Department of Chemistry, Faculty of Science, University of Zanjan, Zanjan, Iran.
Environ Technol. 2020 Apr;41(10):1219-1231. doi: 10.1080/09593330.2018.1526217. Epub 2018 Sep 27.
To preparation of ultra-clean gasoline fuel, a new amphiphilic nanocomposite (TBA-SiWMn@PVA) has been successfully synthesized by supporting sandwich-type silicotungstate polyoxometalate ((n-CH)N)HSiWMnO (TBA-SiWMn) on polyvinylalcohol (PVA) as an efficient catalyst for catalytic oxidative desulphurization (CODS) of gasoline. The synthesized materials were characterized by means of elemental analysis, Mn NMR, Si NMR, XRD, SEM, FT-IR and UV-vis techniques. The catalytic activity of TBA-SiWMn@PVA nanocomposite was tested on real gasoline in the presence of CHCOOH/HO as an oxidant and the results were compared with model sulphur compounds at the same conditions. The TBA-SiWMn@PVA nanocomposite was shown excellent catalytic performance and recoverability for ODS of gasoline with high yield. The effects of the reaction time, reaction temperature, dosage and nature of catalyst were investigated. The reaction mechanism and the kinetic parameters of sulphur compounds oxidation were also discussed. The probable mechanism was proposed the electrophilic mechanism through the formation of a peroxometalate intermediate complex with phase transfer properties. Results were indicated that the kinetics of sulphur oxidation fitted the pseudo-first-order kinetic model. After 5 oxidation runs, the heterogeneous nanocatalyst was separated and recovered easily.
为了制备超清洁汽油燃料,我们成功地合成了一种新型两亲性纳米复合材料(TBA-SiWMn@PVA),通过将夹心型硅钨酸盐多酸((n-CH)N)HSiWMnO(TBA-SiWMn)负载在聚乙烯醇(PVA)上来作为高效催化剂,用于催化氧化脱硫(CODS)汽油。通过元素分析、Mn NMR、Si NMR、XRD、SEM、FT-IR 和 UV-vis 技术对合成材料进行了表征。在 CHCOOH/HO 作为氧化剂的存在下,在实际汽油上测试了 TBA-SiWMn@PVA 纳米复合材料的催化活性,并在相同条件下与模型硫化合物进行了比较。TBA-SiWMn@PVA 纳米复合材料表现出优异的催化性能和可回收性,对汽油的 ODS 具有高收率。考察了反应时间、反应温度、催化剂用量和性质的影响。还讨论了反应机理和硫化合物氧化的动力学参数。提出了通过形成具有相转移性质的过氧金属酸盐中间络合物的亲电机理。结果表明,硫氧化动力学符合准一级动力学模型。经过 5 次氧化运行后,易于分离和回收多相纳米催化剂。