提高碳氧键加氢铜基催化剂稳定性的研究进展

doi:10.16085/j.issn.1000-6613.2023-0011

摘要/Abstract

摘要：

碳氧键加氢反应是一类重要的加氢反应，应用广泛，包括CO、CO₂、酯类、羧酸、酸酐和糠醛等加氢制醇的反应。在反应过程中，催化剂的选择是决定反应程度及加氢产物分布的关键，对突破国外技术垄断和解决能源紧缺问题具有重要的意义。尤其是非贵金属铜基催化剂的研究，设计具有高活性、高选择性的铜基催化剂代替贵金属，具有学术研究价值和工业应用研究的借鉴意义。本文针对铜基催化剂的最大问题——高温下容易烧结和团聚的问题，综述了碳氧键加氢反应中铜基催化剂研究工作，介绍了避免催化剂失活、提高催化剂稳定性的方法，阐述了文献中通过添加不同助剂、载体效应和构造特殊催化剂结构来提高铜基催化剂的稳定性，总结归纳了影响铜基催化剂稳定性的因素：高比表面积和分散度，强金属之间相互作用，高浓度氧空位以增加缺陷位和吸附位点，以及限域作用限制金属迁移和聚集。

关键词: 催化剂, 催化剂载体, 加氢, 失活, 稳定性

Abstract:

Hydrogenation of carbon-oxygen bonds to produce alcohol is a significant hydrogenation reaction with wide applications, such as the hydrogenation of CO, CO₂, esters, carboxylic acids, anhydrides, and furfural. In the reaction process, the catalyst is the key to determine the degree of reaction and the distribution of hydrogenation products. The development of copper-based catalysts with high activity and selectivity to replace precious metals has research value and reference significance for the industrial application. Based the most two serious problems of copper-based catalysts, i.e. facile sintering and agglomeration at high temperatures, the researches of copper-based catalysts in the carbon-oxygen bond hydrogenation reaction are reviewed. The methods to avoid catalyst inactivation and increase catalyst stability are introduced, and the stability enhancement of copper-based catalysts by adding different additives, support effects, and constructing special catalyst structures, are discussed. The factors influencing the catalyst stability such as high oxygen vacancy to promote defect and adsorption sites, and confinement to restrict metal migration and aggregation, are summarized.

Key words: catalyst, catalyst support, hydrogenation, deactivation, stability

中图分类号:

TQ426

于昕瑶, 郜亮, 宗保宁. 提高碳氧键加氢铜基催化剂稳定性的研究进展[J]. 化工进展, 2023, 42(11): 5722-5729.

YU Xinyao, GAO Liang, ZONG Baoning. Progress in improving the stability of Cu-based catalysts for C－O bond hydrogenation[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5722-5729.

图/表 2

参考文献 54

1	VAN DEN BERG R, PARMENTIER T E, ELKJÆR C F, et al. Support functionalization to retard Ostwald ripening in copper methanol synthesis catalysts[J]. ACS Catalysis, 2015, 5(7): 4439-4448.
2	RUCKENSTEIN E, PULVERMACHER B. Growth kinetics and the size distributions of supported metal crystallites[J]. Journal of Catalysis, 1973, 29(2): 224-245.
3	LIFSHITZ I M, SLYOZOV V V. The kinetics of precipitation from supersaturated solid solutions[J]. Journal of Physics and Chemistry of Solids, 1961, 19(1/2): 35-50.
4	AMANN P, KLÖTZER B, DEGERMAN D, et al. The state of zinc in methanol synthesis over a Zn/ZnO/Cu(211) model catalyst[J]. Science, 2022, 376(6593): 603-608.
5	SHYAM K, RAMÍREZ P J, CHEN J G, et al. Active sites for CO₂ hydrogenation to methanol on Cu/ZnO catalysts[J]. Science, 2017, 355(6331): 1296-1299.
6	SEBASTIAN K, MAX T, HANNE F, et al. Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis[J]. Science, 2016, 352(6288): 969-974.
7	MALTE B, FELIX S, IGOR K, et al. The active site of methanol synthesis over Cu/ZnO/Al₂O₃ industrial catalysts[J]. Science, 2012, 336(6083): 893-897.
8	SHAO Yuewen, WANG Junzhe, DU Huining, et al. Importance of magnesium in Cu-based catalysts for selective conversion of biomass-derived furan compounds to diols[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(13): 5217-5228.
9	TOYIR J, DE LA PISCINA P R, FIERRO J L G, et al. Highly effective conversion of CO₂ to methanol over supported and promoted copper-based catalysts: Influence of support and promoter[J]. Applied Catalysis B: Environmental, 2001, 29(3): 207-215.
10	LIU Xianyun, TOYIR J, DE LA PISCINA P R, et al. Hydrogen production from methanol steam reforming over Al₂O₃- and ZrO₂-modified CuOZnOGa₂O₃ catalysts[J]. International Journal of Hydrogen Energy, 2017, 42(19): 13704-13711.
11	彭桂芳. Ba改性铜基复合氧化物的制备与三效催化性能的研究[D]. 汕头: 汕头大学, 2010.
	PENG Guifang. Preparation and investigation on three-way catalytic properties of copper base composite oxide of Ba[D]. Shantou: Shantou University, 2010.
12	BANSODE A, TIDONA B, VON ROHR P R, et al. Impact of K and Ba promoters on CO₂ hydrogenation over Cu/Al₂O₃ catalysts at high pressure[J]. Catalysis Science & Technology, 2013, 3(3): 767-778.
13	ZHANG Hui, ZHANG Guoyan, BI Xue, et al. Facile assembly of a hierarchical core@shell Fe₃O₄@CuMgAl-LDH (layered double hydroxide) magnetic nanocatalyst for the hydroxylation of phenol[J]. Journal of Materials Chemistry A, 2013, 1(19): 5934-5942.
14	SHI Zhisheng, TAN Qingqing, TIAN Chao, et al. CO₂ hydrogenation to methanol over Cu-In intermetallic catalysts: Effect of reduction temperature[J]. Journal of Catalysis, 2019. 379: 78-89.
15	SHI Zhisheng, TAN Qingqing, WU Dongfang, et al. A novel core-shell structured CuIn@SiO₂ catalyst for CO₂ hydrogenation to methanol[J]. AIChE Journal, 2019, 65(3): 1047-1058.
16	高琪. 碱性助剂对铜基催化剂结构及CO₂加氢合成甲醇催化活性的影响[D]. 银川: 宁夏大学, 2019.
	GAO Qi. Effect of alkaline promoter on the structure of copper-based catalysts and the activity of CO₂ hydrogenation to methanol[D]. Yinchuan: Ningxia University, 2019.
17	SŁOCZYŃSKI J, GRABOWSKI R, OLSZEWSKI P, et al. Effect of metal oxide additives on the activity and stability of Cu/ZnO/ZrO₂ catalysts in the synthesis of methanol from CO₂ and H₂ [J]. Applied Catalysis A: General, 2006, 310: 127-137.
18	REN Hong, XU Chenghua, ZHAO Haoyang, et al. Methanol synthesis from CO₂ hydrogenation over Cu/γ-Al₂O₃ catalysts modified by ZnO, ZrO₂ and MgO[J]. Journal of Industrial and Engineering Chemistry, 2015, 28: 261-267.
19	BRANDS D S, POELS E K, BLIEK A. Ester hydrogenolysis over promoted Cu/SiO₂ catalysts[J]. Applied Catalysis A: General, 1999, 184(2): 279-289.
20	王爱丽，贾星原，卢志鹏，等. 稀土元素(La,Ce,Nd)改性Cu/SiO₂催化甲醇脱氢制备甲酸甲酯[J]. 精细石油化工, 2019, 36(1): 20-25.
	WANG Aili, JIA Xingyuan, LU Zhipeng, et al. Methanol dehydrogenation to methyl formate catalyzed by rare earth element (La,Ce,Nd) modified Cu/SiO₂ catalysts[J]. Speciality Petrochemicals, 2019, 36(1): 20-25.
21	VENUGOPAL A, PALGUNADI J, DEOG Jung Kwang, et al. Dimethyl ether synthesis on the admixed catalysts of Cu-Zn-Al-M (M=Ga, La, Y, Zr) and γ-Al₂O₃: The role of modifier[J]. Journal of Molecular Catalysis A: Chemical, 2009, 302(1/2): 20-27.
22	ZHENG Xinlei, LIN Haiqiang, ZHENG Jianwei, 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): 2738-2749.
23	ZHANG X G, WILSON K, LEE A F. Heterogeneously catalyzed hydrothermal processing of C₅—C₆ sugars[J]. Chemical Reviews, 2016, 116(19): 12328-12368.
24	SONG Xiwen, YANG Chengsheng, LI Xianghong, et al. On the role of hydroxyl groups on Cu/Al₂O₃ in CO₂ Hydrogenation[J]. ACS Catalysis, 2022, 12(22): 14162-14172.
25	HU Jun, LI Yangyang, ZHEN Yanping, et al. In situ FTIR and ex situ XPS/HS-LEIS study of supported Cu/Al₂O₃ and Cu/ZnO catalysts for CO₂ hydrogenation[J]. Chinese Journal of Catalysis, 2021, 42(3): 367-375.
26	ZHANG Fan, LIU Yuan, XU Xiaoying, et al. Effect of Al-containing precursors on Cu/ZnO/Al₂O₃ catalyst for methanol production[J]. Fuel Processing Technology, 2018, 178: 148-155.
27	刘艳霞，王丽丽，王琪，等. γ-Al₂O₃对铜基甲醇合成催化剂的促进作用[J]. 厦门大学学报(自然科学版), 2007, 46(5): 661-664.
	LIU Yanxia, WANG Lili, WANG Qi, et al. The promoting effect of γ-Al₂O₃ on copper-based catalysts for methanol synthesis[J]. Journal of Xiamen University (Natural Science). 2007, 46(5): 661-664.
28	LI Fengjiao, WANG Liguo, HAN Xiao, et al. Influence of support on the performance of copper catalysts for the effective hydrogenation of ethylene carbonate to synthesize ethylene glycol and methanol[J]. RSC Advances, 2016, 6(51): 45894-45906.
29	YIN Anyuan, GUO Xiuying, DAI Weilin, et al. The nature of active copper species in Cu-HMS catalyst for hydrogenation of dimethyl oxalate to ethylene glycol: New insights on the synergetic effect between Cu⁰ and Cu⁺ [J]. The Journal of Physical Chemistry C, 2009, 113(25): 11003-11013.
30	WANG Shurong, GUO Wenwen, WANG Haixia, et al. Effect of the Cu/SBA-15 catalyst preparation method on methyl acetate hydrogenation for ethanol production[J]. New Journal of Chemistry, 2014, 38(7): 2792-2800.
31	CHEN Liangfeng, GUO Pingjun, QIAO Minghua, et al. Cu/SiO₂ catalysts prepared by the ammonia-evaporation method: Texture, structure, and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol[J]. Journal of Catalysis, 2008, 257(1): 172-180.
32	CHEN Liangfeng, GUO Pingjun, ZHU Lingjun, et al. Preparation of Cu/SBA-15 catalysts by different methods for the hydrogenolysis of dimethyl maleate to 1,4-butanediol[J]. Applied Catalysis A: General, 2009, 356(2): 129-136.
33	ZHU Yifeng, ZHU Yulei, DING Guoqiang, et al. Highly selective synthesis of ethylene glycol and ethanol via hydrogenation of dimethyl oxalate on Cu catalysts: Influence of support[J]. Applied Catalysis A: General, 2013, 468: 296-304.
34	ANGELO L, KOBL K, TEJADA L M M, et al. Study of CuZnMO _x oxides (M=Al, Zr, Ce, CeZr) for the catalytic hydrogenation of CO₂ into methanol[J]. Comptes Rendus Chimie, 2015, 18(3): 250-260.
35	ARENA F, ITALIANO G, BARBERA K, et al. Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO₂ catalysts in the CO₂ hydrogenation to CH₃OH[J]. Applied Catalysis A: General, 2008, 350(1): 16-23.
36	ARENA F, BARBERA K, ITALIANO G, et al. Synthesis, characterization and activity pattern of Cu-ZnO/ZrO₂ catalysts in the hydrogenation of carbon dioxide to methanol[J]. Journal of Catalysis, 2007, 249(2): 185-194.
37	WITOON T, CHALORNGTHAM J, DUMRONGBUNDITKUL P, et al. CO₂ hydrogenation to methanol over Cu/ZrO₂ catalysts: Effects of zirconia phases[J]. Chemical Engineering Journal, 2016, 293: 327-336.
38	SAMSON K, ŚLIWA M, SOCHA R P, et al. Influence of ZrO₂ structure and copper electronic state on activity of Cu/ZrO₂ catalysts in methanol synthesis from CO₂ [J]. ACS Catalysis, 2014, 4(10): 3730-3741.
39	LI Kongzhai, CHEN Jingguang. CO₂ hydrogenation to methanol over ZrO₂ containing catalysts: Insights into ZrO₂ induced synergy[J]. ACS Catalysis, 2019, 9(9): 7840-7861.
40	ZHU Jiadong, SU Yaqiong, CHAI Jiachun, et al. Mechanism and nature of active sites for methanol synthesis from CO/CO₂ on Cu/CeO₂ [J]. ACS Catalysis, 2020, 10(19): 11532-11544.
41	WANG Weiwei, QU Zhenping, SONG Lixin, et al. CO₂ hydrogenation to methanol over Cu/CeO₂ and Cu/ZrO₂ catalysts: Tuning methanol selectivity via metal-support interaction[J]. Journal of Energy Chemistry, 2020, 40: 22-30.
42	YU Wenzhu, WANG Weiei, LI Shanqing, et al. Construction of active site in a sintered copper-ceria nanorod catalyst[J]. Journal of the American Chemical Society, 2019, 141(44): 17548-17557.
43	LI Shuirong, GONG Jinlong. Strategies for improving the performance and stability of Ni-based catalysts for reforming reactions[J]. Chemical Society Reviews, 2014, 43(21): 7245-7256.
44	YANG Haiyan, GAO Peng, ZHANG Chen, et al. Core-shell structured Cu@m-SiO₂ and Cu/ZnO@m-SiO₂ catalysts for methanol synthesis from CO₂ hydrogenation[J]. Catalysis Communications, 2016, 84: 56-60.
45	AI P P, TAN M H, ISHIKURO Y, et al. Design of an autoreduced copper in carbon nanotube catalyst to realize the precisely selective hydrogenation of dimethyl oxalate[J]. ChemCatChem, 2017, 9(6): 1067-1075.
46	YUE Hairong, ZHAO Yujun, ZHAO Shuo, et al. A copper-phyllosilicate core-sheath nanoreactor for carbon-oxygen hydrogenolysis reactions[J]. Nature Communications, 2013, 4(1): 1-7.
47	CHEN S, DE SOUZA P M, CIOTONEA C, et al. Micro-/mesopores confined ultrasmall Cu nanoparticles in SBA-15 as a highly efficient and robust catalyst for furfural hydrogenation to furfuryl alcohol[J]. Applied Catalysis A: General, 2022, 633(5): 118527.
48	YUAN Zhenle, WANG Lina, WANG Junhua, et al. Hydrogenolysis of glycerol over homogenously dispersed copper on solid base catalysts[J]. Applied Catalysis B: Environmental, 2011, 101(3/4): 431-440.
49	YU X B, VEST T A, GLEASON-BOURE N, et al. Enhanced hydrogenation of dimethyl oxalate to ethylene glycol over indium promoted Cu/SiO₂ [J]. Journal of Catalysis, 2019, 380: 289-296.
50	REN Yingyu, YANG Yusen, CHEN Lifang, et al. Synergetic effect of Cu⁰-Cu⁺ derived from layered double hydroxides toward catalytic transfer hydrogenation reaction[J]. Applied Catalysis B: Environmental, 2022, 314: 121515.
51	ZHANG Fan, XU Xiaoying, QIU Zhengpu, et al. Improved methanol synthesis performance of Cu/ZnO/Al₂O₃ catalyst by controlling its precursor structure[J]. Green Energy & Environment, 2022, 7(4): 772-781.
52	BEHRENS M. Meso- and nano-structuring of industrial Cu/ZnO/(Al₂O₃) catalysts[J]. Journal of Catalysis, 2009, 267(1): 24-29.
53	HOU Xiaoning, QING Shaojun, LIU Yajie, et al. Cu_1- _x Mg _x Al₃ spinel solid solution as a sustained release catalyst: One-pot green synthesis and catalytic performance in methanol steam reforming[J]. Fuel, 2021, 284: 119041.
54	BAHMANPOUR A M, HÉROGUEL F, KILIÇ M, et al. Cu-Al spinel as a highly active and stable catalyst for the reverse water gas shift reaction[J]. ACS Catalysis, 2019, 9(7): 6243-6251.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[6]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[7]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[8]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[9]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[10]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[11]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[12]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[13]	吴海波, 王希仑, 方岩雄, 纪红兵. 3D打印催化材料开发与应用进展[J]. 化工进展, 2023, 42(8): 3956-3964.
[14]	毛善俊, 王哲, 王勇. 基团辨识加氢：从概念到应用[J]. 化工进展, 2023, 42(8): 3917-3922.
[15]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.