Search Results (144)

Atmospheric carbon dioxide (CO₂) has reached an unprecedented 430 ppm, warming the planet by 50% compared with pre-industrial times and prompting a search for a quick and effective solution to control CO₂ emissions. As a robust, renewable, biodegradable, and sustainable material, nanocellulose can serve as a strong support for many active molecules. Nanocellulose, whether in suspension, aerogel, or membrane form, is not sufficient for efficient CO₂ capture and separation; hence, active molecules, such as silanes, amines, zeolites, and metal–organic frameworks (MOFs), are introduced via chemical modification, such as grafting, or via physical mixing as fillers or additives to make nanocellulose effective for CO₂ capture and separation. Introducing amine or silane molecules into nanocellulose has proven to be an effective strategy for achieving a satisfactory CO₂ absorption capacity exceeding 6 mmol/g. Nanocellulose membranes, when fabricated with MOFs or zeolites and used as a coating with polyvinyl alcohol (PVA) to create a thin-film composite membrane (TFC), can achieve CO₂ permeance of more than 600 GPU for CO₂ separation from flue gas, with CO₂/N₂ selectivity close to 40. This review provides an overview of nanocellulose-based CO₂ capture and separation materials developed over the last 10 years, along with the related challenges that must be overcome to meet current performance and demand. To facilitate readability, the author has provided a brief introduction to the origin, performance, and scale-up developments of nanocellulose at the start of this review. Full article

Graphene oxide (GO) membranes present a compelling alternative to the permeability-selectivity trade-off inherent in conventional polymer membranes. However, the incomplete mechanistic understanding and the absence of scalable, defect-controlled fabrication processes continue to hinder their practical deployment. This review synthesizes and integrates transport mechanisms, computational modeling, fabrication, and translational constraints across graphene-based membrane architectures into a comprehensive design-oriented framework. Five key aspects of this synthesis are highlighted. Firstly, the available evidence supports a three-regime transport model, which unifies viscous near-frictionless flow, activated molecular hopping, and solution–diffusion. This reframes selectivity as a tunable function of the C/O ratio and interlayer chemistry. Secondly, a quantitative parity analysis of literature data reveals that classical molecular dynamics tends to overestimate GO laminate water permeance by a representative factor of approximately 3–8× across the matched comparisons examined. This discrepancy can be corrected using a tortuosity–porosity factor derived from wet-state XRD. Machine-learning force fields (GAP, MACE), while still in an early stage of development with limited reported applications, narrow the residual discrepancy to within 1.5–2× in the studies reviewed. Thirdly, a tiered computational roadmap identifies nuclear quantum effects as critical for proton-transport applications but unresolved for water permeance in GO laminate geometry. Fourthly, performance across water nanofiltration, gas separation, ion recovery, and osmotic energy harvesting is benchmarked against commercial references, with explicit caveats regarding the heterogeneity of testing conditions across cited studies, alongside a technology readiness assessment. Lastly, a standardized 500-h hydraulic stability protocol is proposed to facilitate cross-laboratory comparison. Collectively, this synthesis provides a structured, albeit not exhaustively validated, basis for the discussion of next-generation membrane design. Full article

Although coconut water is recognized for its desirable sensory appeal and nutritional composition, its broader industrial use is constrained by the rapid deterioration that occurs after extraction. In this study, crossflow microfiltration of coconut water with a silicon carbide membrane was optimized by investigating pressure and temperature through a face-centered design (FCD) and artificial neural network modeling coupled with a genetic algorithm (ANN–GA). Permeate flux and fouling index were used as process responses, and the optimized condition was further examined in terms of hydraulic resistance, fouling behavior, and retention of minerals and primary metabolites. Pressure and temperature affected the process differently: permeate flux showed marked nonlinear behavior, whereas fouling index was governed mainly by pressure. At the sample level, ANN described permeate flux more accurately than FCD (R² = 0.99 vs. 0.96), whereas FCD showed better grouped cross-validated predictivity across unseen pressure–temperature conditions (Q² = 0.85 vs. 0.57). For the fouling index, FCD outperformed ANN in both sample-level fit and grouped validation (R² = 0.95 vs. 0.60; Q² = 0.70 vs. 0.61). Both approaches converged on the same favorable operating window, and experimental validation at 60 kPa and 35 °C yielded 1085.23 ± 23.12 L h⁻¹ m⁻² and 83.56 ± 1.56%. During concentration mode, flux decline was severe but predominantly reversible, with high clean-water permeance recovery after chemical cleaning. Resistance partition and fouling modeling indicated that the main hydraulic limitation was associated with concentration polarization and external cake-layer buildup rather than irreversible membrane damage. The clarified fraction also preserved high transmission of major minerals and relevant primary metabolites, indicating that the selected condition combined high productivity, manageable fouling, and satisfactory nutritional retention. Full article

Research and development of novel CO₂-selective membranes, called molecular gate membranes (MGMs), has been conducted. Unlike conventional CO₂-selective membranes, MGMs show exceptionally high CO₂ separation over H₂. The membranes and the membrane modules were developed for CO₂ separation at low energy consumption and low cost in pre-combustion processes such as integrated gasification combined cycle (IGCC) and hydrogen production. To date, two candidate membrane materials—poly(ethylene glycol) (PEG)-based and poly(vinyl alcohol) (PVA)-based membranes—have been used. As for PEG-based membrane materials, the effect of operating conditions, such as relative humidity in feed gas and sweep gas and operating pressure, on CO₂ separation performance were investigated. Both CO₂ permeance and selectivity increased with increasing relative humidity on both the feed and permeate sides. The CO₂ permeance increased from the 10⁻¹² to the 10⁻¹¹ order, while the selectivity increased from 2.8 to 25. In addition, it was found that the water vapor permeates from the high to the low relative humidity side with a permeance typically on the order of 10⁻⁸ m³(STP)m⁻²·s⁻¹·Pa⁻¹, regardless of the total pressure difference between the feed side and the permeate side. This finding is important in the design of membrane systems. However, we found that PVA-based membranes exhibited superior thin-film coating ability and higher separation performance compared with PEG-based membranes. As for PVA-based materials, membranes that showed high CO₂ separation performance under high-pressure conditions of 2.4 MPa (the supposed pressure in the IGCC process) were successfully prepared. In addition, the technology to prepare MGMs with a large membrane area was developed by a continuous membrane-forming method, and the membrane elements (diameter: 10–20 cm; length: 20–60 cm) were also fabricated. Pre-combustion CO₂ capture tests of the membrane elements were conducted using coal-derived gasification gas, and it was confirmed that the membrane elements were durable against the real gas, which contained components such as H₂S (on the order of 100 ppm) and CO (32.4%). Full article

Polymeric membranes are widely investigated for CO₂ separation; however, their performance is often limited by the permeability–selectivity trade-off. Incorporating metal–organic frameworks (MOFs) and designing composite membrane architectures are promising strategies to overcome these limitations. This study aims to evaluate the effect of incorporating MOF-74 (Cu and Ni variants) into a polydimethylsiloxane (PDMS) selective layer supported on a polysulfone (PSF) membrane for enhanced CO₂/N₂ separation performance. Dual-layer PDMS/PSF composite membranes were fabricated via phase inversion for the PSF support, followed by solution casting of the PDMS/MOF layer. The developed membrane architecture introduces a synergistic design that combines the mechanical robustness of PSF with the selective transport capability of PDMS and the strong CO₂ affinity of MOF-74, offering an effective strategy for improving gas separation efficiency. Gas permeation performance was assessed using single-gas CO₂ and N₂ measurements at feed pressures of 2–5 bar. The incorporation of MOF-74 improved CO₂ transport properties, with the 1 wt.% Cu-MOF-74 composite membrane achieving a CO₂ permeance of 912.5 GPU and a CO₂/N₂ ideal selectivity of 94.75. The dual-layer configuration significantly enhanced permeance compared with unsupported mixed-matrix membranes while maintaining selectivity. Additionally, the composite membranes exhibited improved mechanical strength due to the PSF support layer. The findings demonstrate that dual-layer PDMS/PSF composite membranes incorporating MOF-74 provide a promising proof-of-concept approach for improving CO₂ separation performance. Further studies involving mixed-gas testing and long-term stability are required to assess their practical applicability. Full article

Biogas upgrading to biomethane is an important route for increasing the energy value of renewable gas streams and enabling their wider use in fuel, heat, and power applications. In the present study, a two-stage membrane process for biogas upgrading was developed and validated using polysulfone (PSF) and polyetherimide (PEI) hollow-fiber membranes. The main original aspects of this work include the formulation of a PEI/DMF/IPA spinning dope composition (27/60/13 wt.%), the mixed-gas testing of PSF and PEI hollow-fiber membranes in a six-component model biogas mixture, and the combined simulation, experimental validation, and techno-economic evaluation of a two-stage membrane process. Mixed-gas permeation experiments with a six-component model biogas mixture were used as the basis for process simulation of four membrane-stage configurations. Only the PSF + PEI cascade simultaneously provided methane recovery above 90%, methane concentration in the product above 95 mol.%, and residual carbon dioxide content below 2 mol.%. Experimental verification confirmed the modeled process concept and demonstrated that the target biomethane quality was achieved at feed flow rates of 0.9–1.1 L min⁻¹, where methane recovery reached 93.5–95.2% and methane purity was 95.5–96.2 mol.%. A preliminary techno-economic analysis for a 100 m³ h⁻¹ unit indicated an upgrading penalty of USD 96.4 per ton of 95.5 mol.% CH₄. PSF membranes provided higher carbon dioxide permeance, whereas PEI membranes exhibited higher CO₂/CH₄ selectivity, which explains the efficiency of their combination in the two-stage scheme. The results show that the proposed PSF + PEI cascade is a promising membrane-based approach for energy-efficient biogas upgrading. Full article

Hybrid gas separation technologies combining different physicochemical mechanisms represent a promising approach for the efficient treatment of complex natural gas mixtures. In this work, a hybrid process integrating gas hydrate crystallization and membrane gas separation was investigated for the upgrading of multicomponent natural gas-containing hydrocarbons (C₁–C₄), acid gases (CO₂ and H₂S), and inert components. Polysulfone hollow-fiber membranes were fabricated, and their gas transport properties were experimentally determined using an eight-component quasi-real natural gas mixture under elevated pressure conditions. The obtained mixed-gas permeance values were used as input parameters for the development of a detailed mathematical model of a hollow-fiber membrane module implemented in the Aspen Custom Modeler. The model was applied to simulate membrane separation of both gas- and hydrate-derived streams produced by the gas hydrate crystallizer. Simulation results were analyzed in terms of hydrocarbon composition, acid gas removal efficiency, and hydrocarbon recovery as a function of the stage-cut. The modeling predictions were validated experimentally using a laboratory membrane module integrated with the gas hydrate crystallization unit. Good agreement between the experimental data and simulation results was observed for all major components. The deviation between modeled and experimental concentrations remained small, while the discrepancy in hydrocarbon recovery was higher and reached approximately 10–20%, which is attributed to the cumulative uncertainty of flow rate and composition measurements. These results confirm the adequacy of the developed model. The hybrid process demonstrates strong complementarity between the thermodynamic selectivity of hydrate formation and the transport selectivity of membrane separation, enabling efficient removal of acid gases while maintaining acceptable hydrocarbon recovery. The results indicate that the proposed gas hydrate–membrane hybrid process is a promising strategy for advanced natural gas purification and upgrading. Full article

Polyetherimide (Ultem-1000) hollow-fiber membranes were developed for biogas purification with emphasis on the relationship between spinning conditions, membrane morphology, gas transport properties, and module performance. Hollow fibers were prepared from dope solutions based on dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP) at different conditions, followed by post-treatment with 1 and 3 wt.% silicone solution in n-heptane to reduce nonselective defects and improve selectivity toward the intrinsic behavior of dense PEI films. SEM analysis revealed that DMF-based fibers formed a more open, macrovoid-rich structure, whereas NMP-based fibers exhibited a more homogeneous sponge-like morphology with a better-defined selective layer. DMF-based fibers experienced faster demixing, which promoted macrovoid formation, increased pore connectivity of the substructure, lowered mass transfer resistance, and at the same time increased the probability of nonselective pathways and defect-related loss of selectivity. This structural evolution was reflected in gas transport properties: untreated DMF fibers showed high mixed-gas permeance but limited selectivity, while NMP fibers demonstrated lower permeance and selectivity values closer to those of the dense film. Silicone post-treatment significantly improved separation performance, with 3 wt.% coating being markedly more effective than 1 wt.% coating. The best compromise between permeance and selectivity was achieved for the DMF-based fibers treated with 3 wt.% silicone, which exhibited CO₂ and H₂S permeances of 39.4 and 47.12 GPU, respectively, together with selectivity values of 22.4, 26.8 and 20.2 for CO₂/CH₄, H₂S/CH₄ and CO₂/N₂. A membrane module containing 500 fibers was studied during the quasi-real biogas upgrading. With increasing stage-cut, the CH₄ concentration in the retentate increased from ~74 to 96 mol.%, while CO₂ decreased from ~21 to 2 mol.%. The results demonstrate that structure control combined with silicone post-treatment is an effective strategy for producing PEI hollow fibers suitable for simultaneous methane enrichment and removal of acid impurities from biogas. Full article

Conventional high-temperature calcination for activating MFI zeolite membranes is energy-intensive and prone to inducing defects. Here, we demonstrate that a rapid ozonation treatment at 200 °C for only 1 h effectively decomposes organic templates while preserving membrane integrity. The resulting membrane exhibits H₂/CH₄ and H₂/N₂ ideal selectivities of 10.3 and 6.5, respectively, at room temperature, with C₃H₈ and SF₆ permeances below the detection limit. These results confirm a dense, defect-minimized architecture and good molecular sieving performance of the zeolite membrane. In contrast, extending ozonation to 48 h leads to defect formation and a marked reduction in selectivity. For H₂/CH₄ mixture separation, the membrane achieves a selectivity of 23.8 at 100 °C, which is highly competitive among reported MFI membranes. In isopropanol dehydration, it achieves a water flux of 2.3 kg·m⁻²·h⁻¹ and a separation factor of 3278 at 70 °C with a 10 wt% water feed, while maintaining >99.5 wt% water content in the permeate over a broad operating temperature range (30–70 °C). This work establishes rapid ozonation as a scalable, energy-efficient activation method for high-performance MFI zeolite membranes in both gas and liquid separations. Full article

The rapid synthesis of high-performance silicalite-1 membranes was systematically investigated by examining the effects of seed size, solution volume, and reactor configuration on membrane growth, microstructure, and gas separation performance. Silicalite-1 seeds (~100 nm and ~1 µm) were dip-coated onto capillary α-alumina supports, followed by secondary growth under controlled conditions. Small seeds (~100 nm) produced high nucleation density, uniform intergrowth, and defect-free membranes, yielding consistently high ideal separation factor for H₂/SF₆ (181–295) and low SF₆ permeance (~10⁻⁹ mol m⁻² s⁻¹ Pa⁻¹) after only 45 min of synthesis. In contrast, larger seeds (~1 µm) enabled faster growth but resulted in less uniform layers with inferior selectivity. Furthermore, a novel reactor design with enhanced heat transfer enabled the rapid silicalite-1 membrane synthesis on conventional large-diameter tubular supports, producing well-intergrown and uniform membranes with high H₂ permeance (4.7 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹) and high ideal separation factors of up to 349 for H₂/SF₆ and 223 for N₂/SF₆. Overall, this study demonstrates that optimization of seed properties, synthesis parameters, and reactor design enables rapid and scalable fabrication of silicalite-1 membranes with robust molecular sieving performance, highlighting their strong potential for SF₆ purification applications. Full article

Efficiently separating propene and propane is paramount for the chemical industry but notoriously difficult due to their minimal size and volatility differences. Here, an efficient strategy to overcome this separation challenge was demonstrated through the design of bimetallic zeolitic imidazolate framework (ZIF)-based mixed-matrix membranes (MMMs). Thin-film composite (TFC) membranes were fabricated by integrating monometallic ZIF-8, ZIF-67, and a synergistic bimetallic ZIF-8-67 into a uniquely formulated ionic liquid–cellulose acetate (IL–CA) polymer matrix. Structural and morphological analyses confirmed the high crystallinity of the ZIF fillers and their seamless integration within the polymer. The resultant ZIF-8-67/IL-CA membrane exhibited notable separation performance, surpassing its monometallic counterparts by a threefold increase in both C₃H₆ permeance and C₃H₆/C₃H₈ ideal selectivity relative to the base membrane. Under industrially relevant mixed-gas testing, the membrane achieved a competitive separation factor of eight for propene over propane. These findings reveal that the strategic integration of bimetallic nodes in ZIFs can unlock synergistic properties unattainable with single-metal frameworks. This work presents a robust and scalable platform for developing next-generation membranes that defy conventional performance trade-offs, paving the way for efficient membrane-based olefin/paraffin separations. Full article

This study presents the techno-economic optimization of a hybrid distillation-membrane process for the complete fractionation of liquefied petroleum gas (LPG), targeting high-purity propane, n-butane, and isobutane recovery. The process employs an initial distillation column to separate propane (99% purity) from a propane-enriched stream, which is subsequently fed to a two-stage membrane system using an MFI zeolite hollow-fiber membrane for n-butane/isobutane separation. Through systematic simulation and sensitivity analysis, different membrane configurations were evaluated. The two-stage process with a partial residue-side reflux configuration demonstrated superior economic performance, achieving a total operating cost of 31.58 USD/h. Key membrane parameters—area, permeance, and separation factor—were optimized to balance separation efficiency with energy consumption and cost. The analysis identified an optimal configuration: a membrane area of 800 m², an n-butane permeance of 0.9 kg·m⁻²·h⁻¹, and a separation factor of 40. This setup ensured high n-alkane recovery while effectively minimizing energy use and capital investment. The study concludes that the optimized distillation-membrane hybrid process offers a highly efficient and economically viable strategy for the full utilization of LPG components. Full article

Polymeric membranes based on chitosan (Cs) were extracted from shrimp shells and evaluated. These membranes were modified using polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and glycerol (Gly) and crosslinked with glutaraldehyde (GA) to examine their suitability for water filtration processes. The Cs exhibited high purity, a total nitrogen content of 6.49%, and an average molecular weight of 456 kDa, all of which are suitable for membrane formation. Four membranes (Cs-GA, B2: Cs-PEG, B5: Cs-PEG-PVP, and B7: Cs-Gly) were characterized by means of FTIR, SEM, AFM, thickness, contact angle, tensile testing, TGA, DSC, and filtration with distilled water at 4.83 bar. B2 and B5 showed thicknesses of 207 and 190 μm and contact angles of 56.7° and 58.9°, lower than that of Cs-GA (89.4°). In filtration, B2 achieved a flux of 2222.70 LMH, a permeance of 460.19 LMH·bar⁻¹, and a hydraulic resistance of 8.79 × 10¹¹ m⁻¹, while Cs-GA, B5, and B7 exhibited fluxes of 24.10, 40.43, and 24.77 LMH, respectively, permeances of 9.75, 8.37, and 5.13 LMH·bar⁻¹, and hydraulic resistances of 4.15 × 10¹³, 4.83 × 10¹³, and 7.89 × 10¹³ m⁻¹, in the same order. Overall, membranes B2 and B5 are recognized as the most promising for water filtration under pressured operating conditions. Full article

A hollow fiber-supported polymeric mixed-matrix membrane, consisting of a Pebax-1657 matrix and graphene nanoplatelet (GNP) fillers as the selective layer, was tested for CO₂/CH₄ gas separation at transmembrane pressures up to 30 bar(a). Using a custom, novel, membrane module, we simultaneously performed permeability/selectivity and in situ electric impedance spectroscopy measurements. This in situ technique is proposed here for the first time. Furthermore, stable mixed-gas selectivities, for 10% CO₂ in CH₄ gas, reaching up to 61.4 (M0) and 68.5 after heat treatment (M2) were observed at 20–30 bar(a), whereas the stressed state (M1) dropped to ~22. Throughout the whole procedure of the three (initial, degraded, and restored) membrane testing assessments, a gradual decline in gas permeability coupled with a corresponding increase in the membrane’s AC resistance, due to membrane compaction, was evident. More specific, the membrane’s AC resistance, R₁, increased from ~96–147 ΜΩ (M0) to ~402–435 ΜΩ (M1) and ~5390–5700 ΜΩ (M2), while the peak-phase frequency f_p decreased from ~1.25 kHz (M0) to ~340 Hz (M1) and ~115 Hz (M2). Overall, this work proposes a new tool/method for connecting membrane’s deterioration phenomena with AC resistance and demonstrates that a facile heat treatment can restore selectivity following compaction, despite the absence of full permeance recovery. Full article

Biomethane is one of the controllable Renewable Energy Sources. It may be derived from biogas, a multicomponent gas mixture, using, among others, membrane processes. The proper optimization of such a process requires the knowledge of the phenomena accompanying each specific biogas–membrane separation system. Therefore, the solubility, permeance and diffusion of CO₂, CH₄, O₂ and N₂ in a polyimide-based sample were described and analyzed using the Dual Mode Sorption and partial immobilization models. The parameters of the models were determined based on pure gas sorption isotherms measured gravimetrically and experimental permeances of the four gases. The membrane swelling caused by CO₂ was observed at temperatures of 293 and 303 K and for pressures higher than 3 bar. The adsorption of CH₄, O₂ and N₂ in the fractional free volume (FFV) has a dominant (>50%) share in their total solubility in the entire pressure range. This makes them sensitive to the presence of CO₂, whose affinity is the strongest towards the tested polyimide-based sample. The diffusion of O₂ is the fastest which makes it competitive with CO₂ in permeation through the membrane, despite its low solubility. The ideal CO₂/O₂ selectivity is thus relatively low (2.3–5.1). Methane, which is competitive in solubility compared to CO₂, was found to diffuse the slowest and as a result, it is also the slowest permeating gas. This translates into the very high CO₂/CH₄ ideal selectivity (33–95.7), which is, however, strongly dependent on temperature and pressure. Full article