选择性催化还原(SCR)是目前去除氮氧化物最有效的方法之一.V2O5/TiO2催化剂被广泛应用于氨法选择性还原氮氧化物(NH3-SCR)反应,但该催化剂存在工作温度高(300–400℃)及SO2氧化率高引起设备腐蚀和管路堵塞等问题,开发低温SCR催化剂具有重要意义.过渡金属氧化物(如Fe2O3,MnOx和CuO等)催化剂用于低温SCR先后见诸文献报道,但这些催化剂在SO2和H2O存在下易失活.近年来柱撑黏土(PILC)引起科学家广泛关注,Yang等首次将V2O5/TiO2-PILC催化剂应用于NH3-SCR反应,发现其催化活性高于传统V2O5/TiO2催化剂.柱撑黏土基催化剂在NH3-SCR反应中也显示出良好抗硫性能,但V2O5/TiO2-PILC催化剂的抗硫机理至今尚未见深入研究.因此我们制备了一系列V2O5/TiO2-PILC催化剂,采用原位漫反射红外等方法详细研究了其抗硫性能较好的原因.首先采用离子交换法制备出TiO2-PILC载体,之后采用浸渍法制备了不同钒含量(质量分数x/%=0,3,4,5)的xV2O5/TiO2-PILC催化剂.同时,制备了传统V2O5/TiO2和V2O5-MoO3/TiO2催化剂作为对比.活性评价结果显示,4V/TiO2-PILC催化剂具有最高的催化活性,其催化性能与传统钒钛催化剂相当.在160℃时,NO转化率可达80%以上.同时,4V/TiO2-PILC催化剂还具有较宽的反应温度窗口,在260–500℃范围内,NO转化率保持在90%以上.向反应体系中加入0.05%SO2和10%H2O后,在低温(160℃以下)时所有催化剂的反应活性都有一定提高,可能是由于SO2的加入提高了催化剂的表面酸性.继续升高温度,4V/TiO2和4V6Mo/TiO2催化剂活性均明显下降,而4V/TiO2-PILC催化剂的活性则未出现明显下降.原位漫反射红外光谱结果显示,SO2在三种催化剂表面的吸附以表面硫酸盐或亚硫酸盐物种以及离子态SO4~(2–)物种形式存在,而在4V/TiO2-PILC催化剂表面离子态SO4~(2–)物种的量最少.X射线光电子能谱及O2程序升温脱附结果显示,在4V/T
A titania pillared interlayered clay(Ti-PILC) supported vanadia catalyst(V2O5/TiO2-PILC) was prepared by wet impregnation for the selective catalytic reduction(SCR) of NO with ammonia. Compared to the traditional V2O5/TiO2 and V2O5-MoO3/TiO2 catalysts, the V2O5/TiO2-PILC catalyst exhibited a higher activity and better SO2 and H2O resistance in the NH3-SCR reaction. Characterization using TPD, in situ DRIFT and XPS showed that surface sulfate and/or sulfite species and ionic SO4~(2-)species were formed on the catalyst in the presence of SO2. The ionic SO4~(2-) species on the catalyst surface was one reason for deactivation of the catalyst in SCR. The formation of the ionic SO4~(2-) species was correlated with the amount of surface adsorbed oxygen species. Less adsorbed oxygen species gave less ionic SO4~(2-) species on the catalyst.