MgO/h-BN 复合载体对 Ba-Ru/MgO/h-BN 氨合成催化剂性能的影响

doi:10.1016/S1872-2067(11)60352-5

催化学报 ›› 2012, Vol. 33 ›› Issue (3): 447-453.DOI: 10.1016/S1872-2067(11)60352-5

MgO/h-BN 复合载体对 Ba-Ru/MgO/h-BN 氨合成催化剂性能的影响

杨晓龙1,2, 唐立平1,2, 夏春谷1, 熊绪茂1, 慕新元1, 胡斌1,*

1中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室, 甘肃兰州 730000; 2中国科学院研究生院, 北京 100049

收稿日期:2011-09-13 修回日期:2011-11-15 出版日期:2012-03-15 发布日期:2015-07-27

Effect of MgO/h-BN Composite Support on Catalytic Activity of Ba-Ru/MgO/h-BN for Ammonia Synthesis

YANG Xiaolong1,2, TANG Liping1,2, XIA Chungu1, XIONG Xumao1, MU Xinyuan1, HU Bin1,*

1State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China; 2Graduate University of Chinese Academy of Sciences, Beijing 100049, China

Received:2011-09-13 Revised:2011-11-15 Online:2012-03-15 Published:2015-07-27

摘要/Abstract

摘要： 采用浸渍法制备了系列不同质量比的 MgO/h-BN 复合载体负载的 Ru 基氨合成催化剂, 采用 X 射线衍射、N2 低温物理吸附、X 射线荧光、扫描电镜、透射电镜、程序升温分析等手段对催化剂进行了详细的表征, 并在固定床反应器上考察了它们在氨合成反应中的催化性能. 结果表明, MgO/h-BN 复合载体中 h-BN 含量对催化剂活性的影响较大, Ba-Ru[1:1] (摩尔比)/MgO/h-BN[8:2] (质量比), Ba-Ru[1:1]/MgO/h-BN[6:4]和 Ba-Ru[1:1]/MgO/h-BN[5:5]催化剂上氨合成活性均高于 Ba-Ru/MgO 催化剂. 在 425 °C, 5.0 MPa, N2/H2 = 1/3 和 5000 h?1 条件下, Ba-Ru[1:1]/MgO/h-BN[8:2]表现出最优催化活性, 达 506.9 ml/(gcat•h). 这可归因于 MgO/h-BN 复合载体上存在较高数量的碱性位, 特别是弱碱性位和中等强度碱性位, 而这些碱性位可能是由 MgO 和 h-BN 之间的相互作用造成.

关键词: 氨合成, 钌催化剂, 氧化镁, 六方氮化硼, 碱性

Abstract: A series of MgO/hexagonal boron nitride (h-BN) composite with different mass ratio were synthesized by impregnation method and used as supports for ruthenium catalysts in ammonia synthesis reaction. The catalysts were characterized by X-ray diffraction, N₂ physical adsorption, X-ray fluorescent spectrometer, scanning electron microscope, transmission electron microscope, temperature programmed reduction of H₂, and temperature programmed desorption of CO₂ (CO₂-TPD). The activity measurements of ammonia synthesis were carried out in a fixed-bed flow reactor with a mixture of N₂ and H₂ atomsphere under steady-state conditions (5.0 MPa, 350–500 °C, 5000 h^–1). The results showed that the rate of ammonia formation was strongly influenced by the h-BN content used in the catalysts preparation process. The Ba-Ru[1:1] (molar ratio of Ba to Ru = 1:1)/MgO/h-BN[8:2] (weight ratio of MgO to h-BN = 8:2), Ba-Ru[1:1]/MgO/h-BN[6:4] and Ba-Ru[1:1]/MgO/h-BN[5:5] catalysts exhibited higher activity than Ba-promoted Ru/MgO catalyst. At 425 °C, 5.0 MPa, flow rate of 5000 h^–1, and a N₂/H₂ = 1/3 atmosphere, the optimum activity of 506.9 ml/(g_cat·h) was achieved when MgO/h-BN[8:2] was used as the catalytic support. The execllent activity was mainly attributed to the basicity of the MgO/h-BN combination-type support, especially “weak” and “medium” basic sites. Large numbers of basic sites were observed from CO₂-TPD characterization due to the interaction between MgO and the h-BN material

Key words: ammonia synthesis, ruthenium catalyst, magnesia, hexagonal boron nitride, basicity

杨晓龙, 唐立平, 夏春谷, 熊绪茂, 慕新元, 胡斌. MgO/h-BN 复合载体对 Ba-Ru/MgO/h-BN 氨合成催化剂性能的影响[J]. 催化学报, 2012, 33(3): 447-453.

YANG Xiao-Long, TANG Li-Ping, XIA Chun-Gu, XIONG Xu-Mao, MU Xin-Yuan, HU Bin. Effect of MgO/h-BN Composite Support on Catalytic Activity of Ba-Ru/MgO/h-BN for Ammonia Synthesis[J]. Chinese Journal of Catalysis, 2012, 33(3): 447-453.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(11)60352-5

https://www.cjcatal.com/CN/Y2012/V33/I3/447

参考文献

1 Bielawa H, Hinrichsen O, Birkner A, Muhler M. Angew Chem, Int Ed, 2001, 40: 1061
2 Truszkiewiz E, Raróg-Pilecka W, Schmidt-Sza?owski K, Jodzis S, Wilczkowska E, ?omot D, Kaszkur Z, Karpiński Z, Kowalczyk Z. J Catal, 2009, 265: 181
3 You Z, Inazu K, Aika K, Baba T. J Catal, 2007, 251: 321
4 Liang C H, Li Z L, Qiu J S, Li C. J Catal, 2002, 211: 278
5 Xu Q C, Lin J D, Fu X Z, Liao D W. Catal Commun, 2008, 9: 1214
6 Iwamoto J, Itoh M, Kajita Y, Saito M, Machida K. Catal Commun, 2007, 8: 941
7 Wu S, Chen J X, Zheng X F, Zeng H S, Zheng C M, Guan N J. Chem Commun, 2003: 2488
8 Murata S, Aika K. J Catal, 1992, 136: 110
9 Miyazaki A, Balint I, Aika K, Nakano Y. J Catal, 2001, 204: 364
10 Jacobsen C J H, Dahl S, Hansen P L, Törnqvist E, Jensen L, Topsøe H, Prip D V, Møenshaug P B, Chorkendorff I. J Mol Catal A, 2000, 163: 19
11 McClaine B C, Becue T, Lock C, Davis R. J Mol Catal A, 2000, 163: 105
12 Cisneros M D, Lunsford J H. J Catal, 1993, 141: 191
13 Jacobsen C J H. J Catal, 2001, 200: 1
14 Szmigiel D, Raróg-Pilecka W, Mi?kiewicz E, Maciejewska E, Kaszkur Z, Sobczak J W, Kowalczyk Z. Catal Lett, 2005, 100: 79
15 Aika K, Ohya A, Ozaki A, Inoue Y, Yasumori I. J Catal, 1985, 92: 305
16 Larichev Y V, Moroz B L, Zaikovskii V I, Yunnusov S M, Kalyuzhnaya E S, Shur V B, Bukhtiyarov V I. J Phys Chem C, 2007, 111: 9427
17 Aika K, Taknao T, Murata S. J Catal, 1992, 136: 126
18 Hansen T W, Wagner J B, Hansen P L, Dahl S, Topsøe H, Jacobsen C J H. Science, 2001, 294: 1508
19 Paine R T, Narula C K. Chem Rev, 1990, 90: 73
20 Song Z, Cai T H, Hanson J C, Rodriguez J A, Hrbek J. J Am Chem Soc, 2004, 126: 8576
21 Jacobsen C J H. US 6 479 027. 2002
22 Postole G, Gervasine A, Caldararu M, Bonnetot B, Auroux A. Appl Catal A, 2007, 325: 227
23 Moggi P, Predieri G, Albanesi G, Papadopulos S, Sappa E. Appl Catal, 1989, 53: L1
24 Yang X L, Zhang W Q, Xia C G, Xiong X M, Mu X Y, Hu B. Catal Commun, 2010, 11: 867
25 Seetharamulu P, Kumar V S, Padmasri A H, Raju B D, Rama Rao K S. J Mol Catal A, 2007, 263: 253
26 Siva Sankar Reddy P, Pasha N, Chalapathi Rao M G V, Lingaiah N, Suryanarayana I, Sai Prasad P S. Catal Commun, 2007, 8: 1406
27 Li D, Ichikuni N, Shimazu S, Uematsu T. Appl Catal A, 1999, 180: 227
28 Seetharamulu P, Hari Prasad Reddy K, Padmasri A H, Rama Rao K S, Raju B D. Catal Today, 2009, 141: 94
29 霍超, 夏庆华, 骆雁, 杨霞珍, 刘化章. 催化学报 (Huo Ch, Xia Q H, Luo Y, Yang X Zh, Liu H Zh. Chin J Catal), 2009, 30: 537
30 Liu Z, Cortés-Concepción J A, Mustian M, Amiridis M D. Appl Catal A, 2006, 302: 232
31 Ku? S, Otremba M, Tórz A, Taniewski M. Appl Catal A, 2002, 230: 263

[1]	刘勇, 赵晓丽, 隆昶, 王晓艳, 邓邦为, 李康璐, 孙艳娟, 董帆. 原位构筑动态Cu/Ce(OH)_x界面用于高活性、高选择性和高稳定性硝酸盐还原合成氨[J]. 催化学报, 2023, 52(9): 196-206.
[2]	周纳, 王家志, 张宁, 王志, 王恒国, 黄岗, 鲍迪, 钟海霞, 张新波. 富含缺陷的Cu@CuTCNQ复合材料增强电催化硝酸盐还原成氨[J]. 催化学报, 2023, 50(7): 324-333.
[3]	陈斌, 蒋亚飞, 肖海, 李隽. 石墨炔负载的双金属单团簇催化剂用于碱性析氢反应[J]. 催化学报, 2023, 50(7): 306-313.
[4]	欧阳玲, 梁杰, 罗永嵩, 郑冬冬, 孙圣钧, 刘倩, Mohamed S. Hamdy, 孙旭平, 应斌武. 电催化合成氨的研究进展[J]. 催化学报, 2023, 50(7): 6-44.
[5]	Sue-Faye Ng, 陈星竹, Joel Jie Foo, 熊墨, Wee-Jun Ong. 2D氮化碳: 通过调节非金属硼掺杂C₃N₅阐明宽酸性及碱性pH范围的光催化析氢的反应机理[J]. 催化学报, 2023, 47(4): 150-160.
[6]	王其忧, 龚钰杰, 谭耀, 资鑫, Reza Abazari, 李红梅, 蔡超, 刘康, 傅俊伟, 陈善勇, 罗涛, 张世国, 李文章, 盛义发, 刘俊, 刘敏. 通过诱导局域电场和电子局域化协同碱性析氢[J]. 催化学报, 2023, 54(11): 229-237.
[7]	田昊, 徐冰君. 六方氮化硼催化的乙烷丙烷共脱氢: 一种C-H键活化和机理研究的有效手段[J]. 催化学报, 2022, 43(8): 2173-2182.
[8]	黄楚强, 周建清, 段丁槊, 周前程, 汪杰明, 彭博文, 余罗, 余颖. 异质原子在碱性电解水催化剂中的作用——反应机理[J]. 催化学报, 2022, 43(8): 2091-2110.
[9]	崔彤, 翟雪君, 郭莉莉, 迟京起, 张昱, 朱家伟, 孙雪梅, 王磊. 自组装百合花状超低Ru, Ni掺杂的Fe₂O₃用于大电流碱性海水电解双功能电催化[J]. 催化学报, 2022, 43(8): 2202-2211.
[10]	安露露, 邓邵峰, 郭煦昀, 刘旭坡, 赵桐辉, 陈科, 朱叶, 付玉喜, 赵旭, 王得丽. Ni₃N/MoO₂平面异质结构实现增强的碱性氢氧化[J]. 催化学报, 2022, 43(12): 3154-3160.
[11]	郭凯, 雷海涛, 李夏亮, 张宗尧, 王亚博, 郭鸿波, 张伟, 曹睿. 碱金属阳离子对铁卟啉电催化CO₂还原的影响[J]. 催化学报, 2021, 42(9): 1439-1444.
[12]	吴倩, 高庆平, 孙丽梅, 郭焕美, 台夕市, 李丹, 刘莉, 凌崇益, 孙旭平. CeO₂修饰Ni₃S₂纳米片用于高效电催化析氧[J]. 催化学报, 2021, 42(3): 482-489.
[13]	仇暘, 谢小红, 李文震, 邵玉艳. 碱性介质中氢氧化反应电催化剂的开发: 从机理认识到材料设计[J]. 催化学报, 2021, 42(12): 2094-2104.
[14]	王翔, 李美俊, 吴自力. 二氧化铈催化剂的氧化还原和酸碱性质的原位光谱表征[J]. 催化学报, 2021, 42(12): 2122-2140.
[15]	张晗, 沈国强, 刘鑫迎, 宁博, 史成香, 潘伦, 张香文, 黄振峰, 邹吉军. 自支撑NiFe LDH-MoS_x集成电极在工业电解水条件下实现高效电解水[J]. 催化学报, 2021, 42(10): 1732-1741.

MgO/h-BN 复合载体对 Ba-Ru/MgO/h-BN 氨合成催化剂性能的影响

Effect of MgO/h-BN Composite Support on Catalytic Activity of Ba-Ru/MgO/h-BN for Ammonia Synthesis

PDF

可视化

被引次数

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics