徐达,王赛赛,马腾云,万立祺,赵佳,蔡海婷,李小年

• 1:浙江工业大学 化学工程学院， 浙江 杭州 310014

摘要(Abstract)：

针对乙炔氢氯化反应无汞催化剂的开发，Ru基催化剂是最具工业潜力的催化剂之一。结合表面积分析仪(BET)、程序升温还原(TPR)、透射电镜(TEM)和程序升温脱附(TPD)，以及动力学实验探究了导致Ru/AC(AC为活性炭)和高温H₂处理后Ru-NPs/AC催化性能差异的原因。在排除内、外扩散的条件下，通过动力学实验判断了反应级数，初步推测了基元反应步骤和决速步骤。结果表明，Ru-NPs/AC相对于Ru/AC总反应速率更低，表观活化能更高，这是由于高温H₂处理后活性组分的分散度降低、Ru物种被还原，并且导致活性中心对C₂H₂的吸附性能降低。

关键词(KeyWords)： 乙炔氢氯化;Ru基催化剂;反应级数;表观活化能;活性中心

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金(22208299)；国家重点研发计划(2021YFA1501801)。

作者(Author): 徐达,王赛赛,马腾云,万立祺,赵佳,蔡海婷,李小年

DOI: 10.3969/j.issn.1003-9015.2024.04.006

参考文献(References)：

• [1] 安晓通. 聚氯乙烯行业的生产现状及发展趋势 [J]. 化工设计通讯, 2019, 45(5): 205. AN X T. Production status and development trend of PVC industry [J]. Chemical Engineering Design Communications, 2019, 45(5): 205.
  [2] 杨惠娣. 聚氯乙烯及其热稳定剂现状与发展趋势 [J]. 中国塑料, 2019, 33(4): 111-119. YANG H D. Current situation and development trends of PVC and its stabilizers [J]. China Plastics, 2019, 33(4): 111-119.
  [3] 高伟杰. 阻燃聚氯乙烯研究进展及在工程中的应用 [J]. 合成材料老化与应用, 2019, 48(5): 132-136. GAO W J. Research progress of flame retardant PVC and their application in engineering [J]. Synthetic Materials Aging and Application, 2019, 48(5): 132-136.
  [4] WANG B L, YUE Y X, PANG X X, et al. Nature of HCl oxidation Au anomalies and activation of non-carbon-material-supported Au catalyst [J]. Journal of Catalysis, 2021, 404: 198-203.
  [5] 王小艳, 王小昌. 电石法聚氯乙烯低汞触媒的研究进展 [J]. 中国氯碱, 2017(4): 11-15. WANG X Y, WANG X C. Research progress of calcium carbide PVC low mercury catalyst [J]. China Chlor-Alkali, 2017(4): 11-15.
  [6] WANG B L, JIN C X, SHAO S J, et al. Electron-deficient Cu site catalyzed acetylene hydrochlorination [J]. Green Energy & Environment, 2023, 8(4): 1128-1140.
  [7] 《关于汞的水俣公约》生效公告 [J]. 电池工业, 2017, 21(3): 53,32. The Minamata Convention on Mercury[J]. Chinese Battery Industry, 2017, 21(3): 53,32.
  [8] LI J, ZHANG H Y, CAI M, et al. Enhanced catalytic performance of activated carbon-supported ru-based catalysts for acetylene hydrochlorination by azole ligands [J]. Applied Catalysis A: General, 2020, 592: 117431.
  [9] LI J, ZHANG H Y, LIANG H X, et al. High-efficiency catalysis of Ru-based catalysts assisted by triazine-based ligands containing different heteroatoms (N, O, S) for acetylene hydrochlorination [J]. Molecular Catalysis, 2022, 519: 112142.
  [10] MAN B C, ZHANG H Y, ZHANG C M, et al. Effect of Ru/Cl ratio on the reaction of acetylene hydrochlorination [J]. New Journal of Chemistry, 2017, 41(23): 14675-14682.
  [11] ZHANG H Y, LI W, JIN Y H, et al. Ru-Co(III)-Cu(II)/SAC catalyst for acetylene hydrochlorination [J]. Applied Catalysis B: Environmental, 2016, 189: 56-64.
  [12] 郭燕燕, 刘鹰, 胡瑞生, 等. 乙炔氢氯化反应非贵金属无汞催化剂的研究进展 [J]. 化工进展, 2014, 33(6): 1486-1490. GUO Y Y, LIU Y, HU R S, et al. Research progress of mercury-free catalysts of non-noble metal for acetylene hydrochlorination [J]. Chemical Industry and Engineering Progress, 2014, 33(6): 1486-1490.
  [13] 宋静, 金奇杰, 计雯钰, 等. WO₃-ZrO₂/TiO₂-CeO₂-MnO₂选择性催化还原NO热动力学和反应机理研究 [J]. 电力科技与环保, 2022, 38(1): 10-17. SONG J, JIN Q J, JI W Y, et al. Kinetics and reaction mechanism of selective catalytic reduction of NO by WO₃-ZrO₂ / TiO₂-CeO₂-MnO₂ [J]. Electric Power Environmental Protection, 2022, 38(1): 10-17.
  [14] KAISER S K, LIN R H, KRUMEICH F, et al. Preserved in a shell: High-performance graphene-confined ruthenium nanoparticles in acetylene hydrochlorination [J]. Angewandte Chemie International Edition, 2019, 58(35): 12297-12304.
  [15] KAISER S K, FAKO E, SURIN I, et al. Performance descriptors of nanostructured metal catalysts for acetylene hydrochlorination [J]. Nature Nanotechnology, 2022, 17(6): 606-612.
  [16] JIN Y H, LI G B, ZHANG J L, et al. Effects of potassium additive on the activity of Ru catalyst for acetylene hydrochlorination [J]. RSC Advances, 2015, 5(47): 37774-37779.
  [17] ZHENG S Z, CAO X Y, ZHOU Q, et al. Gas phase hydrogenolysis of methyl difluoroacetate to 1, 1-difluoroethanol over Ru/C catalysts [J]. Journal of Fluorine Chemistry, 2013, 145: 132-135.
  [18] 黄柳华, 徐壮, 朱明远, 等. 乙炔氢氯化无汞催化动力学及其反应器优化 [J]. 石河子大学学报(自然科学版), 2021, 39(5): 529-536. HUANG L H, XU Z, ZHU M Y, et al. Mercury-free catalytic kinetics of acetylene hydrochlorination and its reactor optimization [J]. Journal of Shihezi University (Natural Science), 2021, 39(5): 529-536.
  [19] WANG B L, ZHANG H F, YUE Y X, et al. Catalytic behavior of au confined in ionic liquid film: A kinetics study for the hydrochlorination of acetylene [J]. Catalysts, 2022, 12(9): 1012.
  [20] XU H, SI J K, LUO G H. The kinetics model and fixed bed reactor simulation of Cu catalyst for acetylene hydrochlorination[J]. International Journal of Chemical Reactor Engineering, 2017, 15(4): 20160165.
  [21] WANG X L, LAN G J, CHENG Z Z, et al. Carbon-supported ruthenium catalysts prepared by a coordination strategy for acetylene hydrochlorination [J]. Chinese Journal of Catalysis, 2020, 41(11): 1683-1691.
  [22] ZHU M Y, KANG L H, 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.
  [23] JIA Y M, NIAN Y, ZHANG J L, et al. Theoretical design of ruthenium single-atom catalysts with different substrates for acetylene hydrochlorination [J]. Molecular Catalysis, 2021, 513: 111826.
  [24] HAN Y, SUN M X, LI W, et al. Influence of chlorine coordination number on the catalytic mechanism of ruthenium chloride catalysts in the acetylene hydrochlorination reaction: A DFT study [J]. Physical Chemistry Chemical Physics, 2015, 17(12): 7720-7730.
  [25] 汪新鑫, 吴广文, 吴浩, 等. 乙炔氢氯化的低汞催化反应动力学研究 [J]. 工业催化, 2014, 22(5): 392-396. WANG X X, WU G W, WU H, et al. Kinetic study of hydrochlorination of acetylene on low-mercury catalyst [J]. Industrial Catalysis, 2014, 22(5): 392-396.
  [26] 李阳, 吴广文, 吴浩, 等. 乙炔氢氯化的无汞催化反应动力学研究 [J]. 工业催化, 2015, 23(4): 307-312. LI Y, WU G W, WU H, et al. Kinetic study of hydrochlorination of acetylene on non-mercury catalyst [J]. Industrial Catalysis, 2015, 23(4): 307-312.