环己酮氨肟化工艺中不可逆失活HTS分子筛的再生  

Regeneration of Irreversible Deactivated Hollow Titanium Silicalite Zeolite From Commercial Cyclohexanone Ammoximation Process

作　　者：夏长久[1] 林民[1] 朱斌[1] 彭欣欣[1] 徐广通[1] 舒兴田[1] 

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,北京100083

出　　处：《石油学报（石油加工）》2018年第2期246-252,共7页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点基础研究发展计划"973"项目(2006CB202500.7-22);中国石化项目(411058;413108)资助

摘　　要：开发了一种简便且高效的商业环己酮氨肟化工艺不可逆失活HTS分子筛的再生方法。将赶醇处理后的硅钛物种与失活HTS分子筛混合物进行二次水热晶化处理,将促进双氧水分解的无定形TiO_2-SiO_2颗粒包埋到分子筛晶体中。TEM、XPS和Py-IR分析表明,二次晶化处理可使失活HTS分子筛溶解和再结晶生长,从而造成无定形TiO_2-SiO_2颗粒被包埋到了分子筛晶内。苯酚羟基化和双氧水分解实验结果表明,将酸性富钛粒子包埋可以阻断其与双氧水分子的直接接触,减弱双氧水无效分解,因此再生HTS具有与新鲜HTS接近的催化性能。同时,本研究为"量体裁衣"式设计分子筛催化材料提供了一条新的视角。A novel and efficient regeneration method of irreversible deactivated HTS zeolite from commercial cyclohexanone ammoximation process has been developed.It is based on the post synthesis treatment of deactivated HTS zeolite with soluble Ti-Si sources under hydrothermal conditions,which cause the encapsulation of amorphous TiO_2-SiO_2 nanoparticles.According to the results of TEM, XPS and Py-IR,it is confirmed that the encapsulation of acidic Ti-rich nanoparticles has occurred during the "dissolution and recrystallization"processing of deactivated HTS with additional Ti-Si sources.Furthermore,it suggests that the encapsulation of Ti-rich nanoparticles reduces the accessibility of H_2O_2 molecules to side reaction active sites.That is why regenerated HTS shows the same catalytic performance as fresh HTS in phenol hydroxylation reaction.Moreover,this research provides a new viewpoint for tailoring catalytic materials.

关 键 词：环己酮氨肟化 HTS分子筛 二次晶化处理 包埋 双氧水分解 

分 类 号：TQ426[化学工程]