【作者】 王建龙；

【导师】 赵地顺；

【作者基本信息】 天津大学 ， 工业催化， 2008， 博士

【摘要】 随着世界环保法规的日趋严格,世界各国对燃料油品中的硫含量提出了更严格的要求。与其他脱硫技术相比,离子液体萃取脱硫技术工艺简单,条件温和,可以在不改变燃料油组分的情况下脱除燃料油油中的硫化物,这些特点使基于离子液体的萃取技术具有良好的应用前景。本文合成了[HMim]Cl/CuCl、[Et3HN]Cl/CuCl离子液体,代替传统的[AMim]+离子,用[HMim]Cl/CuCl离子液体和[Et3HN]Cl/CuCl离子液体进行络合萃取脱硫,研究了离子液体的种类、反应时间、反应温度等工艺条件对脱硫率的影响,汽油脱硫率分别达到86.1%和86.8%。目前国内外萃取脱硫所使用的离子液体大部分是咪唑类离子液体,而使用其他离子液体的研究鲜见报道。本文研究了吡啶类离子液体对汽油的萃取脱硫性能,当阴离子相同时,阳离子取代基越大脱硫效果越好;当阳离子相同时,并不是阴离子越大脱硫效果越好,还与阴离子的性质有关;同时还研究了吡啶离子液体萃取-氧化汽油脱硫的情况。将臭氧高级氧化技术与离子液体萃取相结合,用于FCC汽油氧化-萃取脱硫实验,脱硫率可达87.5%;OH-的加入对离子液体中的臭氧氧化过程有促进作用。使用Br?nsted酸性离子液体萃取-氧化柴油中的含硫化合物,其中Br?nsted酸性离子液体[Hnmp]BF4既是萃取剂,又是催化剂。[Hnmp]BF4可以从油相中萃取DBT,H2O2与离子液体的阳离子形成配合物,然后分解产生自由羟基基团,被萃取到离子液体体系中的DBT被自由羟基氧化成二苯并噻吩砜,油相中不含有硫的氧化产物。将该体系应用于真实柴油的脱硫过程中,脱硫率达到99.4%,表明[Hnmp]BF4离子液体-H2O2体系可以用于柴油的深度脱硫。更多还原

【Abstract】 Along with more attention being paid to environment protection worldwide, most countries have made laws or regulations to restrict the sulfur content in fuel oil with a more rigorous standard. Among these techniques, the extraction desulfurization with ionic liquids, which has many advantages such as low investment, simple techniques, mild conditions, easy separation etc, shows promising as an approach for the deep desulfurization of fuel oil.Several lower cost ionic liquid, such as [Et3HN]Cl/CuCl and [HMim]Cl/CuCl, were prepared and characterized. The effect of experiment condition to desulfurizaiton rate was researched. The sulfur removal were 86.1% and 86.8% respectively when [HMim]Cl/CuCl and [Et3HN]Cl/CuCl ionic liquid were used for extraction desulfurization.In previous researches, ionic liquids employed to desulfurize from fuels are mostly N-alkylimidazolim-based ionic liquids. In this thesis, N-alkyl-pyridinium-based ionic liquids were used in extractive desulfurization. The properties of N-alkyl-pyridinium-based ionic liquids were studied for the first time. The desulfurization ability of ionic liquids connects with the chemical property of ionic liquids, such as the cation or anion structure, size of ionic liquids. With the same anion, increase of cation size by the substitution of a longer alkyl group to the pyridium ring was responsible for the increase of the extractive capacity for thiophene. But a similar phenomenon did not hold with increasing anion size when the cations of ionic liquids were same; desulfurization ability of ILs connects with the chemical property of anion. We also researched the extraction-oxidation desulfurization with N-alkyl-pyridinium-based ionic liquids.Extraction/Oxidation with ionic liquids and O3 are combined to desulfurize the sulfur compound in FCC gasoline. The desulfurization rate could reach 87.5%. O3 oxidation process could be promoted by the addiation of OH-.Br?nsted ionic liquid [Hnmp]BF4 was used to be a catalyst and extractant for desulfurization of model oil and actual diesel fuel. In this process, DBT was oxidized in the ionic liquid phase as it was extracted from oil phase, so a continuous decrease in the concentration of DBT in n-octane was observed for each solvent during the oxidation process. [Hnmp]BF4 is not only the extractant but also the catalyst. One of its catalytic roles is to decompose hydrogen peroxide to form hydroxyl radicals. DBT in the ionic liquids phase was oxidized to its corresponding sulfone by the hydroxyl radicals. Sulfone did not exist in the oil phase because of the high polarity of ionic liquid. DBT sulfone can be detected in the ionic liquid phase.In addition, the ionic liquid was also effective on the ODS of actual diesel fuel. 99.4% sulfur-containing compounds which present in the actual diesel fuel can be removed. The results show that ionic liquids [Hnmp]BF4 could be used in deep desulfurization.更多还原