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.     

Effect of UV irradiation on PC membrane and use of Pd nanoparticles with/without PVP for H2 selectivity enhancement over CO2 and N2 gases

The hydrogen-based economy is one of the possible approaches toward to eliminate the problem of global warming, which are increases because of the gathering of greenhouse gases. Palladium (Pd) is well-known material having a strong affinity to the hydrogen absorbing property and thus appropriate material to embed in the membrane for the improvement of selective permeation of hydrogen gas. In present work, we have functionalized polycarbonate (PC) membranes with the help of UV irradiation to embed the Pd nanoparticles in pores as well as on the surface of the PC membrane. Use of Pd Nanoparticles is helpful to enhance the H₂ selectivity over other gases (CO₂, N_2, etc.). Also, the UV based modification of membrane increases the attachment of Pd Nanoparticles. Further to enhance the Pd nanoparticles attachment, we used PVP binder with Pd nanoparticles solution. Gas permeability measurements of functionalized PC membranes have been carried out, and better selectivity of hydrogen has been found in the functionalized and Pd nanoparticle binded membrane. PC membrane with 48 h UV irradiated and Pd NPs with PVP have been found to have maximum selectivity and permeability for H₂ gas. All the samples being characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy and UV–Vis spectroscopy for their morphological and structural investigation.     

Hydrogen gas separation with controlled selectivity via efficient and cost effective block copolymer coated PET membranes

An efficient way is suggested to reduce the cost of block copolymer (BC) membranes while still taking advantage of their unique properties. It is demonstrated that selectivity can be kept almost the same whereas permeability is varied by using thin copolymer films on robust porous PET polymer membranes which acts as a mechanical support. So, a nanoscopic thin selective layer of the block copolymer (PS-b-P4VP) with additive is casted on the PET porous support. Selective extraction of the additive from the block copolymer thin films leads to the formation of a layer with monodispersed pores on the PET support. Measurements of the gas permeability of PET membranes of different pore size with and without block copolymer coating reveal that permeabilities of BC coated membranes decrease whereas selectivities slightly increase in comparison to the porous PET support. Coating of the membranes with BC plays a valuable role for the selectivity against gases like H₂ over CO₂. The surface morphology of the composite membranes has been determined by atomic force microscopy (AFM) showing the nanoscopic pores. Due to excellent mechanical stability and easy scale up, such membranes may be used in the gas separation technology.     

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.     

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.     

CO2-selective membranes for hydrogen purification and the effect of carbon monoxide (CO) on its gas separation performance

Industrial hydrogen production may prefer CO₂-selective membranes because high-pressure H₂ can therefore be produced without additional recompression. In this study, high performance CO₂-selective membranes are fabricated by modifying a polymer–silica hybrid matrix (PSHM) with a low molecular weight poly(ethylene glycol) dimethyl ether (PEGDME). The liquid state of PEGDME and its unique end groups eliminate the crystallization tendency of poly(ethylene glycol) (PEG). The methyl end groups in PEGDME hinder hydrogen bonding between the polymer chains and significantly enhance the gas diffusivity. In pure gas tests, the membrane containing 50 wt% additive shows CO₂ gas permeability and CO₂/H₂ selectivity of 1637 Barrers and 13 at 35 °C, respectively. In order to explore the effect of real industrial conditions, the gas separation performance of the newly developed membranes has been studied extensively using binary (CO₂/H₂) and ternary gas mixtures (CO₂/H₂/carbon monoxide (CO)). Compared to pure gas performance, the second component (H₂) in the binary mixed gas test reduces the CO₂ permeability. The presence of CO in the feed gas stream decreases both CO₂ and H₂ permeability as well as CO₂/H₂ selectivity as it reduces the concentration of CO₂ molecules in the polymer matrix. The mixed gas results affirm the promising applications of the newly developed membranes for H₂ purification.     

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.     

Effect of mesoporous silica modification on the structure of hybrid carbon membrane for hydrogen separation

An SBA-15/carbon molecular sieve (CMS) composite membrane, using polyetherimide as a precursor and mesoporous silica as filler, was fabricated for hydrogen separation. The effect of mesoporous SBA-15 on the gas transport properties of the composite membrane was evaluated. The permeability and selectivity coefficients of H₂, CO₂, O₂, N₂, and CH₄ were estimated for the pure CMS and SBA-15/CMS composite membranes at a feed pressure of 2-7 atm for 30 °C. The SBA-15/CMS composite membrane had a gas permeability higher than that of the pure CMS membrane, whereas its selectivity was the same. The permeability was found to be independent of pressure; this indicates that the gases are transported through the membrane by a molecular sieve mechanism. The membranes appeared to have a more microporous structure when the mesoporous silica SBA-15 was incorporated. These results concur with the hypothesis that SBA-15 improves gas diffusivity by increasing pore volume.     

Experimental evaluation of graphene oxide/TiO2-alumina nanocomposite membranes performance for hydrogen separation

In recent years, graphene oxide membranes showed interesting performances in terms of high permeating flux and perm-selectivity in several applications of gas separation because of their inherent properties combined to a low energy consumption. In this paper, a graphene oxide layer is coated on modified TiO₂-alumina tubular substrate in order to prepare graphene oxide nanocomposite membranes useful for hydrogen separation. Nanocomposite graphene oxide membrane samples were obtained by using vacuum deep coating method, depositing the graphene oxide solution as single layers on TiO₂-alumina substrate. Temperature and pressure variations were evaluated to achieve high H₂ permeance, high H₂/CO₂ selectivity and membrane performance stability during the experimental tests. Furthermore, it was found that the temperature increase causes a perm-selectivity (H₂/N₂ and H₂/CO₂) decrease, while the transmembrane pressure increase involves a general improvement of the perm-selectivity.     

Enhanced hydrogen purification by graphene - Poly(Dimethyl siloxane) membrane

In this study, a nanocomposite graphene oxide (GO) incorporated poly (dimethyl siloxane) (PDMS) membrane was produced and used for the purification of hydrogen (H₂₎ by separating the (CO₂). The produced membrane was characterized and the single-gas permeability test was performed. Effects of GO addition, trans-membrane pressure and membrane thickness on the gas separation performance of membrane were evaluated as a function of permeability and CO₂/H₂ selectivity. GO addition increased the CO₂/H₂ selectivity and H₂ purification performance. The highest CO2 permeability of 3670 Barrer and CO₂/H₂ selectivity of 11.7 were obtained when the GO loading was 0.5 wt% when the trans-membrane pressure was 0.2 Mpa.     

Thermally rearranged (TR) HAB-6FDA nanocomposite membranes for hydrogen separation

Thermally rearranged (TR) polymers exhibited a good balance of high permeability and high selectivity. For this purpose HAB-6FDA polyimide was synthesized from 3,3 dihydroxy-4,4-diamino-biphenyl (HAB) and 2,2-bis-(3,4-dicarboxyphenyl) hexafluoro propane dianhydride (6FDA) by chemical imidization. Initially, the sample was modified from pure polymer to silica nanofiller doped polymer membrane. Further the modification was done by thermal rearrangement reaction at 350 °C temperature. This modification causes a mass loss in polymer structure and therefore enhances the fractional free volume (FFV). The gases used for the permeation test were H₂, CO₂, N₂ and CH₄. Selectivity was calculated for H₂/CO₂, H₂/N₂ and H₂/CH₄ gas pairs and plotted in the Robeson's 2008 upper bound and compared with reported data. The transport properties of these gases have been compared with the unmodified membrane. Permeability of all the gases has increased to that of unmodified polymer membrane. Thermally rearranged polymer nanocomposite exhibits higher gas permeability than that of silica doped and pure polymer. Also the selectivity for H₂/CO₂ and H₂/N₂ gas pairs exceeds towards Robeson's upper bound limit. It crosses this limit dramatically for H₂/CH₄ gas pair. Polymer nanocomposite can be utilized to obtain high purity hydrogen gas for refinery and petrochemical applications.     

An improvement of the hydrogen permeability of C/Al2O3 membranes by palladium deposition into the pores

The development of compact hydrogen separator based on membrane technology is of key importance for hydrogen energy utilization, and the Pd-modified carbon membranes with enhanced hydrogen permeability were investigated in this work. The C/Al₂O₃ membranes were prepared by coating and carbonization of polyfurfuryl alcohol, then the palladium was introduced through impregnation–precipitation and colloid impregnation methods with a PdCl₂/HCl solution and a Pd(OH)₂ colloid as the palladium resources, and the reduction was carried out with a N₂H₄ solution. The resulting Pd/C/Al₂O₃ membranes were characterized by means of SEM, EDX, XRD, XPS and TEM, and their permeation performances were tested with H₂, CO₂, N₂ and CH₄ at 25 °C. Compared with the colloid impregnation method, the impregnation–precipitation is more effective in deposition of palladium clusters inside of the carbon layer, and this kind of Pd/C/Al₂O₃ membranes exhibits excellent hydrogen permeability and permselectivity. Best hydrogen permeance, 1.9 × 10⁻⁷ mol/m² s Pa, is observed at Pd/C = 0.1 wt/wt, and the corresponding H₂/N₂, H₂/CO₂ and H₂/CH₄ permselectivities are 275, 15 and 317, respectively.     

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.     

High performance composite hollow fiber membranes for CO2/H2 and CO2/N2 separation

The search for a clean energy source as well as the reduction of CO₂ emissions to the atmosphere are important strategies to resolve the current energy shortage and global warming issues. We have demonstrated, for the first time, a Pebax/poly(dimethylsiloxane)/polyacrylonitrile (Pebax/PDMS/PAN) composite hollow fiber membrane not only can be used for flue gas treatment but also for hydrogen purification. The composite membranes display attractive gas separation performance with a CO₂ permeance of 481.5 GPU, CO₂/H₂ and CO₂/N₂ selectivity of 8.1 and 42.0, respectively. Minimizing the solution intrusion using the PDMS gutter layer is the key to achieving the high gas permeance while the interaction between poly(ethylene oxide) (PEO) and CO₂ accounts for the high selectivity. Effects of coating solution concentration and coating time on gas separation performance have been investigated and the results have been optimized. To the best of our knowledge, this is the first polymeric composite hollow fiber membrane for hydrogen purification. The attractive gas separation performance of the newly developed membranes may indicate good potential for industrial applications.     

Developing cross-linked poly(ethylene oxide) membrane by the novel reaction system for H2 purification

In this study, a ‘green” method has been discovered by utilizing the amino functional poly(ethylene oxide) (PEO) and epoxy functional PEO with low molecular weights to synthesis cross-linked membranes for enhancing H₂ purification and CO₂ capture performance by retarding the crystallinity of semi-crystalline polymer of PEO. The cross-linking reaction can happen simply by mixing two materials without using any solvent. The reaction has been characterized by Fourier transform infrared-attenuated total reflectance (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), solid-state ¹³C nuclear magnetic resonance (NMR) and the gel content test. Furthermore, X-ray diffraction (XRD) and differential scanning calorimeter (DSC) confirm the amorphous structure of cross-linked PEO membranes, which should benefit the gas transport. The gas transport properties and the plasticizing phenomenon of CO₂ have been examined in detail. Interestingly, the investigation on CO₂ plasticization phenomenon reveals that the cross-linked PEO membrane should be plasticized immediately after the pressure load. The pressure dependence of CO₂ permeability in the pressure range from 0.25 atm to 30 atm can be separated into two stages based on the permeability increment although the CO₂ permeability continuously increases with the loading pressure. The gas transport results illustrate that CO₂ has much larger permeability than that of any tested gas (including H₂, N₂ and CH₄) attributing to the CO₂-philic characteristic of ethylene oxide (EO) groups in the cross-linked PEO membrane. The good permeability and selectivity make the developed PEO membrane promising for H₂ purification and CO₂ capture applications.     

PVDF/ionic liquid polymer blends with superior separation performance for removing CO2 from hydrogen and flue gas

We have demonstrated, for the first time, a polymer blend comprising poly(vinylidene fluoride) (PVDF) and a room-temperature ionic liquid (RTIL) that shows a high CO₂ permeability of 1778 Barrer with CO₂/H₂ and CO₂/N₂ selectivity of 12.9 and 41.1, respectively. The low viscosity RTIL, 1-ethyl-3-methylimidazolium tetracyanoborate ([emim][B(CN)₄]) possesses a high CO₂ solubility, and plays a significant role in CO₂ separation, whereas PVDF provides the mechanical strength to the blend membranes. A series of PVDF/[emim][B(CN)₄] polymer blends with different compositions were tested for their gas separation performance involving H₂, N₂ and CO₂ in both pure gas and mixed gas conditions. Both optical observation and Maxwell predictions confirm the heterogeneous nature of the PVDF/[emim][B(CN)₄] system. However, compared to miscible ionic liquid based blends, where molecular level interactions may restrain chain flexibility and reduce gas permeability, heterogeneous PVDF/RTIL blend systems show far superior gas transport properties. Most of these blend membranes outperform most reported materials and their gas transport and separation capabilities fall within the attractive region bound by the “2008 Robeson Upper Limit” for CO₂/H₂ and CO₂/N₂ gas pairs, and are also very stable at trans-membrane pressure up to 5 atm. Therefore, they are potential materials for H₂ purification and CO₂ capture from hydrogen production and flue gas.     

Theoretical investigations of permeability and selectivity of Pd–Cu and Pd–Ni membranes for hydrogen separation

Hydrogen is one of the most prospective energy resources with zero polluted emission and high energy utilization, an improved separation and purification performance of hydrogen is critical for application of hydrogen energy. In this work, hydrogen separating performance of Pd–Cu and Pd–Ni alloy membranes are theoretically explored through density functional theory and molecular dynamics calculations. The results demonstrate that both Pd–Cu and Pd–Ni membranes exhibit excellent selectivity to H₂ over N₂, CO, CO₂, CH₄, H₂S at varied temperatures, and are superior to industrial production limit based on predicting permeance of H₂. The outstanding selectivity of Pd–Cu alloy toward H₂ is in accordance with experimental conclusion. Moreover, the DFT calculations are further supported by molecular dynamics simulations, which visually demonstrate the H₂ separation performance of the Pd-based alloys in a dynamic way. This work provides an effective and efficient approach to evaluate the permeability and selectivity of metal alloys membranes for gas separation.     

Hydrogen enrichment and separation from synthesis gas by the use of a membrane reactor

One of the objectives of the CHRISGAS project was to study innovative gas separation and gas upgrading systems that have not been developed sufficiently yet to be tested at a demonstration scale within the time frame of the project, but which show some attractive merits and features for further development. In this framework CIEMAT studied, at bench scale, hydrogen enrichment and separation from syngas by the use of membranes and membrane catalytic reactors.In this paper results about hydrogen separation from synthesis gas by means of selective membranes are presented. Studies dealt with the evaluation of permeation and selectivity to hydrogen of prepared and pre-commercial Pd-based membranes. Whereas prepared membranes turned out to be non-selective, due to discontinuities of the palladium layer, studies conducted with the pre-commercial membrane showed that by means of a membrane reactor it is possible to completely separate hydrogen from the other gas components and produce pure hydrogen as a permeate stream, even in the case of complex reaction system (H₂/CO/CO₂/H₂O) under WGS conditions gas mixtures.The advantages of using a water-gas shift membrane reactor (MR) over a traditional fixed bed reactor (TR) have also been studied. The experimental device included the pre-commercial Pd-based membrane and a commercial high temperature Fe–Cr-based, WGS catalyst, which was packed in the annulus between the membrane and the reactor outer shell. Results show that in the MR concept, removal of H₂ from the reaction side has a positive effect on WGS reaction, reaching higher CO conversion than in a traditional packed bed reactor at a given temperature. On increasing pressure on the reaction side permeation is enhanced and hence carbon monoxide conversion increases.     

Selective and efficient hydrogen separation of Pd–Au–Ag ternary alloy membrane

The widespread demand for clean energy stimulates great interest to hydrogen energy with high energy density and conversion efficiency. Separation technologies by membranes are increasingly applied for hydrogen separation because of its excellent performance and low consumption. In this work, density functional theory simulations is used to study hydrogen separation of Pd–Au–Ag membrane, and the performance of Pd–Au alloy is also compared and discussed. The results indicate that Pd–Au alloy shows superior selectivity to H₂ gas over CO, N₂, CH₄, CO₂ and H₂S gases, which is in line with experimental results. In particular, the separation selectivity of Pd–Au–Ag to H₂ is significantly greater than those for Pd–Au alloy and several currently reported materials. Moreover, the permeability of H₂ in Pd–Au–Ag exceeds the limits for industrial production at deferent temperatures. Our calculations demonstrate that Pd–Au–Ag alloy present excellent performance as a promising membrane for hydrogen separation.     

Molecular-level mixed matrix membranes comprising Pebax and POSS for hydrogen purification via preferential CO2 removal

The molecular-level mixed matrix membranes (MMMs) comprising Pebax^® and POSS have been developed by tuning the membrane preparation process in this work. They exhibit a simultaneous enhancement in CO₂ permeability and CO₂/H₂ selectivity by optimizing the POSS content at extremely low loadings. This is mainly attributed to the large cavity of POSS itself and its effect on the segmental-level polymeric chain packing. More interestingly, the Pebax^®/POSS MMMs reveal a much higher separation performance in the mixed gas test than that in the pure gas test. The highest CO₂/H₂ selectivity reaches 52.3 accompanied by CO₂ permeability of 136 Barrer at 8 atm and 35 °C. This is due to the CO₂-induced plasticization that improves the free volume and polymer chain mobility, hence benefiting the interaction between the polymer matrix and penetrant CO₂. These features may ensure the superiority of Pebax^®/POSS molecular-level MMMs as CO₂-selective membranes in the industrial application of hydrogen purification.