空心钛硅分子筛催化苯甲醛氨肟化制苯甲醛肟反应  

Ammoximation of Benzaldehyde Catalyzed by Hollow Titanium Silicalite Zeolite

作　　者：杨永佳 夏长久[1] 林民[1] 朱斌[1] 刘聿嘉 彭欣欣 罗一斌 舒兴田[1] Yang Yongjia;Xia Changjiu;Lin Min;Zhu Bin;Liu Yujia;Peng Xinxin;Luo Yibin;Shu Xingtian(State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China)

机构地区：[1]中国石化石油化工科学研究院石油化工催化材料与反应工程国家重点实验室

出　　处：《化学反应工程与工艺》2018年第5期440-447,共8页Chemical Reaction Engineering and Technology

基　　金：国家自然科学基金项目（2006CB202500.7-22）

摘　　要：采用钛硅分子筛催化苯甲醛氨肟化合成路线绿色高效,但苯甲醛性质活泼极易发生缩合和氧化等副反应,苯甲醛肟选择性较差。本工作研究了苯甲醛氨肟化反应网络和不同钛物种的催化性能,具有良好扩散性能的空心钛硅分子筛HTS展示出更好的催化性能,且其中孤立骨架四配位钛是氨肟化主反应的催化活性中心。为提高苯甲醛肟选择性,系统考察了催化剂用量、氨水/苯甲醛物质的量比、双氧水/苯甲醛物质的量比、双氧水加料方式以及反应温度等参数对苯甲醛氨肟化反应性能的影响。在优化的反应条件下,苯甲醛转化率和苯甲醛肟选择性可分别达到99.9%和95.8%。同时,HTS分子筛具有较好的稳定性。Ammoximation of benzaldehyde (BA) catalyzed by titanosilicate provides an eco-friendly route for synthesizing benzaldehyde oxime (BAO). However, BA is so active that several side reactions would happen during ammoximation, such as self polymerization and oxidation with H2O2, resulting in low BAO selectivity. Thus, the reaction network and the catalytic performance under different Ti species were evaluated for the ammoximation of BA. It is identified that the four-coordinated framework Ti species are the active centers in the ammoximation reaction. Hollow titanium silicalite (HTS) showed more excellent catalytic performance than TS-1, owing to better properties of diffusion. The effects of various parameters, such as catalyst amount, NH3/BA and H2O2/BA molar ratios, the way of feeding H2O2 and reaction temperature, on the catalytic performance of HTS were investigated in detail. Under the optimized reaction conditions, BA conversion and BAO selectivity are 99.9% and 95.8% respectively. Moreover, the repeated experiment results showed the good catalytic stability of HTS.

关 键 词：空心钛硅分子筛 氨肟化 苯甲醛 苯甲醛肟 

分 类 号：O643[理学—物理化学]