对氯硝基苯在含镧的镍钼硼奈米触媒上的氢化反应

doi:10.1016/S1872-2067(12)60687-1

摘要/Abstract

摘要：

钼和镧是好的镍硼触媒的促进剂, 对于对氯硝基苯氢化反应有好的效果, 因此同时加入钼和镧在镍硼触媒上应该是有趣的研究题目. 本研究利用化学还原法制备了一系列含有不同量镧的镧钼镍触媒, 醋酸镍、钼酸胺及硝酸镧同时加入含有甲醇的水溶液中. 以X光绕射, 穿透式电子显微镜、高分辨率电子显微镜及X光光电能谱仪鉴定了这些触媒. 对氯硝基苯氢化反应是在批次反应器中于333 K、1.2 MPa氢气压力及500 r/min转速下操作. 即使在镍钼硼中加入很少量的镧, 对提高活性及对氯苯胺的选择性都有显著的效果, 加入适量的镧可以抑制镍钼硼的长范围的结晶排列, 并保持镍钼硼在非结晶状态. 镧以氧化态存在, 其功效为阻隔物, 避免镍钼硼聚集, 但是过量的镧会有相反的效果, 镧和镍的适当比例是0.2.

关键词: 硼化镍, 镧, 氢化反应, 含氯硝基苯, 含氯苯胺

Abstract:

Mo and La have been independently reported to be good promoters of NiB nanocluster in the hydrogenation of para-chloronitrobenzene (p-CNB). However, a bi-promoter effect of Mo and La in NiB catalysts has not previously been investigated. In this work, a series of La-Mo-doped, nanosized NiB catalysts with different La contents were prepared by chemical reduction and were characterized by X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The liquid-phase hydrogenation of p-CNB was carried out in a batch reactor at 333 K, 1.2 MPa H₂ pressure and at a spinning rate of 500 r/min. Even doping a small amount of La in NiMoB had a significant effect on its activity and selectivity to p-chloroaniline. The addition of an appropriate amount of La suppressed the growth and long-range order of NiMoB and helped the NiMoB maintain its amorphous state. La was determined to be present in its oxide form and to act as a spacer, preventing NiMoB from sintering and aggregation. However, a high amount of La had an opposite effect, and the optimum ratio of La:Ni was 0.2.

Key words: Nickel, Lanthanum boride, Hydrogenation, Chloronitrobenzene, Chloroaniline

李德馨, 陈郁文. 对氯硝基苯在含镧的镍钼硼奈米触媒上的氢化反应[J]. 催化学报, 2013, 34(11): 2018-2028.

Der-Shing Lee, Yu-Wen Chen. Hydrogenation of p-chloronitrobenzene on La-doped NiMoB nanocluster catalysts[J]. Chinese Journal of Catalysis, 2013, 34(11): 2018-2028.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(12)60687-1

https://www.cjcatal.com/CN/Y2013/V34/I11/2018

参考文献

[1] Liu Y C, Huang C Y, Chen Y W. J Nanopart Res, 2006, 8: 223
[2] Liu Y C, Huang C Y, Chen Y W. Ind Eng Chem Res, 2006, 45: 62
[3] Shen J Y, Hu Z, Zhang Q H, Zhang L F, Chen Y. J Appl Phys, 1992, 71: 5217
[4] Shen J H, Chen Y W. J Mol Catal A, 2007, 273: 265
[5] Shen J Y, Hu Z, Zhang L F, Li Z Y, Chen Y. Appl Phys Lett, 1991, 59: 3545
[6] Su J F, Zhao B, Chen Y W. Ind Eng Chem Res, 2011, 50: 1580
[7] Wang M H, Li H X, Wu Y D, Zhang J. Mater Lett, 2003, 57: 2954
[8] Chen X F, Li H X, Luo H S, Qiao M H. Appl Catal A, 2002, 233: 13
[9] Chen Y. Catal Today, 1998, 44: 3
[10] Chen L F, Chen Y W. Ind Eng Chem Res, 2006, 45: 8866
[11] Li H, Li H X, Dai W L, Wang W J, Fang Z G, Deng J F. Appl Surf Sci, 1999, 152: 25
[12] Li H X, Luo H S, Zhuang L, Dai W L, Qiao M H. J Mol Catal A, 2003, 203: 267
[13] Li H, Zhao Q F, Li H X. J Mol Catal A, 2008, 285: 29
[14] Li H X, Wu Y D, Zhang J, Dai W L, Qiao M H. Appl Catal A, 2004, 275: 199
[15] Li H, Zhang J, Li H X. Catal Commun, 2007, 8: 2212
[16] Wang W Y, Yang Y Q, Luo H A, Liu W Y. Catal Commun, 2010, 11: 803
[17] Zhao B, Chen Y W. J Non-Cryst Solids, 2010, 356: 839
[18] Liu Y C, Chen Y W. Ind Eng Chem Res, 2006, 45: 2973
[19] Ning J B, Xu J, Liu J, Miao H, Ma H, Chen C, Li X Q, Zhou L P, Yu W Q. Catal Commun, 2007, 8: 1763
[20] Yamashita H, Yoshikawa M, Funabiki T, Yoshida S. J Chem Soc, Faraday Trans I, 1986, 82: 1771
[21] Hou Y J, Wang Y Q, He F, Han S, Mi Z T, Wu W, Min E Z. Mater Lett, 2004, 58: 1267
[22] Fang J, Chen X Y, Liu B, Yan S R, Qiao M H, Li H X, He H Y, Fan K N. J Catal, 2005, 229: 97
[23] Deng J F, Li H X, Wang W J. Catal Today, 1999, 51: 113
[24] Dai W L, Qiao M H, Deng J F. Appl Surf Sci, 1997, 120: 119
[25] Hoelderich W F. Catal Today, 2000, 62: 115
[26] Okamoto Y, Nitta Y, Imanaka T, Teranishi S. J Chem Soc, Faraday Trans 1, 1979, 75: 2027
[27] Linderoth S, Mørup S. J Appl Phys, 1991, 69: 5256
[28] Lü L H, Ma Y H, Guo F, Ma R H, Xin J N, Wang Y, Kenji N. Fine Chem (吕连海, 马永欢, 郭方, 马荣华, 辛俊娜, 王越, 根岸贤治. 精细化工), 2008, 25: 251
[29] Ma Y F, Li W, Zhang M H, Zhou Y, Tao K Y. Appl Catal A, 2003, 243: 215
[30] Parks G L, Pease M L, Burns A W, Layman K A, Bussell M E, Wang X Q, Hanson J, Rodriguez J A. J Catal, 2007, 246: 277
[31] Rajesh B, Sasirekha N, Lee S P, Kuo H Y, Chen Y W. J Mol Catal A, 2008, 289: 69
[32] Moulder J F, Stickle W F, Sobol P E, Bomben K D. Handbook of X-Ray Photoelectron Spectroscopy. Minnesota: Physical Electronics, Inc., 1995
[33] Xu Q, Liu X M, Chen J R, Li R X, Li X J. J Mol Catal A, 2006, 260: 299
[34] Yan X P, Liu M H, Liu H F, Liew K Y. J Mol Catal A, 2001, 169: 225
[35] Yan X H, Sun J Q, Wang Y W, Yang J F. J Mol Catal A, 2006, 252: 17
[36] Yan X H, Sun J Q, Xu Y H, Yang J F. Chin J Catal (严新焕, 孙军庆, 徐颖华, 杨建峰. 催化学报), 2006, 27: 119
[37] Zhao B, Chou C J, Chen Y W. Ind Eng Chem Res, 2010, 49: 1669
[38] Liu M H, Yu W Y, Liu H F, Zheng J M. J Colloid Interface Sci, 1999, 214: 231
[39] Han X X, Zhou R X, Lai G H, Zheng X M. Catal Today, 2004, 93-95: 433
[40] Han X X, Zhou R X, Zheng X M, Jiang H. J Mol Catal A, 2003, 193: 103
[41] Coq B, Tijani A, Figuéras F. J Mol Catal, 1992, 71: 317
[42] Coq B, Tijani A, Dutartre R, Figueras F. J Mol Catal, 1993, 79: 253
[43] Noller H, Lin W M. J Catal, 1984, 85: 25