铁基离子液体高温湿法氧化硫化氢脱硫工艺研究（摘要）

煤炭资源一方面是能源的主要提供者，另一方面也是主要的环境污染源。以煤气化为基础的多联产技术是目前煤炭高效清洁利用的主要途径，高温煤气净化主要包括除尘、脱微量有害物质（如Na、K等金属；HCl、HF等气体）、脱硫（其中90％为H2S）。高温煤气脱硫是其中的关键技术之一，在高温条件下脱除气体中的硫是为了利用煤气的显热，防止后续反应所使用的各种催化剂中毒，提高催化反应的效率和催化剂的寿命。煤气的高温脱硫技术已成为能源领域研究的热点。

脱硫技术进展

当今,世界各国对油品的消耗量日益增加。由于人们对环境意识的逐渐增强,使得石油炼制工业必须继续走深加工的道路,大力发展脱硫技术。介绍了国内外脱硫技术最新进展,阐述了各种不同脱硫技术的性能、特点、反应原理和应用现状,并预测了脱硫技术的发展趋势。

填料塔多种高效脱硫工艺的性能对比研究

目前湿法脱硫是烟气脱硫技术中最主要的工艺，为了挖掘湿式脱硫技术的潜能，研究提高脱硫效率和脱硫的稳定性，本课题对气液并流脱硫的．流体力学性能、改良的浆液脱硫工艺以及室温离子液体脱硫工艺等方面进行了深入研究，力求综合、全面地总结湿法脱硫工艺，主要研究内容如下：

燃料油脱硫的研究进展

近些年来,随着节能减排力度的加大,工业生产不断节能环保化,各国对燃料油中的硫含量标准要求也越来越高。目前脱硫的方法较多,本文主要介绍近年来国内外燃料油脱硫的研究进展,概述了三大类技术,氧化脱硫技术(使用过氧化氢、空气和固体氧化剂)、吸附脱硫技术(碳基材料、分子筛和金属有机骨架材料)、离子液体脱硫技术和生物脱硫技术的脱硫机理,并对其进行分析评价以及对未来的展望。

Desulfurization of Diesel Fuel by Extraction with [BF4]^--based Ionic Liquids

The extractive removal of sulfur compounds （S-compounds） from Dongying and Liaohe diesel fuels with [BF4]^--based ionic liquids were systematically investigated. The results show that the absorption capacity of an ionic liquid for the S-compounds in diesel fuels relies on its structure and its size. In the case of the two examined diesel fuels, both elongating the cation tail length and increasing the mass ratio of ionic liquid/diesel fuel promote the desulfurization ability of the examined ionic liquids. The results also show that imidazolium-based ionic liquids display higher extraction efficiencies than pyridinium-based ionic liquids, presumably owing to the fact that the rings of the S-compounds are similar to the imidazolium head ring. With the 1 ： 1 mass ratio of ionic liquid/diesel fuel, the rates of the first desulfurization of Dongying and Liaohe diesel fuels using [C8mim][BF4] amount to 29.96% and 39.76%, suggesting that [C8mim][BF4] is a promising extractant for desulfurization of these diesel fuels.

Ternary System of Fe-based Ionic Liquid,Ethanol and Water for Wet Flue Gas Desulfurization

Fe-based ionic liquid （Fe-IL） was synthesized by mixing FeCl3·6H2O and 1-butyl-3-methylimidazolium chloride [Bmim]C1 in this paper. The phase diagram of a ternary Fe-IL, ethanol and water system was investigated to construct a ternary desulfurization solution for wet flue gas desulfurization. The effects of flow rate and concentration of SO2, reaction temperature, pH and Fe-IL fraction in aqueous desulfurization solution on the desulfiariza- tion efficiency were investigated. The results shows that the best composition of ternary desulfurization solution of Fe-IL, ethanol and water is 1 ： 1.5 ： 3 by volume ratio, and pH should be controlled at 2.0. Under such conditions, a desulfurization rate greater than 90% could be obtained. The product of sulfuric acid had inhibition effect on the wet desulfurization process. With applying this new ternary desulfurization solution, not only the catalyst Fe-IL can be recycled and reused, but also the product sulfuric acid can be separated directly from the ternary desulfurization system.

Catalytic Oxidative Desulfurization of Gasoline Using Vanadium(V)-substituted Polyoxometalate/H_2O_2/Ionic Liquid Emulsion System

Aiming at deep desulfurization of gasoline,three amphiphilic catalysts [C18H37N(CH3)3]3+x [PMo12-xVxO40](x=1,2,or 3) were prepared and characterized.The amphiphilic vanadium(V)-substituted polyoxometalates were dissolved in water-immiscible ionic liquid([Bmim]PF6),forming a H2O2-in-[Bmim]PF6 emulsion desulfurization system with 30 m% H2O2 serving as the oxidant.The catalytic oxidation of sulfur-containing model oil has been studied in detail under various reaction conditions using this system.The ionic liquid emulsion system showed high catalytic oxidative activity in the treatment of commodity gasoline.Furthermore,the mechanism of catalytic oxidative desulfurization was also elaborated.

Effect of water on extractive desulfurization of fuel oils using ionic liquids： A COSMO-RS and experimental study

When evaluating ionic liquids （ILs） for extractive desulfurization （EDS） of fuel oils, the inevitable presence of water in the system may have a significant and in many cases strongly negative effect. However, few studies have considered this particular issue and a promoted water effect on EDS is scarcely reported. In this work, COSMO-RS was firstly employed to calculate the capacity and selectivity for EDS of various IL/H20 mixtures, which cover different IL characters and a wide water concentration range. Experiments were then conducted with a representative IL [C4MIM]IH2P04], whose stable and even promoted extraction performance with a small amount of water was suggested by COSMO-RS. Through analyses of the desulfurization ratio, the cross- solubility and the water content in the desulfurized fuel, the promoted effect of water within a certain range （〈 10 wt%） was experimentally demonstrated. Moreover, such effect of water was explained combining the viscosity, the solvent-solute interactions and the COSMO-RS based analysis.

Regulating sulfur removal efficiency of fuels by Lewis acidity of ionic liquids

It is urgent to develop a new deep desulfurization process of fuels as the environmental pollution increases seriously. In this work, a series of Lewis acidic ionic liquids （ILs） [C43MPy]Cl/nZnCl2 （n=1, 1.5, 2, 3） were synthesized and used in extraction and catalytic oxidative desulfurization （ECOD） of the fuels. The effects of the Lewis acidity of ILs, the molar ratio of H2O2/sulfur, temperatures, and different substrates including dibenzothiophene （DBT）, benzothiophene （BT） and thiophene （TS）, on sulfur removal were investigated. The results indicated that [C43MPy]Cl/3ZnCl2 presented near 100% DBT removal of model oil under conditions of 323 K, H2O2/DBT molar ratio 6：1. Kinetics for the removal of DBT, BT and TS by the [C43MPy]Cl/3ZnCl2-H2O2 system at 323 K is first-order with the apparent rate constants of 1.1348, 0.2226 and 0.0609 h-1, and the calculated apparent activation energies for DBT, BT and TS were 61.13, 60.66, and 68.14 kJ/mol from 298 to 308 K, re- spectively. After six cycles of the regenerated [C43MPy]Cl/3ZnCl2, the sulfur removal had a slight decrease. [C43MPy]Cl/ 3ZnCl2 showed a good desulfurization performance under optimal conditions.

Simultaneous desulfurization and denitrogen of liquid fuels using two functionalized group ionic liquids

Deep desulfurization of liquid fuels is an important and challenging issue in worldwide petroleum refining industry.Extraction and catalytic oxidative desulfurization(ECODS)of liquid fuels using a series of ionic liquids(ILs)with two functionalized groups,such as[(CH2)2COOHmim]Cl/n Fe Cl3,[(CH2)2COOHmim]Cl/n Zn Cl2,and[Amim]Cl/n Fe Cl3,was studied.In the ECODS,the ILs were used as both extractant and catalyst and 30 wt%hydrogen peroxide(H2O2)solution as oxidant.The effects of molar ratios of[(CH2)2COOHmim]Cl(or[Amim]Cl)to Fe Cl3(or Zn Cl2)in ILs,H2O2/sulfur(O/S)molar ratio,reaction temperature,and the nature of sulfur compounds on sulfur removal were investigated.The natures of the functional groups(–COOH,–CH2–CH=CH2)in cations and the acid strength of anions play important roles in the ECODS and affect the reaction time,temperature,and desulfurization efficiency of different substrates.Also,nitrogen-containing compounds(pyridine,pyrrole,and quinoline)could be removed simultaneously in the ECODS and had different effects on dibenzothiophene removal.