The effect of ethane on the performance of commercial polyphenylene oxide and Cardo-type polyimide hollow fiber membranes in CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation applications

Impurities such as hydrogen sulfide, water vapor and heavy hydrocarbons in natural gas have considerable effects on the membrane performance. Small amounts of condensable and polymer soluble components in the feed gas cause swelling or plasticization of glassy membranes, leading to a reduction in membrane selectivity. In the present research the influence of ethane was investigated on the permeance and selectivity of two commercially available hollow fiber membranes, namely Cardo-type polyimide and PPO hollow fibers for CO₂/CH₄ separations. It was concluded that the gas mixture permeation rate was increased in the presence of C₂H₆. However, the CO₂/CH₄ separation factors remained almost the same in the presence and absence of the C₂H₆.     

Separation of Hydrogen from Carbon Monoxide Using a Hollow Fiber Polyimide Membrane: Experimental and Simulation

The separation of hydrogen from carbon monoxide (syngas ratio adjustment) with polymeric membranes was investigated in this work. A polyimide hollow fiber membrane module was used for hydrogen separation. This polymer has shown large permeability and selectivity for hydrogen separation (selectivity of ca. 30). Permeation tests were carried out at different feed conditions. Feed flow rates were varied between 150–300 mL/min, temperature was varied in the range of 20–80 °C and feed pressure was varied between 5–9 bar. Mixtures containing 0–50 % carbon monoxide were used when carrying out experiments. Measured membrane permeances for hydrogen and carbon monoxide were about 70–100 GPU (gas permeation units) and 3–5.5 GPU, respectively. In addition, a mathematical model for simulation of gas separation in hollow fiber membrane modules with all flow patterns (crossflow, countercurrent and cocurrent) was presented. This model can be used for calculation of membrane performance or its required surface area for a specific separation. Experimental results have shown good correlation with simulation results. Plasticization, competitive sorption and concentration polarization effect of carbon monoxide on membrane performance is shown with experimental results. This effect reduced hydrogen permeances in mixed gas experiments.     

Fabrication of polyimide hollow fiber membrane with well‐defined adsorption channels and binding sites for organics separation

Significant attention has been focused in developing polymeric membranes with special separation function. Disclosed herein is the design of a solvent resistant hollow fiber membrane with multi architectures including self‐supported passageway, three‐dimensional adsorption channels, and binding sites for organics sulfur. A new strategy has been proposed for high‐performance polyimide hollow fiber membranes by tuning the imidization behavior. The evolution of structure and performance with the proposed imidization routes has been investigated based on detailed analysis of FT‐IR, TGA, and mechanical properties. The results show that the functional zeolites are incorporated into three‐dimensional polyimide matrix. The well‐defined transport channels at micrometer scale in membrane provide high‐efficiency working space. The effective binding behavior of designed hollow fiber membrane chromatography for organic sulfur compounds has been confirmed by the comparative analysis on dynamic breakthrough curves. The related discussions have some general suggestions in promoting the new application of membrane chromatography for the quick separation and purification of sulfur, and present a potential alternative for the production of sulfur‐free hydrogen source for fuel cell applications. POLYM. ENG. SCI., 58:1024–1032, 2018. © 2017 Society of Plastics Engineers     

Effect of the preparation conditions on the morphology and performance of poly(imide) hollow fiber membranes

Poly(imide) (PI) hollow fiber membranes were prepared by using classical phase inversion process. Effects of different external coagulation bath temperatures (ECBT) and various bore flow rates (BFR) on the morphology and separation performance of the membranes were studied. Cross‐section, inner and outer structures were characterized by using scanning electron microscope and atomic force microscopy (AFM). Mean pore size, pore size distribution, and mean roughness of the PI hollow fibers surfaces were estimated by AFM. It was found that the hollow fibers morphology composed of sponge‐like and finger‐like structures with different ECBT and BFR. A circular shape of the nodules with different sizes was observed in the outer surface of the PI hollow fibers. Mean pore size of the outer surface increases with increasing ECBT and BFR. The important result observed in this study is that the ECBT clearly has the largest effect on hollow fiber PI membrane roughness compared with the BFR. Pure water permeability of the PI hollow fibers was improved with increase of ECBT and BFR. The solute rejection (R%) was reduced when the ECBT and BFR was increased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40428.     

Chemical stability of polyimide membranes at temperatures near Tg

The success of polymeric membranes for use in high temperature gas separation applications relies, in part, on the chemical stability of these materials in separation environment. This paper details experimental evaluation of the stability of the membranes prepared using a polyimide as the selective separating layer when exposed to butane/butene/hydrogen mixtures at temperatures near the glass transition temperature of the polymer, 310°C. Further, the effects of small concentrations of sulfur and ammonia compounds in the feed mixture were investigated, as was the influence of a simulated air leak. The gas transport rates and selectivities were unchanged when testing in the hydrocarbon/hydrogen environment for over 30 days. Further, no changes in transport properties were observed when hydrogen sulfide or ammonia was added to the feed mixture. However, degradation due to oxygen exposure was observed. The chemical stability of the polyimide layer appears to be sufficient to be utilized for the separation of high temperature petrochemical streams. © 1995 John Wiley & Sons, Inc.     

Water vapor permeation and compressed air dehydration performances of modified polyimide membrane

In this paper, modification of polyimide hollow fiber membrane was carried out by introduction of tetrabutylammonium naphthalenesulfonate (BAN) into the membrane matrix. Permeation performance of modified hollow fibers was investigated helps to compressed air dehydration ability across the membrane. The experimental results showed that water sorption and water vapor permeability obviously increase with increase on BAN content in modified membranes, and air dehydration performance was improved by increasing BAN in membrane and ratio of sweeping gas. Moreover, operational pressure and feed flux also impose on important effect on compressed air dehydration capability.     

Oxygen selective ceramic hollow fiber membranes for partial oxidation of methane

A BaCo_xFe_yZr_zO_3?δ (BCFZ) perovskite hollow fiber membrane was used to construct reactors for the partial oxidation of methane (POM) to syngas. The performance of the BCFZ fibers in the POM was studied (i) without any catalyst, (ii) with catalyst‐coated fibers, and (iii) with catalyst packed around the fibers. In addition to the performance in the POM, the stability of the BCFZ hollow fiber membranes was investigated for the different catalyst arrangements. Best stability of the BCFZ hollow fiber membrane reactor in the POM could be obtained if the reforming catalyst is placed behind the oxygen permeation zone. It was found that a direct contact of the catalyst and the fiber must be avoided which could be achieved by coating the fiber with a gold film. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Oxyfuel combustion using a catalytic ceramic membrane reactor

Membrane catalytic combustion (MCC) is an environmentally friendly technique for heat and power generation from methane. This work demonstrates the performances of a MCC perovskite hollow fibre membrane reactor for the catalytic combustion of methane. The ionic–electronic La_0.6Sr_0.4Co_0.2Fe_0.8O₃₋ (LSCF6428) mixed conductor, in the form of an oxygen-permeable hollow fibre membrane, has been prepared successfully by means of a phase-inversion spinning/sintering technique. For this process polyethersulfone (PESf) was used as a binder, N-methyl-2-pyrrollidone (NMP) as solvent and polyvinylpyrrolidone (PVP, K16-18) as an additive. With the prepared LSCF6428 hollow fibre membranes packed with catalyst, hollow fibre membrane reactors (HFMRs) have been assembled to perform the catalytic combustion of methane. A simple mathematical model that combines the local oxygen permeation rate with approximate catalytic reaction kinetics has been developed and can be used to predict the performance of the HFMRs for methane combustion. The effects of operating temperature and methane and air feed flow rates on the performance of the HFMR have been investigated both experimentally and theoretically. Both the methane conversion and oxygen permeation rate can be improved by means of coating platinum on the air side of the hollow fibre membranes.     

Removal of Volatile Organic Compounds from Water by Pervaporation Using Polyetherimide-Polyethersulfone Blend Hollow Fiber Membranes

Abstract

Removal of volatile organic compounds (VOCs) such as 1,2-dichloroethane, trichloroethylene, chlorobenzene and toluene from water solutions through polyetherimide (PEI)-polyethersulfone (PES) blend hollow fiber membranes was investigated by pervaporation (PV) in this work. The separation performances of the membranes were researched by varying the spinning conditions (such as coagulation temperature and air gap distance) for the preparation of the hollow fibers and the operation conditions (such as velocity, concentration, and temperature of feed liquids). For the PEI-PES blend hollow fiber membrane prepared when the air gap was 7 cm and the temperature of coagulation bath was 45°C, it possessed high selectivity to the aqueous solutions containing 0.04 wt.% of VOCs at 20°C. The separation factors to 1,2-dichloroethane, trichloroethylene, chlorobenzene and toluene were 7069, 5759, 3952, and 3205, respectively. It was found that the pervaporation performance of the blend hollow fiber membrane was strongly related to the molecular size of the VOCs. The order of the selectivities was 1,2-dichloroethane > trichloroethylene > chlorobenzene > toluene.     

Effect of polyvinylpyrrolidone molecular weights on morphology,oil/water separation,mechanical and thermal properties of polyetherimide/polyvinylpyrrolidone hollow fiber membranes

We prepared polyetherimide (PEI) hollow fiber membranes using polyvinylpyrrolidones (PVP) with different molecular weights (PVP 10,000, PVP 40,000, and PVP 1,300,000) as additives for oil/water separation. Asymmetric hollow fiber membranes were fabricated by wet phase inversion technique from 25 wt % or 30 wt % solids of 20 : 5 : 75 or 20 : 10 : 70 (weight ratio) PEI/PVP/N‐metyl‐2‐pyrrolidone (NMP) solutions and a 95 : 5 NMP/water solution was used as bore fluid to eliminate resistance on the internal surface. Effects of PVP molecular weights on morphology, oil‐surfactant‐water separation characteristics, mechanical, and thermal properties of PEI/PVP hollow fiber membranes were investigated. It was found that an increase in PVP molecular weight and percentage in PEI/PVP dope solution resulted in the membrane morphology change from the finger‐like structure to the spongy structure. Without sodium hypochlorite posttreatment, hollow fiber membranes with higher PVP molecular weights had a higher rejection but with a lower water flux. For oil‐surfactant‐water emulsion systems (1600 ppm surfactant of sodium dodecylbenzenesulfonate and 2500 ppm oil of n‐decane), experimental results illustrated that the rejection rates for surfactant, total organic carbon, and oil were 76.1 ≈ 79.8%, 91.0 ≈ 93.0%, and more than 99%, respectively. Based on the glass transition temperature values, PVP existed in hollow fiber membranes and resulted in the hydrophilicity of membranes. In addition, using NaOCl as a posttreatment agent for membranes showed a significant improvement in membrane permeability for PVP with a molecular weight of 1300 K, whereas the elongation at break of the treated hollow fiber membranes decreased significantly. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2220–2233, 1999     

添加剂和凝结剂温度对用无溶剂致相位分离法生产高性能PVDF/聚醚F127混合中空光纤膜的影响(英文)

Poly(vinylidene fluoride)(PVDF) has become one of the most popular materials for membrane prepara-tion via nonsolvent induced phase separation(NIPS) process.In this study,an amphiphilic block copolymer,Plu-ronic F127,has been used as both a pore-former and a surface-modifier in the fabrication of PVDF hollow fiber membranes to enhance the membrane permeability and hydrophilicity.The effects of 2nd additive and coagulant temperature on the formation of PVDF/Pluronic F127 membranes have also been investigated.The as-spun hollow fibers were characterized in terms of cross-sectional morphology,pure water permeation(PWP),relative molecular mass cut-off(MWCO),membrane chemistry,and hydrophilicity.It was observed that the addition of Pluronic F127 significantly increased the PWP of as-spun fibers,while the membrane contact angle was reduced.However,the size of macrovoids in the membranes was undesirably large.The addition of a 2nd additive,including lithium chlo-ride(LiCl) and water,or an increase in coagulant temperature was found to effectively suppress the macrovoid for-mation in the Pluronic-containing membranes.In addition,the use of LiCl as a 2nd additive also further enhanced the PWP and hydrophilicity of the membranes,while the surface pore size became smaller.PVDF hollow fiber with a PWP as high as 2530 L?m?2?h?1?MPa?1,a MWCO of 53000 and a contact angle of 71° was successfully fabricated with 3%(by mass) of Pluronic F127 and 3%(by mass) of LiCl at a coagulant temperature of 25 °C,which shows better performance as compared with most of PVDF hollow fiber membranes made by NIPS method.     

Poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐co‐HFP) hollow fiber membranes prepared from PVDF‐co‐HFP/PEG‐600Mw/DMAC solution for membrane distillation

Poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐co‐HFP) hollow fiber membranes were prepared by using the phase inversion method. The effect of polyethylene glycol (PEG‐600Mw) with different concentrations (i.e., 0, 5, 7, 10, 12, 15, 18, and 20 wt %) as a pore former on the preparation and characterization of PVDF‐co‐HFP hollow fibers was investigated. The hollow fiber membranes were characterized using scanning electron microscopy, atomic force microscopy, and porosity measurement. It was found that there is no significant effect of the PEG concentration on the dimensions of the hollow fibers, whereas the porosity of the hollow fibers increases with increase of PEG concentration. The cross‐sectional structure changed from a sponge‐like structure of the hollow fiber prepared from pure PVDF‐co‐HFP to a finger‐like structure with small sponge‐like layer in the middle of the cross section with increase of PEG concentration. A remarkable undescribed shape of the nodules with different sizes in the outer surfaces, which are denoted as “twisted rope nodules,” was observed. The mean surface roughness of the hollow fiber membranes decreased with an increase of PEG concentration in the polymer solution. The mean pore size of the hollow fibers gradually increased from 99.12 to 368.91 nm with increase of PEG concentration in polymer solution. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

热致相分离法iPP中空纤维微空膜结构与性能--稀释剂的作用

Isotactic polypropylene （iPP） hollow fiber microporous membranes were prepared using thermally induced phase separation （TIPS） method. Di-n-butyl phthalate （DBP）, dioctyl phthalate （DOP）, and the mixed solvent were used as diluents. The effect of α （DOP mass fraction in diluent） on the morphology and performance of the hollow fiber was investigated. With increasing α, the morphology of the resulting hollow fiber changes from typical cellular structure to mixed structure, and then to typical particulate structure. As a result, the permeability of the hollow fiber increases sharply, and the mechanical properties of the hollow fiber decrease obviously. It is suggested that the morphology and performances of iPP hollow fiber microporous membrane can be controlled via adjusting the compatibility between iPP and diluent.     

聚酰亚胺中空纤维膜的热亚胺化及碳化的研究

聚酰亚胺（P1）是一种性能忧良的新型膜材料。就其在热亚胺化过程中的一些因素对膜性能影响及碳化过程中的PI膜结构变化怍一定的研究与分析讨论,从而推断其可能的结构变化,     

镍基非对称中空纤维膜用于乙醇自热重整制氢

采用纺丝-烧结技术制备了具有内表面致密皮层的外支撑式金属镍非对称中空纤维膜,并用于乙醇自热重整（EATR）制氢,研究了温度、进料流速、吹扫气流速、水醇比（S/C）以及氧醇比（O₂/C）等操作条件对膜制氢性能的影响。结果表明,金属镍非对称中空纤维膜既具有优异的EATR催化活性,又有良好的透氢性能。在500～1000℃、S/C=4、O₂/C=0.8的条件下乙醇可完全转化,H₂产率和H₂渗透通量可分别达到81.59%和13.99 mmol/（m²·s）,增加进料中氧气含量可显著抑制膜表面积炭,但同时也会降低氢气产率和一氧化碳选择性。     

耐溶剂聚酰亚胺/陶瓷复合膜的制备及性能表征

采用3,3',4,4'-二苯酮四羧酸二酐(BTDA)、4,4'-二氨基二苯基甲烷(MDA)和4,4'-二氨基联苯(Bz)按一定比例共聚合成了一类新的共聚型聚酰亚胺(PI-BTDA/MDA/Bz),通过调整MDA和Bz的比例制备了4种具有不同化学结构的聚酰亚胺均质膜,测试了这些聚酰亚胺均质膜对水的接触角和在N,N-二甲基甲酰胺中的溶胀性。实验结果表明:BTDA、MDA、Bz的摩尔比为5:4:1时,所得的聚酰亚胺均质膜亲水性最好,且耐溶剂性能最优。以此比例的聚酰胺酸为铸膜液,0.2mm孔径的Al₂O₃陶瓷膜片为支撑体,制备了聚酰亚胺复合膜,并考察了进料温度和进料浓度对复合膜分离性能的影响。     

Solvent-resistant ultrafine nonwoven fibrous membranes by ultraviolet-assisted electrospinning of organo-soluble photosensitive polyimide resin

An ultraviolet-assisted electrospinning (UVAES) method was investigated to improve the solvent stability of soluble polyimide (PI) electrospun ultrafine fibrous membranes (UFMs) to assist in the development of fibrous polymeric materials with improved resistance to harsh environmental conditions and to expand the potential applications for such soft filaments. A preimidized soluble negative photosensitive polyimide (PSPI) was synthesized via an one-step thermal polycondensation from 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 1,1′-bis(4-amino-3,5-dimethylphenyl)-1-(3′-trifluoromethylphenyl)methane (TFMDA). The PI resin was then fabricated into UFMs by both conventional electrospinning (ES) and UVAES with N,N-dimethylacetamide (DMAc) as the solvent. During spinning, photo crosslinking reaction occurred, accompanied by simultaneous micro-jets of PI-UV ultrafine fibers in the UVAES procedure. This created fibers that were thermally stable at higher than 500°C, reflection over 77% of the 457-nm- wavelength light, whiteness index (WI) higher than 83, and enhanced solvent resistance in DMAc. Generally speaking, compared with the PI UFMs fabricated by conventional ES procedure, the PI-UV UFMs obtained by the newly-developed UVAES procedure showed much superior solvent resistance, comparable thermal stability, slightly decreased optical reflectance and WI values, and reduced fiber diameters. These properties are of great value to future applications in microelectronics and wearable technology.     

Effect of TEP content in cooling bath on porous structure,crystalline and mechanical properties of PVDF hollow fiber membranes

Poly (vinylidene fluoride) (PVDF) hollow fiber membranes were prepared by adding triethyl phosphate (TEP) to the cooling water bath in a modified thermally induced phase separation process. The effect of TEP content in the cooling bath on the porous structure, crystallinity, thermal and mechanical properties of PVDF hollow fiber membranes was investigated. The melting temperature and crystallinity of the membranes were determined using differential scanning calorimetry. The crystalline and cross‐section morphology of the hollow fiber membranes were investigated using wide angle X‐ray diffraction and scanning electron microscopy. The resulting membrane exhibited a nearly symmetric structure. The results showed that the TEP content in the cooling bath had a crucial role on the membrane formation, which was also confirmed from the morphology and mechanical properties of the hollow fibers. The porosity, average pore size, crystallinity, Young's modulus, max stress, and elongation at breakage of the hollow fiber membranes can be related to the amount of TEP in the cooling bath. Better pore connectivity was obtained in hollow fiber membranes when the weight ratio of TEP to water was 40:60. POLYM. ENG. SCI., 54:2207–2214, 2014. © 2013 Society of Plastics Engineers     

Effect of polyethylene glycol molecular weights and concentrations on polyethersulfone hollow fiber ultrafiltration membranes

Polyethersulfone (PES) hollow‐fiber membranes were fabricated using poly(ethyleneglycol) (PEG) with different molecular weights (MW = PEG200, PEG600, PEG2000, PEG6000, and PEG10000) and poly(vinyl pyrrolidone) PVP40000 as additives and N‐methyl‐2‐pyrrolidone (NMP) as a solvent. Asymmetric hollow‐fiber membranes were spun by a wet phase‐inversion method from 25 wt % solids of 20 : 5 : 75 (weight ratio) PES/PEG/NMP or 18 : 7 : 75 of PES/(PEG600 + PVP40000)/NMP solutions, whereas both the bore fluid and the external coagulant were water. Effects of PEG molecular weights and PEG600 concentrations in the dope solution on separation properties, morphology, and mechanical properties of PES hollow‐fiber membranes were investigated. The membrane structures of PES hollow‐fiber membranes including cross section, external surface, and internal surface were characterized by scanning electron microscopy and the mechanical properties of PES hollow‐fiber membranes were discussed. Bovine serum albumin (BSA, MW 67,000), chicken egg albumin (CEA, MW 45,000), and lysozyme (MW 14,400) were used for the measurement of rejection. It was found that with an increase of PEG molecular weights from 200 to 10,000 in the dope solution, membrane structures were changed from double‐layer fingerlike structure to voids in the shape of spheres or ellipsoids; moreover, there were crack phenomena on the internal surfaces and external surfaces of PES hollow‐fiber membranes, pure water permeation fluxes increased from 22.0 to 64.0 L m^?2 h^?1 bar^?1, rejections of three protein for PES/PEG hollow‐fiber membranes were not significant, and changes in mechanical properties were decreased. Besides, with a decrease of PEG600 concentrations in the dope solution, permeation flux and elongation at break decreased, whereas the addition of PVP40000 in the dope solution resulted in more smooth surfaces (internal or external) of PES/(PEG600 + PVP40000) hollow‐fiber membranes than those of PES/PEG hollow‐fiber membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3398–3407, 2004     

The effect of carbon fiber content on the friction and wear properties of carbon fiber reinforced polyimide composites

The current study examines the tribological performance of polyimide and carbon fiber reinforced polyimide (CF/PI) under dry sliding condition. Different contents of carbon fibers were employed as reinforcement. All filled and unfilled polyimide composites were tested against CGr15 ball and representative testing was performed. The effects of carbon fiber content on tribological properties of the composites were investigated. The worn surface morphologies of neat PI and its composites were examined by scanning electron microscopy and the wear mechanisms were discussed. Moreover, all filled polyimides have superior tribological characteristics to unfilled polyimides. The optimum wear reduction was obtained when the content of carbon fiber is 20 vol %. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008