Ti-Beta分子筛的控制合成及高效催化环己烯环氧化

doi:10.7503/cjcu20180844

摘要/Abstract

摘要：

构建了以H₂O₂为氧化剂催化环己烯合成环氧环己烷的高效、绿色催化反应体系. 在不加入铝源的情况下, 以四乙基氢氧化铵(TEAOH)为模板剂, 通过改进的干胶转化法控制H₂O/SiO₂摩尔比为1.5合成出Ti-Beta分子筛. 实验结果表明, 适宜的酸碱性、含水量以及模板剂用量显著影响分子筛的结晶度, 同时影响晶粒尺寸和晶粒尺寸的均一性. 通过对Ti-Beta分子筛原粉进行焙烧处理制得Ti-Beta分子筛催化剂, 再通过对反应溶剂、反应温度和反应时间的筛选和优化, 获得最优催化反应条件, 在该条件下, 环己烯转化率可达33.5%, 环氧环己烷选择性可达99.6%. 实验结果表明该催化剂是一种高效的多相催化剂.

关键词: 过氧化氢, 干胶转化, Ti-Beta分子筛, 催化环氧化, 环己烯

Abstract:

The construction of a green catalytic reaction system with characteristic of high efficiency for the synthesis of epoxycyclohexane by catalytic epoxidation of cyclohexene with H₂O₂ was focused. We succeeded in synthesizing Ti-Beta zeolites in the absence of Al by the dry-gel conversion method using tetraethylammonium hydroxide(TEAOH) as the structure directing agent with n(H₂O)/n(Si) of about 1.5. We found that the crystallization, the uniformity of crystal and size of Ti-Beta were significantly affected by proper acidity and basicity, the amount of water and template dosage. Then, highly efficient Ti-Beta catalyst was prepared by calcination treatment of the raw powder. Under the optimal catalytic reaction conditions, the cyclohexene conversion of 33.5% and the epoxidation selectivity of 99.6% were achieved. The results indicate that Ti-Beta is an excellent heterogeneous catalyst.

Key words: H₂O₂, Dry-gel conversion, Ti-Beta zeolite, Catalytic epoxidation, Cyclohexene

中图分类号:

O643

TrendMD:

刘新超, 赵亚榕, 袁珍闫, 周丹, 鲁新环, 夏清华. Ti-Beta分子筛的控制合成及高效催化环己烯环氧化. 高等学校化学学报, 2019, 40(6): 1222.

LIU Xinchao,ZHAO Yarong,YUAN Zhenyan,ZHOU Dan,LU Xinhuan,XIA Qinghua. Controllable Synthesis of Ti-Beta Zeolite and Efficiently Catalytic Epoxidation of Cyclohexene^†. Chem. J. Chinese Universities, 2019, 40(6): 1222.

图/表 8

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No.	n(H₂O)/n(SiO₂)	n(NaOH)/n(SiO₂)	n(HF)/n(SiO₂)	n(TEAOH)/n(SiO₂)	Crystalline phase^a	Crystallinity^b(%)
1	1.0	0.01	0.3	0.45	—	—
2	1.2	0.01	0.3	0.45	BEA	98
3	1.5	0.01	0.3	0.45	BEA	100
4	2.0	0.01	0.3	0.45	—	—
5	3.0	0.01	0.3	0.45	—	—
6	1.5	0	0.3	0.45	BEA	63
7	1.5	0.05	0.3	0.45	BEA	97
8	1.5	0.015	0.3	0.45	BEA	75
9	1.5	0.01	0	0.45	—	—
10	1.5	0.01	0.15	0.45	—	—
11	1.5	0.01	0.4	0.45	BEA	99
12	1.5	0.01	0.3	0.15	—	—
13	1.5	0.01	0.3	0.25	BEA	89
14	1.5	0.01	0.3	0.35	BEA	99
16	1.5	0.01	0.3	0.5	BEA	92

No.	n(H₂O)/n(SiO₂)	n(NaOH)/n(SiO₂)	n(HF)/n(SiO₂)	n(TEAOH)/n(SiO₂)	Crystalline phase^a	Crystallinity^b(%)
1	1.0	0.01	0.3	0.45	—	—
2	1.2	0.01	0.3	0.45	BEA	98
3	1.5	0.01	0.3	0.45	BEA	100
4	2.0	0.01	0.3	0.45	—	—
5	3.0	0.01	0.3	0.45	—	—
6	1.5	0	0.3	0.45	BEA	63
7	1.5	0.05	0.3	0.45	BEA	97
8	1.5	0.015	0.3	0.45	BEA	75
9	1.5	0.01	0	0.45	—	—
10	1.5	0.01	0.15	0.45	—	—
11	1.5	0.01	0.4	0.45	BEA	99
12	1.5	0.01	0.3	0.15	—	—
13	1.5	0.01	0.3	0.25	BEA	89
14	1.5	0.01	0.3	0.35	BEA	99
16	1.5	0.01	0.3	0.5	BEA	92

Sample	n(SiO₂)∶n(TiO₂)∶n(TEAOH)∶n(NaOH)∶ n(HF)∶n(H₂O)	XPS result(molar ratio)			S_BET/(m²·g^-1)	Conv.(%)	Sel.(%)	Yield(%)
Sample	n(SiO₂)∶n(TiO₂)∶n(TEAOH)∶n(NaOH)∶ n(HF)∶n(H₂O)	Si/Ti	Si/Na	Si/Al	S_BET/(m²·g^-1)	Conv.(%)	Sel.(%)	Yield(%)
Ti-Beta-1	1.0∶0.03∶0.45∶0.01∶0.3∶1.5	23	57	∞	403	33.5	99.8	33.4
Ti-Beta-2	1.0∶0.03∶0.45∶0.01∶0.3∶1.2	9	52	∞	339	23.3	99.6	23.2
Ti-Beta-3	1.0∶0.03∶0.45∶0.005∶0.3∶1.5	17	59	∞	385	32.4	94.3	30.6
Ti-Beta-4	1.0∶0.03∶0.45∶0.01∶0.4∶1.5	34	90	∞	32	1.2	92.3	1.1
Ti-Beta-5	1.0∶0.03∶0.35∶0.01∶0.3∶1.5	7	31	∞	355	25.6	94.4	24.2
Ti-Beta-6	1.0∶0.03∶0.50∶0.01∶0.3∶1.5	36	85	∞	199	0.2	93.6	0.2

Sample	n(SiO₂)∶n(TiO₂)∶n(TEAOH)∶n(NaOH)∶ n(HF)∶n(H₂O)	XPS result(molar ratio)			S_BET/(m²·g^-1)	Conv.(%)	Sel.(%)	Yield(%)
Sample	n(SiO₂)∶n(TiO₂)∶n(TEAOH)∶n(NaOH)∶ n(HF)∶n(H₂O)	Si/Ti	Si/Na	Si/Al	S_BET/(m²·g^-1)	Conv.(%)	Sel.(%)	Yield(%)
Ti-Beta-1	1.0∶0.03∶0.45∶0.01∶0.3∶1.5	23	57	∞	403	33.5	99.8	33.4
Ti-Beta-2	1.0∶0.03∶0.45∶0.01∶0.3∶1.2	9	52	∞	339	23.3	99.6	23.2
Ti-Beta-3	1.0∶0.03∶0.45∶0.005∶0.3∶1.5	17	59	∞	385	32.4	94.3	30.6
Ti-Beta-4	1.0∶0.03∶0.45∶0.01∶0.4∶1.5	34	90	∞	32	1.2	92.3	1.1
Ti-Beta-5	1.0∶0.03∶0.35∶0.01∶0.3∶1.5	7	31	∞	355	25.6	94.4	24.2
Ti-Beta-6	1.0∶0.03∶0.50∶0.01∶0.3∶1.5	36	85	∞	199	0.2	93.6	0.2

Solvent	Conv.(%)	Sel.(%)	Yield(%)
Methanol	33.5	99.6	33.4
Acetone	16.2	92.2	14.9
Acetonitrile	12.3	96.2	11.8
Ethanol	18.4	90.2	16.6
1,4-Dioxane	1.2	54.6	0.7
1,2-Dichloroethane	2.2	52.3	1.2
Ethyl acetate	8.1	1.5	0.1