过渡金属改性的ZSM-5催化剂应用于甲硫醚转化制甲硫醇

doi:10.3866/PKU.WHXB201404181

摘要/Abstract

摘要：

负载过渡金属的ZSM-5 催化剂用于催化甲硫醚（DMS）转化成甲硫醇（MT）的反应. 实验结果表明，催化剂的甲硫醚转化率提高和甲硫醇选择性降低的趋势一样，都是以下顺序：Co/ZSM-5>Mo/ZSM-5>Ni/ZSM-5>W/ZSM-5. 表征结果表明，由于过渡金属阳离子（W⁶⁺、Ni²⁺、Co³⁺、Mo⁶⁺）比Al³⁺活泼，而改性过程中W⁶⁺、Ni²⁺、Co³⁺、Mo⁶⁺分别代替了部分Al³⁺，使得改性催化剂对DMS和MT的化学吸附作用更强. 过渡金属的引入使得ZSM-5总酸度增强，提高了C―S键的裂解能力，从而改进了催化转化DMS的能力. 研究结果发现，在转化DMS的过程中，金属活性位和酸性位之间通过强的协同效应起作用.

关键词: ZSM-5, 过渡金属, 甲硫醚, 甲硫醇

Abstract:

ZSM-5-supported transition metal catalysts were prepared and used to catalyze the conversion of dimethyl sulfide (DMS) into methanethiol (MT). Test results indicated that the activities of the catalysts for the conversion of DMS increased as follows: Co/ZSM-5>Mo/ZSM-5>Ni/ZSM-5>W/ZSM-5. The decrease in MT selectivity followed the same trend. The characterization results showed that transition metal cations (W⁶⁺, Ni²⁺, Co³⁺, Mo⁶⁺) replaced some Al³⁺ sites leading to more active in chemiadsorption of DMS and MT since transition metal cations are more active than A^l3+. The incorporation of transition metals into ZSM-5 enhances the total acidity of ZSM-5 and increases its capacity to rupture C―S bonds. This subsequently improves its catalytic behavior in the conversion of DMS. We found that the metal active sites and closely situated acidic sites have a strong synergistic effect when converting DMS.

Key words: ZSM-5, Transition metal, Dimethyl sulfide, Methanethiol

MSC2000:

O643

陈世萍, 王伟明, 刘迎伟, 魏育才, 袁成龙, 方维平, 杨意泉. 过渡金属改性的ZSM-5催化剂应用于甲硫醚转化制甲硫醇[J]. 物理化学学报, 2014, 30(6): 1148-1154.

CHEN Shi-Ping, WANG Wei-Ming, LIU Ying-Wei, WEI Yu-Cai, YUAN Cheng-Long, FANG Wei-Ping, YANG Yi-Quan. Transition Metal Promoted ZSM-5 Catalysts for the Conversion of Dimethyl Sulfide into Methanethiol[J]. Acta Phys. -Chim. Sin., 2014, 30(6): 1148-1154.

参考文献

(1) Kastner, J. R.; Buquoi, Q.; Gangavaram, R.; Das, K. C. Envir. Sci. Technol. 2005, 39, 1835. doi: 10.1021/es0499492
(2) Demessie, E. S.; Devulapelli, V. G. Appl. Catal. B: Environ. 2008, 84, 408. doi: 10.1016/j.apcatb.2008.04.025
(3) Gutiérrez, O.; Kaufmann, C.; Hrabar, A.; Zhu, Y.; Lercher, J. J. Catal. 2011, 280, 264. doi: 10.1016/j.jcat.2011.03.027
(4) Chandra, S.; Soni, K.; Bunkar, R.; Sharma, M.; Singh, B.; Mahato, A. N.; Vijayaraghavan, R. Catal. Commun. 2009, 11, 77. doi: 10.1016/j.catcom.2009.08.014
(5) Beach, L. K. Preparation of Alkyl Mercaptans. US Patent 2667515, 1954-1-26.
(6) Chen, S. P.; Zhang, Y. H.;Wu, M.; Fang,W. P.; Yang, Y. Q. Appl. Catal. A 2012, 431-432, 151.
(7) Chen, S. P.;Wang,W. M.; Zhang, Y. H.;Wei, Y. C.; Fang,W. P.; Yang, Y. Q. J. Mol. Catal. A: Chem. 2012, 365, 60. doi: 10.1016/j.molcata.2012.08.009
(8) Chang, J. S.; Yu, H. B.; Jiang, X. D.; Ma, Y. Q.; Cheng, H.; Zhao, H. Ind. Catal. 2005, 13, 32. [常俊石, 于海斌, 姜雪丹, 马月谦, 成宏, 赵虹. 工业催化, 2005, 13, 32.]
(9) Zhang, Y. H.; Chen, S. P.; Yuan, C. L.; Fang,W. P.; Yang, Y. Q. Chin. J. Catal. 2012, 33, 317. [张元华, 陈世萍, 袁成龙, 方维平, 杨意泉. 催化学报, 2012, 33, 317.]
(10) Barth, J. O. Process for Preparing Methyl Mercaptan from Dialkyl Sulphides and Dialkyl Polysulphides. US Patent 7576243, 2009-8-18.
(11) Mashkina, A. V. Petro. Chem. 2009, 49, 441.
(12) Ziolek, M.; Kujawa, J.; Saur, O.; Lavalley, J. C. J. Phys. Chem. 1993, 97, 9761. doi: 10.1021/j100140a037
(13) Plaisance, C. P.; Dooley, K. M. Catal. Lett. 2009, 128, 449. doi: 10.1007/s10562-008-9772-2
(14) Satokawa, S.; Kobayashi, Y.; Fujiki, H. Appl. Catal. B: Environ. 2005, 56, 51. doi: 10.1016/j.apcatb.2004.06.022
(15) Hwang, C. L.; Tai, N. H. Appl. Catal. A 2011, 393, 251. doi: 10.1016/j.apcata.2010.12.004
(16) Ding, L. H.; Zheng, Y. Catal Commun. 2006, 7, 1035. doi: 10.1016/j.catcom.2006.05.006
(17) Chen, A. P.;Wang, Q.; Li, Q. L.; Hao, Y. J.; Fang,W. P.; Yang, Y. Q. J. Mol. Catal. A: Chem. 2008, 238, 69.
(18) Fan, X. L.; Liu, Y.; Du, X. J.; Liu, C.; Zhang, C. Acta Phys. -Chim. Sin. 2013, 29, 263. [范晓丽, 刘燕, 杜秀娟, 刘崇, 张超. 物理化学学报, 2013, 29, 263.] doi: 10.3866/PKU.WHXB201211231
(19) Koranyi, T. I.; Moreau, F.; Rozanov, V. V.; Rozanova, E. A. J. Mol. Struct. 1997, 410, 103.
(20) Hwang, C. L.; Tai, N. H. Appl. Catal. B 2010, 93, 363. doi: 10.1016/j.apcatb.2009.10.009
(21) Maia, A. J.; Louis, B.; Lam, Y. L.; Pereira, M. M. J. Catal. 2010, 269, 103. doi: 10.1016/j.jcat.2009.10.021
(22) Garcia, C. L.; Johannes, A. L. J. Phys. Chem. 1991, 95, 10729. doi: 10.1021/j100179a040
(23) Mashkina, V. Y. Appl. Catal. A 1994, 109, 45. doi: 10.1016/0926-860X(94)85002-X
(24) Sazama, P.; Dedecek, J.; Gábová, V.;Wichterlová, B.; Spoto, G.; Bordiga, S. J. Catal. 2008, 254, 180. doi: 10.1016/j.jcat.2007.12.005
(25) Luz, R. G.; Hermes, F.; Bertmer, M.; Enrique, R. C.; Antonio, J. L.; Simon, U. Appl. Catal. A 2007, 328, 174. doi: 10.1016/j.apcata.2007.06.003
(26) Wang,W. L.; Liu, B. J.; Zeng, X. J. Acta Phys. -Chim. Sin. 2008, 24, 2102. [王文兰, 刘百军, 曾贤君. 物理化学学报, 2008, 24, 2102.] doi: 10.3866/PKU.WHXB20081128
(27) Seong, M. J.; Demoulin, O.; Grange, P. J. Mol. Catal. A: Chem. 2005, 236, 94. doi: 10.1016/j.molcata.2005.03.028
(28) Pecoraro, T. A.; Chianelli, F. R. J. Catal. 1981, 67, 430. doi: 10.1016/0021-9517(81)90303-1
(29) Mashkina, A. V.; Gruncald, V. R.; Borodin, B. P.; Nasteka, V. I.; Yakovleva, V. N.; Khairulina, L. N. React. Kinet. Catal. Lett. 1991, 43, 361. doi: 10.1007/BF02064698
(30) Koshelev, S. N.; Paukshtis, E. A.; Sagitullin, R. S.; Bezrukov, A. V.; Mashkina, A. V. React. Kinet. Catal. Lett. 1985, 27, 387. doi: 10.1007/BF02070480
(31) Ziolek, M.; Kujawa, J.; Saur, O.; Lavalley, J. C. J. Mol. Catal. A 1995, 97, 49. doi: 10.1016/1381-1169(94)00068-9

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