镧铈复合氧化物修饰的Cu-Co合金催化剂用于合成气直接制乙醇

摘要 Cu-Co双金属的结构和组成决定了其催化合成气直接制乙醇的性能。通过柠檬酸络合辅助的等体积浸渍法制备了ZrO₂负载的钙钛矿型复合氧化物La_0.95Ce_0.05Co_0.7Cu_0.3O₃，经原位还原，得到了La-Ce-O掺杂的ZrO₂担载的Cu-Co双金属催化剂。结果表明，催化剂中活性组分以Cu-Co合金的形式存在，且Cu-Co合金高度分散于载体表面，而La-Ce-O以复合氧化物的形式存在。该催化剂用于合成气直接制乙醇，在温度为280℃，压力为4 MPa，空速为3 900 mL·（g·h）^-1，V（H₂）∶V（CO）∶V（N₂）=8∶4∶1的反应条件下，CO转化率为9%，总醇的选择性为29.7%，总醇中乙醇的选择性为63.5%，具有优良的催化性能。

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	金武
	刘贵龙
	安康
	王嘉明
	宋兆钰
	刘源

关键词：铜钴合金乙醇合成合成气铈钙钛矿型复合氧化物

Abstract： The catalytic performances of copper-cobalt catalysts for direct ethanol synthesis from syngas were determined by the structure and composition of bi-metallic Cu-Co. The perovskite-type composite oxide of La_0.95Ce_0.05Co_0.7Cu_0.3O₃ supported on ZrO₂ was prepared via an incipient wetness impregnation combing citrate complexing method, after in-situ reduction, Cu-Co bimetal loaded on La-Ce-O doped ZrO₂ was obtained. The results showed that the active components in the catalyst were in forms of Cu-Co alloy and Cu-Co alloy were highly dispersed on the surface of ZrO₂, while La-Ce-O were in forms of composite oxide. The catalyst exhibited excellent catalytic performance for direct ethanol synthesis from syngas, specially, the conversion of CO is 9%, the selectivity of alcohol is 31.4% and the selectivity of ethanol is 63.5% at a GHSV of 3 900 mL·(g·h)^-1 in the syngas mixture of H₂/CO/N₂=8/4/1, 4 MPa and 280℃ in the fixed-bed reactor.

Keywords： copper-cobalt alloy； ethanol synthesis； syngas； cerium； perovskite-type oxide

Received 2019-12-15;

Fund:国家自然科学基金（51904152）；天津市生态环境治理科技重大专项项目专项（18ZXSZSF00070）。

Corresponding Authors: 刘源,E-mail:yuanliu@tju.edu.cn。 Email: yuanliu@tju.edu.cn

About author: 金武(1994-),男,硕士研究生,现从事多相催化方面的研究。

引用本文:

金武, 刘贵龙, 安康, 王嘉明, 宋兆钰, 刘源.镧铈复合氧化物修饰的Cu-Co合金催化剂用于合成气直接制乙醇[J]. 化学工业与工程, 2020,37(6): 1-9

Jin Wu, Liu Guilong, An Kang, Wang Jiaming, Song Zhaoyu, Liu Yuan.La-Ce-O Modified Cu-Co Alloy Catalysts for Direct Ethanol Synthesis from Syngas[J]. Chemcial Industry and Engineering, 2020,37(6): 1-9

[1] Pan X, Fan Z, Chen W, et al. Enhanced ethanol production inside carbon-nanotube reactors containing catalytic particles[J]. Nature Materials, 2007, 6(7):507-511
[2] Fang Y, Liu Y, Zhang L. LaFeO₃^- supported nano Co-Cu catalysts for higher alcohol synthesis from syngas[J]. Applied Catalysis A:General, 2011, 397(1/2):183-191
[3] Wang P, Bai Y, Xiao H, et al. Effect of the dimensions of carbon nanotube channels on copper-cobalt-cerium catalysts for higher alcohols synthesis[J]. Catalysis Communications, 2016, 75:92-97
[4] Xiao K, Bao Z, Qi X, et al. Advances in bifunctional catalysis for higher alcohol synthesis from syngas[J]. Chinese Journal of Catalysis, 2013, 34(1):116-129
[5] Liu G, Niu T, Cao A, et al. The deactivation of Cu-Co alloy nanoparticles supported on ZrO₂ for higher alcohols synthesis from syngas[J]. Fuel, 2016, 176:1-10
[6] He L, Teng B, Zhang Y, et al. Development of composited rare-earth promoted cobalt-based Fischer-Tropsch synthesis catalysts with high activity and selectivity[J]. Applied Catalysis A:General, 2015, 505:276-283
[7] Nematollahi B, Rezaei M, Lay E N. Synthesis of nanocrystalline CeO₂ with high surface area by the Taguchi method and its application in methanation[J]. Chemical Engineering & Technology, 2015, 38(2):265-273
[8] Cwele T, Mahadevaiah N, Singh S, et al. Effect of Cu additives on the performance of a cobalt substituted ceria (Ce_0.90Co_0.10O₂-δ) catalyst in total and preferential CO oxidation[J]. Applied Catalysis B:Environmental, 2016, 182:1-14
[9] Liu G, Geng Y, Pan D, et al. Bi-metal Cu-Co from LaCo_1-xCu_xO₃ perovskite supported on zirconia for the synthesis of higher alcohols[J]. Fuel Processing Technology, 2014, 128:289-296
[10] Tien-Thao N, Zahedi-Niaki M H, Alamdari H, et al. Co-Cu metal alloy from LaCo_1-xCu_xO₃ Perovskites as catalysts for higher alcohol synthesis from syngas[J]. International Journal of Chemical Reactor Engineering, 2007, 5(1):1-12
[11] Tien-Thao N, Alamdari H, Zahedi-Niaki M H, et al. LaCo_1-xCu_xO₃-δ perovskite catalysts for higher alcohol synthesis[J]. Applied Catalysis A:General, 2006, 311:204-212
[12] Liu G, Pan D, Niu T, et al. Nanoparticles of Cu-Co alloy supported on high surface area LaFeO₃-Preparation and catalytic performance for higher alcohol synthesis from syngas[J]. RSC Advances, 2015, 5(4):31637-31647
[13] Kirchnerova J, Alifanti M, Delmon B. Evidence of phase cooperation in the LaCoO₃-CeO₂-Co₃O₄ catalytic system in relation to activity in methane combustion[J]. Applied Catalysis A:General, 2002, 231(1/2):65-80
[14] Yang E, Kim N Y, Noh Y S, et al. Steam CO₂ reforming of methane over La_1-xCe_xNiO₃ perovskite catalysts[J]. International Journal of Hydrogen Energy, 2015, 40(35):11831-11839
[15] Leofanti G, Padovan M, Tozzola G, et al. Surface area and pore texture of catalysts[J]. Catalysis Today, 1998, 41(1/2/3):207-219
[16] Jiao Y, Zhang J, Du Y, et al. Steam reforming of hydrocarbon fuels over M (Fe, Co, Ni, Cu, Zn)-Ce bimetal catalysts supported on Al₂O₃[J]. International Journal of Hydrogen Energy, 2016, 41(24):10473-10482
[17] Toniolo F S, Magalhães R N S H, Perez C A C, et al. Structural investigation of LaCoO₃ and LaCoCuO₃ perovskite-type oxides and the effect of Cu on coke deposition in the partial oxidation of methane[J]. Applied Catalysis B:Environmental, 2012, 117/118:156-166
[18] Lisi L, Bagnasco G, Ciambelli P, et al. Perovskite-Type oxides:II. Redox properties of LaMn_1-xCu_xO₃ and LaCo_1-xCu_xO₃ and methane catalytic combustion[J]. Journal of Solid State Chemistry, 1999, 146(1):176-183
[19] Koranne M M, Goodwin J G, Marcelin G. Characterization of silica- and alumina-supported vanadia catalysts using temperature programmed reduction[J]. Journal of Catalysis, 1994, 148(1):369-377
[20] Song Z, Shi X, Ning H, et al. Loading clusters composed of nanoparticles on ZrO₂ support via a perovskite-type oxide of La_0.95 Ce_0.05 Co_0.7 Cu_0.3 O₃ for ethanol synthesis from syngas and its structure variation with reaction time[J]. Applied Surface Science, 2017, 405:1-12
[21] Guo S, Li S, Zhong H, et al. Mixed oxides confined and tailored cobalt nanocatalyst for direct ethanol synthesis from syngas:A catalyst designing by using perovskite-type oxide as the precursor[J]. Industrial & Engineering Chemistry Research, 2018, 57(6):2404-2415