动态法晶化合成钛硅分子筛及其脱硫性能研究

唐明宇; 王海彦; 任铁强; 魏民; 孙娜; 先宏飞

doi:10.19906/j.cnki.JFCT.2021054

动态法晶化合成钛硅分子筛及其脱硫性能研究

doi: 10.19906/j.cnki.JFCT.2021054

1.
辽宁石油化工大学石油化工学院，辽宁抚顺 113001
2.
辽宁美亚制药有限公司，辽宁抚顺 113001

基金项目: 国家自然科学基金（2017LQN006）和辽宁省教育厅科研项目（L2019014）资助

详细信息

作者简介:
唐明宇：yytmy091928@163.com

通讯作者:
E-mail：fswhy@126.com

中图分类号: TQ426.6
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- 被引次数: 0
出版历程
- 收稿日期: 2021-03-04
- 修回日期: 2021-05-07
- 网络出版日期: 2021-06-04
- 刊出日期: 2021-11-30

Preparation of TS-1 by dynamic method and study on the performance of thiophene sulfur removal

1.
College of Chemistry, Chemical Engineering, and Environmental Engineering, Liaoning Shihua University, Fushun 113001, China
2.
Liaoning Medya Pharmaceuticals Company Limited, Fushun 113001, China

Funds: The project was supported by the National Natural Science Foundation of China (2017LQN006) and the Education Department of Liaoning Province (L2019014)

摘要

摘要: 本研究以四丙基氢氧化铵（TPAOH）为模板剂，正硅酸乙酯（TEOS）为硅源，钛酸四丁酯（TBOT）为钛源，在动态晶化釜内合成形貌规则且粒径约为600 nm的TS-1分子筛。通过改变TBOT的用量，进而改变初始合成液中的硅钛比，考察硅钛比对TS-1分子筛的影响，并采用SEM、TEM、XRD、FT-IR、UV-vis、XPS、N₂吸附-脱附技术对制得的催化剂进行表征。将合成得到的TS-1分子筛应用于以噻吩正辛烷为模拟油的体系中，考察TS-1分子筛催化氧化脱硫性能。
- 钛硅分子筛 /
- 动态釜 /
- 硅钛比 /
- 催化氧化脱硫
Abstract: Using TPAOH as the template, TEOS as the silicon source and TBOT as the titanium source, the as-prepared samples utilizing a dynamic crystallizating kettle possessed regular morphology and the average particle size of 600 nm. By modulating the dosage of TBOT, and then changing the molar ratio of titanium to silicon in the initial synthesis solution, the effect of silicon to titanium ratio on TS-1 molecular sieve was investigated. TS-1 zeolite properties were characterized by means of SEM, TEM, XRD, FT-IR, UV-vis, XPS, N₂ adsorption and desorption technology. Finally, using a simulated system of thiophene n-octane dissolved in octane, the catalytic oxidative desulfurization performance of TS-1 zeolite was investigated.
- titanium silicon zeolite /
- dynamic crystallizating kettle /
- the ratio of titanium to silicon /
- catalytic oxidative desulfurization

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FIG. 1066. FIG. 1066.

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图 1 不同方式制备TS-1分子筛的XRD、紫外可见光谱谱图

Figure 1 XRD patterns, UV-vis spectra of TS-1 samples prepared in different ways

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图 2 不同硅钛比TS-1样品的XRD谱图

Figure 2 XRD patterns of TS-1 samples with different ratios of silicon to titanium

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图 3 不同硅钛比TS-1样品的SEM照片

(a): TS-1(20); (b): TS-1(30); (c): TS-1(40)

Figure 3 SEM images of TS-1 samples with different ratios of silicon to titanium

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图 4 TS-1(30)样品的TEM照片

Figure 4 TEM images of TS-1(30) sample

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图 5 不同硅钛比TS-1的傅里叶变换红外光谱谱图

Figure 5 FT-IR spectra of TS-1 samples with different ratios of silicon to titanium

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图 6 不同硅钛比TS-1样品的紫外可见光谱谱图

Figure 6 UV-vis spectra of TS-1 samples with different ratios of silicon to titanium

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图 7 不同硅钛比TS-1样品的氮气吸附-脱附等温线

Figure 7 Relative pressure N₂ adsorption-desorption isotherms of TS-1 samples with different ratios of silicon to titanium

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图 8 不同硅钛比TS-1样品的 DFT孔径分布

Figure 8 DFT pore size distributions of TS-1 samples with different ratios of silicon to titanium

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图 9 不同硅钛比TS-1样品的 XPS谱图

Figure 9 XPS spectra of TS-1 samples with different ratios of silicon to titanium

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图 10 不同硅钛比TS-1样品在H₂O₂中催化氧化噻吩

Figure 10 Catalytic oxidation of thiophene (Th) with H₂O₂ over TS-1 samples with different ratios of silicon to titanium

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表 1 合成TS-1分子筛初始合成液组成

Table 1 Initial gel composition of TS-1 synthesis

Sample	Initial gel composition
TS-1(20)	1.0SiO₂∶0.050TiO₂∶0.3TPAOH∶50H₂O
TS-1(30)	1.0SiO₂∶0.033TiO₂∶0.3TPAOH∶50H₂O
TS-1(40)	1.0SiO₂∶0.025TiO₂∶0.3TPAOH∶50H₂O

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表 2 不同硅钛比TS-1体相的元素原子百分比

Table 2 Elements atomic percentage of overall TS-1 samples with different ratios of silicon to titanium

Sample	Element atomic percentage/%
TS-1(20)	62.52	36.78	0.69
TS-1(30)	60.01	39.26	0.73
TS-1(40)	60.58	38.95	0.47

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表 3 不同硅钛比TS-1的孔结构性质

Table 3 Pore structure properties of TS-1 samples with different ratios of silicon to titanium

Sample	S_t/ （m²·g⁻¹）	S_m/ （m²·g⁻¹）	d_p/ nm	v_m/ （cm³·g⁻¹）	v_t/ （cm³·g⁻¹）
TS-1(20)	512.4	483.6	2.154	0.21	0.28
TS-1(30)	513.9	483.4	2.275	0.21	0.29
TS-1(40)	464.0	418.6	2.168	0.18	0.25

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表 4 不同物质光电能谱峰处结合能

Table 4 Binding energy of different samples

Sample	Ti 2p_3/2 E/eV
Sample	α	β
TS-1	460.0 ± 0.2	457.9 ± 0.2
TiO₂ + SiO₂	−	458.0
TiO₂	−	458.8
α represents the binding energy at the spectral peak of framework titanium; β represents the binding energy at the spectral peak of non-framework titanium (TiO₂)

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表 5 不同硅钛比TS-1表相的元素原子百分比

Table 5 Elements atomic percentage of surface TS-1 samples with different ratios of silicon to titanium

Sample	Element atomic percentage/%
TS-1(20)	60.17	29.91	0.68
TS-1(30)	59.42	29.90	0.68
TS-1(40)	59.51	30.46	0.29

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