离子液体中过氧钼酸盐催化燃油深度氧化脱硫

以过氧化氢为氧化剂,[Omim]PF₆离子液体为萃取剂,[C₁₆mim]₂ Mo₂O₁₁为催化剂建立了萃取催化氧化脱硫体系（ECODS）。该反应体系在非常温和的条件下可使DBT的脱除率最高达到99.4%,大大优于单纯的萃取脱硫和萃取氧化脱硫体系。不同硫化物在该体系下的脱硫效果为：DBT >BT >TH。催化体系循环使用10次后催化反应活性未见明显下降。将此催化体系直接用于市售的汽油和柴油,可使其中硫含量降低至12.70mg/L和11.62mg/L。     

离子液体在FCC汽油烷基化脱硫中的应用研究

制备了一种带—SO3H官能团的Brnsted酸性离子液体[SO3H-C6H4-CH2-mim]HSO4,应用于FCC汽油烷基化脱硫。结果表明,离子液体对噻吩类硫化物均有较好的脱除效果,脱硫率可达70%以上;离子液体催化大港FCC汽油烷基化脱硫反应的较佳工艺条件为:反应温度75℃,反应时间120 min左右,离子液体加入量10%,二烯烃加入量3%。在此条件下,离子液体可将大港FCC汽油中的总硫含量由186μg/g降至90μg/g,脱硫率51.6%,汽油收率96.1%,抗爆指数下降1.4个单位。     

Fe基离子液体中Schiff碱Co络合物催化氧化燃油脱硫

将离子液体FeCl3/BmimCl与Schiff碱Co络合物CoL组成催化体系,以氧气为氧化剂,噻吩的正辛烷溶液为模拟油,考察该脱硫体系脱除模拟油中噻吩硫的性能。结果表明,最佳脱硫条件为：模拟油25mL;IL-FeCl3/BmimCl摩尔比为1,8mL;O250mL/min;反应温度62℃;CoL0.13g;时间6h,最终脱硫率可达96%（质量分数）,脱硫后油品中噻吩含量最终可降到50μg/g以下。噻吩的氧化产物为SO42-离子。离子液体再生4次后脱硫性能开始下降。该脱硫体系对实际柴油中的噻吩硫催化氧化脱硫效果可达100%,该脱硫体系具有实际应用意义。     

离子液体在汽油脱硫中的应用

选用[3（C4H9）4.C6H11NO]和[ZnCl2.3（NH2）2CO]两种离子液对E-97汽油和模拟汽油进行脱硫试验。考察了离子液体对E-97汽油和模拟汽油脱硫工艺条件。较佳脱硫条件：温度为约50℃,剂油比为3：1,萃取时间为30min,经6次脱硫后,E-97汽油的脱硫率为97.14%,对模拟汽油脱硫率为88.09%。[3（C4H9）4.C6H11NO]对E-97汽油的脱硫率为30.95%,对模拟汽油的脱硫率为16.92%。实验结果证明[ZnCl2.3（NH2）2CO]的脱硫效果较好。     

离子液体在燃油脱硫技术领域的应用

重点介绍了离子液体在燃油脱硫技术方面的应用进展,主要介绍了直接萃取脱硫、萃取-氧化脱硫、催化氧化脱硫和电化学聚合脱硫技术,催化氧化脱硫技术具有反应条件温和、时间短、操作简单、易分离的优势,具有较好的应用前景,分析了离子液体在工业化过程中的应用方向和亟待解决的问题。     

Oxidation desulfurization of fuel using pyridinium-based ionic liquids as phase-transfer catalysts

In this work, several ionic liquids based on pyridinium cations are prepared. The ionic liquids are employed as phase-transfer catalysts (PTCs) for phase-transfer catalytic oxidation of dibenzothiophene (DBT) dissolved in n-octane. The partition coefficients of DBT between ionic liquids and n-octane are investigated. Then H₂O₂-formic acid is used as an oxidant and ionic liquids are used as PTCs. The reaction turns to be heterogeneous and desulfurization rate of DBT increased apparently. When IL ([BPy]HSO₄) is used as PTC, and the condition are: temperature is 60 °C, time is 60 min, H₂O₂/sulfur molar ratio (O/S) is 4, the desulfurization rate reaches the maximum (93.3%), and the desulfurization of the real gasoline is also investigated, 87.7% of sulfur contents are removed under optima reaction conditions. The PTC [BPy]HSO₄ can be recycled for five times without significant decrease in activity.     

离子液体萃取燃料油脱硫技术的研究进展

分析了离子液体萃取脱硫机理以及离子液体的结构、硫化物类型、萃取温度、萃取时间、剂油比等因素对脱硫效果的影响规律,并对离子液体再生方式进行了比较。认为研究开发价格低廉、适于大规模工业化使用的离子液体、增大硫化物的萃取选择性、提高离子液体的再生利用率、完善工业化应用所必需的各种基础数据以及离子液体萃取脱硫技术与其它工艺的组合将是离子液体萃取脱硫技术今后发展的主要任务。     

Molecular dynamics simulation of desulfurization by ionic liquids

Ionic liquids (ILs) have shown an excellent performance for removing the sulfur compounds of fuel. In this work, molecular dynamic simulations were performed to screen suitable IL instead of the traditional method which is inefficient. DBT and DBTO₂ were used as model compounds to study the mechanism of desulphurization. An all‐atom force field was proposed for dibenzothiophene (DBT) and dibenzothiophene 5,5‐dioxide (DBTO₂). The calculated results are in good agreement with the experimental value. We investigated the interaction between the model compounds and a series of ILs composed of 1‐alkyl‐3‐methylimidazolium cations ([C_nmim]⁺, n = 4, 6, 8, 10) and BF, PF anions. We found that the interaction between hydrogen atoms in imidazolium ring and oxygen atoms in DBTO₂ is stronger than that of sulfur atoms in DBT, and it means that DBTO₂ is extracted by ILs more easily than DBT. In this work, we also compared and discussed the desulphurization mechanism as a function of different ILs, sulfur contents, temperatures, and inclusion of water or not. The above results may help us design extractant and improve the operating conditions. © 2010 American Institute of Chemical Engineers AIChE J, 56: 2983–2996, 2010     

复合离子液体组成对硫化氢的氧化脱硫性能的影响

针对纯铁基离子液体（Fe-IL）在脱硫过程中气液传质效率较低、铁活性不高等缺陷导致的脱硫液易被击穿、硫容小和再生缓慢等问题,以铁基离子液体（Fe-IL）为基质,选用锌基离子液体（Zn-IL）、锰基离子液体（Mn-IL）和1,3-二甲基咪唑啉酮（DMI）为助剂,调节相互之间的质量比配制复合离子液体基脱硫液,并试验上述混合溶液的脱硫效果。实验结果表明,复合金属离子液体之间具有协同强化脱硫的作用,1,3-二甲基咪唑啉酮对铁基离子液体脱硫有着较好的活化作用,其中铁锌基离子液体与1,3-二甲基咪唑啉酮组成的复合液脱硫效果更为理想。     

Methanolysis of poly(lactic acid) using acidic functionalized ionic liquids as catalysts

The methanolysis of poly(lactic acid) (PLA) was studied by using acidic ionic liquids (ILs) as catalyst in detail. The results showed that HSO₃‐functionalized ILs exhibited higher catalytic activity than non‐functionalized ILs and traditional acid catalyst such as H₂SO₄. The influences of experimental parameters, such as the amount of catalyst, reaction temperature, methanolysis time, and dosages of methanol on the conversion of PLA, yield of methyl lactate were investigated. Under the optimal conditions, using 1‐methyl‐3‐(3‐sulfopropyl)‐immidazolium hydrogen sulfate ([HSO₃‐pmim][HSO₄]) as catalyst, the IL could be reused up to six times without apparent decrease in the conversion of PLA and yield of methyl lactate. The kinetics of the reaction was also investigated. The results indicated that the methanolysis of PLA in [HSO₃‐pmim][HSO₄] was a first‐order kinetic reaction with activation energy of 47.01 kJ/mol and Arrhenius constant of 2.7 × 10⁷ min^?1. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40817.     

离子液体反应型萃取燃油脱硫研究进展

随着社会不断发展,汽、柴油的消耗量逐年增大,开发温和条件下对芳香族硫化物具有优异脱除性能的非加氢脱硫方法对我国汽、柴油标准升级具有重要意义。萃取脱硫法能够在室温常压条件下脱除油品中的芳香族硫化物,且能够通过萃取剂结构设计实现选择性脱硫。综述了近年来离子液体反应型萃取脱硫方法的研究进展,主要探讨了离子液体反应型萃取脱硫方法的原理和萃取作用机制,重点论述了离子液体反应型萃取脱硫方法中离子液体设计、氧化剂类型、外场强化作用、离子液体的分离回收等研究现状,分析了制约反应型萃取脱硫广泛工业化应用的瓶颈,并提出合适的解决策略,以期推动基于离子液体反应型萃取脱硫方法和技术的进一步工业化应用。     

Extractive desulfurization of model fuels with a nitrogen-containing heterocyclic ionic liquid

A nitrogen-containing ionic liquid was synthesized using an aromatic nitrogen-containing heterocyclic and an amino acid, and applied to the extractive desulfurization process to remove benzothiophene, dibenzothiophene, and 4,6-dimethyldibenzothiphene from a model fuel oil. Chemical characterizations and simulation using Gaussian 09 software confirmed the rationality of an ionic liquid structure. Classification of non-covalent interactions between the ionic liquid and the three sulfur-containing contaminants was studied by reduced density gradient analysis. The viscosity of the ionic liquid was adjusted by addition of polyethylene glycol. Under extraction conditions of the volume of ionic liquid to oil as 1:1 and temperature as room temperature, the desulfurization selectivity of ionic liquid followed the order of 4,6-dimethyldibenzothiphene (15 min) < benzothiophene (15 min) ≈ dibenzothiophene (10 min). Addition of p-xylene and cyclohexene to the fuel oil had little effect. The extractant remained stable and effective after multiple regeneration cycles.     

醇胺类离子液体合成及其烟气脱硫特性

介绍了一种新的离子液体合成法——水浴微波法,以乙醇胺、二乙醇胺、三乙醇胺和N,N-二甲基乙醇胺为阳离子,甲酸、乙酸和乳酸为阴离子,合成一系列醇胺类离子液体。以乙醇胺乳酸盐离子液体为例,通过正交实验(L₉(3⁴))分析,得到最佳合成条件为：合成时间30 min,温度65 ℃,微波功率300 W,乙醇胺与乳酸的摩尔比1︰1.1。在此条件下,除N,N-二甲基乙醇胺类离子液体外,其余8种离子液体产率均保持90 %以上。乙醇胺乳酸盐对SO₂具有较高的吸收容量,吸收的SO₂与乙醇胺乳酸盐的摩尔比为1.063,选其作为最佳吸收剂进行脱硫性能研究。研究发现,适宜吸收温度为25 ℃,解吸温度和解吸时间分别为90 ℃和60 min。实验同时表明,水浴微波法可以加速SO₂的解吸过程。     

己内酰胺类离子液体催化合成N-单烷基苯胺

  在己内酰胺类Brønsted酸离子液体催化下,苯胺和溴丙烷发生N-烷基化反应,高选择性地制备N-单烷基苯胺。考察了苯胺和溴丙烷摩尔比、缚酸剂用量、反应温度、反应时间、催化剂用量和催化剂类型等因素对反应结果的影响。确定其最佳反应条件为：n(苯胺)∶n(溴丙烷)∶n(催化剂)∶n(三乙胺)= 1.0∶1.0∶0.05∶2.0,反应温度60 ℃,反应时间为1.0 h,在上述反应条件下,苯胺的转化率可达到92.40%,N-单烷基苯胺的选择性可达到93.40%。     

Computer‐aided design of ionic liquids as solvents for extractive desulfurization

Although ionic liquids (ILs) have been widely explored as solvents for extractive desulfurization (EDS) of fuel oils, systematic studying of the optimal design of ILs for this process is still scarce. The UNIFAC‐IL model is extended first to describe the EDS system based on exhaustive experimental data. Then, based on the obtained UNIFAC‐IL model and group contribution models for predicting the melting point and viscosity of ILs, a mixed‐integer nonlinear programming (MINLP) problem is formulated for the purpose of computer‐aided ionic liquid design (CAILD). The MINLP problem is solved to optimize the liquid‐liquid extraction performance of ILs in a given multicomponent model EDS system, under consideration of constraints regarding the IL structure, thermodynamic and physical properties. The top five IL candidates preidentified from CAILD are further evaluated by means of process simulation using ASPEN Plus. Thereby, [C₅MPy][C(CN)₃] is identified as the most suitable solvent for EDS. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1013–1025, 2018     

离子液体催化合成环己烷1,2-二甲酸二丁酯

以3-磺酸基丙基三乙基铵硫酸氢盐离子液体为催化剂,考察了反应时间、醇酸摩尔比、催化剂的用量对合成环己烷1,2-二甲酸二丁酯的影响及催化剂的重复利用性能。结果表明,反应时间8 h,醇与酸酐摩尔比为2.5∶1,催化剂用量为1%(以环己烷1,2-二甲酸酐质量计),反应温度150℃时,酯化率达99.2%,产品纯度为99.26%,且催化剂具有良好重复利用效果。     

A review of ionic liquids as catalysts for transesterification reactions of biodiesel and glycerol carbonate production

Biodiesel production has been rapidly increasing due to the strong governmental policies and incentives provided leading to an oversupply of its by-product, glycerol. Therefore, finding ways of utilizing glycerol is essential to increase the net energy and sustainability of biodiesel. Ionic liquids have been used successfully as catalyst for both the production of biodiesel and the conversion of glycerol to glycerol carbonate. These catalysts are relatively environmentally friendly as they have the potential to enable sustainable processes. Herein, the prospect of using ionic liquids to catalyze transesterification triglycerides for the production of biodiesel and the conversion of glycerol to glycerol carbonate will be discussed. Elucidation of the reaction mechanism is expected to provide an in-depth understanding of the process with respect to the effects of cation and anion based on the reactions of interest.     

功能化离子液体催化合成甘油单月桂酸酯

合成了由吡啶、N-甲基咪唑、N-甲基-2-吡咯烷酮提供有机阳离子, 磷钨酸、对甲苯磺酸提供阴离子的6种离子液体。使用NMR、FT-IR和TG对离子液体表征, 并考察它们催化甘油与月桂酸酯化的催化效果。结果表明, 这些离子液体都具有较好的热稳定性, 以1-(丁基-4-磺酸基)-3-甲基咪唑磷钨酸盐离子液体的热稳定性最好。在最佳条件使用离子液体催化甘油与月桂酸反应时, 阴离子的种类对月桂酸的转化率影响较大, 以对甲苯磺酸为阴离子的离子液体催化反应时, 月桂酸转化率较以磷钨酸为阴离子的离子液体的高;1-(丁基-4-磺酸基)-3-甲基咪唑对甲苯磺酸盐离子液体做催化剂时甘油单月桂酸酯的产率最高。催化剂重复使用性方面, 离子液体重复使用5次催化活性没有明显变化。     

[Cnmim]Br/FeCl3型离子液体萃取脱除二苯并噻吩

合成了6种咪唑型离子液体[C_3-8mim]Br/FeCl₃,采用红外光谱和拉曼光谱对其进行表征,并考察了离子液体对二苯并噻吩的萃取脱除效果。结果发现,[C₃mim]Br/FeCl₃的萃取脱硫效果最佳,升高温度和增大剂油比均有利于脱硫率的提高,剂油比1:1(体积比)时,萃取时间达到12 min就可使脱硫率高达92%。且萃取反应完成后,离子液体不做处理继续重复使用,重复使用5次,脱硫率可以达到60%。     

Protic and aprotic anionic oligomeric ionic liquids

We report on synthesis of linear and hyperbranched protic and aprotic anionic oligomeric ionic liquids (OILs). α,ω-Dicarboxy- and α,ω-disulfooligo(ethylene oxide)s, α-carboxy- and α-sulfooligo(ethylene oxide monomethyl ether)s, and di[(α-carboxyoligo(ethylene oxide monomethyl ether)] were synthesized using reaction of oligo(ethylene oxide diol) (MW 1000) and its monomethyl ether (MW 750) with phthalic-, 2-sulfobenzoic anhydride and pyromellitic dianhydride. Di- and mono-substituted anionic OILs were prepared by neutralizing these compounds with N-methylimidazole. Aprotic anionic OILs were synthesized by reaction of sodium salts of the prepared oligomeric di- and monoacids with 1,3-dimethyl imidazolium iodide. Hyperbranched protic and aprotic anionic OILs were prepared in a similar manner. The structure, thermal stability and ionic conductivity of the synthesized compounds in the range of 20–120 °C in anhydrous conditions is governed by the molecular architecture of the oligomeric chains and the type of the cation/anion moieties. OILs under study are amorphous at room temperature but some protic and aprotic linear-chain OILs prone to form a low melting temperature crystalline phase. The ionic conductivity of the synthesized OILs can be varied in broad range reaching 10⁻³ S/cm value at temperatures over 100 °C under anhydrous conditions.