离子液介质中生物催化与生物转化的研究进展

Ionic liquids have negligibly low vapor pressure, high stability and polarity. They are regarded as green solvents. Enzymes, especially lipases, as well as whole-cell of microbe, are catalytically active in ionic liquids or aqueous-ionic liquid biphasic systems. Up to date, there have been many reports on enzyme-exhibited features and enzyme-mediated reactions in ionic liquids. In many cases, remarkable results with respect to yield, catalytic activity, stability and (enantio-, regio-) selectivity were obtained in ionic liquids in comparison with those observed in conventional media. Accordingly, ionic liquids provide new possibilities for the application of new type of solvent in biocatalytic reactions.     

离子液体捕集二氧化碳的研究进展(英文)

Due to their negligible volatility,reasonable thermal stability,strong dissolubility,wide liquid range and tunability of structure and property,ionic liquids have been regarded as emerging candidate reagents for CO2 cap-ture from industries gases.In this review,the research progresses in CO2 capture using conventional ionic liquids,functionalized ionic liquids,supported ionic-liquids membranes,polymerized ionic liquids and mixtures of ionic liquids with some molecular solvents were investigated and reviewed.Discussion of relevant research fields was presented and the future developments were suggested.     

New Alkylation Route of Benzene with Ethylene Catalyzed by [bmim]Cl/FeCl_3 Ionic Liquid

Up to now the mechanism of Friedel-Crafts reactions catalyzed by ionic liquid have not been fully understood, while carbocation mechanism was assumed. It was found that the source of H and the route of reaction initiated the alkylation of benzene with ethylene catalyzed by [bmim]Cl/FeCl3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity for the alkylation of benzene with ethylene suggests that there exists a new catalytic route. The distinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR     

离子液体；石油沥青质的新型溶剂

The dissolution of petroleum asphaltenes with ionic liquids is studied for the first time. The results show that the ionic liquids could be used as novel solvents for asphaltenes. The important parameters governing the ability of ionic liquids for dissolution of asphaltenes are discussed. It is found that, the ionic liquids based on the cations containing a conjugated aromatic core or the anions which are strong hydrogen bond acceptors are most effective, whereas the ionic liquids containing ＇non coordinating＇ anions such as [BF4]^- and [PF6]^- are nonsolvents for asphaltenes. Increase in the effective anion charge density enhances the ability of ionic liquids to break the extensive asphaltene associations and thus enhances the solubility of asphaltenes in the ionic liquid. The dissolution ability of ionic liquid decreases apparently with increasing the substituted alkyl chain length of its cationic head ring. Temperature is found to play an important role on dissolution of asphaltenes, and the dissolution can be significantly imoroved bv microwave heatinz.     

离子液体催化的芳烃氯甲基化反应

Ionic liquids have been used as catalysts for Blanc reaction of toluene. The effects of reaction temperature, reaction time and dosage of the ionic liquid catalyst have been investigated, and the catalytic performance of different ionic liquid catalysts for toluene chloromethylation was also studied. The reaction was found to proceed under mild conditions with excellent conversion （up to 90%） in the absence of Lewis acids. The ionic liquids could be recycled and reused without loss of their catalytic activities.     

离子液体在6号溶剂油改质中的应用

A new method of upgrading 6# solvent oils using different ionic liquids as catalysts in a continuous apparatus is studied in this paper. The results show that aromatics, olefins and small quantity of sulfurs can be removed simultaneously. Using complex ionic liquid modified with CuCl as catalyst, olefins are removed completely, the mass concentrations of aromatics and sulfurs in solvent oil are 0.36% and 0.0058%, respectively, and the bromic index is zero. The sulfur removal rate decreases gradually with increasing of running time. The refined 6# solvent oil is corresponded to the quality standards of GB16629-1996, which request that the mass concentrations of aro-matics, sulfurs and bromic index are 1%, 0.012% and 1000, respectively. The loss of solvent oil is less than 3%.     

Statistical mechanics and artificial intelligence to model the thermodynamic properties of pure and mixture of ionic liquids

In this paper, the volumetric properties of pure and mixture of ionic liquids are predicted using the developed statistical mechanical equation of state in different temperatures, pressures and mole fractions. The temperature dependent parameters of the equation of state have been calculated using corresponding state correlation based on only the density at 298.15 K as scaling constants. The obtained mean of deviations of modified equation of state for density of al pure ionic liquids for 1662 data points was 0.25%. In addition, the performance of the arti-ficial neural network (ANN) with principle component analysis (PCA) based on back propagation training with 28 neurons in hidden layer for predicting of behavior of binary mixtures of ionic liquids was investigated. The AADs of a col ection of 568 data points for al binary systems using the EOS and the ANN at various temperatures and mole fractions are 1.03%and 0.68%, respectively. Moreover, the excess molar volume of all binary mixtures is predicted using obtained densities of EOS and ANN, and the results show that these properties have good agree-ment with literature.     

Effect of Ionic Liquids on Organic Reactions Based on Activity Coefficients at Infinite Dilution

It is important to know how ILs（ionic liquids） influence organic reaction. In this paper, activity coefficients at infinite dilution of more than 80 organic compounds in ILs are collected and analyzed systematically. Through the study on typical organic reactions happened in ILs, such as Diels-Alder, esterification and Friedel-Crafts reaction, the ratio of activity coefficients at infinite dilution of products and reactants is employed to estimate different effects of different structural ILs on the rate and selectivity of reactions.     

Separation of light hydrocarbons with ionic liquids: A review

Light hydrocarbons(C_1–C_4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of highpurity or even polymer-grade light hydrocarbons. However, traditional methods such as cryogenic distillation and solvent absorption are energy-intensive and environmentally unfriendly processes. Ionic liquids(ILs) as a new alternative to organic solvents have been proposed as promising green media for light hydrocarbon separation due to their unique tunable structures and physicochemical properties resulting from the variations of the cations and anions such as low volatility, high thermal stability, large liquidus range, good miscibility with light hydrocarbons, excellent molecular recognition ability and adjustable hydrophylicity/hydrophobicity. In this review, the recent progresses on the light hydrocarbon separation using ILs are summarized, and some parameters of ILs that influence the separation performance are discussed.     

[bmim]Cl／FeCl3离子液体催化苯与乙烯烷基化反应的新型机理

Up to now the mechanism of Friedel-Crafts reactions catalyzed by ionic liquid have not been fully understood, while carbocation mechanism was assumed. It was found that the source of H and the route of reaction initiated the alkylation of benzene with ethylene catalyzed by [bmim]Cl/FeCl3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity for the alkylation of benzene with ethylene suggests that there exists a new catalytic route. The distinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR analysis of [bmim]Cl after titration with water free KOH in alcohol solution. In addition, the chemical shifts of proton on the [bmim]Cl ring, especially 2-H, are sensitive to the change of FeCl3 content and shifted downfield when FeCl3 was added into [bmim]Cl to form ionic liquid. Thus 2-H was easy to be disengaged from imidazolium ring with formation of H^ to initiate the reaction. The isotope-substituted method was employed to prove this mechanism, through the GC-MS analysis of alkylation products of deuterated benzene with ethylene. The route of alkylation catalyzed by FeC13 ionic liquid was found to follow the carbocation mechanism, the resource of H was presented and proved using HNMR analysis of ionic liquid to inspect the intensity change of 2-H. It was found that the intensity of 2-H reduced 23% after reaction showing that the H arising from alkylation reaction was supplied by 2-H on the imidazole ring.     

芳烃与烯烃烷基化反应的催化机理进展

芳烃与烯烃的反应在有机合成中应用广泛。随着环保要求的提高，用于芳烃烷基化反应的传统催化剂逐渐被新型绿色催化剂所替代。近年来研究发现离子液体和分子筛对该反应具有高效催化作用且环境友好。本文探讨了离子液体和分子筛的酸性，总结了相应的的催化机理，对有关实验和理论研究工作进行了分析。同时揭示了离子液体和分子筛的结构对其催化性能的影响，为烷基化反应进一步研究奠定了基础。分析表明离子液体既能作为B酸，也能作为L酸起催化作用；分子筛主要作为B酸起催化作用，同时其催化性能与孔道结构、孔径大小及反应物尺寸密切相关。离子液体的稳定性较差、成本较高，而分子筛失活较快，未来需围绕提高离子液体稳定性、改进其制备方法以降低成本及改善分子筛结构以延长使用周期等方面展开研究。     

离子液体应用研究进展

由于离子液体具有较低的熔点、良好的导电性和可以忽略的蒸汽压等优点,引起了科学界和工业界的广泛瞩目.随着研究的日益深入,室温离子液体已经被开发和应用到诸多领域.对室温离子液体应用的研究进展进行了综述,详细介绍了离子液体在电化学、化学反应、分离过程以及在新材料等方面的应用.并对该领域的研究前景作了展望.     

离子液体在芳酮合成酰化反应中的应用

作为环境友好的新型反应介质,离子液体已广泛应用于各类反应之中.重点介绍了金属卤化物型离子液体和非金属卤化物型离子液体作为催化剂和溶剂分别在Friedel-Crafts酰基化反应中的应用.结果表明,离子液体催化Friedel-Crafts酰基化反应合成芳酮,具有无污染、催化效率高、可重复使用等优点,同时还可以作为溶剂满足合成芳酮绿色环保的需要.     

离子液体制备及其化工应用进展

回顾了离子液体的发展阶段及作为一种新型的绿色环保有机化合物具有的一些优异性质,如低的饱和蒸气压、良好的溶解性、热稳定性、高电导率和宽的电化学窗口等。综述了离子液体的种类、构效关系及制备方法,介绍了离子液体在萃取分离方面的应用,作为溶剂在各类常见的有机反应中的影响和优势,包括氧化反应、Friedel-Crafts反应、Diels-Alder反应、碳-碳偶联反应、酯化反应、环氧化反应等。与传统催化剂进行比较,突出了不同类型的离子液体催化剂对不同催化反应效果的优势,指出了离子液体催化剂发展的趋势。提出了离子液体今后将突出在节能减排、非均相高效催化方面的应用前景。     

绿色溶剂离子液体在化学反应中的应用

离子液体用作化学反应的溶剂，对提高化学反应速率、选择性，或实现催化剂的循环利用及产物分离都具有明显的优势，而且对许多化学反应，离子液体还具有催化功能。这对于开发新的化学工艺，实现绿色化学过程具有重要的意义。本文主要介绍离子液体在化学反应中的应用最新进展及其工业化前景。     

Microstructured reactors and supports for ionic liquids

Different types of microstructures and their applications with respect to the synthesis and the use of ionic liquids are presented. Microstructured reactors are suitable for reactions with fast intrinsic kinetics, requiring high mass and heat transfer performances. Chemical synthesis can be performed safely under operating condition (e.g. high temperature, pressure, etc.) difficult to obtain in traditional reactors. The examples presented clearly indicate that microstructured reactors offer superior performance for the synthesis of ionic liquids in comparison to conventional equipment. For the use of ionic liquids as reaction media, existing ionic liquids show some limitations due to their higher viscosity compared to conventional solvents. Therefore, future research should be focused on the development of low viscosity ionic liquids.The approaches to use ionic liquids in microstructured reactors and in combination with microstructured supports for catalytic reactions show many advantages in view of high product selectivity and yield. The use of supported ionic liquids on microstructured materials seems to be particularly promising for gas phase as well as for gas/liquid reactions.     

离子液体中金属的电沉积

与普通有机溶剂相比,室温离子液体具有很宽的电化学窗口,优良的导电性,不挥发,热稳定性较高等优点.离子液体作为新一代绿色溶剂正日益受到重视.将离子液体分为AlCl3型离子液体和非AlCl3型离子液体两类,分别评述了在这两类离子液体中金属电沉积的研究进展.     

纤维素在离子液体中反应的研究进展

近年来,离子液体作为一种新型绿色化学溶剂,引起了人们广泛的兴趣,离子液体在化学反应中的研究已成为目前的热点课题之一。纤维素是天然的可再生生物资源,其利用价值是不可估量的。总结了纤维素在离子液体中发生的酰化反应、酯化反应、三苯甲基化反应、水解反应和热解反应。     

离子液体催化合成酯研究进展

概述了不同种类离子液体在催化酯化反应中的应用。采用离子液体催化酯化反应,催化剂热稳定性好、效率高、环境友好且可回收重复利用,克服了传统方法普遍存在的副反应多、催化剂不易回收、设备腐蚀性大、环境污染以及后处理困难等缺点。探索了离子液体催化酯化的反应机理,指出了离子液体新体系发展需要解决的瓶颈问题及其在催化酯化反应中存在的不足,展望了离子液体在催化酯化反应中的发展方向。