Effect of Feed Composition on the Gas Separation Performance of Binary and Ternary Mixed Matrix Membranes

Binary and ternary component mixed matrix membranes comprised of zeolite 4A and p-nitroaniline (pNA) in the polycarbonate (PC) matrix were prepared and appraised in gas separation. For comparison, homogenous membranes of PC and PC/pNA membranes were also investigated. The membranes were utilized to separate binary mixtures of CO₂/CH₄, H₂/CH₄, and CO₂/N₂. The effect of feed composition on the separation performance of membranes was investigated. Separation factors and ideal selectivities were similar for the PC membrane. A similar trend was also observed with the PC/pNA membrane. The separation factors of the PC/pNA membrane for CO₂/CH₄ were almost twice as high as those of the PC membrane regardless of the feed composition. The ideal selectivities were, however, higher than separation factors for PC/zeolite 4A and PC/pNA/zeolite 4A membranes. The PC/ pNA/zeolite 4A membrane has separation factors of 18 for 77% CO₂/ 23% CH₄ mixture, and 40 for 20% CO₂/ 80% CH₄ mixture, respectively. The separation factors of the mixed matrix membranes depended on the feed composition strongly. The PC/ pNA/zeolite 4A membrane had higher separation factors and lower permeabilities than the PC/zeolite 4A membrane. pNA assisted to eradicate partly the detrimental effects of interfacial voids and improved the molecular sieving effect of zeolite 4A dispersed in the PC.     

Effect of Dispersed Multi-Walled Carbon Nanotubes on Mixed Matrix Membrane for O2/N2 Separation

Mixed matrix membranes (MMMs) consisting of multiwalled carbon nanotubes (MWCNTs) embedded within polyetherimide were prepared. Surfactants of different charges were utilized to disperse the nanotubes through a simple non-covalent approach. The characterization results suggest that proper selection of the dispersing agent contributed to better dispersion of nanotubes. The MMMs exhibited improved thermal stability and mechanical strength, which indicate the improvement of dispersion and compatibility within the polymer matrix. The resulting membrane exhibited permeance improvement of O₂ and N₂ as much as 87.7% and 120% respectively compared to that of neat polyetherimide. The results implied that Triton-X100 treated MWCNTs is a promising filler to enhance gas permeability.     

Y型沸石/炭杂化膜的制备及其气体分离性能

以聚酰胺酸为前驱体,Y型沸石为掺杂物,经高温炭化制备了Y型沸石/炭杂化膜.通过纯组分气体(H2,CO2,O2,N2)的渗透实验对杂化膜的气体渗透性能进行测定,并使用透射电镜,X射线衍射对杂化膜的微结构进行表征.研究了沸石的含量以及炭化温度对杂化炭膜的气体渗透性能和微结构的影响.结果表明,随着膜内沸石含量的提高,Y型沸石/炭杂化膜的气体渗透性能明显提高,而随着炭化温度的升高,Y型沸石/炭杂化膜的渗透系数降低,选择性提高.与纯炭膜相比,Y型沸石/炭杂化膜在保持高O2N2选择性的前提下,其渗透性能显著提高.炭化温度为700℃,沸石含量为15%,Y型沸石/炭杂化膜O2的气体渗透系数为501 bareer,O2/N2选择性为15.6.当炭化温度超过800℃以后,杂化膜中的沸石晶体结构被破坏,其气体渗透系数接近纯炭膜的气体渗透系数.因此,保持沸石孔道结构的完整是制备高性能沸石/炭杂化膜的关键因素之一.     

Magnetic Mixed Matrix Membranes Consisting of PPO Matrix and Magnetic Filler in Gas Separation

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and magnetic neodymium powder particles MQP-14-12 have been used for the preparation of magnetic mixed matrix membranes. Permeability diffusion and sorption coefficients of O₂, N₂, and synthetic air components were estimated for homogeneous and heterogeneous membranes using the Time Lag method based on dynamic experiments in a constant pressure system. The influence of magnetic field and magnetic powder particles on the gas transport properties of MMMs was studied. The results showed that the membrane permeation properties were improved with the magnetic neodymium particle filling. It was observed that the magnetic ethylcellulose and poly(2,6-dimethyl-1,4-phenylene oxide) membranes showed higher gas permeability, while their permselectivity and solubility were rather maintained or slightly increased. The results also showed that the magnetic powder addition enhanced gas diffusivity significantly in EC and PPO membranes.     

Effect of Raw Multi-Wall Carbon Nanotubes on Morphology and Separation Properties of Polyimide Membranes

Raw multi wall carbon nanotubes (r-MWCNTs) were embedded as fillers inside the polyimide (PI) matrix and PI/r-MWCNTs mixed matrix membranes were fabricated by the phase inversion method. The TEM images and permeation results using helium as test gas showed that r-MWCNTs were generally closed ended and acted as impermeable nano particles. Gas permeation tests using CO₂ and CH₄ showed that the addition of r-MWCNTs into the dope solution increased the CO₂/CH₄ separation factor while decreasing the carbon dioxide and methane permeances. When the r-MWCNTs content was increased from 0% to 6 wt.%, permeance of CO₂ in the flat sheet mixed matrix membranes decreased from 9.15 GPU to 5.49 GPU and CO₂/CH₄ separation factor increased from 19.05 to 45.75. Identical to flat sheet mixed matrix membranes, the addition of 2 wt.% r-MWCNTs into a spinning dope increased the CO₂/CH₄ separation factor from 46.61 to 72.20. The glass transition temperature of the mixed matrix flat sheet membranes increased with an increase in the r-MWCNTs content. This implies a good segmental-level attachment between the two phases that forms a rigidified polymer region at the polymer/r–MWCNTs interface. FESEM images showed well dispersed r-MWCNTs in the polymer matrix at a loading of 2 wt% r-MWCNTs.     

MOF‐Based Mixed‐Matrix Membranes in Gas Separation – Mystery and Reality

Microporous additives like nanosized metal‐organic framework (MOF) particles can improve the gas separation performance of polymer membranes. These membranes which consist of added filler particles in a continuous polymer phase are called mixed‐matrix membranes (MMM). While inorganic zeolites and organic polymers do not match well, the preparation of defect‐free MOF‐based MMMs is much easier. However, some problems can also occur during the preparation. Solutions how to avoid them and prepare perfect MMMs are given. In practical gas separation, the selectivity of the MMMs was found to be even higher than predicted by the Maxwell model.     

膜技术在含烃类气体分离中的研究及前景

气体膜分离技术在膜分离中占有相当的比重。简要介绍了气体膜分离技术的基本原理,并对天然气、沼气、炼厂气等含烃类气体的膜法处理技术与传统加工技术进行对比,突出了膜法的技术及经济优势。着重介绍了用于含烃气体处理的各种材质膜的研究以及应用现状,并对气体分离膜、膜组件的发展及应用前景进行的简单的阐述。     

Novel Composite Membranes for Gas Separation: Preparation and Performance

High performance composite membranes based on molecular sieving silica (MSS) were synthesized using sols containing silicon co-polymers (methyltriethoxysilane and tetraethylorthosilicate). Alpha alumina supports were treated with hydrochloric acid prior to sol deposition. Permselectivity of CO2 over CH4 as high as 16.68 was achieved whilst permeability of CO2 up to 36.7 GPU (10–6 cm3 (STP) cm–2 · s–1 · cm Hg–1) was measured. The best membrane's permeability was finger printed during various stages of the synthesis process showing an increase in CO2/CH4 permselectivity by over 25 times from initial support condition (no membrane film) to the completion of pore structure tailoring. Transport measurement results indicate that the membrane pretreated with HCl has highest permselectivity and permeation rate. In particular, there is a definite cut-off pore size between 3.3 and 3.4 angstroms which is just below the kinetic diameters of Ar and CH4. This demonstrates that the mechanism for the separation in the prepared composite membrane is molecular sieving (activated diffusion), rather than Knudsen diffusion.     

高气速选择性分离氨碳混和气模拟实验

采用二级串联鼓泡吸收器对NH3／CO2摩尔比为2：1的混和气体进行高气速选择性吸收，获得氨的总吸收率为96．7％，二氧化碳的总吸收率为33．1％，二级吸收器出口气相CO2摩尔含量达90．9％，液相氨碳摩尔比为5．85。将此吸收液在加压下精馏分离氨，基本可以把吸收液中游离氨回收。分离游离氨后的溶液在常压下进行解吸，蒸馏塔出口液体含NH3和CO2量仅为0．014％和0．006％，解吸气回串联吸收器进行循环吸收分离。对预计工业分离过程进行物料和能量衡算，分离1kg液氨需1MPa的蒸汽约3.2kg。     

Synthesis and Characterization of Polyimide Mixed Matrix Membranes

Polyimides of Matrimid 5218 and P84 as backbone and different fillers including silica aerosil, zeolite 4A, carbon nanotubes, and carbon molecular sieves were used to synthesize flat mixed matrix membranes (MMMs). Effects of different polymer types and concentrations, different filler types and contents, and fabrication procedure were investigated. Scanning Electron Microscopy (SEM) analysis showed acceptable connections between the two phases and the MMMs performed higher performance compared to the polymeric membranes. Thermal treatment of the MMMs, as a defect repairing technique, was found very effective. Performed pervaporation and gas permeation experiments showed better separation performances of the MMMs with respect to those of the neat polymeric membranes. The results showed up to seven and two times increment in separation factors of MMMs regarding to neat polymeric membranes for pervaporation and gas separation experiments, respectively, while permeation rates nearly remained constant indicating effectiveness of the proper filler incorporation within polymer matrices approach.     

GO-TSC/聚酰亚胺混合基质膜的制备及气体分离性能研究

使用氨基硫脲（TSC）对氧化石墨烯（GO）进行改性,制备GO-TSC层状复合材料。随后,将该复合材料加入到Matrimid^®5218（PI）基质中,制备用于二氧化碳分离的混合基质膜（MMMs）。通过TGA、SEM及气体分离性能测试考察了GO-TSC对膜热稳定性、结构和气体分离性能等的影响。SEM结果显示GO-TSC可均匀分散在聚合物基质上并与基质紧密结合;TGA结果显示混合基质膜在250 ℃以上仍保持稳定。与纯PI膜相比,MMMs显著增强了二氧化碳的渗透性。GO-TSC中所含的氨基与二氧化碳具有良好的亲和力,增加的碱性位点可以有效地转运二氧化碳。GO-TSC的层状结构增加了气体的传输路径,不利于大动态直径气体（甲烷、氮气）的通过,从而提高了分离性能。GO-TSC负载量为0.75%（质量分数）时混合基质膜的分离性能最佳。相比较纯PI膜,混合基质膜的二氧化碳渗透系数和二氧化碳/甲烷、二氧化碳/氮气分离系数分别提高了42.16%、95.79%和83.72%。     

单外皮层PES中空纤维气体分离膜制备的研究

以聚醚砜(PES)作膜材料,N-甲基吡咯烷酮(NMP)为溶剂,乙醇(Ethanol)作非溶剂,NMP-Water为芯液,获得PES/NMP/Ethanol铸膜液[m(PES)∶m(NMP)∶m(Ethanol)=35∶57∶8],采用相转化法制备了PES中空纤维气体分离不对称膜,研究了保存时间、硅橡胶种类、芯液浓度、芯液流量和凝胶温度等对PES中空纤维膜O2/N2渗透性能的影响。同时,分析了单外皮层PES中空纤维气体分离膜的结构,讨论了PES中空纤维气体分离膜的机械性能。当芯液组成的m(NMP)∶m(H2O)=86∶14和凝胶温度17℃时,涂3%硅橡胶A后的PES中空纤维气体分离膜气体分离性能如下:αO2/N2=6.68,JO2=2.26GPU,JN2=0.33GPU。     

气体膜分离技术及应用

简要介绍了有关气体膜分离的基本原理、材料及其在氢气分离回收、空气分离和酸性气处理中的应用,并对气体膜分离的发展前景提出了自己的见解。     

气体膜分离技术的进展及其应用

介绍了气体分离膜材料的种类;叙述了介绍了气体膜分离技术在分离空气制备富氧、富氮,水蒸气、有机蒸汽的分离和氢气回收等工业领域的应用.介绍了气体膜分离技术的研究进展,并提出了我国气体膜分离技术发展方向.     

Matrimid® 5218 in preparation of membranes for gas separation: Current state-of-the-art

Over the last decades, different polymers have been used as continuous phase for preparing selective membranes for gas separation. Today, some of these materials have been consolidated commercially; however, the necessity to improve the performance (in terms of permeability/selectivity) of polymeric membranes above Robeson’s upper bound has been conducted by blending polymers, use of additives, implementation new methods, development of new materials, coating films, development of mixed matrix membranes, and so on. One of the most recent approaches is the use of polymers such as polyimides, i.e., Matrimid® 5218, which has demonstrated, to provide remarkable gas separation performance using the attempts aforementioned. The aim of this work is to present the current state-of-the-art of the use of Matrimid® 5218 in preparation of membrane for gas separation. The progress in this field is summarized and discussed chronologically in two periods, decade (from 1998 to 2008) and current (from 2009 up to now) frameworks. This contribution leads to take a complete and compelling overview of the state-of-the-art based on Matrimid. Furthermore, the main approaches, aim of study, gas separation evaluated, main techniques used for membrane characterization, main supplier of the polymer, main secondary materials for blending, fillers incorporated into the matrix, and remark of the study are summarized in detail. Finally, it denotes the prospects and future trends on use of Matrimid® 5218 for membrane applications.     

聚酰亚胺膜气体渗透性的改性进展

聚酰亚胺分离膜(PI)是由芳香二酐和二胺单体缩聚而成的,它是主链含有酰亚胺环的一类高聚物。因其具有良好的气体分离性能、热稳定性、耐溶剂性等特性而受到人们的广泛关注。但是,其气体渗透-选择性的平衡问题限制了其在气体分离领域的广泛应用。因此,研究者们将目光转向了聚酰亚胺膜气体渗透性的改性方面,使其具有良好的气体渗透性,用于混合气体的高效分离。文章综述了近年来研究者对聚酰亚胺气体渗透性的研究进展,详细介绍了共混改性、交联改性和分子结构改性方面的最新研究成果,并总结展望了聚酰亚胺膜今后的研究趋势。为未来高效分离膜的研发提供了参考。     

聚酯型聚氨酯膜的溶胀性能及膜分离性能研究

研究通过两步法反应,制备了一系列聚酯型聚氨酯（包括环糊精嵌段）,并采用红外,热分析等手段对其结构与性能进行了表征,并且考察了链段中的环糊精对膜溶胀性能的影响以及膜对不同混合物体系的分离性能。结果表明,链段中含环糊精的膜在有机混合物中有较大的溶胀度,聚酯型聚氨酯对于苯-环己烷和水-乙醇体系均有较好的分离性能。     

Efficient CO2 Separation Using a PIM-PI-Functionalized UiO-66 MOF Incorporated Mixed Matrix Membrane in a PIM-PI-1 Polymer

Metal–organic framework (MOF) incorporated mixed–matrix membranes (MMMs) attract great interest for gas separation applications because they overcome limitations faced by typical polymer membranes, including permeability–selectivity trade-off, aging effect, and plasticization phenomenon. However, optimal MOF–polymer interface compatibility is the key challenge in fabricating defect-free high-performance gas-separation MMMs. Here, a surface modification strategy of the UiO-66-NH₂ MOF using a covalently bound PIM-PI-oligomer is developed to engineer interface compatibility with the polymer that has an identical chemical structure (PIM-PI-1) in the MMMs. A series of MMMs are prepared with different loadings of homogeneously distributed PIM-PI-functionalized MOFs (PPM). Significant improvements in CO₂/N₂ and CO₂/CH₄ selectivity and permeability are achieved with these MMMs, ranging from 5 to 10 wt% of the PPM loadings. The MMM with 10 wt% loading (PPM-10@MMM) shows a CO₂ permeability of 3827.3 Barrer and a CO₂/N₂ and CO₂/CH₄ selectivity of 24 and 13.4, respectively. This surpasses the 2008 Robeson upper bound for CO₂/N₂ and is very close to the 2008 upper bound for CO₂/CH₄. The experimental results are further compared using Maxwell's equation for MMMs. The resulting MMMs show a plasticization resistance against CO₂ up to 25 atm pressure and anti-aging performance for 180 h.     

Separation of CO2/N2 Gas Mixture through Carbon Membranes: Monte Carlo Simulation

Abstract

Monte Carlo simulation method is employed to investigate separation behavior of gas mixture composed of carbon dioxide and nitrogen through a model carbon membrane under the different conditions. The simulation gives insight into the separation mechanism to a certain extent, which is based on the loading and diffusion of carbon dioxide and nitrogen in the carbon membrane with different pore size. The simulation results indicate that the carbon dioxide can be adsorbed on the surface of membrane wall more strongly, whereas the diffusion rate of nitrogen is more prominent. When the separation condition alters, the influence of the two main factors mentioned above on transport of gas molecules in membranes becomes different. Therefore, the equilibrium selectivity of nitrogen and carbon dioxide changes correspondingly.     

A Review Featuring Fabrication,Properties, and Application of Polymeric Mixed Matrix Membrane Reinforced with Different Fillers

Mixed matrix membrane is composed of polymer matrix reinforced with organic or inorganic particles to improve its performance. This review presents comprehensive study on fabrication, properties, and application of polymeric composite-based mixed matrix membrane. Inorganic fillers (silica, alumina, and zeolite) are extensively used in mixed matrix membrane due to low cost, abundance, and simplistic surface treatment. Organic fillers (graphene and carbon nanotube) are also preferred due to low specific gravity, and high thermal, flame, and chemical resistance. Reinforcement of these nanofiller during membrane provides flux enhancement and low fouling. Various applications of mixed matrix membrane such as in tissue engineering, catalysis, and electrochemistry have also been discussed.