Pd-Ce/Al_2O_3催化剂用于低浓度甲烷催化燃烧
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摘要
采用浸渍法制备了Pd-Ce/γ-Al_2O_3系列催化剂,研究了催化剂对低浓度甲烷催化燃烧反应活性的影响,采用扫描电镜(SEM)、氮气吸脱附曲线以及H_2程序升温还原(H2-TPR)技术对催化剂结构特征和化学性质进行表征和分析.针对焙烧温度、助剂添加量对催化活性的影响进行了研究,并对催化剂循环使用的催化活性进行了考察.结果表明:焙烧温度为550℃时催化效率最佳,相同催化温度下效率最高相差40%左右,双金属Pd-Ce催化剂较之单金属Pd催化剂有助于提高甲烷催化活性,但催化效果并不明显,经多次循环反应后可明显提高其催化活性,与首次实验相比,催化效率最高相差约50%左右,分析原因可能为催化剂经多次催化反应使催化活性组分Pd O与CeO_2之间的协同作用加强,提高PdO的分散度并降低催化剂表面吸附氧的脱附能,从而提高了催化剂的催化活性.
Bimetallic Pd-Ce/γ-Al_2O_3 series catalysts were prepared by impregnation method in our experiment. Effects of the catalysts performance on the low concentration methane catalytic combustion were investigated.Structures and chemical properties of the catalysts were characterized and analyzed by scanning electron microscopy(SEM), N_2 adsorption/desorption isotherms and H_2-temperature programmed reduction(H_2-TPR). Effects of different calcination temperature and additive dosage on catalytic activities were studied; the catalytic activity of the recycling catalysts was investigated at the same time.The results showed that the optimal calcination temperature was 550℃, the highest efficiency difference of about 40% at the same catalytic temperature. Compared with the single metal catalyst, bimetallic catalyst was benefit to improve the catalytic activity, but the catalytic effect was not obvious. However, the catalytic activity could be improved significantly when being used for many times, compared with the first experiment, the catalytic efficiency of the highest difference of about 50%. The probably reason were that the synergistic effects between Pd O and CeO_2 could be strengthen, the dispersion of the Pd O could be improved, and the desorption energy of the adsorption oxygen could be reduced, all of which enhanced the catalyst activity.
Bimetallic Pd-Ce/γ-Al_2O_3 series catalysts were prepared by impregnation method in our experiment. Effects of the catalysts performance on the low concentration methane catalytic combustion were investigated.Structures and chemical properties of the catalysts were characterized and analyzed by scanning electron microscopy(SEM), N_2 adsorption/desorption isotherms and H_2-temperature programmed reduction(H_2-TPR). Effects of different calcination temperature and additive dosage on catalytic activities were studied; the catalytic activity of the recycling catalysts was investigated at the same time.The results showed that the optimal calcination temperature was 550℃, the highest efficiency difference of about 40% at the same catalytic temperature. Compared with the single metal catalyst, bimetallic catalyst was benefit to improve the catalytic activity, but the catalytic effect was not obvious. However, the catalytic activity could be improved significantly when being used for many times, compared with the first experiment, the catalytic efficiency of the highest difference of about 50%. The probably reason were that the synergistic effects between Pd O and CeO_2 could be strengthen, the dispersion of the Pd O could be improved, and the desorption energy of the adsorption oxygen could be reduced, all of which enhanced the catalyst activity.
引文
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[2]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.
[3]王帆.Ce对Pd-Pt/Al2O3催化剂甲烷催化燃烧性能的影响[J].科技传播,2013,9(2):117-118.
[4]Park J H,Ahn J H,Sim H I,et al.Low-temperature combustion of methane using Pd O/Al2O3 catalyst influence of crystalline phase of Al2O3 support[J].Catalysis Communications,2014,56:157-163.
[5]Ozawa Y,Tochihara Y,Nagai M.Pd O/Al2O3 in catalytic combustion of methane:Stabilization and deactivation[J].Chemical Engineering Science,2003,58(3-6):671-677.
[6]Park J H,Cho J H,Kim Y J,et al.Hydrothermal stability of Pd/Zr O2 catalysts for high temperature methane combustion[J].Applied Catalysis B:Environmental,2014,160:135-143.
[7]皮冬.Pd基催化剂的低浓度甲烷催化燃烧实验研究[D].北京:中国科学技术大学,2016.
[8]Ahmed I O,Jehad K A,Fathima L,et al.A bimetallic catalyst on a dual component support for lowt emperature total methane oxidation[J].Applied Catalysis B:Environmental,2016,187:408-418.
[9]唐国旗,张春富,孙长山,等.活性氧化铝载体的研究进展[J].化工进展,2011,30(8):1756-1765.
[10]Janina O,Miros?aw Z,Katarzyna B.Methane combustion over bimetallic Ru-Re/γ-Al2O3 catalysts:Effect of Re and pretreatments[J].Applied Catalysis B:Environmental,2016,194:22–31.
[11]Kinnunen N M,Hirvi J T,Suvanto M,et al.Methane combustion activity of Pd-Pd Ox-Pt/Al2O3 catalyst:The role of platinum promoter[J].Journal of Molecular Catalysis A:Chemical,2012,356:20-28.
[12]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.
[13]Anis H F,Wasim U K,Ahmed S A,et al.Production of hydrogen from methane over lanthanum supported bimetallic catalysts[J].International Journal of Hydrogen Energy,2016,41:8193-8198.
[14]高月明,于庆君,易红宏,等.Cu-ZSM-5对燃气烟气中NO的吸附特性[J].中国环境科学,2016,36(8):2275-2281.
[15]胡强,熊志波,白鹏,等.铈钛掺杂促进铁氧化物低温SCR脱硝性能的机理[J].中国环境科学,2016,36(8):2304-2310.
[16]黄海凤,张细雄,豆闶,等.氧化物载体对Ni-V催化剂催化燃烧二氯甲烷的影响[J].中国环境科学,2016,36(11):3273-3279.
[17]苑兴洲,陈绍云,陈恒,等.甲烷在Cr改性Pd/Al2O3催化剂上的催化燃烧性能[J].化工进展,2014,33(12):3258-3262,3282.
[18]赵世芳,杨玉霞,徐贤伦.Pd-Ce/γ-Al2O3催化剂上甲烷催化燃烧性能的研究[J].天然气化工,2009,34(1):1-4,16.
[19]张继光.催化剂制备过程技术[M].北京:中国石化出版社,2004:11-15.
[20]孙路石,秦晓楠,逄鹏,等.La/Mn改性Pd/γ-Al2O3催化剂对甲烷催化燃烧的影响[J].中国电机工程学报,2009,29(11):26-31.
[21]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.
[22]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/Al2O3 catalysts[J].Applied Catalysis A:general,2001,210(1/2):275-286.
[23]Luo M F,Hou Z Y,Yuan X X,et al.Characterization study of Ce O2 supported Pd catalyst for low-temperature carbon monoxide oxidation[J].Catalysis Letters,1998,50(3/4):205-209.
[24]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,2014:58-61.
[25]李霄宇.低浓度甲烷催化燃烧整体式催化剂的研究[D].北京:北京化工大学,2008:47-48.
[26]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,2008:43-44.
[27]黄敬敬,贾志刚,刘翻艳.Ce改性Pd基整体式催化剂的结构特征及其甲烷催化燃烧性能[J].工业催化,2013,21(5):23-29.
[28]任红海.H2O2氧化苯乙烯合成环氧苯乙烷的工艺研究[D].郑州:郑州大学,2012,35.