Citation: WANG Zi-qing, LIN Jian-xin, WANG Rong, WEI Ke-mei. Ammonia synthesis over ruthenium supported on modified zirconia: Relationships between the catalyst structure and activity[J]. Journal of Fuel Chemistry and Technology, ;2012, 40(12): 1472-1479. shu

Ammonia synthesis over ruthenium supported on modified zirconia: Relationships between the catalyst structure and activity

1.
National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou 350002, China

Corresponding author: LIN Jian-xin,
Received Date: 17 May 2012
Available Online: 14 July 2012
Fund Project: 国家科技支撑计划(2007BAE08B02) (2007BAE08B02)中国石油科技创新基金(2010D-5006-0502)。 (2010D-5006-0502)

Modified zirconia (ZrO₂) were synthesized by high temperature calcination of ZrO(OH)₂ gels digested in alkalic solution; with the modified ZrO₂ as support, ruthenium catalysts for ammonia synthesis were prepared with K₂RuO₄ solution. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed reduction of hydrogen (H₂-TPR), temperature programmed desorption of CO₂ (CO₂-TPD), nitrogen sorption, X-ray fluorescence spectroscopy (XRF), and CO chemisorption; the relationship between the catalyst structure and its catalytic activity was especially discussed. The results revealed that the digestion either in KOH or NH₄OH solution can enhance the surface area of the ZrO₂ support, while digestion in KOH is able to obtain the support with high basicity, which benefits to getting the ruthenium catalyst of high activity. The strong basicity of the modified ZrO₂ support, rather than the high ruthenium dispersion, plays a more important role in enhancing the activity of the supported ruthenium catalyst. For ammonia synthesis under 425 ℃, 5 MPa and a space velocity of 10 000 h^-1, NH₃ outlet concentration over Ru/ZrO₂-KOH is 5.96%, which is 11%, 143% and 103% higher than those of K-Ru/ZrO₂-NH₄OH, K-Ru/ZrO₂-CP and Ru/ZrO₂-NH₄OH, respectively.
- digestion in basic solution,
- zircona,
- ruthenium,
- ammonia synthesis,
- basicity
1. [1]
  [1] 王自庆, 张留明, 林建新,王榕, 魏可镁. 纳米材料负载钌催化剂的制备与应用[J]. 催化学报, 2012, 33(3): 377-388. (WANG Zi-qing, ZHANG Liu-ming, LIN Jian-xin, WANG Rong, WEI Ke-mei. Preoaration and application of nanometer materials supported ruthenium catalysts[J]. Chinese Journal of Catalysis, 2012, 33(3): 377-388.)
2. [2]
  [2] 郑晓玲, 傅武俊, 俞裕斌, 张淑娟, 许交兴, 魏可镁. 助剂对Ru/C催化剂的表面性质及氨合成催化性能的影响[J]. 燃料化学学报, 2003, 31(1): 86-91. (ZHENG Xiao-ling, FU Wu-jun, YU Yu-bin, ZHANG Shu-juan, XU Jiao-xing, WEI Ke-mei. Effect of promoter on surface properties and catalytic activity of Ru/C catalyst for ammonia synthesis[J]. Journal of Fuel Chemistry and Technology, 2003, 31(1): 86-91.)
3. [3]
  [3] 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.)
4. [4]
  [4] SEETHARAMULU P, SIVA KUMAR V, PADMASRI A H, DAVID RAJU B, RAMA RAO K S. A highly active nano-Ru catalyst supported on novel Mg-Al hydrotalcite precursor for the synthesis of ammonia[J]. J Mol Catal A, 2007, 263(1/2): 253-258.
5. [5]
  [5] SZMIGIEL D, RARG-PILECKA W, MIKIEWCZ E, GLISKI M, KIELAK M, KASZKUR Z, KOWALCZYK Z. Ammonia synthesis over ruthenium catalysts supported on high surface area MgO and MgO-Al₂O₃ systems[J]. Appl Catal A, 2004, 273(1/2):105-112.
6. [6]
  [6] 张燕杰, 詹瑛瑛, 曹彦宁, 陈崇启, 林性贻,郑起. 以水热法合成的 ZrO₂ 负载 Au 催化剂上的低温水煤气变换反应[J].催化学报, 2012, 33(2): 230-236. (ZHANG Yan-jie, ZHAN Ying-ying, CAO Yan-ning, CHEN Chong-qi, LIN Xing-ying, ZHENG Qi. Low-temperature water-gas shift reaction over Au/ZrO₂ catalysts using hydrothermally synthesized zirconia as supports[J]. Chinese Journal of Catalysis, 2012, 33(2): 230-236.)
7. [7]
  [7] 刘水刚, 李军平, 赵宁, 魏伟, 孙予罕. 介孔 Ni/CaO₂-ZrO₂ 纳米复合物催化甲烷和二氧化碳重整[J]. 催化学报, 2007, 28(11): 1019-1023. (LIU Shui-gang, LI Jun-ping, ZHAO Ning, WEI Wei, SUN Yu-han. CO₂ reforming of CH₄ over mesoporous Ni/CaO₂-ZrO₂nanocomposite[J]. Chinese Journal of Catalysis, 2007, 28(11): 1019-1023.)
8. [8]
  [8] 王慧, 刘水刚, 张文郁, 赵宁, 魏伟, 孙予罕. 高稳定性CaO-ZrO₂ 固体碱催化剂的表征和催化性能[J].化学学报, 2006, 64(24): 2409-2413. (WANG Hui, LIU Shui-gang, ZHANG Wen-yu, WEI Wei, SUN Yu-han. Characterization and catalytic properties of highly stable CaO-ZrO₂catalysts[J]. Acta Chimica Sinica, 2006, 64(24): 2409-2413. )
9. [9]
  [9] WANG Y, HUANG W Y, WU Z, CHUN Y, ZHU J H. Superbase derived from zirconia-supported potassium nitrate[J]. Mater Lett, 2000, 64(4): 198-204.
10. [10]
  [10] WANG Y, HUANG W Y, CHUN Y, XIA J R, ZHU J H. Dispersion of potassium nitrate and the resulting strong basicity on zirconia[J]. Chem Mater, 2001, 13(2): 670-677.
11. [11]
  [11] YIN S-F, XU B-Q, WANG S-J, AU C-T. Nanosized Ru on high-surface-area superbasic ZrO₂-KOH for efficient generation of hydrogen via ammonia decomposition[J]. Appl Catal A, 2006, 301(2): 202-210.
12. [12]
  [12] 尹双凤, 徐柏庆. 碱液回流老化制备高表面积二氧化锆[J]. 催化学报, 2002, 23(3): 214-218. (YIN Shuang-feng, XU Bo-qing. Preparation of high surface area zirconia by reflux digestion in basic solution[J]. Chinese Journal of Catalysis, 2002, 23(3): 214-218)
13. [13]
  [13] 尹双凤, 李莉, 王恒秀, 徐柏庆. 碱液回流老化ZrO(OH)₂制备纳米晶 ZrO₂ 的影响因素[J]. 化学学报, 2003, 61(6): 869-877. (YIN Shuang-feng, LI Li, WANG Heng-xiu, XU Bo-qing. Effects of ZrO(OH)₂ reflux-digestion on the preparation of ZrO₂ nanocrystals[J]. Acta Chimica Sinica, 2003, 61(6): 869-877)
14. [14]
  [14] YIN S-F, XU B-Q. On the preparation of high-surface-area nano-zirconia by reflux-digestion of hydrous zirconia gel in basic solution[J]. ChemPhysChem, 2003, 4(6): 277-281.
15. [15]
  [15] 王榕, 谢峰, 孔繁华, 张天釜, 张春光, 魏可镁, 俞秀金, 林建新, 倪军, 林炳裕. 一种活性炭负载钌催化剂中钌的回收方法: 中国, 101638727. 2010-02-03. (WANG Rong, XIE Feng, KONG Fan-hua, ZHANG Tian-fu, ZHANG Chun-guang, WEI Ke-mei, YU Xiu-jin, LIN Jian-xin, NI Jun, LIN Bin-yu. A method for recovery of ruthenium from ruthenium catalyst supported activated carbon: CN, 101638727. 2010-02-03.)
16. [16]
  [16] CHUAH G K, JAENICKE S, PONG B K. The preparation of high-surface-area zirconia: II Influence of precipitating agent and digestion on the morphology and microstructure of hydrous zirconia[J]. J Catal, 1998, 175(1): 80-92.
17. [17]
  [17] GVNTER M M, RESSLER T, JENTOFT R E, BEMS B. Redox behavior of copper oxide/zinc oxide catalysts in the steam reforming of methanol studied by in situ X-Ray diffraction and absorption spectroscopy [J]. J Catal, 2001, 203(1): 133-149.
18. [18]
  [18] 王路存, 刘永梅, 曹勇, 吴贵升, 姚成漳, 戴维林, 贺鹤勇, 范康年. 草酸盐固相合成法制备高性能Cu/ZnO甲醇水蒸气重整催化剂[J]. 化学学报2007, 65(2): 173-176. (WANG Lu-cun, LIU Yong-mei, CAO Yong, WU Gui-sheng, YAO Cheng-zhang, DAI Wei-lin, HE He-yong, FAN Kang-nian. Highly effective methanol steam reforing Cu/ZnO catalyst prepared by s dry mechanochemical approach based on oxalate precursor synthesis[J]. Acta Chimic Sinica, 2007, 65(2): 173-176.)
19. [19]
  [19] DUWEZ P, ODELL F, BROWN F H. Stabilization ZrO₂ with CeO₂ and MgO[J]. J Am Ceram Soc, 1952, 35(5): 107-113.
20. [20]
  [20] 钱逸泰. 结晶化学导论[M]. 3 版. 合肥: 中国科学技术大学出版社, 2009: 289. (QIAN Yi-tai. Introduction of crystalline chemical[M]. 3 nd ed. Hefei: University of Science and Technology of China Press, 2009: 289.)
21. [21]
  [21] 王英, 朱建华, 淳远, 吴振, 何永刚. 氧化锆负载含氧酸钾盐研制固体碱[J]. 石油学报(石油加工), 2000, 16(1): 1-6. (WANG Ying, ZHU Jian-hua, CHUN Yuan, WU Gang, HE Yong-liang. Solid superbase derived from potassium salts of oxyacid on zirconia[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2000, 16(1): 1-6.)
22. [22]
  [22] SUN G, XU A, HE Y, YANG M, DU H, SUN C. Ruthenium catalysts supported on high-surface-area zirconia for the catalytic wet oxidation of N, N-dimethyl formamide[J]. J Hazard Mater, 2008, 156(1/3): 335-341.
23. [23]
  [23] IWAMOTO J, ITOH M, KAJITA Y, SAITO M, MACHIDA K. Ammonia synthesis on magnesia supported ruthenium catalysts with mesoporous structure[J]. Catal Commun, 2007, 8(6): 941-944.
24. [24]
  [24] SEETHARAMULU P, HARI PRASAD REDDY K, PADMASRI A H, RAMA RAO K S, DAVID RAJU B. Role of promoters on highly active nano-Ru catalyst supported on Mg-Al hydrotalcite precursor for the synthesis of ammonia[J]. Catal Today, 2009, 141(1/2): 94-98.
25. [25]
  [25] YOU Z, INAZU K, AIKA K-I, BABA T. Electronic and structural promotion of barium hexaaluminate as a ruthenium catalyst support for ammonia synthesis[J]. J Catal, 2007, 251(2): 321-331.
26. [26]
  [26] 杨晓龙, 夏春谷, 唐立平, 熊绪茂, 慕新元,胡斌. 氧化镁载体和氧化钡助剂对钌基氨合成催化剂结构和性能的影响[J]. 无机化学学报, 2011, 27(8): 1541-1549. (YANG Xiao-long, XIA Chun-gu, TANG Li-ping, XIONG Xu-mao, MU Xin-yuan, HU Bin.MgO support and BaO promoter on structure and catalytic activity of ruthenium catalysts for ammonia synthesis[J]. Chinese Journal of Inorgnanic Chemistry, 2011, 27(8): 1541-1549.)
27. [27]
  [27] ISHIKAWA H, KONDO J N, DOMEN K. Hydrogen adsorption and spillover on Ru/ZrO₂[M]. Stud Surf Sci Catal, 1997, 112: 73-80.
28. [28]
  [28] ISHIKAWA H, KONDO J N, DOMEN K. Hydrogen adsorption on Ru/ZrO₂ studied by FT-IR[J]. J Phys Chem B, 1999, 103(16): 3229-3234.
29. [29]
  [29] YIN S-F, ZHANG Q-H, XU B-Q, ZHU W-X, NG C-F, AU C-T. Investigation on the catalysis of COx-free hydrogen generation from ammonia[J]. J Catal, 2004, 224(2): 384-396.
30. [30]
  [30] 徐春凤, 欧阳亮, 张佳, 周斌, 李瑛, 刘化章. 氮化硼载体对 Ru-Ba/BN 氨合成催化剂性能的影响[J].催化学报, 2010, 31(6): 677-682. (XU Chun-feng, OU Yang-liang, ZHANG Jia, ZHOU Bin, LI Ying, LIU Hua-zhang. Effect of boron nitride support on catalytic activity of Ru-Ba/BN for ammonia synthesis[J]. Chinese Journal of Catalysis, 2010, 31(6): 677-682.)
31. [31]
  [31] LUO X, WANG R, NI J, LIN J X, LIN B Y, XU X M, WEI K M. Effect of La₂O₃ on Ru/CeO₂-La₂O₃ catalyst for ammonia synthesis[J]. Catal Lett, 2009, 133(3/4): 382-387.
32. [32]
  [32] 杨晓龙, 唐立平, 熊绪茂, 慕新元,胡斌. 焙烧气氛对Ba-Ru/MgO催化剂氨合成性能的影响[J]. 工业催化, 2012, 20(3): 8-14. (YANG Xiao-long, TANG Li-ping, Xiong Xu-mao, MU Xin-yuan, HU Bin. Effect of calcination atmosphere on the performance of Ba-Ru/MgO catalysts for ammonia synthesis[J]. Industral Catalysis, 2012, 20(3): 8-14.)
33. [33]
  [33] 杨晓龙, 唐立平, 夏春谷, 熊绪茂, 慕新元, 胡斌. 不同MgO担体对Ba-Ru/MgO氨合成催化剂物化性质和反应性能的影响[J]. 分子催化, 2012, 26(1): 1-9. (YANG Xiao-long, TANG Li-ping, XIA Chun-gu, Xiong Xu-mao, MU Xin-yuan, HU Bin. Effect of different suppotrs on physical and chemical properities and catalytic activity over Ba-Ru/MgO ammonia synthesis catalysts[J]. Journal of Molecular Catalysis(China), 2012, 26(1): 1-9.)
34. [34]
  [34] LIANG C, WEI Z, XIN Q, LI C. Ammonia synthesis over Ru/C catalysts with different carbon promoted by barium and potassium compounds [J]. Appl Catal A, 2001, 208(1/2): 193-201.
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