An NMR study of hydrofluorocarbon mixed-gas solubility and self-diffusivity in the ionic liquid 1-ethyl-3-methylimidazolium dicyanamide

IF 2.8 3区 工程技术 Q3 CHEMISTRY, PHYSICAL
Miguel Viar , Fernando Pardo , Gabriel Zarca , Leoncio Garrido , Ane Urtiaga
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Abstract

To date, the design of advanced separation processes, such as the extractive distillation with ionic liquids (ILs), for the separation of common close-boiling refrigerant blends relies almost exclusively on binary equilibrium data obtained for single-gas/solvent systems, thus neglecting the influence of possible mixture effects. In this work, Nuclear Magnetic Resonance (NMR) spectroscopy and pulsed gradient spin echo (PGSE) NMR are proposed for the sequential assessment of the single and mixed-gas vapor-liquid equilibrium and self-diffusivity of two fluorinated refrigerants, difluoromethane (R-32) and pentafluoroethane (R-125), in the IL 1-ethyl-3-methylimidazolium dicyanamide at 303.1 K and pressures up to 4 bar, either as pure R-32 or using the commercial refrigerant blend R-410A. The results confirmed that the mixed-gas solubility and self-diffusivities were essentially equal to those obtained with pure feed gas, thus significant mixing effects were not observed for this particular system. However, an increase in the self-diffusion coefficients was observed with the concentration of absorbed gas, which was more significant for the smallest hydrofluorocarbon (R-32) than for R-125. This technique also allowed evaluating the mobility of the IL moieties, which was slightly higher for the IL anion. Moreover, the self-diffusion coefficients of the IL ions also increased with the amount of gas absorbed, yet less markedly than for the refrigerants. Overall, the NMR technique proved to be an accurate method for the rapid screening of possible mixture effects in equilibrium and transport properties of refrigerant and IL systems, thus providing essential information for designing novel advanced separation processes.

Abstract Image

氢氟碳化合物在离子液体1-乙基-3-甲基咪唑双氰酰胺中混合气体溶解度和自扩散率的核磁共振研究
迄今为止,用于分离常见近沸点制冷剂混合物的先进分离工艺(如离子液体萃取精馏)的设计几乎完全依赖于单一气体/溶剂系统获得的二元平衡数据,从而忽略了可能的混合效应的影响。在这项工作中,提出了核磁共振(NMR)波谱和脉冲梯度自旋回波(PGSE) NMR序列评估两种含氟制冷剂,二氟甲烷(R-32)和五氟乙烷(R-125),在303.1 K和压力高达4 bar的IL -1 -乙基-3-甲基咪唑双氰酰胺中,无论是纯R-32还是使用商业制冷剂混合R-410A,单一和混合气体汽液平衡和自扩散率。结果证实,混合气体的溶解度和自扩散率与纯原料气基本相等,因此在该特定体系中未观察到明显的混合效应。然而,自扩散系数随吸收气体浓度的增加而增加,对最小的氢氟烃(R-32)比R-125更为显著。该技术还可以评估IL部分的迁移率,IL阴离子的迁移率略高。此外,IL离子的自扩散系数也随气体吸收量的增加而增加,但不如制冷剂明显。总的来说,核磁共振技术被证明是一种准确的方法,可以快速筛选制冷剂和IL系统的平衡和输运特性中可能的混合效应,从而为设计新的先进分离工艺提供必要的信息。
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来源期刊
Fluid Phase Equilibria
Fluid Phase Equilibria 工程技术-工程:化工
CiteScore
5.30
自引率
15.40%
发文量
223
审稿时长
53 days
期刊介绍: Fluid Phase Equilibria publishes high-quality papers dealing with experimental, theoretical, and applied research related to equilibrium and transport properties of fluids, solids, and interfaces. Subjects of interest include physical/phase and chemical equilibria; equilibrium and nonequilibrium thermophysical properties; fundamental thermodynamic relations; and stability. The systems central to the journal include pure substances and mixtures of organic and inorganic materials, including polymers, biochemicals, and surfactants with sufficient characterization of composition and purity for the results to be reproduced. Alloys are of interest only when thermodynamic studies are included, purely material studies will not be considered. In all cases, authors are expected to provide physical or chemical interpretations of the results. Experimental research can include measurements under all conditions of temperature, pressure, and composition, including critical and supercritical. Measurements are to be associated with systems and conditions of fundamental or applied interest, and may not be only a collection of routine data, such as physical property or solubility measurements at limited pressures and temperatures close to ambient, or surfactant studies focussed strictly on micellisation or micelle structure. Papers reporting common data must be accompanied by new physical insights and/or contemporary or new theory or techniques.
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