原位共沉淀法制备Ni-Mg-Al-LDHs/γ-Al<sub>2</sub>O<sub>3</sub>催化前驱体在甲烷二氧化碳重整反应体系中的性能评价

引用本文: 张晓晴, 徐艳, 杨春辉, 张燕平, 印永祥, 尚书勇. 原位共沉淀法制备Ni-Mg-Al-LDHs/γ-Al₂O₃催化前驱体在甲烷二氧化碳重整反应体系中的性能评价[J]. 物理化学学报, 2015, 31(5): 948-954. doi: 10.3866/PKU.WHXB201503111 shu

Citation: ZHANG Xiao-Qing, XU Yan YAN, YANG Chun-Hui, ZHANG Yan-Ping, YIN Yong-Xiang, SHANG Shu-Yong. In-situ Co-Precipitation of Ni-Mg-Al-LDH Catalytic Precursor on γ-Al₂O₃ for Dry Reforming of Methane: Synthesis and Evaluation[J]. Acta Physico-Chimica Sinica, 2015, 31(5): 948-954. doi: 10.3866/PKU.WHXB201503111 shu

原位共沉淀法制备Ni-Mg-Al-LDHs/γ-Al₂O₃催化前驱体在甲烷二氧化碳重整反应体系中的性能评价

张晓晴 ^1, ,
徐艳 ^3, ,
杨春辉 ^1, ,
张燕平 ^1, ,
印永祥 ^1, ,
尚书勇 ^2,

基金项目:
国家自然科学基金(11075113) (11075113)

四川省科技基金(2012GZ0114)资助项目 (2012GZ0114)

摘要:

通过原位共沉淀的方法在γ-Al₂O₃表面上合成了Ni-Mg-Al-LDHs (水滑石), 合成的Ni-Mg-Al-LDHs/γ-Al₂O₃作为催化前驱体经过不同的热处理还原方式得到催化剂Cat-1、Cat-2和Cat-3. 用X射线衍射(XRD)、透射电镜(TEM)、N₂吸附-脱附测试(BET)以及热重-差热分析(TG-DTA)对催化剂的形貌结构和抗积碳能力进行了表征测试; 通过甲烷二氧化碳重整反应体系对催化剂的反应活性和稳定性进行了评价. 结果表明催化剂前驱体的预处理方式对催化剂的反应性能具有较大的影响. Ni-Mg-Al-LDHs/γ-Al₂O₃ 直接经过H2/Ar 常压高频冷等离子体炬的分解还原所获得的催化剂Cat-3 表现出了最佳的催化活性和稳定性. TEM表征表明催化活性组分在Cat-3上的分散性更好, 颗粒粒径更小. BET结果证明Cat-3具备较大的比表面积(195.8 m²·g^-1). Ni-Mg-Al 水滑石的结构赋予了催化剂活性组分在载体γ-Al₂O₃上均匀的分散性, 同时常压高频冷等离体炬对催化剂的表面结构以及活性组分的还原具有进一步的优化作用, 两者的协同作用使Ni-Mg-Al-LDHs/γ-Al₂O₃在甲烷二氧化碳反应体系中具备优良的催化活性和抗积碳性能.

关键词:

English

In-situ Co-Precipitation of Ni-Mg-Al-LDH Catalytic Precursor on γ-Al₂O₃ for Dry Reforming of Methane: Synthesis and Evaluation

1.
1 School of Chemical Engineering, Sichuan University, Chengdu 610065, P. R. China;
2 Institute for Chemical Engineering and Technology, Yibin University, Yibin 644000, Sichuan Province, P. R. China;
3 School of Chemistry and Chemical Engineering, Xuzhou Institute of Technology, Xuzhou 221111, Jiangsu Province, P. R. China
Received Date: 20 November 2014
Available Online: 08 May 2015
Fund Project:
国家自然科学基金(11075113)

四川省科技基金(2012GZ0114)资助项目

Abstract:

A series of novel catalysts derived from Ni-Mg-Al-LDHs (LDHs: layered double hydroxides) were synthesized in-situ on γ-Al₂O₃ and evaluated in CO₂ reforming of CH₄ (dry reforming of methane, DRM) reaction system. The catalytic precursors were decomposed and reduced by calcination and an atmospheric plasma technique, respectively. Activity and stability tests showed that the catalytic properties were greatly affected by the pretreatment method. The best catalytic performance was obtained with the catalyst that was directly reduced and decomposed using an atmospheric H₂/Ar plasma jet. Compared with the pure LDH precursor, Ni- Mg-Al-LDHs/γ-Al₂O₃ had much greater mechanical strength, because of the γ-Al₂O₃ support. This feature extends the long lifetime of catalyst at high temperatures. X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂-adsorption-desorption, and thermogravimetry-differential thermal analysis (TG-DTA) results showed that the excellent catalytic performance was based on the small particle size and uniform dispersion of active Ni crystals, as well as the high mechanical strength and large specific surface area of the catalyst.

Key words:

1. [1]
  
  (1) Tao, X. M.; Bai, M. G.; Li, X. A.; Long, H. L.; Shang, S. Y.; Yin, Y. X.; Dai, X. Y. Prog. Energy Combust. Sci. 2011, 37, 113. doi: 10.1016/j.pecs.2010.05.001
  (1) Tao, X. M.; Bai, M. G.; Li, X. A.; Long, H. L.; Shang, S. Y.; Yin, Y. X.; Dai, X. Y. Prog. Energy Combust. Sci. 2011, 37, 113. doi: 10.1016/j.pecs.2010.05.001
2. [2]
  (2) Brock, S. L.; Shimojo, T.; Suib, S. L.; Hayashi, Y.; Matsumoto, H. Research on Chemical Intermediates 2002, 28, 13. doi: 10.1163/156856702760129465(2) Brock, S. L.; Shimojo, T.; Suib, S. L.; Hayashi, Y.; Matsumoto, H. Research on Chemical Intermediates 2002, 28, 13. doi: 10.1163/156856702760129465
3. [3]
  (3) Bradford, M. C. J.; Vannice, M. A. Catal. Rev.-Sci. Eng. 1999, 41, 1. doi: 10.1081/CR-100101948(3) Bradford, M. C. J.; Vannice, M. A. Catal. Rev.-Sci. Eng. 1999, 41, 1. doi: 10.1081/CR-100101948
4. [4]
  (4) Liu, D.; Wang, Y.; Shi, D.; Jia, X.; Wang, X.; Borgna, A.; Lau, R.; Yang, Y. International Journal of Hydrogen Energy 2012, 37, 10135. doi: 10.1016/j.ijhydene.2012.03.158(4) Liu, D.; Wang, Y.; Shi, D.; Jia, X.; Wang, X.; Borgna, A.; Lau, R.; Yang, Y. International Journal of Hydrogen Energy 2012, 37, 10135. doi: 10.1016/j.ijhydene.2012.03.158
5. [5]
  (5) Son, I. H.; Lee, S. J.; Soon, A.; Roh, H. S.; Lee, H. Applied Catalysis B-Environmental 2013, 134, 103.(5) Son, I. H.; Lee, S. J.; Soon, A.; Roh, H. S.; Lee, H. Applied Catalysis B-Environmental 2013, 134, 103.
6. [6]
  (6) Enger, B. C.; Lodeng, R.; Holmen, A. Applied Catalysis AGeneral 2008, 346, 1. doi: 10.1016/j.apcata.2008.05.018(6) Enger, B. C.; Lodeng, R.; Holmen, A. Applied Catalysis AGeneral 2008, 346, 1. doi: 10.1016/j.apcata.2008.05.018
7. [7]
  (7) Lin, J. J.; Chan, Y. N.; Lan, Y. F. Materials 2010, 3, 2588. doi: 10.3390/ma3042588(7) Lin, J. J.; Chan, Y. N.; Lan, Y. F. Materials 2010, 3, 2588. doi: 10.3390/ma3042588
8. [8]
  (8) Guo, Z. L.; Huang, L. Q.; Chu, W.; Luo, S. Z. Acta Physico- Chimica Sinica 2014, 30, 723. [郭章龙, 黄丽琼, 储伟, 罗仕忠. 物理化学学报, 2014, 30, 723.] doi: 10.3866/PKU.WHXB201402242(8) Guo, Z. L.; Huang, L. Q.; Chu, W.; Luo, S. Z. Acta Physico- Chimica Sinica 2014, 30, 723. [郭章龙, 黄丽琼, 储伟, 罗仕忠. 物理化学学报, 2014, 30, 723.] doi: 10.3866/PKU.WHXB201402242
9. [9]
  (9) Zumreoglu-Karan, B.; Ay, A. N. Chem. Pap. 2012, 66, 1. doi: 10.2478/s11696-011-0100-8(9) Zumreoglu-Karan, B.; Ay, A. N. Chem. Pap. 2012, 66, 1. doi: 10.2478/s11696-011-0100-8
10. [10]
  (10) Tonelli, D.; Scavetta, E.; Giorgetti, M. Anal. Bioanal. Chem. 2013, 405, 603. doi: 10.1007/s00216-012-6586-2(10) Tonelli, D.; Scavetta, E.; Giorgetti, M. Anal. Bioanal. Chem. 2013, 405, 603. doi: 10.1007/s00216-012-6586-2
11. [11]
  (11) h, K. H.; Lim, T. T.; Dong, Z. Water Res. 2008, 42, 1343. doi: 10.1016/j.watres.2007.10.043(11) h, K. H.; Lim, T. T.; Dong, Z. Water Res. 2008, 42, 1343. doi: 10.1016/j.watres.2007.10.043
12. [12]
  (12) Takehira, K.; Shishido, T.; Wang, P.; Kosaka, T.; Takaki, K. Journal of Catalysis 2004, 221, 43. doi: 10.1016/j.jcat.2003.07.001(12) Takehira, K.; Shishido, T.; Wang, P.; Kosaka, T.; Takaki, K. Journal of Catalysis 2004, 221, 43. doi: 10.1016/j.jcat.2003.07.001
13. [13]
  (13) Bhattacharyya, A.; Chang, V.W.; Schumacher, D. J. Applied Clay Science 1998, 13, 317. doi: 10.1016/S0169-1317(98)00030-1(13) Bhattacharyya, A.; Chang, V.W.; Schumacher, D. J. Applied Clay Science 1998, 13, 317. doi: 10.1016/S0169-1317(98)00030-1
14. [14]
  (14) Tsyganok, A. I.; Tsunoda, T.; Hamakawa, S.; Suzuki, K.; Takehira, K.; Hayakawa, T. Journal of Catalysis 2003, 213, 191. doi: 10.1016/S0021-9517(02)00047-7(14) Tsyganok, A. I.; Tsunoda, T.; Hamakawa, S.; Suzuki, K.; Takehira, K.; Hayakawa, T. Journal of Catalysis 2003, 213, 191. doi: 10.1016/S0021-9517(02)00047-7
15. [15]
  (15) Long, H.; Xu, Y.; Zhang, X.; Hu, S.; Shang, S.; Yin, Y.; Dai, X. Journal of Energy Chemistry 2013, 22, 733. doi: 10.1016/S2095-4956(13)60097-2(15) Long, H.; Xu, Y.; Zhang, X.; Hu, S.; Shang, S.; Yin, Y.; Dai, X. Journal of Energy Chemistry 2013, 22, 733. doi: 10.1016/S2095-4956(13)60097-2
16. [16]
  (16) Gennequin, C.; Safariamin, M.; Siffert, S.; Aboukais, A.; Abi- Aad, E. Catalysis Today 2011, 176, 139. doi: 10.1016/j.cattod.2011.01.029(16) Gennequin, C.; Safariamin, M.; Siffert, S.; Aboukais, A.; Abi- Aad, E. Catalysis Today 2011, 176, 139. doi: 10.1016/j.cattod.2011.01.029
17. [17]
  (17) Wang, Q.; Ren, W.; Yuan, X.; Mu, R.; Song, Z.; Wang, X. International Journal of Hydrogen Energy 2012, 37, 11488. doi: 10.1016/j.ijhydene.2012.05.010(17) Wang, Q.; Ren, W.; Yuan, X.; Mu, R.; Song, Z.; Wang, X. International Journal of Hydrogen Energy 2012, 37, 11488. doi: 10.1016/j.ijhydene.2012.05.010
18. [18]
  (18) nzalez, A. R.; Asencios, Y. J. O.; Assaf, E. M.; Assaf, J. M. Appl. Surf. Sci. 2013, 280, 876. doi: 10.1016/j.apsusc.2013.05.082(18) nzalez, A. R.; Asencios, Y. J. O.; Assaf, E. M.; Assaf, J. M. Appl. Surf. Sci. 2013, 280, 876. doi: 10.1016/j.apsusc.2013.05.082
19. [19]
  (19) Wang, J.; Fan, G. L.; Wang, H.; Li, F. Ind. Eng. Chem. Res. 2011, 50, 13717. doi: 10.1021/ie2015087(19) Wang, J.; Fan, G. L.; Wang, H.; Li, F. Ind. Eng. Chem. Res. 2011, 50, 13717. doi: 10.1021/ie2015087
20. [20]
  (20) Gabrovska, M.; Edreva-Kardjieva, R.; Crisan, D.; Tzvetkov, P.; Shopska, M.; Shtereva, I. React. Kinet. Mech. Catal. 2012, 105, 79. doi: 10.1007/s11144-011-0378-0(20) Gabrovska, M.; Edreva-Kardjieva, R.; Crisan, D.; Tzvetkov, P.; Shopska, M.; Shtereva, I. React. Kinet. Mech. Catal. 2012, 105, 79. doi: 10.1007/s11144-011-0378-0
21. [21]
  (21) Wang, Q.; Zhang, X.; Zhu, J.; Guo, Z.; O'Hare, D. Chemical Communications 2012, 48, 7450. doi: 10.1039/c2cc32708b(21) Wang, Q.; Zhang, X.; Zhu, J.; Guo, Z.; O'Hare, D. Chemical Communications 2012, 48, 7450. doi: 10.1039/c2cc32708b
22. [22]
  (22) Liu, Z.; Zhou, J.; Cao, K.; Yang, W.; Gao, H.; Wang, Y.; Li, H. Applied Catalysis B-Environmental 2012, 125, 324. doi: 10.1016/j.apcatb.2012.06.003(22) Liu, Z.; Zhou, J.; Cao, K.; Yang, W.; Gao, H.; Wang, Y.; Li, H. Applied Catalysis B-Environmental 2012, 125, 324. doi: 10.1016/j.apcatb.2012.06.003
23. [23]
  (23) Kathiraser, Y.; Thitsartarn, W.; Sutthiumporn, K.; Kawi, S. Journal of Physical Chemistry C 2013, 117, 8120. doi: 10.1021/jp401855x(23) Kathiraser, Y.; Thitsartarn, W.; Sutthiumporn, K.; Kawi, S. Journal of Physical Chemistry C 2013, 117, 8120. doi: 10.1021/jp401855x
24. [24]
  (24) Hou, Z. Y.; Yashima, T. Applied Catalysis A-General 2004, 261, 205. doi: 10.1016/j.apcata.2003.11.002(24) Hou, Z. Y.; Yashima, T. Applied Catalysis A-General 2004, 261, 205. doi: 10.1016/j.apcata.2003.11.002
25. [25]
  (25) Nazemi, M. K.; Sheibani, S.; Rashchi, F.; nzalez-DelaCruz, V. M.; Caballero, A. Advanced Powder Technology 2012, 23, 833. doi: 10.1016/j.apt.2011.11.004(25) Nazemi, M. K.; Sheibani, S.; Rashchi, F.; nzalez-DelaCruz, V. M.; Caballero, A. Advanced Powder Technology 2012, 23, 833. doi: 10.1016/j.apt.2011.11.004
26. [26]
  (26) Lopez-Fonseca, R.; Jimenez- nzalez, C.; de Rivas, B.; Gutierrez-Ortiz, J. I. Applied Catalysis A-General 2012, 437, 53.(26) Lopez-Fonseca, R.; Jimenez- nzalez, C.; de Rivas, B.; Gutierrez-Ortiz, J. I. Applied Catalysis A-General 2012, 437, 53.
27. [27]
  (27) Zhang, Y. P.; Zhu, X. L.; Pan, Y. X.; Liu, C. J. Chinese Journal of Catalysis 2008, 29, 1058. [张月萍, 祝新利, 潘云翔, 刘昌俊. 催化学报, 2008, 29, 1058.](27) Zhang, Y. P.; Zhu, X. L.; Pan, Y. X.; Liu, C. J. Chinese Journal of Catalysis 2008, 29, 1058. [张月萍, 祝新利, 潘云翔, 刘昌俊. 催化学报, 2008, 29, 1058.]
28. [28]
  (28) Li, M. Z.; Fan, G. L.; Qin, H.; Li, F. Ind. Eng. Chem. Res. 2012, 51, 11892. doi: 10.1021/ie3008659
  (28) Li, M. Z.; Fan, G. L.; Qin, H.; Li, F. Ind. Eng. Chem. Res. 2012, 51, 11892. doi: 10.1021/ie3008659

扫一扫看文章

计量

PDF下载量: 332
文章访问数: 690
HTML全文浏览量: 53

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

原位共沉淀法制备Ni-Mg-Al-LDHs/γ-Al₂O₃催化前驱体在甲烷二氧化碳重整反应体系中的性能评价

English

In-situ Co-Precipitation of Ni-Mg-Al-LDH Catalytic Precursor on γ-Al₂O₃ for Dry Reforming of Methane: Synthesis and Evaluation

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

原位共沉淀法制备Ni-Mg-Al-LDHs/γ-Al2O3催化前驱体在甲烷二氧化碳重整反应体系中的性能评价

English

In-situ Co-Precipitation of Ni-Mg-Al-LDH Catalytic Precursor on γ-Al2O3 for Dry Reforming of Methane: Synthesis and Evaluation

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

原位共沉淀法制备Ni-Mg-Al-LDHs/γ-Al₂O₃催化前驱体在甲烷二氧化碳重整反应体系中的性能评价

In-situ Co-Precipitation of Ni-Mg-Al-LDH Catalytic Precursor on γ-Al₂O₃ for Dry Reforming of Methane: Synthesis and Evaluation

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs