马时运¹,卜佳玉¹,段艳²,侯凯湖¹

• 1:河北工业大学 化工学院，天津 300130
• 2:百色学院 化学与环境工程学院，广西 百色 533000

摘要(Abstract)：

在以环丁砜为原料选择性加氢脱氧制备四氢噻吩的过程中，本体型Ni-Mo催化剂存在缓慢失活和选择性下降的现象。采用X射线衍射（XRD）、X射线能谱（EDS）、N₂吸附-脱附（BET）、同步热分析（DSC-TGA）、电感耦合等离子发射光谱（ICP-AES）、扫描电镜（SEM）等方法，分别对新鲜和失活催化剂进行了表征，探讨了本体型Ni-Mo催化剂在催化环丁砜选择性加氢脱氧过程中性能劣化的原因，并对失活催化剂进行了再生研究。结果表明，Ni、Mo活性组分的深度硫化形成的Ni-Mo-S相是催化剂催化性能下降的主要原因，而导致催化剂比表面积和孔径降低的积炭则对催化剂性能的影响较小；失活催化剂具有良好的再生性能。

关键词(KeyWords)： 环丁砜;四氢噻吩;加氢脱氧;失活;再生

Abstract:

Keywords:

基金项目(Foundation):

作者(Author): 马时运¹,卜佳玉¹,段艳²,侯凯湖¹

DOI: 10.3969/j.issn.1003-9015.2017.04.015

参考文献(References)：

• [1] ZHAO Da-sheng (赵大生), LIU Hai-yan (刘海燕). New synthsis process of tetrahydrothiophene (四氢噻吩合成新工艺)[J]. Heilongjiang Science (黑龙江科学), 2010(2):23-25.
  [2] ZHU Zhi-qiang (朱志强). The application and importance of natural gas and odor agent in the life of residents (天然气加臭剂在居民生活用气中的用途及重要性)[J]. Science Technology Innovation and Application (科技创新与应用), 2013(36):49-49.
  [3] LI Pi-gao (李丕高), LI Gang (李刚). Improvement on the synthesis of tetrahydrothiophene (四氢噻吩合成方法的改进)[J]. Chinese Journal of Synthetic Chemistry (合成化学), 2007, 15(3):374-375.
  [4] LI Hong-bin (李鸿滨). Production technology and market analysis of tetrahydrothiophene (四氢噻吩的生产技术与市场分析)[J]. Chemical Intermediate (化工中间体), 2006(6):12-19.
  [5] Ermakova A, Mashkina A V, Sakhaltueva L G. Kinetic study of catalytic hydrogenation of thiophene on a palladium sulfide catalyst[J]. Kinetics and Catalysis, 2002, 43(4):528-536.
  [6] Keith L J, Easley W K, Wagner W S. Tetrahydrothiophene[M]. New York:John Wiley & Sons, 2003.
  [7] DUAN Yan (段艳), WANG Xin (王欣), HOU Kai-hu (侯凯湖). Preparation and evaluation of unsupported Ni-Mo catalysts for synthesis of tetrahydrothiophene (合成四氢噻吩非负载Ni-Mo催化剂的制备与表征)[J]. Chemical Reaction Engineering and Technology (化学反应工程与工艺), 2016, 32(2):164-169.
  [8] DUAN Yan (段艳), WANG Xin (王欣), HOU Kai-hu (侯凯湖). Effects of reduction conditions on unsupported Ni-Mo composite oxide catalysts for selective hydrodeoxygenation (还原条件对Ni-Mo非负载催化剂选择性加氢脱氧的影响)[J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2016, 30(6):1451-1457.
  [9] Yin C, Zhao L, Bai Z, et al. A novel porous ammonium nickel molybdate as the catalyst precursor towards deep hydrodesulfurization of gas oil[J]. Fuel, 2013, 107(9):873-878.
  [10] Wang H, Enrique I. Mechanism and site requirements of thiophene hydrodesulfurization catalyzed by supported Pt clusters[J]. Chemcatchem, 2011, 3(7):1166-1175.
  [11] Struis R P W J, Schildhauer T J, Czekaj I, et al. Sulphur poisoning of Ni catalysts in the SNG production from biomass:ATPO/XPS/XAS study[J]. Applied Catalysis A:General, 2009, 362(1-2):121-128.
  [12] Marin-Flores O, Turba T, Ellefson C, et al. Sulfur poisoning of molybdenum dioxide during the partial oxidation of a Jet-A fuel surrogate[J]. Applied Catalysis, 2011, 105(1-2):61-68.
  [13] JIN Xin (金鑫). Preparation and catalytic properties of unsupported transition metal sulfides by thermal decomposition method (非负载过渡金属硫化物热解法制备及催化性能)[D]. Dalian (大连):Dalian University of Technology (大连理工大学), 2010.
  [14] Fujikawa T, Ribeiro F H, Somorjai G A. Hydrodesulfurization of tetrahydrothiophene over evaporated Mo, Co and Mo-Co model catalysts[J]. Catalysis Letters, 1999, 63(1):21-26.
  [15] Mashkina A V. Thiophene hydrogenation to tetrahydrothiophene over tungsten sulfide catalysts[J]. Kinetics and Catalysis, 2003, 44(2):277-282.
  [16] LI Li-min (李利民), WANG Li-kui (王利魁). Promoters and sulfurizing degree of sulfurized WGS catalyst K-Ni-Mo/Al₂O₃(K-Ni-Mo/Al₂O₃耐硫变换催化剂硫化态与硫化度研究)[J]. Journal of Zhengzhou University (Natural Science Edition) (郑州大学学报(理学版)), 2001, 33(4):66-69.
  [17] SUN Wan-fu (孙万付), MA Bo (马波), SUO Ji-shuan (索继栓), et al. Study of coke deposition behavior of hydrocracking catalyst (加氢裂化催化剂积炭行研究)[J]. Chinese Journal of Catalysis (催化学报), 2000, 21(3):269-272.
  [18] Girard V, Baudot A, Chiche D, et al. Rational selection of single oxide sorbents for syngas desulfurization regenerable at reduced temperature:thermochemical alculations and experimental study[J]. Fuel, 2014, 128(21):220-230.
  [19] JI Ke-ming (吉可明), MENG Fan-hui (孟凡会), LI Zhong (李忠). Recent advances in research on carbon deposition and deactivation of Ni supported catalysts (Ni负载催化剂积炭失活的研究进展)[J]. Natural Gas Chemical Industry (C1 Chemistry and Technology) (天然气化工(C1化学与化工)), 2015(1):83-88.
  [20] SANG Xiao-yi (桑小义), LI Hui-feng (李会峰), LI Ming-feng (李明丰), et al. Research advances of catalysts for the hydrodeoxygenation of oxygenic compounds (含氧化合物加氢脱氧催化剂研究进展)[J]. Acta Petrolei Sinica (Petroleum Processing Section) (石油学报(石油加工)), 2014, 30(6):1119-1127.