正硅酸四乙酯（TEOS）水解行为对TS-1分子筛钛物种分布的影响

耿安英; 丁国强; 佘豪豪; 王洪星; 李显清; 朱玉雷

doi:10.1016/S1872-5813(22)60022-7

正硅酸四乙酯（TEOS）水解行为对TS-1分子筛钛物种分布的影响

doi: 10.1016/S1872-5813(22)60022-7

耿安英^{1, 2,},
丁国强³,
佘豪豪^{1, 2},
王洪星^{1, 2},
李显清³,
朱玉雷^{1, 3, ,}

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049
3.
中科合成油技术股份有限公司, 北京 101407

详细信息

通讯作者:
Tel: +86-010-69667798, E-mail: zhuyulei@sxicc.ac.cn

中图分类号: O643
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出版历程
- 收稿日期: 2022-03-29
- 修回日期: 2022-04-15
- 录用日期: 2022-04-16
- 网络出版日期: 2022-04-29
- 刊出日期: 2022-11-30

Effect of hydrolysis of tetraethyl orthosilicate (TEOS) on titanium distribution of TS-1 zeolite

GENG An-ying^{1, 2
,},
DING Guo-qiang³,
SHE Hao-hao^{1, 2},
WANG Hong-xing^{1, 2},
LI Xian-qing³,
ZHU Yu-lei^{1, 3
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
Synfuels China Co. Ltd, Beijing 101407, China

More Information

Corresponding author: Tel: +86-010-69667798, E-mail: zhuyulei@sxicc.ac.cn

摘要

摘要: 采用FT-IR技术跟踪正硅酸四乙酯 (TEOS) 水解过程并结合XRF、UV-vis等表征探讨了水解时间对TS-1分子筛中钛物种分布的影响。以1-己烯环氧化为模型反应对TS-1分子筛的催化氧化性能进行了评价。结果表明，TEOS适度水解能有效抑制非骨架钛形成，提高骨架钛含量，而水解时间较短或过长均不利于钛进入骨架，并会明显降低TS-1分子筛的催化性能。TEOS水解2 h 后制得的TS-1分子筛具有最佳的1-己烯环氧化催化性能，在常压60 ℃反应条件下1-己烯转化率可达到37.5%，产物1,2-环氧己烷选择性可维持在85%左右，这一结果对费托烯烃环氧化催化剂的开发具有指导作用。
- TS-1分子筛 /
- 正硅酸四乙酯 /
- 水解 /
- 1-己烯环氧化
Abstract: The hydrolysis process of tetraethyl orthosilicate (TEOS) was tracked by FT-IR analysis, and the effect of hydrolysis time on the distribution of titanium species in TS-1 zeolites was discussed through XRF and UV-Vis. The catalytic oxidation performance of TS-1 zeolite was tested by 1-hexene epoxidation as a model reaction. The results show that moderate hydrolysis of tetraethyl orthosilicate can effectively inhibit the formation of extra-framework Ti and increase the content of framework Ti. However, shorter or longer hydrolysis time is not conducive to the entry of titanium into the skeleton, and reduce the catalytic performance of TS-1 zeolites. TS-1 prepared with 2 h TEOS hydrolysis time has the best catalytic performance for epoxidation of 1-hexene. Under the reaction conditions of atmospheric pressure and 60 ℃, the conversion of 1-hexene can reach 37.5% and the selectivity of 1,2-epoxy hexane can maintain at about 85%, and the result has a guiding role for the development of olefin epoxidation catalyst.
- TS-1 zeolites /
- tetraethyl orthosilicate /
- hydrolysis /
- 1-hexene epoxidation

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FIG. 1988. FIG. 1988.

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图 1 TEOS水解不同时间后溶胶的FT-IR谱图

Figure 1 FT-IR spectra of sols with different hydrolysis time of TEOS

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图 2 TEOS水解过程中880 (a)、1640 (a) 和1225 cm⁻¹ (b) 处峰面积的变化

Figure 2 Change of the integrated areas for 880 (a), 1640 (a) and 1225 cm⁻¹ (b) during hydrolysis of TEOS

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图 3 不同TS-1分子筛样品的XRD谱图 (a) 和相对结晶度 (b)

Figure 3 XRD patterns (a) and relative crystallinity (b) of different TS-1 samples

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图 4 不同TS-1分子筛样品的SEM照片

Figure 4 SEM images of different TS-1 samples

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图 5 不同TS-1分子筛样品的UV-vis谱图及其在210和330 nm处的分峰谱图

Figure 5 UV-vis spectra and the corresponding deconvolution band at 210 and 330 nm of different TS-1 samples

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图 6 不同TS-1分子筛样品的FT-IR谱图和I₉₆₀/I₈₀₀曲线

Figure 6 FT-IR spectra (a) and the curves of I_960/I₈₀₀ (b) of different TS-1 samples

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图 7 1-己烯环氧化反应

Figure 7 Epoxidation of 1-hexene

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图 8 不同TS-1分子筛样品的反应性能

Figure 8 Reaction results of different TS-1 samples

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图 9 TEOS水解时间调节TS-1分子筛晶化过程

Figure 9 Discussion on TEOS hydrolysis time regulating the crystallization process of TS-1 zeolites (a): TS-1-0.5, TS-1-1; (b): TS-1-2, TS-1-3; (c): TS-1-4, TS-1-5

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表 1 不同TS-1分子筛样品的Si/Ti值和固收率

Table 1 Si/Ti values and solid yield of different TS-1 samples

Sample	Solid yield^a/%	Si/Ti^b	Ti/(Si+Ti)^c/%	Average particle size^d/nm
TS-1-0	0	−	−	−
TS-1-0.5	40.1	45.3	0.049	352
TS-1-1	89.9	43.6	0.053	358
TS-1-2	90.5	48.5	0.043	366
TS-1-3	91.9	55.7	0.032	275
TS-1-4	91.8	58.0	0.030	224
TS-1-5	91.5	64.4	0.024	187
^a: ${\rm{Solid}}\;{\rm{yield}} =\dfrac{{m}_{2}\times {M}_{1}}{{m}_{1}\times {M}_{2}}\times 100\%\; $, m₁ is the amount of TEOS added during feeding; M₁ is the relative molecular weight of TEOS, and its value is 208.33 g/mol; M₂ is the relative molecular weight of SiO₂, and its value is 60.08 g/mol; M₂ is the mass of SiO₂ actually obtained; ^{b, c}: Si/Ti and Ti/(Si+Ti) in solid is determined by XRF; ^d: Average particle size is obtained by SEM image

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表 2 不同TS-1分子筛样品的UV-vis分峰

Table 2 Diffuse reflectance UV-visible result of different TS-1 samples

Sample	Deconvoluted bands and assignments: λ_max, nm (relative intensity/%)
Sample	Ti(OSi)₄ (~210 nm)	anatase TiO₂ (~330 nm)
TS-1-0.5	91.9	8.1
TS-1-1	93.5	6.5
TS-1-2	100.0	0
TS-1-3	100.0	0
TS-1-4	96.9	3.1
TS-1-5	97.3	2.7

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