Effect of Ti-Si Mixed Oxide Support on Gold Catalysts for Gas-Phase Epoxidation of Propylene
- 化学化工－已发表论文 
以TiCl4和SiCl4为原料,采用水解和非水水解溶胶-凝胶两种方法制备了一系列不同Ti含量的Ti-Si复氧化物载体,继而用沉积-沉淀法制得载金催化剂.采用X射线衍射、紫外-可见漫反射光谱、N2吸附和高分辨透射电镜对催化剂进行了表征,并考察了催化剂在氢气和氧气存在下的丙烯气相环氧化催化性能.研究表明,钛含量在6%~14%范围内时,两种方法制得的Ti-Si复氧化物均为无定形结构,但采用非水水解溶胶-凝胶法制得的载体比表面积较高.以非水水解溶胶-凝胶法制备的钛含量10%的Ti-Si复氧化物为载体得到的载金催化剂表现出较高的活性和选择性,反应60min时,丙烯转化率为5.7%,240min后降为3.3%,环氧丙烷的选择性稳定于95%左右.还考察了非水水解溶胶-凝胶的陈化时间和金沉积-沉淀溶液的pH值等对反应结果的影响.Titania-silica mixed oxides prepared by hydrolytic and one-step non-hydrolytic sol-gel routes using TiCl_4 and SiCl_4 as precursors were employed as the gold catalyst supports for gas-phase epoxidation of propylene in O_2 and H_2. Characterization studies of the supports and catalysts were performed by means of X-ray diffraction, ultraviolet-visible absorption spectroscopy, N_2 adsorption, and high-resolution transmission electron microscopy. The results indicated that the amorphous Ti-Si mixed oxides containing 6%-14% of Ti could be prepared by both sol-gel routes, but those by non-hydrolytic sol-gel afforded higher surface area and significant mesopores. A superior catalytic performance was obtained with the gold catalyst supported on the non-hydrolytic sol-gel Ti-Si mixed oxide containing 10% of Ti. The propylene conversion was 5.7% at the initial 60 min and 3.3% at 240 min of time on stream. The selectivity for propylene oxide was as high as 95%. The influences of aging time for the non-hydrolytic sol-gel and pH value for the Au deposition-precipitation on the performance of the Au catalyst were also discussed.