Experimental investigation of natural polysaccharide-based mixed matrix membrane modified with graphene oxide and Pd-nanoparticles for enhanced gas separation performance

In this work, we proposed a mixed matrix membrane prepared by using a glycerol modified guar gum (GGP) polymer matrix incorporated with graphene oxide (GO). The influence of varying GO concentration on the gas separation performance was investigated and 2 wt% was found to be the optimum concentration for high performance. The 2 wt% GO mixed matrix membranes were further modified with Pd nanoparticles. When GO, and Pd nanoparticles were mixed, CO₂ permeability increased by 49.94%, while the permeability of H₂ gas molecules decreased by 98.11%, respectively, compared to the pristine GGP membrane. The selectivity of CO₂/H₂ was obtained as 18.27. The glass transition temperature of the membrane increased from 85 to 95.2 °C, tensile strength and elongation of the break were significantly improved by 29.09% and 84.37% through the addition of Pd and GO into the membrane. The scanning electron microscopy revealed a dense top surface after GO nanosheets incorporation. Further, the thermogravimetric analysis proposes that the modified membrane is thermally stable than GGP. Henceforth, the study suggests GO incorporation and Pd nanoparticles modification of guar gum membrane is a promising gas separation membrane with potentially high selectivity for CO₂ gas.     

Incorporation of thermally labile additives in polyimide carbon membrane for hydrogen separation

In this study, three thermally labile additives microcrystalline cellulose (MCC), nanocrystalline cellulose (NCC), and polyvinylpyrrolidone (PVP) were introduced to the P84-copolyimide (PI) solution. PI-based carbon tubular membranes were fabricated using dip-coating method, followed by sample characterizations in order to determine their structural morphologies, thermal stability and gas permeation performance. NCC was added as the membrane pore former for the hydrogen gas (H₂) separation. While tests involving pure H₂ and N₂ permeation were carried out at room temperature, carbon membranes were carbonized at a final temperature of 800 °C, with the heating rate of 3 °C/min under the Ar flow. Excellent result of H₂/N₂ selectivity was obtained with value of 430.06 ± 4.16. Addition of NCC has significantly increased the number of pore channels in the membrane, hence, contributing to high gas permeance and selectivity. NCC has shown potential as a good additive for an enhanced hydrogen separation performance.     

H2 permeation and its influence on gases through a SAPO-34 zeolite membrane

This work analysed the permeation of binary and ternary H₂-containing mixtures through a SAPO-34 membrane, aiming at investigating how hydrogen influences and its permeation is influenced by the presence of the other gaseous species, such as CO₂ and CH₄. We considered the behaviour of various gas mixtures in terms of permeability and selectivity at various temperatures (25–300 °C), feed pressures (400–1000 kPa) and compositions by means of an already validated mass transport model, which is based on surface and gas translation diffusion. We found that the presence of CO₂ and CH₄ in the H₂-containing mixtures influences in a similar way the H₂ permeation, reducing its permeability of about 80% compared to the single-gas value because of their stronger adsorption. On the other hand, H₂ promotes the permeation of CO₂ and CH₄, causing an increment of their permeability with respect to those as single gases. These combined effects reflected in interesting selectivity values in binary mixture (e.g., CO₂/H₂ about 11 at 25 °C, H₂/CH₄ about 9 at 180 °C), which showed the potential of SAPO-34 membranes in treating of H₂-containing mixtures.     

Stability investigation of polyPOSS-imide membranes for H2 purification and their application in the steel industry

In the present work, the high-temperature and long-term hydrothermal stability of novel polyPOSS-imide membranes for high-temperature hydrogen separation is investigated. The polyPOSS-imide membranes are found to exhibit an appropriate stability up to 300 °C. Above this temperature the membrane selectivity rapidly decreases, which is seemingly related to changes in the molecular structure coupled to silanol condensation forming siloxane groups. Surprisingly, the exposure of the membrane to temperatures of up to 300 °C even increases the H₂ permeance together with the selective feature of the polyPOSS-imide layer. Subsequently, the long-term hydrothermal stability of the polyPOSS-imide membranes was investigated over a period of close to 1000 h at 250 °C exposing the membrane to 10 mol% steam in the feed. An increase in H₂/CH₄ selectivity was observed upon water addition, and even though a minor drop was noticed over time during the hydrothermal operation, the selectivity exceeds the initial selectivity obtained in the dry feed atmosphere. After the removal of steam from the feed the performance returns to its original state prior to the exposure to any steam showing an appropriate steam stability of the polyPOSS-imide membranes. A conceptual process design and assessment was performed for application of these membranes involving a combination of carbon reuse and electrification of the steel making process with co-production of hydrogen. The results indicate a CO₂ avoidance of 14%. The CO₂ reduction achieved using renewable electricity in the proposed scheme is a factor 2.76 higher compared to a situation where the same renewable electricity would be fed in the electricity grid.     

Development of hydrogen selective microporous PVDF membrane

Hydrogen is a sustainable clean and green energy source used to eliminate the problem of greenhouse effect. In the present work, the feasibility of gas permeability in separation of H₂ from CO₂ and N₂ have been examined using polyvinylidene fluoride (PVDF) membranes synthesised in our laboratory by the phase inversion process. Effect of various non-solvent additives, such as lithium chloride (LiCl) and Tetraethoxysilane (TEOS) in the PVDF dope solution, have been studied. The resulted asymmetric flat sheet microporous hydrophobic membrane, shows higher hydrogen permeability and selectivity over other gases (CO₂ & N₂). It has been observed that the MT5 membrane has shown the highest selectivity for hydrogen in comparison to CO₂ and N₂. The highest value of selectivity was obtained as 4.8 and 3.7 in case of H₂/CO₂ and H₂/N₂ respectively. The permeability of membrane has been obtained in the range of 2.3–4.2 mega barrer. SEM analysis is used for the investigation of membrane surface morphology.     

Vanadium-ceria catalysts for H2S abatement from biogas to feed to MCFC

Vanadium-based catalysts supported on ceria were studied for the direct and selective oxidation of H₂S to sulphur and water at low temperature.Catalysts with two vanadium loading (20–50 wt% of V₂O₅) were prepared, characterized and tested at temperature of 150–200 °C in order to identify the best catalytic formulation. The most promising catalyst was the sample with the 20 wt% of V₂O₅ that showed 99% of sulphur selectivity and equilibrium H₂S conversion at 150 °C.The effect of the components of a typical biogas stream (CH₄, CO₂ and H₂O) was studied at 150 °C in order to investigate the possible formation of secondary products such COS, CS₂. No significant effect was observed in terms of H₂S conversion (99%) and selectivity to SO₂ (<1%) by adding CH₄ and CO₂ to the feed stream. Furthermore, the effect of the H₂S inlet concentration, temperature, contact time and molar feed ratio (O₂/H₂S) were also investigated at a reaction temperature of 80 °C.Finally, time on stream tests of 30 h were performed at 80 and 120 °C, in order to examine the catalyst stability.     

Carbon tubular membranes from nanocrystalline cellulose blended with P84 co-polyimide for H2 and He separation

In this study, carbon tubular membranes were produced by employing P84 co-polyimide as a precursor material and nanocrystalline cellulose (NCC) as an additive. The synthesized NCC which was derived from recycled newspaper was used as a pore forming agent for the membrane. Various carbonization temperatures (600, 700, 800, and 900 °C) were used while the stabilization temperature was kept at 300 °C. The measurements of pure gases' (He, H₂, and N₂) permeance through all carbon tubular membranes produced were carried out at feed pressure of 8 bars. The results showed that higher carbonization temperatures resulted in more selective but less productive carbon membranes. The outcome of this study suggested that carbon tubular membrane fabricated from NCC blending with P84 co-polyimide as a promising candidate for H₂ and He recovery application with H₂/N₂ and He/N₂ selectivity of 434.68 ± 1.39 and 463.86 ± 8.12, respectively.     

GNs/MOF-based mixed matrix membranes for gas separations

NU-1000 and graphene nanosheet (GNs) with different loadings have been used as fillers to prepare mixed matrix membranes (MMMs) with polyethersulfone (PES). The high performance of the MMMs has been successfully fabricated for the evaluation of gas separation at 1 bar and various temperatures (20, 40, 60 °C). The successful fabrication of the MMMs were confirmed by using SEM, FTIR, AFM, and XRD. The crystalline nature of GNs and NU-1000 in the MMMs are evidenced by XRD, which confirms the successful fabrication of the MMMs. In addition, the thermal stability of the MMMs was enhanced with the increase of the GNs. Separation performance of H₂ was superior to CO₂, N₂ and CH₄ separation on the MMMs which is a critical for producing energy. The best gas separation results in terms of both permeability and selectivity were obtained with 0.03% GNs and 10% NU-1000. PG3N membrane presented maximum H₂/CO₂, H₂/N₂ and H₂/CH₄ selectivity of 5, 4.2, 3.3 at 20 C, respectively. With an increase in temperature, the permeability increased, while the selectivity of all the MMMs decreased. The MMMs exhibited excellent gas separation capability, which offers unique opportunities for potential large-scale practical applications.     

Enhancing hydrogen gas separation performance of thin film composite membrane through facilely blended polyvinyl alcohol and PEBAX

Polymeric membranes offer economic separation processes but are less explored for H₂ separation application. This work aims to unveil the H₂ separation potential of polymeric membrane by developing PVA-based reverse selective composite membrane. CO₂-selective PEBAX was blended at different PVA:PEBAX ratio. The effect of PEBAX blending on membrane morphology, crystallinity and gas separation behavior was studied. Incorporation of PEBAX at <50 wt% resulted in composite with improved CO₂ permeability but selectivity loss. Blending of >60 wt% PEBAX enhanced both permeance and selectivity of the resulted composite as the host matrix was dominated by this PEO containing material thus greatly enhancing polymer chain mobility and promoting CO₂-solubility. The best composite which contains 60 wt% PEBAX exhibited CO₂ permeability of 20.0 Barrer and CO₂/H₂ selectivity of 7.6. This performance surpasses the Robeson's boundary and unleashes the potential of tailoring the properties of polymeric nanocomposite membrane for H₂ separation application through facile PVA/PEBAX blending.     

Enhanced hydrogen permeability and reverse water–gas shift reaction activity via magneli Ti4O7 doping into SrCe0.9Y0.1O3−δ hollow fiber membrane

Hydrogen proton conducting perovskite-based hollow fiber membrane is an attractive hydrogen separation technology that shows higher stability relative to Pd-based membranes above 800 °C. One of the challenges towards high hydrogen (H₂) permeability on such proton conducting membrane is enabling simultaneously high proton and electronic conductivities to be achieved in single phase membrane. This has been addressed by developing dual-phase membrane. Here, we showed another promising approach, i.e., exploitation of beneficial phase reactions to create new conductive phases along the grain boundaries. By doping up to 8 wt. % magneli Ti₄O₇ into SrCe_0.9Y_0.1O_3?δ (SCY), Ce-doped SrTiO₃ and Y-doped CeO₂ were created in-between SCY grains. Electrical conductivity tests confirmed higher conductivities for 5 and 8 wt. % Ti₄O₇-doped SCY relative to SCY between 750 and 950 °C. These higher conductivities manifested into higher H₂ permeation fluxes for the doped SCY membranes. The highest flux of 0.17 mL min^?1 cm^?2 was observed for 5 wt. % Ti₄O₇-doped SCY at 900 °C when 50 vol. % H₂/He and 100 vol. % N₂ were used in the feed side and the permeate side, respectively. This is much higher than the flux of 0.05 mL min^?1 cm^?2 obtained from SrCe_0.9Y_0.1O₃ membrane at identical condition. More essential is the fact that the doped SCY membranes displayed catalytic activity for the reverse water-gas shift (RWGS) reaction which consumed H₂ in the permeate side; increasing the H₂ flux up to 0.57 mL min^?1 cm^?2 at 900 °C. The 5 wt. % Ti₄O₇-doped SCY furthermore showed stable flux for more than 140 h at 850 °C despite the formation of minor amount of SrCO₃ in H₂-CO₂-containing atmosphere; highlighting its potential application as membrane reactor for RWGS or dehydrogenation reaction.     

Hydrogen separation and purification with poly (4-methyl-1-pentyne)/MIL 53 mixed matrix membrane based on reverse selectivity

The effect of MIL 53 (Al) metal organic framework on gas transport properties of poly (4-methyl-1-pentyne) (PMP) was determined based on reverse selectivity. Mixed matrix membranes (MMMs) were fabricated considering various weight percent of MIL 53 particles. The reverse MMMs permselectivities were evaluated through measurement of pure CO₂ and H₂ permeation together with calculation of CO₂/H₂ selectivity. The PMP/MIL 53 (Al) MMMs exhibited privileged CO₂/H₂ permselectivity in comparison with the neat PMP. In addition, CO₂ solubility coefficient was significantly increased with increasing the MIL 53 loading, while the H₂ solubility coefficient was almost remained unchanged. Moreover with increasing the feed pressure the permeability of CO₂ and CO₂/H₂ selectivity were dramatically enhanced, especially at higher filler loadings. Therefore, it was observed that the reverse selectivity of MMMs was enhanced so that the Robeson upper bound was overcome. The best yielding membranes (PMP/30 wt.% MIL 53) represented the CO₂ permeability and CO₂/H₂ selectivity of 377.24 barrer and 24.91 for pure gas experiments respectively.     

High performance ZIF-8/PBI nano-composite membranes for high temperature hydrogen separation consisting of carbon monoxide and water vapor

Two types of advanced nano-composite materials have been formed by incorporating as-synthesized wet-state zeolitic imidazolate frameworks-8 (ZIF-8) nano-particles into a polybenzimidazole (PBI) polymer. The loadings of ZIF-8 particles in the two membranes (i.e., 30/70 (w/w) ZIF-8/PBI and 60/40 (w/w) ZIF-8/PBI) are 38.2 vol % and 63.6 vol %, respectively. Due to different ZIF-8 loadings, variations in particle dispersion, membrane morphology and gas separation properties are observed. Gas permeation results suggest that intercalation occurs when the ZIF-8 loading reaches 63.6 vol %. The incorporation of ZIF-8 particles significantly enhances both solubility and diffusion coefficients but the enhancement in diffusion coefficient is much greater. Mixed gas tests for H₂/CO₂ separation were conducted from 35 to 230 °C, and both membranes exhibit remarkably high H₂ permeability and H₂/CO₂ selectivity. The 30/70 (w/w) ZIF-8/PBI membrane has an H₂/CO₂ selectivity of 26.3 with an H₂ permeability of 470.5 Barrer, while the 60/40 (w/w) ZIF-8/PBI membrane has an H₂/CO₂ selectivity of 12.3 with an H₂ permeability of 2014.8 Barrer. Mixed gas data show that the presence of CO or water vapor impurity in the feed gas stream does not significantly influence the membrane performance at 230 °C. Thus, the newly developed H₂-selective membranes may have bright prospects for hydrogen purification and CO₂ capture in realistic industrial applications such as syngas processing, integrated gasification combined cycle (IGCC) power plant and hydrogen recovery.     

Graphite coating on alumina substrate for the fabrication of hydrogen selective membranes

Development of composite membranes is a suitable alternative to improve the hydrogen flux through palladium membranes. The porous substrate should not represent a barrier to gas permeation, but the roughness of its surface should be sufficiently smooth for the deposition of a thin and defect-free metal layer. In this study, the performances of the modification of the outer surface of an asymmetric alumina hollow fibre substrate by the deposition of a graphite layer were evaluated. The roughness of the substrate outer surface was reduced from 120 to 37 nm after graphite coating. After graphite coating, the hydrogen permeance through the composite membrane produced with 2 Pd plating cycles was of 1.02 × 10^?3 mol s^?1 m^?2 kPa^?1 at 450 °C and with infinite H₂/N₂ selectivity. Similar hydrogen permeance was obtained with the composite membrane without graphite coating, also at infinite H₂/N₂ selectivity, but 3 Pd plating cycles were necessary. Thus, graphite coating on asymmetric alumina hollow fibres is a suitable alternative to reduce the required palladium amount to produce hydrogen selective membranes.     

Selective deposition of Pd nanoparticles in porous PET membrane for hydrogen separation

Hydrogen purification based on Pd deposition in porous polymeric membranes show promising results for hydrogen permeability and selectivity. It is due to high absorption property of Pd nanoparticles. In this work, gas permeability of carboxylic group functionalized Polyethylene terephthalate (PET) membranes with different time of functionalization have been examined. It has been found that PET membrane having more –COOH group shows higher selectivity for Hydrogen (H₂). Further to improve the selectivity, these carboxylated PET membranes dipped in Pd nanoparticles solution for 6 h and found more selective for H₂ in comparison to Carbon dioxide (CO₂) and Nitrogen (N₂). As the carboxylation increases selectivity of H₂ improves drastically in the beginning and nearly get saturated after 24 h. Similar trend has been observed for these membranes after Pd nanoparticles deposition. Fourier transform infrared spectroscopy (FTIR) spectra of these membranes revealed that intensity of peaks related to –COOH group at 2968 cm^?1 & 1716 cm^?1 increases with functionalization time. Field Emission Scanning Electron Microscopy (FESEM) was used to study the surface morphology of membranes.     

Palladium nanoparticle binding in functionalized track etched PET membrane for hydrogen gas separation

In this work, track-etched poly (ethylene terephthalate) (PET) membranes having different pore sizes were functionalized by the carboxylic groups and the amino groups. Palladium (Pd) nanoparticles of average diameter 5 nm were synthesized chemically and deposited onto pore walls as well as on the surface of these pristine and functionalized membranes. Effect of Pd nanoparticles binding on these membranes were explored and aminated membrane were found to bind more Pd nanoparticles due to its affinity. The morphology of these composite membranes is characterized by Scanning Electron Microscope (SEM) for confirmation of Pd nanoparticle deposition on pore wall as well as on the surface. Gas permeability of functionalized and non-functionalized membranes for hydrogen and carbon dioxide has been examined. From the gas permeability data of hydrogen (H₂) and carbon dioxide (CO₂) gases, it was observed that these membranes have higher permeability for H₂ as compared with CO₂. Due to absorption of hydrogen by Pd nanoparticles selectivity of H₂ over CO₂ was found higher as compared to without Pd embedded membranes. Such type of membranes can be used to develop hydrogen selective nanofilters for purification/separation technology.     

585 divacancy-defective germanene as a hydrogen separation membrane: A DFT study

As sustainable and clean energy, hydrogen is the most attractive and promising energy source in the future. Membrane separation is attractive due to its high hydrogen separation performance and low energy consumption. Van-der-Waals-corrected density functional theory (DFT) calculations are performed to investigate the hydrogen separation performance of 585 divacancy-defective germanene (585 germanene). It is found that the 585 germanene presents a surmountable energy barrier (0.34 eV) for hydrogen molecule passing through the membrane, and that membrane exhibits extremely high selectivity for H₂ molecules over CO, CO₂, N₂, CH₄ and H₂S molecules in a wide range of temperatures. Meanwhile, the hydrogen permeance of 585 germanene can reach 1.94 × 10^?7 mol s^?1 m^?2 Pa^?1 at the low limit temperature of methane reforming (at 450 K), which is higher than the industrially acceptable gas permeance. With high selectivity and permeance, the 585 germanene is a promising candidate for hydrogen separation.     

Experimental investigation of CO tolerance in high temperature PEM fuel cells

In the present work, the effect of operating a high temperature proton exchange membrane fuel cell (HT-PEMFC) with different reactant gases has been investigated throughout performance tests. Also, the effects of temperature on the performance of a HT-PEMFC were analyzed at varying temperatures, ranging from 140 °C to 200 °C. Increasing the operating temperature of the cell increases the performance of the HT-PEMFC. The optimum operating temperature was determined to be 160 °C due to the deformations occurring in the cell components at high working temperatures. To investigate the effects of CO on the performance of HT-PEMFC, the CO concentration ranged from 1 to 5 vol %. The current density at 0.6 V decreases from 0.33 A/cm² for H₂ to 0.31 A/cm² for H₂ containing 1 vol % CO, to 0.29 A/cm² for 3 vol % CO, and 0.25 A/cm² for 5 vol % CO, respectively. The experimental results show that the presence of 25 vol % CO₂ or N₂ has only a dilution effect and therefore, there is a minor impact on the HT-PEMFC performance. However, the addition of CO to H₂/N₂ or H₂/CO₂ mixtures increased the performance loss. After long-term performance test for 500 h, the observed voltage drop at constant current density was obtained as ～14.8% for H₂/CO₂/CO (75/22/3) mixture. The overall results suggest that the anode side gas mixture with up to 5 vol % CO can be supplied to the HT-PEMFC stack directly from the reformer.     

CO2 methanation over ordered mesoporous NiRu-doped CaO-Al2O3 nanocomposites with enhanced catalytic performance

The ordered mesoporous NiRu-doped CaO-Al₂O₃ nanocomposites were synthesized via a facile evaporation-induced self-assembly method for CO₂ methanation. Metallic Ni and Ru species retained the single-component heterostructure rather than NiRu alloy over the 600 °C-reduced catalysts. Owing to the synergistic effect of bimetallic Ni–Ru as well as the improved H₂ and CO₂ chemisorption capacities after the addition of Ru and CaO promoters, the ordered mesoporous 10N1R2C-OMA catalyst exhibited enhanced catalytic activity and selectivity, which achieved the maximum CO₂ conversion of 83.8% and CH₄ selectivity of 100% at 380 °C, 0.1 MPa, 30000 mL g^?1 h^?1. In a 550 °C-109 h-lifetime test, the ordered mesoporous 10N1R2C-OMA catalyst showed high stability and superior anti-sintering property due to the confinement effect of the ordered mesostructure.     

Preparation and characterization of PPSU/PBNPI blend membrane for hydrogen separation

Novel polymer blend membranes of poly(bisphenol A-co-4-nitrophthalic anhydride-co-1,3-phenylenediamine) (PBNPI) and polyphenylsulfone (PPSU) in different weight ratios were prepared by a solution casting technique with N-methyl-2-pyrrolidone (NMP) as solvent. The effects of blend polymer composition on the membrane structure and the H₂, CO₂ and CH₄ separation performance were investigated. The membranes appear macroscopically miscible but microscopically immiscible based on thin-film X-ray diffraction investigations. A remarkably and continuously enhanced permeability has been achieved for these gases with increasing PPSU content from 0 to 50%. The highest pure H₂, CO₂ and CH₄ permeability are, respectively, equal to 40.4, 34.1 and 8.0 barrer.     

Fabrication & performance study of a palladium on alumina supported membrane reactor: Natural gas steam reforming,a case study

In this work, a synthetic mixture of natural gas is considered in a steam reforming process for generating hydrogen by using a membrane reactor housing a composite membrane constituted of a Pd-layer (13 μm) supported on alumina. The Pd/Al₂O₃ membrane separates part of the produced hydrogen through its selective permeation, although it shows a relatively low H₂/N₂ ideal selectivity (>200 at 0.5 bar of trans-membrane pressure and T = 425 °C).The steam reforming reaction is performed at 420 °C, by varying the gas hourly space velocity between 4400 h^?1 and 6900 h^?1 and by using two different mixtures containing some common impurities found within natural gas pipeline. Specifically, the effect of N₂ and CO₂ as impurities in the feed line is analyzed. The reaction pressure and steam-to-carbon ratio (S/C) are kept constant at 3.0 bar (abs.) and 3.5/1, respectively.The best performance of the Pd-based membrane reactor is obtained at 420 °C, 3.0 bar and 100 mL/min of sweep-gas, yielding a methane conversion of 55% and hydrogen recovery >90%.