预处理方法对Ni-Co双金属催化剂性能与结构的影响

引用本文: 赵健, 周伟, 徐军科, 马建新. 预处理方法对Ni-Co双金属催化剂性能与结构的影响[J]. 物理化学学报, doi: 10.3866/PKU.WHXB201301315 shu

Citation: ZHAO Jian, ZHOU Wei, XU Jun-Ke, MA Jian-Xin. Effect of Pretreatment Routes on the Performance and Structure of Ni-Co Bimetallic Catalysts[J]. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB201301315 shu

预处理方法对Ni-Co双金属催化剂性能与结构的影响

基金项目:
科技部国际合作项目先进储氢技术研发及系统示范(2010DFA64080)资助 (2010DFA64080)

摘要:

浸渍法制备了Ni-Co/La₂O₃-γ-Al₂O₃双金属催化剂, 经氢气还原预处理后, 再分别由一氧化碳、甲烷和二氧化碳进行再次预处理, 考察了预处理方法对该催化剂上沼气重整制氢性能的影响, 并运用X射线衍射(XRD)、热重-差示扫描量热(TG-DSC)、透射电子显微镜(TEM)等手段对催化剂进行了表征. 结果表明, 与传统氢气还原预处理相比, 经氢气与一氧化碳预处理后, 催化剂性能无明显变化; 经氢气与甲烷预处理后, 催化剂性能明显变差; 而经氢气和二氧化碳预处理后, 催化剂性能明显变优, 且能基本消除该催化剂上沼气重整反应的诱导期. 分析结果表明, 经氢气和二氧化碳预处理后, 催化剂中金属颗粒较小, 分布较均匀, 粒径分布范围较窄, 从而减少了催化剂表面碳的沉积, 增强了催化剂的抗积炭性能, 可延长催化剂的使用寿命.

关键词:

English

Effect of Pretreatment Routes on the Performance and Structure of Ni-Co Bimetallic Catalysts

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;
4 Shanghai Baoshan Environmental Monitoring Station, Shanghai 201901, P. R. China
Received Date: 04 December 2012
Available Online: 25 March 2013
Fund Project:
科技部国际合作项目先进储氢技术研发及系统示范(2010DFA64080)资助

Abstract:

Ni-Co/La₂O₃-γ-Al₂O₃ catalysts for biogas reforming were prepared by conventional incipient wetness impregnation and pretreated first by hydrogen reduction and then by pure carbon monoxide, methane and carbon dioxide, respectively. The effect of pretreatment route on the biogas reforming performance of the catalysts was investigated. The catalysts were characterized with X-ray diffraction (XRD), thermogravimetric and differential scanning calorimetry (TG-DSC), and transmission electron microscopy (TEM), and the relationship between the performance and the structural properties of the catalysts was investigated. The results indicated that, compared with the performance of catalysts pretreated by the traditional hydrogen reduction, the performance of catalysts pretreated by hydrogen and carbon monoxide did not change significantly, while the performance of catalysts pretreated by hydrogen and methane deteriorated obviously. Nevertheless, the performance of catalysts pretreated by hydrogen and carbon dioxide was dramatically enhanced and the long adjustment period of the biogas reforming catalysts was basically eliminated. The characterization results showed that the active metal particle size of the catalysts pretreated by hydrogen and carbon dioxide was smaller on average and distributed more evenly and much more narrowly, which notably enhanced the catalysts' carbon resistance and prolonged the catalysts' longevity.

Key words:

1. [1]
  
  (1) Xu, J. K.; Shen, L. H.; Zhou, W.; Ma, J. X. Acta Phys. -Chim.Sin. 2011, 27 (3), 697. [徐军科,沈利红,周伟,马建新. 物理化学学报, 2011, 27 (3), 697.] doi: 10.3866/PKU.WHXB20110309
  (1) Xu, J. K.; Shen, L. H.; Zhou, W.; Ma, J. X. Acta Phys. -Chim.Sin. 2011, 27 (3), 697. [徐军科,沈利红,周伟,马建新. 物理化学学报, 2011, 27 (3), 697.] doi: 10.3866/PKU.WHXB20110309
2. [2]
  (2) Feng, Y. Z.; u, Y.; Yang, G. H.; Qin, X. W.; Song, Z. L.Renew. Sust. Energ. Rev. 2012, 16 (8), 5617.(2) Feng, Y. Z.; u, Y.; Yang, G. H.; Qin, X. W.; Song, Z. L.Renew. Sust. Energ. Rev. 2012, 16 (8), 5617.
3. [3]
  (3) Li, C. L.; Fu, Y. L.; Bian, G. Z. Acta Phys. -Chim. Sin. 2003, 19 (10), 902. [李春林, 伏义路, 卞国柱. 物理化学学报, 2003, 19 (10), 902.] doi: 10.3866/PKU.WHXB20031004(3) Li, C. L.; Fu, Y. L.; Bian, G. Z. Acta Phys. -Chim. Sin. 2003, 19 (10), 902. [李春林, 伏义路, 卞国柱. 物理化学学报, 2003, 19 (10), 902.] doi: 10.3866/PKU.WHXB20031004
4. [4]
  (4) Meshkani, F.; Rezaei, M. J. Nat. Gas. Chem. 2011, 20, 198.doi: 10.1016/S1003-9953(10)60169-7(4) Meshkani, F.; Rezaei, M. J. Nat. Gas. Chem. 2011, 20, 198.doi: 10.1016/S1003-9953(10)60169-7
5. [5]
  (5) Corthals, S.; Nederkassel, J. V.; Winne, H. D.; Geboers, J.;Jacobs, P.; Sels, B. Appl. Catal. B-Environ. 2011, 105, 263. doi: 10.1016/j.apcatb.2011.04.008(5) Corthals, S.; Nederkassel, J. V.; Winne, H. D.; Geboers, J.;Jacobs, P.; Sels, B. Appl. Catal. B-Environ. 2011, 105, 263. doi: 10.1016/j.apcatb.2011.04.008
6. [6]
  (6) Tao, X. M.; Bai, M. G.; Li, X.; Long, H. L.; Shang, S. Y.; Yin, Y.X.; Dai, X. Y. Prog. Energ. Combust. Sci. 2011, 37, 113. doi: 10.1016/j.pecs.2010.05.001(6) Tao, X. M.; Bai, M. G.; Li, X.; Long, H. L.; Shang, S. Y.; Yin, Y.X.; Dai, X. Y. Prog. Energ. Combust. Sci. 2011, 37, 113. doi: 10.1016/j.pecs.2010.05.001
7. [7]
  (7) Yu, C. C.; Ding, X. J. Chin. J. Mol. Catal. 1993, 7, 151. [余长春,丁雪加. 分子催化, 1993, 7, 151.](7) Yu, C. C.; Ding, X. J. Chin. J. Mol. Catal. 1993, 7, 151. [余长春,丁雪加. 分子催化, 1993, 7, 151.]
8. [8]
  (8) Sun, X. X.; Li, X. M.; Li, J. H.; Fan, Y. M.; Xu, H. Y.; Su, Y.;Shi, K. Y.; Xu, G. L. Chem. J. Chin. Univ. 1992, 10, 1302.[孙希贤,李新民, 李建华,范业梅,徐恒泳,苏玉,史克英,徐国林. 高等学校化学学报, 1992, 10, 1302.](8) Sun, X. X.; Li, X. M.; Li, J. H.; Fan, Y. M.; Xu, H. Y.; Su, Y.;Shi, K. Y.; Xu, G. L. Chem. J. Chin. Univ. 1992, 10, 1302.[孙希贤,李新民, 李建华,范业梅,徐恒泳,苏玉,史克英,徐国林. 高等学校化学学报, 1992, 10, 1302.]
9. [9]
  (9) Ni, J.; Chenb, L. W.; Lin, J. Y.; Kawi, S. Nano Energ. 2012, 1 (5), 674. doi: 10.1016/j.nanoen.2012.07.011(9) Ni, J.; Chenb, L. W.; Lin, J. Y.; Kawi, S. Nano Energ. 2012, 1 (5), 674. doi: 10.1016/j.nanoen.2012.07.011
10. [10]
  (10) Xu, J. K.; Li, Z. J.; Wang, J. H.; Zhou, W.; Ma, J. X. ActaPhys. -Chim. Sin. 2009, 25 (2), 253. [徐军科,李兆静, 汪吉辉,周伟,马建新.物理化学学报, 2009, 25 (2), 253.] doi: 10.3866/PKU.WHXB20090210(10) Xu, J. K.; Li, Z. J.; Wang, J. H.; Zhou, W.; Ma, J. X. ActaPhys. -Chim. Sin. 2009, 25 (2), 253. [徐军科,李兆静, 汪吉辉,周伟,马建新.物理化学学报, 2009, 25 (2), 253.] doi: 10.3866/PKU.WHXB20090210
11. [11]
  (11) Yu, X. P.; Wang, N.; Chu, W.; Liu, M. Chem. Eng. J. 2012, 209,623.(11) Yu, X. P.; Wang, N.; Chu, W.; Liu, M. Chem. Eng. J. 2012, 209,623.
12. [12]
  (12) Lv, X. Y.; Chen, J. F.; Tan, Y. S.; Zhang, Y. Catal. Commun.2012, 20, 6. doi: 10.1016/j.catcom.2012.01.002(12) Lv, X. Y.; Chen, J. F.; Tan, Y. S.; Zhang, Y. Catal. Commun.2012, 20, 6. doi: 10.1016/j.catcom.2012.01.002
13. [13]
  (13) Chen, J. X.; Qiu, Y. J.; Zhang, J. Y.; Su, W. H. Acta Phys. -Chim.Sin. 2004, 20 (1), 76. [陈吉祥, 邱业君,张继炎, 苏万华.物理化学学报, 2004, 20 (1), 76.] doi: 10.3866/PKU.WHXB20040116(13) Chen, J. X.; Qiu, Y. J.; Zhang, J. Y.; Su, W. H. Acta Phys. -Chim.Sin. 2004, 20 (1), 76. [陈吉祥, 邱业君,张继炎, 苏万华.物理化学学报, 2004, 20 (1), 76.] doi: 10.3866/PKU.WHXB20040116
14. [14]
  (14) Husserl, J. J.; Velen, J. P. V. M. J.; Koser, R. Activation Route ofCatalysts for Fischer Tropsch Synthesis. CN Patent 10 1796166A, 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.](14) Husserl, J. J.; Velen, J. P. V. M. J.; Koser, R. Activation Route ofCatalysts for Fischer Tropsch Synthesis. CN Patent 10 1796166A, 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.]
15. [15]
  (15) Green, M. L. H.; Xiao, T. C. Activation Route for CobaltCompound 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.](15) Green, M. L. H.; Xiao, T. C. Activation Route for CobaltCompound 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.]
16. [16]
  (16) Xu, J. K.; Ren, K. W.; Wang, X. L.; Zhou, W.; Pan, X. M.; Ma,J. X. Acta Phys. -Chim. Sin. 2008, 24 (9), 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 (9), 1568.] doi: 10.3866/PKU.WHXB20080907(16) Xu, J. K.; Ren, K. W.; Wang, X. L.; Zhou, W.; Pan, X. M.; Ma,J. X. Acta Phys. -Chim. Sin. 2008, 24 (9), 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 (9), 1568.] doi: 10.3866/PKU.WHXB20080907
17. [17]
  (17) Benito, M.; García, S.; Ferreira-Aparicio, P.; Serrano, L. G.;Daza, L. J. Power Sources 2007, 169 (1), 177. doi: 10.1016/j.jpowsour.2007.01.046(17) Benito, M.; García, S.; Ferreira-Aparicio, P.; Serrano, L. G.;Daza, L. J. Power Sources 2007, 169 (1), 177. doi: 10.1016/j.jpowsour.2007.01.046
18. [18]
  (18) Xu, J. K.; Li, Z. J.; Wang, J. H.; Zhou, W.; Ma, J. X. Int. J.Hydrog. Energy 2010, 35 (23), 13013.(18) Xu, J. K.; Li, Z. J.; Wang, J. H.; Zhou, W.; Ma, J. X. Int. J.Hydrog. Energy 2010, 35 (23), 13013.
19. [19]
  (19) Tomishige, K.; Chen, Y. G.; Fujimoto, K. J. Catal. 1999, 181,91. doi: 10.1006/jcat.1998.2286(19) Tomishige, K.; Chen, Y. G.; Fujimoto, K. J. Catal. 1999, 181,91. doi: 10.1006/jcat.1998.2286
20. [20]
  (20) Solymosi, F. J. Mol. Catal. 1991, 65 (3), 337. doi: 10.1016/0304-5102(91)85070-I(20) Solymosi, F. J. Mol. Catal. 1991, 65 (3), 337. doi: 10.1016/0304-5102(91)85070-I
21. [21]
  (21) Damyanova, S.; Bueno, J. M. C. Appl. Catal. A 2003, 253 (1),135. doi: 10.1016/S0926-860X(03)00500-3(21) Damyanova, S.; Bueno, J. M. C. Appl. Catal. A 2003, 253 (1),135. doi: 10.1016/S0926-860X(03)00500-3
22. [22]
  (22) Nagaoka, K.; Seshan, K.; Aika, K.; Lercher, J. A. J. Catal. 2001,197, 34. doi: 10.1006/jcat.2000.3062
  (22) Nagaoka, K.; Seshan, K.; Aika, K.; Lercher, J. A. J. Catal. 2001,197, 34. doi: 10.1006/jcat.2000.3062

扫一扫看文章

计量

PDF下载量: 666
文章访问数: 992
HTML全文浏览量: 12

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

预处理方法对Ni-Co双金属催化剂性能与结构的影响

English

Effect of Pretreatment Routes on the Performance and Structure of Ni-Co Bimetallic Catalysts

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？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

预处理方法对Ni-Co双金属催化剂性能与结构的影响

English

Effect of Pretreatment Routes on the Performance and Structure of Ni-Co Bimetallic Catalysts

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？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs