CO2萃取分离离子液体［bmim］［PF6］与萘的高压相平衡

采用紫外光谱在线检测的静态相平衡方法,在温度313～333 K、压力8～20 MPa、萘的液相浓度0.0169～0.378 mol·kg^-1的范围内,测定了CO₂+［bmim］［PF₆］+萘三元系中萘在富含CO₂相的浓度。结果表明,在所测温度和压力范围内,萘在富含CO₂相的浓度随着温度的升高而减小,随着压力的升高而增大,而且随着萘在液相中的浓度的减小而减小。在一定的温度压力条件下,萘在富含CO₂相的浓度与萘在液相中的浓度近似呈双对数线性关系。采用Chrastil缔合模型关联了所有溶解度数据,平均相对偏差为14.9 %。此外,还探讨了CO₂萃取分离离子液体与高沸点有机物的操作模式,发现釜式间歇操作较为适宜。     

Solubility of N2O and CO2 in n-Dodecane

The solubility of CO₂ and N₂O in a physical solvent, n-dodecane [C.A. Registry N° 124–18–5], has been measured at 40, 80 and 120°C at pressures up to 9.6 MPa. The experimental results were correlated by the Peng-Robinson (1976) equation of state, and the interaction parameters, the Henry's constants and the N₂O analogy parameters were obtained.     

Solubilities and diffusivities of N2O and CO2 in aqueous sulfolane solutions

The solubilities of N₂O and CO₂ in aqueous sulfolane solutions and pure sulfolane solvent, and the diffusivities of N₂O in aqueous sulfolane solutions were measured and correlated over the temperature range from 20° to 85°C; also, the data for density and viscosity that were needed in this experimental work were measured. This experiment revealed that the parameter of N₂O analogy method depends not only on the temperature, but also on the character of the solvent. Therefore, different solvents possess different analogy parameters. Only for dilute aqueous solutions can the parameter be replaced by the analogy parameter of water. The results also proved that the sum of volume fractions contribution is a simple method to estimate the solubility in aqueous sulfolane solutions over the whole range of the concentrations and experimental temperatures, with an average deviation of less than 4·0%.     

[bmim][BF_4]、[bmim][PF_6]离子液体及其与DMF二元体系在293.15～338.15K下的粘度

为获得离子液体与有机物物理性质的数据,常压下,293.15～338.15 K温度范围内,分别测定了1-丁基-3-甲基咪唑四氟硼酸盐（[bmim][BF4]）、1-丁基-3-甲基咪唑六氟磷酸盐（[bmim][PF6]）2种咪唑类离子液体以及它们和N,N-二甲基甲酰胺（DMF）构成的2个二元体系的粘度,采用Vogel-Tamman-Fulcher（VFT）方程和Arrhenius-like方程对所测粘度数据进行关联。结果表明,同一温度下,3种纯溶液粘度大小顺序依次为：DMF〈[bmim][BF4]〈[bmim][PF6]。[bmim][BF4]、[bmim][PF6]离子液体及其与DMF构成的二元体系的粘度均随着温度的升高和DMF摩尔分率的增加而降低。实验条件下,DMF＋[bmim][BF4]和DMF＋[bmim][PF6]二元体系的粘度变化范围分别为1.26～125.5 MPa·s和1.11～165.7 MPa·s。VFT方程对于DMF-[bmim][BF4]与DMF-[bmim][PF6]体系的关联结果比Arrhenius-like方程较好,其总平均绝对误差、总平均相对误差、以及总平均标准方差分别为0.561 9 MPa·s和0.918 6 MPa·s、0.026 8 MPa·s和0.020 9 MPa·s、0.725 5 MPa·s和1.125 1 MPa·s。     

Thermal conductivity of the ionic liquid [HMIm][Tf2N] with compressed carbon dioxide

The liquid thermal conductivity of the ionic liquid (IL), 1-hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)amide ([HMIm][Tf₂N]), saturated with compressed vapor and supercritical carbon dioxide was measured over three isotherms (298.15, 323.15, and 348.15 K) and pressures up to approximately 20 MPa using a transient hot-wire technique. Pure [HMIm][Tf₂N] thermal conductivity was also measured over a temperature range of 293.15–353.15 K at ambient pressure and with hydrostatic pressure to approximately 20 MPa. Literature vapor–liquid equilibrium data were used to predict the liquid CO₂ composition at the conditions investigated. Initially, the liquid thermal conductivity slightly decreased with pressure/composition of CO₂ followed by a gradual increase that is mainly attributed to hydrostatic pressure effects. Simple composition-based mixing rules for mixture properties are not qualitatively nor quantitatively accurate. These data could be used to engineer heat transfer equipment required for a variety of proposed IL applications in CO₂ capture, absorption refrigeration, biphasic CO₂/IL reaction platforms, etc.     

离子液体[bmim][Tf2N]的分子动力学模拟

建立了离子液体1-正丁基3-甲基咪唑双（三氟甲基磺酰基）酰亚胺（[bmim][Tf₂N]）的全原子模型,并分别在五种不同的温度和五种不同的压力下对其进行了分子动力学模拟。将[bmim][Tf₂N]密度的模拟结果与实验结果进行了比较,两者吻合良好,验证了模型准确性。此外,还对[bmim][Tf₂N]内部的相互作用能随温度和压力的变化规律进行了分析,结果表明：离子液体内部的库仑能、范德华能、长程作用能均随温度的升高而增加,系统达到平衡所需时间随之变短;相对温度而言,压力对离子液体内部相互作用能的影响较小;在各种相互作用能中,范德华能随温度和压力的变化最大;温度和压力对离子液体的构型不会产生影响。     

Diffusion coefficients and phase equilibria of carbon dioxide–ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) system

This article presents the mutual diffusion coefficients of a carbon dioxide–ionic liquid, [bmim][PF₆], system at temperatures of 313.15 and 323.15 K and pressures of 5 and 8 MPa. In order to estimate the diffusion coefficients, we have carried out experiments to find time-dependent carbon dioxide solubilities in the ionic liquid and then fit a transport model to the data. In a system containing high pressure carbon dioxide and ionic liquid, carbon dioxide dissolves in the liquid until its equilibrium mole fraction is reached. During this process, the position of the liquid–vapour interface and the density of the liquid phase change. To account for the variation in liquid density, an equation fit to the experimental density data is included in the transport model. To track the moving interface, the volume-of-fluid method is used. The diffusivities at dilute concentration and at thermodynamic phase equilibrium are determined and compared with the literature values and those obtained from correlations.     

离子液体支撑液膜技术及其在气体分离中的研究进展

分析离子液体支撑液膜的气体分离机理,总结目前离子液体支撑液膜的制备方法以及不同膜材料、不同离子液体及其亲疏水性对离子液体支撑液膜稳定性的影响。介绍离子液体支撑液膜在气体分离中的应用,对离子液体支撑液膜的工业化前景进行了展望。     

离子液体[bmim]PTSA中松香乙酯的微波辅助合成

以1-正丁基-3-甲基咪唑对甲苯磺酸盐离子液体([bmim]PTSA)作溶剂和催化剂,在微波辐射下通过松香与乙醇的直接酯化反应合成了松香乙酯。探索了催化剂种类、离子液体种类、离子液体用量、反应温度、反应时间等因素对反应酯化率的影响,确定最佳反应条件为:反应温度100℃,反应时间1 h,[bmim]PTSA对松香质量比4∶1。在此条件下,酯化率达95.5%。该离子液体易于与反应产物分离,且可以重复使用。     

用于CO_2吸收的离子液体的合成、表征及吸收性能

以N-甲基咪唑和3-溴丙胺氢溴酸盐为起始原料,合成了一种含氨基的离子液体(ionic liquid,IL)——1-(1-氨基丙基)-3-甲基咪唑溴盐(简写为[NH2p-mim]Br),总产率为90.1%,溴含量为0.980 mol Br/mol IL,胺含量为0.948 mol NH2/mol IL。探讨了合成工艺,并通过1HNMR、13CNMR、IR和MS对产物结构进行了表征。吸收实验结果表明,该离子液体能够有效地吸收CO2,在40℃和106 kPa下,质量分数为45%的离子液体水溶液吸收CO2至饱和时,溶液中CO2的摩尔分数可达0.444 mol CO2/mol IL,接近理论吸收量0.5 mol CO2/mol IL;在90℃的真空状态下,吸收的CO2能够完全解吸,重复吸收实验表明,该离子液体吸收CO2的能力无明显下降。     

离子液体[bmim]PF6对聚乳酸的增塑作用

合成了离子液体[bmim]PF6(1-丁基-3-甲基咪唑六氟磷酸盐),并对其进行了表征。用TG、DSC和偏光显微镜等手段研究了[bmim]PF6对聚乳酸的增塑作用,并比较了它与聚乙二醇300(PEG300)的增塑效果。热重分析结果表明,PEG300作增塑剂时,由于其热降解温度较低,聚乳酸热稳定性变差;离子液体[bmim]PF6作增塑剂时,由于其热失重温度高于聚乳酸热降解温度,用其增塑的聚乳酸热稳定性变好。当[bmim]PF6的质量分数从2%增加到10%时,聚乳酸材料的玻璃化转变温度(Tg)随之降低,当加入质量分数为10%的[bmim]PF6时,聚乳酸材料的Tg降至40℃。偏光显微镜观察看出,加入[bmim]PF6后聚乳酸分子链段的活动能力增强,促进了聚乳酸的结晶,且随其用量增加,结晶度增加。该文报道工作的新颖性,已为教育部科技查新工作站(Z12)于2008年2月26日出具的第ZDT2008017号《科技查新报告》所证实。     

离子液体膜材料分离二氧化碳的研究进展

离子液体由于具有不易挥发、结构可调、对CO₂有良好的吸收性能等特点而成为当前CO₂分离领域的研究热点,但因高黏度和高成本问题而限制了其工业化应用。将离子液体与气体分离膜材料结合,得到的新型分离膜材料兼具离子液体和膜的优势,成为当前离子液体研究领域的趋势之一。针对这一热点问题,综述了离子液体支撑液膜、聚离子液体膜和离子液体共混/杂化膜在CO₂分离方面的研究现状和进展,讨论了离子液体结构和含量对膜分离性能、稳定性等的影响。相关研究表明,离子液体共混/杂化膜具有较高的分离性能和稳定性,是一种很有应用前景的CO₂分离材料。提出该领域的重点发展方向,即开发新的功能化离子液体共混/杂化膜材料是解决高渗透通量与高稳定性之间矛盾、强化CO₂分离性能的有效途径,深入研究离子液体共混/杂化膜的形成机制、气体在膜中的渗透行为以及CO₂分离机理。     

负载[APMIm][Br]离子液体吸收CO2的性能

1-氨丙基-3-甲基咪唑溴盐（[APMIm][Br]）离子液体通过化学反应捕集CO₂。采用浸渍-蒸发将[APMIm][Br]离子液体负载在硅胶表面,通过比表面孔隙吸附测定仪、热重分析仪（TGA）对吸收剂的结构与性能进行研究,负载量为10%～50%,温度为303.15～323.15 K,CO₂浓度分别为10%、30%、50%。结果表明：硅胶表面的离子液体薄膜厚度达到86 nm（负载40%）时,具有最快的吸收速率,且受CO₂浓度和温度变化的影响较小,平衡吸收量在50% CO₂体系中达到理论吸收量的80%,随着温度的升高而降低,当负载量为50%时,膜厚增加到230 nm,导致吸收速率和平衡吸收量大幅度下降。值得注意的是：负载离子液体吸收剂在循环使用3次之后,结构与性能均保持不变,表现出一定的工业运用前景。     

金属Al和不锈钢在[bmim]BF4离子液体中的电化学

离子液体作为有潜力的绿色电化学介质,在电解、电镀、电催化、电分析化学等领域具有非常好的应用前景。本文采用循环伏安法和塔夫尔曲线法研究了金属Al和不锈钢在[bmim]BF4离子液体中的电化学行为,结果表明金属Al在[bmim]BF4离子液体中非常稳定,不锈钢在该离子液体中显示一定的活性。     

Investigation of Ionic Liquids for the Separation of Butanol and Water

Abstract

With the continual rise in the cost of fossil fuel based energy, research into economic and sustainable alternatives is of increasing importance. One significant source of increased cost and demand is the consumption of fossil fuels for automotive fuels. While ethanol has received the most attention as a fuel additive; butanol could be a better direct fuel alternative owing to its physical properties and energy value when compared to ethanol. Commercial butanol is nearly exclusively produced from petroleum feedstocks currently; however, some recent interest has begun to refocus on its generation via fermentation. Unfortunately, this production is limited due to the nature of the process and the use of energy-intensive separation techniques. Ionic liquids are novel green solvents that have the potential to be employed as an extraction agent to remove butanol from the aqueous fermentation media. A hurdle to this potential is the limited availability of solubility data for ionic liquids. This research investigates the phase behavior of two ionic liquids, butanol, and water. Additionally, issues related to the implementation of the investigated ionic liquids are discussed.     

CO_2/[Bmim]Br-AlCl_3/苯体系相平衡研究

在温度40～80℃、压力1.50～12.00 Mpa条件下,测定了CO2在氯铝酸离子液体([Bmim]Br-AlCl3)中的溶解度:在60℃以及3.00～10.00 Mpa条件下,测定了CO2/[Bmim]Br-AlCl3苯三元体系中气液相平衡数据,获得了三组分物系的相图.实验结果表明:在低压条件下,CO2在离子液体中的溶解度(xco2)随压力增加而升高;当温度在40～80℃、压力9.00～10.00 Mpa范围内,xco2分别达到最大值.在CO2/[Bmim]Br-AlCl3/苯三元体系中,根据各组分的最初摩尔比的不同,平衡体系中分别会出现气-液两相及气-液-液三相.压力对富苯相中各组分影响较富离子液体更大:在60℃,lO.00 Mpa条件下,体系中有新相生成,气-液两相区转变为气-液-液三相区.     

离子液体支撑液膜分离CO2的研究进展

总结了离子液体支撑液膜分离CO2的研究进展,简要分析了气体在离子液体支撑液膜中的传质机理;介绍了离子液体支撑液膜的制备方法及影响离子液体支撑液膜稳定性的因素;指出了今后用于分离CO2的离子液体支撑液膜的发展方向。     

R1234yf+CO2和R1234ze (E)+CO2二元混合物的比容平移Soave-Redlich-Kwong方程

采用温度相关比容平移项的比容平移Soave-Redlich-Kwong（VTSRK）方程计算新工质R1234yf和R1234ze（E）的热力学性质以及两种物质与CO₂的二元混合物性质,混合物计算采用van der Waals混合规则,二元交互作用系数由密度数据拟合得到。对纯净物计算与专用状态方程进行对比,VTSRK方程比SRK方程显著改善了液相密度表征效果。对混合物的密度计算结果与实验数据进行对比,对于R1234yf+CO₂二元混合体系方程与实验数据相对均方根偏差为1.17%,对于R1234ze（E）+CO₂二元混合体系相对均方根偏差为0.82%。结果显示,采用温度相关比容平移项的VTSRK方程应用于R1234yf和R1234ze（E）纯流体以及R1234yf+CO₂和R1234ze（E）+CO₂密度性质计算,可获得较高精度。