杂原子掺杂beta分子筛的烯烃环氧化催化性能

doi:10.16085/j.issn.1000-6613.2021-2097

摘要/Abstract

摘要：

采用液-固相同晶取代法分别制备了W、Mo、V和Ti掺杂的四种杂原子beta分子筛，并以环己烯和环辛烯为探针底物分子，系统性评价了W-beta、Mo-beta、V-beta和Ti-beta催化烯烃环氧化反应性能。结果表明，所制备的四种杂原子beta分子筛均具有较高的结晶度，且完好继承了母体Al-beta分子筛的微孔结构与纳米颗粒形貌；由于离子半径和M—O键长的差异，W和Mo的骨架掺入量相对较低，V和Ti的掺入量相对较高；催化烯烃环氧化反应中，有限的活性金属含量导致W-beta和Mo-beta催化环烯烃的转化率低于V-beta和Ti-beta，但W-beta、Mo-beta、V-beta的反应转换频率（TOF）较高，说明W、Mo、V金属位点的活性更高；催化环己烯环氧化反应中，V-beta催化剂易引发烯丙基氧化副反应，环氧化物选择性低于其他三种催化剂，且V活性组分氧化物形态含量较高，反应过程中易脱落，导致V-beta催化剂循环再生性能较差；Ti掺杂beta催化剂表现出最佳的烯烃环氧化反应性能，提高Ti含量可有效提高反应转化率，但骨架Ti掺入量存在极值，过多的Ti物种趋向于氧化物形态，降低反应活性（TOF值），因此适宜的骨架Ti掺杂有利于Ti-beta分子筛催化烯烃环氧化反应。

关键词: 杂原子分子筛, beta分子筛, 同晶取代, 烯烃环氧化, 环氧化合物

Abstract:

Four types of heteroatom-substituted beta zeolites were prepared by a post-synthetic method. Nanosized Al-beta was used as the dealumination substrate, followed by the incorporation of 4—6 transition-metal atoms (W, Mo, V, and Ti) into the framework of dealuminated beta. The obtained heteroatom-substituted beta zeolites (W-beta, Mo-beta, V-beta, and Ti-beta ) well inherited the high crystallinity, large micropore volume and nanoparticle morphology from their parent Al-beta. However, the incorporation amounts of various heteroatoms were different due to the discrepancy in ion radiuses and M—O bond lengths, and V-beta, and Ti-beta showed much higher metal contents than W-beta and Mo-beta. The beta zeolites were further used as catalysts for the epoxidation of cyclohexene and cyclooctene. W-beta and Mo-beta revealed lower conversions of cyclic olefins but higher turnover frequency (TOF) values than V-beta and Ti-beta, indicating the higher activities of the W and Mo active sites. V-beta exhibited the highest conversion of cyclohexene due to its high content of V, but the epoxide selectivity over V-beta was much lower than that over the other heteroatom-substituted beta catalysts, which could be ascribed to the excess oxide species that promoted the side reaction of allylic oxidation. Besides, serious leaching of V species were observed for the V-beta catalyst that led to a poor recyclability in liquid-phase epoxidation reaction. Among all the heteroatom-substituted beta catalysts, Ti-beta exhibited the highest conversion and epoxide selectivity in the catalytic epoxidation of cyclic olefins. Moreover, the Ti active species in Ti-beta were quite stable, which further gave a superior recyclability of Ti-beta. In addition, the conversion of cyclic olefins over Ti-beta can be enhanced by increasing the content of Ti, but the excess Ti species tend to form the low-activity oxides and reduce the TOF value.

Key words: heteroatom-substituted zeolite, beta zeolite, isomorphous substitution, alkene epoxidations, epoxides

中图分类号:

O643.36

吴玉帅, 尤晴, 董旭杰, 朱子麒, 王旭, 陈汇勇, 马晓迅. 杂原子掺杂beta分子筛的烯烃环氧化催化性能[J]. 化工进展, 2022, 41(8): 4192-4203.

WU Yushuai, YOU Qing, DONG Xujie, ZHU Ziqi, WANG Xu, CHEN Huiyong, MA Xiaoxun. Synthesis of heteroatom-substituted beta zeolites for catalytic epoxidation of cyclic olefins[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4192-4203.

图/表 14

表1 各杂原子beta分子筛的金属含量及掺杂金属的离子半径、电负性和金属—氧键键长数据

分子筛	金属离子	金属含量 /μmol·g^-1	离子半径 /?	电负性	金属-氧键	键长 /?
Ti-beta	Ti⁴⁺	272	0.605	1.54	Ti—O	1.80
V-beta	V⁵⁺	157	0.59	1.63	V—O	1.755
Mo-beta	Mo⁶⁺	12	0.59	2.16	Mo—O	1.83
W-beta	W⁶⁺	27	0.61	2.36	W—O	1.90

图1 母体Al-beta、脱铝deAl-beta和杂原子W-beta、Mo-beta、V-beta和Ti-beta分子筛XRD图谱

图2 脱铝deAl-beta和杂原子W-beta、Mo-beta、V-beta和Ti-beta分子筛的FTIR图谱

图3 杂原子W-beta、Mo-beta、V-beta和Ti-beta分子筛的UV-vis图谱

图4 母体Al-beta、脱铝deAl-beta和杂原子W-beta、Mo-beta、V-beta和Ti-beta分子筛SEM图片

图5 W-beta、Mo-beta、V-beta、Ti-beta和Al-beta分子筛的N2吸附-脱附等温线

表2 母体Al-beta和杂原子W-beta、Mo-beta、V-beta和Ti-beta分子筛的织构性质数据

分子筛	微孔比表面积/m²·g^-1	外比表面积/m²·g^-1	总比表面积/m^2·g^-1	微孔孔容/cm³·g^-1	总孔容/cm³·g^-1
W-beta	481	67	548	0.18	0.40
Mo-beta	481	61	542	0.17	0.35
V-beta	493	69	561	0.19	0.40
Ti-beta	500	67	567	0.19	0.34

图6 W-beta、Mo-beta、V-beta和Ti-beta催化环己烯和环辛烯环氧化的转化率与环氧化产物选择性（反应条件：0.01mol反应底物、0.01mol氧化剂、10mL溶剂乙腈、0.05g催化剂、反应温度60℃、反应时间2h）

图7 V-beta和Ti-beta催化剂上环己烯和环辛烯转化率随反应时间的变化曲线（反应条件：0.01mol反应底物、0.01mol氧化剂、10mL溶剂乙腈、0.05g催化剂、反应温度60℃）

表3 杂原子beta分子筛催化环己烯和环辛烯环氧化反应性能

催化剂	环己烯					环辛烯
	转化率/%	选择性/%			转换频率（TOF）/h^-1	转化率/%	选择性/%	转换频率（TOF）/h^-1
	转化率/%	环氧环己烷	环己二醇	其他	转换频率（TOF）/h^-1	转化率/%	选择性/%	转换频率（TOF）/h^-1
W-beta	2.1	49.1	44.2	6.7	77.8	2.3	99.3	85
Mo-beta	1.0	46.9	48.6	4.5	83.3	0.9	99.3	75
V-beta	25.2	30.1	44.7	25.2	160.5	13.9	99.2	88.5
Ti-beta	20.8	50.4	43.5	6.6	76.4	16.6	99.2	61

图8 V-beta和Ti-beta催化环辛烯环氧化稳定性评价（反应条件：0.01mol反应底物、0.01mol氧化剂、10mL溶剂乙腈、0.05g催化剂、反应温度60℃）

图9 V-beta和Ti-beta催化环辛烯环氧化反应的循环再生性能评价（反应条件：0.01mol反应底物、0.01mol氧化剂、10mL溶剂乙腈、0.05g催化剂、反应温度60℃、反应时间2h）

表4 文献报道的Ti-beta分子筛催化烯烃环氧化反应性能

样品名称	环己烯		环辛烯		参考文献
样品名称	转化率/%	选择性/%	转化率/%	选择性/%	参考文献
Ti-beta	20.8	50.4	16.6	99.2	本工作
Ti-beta-0.015	10.9	49.5			［28］
Ti-beta-PS	9.2	69.1			［36］
Ti-beta-DT	16.2	68.6			［54］
Ti-beta	7.7	47.4			［55］
Ti-beta			4.6	＞99	［56］
M-Ti-beta			6.9	＞99	［16］

图10 钛含量对Ti-beta催化环辛烯环氧化反应的影响（反应条件：0.01mol反应底物、0.01mol氧化剂、10mL溶剂乙腈、0.05g催化剂、反应温度60℃、反应时间2h）

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