钡离子对镍基钙钛矿分解氨的影响
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摘要
镍基钙钛矿分解氨制取氢气虽有稳定性好、价格低廉的优点,但也有完全分解温度偏高的缺点。为降低完全分解氨制取氢气的温度,实验采用柠檬酸络合法,通过改变A位掺杂离子与掺杂量对LaNiO3改性,并改变载体及负载量,制备一系列的催化剂。采用XRD、SEM、TEM表征技术进行表征,考察了Ba含量对催化剂结构与性能的影响。实验表明在催化剂装填量为1m L、空速为10000h–1、原料气为纯氨的条件下,氨分解的最佳电子助剂离子为Ba、最优催化剂为w(NiO)=20%的La0.9Ba0.1NiO3/MCM-41,氨气完全分解温度由650℃降为575℃。随着Ba掺杂量的增加,催化剂活性先增加,在x=0.1达到最大值,之后减小,掺杂Ba过多催化剂的结构由钙钛矿变为非钙钛矿,非钙钛矿结构的催化剂活性不如钙钛矿。
Nickel-based perovskite catalyst,for decomposing ammonia to produce hydrogen,has good stability and low cost,but also requires high decomposition temperature. In order to reduce the complete temperature decomposition of ammonia,experiments,using citrate method,by changing the A-site doping ions and doping amounts to modify LaNiO3,were conducted with changed carriers and load amounts to prepare a series of catalysts. With XRD,SEM,TEM characterization,the effects of Ba on the structure and properties of catalyst were studied. Under the conditions of catalyst loading amount of 1m L,space velocity of 10000h-1,and pure ammonia as feed gas,the best electronic aids ions of ammonia decomposition is Ba,the best catalyst is w(NiO) = 20% of La0.9Ba0.1NiO3/MCM-41,which can make the complete decomposition temperature decrease from 650℃ to 575℃. With the increase of Ba doping amount,catalyst activity first increased,reaches a maximum at x = 0.1,and then decreased. Due to too much Ba doping,the structure of the catalyst change from perovskite to non-perovskite. The catalyst activity of perovskite is better than that of non-perovskite.
Nickel-based perovskite catalyst,for decomposing ammonia to produce hydrogen,has good stability and low cost,but also requires high decomposition temperature. In order to reduce the complete temperature decomposition of ammonia,experiments,using citrate method,by changing the A-site doping ions and doping amounts to modify LaNiO3,were conducted with changed carriers and load amounts to prepare a series of catalysts. With XRD,SEM,TEM characterization,the effects of Ba on the structure and properties of catalyst were studied. Under the conditions of catalyst loading amount of 1m L,space velocity of 10000h-1,and pure ammonia as feed gas,the best electronic aids ions of ammonia decomposition is Ba,the best catalyst is w(NiO) = 20% of La0.9Ba0.1NiO3/MCM-41,which can make the complete decomposition temperature decrease from 650℃ to 575℃. With the increase of Ba doping amount,catalyst activity first increased,reaches a maximum at x = 0.1,and then decreased. Due to too much Ba doping,the structure of the catalyst change from perovskite to non-perovskite. The catalyst activity of perovskite is better than that of non-perovskite.
引文
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[3]陈恒志,郭正奎.天然气制氢反应器的研究进展[J].化工进展,2012,31(1):10-18.
[4]于娇娇,苏伟,孙艳.水制氢技术研究进展[J].化学工业与工程,2012,29(5):58-63.
[5]楚婷婷,王慧,冯彩霞,等.可见光分解水制氢催化剂研究进展[J].化工进展,2012,31(10):2228-2233.
[6]都学敏,党政,张智峰,等.甲醇水溶液超声波制氢实验研究[J].化工学报,2011,62(6):1669-1674.
[7]闫月君,刘启斌,隋军,等.甲醇水蒸气催化重整制氢技术研究进展[J].化工进展,2012,31(7):1468-1476.
[8]苏玉蕾,王少波.氨分解制氢技术[J].舰船防化,2009(6):6-9.
[9]Chen Jiuling,Zhu Zhonghua,Wang Shaobin.Effects of nitrogen doping on the structure of carbon nanotubes(CNTs)and activity of Ru/CNTs in ammonia decomposition[J].Chemical Engineering Journal,2010,156(2):404-410.
[10]Zheng Weiqing,Zhang Jian,Ge Qingjie.Effects of Ce O2 addition on Ni/Al2O3 catalysts for the reaction of ammonia decomposition to hydrogen[J].Applied Catalysis B:Environmental,2008,80(2):98-105.
[11]Cao Jian-Liang,Yan Zhao-Li,Deng Qing-Fang.Mesoporous modified-red-mud supported Ni catalysts for ammonia decomposition to hydrogen[J].International Journal of Hydrogen Energy,2014,39(11):5747-5755.
[12]倪平,储伟,王立楠,等.氨催化分解制备无COx的氢气催化剂研究进展[J].化工进展,2006,25(7):739-743.
[13]Yin Shuang-Feng,Xu Bo-Qing,Wang Shui-Ju.Nanosized Ru on high-surface-area superbasic Zr O2-KOH for efficient generation of hydrogen via ammonia decomposition[J].Applied Catalysis A:General,2006,301(2):202-210.
[14]倪平,储伟,罗仕忠,等.钡修饰Ir/Si O2催化剂对氨分解促进作用的研究[J].合成化学,2007,15(4):407-411.
[15]亓淑艳,冯静.K+掺杂对钙钛矿氧化物La0.7Sr0.3-xKxMn O3(0.05≤x≤0.3)的结构及磁性的影响[J].应用化学,2008,25(7):825-828.
[16]Huang Ruihuan,Lan Bingyan,Chen Zhongying.Catalytic ozonation of p-chlorobenzoic acid over MCM-41 and Fe loaded MCM-41[J].Chemical Engineering Journal,2012,180:19-24.
[17]Choudhary T V,Sivadinarayana C,Goodman D W.Catalytic ammonia decomposition:COx-free hydrogen production for fuel cell applications[J].Catalysis Letters,2001,72(3-4):197-201.