SO_2对Pd掺杂La_(0.9)Sr_(0.1)MnO_3催化剂去除NO_x和碳烟的影响
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摘要
采用柠檬酸络合法制备了掺杂贵金属Pd的La_(0.9)Sr_(0.1)Mn_(0.03)Pd_(0.97)O_3钙钛矿型催化剂,并通过X射线衍射光谱及暂态响应、扫描电子显微镜、傅立叶变换红外光谱及程序升温等技术研究了Pd对钙钛矿形貌结构和NO_x转化率的影响以及SO_2对La_(0.9)Sr_(0.1)Mn_(0.97)Pd_(0.03)O_3催化剂脱除NO_x的作用机制.结果显示,Pd的成功掺入增大了原催化剂的比表面积,使得催化剂中的活性组分与NO_x能够反应的更加充分,有效提高了催化剂对NO的转化率.催化剂La_(0.9)Sr_(0.1)Mn_(0.97)Pd_(0.03)O_3在含SO_2气氛下反应后出现了微弱的硫酸盐相,说明硫使催化剂发生了一定程度的钝化.在较低浓度SO_2存在时催化剂对NO的转化效率维持在80%以上,碳烟的起燃温度为353℃,但随着SO_2浓度的增加NO的转化效率最高只有67%,碳烟的起燃温度升高到368℃.
The perovskite catalyst La_(0.9)Sr_(0.1)Mn_(0.03)Pd_(0.97)O_3 doped with noble metal Pd was prepared by citrate method. The effects of noble metal Pd dopant on the morphology structure of perovskite and the NO_x conversion, and the mechanism of SO_2 on the NO_x removal performance of La_(0.9)Sr_(0.1)Mn_(0.97)Pd_(0.03)O_3 catalyst was investigated in this paper using X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and the transient response method.Results show that incorporating the noble metal Pd into the catalyst increased the specific surface area of the original catalyst, created a suitable place for NO contact, and improved the NO conversion of the catalyst effectively. The catalyst La_(0.9)Sr_(0.1)Mn_(0.97)Pd_(0.03)O_3 has a weak sulfate phase after reacting in an SO_2 atmosphere, indicating that sulfur resulted in a certain degree deactivation to the catalyst. The conversion efficiency of NO_x was maintained above 80% and the temperatures of soot combustion is 353℃ in the presence of a lower concentration of SO_2. When the concentration of SO_2 increased, the temperatures of soot combustion increased to 368℃ and the conversion efficiency of NO_x was only at 67%.
The perovskite catalyst La_(0.9)Sr_(0.1)Mn_(0.03)Pd_(0.97)O_3 doped with noble metal Pd was prepared by citrate method. The effects of noble metal Pd dopant on the morphology structure of perovskite and the NO_x conversion, and the mechanism of SO_2 on the NO_x removal performance of La_(0.9)Sr_(0.1)Mn_(0.97)Pd_(0.03)O_3 catalyst was investigated in this paper using X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and the transient response method.Results show that incorporating the noble metal Pd into the catalyst increased the specific surface area of the original catalyst, created a suitable place for NO contact, and improved the NO conversion of the catalyst effectively. The catalyst La_(0.9)Sr_(0.1)Mn_(0.97)Pd_(0.03)O_3 has a weak sulfate phase after reacting in an SO_2 atmosphere, indicating that sulfur resulted in a certain degree deactivation to the catalyst. The conversion efficiency of NO_x was maintained above 80% and the temperatures of soot combustion is 353℃ in the presence of a lower concentration of SO_2. When the concentration of SO_2 increased, the temperatures of soot combustion increased to 368℃ and the conversion efficiency of NO_x was only at 67%.
引文
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[28]Zhang Zhaoshun,Mark Crocker,Chen Bingbing,Bai Zhifeng,Wang Xinkui,Shi Chuan,Pt-free,non-thermal plasma-assisted NOxstorage and reduction over M/Ba/Al2O3(M=Mn,Fe,Co,Ni,Cu)catalyst[J].Catalysis Today,2015,256:115–123.
[2]陆凯波,刘双喜,李振国,等.国Ⅳ柴油机颗粒物与颗粒态多环芳烃排放特征[J].中国环境科学,2016,36(2):376-381.
[3]朱清霞.柴油机的尾气处理技术[J].科技资讯,2014,13(9):63-68.
[4]Zhao Zhen,Zhang Guizhen,Liu Jian,et al.Latest research progresses in catalysts for the purification of exhaust gases from diesel engines[J].Chinese Journal of Catalysis,2008,29(3):303-312.
[5]Isabella Nova,Lidia Castoldi,Luca Lietti,et al.NOx adsorption study over Pt-Ba/alumina catalysts:FT-IR and pulse experiments,Journal of Catalysis,2004,222:377–388.
[6]江同.柴油/LPG双燃料发动机工作状态的控制及性能研究[D].浙江大学,2004.
[7]Brisley,Robert James,Twigg,et al.Catalytic wall-flow filter:US,B01J 35/00(20060101)6753294[P].2004:6-22.
[8]环境保护部.关于征求国家环境保护标准《车用压燃式、气体燃料点燃式发动机与汽车排气污染物排放限值及测量方法(中国第六阶段)(征求意见稿)》意见的函[EB/OL].http://www.mep.gov.cn/gkml/hbb/bgth/201610/t20161017_365634.ht m/2016-10-11.
[9]Cao Chunmei,Xing Lingli,Yang Yuexi,et al.The monolithic transition metal oxide crossed nanosheets used for diesel soot combustion under gravitational contact mode[J].Applied Surface Science,2017,406:245-253.
[10]Li Lei,Shen Xiangqian,Wang Pan,et al.Soot capture and combustion for perovskite La-Mn-O based catalysts coated on honeycomb ceramic in practical diesel exhaust[J].Applied Surface Science,2011,257:9519-9524.
[11]Zhang Xiaojing,Li Yong,Li Huaju,et al.Preparation of La Fe0.95Pd0.05O3 perovskites and their catalytic performances in methane combustion[J].Journal of Natural Gas Chemistry,2012,21:113-118.
[12]孙志强,王虹.La1-x Srx Co0.5Mn0.5O3催化剂同时去除柴油机碳颗粒和NOx的性能[J].石油化工高等学校学报,2007,20(1):35-38.
[13]Liu J,Zhao Z,Xu C M,et al.Simultaneous removal of NOx and diesel soot particulates over nanometric La2-x Kx Cu O4 complex oxide catalysts[J].Catalysis Today,2007,119(1-4):267-272.
[14]Wang H,Zhao Z,Xu C M,et al.,Nanometric La1-x Kx Mn O3perovskite-type oxides&highly active catalysts for the combustion of diesel soot particle under loose contact conditions[J].Catalysis.Lett.2005,102:251-256.
[15]Liu J,Zhao Z,Xu C M,et al.,Study of the catalytic combustion of diesel soot over nanometric lanthanum-cobalt mixed oxide catalysts[J].Reaction Kinetics and Catalysis Lett,2005,87:107-114.
[16]Denton P,Giroir-Fendler A,Praliaud H,et al.Role of the nature of the support(alumina or silica),of the support porosity,and of the Pt dispersion in the selective reduction of NO by C3H6 under lean-bum condition[J].Journal of Catalysis,2000,189(2):410-420.
[17]俞守耕.柴油车尾气后处理技术的进展[J].贵金属,2003,24(1):62-66.
[18]王林江,郭子峰,吴群英.柴油车尾气净化四效催化技术进展[J].工业催化,2009,17(5):3-6.
[19]Yang F,Kim S,Takamura Y,et al.Strain effect on the electrical conductivity of epitaxial La0.67Sr0.33Mn O3 thin films[J].Scripta Materialia,2011,65(1):29-32.
[20]Cimino S,Lisi L,Pirone R,et al.Methane combustion on perovskites-based structured catalysts[J].Catalysis Today,2000,59(1/2):19-31.
[21]Armstrong E N,Striker T,Ramaswamy V,et al.NOx adsorption behavior of La Fe O3 and La Mn O3 and its influence on potentiometric sensor response[J].Sensors and Actuators B,2011,158(1):159-170.
[22]Hirohisa Tanaka,Noritaka Mizuno,Makoto Misono,Catalytic activity and structural stability of La0.9Ce0.1Co1-x Fex O3perovskite catalysts for automotive emissions control[J].Applied Catalysis-A,2003,244(2):371-382.
[23]Femina Patel,Sanjay Patel,La1-x Srx Co O3(x=0,0.2)perovskites type catalyst for carbon monoxide emission control from autoexhaust[J].Procedia Engineering,2013,51:324-329.
[24]E.A.Parvaneh,K.Abbasali,Z.A.Hessam et al.Effects of excess manganese in lanthanum manganite perovskite on lowering oxidation light-off temperature for automotive exhaust gas pollutants[J].Chemical Engineering Journal,2011,169:282-289.
[25]Tanaka H,Takahashi I,Advances in designing perovskite catalysts[J].J-SAE,1993,47(10):51-58.
[26]Tanaka H,Fujikawa H,Takahashi I.,Excellent oxygen storage capacity of perovskite-PD three-way catalysts[C].SAE paper950256,1995.
[27]姚文生,镧钴钙钛矿催化剂制备及去除氮氧化物和碳烟性能研究[D].天津:天津大学化工学院,2009.
[28]Zhang Zhaoshun,Mark Crocker,Chen Bingbing,Bai Zhifeng,Wang Xinkui,Shi Chuan,Pt-free,non-thermal plasma-assisted NOxstorage and reduction over M/Ba/Al2O3(M=Mn,Fe,Co,Ni,Cu)catalyst[J].Catalysis Today,2015,256:115–123.
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