Moya Cristian, Alonso-Morales Noelia, de Riva Juan, Morales-Collazo Oscar, Brennecke Joan F, Palomar Jose
Sección de Ingeniería Química (Dpto. Química Física Aplicada) , Universidad Autónoma de Madrid , 28049 Madrid , Spain.
McKetta Department of Chemical Engineering , University of Texas at Austin , Austin , Texas 78712-1589 , United States.
J Phys Chem B. 2018 Mar 8;122(9):2616-2626. doi: 10.1021/acs.jpcb.7b12137. Epub 2018 Feb 28.
The performance of an ionic liquid with an aprotic heterocyclic anion (AHA-IL), trihexyl(tetradecyl)phosphonium 2-cyanopyrrolide ([P][2-CNPyr]), for CO capture has been evaluated considering both the thermodynamics and the kinetics of the phenomena. Absorption gravimetric measurements of the gas-liquid equilibrium isotherms of CO-AHA-IL systems were carried out from 298 to 333 K and at pressures up to 15 bar, analyzing the role of both chemical and physical absorption phenomena in the overall CO solubility in the AHA-IL, as has been done previously. In addition, the kinetics of the CO chemical absorption process was evaluated by in situ Fourier transform infrared spectroscopy-attenuated total reflection, following the characteristic vibrational signals of the reactants and products over the reaction time. A chemical absorption model was used to describe the time-dependent concentration of species involved in the reactive absorption, obtaining kinetic parameters (such as chemical reaction kinetic constants and diffusion coefficients) as a function of temperatures and pressures. As expected, the results demonstrate that the CO absorption rate is mass-transfer-controlled because of the relatively high viscosity of AHA-IL. The AHA-IL was encapsulated in a porous carbon sphere (Encapsulated Ionic Liquid, ENIL) to improve the kinetic performance of the AHA-IL for CO capture. The newly synthesized AHA-ENIL material was evaluated as a CO sorbent with gravimetric absorption measurements. AHA-ENIL systems preserve the good CO absorption capacity of the AHA-IL but drastically enhance the CO absorption rate because of the increased gas-liquid surface contact area achieved by solvent encapsulation.
已从现象的热力学和动力学两方面评估了具有非质子杂环阴离子的离子液体(AHA-IL)——三己基(十四烷基)鏻2-氰基吡咯烷鎓([P][2-CNPyr])用于捕获CO的性能。在298至333K以及高达15巴的压力下,对CO-AHA-IL系统的气液平衡等温线进行了吸收重量法测量,如之前所做的那样,分析了化学吸收和物理吸收现象在AHA-IL中CO整体溶解度中的作用。此外,通过原位傅里叶变换红外光谱-衰减全反射法评估了CO化学吸收过程的动力学,跟踪反应时间内反应物和产物的特征振动信号。使用化学吸收模型来描述反应吸收中所涉及物质随时间变化的浓度,获得了作为温度和压力函数的动力学参数(如化学反应动力学常数和扩散系数)。正如预期的那样,结果表明由于AHA-IL的粘度相对较高,CO吸收速率受传质控制。将AHA-IL封装在多孔碳球中(封装离子液体,ENIL)以提高AHA-IL捕获CO的动力学性能。通过重量吸收测量对新合成的AHA-ENIL材料作为CO吸附剂进行了评估。AHA-ENIL系统保留了AHA-IL良好的CO吸收能力,但由于溶剂封装增加了气液表面接触面积,极大地提高了CO吸收速率。