空心钛硅分子筛催化材料:从理性设计到工业应用  

HOLLOW TITANIUM SILICATE MOLECULAR SIEVE CATALYTIC MATERIAL:FROM RATIONAL DESIGN TO COMMERCIAL APPLICATIONS

作　　者：夏长久 杨焯 林民 朱斌 彭欣欣 汪燮卿 舒兴田 Xia Changjiu;Yang Chao;Lin Min;Zhu Bin;Peng Xinxin;Wang Xieqing;Shu Xingtian(State Key Laboratary of Molecular Transformation and Reaction Engineering,SINOPEC Research Institute of Petroleum Processing,Beijing 100083)

机构地区：[1]石油化工分子转化与反应工程全国重点实验室,中石化石油化工科学研究院有限公司,北京100083

出　　处：《石油炼制与化工》2024年第1期18-27,共10页Petroleum Processing and Petrochemicals

基　　金：国家自然科学基金资助项目(21808244,22278441)。

摘　　要：针对传统钛硅分子筛存在选择性差、活性低和合成重现性差等问题,从“钛状态”和“晶内孔结构”入手,中国石油化工集团有限公司开发了具有自主知识产权的系列空心钛硅分子筛(HTS)催化材料,支撑国内首套环己酮氨肟化和丙烯环氧化技术实现了工业化。由于模板剂四丙基铵阳离子(TPA+)无法进入分子筛晶内,推测分子筛晶内缺陷溶解和溶解的硅钛物种沿着分子筛外表面再结晶是产生晶内空心和形貌变化的根本原因。综述了近年来HTS在结构设计、催化性能强化和催化氧化应用方面的研究进展,重点归纳总结了HTS在工业中的应用情况。In response to the problems of traditional titanium silicate(TS-1)molecular sieve,such as poor selectivity,low activity and poor synthesis reproducibility,SINOPEC Corporation began to organize technical research starting with the“titanium state”and the“intracrystalline pore structure”in the 1990s,a series of hollow titanium silicate molecular sieves with independent intellectual property rights were developed,which supported the first industrialization of cyclohexanone ammoximation and propylene epoxidation technology in China.Furthermore,due to the intracrystalline reaction of propylene epoxidation and the fact that surface titanium is easy to decompose H 2O 2,the framework titanium is mainly distributed in the crystal of molecular sieve to reduce the ineffective decomposition of H 2O 2.It is found that the type and number of defects have an important effect on the size and distribution of the voids,that is,the regular bulk and irregular banded voids are produced by the skeleton point defects and the grain boundary defects,respectively.Because the template cationic TPA+can not enter the crystal of molecular sieve,it is inferred that the defect-dissolved and dissolved silicon-titanium species recrystallization along the external surface of molecular sieve is the basic reason of the hollow and morphology change.The research progress of HTS in structural design,catalytic performance enhancement,and catalytic oxidation applications in recent yearsis aree reviewed,with a focus on summarizing the industrial applications of HTS.

关 键 词：钛硅分子筛 晶内封闭介孔 催化氧化 环己酮氨肟化 丙烯环氧化 

分 类 号：TQ426[化学工程]