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Desulfurization of fuels with ionic liquids by extraction and oxidative extraction processes

机译:通过萃取和氧化萃取工艺用离子液体对燃料进行脱硫

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摘要

The excessive emission of pollutants to the atmosphere has been a problem during the last few decades due to, among other reasons, the massive use of transports. In order to avoid this problem, many methods are being investigated as an alternative to the classical hydrodesulfurization technique, such as adsorption, biodesulfurization, extraction and oxidation. The extractive desulfurization is one of the most promising alternatives. Moreover, its enhancement with selective oxidation of sulfur compounds has been a trending field of research over the last years.Ionic liquids have turned into perfect solvents for many different tasks. Since they are composed by a cation and an anion, plenty combinations are possible, giving to these designer solvents different and defined properties. Among them, the negligible vapor pressure make these solvents easily recoverable while also avoiding atmospheric contamination. Amid other applications, ionic liquids are being proposed for the extraction of sulfur from fuels.In this work four ionic liquids, 1-hexyl-2,4-dimethylpyridinium bis(trifluoromethylsulfonyl)imide, [C62,4mmpy][NTf2], 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C2mim][NTf2], 1-ethyl-3-methylimidazolium acetate, [C2mim][OAc] and 1-ethyl-3-methylimidazolium diethylphosphate, [C2mim][DEP], were studied for the desulfurization of fuels. Liquid-liquid equilibrium data were obtained for the systems ionic liquid + thiophene + toluene, ionic liquid + thiophene + hexane and ionic liquid + pyridine + hexane at 298.15 K and atmospheric pressure. The obtained data were correlated using the UNIQUAC and NRTL models. The suitability of the ionic liquids as solvents was evaluated in terms of solute distribution ratio and selectivity.Then, the ionic liquids were tested in a three-stage extractive desulfurization using synthetic samples of fuels (gasoline and diesel oil). With the aim of enhancing the process, an oxidative desulfurization was also studied. Besides the traditional oxidative system for desulfurization (acetic acid and hydrogen peroxide), different ionanofluids, formed by the ionic liquid and metallic oxide nanoparticles (Cr2O3, Al2O3, TiO2), were tested as oxocatalytic system. In the case of H2O2-AcOH system, the research on the model fuels was carried out to optimize the operation conditions (ratio of oxidant and catalyst, temperature, extraction times and operation mode).Finally, the extractive and oxidative desulfurization methods were tested using the four ILs with real gasoline and diesel oil samples. Based on the results, [C2mim][OAc] is suggested for the desulfurization of gasoline in an extractive desulfurization process, whereas [C2mim][NTf2] is preferred for the oxidative desulfurization of diesel oil.
机译:在过去的几十年中,除其他原因外,由于大量使用交通工具,污染物向大气中的过量排放一直是一个问题。为了避免此问题,正在研究许多方法来替代经典的加氢脱硫技术,例如吸附,生物脱硫,萃取和氧化。萃取脱硫是最有前途的替代方法之一。此外,近年来通过选择性氧化硫化合物来增强其性能已成为研究的趋势。离子液体已成为完成许多不同任务的理想溶剂。由于它们是由阳离子和阴离子组成的,因此可以进行多种组合,从而为这些设计器溶剂提供不同的定义属性。其中,可忽略的蒸气压使得这些溶剂易于回收,同时还避免了大气污染。在其他应用中,提出了一种离子液体,用于从燃料中提取硫。在这项工作中,四种离子液体,即1-己基-2,4-二甲基吡啶双(三氟甲基磺酰基)酰亚胺,[C62,4mmpy] [NTf2],1-乙基-3-甲基咪唑双(三氟甲基磺酰基)酰亚胺,[C2mim] [NTf2],1-乙基-3-甲基咪唑乙酸盐,[C2mim] [OAc]和1-乙基-3-甲基咪唑二磷酸二乙酯,[C2mim] [DEP],研究了燃料的脱硫。在298.15 K和大气压下,获得了离子液体+噻吩+甲苯,离子液体+噻吩+己烷和离子液体+吡啶+己烷的液-液平衡数据。使用UNIQUAC和NRTL模型对获得的数据进行关联。根据溶质分布比和选择性评估了离子液体作为溶剂的适用性,然后使用合成燃料(汽油和柴油)样品在三阶段萃取脱硫中测试了离子液体。为了增强工艺,还研究了氧化脱硫。除了传统的用于脱硫的氧化系统(乙酸和过氧化氢)以外,还测试了由离子液体和金属氧化物纳米粒子(Cr2O3,Al2O3,TiO2)形成的不同离子流作为氧催化体系。在H2O2-AcOH系统中,对模型燃料进行了研究,以优化操作条件(氧化剂和催化剂的比例,温度,萃取时间和操作方式)。最后,使用萃取和氧化脱硫方法进行了测试。具有真实汽油和柴油样品的四个IL。根据结果​​,建议在萃取脱硫过程中使用[C2mim] [OAc]进行汽油脱硫,而对于柴油的氧化脱硫则建议使用[C2mim] [NTf2]。

著录项

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    Rodríguez Cabo Borja;

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  • 年度 2014
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  • 原文格式 PDF
  • 正文语种 eng
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