离子液体萃取脱硫的研究

合成了一系列离子液体用于模拟油的萃取脱硫实验,考察了不同离子液体及其与模拟油的质量比、反应温度和反应时间等因素对模拟油萃取脱硫效果的影响。实验结果表明,离子液体1-丁基-3-乙基咪唑氯盐([BEIM]Cl)的萃取脱硫效果明显优于其他离子液体。当以[BEIM]Cl为萃取剂时,萃取脱硫的最优条件为:[BEIM]Cl与模拟油的质量比1.0,萃取温度30℃,萃取时间30min。在此条件下,单级脱硫率可达52.02%;经5级脱硫后,总脱硫率高达96.56%。采用溶剂反萃取法对[BEIM]Cl进行了再生,再生后[BEIM]Cl的脱硫率可达新鲜[BEIM]Cl的95%。     

负载型离子液体在氧化脱硫中的应用进展

离子液体是一类新兴的绿色溶剂和催化剂,负载型离子液体可同时表现出离子液体和载体材料的优点,如较高的催化活性和较大的比表面积,因此成为研究热点。将离子液体负载到载体上可大大降低离子液体的用量并提高利用率,将其应用于燃油脱硫过程中可提高离子液体的氧化活性。笔者综述了负载型离子液体的制备方法,并介绍了负载型Lewis酸离子液体、负载型Br?nsted酸离子液体、负载型多金属氧酸盐离子液体作为催化剂进行燃油催化氧化脱硫性能的研究进展。部分负载型离子液体需加入中性离子液体或有机溶剂作萃取剂才能发挥催化作用,或吸附硫化物并将其催化氧化为砜类物质,达到深度脱硫的目的。     

Deep Desulfurization of Diesel Fuel by Extraction with Task-Specific Ionic Liquids

Abstract

Extraction of S-compounds from diesel oil by task-specific ionic liquids has been investigated. The influences of different ionic liquids, extraction time, extraction temperature, different S-compounds, the amount, and the recycling of ionic liquid were studied. This process is capable of removing up to 56% of dibenzothiophene in model diesel oil under optimum extraction conditions. At the same time, this process was applied to the real predesulfurized diesel oils. The results indicate that such a process could be an alternative to common hydrodesulfurization for deep desulfurization.     

Extractive Desulfurization of Gasoline Using Ionic Liquid Based on CuCl

Abstract

CuCl-based ionic liquid ([HMim]Cl/CuCl) was synthesized by mixing 1-hydracid-3-methylimidazolium chloride ([HMim]Cl) with CuCl. Ionic liquid ([HMim]Cl/CuCl) was employed as an extractant remove sulfur from gasoline. It was found that [HMim]Cl/CuCl can remove sulfur-containing compounds from gasoline at room temperature. The extractive desulfurization mechanism of ionic liquid was proposed. The effects of extractive conditions on desulfurization of gasoline was investigated. The used ionic liquids can be regenerated by re-extraction using tetrachloromethane and reused five times.     

Application of High Shear Agitation for Desulfurization of Gasoline Using Ionic Liquids

The high shear agitation device was first adopted for gasoline desulfurization by ionic liquids. The effect of benzylimidazol fluoborate in desulfurization of gasoline and the influence of moisture on deuslfurization rate were investigated. The experimental results showed that the ionic liquid could effectively decrease the sulfur content of gasoline and the optimal conditions were as follows: The reaction could be carried out at room temperature, a volumetric ratio between oil and the liquid of 2∶1, a volumetric ratio between water and ionic liquid of 0.04∶1, a rotational speed of 5 krad/s, and a reaction time of 1 minute. The desulfurization rate of gasoline reached 53.6%, and the gasoline yield was up to 97.3%. The ionic liquid could be recycled for repeated use, and the use of high shear agitation for gasoline would have good prospects.     

金属络合类离子液体用于汽油萃取脱硫的研究

本文由原料[Et₃NH]Cl、无水FeCl₃和无水CuCl合成了离子液体[Et₃NH]Cl-FeCl₃/CuCl,考察了其萃取脱硫性能。结果表明：在对模拟汽油（噻吩溶于正辛烷）和FCC汽油脱硫时,离子液体[Et₃NH]Cl-FeCl₃/CuCl均表现出了较好的脱硫性能。当离子液体和模拟汽油的体积比V(IL):V(oil)=0.08,时间t=50min,温度T=50℃时,模拟汽油中噻吩的脱除率能够达到 93.9%。在相同的温度和时间条件下,当离子液体和FCC汽油的体积比V(IL):V(oil)=0.1时,经过三次萃取,能够获得低硫（硫含量小于10μg/g）FCC汽油,FCC汽油的收率为94.3%。离子液体具有较好的循环使用能力,循环使用5次后,汽油中噻吩的脱除率没有明显降低。     

Oxidative Desulfurization of Dibenzothiophene Catalyzed by VO(acac)2 in Ionic Liquids at Room Temperature

A simple extraction and catalytic oxidative desulfurization (ECODS) system composed of VO(acac)₂, 30% H₂O₂, and 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄) has been found to be suitable for the deep removal of dibenzothiophene (DBT) in model oil at room temperature. The optimal conditions were as follows: [n(H₂O₂)/n(DBT)/n(catalyst) = 100:20:1], model oil = 5 mL, ionic liquid [IL] = 1 mL, T = 30°C, t = 2 hr. With the ECODS system, the sulfur removal of DBT could reach 99.6%, which was superior to that of the simple extraction with IL (15.6%) or oxidation without catalyst (17.1%). The IL could be recycled five times without a significant decrease in activity.     

离子液体萃取燃料油深度脱硫的研究进展

综述了各种类型的离子液体(ILs)萃取燃料油深度脱硫的研究进展。介绍了ILs中阴阳离子的萃取脱硫机理;对用于萃取脱硫的ILs的阳离子和阴离子进行了分类,阳离子从其演变过程分为单环芳烃阳离子、烷基改性的单环芳烃阳离子和多环芳烃阳离子,阴离子按其性质主要分为低黏度二腈胺根类、酸酯类和多卤代金属类,并讨论了它们的优缺点和发展历程;对ILs的再生方法进行了比较。最后提出了ILs萃取脱硫技术发展的重点是提高ILs萃取芳烃硫化物的分配系数和ILs的再生利用率。     

离子液体在燃料油脱硫中的应用进展

离子液体用于燃料油脱硫是一种环境友好的新技术。综述了离子液体用于燃料油脱硫的几种方法,包括直接萃取法、氧化-萃取法、络合萃取法和烷基化法,介绍了离子液体的几种再生方法,并进行了对比。     

The Deep Oxidative Desulfurization of Fuels Using Na2WO4.2H2O in Acidic Ionic Liquids

The catalytic oxidation desulfurization system is composed of Na₂WO₄.2H₂O, H₂O₂, acidic ionic liquid, and phase transfer catalyst has been found suitable for deep removal of organic sulfur in fuels. Under the optimal conditions, the desulfurization efficiency is virtually 100%. Moreover, this acidic ionic liquid can be recycled five times without obviously decrease in activity. Meanwhile, the mechanism of oxidation desulfurization was also elaborated.     

The Deep Oxidative Desulfurization of Fuels Catalyzed by Surfactant-type Octamolybdate in Acidic Ionic Liquids

Four surfactant-type octamolybdates were synthesized, characterized, and then used as effective catalysts associated with H₂O₂ as oxidant in the acidic ionic liquid, which has been found suitable for deep removal of organic sulfur in fuels. Under the favorable conditions, the sulfur removal could reach almost 100%, which was much better than desulfurization performance by the simple extraction with acidic ionic liquid. Moreover, this acidic ionic liquid can be recycled six times by distillation without obviously decrease in activity. Meanwhile, the mechanism of oxidation desulfurization was also elaborated.     

Remove Olefin from Diesel Oil with Chloroaluminate(III) Ionic Liquids

Abstract

Ionic liquids are low-melting-point salts that represent an exciting new class of reaction solvents. In this article, the author mainly refers to the effects of the olefin removal in the diesel oil using [bmim]Br-AlCl₃ (where [bmim] is 1-butyl-3-methylimidazolium cation) ionic liquid. The result shows the better performance in the olefin removal. Therefore, an environmental friendly approach for olefin removal from diesel is provided.     

Deep Oxidative Desulfurization of Dibenzothiophene in Simulated Diesel with Tungstate and H2O2 in Ionic Liquids

Abstract

A green extraction and catalytic oxidative desulfurization (ECODS) system composed of simple tungsten-containing catalyst, 30 wt% H₂O₂, and ionic liquids was discovered suitable for the deep removal of dibenzothiophene (DBT) in simulated diesel. In the case of the system comprising Na₂WO₄ · 2H₂O, 30 wt% H₂O₂ and 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄), the removal of DBT could reach 99.7% at 60°C for 3 hr, which was superior to mere solvent extraction with ionic liquid or catalytic oxidation without ionic liquid. This desulfurization system could be recycled five times with a small decrease in activity.     

磷酸酯类离子液体在燃油深度脱硫中的应用

研究了3种磷酸酯类离子液体,即1,3-二甲基咪唑磷酸二甲酯盐([MM im]DM P)、1-乙基-3-甲基咪唑磷酸二乙酯盐([EM im]DEP)和1-丁基-3-甲基咪唑磷酸二丁酯盐([BM im]DBP)的制备过程,考察了这3种磷酸酯类离子液体对模型油中3-甲基噻吩、苯并噻吩和二苯并噻吩的脱除效果及磷酸酯类离子液体的电化学再生方法。实验结果表明,这3种磷酸酯类离子液体的脱硫能力强弱顺序为:[EM im]DEP>[BM im]DBP[MM im]DM P;且对二苯并噻吩的脱除效果最好,对苯并噻吩的脱除效果次之,对3-甲基噻吩的脱除效果较差。以[EM im]DEP为萃取剂,油剂质量比为1∶1时,经5次萃取后,二苯并噻吩的脱除率可达到99.5%。利用电解法对[EM im]DEP进行了再生,在5~10V电压下电解10h,[EM im]DEP的脱硫率可以达到新鲜[EM im]DEP的90%以上。     

Ionic Liquid-based Extraction of Sulfur Compounds From Gasoline as a Complementary Process to Oxidative Desulfurization

The extractive desulfurization of a model and several real gasoline samples was investigated using imidazolium-based ionic liquids (ILs). Factorial design of experiments indicated that, among several process variables, the number of extraction steps and the IL/gasoline volume ratio were statistically highly significant. The results showed a desulfurization efficiency of 95.2% under the optimal conditions. The following order was observed for the extraction of thiophenic compounds: benzothiophene>thiophene>3-methylthiophene>2-methylthiophene, with 96.1% removal efficiency for the first one. The IL extraction was applied as a complementary process for the oxidative desulfurization by hydrogen peroxide and formic acid, which provided high efficiency and selectivity for desulfurization of gasoline.     

离子液体萃取耦合过氧钒配合物催化氧化燃油脱硫

<正>燃油中的硫化物燃烧后产生的SOx严重威胁着人类的健康。目前,工业上的脱硫技术主要为加氢脱硫(HDS)技术,但对于二苯并噻吩(DBT)及其衍生物,HDS技术很难将它们除去。萃取耦合氧化脱硫法被认为是一种具有很好应用前景的深度脱     

离子液体用于燃料油深度脱硫的研究进展

首先介绍了加氢催化脱硫和其他脱硫技术的特点,综述了近年来国内外利用离子液体在萃取脱硫、萃取脱硫与氧化脱硫耦合、萃取脱硫与生物脱硫耦合等方面的研究。认为离子液体萃取脱硫具有操作简便、可循环使用、无需氢气、环境友好、能深度脱硫等特点,是一项具有广阔发展前景的技术。若要实现该技术的工业化应用,还需进一步加强离子液体在合成工艺、脱硫选择性及回收再生等方面的研究。     

Deep Desulfurization of Model Oil by Extraction with a Low-viscosity Ionic Liquid [BMIM]SCN

In this work, a low-viscosity ionic liquid 1-buthyl-3-methylimidazole thiocyanate ([BMIM]SCN) was utilized as extractant for the extractive desulfurization of thiophene in model oil. Several conditions were investigated respectively, including extraction time, temperature, and volume ratio of ionic liquid to model oil. Also the kinetics of extraction of thiophene were proposed. Under the optimal extractive conditions, the removal of thiophene in model oil was 55.6%. Other sulfur compounds and real oil were also investigated. Furthermore, the total desulfurization efficiency could reach 98.3%. In addition, the ionic liquid could be recycled seven times with negligible decrease in activity.     

一种新型润滑剂——离子液体的摩擦学研究现状

随着人们对润滑剂综合性能要求的提高,各国科学家都致力于开发研究高性能的新型润滑材料.离子液体具有低熔点、不易燃、挥发性低和热稳定性高等特点,有望成为理想的、绿色的、极具发展前途的新型润滑剂,离子液体的摩擦学研究已越来越受到关注.文章简述了离子液体的概念、组成和特点,全面介绍了离子液体的摩擦学研究现状,其中包括常见离子液体和功能化离子液体的摩擦学性能研究以及离子液体中纳米微粒的制备及其摩擦学研究情况,并对今后离子液体的摩擦学研究趋势进行了展望.