Citation: YE Tong-Qi, ZHANG Zhao-Xia, XU Yong, YAN Shi-Zhi, ZHU Jiu-Fang, LIU Yong, LI Quan-Xin. Higher Alcohol Synthesis from Bio-Syngas over Na-Promoted CuCoMn Catalyst[J]. Acta Physico-Chimica Sinica, ;2011, 27(06): 1493-1500. doi: 10.3866/PKU.WHXB20110610 shu

Higher Alcohol Synthesis from Bio-Syngas over Na-Promoted CuCoMn Catalyst

1.
1. Anhui Key Laboratory of Biomass Clean Energy, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China;
2. Hefei Tianyan Green Energy Development Co., Ltd., Hefei 230026, P. R. China

Received Date: 20 January 2011
Available Online: 22 April 2011
Fund Project: 国家自然科学基金(50772107) (50772107) 国家重点基础研究发展规划(973) (2007CB210206) (973) (2007CB210206)国家高技术研究发展计划(863) (2009AA05Z435)资助项目 (863) (2009AA05Z435)

Na-promoted CuCoMn catalysts were successfully applied to the highly efficient production of higher alcohols from bio-syngas, which was derived from biomass gasification. The influence of Na content and synthesis conditions (temperature, pressure, and gas hourly space velocity (GHSV)) on higher alcohol synthesis was investigated. The CuCoMnNa_0.1 catalyst gave the best performance for higher alcohol synthesis. Carbon conversion increased significantly with an increase in temperature at lower than 300 °C but alcohol selectivity showed an opposite trend. A higher pressure was found to be beneficial for higher alcohol synthesis. Increasing the GHSV reduced carbon conversion but increased the yield of higher alcohols. The maximum higher alcohol yield that was derived from bio-syngas was 304.6 g·kg^-1·h^-1 with the C₂₊ alcohols (C₂-C₆ higher alcohols) of 64.4% (w, mass fraction) under the conditions used. The distributions of the alcohols and the hydrocarbons were consistent with Anderson-Schulz-Flory (ASF) plots. Adding Na to the CuCoMn catalysts led to an increase in the selectivity toward the higher alcohols and promoted the dispersion of the active elements, copper and cobalt. X-ray photoelectron spectroscopy (XPS) results suggested that Cu was present as a mixture of Cu⁺ and Cu⁰ on the catalyst′s surface after use and Co was present as a mixture of Co²⁺/Co³⁺ and Co⁰. With an increase in sodium addition the Cu⁰/Cu⁺ ratio and the Co⁰ intensity both decreased.
- Biomass,
- Bio-syngas,
- Higher alcohol,
- ASF distribution,
- CuCoMnNa catalyst
1. [1]
  
  (1) Navarro, R. M.; Pena, M. A.; Fierro, J. L. G. Chem. Rev. 2007, 107, 3952.
2. [2]
  (2) Zhang, Q.; Chang, J.;Wang, T. J.; Xu, Y. Energy Convers. Manage. 2007, 48, 87
3. [3]
  (3) Li, H. Y.; Xu, Q. L.; Xue, H. S.; Yan, Y. J. Renewable Energy 2009, 34, 2872.
4. [4]
  (4) Czernik, S.; Bridgwater, A. V. Energy & Fuels 2004, 18, 590.
5. [5]
  (5) Zhou, M.; Yan, L. F.;Wang, Y. Q.; Guo, Q. X.; Zhu, Q. S. Chin. J. Chem. Phys. 2005, 18, 69.
6. [6]
  [周密, 闫立峰, 王益群, 郭庆祥, 朱清时. 化学物理学报, 2005, 18, 69.]
7. [7]
  (6) Tijmensen, M. J. A.; Faaij, A. P. C.; Hamelinck, C. N.; Van Hardeveld, M. R. M. Biomass Bioenergy 2002, 23, 129.
8. [8]
  (7) Steen, E. V.; Claeys, M. Chem. Eng. Technol. 2008, 31, 655.
9. [9]
  (8) Xu, X. D.; Doesburg, E. B. M.; Sckolen, J. J. F. Catal. Today 1987, 2, 125.
10. [10]
  (9) Verkerk, A. N.; Jaeger, B.; Finkeldei, C. H.; Keim,W. Appl. Catal. A 1999, 186, 407.
11. [11]
  (10) Subramani, V.; Gangwal, S. K. Energy & Fuels 2008, 22, 814.
12. [12]
  (11) Li, Z. R.; Fu, Y. L.; Jiang, M.; Hu, T. D.; Liu, T.; Xie, Y. N. Chin. J. Chem. Phys., 2001, 14, 355.
13. [13]
  [李忠瑞, 伏义路, 姜明, 胡天斗, 刘涛, 谢亚宁. 化学物理学报, 2001, 14, 355.]
14. [14]
  (12) Zhang,W.; Luo, H. Y.; Zhou, H.W.;Wu, Z. H.; Huang, S. Y.; Liu, C. Z.; Chu, H. P.; Lin, P. Z.; Lin, L.W. Chin. J. Catal. 1999, 20, 285.
15. [15]
  [张伟, 罗洪源, 周焕文, 吴治华, 黄世煜, 刘崇早, 初惠萍, 林培滋, 林励吾. 催化学报, 1999, 20, 285.]
16. [16]
  (13) Ojeda, M.; Granados, M. L.; Rojas, S.; Terreros, P.; Garcia-Garcia, F. J.; Fierro, J. L. G. Appl. Catal. A 2004, 261, 47.
17. [17]
  (14) Boz, I. Catal. Lett. 2003, 87, 187.
18. [18]
  (15) Tien-Thao, N.; Zahedi-Niaki, M. H.; Alamdari, H.; Kaliaguine, S. J. Catal. 2007, 245, 348.
19. [19]
  (16) Dalmona, J. A.; Chaumetteb, P.; Mirodatos, C. Catal. Today 1992, 15, 101.
20. [20]
  (17) Su, Y. L.; Liu, B.; Pei, S. P.;Wang, X. Y.; Liu, Z. M. Chin. J. Catal. 2004, 25, 683.
21. [21]
  [苏运来, 刘博, 裴素朋, 王向宇, 刘中民. 催化学报, 2004, 25, 683.]
22. [22]
  (18) Xu, R.;Wei,W.; Li,W. H.; Hu, T. D.; Sun, Y. H. J. Mol. Catal. A 2005, 234, 75.
23. [23]
  (19) Gupta, M.; Spivey, J. J. Catal. Today 2009, 147, 126.
24. [24]
  (20) Chen, X. P.;Wu, G. S.;Wang, X. Z.; Sun, Y. H.; Zhong, B. Chin. J. Catal. 2000, 21, 301.
25. [25]
  [陈小平, 吴贵升, 王秀芝, 孙予罕, 钟炳. 催化学报, 2000, 21, 301.]
26. [26]
  (21) Li, D. B.; Qi, H. J.; Li,W. H.; Sun, Y. H.; Zhong, B. Acta Phys. -Chim. Sin. 2006, 22, 1132.
27. [27]
  [李德宝, 齐会杰, 李文怀, 孙予罕, 钟炳. 物理化学学报, 2006, 22, 1132.]
28. [28]
  (22) Ma, X. M.; Lin, G. D.; Zhang, H. B. Chin. J. Catal. 2006, 27, 1019.
29. [29]
  [马晓明, 林国栋, 张鸿斌. 催化学报, 2006, 27, 1019.]
30. [30]
  (23) Sugier, A.; Freund, E.; Malmaison, R. Process for Manufacturing Alcohols and More Particularly Saturated Linear
31. [31]
  Primary Alcohols from Synthesis Gas. US Pat. Appl. 105312, 1981.
32. [32]
  (24) Spivey, J. J.; Kumar, C. S. S. R.; Balaji, G.; Subramanian, N. D. Catal. Today 2009, 147, 100.
33. [33]
  (25) Xu, H. Y.; Chu,W.; Deng, S. Y. Acta Phys. -Chim. Sin. 2010, 26, 345.
34. [34]
  [徐慧远, 储伟, 邓思玉. 物理化学学报, 2010, 26, 345.]
35. [35]
  (26) Mehr, J. Y.; Islami, M.; Peyrovi, M. H.; Mahdavi, V. Appl. Catal. A 2005, 281, 259.
36. [36]
  (27) Zhang, H. B.; Dong, X.; Lin, G. D.; Liang, X. L.; Li, H. Y. Chem. Commun. 2005, 5094.
37. [37]
  (28) Kan, T.; Xiong, J. X.; Li, X. L.; Ye, T. Q.; Yuan, L. X.; Torimoto, Y.; Yamamoto, M.; Li, Q. X. Int. J. Hydrog. Energy 2010, 35, 518.
38. [38]
  (29) Yuan, L. X.; Chen, Y. Q.; Song, C. F.; Ye, T. Q.; Guo, Q. X.; Zhu, Q. S.; Torimoto, Y.; Li, Q. X. Chem. Commun. 2008, 41, 5215.
39. [39]
  (30) Ye, T. Q.; Yuan, L. X.; Chen, Y. Q.; Kan, T.; Tu, J.; Zhu, X. F.; Torimoto, Y.; Yamamoto, M.; Li, Q. X. Catal. Lett. 2009, 127, 323.
40. [40]
  (31) Liu, Y.; Chen, F.; Zhuang, S. X.;Wang, J.; Ma, R. CN Patent CN101191060A, 2007.
41. [41]
  [刘勇, 陈枫, 庄叔贤, 王家俊, 马仁贵. 一种由固体生物质制备合成气的方法和设备: 中国, CN101191060A, 2007]
42. [42]
  (32) Aquino, A. D.; Cobo, A. J. G. Catal. Today 2001, 65, 209.
43. [43]
  (33) Chen, B. S.; Zhao, J. S.; Zhang, L.; Xiong, G. X.; Sheng, S. S. Chin. J. Catal. 1990, 11, 265.
44. [44]
  [陈宝树, 赵九生, 张鎏, 熊国兴, 盛世善. 催化学报, 1990, 11, 265.]
45. [45]
  (34) Li, S.; Li, A.; Krishnamoorthy, S.; Iglesia, E. Catal. Lett. 2001, 77, 197.
46. [46]
  (35) Mross,W. D. Catal. Rev. Sci. Eng. 1983, 25, 591.
47. [47]
  (36) Courty, P.; Durand, D.; Freund, E.; Sugier, A. J. Mol. Catal. 1982, 17, 241.
48. [48]
  (37) Laan, G. P. V.; Beenackers, A. A. C. M. Catal. Rev. Sci. Eng. 1999, 41, 255.
49. [49]
  (38) Sachtler,W. M. H.; Ichikawa, M. J. Phys. Chem. 1986, 90, 4752.
50. [50]
  (39) Dry, M. E. Catal. Today 2002, 71, 227.
51. [51]
  (40) Huang, X.; Curtis, C.W.; Roberts, C. B. Fuel Chemistry Division Preprints 2002, 47, 150.
52. [52]
  (41) Schulz, H. Appl. Catal. A 1999, 186, 3.
53. [53]
  (42) Yang, B. L.; Chan, S. F.; Chang,W. S.; Chen, Y. Z. J. Catal. 1991, 130, 52.
54. [54]
  (43) Li, D. B.; Yang, C.; Li,W. H.; Sun, Y. H.; Zhong, B. Top. Catal. 2005, 32, 233.
55. [55]
  (44) Velu, S.; Suzuki, K.; pinath, C. S. J. Phys. Chem. B 2002, 106, 12737
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