Ni-Co双金属催化剂上沼气重整制氢机理

引用本文: 徐军科, 沈利红, 周伟, 马建新. Ni-Co双金属催化剂上沼气重整制氢机理[J]. 物理化学学报, 2011, 27(03): 697-704. doi: 10.3866/PKU.WHXB20110309 shu

Citation: XU Jun-Ke, SHEN Li-Hong, ZHOU Wei, MA Jian-Xin. Mechanism of Biogas Reforming for Hydrogen Production over Ni-Co Bimetallic Catalyst[J]. Acta Physico-Chimica Sinica, 2011, 27(03): 697-704. doi: 10.3866/PKU.WHXB20110309 shu

Ni-Co双金属催化剂上沼气重整制氢机理

基金项目:
科技部国际合作重点项目(2007DFC61690) (2007DFC61690)

汉高同济教席(081591)资助 (081591)

摘要:

用传统湿式浸渍法制备了La₂O₃掺杂的商业γ-Al₂O₃负载的沼气重整催化剂Ni-Co/La₂O₃-γ-Al₂O₃, 并用程序升温加氢(TPH)、程序升温氧化(TPO)、程序升温表面反应(TPSR)、程序升温脱附(TPD)及脉冲实验对催化剂进行了表征. 结果表明, 沼气重整过程中Ni-Co/La₂O₃-γ-Al₂O₃催化剂上的表面碳物种主要来源于CH₄的裂解, CO₂的贡献很小. CH₄裂解能够产生三种活性不同的碳物种, 即C_α、C_β与C_γ. 随着反应的进行, C_α物种减小而C_β与C_γ物种增加, 且C_γ物种能够转变为惰性的石墨碳. 重整反应过程中CH₄与CO₂的活化能相互促进. 催化剂表面的O物种与C反应生成CO或与CH_x反应生成CH_xO再分解为CO与吸附态的H物种, 可能是Ni-Co/La₂O₃-γ-Al₂O₃催化剂上沼气重整的速率控制步骤.

关键词:

镍
/ 钴
/ 双金属催化剂
/ 沼气重整
/ 制氢
/ 机理

English

Mechanism of Biogas Reforming for Hydrogen Production over Ni-Co Bimetallic Catalyst

1.
1. Clean Energy Automotive Engineering Center, Tongji University, Shanghai 201804, P. R. China;
2. Shanghai Baoshan Environmental Monitoring Station, Shanghai 201901, P. R. China;
3. School of Automotive Engineering, Tongji University, Shanghai 201804, P. R. China
Received Date: 27 September 2010
Available Online: 03 March 2011
Fund Project:
科技部国际合作重点项目(2007DFC61690)

汉高同济教席(081591)资助

Abstract:

Ni-Co bimetallic catalysts supported on commercial γ-Al₂O₃ modified with La₂O₃ were prepared by conventional incipient wetness impregnation for biogas reforming. The catalysts were characterized using temperature-programmed hydrogenation (TPH), temperature-programmed oxygenation (TPO), temperature-programmed surface reaction (TPSR), temperature-programmed desorption (TPD), and a pulse experiment. During biogas reforming the surface carbon species on Ni-Co/La₂O₃-γ-Al₂O₃ originated mainly from the cracking of CH₄ and the contribution of CO₂ was insignificant. Cracking of CH₄ results in three carbon species of C_α, C_β, and C_γ, which have different reaction activities. During the reaction, the amount of C_α decreased but C_β and C_γ increased. In addition, C_γ could be changed into inactive graphite carbon. The activation of CH₄ and CO₂ was mutually promoted in the reforming reaction. It was revealed that the controlling step for biogas reforming over the Ni-Co/La₂O₃-γ-Al₂O₃ catalyst could be the reaction of the surface species of O with C to form CO or with CH_x to give CH_xO followed by the formation of CO and adsorbed H.

Key words:

1. [1]
  
  (1) Effendi, A.; Hellgardt, K.; Zhang, Z.; Yoshida, G. T. Fuel 2005, 84, 869.
  (1) Effendi, A.; Hellgardt, K.; Zhang, Z.; Yoshida, G. T. Fuel 2005, 84, 869.
2. [2]
  (2) Duerr, M.; Gair, S.; Cruden, A.; McDonald, J. Int. J. Hydrog. Energy 2007, 32, 705.(2) Duerr, M.; Gair, S.; Cruden, A.; McDonald, J. Int. J. Hydrog. Energy 2007, 32, 705.
3. [3]
  (3) Purwanto, H.; Akiyama, T. Int. J. Hydrog. Energy 2006, 31, 491.(3) Purwanto, H.; Akiyama, T. Int. J. Hydrog. Energy 2006, 31, 491.
4. [4]
  (4) Barrai, F.; Jackson, T.; Whitmore, N.; Castaldi, M. J. Catal. Today 2007, 129, 391.(4) Barrai, F.; Jackson, T.; Whitmore, N.; Castaldi, M. J. Catal. Today 2007, 129, 391.
5. [5]
  (5) Effendi, A.; Zhang, Z. G.; Hellgardt, K.; Hondaa, K.; Yoshida, T. Catal. Today 2002, 77, 181.(5) Effendi, A.; Zhang, Z. G.; Hellgardt, K.; Hondaa, K.; Yoshida, T. Catal. Today 2002, 77, 181.
6. [6]
  (6) Yentekakis, I. V.; Papadam, T.; ula, G. Solid State Ionics 2008, 179, 1521.(6) Yentekakis, I. V.; Papadam, T.; ula, G. Solid State Ionics 2008, 179, 1521.
7. [7]
  (7) Ashrafi, M.; Pr?ll, T.; Pfeifer, C.; Hofbauer, H. Energ. Fuel 2008, 22, 4182.(7) Ashrafi, M.; Pr?ll, T.; Pfeifer, C.; Hofbauer, H. Energ. Fuel 2008, 22, 4182.
8. [8]
  (8) Ashrafi, M.; Pfeifer, C.; Pröll, T.; Hofbauer, H. Energ. Fuel 2008, 22, 4190.(8) Ashrafi, M.; Pfeifer, C.; Pröll, T.; Hofbauer, H. Energ. Fuel 2008, 22, 4190.
9. [9]
  (9) Chun, Y. N.; Song, H. W.; Kim, S. C.; Lim, M. S. Energ. Fuel 2008, 22, 123.(9) Chun, Y. N.; Song, H. W.; Kim, S. C.; Lim, M. S. Energ. Fuel 2008, 22, 123.
10. [10]
  (10) Barrai, F.; Jackson, T.; Whitmore, N.; Castaldi, M. J. Catal. Today 2007, 129, 391.(10) Barrai, F.; Jackson, T.; Whitmore, N.; Castaldi, M. J. Catal. Today 2007, 129, 391.
11. [11]
  (11) Muradov, N.; Smith, F. Energ. Fuel 2008, 22, 2053.(11) Muradov, N.; Smith, F. Energ. Fuel 2008, 22, 2053.
12. [12]
  (12) Xu, J. K.; Ren, K. W.; Wang, X. L.; Zhou, W.; Pan, X. M.; Ma, J. X. Acta Phys. -Chim. Sin. 2008, 24, 1568.(12) Xu, J. K.; Ren, K. W.; Wang, X. L.; Zhou, W.; Pan, X. M.; Ma, J. X. Acta Phys. -Chim. Sin. 2008, 24, 1568.
13. [13]
  [徐军科, 任克威, 王晓蕾, 周伟, 潘相敏, 马建新. 物理化学学报, 2008, 24, 1568.][徐军科, 任克威, 王晓蕾, 周伟, 潘相敏, 马建新. 物理化学学报, 2008, 24, 1568.]
14. [14]
  (13) Xu, J. K.; Zhou, W.; Li, Z. J.; Wang, J. H.; Ma, J. X. Int. J. Hydrog. Energy 2009, 34, 6646.(13) Xu, J. K.; Zhou, W.; Li, Z. J.; Wang, J. H.; Ma, J. X. Int. J. Hydrog. Energy 2009, 34, 6646.
15. [15]
  (14) Xu, J. K.; Zhou, W.; Li, Z. J.; Wang, J. H.; Ma, J. X. Int. J. Hydrog. Energy 2010, 35, 13013.(14) Xu, J. K.; Zhou, W.; Li, Z. J.; Wang, J. H.; Ma, J. X. Int. J. Hydrog. Energy 2010, 35, 13013.
16. [16]
  (15) Xu, J. K.; Zhou, W.; Wang, J. H.; Li, Z. J.; Ma, J. X. Chinese J. Catal. 2009, 30, 1076.(15) Xu, J. K.; Zhou, W.; Wang, J. H.; Li, Z. J.; Ma, J. X. Chinese J. Catal. 2009, 30, 1076.
17. [17]
  (16) Wang, H. Y.; Au, C. T. Catal. Lett. 1996, 38, 77.(16) Wang, H. Y.; Au, C. T. Catal. Lett. 1996, 38, 77.
18. [18]
  (17) Wang, H. Y.; Au, C. T. Appl. Catal. A 1997, 155, 239.(17) Wang, H. Y.; Au, C. T. Appl. Catal. A 1997, 155, 239.
19. [19]
  (18) Kim, G. J.; Cho, D. S.; Kim, K. H.; Kim. J. H.; Catal. Lett. 1994, 28, 41.(18) Kim, G. J.; Cho, D. S.; Kim, K. H.; Kim. J. H.; Catal. Lett. 1994, 28, 41.
20. [20]
  (19) Zhang, Z. L.; Verykios, X. E. Catal. Lett. 1996, 38, 175.(19) Zhang, Z. L.; Verykios, X. E. Catal. Lett. 1996, 38, 175.
21. [21]
  (20) Nakamura, J.; Aikawa, K.; Sato, K.; Uchijima, T. Catal. Lett. 1994, 25, 265.(20) Nakamura, J.; Aikawa, K.; Sato, K.; Uchijima, T. Catal. Lett. 1994, 25, 265.
22. [22]
  (21) Erd?helyi, A.; Fodor, K.; Solymosi, F. Stud. Surf. Sci. Catal. 1997, 107, 525.(21) Erd?helyi, A.; Fodor, K.; Solymosi, F. Stud. Surf. Sci. Catal. 1997, 107, 525.
23. [23]
  (22) Xu, Z. L. Journal of Jilin Normal University (Natural Science Edition) 2003, 20.(22) Xu, Z. L. Journal of Jilin Normal University (Natural Science Edition) 2003, 20.
24. [24]
  [徐占林. 吉林师范大学学报: 自然科学版, 2003, 20.][徐占林. 吉林师范大学学报: 自然科学版, 2003, 20.]
25. [25]
  (23) Bradford, M. C. J.; Vannice, M. A. J.Catal. 1998, 173, 157.(23) Bradford, M. C. J.; Vannice, M. A. J.Catal. 1998, 173, 157.
26. [26]
  (24) Schuurman, Y.; Marquez-Alvarez, C.; Kroll, V. C. H.; Mirodatos, C. Catal. Today 1998, 46, 185.(24) Schuurman, Y.; Marquez-Alvarez, C.; Kroll, V. C. H.; Mirodatos, C. Catal. Today 1998, 46, 185.
27. [27]
  (25) Hu, Y. H.; Ruckenstein, E. J. Phys. Chem. B 1997, 101, 7563.(25) Hu, Y. H.; Ruckenstein, E. J. Phys. Chem. B 1997, 101, 7563.
28. [28]
  (26) Chang, J. S.; Park, S. E.; Yoo, J. W.; Park, J. N. J. Catal. 2000, 195, 1.(26) Chang, J. S.; Park, S. E.; Yoo, J. W.; Park, J. N. J. Catal. 2000, 195, 1.
29. [29]
  (27) Kroll, V. C. H.; Swann, H. M.; Lacombe, S.; Mirodatos, C. J. Catal. 1996, 164, 387.(27) Kroll, V. C. H.; Swann, H. M.; Lacombe, S.; Mirodatos, C. J. Catal. 1996, 164, 387.
30. [30]
  (28) Osaki, T.; Masuda, H.; Horiuchi, T.; Mori, T. Catal. Lett. 1995, 34, 59.(28) Osaki, T.; Masuda, H.; Horiuchi, T.; Mori, T. Catal. Lett. 1995, 34, 59.
31. [31]
  (29) Luo, J. Z.; Yu, Z. L.; Ng, C. F.; Au, C. T. J. Catal. 2000, 194, 198.(29) Luo, J. Z.; Yu, Z. L.; Ng, C. F.; Au, C. T. J. Catal. 2000, 194, 198.
32. [32]
  (30) Darujati, A. R. S.; Thomson, W. J. Chem. Eng. Sci. 2006, 61, 4309.(30) Darujati, A. R. S.; Thomson, W. J. Chem. Eng. Sci. 2006, 61, 4309.
33. [33]
  (31) Nandini, A.; Pant, K. K.; Dhingra, S. C. Appl. Catal. A 2006, 308, 119.(31) Nandini, A.; Pant, K. K.; Dhingra, S. C. Appl. Catal. A 2006, 308, 119.
34. [34]
  (32) Tsipouriari, V. A.; Verykios, X. E. Catal. Today 2001, 64, 83.(32) Tsipouriari, V. A.; Verykios, X. E. Catal. Today 2001, 64, 83.
35. [35]
  (33) Qian, L.; Yan, Z. F. Journal of Fudan University (Natural Science) 2003, 42, 392.(33) Qian, L.; Yan, Z. F. Journal of Fudan University (Natural Science) 2003, 42, 392.
36. [36]
  [钱岭, 阎子峰. 复旦学报: 自然科学版, 2003, 42, 392.][钱岭, 阎子峰. 复旦学报: 自然科学版, 2003, 42, 392.]
37. [37]
  (34) Zhang, Z. L.; Verykios, X. E. Catal. Today 1994, 21, 589.(34) Zhang, Z. L.; Verykios, X. E. Catal. Today 1994, 21, 589.
38. [38]
  (35) Guo, J. J.; Lou, H.; Zheng, X. M. Carbon 2007, 45, 1314.
  (35) Guo, J. J.; Lou, H.; Zheng, X. M. Carbon 2007, 45, 1314.

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

Ni-Co双金属催化剂上沼气重整制氢机理

English

Mechanism of Biogas Reforming for Hydrogen Production over Ni-Co Bimetallic Catalyst

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Ni-Co双金属催化剂上沼气重整制氢机理

English

Mechanism of Biogas Reforming for Hydrogen Production over Ni-Co Bimetallic Catalyst

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

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CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

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