Citation: Christiaan H. L. Tempelman, Xiaochun Zhu, Emiel J. M. Hensen. Activation of Mo/HZSM-5 for methane aromatization[J]. Chinese Journal of Catalysis, ;2015, 36(6): 829-837. doi: 10.1016/S1872-2067(14)60301-6 shu

Activation of Mo/HZSM-5 for methane aromatization

1.
Laboratory of Inorganic Materials Chemistry, Schuit Institute of Catalysis, Eindhoven University of Technology, Den Dolech 2, 5612 AZ Eindhoven, The Netherlands

Corresponding author: Emiel J. M. Hensen,
Received Date: 7 December 2014
Available Online: 29 January 2015
Fund Project: This work was supported by the European Union through the EU-FP7 NEXT-GTL consortium (NMP3-LA-2009-229183). (NMP3-LA-2009-229183)

The effect of Mo/HZSM-5 pretreatment at 973 K in inert (He), oxidizing (artificial air), and carburizing (CH₄/He mixture) atmospheres on its performance in non-oxidative methane dehydroaromatization (MDA) was investigated. The effect of post-synthesis silylation on deactivation of external acid sites was also studied. Precarburization resulted in increased aromatic selectivity and improved catalyst stability. The benzene selectivity was the highest for the silylated Mo/HZSM-5 catalyst (benzene + naphthalene selectivity after 1 h on stream was close to 100%). The deactivation of precarburized zeolites was less pronounced than that of zeolites heated in air or He. During heating in air or He, larger fractions of the molybdenum oxide species diffused into the micropores than during heating in methane. Carburization of the molybdenum oxide species in the micropores during MDA resulted in the formation of molybdenum carbide particles, and these contributed to pore blocking, making the Brønsted acid sites inaccessible. The formation of molybdenum carbides during heating in methane resulted in a less mobile Mo phase. It is argued that the presence of molybdenum carbide particles in the micropores contributes to rapid catalyst deactivation, in addition to the formation of hard coke on the external surface.
- Methane aromatization,
- Molybdenum,
- HZSM-5,
- Pretreatment,
- Carburization,
- Silylation
1. [1]
  [1] British Petroleum. BP Statistical Review of World Energy. London: BP, 2013
2. [2]
  [2] Holmen A. Catal Today, 2009, 142: 2
3. [3]
  [3] Sousa-Aguiar E F, Appel L G, Mota C. Catal Today, 2005, 101: 3
4. [4]
  [4] Perego C, Bortolo R, Zennaro R. Catal Today, 2009, 142: 9
5. [5]
  [5] Rostrup-Nielsen J R. Catal Today, 2002, 71: 243
6. [6]
  [6] Zhang W P, Ma D, Han X W, Liu X M, Bao X H, Gao X W, Wang X S. J Catal, 1999, 188: 393
7. [7]
  [7] Wang L S, Tao L X, Xie M S, Xu G F, Huang J S, Xu Y D. Catal Lett, 1993, 21: 35
8. [8]
  [8] Xu Y D, Liu S T, Wang L S, Xie M S, Guo X X. Catal Lett, 1995, 30: 135
9. [9]
  [9] Liu W, Xu Y, Wong S T, Wang L, Qiu J, Yang N. J Mol Catal A, 1997, 120: 257
10. [10]
  [10] Majhi S, Mohanty P, Wang H, Pant K K. J Enery Chem, 2013, 22: 543
11. [11]
  [11] Ren D M, Wang X S, Li G, Cheng X J, Long H Y, Chen L D. J Nat Gas Chem, 2010, 19: 646
12. [12]
  [12] Ma S Q, Guo X G, Zhao L X, Scott S, Bao X H. J Enery Chem, 2013, 22: 1
13. [13]
  [13] Iliuta M C, Iliuta I, Grandjean B P A, Larachi F. Ind Eng Chem Res, 2003, 42: 3203
14. [14]
  [14] Behrsing T, Jaeger H, Sanders J V. Appl Catal, 1989, 54: 289
15. [15]
  [15] Su L L, Liu L, Zhuang J Q, Wang H X, Li Y G, Shen W J, Xu Y D, Bao X H. Catal Lett, 2003, 91: 155
16. [16]
  [16] Chen L Y, Lin L W, Xu Z S, Li X S, Zhang T. J Catal, 1995, 157: 190
17. [17]
  [17] Liu S, Wang L, Ohnishi R, Ichikawa M. Kinet Catal, 2000, 41: 132
18. [18]
  [18] Weckhuysen B M, Rosynek M P, Lunsord J H. Catal Lett, 1998, 52: 31
19. [19]
  [19] Ma D, Wang D Z, Su L L, Shu Y Y, Xu Y D, Bao X H. J Catal, 2002, 208: 260
20. [20]
  [20] Descorme C, Gelin P, Lecuyer C, Primet A. Appl Catal B, 1997, 13: 185
21. [21]
  [21] Ding W P, Meitzner G D, Iglesia E. J Catal, 2002, 206: 14
22. [22]
  [22] Liu H M, Li Y, Shen W J, Bao X H, Xu Y D. Catal Today, 2004, 93: 65
23. [23]
  [23] Kikuchi S, Kojima R, Ma H T, Bai J, Ichikawa M. J Catal, 2006, 242: 349
24. [24]
  [24] Tempelman C H L, de Rodrigues V O, van Eck E R H, Magusin P C M M, Hensen E J M. Microporous Mesoporous Mater, 2015, 203: 259
25. [25]
  [25] Tempelman C H L, Hensen E J M. Unpublished results.
26. [26]
  [26] Ismagilov Z R, Matus E V, Tsikoza L T. Energy Environ Sci, 2008, 1: 526
27. [27]
  [27] Lacheen H S, Iglesia E. Phys Chem Chem Phys, 2005, 7: 538
28. [28]
  [28] Shu J, Adnot A, Grandjean B P A. Ind Eng Chem Res, 1999, 38: 3860
29. [29]
  [29] Shu Y Y, Ma D, Xu L Y, Xu Y D, Bao X H. Catal Lett, 2000, 70: 67
30. [30]
  [30] Zhang C L, Li S A, Yuan Y, Zhang W X, Wu T H, Lin L W. Catal Lett, 1998, 56: 207
31. [31]
  [31] Liu S T, Wang L S, Ohnishi R, Ichikawa M. J Catal, 1999, 181: 175
32. [32]
  [32] Wang L S, Xu Y D, Wong S T, Cui W, Guo X X. Appl Catal A, 1997, 152: 173
33. [33]
  [33] Wang D J, Lunsford J H, Rosynek M P. J Catal, 1997, 169: 347
34. [34]
  [34] Jiang H, Wang L, Cui W, Xu Y, Catal Lett, 1999, 57: 95
35. [35]
  [35] Zheng S R, Heydenrych H R, Jentys A, Lercher J A. J Phys Chem B, 2002, 106: 9552
36. [36]
  [36] Lippens B C, de Boer J H. J Catal, 1965, 4: 319
37. [37]
  [37] Datka J, Turek A M, Jehng J H, Wachs I E. J Catal, 1992, 135: 136
38. [38]
  [38] Ma D, Shu Y Y, Bao X H, Xu Y D. J Catal, 2000, 189: 314
39. [39]
  [39] Ma D, Shu Y Y, Cheng M J, Xu Y D, Bao X H. J Catal, 2000, 194: 105
40. [40]
  [40] Solymosi F, Cserényi J, Szöke A, Bánsági T, Oszkó A. J Catal, 1997, 165: 150
41. [41]
  [41] Tessonnier J P, Louis B, Rigolet S, Ledoux M J, Pham-Huu C. Appl Catal A, 2008, 336: 79
42. [42]
  [42] Liu B S, Jiang L, Sun H, Au C T. Appl Surf Sci, 2007, 253: 5092
43. [43]
  [43] Beck L W, Xu T, Nicholas J B, Haw J F. J Am Chem Soc, 1995, 117: 11594
44. [44]
  [44] Hensen E J M, Poduval D G, Ligthart D A J M, van Veen J A R, Rigutto M S. J Phys Chem C, 2010, 114: 8363
45. [45]
  [45] Haro-Poniatowski E, Julien C, Pecquenard B, Livage J, Camacho-López M A. J Mater Res, 1998, 13: 1033
46. [46]
  [46] Borry III R W, Kim Y H, Huffsmith A, Reimer J A, Iglesia E. J Phys Chem B, 1999, 103: 5787
47. [47]
  [47] Lacheen H S, Iglesia E. J Catal, 2005, 230: 173
48. [48]
  [48] Liu H M, Bao X H, Xu Y D. J Catal, 2006, 239: 441
49. [49]
  [49] Bouchy C, Schmidt I, Anderson J R, Jacobsen C J H, Derouane E G, Derouane-Abd Hamid S B. J Mol Catal A, 2000, 163: 283
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