New permeation models for nanocomposite polymeric membranes filled with nonporous particles

In this article, permeation models for nanocomposite polymeric membranes (NCPMs) filled with nonporous particles are discussed and two new models for prediction of effective permeability of NCPMs are proposed. To derive these models, the presence of interfacial layer at the surface of the nanofiller particles as well as the impact of two important phenomena namely creating void volumes and increasing free volume at the interface layer are taken into account. The capability of the models for prediction of reliable results is checked against available experimental data on permeability of NCPMs and is also compared with other presented models for such membranes. The new proposed models show profound superiority over the well known models such as “Bruggeman model in limit” which offers fairly good prediction for NCPMs.     

Study on CO2 facilitated separation of mixed matrix membranes containing surface modified MWCNTs

Mixed matrix membranes (MMMs) for CO₂-facilitated separation were prepared by incorporating different surface-modified multiwalled carbon nanotubes (MWCNTs) in a fixed carrier membrane material. Polymer containing amino groups, poly(vinylalcohol-co-vinylamine) (VA-co-VAm) was synthesized as polymeric matrix. MWCNTs as well as MWCNTs surface-modified with  OH and  NH₂ were applied as nanofillers. The physical property, chemical structure, and membrane morphology were characterized by FT-IR, TG, XRD, DSC, CA, XPS, and SEM. The effects of content, functional group, temperature, and pressure on gas permselectivity were studied. Results show that the incorporation of nanofillers can effectively restrict the polymer chain packing and lead to low crystallinity. The MMMs exhibited higher CO₂ permselectivity than the pure polymeric membrane. For all the MMMs, the CO₂ permeance and selectivity increased with MWCNTs contents to a maximum and then decreased. MWCNT-NH₂ can be regarded as the most effective nanofiller. MMMs with 2.0 wt % MWCNT-NH₂ displayed the highest CO₂ permeance of 132 GPU and CO₂/N₂ selectivity of 74. Both CO₂ permeance and selectivity were decreased with feed gas pressure and temperature. The membrane exhibited good stability in the testing with the binary gas mixtures of CO₂/N₂ for 110 h under 0.54 MPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47848.     

Microstructure and gas permeation performance of porous silicon nitride ceramics with unidirectionally aligned channels

Porous Si₃N₄ ceramics with unidirectionally aligned channels were prepared via freezing ceramics suspension with distinct solid contents under different freezing temperatures. The samples obtained using lower solid content in ceramic suspension at higher freezing temperature exhibit larger Darcian and non-Darcian constants due to their higher open porosity, larger pore size and lower tortuosity. Moreover the investigation on individual contributions of viscous energy losses and inertial energy losses on the total pressure drop during permeation process indicates that with decreasing the solid content or the freezing temperature the viscous energy losses increase but the inertial energy losses decrease for samples owing to the differences in their pore structures. It is worth mentioning that porous Si₃N₄ ceramics with unidirectionally aligned channels exhibit larger Darcian and non-Darcian constants than those with similar pore size distributions and open porosity owing to their lower tortuosity, thus rendering them appropriate for filters and membrane supports.     

Enhanced gas separation properties by using nanostructured PES‐Zeolite 4A mixed matrix membranes

The polymer–zeolite mixed matrix membranes were fabricated by incorporating nanosized or microsized zeolite 4A into polyethersulfone. A comparison of zeolite 4A nanocrystals and microcrystals was made by using SEM, XRD, N₂ adsorption–desorption measurements. Zeolite particles were well‐distributed in the polymer phase, as reflected by the SEM images. The effects of the zeolite 4A particle size on the gas permeation performance were studied. Experimental results demonstrate that mixed matrix membranes exhibit decreased gas permeabilities due to the barrier effect of zeolite particles. The obtained permselectivity is greatly enhanced for He/N₂, H₂/N₂, He/CO₂, and H₂/CO₂ gas pairs, especially for nanosized zeolite 4A mixed matrix membranes. The gas permeation performance difference is observed between the nanostructured and microstructured membranes, which is attributed to a combined effect of different zeolite composition and different particle size. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3800–3805, 2006     

Selection of oxygen permeation models for different mixed ionic‐electronic conducting membranes

Permeation data of several mixed ionic‐electronic conducting (MIEC) membranes were analyzed by two oxygen permeation models (i.e., Zhu's model and Xu–Thomson's model), respectively, to find a concise method to guide the choice of permeation models. We found that Zhu's model can well fit the permeation data of perovskite‐type membranes, like Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ (BSCF) and BaCe_0.05Fe_0.95O_3‐δ (BCF), and dual‐phase membranes, like 75 wt % Ce_0.85Sm_0.15O_1.925–25 wt % Sm_0.6Sr_0.4Al_0.3Fe_0.7O_3‐δ (SDC‐SSAF), whose oxygen vacancy concentrations are almost independent of the oxygen partial pressure at elevated temperatures. However, Zhu's model was not appropriate for membranes whose oxygen vacancy concentration changed obviously with oxygen partial pressure at elevated temperatures, such as La_0.6Sr_0.4Co_0.2Fe_0.8O_3‐δ (LSCF) and La_0.7Sr_0.3CoO_3‐δ (LSC). On the contrary, Xu–Thomson's model can fit the data of LSCF and LSC well, but it is inapplicable for BSCF, BCF, and SDC‐SSAF. Therefore, the dependence of oxygen vacancy concentration on oxygen partial pressure was suggested as an index for the selection of the permeation models. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4043–4053, 2017     

Structural and transport properties of polydimethylsiloxane based polyurethane/silica particles mixed matrix membranes for gas separation

Mixed matrix membranes of synthesized polyurethane (PU) based on toluene diisocyanate (TDI), polydimethylsiloxane (PDMS) and polytetramethylene glycol (PTMG) with polyvinyl alcohol based polar silica particles were prepared by solution casting technique. The homogeneity and thermal properties of the prepared PDMS-PU/silica membranes were characterized using scanning electron microscope (SEM), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The SEM micrographs confirmed the distribution of silica particles in the polymer matrix without agglomerations. Gas permeation properties of membranes with different silica contents were studied for pure CO₂, CH₄, O₂, He and N₂ gases. The obtained results indicated the permeability of the condensable and polar CO₂ gas was enhanced whereas permeability of other gases decreased upon increasing the silica content of the mixed matrix membranes. The permeability of CO₂ and its selectivity over N₂ was increased from 68.4 Barrer and 22 in pure PDMS-PU to 96.7 Barrer and 64.4 in the mixed matrix membranes containing 10 wt% of the silica particles.     

Enhanced compatibility and selectivity in mixed matrix membranes for propylene/propane separation

Mixed matrix membranes (MMMs) based on metal–organic framework (MOF) have great promising application in separation of gas mixtures. However, achieving a good interfacial compatibility between polymer and MOF is not straightforward. In this work, focusing on one of the most challenging olefin/paraffin separations: propylene/propane (C₃H₆/C₃H₈), we demonstrate that modification of the MOF filler via dopamine polymerization using a double solvent approach strongly improves interfacial compatibility. The resulting membranes show an outstanding separation performance and long-term stability with propylene permeability nearly 90 Barrer and propylene/propane selectivity close to 75. We anticipate that similar MOF modification strategies may help solve the problem of interface defects in the manufacture of MMMs and be extended to other porous fillers.     

PEO/聚吡咯中空纳米微球混合基质膜的制备及其CO2渗透分离性能

采用壳层具有介孔结构的聚吡咯中空纳米微球作为填料,和聚氧化乙烯单体共混自由基聚合制备了混合基质膜。结果表明,聚吡咯微球与基质相容性较好,未见明显团聚现象和缺陷。混合基质膜的渗透系数随填料含量的增加先增大后减少,在0.5%处达到最大值,CO₂渗透系数增长31%;CO₂/N₂分离系数有所降低,CO₂/CH₄分离系数则变化不大。研究表明,由于聚合物链段对微球壳层的介孔填充,气体在膜内的扩散系数不升反降,渗透系数的提高主要是由于溶解度系数的变化,而这也导致了溶解选择性的变化,进而影响了分离系数。     

Synthesis of PEO/hollow polypyrrole nanoparticle mixed matrix membranes for CO2 separation

The hollow polypyrrole nanoparticle with porous shell was incorporated into poly(ethylene oxide) monomer to fabricate the mixed matrix membrane by free radical polymerization. Morphology of the membranes showed the polymeric filler had good interfacial compatibility with the polymeric matrix without obvious defect. The results showed that the gas permeability of membranes increased at first and then decreased as the filler loading increased, while the permselectivity of CO₂/N₂ decreased_{andthat of CO2/CH4 maintained constant basically. The research showed that the diffusion coefficients decreased due to the blockage of the pore in shell of nanoparticles by polymeric matrix, the improvement of the gas permeability was mainly contributed by the improvement of the solubility coefficient, which also affected the solubility selectivity and then the permselectivity. The optimum nanoparticle loading was around 0.5%. In this case, the permeability of CO2 was about 6.5×10^-11 cm³?cm?cm^-2?s^-1?Pa^-1 (31% higher than the pristine polymeric membranes), while the permselectivity of CO2/N2 was about 30 (34% lower than that of the pristine polymeric membranes) and the permselectivity of CO2/CH4 was about 14 without significant sacrifice. The result showed the polypyrrole nanoparticles with porous shell was potential for application in CO2/CH4 separation.}     

Effect of chemically modified clinoptilolite on the thermal,morphological, and gas separation properties of mixed matrix membranes

Mixed matrix membranes (MMM) based on polysulfone and chemically modified clinoptilolite were prepared. Clinoptilolite enriched with Ca²⁺, K⁺, and Na⁺ by ion exchange at two test temperatures was prepared. Chemical composition was monitored by energy dispersive X‐ray spectroscopy. X‐ray diffraction, thermogravimetric analysis, and N₂ adsorption–desorption isotherms were also performed. Thermal and morphological properties of MMM were evaluated. CH₄/CO₂ gas mixture permeability tests at different upstream pressure were carried out. Type of exchanged cation in modified clinoptilolite affected the CO₂ permeability. An improvement on the CO₂/CH₄ selectivity values in the MMM compared to the polymeric membrane was appreciated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45659.     

Hydrogen separation through palladium-copper membranes on porous stainless steel with sol-gel derived ceria as diffusion barrier

Pd-Cu alloy membrane was prepared by electroless plating on porous stainless steel (PSS) support. Sol-gel derived ceria was introduced as the intermediate layer by a sol-dip-coating method to prevent intermetallic diffusion and to enhance the affinity between the support and membrane. Ceria layer moderates the pore size and porosity of the support effectively to meet the needs of the alloy layer deposition. Permeation test was carried out in a high temperature range, i.e. 573-773 K with a pressure difference of 0.1 MPa. The results showed that properly prepared ceria layer was effective as the diffusion barrier in the temperature range examined, which is suitable for water-gas shift reaction. The performance of the membranes in this work is also compared with that in our previous work in which pure Pd membrane and yttrium stabilized zirconia intermediate layer were examined.     

改善无机填料混合基质膜气体分离性能的研究进展

混合基质膜（MMMs）是结合了无机填料和有机基质特点的一类膜材料,因其在气体分离应用上具有良好的渗透通量和分离性能被广泛关注。无机填料诸如二氧化硅纳米颗粒球、沸石分子筛、金属有机框架（MOF）、氧化石墨烯（GO）、碳纳米管（CNT）均被广泛应用于混合基质膜的制备,但是碍于无机填料在有机相中的分散性问题、两相相容性问题和界面缺陷问题,常会导致较差的气体分离性能。针对近年通过对无机填料进行表面官能化修饰、共价交联、多元填充、调控形貌等来改善混合基质膜气体分离性能的研究进行总结和阐述,并对其未来的发展趋势进行了展望。     

Functionalized carbon nanotubes mixed matrix membranes of polymers of intrinsic microporosity for gas separation

ABSTRACT: The present work reports on the gas transport behavior of mixed matrix membranes (MMM) which were prepared from multi-walled carbon nanotubes (MWCNTs) and dispersed within polymers of intrinsic microporosity (PIM)-1 matrix. The MWCNTs were chemically functionalized with poly(ethylene glycol) (PEG) for a better dispersion in the polymer matrix. MMM-incorporating functionalized MWCNTs (f-MWCNTs) were fabricated by dip-coating method using microporous polyacrylonitrile membrane as a support and were characterized for gas separation performance. Gas permeation measurements show that MMM incorporated with pristine or functionalized MWCNTs exhibited improved gas separation performance compared to pure PIM-1. The f-MWCNTs MMM show better performance in terms of permeance and selectivity in comparison to pristine MWCNTs. The gas permeances of the derived MMM are increased to approximately 50% without sacrificing the selectivity at 2 wt.% of f-MWCNTs' loading. The PEG groups on the MWCNTs have strong interaction with CO2 which increases the solubility of polar gas and limit the solubility of nonpolar gas, which is advantageous for CO2/N2 selectivity. The addition of f-MWCNTs inside the polymer matrix also improved the long-term gas transport stability of MMM in comparison with PIM-1. The high permeance, selectivity, and long term stability of the fabricated MMM suggest that the reported approach can be utilized in practical gas separation technology.     

Oxygen transport kinetics of MIEC membranes coated with different catalysts

Oxygen permeation through mixed ionic‐electronic conducting membrane may be controlled by oxygen bulk diffusion and/or oxygen interfacial exchange kinetics. In this article, we chose BaCe_0.05Fe_0.95O_3‐δ (BCF) as a representative to study the oxygen transport resistances of the membrane coated with different porous catalysts, including BCF itself, Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ (BSCF) and Sm_0.5Sr_0.5CoO_3‐δ (SSC). The oxygen transport resistances of bulk, gas‐solid interfaces of feed‐side and sweep‐side of the catalyst‐coated membranes can be separately obtained through a linear regression of experimental data according to an oxygen permeation model. The three resistances of the membrane coated with BCF catalyst are smaller than those of the membrane coated with BSCF and SSC catalysts, although BSCF catalyst itself has the fastest bulk diffusion and interfacial exchange kinetics. The catalytic activities of BSCF and SSC catalysts on BCF membranes are impacted by the transport kinetics of catalysts, microstructure of catalyst layers, and cationic inter‐diffusion between the membrane and catalysts. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2803–2812, 2016     

Fabrication of mixed‐matrix membranes with MOF‐derived porous carbon for CO2 separation

Mixed‐matrix membranes (MMMs) have shown great advantages but still face some challenges, such as the trade‐off between permeability and selectivity, stability, and the lack of efficient ways to enhance them simultaneously. Here, the fabrication of MMMs with metal‐organic frameworks derived porous carbons (MOF‐PCs) as fillers which exhibit selective‐facilitating CO₂ transport passage originating from interactions between fillers and CO₂ is showed. With the aid of the developed multicalcination method, MOF‐PCs with variable N‐contents were prepared and incorporated into PPO‐PEG matrix for the first time to prepare MMMs, which show excellent separation performance for CO₂/CH₄ mixture with a tunable separation performance by combining different N‐contents and surface areas of MOF‐PCs. Moreover, the developed MMMs have hydrothermal and chemical stability. This work not only presents a series of MMMs with both good separation properties and stability, it also provides useful information for guiding the fabrication of high performance MMMs for practical application. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3400–3409, 2018     

PBI/Clinoptilolite mixed-matrix membranes for binary (N2/CH4) and ternary (CO2/N2/CH4) mixed gas separation

In this work, polybenzimidazole (PBI)-based mixed matrix membranes (MMMs) with natural zeolite were prepared and their transport properties for binary (N₂/CH₄) and ternary (CO₂/N₂/CH₄) mixed-gas separation were studied. The MMMs, were prepared with PBI as polymeric matrix and Mexican natural zeolite clinoptilolite enriched with cations of Ca²⁺ as filler. The thermal properties analysis of the PBI and MMMs studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) indicates that the MMMs membranes have Tg higher than 350°C and decomposition temperatures above 600°C compared with the pristine membranes. PBI membrane and MMMs were analyzed by X-Ray Diffraction (XRD) and the diffraction patterns showed the zeolite signals combine with the amorphous dome from the polymeric matrix. In addition, the perm-selectivity properties of the polymeric membranes and MMMs were tested with binary (N₂/CH₄; 10/90 mol%) and ternary (CO₂/N₂/CH₄; 5/10/85 mol%) gas mixtures at different pressure rates (50, 150 and 300 psi). The perm-selectivity properties of the MMMs membranes show an improvement in their values about 30% higher compared to the PBI polymeric membranes, favoring the permeation of CO₂ and N₂.