Cu的负载方法对CuSAPO-34脱除柴油车尾气中NOx的影响

采用X射线衍射、扫描电镜、原子吸收、程序升温还原、X射线吸收近边吸收谱、X射线光电子能谱、氮吸附等手段对水热合成(HS)、等体积浸渍(PVI)与离子交换(IE)法制备的CuSAPO-34样品进行了表征,并评价了老化前后催化剂上C₃H₆-SCR与NH₃-SCR脱除模拟柴油车尾气中NO_x的反应活性.结果表明,IE法制得的催化剂活性最高,尤其在C₃H₆-SCR低温阶段;PVI法制得的催化剂活性最差.制备方法影响CuSAPO-34催化剂的比表面积、孔径分布和活性组分价态从而改变其催化活性.各催化剂均存在Cu⁺和Cu²⁺,但比例明显不同.HS样品以Cu²⁺为主,另两种样品则含较多的Cu⁺.老化不仅部分破坏了分子筛的形貌、降低了分子筛的比表面积,尤其是表面Cu含量,而且有部分Cu生成了CuSO₄,使得老化后催化剂的脱硝活性降低.PVI法制得的催化剂老化后活性下降幅度最小,表明该分子筛抗老化能力较强.

Effect of CuSAPO-34 catalyst preparation method on NOx removal from diesel vehicle exhausts

CuSAPO-34 samples prepared by hydrothermal synthesis (HS), pore-volume impregnation (PVI), and ion-exchange (IE) methods were characterized using X-ray diffraction, scanning electronic microscopy, atomic absorption spectroscopy, temperature-programmed reduction with hydrogen, X-ray absorption near-edge structure spectroscopy, X-ray photoelectron spectroscopy, and N₂ adsorption. The selective catalytic reduction (SCR) ability over CuSAPO-34 for NO_x from a simulated diesel exhaust was investigated through C₃H₆-SCR and NH₃-SCR, before and after aging of the CuSAPO-34 catalyst. The results indicated that the sample prepared by IE had significantly better activity compared with those prepared using HS and PVI, especially in C₃H₆-SCR at temperatures below 300℃. The activity of CuSAPO-34 in NO SCR was affected by the preparation method as a result of changes in the specific area (A_BET), pore-size distribution, and the valence state of the active component. The active component of the catalyst prepared by HS was mainly Cu²⁺, whereas those of samples prepared by IE and PVI were mainly Cu⁺. Aging treatment can destroy the structure of the catalyst, decrease its surface area, and reduce the number of active Cu components on the catalyst surface, leading to a visible decrease in catalytic activity. The CuSAPO-34 prepared using the PVI method had the smallest decrease in NO SCR activity after aging, showing that it had better anti-aging properties.