降冰片二烯光异构化钛催化剂的研究-化学工艺专业论文.docxVIP

摘 摘 要 制备了Zn掺杂Ti02、La掺杂ZnO／Ti02、Ti-MCM一41和MCM—Ti02催化剂， 利用XRD、BET、TEM、XPS、DR Uv-vis、FT-IR、N2吸附．脱附等技术对催化 剂进行了表征，在光反应器中进行了降冰片二烯异构化生成四环烷的反应，研究 了制备方法对催化剂的结构和性能的影响规律。 采用化学沉淀法制备YZn掺杂的Ti02。结果表明，Zn的掺杂使Ti02发生不同 程度的晶格畸变，催化剂的粒径减小，比表面积和表面羟基含量增大，催化剂的 活性也随之提高。与低温煅烧相比，高温煅烧使催化剂的粒径增大，比表面积和 表面羟基含量下降，对催化剂活性不利。Zn的最佳掺杂量为l％，反应12小时， 降冰片二烯的转化率为88％，四环烷的选择性为100％。 采用共沉淀法制备了ZnO／Ti02复合物和La掺杂的ZnO／Ti02。发现ZnO／Ti02形 成了锐钛矿和ZnTi03的混晶结构。La掺杂ZnO／Ti02催化剂仍保持了混晶结构，并 且紫外吸收峰的强度和表面羟基含量均增大。10％La掺杂的ZnO／Ti02催化活性最 佳，反应12个小时降冰片二烯的转化率可达93．58％，四环烷的选择性为100％。 采用水热法和液相移植法制备了Ti骨架取代的Ti．MCM．41和孑L道氧化钛修 饰的MCM．Ti02，对催化剂的结构特征和钛的存在形式进行了研究。结果表明骨 架钛的形成是Ti．MCM一41介孔分子筛催化活性提高的决定性因素，长程有序性、 比表面积等因素对介孔分子筛的催化活性影响不大。当硅钛比为30时，反应12 小时降冰片二烯的转化率为92％，四环烷的选择性为100％。虽然MCM．Ti02的 钛含量最大(8m01％)，但由于没有形成骨架钛，因此催化活性不如Ti-MCM．41 高。 关键词： 降冰片二烯，光异构化，四环烷，Ti02，半导体复合，MCM．41分子 筛 ABSTRACTA ABSTRACT A series of Zn doped Ti02 catalysts，La doped ZnO用02 composite catalysts and Ti substituted Ti—MCM-4 1 were prepared and characterized by XRD，BET,TEM， XPS，diffuse reflectance Uv．Vis spectra，FT-IR N2 absorption·desorption．The photoisomerization reaction of norbornadiene tO form quadricyclane was carried out in a photoreactor in order to study the effects of the structure of the catalysts on their catalytic activity． Zn doped Ti02 catalysts were prepared by chemical precipitation method．The results show也at the Zn dopant caused the distortion of Ti02 lattice and血e decrease in the particle size，and increase in the specific surface and hydroxyl content on the surface of the catalysts，resulting in the improvement of the Ti02 acivity．Relatively high calcination temperature was harmful to the activity of catalysts because of the large particle size，low specific surface and hydroxyl content on the surface of catalysts compared with that at low calcination temperature．The optimal amount of the Zn dopant was 1％(wt)．The conversion of norbornadiene and selectivity tO quadricyclane over the 1％Zn-Ti02 catalyst can reach 88％and 1 00％，respectivel3’， after the reaction of 12 hours． The