离子液体及其应用进展

主要概述了离子液体及其发展概况,离子液体的种类特性以及合成方法.重点归纳了离子液体作为溶剂的优越性以及离子液体在化学反应、电化学、催化化学和分离纯化中的应用,并指出了离子液体在大规模工业应用方面存在的问题.     

离子液体及其在电化学中的应用

离子液体即在室温或接近室温下呈液态的完全由离子构成的物质,作为环境友好和“可设计性”溶剂正在引起越来越多的重视。它具有熔点低、蒸汽压小、酸性可调及良好的溶解度、粘度和密度等特点。综述了离子液体的组成、分类、性质、制备和纯化,就离子液体在电池技术、电合成、电沉积、电容器等电化学方面的应用和研究进展加以阐述,并对该领域的研究前景作了展望。     

Ionic Liquids in Oxygen Compression

Ionic liquids are still a relatively new and very promising class of substances which have received increased research attention in recent years. Due to their unique physical and chemical properties these compounds are ideal for use in industrial applications and also offer a variety of very interesting possibilities in process technology, with a high potential of increasing performance and reducing investment and operating costs [1]. Ionic liquids are remarkable for their high chemical inertness and good lubricity. Therefore, one very promising application is the lubricated compression of oxygen as an alternative to the dry compression technique that has to be used because of the extremely high reactivity of pure oxygen with organic lubricating media. A screening of the relevant parameters including thermal stability, flammability, chemical inertness to pure oxygen, corrosiveness, tribological behavior and oxygen solubility was performed. Based on the results obtained, the most suitable ionic liquid was identified and used in a screw compressor setup that achieves a final pressure of 30 bar with a delivery volume of up to 200 Nm³/h.     

Recent Developments and Applications of Ionic Liquids in Gas Separation Membranes

Flue gas emissions and the harmful effects of these gases urge to separate and capture these unwanted gases. Ionic liquids due to negligible vapor pressure, thermal stability, and wide electrochemical stability have expanded its application in gas separations. A comprehensive overview of the recent developments and applications of ionic liquid membranes (ILMs) for gas separation is given. The three general classifications of ILMs, such as supported ionic liquid membranes (SILMs), ionic liquid polymeric membranes (ILPMs), and ionic liquid mixed‐matrix membranes (ILMMMs) along with their applications, for the separation of various mixed gases systems is discussed in detail. Furthermore, issues, challenges, computational study, and future perspectives for ILMs are also considered.     

Ionic Liquids as Operating Fluids in High Pressure Applications

During the past years a growing number of scientists and engineers have investigated ionic liquids because of their outstanding advantages in several areas. Their unique physical properties and specific chemical behavior make these liquids very interesting for new and innovative applications. For commercial implementation ionic liquids have to meet a number of requirements. For use in high pressure applications they should have a low compressibility, an adjustable gas solubility and a superior lubricating ability. A screening of the relevant parameters was conducted in several experimental setups built for these purposes. Most of these parameters were also examined under long term conditions with regard to real process conditions and safety guarantee in possible high pressure applications. A major application is the compression of oxygen using ionic liquid as operating fluid. Besides, there are many more applications where the superior chemical and physical properties of ionic liquids are of high potential benefit.     

Ionic Liquids as New Solvents for Textile Fiber Formation and Modification

Ionic liquids (ILs) with their special characteristics such as low melting point, high thermal stability, electrical conductivity, and good solubility in different chemical liquids, are widely used as new solvents for a large range of inorganic, organic, and polymeric materials. The development of ILs created a great untapped potential for commercial and academic applications to increase operating efficiencies of many chemical processes, including the processing of textiles. A summarizing introduction about ILs, their characterization, the general applications, and the major challenges is presented, followed by previous researches on using ILs for textile fiber formation and modification of their properties.     

Modification of Nafion Membranes by Impregnation with Ionic Liquids

Nafion 117 membranes were impregnated with various imidazolium (1‐hexyl‐3‐methyl‐imidazolium/HMI, 1‐butyl‐3‐methyl‐imidazolium/BMI) and pyrrolidinium (1‐butyl‐1‐methyl‐pyrrolidinium/BMPyr) based ionic liquids bearing hydrophobic (tris(pentafluoroethyl)trifluorophosphate/FAP, bis(trifluoromethylsulfonyl)imide/BTSI, hexafluorophosphate/PF₆) and more hydrophilic (tetrafluoroborate/BF₄) anions. The modified membranes were characterized in terms of uptake behavior, washing out of the ionic liquids by water, swelling in humidified environment, thermal stability, mechanical properties, ion exchange capacity and ion conductivity. Upon this treatment, the ionic liquids' cations partially replace the protons of the sulfonic acid groups in Nafion. While the ionic liquids act as potent plasticizers in the polymer matrix, thermal stability of these systems remains unchanged and swelling by water of the dried ionomer membranes is reduced. Ion conductivities at 120 °C under dry conditions have been found to be up to 100 times higher than for dry Nafion 117. In particular, modification of Nafion by ionic liquids bearing the bulky hydrophobic FAP anion seems promising.     

咪唑类离子液体的制备与合成

离子液体作为一类新型绿色介质,近年来获得了突飞猛进的发展。本文简单介绍了离子液体的种类及性质,列举了常用的常规法、微波法、超声法和电化学法等辅助合成方法;重点介绍了目前主要的功能化和手性咪唑离子液体合成方法。     

Continuous Transesterification with Acidic Ionic Liquids as Homogeneous Catalysts

Ionic liquids (ILs) are recyclable acid catalysts for transesterification reactions. In the present study, different acidic ILs were examined in this reaction, with special focus on their recyclability. Furthermore, the IL‐catalyzed transesterification reaction was realized in continuous operation. A miniplant reactor with technically representative design and operating characteristics was used for this study. The applied rig has a volume of 5 L and an external thermosyphon reboiler. The miniplant reactor can be operated in batch and in continuous mode. ILs functionalized with a sulfonic acid group were found to be the most suitable IL catalysts for the transesterification reactions under investigation. Using these ILs, reaction rates as high as for H₂SO₄ could be realized. Moreover, the IL catalyst was demonstrated to be active for at least 1000 h of operation time.     

甲基丙烯酸甲酯和苯乙烯在离子液体中的自由基聚合

甲基丙烯酸甲酯和苯乙烯经4,4’-偶氮-双(4-氰基戊酸)引发,分别在离子液体([C4mim][PF6])和苯中进行了自由基聚合反应,比较了相同引发剂和单体投料比下,2种介质体系中的聚合速率、相对分子质量和分子量分布,得出2种单体在[C4mim][PF6]中的聚合速率、相对分子质量明显高于苯中的产物,且[C4mim][PF6]经多次重复使用,均能得到性能稳定的聚合产物。     

Kinetic Model of Two‐Phase Epoxidation with Ionic Liquids as Micellar Catalysts

The biphasic catalytic epoxidation of cyclooctene using the ionic liquid (IL) 1,2‐dimethyl‐3‐octyl‐imidazolium perrhenate ([OMMIM]ReO₄) as micellar catalyst and H₂O₂ as oxidant was investigated. Kinetic experiments were carried out in the intrinsic kinetic regime as proved by variation of stirring rate and temperature. Variation of catalyst concentration allowed for determination of the critical micellar concentration (CMC) of the catalytic IL. The effect of substrate concentrations on the reaction rate was also assessed. Based on the experiments, a kinetic model adapted from enzyme catalysis was proposed to account for the micellar reaction environment. The model takes into account the onset of micelle formation at the CMC. The application of the kinetic model illustrated the good agreement with the experimental data. The model will be applied to other micellar epoxidation reactions and for the design of an appropriate reaction setup in the future.     

功能型离子液体萃取氧化脱硫研究

合成了一系列含有不同阴离子的1-烷基-3-甲基咪唑型离子液体,以35%H2O2以及冰醋酸为氧化剂,分别考察了不同条件下离子液体对模拟油品和实际油品的脱硫效果。结果表明,离子液体阴离子的酸性以及阳离子烷基碳链的长度对脱硫效果具有显著影响,其中具有较长碳链的强酸性硫酸氢盐类离子液体在剂︰油︰氧化剂=1︰25︰1,30℃条件下对模拟油品与实际油品均具有较高的脱硫率,对模拟油品一次脱硫率在90%以上,对抚顺石化公司石油二厂汽油、柴油一次脱硫率在80%以上,其中汽油含硫量降至10 mg/kg左右,达到欧V标准,显示了非常好的工业应用前景。     

Studies on Thermal Properties of Selected Aprotic and Protic Ionic Liquids

Abstract

We describe herein the thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) investigations of the thermal properties of selected room-temperature ionic liquids (RTILs). The dependence of the thermal properties on both cation and anion structures of RTILs was systematically studied. The ionic liquids (ILs) investigated here include 28 different imidazolium-based ILs, 22 ammonium-based ILs, and 16 amide-based ILs. In general, these three cation classes exhibit different thermal behaviors but follow a quite systematic trend as expected from the corresponding structural variation. The ILs with bromide as the conjugate anion have lower thermal stabilities than those with bis(trifluoromethane sulfonyl) imide or bis(perfluoroethyl sulfonyl) imide as the conjugate anion. The mass of TGA samples and scan rate were found to have a systematic effect on the decomposition temperature of ILs, highlighting the caution needed in reporting TGA results.     

离子液辅助制备二氧化锰及催化性能研究

以高锰酸钾和三乙醇胺型离子液为原料合成了二氧化锰,采用X射线衍射技术和扫描电子显微镜考察了二氧化锰的相组成和形貌,并以酸性品红为降解对象考察了二氧化锰的催化性能。结果表明：催化剂的加入量,双氧水的加入量,pH值和焙烧温度对于催化剂的降解活性都有显著的影响,酸性品红降解的最佳条件为：0.05 g的二氧化锰,pH等于7,双氧水的加入量为2 mL。实验还表明催化剂高温煅烧后活性会下降。     

Numerical Simulation of Absorbing CO2 with Ionic Liquids

Although separating CO₂ from flue gas with ionic liquids has been regarded as a new and effective method, the mass transfer properties of CO₂ absorption in these solvents have not been researched. In this paper, a coupled computational fluid dynamic (CFD) model and population balance model (PBM) was applied to study the mass transfer properties for capturing CO₂ with ionic liquids solvents. The numerical simulation was performed using the Fluent code. Considering the unique properties of ionic liquids, the Eulerian‐Eulerian two‐flow model with a new drag coefficient correlation was employed for the gas‐liquid fluid dynamic simulation. The gas holdup, interfacial area, and bubble size distribution in the bubble column reactor were predicted. The mass transfer coefficients were estimated with Higbie's penetration model. Furthermore, the velocity field and pressure field in the reactor were also predicted in this paper.     

New Ammonium- and 1,2,4-Triazolium-Based Ionic Liquids for Wood Preservation

Biological activity of new potential wood preservatives—ammonium- and triazolium-based ionic liquids—was determined employing screening agar-plate, agar-block, and perlite-block methods. Experiments were carried out on Scots pine (Pinus sylvestris L.) and beech (Fagus sylvatica L.) wood. This study examined the effect of the ionic liquid structure on anti-fungal efficacy, depth of penetration, and fixation in wood. It was stated that the fungicidal value of new ammonium compounds depended, above all, upon the cation structure; for Coniophora puteana, it ranged from 2.7 kg m^?3 to 4.6 kg m^?3. These compounds effectively protected Scots pine wood against the action of mold fungi. Ammonium ionic liquids with a nitrite anion were characterized by strong fungitoxic properties, stronger than ammonium nitrates. The application in the amount of 15 g m^?2 caused an insignificant growth of mold fungi on the surface of Scots pine wood. For the mixture of 7.5% tebuconazole and 7.5% propiconazole dissolved in ionic liquids, the synergistic effect against mold fungi at the application of 15 g m^?2 was found. Dissolving tebuconazole in didecyldimethylammonium nitrate repeatedly lowered the fungicidal value against brown-rot fungi, as well as increased penetration of the ionic liquids in wood. This was associated with reduced viscosity of this ionic liquid caused by the addition of 1,2,4-triazole derivatives. Quaternary derivatives of 1,2,4-triazoles showed very high activity against blue stain and wood-decaying fungi. Additionally, most of the test compounds were well-fixed in Scots pine wood. The spectral study in infrared confirmed that nitrite, nitrate anions, and didecyldimethylammonium cation were retained in the treated wood.     

Ionic electroactive polymer actuators based on nano‐carbon electrodes

This review paper focuses on the recent studies of electroactive polymer actuators that have a triple‐layered configuration composed of an ionic‐gel electrolyte layer sandwiched by nano‐carbon dispersed ionic‐liquid gel electrode layers (bucky‐gel actuator) for the purpose of development of practical devices. The review covers recent studies of the developments of the materials of the bucky‐gel actuators and their electromechanical modeling. In the final section, the application to an ultra‐thin and ultra‐light Braille display based on the bucky‐gel actuator is described. © 2013 Society of Chemical Industry     

离子液体在高分子材料中的应用

离子液体是室温下呈液态的离子化合物,是一类新型的"软"功能材料或介质,具有优良的可设计性,它作为一种绿色溶剂,具有很多独特的物理化学性能,可广泛应用于高分子材料中,本文介绍了离子液体在高分子溶解,合成,改性,降解等方面的应用。并展望了离子液体在高分子材料领域中的应用。     

CO2/离子液体混合物相平衡的研究进展

离子液体对二氧化碳有良好的溶解性能,可以实现二氧化碳的固定与转化。超临界二氧化碳可以从离子液体/有机物体系中选择性萃取有机物,避免相间的交叉污染,实现离子液体的回收。从CO2在离子液体中的溶解度实验测定方法、CO2/离子液体二元体系高压相平衡测定、SC-CO2/离子液体/有机物的三元体系相平衡研究以及模型预测四个方面介绍了CO2/离子液体体系相平衡研究的最近进展,分析了这一研究领域的发展方向。     

Novel Process Options for Application of Zeolites in Supercritical Fluids and Ionic Liquids

Supercritical fluids and ionic liquids offer attractive opportunities for modifying and applying zeolites as adsorbents and catalysts. After a brief introduction to the most important properties of these solvents, examples of zeolite applications in supercritical fluids and ionic liquids from the recent literature are discussed. Particular emphasis is put on the influence of reaction media on the processes occurring in the zeolitic pore systems, e.g., during shape‐selective conversions in zeolite catalysts. The present potential and future challenges for the application of zeolites in supercritical fluids and ionic liquids are identified. Most attractive process options arise from a combined use of both ionic liquids and supercritical fluids in integrated reaction schemes.