助剂对NiMgAl催化剂的结构和甲烷二氧化碳重整反应性能的影响

引用本文: 郭章龙, 黄丽琼, 储伟, 罗仕忠. 助剂对NiMgAl催化剂的结构和甲烷二氧化碳重整反应性能的影响[J]. 物理化学学报, 2014, 30(4): 723-728. doi: 10.3866/PKU.WHXB201402242 shu

Citation: GUO Zhang-Long, HUANG Li-Qiong, CHU Wei, LUO Shi-Zhong. Effects of Promoter on NiMgAl Catalyst Structure and Performance for Carbon Dioxide Reforming of Methane[J]. Acta Physico-Chimica Sinica, 2014, 30(4): 723-728. doi: 10.3866/PKU.WHXB201402242 shu

助剂对NiMgAl催化剂的结构和甲烷二氧化碳重整反应性能的影响

基金项目:
国家重点基础研究规划项目（973）（2011CB201202）资助

摘要:

向担载镍基催化剂NiMgAl 中添加助剂（Co，Ir 或Pt）制备了三种助剂促进型催化剂，通过氢气程序升温还原（H₂-TPR），CO₂/CH₄程序升温表面反应（CO₂/CH₄-TPSR）和CO₂程序升温脱附（CO₂-TPD）等方法对催化剂进行表征. 助剂对催化剂性能的影响通过甲烷干重整实验进行评价. 添加少量的Pt 或Ir 助剂可以降低Ni 活性组分的还原温度和提高反应性能. 添加助剂的样品与原始NiMgAl催化剂相比能够降低反应的活化能，添加Co或Ir 助剂的催化剂与NiMgAl 催化剂相比活化能有了明显的降低. NiMgAl 催化剂的活化能为51.8 kJ·mol^-1，添加Pt 助剂的NiPtMgAl 催化剂活化能降至26.4 kJ·mol^-1. NiMgAl 催化剂中添加Pt 助剂制备的催化剂具有较好的催化活性和较低的活化能. CH₄-TPSR和CO₂-TPSR结果表明添加Pt 助剂可以在更低的温度下（与NiMgAl催化剂相比）提高CH₄的活化能力，并在催化剂表面形成更多的碳物种. CO₂-TPD结果显示，添加助剂的催化剂与NiMgAl样品相比在反应温度区间内增加了CO₂的吸附/脱附量.

关键词:

English

Effects of Promoter on NiMgAl Catalyst Structure and Performance for Carbon Dioxide Reforming of Methane

1.
1 Department of Chemical Engineering, Sichuan University, Chengdu 610065, P. R. China;
2 Department of Chemical Engineering, Yunnan Open University, Kunming 650223, P. R. China
Received Date: 06 December 2013
Available Online: 31 March 2014
Fund Project:
国家重点基础研究规划项目（973）（2011CB201202）资助

Abstract:

Catalysts were prepared by adding different types of promoter (Co, Ir, or Pt) to the supported nickel catalyst NiMgAl samples. These catalysts were characterized by H₂ temperature-programmed reduction (H₂-TPR), CO₂/CH₄ temperature-programmed surface reactions (CO₂/CH₄-TPSR), and CO₂ temperatureprogrammed desorption (CO₂-TPD). The effects of the catalyst structure on catalytic performance in the methane dry reforming reaction with carbon dioxide were investigated. The addition of a small amount of promoter (Pt or Ir) can lower the reduction temperature of the nickel active component, and enhance performance in the methane dry reforming reaction. The catalysts with Co or Ir promoter feature lower activation energies than the unmodified NiMgAl catalyst. The activation energy was 51.8 kJ·mol^-1 for the NiMgAl sample, decreasing to 26.4 kJ·mol^-1 for the NiPtMgAl catalyst, which showed overall better catalytic performance. Results of CH₄-TPSR and CO₂-TPSR demonstrate that the NiPtMgAl catalyst can generate more active carbon species on the catalyst surface. The CO₂-TPD results show that adding a promoter can increase the CO₂ adsorbed/desorbed amount compared with the unmodified NiMgAl catalyst over the same reaction temperature range.

Key words:

Carbon dioxide reforming of methane
/ Nickel-based catalyst
/ Pt promoter
/ Catalytic activity
/ Activation energy
/ Temperature-programmed surface reaction

1. [1]
  
  (1) Wang, Q.; Luo, J. Z.; Zhong, Z. Y.; Borgna, A. Energ. Environ. Sci. 2011, 4, 42. doi: 10.1039/c0ee00064g
  (1) Wang, Q.; Luo, J. Z.; Zhong, Z. Y.; Borgna, A. Energ. Environ. Sci. 2011, 4, 42. doi: 10.1039/c0ee00064g
2. [2]
  (2) Chu,W.; Ran, M. F.; Zhang, X.;Wang, N.;Wang, Y. F.; Xie, H. P.; Zhao, X. S. J. Energy Chem. 2013, 22, 136. doi: 10.1016/S2095-4956(13)60018-2(2) Chu,W.; Ran, M. F.; Zhang, X.;Wang, N.;Wang, Y. F.; Xie, H. P.; Zhao, X. S. J. Energy Chem. 2013, 22, 136. doi: 10.1016/S2095-4956(13)60018-2
3. [3]
  (3) Hansen, J.; Sato, M. Proc. Natl. Acad. Sci. U. S. A. 2004, 101, 16109. doi: 10.1073/pnas.0406982101(3) Hansen, J.; Sato, M. Proc. Natl. Acad. Sci. U. S. A. 2004, 101, 16109. doi: 10.1073/pnas.0406982101
4. [4]
  (4) von der Assen, N.; Jung, J.; Bardow, A. Energ. Environ. Sci. 2013, 6, 2721. doi: 10.1039/c3ee41151f(4) von der Assen, N.; Jung, J.; Bardow, A. Energ. Environ. Sci. 2013, 6, 2721. doi: 10.1039/c3ee41151f
5. [5]
  (5) Serrano-Ruiz, J. C.; Dumesic, J. A. Energ. Environ. Sci. 2011, 4, 83. doi: 10.1039/c0ee00436g(5) Serrano-Ruiz, J. C.; Dumesic, J. A. Energ. Environ. Sci. 2011, 4, 83. doi: 10.1039/c0ee00436g
6. [6]
  (6) Ashcroft, A. T.; Cheetham, A. K.; Green, M. L. H.; Vernon, P. D. F. Nature 1991, 352, 225. doi: 10.1038/352225a0(6) Ashcroft, A. T.; Cheetham, A. K.; Green, M. L. H.; Vernon, P. D. F. Nature 1991, 352, 225. doi: 10.1038/352225a0
7. [7]
  (7) Ramos, L.; Zeppieri, S. Fuel 2013, 110, 141. doi: 10.1016/j.fuel.2012.12.045(7) Ramos, L.; Zeppieri, S. Fuel 2013, 110, 141. doi: 10.1016/j.fuel.2012.12.045
8. [8]
  (8) Chu,W.;Wang, L. N.; Chernavsk, P. A.; Khodakov, A. Y. Angew. Chew. Int. Edit. 2008, 47, 5052. doi: 10.1002/anie.v47:27(8) Chu,W.;Wang, L. N.; Chernavsk, P. A.; Khodakov, A. Y. Angew. Chew. Int. Edit. 2008, 47, 5052. doi: 10.1002/anie.v47:27
9. [9]
  (9) Ha, K. S.; Bae, J.W.;Woo, K. J.; Jun, K.W. Environ. Sci. Technol. 2010, 44, 1412. doi: 10.1021/es902784x(9) Ha, K. S.; Bae, J.W.;Woo, K. J.; Jun, K.W. Environ. Sci. Technol. 2010, 44, 1412. doi: 10.1021/es902784x
10. [10]
  (10) Wang, N.; Chu,W.; Zhang, T.; Zhao, X. S. Chem. Eng. J. 2011, 170, 457. doi: 10.1016/j.cej.2010.12.042(10) Wang, N.; Chu,W.; Zhang, T.; Zhao, X. S. Chem. Eng. J. 2011, 170, 457. doi: 10.1016/j.cej.2010.12.042
11. [11]
  (11) Aldashukurova, G. B.; Mironenko, A. V.; Mansurov, Z. A.; Shikina, N. V.; Yashnik, S. A.; Kuznetsov, V. V.; Ismagilov, Z. R. J. Energy Chem. 2013, 22, 811. doi: 10.1016/S2095-4956(13)60108-4(11) Aldashukurova, G. B.; Mironenko, A. V.; Mansurov, Z. A.; Shikina, N. V.; Yashnik, S. A.; Kuznetsov, V. V.; Ismagilov, Z. R. J. Energy Chem. 2013, 22, 811. doi: 10.1016/S2095-4956(13)60108-4
12. [12]
  (12) Zhang, J. G.;Wang, H.; Dalai, A. K. J. Catal. 2007, 249, 300 300. doi: 10.1016/j.jcat.2007.05.004(12) Zhang, J. G.;Wang, H.; Dalai, A. K. J. Catal. 2007, 249, 300 300. doi: 10.1016/j.jcat.2007.05.004
13. [13]
  (13) Crisafulli, C.; Scire, S.; Minico, S.; Solarino, L. Appl. Catal. AGen. 2002, 225, 1. doi: 10.1016/S0926-860X(01)00585-3(13) Crisafulli, C.; Scire, S.; Minico, S.; Solarino, L. Appl. Catal. AGen. 2002, 225, 1. doi: 10.1016/S0926-860X(01)00585-3
14. [14]
  (14) Meshkani, F.; Rezaei, M. Int. J. Hydrog. Energy 2010, 35, 10295. doi: 10.1016/j.ijhydene.2010.07.138(14) Meshkani, F.; Rezaei, M. Int. J. Hydrog. Energy 2010, 35, 10295. doi: 10.1016/j.ijhydene.2010.07.138
15. [15]
  (15) Chen, Y. G.; Tomishige, K.; Yokoyama, K.; Fujimoto, K. Appl. Catal. A-Gen. 1997, 165, 335. doi: 10.1016/S0926-860X(97)00216-0(15) Chen, Y. G.; Tomishige, K.; Yokoyama, K.; Fujimoto, K. Appl. Catal. A-Gen. 1997, 165, 335. doi: 10.1016/S0926-860X(97)00216-0
16. [16]
  (16) Jose-Alonso, D. S.; Illan- mez, M. J.; Roman-Martinez, M. C. Int. J. Hydrog. Energy 2013, 38, 2230. doi: 10.1016/j.ijhydene.2012.11.080(16) Jose-Alonso, D. S.; Illan- mez, M. J.; Roman-Martinez, M. C. Int. J. Hydrog. Energy 2013, 38, 2230. doi: 10.1016/j.ijhydene.2012.11.080
17. [17]
  (17) Pawelec, B.; Damyanova, S.; Arishtirova, K.; Fierro, J. L. G.; Petrov, L. Appl. Catal. A-Gen. 2007, 323, 188. doi: 10.1016/j.apcata.2007.02.017(17) Pawelec, B.; Damyanova, S.; Arishtirova, K.; Fierro, J. L. G.; Petrov, L. Appl. Catal. A-Gen. 2007, 323, 188. doi: 10.1016/j.apcata.2007.02.017
18. [18]
  (18) Garcia-Dieguez, M.; Pieta, I. S.; Herrera, M. C.; Larrubia, M. A.; Alemany, L. J. J. Catal. 2010, 270, 136. doi: 10.1016/j.jcat.2009.12.010(18) Garcia-Dieguez, M.; Pieta, I. S.; Herrera, M. C.; Larrubia, M. A.; Alemany, L. J. J. Catal. 2010, 270, 136. doi: 10.1016/j.jcat.2009.12.010
19. [19]
  (19) Huang, T.; Huang,W.; Huang, J.; Ji, P. Fuel Process. Technol. 2011, 92, 1868. doi: 10.1016/j.fuproc.2011.05.002(19) Huang, T.; Huang,W.; Huang, J.; Ji, P. Fuel Process. Technol. 2011, 92, 1868. doi: 10.1016/j.fuproc.2011.05.002
20. [20]
  (20) Xue,W. J.; Zhang, X. Y.; Li, P.; Liu, Z. T.; Hao, Z. P.; Ma, C. Y. Acta Phys. -Chim. Sin. 2011, 27, 1730. [薛雯娟, 张新艳, 李鹏, 刘昭铁, 郝郑平, 麻春艳. 物理化学学报, 2011, 27, 1730.]d oi: 10.3866/PKU.WHXB20110719(20) Xue,W. J.; Zhang, X. Y.; Li, P.; Liu, Z. T.; Hao, Z. P.; Ma, C. Y. Acta Phys. -Chim. Sin. 2011, 27, 1730. [薛雯娟, 张新艳, 李鹏, 刘昭铁, 郝郑平, 麻春艳. 物理化学学报, 2011, 27, 1730.]d oi: 10.3866/PKU.WHXB20110719
21. [21]
  (21) Yao, L.; Zhu, J. Q.; Peng, X. X.; Tong, D. M.; Hu, C.W. Int. J. Hydrog. Energy 2013, 38, 7268. doi: 10.1016/j.ijhydene.2013.02.126(21) Yao, L.; Zhu, J. Q.; Peng, X. X.; Tong, D. M.; Hu, C.W. Int. J. Hydrog. Energy 2013, 38, 7268. doi: 10.1016/j.ijhydene.2013.02.126
22. [22]
  (22) Wang, L.; Li, D. L.; Koike, M.;Watanable, H.; Xu, Y.; Nakagawa, Y.; Tomishige, K. Fuel 2013, 112, 654. doi: 10.1016/j.fuel.2012.01.073(22) Wang, L.; Li, D. L.; Koike, M.;Watanable, H.; Xu, Y.; Nakagawa, Y.; Tomishige, K. Fuel 2013, 112, 654. doi: 10.1016/j.fuel.2012.01.073
23. [23]
  (23) Lin,W.W.; Cheng, H. Y.; He, L. M.; Yu, Y. C.; Zhao, F. Y. J. Catal. 2013, 303, 110. doi: 10.1016/j.jcat.2013.03.002(23) Lin,W.W.; Cheng, H. Y.; He, L. M.; Yu, Y. C.; Zhao, F. Y. J. Catal. 2013, 303, 110. doi: 10.1016/j.jcat.2013.03.002
24. [24]
  (24) de Miguel, S. R.; Vilella, I. M. J.; Maina, S. P.; Jose-Alonso, D. S.; Roman-Martinez, M. C.; Illan- mez, M. J. Appl. Catal. AGen. 2012, 435, 10.(24) de Miguel, S. R.; Vilella, I. M. J.; Maina, S. P.; Jose-Alonso, D. S.; Roman-Martinez, M. C.; Illan- mez, M. J. Appl. Catal. AGen. 2012, 435, 10.
25. [25]
  (25) El-Temtamy, S. A.; Ghoneim, S. A.; El-Morsy, A. K.; El-Naggar, A. Y.; El-Salamouny, R. A. Petrol Sci. Technol. 2009, 27, 1661. doi: 10.1080/10916460802455897(25) El-Temtamy, S. A.; Ghoneim, S. A.; El-Morsy, A. K.; El-Naggar, A. Y.; El-Salamouny, R. A. Petrol Sci. Technol. 2009, 27, 1661. doi: 10.1080/10916460802455897
26. [26]
  (26) Yu, X. P.;Wang, N.; Chu,W.; Liu, M. Chem. Eng. J. 2012, 209, 623. doi: 10.1016/j.cej.2012.08.037(26) Yu, X. P.;Wang, N.; Chu,W.; Liu, M. Chem. Eng. J. 2012, 209, 623. doi: 10.1016/j.cej.2012.08.037
27. [27]
  (27) Li, C. L.; Fu, Y. L.; Bian, G. Z. Acta Phys. -Chim. Sin. 2003, 19, 902. [李春林, 伏义路, 卞国柱. 物理化学学报, 2003, 19, 902.] doi: 10.3866/PKU.WHXB20031004(27) Li, C. L.; Fu, Y. L.; Bian, G. Z. Acta Phys. -Chim. Sin. 2003, 19, 902. [李春林, 伏义路, 卞国柱. 物理化学学报, 2003, 19, 902.] doi: 10.3866/PKU.WHXB20031004
28. [28]
  (28) Qin, Z. Q.; Gao,W. G.;Wang, H.; Han, C.; Guo,W. Chemical Industry and Engineering Progress 2013, 32, 820. [覃志强, 高文桂, 王华, 韩冲, 郭伟. 化工进展, 2013, 32, 820.](28) Qin, Z. Q.; Gao,W. G.;Wang, H.; Han, C.; Guo,W. Chemical Industry and Engineering Progress 2013, 32, 820. [覃志强, 高文桂, 王华, 韩冲, 郭伟. 化工进展, 2013, 32, 820.]
29. [29]
  (29) Wang, N.; Shen, K.; Yu, X. P.; Qian,W. Z.; Chu,W. Catal. Sci. Technol. 2013, 3, 2278. doi: 10.1039/c3cy00299c
  (29) Wang, N.; Shen, K.; Yu, X. P.; Qian,W. Z.; Chu,W. Catal. Sci. Technol. 2013, 3, 2278. doi: 10.1039/c3cy00299c

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

助剂对NiMgAl催化剂的结构和甲烷二氧化碳重整反应性能的影响

English

Effects of Promoter on NiMgAl Catalyst Structure and Performance for Carbon Dioxide Reforming of Methane

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

助剂对NiMgAl催化剂的结构和甲烷二氧化碳重整反应性能的影响

English

Effects of Promoter on NiMgAl Catalyst Structure and Performance for Carbon Dioxide Reforming of Methane

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

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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