摘 要 　　　为了减少含硫化合物对环境的污染，世界各国纷纷制定法规限制燃油中的硫含量，要求生产和使用更加环境友好的超低硫汽油和柴油。氧化脱硫由于反应条件温和，不使用昂贵的氢源，尤其是油品中含硫化合物空间位阻越大氧化活性越高等特点，被认为应用前景较好的一种脱硫技术。近年来，乳液因其能降低油水两相的表面张力被用于油品的超深度脱硫研究中。Pickering乳液是以具有亲水性(疏水性)的固体粒子替代传统表面活性剂制得的热力学和动力学均稳定的分散体系。本文以固体粒子替代表面活性剂制备了Pickering乳液，考察了影响Pickering乳液形成和稳定性的重要因素，并研究了Pickering乳液作为相界面催化的应用性能。 　　　以MoO3/滑石粉和H3PW12O40/滑石粉复合粒子稳定的正辛烷/水乳液为介质，进行了Pickering乳液体系中苯并噻吩的氧化-萃取脱硫研究。以过氧化氢为氧化剂，在温和条件下，利用具有一定疏水性能的固体粒子负载活性组分制备催化剂，将催化剂分散于油水相界面，将含苯并噻吩的模拟油在乳液(油/水)氧化体系中氧化并用DMF等体积萃取。该乳液体系由催化剂，苯并噻吩油品以及过氧化氢水溶液组成(O/W)。发现该催化剂在水包油体系中对于苯并噻吩硫化物的氧化具有较高的催化氧化活性，能以化学计量比的过氧化氢(O/S=6)为氧化剂，将含硫化合物氧化成相应的砜或亚砜。实验结果表明，通过DMF等体积萃取生成的砜可以从正辛烷中分离。经过氧化和三次萃取过程，苯并噻吩的硫含量从255 µg/mL降至1 µg/mL。 　　　以MoO3/滑石粉和H3PW12O40/滑石粉复合粒子稳定的正辛烷/DMF乳液为介质，进行了Pickering乳液体系中苯并噻吩的氧化脱硫研究。以过氧化氢为氧化剂，在温和条件下直接氧化。此Pickering乳液氧化体系操作简单，无附加设备投资。实验结果发现该催化剂在O/S=3，反应温度为50 ℃，480 rpm条件下反应90 min表现出较高的催化氧化活性，脱硫率高达89%，苯并噻吩硫含量从255 µg/mL降至28 µg/mL。

ABSTRACT 　　　In order to reduce pollution of sulfur compounds for the environment, various countries have introduced regulations to limit the sulfur content, which requests to produce and use the environmentally friendly ultra-low sulfur oil. Oxidation desulfurization, as a new desulfurization technology, because of mild reaction condition and no expensive hydrogen involving, has moved widely in favour of the researchers. Especially for the oil with high steric hindrance, it displays higher oxidative activity. 　　　Pickering emulsion is a stable disperse system in the aspect of thermodynamics and dynamics, which can replace the traditional chemical emulsifier. Because of its low cost, non-toxic and environmental protection, it has application value on food, catalysis and cosmetics. This paper, based on solid particles as emulsifier to prepare Pickering emulsion, has investigated the infection factors of the formation and stabilization in Pickering emulsion system and the performance on catalysis in phase boundary. 　　　We have used direct precipitation to preparate ZnO particles and made MoO3/ZnO, H3PW12O40/ZnO, MoO3/talc and H3PW12O40/talc composite particles with impregnation method. SEM test showed that the needle structure of ZnO particles is not obvious and its average particle size was 5 µm; MoO3 with sheets dispersed evenly on ZnO surface and average particle size was 30 µm; H3PW12O40 with needles dispersed evenly on ZnO surface and average particle size was 15 µm; Talcum powder had obvious flake structure. FTIR test indicated that, talcum powder particles, MoO3/talc and H3PW12O40/talc composite particle surface had a lot of hydroxyl. MoO3 exited mainly by eight coordination form and equably dispersed in talcum powder surface. H3PW12O40 still kept Keggin uniform structure and distribution equably on talcum powder surface. XRD proved the infrared spectrum analysis. The MoO3/ZnO, H3PW12O40/ZnO, MoO3/talc and H3PW12O40/talc composite particles, as emulsifier, was made the O/W type of Pickering emulsion respectively. And we also study the factors of varieties of particles and oil and water volume ratio on Pickering emulsion. 　　　We do research the process of oxidation-extraction desulfurization in Pickering emulsion system with MoO3/talc and H3PW12O40/talc as emulsifier, using n-octane and water as two phases. The benzothiophene was oxidised and extracted by equal volum of DMF with hydrogen peroxide as the oxidant in mild conditions. In this system, it contained catalysts, water phase and oil phase. According to the experiments, the catalysts showed high catalytic oxidative activity. When the O/S molar ratio reached at 6, it can prove to be sulphone. The results demonstrate that the sulphone can be separated by DMF and the content of sulfur can be reduced from 255µg/mL to 1µg/mL. 　　　We also do research the process of oxidation-extraction desulfurization in Pickering emulsion system with MoO3/talc and H3PW12O40/talc as emulsifier, using n-octane and DMF as two phases. It can be oxidized directly with hydrogen peroxide as the oxidant in mild conditions. The study found that it expressed high catalytic oxidative activity in condition of T=50℃ and t=90min, which the desulfurization degree can be achieve at 89% and the content of sulfur can be reduced from 255µg/mL to 28µg/mL.