生物质基固体酸催化汽油烷基化脱硫的研究

The OATS(olefinic alkylation of thiophenic sulfur) method mainly utilizes solid acid as the catalyst to alkylate thiophen sulfur species with the olefins in gasoline,leading to the increase in the molecular weight and the boiling point of thiophenic compounds.Then the heavier thiophene derivatives can be removed from gasoline by distillation, thereby achieving the goal of FCC gasoline desulfurization. Compared with the HDS(hydrodesulfurization) desulfurization process，the OATS method exhibits the obvious advantages of low cost and high octane number keeping.Therefore,it shows promising application forward in the petrochemical industry.The solid acids from biomass have been paid much attention due to their easy biodegradation, high catalytic efficiency and good recyclability in the application. This research will investigate the effect of the surface acidity on the FCC gasoline OATS desulfurization reaction via the solid acid surface acidity adjustment by using solid-state NMR and IR spectroscopy. The relationship between the acidity of solid acid from biomass and the activity of the OATS desulfurization will be revealed.In situ solid-state NMR，FT-IR and quencher techniques are employed to capture the adsorbent，reaction intermediate and production in the reaction.The reaction mechnism of the OATS desulfurization by the solid acid will be elucidated based on the experimental data as well as quantum chemical calculation.Thus theory support for the application of the solid acid catalytic materials from biomass in OATS reaction will be provided.

烷基化脱硫主要采用固体酸催化汽油中的噻吩类硫化物与其本身含有的烯烃发生烷基化反应，生成相对分子量更大沸点更高的烷基噻吩，然后通过蒸馏的方法分离出高沸点硫化物以达到脱硫的目的，与加氢脱硫法相比具有明显的成本和保持辛烷值等方面的优势，因此在石化工业中具有良好的应用前景。生物质基固体酸具有可降解，催化效率高，易回收利用等优点日益受到人们的关注。本项目拟采用生物质基固体酸催化汽油烷基化脱硫反应，利用固体核磁共振、红外光谱等手段深入研究此类固体酸的表面酸性对催化裂化汽油烷基化脱硫反应的影响，揭示生物质基固体酸催化剂的酸性和烷基化脱硫活性之间的关联关系，并利用原位固体核磁共振和原位红外光谱实验包括骤冷技术捕捉烷基化脱硫反应中的吸附态、反应中间体和产物的信息，结合量化理论计算，阐明固体酸催化汽油烷基化脱硫的反应机理，从而为生物质基固体酸催化材料在烷基化脱硫中的应用提供理论依据。

生物质基固体酸具有可降解，催化效率高，易回收利用等优点日益受到人们的关注，将其应用到酸催化的汽油烷基化脱硫反应中是一种新的尝试。项目以葡萄糖，纤维素等生物质为原料，采用水热合成法制备了粒径均一分散性能好的碳微球，利用接枝、酸化磺化等后处理手段成功将-SO3H,-COOH和-OH等酸性基团嫁接到碳微球表面，增加了固体酸催化剂的酸性和活性位可接近性，进而大大提高了催化剂的催化活性。同时，利用生物质稻壳制备了SiO2微球，以SiO2微球为载体，通过浸渍，接枝，酸性离子液体固载，加入磁核等方法制备了系列功能化固体酸，研究结果表明，功能化提高了催化材料的酸性和催化活性。最后，通过捕捉中间产物，还研究了碳微球固体酸应用于烷基化脱硫过程的反应机制，提出了噻吩烷基化脱硫的碳正离子微观反应机理，给出了碳微球固体酸催化烷基化脱硫反应的具体反应历程，从而为生物质基固体酸催化材料在烷基化脱硫中的应用提供依据。