离子液体[Bmim][NTf2]对CO2在碳酸二乙酯中溶解性能的强化

采用恒定容积法在温度范围308.15~328.15 K、压力范围0~3 MPa条件下测定了CO₂在碳酸二乙酯（DEC）、离子液体[Bmim][NTf₂]以及二者不同质量分数配比混合溶剂中的溶解度,并用COSMO-RS模型研究了离子液体的加入对DEC蒸气分压的影响。实验表明,在相同实验条件下CO₂在[Bmim][NTf₂]中的溶解度大于在DEC中的溶解度。[Bmim][NTf₂]的加入可强化CO₂在DEC中的溶解性能,在相同温度下CO₂在混合溶剂中的溶解度随[Bmim][NTf₂]质量分数增加而增大,在相同浓度的混合溶剂中CO₂的溶解度随温度升高而降低。COSMO-RS模型计算表明,DEC的蒸气分压下降的分数随混合溶剂中离子液体质量分数增加而增大,而对于相同质量分数配比的混合溶剂温度对DEC的蒸气分压影响较小。     

Solubility of CO2 in three cellulose-dissolving ionic liquids

The solubility of CO₂ in three cellulose-dissolving ionic liquids (1-ethyl-3-methylimidazolium diethylphosphate, [Emim][DEP], 1-allyl-3-methylimidazolium chloride, [Amim][Cl], and 1-butyl-3-methylimidazolium chloride, [Bmim][Cl]) at temperatures within 298 and 356 K and pressures up to 6.5 MPa was determined using a Van Ness-type apparatus (static isochoric). It was demonstrated that this device can work in isothermal and isoplethal modes, being the latter faster and more precise. Moreover, it was possible to determine CO₂ solubilities in metastable liquid [Bmim][Cl]. Experimental data were modeled using the Extended Henry's law correlation and the group contribution equation of state. New parameters for the binary interaction of CO₂ with ionic liquid groups were calculated.     

Investigation of Ternary Mixtures Containing 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)azanide,Ethylene Carbonate and Lithium Bis(trifluoromethanesulfonyl)azanide

Temperature-dependent viscosity, conductivity and density data of ternary mixtures containing 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)azanide (EMIM-TFSA), ethylene carbonate (EC), and lithium bis(trifluoromethanesulfonyl)azanide (Li-TFSA) were determined at atmospheric pressure in the temperature range of 20 to 80 °C. Differential scanning calorimetry (DSC) measurements were performed to characterize phase conditions of the mixtures in a temperature range of −120 to +100 °C. The viscosity data were fitted according to the Vogel-Fulcher-Tammann-Hesse (VFTH) equation and analyzed with the help of the fractional Walden rule. In this study, fundamental physicochemical data about the mixtures are provided and discussed as a basis for structure-property relationship calculations and for potential use of those mixtures as electrolytes for various applications.     

Bis(trifluoromethylsulfonyl)imide Ionic Liquids Applied for Fine-Tuning the Cure Characteristics and Performance of Natural Rubber Composites

The goal of this work was to apply ionic liquids (ILs) with bis(trifluoromethylsulfonyl)imide anion (TFSI) for fine-tuning the cure characteristics and physico-chemical properties of elastomer composites based on a biodegradable natural rubber (NR) matrix. ILs with TFSI anion and different cations, such as alkylpyrrolidinium, alkylammonium, and alkylsulfonium cations, were applied to increase the efficiency of sulfur vulcanization and to improve the performance of NR composites. Thus, the influence of ILs on the vulcanization of NR compounds, as well as crosslink density and physical properties of NR vulcanizates, including tensile properties, thermal stability, and resistance to thermo-oxidative aging was explored. The activity of ILs seems to be strongly dependent on their cation. Pyrrolidinium and ammonium ILs effectively supported the vulcanization, reducing the optimal vulcanization time and temperature of NR compounds and increasing the crosslink density of the vulcanizates. Consequently, vulcanizates with these ILs exhibited higher tensile strength than the benchmark without IL. On the other hand, sulfonium ILs reduced the torque increment owing to the lower crosslinking degree of elastomer but significantly improved the resistance of NR composites to thermo-oxidation. Thus, TFSI ILs can be used to align the curing behavior and performance of NR composites for particular applications.     

Charging/discharging kinetics of poly(3,4-ethylenedioxythiophene) in 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide ionic liquid under galvanostatic conditions

The constant current charging/discharging experiments of poly(3,4-ethylenedioxythiophene) (PEDOT), modified electrodes in room temperature ionic liquid, for instance 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide, were performed for two types of cell configurations, three and two-electrode cells. In each case, a linear variation of the voltage with respect to time was observed. The electrochemical responses were analyzed in term of a series combination of a resistance R and a capacitor C. Accordingly, the capacitance of the modified electrodes was determined. One observed a linear variation of the capacitance as a function of the amount of PEDOT. This capacitance described the chemical capacitance of PEDOT that reflected the capability of the system to accept or release additional charge carriers on a given variation of the chemical potential. Also, the electrochemical response during constant current charging/discharging experiments for two-electrode cell in which the same amount of PEDOT was deposited on each electrode showed a type I electrochemical supercapacitor response. This kind of an electrochemical chain allowed us to mimic and to analyze the electrical responses of an electrochemical actuator based on an interpenetrating polymer networks containing PEDOT that was able to work in air.     

CO2在磷酸三丁酯中溶解度的测定

采用恒定容积压降法测定了温度303.5~363.8 K、压力0.5~4.5 MPa条件下CO2在磷酸三丁酯(TBP)中的溶解度. 结果表明,CO2在TBP中的溶解度随压力升高而增大,但随平衡温度升高而减小;在0~4.5 MPa范围内,该溶解度较在工业常用物理吸收剂中更大,约为在乙醇中的2.4倍,甲醇中的1.4倍,N-甲基吡咯烷酮中的1.2倍及碳酸丙烯酯中的1.1倍. CO2以分子形式溶解于TBP中,TBP吸收CO2以物理吸收为主,TBP中含有的酯键及磷酰基团极大地促进了其对CO2的吸收.     

超临界CO2在聚合物中的溶解度和扩散性研究

用重量分析法测量了静态条件下CO2在聚苯乙烯(PS)中的溶解度,研究了溶解度与压力和温度的关系,估算了CO2在聚合物PS中的扩散系数。用Henry系数表示了溶解度与温度的关系。实验压力在5-30MPa范围、温度在40-200℃范围。实验数据表明:CO2在PS中的溶解度随着压力的增加而增加,但随着温度的增加而降低。CO2在PS中的扩散系数随饱和时间增加而增加。当吸附量达到一定值时,扩散系数呈下降趋势。     

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.     

Modeling of CO2 Solubility in Selected Imidazolium-Based Ionic Liquids

This study explores the use of COSMO-RS model and Peng-Robinson (PR) equation of state (EoS) to predict the solubility of carbon dioxide (CO₂) in specific ionic liquids (ILs). COSMO-RS was employed to estimate of CO₂ solubility at atmospheric pressure in eight imidazolium-based ILs resulting from the combination of ethyl, butyl, hexyl, and octyl-imidazolium cations with two anions: bis(trifluoromethylsulfonyl)imide ([Tf₂N]) and Trifluoromethanesulfonate ([TFO]). The results indicated relatively acceptable qualitative consistency between the experimental and predicted values. The PR EoS was employed at high pressure by tuning the interaction parameters to fit the experimental data reported in the literature. The model demonstrated excellent accuracy in predicting the solubility of CO₂ at pressure values less than the critical pressure of CO₂; however, at higher pressures, the calculated solubility diverged from the experimental values. Furthermore, the type of anion and cation used in the IL affected the performance of the PR EoS.     

Prediction of ethane and CO2 solubilities in heavy norma paraffins using generalized-parameter soave and peng-robinson equations of state

A study was made of the abilities of the Soave and Peng-Robinson equations to represent the phase behavior of ethane + n-paraffin and CO₂ + n-paraffin systems. These equations are capable of describing the phase behavior of such systems; however, the level of precision obtained varies with the degree of complexity used in representing the interaction parameters in the mixing rules employed. For ethane/C0₂ with n-paraffins extending from C₃ to n-C₄₄, an uncertainty of about 1 % is obtained for bubble point pressures (or about 0.005 mole fraction for solubilities) when two system-specific interaction parameters per isotherm are used. Simple generalized correlations are presented for the equation-of-state interaction parameters which allow prediction of the bubble point pressures with an expected uncertainty of about 5.7% (0.014 in mole fraction).     

离子液体中电化学还原CO2研究评述与展望

近百年来,伴随着矿石燃料的大量消耗,CO₂的排放量剧增,引发了全球性的生态环境和社会问题。CO₂同时也是廉价且可再生的碳资源,可作为生产醇、醚、酸、酯等重要化工品的原料。在众多吸引力十足的CO₂利用路线中,作为清洁、可控的反应过程,电化学还原固定CO₂技术在温和条件下生产化学品方面具有独特的优势。离子液体以其特有的性质被广泛用于电化学还原CO₂过程,本文对目前国内外离子液体介质中电化学还原CO₂的研究现状进行了综述,介绍了离子液体介质中电化学还原CO₂的主要反应及基本原理;针对离子液体对CO₂高效活化和转化等关键科学问题进行深入探讨,提出新型功能化离子液体的应用将成为CO₂电化学还原领域的发展方向和热点。     

Polyurethane-based poly (ionic liquid)s for CO2 removal from natural gas

Carbon dioxide separation from CH₄ is important to the environment and natural gas processing. Poly (ionic liquid)s (PILs) based on polyurethane structures are considered as potential materials for CO₂ capture. Thus, a series of anionic PILs based on polyurethane were synthesized. The effects of polyol chemical structure and counter-cations (imidazolium, phosphonium, ammonium, and pyridinium) in CO₂ sorption capacity and CO₂/CH₄ separation performance were evaluated. The synthesized PILs were characterized by NMR, DSC, TGA, dinamical mechanical thermo analysis (DMTA), SEM, and AFM. CO₂ sorption, reusability, and CO₂/CH₄ selectivity were assessed by the pressure-decay technique. The counter-cation and polyol chemical structure play an important role in CO₂ sorption and CO₂/CH₄ selectivity. PILs exhibited competitive thermal mechanical properties. Results showed that PILPC-TBP was the best poly (ionic liquid) for CO₂/CH₄ separation. Moreover, poly (liquid ionic) base polyol (polycarbonate) with phosphonium (PILPC-TBP) demonstrated higher CO₂ sorption capacity (21.4 mgCO₂/g at 303.15 K and 0.08 MPa) as compared to other reported poly (ionic liquids). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47536.     

High-pressure phase behavior of carbon dioxide in ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Phase equilibrium data of carbon dioxide in the ionic liquid 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf₂N]) are presented at high pressures up to about 30 MPa and at temperatures between 298.15 K and 343.15 K. The solubilities at a given temperature were determined by measuring the bubble point pressure of the ionic liquid solution with carbon dioxide dissolved using the high-pressure equilibrium apparatus equipped with a variable-volume view cell. Solubility results are reported for carbon dioxide concentrations ranging from 0.21 up to 0.80 mole fraction. Carbon dioxide gave very high solubilities in the ionic liquid at lower pressures, while the equilibrium pressure increased very steeply at higher concentrations of carbon dioxide. The solubility of carbon dioxide in the ionic liquid decreased with an increase in temperature.     

碱性离子液体-NaOH/MEA混合体系的CO2吸收性能

为了改善有机醇胺与无机碱液对生物质燃气中CO2的吸收性能,制备了具有代表性的4种功能化离子液体:[TMG]+ [C3H4N2]-、[TMG]+[TFEA]-、[MEA]+[BF4]-、[MEA]+[CHOO]-,并按一定的比例分别与NaOH溶液和乙醇胺(MEA)溶液复配组成新型CO2吸收剂,以研究其对CO2的吸收特性.实验结果显示,MEA-[TMG]+[C3H4N2]-、MEA-[MEA]+[CHOO]-和NaOH-[MEA]+[CHOO]-对CO2的吸收去除率高于单纯的MEA和NaOH溶液,而MEA-[TMG]+[TFEA]-、MEA-[MEA]+[BF4]-和NaOH-[MEA]+[BF4]-对CO2的去除率则低于单纯碱液吸收剂.同时发现,当离子液体[MEA]+[CHOO]-与MEA的混合比例为2∶3时,混合溶剂对CO2的吸收效果比MEA溶液的显著提高,生物质燃气中CO2去除率从91.3％增加至95.7％.     

溢流法测定超临界CO_2在聚己酸内酯中的溶解

以超临界CO2作为溶剂,采用溢流法研究聚己酸内酯(PCL)在CO2中的溶胀过程和超临界CO2/PCL体系的热力学平衡规律。考察了温度、压力对溶解度的变化趋势,分析加入有机溶剂后对CO2在聚合物中的溶解度的影响,并应用P-T(Patel-Teja)方程作为热力学模型分析和计算溶解规律。结果表明:CO2的溶解度随温度升高而降低,随压力增大而增大,有机溶剂的加入能够进一步提高CO2的溶解度,在相同的温度压力条件下,加入相当于CO2质量的2.26%的二氯甲烷,最多可使溶解度增加28.06%。在温度313.15—353.15 K、压力10—20 MPa范围内,P-T方程能较好地预测CO2在PCL中的溶解度,其相对误差在-12.53%—12.01%。     

基于半经验模型的CO_2在聚合物中的溶解度计算

为了评价CO2在聚合物中溶解度计算的5种半经验模型,通过计算CO2在10种聚合物中溶解度的误差平均值和标准差,比较了各个模型的性能。结果表明:预测效果的主要影响因素是模型方程式复杂程度及方程式的变量。从预测结果看,A-L模型优于Chrastil模型及其修正的密度型模型;5种模型中,Gordillo模型的预测精度及预测稳定性较好。     

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.     

Optimal Design Issues of a Methanol Synthesis Reactor from CO2 Hydrogenation

Methanol production through CO₂ hydrogenation was investigated in a series of fixed-bed reactors. Staging of the reactor into several smaller reactors is considered to enhance methanol production, in addition to maximizing a measure of annual profit. The degrees of freedom of the reactor system are the number of stages, the cooling medium temperature, the heat transfer area, and the volume of the stages. Depending on the objective function (OF) criteria, staging of the reactor increases the OF values to various extents. When the objective is to maximize the methanol production, the OF of a three-stage reactor system with an inlet H₂/CO₂ ratio of 2 is 2.61 % higher than in the single-stage configuration. Staging of the reactor also increases the synthesis gas conversion to methanol. However, if maximizing the annual profit is the objective, the profitability of the two-stage configuration is 2.05 % greater than in the case with one reactor, due to the higher methanol production of the staged reaction system.     

[EMIM]HSO4离子液体的合成及其在氧化铝电解中的应用

以N-甲基咪唑为原料合成了[EMIM]HSO4离子液体,采用红外光谱、核磁氢谱和热分析对产物进行了表征,并测定了与电解相关的物理性质,如密度、表面张力、粘度和电导率等,通过研究Al2O3在[EMIM]HSO4离子液体中的溶解度和电化学行为,探讨了其直接电解的可能性. 结果表明,[EMIM]HSO4在加热至270℃前比较稳定,密度和粘度均随温度升高而减小,在100℃时摩尔电导率为2.890 S×cm2/mol,满足电解质要求. 20℃时测得Al2O3在[EMIM]HSO4中的溶解度为3.81 g/L,满足直接电沉积对溶解度的要求. Al2O3在Pt电极上能发生电沉积,在-0.26 V发生铝的欠电位沉积,-0.54 V发生铝的沉积,电解过程受扩散控制.