Citation: HU Xiao-Yan, LI Chun-Yi, YANG Chao-He. Catalytic Cracking Behavior of n-Heptane over HZSM-5 Catalyst[J]. Acta Physico-Chimica Sinica, ;2010, 26(12): 3291-3298. doi: 10.3866/PKU.WHXB20101133 shu

Catalytic Cracking Behavior of n-Heptane over HZSM-5 Catalyst

1.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266555, Shandong Province, P. R. China

Received Date: 12 July 2010
Available Online: 14 October 2010
Fund Project: 国家重点基础研究发展规划项目(973) (2006CB202505)资助 (973) (2006CB202505)

The catalytic cracking of n-heptane, which was selected as a model compound for the paraffin of light straight-run naphtha, was studied over HZSM-5 catalyst in a fixed-bed microreactor. Its catalytic behavior was compared with that of 1-heptene and the effects of hydrothermal treatment and catalyst carrier were evaluated. The results showed that compared with the cracking of 1-heptene, the concentration of hydrogen, methane, and ethane was much higher in the cracked gas obtained from the cracking of n-heptane. We concluded that this mainly originated from the monomolecular cracking pathway while the content of propylene and butylene in liquefied petroleum gas (LPG) was much lower. Upon hydrothermal treatment, the total amount of acid decreased sharply, especially the strong Brönsted acid (B acid) sites, leading to a steep decline in catalytic activity. This was accompanied by the improved propylene/ propane and butylene/butane molar ratios in the products. Meanwhile, the ratio between the C₃ and C₄ products decreased, suggesting a decrease in the occurrence of monomolecular cracking. The carrier also significantly influenced the cracking behavior of n-heptane. We found that the presence of Lewis acid (L acid) sites in the carrier improved the n-heptane conversion and promoted the bimolecular cracking pathway. Generally, compared with the olefin reactant, paraffin usually shows much lower reactivity and light olefin selectivity and, therefore, it is not a desirable feed for the catalytic cracking reaction over the zeolite catalyst for the purpose of light olefin production.
- Catalytic cracking,
- HZSM-5,
- Monomolecular cracking,
- Light olefin selectivity,
- Acidity,
- Carrier,
- C₃/C₄ molar ratio
1. [1]
  
  1. Ren, T.; Patel, M.; Blok, K. Energy, 2006, 31: 425
2. [2]
  2. Corma, A.; Melo, F. V.; Sauvanaud, L.; Ortega, F. J. Appl. Catal. A, 2004, 265: 195
3. [3]
  3. Li, C. Y.; Yuan, Q. M.; Chen, X. B.; Yang, C. H.; Shan, H. H.; Zhang, J. F. J. Acta Univ. Petro. (Edi. Natu. Sci.), 2007, 31: 118
4. [4]
  [李春义, 袁起民, 陈小博, 杨朝合, 山红红, 张建芳. 中国石油大学学报(自然科学版), 2007, 31: 118]
5. [5]
  4. Li, C. Y.; Yang, C. H.; Shan. H. H. Ind. Eng. Chem. Res., 2007, 46: 4914
6. [6]
  5. Duan, X. H.; Shan, H. H.; Chen, X. B.; Yang, C. H.; Li, C. Y. Acta Petrolei Sinica (Petro. Pro. Sec.), 2008, 24: 28
7. [7]
  [段秀华, 山红红, 陈小博, 杨朝合, 李春义. 石油学报(石油加工), 2008, 24: 28]
8. [8]
  6. Corma, A.; Planelles, J.; Sánchez-Marín, J.; Tomás, F. J. Catal., 1985, 93: 30
9. [9]
  7. Corma, A.; Montón, J. B.; Orchillés, A. V. Appl. Catal., 1986, 23: 255
10. [10]
  8. Corma, A.; Miguel, P. J.; Orchillés, A. V. Appl. Catal. A, 1994, 117: 29
11. [11]
  9. Yan, L. J.; Fu, J.; He, M. Y. Acta Petrolei Sinica (Petro. Pro. Sec.), 2008, 16: 15
12. [12]
  [阎立军, 傅军, 何鸣元. 石油学报(石油加工), 2008, 16: 15]
13. [13]
  10. Yan, L. J.; Fu, J.; He, M. Y. Acta Petrolei Sinica (Petro. Pro. Sec.), 2008, 16: 6
14. [14]
  [阎立军, 傅军, 何鸣元. 石油学报(石油加工), 2008, 16: 6]
15. [15]
  11. Jolly, S.; Saussey, J.; Bettahar, M. M.; Lavalley, J. C.; Benazzi, E. Appl. Catal. A, 1997, 156: 71
16. [16]
  12. Watson, B. A.; Klein, M. T.; Harding, R. H. Ind. Eng. Chem. Res., 1996, 35: 1506
17. [17]
  13. Wang,W. L.; Liu, B. J.; Zeng, X. J. Acta Phys. -Chim. Sin., 2008, 24: 2102
18. [18]
  [王文兰, 刘百军, 曾贤君. 物理化学学报, 2008, 24: 2102]
19. [19]
  14. Babitz, S. M.;Williams, B. A.; Miller, J. T.; Snurr, R. Q.; Haag, W. O.; Kung, H. H. Appl. Catal. A, 1999, 179: 71
20. [20]
  15. Rane, N.; Kersbulck, M.; Santen, R. A. van Hensen, E. J. M. Microporous Mesoporous Mat., 2008, 110: 279
21. [21]
  16. Marques, J. P.; Gener, I.; Lopes, J. M.; Ribeiro, F. R.; Guisnet, M. Catal. Today, 2005, 107-108: 726
22. [22]
  17. Kissin, Y. V. Catal. Rev., 2001, 43: 85 18. Corma, A.; Orchillés, A. V. Microporous Mesoporous Mat., 2000, 35-36: 21
23. [23]
  19. Long, J.;Wei, X. L. Acta Petrolei Sinica (Petro. Pro. Sec.), 2007, 23: 1
24. [24]
  [龙军, 魏晓丽. 石油学报(石油加工), 2007, 23: 1]
25. [25]
  20. Planelles, J.; Sanchez-Marin, J.; Tomas, F. J. Mol. Catal., 1985, 32: 365
26. [26]
  21. Wielers, A. F. H.; Vaarkamp, M.; Post, M. F. M. J. Catal., 1991, 127: 51
27. [27]
  22. Mirodatos, C.; Barthomeuf, D. J. Catal., 1988, 114: 121
28. [28]
  23. Luo, L.W.; Lu, R. Q. J. Fuel Chem. Tech., 2004, 32: 606
29. [29]
  24. Brait, A.; Koopmans, A.;Weinstabl, H. Ind. Eng. Chem. Res., 1998, 37: 873
30. [30]
  25. Tung, S. E.; McIninch, E. J. Catal., 1968, 10: 166
31. [31]
  26. Liu, X. B.; Xu, H. Y.; Li,W. Z.; Chen, Y. X. Acta Petrolei Sinica (Petro. Pro. Sec.), 2004, 20: 88
32. [32]
  [刘雪斌, 徐恒泳, 李文钊, 陈燕馨. 石油学报(石油加工), 2004, 20: 88]
33. [33]
  27. Zhang, C. L.; Zhu, H. O.; Liu, X. B.; Li,W. Z.; Xu, H. Y. J. Fuel Chem. Tech., 2006, 34: 439
34. [34]
  [张存龙, 朱海欧, 刘雪斌, 李文钊, 徐恒泳. 燃料化学学报, 2006, 34: 439]
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