Modelling of multicomponent gas separation with asymmetric hollow fibre membranes—methane enrichment from biogas

A mathematical model for the dynamic performance of gas separation with high flux, asymmetric hollow fibre membranes was developed considering the permeate pressure build‐up inside the fibre bore and cross flow pattern with respect to the membrane skin. The solution technique provides reliable examination of pressure and concentration profiles along the permeator length (both residue/permeate streams) with minimal effort. The proposed simulation model and scheme were validated with experimental data of gas separation from literature. The model and solution technique were applied to investigate dynamic performance of several membrane module configurations for methane recovery from biogas (landfill gas or digester gas), considering biogas as a mixture of CO₂, N₂ and CH₄. Recycle ratio plays a crucial role, and optimum recycle ratio vital for the retentate recycle to permeate and permeate recycle to feed operation was found. From the concept of two recycle operations, complexities involved in the design and operation of continuous membrane column were simplified. Membrane permselectivity required for a targeted separation to produce pipeline quality natural gas by methane‐selective or nitrogen‐selective membranes was calculated. © 2012 Canadian Society for Chemical Engineering     

An overview of the mathematical modelling of liquid membrane separation processes in hollow fibre contactors

Liquid membranes have traditionally been employed for liquid/liquid mass transfer and have found applications in industrial, biomedical and analytical fields as well as in hydrometallurgical processes, wastewater treatment and remediation of polluted groundwater. However, in spite of the known advantages of liquid membranes, there are few examples of industrial application. The development of reliable mathematical models and design parameters (mass transport coefficients and equilibrium or kinetic parameters associated with the interfacial reactions) is a necessary step for design, cost estimation, process optimisation and scale‐up. This work reports an overview of the different approaches that have been proposed in the literature to the mathematical modelling of liquid membrane separation processes in hollow fibre contactors providing, at the same time, a useful guideline to characterise the mass transport phenomena and a tool for the optimal design and intensification of separation processes. Copyright © 2009 Society of Chemical Industry     

Poly(vinyl chloride) (PVC) hollow fibre membranes for gas separation

Poly(vinyl chloride) (PVC) gas separation hollow fibre membranes were produced from multicomponent dopes using dry/wet forced convection spinning. Membranes spun from a low polymer content solution exhibited disappointing gas separation properties. Their low selectivities were indicative of thick skins and high surface porosities. In contrast, high polymer content spun fibres showed good gas separation properties. Selectivities were high, active layers relatively thin and surface porosities moderate. Coating with poly(dimethylsiloxane) nullified the surface pores. The favourable performance of the high polymer content spun fibres was also related to shear rate and forced convection residence time during spinning. To the knowledge of the authors, this work represents the first reported success in producing PVC hollow fibre membranes with morphologies suitable for gas separation. The development of PVC hollow fibres relates to the ultimate quest to produce membranes capable of reliably separating oxygen and ozone gas mixtures.     

大规模膜法空气分离技术应用进展

富氧空气、氧气、氮气以及其他一些空气分离产品应用领域的增加 ,极大地推动了空气分离新技术的大规模发展。膜法空气分离以其节能、便利、安全等优异特性在空气分离产品的工业生产中展现出了极大的发展潜力。综述了现有膜材料的氧氮分离性能、制氧装置和制氮装置的研究开发及其在柴油发动机富氧燃烧等方面的应用研究 ,分析了膜法空气分离大规模商业化必须克服的技术障碍 ,从新型高性能膜材料的合成与制备方面提出了实现大规模膜法空气分离应用应采取的措施。     

Novel composite hollow fibre gas separation membranes with high selectivity and improved solvent resistance

Composite gas separation membranes with a 0.1–3 μm thick film of Hyflon AD 60X on a porous hollow fibre ultrafiltration membrane support of amorphous poly(ether ether ketone), were prepared. The influence of the coating conditions on the film thickness and on the pure gas transport properties was studied. The gas transport properties were related to the film thickness and to the morphology of the supporting UF membrane.     

Upscaling of asymmetric hollow fiber-supported thin film membranes for oxygen separation from air: Proof of concept

Hollow fiber membranes demonstrate various advantages for high performance oxygen separation. However, the small diameters of hollow fibers and the brittleness of ceramics limit their mechanical strength, imposing great difficulties on stack and module development. Gas-tight sealing is another challenge for upscaling of hollow fiber membrane technology. Low temperature sealant materials of epoxy resin or silicon are typically used for hollow fiber stacks, requiring that the sealing portions be located out of hot zone. Consequently, only partial length of hollow fibers participates in oxygen permeation. In this study, upscaling of our recently developed asymmetric hollow fiber-supported thin film membranes is conducted, where individual hollow fibers are assembled in parallel to form a stack. A reliable gas-tight sealing is obtained by combining ceramic paste with conductive adhesive ink cohesively. Comprehensive oxygen permeation test is conducted with the sealing portions being in hot zone and compared with a single hollow fiber membrane. Fundamental mechanism is discussed to understand the performances and their differences. An accelerated long-term test (∼320 h, 16 thermal cycles) demonstrates excellent stability and robustness of the stack and sealing. The characterization of post-test samples further confirms excellent stability and robustness of the phases and microstructures of the stack.     

高性能气体分离聚苯胺膜

系统论述了聚苯胺自支撑膜和复合膜对气体的分离性能。聚苯胺自支撑膜、聚苯胺 /尼龙、聚苯胺 /氧化铝复合膜经去掺杂尤其是二次掺杂后 ,气体分离系数会显著提高 ,而透气系数略有提高。二次掺杂态聚苯胺自支撑膜和复合膜都具有极高的氧氮分离性能 ,已超过了一般聚合物材料的上限 ,最优异的聚苯胺膜的氧氮选择分离系数可达 30 ,它在包括有高选择性能膜材料聚酰亚胺、聚吡咙、聚三唑等在内的所有聚合物膜中排行第一 ,对空气分离显示出极大优势。预计聚苯胺复合膜及纳米膜在医疗保健等领域具有很大应用潜力     

Synthesis and characterization of superoleophobic fumed alumina nanocomposite coated via the sol-gel process onto ceramic-based hollow fibre membrane for oil-water separation

Oily wastewater treatment is a global challenge due to the substantial amount of effluent resulted from many industrial and domestic activities. To overcome the challenge of using existing treatment approach and fouling, superoleophobic coatings were fabricated. In this study, a superoleophobic membrane surface was obtained using the sol-gel technique with perfluorooctanoate (PFO), poly (diallyl dimethylammonium chloride) (PDADMAC), and nanoparticles as complex-polymer nanocomposites. The effects of coating cycles on the surface structure, chemical properties, surface chemistry, and oleophobicity of the surface were examined using field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and oil contact angle measurement. The results showed that the coated layer successfully adhered to the substrate surface. However, the chemical stability with respect to oil contact angle (OCA) revealed a decline at pH 7 and pH 9 and maintained stability at pH 3. Besides, oil flux at 63.0 L/m². h was achieved for PDADMAC-Al₂O₃/44 wt% PFO and the highest separation efficiency of 98% was obtained. Furthermore, the oil rejection decreases as the oil concentration increases from 1 to 3 g/L. OCA of 155° was obtained after 5 coating cycles. Apart from mitigating substrate fouling, the superoleophobic and superhydrophilic coating can be applied to a ceramic-based hollow fibre membrane and efficiently used for the separation of oil from oily wastewater.     

Analysis of hollow fibre membrane systems for multicomponent gas separation

This paper analysed the performance of a membrane system over key design/operation parameters. A computation methodology is developed to solve the model of hollow fibre membrane systems for multicomponent gas feeds. The model represented by a nonlinear differential algebraic equation system is solved via a combination of backward differentiation and Gauss–Seidel methods. Natural gas sweetening problem is investigated as a case study. Model parametric analyses of variables, namely feed gas quality, pressure, area, selectivity and permeance, resulted in better understanding of operating and design optima. Particularly, high selectivities and/or permeabilities are shown not to be necessary targets for optimal operation. Rather, a medium selectivity (<60 in the given example) combined with medium permeance (∼300–500 × 10⁻¹⁰ mol/s m² Pa in the given case study) is more advantageous. This model-based membrane systems engineering approach is proposed for the synthesis of efficient and cost-effective multi-stage membrane networks.     

Graphene oxide membranes supported on the ceramic hollow fibre for efficient H2 recovery

The special channels and intrinsic defects within GO laminates make it a very potential candidate for gas separation in recent years. Herein, the gas separation performance of GO membranes prepared on the surface of ceramicα-Al_2O_3 hollow fibre was investigated systematically. The microstructures of ceramic hollow fibre supported GO membranes were optimized by adjusting operation conditions. And, the GO membrane fabricated at 30 min exhibited great promising H_2 recovery ability from H_2/CO_2 mixture. At room temperature, the H_2 permeance was over 1.00 × 10~(-7)mol·m~(-2)·s~(-1)·Pa~(-1)for both single gas and binary mixture. The corresponding ideal selectivity and mixture separation factor reached around 15 and 10, respectively. In addition, humility, operation temperature, H_2 concentration in the feed and the reproducibility were also studied in this work.     

Preparation of defect-free asymmetric membranes for gas separations

A technique was developed to prepare defect-free, asymmetric, polymer membranes for gas separation. The preparation method eliminates the need for coatings, which are usually required to render asymmetric, polymer based, membranes gas selective. In this method, a casting solution containing a polymer, solvent, and salt additive is given a desired shape and immersed in a coagulation bath containing a nonsolvent. The nonsolvent is selected to have a low affinity for both the solvent and salt additive. After the complete coagulation of the membrane, the additive salt is leached out in a second bath. This leads to the formation of an asymmetric membrane that has a well-interconnected porous network. The fine membrane structure is preserved by solvent exchange before it is finally dried. Polyetherimide (PEI) (Ultem® 1000) membranes were prepared from casting solutions containing 23, 25, and 26.5% (wt) PEI, various amounts of lithium nitrate and N-methyl-2-pyrrolidinone (NMP). Membrane performance was determined for the separation of oxygen from air. The effects of polymer concentration, additive salt concentration and the drying process on oxygen permeance, and the actual separation factor of the membrane are discussed. The addition of a small amount of solvent to the coagulation bath improved the leaching of the salt additive and produced membranes with a more open structure. A polymer concentration of 23% produced membranes with the highest performance. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1471–1482, 1999     

Hydrogen separation at elevated temperatures using metallic nickel hollow fiber membranes

Nickel is a cheaper metallic material compared to palladium membranes for H₂ separation. In this work, metallic Ni hollow fiber membranes were fabricated by a combined phase inversion and atmospheric sintering method. The morphology and membrane thickness of the hollow fibers was tuned by varying the spinning parameters like bore liquid flow rate and air gap distance. H₂ permeation through the Ni hollow fibers with N₂ as the sweep gas was measured under various operating conditions. A rigorous model considering temperature profiles was developed to fit the experimental data. The results show that the hydrogen permeation flux can be well described by using the Sieverts’ equation, implying that the membrane bulk diffusion is still the rate‐limiting step. The hydrogen separation rate in the Ni hollow fiber module can be improved by 4–8% when switching the co‐current flow to the countercurrent flow operation. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3026–3034, 2017     

The effects of spinning conditions on asymmetric 6FDA/6FDAM polyimide hollow fibers for air separation

We have found that the chemistries of inner and external coagulants, gelation bath temperature, and air gap distance have profound effects on 6FDA-polyimde hollow-fiber morphology and performance. This 6FDA-polyimide is made of 50 mol % 2,2′-bis(3,4′-dicarboxyphenyl) hexafluoro propane dianhydride (6FDA) and 50 mol % 2,2′-bis(3-aminophenyl) hexafluoro propane (4,4′ 6F-diamine) (6FDAM). An increase in air gap distance tends to induce three-dimensional open-cell pore formation. Raising bath temperature has a similar effect. Multilayer finger-void structure can be completely eliminated if one properly chooses a bore-fluid flow rate and a gelation bath temperature. Experimental data demonstrate that the location of the dense layer can be shifted from the inner skin to the outer skin based on the chemistry (solubility parameter) of coagulants. The location of finger voids is also dependent on the chemistry of coagulants, and the dense layer location may shift from the inner surface to the external surface or appear in both surfaces dependent on the differences in solubility and coagulation rate. A defect-free 6FDA/6FDAM polyimide fiber with a selectivity of 4.73 and a permeance of 38.1 GPU is produced. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1555–1569, 1997     

Preparation and properties of hollow fibre nanofiltration membrane with continuous coffee-ring structure

Polyamide(PA)hollow fibre composite nanofiltration(NF)membranes with a coffee-ring structure and beneficial properties were prepared by adding graphene oxide(GO)into the interfacial polymerization process.The presentation of the coffee-ring structure was attributed to the heterogeneous,finely dispersed multiphase reaction system and the“coffee-stain”effect of the GO solution.When the piperazine concentration was 0.4 wt-%,the trimesoyl chloride concentration was 0.3 wt-%,and the GO concentration was 0.025 wt-%,the prepared NF membranes showed the best separation properties.The permeate flux was 76 L·m^?2·h^?1,and the rejection rate for MgSO4 was 98.6%at 0.4 MPa.Scanning electron microscopy,atomic force microscopy,and attenuated total reflectance-Fourier transform infrared spectroscopy were used to characterize the chemical structure and morphology of the PA/GO NF membrane.The results showed that GO was successfully entrapped into the PA functional layer.Under neutral operating conditions,the PA/GO membrane showed typical negatively charged NF membrane separation characteristics,and the rejection rate decreased in the order of Na2SO₄>MgSO₄>MgCl₂>NaCl.The PA/GO NF membrane showed better antifouling performance than the PA membrane.     

Simultaneously tuning dense skin and porous substrate of asymmetric hollow fiber membranes for efficient purification of aggressive natural gas

Highly permeable, selective, and stable asymmetric membranes are required to replace the traditional separation approaches for natural gas purification with higher energy efficiency and smaller footprints. Herein, we report on the design and engineering of defect-free asymmetric hollow fiber membranes with a thin dense skin and highly porous substrate to effectively deal with aggressive natural gas. A crosslinkable polymer with rigid molecular structure and high molecular weight was synthesized for developing spinning dope with desirable solution properties. Phase separation behavior of the polymer was carefully controlled by systematic formulation of the dope composition and optimizing spinning conditions, thereby realizing simultaneously tuning dense skins and porous substrates of the spun asymmetric hollow fiber membranes. The crosslinked hollow fiber membrane, with well-preserved delicate asymmetric nanostructures, exhibited unprecedentedly high and stable separation performance for long-term processing extremely aggressive CO₂/CH₄ mixtures (with pressure up to 820 psi containing C6⁺ hydrocarbons), thereby showing great potential for practical application of natural gas purification. This work offers a new platform to create hollow fiber membranes with both high permeance and plasticization resistance in natural gas service. © 2019 American Institute of Chemical Engineers AIChE J, 65: 1269–1280, 2019     

Polydimethylsiloxane/postmodified MIL‐53 composite layer coated on asymmetric hollow fiber membrane for improving gas separation performance

Composite layer containing postmodified MIL‐53 (P‐MIL‐53) was exploited to be coated on as‐fabricated asymmetric hollow fiber membrane for improving gas separation performance. The morphology and pore size distribution of P‐MIL‐53 particles were characterized by SEM and N₂ adsorption isotherm. The EDX mapping and FTIR spectra were performed to confirm the presence of P‐MIL‐53 deposited on the outer surface of hollow fiber membranes. The results of pure gas permeation measurement indicated that incorporation of P‐MIL‐53 particles in coating layer could improve permeation properties of hollow fiber membranes. By varying coating times and P‐MIL‐53 content, the membrane coated with PDMS/15%P‐MIL‐53 composite by three times achieved best performance. Compared to pure PDMS coated membrane, CO₂ permeance was enhanced from 29.96 GPU to 40.24 GPU and ideal selectivity of CO₂/N₂ and CO₂/CH₄ also increased from 23.28 and 26.95 to 28.08 and 32.03, respectively. The gas transport through composite membrane was governed by solution‐diffusion mechanism and CO₂ preferential adsorption of P‐MIL‐53 contributed to considerable increase of CO₂ solubility resulting in accelerated permeation rate. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44999.     

超声对聚偏氟乙烯中空纤维超滤膜的清洗研究

文章探讨了超声清洗对聚偏氟乙烯(PVDF)中空纤维超滤膜的损坏及其通量的影响。实验表明,膜面的破坏随声强和处理时间的增加而增加,但声强在2 200 W/m2时,处理30 h膜面无损坏。新膜易被饱和CaC l2溶液污染,通量下降明显。清洗实验表明,超声和稀柠檬酸协同作用能较易地除去新膜表面的污垢,使其通量恢复到初始通量的81%,而仅用酸洗只能使膜通量恢复到初始通量的66.3%。对于污染较重的膜必须用稀酸浸泡,浸泡7 h后,超声和稀柠檬酸协同清洗可使通量恢复到初始通量的73.2%,明显高于无浸泡时的56.2%。     

Characterization of crosslinked hollow fiber membranes

As the applications for polymeric membranes expand, new challenges arise. One of the largest of these challenges is the plasticization caused by strongly swelling penetrants such as carbon dioxide at elevated pressures. A considerable amount of material research has investigated crosslinking of dense film membranes to increase plasticization resistance. This paper extends such materials research to include more practically relevant asymmetric hollow fibers. Crosslinkable polyimide fibers were spun and an ester crosslinking reaction was studied using chemical and spectroscopic techniques to characterize the extent of crosslinking and to relate the effect of the reaction on fiber stability. CO₂ permeance and CO₂/CH₄ selectivity were studied at a variety of pressures and temperatures over time to yield indications of real-world separation performance.     

Preparation and characterization of several types of polyvinyl butyral hollow fiber membranes by thermally induced phase separation

Hollow fiber membranes were prepared by thermally induced phase separation from three types of polyvinyl butyral (PVB) and a blend of two of these polymers. Although the difference in the chemical composition of the PVB polymers used was not remarkable, their respective membrane performances were quite different. With a high phase separation temperature the pore size of the prepared membrane was large, because structure growth occurred for a long time. Water permeability tests of the wet membranes showed the results that corresponded to the pore sizes of the membranes. By contrast, the results for the dried membrane appeared to be related to the hydrophilicity of the PVB polymer and independent of pore size in the wet condition. Although the membrane with high wettability had low mechanical strength, the membrane from the polymer blend of two different PVB polymers showed adequate wettability and mechanical strength. This produced a hollow fiber membrane with favorable characteristics for application in water treatment. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Simulation of gas separation using partial element stage cut modeling of hollow fiber membrane modules

A mathematical model is developed to simulate a gas separation process using a hollow fiber membrane module. In particular, a new numerical technique is introduced based on flash calculation. Such analysis allows identifying the required membrane properties needed to reach module performance of interest. This model is validated for six different gas separation cases taken from literature. Then, the validated model is used to investigate the effect of O₂ and N₂ permeances on O₂ recovery and O₂ mole fraction in the permeate stream. A realistic two‐stage air enrichment process is also proposed for O₂ production using an industrial module with different fibers numbers. Moreover, this model is used to simulate a natural gas purification process using a single unit to determine the required membrane separation area and CH₄ loss. Finally, a two‐stage process is proposed to equally enhance CH₄ retentate mole fraction and decrease CH₄ loss. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1766–1777, 2018