CO2/N2 separation using supported ionic liquid membranes with green and cost-effective [Choline][Pro]/PEG200 mixtures

The high price and toxicity of ionic liquids(ILs) have limited the design and application of supported ionic liquid membranes(SILMs) for CO_2 separation in both academic and industrial fields. In this work, [Choline][Pro]/polyethylene glycol 200(PEG200) mixtures were selected to prepare novel SILMs because of their green and costeffective characterization, and the CO_2/N_2 separation with the prepared SILMs was investigated experimentally at temperatures from 308.15 to 343.15 K. The temperature effect on the permeability, solubility and diffusivity of CO_2 was modeled with the Arrhenius equation. A competitive performance of the prepared SILMs was observed with high CO_2 permeability ranged in 343.3–1798.6 barrer and high CO_2/N_2 selectivity from 7.9 to 34.8.It was also found that the CO_2 permeability increased 3 times by decreasing the viscosity of liquids from 370 to38 m Pa·s. In addition, the inherent mechanism behind the significant permeability enhancement was revealed based on the diffusion-reaction theory, i.e. with the addition of PEG200, the overall resistance was substantially decreased and the SILMs process was switched from diffusion-control to reaction-control.     

胆碱脯氨酸/RTILs支撑液膜的CO2/N2分离性能

选用不同种类的室温型离子液体（RTILs）与胆碱脯氨酸离子液体进行混合分别制得[Choline][Pro]/[EMIm][N（CN）₂]、[Choline][Pro]/[bmim][PF₆]以及[Choline][Pro]/[HMIm][NTf₂]混合离子液体,并将其应用于离子液体支撑液膜（SILMs）。考察操作温度、操作压差、RTILs种类和含量对SILMs分离CO₂/N₂性能的影响。结果表明胆碱脯氨酸/RTILs系列SILMs的CO₂通量在343.3～1936.9 barrer之间变化并且CO₂/N₂选择性为10.3～34.8。对CO₂膜过程内在机制探索表明随着[HMIm][NTf₂]离子液体在混合离子液体中比例的增加,总阻力1/K_m会呈现先降低后升高的趋势。与实验现象中随着[HMIm][NTf₂]离子液体在混合离子液体中比例的增加CO₂先升高后降低相符。     

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。     

新型聚离子液体的制备及其捕获CO_2性能研究

CO2的捕获和封存是当前关注的重要问题。采用自由基聚合制备了一种新型聚离子液体,聚四亚乙基五胺丙烯酸盐(PTEPAA),并对其捕获CO2性能进行了研究。结果表明,PTEPAA捕获CO2具有捕获容量高、速度快、高度可逆的特点,在低温捕获的CO2可以在高温下有效解吸,捕获/解吸过程可以重复进行,PTEPAA可再生。每个捕获/解吸循环,每克PTEPAA可以分离大约0.24克CO2。PTEPAA作为一种新型固态CO2捕获材料,在烟气及燃气脱碳领域表现出良好的应用潜力。     

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。     

Mass‐transfer rate enhancement for CO2 separation by ionic liquids: Theoretical study on the mechanism

To promote the development of ionic liquid (IL) immobilized sorbents and supported IL membranes (SILMs) for CO₂ separation, the kinetics of CO₂ absorption/desorption in IL immobilized sorbents was studied using a novel method based on nonequilibrium thermodynamics. It shows that the apparent chemical‐potential‐based mass‐transfer coefficients of CO₂ were in three regions with three‐order difference in magnitude for the IL‐film thicknesses in microscale, 100 nm‐scale, and 10 nm‐scale. Using a diffusion‐reaction theory, it is found that by tailoring the IL‐film thickness from microscale to nanoscale, the process was altered from diffusion‐control to reaction‐control, revealing the inherent mechanism for the dramatic rate enhancement. The extension to SILMs shows that the significant improvement of CO₂ flux can be obtained theoretically for the membranes with nanoscale IL‐films, which makes it feasible to implement CO₂ separation by ILs with low investment cost. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4437–4444, 2015     

Improving Physical Adsorption of CO2 by Ionic Liquids‐Loaded Mesoporous Silica

CO₂ sorption capacities of the neat and silica‐supported 1‐butyl‐3‐methylimidazolium‐based ionic liquids (ILs) were measured under atmospheric pressure. The silica‐supported ILs were synthesized by the impregnation‐vaporization method and charactrized by N₂ adsorption/desorption and thermogravimeteric analysis (TGA). Evaluation of the effects of influential factors on sorption capacity demonstrated that by increase of the temperature, flow rate, and the weight percentage of ILs in sorbents, the sorption capacity decreases. Among the sorbents, [Bmim][TfO] and SiO₂‐[Bmim][BF₄](50) had the highest capacity. By increasing the IL portion in SiO₂‐[Bmim][BF₄], the selectivity for CO₂ to CH₄ could be improved. The CO₂‐rich sorbents could be easily recycled.     

离子液体水溶液-气体水合物对CO2的双捕获工艺

设计了以离子液体[APMIM]Br水溶液吸收-生成水合物捕获CO2工艺流程,并利用CO2在该离子水溶液中的溶解度数据和在其中生成CO2水合物的相平衡实验数据进行物料衡算. 考察了水含量、压力和液气流量比对气体吸收-水合物生成的CO2双重捕获效果的影响,对比了气体水合物与离子液体水溶液捕获CO2的能力. 结果表明,在较高压力和水含量条件下,水合物捕获CO2的效应强于离子液体溶液;较低压力下离子液体溶液吸收CO2起主要作用. 与纯水合物法相比,双捕获工艺具有一定优势,且突破了单纯水合物脱碳的压力和CO2含量要求高的局限性. 当原料气中CO2低于65%(j)时,系统的脱碳效率低于40%,对于CO2含量较低的气体,其CO2的脱除性能回归至单纯离子液体溶液体系.     

Membranes for CO2 /CH4 and CO2/N2 Gas Separation

Membrane technology has emerged as a leading tool worldwide for effective CO₂ separation because of its well-known advantages, including high surface area, compact design, ease of maintenance, environmentally friendly nature, and cost-effectiveness. Polymeric and inorganic membranes are generally utilized for the separation of gas mixtures. The mixed-matrix membrane (MMM) utilizes the advantages of both polymeric and inorganic membranes to surpass the trade-off limits. The high permeability and selectivity of MMMs by incorporating different types of fillers exhibit the best performance for CO₂ separation from natural gas and other flue gases. The recent progress made in the field of MMMs having different types of fillers is emphasized. Specifically, CO₂/CH₄ and CO₂/N₂ separation from various types of MMMs are comprehensively reviewed that are closely relevant to natural gas purification and compositional flue gas treatment     

Separation of N2O and CO2 using Room-Temperature Ionic Liquid [bmim][Ac]

We have developed a ternary equation of state (EOS) model for the N₂O/CO₂/1-butyl-3-methylimidazolium acetate ([bmim][Ac]) system in order to understand the separation of N₂O and CO₂ using room-temperature ionic liquids (RTILs). The present model is based on a generic RK (Redlich-Kwong) EOS, with empirical interaction parameters for each binary system. The interaction parameters have been determined using our measured VLE (vapor-liquid-equilibrium) data for N₂O/[bmim][Ac] and literature data for CO₂/[bmim][Ac] and N₂O/CO₂. The binary EOS model for the N₂O/[bmim][Ac] system correctly predicted the liquid-liquid phase separation found in VLLE experiments. The validity of the ternary EOS model has been checked by conducting VLE experiments for the N₂O/CO₂/[bmim][Ac] system over a temperature range from 296 to 313 K. With this EOS model, solubility (VLE) behavior has been calculated for various (T, P, and feed compositions) conditions. Over a range of N₂O/CO₂ feed ratios, the N₂O/CO₂ gas selectivity [α _{N 2 O/CO 2}  = (y _{N 2 O} /x _{N 2 O} )/(y _{CO 2} /x _{CO 2} )] increases by at least 5 orders of magnitude when adding [bmim][Ac] (α = 1 × 10² to 1 × 10⁷), compared with the absence of the ionic liquid (α = 0.96 to 0.98). The addition of [bmim][Ac] may provide a practical means of separating CO₂ and N₂O.

Supplemental materials are available for this article. Go to the publisher's online edition of Separation Science and Technology to view the free supplemental file.     

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.     

Design of Functionalized Room-Temperature Ionic Liquid-Based Materials for CO2 Separations and Selective Blocking of Hazardous Chemical Vapors

The design and synthesis of several new types of functionalized room-temperature ionic liquids (RTILs), ionic polymers based on RTILs (i.e., poly(RTIL)s), poly(RTIL)-RTIL solid-liquid composites, and gelled RTIL systems for gas separations and reactive vapor transport applications are presented. The design concepts behind these new RTIL materials are discussed in the context of first, CO₂ removal from CH₄ and N₂ for natural gas purification and greenhouse gas reduction, respectively; and second selective blocking or sorption of chemical warfare agent simulant and toxic industrial compound vapors from water vapor for protection applications. The role of the RTIL components and their unique properties in these two separations areas will be highlighted.     

Mass Transfer Analysis of CO2 Capture by PVDF Membrane Contactor and Ionic Liquid

Post‐combustion processes based on ionic liquids (ILs) and membrane contactors are attractive alternatives to traditional systems. Here, a gas stream composed of 15 % CO₂ and 85 % N₂ flowed through the lumen side of a hollow‐fiber membrane contactor containing poly(vinylidene fluoride)‐IL (PVDF‐IL) fibers. The IL 1‐ethyl‐3‐methylimidazolium acetate [emim][Ac] served as an absorbent due to its high chemical absorption and CO₂ solubility. The overall mass transfer coefficient (K_overall), activation energy (E_a), and resistances of the hollow‐fiber membrane were quantified. The K_overall value was one order of magnitude higher than those reported in previous works with conventional solvents, and the E_a was lower than formerly stated values for other solvents. A theoretical simulation was conducted to estimate the operational parameters required for 90 % CO₂ capture and to quantify intensification effects related to CO₂ absorption in a packed column.     

Low-pressure CO2 sorption in ammonium-based poly(ionic liquid)s

Ammonium-based ionic liquid monomers and their corresponding polymers [poly(ionic liquid)s] are synthesized and characterized for CO₂ sorption. The polymers have much higher CO₂ sorption capacities than the room-temperature ionic liquids and imidazolium-based poly(ionic liquid)s. For example, P[VBTMA][PF₆] with polystyrene backbone has a CO₂ sorption capacity of 10.67 mol%. The CO₂ sorption is selective over N₂ and O₂. The effects of cation, backbone, substituent, anion and crosslinking on CO₂ sorption are discussed. The sorption mechanism study indicates that CO₂ sorption by the poly(ionic liquid)s is a bulk and surface phenomenon.     

接枝型聚离子液体聚砜膜制备及CO2分离性能 （着急）

聚离子液体是一种具有较高CO2选择性的新型膜材料,然而,由于可聚合离子液体的种类少、价格昂贵,难以实现工业应用。对此,本文提出以商业化芳族聚合物聚砜（PSf）为基础材料,通过简单可控的氯甲基化和咪唑鎓化反应,制备接枝型聚离子液体—咪唑鎓化聚砜（PSf-g-[MIm][Cl]）膜。研究了咪唑鎓化程度、操作温度、操作压力对膜性能的影响,结果表明该膜材料具有较好的压力稳定性,并且咪唑鎓（MIm）基团含量会极大的影响其性能,随着咪唑鎓化程度的增加,膜内MIm基团逐渐形成连续的传递通道,CO2渗透系数和选择性显著提高。本文制备的聚离子液体,咪唑鎓化程度最高达172%,具有良好的成膜性,在25 ℃、0.4 MPa以及增湿条件下进行测试,CO2渗透系数达到66.4 barrer,CO2/N2选择性为118.4。     

Synthesis and optimization of high-performance amine-based polymer for CO2 separation

Membrane technology features inspiring excellence from numerous separation technologies for CO₂ capture from post-combustion gas. Polyvinylamine (PVAm)-based facilitated transport membranes show significantly high separation performance, which has been proven promising for industrial scale-up. However, commercialized PVAm with low molecular weight and excessive crystallinity is not available to prepare high-performance membranes. Herein, the synthesis process of PVAm was optimized by regulating polymerization and acidic hydrolytic conditions. The membranes based on PVAm with a molecular weight of 154 kDa and crystallinity of 11.37% display high CO₂ permeance of 726 GPU and CO₂/N₂ selectivity of 55 at a feed gas pressure of 0.50 MPa. Furthermore, we established a PVAm synthesis reactor with an annual PVAm solution (1%(mass)) capacity of over 7000 kg and realized the scaled-up manufacture of both PVAm and composite membranes.     

Adsorption and separation of CO2/N2 and CO2/CH4 by 13X zeolite

Accumulation of greenhouse gases in the atmosphere is responsible for increased global warming of our planet. The increasing concentration of carbon dioxide mainly from flue gas, automobile and landfill gas (LFG) emissions are major contributors to this problem. In this work, CO₂, CH₄ and N₂ adsorption was studied on Ceca 13X zeolite by determining pure and binary mixture isotherms using a constant volume method and a concentration pulse chromatographic technique at 40 and 100°C. The experimental data were then compared to the predicted binary behaviour by extended Langmuir model. Results showed that the extended Langmuir theoretical adsorption model can only be applied as an approximation to predict the experimental binary behaviour for the systems studied. Equilibrium phase diagrams were obtained from the experimental binary isotherms. For these systems, the integral thermodynamic consistency tests were also conducted. It was found that Ceca 13X exhibits large CO₂/CH₄ and CO₂/N₂ selectivity and could find application in landfill gas purification, CO₂ removal from natural gas and CO₂ removal from ambient air or flue gas streams. © 2011 Canadian Society for Chemical Engineering     

CO2/N2开关微乳液及其油污洗涤和分离性能

采用等摩尔的十二烷基苯磺酸钠与N-十二烷基-N,N-二甲基叔胺为主乳化剂,正丁醇为助乳化剂,正庚烷为油相,制得O/W型微乳液。在CO_2/N_2交替作用下,可实现微乳液-相分离-微乳液的可逆转换;原始微乳液与复原微乳液半径分别为(10.89±0.21)和(11.50±0.47)nm。该微乳液对多孔固体和织物表面烃类矿物油的洗油率分别为99.13%±0.32%和98.30%±0.28%,对油砂表面原油的洗油率为54.52%±0.25%。活性物质量分数相等时,微乳稀释液对织物表面油性记号笔渍的去污力是市售洗衣粉的1.90倍;而微乳原液的去污力是市售洗衣粉的2.02倍。洗后含油废液通入CO_2可迅速实现油水分层,分离油相后的残余水相经阴、阳离子交换树脂和活性炭常规处理,COD和TOC分别为40.62和17.51 mg/L,符合GB 18918-2002中一级水排放标准(COD≤100 mg/L,TOC≤20 mg/L)。     

Development of ethanolamine‐based ionic liquid membranes for efficient CO2/CH4 separation

This study is focused on the development of ionic liquids (ILs) based polymeric membranes for the separation of carbon dioxide (CO₂) from methane (CH₄). The advantage of ILs in selective CO₂ absorption is that it enhances the CO₂ selective separation for the ionic liquid membranes (ILMs). ILMs are developed and characterized with two different ILs using the solution‐casting method. Three different blend compositions of ILs and polysulfone (PSF) are selected for each ILMs 10, 20, and 30 wt %. Effect of the different types of ILs such as triethanolamine formate (TEAF) and triethanolamine acetate (TEAA) are investigated on PSF‐based ILMs. Field emission scanning electron microscopy analysis of the membranes showed reasonable homogeneity between the ILs and PSF. Thermogravimetric analysis showed that by increasing the ILs loading thermal stability of the membranes improved. Mechanical analysis on developed membranes showed that ILs phase reduced the amount of plastic flow of the PSF phase and therefore, fracture takes place at gradually lower strains with increasing ILs content. Gas permeation evaluation was carried out on the developed membranes for CO₂/CH₄ separation between 2 bar to 10 bar feed pressure. Results showed that CO₂ permeance increases with the addition of ILs 10–30 wt % in ILMs. With 20–30 wt % TEAF‐ILMs and TEAA‐ILMs, the highest selectivity of a CO₂/CH₄ 53.96 ± 0.3, 37.64 ± 0.2 and CO₂ permeance 69.5 ± 0.6, 55.21 ± 0.3 is observed for treated membrane at 2–10 bar. The selectivity using mixed gas test at various CO₂/CH₄ compositions shows consistent results with the ideal gas selectivity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45395.     

Stepped enhancement of CO2 adsorption and separation in IL-ZIF-IL composites with shell-interlayer-core structure

Development of materials with excellent separation performance remains an ongoing challenge in separation science and technology. Herein, a novel strategy was proposed to gradually enhance gas separation performance in micro/nano-materials, by constructing a shell-interlayer-core structure using ionic liquid (triethylenetetramine lactate, [TETA]L) and zeolitic imidazolate framework (ZIF-8). Such structure includes outer [TETA]L shell, interlayer of ZIF-8, and inner [TETA]L core, endowing the composite with more evident molecular sieving separation for CO₂ mixtures than the reported materials. A high CO₂ adsorption amount (1.53 mmol/g at 298 K and 1.0 bar) is maintained, while the uptakes for CH₄ and N₂ are very low. Corresponding ideal adsorbed solution theory selectivities are 260–1,990 and 1,688–5,572 for CO₂/CH₄ and CO₂/N₂ mixtures at the range of tested pressures. In addition, the separation performance can be controlled by varying the shell-interlayer-core structure with IL inside, outside or on both sides of ZIF-8 and the thickness of outer shell.