Poly(amide-6-b-ethylene oxide)/SAPO-34 mixed ma-trix membrane for CO2separation

In this paper, poly（amide-6-b-ethylene oxide） （Pebax1657）/SAPO-34 mixed matrix membranes （MMMs） were prepared by solvent-evaporation method with acetic acid as a novel solvent. CO2, N2, CH4 and H2 permeation properties were investigated, and the physical properties of Pebax/SAPO-34 MMMs were characterized by XRD and SEM. At low SAPO-34 content, it was homogeneously distributed in the Pebax ma- trix, and then precipitated and agglomerated at high SAPO-34 content. The crystallinity of Pebax phase in Pebax/SAPO-34 MMMs decreased initially and then rebounded as a result of phase separation. With the increase of transmembrane pressure difference, CO2 permeability was en- hanced due to the effect of pressure-induced plasticization. Owing to the happening of stratification, the CO2 permeability of Pebax/SAPO-34 MMMs （50 wt% SAPO-34） increased to 338 Barrer from 111 Barrer of pristine Pebax, while the selectivities of CO2/CH4 and CO2/N2 were almost unchanged. Compared with the pristine Pebax, the gas separation performances of Pebax/SAPO-34 MMMs were remarkably enhanced.     

Poly(amide-6-b-ethylene oxide)/SAPO-34 mixed matrix membrane for CO2 separation

In this paper, poly(amide-6-b-ethylene oxide) (Pebax1657)/SAPO-34 mixed matrix membranes (MMMs) were prepared by solvent-evaporation method with acetic acid as a novel solvent. CO₂, N₂, CH₄ and H₂ permeation properties were investigated, and the physical properties of Pebax/SAPO-34 MMMs were characterized by XRD and SEM. At low SAPO-34 content, it was homogeneously distributed in the Pebax matrix, and then precipitated and agglomerated at high SAPO-34 content. The crystallinity of Pebax phase in Pebax/SAPO-34 MMMs decreased initially and then rebounded as a result of phase separation. With the increase of transmembrane pressure difference, CO₂ permeability was enhanced due to the effect of pressure-induced plasticization. Owing to the happening of stratification, the CO₂ permeability of Pebax/SAPO-34 MMMs (50 wt% SAPO-34) increased to 338 Barrer from 111 Barrer of pristine Pebax, while the selectivities of CO₂/CH₄ and CO₂/N₂ were almost unchanged. Compared with the pristine Pebax, the gas separation performances of Pebax/SAPO-34 MMMs were remarkably enhanced.     

Pebax/poly(vinyl alcohol) mixed matrix membrane incorporated by amine-functionalized graphene oxide for CO2 separation

Graphene oxide nanoparticles (GO) were firstly functionalized using p-phenylenediamine and then utilized as nanofillers to prepare poly(ether-block-amide) (Pebax®-1657)/poly(vinyl alcohol) (PVA-60000)-based mixed-matrix membranes. The modified GO as well as the fabricated mixed matrix membranes underwent some characterization analyses, including FTIR, TGA, XRD, FESEM, and EDX. The influence of amine-modified nanoparticles content (2, 4, and 6 wt%), and feed pressure on CO₂, CH₄, and N₂ permeabilitis and ideal CO₂/CH₄ and CO₂/N₂ selectivities values of the MMMs were investigated. The permeation experiments demonstrated that Pebax/PVA (10 and 15 wt%) blend membranes caused an increase in CO₂ permeability owing to the high affinity of polar CO₂ molecules to polar PVA segments. Moreover, the incorporation of 6 wt% amine-functionalized GO into the Pebax/PVA (10 wt%) and Pebax/PVA (15 wt%) blend polymer raised the CO₂ permeability and CO₂/CH₄ and CO₂/N₂ selectivity by nearly 43%, 28%, and 37%, respectively, due to the higher CO₂ adsorption capacity of the amine-functionalized GO.     

Mixed matrix membrane comprising polyimide with crystalline porous imide‐linked covalent organic framework for N2/O2 separation

An imide‐linked covalent organic framework (COF) was successfully synthesized by directly heating a mixture of melamine and biphenyltetracarboxylic dianhydride (BPDA) in a tubular oven at 335°C. The crystalline and nanostructure of this COF was characterized by X‐ray diffraction (XRD) and Brunauer‐Emmett‐Teller (BET). A mixed matrix membrane (MMM) was prepared by blending the COF into the commercial P84 polyimide in solution. It is found that the COF particles not only act as gas channels for N₂ and O₂ permeation but also provided an inverse permselective property with higher permeability of N₂. The effect of COF nanostructure and its loading amount on N₂ and O₂ permeability and selectivity has been investigated.     

多孔材料表面修饰聚酰亚胺非对称混合基质膜对CO2/N2和CO2/CH4的气体分离

兼具高通量和高选择性的气体分离膜是研究膜分离材料的目标.采用相转化法制备了聚酰亚胺非对称膜,并将其作为基底膜材料,分别在其表面修饰掺有金属有机框架材料Cu₃(BTC)₂ (1, 3, 5-均苯三甲酸合铜),沸石咪唑酯骨架材料ZIF-8以及镁铝水滑石MgAl-LDHs的聚酰胺酸溶液,经热亚胺化后制成非对称混合基质膜.研究了该系列非对称混合基质膜的结构特性和对CO₂、CH₄和N₂气体分离性能;考察了ZIF-8的掺杂量对非对称混合基质膜透气性能的影响.结果表明非对称聚酰亚胺膜的表面修饰可有效地改变膜的表面性质,掺杂ZIF-8的非对称混合基质膜气体的透气性能和选择性都增加,且掺杂量为5% (w)时CO₂/N₂和CO₂/CH₄的理想选择性分别高达24和83,为合成高效的CO₂分离膜提供了借鉴.     

Simultaneous anion and cation exchange chromatography of whey proteins using a customizable mixed matrix membrane

Membrane chromatography can overcome some of the limitations of packed bed column chromatography but preparation of adsorptive membranes usually involves complex and harsh chemical modifications. Mixed matrix membranes (MMMs) require only the physical incorporation of an ion exchange resin into the membrane polymer solution prior to membrane casting. An advantage of MMMs not previously exploited is that resins with differing adsorptive functionalities can be conveniently embedded within a single membrane at any desired ratio. This presents the opportunity to customize an adsorptive membrane to suit the expected protein profile of a raw feed stream e.g. bovine whey or serum. In this work, a novel mixed mode interaction MMM customized to extract all major proteins from bovine whey was synthesized in a single membrane by incorporating 42.5 wt% Lewatit MP500 anionic resin and 7.5 wt% SP Sepharose cationic resin into an ethylene vinyl alcohol base polymer casting solution. The mixed mode MMM developed was able to bind both basic and acidic proteins simultaneously from whey, with binding capacities of 7.16±2.24 mg α-lactalbumin g(-1) membrane, 11.40±0.73 mg lactoferrin (LF)g(-1) membrane, 59.21±9.90 mg β-lactoglobulin g(-1) membrane and 6.79±1.11 mg immunoglobulin Gg(-1) membrane (85 mg total protein g(-1) membrane) during batch fractionation of LF-spiked whey. A 1000 m(2) spiral-wound membrane module (200 L membrane volume, 1m(3) module volume) is predicted to be able to produce approximately 25 kg total whey protein per h.     

Preparation of mixed matrix membranes based on polyimide and aminated graphene oxide for CO2 separation

The aminated graphene oxide (GO) was prepared by the functionalization of pristine GO with ethylenediamine and then dispersed into the poly(amic acid) (the precursor of polyimide [PI]) solution followed by the chemical imidization to successfully fabricate the PI/amine‐functionalized GO mixed matrix membranes (MMMs) using in‐situ polymerization method. Chemical structure and morphology of the GO before and after amine modification were characterized by scanning electron microscopy, Raman spectrum, Fourier transform infrared, and X‐ray photoelectron spectroscopy. Scanning electron microscopy indicated that fine dispersion of GO throughout PI matrix was achieved, which indicates that the in‐situ polymerization approach can enhance the interfacial interaction between the GO and the PI matrix, and then improve the dispersion of carbon material in the polymer matrix. Compared with the conventional solution mixture method, the MMMs prepared with in‐situ polymerization method showed excellent CO₂ permeability and CO₂/N₂ selectivity. The MMMs doped with 3 wt.% aminated GO exhibited maximum gas separation performance with a CO₂ permeability of 12.34 Barrer and a CO₂/N₂ selectivity of 38.56. These results suggest that the amino groups on GO have strong interaction with the CO₂ molecules, which can significantly increase the solubility of polar gas. Our results provide an easy and efficient way to prepare MMMs with good mechanical behavior and excellent gas separation performance.     

Enzyme capturing and concentration with mixed matrix membrane adsorbers

This study reports the use of membrane adsorbers for lysozyme (LZ) capturing and concentration: the membrane adsorbers are prepared by incorporation of ion exchange resins into an EVAL porous matrix. The mixed matrix membrane (MMM) adsorber possesses an open and interconnected porous structure with a large ion exchange surface available for enzyme adsorption. The adsorptive membrane features both a high static as well as a high dynamic LZ adsorption capacity. The measured LZ adsorption isotherm is of the Langmuir type, with a maximum adsorption capacity of 147 mg LZ/ml membrane. Dynamic LZ adsorption capacity at a flux of 25 l/h/m² was 63 mg LZ/ml membrane, which is significantly higher than the equivalent commercial membrane Sartobind C. Since the kinetics of desorption processes are faster than the kinetics of adsorption processes, the performance can be improved by exerting the desorption processes at higher fluxes than the adsorption processes. The MMM can be reused in multiple adsorption/desorption cycles maintaining the high binding capacity performance. Fluorescence spectra of the LZ after adsorption and elution were similar to native LZ. This is confirmed by activity tests showing that the activity of LZ was maintained after an adsorption and desorption cycle.     

Enzyme immobilization on a pH-responsive porous polymer membrane for enzymatic kinetics study

Immobilization of enzymes onto carriers is a rapidly growing research area aimed at increasing the stability, reusability and enzymolysis efficiency of free enzymes. In this work, the role of phase-separation and a pH-responsive “hairy” brush, which greatly affected the topography of porous polymer membrane enzyme reactors (PMER), was explored. The porous polymer membrane was fabricated by phase-separation of poly(styrene-co-maleic anhydride-acrylic acid) and poly(styrene-ethylene glycol). Notably, the topography and pores size of the PMER could be controlled by phase-separation and a pH-responsive “hairy” brush. For evaluating the enzymolysis efficiency of d-amino acid oxidase (DAAO) immobilized carrier (DAAO@PMER), a chiral ligand exchange capillary electrophoresis method was developed with d-methionine as the substrate. The DAAO@PMER showed good reusability and stability after five continuous runs. Notably, comparing with free DAAO in solution, the DAAO@PMER exhibited a 17.7-folds increase in catalytic velocity, which was attributed to its tailorable topography and pH-responsive property. The poly(acrylic acid) moiety of poly(styrene-co-maleic anhydride-acrylic acid) as the pH-responsive “hairy” brush generated topography changing domains upon adjusting the buffer pH, which enable the enzymolysis efficiency of DAAO@PMER to be tuned based upon the well-defined architectures of the PMER. This approach demonstrated that the topographical changes formed by phase-separation and the pH-responsive “hairy” brush indeed made the proposed porous polymer membrane as suitable supports for enzyme immobilization and fitting for enzymolysis applications, achieving high catalytic performance.     

A simple microextraction and preconcentration approach based on a mixed matrix membrane

A simple adsorption/desorption procedure using a mixed matrix membrane (MMM) as extraction medium is demonstrated as a new miniaturized sample pretreatment and preconcentration technique. Reversed-phase particles namely polymeric bonded octadecyl (C₁₈) was incorporated through dispersion in a cellulose triacetate (CTA) polymer matrix to form a C₁₈-MMM. Non-steroidal anti-inflammatory drugs (NSAIDs) namely diclofenac, mefenamic acid and ibuprofen present in the environmental water samples were selected as targeted model analytes. The extraction setup is simple by dipping a small piece of C₁₈-MMM (7 mm × 7 mm) in a stirred 10 mL sample solution for analyte adsorption process. The entrapped analyte within the membrane was then desorbed into 100 μL of methanol by ultrasonication prior to high performance liquid chromatography (HPLC) analysis. Each membrane was discarded after single use to avoid any analyte carry-over effect. Several important parameters, such as effect of sample pH, salting-out effect, sample volume, extraction time, desorption solvent and desorption time were comprehensively optimized. The C₁₈-MMM demonstrated high affinity for NSAIDs spiked in tap and river water with relative recoveries ranging from 92 to 100% and good reproducibility with relative standard deviations between 1.1 and 5.5% (n = 9). The overall results obtained were found comparable against conventional solid phase extraction (SPE) using cartridge packed with identical C₁₈ adsorbent.     

密胺苯二醛多孔聚合物/聚二甲基硅氧烷混合基质膜的制备及气体分离性能

以溶液复合成膜法制备了密胺苯二醛多孔聚合物(MA)/聚二甲基硅氧烷(PDMS)混合基质膜,利用扫描电镜(SEM)表征了混合基质膜的形貌。考察了不同MA用量下MA/PDMS混合基质膜的气体分离性能,结果表明,MA的加入可以在提高PDMS膜渗透系数的同时提高CO_2气体分离选择性;随着混合基质膜中MA含量的增加,混合基质膜的渗透系数均明显提高,气体分离选择性则先增大后减小。双组分混合气体分离测试结果表明,MA/PDMS(1.2%(w,质量分数))混合基质膜对CO_2/N_2和CO_2/CH_4的分离选择性分别是19.2和6.0,CO_2的渗透系数达到8100Barrer,均高于纯PDMS膜。MA/PDMS(1.2%(w))混合基质膜对CO_2/N_2混合气的分离性能突破了Robeson上限。     

Study on the effect of process parameters on CO2/CH4 binary gas separation performance over NH2-MIL-53(Al)/cellulose acetate hollow fiber mixed matrix membrane

The aim of current work is to study the interaction of process parameters including, temperature, CO₂ feed composition and feed pressure were towards CO₂ separation from CO₂/CH₄ binary gas mixture over hollow fiber mixed matrix membrane using design of experiment (DoE) approach. The hollow fiber mixed matrix membrane (HFMMM) containing NH₂-MIL-53(Al) filler and cellulose acetate polymer was successfully spun and fibers with outer diameter of approximately 250–290 nm were obtained. The separation results revealed that the increment of temperature from 30 °C to 50 °C reduced the CO₂/CH₄ separation factor while, increasing feed pressure from 3 bar to 15 and increment of CO₂ feed composition from 15 to 42.5 vol% increased the separation factor of HFMMM. The DoE results showed that the feed pressure was the most significant process parameter that intensely affected the CH₄ permeance, CO₂ permeance and CO₂/CH₄ separation factor. Based on the experimental results obtained, maximum CO₂ permeance of 3.82 GPU was achieved at feed pressure of 3 bar, temperature of 50 °C and CO₂ feed composition of 70 vol%. Meanwhile, minimum CH₄ permeance of 0.01 GPU was obtained at feed pressure of 15 bar and temperature of 30 °C and CO₂ feed composition of 70 vol%. Besides, maximum CO₂/CH₄ separation factor of 14.4 was achieved at feed pressure of 15 bar and temperature of 30 °C and CO₂ feed composition of 15 vol%. Overall, the study on the interaction between separation processes parameters using central composite design (CCD) coupled with response surface methodology (RSM) possesses significant importance prior to the application of NH₂-MIL-53(Al)/Cellulose Acetate HFMMM at industrial scale of natural gas purification.     

Formation of porous flat membrane by phase separation with supercritical CO2

Microporous polystyrene membranes were prepared by the phase separation process using the supercritical CO₂ as a nonsolvent for the polymer solution. The thin polymer solution in a laboratory dish was located inside a cell and the supercritical CO₂ was introduced to induce the phase separation. The dry flat microporous membranes were obtained without collapse of the structure after the CO₂ pressure was diminished. Effects of the experimental conditions such as the CO₂ pressure, the polymer concentration and the temperature on the average pore size and membrane porosity were investigated.     

The beneficial impacts of functional groups of CNT on structure and gas separation properties of PEBA mixed matrix membranes

Incompatibility between filler and polymer chains accompanied by particle agglomeration has a detrimental effect on the performance of mixed matrix membranes (MMMs). To obviate intermolecular forces of different additives, functional groups (-COOH, –NCO, and –NH₂) were grafted on the surface of multi-walled carbon nanotubes (MWCNTs) which were then incorporated as fillers in the poly(ether-block-amide) (PEBA) polymeric matrix in the range of 0.1–1 wt% loading. CO₂ permeability and ideal CO₂/N₂ and CO₂/CH₄ selectivity of MMMs was compared with the neat membrane, and the results revealed favorable enhancement and surpassed CO₂/N₂ Robeson's upper bound under 4–10 bar in the range of 15–55 °C. Mixed gas separation performance of MMMs, which is of vital importance in industrial applications, was also investigated. The results indicate that MWCNT-NCO created superior grafts with the polymer chains, and MMMs with this additive had a better gas separation performance with high mechanical and thermal stability.     

Hierarchical porous polymer beads prepared by polymerization-induced phase separation and emulsion-template in a microfluidic device

Porous polymer beads（PPBs） containing hierarchical bimodal pore structure with gigapores and meso-macropores were prepared by polymerization-induced phase separation（PIPS） and emulsion-template technique in a glass capillary microfluidic device（GCMD）. Fabrication procedure involved the preparation of water-in-oil emulsion by emulsifying aqueous solution into the monomer solution that contains porogen. The emulsion was added into the GCMD to fabricate the（water-in-oil）-in-water double emulsion droplets. The flow rate of the carrier continuous phase strongly influenced the formation mechanism and size of droplets. Formation mechanism transformed from dripping to jetting and size of droplets decreased from 550 μm to 250 μm with the increase in flow rate of the carrier continuous phase. The prepared droplets were initiated for polymerization by on-line UV-irradiation to form PPBs. The meso-macropores in these beads were generated by PIPS because of the presence of porogen and gigapores obtained from the emulsion-template. The pore morphology and pore size distribution of the PPBs were investigated extensively by scanning electron microscopy and mercury intrusion porosimetry（MIP）. New pore morphology was formed at the edge of the beads different from traditional theory because of different osmolarities between the water phase of the emulsion and the carrier continuous phase. The morphology and proportion of bimodal pore structure can be tuned by changing the kind and amount of porogen.     

Highly selective multilayer polymer thin films for CO2/N2 separation

Multilayer thin films of poly(ethylene oxide) (PEO) and poly(methacrylic acid) (PMAA), deposited via layer‐by‐layer (LbL) assembly from aqueous solutions, are investigated for CO₂/N₂ separation. Eight and ten bilayer (217 and 389 nm thick, respectively) PEO/PMAA thin films deposited on a 25 μm polystyrene substrate exhibit CO₂/N₂ selectivities of 142 and 136, respectively. These are the highest reported to‐date for this gas pair separation using a homogeneous polymer film. While further work remains to improve CO₂ permeability, these results indicate the potential of LbL assemblies as standalone CO₂ separation membranes for low‐flux/high‐purity applications, or as part of a composite and/or mixed‐matrix membrane for high‐flux applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1730–1737     

Carbonaceous nanomaterials immobilised mixed matrix membrane microextraction for the determination of polycyclic aromatic hydrocarbons in sewage pond water samples

In this study, the potential for carbonaceous nanomaterials to be used as adsorbents for the mixed matrix membrane (MMM) microextraction and preconcentration of organic pollutants was demonstrated. For this method, multiwall carbon nanotubes (MWCNT) and single layer graphene (SLG) nanoparticles were individually incorporated through dispersion in a cellulose triacetate (CTA) polymer matrix to form a MWCNT-MMM and SLG-MMM, respectively. The prepared membranes were evaluated for the extraction of selected polycyclic aromatic hydrocarbons (PAHs) present in sewage pond water samples. The extraction was performed by dipping a small piece of membrane (7 mm × 7 mm) in a stirred 7.5 mL sample solution to initiate the analyte adsorption. This step was followed by an analyte desorption into 60 μL of methanol prior to high performance liquid chromatography (HPLC) analysis. When the optimum SLG-MMM microextraction technique was applied to spiked sewage pond water samples, the detection limit of the method for the PAHs were in the range of 0.02–0.09 ng/mL, with relative standard deviations of between 1.4% and 7.8%. Enrichment factors of 54–100 were achieved with relative recoveries of 99%–101%. A comparison was also made between the proposed approach and standard solid phase extraction using polymeric bonded octadecyl (C₁₈) cartridges.     

Matrimid–polyaniline/clay mixed‐matrix membranes with plasticization resistance for separation of CO2 from natural gas

Mixed‐matrix membranes (MMMs) of Matrimid® and polyaniline/clay (PC) are investigated for CO₂/CH₄ separation and CO₂‐induced plasticization. PC particles are synthesized through in‐situ polymerization of aniline in the presence of organophilic clay and then incorporated into Matrimid by solution casting method. Chemical structure and morphology of PC powder and fabricated membranes are analyzed by Fourier transform infrared (FTIR), X‐ray diffraction (XRD), differential scanning calorimetry/thermogravimetric analysis (DSC/TGA) and scanning electron microscopy (SEM). The XRD spectra of PC particles show the exfoliation of silicate layers throughout the polyaniline (PAni) matrix, and SEM images indicate flower‐petal morphology for PC particles. The permeability values of CO₂ and CH₄ increase 30–35% by incorporation of 10 wt% PC without any significant drop in selectivity. PC particles with flower‐petal morphology plays an important role in increasing the gas permeability values of both gases while Matrimid is the only phase that controls CO₂/CH₄ selectivity. The plasticization pressure was increased to 30 bar by incorporation of 10 wt% PC in the Matrimid matrix. CO₂ permeability and p_plast improved 35% and 200%, respectively, resulting in 300% enhancement in the capacity of MMM in the purification of natural gas with a selectivity of about 40. Copyright © 2016 John Wiley & Sons, Ltd.