有机碱改性小晶粒TS-1分子筛的研究  

Study on small crystal TS-1 molecular sieve modified with organic bases

作　　者：范新川 FAN Xinchuan(China Pingmei Shenma Holding Group Co.,Ltd.,Pingdingshan 467000)

机构地区：[1]中国平煤神马控股集团有限公司,河南平顶山467000

出　　处：《合成纤维工业》2022年第5期46-51,共6页China Synthetic Fiber Industry

摘　　要：选择TS-1分子筛微球颗粒作为原粉,选用不同种类的有机碱对其进行改性,采用X射线衍射、红外光谱等方法分析其结晶度、骨架结构及钛含量、孔结构及孔径分布,并以环己酮氨肟化制环己酮肟反应为探针,对改性后的TS-1分子筛的催化性能进行评价。结果表明:醇胺类碱和氢氧化季铵碱改性TS-1分子筛的结晶度高于烷基胺改性试样,二乙醇胺改性试样的结晶度最高,乙二胺改性试样的结晶度仅为原粉的50%;有机碱改性后,TS-1分子筛中骨架钛含量均有所下降,烷基胺改性试样的骨架钛含量稍高于醇胺类碱和氢氧化季铵碱改性试样;乙醇胺和乙二胺改性TS-1分子筛的总比表面积低于原粉,其余有机碱改性TS-1分子筛的总比表面积均高于原粉;在所选用的有机碱中,四丙基氢氧化铵(TPAOH)改性的TS-1分子筛催化活性较高,环己酮转化率达98.79%,产物环己酮肟选择性达99.51%,TPAOH改性TS-1分子筛适合用于环己酮氨肟化反应。TS-1 molecular sieve microspheres were selected as raw powder and modified with different kinds of organic bases.The crystallinity,framework structure,titanium content,pore structure and pore size distribution were analyzed by X-ray diffraction and infrared spectroscopy.The catalytic performance of modified TS-1 molecular sieve was evaluated by using cyclohexanone ammoximation to cyclohexanone oxime as a probe.The results showed that the crystallinity of TS-1 molecular sieve modified with alkanolamine base and quaternary ammonium hydroxide base was higher than that of the sample modified with alkyl amine;the crystallinity of the sample modified with diethanolamine was the highest,and the crystallinity of the sample modified with ethylenediamine was only 50%of the raw powder;the content of skeleton titanium in TS-1 molecular sieve decreased after organic bases modification,and the content of skeleton titanium in the samples modified with alkyl amine was slightly higher than that in the samples modified with alkanolamine base and quaternary ammonium hydroxide base;the total specific surface area of TS-1 molecular sieve modified with ethanolamine and ethylenediamine was lower than that of the raw powder,while the total specific surface area of TS-1 molecular sieve modified with other organic bases was higher than that of the raw powder;among the selected organic bases,TS-1 molecular sieve modified with tetrapropylammonium hydroxide(TPAOH)had higher catalytic activity and provided a cyclohexanone conversion of 98.79%and cyclohexanone oxime selectivity of 99.51%,and TS-1 molecular sieve modified with TPAOH was suitable for cyclohexanone ammoximation reaction.

关 键 词：催化剂 钛硅分子筛 有机碱 改性 结构 催化性能 

分 类 号：TQ314.242[化学工程—高聚物工业]