离子液体支撑液膜的CO2/CH4分离性能

由于离子液体对CO₂具有较好的溶解选择性,离子液体支撑液膜分离CO₂越来越受到关注。比较了含3种不同阴离子的常规离子液体([bmim][BF₄]、[bmim][PF₆]、[bmim][Tf₂N])作为支撑液膜的液膜相分离CO₂/CH₄的性能,考察了咪唑环上烷基链长对离子液体支撑液膜性能的影响。考虑向离子液体中引入胺基和羧基等亲CO₂基团,制备了1-丁基-3-甲基咪唑丙氨酸离子液体([bmim][β-Ala]),考察了 [bmim][β-Ala]支撑液膜分离CO₂/CH₄的性能,并对在CO₂渗透测试前后的支撑液膜进行了FT-IR分析,发现氨基酸离子液体中的-NH₂和CO₂的较强作用以及该离子液体的高黏性影响了CO₂的透过性,使[Bmim][β-Ala]支撑液膜的CO₂透过率低。     

离子液体二氧化碳分离膜研究进展

离子液体支撑液膜在较大跨膜压差（0.25～0.3MPa）下的稳定性较差,具有较好稳定性的聚离子液体膜和离子液体-聚合物共混膜等逐渐被关注。本文综述了离子液体支撑液膜、聚离子液体膜、离子液体?聚合物共混膜等离子液体膜CO2分离性能、分离机理及稳定性的最新研究进展,介绍了无机颗粒-离子液体-聚合物共混膜的研究现状。指出离子液体膜的高CO2渗透通量与高稳定性之间的矛盾、共混膜结构调控难等问题是其工业化应用的主要障碍,提出开发新的膜材料、改进制膜工艺以减小膜厚、优化膜结构是提高膜的CO2渗透和分离性能,并保持膜稳定性的有效途径。无机颗粒-离子液体-聚合物共混膜兼有较高的CO2分离性能和较好稳定性,具有良好的应用前景,对其制备方法、结构、性能及CO2分离机理的研究将成为这一领域的热点。     

用于CO2/CH4分离的cPIM-1/ZIF-8混合基质膜的制备

自聚微孔聚合物（PIM-1）虽具有良好的CO₂渗透性能,但其气体选择性普遍较差,限制其在CO₂/CH₄分离领域的应用。本文以N,N-二甲基甲酰胺（DMF）为溶剂制备ZIF-8纳米粒子,将其引入到羧基化的PIM-1基质中,制备了cPIM-1/ZIF-8混合基质膜,用于CO₂/CH₄分离。结果表明：由于合成ZIF-8的溶剂也是cPIM-1的良溶剂,使得两者之间具有良好的界面相容性,从而使ZIF-8添加量高达质量分数45%。随着ZIF-8添加量的增加,膜的CO₂渗透速率持续增加,CO₂/CH₄选择性呈现先上升后下降的趋势。当ZIF-8添加量为质量分数25%时,膜的CO₂/CH₄分离性能最好,即CO₂渗透系数为3942 Barrer,CO₂/CH₄选择性为18.7,较cPIM-1纯膜分别提高了 84%和43%,成功地超越了Robeson分离上限。     

Atmospheric CO2/CH4 permeability of EVA copolymer/SiO2 composite membrane for biogas purification

The CO₂ and CH₄ permeabilities of poly(ethylene-co-vinyl acetate) (EVA)/SiO₂ composite membrane were investigated at atmospheric pressure. The membranes were fabricated by compression molding and characterized by Fourier transformed infrared spectroscopy, differential scanning calorimetry, a universal testing machine, and a contact angle analyzer. The effect of vinyl acetate content (18–33 wt%) was evaluated for both single-gas and mixed-gas permeation systems. A non-pressurized homemade-permeation cell was used for the single-gas permeation of CO₂ and CH₄, while a tubular membrane was utilized for a continuous separation of CO₂/CH₄ mixture. CO₂ flux was readily increased (from 0.7 to 2.0 ml/m².s) with vinyl acetate content (18–33 wt%). The enhanced CO₂ permeability is attributed to the increase in polarity and also the decrease in crystallinity of the membrane. A satisfied gas separation selectivity (CO₂/CH₄) of 4.31 could be obtained from tubular membrane with 28 wt% VA content. The incorporation of SiO₂ as a filler (0.5–2.0 wt%) especially increased the membrane polarity and hence the CO₂ flux up to 6.0 ml/m².s. However, the CH₄ flux was not affected by VA and SiO₂ contents.     

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     

New high permeable polysulfone/ionic liquid membrane for gas separation

In this study, the effects of 1-Ethyl-3-methylimidazolium tetrafluoroborate ionic liquid on CO₂/CH₄ separation performance of symmetric polysulfone membranes are investigated. Pure polysulfone membrane and ionic liquid-containing membranes are characterized. Field emission scanning electron microscopy (FE-SEM) is used to analyze surface morphology and thickness of the fabricated membranes. Energy dispersive spectroscopy (EDS) and elemental mapping, Fourier transform infrared (FTIR), thermal gravimetric (TGA), X-ray diffraction (XRD) and Tensile strength analyses are also conducted to characterize the prepared membranes. CO₂/CH₄ separation performance of the membranes are measured twice at 0.3 MPa and room temperature (25 °C). Permeability measurements confirm that increasing ionic liquid content in polymer-ionic liquid membranes leads to a growth in CO₂ permeation and CO₂/CH₄ selectivity due to high affinity of the ionic liquid to carbon dioxide. CO₂ permeation significantly increases from 4.3 Barrer (1 Barrer=10^-10 cm³(STP)·cm·cm^-2·s^-1·cmHg^-1, 1cmHg=1.333kPa) for the pure polymer membrane to 601.9 Barrer for the 30 wt% ionic liquid membrane. Also, selectivity of this membrane is improved from 8.2 to 25.8. mixed gas tests are implemented to investigate gases interaction. The results showed, the disruptive effect of CH₄ molecules for CO₂ permeation lead to selectivity decrement compare to pure gas test. The fabricated membranes with high ionic liquid content in this study are promising materials for industrial CO₂/CH₄ separation membranes.     

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.     

Current Status and Future Prospect of Polymer‐Layered Silicate Mixed‐Matrix Membranes for CO2/CH4 Separation

The mixed‐matrix membrane (MMM), a state‐of‐the‐art polymer‐inorganic hybrid, is a relatively recent addition to the membrane family which adopts the synergistic advantages of the polymer and inorganic phase. Although marked improvement has been achieved by MMMs in CO₂/CH₄ separation, the development of a defect‐free structure to transcend the Robeson upper bound limit remains a challenge. In previous years, a number of inorganic materials with diverse nature have been studied for CO₂/CH₄ separation; however, layered silicates have not attracted much attention despite their superior thermal and mechanical properties. Analyses of the potential of using layered silicates as inorganic fillers in MMM fabrication for CO₂/CH₄ separation are reviewed. Additionally, the immediate challenges toward successful formation of layered silicate‐based MMM and future prospects are addressed.     

CO2/CH4 separation using inside coated thin film composite hollow fiber membranes prepared by interfacial polymerization

Carbon dioxide(CO_2) is greenhouse gas which originates primarily as a main combustion product of biogas and landfill gas. To separate this gas, an inside coated thin film composite(TFC) hollow fiber membrane was developed by interfacial polymerization between 1,3–cyclohexanebis–methylamine(CHMA) and trimesoyl chloride(TMC). ATR-FTIR, SEM and AFM were used to characterize the active thin layer formed inside the PSf hollow fiber. The separation behavior of the CHMA-TMC/PSf membrane was scrutinized by studying various effects like feed gas pressure and temperature. Furthermore, the influence of CHMA concentration and TMC concentration on membrane morphology and performance were investigated. As a result, it was found that mutually the CHMA concentration and TMC concentration play key roles in determining membrane morphology and performance. Moreover, the CHMA-TMC/PSf composite membrane showed good CO_2/CH_4 separation performance. For CO_2/CH_4 mixture gas(30/70 by volume) test, the membrane(PD1 prepared by CHMA 1.0% and TMC 0.5%) showed a CO_2 permeance of 25 GPU and the best CO_2/CH_4 selectivity of 28 at stage cut of 0.1. The high CO_2/CH_4 separation performance of CHMA-TMC/PSf thin film composite membrane was mostly accredited to the thin film thickness and the properties of binary amino groups.     

Development of thin‐film composite membranes for carbon dioxide and methane separation using sulfonated poly(phenylene oxide)

Novel membranes based on sulfonated poly (phenylene oxide) (SPPO) was developed. SPPO membranes in the hydrogen form were converted to metal ion forms. The effect of exchange with metal ions including monovalent (Li⁺, Na⁺, K⁺), divalent (Mg²⁺, Ba²⁺, Ca²⁺) and trivalent (Al³⁺) ions was investigated in terms of permeation rate and permeation rate ratios for CO₂ and CH₄ gases. Both dense homogeneous membranes and thin‐film composite (TFC) membranes were studied for their gas separation characteristics. The effect of membrane preparation conditions and operating parameters on the membrane performance were also investigated. The selectivity of the TFC membrane increased as the cationic charge density increased as a result of electrostatic cross‐linking. TFC membrane of very high selectivity was achieved by coating a thin layer of SPPO‐Mg on a PES substrate. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 735–742, 2000     

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/CH4高分子气体分离膜材料研究进展

气体膜分离法正在成为分离CO2/CH4体系的一项重要技术。概括介绍了该领域国内外的主要高分子膜材料的研究进展,重点介绍了聚酰亚胺膜和促进传递膜材料,并提出了膜材料的改进方向,以期为制得更好的膜提供帮助。     

金属有机骨架材料在CO2/CH4吸附分离中的研究进展

CO₂/CH₄分离能耗高是生物甲烷过程核心难题之一。金属有机骨架材料（metal organic frameworks,MOFs）由于其优异的CO₂吸附分离性能,被视为最具潜力的CO₂分离捕集材料,近年来引起了广泛的关注。本文结合沼气的特点和MOFs研究的最新进展,对MOFs材料在CO₂/CH₄吸附分离过程的相关实验研究工作进行了综述。     

An atomistic simulation towards molecular design of silica polymorphs nanoparticles in polysulfone based mixed matrix membranes for CO2/CH4 gas separation

Incorporation of inorganic fillers into Polysulfone (PSF) to constitute mixed matrix membranes (MMMs) has become a viable solution to prevail over limitations of the pristine materials in natural gas sweetening process. Nevertheless, preparation of MMMs without defects and empirical investigation of membrane that exhibits characteristic of improved CO₂/CH₄ separation performance at experimental scale are difficult that require prior knowledge on compatibility between the filler and polymer. A computational framework has been conducted to construct validated PSF based MMMs using silica (SiO₂) as inorganic fillers. It is known that nanosized SiO₂ can coexist in varying polymorph configurations (ie, α-Quartz, α-Cristobalite, α-Tridymite) but molecular simulation study of SiO₂ polymorphs to form MMMs is limited. Therefore, this work is a pioneering study to elucidate feasibility in facile utilization of polymorphs to improve gas separation performance of MMMs. Physical properties and gas transport behavior of the simulated PSF based MMMs with different SiO₂ polymorphs and loadings have been elucidated. The optimal MMM has been found to be PSF/25 wt% α-Cristobalite at 55°C. The success in molecular simulation has shed light on how computational tools can provide understandings at molecular level to elucidate compatibility between varying pristine materials to MMMs for natural gas processing.     

CO2/CH4 Separation by Adsorption using Nanoporous Metal organic Framework Copper‐Benzene‐1,3,5‐tricarboxylate Tablet

Equilibrium data for carbon dioxide and methane adsorption on nanoporous metal organic framework Cu‐BTC powder and tablets were measured in a magnetic suspension balance in the temperature range of 308–373 K and a pressure range of 0–7 bar and fitted with Langmuir model. The tablets adsorption loading is 0.63 mol kg^–1 for methane and 3.1 mol kg^–1 for carbon dioxide at 1 bar and 308 K, while these values are 0.77 and 3.9 mol kg^–1 for powder in the same conditions. Isosteric heats of adsorption were 22.8 and 15.0 kJ mol^–1 for carbon dioxide and methane, respectively, on both adsorbents, which indicates a strong adsorption of carbon dioxide. Also, single and binary breakthrough curves were measured in the same temperature range and atmospheric pressure by using Cu‐BTC tablets as adsorbent. A complete model was used in the simulation of breakthrough curves and good agreement was observed with experimental data.