Citation: ZHAO Jian, ZHOU Wei, MA Jian-Xin. Effect of CO₂ Pretreatment Operation Conditions on the Catalytic Performance and Structure of Ni-Co Bimetallic Catalyst[J]. Acta Physico-Chimica Sinica, ;2014, 30(7): 1325-1331. doi: 10.3866/PKU.WHXB201405042 shu

Effect of CO₂ Pretreatment Operation Conditions on the Catalytic Performance and Structure of Ni-Co Bimetallic Catalyst

ZHAO Jian ^1,2 ,
ZHOU Wei ^2,3 ,
MA Jian-Xin ^1,2,3,

1.
1. School of Resource and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China;
2. Clean Energy Automotive Engineering Center, Tongji University, Shanghai 201804, P. R. China;
3. School of Automotive Studies, Tongji University, Shanghai 201804, P. R. China

Received Date: 6 February 2014
Available Online: 4 May 2014
Fund Project:

The performance of the Ni-Co bimetallic catalyst was significantly improved by a novel H₂ and CO₂ (HCD) pretreatment in the dry reforming of methane compared with traditional H₂ pretreatment. The effects of the HCD pretreatment operating conditions, such as pretreatment time, temperature, gas feeding ratio, and gas flow rate, on the catalytic performance of Ni-Co bimetallic catalyst were investigated. The optimal pretreatment time, temperature, gas feeding ratio (CH₄/CO₂), and gas flow rate were 0.5-1 h, 780-800 ℃, 0:10, and 175-200 mL·min^-1, respectively. Biogas was simulated with CH₄ and CO₂ in a volume ratio of 1 and without any other diluted gas. The catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetry (TG) coupled to differential scanning calorimetry (DSC). In a 511 h stability test under the optimized operating conditions, the catalyst pretreated with both H₂ and CO₂ exhibited excellent stability. The average conversions of CH₄ and CO₂, selectivities for H₂ and CO, and volume ratio of H₂/CO were 96%, 97%, 98%, 99%, and 0.98, respectively. The average carbon deposition rate over the Ni-Co bimetallic catalyst was only about 0.2 mg·g^-1·h^-1. The characterization results revealed that the sintering speed of the metal greatly decreased with testing time, and the metal particle will not greatly sinter with further testing time. The amount of deposited carbon on the catalyst gradually decreased and growth of filamentous carbon over the surface of the catalyst could be inhibited. The performance of the Ni-Co bimetallic catalyst was significantly improved by a novel H₂ and CO₂ (HCD) pretreatment in the dry reforming of methane compared with traditional H₂ pretreatment. The effects of the HCD pretreatment operating conditions, such as pretreatment time, temperature, gas feeding ratio, and gas flow rate, on the catalytic performance of Ni-Co bimetallic catalyst were investigated. The optimal pretreatment time, temperature, gas feeding ratio (CH₄/CO₂), and gas flow rate were 0.5-1 h, 780-800 ℃, 0:10, and 175-200 mL·min^-1, respectively. Biogas was simulated with CH₄ and CO₂ in a volume ratio of 1 and without any other diluted gas. The catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetry (TG) coupled to differential scanning calorimetry (DSC). In a 511 h stability test under the optimized operating conditions, the catalyst pretreated with both H₂ and CO₂ exhibited excellent stability. The average conversions of CH₄ and CO₂, selectivities for H₂ and CO, and volume ratio of H₂/CO were 96%, 97%, 98%, 99%, and 0.98, respectively. The average carbon deposition rate over the Ni-Co bimetallic catalyst was only about 0.2 mg·g^-1·h^-1. The characterization results revealed that the sintering speed of the metal greatly decreased with testing time, and the metal particle will not greatly sinter with further testing time. The amount of deposited carbon on the catalyst gradually decreased and growth of filamentous carbon over the surface of the catalyst could be inhibited. Thereby, great catalytic activity and stability could be obtained during the dry reforming of methane reaction.
- Biogas reforming,
- Hydrogen production,
- Ni-Co catalyst,
- Pretreatment,
- Operation condition
1. [1]
  
  (1) Lombardi, L.; Carnevale, E.; Corti, A. Energy 2006, 31, 3208. doi: 10.1016/j.energy.2006.03.034
2. [2]
  (2) Zhang, Z. G.; Xu, G.W.; Chen, X.; Honda, K.; Yoshida, T. Fuel Process Technol. 2004, 85, 1213. doi: 10.1016/j.fuproc.2003.10.017
3. [3]
  (3) Purwanto, H.; Akiyama, T. Int. J. Hydrog. Energy 2006, 31, 491. doi: 10.1016/j.ijhydene.2005.04.021
4. [4]
  (4) Effendi, A.; Hellgardt, K.; Zhang, Z. G.; Yoshida, T. Fuel 2005, 84, 869.
5. [5]
  (5) ula, G.; Kiousis, V.; Nalbandian, L.; Yentekakis, I.V. Solid State Ionics 2006, 177, 2119.
6. [6]
  (6) Kolbitsch, P.; Pfeifer, C.; Hofbauer, H. Fuel 2008, 87, 701.
7. [7]
  (7) Muradov, N.; Smith, F.; T-Raissi, A. Int. J. Hydrog. Energy 2008, 33, 2023. doi: 10.1016/j.ijhydene.2008.02.026
8. [8]
  (8) Barrai, F.; Jackson, T.; Whitmore, N.; Castaldi, M. J. Catal. Today 2007, 129, 391. doi: 10.1016/j.cattod.2007.07.024
9. [9]
  (9) Effendi, A.; Zhang, Z. G.; Hellgardt, K.; Hondaa, K.; Yoshida, T. Catal. Today 2002, 77, 181. doi: 10.1016/S0920-5861(02)00244-4
10. [10]
  (10) Zanganeh, R.; Rezaei, M.; Zamaniyan, A. Int. J. Hydrog. Energy 2013, 38, 3012.
11. [11]
  (11) Shang, R.; Guo, X.; Mu, S.;Wang, Y.; Jin, G.; Kosslick, H. Int. J. Hydrog. Energy 2011, 36, 4900.
12. [12]
  (12) Serrano-Lotina, A.; Daza, L. J. Power Sources 2013, 238, 81.
13. [13]
  (13) Solymosi, F.; Kutsan, G.; Erdöhelyi, A. Catal. Lett. 1991, 11, 149.
14. [14]
  (14) Múnera, J. F.; Irusta, S.; Cornaglia, L. M.; Lombardo, E. A.; Vargas Cesar, D.; Schmal, M. J. Catal. 2007, 245, 25.
15. [15]
  (15) Zhang,W. D.; Liu, B. S.; Zhu, C.; Tian, Y. L. Appl. Catal. A 2005, 292, 138.
16. [16]
  (16) Rostrup-Nielsen, J. R. Studies in Surface Science and Catalysis 1988, 36, 73.
17. [17]
  (17) Zhang, J.;Wang, H.; Dalai, A. K. Appl. Catal. A 2008, 339, 121.
18. [18]
  (18) Foo, S. Y.; Cheng, C. K.; Nguyen, T. H.; Kennedy, E. M.; Dlu rski, B. Z.; Adesina, A. A. Catal. Commun. 2012, 26, 183.
19. [19]
  (19) Hu, Y. H.; Ruckenstein, E. Adv. Catal. 2004, 48, 297.
20. [20]
  (20) Kado, S.; Urasaki, K.; Sekine, Y.; Fujimoto, K. Chem. Commun. 2001, No. 5, 415.
21. [21]
  (21) Nagai, M.; Nakahira, K.; Ozawa, Y.; Namiki, Y.; Suzuki, Y. Chem. Eng. Sci. 2007, 62, 4998.
22. [22]
  (22) Chen, Y. G.; Tomishige, K.; Yokoyama, K.; Fujimoto, K. J. Catal. 1999, 184, 479.
23. [23]
  (23) Green, M. L. H.; Xiao, T. C. Activation Route for Cobalt Compound Based and Carried Catalysts. CN Patent 1541139A, 2004-01-27. [马尔科姆·莱斯利·候德·格林, 肖天存. 含有钴化合物和载体的催化剂的活化方法: 中国, CN1541139A[P]. 2004-01-27.]
24. [24]
  (24) Husserl, J. J.; Velen, J. P. V. M. J.; Koser, R. Activation Route of Catalysts for Fischer Tropsch Synthesis. CN Patent 101796166A, 2010-08-04. [胡塞尔·J·J, 扬塞梵维伦·M·J, 科泽·R. 费-托催化剂的活化方法: 中国, CN101796166A[P]. 2010-08-04.]
25. [25]
  (25) Zhao, J.; Zhou,W.; Xu, J. K.; Ma, J. X. Acta Phys. -Chim. Sin. 2013, 29, 806. [赵健, 周伟, 徐军科, 马建新. 物理化学学报, 2013, 29, 806.]
26. [26]
  (26) Zhao, J.; Zhou,W.; Xu, J. K.; Ma, J. X. Chin. J. Catal. 2013, 34, 1826. [赵健, 周伟, 徐军科, 周伟, 马建新. 催化学报, 2013, 34, 1826.]
27. [27]
  (27) Solymosi, F. J. Mol. Catal. 1991, 65, 337.
28. [28]
  (28) Erdohelyi, A.; Cserenyi, J.; Solymosi, F. J. Catal. 1993, 141, 287.
29. [29]
  (29) Solymosi, F.; Erdöhelyi, A.; Cserényi, J. Catal. Lett. 1992, 16, 399.
30. [30]
  (30) Benito, M.; García, S.; Ferreira-Aparicio, P.; García Serrano, L.; Daza, L. J. Power Sources 2007, 169, 177.
31. [31]
  (31) Xu, J. K.; Li, Z. J.;Wang, J. H.; Zhou,W.; Ma, J. X. Acta Phys. -Chim. Sin. 2009, 25, 253. [徐军科, 李兆静, 汪吉辉, 周伟, 马建新. 物理化学学报, 2009, 25, 253.]
32. [32]
  (32) Serrano-Lotina, A.; Daza, L. J. Power Sources 2013, 238, 81.
33. [33]
  (33) Xu, J. K.; Zhou,W.; Li, Z. J.;Wang, J. H.; Ma, J. X. Int. J. Hydrog. Energy 2009, 34, 6646.
34. [34]
  (34) Patterson, A. L. Phys. Rev. 1939, 56, 978. doi: 10.1103/PhysRev.56.978
35. [35]
  (35) Chen, D.; Lødeng, R.; Anundskås, A.; Olsvik, O.; Holmen, A. Chem. Eng. Sci. 2001, 56, 1371. doi: 10.1016/S0009-2509(00)00360-2
36. [36]
  (36) Kim, J. H.; Suh, D. J.; Park, T. J.; Kim, K. L. Appl. Catal. AGen. 2000, 197, 191.
37. [37]
  (37) Freund, H. J.; Messmer, R. P. Surf. Sci. 1986, 172, 1.
38. [38]
  (38) Uetsuka, H.;Watanabe, K.; Kunimori, K. Surf. Sci. 1996, 363, 73.
39. [39]
  (39) Dvelyn, M. P.; Hamza, A. V.; Gdowski, G. E. Surf. Sci. 1986, 167, 451.
40. [40]
  (40) Chen, Y. G.; Tomishige, K.; Yokoyama, K.; Fujimoto, K. J. Catal. 1998, 184, 479.
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Effect of CO₂ Pretreatment Operation Conditions on the Catalytic Performance and Structure of Ni-Co Bimetallic Catalyst