过渡金属Ni对Pd/Al_2O_3催化剂甲烷催化燃烧性能的影响
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摘要
考察过渡金属Ni对Pd/Al_2O_3催化剂甲烷催化燃烧活性的影响以及过渡金属负载量及循环条件对甲烷降解性能的影响,采用扫描电镜、N_2吸附-脱附以及H_2程序升温还原技术对催化剂进行表征。结果表明,过渡金属Ni的添加对催化剂在(375~475)℃下的甲烷催化燃烧活性产生影响。催化剂经多次重复使用后,催化燃烧活性提高。分析原因为经过渡金属Ni改性后,可与载体形成NiAl_2O_4尖晶石,促进活性组分形成较小晶粒,并改善活性组分分散度,提高催化剂催化活性。
The influence of transition metal Ni modification on behaviors of Pd/Al_2O_3 catalysts for methane combustion was investigated.The effects of nickel loadings and the circulation condition decomposition of methane were studied.The catalysts were characterized by SEM,N_2 adsorption/desorption isotherms and H_2-TPR.The results showed that Ni modification affected catalytic activity of Pd/Al_2O_3 for methane catalytic combustion at the temperature(375-475) ℃.The catalytic activity increased after times of circulation,which was attributed to that nickel formed NiAl_2O_4 spinel with the carrier,promoted formation of smaller particles of active component and improved its dispersion.
The influence of transition metal Ni modification on behaviors of Pd/Al_2O_3 catalysts for methane combustion was investigated.The effects of nickel loadings and the circulation condition decomposition of methane were studied.The catalysts were characterized by SEM,N_2 adsorption/desorption isotherms and H_2-TPR.The results showed that Ni modification affected catalytic activity of Pd/Al_2O_3 for methane catalytic combustion at the temperature(375-475) ℃.The catalytic activity increased after times of circulation,which was attributed to that nickel formed NiAl_2O_4 spinel with the carrier,promoted formation of smaller particles of active component and improved its dispersion.
引文
[1]林雪峰,刘胜,邸志强.我国煤层气利用综述[J].煤炭技术,2010,29(4):1-3.Lin Xuefeng,Liu Sheng,Di Zhiqiang.Review of utilization of coal-bed gas in our country[J].Coal Technology,2010,29(4):1-3.
[2]刘文革,郭德勇,徐鑫.煤矿乏风甲烷氧化新型Pd/Al2O3催化剂的合成[J].煤炭学报,2012,37(2):336-340.Liu Wenge,Guo Deyong,Xu Xin.Synthesis of a novel Pd/Al2O3catalyst for ventilation air methane combustion with excellent catalytic activity in low temperatures[J].Journal of China Coal Society,2012,37(2):336-340.
[3]刘文革,张斌川,刘馨,等.中国煤矿区甲烷零排放[J].中国煤层气,2005,2(2):6-9.Liu Wenge,Zhang Binchuan,Liu Xin,et al.Zero emission of coal mine methane in China[J].China Coalbed Methane,2005,2(2):6-9.
[4]韩倩茜,史兵兵,江志东.与钇稳定化锆复合的La0.8Sr0.2Mn0.5Ni0.5O3催化剂用于低浓度甲烷催化燃烧[J].化学反应工程与技术,2011,27(6):488-495.Han Qianqian,Shi Bingbing,Jiang Zhidong.La0.8Sr0.2Mn0.5Ni0.5O3composited with yttrium stabilized zirconia for catalytic lean burn of methane[J].Chemical Reaction Engineering and Technology,2011,27(6):488-495.
[5]冯涛,王鹏飞,陈丽娟,等.煤矿乏风低浓度瓦斯燃烧催化剂的制备及其性能研究[J].安全与环境学报,2013,13(5):170-174.Feng Tao,Wang Pengfei,Chen Lijuan,et al.Preparation of the combustion catalyst for coal mine ventilation air methane and its properties[J].Journal of Safety and Environment,2013,13(5):170-174.
[6]陆殿乔,马磊,张群峰,等.碱土金属改性对Pd O/γ-Al2O3催化甲烷燃烧起燃活性的影响[J].工业催化,2010,18(12):13-18.Lu Dianqiao,Ma Lei,Zhang Qunfeng,et al.Effects of alkaline earth modification on light-off activity of Pd O/γ-Al2O3for methane combustion[J].Industrial Catalysis,2010,18(12):13-18.
[7]Garbowski E,Feumi-Jantou C,Mouaddib N,et al.Catalytic combustion of methane over palladium supported on alumina catalysts-evidence for reconstruction of particles[J].Applied Catalysis A:General,1994,109(2):277-291.
[8]Yang L F,Shi C K,He X E,et al.Catalytic combustion ofmethane over Pd O supported on Mg-modified alumina[J].Applied Catalysis B:Environmental,2002,38(2):117-125.
[9]Yue B H,Zhou X R,Wang Y J,et al.Study of the methane combustion and TPR/TPO properties of Pd/Ce-Zr-M/Al2O3catalysts with M=Mg,Ca,Sr,Ba[J].Journal of Molecular Catalysis A:Chemical,2005,238(1/2):241-249.
[10]肖利华,孙鲲鹏,徐贤伦.Ce O2-MOx(M=La3+,Ca2+)改性Pd/γ-Al2O3催化甲烷燃烧性能[J].物理化学学报,2008,24(11):2108-2113.Xiao Lihua,Sun Kunpeng,Xu Xianlun.Catalytic combustion of methane over Ce O2-MOx(M=La3+,Ca2+)solid solution promoted Pd/γ-Al2O3catalysts[J].Acta PhysicoChimica Sinica,2008,24(11):2108-2113.
[11]谢慧琳,张蔚欣,朱贵有,等.改性介孔硅负载铂催化合成农用增效剂[J].化工学报,2016,67(9):3699-3706.Xie Huilin,Zhang Weixin,Zhu Guiyou,et al.Study on agricultural synergist prepared by modified mesoporous silica supported platinum catalyst[J].CIESC Journal,2016,67(9):3699-3706.
[12]房师平,陈宏德,田群,等.Pd/CZ/Al2O3催化剂的制备、表征与三效催化性能[J].环境科学,2005,26(5):12-16.Fang Shiping,Chen Hongde,Tian Qun,et al.Preparation,characterization and three way catalytic performance for Pd/CZ/Al2O3catalyst[J].Environmental Science,2005,26(5):12-16.
[13]李伶聪,胡瑞生,白雅琴,等.掺杂型烧绿石La2Sn1.7Co0.3O7-δ逆负载Ce O2催化剂的甲烷催化燃烧性能[J].高等学校化学学报,2015,36(7):1328-1336.Li Lingcong,Hu Ruisheng,Bai Yaqin,et al.Inverse Ce O2/La2Sn1.7Co0.3O7-δcatalyst for methane catalytic combustion[J].Chemical Journal of Chinese Universities,2015,36(7):1328-1336.
[14]Noronha F B,Baldanza M A S,Monteiro R S,et al.The nature of metal oxide on adsorptive and catalytic properties of Pd/Me Ox/Al2O3catalysts[J].Applied Catalysis A:General,2001,210(1/2):275-286.
[15]Luo M F,Hou Z Y,Yuan X X,et al.Characterization study of Ce O2supported Pd catalyst for low-temperature carbon monoxide oxidation[J].Catalysis Letters,1998,50(3/4):205-209.
[16]訾学红.甲烷催化燃烧技术基础研究[D].北京:北京工业大学,2012.Zi Xuehong.The fundamental research on catalytic combustion of methane[D].Beijing:Beijing University of Technology,2012.
[17]王智辉.用于甲烷催化燃烧的金属氧化物及贵金属催化剂制备、表征及性能研究[D].广州:华南理工大学,2014.Wang Zhihui.Synthesis,characterization and catalytic activity of mixed metal oxides and noble metal catalysts for methane combustion[D].Guangzhou:South China University of Technology,2014.
[18]刘莹,王胜,高典楠,等.Ni的引入对Pd/Al2O3催化甲烷催化燃烧性能的影响[J].催化学报,2012,33(8):1354-1359.Liu Ying,Wang Sheng,Gao Diannan,et al.Effect of Ni addition on methane catalytic combustion performance of Pd/Al2O3catalyst[J].Chinese Journal of Catalysis,2012,33(8):1354-1359.
[19]杨祖照.Pd基催化剂用于甲烷催化燃烧的实验研究[D].北京:华北电力大学,2008.Yang Zuzhao.Experimental investigation of catalytic combustion of methane on Pd-based catalysts[D].Beijing:North China Electric Power University,2008.
[20]胡劲召,李凤仪,石秋杰.低钯型Pd-Ni-La-Ce催化剂氧化性能研究[J].中国稀土学报,2003,21(s2):72-75.Hu Jinzhao,Li Fengyi,Shi Qiujie.Study on low content palladium Pd-Ni-La-Ce catalyst on oxidation activities[J].Journal of the Chinese Rare Earth Society,2003,21(s2):72-75.
[21]邓存,谢鸿芳,黄炎琳,等.负载型镍催化剂催化性能研究[J].吉林化工学院学报,1996,13(4):18-22.Deng Cun,Xie Hengfang,Huang Yanlin,et al.The catalytical performance of supported nickel catalyst[J].Journal of Jilin Institure of Chemical Technology,1996,13(4):18-22.
[2]刘文革,郭德勇,徐鑫.煤矿乏风甲烷氧化新型Pd/Al2O3催化剂的合成[J].煤炭学报,2012,37(2):336-340.Liu Wenge,Guo Deyong,Xu Xin.Synthesis of a novel Pd/Al2O3catalyst for ventilation air methane combustion with excellent catalytic activity in low temperatures[J].Journal of China Coal Society,2012,37(2):336-340.
[3]刘文革,张斌川,刘馨,等.中国煤矿区甲烷零排放[J].中国煤层气,2005,2(2):6-9.Liu Wenge,Zhang Binchuan,Liu Xin,et al.Zero emission of coal mine methane in China[J].China Coalbed Methane,2005,2(2):6-9.
[4]韩倩茜,史兵兵,江志东.与钇稳定化锆复合的La0.8Sr0.2Mn0.5Ni0.5O3催化剂用于低浓度甲烷催化燃烧[J].化学反应工程与技术,2011,27(6):488-495.Han Qianqian,Shi Bingbing,Jiang Zhidong.La0.8Sr0.2Mn0.5Ni0.5O3composited with yttrium stabilized zirconia for catalytic lean burn of methane[J].Chemical Reaction Engineering and Technology,2011,27(6):488-495.
[5]冯涛,王鹏飞,陈丽娟,等.煤矿乏风低浓度瓦斯燃烧催化剂的制备及其性能研究[J].安全与环境学报,2013,13(5):170-174.Feng Tao,Wang Pengfei,Chen Lijuan,et al.Preparation of the combustion catalyst for coal mine ventilation air methane and its properties[J].Journal of Safety and Environment,2013,13(5):170-174.
[6]陆殿乔,马磊,张群峰,等.碱土金属改性对Pd O/γ-Al2O3催化甲烷燃烧起燃活性的影响[J].工业催化,2010,18(12):13-18.Lu Dianqiao,Ma Lei,Zhang Qunfeng,et al.Effects of alkaline earth modification on light-off activity of Pd O/γ-Al2O3for methane combustion[J].Industrial Catalysis,2010,18(12):13-18.
[7]Garbowski E,Feumi-Jantou C,Mouaddib N,et al.Catalytic combustion of methane over palladium supported on alumina catalysts-evidence for reconstruction of particles[J].Applied Catalysis A:General,1994,109(2):277-291.
[8]Yang L F,Shi C K,He X E,et al.Catalytic combustion ofmethane over Pd O supported on Mg-modified alumina[J].Applied Catalysis B:Environmental,2002,38(2):117-125.
[9]Yue B H,Zhou X R,Wang Y J,et al.Study of the methane combustion and TPR/TPO properties of Pd/Ce-Zr-M/Al2O3catalysts with M=Mg,Ca,Sr,Ba[J].Journal of Molecular Catalysis A:Chemical,2005,238(1/2):241-249.
[10]肖利华,孙鲲鹏,徐贤伦.Ce O2-MOx(M=La3+,Ca2+)改性Pd/γ-Al2O3催化甲烷燃烧性能[J].物理化学学报,2008,24(11):2108-2113.Xiao Lihua,Sun Kunpeng,Xu Xianlun.Catalytic combustion of methane over Ce O2-MOx(M=La3+,Ca2+)solid solution promoted Pd/γ-Al2O3catalysts[J].Acta PhysicoChimica Sinica,2008,24(11):2108-2113.
[11]谢慧琳,张蔚欣,朱贵有,等.改性介孔硅负载铂催化合成农用增效剂[J].化工学报,2016,67(9):3699-3706.Xie Huilin,Zhang Weixin,Zhu Guiyou,et al.Study on agricultural synergist prepared by modified mesoporous silica supported platinum catalyst[J].CIESC Journal,2016,67(9):3699-3706.
[12]房师平,陈宏德,田群,等.Pd/CZ/Al2O3催化剂的制备、表征与三效催化性能[J].环境科学,2005,26(5):12-16.Fang Shiping,Chen Hongde,Tian Qun,et al.Preparation,characterization and three way catalytic performance for Pd/CZ/Al2O3catalyst[J].Environmental Science,2005,26(5):12-16.
[13]李伶聪,胡瑞生,白雅琴,等.掺杂型烧绿石La2Sn1.7Co0.3O7-δ逆负载Ce O2催化剂的甲烷催化燃烧性能[J].高等学校化学学报,2015,36(7):1328-1336.Li Lingcong,Hu Ruisheng,Bai Yaqin,et al.Inverse Ce O2/La2Sn1.7Co0.3O7-δcatalyst for methane catalytic combustion[J].Chemical Journal of Chinese Universities,2015,36(7):1328-1336.
[14]Noronha F B,Baldanza M A S,Monteiro R S,et al.The nature of metal oxide on adsorptive and catalytic properties of Pd/Me Ox/Al2O3catalysts[J].Applied Catalysis A:General,2001,210(1/2):275-286.
[15]Luo M F,Hou Z Y,Yuan X X,et al.Characterization study of Ce O2supported Pd catalyst for low-temperature carbon monoxide oxidation[J].Catalysis Letters,1998,50(3/4):205-209.
[16]訾学红.甲烷催化燃烧技术基础研究[D].北京:北京工业大学,2012.Zi Xuehong.The fundamental research on catalytic combustion of methane[D].Beijing:Beijing University of Technology,2012.
[17]王智辉.用于甲烷催化燃烧的金属氧化物及贵金属催化剂制备、表征及性能研究[D].广州:华南理工大学,2014.Wang Zhihui.Synthesis,characterization and catalytic activity of mixed metal oxides and noble metal catalysts for methane combustion[D].Guangzhou:South China University of Technology,2014.
[18]刘莹,王胜,高典楠,等.Ni的引入对Pd/Al2O3催化甲烷催化燃烧性能的影响[J].催化学报,2012,33(8):1354-1359.Liu Ying,Wang Sheng,Gao Diannan,et al.Effect of Ni addition on methane catalytic combustion performance of Pd/Al2O3catalyst[J].Chinese Journal of Catalysis,2012,33(8):1354-1359.
[19]杨祖照.Pd基催化剂用于甲烷催化燃烧的实验研究[D].北京:华北电力大学,2008.Yang Zuzhao.Experimental investigation of catalytic combustion of methane on Pd-based catalysts[D].Beijing:North China Electric Power University,2008.
[20]胡劲召,李凤仪,石秋杰.低钯型Pd-Ni-La-Ce催化剂氧化性能研究[J].中国稀土学报,2003,21(s2):72-75.Hu Jinzhao,Li Fengyi,Shi Qiujie.Study on low content palladium Pd-Ni-La-Ce catalyst on oxidation activities[J].Journal of the Chinese Rare Earth Society,2003,21(s2):72-75.
[21]邓存,谢鸿芳,黄炎琳,等.负载型镍催化剂催化性能研究[J].吉林化工学院学报,1996,13(4):18-22.Deng Cun,Xie Hengfang,Huang Yanlin,et al.The catalytical performance of supported nickel catalyst[J].Journal of Jilin Institure of Chemical Technology,1996,13(4):18-22.