稀土双钙钛矿型铝系催化剂的制备及甲烷催化燃烧性能研究
|
摘要
天然气传统燃烧利用方式不仅造成严重的环境污染,而且能源利用效率低。催化燃烧技术作为一种环境友好且燃烧效率高的能源利用方式越来越受到重视。
本文采用柠檬酸溶胶-凝胶法制备了铝系La2BAlO6(B=Co、Ni、Mn)稀土双钙钛矿型催化剂,并与相应的稀土单钙钛矿型催化剂LaBO3(B=Co、Ni、Mn、Al)进行了比较,考察了焙烧温度对双钙钛矿型氧化物的影响,探讨了A位上Sr取代La对钙钛矿型复合氧化物催化剂的甲烷催化燃烧性能的影响。利用X射线粉末衍射(XRD)、H2-程序升温还原(H2-TPR)、比表面(BET)、扫描电镜(SEM)、傅立叶变换红外吸收光谱(FT-IR)和磁性测试等手段对样品进行了表征,以甲烷催化燃烧反应为探针考察了其催化活性,并与其物理化学性能进行了关联。
实验结果表明,在空气气氛中1100℃焙烧3h后,铝系La-B-Al-O(B=Co、Ni、Mn)催化剂均形成了单相的La2CoAlO6、La2NiAlO6和La2MnAlO6稀土双钙钛矿型化合物。其中La2NiAlO6表现出较好的甲烷催化燃烧活性,其起燃温度(T10)和完全转化温度(T90)分别为433.1℃和649.7℃, La2CoAlO6次之,La2MnAlO6:最差。从催化剂的H2-TPR谱图中发现,La2NiAlO6较好的甲烷催化燃烧活性与其较低的还原峰温有天。
同时,对稀土双钙钛矿型La-B-Al-O(B=Co、Ni、Mn)系列催化剂与相应的单钙钛矿型La-B-O(B=Co、Ni、Mn、Al)系列催化剂进行了系统的比较。活性测试结果表明,双钙钛矿系列催化剂活性均优于相应的单钙钛矿型催化剂,与相应的两种单钙钛矿型催化剂混合物相比,双钙钛矿仍表现出良好的催化活性,这说明在双钙钛矿催化剂La2BAlO6(B=Co、Ni、Mn)结构中,B位元素与Al元素之间存在着协同作用,而这种协同作用对甲烷催化燃烧反应是有利的。
在此基础上,重点考察了不同焙烧温度对La2NiAlO6结构及甲烷催化燃烧活性的影响。结果表明,当焙烧温度提高到800℃时,La-Ni-Al-O体系开始形成了双钙钛矿的结构,此后随着焙烧温度的升高,La2NiAlO6的晶型逐步完善。
最后,发现在A位上用少量Sr取代La有助于双钙钛矿型催化剂La2NiAlO6催化活性的提高,但掺杂过高反而会使其催化活性下降。双钙钛矿La1.90Sr0.10NiAlO6的活性最好,比表面积最大,其起燃温度(T10)和完全转化温度(T90)分别为398.7℃和622.9℃。
Conventional combustion of natural gas (i.e.methane) not only causes serious air pollution,but also has low utilization efficiency.Catalytic combustion of methane as an environmentally friendly is becoming more and more attractive in recent years due to the high combustion efficiency.
In this paper, the rare earth double perovskite-type catalysts La2BAlO6(B=Co、Ni、Mn) were prepared by the sol-gel method using citric acid as complex agent, and compared with the corresponding single perovskite-type catalysts LaBO3(B=Co、Ni、Mn、Al). Moreover, the influence of the calcination temperature of the double perovskite-type oxides and Sr replace La in A-site of perovskite oxide catalyst on the performance of methane combustion was studied. The catalysts were characterized by X-ray powder diffraction (XRD), H2-temperature-programmed reduction (H2-TPR), specific surface area (BET), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and magnetic property measurement, and was tested for methane combustion.
Results showed that a single-phase rare-earth double perovskite oxide La2BAlO6(B=Co、Ni、Mn) could be formed by calcinations at 1100℃for 3 h. The La2NiAlO6 demonstrates the best catalytic activity for methane combustion. It has a light-off temperature (T10)of 433.1℃and a total conversion temperature (T90) of 649.7℃, then the La2CoAlO6, and La2MnA106 is the worst. Furthermore, La2NiAlO6 samples show excellent catalytic activity for methane combustion which could be related to the decrease of reduction temperature observed in H2-TPR experiments, probably due to an increased oxygen mobility promoted by the presence of aluminum.
Meanwhile compared the rare earth double perovskite-type La2BAlO6(B=Co、Ni、Mn) series catalysts with the corresponding single perovskite-type catalysts LaBO3(B=Co、Ni、Mn、Al). Catalytic activity testing results showed that double perovskite series catalytic activity are superior to the corresponding single perovskite catalyst. In addition, the double perovskite still showed good catalytic activity which compared to the mixture of two kinds single perovskite catalysts. This explained that exist synergy between B-site element and Al elements in double perovskite catalyst La2BAlO6 (B= Co, Ni, Mn) structure, and this synergy effect on methane catalytic combustion reaction is favorable.
Furthermore, the influence of the calcination temperature of the double perovskite-type oxides La2NiAlO6 on the physicochemical properties and the performance of methane combustion was studied. The results indicated that, La-Ni-Al-O system could be formed double perovskite-type oxides La2NiAlO6 at 800℃, with increasing the calcination temperature the structure of double perovskite La2NiAlO6 is perfect
In the end, the perovskite oxide catalysts La2NiAlO6 of A-site replaced Sr were synthesized through citric acid method. The catalytic activity of La2NiAlO6 for the performance of methane combustion was studied, appropriate replace content is beneficial to enhance catalytic activity of La2NiAlO6.The results showed that, double perovskite Lai.90Sr0.10NiAlO6 has the higher surface area, and it has the best activity for methane combustion, whose T10 and T90 were 398.7℃and 622.9℃, respectively.
本文采用柠檬酸溶胶-凝胶法制备了铝系La2BAlO6(B=Co、Ni、Mn)稀土双钙钛矿型催化剂,并与相应的稀土单钙钛矿型催化剂LaBO3(B=Co、Ni、Mn、Al)进行了比较,考察了焙烧温度对双钙钛矿型氧化物的影响,探讨了A位上Sr取代La对钙钛矿型复合氧化物催化剂的甲烷催化燃烧性能的影响。利用X射线粉末衍射(XRD)、H2-程序升温还原(H2-TPR)、比表面(BET)、扫描电镜(SEM)、傅立叶变换红外吸收光谱(FT-IR)和磁性测试等手段对样品进行了表征,以甲烷催化燃烧反应为探针考察了其催化活性,并与其物理化学性能进行了关联。
实验结果表明,在空气气氛中1100℃焙烧3h后,铝系La-B-Al-O(B=Co、Ni、Mn)催化剂均形成了单相的La2CoAlO6、La2NiAlO6和La2MnAlO6稀土双钙钛矿型化合物。其中La2NiAlO6表现出较好的甲烷催化燃烧活性,其起燃温度(T10)和完全转化温度(T90)分别为433.1℃和649.7℃, La2CoAlO6次之,La2MnAlO6:最差。从催化剂的H2-TPR谱图中发现,La2NiAlO6较好的甲烷催化燃烧活性与其较低的还原峰温有天。
同时,对稀土双钙钛矿型La-B-Al-O(B=Co、Ni、Mn)系列催化剂与相应的单钙钛矿型La-B-O(B=Co、Ni、Mn、Al)系列催化剂进行了系统的比较。活性测试结果表明,双钙钛矿系列催化剂活性均优于相应的单钙钛矿型催化剂,与相应的两种单钙钛矿型催化剂混合物相比,双钙钛矿仍表现出良好的催化活性,这说明在双钙钛矿催化剂La2BAlO6(B=Co、Ni、Mn)结构中,B位元素与Al元素之间存在着协同作用,而这种协同作用对甲烷催化燃烧反应是有利的。
在此基础上,重点考察了不同焙烧温度对La2NiAlO6结构及甲烷催化燃烧活性的影响。结果表明,当焙烧温度提高到800℃时,La-Ni-Al-O体系开始形成了双钙钛矿的结构,此后随着焙烧温度的升高,La2NiAlO6的晶型逐步完善。
最后,发现在A位上用少量Sr取代La有助于双钙钛矿型催化剂La2NiAlO6催化活性的提高,但掺杂过高反而会使其催化活性下降。双钙钛矿La1.90Sr0.10NiAlO6的活性最好,比表面积最大,其起燃温度(T10)和完全转化温度(T90)分别为398.7℃和622.9℃。
Conventional combustion of natural gas (i.e.methane) not only causes serious air pollution,but also has low utilization efficiency.Catalytic combustion of methane as an environmentally friendly is becoming more and more attractive in recent years due to the high combustion efficiency.
In this paper, the rare earth double perovskite-type catalysts La2BAlO6(B=Co、Ni、Mn) were prepared by the sol-gel method using citric acid as complex agent, and compared with the corresponding single perovskite-type catalysts LaBO3(B=Co、Ni、Mn、Al). Moreover, the influence of the calcination temperature of the double perovskite-type oxides and Sr replace La in A-site of perovskite oxide catalyst on the performance of methane combustion was studied. The catalysts were characterized by X-ray powder diffraction (XRD), H2-temperature-programmed reduction (H2-TPR), specific surface area (BET), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and magnetic property measurement, and was tested for methane combustion.
Results showed that a single-phase rare-earth double perovskite oxide La2BAlO6(B=Co、Ni、Mn) could be formed by calcinations at 1100℃for 3 h. The La2NiAlO6 demonstrates the best catalytic activity for methane combustion. It has a light-off temperature (T10)of 433.1℃and a total conversion temperature (T90) of 649.7℃, then the La2CoAlO6, and La2MnA106 is the worst. Furthermore, La2NiAlO6 samples show excellent catalytic activity for methane combustion which could be related to the decrease of reduction temperature observed in H2-TPR experiments, probably due to an increased oxygen mobility promoted by the presence of aluminum.
Meanwhile compared the rare earth double perovskite-type La2BAlO6(B=Co、Ni、Mn) series catalysts with the corresponding single perovskite-type catalysts LaBO3(B=Co、Ni、Mn、Al). Catalytic activity testing results showed that double perovskite series catalytic activity are superior to the corresponding single perovskite catalyst. In addition, the double perovskite still showed good catalytic activity which compared to the mixture of two kinds single perovskite catalysts. This explained that exist synergy between B-site element and Al elements in double perovskite catalyst La2BAlO6 (B= Co, Ni, Mn) structure, and this synergy effect on methane catalytic combustion reaction is favorable.
Furthermore, the influence of the calcination temperature of the double perovskite-type oxides La2NiAlO6 on the physicochemical properties and the performance of methane combustion was studied. The results indicated that, La-Ni-Al-O system could be formed double perovskite-type oxides La2NiAlO6 at 800℃, with increasing the calcination temperature the structure of double perovskite La2NiAlO6 is perfect
In the end, the perovskite oxide catalysts La2NiAlO6 of A-site replaced Sr were synthesized through citric acid method. The catalytic activity of La2NiAlO6 for the performance of methane combustion was studied, appropriate replace content is beneficial to enhance catalytic activity of La2NiAlO6.The results showed that, double perovskite Lai.90Sr0.10NiAlO6 has the higher surface area, and it has the best activity for methane combustion, whose T10 and T90 were 398.7℃and 622.9℃, respectively.
引文
[1]陆家亮.中国天然气工业发展形势及发展建议.天然气工业[J],2009,29(1)：8-12.
[2]Yuri F. Makogon. Natural gas hydrates - A promising source of energy. Journal of Natural Gas Science and Engineering [J],2010,2:49-59
[3]Junchen Li, Xiucheng Dong,Jianxin Shangguan etc. Forecasting the growth of China's natural gas consumption. Energy[J],2011,36:1380-1385
[4]江怀友,钟太贤,宋新民等.世界天然气资源现状与展望.中国能源[J],2009,31(3)：40-42.
[5]周新文,朱万美.天然气“西气东输”与“俄气南供”.城市燃气[J],2002,331,25-28
[6]姜德群.我区已探明石油天然气产地46处.内蒙古晨报[J],2009,6.21.
[7]Hailong Li, Mario Ditaranto, David Berstad. Technologies for increasing CO2 concentration in exhaust gas from natural gas-fired power production with post-combustion, amine-based CO2 capture. Energy[J],2011,36(2): 1124-1133
[8]郭玉华.含镁复合氧化物催化剂催化甲烷燃烧性能的研究[D].宁夏大学硕士学位论文,2005,12
[9]徐金光,田志坚,王军威等.超临界干燥方法对甲烷燃烧催化剂LaMnAl11O19结构及活性的影响.催化学报[J],2002,23(5)：477-480.
[10]张世红,王棋,周琦.催化燃烧炉特性的实验研究.北京建筑工程学院学报[J].2003,3(19)：1-4
[11]Fengxiang Yin,Shengfu Ji,Biaohua Chen,etc.Preparation and characterization of LaFe1-xMgxO3/Al2O3/ FeCrAl Catalytic properties in methane combustion. Applied Catalysis B:Environmental [J],2006,66:270-273.
[12]WEI Yong gang, WANG Hua, LI Kong zhai. Ce-Fe-O mixed oxide as oxygen carrier for the direct partial oxidation of methane to syngas. Journal of Rare Earths [J],2010,28(4)560-565
[13]高典楠,王胜,刘莹等.焙烧温度对Pd/Al2O3催化剂上甲烷燃烧反应性能的影响.催化学报[J],2010,31(11)：1363—1368
[14]Chen Li, Wendong Wang, Ning Zhao etc. Structure properties and catalytic performance in methane combustion of double perovskites Sr2Mg1-xMnxMoO6-δ. Applied Catalysis B:Environmental [J],2011,102 (1) 78-84
[15]Cimino, S. M.P. Casaletto, L. Lisi, G. Russo. Pd-LaMnO3 as dual site catalysts for methane combustion. Applied Catalysis A[J],2007,15(2):238-243.
[16]徐金光,田志坚,索掌怀等.反相微乳液法制备LaMnAl11O19-α.甲烷燃烧催化剂.催化学报[J],2005,26(8)：665—668
[17]Choudhary, T. V.; Banerjee, S.; Choudhary, V R. Catalysts for combustion of methane and lower alkanes, Appl. Catal. A [J],2002,234:1-23
[18]Li-hua Xiao, Kun-peng Sun, Xian-lun Xu etc. Low-temperature catalytic combustion of methane over Pd/CeO2 prepared by deposition-precipitation method. Catal. Commun. [J],2005,6:796-801
[19]Arosio, F.; Colussi, S.; Trovarelli, A.; Groppi, G. Effect of alternate CH4-reducing/lean combustion treatments on the reactivity of fresh and S-poisoned Pd/CeO2/Al2O3 catalysts. Appl. Catal. B: Environmental [J],2008,80:335-342
[20]Z. M. Liu, Y. Q. Chen, J.B. Zhong, J.L.Wang. Effect of Fe203 Loading Amount on Catalytic Properties of Monolithic Fe2O3/Ce0.67Zr0.33O2-Al2O3 Catalyst for Methane Combustion. Journal of rare earth[J],2007,25: 585-589.
[21]O.Salvador, R. Paredes, V. Fernando, etc. Sulphur poisoning of transition metal oxides used as catalysts for methane Combustion. Applied Catalysis A:General [J],2008,341:174-180.
[22]戴洪兴,何洪,李佩珩等.稀土钙钛矿型氧化物催化剂的研究进展.中国稀土学报[J],2003,21(12),1-15
[23]S. V.Nguyen, V.Szabo, D Trong On, etc. Mesoporous silica supported LaCoO3 perovskites as catalysts for methane oxidation.Microporous and Mesoporous Materials [J],2002,54,51-61
[24]Batiot-Dupeyrat, C.; Martinez-Ortega, F.; Ganneb,M.etc.Methane catalytic combustion on La-based perovskite type catalysts in high temperature isothermal conditions. Appl. Catal. A[J],2001,206,205-215
[25]Zhong, Z. Y.; Chen, K. D.; Ji, Y. etc. Methane combustion over B-site partially substituted perovskite-type LaFeO3 prepared by sol-gel method. Appl. Catal. A [J],1997,156,29-41
[26]Imamura M, Matsubayashi N, Shimada H. Catalytically active oxygen species in La1-xSrxCoO3-δ studied by XPS and XAFS spectroscopy. J. Phys. Chem. B[J],2000,104 (31):7348.
[27]Li R, Ma J T, Xu J L, etc. Studies on the surface oxygenspecies and the catalytic activity for CO oxidation of La1-xSrxCo1-xMnxO3-δ a perovskite-type oxide catalyst. Catal. Lett. [J],2000,70 (2):363.
[28]M.O. Cofmell, A.K.Norman, C.F.Hultennann. Catalytic oxidation over lanthanum-transition metal perovskite materials. Catalysis Today[J],1999,47:123-132.
[29]J. G. McCarthy, H. Wise. Perovskite catalysts for methane combustion [J]. Catalysis Today,1990,8:231-248.
[30]A. Kaddouri, S. Ifrah. Microwave-assisted synthesis of La1-xBxMnO3.15 (B= Sr, Ag; x= 0 or 0.2) via manganese oxides susceptors and their activity in methane combustion. Catalysis Communications[J],2006,7: 109-113.
[31]P. Gina, R. Patricio, Z. Rau'l, etc. Effect of the preparation method on the catalytic activity of La1-xCaxFeO3 perovskite-type oxides. Catalysis Today[J],2008,133-135:420-427.
[32]Z. Taheri, K. Nazari, A.A. Safekordi, N. Seyed-Matin, et al. Oxygen permeation and oxidative coupling of methane in membrane reactor:A new facile synthesis method for selective perovskite catalyst. Journal of Molecular Catalysis A:Chemical [J],2008,286:79-86.
[33]P. Gina, C. Claudia, P. Octavio, E. C.Luis. Structural, magnetic and catalytic properties of perovskite-type mixed oxides LaMn1-yCoyO3(y= 0.0,0.1,0.3,0.5,0.7,0.9,1.0). Journal of Molecular Catalysis A:Chemical[J], 2008,282:158-166.
[34]K.I.Kobayashi, T.Kimura, etc. Room-temperature magnetoresistance in an oxide materialwith an ordered double-perovskite structure. Nature[J],1998,395:677-680.
[35]Maignan, A.; Raveau, B.; Martin, C.; Hervieu, M.. Large Intragrain Magnetoresistance above Room Temperature in the Double Perovskite Ba2FeMoO6. Journal of Solid State Chemistry[J] 1999,144,224.-227
[36]苗月,袁宏宽,陈洪.双钙钛矿Sr2-xLaxCrRe06的电子结构和磁性.物理化学学报[J],2008,24(3),448-452
[37]Huang, Y. H.; Dass, R.I.; King, Z.L. Double perovskites as anode meterials for solid-oxide fuel cells. Science[J],2006,312,254-257
[38]Anurag G, Varma G.D.. Enhanced magnetoresistance in double perovskite Sr2FeMoO6 through SrMoO4 tunneling barriers. Materials Science and Engineering B[J],2007,143:64-69
[39]Fuertes V.C., Blanco M.C., Franco D.G, etc. NewferromagneticLa3Co2TaO9 double perovskite:Structural and magnetic properties. Physica B[J],2009,404:2717-2719
[40]Saez-Puche R., Climent-Pascual E., Ruiz-Bustos R., etc. Non-collinear magnetic structure of the Sr2 ErRuO6 double perovskite. Progress in Solid State Chemistry [J],2007,35:211-219
[41]Falcon H., Barbero J.A.. Double perovskite oxides A2FeMoO6-δ (A= Ca, Sr and Ba) as catalysts for methane combustion. Appl. Catal. B Environ. [J],2004,53:37-45
[42]戴莹莹,胡瑞生,杨忠苹.双钙钛矿La2BSnO_6(B=Cu、Ni)材料的制备及催化性能.现代化工[J].2007,27：342-344
[43]胡瑞生,包莫日根高娃,徐娜等.新型催化材料Sr2FeMoO6的葡萄糖溶胶-凝胶法合成及甲烷催化燃烧性能.化工学报[J],2008,59(6)：1418-1424
[44]李言荣,恽正中.材料物理学概论[M].北京：清华大学出版社,2001.134.
[45]Pecchi, G.; Campos, C.; Pena, O.; Cadus, L. E. Structural, magnetic and catalytic properties of perovskite-type mixed oxides LaMn1-yCoyO3 (y= 0.0,0.1,0.3,0.5,0.7,0.9,1.0).Journal of Molecular Catalysis A:Chemical[J],2008,282,158-166
[46]Shaheen, R.; Bashir, J. Ca2CoNbO6: A new monoclinically distorted double perovskite.Solid State Sciences [J],2010,12,1496-1499
[47]康振晋,孙尚梅,郭振平.钙钛矿结构类型的功能材料的结构单元和结构演变.化学通报[J],2000,4：23-26.
[48]Michael R.H.,Scot T.M., etc. Environmental Applications of Semiconductor Photocatalysis.Chem.Rev[J], 1995,95:69-96
[49]Roa-Rojas J., Salazar C. M., Llamosa D. P.etc. Magnetoelectric response of new Sr2TiMnO6 manganite-like material, Journal of Magnetism and Magnetic Materials[J],2008,320,104-106
[50]秦善,王汝成.钙钛矿(ABX3)型结构畸变的几何描述及其应用.地质学报[J],2004,78(3)：345-351
[51]近藤精一,石川达雄,安部郁夫.吸附科学[M],原著第二版.北京：化学[业出版社,2010,31-35
[52]Petrovic, S.; Terlecki-Baricevic, A.; Karanovic, L.; Kirilov-Stefanov, P.; Zdujic, M.; Dondur, V.; Paneva, D.; Mitov, I.; Rakic, V. Appl. Catal. B:Environmental [J],2008,79:186
[53]徐秀峰,索掌怀,李大力等MnOx/Al2O3、MnOx/BaO-Al2O3催化剂的制备、表征及其对甲烷低温燃烧的催化活性.分子催化[J],2001,15(4)：259-262
[54]李然家,余长春,代小平等.钙钛矿型La0.8Sr0.2FeO3中的晶格氧用于甲烷选择氧化制取合成气.催化学报[J],2002,23(11)：549-554
[55]Ciambelli, P.; Cimino, S.; Lasorella, G.; CO oxidation and methane combustion on LaAl1-xFexO3 perovskite solid solutions. Appl. Catal. B:Environmental[J],2002,37:231-241
[56]N.Tien-Thao,H.Alamdari, M.H.Zahedi-Niaki, S.Kaliaguine. LaCo1-xCuxO3-δ perovskite catalysts for higher alcohol synthesi. Applied Catalysis A:General [J],2006,311:204-212
[57]R.Lago, GBini, M.A.Pena, J.L.GFierro. Partial Oxidation of Methane to Synthesis Gas Using LnCoO3 Perovskites as Catalyst Precursors. Journal of Catalysis [J],1997,167:198-209
[58]Hongqing Chen, Hao Yu, Feng Peng, Guangxing Yang, Hongjuan Wang, JianYang, Yong Tang. Autothermal reforming of ethanol for hydrogen production over perovskite LaNiO3. Chemical Engineering Journal [J],2010,03:054
[59]Levasseur B., Kaliaguine S.. Methanol oxidation on LaBO3 (B= Co, Mn, Fe) perovskite-type catalysts prepared by reactive grinding. Applied Catalysis A:General[J],2008,343:29-38
[60]S.Cimino, L.Lisi, S.De Rossi etc. Methane combustion and CO oxidation on LaAl1-xMnxO3 perovskite-type oxide solid solutions. Appl. Catal. B:Environmental [J] 2003,43:397-406
[61]王磊,曾少华,张丽娟等La0.75Sr0.25Mn1-xNixO3+δ.材料的制备及其催化甲烷部分氧化性能.催化学报[J],2009,30(3)：247-253
[62]Nguyen Tien-Thao,Houshang Alamdari,Serge Kaliaguine. Characterization and reactivity of nanoscale La(Co,Cu)O3 perovskite catalyst precursors for CO hydrogenation, Journal of Solid State Chemistry [J],2008, 181:2006-2019
[63]阮圣平,董玮,吴凤清等.纳米晶钛酸钡的介电性能.物理化学学报[J],2003,19(1)：17-20
[64]胡瑞生,阿山,吕宏缨等.焙烧温度对稀土钴系复合氧化物催化剂结构与性能的影响,分子催化[J],2002,16(2)：127-130
[65]刘社田,于作龙,吴越.钙钛矿型复合氧化物LaMyM'1-yO3的结构与红外光谱研究.无机材料学报[J],1994,9(2)：184-190
[66]Zhao X., Yang Q.H., Cui J.J.. XPS study of surface absorbed oxygen of ABO3 mixed oxides, Journal of Rare Earths[J],2008,26(4):511-514
[67]贾起民,郑永令,陈暨耀.电磁学[M]第二版.北京：高等教育出版社,2001.423-427
[68]Ghigna, P, Scavini, M, Mazzoli, C. Experimental disentangling of orbital and lattice energy scales by inducing cooperative Jahn-Teller melting in KCu1-xMgxF3 solid solutions. Physical Review B[J],2010,81(7):420
[69]Zhao X., Yang Q.H., Cui J.J.. XPS study of surface absorbed oxygen of ABO3 mixed oxides, JOURNAL OF RARE EARTHS[J],2008,26(4):511-514
[70]Xue H., Li Z.H., Wang X.X., etc, Studies on nanocrystalline (Sr,Pb)TiO3 solid solutions prepared via a facile self-propagating combustion method, Journal of Physics and Chemistry of Solids[J],2007,68:2326-2331
[71]Rosa Pereniguez, Victor M. Gonzalez-DelaCruz, Juan P.Holgado, Alfonso Caballero*. Synthesis and characterization of a LaNiO3 perovskite as precursor for methane reforming reactions catalysts.
[72]牛春艳,徐占林,赵丽娜等.钙钛矿型复合氧化物LaNiO3的制备及其在CH4/CO2重整反应中的应用.应用化工[J],2006,35(12)：941-945
[73]王永钊,赵永祥,高春光等.焙烧温度对C0304常温氧化CO催化性能的影响分子催化.分子催化[J],2007,21(4)：334.
[74]Baohua Yue, Renxian Zhou, etc. Promotional effect of Ca on the Pd/Ce-Zr/Al2O3 catalyst for low-temperature catalytic combustion of methane. Fuel Processing Technolony[J],2008,89:728-735.
[75]王玉和,刘红梅,徐柏庆.NiO-MgO固溶体的形成对Ni/MgO-AN催化CO2重整CH4反应活性和稳定性的影响.催化学报[J],2005,26(12)：1117-1121
[76]Keita Taniguchia, Noriyuki Okinakab, Tomohiro Akiyamab. Preparation and characterization of La1-xKxFeO3 (x=0-1) by self-propagating high-temperature synthesis for use as soot combustion catalyst. Journal of Alloys and Compounds[J],2011,509:4084-4088
[77]Zhiming Gao, Ruiyan Wang. Catalytic activity for methane combustion of the perovskite-type La1-xSrxCoO3-δ oxide prepared by the urea decomposition method. Applied Catalysis B:Environmental[J], 2010,98:147-153
[2]Yuri F. Makogon. Natural gas hydrates - A promising source of energy. Journal of Natural Gas Science and Engineering [J],2010,2:49-59
[3]Junchen Li, Xiucheng Dong,Jianxin Shangguan etc. Forecasting the growth of China's natural gas consumption. Energy[J],2011,36:1380-1385
[4]江怀友,钟太贤,宋新民等.世界天然气资源现状与展望.中国能源[J],2009,31(3)：40-42.
[5]周新文,朱万美.天然气“西气东输”与“俄气南供”.城市燃气[J],2002,331,25-28
[6]姜德群.我区已探明石油天然气产地46处.内蒙古晨报[J],2009,6.21.
[7]Hailong Li, Mario Ditaranto, David Berstad. Technologies for increasing CO2 concentration in exhaust gas from natural gas-fired power production with post-combustion, amine-based CO2 capture. Energy[J],2011,36(2): 1124-1133
[8]郭玉华.含镁复合氧化物催化剂催化甲烷燃烧性能的研究[D].宁夏大学硕士学位论文,2005,12
[9]徐金光,田志坚,王军威等.超临界干燥方法对甲烷燃烧催化剂LaMnAl11O19结构及活性的影响.催化学报[J],2002,23(5)：477-480.
[10]张世红,王棋,周琦.催化燃烧炉特性的实验研究.北京建筑工程学院学报[J].2003,3(19)：1-4
[11]Fengxiang Yin,Shengfu Ji,Biaohua Chen,etc.Preparation and characterization of LaFe1-xMgxO3/Al2O3/ FeCrAl Catalytic properties in methane combustion. Applied Catalysis B:Environmental [J],2006,66:270-273.
[12]WEI Yong gang, WANG Hua, LI Kong zhai. Ce-Fe-O mixed oxide as oxygen carrier for the direct partial oxidation of methane to syngas. Journal of Rare Earths [J],2010,28(4)560-565
[13]高典楠,王胜,刘莹等.焙烧温度对Pd/Al2O3催化剂上甲烷燃烧反应性能的影响.催化学报[J],2010,31(11)：1363—1368
[14]Chen Li, Wendong Wang, Ning Zhao etc. Structure properties and catalytic performance in methane combustion of double perovskites Sr2Mg1-xMnxMoO6-δ. Applied Catalysis B:Environmental [J],2011,102 (1) 78-84
[15]Cimino, S. M.P. Casaletto, L. Lisi, G. Russo. Pd-LaMnO3 as dual site catalysts for methane combustion. Applied Catalysis A[J],2007,15(2):238-243.
[16]徐金光,田志坚,索掌怀等.反相微乳液法制备LaMnAl11O19-α.甲烷燃烧催化剂.催化学报[J],2005,26(8)：665—668
[17]Choudhary, T. V.; Banerjee, S.; Choudhary, V R. Catalysts for combustion of methane and lower alkanes, Appl. Catal. A [J],2002,234:1-23
[18]Li-hua Xiao, Kun-peng Sun, Xian-lun Xu etc. Low-temperature catalytic combustion of methane over Pd/CeO2 prepared by deposition-precipitation method. Catal. Commun. [J],2005,6:796-801
[19]Arosio, F.; Colussi, S.; Trovarelli, A.; Groppi, G. Effect of alternate CH4-reducing/lean combustion treatments on the reactivity of fresh and S-poisoned Pd/CeO2/Al2O3 catalysts. Appl. Catal. B: Environmental [J],2008,80:335-342
[20]Z. M. Liu, Y. Q. Chen, J.B. Zhong, J.L.Wang. Effect of Fe203 Loading Amount on Catalytic Properties of Monolithic Fe2O3/Ce0.67Zr0.33O2-Al2O3 Catalyst for Methane Combustion. Journal of rare earth[J],2007,25: 585-589.
[21]O.Salvador, R. Paredes, V. Fernando, etc. Sulphur poisoning of transition metal oxides used as catalysts for methane Combustion. Applied Catalysis A:General [J],2008,341:174-180.
[22]戴洪兴,何洪,李佩珩等.稀土钙钛矿型氧化物催化剂的研究进展.中国稀土学报[J],2003,21(12),1-15
[23]S. V.Nguyen, V.Szabo, D Trong On, etc. Mesoporous silica supported LaCoO3 perovskites as catalysts for methane oxidation.Microporous and Mesoporous Materials [J],2002,54,51-61
[24]Batiot-Dupeyrat, C.; Martinez-Ortega, F.; Ganneb,M.etc.Methane catalytic combustion on La-based perovskite type catalysts in high temperature isothermal conditions. Appl. Catal. A[J],2001,206,205-215
[25]Zhong, Z. Y.; Chen, K. D.; Ji, Y. etc. Methane combustion over B-site partially substituted perovskite-type LaFeO3 prepared by sol-gel method. Appl. Catal. A [J],1997,156,29-41
[26]Imamura M, Matsubayashi N, Shimada H. Catalytically active oxygen species in La1-xSrxCoO3-δ studied by XPS and XAFS spectroscopy. J. Phys. Chem. B[J],2000,104 (31):7348.
[27]Li R, Ma J T, Xu J L, etc. Studies on the surface oxygenspecies and the catalytic activity for CO oxidation of La1-xSrxCo1-xMnxO3-δ a perovskite-type oxide catalyst. Catal. Lett. [J],2000,70 (2):363.
[28]M.O. Cofmell, A.K.Norman, C.F.Hultennann. Catalytic oxidation over lanthanum-transition metal perovskite materials. Catalysis Today[J],1999,47:123-132.
[29]J. G. McCarthy, H. Wise. Perovskite catalysts for methane combustion [J]. Catalysis Today,1990,8:231-248.
[30]A. Kaddouri, S. Ifrah. Microwave-assisted synthesis of La1-xBxMnO3.15 (B= Sr, Ag; x= 0 or 0.2) via manganese oxides susceptors and their activity in methane combustion. Catalysis Communications[J],2006,7: 109-113.
[31]P. Gina, R. Patricio, Z. Rau'l, etc. Effect of the preparation method on the catalytic activity of La1-xCaxFeO3 perovskite-type oxides. Catalysis Today[J],2008,133-135:420-427.
[32]Z. Taheri, K. Nazari, A.A. Safekordi, N. Seyed-Matin, et al. Oxygen permeation and oxidative coupling of methane in membrane reactor:A new facile synthesis method for selective perovskite catalyst. Journal of Molecular Catalysis A:Chemical [J],2008,286:79-86.
[33]P. Gina, C. Claudia, P. Octavio, E. C.Luis. Structural, magnetic and catalytic properties of perovskite-type mixed oxides LaMn1-yCoyO3(y= 0.0,0.1,0.3,0.5,0.7,0.9,1.0). Journal of Molecular Catalysis A:Chemical[J], 2008,282:158-166.
[34]K.I.Kobayashi, T.Kimura, etc. Room-temperature magnetoresistance in an oxide materialwith an ordered double-perovskite structure. Nature[J],1998,395:677-680.
[35]Maignan, A.; Raveau, B.; Martin, C.; Hervieu, M.. Large Intragrain Magnetoresistance above Room Temperature in the Double Perovskite Ba2FeMoO6. Journal of Solid State Chemistry[J] 1999,144,224.-227
[36]苗月,袁宏宽,陈洪.双钙钛矿Sr2-xLaxCrRe06的电子结构和磁性.物理化学学报[J],2008,24(3),448-452
[37]Huang, Y. H.; Dass, R.I.; King, Z.L. Double perovskites as anode meterials for solid-oxide fuel cells. Science[J],2006,312,254-257
[38]Anurag G, Varma G.D.. Enhanced magnetoresistance in double perovskite Sr2FeMoO6 through SrMoO4 tunneling barriers. Materials Science and Engineering B[J],2007,143:64-69
[39]Fuertes V.C., Blanco M.C., Franco D.G, etc. NewferromagneticLa3Co2TaO9 double perovskite:Structural and magnetic properties. Physica B[J],2009,404:2717-2719
[40]Saez-Puche R., Climent-Pascual E., Ruiz-Bustos R., etc. Non-collinear magnetic structure of the Sr2 ErRuO6 double perovskite. Progress in Solid State Chemistry [J],2007,35:211-219
[41]Falcon H., Barbero J.A.. Double perovskite oxides A2FeMoO6-δ (A= Ca, Sr and Ba) as catalysts for methane combustion. Appl. Catal. B Environ. [J],2004,53:37-45
[42]戴莹莹,胡瑞生,杨忠苹.双钙钛矿La2BSnO_6(B=Cu、Ni)材料的制备及催化性能.现代化工[J].2007,27：342-344
[43]胡瑞生,包莫日根高娃,徐娜等.新型催化材料Sr2FeMoO6的葡萄糖溶胶-凝胶法合成及甲烷催化燃烧性能.化工学报[J],2008,59(6)：1418-1424
[44]李言荣,恽正中.材料物理学概论[M].北京：清华大学出版社,2001.134.
[45]Pecchi, G.; Campos, C.; Pena, O.; Cadus, L. E. Structural, magnetic and catalytic properties of perovskite-type mixed oxides LaMn1-yCoyO3 (y= 0.0,0.1,0.3,0.5,0.7,0.9,1.0).Journal of Molecular Catalysis A:Chemical[J],2008,282,158-166
[46]Shaheen, R.; Bashir, J. Ca2CoNbO6: A new monoclinically distorted double perovskite.Solid State Sciences [J],2010,12,1496-1499
[47]康振晋,孙尚梅,郭振平.钙钛矿结构类型的功能材料的结构单元和结构演变.化学通报[J],2000,4：23-26.
[48]Michael R.H.,Scot T.M., etc. Environmental Applications of Semiconductor Photocatalysis.Chem.Rev[J], 1995,95:69-96
[49]Roa-Rojas J., Salazar C. M., Llamosa D. P.etc. Magnetoelectric response of new Sr2TiMnO6 manganite-like material, Journal of Magnetism and Magnetic Materials[J],2008,320,104-106
[50]秦善,王汝成.钙钛矿(ABX3)型结构畸变的几何描述及其应用.地质学报[J],2004,78(3)：345-351
[51]近藤精一,石川达雄,安部郁夫.吸附科学[M],原著第二版.北京：化学[业出版社,2010,31-35
[52]Petrovic, S.; Terlecki-Baricevic, A.; Karanovic, L.; Kirilov-Stefanov, P.; Zdujic, M.; Dondur, V.; Paneva, D.; Mitov, I.; Rakic, V. Appl. Catal. B:Environmental [J],2008,79:186
[53]徐秀峰,索掌怀,李大力等MnOx/Al2O3、MnOx/BaO-Al2O3催化剂的制备、表征及其对甲烷低温燃烧的催化活性.分子催化[J],2001,15(4)：259-262
[54]李然家,余长春,代小平等.钙钛矿型La0.8Sr0.2FeO3中的晶格氧用于甲烷选择氧化制取合成气.催化学报[J],2002,23(11)：549-554
[55]Ciambelli, P.; Cimino, S.; Lasorella, G.; CO oxidation and methane combustion on LaAl1-xFexO3 perovskite solid solutions. Appl. Catal. B:Environmental[J],2002,37:231-241
[56]N.Tien-Thao,H.Alamdari, M.H.Zahedi-Niaki, S.Kaliaguine. LaCo1-xCuxO3-δ perovskite catalysts for higher alcohol synthesi. Applied Catalysis A:General [J],2006,311:204-212
[57]R.Lago, GBini, M.A.Pena, J.L.GFierro. Partial Oxidation of Methane to Synthesis Gas Using LnCoO3 Perovskites as Catalyst Precursors. Journal of Catalysis [J],1997,167:198-209
[58]Hongqing Chen, Hao Yu, Feng Peng, Guangxing Yang, Hongjuan Wang, JianYang, Yong Tang. Autothermal reforming of ethanol for hydrogen production over perovskite LaNiO3. Chemical Engineering Journal [J],2010,03:054
[59]Levasseur B., Kaliaguine S.. Methanol oxidation on LaBO3 (B= Co, Mn, Fe) perovskite-type catalysts prepared by reactive grinding. Applied Catalysis A:General[J],2008,343:29-38
[60]S.Cimino, L.Lisi, S.De Rossi etc. Methane combustion and CO oxidation on LaAl1-xMnxO3 perovskite-type oxide solid solutions. Appl. Catal. B:Environmental [J] 2003,43:397-406
[61]王磊,曾少华,张丽娟等La0.75Sr0.25Mn1-xNixO3+δ.材料的制备及其催化甲烷部分氧化性能.催化学报[J],2009,30(3)：247-253
[62]Nguyen Tien-Thao,Houshang Alamdari,Serge Kaliaguine. Characterization and reactivity of nanoscale La(Co,Cu)O3 perovskite catalyst precursors for CO hydrogenation, Journal of Solid State Chemistry [J],2008, 181:2006-2019
[63]阮圣平,董玮,吴凤清等.纳米晶钛酸钡的介电性能.物理化学学报[J],2003,19(1)：17-20
[64]胡瑞生,阿山,吕宏缨等.焙烧温度对稀土钴系复合氧化物催化剂结构与性能的影响,分子催化[J],2002,16(2)：127-130
[65]刘社田,于作龙,吴越.钙钛矿型复合氧化物LaMyM'1-yO3的结构与红外光谱研究.无机材料学报[J],1994,9(2)：184-190
[66]Zhao X., Yang Q.H., Cui J.J.. XPS study of surface absorbed oxygen of ABO3 mixed oxides, Journal of Rare Earths[J],2008,26(4):511-514
[67]贾起民,郑永令,陈暨耀.电磁学[M]第二版.北京：高等教育出版社,2001.423-427
[68]Ghigna, P, Scavini, M, Mazzoli, C. Experimental disentangling of orbital and lattice energy scales by inducing cooperative Jahn-Teller melting in KCu1-xMgxF3 solid solutions. Physical Review B[J],2010,81(7):420
[69]Zhao X., Yang Q.H., Cui J.J.. XPS study of surface absorbed oxygen of ABO3 mixed oxides, JOURNAL OF RARE EARTHS[J],2008,26(4):511-514
[70]Xue H., Li Z.H., Wang X.X., etc, Studies on nanocrystalline (Sr,Pb)TiO3 solid solutions prepared via a facile self-propagating combustion method, Journal of Physics and Chemistry of Solids[J],2007,68:2326-2331
[71]Rosa Pereniguez, Victor M. Gonzalez-DelaCruz, Juan P.Holgado, Alfonso Caballero*. Synthesis and characterization of a LaNiO3 perovskite as precursor for methane reforming reactions catalysts.
[72]牛春艳,徐占林,赵丽娜等.钙钛矿型复合氧化物LaNiO3的制备及其在CH4/CO2重整反应中的应用.应用化工[J],2006,35(12)：941-945
[73]王永钊,赵永祥,高春光等.焙烧温度对C0304常温氧化CO催化性能的影响分子催化.分子催化[J],2007,21(4)：334.
[74]Baohua Yue, Renxian Zhou, etc. Promotional effect of Ca on the Pd/Ce-Zr/Al2O3 catalyst for low-temperature catalytic combustion of methane. Fuel Processing Technolony[J],2008,89:728-735.
[75]王玉和,刘红梅,徐柏庆.NiO-MgO固溶体的形成对Ni/MgO-AN催化CO2重整CH4反应活性和稳定性的影响.催化学报[J],2005,26(12)：1117-1121
[76]Keita Taniguchia, Noriyuki Okinakab, Tomohiro Akiyamab. Preparation and characterization of La1-xKxFeO3 (x=0-1) by self-propagating high-temperature synthesis for use as soot combustion catalyst. Journal of Alloys and Compounds[J],2011,509:4084-4088
[77]Zhiming Gao, Ruiyan Wang. Catalytic activity for methane combustion of the perovskite-type La1-xSrxCoO3-δ oxide prepared by the urea decomposition method. Applied Catalysis B:Environmental[J], 2010,98:147-153