Study on the oxidative desulfurization performance of SiO2-supported divanadium-substituted phosphotungstate hybrid material
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摘要: 利用磷酸氢二钠、偏钒酸纳和钨酸钠为原料，合成了具有Keggin结构的磷钨钒杂多化合物（H5PW10V2O40），并与1-丁基-3-甲基咪唑溴（BmimBr）离子液体反应生成一种杂多酸杂化材料（[Bmim]5PW10V2O40）。利用红外光谱（FT-IR）、X射线衍射光谱（XRD）和紫外可见光谱（UV-vis）对所合成的杂多酸杂化材料进行表征。结果表明，[Bmim]5PW10V2O40具有咪唑阳离子基团和Keggin型杂多阴离子基团的结构特征，并且两种基团之间存在相互作用。以SiO2为载体制备负载型的杂多酸杂化材料催化剂[Bmim]5PW10V2O40/SiO2，以H2O2作为氧化剂，考察该催化剂对模拟油中DBT的氧化性能，并优化氧化反应条件，在反应温度40℃，O/S物质的量比为3.0的条件下，反应50 min，模拟油品中的DBT的转化率可以达到100%。催化剂可以通过离心法分离，经过干燥之后，可以循环使用至少七次，而对DBT的氧化活性没有降低。Abstract: The Keggin type H5PW10V2O40 was synthesized by Na2HPO4, NaVO3 and Na2WO4·12H2O. The divanadium-substituted phosphotungstate hybrid material [Bmim]5PW10V2O40 was synthesized by reacting H5PW10V2O40 and 1-butyl-3-methylimidazolium bromide ([Bmim]Br). The FT-IR, XRD and UV-vis characterization results show that the [Bmim]5PW10V2O40 hybrid materials possess Keggin structure and the interactions between the [Bmim]+ and the [PW10V2O40]5-. The SiO2-supported [Bmim]5PW10V2O40/SiO2 was prepared and used for oxidative desulfurization of dibenzothiophene (DBT) with the H2O2 as the oxidant. The experimental results show that the DBT conversion can reach 100% in the [Bmim]5PW10V2O40/SiO2-H2O2 oxidation system under the conditions of 40℃, oxigen/sulfur mol ratio 3.0 and 50 min reaction time. The catalyst was easily separated by centrifugation and could be reused for seven times without decreasing in oxidative desulfurization activity after drying treatment.
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Key words:
- divanadium-substituted phosphotungstate /
- H2O2 /
- DBT /
- oxidative desulfurization /
- hybrid material
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图 1 [Bmim]5PW10V2O40和[Bmim]3PW12O40的FT-IR谱图
Figure 1 FT-IR of [Bmim]5PW10V2O40 and [Bmim]3PW12O40
图 2 [Bmim]5PW10V2O40和[Bmim]3PW12O40的XRD谱图
Figure 2 XRD of [Bmim]5PW10V2O40 and [Bmim]3PW12O40
图 3 [Bmim]5PW10V2O40和[Bmim]3PW12O40样品的UV-vis谱图
Figure 3 UV-vis spectra of [Bmim]5PW10V2O40 and [Bmim]3PW12O40 sample
图 4 温度对DBT在[Bmim]5PW10V2O40/SiO2-H2O2体系中转化率的影响
Figure 4 Influence of reaction temperature on the catalytic performance of [Bmim]5PW10V2O40/SiO2 on the ODS of DBT with a O/S molar ratio of 3.0
图 5 O/S物质的量比对DBT在[Bmim]5PW10V2O40/SiO2-H2O2体系中转化率的影响
Figure 5 Influence of different O/S molar ratio on the ODS performance of DBT over [Bmim]5PW10V2O40/SiO2 at 40 ℃
图 6 催化剂的循环使用性能
Figure 6 Catalytic performances of fresh and reused [Bmim]5PW10V2O40/SiO2
表 1 H3PW12O40和H5PW10V2O40的元素分析
Table 1 Elemental analysis of H3PW12O40 and H5PW10V2O40
Sample Actual content of atom w/% Atomic ratio W P V W/P V/P H3PW12O40 76.82 1.09 - 11.97 - H5PW10V2O40 69.85 1.15 3.98 10.28 2.10 
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表 2 不同催化剂的比表面积及其氧化DBT的活性
Table 2 Specific surface area and catalytic activity in DBT oxidation on different catalysts
Catalyst Specific surface area A/(m2·g-1) DBT conversion x/% SiO2 263.5 0.0 [Bmim]3PW12O40 17.3 13.5 [Bmim]5PW10V2O40 16.8 21.4 10% [Bmim]5PW10V2O40/SiO2 220.1 43.8 20% [Bmim]5PW10V2O40/SiO2 196.4 100.0 30% [Bmim]5PW10V2O40/SiO2 168.7 78.4 40% [Bmim]5PW10V2O40/SiO2 139.2 64.9 20% [Bmim]3PW12O40/SiO2 194.9 62.8
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