Li Qian, Meng Ming, Zou Zhi-Qiang, Li Xin-Gang, Zha Yu-Qing
Tianjin Key Laboratory of Applied Catalysis Science & Engineering, Department of Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300072, PR China.
J Hazard Mater. 2009 Jan 15;161(1):366-72. doi: 10.1016/j.jhazmat.2008.03.103. Epub 2008 Mar 30.
A series of potassium-promoted hydrotalcite-based CoMgAlO mixed oxide catalysts used for simultaneous soot combustion and nitrogen oxides storage were prepared by impregnation method. The techniques of TG/DTA, XRD, H2-TPR and in situ DRIFTS were employed for catalyst characterization. Over the catalyst containing 7.5% or 10% K, the soot ignition temperature (Ti=260 degrees C) and total removal temperature (Tf=390 degrees C) are decreased by 180 degrees C and 273 degrees C, respectively, as compared with the uncatalyzed reaction. The results of kinetic calculation show that the presence of K-promoted catalysts decreases the activation energy of soot combustion from 207kJ/mol to about 160kJ/mol. When 400ppm NO is introduced, lower characteristic temperatures or higher reaction rate for soot oxidation is achieved. Simultaneously, relatively larger nitrogen oxides storage capacity is obtained. It is revealed by H2-TPR that the addition of K increases the amount of active Co sites and the mobility of bulk lattice oxygen due to the low melting point of K-containing compounds, the low valence of K+ and the strong interaction between K and Mg(Al). For nitrogen oxides storage, different routes via chelating bidentate nitrates, monodentate nitrates and ionic nitrates are confirmed by in situ DRIFTS over the CoMgAlO catalysts with potassium loadings of 0, 1.5 and 7.5%, respectively.
采用浸渍法制备了一系列用于同时催化碳烟燃烧和氮氧化物储存的钾促进水滑石基CoMgAlO混合氧化物催化剂。运用TG/DTA、XRD、H2-TPR和原位DRIFTS技术对催化剂进行表征。与未催化反应相比,在含7.5%或10% K的催化剂上,碳烟着火温度(Ti = 260℃)和完全去除温度(Tf = 390℃)分别降低了180℃和273℃。动力学计算结果表明,钾促进催化剂的存在使碳烟燃烧的活化能从207kJ/mol降至约160kJ/mol。当引入400ppm NO时,可实现较低的碳烟氧化特征温度或较高的反应速率。同时,获得了相对较大的氮氧化物储存容量。H2-TPR表明,由于含钾化合物熔点低、K+价态低以及K与Mg(Al)之间的强相互作用,K的添加增加了活性Co位点的数量和体相晶格氧的迁移率。对于氮氧化物储存,原位DRIFTS分别在钾负载量为0、1.5%和7.5%的CoMgAlO催化剂上证实了通过螯合双齿硝酸盐、单齿硝酸盐和离子硝酸盐的不同途径。