylene glycol over Cu/SiO₂ catalyst[J]. Journal of Energy Chemistry, 2012, 21(6):753-758
[2] Wen C, Cui Y, Dai W, et al. Solvent feedstock effect: The insights into the deactivation mechanism of Cu/SiO₂ catalysts for hydrogenation of dimethyl oxalate to ethylene glycol[J]. Chemical Communications, 2013, 49(45):5 195-5 197
[3] 迟涵文, 赵玉军, 王胜平, 等. Cu-MCM-41催化剂的制备及在草酸酯加氢制乙二醇催化性能[J]. 化学工业与工程,2013, 30(3): 1-6 Chi Hanwen, Zhao Yujun, Wang Shengpin, et al. Preparation of Cu-MCM-41 catalyst and catalytic performance for hydrogenation of dimethyl oxalate to ethylene glycol[J]. Chemical Industry and Engineering, 2013, 30(3): 1-6(in Chinese)
[4] 王博, 赵硕, 赵玉军, 等. 球磨时间对Cu/SiO₂规整结构催化剂草酸酯加氢性能与涂层黏结性影响[J]. 化学工业与工程,2015, 32(2): 6-12 Wang Bo, Zhao Shuo, Zhao Yujun, et al. Effect of milling time on the Cu/SiO₂ monolithic catalyst for hydrogenation of dimethyl oxalate and the adhesion of washcoat[J]. Chemical Industry and Engineering, 2015, 32(2): 6-12(in Chinese)
[5] He Z, Lin H, He P, et al. Effect of boric oxide doping on the stability and activity of a Cu-SiO₂ catalyst for vapor-phase hydrogenation of dimethyl oxalate to ethylene glycol [J]. Journal of Catalysis, 2011, 277(1): 54-63
[6] Zheng X, Lin H, Zheng J, et al. Lanthanum oxide-modified Cu/SiO₂ as a high-performance catalyst for chemoselective hydrogenation of dimethyl oxalate to ethylene glycol [J]. ACS Catalysis, 2013, 3(12): 2 738-2 749
[7] Yu W, Zhao J, Ma H, et al. Aqueous hydrogenolysis of glycerol over Ni-Ce/AC catalyst: Promoting effect of Ce on catalytic performance[J]. Applied Catalysis A: General, 2010, 383(1/2): 73-78
[8] Liu J, Zhu L, Pei Y, et al. Ce-Promoted Ru/SBA-15 catalysts prepared by a "two solvents" impregnation method for selective hydrogenation of benzene to cyclohexene[J]. Applied Catalysis A: General, 2009, 353(2): 282-287
[9] Ye L, Duan X, Lin H, et al. Improved performance of magnetically recoverable Ce-promoted Ni/Al₂O₃ catalysts for aqueous-phase hydrogenolysis of sorbitol to glycols[J]. Catalysis Today, 2012, 183(1): 65-71
[10] Morales I, Vila F, Mariscal R, et al. Hydrogenolysis fo glycerol to obtain 1,2-propanediol on Ce-promoted Ni/SBA catalysts[J]. Applied Catalysis B: Environmental, 2012, 117/118: 253-259
[11] Zafiris G, Gorte R. Evidence for low-temperature oxygen migration from ceria to Rh[J]. Journal of Catalysis, 1993, 139(2): 561-567
[12] Calles J, Carrero A, Vizcaino A. Ce and La modification of mesoporous Cu-Ni/SBA-15 catalysts for hydrogen production through ethanol steam reforming[J]. Microporous and Mesoporous Materials, 2009, 119(1/3): 200-207
[13] Kohler M, Cant N, Wainwright M, et al. Infrared spectroscopic studies of carbon monoxide adsorbed on a series of silica-supported copper catalysts in different oxidation states[J]. Journal of Catalysis, 1989, 117(1): 188-201
[14] Pritchard J, Catterick T, Gupta R. Infrared spectroscopy of chemisorbed carbon monoxide on copper[J]. Surface Science, 1975, 53(1): 1-20
[15] Subramanian N, Kumar C, Watanabe K, et al. A DRIFTS study of CO adsorption and hydrogenation on Cu-based core-shell nanoparticles[J]. Catalysis Science & Technology, 2012, 2: 621-631
[16] Gong J, Yue H, Zhao Y, et al. Synthesis of ethanol via syngas on Cu/SiO₂ catalysts with balanced Cu⁰-Cu⁺ sites [J]. Journal of the American Chemical Society, 2012, 134(34): 13 922-13 925
[17] Van Der Grift C, Wielers A, Jogh B, et al. Effect of the reduction treatment on the structure and reactivity of silica-supported copper particles [J]. Journal of Catalysis, 1991, 131(1): 178-189
[18] Bancquart S, Vanhove C, Pouilloux Y, et al. Glycerol transesterification with methyl stearate over solid basic catalysts: I. Relationship between activity and basicity[J]. Applied Catalysis A: General, 2001, 218(1/2): 1-11
[19] Poels E, Brands D. Modification of Cu/ZnO/SiO₂ catalysts by high temperature reduction[J]. Applied Catalysis A: General, 2000, 191(1/2): 83-96
[20] Toupance T, Kermarec M, Lambert J F, et al. Conditions of formation of copper phyllosilicates in silica-supported copper catalysts prepared by selective adsorption [J]. Journal of Physical Chemistry B, 2002, 106(9): 2 277-2 286
[21] Lu Z, Li S, Chen C, et al. A first-principle study on the interfacial properties of Cu/CeO₂(110) [J]. Acta Phys Sin, 2013, 62(11): 11 7301-1-11 7301-7. doi: 10.7498/aps. 62.117 301