Citation: Dan Dang, Ze Wang, Weigang Lin, Wenli Song. Synthesis of anisole by vapor phase methylation of phenol with methanol over catalysts supported on activated alumina[J]. Chinese Journal of Catalysis, ;2016, 37(5): 720-726. doi: 10.1016/S1872-2067(15)61074-9 shu

Synthesis of anisole by vapor phase methylation of phenol with methanol over catalysts supported on activated alumina

1.
State Key Laboratory of Multi-Phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Corresponding author: Ze Wang,
Received Date: 19 February 2016
Available Online: 25 February 2016
Fund Project: 国家自然科学基金(51476180) (51476180)国家重点基础研究发展计划(973计划,2014CB744304). (973计划,2014CB744304)

The synthesis of anisole by vapor phase methylation of phenol with methanol over activated alumina (AA) supported catalysts was investigated in a fixed bed reactor. KH₂PO₄/AA gave the best performance among the eight tested catalysts. The catalyst was prepared by loading KH₂PO₄ on AA and then calcining at the optimized temperature of 700 ℃ for 8 h. In the vapor phase reaction, the level of anisole yield (LAY) has a maximum at 400-450 ℃ when the temperature varied from 300 to 500 ℃, which decreased slightly with increasing WHSV and increased distinctly with increasing mole fraction of methanol. On comparing O-methylation and C-methylation of phenol, a low temperature, high WHSV (short residence time), and a low methanol concentration over the KH₂PO₄/AA catalyst with higher K contents were found to increase anisole selectivity by O-methylation of phenol. The reaction routes to the major products and the catalytic mechanism were suggested, and a ‘K-acid' bifunctional process may be a critical factor to the formation of anisole.
- Phenol,
- Methanol,
- Catalysis,
- Anisole,
- Methylation
1. [1]
  [1] G. N. Kirichenko, V. I. Glazunova, A. V. Balaev, U. M. Dzhemilev, Petrol. Chem., 2008, 48, 389-392.
2. [2]
  [2] X. J. Song, C. S. Wang, Fine Chem., 2000, 17, 42-44.
3. [3]
  [3] Z. H. Fu, Y. Ono, Catal. Lett., 1993, 21, 43-47.
4. [4]
  [4] S. Ouk, S. Thiebaud, E. Borredon, P. Le Gars, Green Chem., 2002, 4, 431-435.
5. [5]
  [5] G. D. Wu, X. L. Wang, B. Chen, J. P. Li, N. Zhao, W. Wei, Y. H. Sun, Appl. Catal. A, 2007, 329, 106-111.
6. [6]
  [6] Y. Ono, Catal. Today, 1997, 35, 15-25.
7. [7]
  [7] M. Renavd, P. D. Chantal, S. Kaliaguine, Can. J. Chem. Eng., 1986, 64, 787-791.
8. [8]
  [8] S. R. Kirumakki, N. Nagaraju, K. V. R. Chary, S. Narayanan, J. Catal., 2004, 221, 549-559.
9. [9]
  [9] S. C. Lee, S. W. Lee, K. S. Kim, T. J. Lee, D. H. Kim, J. C. Kim, Catal. Today, 1998, 44, 253-258.
10. [10]
  [10] M. E. Sad, C. L. Padró, C. R. Apesteguía, J. Mol. Catal. A, 2010, 327, 63-72.
11. [11]
  [11] K. G. Bhattacharyya, A. K. Talukdar, P. Das, S. Sivasanker, J. Mol. Catal. A, 2003, 197, 255-262.
12. [12]
  [12] M. E. Sad, C, L, Padró, C. R. Apesteguía, Appl. Catal. A, 2008, 342, 40-48.
13. [13]
  [13] K. Sreekumar, S. Sugunan, J. Mol. Catal. A, 2002, 185, 259-268.
14. [14]
  [14] Q. Y. Yu, X. Y. Chou, C. H. Xu, Z. L. Xu, Speciality Petrochem., 2009, 26, 12-14.
15. [15]
  [15] L. Xu, S. J. Wu, W. X. Zhang, M. J. Jia, G. Liu, Acta Phys. Chim. Sin., 2009, 25, 242-246.
16. [16]
  [16] G. Sarala Devi, D. Giridhar, B. M. Reddy, J. Mol. Catal. A, 2002, 181, 173-178.
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沈阳化工大学材料科学与工程学院沈阳 110142