Surface modification of α-alumina support in synthesis of silica membrane for hydrogen purification

In this work, an experimental study was carried out on the synthesis of silica membrane for hydrogen purification, in which synthesis of γ-alumina intermediate layer using cheaper and safer source was investigated. For this purpose, aluminum hydroxide was selected and the bohmite sols were prepared by acid or base catalyzed hydrolysis of the different salts for comparing with alkoxide source. The SEM micrographs showed no distinct γ-alumina layer on the substrate coated by base catalyzed sol of salt (sample 1), while a homogeneous γ-alumina layer was formed by acid catalyzed sol of salt (sample 2). After γ-alumina layer formation, the gas permeance mechanism was approximately changed. These results were similar to SEM results and N₂ permeance experiments of sample 3 in which substrate was coated with alkoxide sol. However, the γ-alumina layer of sample 2 had no good adhesion to the substrate. Nevertheless, use of aluminum hydroxide can be promised to synthesis of γ-alumina layer; the membrane was synthesized on the modified support with aluminum tri-sec-butylate sol. In particular, in the synthesized silica membrane as the temperature increases, permselectivity of H₂/CO₂ and H₂/N₂ increases from 4.7 and 7.3 at room temperature to 9.4 and 11.6 at 100 °C and to 23.4 and 31.3 at 200 °C, respectively.     

A novel strategy for surface modification of polyimide membranes by vapor-phase ethylenediamine (EDA) for hydrogen purification

In this study, vapor-phase ethylenediamine (EDA) is utilized to specifically modify the physicochemical properties of the outer surface of polyimide membranes without modifying the internal membrane structure for hydrogen purification. The surfaces of polyimide membranes before and after EDA-vapor modification have been characterized by Fourier transform infrared-attenuated total reflectance (FTIR-ATR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), which confirmed the modification mechanism including the conversion of imide groups into amide groups with simultaneous cross-linking between polymer chains and a physical decrement in d-space. Based on pure gas permeation tests, only a 10-min vapor-phase EDA treatment can significantly improve H₂/CO₂ selectivity (up to ∼100). This is attributed to intensive surface modification by EDA vapor, hence rendering this simple and yet novel technique more effectively for hydrogen purification than the conventional solution approach. Although the H₂/CO₂ separation performance in mixed gas tests is not as superior as that in pure gas permeation tests, mixed gas results affirmed impressive H₂/CO₂ separation performance of vapor-phase EDA modified polyimide membranes. This novel vapor modification strategy appears to be promising for large-scale processes, especially the modification of hollow fiber membranes for industrial hydrogen purification.     

Some fundamental aspects in electrochemical hydrogen purification/compression

The electrochemical concentration of hydrogen from a poor hydrogen–inert gas mixture has been investigated by means of an electrochemical cell similar in construction to a hydrogen–air fuel cell, hydrogen being transported as hydrated protons, thorough a Nafion membrane, from the inlet (anode) to the outlet (cathode) compartments of the cell. Galvanostatic and tensiostatic mode of operation have been investigated: in the first case and erratic behaviour of the cell has been observed, mainly because of the non-controllable variations of the membrane water content. Under tensiostatic condition the role of the applied voltage, feed flow rate, water vapour content in the feed mixture and temperature has been studied, with two different designs of the gas feed distribution plates. From the analysis of experimental data it is possible to evaluate the current efficiency, the hydrogen recovery, the hydrogen purity, the exergy gain and the coefficient of performance of the cell.     

Hybrid proton conducting membranes based on sulfonated cross-linked polysiloxane network for direct methanol fuel cell

A series of novel hybrid membranes based on sulfonated poly(arylene ether ketone)s (SNPAEKs), polysiloxane (KH-560) and sulfonated curing agent (BDSA) has been prepared by sol-gel and cross-linking reaction for direct methanol fuel cells (DMFCs). All the hybrid membranes (SKB-xx) show high thermal properties and improved oxidative stability compared with the pristine SNPAEK membrane. The sulfonated cross-linked polysiloxanes networks in the hybrid membranes enhance the mechanical properties and reduce the swelling ratio. The swelling ratio of SKB-20 is 22%, which is much lower than that of the pristine SNPAEK (37%) at 80 °C. Meanwhile, SKB-xx membranes with greatly reduced methanol permeabilities show comparative proton conductivities to pristine SNPAEK membranes. Notably, the proton conductivities of SKB-5 and SKB-10 reach to 0.192 S cm⁻¹ and 0.179 S cm⁻¹ at 80 °C, respectively, which are even higher than the 0.175 S cm⁻¹ of SNPAEK.     

Surface and interface engineering in CO2-philic based UiO-66-NH2-PEI mixed matrix membranes via covalently bridging PVP for effective hydrogen purification

We report on the fabrication of the defect-free mixed-matrix membrane (MMM) based on the polyethylenimine (PEI) matrix with uniformly dispersed metal-organic framework (MOF) filler UiO-66-NH₂, covalently bonded by polyvinylpyrrolidone (PVP). The key feature of the molecular level-controlled filler deposition in prepared UiO-66-NH₂-PVP-PEI membranes was bridging the MOF particles to the PEI polymer matrix via PVP polymer chains. Such an approach improved the polymer-filler interface interactions and boosted the MOF dispersion into the polymer matrix for higher MOF loadings up to 23 wt %. The overall membrane structure and properties were characterized using FTIR, XRD, TG, DSC, SEM and 3D optical profiler techniques. Obtained results revealed the uniform dispersion of UiO-66-NH₂, the strong polymer-filler interface interactions and entanglement of PEI with UiO-66-NH₂-PVP. Furthermore, the outstanding CO₂/H₂ separation performance was determined for the UiO-66-NH₂-PVP-PEI membrane with 18 wt % of MOF loading; the average CO₂ permeability of 394 Barrer and the separation factor of 12 for circa 100 h of the membrane testing overcome the 2008 Robeson reverse upper bound limit. Such improved CO₂/H₂ separation performance was achieved due to the combination of the diffusion-solution mechanism with the preferential adsorption of the CO₂ via the reversible bicarbonate reaction with amino groups of the UiO-66-NH₂ and PEI which acts as fixed CO₂ carrier sites in MMM structure.     

A comparison of the performance and stability of Pd/BCC metal composite membranes for hydrogen purification

Composite membranes were fabricated by sputtering 100 nm of Pd on to both sides of dense BCC metal foils (V, Ta, Nb). Under pure H₂ gas testing at 500 °C the maximum permeability of all three metals exceeds previously reported values and closely approach theoretical limits. However, the stability of each membrane varied significantly due to unique failure mechanisms. Pd/V membranes failed quickly (<20 h) due to a combination of Pd–V interdiffusion and high susceptibility to oxidation as shown through microscopy and compositional analysis. The Pd/Ta membranes were the most resilient to oxygen, but their mechanical integrity was relatively poor and they failed within 48 h due to Pd–Ta interdiffusion. In contrast, Pd/Nb membranes exhibited high permeability throughout the 168 h of testing, with no Pd–Nb interdiffusion observed. The decline in permeability observed during testing was attributed to partial Pd delamination as a result of membrane deformation. These results provide pathways for further development of these membranes.     

Module design of silica membrane reactor for hydrogen production via thermochemical IS process

The potential of the silica membrane reactors for use in the decomposition of hydrogen iodide (HI) was investigated by simulation with the aim of producing CO₂-free hydrogen via the thermochemical water-splitting iodine-sulfur process. Simulation model validation was done using the data derived from an experimental membrane reactor. The simulated results showed good agreement with the experimental findings. The important process parameters determining the performance of the membrane reactor used for HI decomposition, namely, reaction temperature, total pressures on both the feed side and the permeate side, and HI feed flow rate were investigated theoritically by means of a simulation. It was found that the conversion of HI decomposition can be improved by up to four times (80%) or greater than the equilibrium conversion (20%) at 400 °C by employing a membrane reactor equipped with a tubular silica membrane. The features to design the membrane reactor module for HI decomposition of the thermochemical iodine-sulfur process were discussed under a wide range of operation conditions by evaluating the relationship between HI conversion and number of membrane tubes.     

Rapid thermal processing of tubular cobalt oxide silica membranes

This work is the first demonstration of rapid thermal processing techniques as applied to metal oxide/silica membranes on tubular geometries. A procedure was developed which combined fast sol–gel synthesis, rapid calcination steps and a thermal annealing stage to reduce the membrane fabrication time by more than two-thirds, from a conventional process taking seven or more days to less than two. A significant aspect of this major development was the use of a pre-hydrolysed silica precursor ethyl silicate 40 (ES40), instead of the generally preferred tetraethyl orthosilicate (TEOS) which eliminated the need for the researcher specific and time consuming sol–gel reaction stages prior to membrane fabrication. As a result, modified-silica membranes containing cobalt oxides could be directly calcined at 600 °C, instead of conventional thermal process which require slow ramping rates of ≤1 °C min⁻¹ to avoid cracking. As-prepared membranes delivered H₂ permeances of 5 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 450 °C and H₂/N₂ permselectivities of 54. The RTP techniques demonstrated in this work greatly reduced the production time and should both allow researchers to significantly increase their productivity and ultimately reduce the barriers for deployment of inorganic membranes into industrial applications.     

Metal organic frameworks for hydrogen purification

High purity hydrogen is one of the key factors in determining the lifetime of proton exchange membrane (PEM) fuel cells. However, the current industrial processes for producing high purity hydrogen are not only expensive, but also come with low energy efficiencies and productivity. Finding more cost-effective methods of purifying hydrogen is essential for ensuring wider scale deployment of PEM fuel cells. Among various hydrogen purification methods, adsorption in porous materials and membrane technologies are seen as two of the most promising candidates for the current industrial hydrogen purification methods, with metal organic frameworks (MOF) being particularly popular in research over the last decade. Despite many available reviews on MOFs, most focus on synthesis and production, with few reports focused on performance for hydrogen purification. This review describes the working principle and performance parameters of adsorptive separations and membrane materials and identifies MOFs that have been reported for hydrogen purification. The MOFs are summarised and their performance in separating hydrogen from common impurities (CO₂, N₂, CH₄, CO) is compared systematically. The challenges of commercial application of MOFs for hydrogen purification are discussed.     

Evaluation of silica membrane reactor performance for hydrogen production via methanol steam reforming: Modeling study

The aim of this work is to analyze the potential application of microporous silica membrane reactor carrying out methanol steam reforming reaction for hydrogen production. As a further study, a comparison with dense Pd–Ag membrane reactor and a traditional reactor, working at the same operating conditions of silica membrane reactor, is realized.     

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.     

Devlopment of palladium/ceramic membranes for hydrogen separation

This paper presents the major objectives involved in the development of a thin-layer palladium/ceramic composite membranes. These are (a) electroless plating of palladium on ceramic substrate, (b) characterization of palladium/ceramic composite formed, (c) evaluation of selectivity of the composite membranes for hydrogen separation. Commercially available ceramic was used as substrate for deposition of hydrogen selective layers. The substrate was coated with a thin palladium layer by electroless plating. The plating technique allowed to vary the thickness by depositing multiple metal layers. The details of the plating procedures and formulations of the plating solutions are presented. The palladium/ceramic composite membranes were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and measuring the thickness of the coated film by a weight-gain method. The palladium film thicknesses were determined to be between 2 μm and 5 μm. Sorption performances of composite membranes were evaluated using temperature swing sorption process (TSSP). A gases mixture, provided from biomass gasification process, containing about 40-50% vol. H₂ and numerous other gases such as CO, CO₂, CH₄, hydrocarbons C₂-C₁₀, was used for the tests. In a first step, at first temperature (5-10 °C), the palladium/ceramic composites sorb only hydrogen from mixture and form hydride, all other components leave the sorbent. Then, subsequently, in a second step, energy is added to the sorbent, thus bringing it to a second temperature (105-120 °C) and hydrogen is desorbed while the pressure is reduced. The hydrogen obtained in desorption step is of a high purity (>99.5% vol). The results obtained show that this kind of composite membranes have certain separation selectivity for hydrogen and can have good industrial applications.     

Preparation of a novel bimodal catalytic membrane reactor and its application to ammonia decomposition for COx-free hydrogen production

A novel bimodal catalytic membrane reactor (BCMR) consisting of a Ru/γ-Al₂O₃/α-Al₂O₃ bimodal catalytic support and a silica separation layer was proposed. The catalytic activity of the support was successfully improved due to enhanced Ru dispersion by the increased specific surface area for the γ-Al₂O₃/α-Al₂O₃ bimodal structure. The silica separation layer was prepared via a sol–gel process, showing a H₂ permeance of 2.6 × 10⁻⁷ mol Pa⁻¹ m⁻² s⁻¹, with H₂/NH₃ and H₂/N₂ permeance ratios of 120 and 180 at 500 °C. The BCMR was applied to NH₃ decomposition for CO_x-free hydrogen production. When the reaction was carried out with a NH₃ feed flow rate of 40 ml min⁻¹ at 450 °C and the reaction pressure was increased from 0.1 to 0.3 MPa, NH₃ conversion decreased from 50.8 to 35.5% without H₂ extraction mainly due to the increased H₂ inhibition effect. With H₂ extraction, however, NH₃ conversion increased from 68.8 to 74.4% due to the enhanced driving force for H₂ permeation through the membrane.     

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.     

Artificial neural network based optimization for hydrogen purification performance of pressure swing adsorption

A pressure swing adsorption (PSA) cycle model is implemented on Aspen Adsorption platform and is applied for simulating the PSA procedures of ternary-component gas mixture with molar fraction of H₂/CO₂/CO = 0.68/0.27/0.05 on Cu-BTC adsorbent bed. The simulation results of breakthrough curves and PSA cycle performance fit well with the experimental data from literature. The effects of adsorption pressure, product flow rate and adsorption time on the PSA system performance are further studied. Increasing adsorption pressure increases hydrogen purity and decreases hydrogen recovery, while prolonging adsorption time and reducing product flow rate raise hydrogen recovery and lower hydrogen purity. Then an artificial neural network (ANN) model is built for predicting PSA system performance and further optimizing the operation parameters of the PSA cycle. The performance data obtained from the Aspen model is used to train ANN model. The trained ANN model has good capability to predict the hydrogen purification performance of PSA cycle with reasonable accuracy and considerable speed. Based on the ANN model, an optimization is realized for finding optimal parameters of PSA cycle. This research shows that it is feasible to find optimal operation parameters of PSA cycle by the optimization algorithm based on the ANN model which was trained on the data produced from Aspen model.     

Insights on perovskite-type proton conductive membranes for hydrogen permeation

Hydrogen has received widespread attention because as its diverse delivery methods and no GHG emissions. The use of membrane separation can effectively replace the costly low-temperature distillation and pressure swing adsorption technology to achieve the purpose of low-cost hydrogen enrichment. As a promising hydrogen separation material, perovskite-type proton conductor hydrogen permeable membrane has been practically applied in hydrogen separation and purification process. In this paper, the principle of hydrogen permeability of perovskite-type proton conductor hydrogen permeable membrane is expounded, and its preparation method and application are summarized, and the development trend of the material is discussed.     

Time and frequency domain analysis of hydrogen permeation across PdCu metallic membranes for hydrogen purification

Hydrogen permeation is a process used in the industry for purification purposes. Palladium alloys (PdAg and PdCu) are commonly used as membrane material. In this communication, we report on the kinetics of hydrogen permeation across Pd_0.47Cu_0.53 metallic membranes which can be used in catalytic crackers of biofuels. The permeation mechanism is a multi-step process including surface chemisorption of molecular hydrogen (upstream side of the membrane), hydrogen diffusion across bulk regions, hydrogen recombination (downstream side of the membrane) and evolution. The role of different operating parameters (temperature, surface state, sample microstructure) is analyzed and discussed using both time and frequency domain experiments. Experimental pneumato-chemical impedance diagrams show that there is no significant rate-limitation at surfaces, except at low temperatures close to room temperature. Diffusion-controlled transport of hydrogen across the membrane is rate-determining. However, the value of the hydrogen diffusion coefficient does not rise exponentially with operating temperature in the 40–400 °C temperature range under investigation, as expected for a thermally activated diffusion process. At temperatures as low as 300 °C, new rate-limitations appear. They can be attributed to recrystallization and/or phase transformation processes induced by temperature and the presence of hydrogen.     

Modeling and optimal design of cyclic processes for hydrogen purification using hydride-forming metals

Hydrogen at high purity degrees can be obtained by using the well-known Pressure Swing Adsorption (PSA) process. In this paper, a Pressure Swing Absorption (PSAb) alternative operating batch wise is analyzed. An optimal design of cyclic processes for hydrogen purification using hydride-forming metals as absorption material is addressed. The selected case study is a thermo-chemical treatment process that consumes high purity hydrogen to reduce oxides and generates a waste stream that contains residual H₂. PSAb process is fed with this hydrogen-poor stream; and high purity hydrogen recovery levels are obtained. A mathematical model based on an energy integrated scheme is presented to develop the optimal process design and to obtain optimal operating conditions. Various optimized solutions are compared by modifying key parameters or restriction equations. Thus, an interesting trade-off between H₂ recovery and system size is analyzed. Large systems operate at large cycle times, obtaining up to 98% of H₂ recovery in the order of hours, whereas small systems can recover up to 60% of H₂ in short cycles of a few seconds.     

Development of hydrogen-selective CAU-1 MOF membranes for hydrogen purification by ‘dual-metal-source’ approach

Hydrogen provides reliable, sustainable, environmental and climatic friendly energy to meet world's energy requirement and it also has high energy density. Hydrogen is relevant to all of the energy sectors-transportation, buildings, utilities and industry. In all of these sectors, hydrogen-rich gas streams are needed. Thus, hydrogen-selective membrane technology with superior performances is highly demanded for separation and purification of hydrogen gas mixtures. In this study, novel [Al₄(OH)₂(OCH₃)₄(H₂N-BDC)₃]·xH₂O (CAU-1) MOF membranes with accessible pore size of 0.38 nm are evaluated for this goal of hydrogen purification. High-quality CAU-1 membranes have been successfully synthesized on α-Al₂O₃ hollow ceramic fibers (HCFs) by secondary growth assisted with the homogenously deposited CAU-1 nanocrystals with a size of 500 nm as seeds. The energy-dispersive X-ray spectroscopy study shows that the HCFs substrates play dual roles in the membrane preparation, namely aluminum source and as a support. The crystals in the membrane are intergrown together to form a continuous and crack-free layer with a thickness of 4 μm. The gas sorption ability of CAU-1 MOF materials is examined by gas adsorption measurement. The isosteric heats of adsorption with average values of 4.52 kJ/mol, 12.90 kJ/mol, 12.82 kJ/mol and 27.99 kJ/mol are observed for H₂, N₂, CH₄, and CO₂ respectively, indicating different interactions between CAU-1 framework and these gases. As-prepared HCF supported CAU-1 membranes are tested by single and binary gas permeation of H₂/CO₂, H₂/N₂ and H₂/CH₄ at different temperatures, feed pressures and testing time. The permeation results show preferential permeance of H₂ over CO₂, N₂, and CH₄ with high separation factors of 12.34, 10.33, and 10.42 for H₂/CO₂, H₂/N₂, H₂/CH₄, respectively. The temperature, pressure and test time dependent studies reveal that HCFs supported CAU-1 membranes possess high stability, resistance to cracking, temperature cycling, high reproducibility, these of which combined with high separation efficiency make this type of MOF membranes are promising for hydrogen recycling from industrial exhausts.     

Preparation of mixed matrix composite membrane for hydrogen purification by incorporating ZIF-8 nanoparticles modified with tannic acid

The incompatibility between nanofillers and polymer, caused by the agglomeration of nanoparticles and their weak interaction with each other, is still a challenge to develop mixed matrix composite membrane. Herein, we introduced the ZIF-8-TA nanoparticles synthesized by in situ hydrophilic modification into the hydrophilic poly(vinylamine) (PVAm) matrix to prepare composite membranes for H₂ purification. The dispersion of ZIF-8 in water was improved by tannic acid modification, and the compatibility between ZIF-8 particles and PVAm matrix was enhanced by chemical crosslinking between the quinone groups in oxidized tannic acid (TA) and the amino groups in PVAm. Moreover, the compatibility between hydrophobic polydimethylsiloxane (PDMS) gutter layer and hydrophilic separation layer was achieved by the adhesion of TA-Fe³⁺ complex to the surface of PDMS layer during membrane preparation. The interlayer hydrophilic modification and the formation of separation layer were accomplished in one step, which simplified the preparation process. The experimental results indicated that when the TA addition used for modification was 0.5 g and the ZIF-8-TA_0.5 content in membrane was 12 wt%, the prepared membrane showed the best separation performance with the CO₂ permeance of 987 GPU and the CO₂/H₂ selectivity of 31, under the feed gas pressure of 0.12 MPa.