Search Results (82)

Highly permeable and selective membranes are crucial for energy-efficient gas separation. Two-dimensional (2D) graphitic carbon nitride (g-C₃N₄) has attracted significant attention due to its unique structural characteristics, including ultra-thin thickness, inherent surface porosity, and abundant amine groups. However, the interfacial defects caused by poor compatibility between g-C₃N₄ and polymers deteriorate the separation performance of membrane materials. In this study, amino-functionalized g-C₃N₄ nanosheets (CN@PEI) was prepared by a post-synthesis method, then blended with the polymer Pebax to fabricate Pebax/CN@PEI mixed matrix membranes (MMMs). Compared to g-C₃N₄, MMMs with CN@PEI loading of 20 wt% as nanofiller exhibited a CO₂ permeance of 241 Barrer as well as the CO₂/CH₄ and CO₂/N₂ selectivity of 39.7 and 61.2, respectively, at the feed gas pressure of 2 bar, which approaches the 2008 Robeson upper bound and exceeded the 1991 Robeson upper bound. The Pebax/CN@PEI (20) membrane showed robust stability performance over 70 h continuous gas permeability testing, and no significant decline was observed. SEM characterization revealed a uniform dispersion of CN@PEI throughout the Pebax matrix, demonstrating excellent interfacial compatibility between the components. The increased free volume fraction, enhanced solubility, and higher diffusion coefficient demonstrated that the incorporation of CN@PEI nanosheets introduced more CO₂-philic amino groups and disrupted the chain packing of the Pebax matrix, thereby creating additional diffusion channels and facilitating CO₂ transport. Full article

Cu-BTC (HKUST-1) metal–organic framework (MOF) is widely recognized for its carbon capture capability due to its unsaturated copper sites, high surface area, and well-defined porous structure. This study developed mixed matrix membranes (MMMs) using cellulose triacetate (CTA), incorporating bimetallic Ni-Cu-BTC MOFs for CO₂/CH₄ separation, and benchmarked them against membranes fabricated with monometallic Cu-BTC. CTA was selected for its biodegradability, membrane-forming properties, and cost-effectiveness. The optimized membrane with 10 wt.% Ni-Cu-BTC achieved a CO₂ permeability of 22.9 Barrer at 25 °C and 5 bar—more than twice that of pristine CTA—with a CO₂/CH₄ selectivity of 33.8. This improvement stems from a 51.66% increase in fractional free volume, a 49.30% rise in the solubility coefficient, and a 51.94% boost in the diffusivity coefficient. Dual-sorption model analysis further confirmed enhanced solubility and adsorption mechanisms. These findings establish CTA/Ni-Cu-BTC membranes as promising candidates for high-performance CO₂ separation in natural gas purification and related industrial processes. Full article

The rigid V-shaped Tröger’s base (TB) unit has been proven efficacious in creating microporosity, making TB-based polyimides (PIs) exhibiting significant advantages in simultaneously increasing gas permeability and selectivity for the separation industry. However, TB-based PIs commonly display undesired mechanical performance due to the low molecular weight resulting from the evident steric hindrance and low reactivity of TB-containing diamines. Herein, a novel diamine-containing bisimide linkage (BIDA) has been synthesized and then polymerized with paraformaldehyde via a moderate “TB polymerization” strategy to furnish polymers simultaneously, including imide linkages and TB units in the polymer main chains, namely, TB-PIs. This TB polymerization strategy avoids the direct polymerization of dianhydride with low-reactivity TB diamine. After incorporating a meta-methyl substituent into BIDA diamine, the m-MBIDA diamine-derived m-MTBPI ultimately exhibits a high molecular weight, good tensile strength (90.4 MPa) and an outstanding fracture toughness (45.1 MJ/m³). And more importantly, the m-MTBPI membrane displays an evidently enhanced gas separation ability in comparison with BIDA-derived TBPI, with overall separation properties much closer to the 1991 Robeson upper bound. Moreover, no sign of plasticization appears for the m-MTBPI membrane when separating a high-pressure CO₂/CH₄ mixture (v/v = 1/1) up to 20 bar, with the CO₂/CH₄ mixed-gas separation performance approaching the 2018 upper bound. Full article

Membrane technology has been widely used in industrial CO₂ capturing, gas purification and gas separation, arousing attention due to its advantages of high efficiency, energy saving and environmental protection. In the context of reducing global carbon emissions and combating climate change, it is particularly important to capture and separate greenhouse gasses such as CO₂. Zr-MOF can be used as a multi-dimensional modification on the polymer membrane to prepare self-assembled MOF-based mixed matrix membranes (MMMs), aiming at the problem of weak adhesion or bonding force between the separation layer and the porous carrier. When defective UiO-66 is applied to PVDF membrane as a functional layer, the CO₂ separation performance of the PVDF membrane is significantly improved. TUT-UiO-3-TTN@PVDF has a CO₂ permeation flux of 14,294 GPU and a selectivity of 27 for CO₂/N₂ and 18 for CO₂/CH₄, respectively. The CO₂ permeability and selectivity of the membrane exhibited change after 40 h of continuous operation, significantly improving the gas separation performance and showing exceptional stability for large-scale applications. Full article

Biogas, one of the important controllable renewable energy sources, may be split into two streams: bio-CH₄ and bio-CO₂ using, among others, membrane processes. The proper optimization of such processes requires the knowledge of phenomena accompanying each specific CH₄–CO₂–membrane system (e.g., competitive sorption or swelling). The phenomena were analyzed for the polysulfone-based membrane used in a developed adsorptive–membrane system for biogas separation. The Dual Mode Sorption and partial immobilization models were used to describe the solubility and diffusion of CO₂, CH₄ and their mixtures in this material. The parameters of the models were determined based on pure-gas sorption isotherms measured gravimetrically and permeances of CO₂/CH₄ mixture components from our previous studies. It was found, among other things, that the membrane swelling caused by CO₂ was observed for pressures higher than 5 bar. The real selectivity (permselectivity) of CO₂ vs. CH₄ is significantly lower than the selectivity of pure gases (ideal selectivity), while the solubility selectivity of CO₂ vs. CH₄ in the mixture is higher than that of pure gases. This is due to the better affinity of CO₂ towards the tested polysulfone membrane, making CO₂ the dominant component in competitive sorption. The reduction in the permselectivity is mainly due to an approximately two-fold decrease in the CO₂ diffusion rate in the presence of CH₄. It was also found that the fraction of solubility in the fractional free volume (FFV) is dominant for both gases, pure and mixed, reaching 65–73% of the total solubility. Moreover, in CO₂/CH₄ mixtures, the mobility of methane in FFV disappears, which additionally confirms the displacement of methane by CO₂ from FFV. Full article

CO₂ separation is an important environmental method mainly used in reducing CO₂ emissions to mitigate anthropogenic climate change. The use of mixed-matrix membranes (MMMs) arrives as a possible answer, combining the high selectivity of inorganic membranes with high permeability of organic membranes. However, the combination of these materials is challenging due to their opposing nature, leading to poor interactions between polymeric matrix and inorganic fillers. Many additives have been tested to reduce interfacial voids, some of which showed potential in dealing with compatibility problems, but most of them lack further studies and optimization. Deep eutectic solvents (DESs) have emerged as IL substitutes since they are cheaper and environmentally friendly. Choline chloride-based deep eutectic solvents were studied as additives in polyethersulfone (PES)/SAPO-34 membranes to improve CO₂ permeability and CO₂/N₂ and CO₂/CH₄ selectivity. SAPO-34 crystals of 150 nm with a high surface area and microporosity were synthesized using dry-gel methodology. The PES/SAPO-34 membranes were optimized following previous work and used in a defined composition, using 5 or 10 w/w% of DES during membrane preparation. All MMMs were characterized by their ideal gas permeability using N₂ and CO₂ pure gasses. Selected membranes were also tested using CH₄ pure gas. The results presented that 5 w/w%, in polymer mass, of ChCl–glycerol presented the best result over the synthesized membranes. An increase of 200% in CO₂ permeability maintains the CO₂/N₂ selectivity for the non-modified PES/SAPO-34 membrane. A CO₂/CH₄ selectivity of 89.7 was obtained in PES/SAPO-34/ChCl-glycerol membranes containing 5 w/w% of this DES, which is an outstanding ideal separation performance for MMMs when compared to other results in the literature. FTIR analysis reiterates the presence of glycerol in the membranes prepared. Dynamic Mechanical Thermal Analysis (DMTA) shows that the addition of 5 w/w% of DES does not impact the membrane flexibility or polymer structure. However, in concentrations higher than 10 w/w%, the inclusion of DES could lead to high membrane rigidification without impacting the overall thermal resistance. SEM analysis of DES-enhanced membranes presented asymmetric final membranes and reaffirmed the results obtained in DMTA about rigidified structures and lower zeolite–polymer interaction with higher concentrations of DES. Full article

The global energy market is shifting toward renewable, sustainable, and low-carbon hydrogen energy due to global environmental issues, such as rising carbon dioxide emissions, climate change, and global warming. Currently, a majority of hydrogen demands are achieved by steam methane reforming and other conventional processes, which, again, are very carbon-intensive methods, and the hydrogen produced by them needs to be purified prior to their application. Hence, researchers are continuously endeavoring to develop sustainable and efficient methods for hydrogen generation and purification. Membrane-based gas-separation technologies were proven to be more efficient than conventional technologies. This review explores the transition from conventional separation techniques, such as pressure swing adsorption and cryogenic distillation, to advanced membrane-based technologies with high selectivity and efficiency for hydrogen purification. Major emphasis is placed on various membrane materials and their corresponding membrane performance. First, we discuss various metal membranes, including dense, alloyed, and amorphous metal membranes, which exhibit high hydrogen solubility and selectivity. Further, various inorganic membranes, such as zeolites, silica, and CMSMs, are also discussed. Major emphasis is placed on the development of polymeric materials and membranes for the selective separation of hydrogen from CH₄, CO₂, and N₂. In addition, cutting-edge mixed-matrix membranes are also delineated, which involve the incorporation of inorganic fillers to improve performance. This review provides a comprehensive overview of advancements in gas-separation membranes and membrane materials in terms of hydrogen selectivity, permeability, and durability in practical applications. By analyzing various conventional and advanced technologies, this review provides a comprehensive material perspective on hydrogen separation membranes, thereby endorsing hydrogen energy for a sustainable future. Full article

Driven by environmental and economic considerations, this study explores the viability of utilizing coconut juice residues (CJRs), a byproduct from coconut milk production, as a carbon source for bacterial cellulose (BC) synthesis in the form of a versatile bio-membrane. This work investigates the use of optimization modeling as a tool to find the optimal conditions for BC cultivation in consideration of waste minimization and resource sustainability. Optimization efforts focused on three parameters, including pH (4–6), cultivation temperature (20–30 °C), and time (6–10 days) using Design Expert (DE) V.13. The maximum yield of 9.31% (g/g) was achieved when the cultivation took place at the optimal conditions (pH 6, 30 °C, and 8 days). This approach aligns with circular economy principles, contributing to sustainable resource management and environmental impact reduction. The experimental and predicted optimal conditions from DE V.13 were in good agreement, validating the study’s outcomes. The predictive model gave the correlations of the optimal conditions in response to the highest yield and maximum eco-efficiency. The use of prediction modeling resulted in a useful tool for forecasting and obtaining guidelines that can assist other researchers in calculating optimal conditions for a desired yield. Acetylation of the BC resulted in cellulose acetate (CA) membranes. The CA membrane exhibited the potential to separate CO₂ from a CH₄/CO₂ mixed gas with a CO₂ selectivity of 1.315 in a membrane separation. The promising gas separation results could be further explored to be utilized in biogas purification applications. Full article

A considerable number of Combined Heat and Power (CHP) systems continue to depend on fossil fuels like oil and natural gas, contributing to significant environmental pollution and the release of greenhouse gases. Two V-gutter flame holder prototypes (P1 and P2) with the same expansion angle, fueled with pure hydrogen (100% H₂) or hydrogen–methane mixtures (60% H₂ + 40% CH₄, 80% H₂ + 20% CH₄), intended for use in cogeneration applications, have been designed, manufactured, and tested. Throughout the tests, the concentrations of CO₂, CO, and NO in the flue gas were monitored, and particle image velocimetry (PIV) measurements were performed. The CO, CO₂, respectively, and NO emissions gradually decreased as the percentage of H₂ in the fuel mixture increased. The NO emissions were significantly lower in the case of prototype P2 in comparison with prototype P1 in all measurement points for all used fuel mixtures. The shortest recirculation zone was observed for P1, where the axial velocity reaches a negative peak of approximately 12 m/s at roughly 50 mm downstream of the edge of the flame holder, and the recirculation region spans about 90 mm. In comparison, the P2 prototype has a length of the recirculation region span of about 100 mm with a negative peak of approximately 14 m/s. The data reveal high gradients in flow velocity near the flow separation point, which gradually smooth out with increasing downstream distance. Despite their similar design, P2 consistently performs better across all measured velocity components. This improvement can be attributed to the larger fuel injection holes, which enhance fuel–air mixing and combustion stability. Additionally, the presence of side walls directing the flow around the flame stabilizer further aids in maintaining a stable combustion process. Full article

The ability to efficiently separate CO₂ from other light gases using membrane technology has received a great deal of attention due to its importance in applications such as improving the efficiency of natural gas and reducing greenhouse gas emissions. A wide range of materials has been employed for the fabrication of membranes. This paper highlights the work carried out to develop novel advanced membranes with improved separation performance. We integrated a polymerizable and amino acid ionic liquid (AAIL) with zeolite to fabricate mixed matrix membranes (MMMs). The MMMs were prepared with (vinylbenzyl)trimethylammonium chloride [VBTMA][Cl] and (vinylbenzyl)trimethylammonium glycine [VBTMA][Gly] as the polymeric support with 5 wt% zeolite particles, and varying concentrations of 1-butyl-3-methylimidazolium glycine, [BMIM][Gly] (5–20 wt%) blended together. The membranes were fabricated through photopolymerization. The extent of polymerization was confirmed using FTIR. FESEM confirmed the membranes formed are dense in structure. The thermal properties of the membranes were measured using TGA and DSC. CO₂ and CH₄ permeation was studied at room temperature and with a feed side pressure of 2 bar. [VBTMA][Gly]-based membranes recorded higher CO₂ permeability and CO₂/CH₄ selectivity compared to [VBTMA][Cl]-based membranes due to the facilitated transport of CO₂. The best performing membrane Gly-Gly-20 recorded permeance of 4.17 GPU and ideal selectivity of 5.49. Full article

The use of mixed matrix membranes (MMMs) comprising metal–organic frameworks (MOFs) for the separation of CO₂ from flue gas has gained recognition as an effective strategy for enhancing gas separation efficiency. When incorporating porous materials like MOFs into a polymeric matrix to create MMMs, the combined characteristics of each constituent typically manifest. Nevertheless, the inadequate dispersion of an inorganic MOF filler within an organic polymer matrix can compromise the compatibility between the filler and matrix. In this context, the aspiration is to develop an MMM that not only exhibits optimal interfacial compatibility between the polymer and filler but also delivers superior gas separation performance, specifically in the efficient extraction of CO₂ from flue gas. In this study, we introduce a modification technique involving the grafting of poly(ethylene glycol) diglycidyl ether (PEGDE) onto a UiO-66-NH₂ MOF filler (referred to as PEG-MOF), aimed at enhancing its compatibility with the 6FDA-durene matrix. Moreover, the inherent CO₂-philic nature of PEGDE is anticipated to enhance the selectivity of CO₂ over N₂ and CH₄. The resultant MMM, incorporating 10 wt% of PEG-MOF loading, exhibits a CO₂ permeability of 1671.00 Barrer and a CO₂/CH₄ selectivity of 22.40. Notably, these values surpass the upper bound reported by Robeson in 2008. Full article

Mixed matrix membranes (MMMs) provide the opportunity to test new porous materials in challenging applications. A series of low-cost porous organic polymer (POPs) networks, possessing tunable porosity and high CO₂ uptake, has been obtained by aromatic electrophilic substitution reactions of biphenyl, 9,10-dihydro-9,10-dimethyl-9,10-ethanoanthracene (DMDHA), triptycene and 1,3,5-triphenylbenzene (135TPB) with dimethoxymethane (DMM). These materials have been characterized by FTIR, ¹³C NMR, WAXD, TGA, SEM, and CO₂ uptake. Finally, different loadings of these POPs have been introduced into Matrimid, Pebax, and chitosan:polyvinyl alcohol blends as polymeric matrices to prepare MMMs. The CO₂/CH₄ separation performance of these MMMs has been evaluated by single and mixed gas permeation experiments at 4 bar and room temperature. The effect of the porosity of the porous fillers on the membrane separation behavior and the compatibility between them and the different polymer matrices on membrane design and fabrication has been studied by Maxwell model equations as a function of the gas permeability of the pure polymers, porosity, and loading of the fillers in the MMMs. Although the gas transport properties showed an increasing deviation from ideal Maxwell equation prediction with increasing porosity of the POP fillers and increasing hydrophilicity of the polymer matrices, the behavior of biopolymer-based CS:PVA MMMs approached that of Pebax-based MMMs, giving scope to not only new filler materials but also sustainable polymer choices to find a place in membrane technology. Full article

Yinggema lignite (YL) was pretreated with isometric acetone/carbon disulfide mixed solvent to obtain the residue (R_YL) and, then, R_YL was separated by density difference with carbon tetrachloride to obtain the light residue (LR_YL). The flash pyrolysis performances of YL and LR_YL were analyzed by thermogravimetry–Fourier transform infrared spectrometer–Gas chromatography/mass spectrometer (TG-FTIR-GC/MS). The results showed that solvent pretreatment could remove some small molecules in the coal and swell the used coal, leading to the increase in pyrolysis reactivity. The intensity and absorption peak area of C=O from LR_YL were significantly reduced compared to YL, resulting from the high hydrogen-donating ability of acetone. The main gaseous products of both samples are H₂O, CH₄, CO₂, and CO; the hydrocarbons detected by GC/MS in the pyrolysis products of YL and LR_YL at 450 °C were mainly alkanes, alkenes, and arenes, with the higher relative contents of alkanes of 31.1% and 36.2%, followed by arenes of 27.1% and 22.6%, respectively. The oxygen-containing compounds were mainly alcohols and phenols. It is speculated that the pretreated coal could expose more oxygen-containing functional groups, facilitating their conversion to phenolic hydroxyl groups during the pyrolysis process, resulting in more phenolic compounds. Full article

Carbon dioxide (CO₂) absorption in a non-aqueous solution is a potential technology for reducing greenhouse gas emissions. In this study, a non-aqueous solvent, sulfolane and dimethylsulfoxide (DMSO), was functionalized with a deep eutectic solvent (DES) consisting of choline hydroxide and polyamines diethylenetriamine (DETA) and triethylenetetramine (TETA). The non-aqueous absorbents’ CO₂ absorption ability was investigated in a high-pressure absorption reactor with a variable absorption temperature (303.15–333.15 K) and pressure (350–1400 kPa). The results showed that 2M ChOH:TETA−DMSO solution had the highest CO₂ loading capacity when compared with other screened solutions, such as 2M ChOH:TETA−Sulfolane, 2M ChOH:DETA−DMSO and 2M ChOH:DETA−Sulfolane. It was also found that the absorption capacity increased with increasing pressure and decreased with temperature. The highest CO₂ absorption by 2M ChOH:TETA−DMSO was observed at a partial pressure of 1400 kPa at 303.15 K 1.2507 mol CO₂/mol DES. The use of a non-aqueous solvent in the mixture showed a phase separation phenomenon after the CO₂ absorption reaction due to the formation of insoluble carbamate salt, which was identified through FTIR analysis. These findings suggest that the use of a DES polyamine mixed with a non-aqueous solvent could be a promising solution for CO₂ capture. Full article

In the present work, Pebax-1657, a commercial multiblock copolymer (poly(ether-block-amide)), consisting of 40% rigid amide (PA6) groups and 60% flexible ether (PEO) linkages, was selected as the base polymer for preparing dense flat sheet mixed matrix membranes (MMMs) using the solution casting method. Carbon nanofillers, specifically, raw and treated (plasma and oxidized) multi-walled carbon nanotubes (MWCNTs) and graphene nanoplatelets (GNPs) were incorporated into the polymeric matrix in order to improve the gas-separation performance and polymer’s structural properties. The developed membranes were characterized by means of SEM and FTIR, and their mechanical properties were also evaluated. Well-established models were employed in order to compare the experimental data with theoretical calculations concerning the tensile properties of MMMs. Most remarkably, the tensile strength of the mixed matrix membrane with oxidized GNPs was enhanced by 55.3% compared to the pure polymeric membrane, and its tensile modulus increased 3.2 times compared to the neat one. In addition, the effect of nanofiller type, structure and amount to real binary CO₂/CH₄ (10/90 vol.%) mixture separation performance was evaluated under elevated pressure conditions. A maximum CO₂/CH₄ separation factor of 21.9 was reached with CO₂ permeability of 384 Barrer. Overall, MMMs exhibited enhanced gas permeabilities (up to fivefold values) without sacrificing gas selectivity compared to the corresponding pure polymeric membrane. Full article