乙炔氢氯化Au-Cu/AC催化剂中Cu价态对Au价态稳定性的影响

doi:10.16085/j.issn.1000-6613.2020-0156

摘要/Abstract

摘要：

Au-Cu/AC无汞催化剂在乙炔氢氯化反应中具有潜在的工业应用价值。本文采用蒸汽诱导还原及H₂还原对Au-Cu/AC催化剂上负载的Cu价态进行调控制备，并采用X射线多晶衍射、程序升温脱附、程序升温还原、 X射线光电子能谱、扫描电镜等对反应前后的催化剂进行对比表征，研究了其对Au价态和对乙炔氢氯化反应催化活性的影响。结果表明，分别制备得到含Cu(Ⅱ) 83.68%、Cu(Ⅰ) 70.92%、Cu(0) 77.37%的催化剂，以Au/AC催化剂为基准，在新鲜催化剂上，Cu(Ⅱ)使Au(Ⅰ)的含量从47.65%降低至15.71%，Au(0)增加至62.09%，Cu(Ⅰ)使得Au(Ⅲ)、Au(Ⅰ)的含量下降至14.83%和33.2%，Cu(0)使Au(0)的含量增加至69.99%；在反应过程中，Cu(Ⅱ)、Cu(Ⅰ)分别使Au(0)含量的增长百分比减少为13.81%和15.03%，Cu(Ⅰ)有利于维持Au(Ⅰ)的稳定，抑制Au离子还原为Au(0)，促使反应前后Au(Ⅰ)的含量稳定在33%左右，Cu(Ⅱ)在反应中还原为Cu(Ⅰ)，继而提高Au(Ⅰ)含量，Cu(0) 吸附大量乙炔引发副反应，促进了Au被还原为Au(0)，Au(Ⅲ)、Au(Ⅰ)的总含量降低至10.35%，催化剂稳定性下降，丰富了乙炔氢氯化无汞催化剂中铜协同金的应用基础理论。

关键词: 乙炔氢氯化, 催化剂, 制备, 稳定性, 金, 铜

Abstract:

Au-Cu/AC mercury-free catalyst has potential in industrial application for acetylene hydrochlorination. In this paper, vapor-induced selective reduction and H₂ reduction were used to control the Cu valence on the Au-Cu/AC catalyst. The structures of fresh and used catalysts were characterized by XRD, C₂H₂-TPD, H₂-TPR, XPS, SEM, etc., and the effects of Cu valence on the valence state of Au as well as the catalytic activity of acetylene hydrochlorination were studied. Catalysts containing 83.68% Cu(Ⅱ), 70.92% Cu(Ⅰ), and 77.37% Cu(0) were prepared. Compared with the Au/AC catalyst, the Cu(Ⅱ) on the fresh Au-Cu/AC catalyst reduced the content of Au(Ⅰ) from 47.65% to 15.71%, increased that of Au(0)to 62.09%, and Cu(Ⅰ) caused Au(Ⅲ) and Au (Ⅰ) contents decreased to 14.83% and 33.2% respectively, while the Cu(0) increased Au(0) content to 69.99%. During the reaction, Cu(Ⅱ) and Cu(Ⅰ) reduced the percentage increase of Au(0) content to 13.81% and 15.03% respectively. Cu(Ⅰ) is beneficial to maintain the stability of Au(Ⅰ), inhibit the reduction of Au ions to Au(0), and promote Au(Ⅰ) content being maintained at about 33%. Cu(Ⅱ) was reduced to Cu(Ⅰ) in the reaction, which increased the Au(Ⅰ) content. Cu(0) adsorbed a large amount of acetylene to initiate side reactions, which promoted the reduction of Au to Au(0), reduced the total contents of Au(Ⅲ) and Au(Ⅰ) to 10.35%, and thus lowered the stability of the catalyst. The results have enriched the basic theory of copper synergism in mercury-free catalyst for acetylene hydrochlorination.

Key words: acetylene hydrochlorination, catalyst, preparation, stability, gold, copper

中图分类号:

O643

王宁, 赵基钢, 丛梅, 董志林, 袁向前, 孙辉. 乙炔氢氯化Au-Cu/AC催化剂中Cu价态对Au价态稳定性的影响[J]. 化工进展, 2020, 39(11): 4480-4487.

Ning WANG, Jigang ZHAO, Mei CONG, Zhilin DONG, Xiangqian YUAN, Hui SUN. Effect of Cu valence on the stability of Au valence in Au-Cu/AC catalysts for acetylene hydrochlorination[J]. Chemical Industry and Engineering Progress, 2020, 39(11): 4480-4487.

参考文献

1	YAN B, LU W, CHENG Y. China goes green: cleaner production of chemicals[J]. Green Processing and Synthesis, 2012, 1(1): 33-47.
2	曹战国, 肖国营, 曹贺鸣. 我国电石法PVC行业面对《关于汞的水俣公约》时限挑战须采取的积极措施及建议[J]. 聚氯乙烯, 2018, 46(10): 7-17.
2	CAO Zhanguo, XIAO Guoying, CAO Heming. Positive measures and suggestions for China’s calcium carbide method PVC industry facing the time limit challenge of Minamata Convention on Mercury [J]. Polyvinyl chloride, 2018, 46 (10): 7-17.
3	李东周. 新型PVC低汞催化剂工业化[J]. 中国石油和化工, 2014(9):53-53.
3	LI Dongzhou. New low mercury catalyst for industrialization of PVC[J]. China Petroleum and Chemical Industry, 2014(9): 53-53.
4	周军, 张学鲁, 李春华. 聚氯乙烯低汞化实践与总结[J]. 中国氯碱, 2014 (7): 15-18.
4	ZHOU Jun, ZHANG Xuelu, LI Chunhua. Polyvinyl chloride low mercury practice and summary [J]. China Chlor-Alkali, 2014(7): 15-18.
5	张家亮, 李卓, 张威. 低汞触媒在电石法PVC中的应用[J]. 聚氯乙烯, 2019(7):29-31.
5	ZHANG Jialiang, LI Zhuo, ZHANG Wei. Application of low-level mercury catalyst in calcium carbide based PVC [J]. Polyvinyl Chloride, 2019 (7): 29-31.
6	NKOSI B, COVILLE N J, HUTCHINGS G J. Reactivation of a supported gold catalyst for acetylene hydrochlorination[J]. Journal of the Chemical Society, Chemical Communications, 1988 (1): 71-72.
7	NKOSI B, COVILLE N J, HUTCHINGS G J. Vapour phase hydrochlorination of acetylene with group Ⅷ and IB metal chloride catalysts[J]. Applied Catalysis, 1988, 43(1): 33-39.
8	ZHU M, KANG L, SU Y, et al. MCl_x(M=Hg, Au, Ru; x=2,3) catalyzed hydrochlorination of acetylene—a density functional theory study[J]. Canadian Journal of Chemistry, 2013, 91(2): 120-125.
9	邓国才, 吴本湘. 乙炔法合成氯乙烯固相非汞催化剂的研制[J]. 聚氯乙烯, 1994 (6): 5-9.
9	DENG Guocai, WU Benxiang. Preparation of solid-phase non-mercury catalyst for vinyl chloride synthesis by acetylene method [J]. Polyvinyl Chloride, 1994 (6): 5-9
10	LI H, WANG F, CAI W, et al. Hydrochlorination of acetylene using supported phosphorus-doped Cu-based catalysts[J]. Catalysis Science & Technology, 2015, 5(12): 5174-5184.
11	SMITH D M, WALSH P M, SLAGER T L. Studies of silica-supported metal chloride catalysts for the vapor-phase hydrochlorination of acetylene[J]. Journal of Catalysis, 1968, 11(2): 113-130.
12	NKOSI B, ADAMS M D, COVILLE N J, et al. Hydrochlorination of acetylene using carbon-supported gold catalysts: a study of catalyst reactivation[J]. Journal of Catalysis, 1991, 128(2): 378-386.
13	NKOSI B, COVILLE N J, HUTCHINGS G J, et al. Hydrochlorination of acetylene using gold catalysts: a study of catalyst deactivation[J]. Journal of Catalysis, 1991, 128(2): 366-377.
14	MALTA G, KONDRAT S A, FREAKLEY S J, et al. Identification of single-site gold catalysis in acetylene hydrochlorination[J]. Science, 2017, 355(6332): 1399-1403.
15	KAISER S K, LIN R, MITCHELL S, et al. Controlling the speciation and reactivity of carbon-supported gold nanostructures for catalysed acetylene hydrochlorination[J]. Chemical Science, 2019, 10(2): 359-369.
16	YE L, DUAN X, WU S, et al. Self-regeneration of Au/CeO₂ based catalysts with enhanced activity and ultra-stability for acetylene hydrochlorination[J]. Nature Communications, 2019, 10(1): 914.
17	MA J, WANG S, SHEN B. Study on the effects of acetylene on an Au-Cu/C catalyst for acetylene hydrochlorination using Monte Carlo and DFT methods[J]. Reaction Kinetics, Mechanisms and Catalysis, 2013, 110(1): 177-186.
18	ZHANG H, DAI B, WANG X, et al. Hydrochlorination of acetylene to vinyl chloride monomer over bimetallic Au-La/SAC catalysts[J]. Journal of Industrial and Engineering Chemistry, 2012, 18(1): 49-54.
19	ZHAO J, XU J T, XU J H, et al. Activated‐carbon‐supported gold-cesium () as highly effective catalysts for hydrochlorination of acetylene to vinyl chloride[J]. ChemPlusChem, 2015, 80(1): 196-201.
20	ZHANG H, DAI B, LI W, et al. Non-mercury catalytic acetylene hydrochlorination over spherical activated-carbon-supported Au-Co(Ⅲ)-Cu(Ⅱ) catalysts[J]. Journal of Catalysis, 2014, 316: 141-148.
21	YAMAMOTO Y, MATSUZAKI T, OHDAN K, et al. Structure and electronic state of PdCl₂-CuCl₂ catalysts supported on activated carbon[J]. Journal of Catalysis, 1996, 161(2): 577-586.
22	赵璞君, 王富民, 蔡旺锋, 等. 乙炔氢氯化反应铜系催化剂的反应机理[J]. 分子催化, 2014(3): 259-267.
22	ZHAO Pujun, WANG Fumin, CAI Wangfeng, et al. Reaction mechanism of acetylene hydrochlorination in Cu-based catalyst[J]. Molecular Catalysis, 2014(3): 259-267.
23	JIANG W J, YIN Y, LIU X Q, et al. Fabrication of supported cuprous sites at low temperatures: an efficient, controllable strategy using vapor-induced reduction[J]. Journal of the American Chemical Society, 2013, 135(22): 8137-8140.
24	王声洁. 乙炔氢氯化非汞催化反应制取氯乙烯单体研究[D]. 上海: 华东理工大学, 2010.
24	WANG Shengjie. Study on non-mercury catalytic acetylene hydrochlorination to produce vinyl chloride monomer(VCM) [D]. Shanghai: East China University of Science and Technology, 2010.
25	QIN J X, TAN P, JIANG Y, et al. Functionalization of metal-organic frameworks with cuprous sites using vapor-induced selective reduction: efficient adsorbents for deep desulfurization[J]. Green Chemistry, 2016, 18(11): 3210-3215.
26	李志红, 黄伟, 左志军, 等. 用XPS研究不同方法制备的CuZnAl一步法二甲醚合成催化剂[J]. 催化学报, 2009, 30(2): 171-177.
26	LI Zhihong, HUANG Wei, ZUO Zhijun, et al. XPS study on CuZnAl catalysts prepared by different methods for direct synthesis of dimethyl ether[J]. Chinese Journal of Catalysis, 2009, 30 (2): 171-177.
27	YANO T, EBIZUKA M, SHIBATA S, et al. Anomalous chemical shifts of Cu 2p and Cu LMM auger spectra of silicate glasses[J]. Journal of Electron Spectroscopy and Related Phenomena, 2003, 131:133-144.
28	ZHANG J, HE Z, LI W, et al. Deactivation mechanism of AuCl₃ catalyst in acetylene hydrochlorination reaction: a DFT study[J]. RSC Advances, 2012, 2(11): 4814-4821.
29	CONTE M, CARLEY A F, HEIRENE C, et al. Hydrochlorination of acetylene using a supported gold catalyst: a study of the reaction mechanism[J]. Journal of Catalysis, 2007, 250(2): 231-239.
30	LIU X, CONTE M, ELIAS D, et al. Investigation of the active species in the carbon-supported gold catalyst for acetylene hydrochlorination[J]. Catalysis Science & Technology, 2016, 6(13): 5144-5153.

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