通过掺杂不同金属元素对SO_4~(2-)/ZrO_2型固体超强酸进行改性,应用共沉淀法制备了一系列固体酸催化剂SO_4~(2-)/ZrO_2、SO_4~(2-)/ZrO_2-ZnO、SO_4~(2-)/ZrO_2-Fe_2O_3、SO_4~(2-)/ZrO_2-CuO、SO_4~(2-)/ZrO_2-Al_2O_3,利用氧气作氧化剂进行催化氧化脱除噻吩硫化物动力学实验.研究结果表明,掺杂了Zn、Fe和Cu的SO_4~(2-)/ZrO_22型催化剂催化氧化效果较SO_4~(2-)/ZrO_2都有明显提高,其中添加了金属Zn的SO_4~(2-)/ZrO_2-ZnO催化氧化效果最好,在反应温度为50℃,能达到100%的脱硫率.对合成的系列固体酸进行了X射线衍射(XRD)、氨程序升温脱附(NH3-TPD)的表征,结果表明,催化剂样品中四方相ZrO_2的含量越高,表面酸含量越大,其催化氧化噻吩硫化物的活性越高.
The solid super acid catalyst SO_4~(2-)/ZrO_2 was modified by doping with different metal oxides,and then a series of modified solid super acid catalysts such as, SO_4~(2-)/ZrO_2, SO_4~(2-)/ZrO_2-ZnO, SO_4~(2-)/ZrO_2-Fe_2O_3, SO_4~(2-)/ZrO_2-CuO and SO_4~(2-)/ZrO_2-Al_2O_3 were obtained by coprecipitation method. With oxygen as oxidant,the catalytic oxidation kinetic experiments of thiophene over the modified solid super acid catalysts were carried out. Results showed that doping Zn,Fe,Cu metal oxides to SO_4~(2-)/ZrO_2 can improve the catalytic oxidation activity of the catalysts, of which the catalytic activity of SO_4~(2-)/ZrO_2-ZnO was the highest and the conversion efficiency of thiophene can reach 100% at 50℃. The characterization results of the catalysts by powder X-ray diffraction (XRD)and temperature programmed desorption of ammonia (NH_3-TPD) showed that the more the content of T-ZrO_2 on the catalyst surfaces was,the more its acid amounts was,and thus it had higher catalytic activity.
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