Supported and laminated Pd-based metallic membranes

Composite metallic membranes for the separation and the production of hydrogen have been prepared by using thin Pd–Ag foils (with silver content 23–25 at%) reinforced by metallic (stainless steel, nickel, niobium) structures. Essentially, the cost reduction for the Pd-based membranes has been achieved through two different methods used in the production of composite membranes. A procedure of diffusion welding was used to join Pd–Ag thin foils with expanded metals (stainless steel) and perforated metals (nickel): the thin palladium foil in these membranes assures both the high hydrogen permeability and the perm-selectivity, while the metallic support provides the mechanical strength. A second procedure investigated for the production of composite laminated membranes consists in coating non-noble metals with very thin palladium layers: in this case, Pd–Ag foils have been applied over nickel, iron and niobium sheets through the diffusion welding procedure, and then the thickness of the laminated metal has been reduced down to the desiderated value by cold rolling.

Permeation tests carried out on these composite membranes have shown hydrogen permeability data to be in accord to previously studied literature; furthermore, the complete hydrogen selectivity, and the observed chemical and physical stability, have demonstrated the applicability of these procedures to processes for separating and producing pure hydrogen.     

Preparation, testing and modelling of a hydrogen selective Pd/YSZ/SS composite membrane

A palladium selective tubular membrane has been prepared to separate and purify hydrogen. The membrane consists of a composite material, formed by different layers: a stainless steel support (thickness of 1.9 mm), an yttria-stabilized zirconia interphase (thickness of 50 μm) prepared by Atmospheric Plasma Spraying and a palladium layer (thickness of 27.7 μm) prepared by Electroless Plating. The permeation properties of the membrane have been tested at different operating conditions: retentate pressure (1-5 bar), temperature (350-450 °C) and hydrogen molar fraction of feed gas (0.7-1). At 400 °C, a permeability of 1.1 × 10⁻⁸ mol/(s m Pa^0.5) and a complete selectivity to hydrogen were obtained. The complete retention of nitrogen was maintained for all tested experiment conditions, with both single and mixtures of gases, ensuring 100% purity in the hydrogen permeate flux.A rigorous model considering all the resistances involved in the hydrogen transport has been applied for evaluating the relative importance of the different resistances, concluding that the transport through the palladium layer is the controlling one. In the same way, a model considering the axial variations of hydrogen concentration because of the cylindrical geometry of the experimental device has been applied to the fitting of the experimental data. The best fitting results have been obtained considering Sieverts’-law dependences of the permeation on the hydrogen partial pressure.     

High pressure membrane separator for hydrogen purification of gas from hydrothermal treatment of biomass

For hydrogen purification and green hydrogen production in the context of biomass hydrothermal gasification, a palladium membrane system with microchannels on feed and permeate side was studied. The high pressure in the product gas of the hydrothermal process could potentially be used to generate pressurized pure hydrogen on the permeate side. Stabilizing the membrane by an additional porous metal support, experimental verification of the concept was done at feed pressure up to 50 bar and permeate pressure up to 20 bar. The temperatures were varied between 370 °C and 425 °C. The device was found to be highly selective and efficient for pure hydrogen separation. The membrane was characterized regarding the hydrogen flux and a deviation of the permeation from Sievert's law above 30 bars feed pressure was found. Generally, the microchannels on the feed side minimized concentration polarization effects, leading to high hydrogen fluxes with hydrogen feed mixtures and with real gas samples from hydrothermal gasification.     

A numerical approach of conjugate hydrogen permeation and polarization in a Pd membrane tube

A numerical method accounting for conjugate hydrogen permeation in a dense palladium (Pd) membrane tube is developed. In the method, hydrogen permeation across the membrane is treated by introducing a source–sink pair and a gas mixture produced from water gas shift reactions serves as the feed gas of the membrane tube. The influences of flow patterns of feed gas and sweep gas as well as their flow rates on hydrogen separation are investigated. A concentration polarization index (CPI) is also conducted to indicate the extent of polarization along the membrane surface. The predicted results suggest that counter-current modes are able to give the better performance of hydrogen separation compared to co-current modes, and hydrogen can be completely recovered if the flow rate of feed gas is low to a certain extent. However, lower flow rates of feed gas and sweep gas will trigger serious concentration polarization. With counter-current modes, the feed gas sent into the membrane tube from the lumen side or the shell side is flexible. The optimum Reynolds number of sweep gas in accordance with the Reynolds number of feed gas is correlated by an arctangent function. This provides a useful reference for the operation of hydrogen separation by controlling sweep gas.     

Hydrogen permeation enhancement in a Pd membrane tube system under various vacuum degrees

Hydrogen purification using palladium (Pd) membrane technology has been seen as a potential solution for producing pure hydrogen form hydrogen-rich gas. Compared to traditional practices of operating the permeate side of the membrane at atmospheric pressure, in this study, a vacuum is applied. The effects of various vacuum degrees applied to the permeate side of the Pd membrane are investigated and compared to the results under normal operation without a vacuum. The feed gas used for experiments consists of a mixture of hydrogen (70 vol%) and nitrogen (30 vol%). Three membrane operating temperatures (320, 350, and 380 °C), four pressure differences (2, 3, 4, and 5 atm) across the membrane, and four vacuum degrees (−15, −30, −45, and −53 kPa) applied to the permeate side are considered. For the three operating temperatures, the best improvements in the performance of hydrogen permeation are at 320 and 350 °C when a −53 kPa vacuum is applied, resulting in 79.4% and 79.1% improvements, respectively, compared to normal operations. Increasing temperatures leads to an increase in H₂ permeation both with and without a vacuum; however, best performances of H₂ permeation are observed in cases without a vacuum.     

Effect of sweep gas on hydrogen permeation of supported Pd membranes: Experimental and modeling

Membrane reactor processes are being increasingly proposed as an attractive solution for pure hydrogen production due to the possibility to integrate production and separation inside a single reactor vessel. High hydrogen purity can be obtained through dense metallic membranes, especially palladium and its alloys, which are highly selective to hydrogen. The use of thin membranes seems to be a good industrial solution in order to increase the hydrogen flux while reducing the cost of materials. Typically, the diffusion through the membrane layer is the rate-limiting step and the hydrogen permeation through the membrane can be described by the Sieverts’ law but, when the membrane becomes thinner, the diffusion through the membrane bulk becomes less determinant and other mass transfer limitations might limit the permeation rate. Another way to increase the hydrogen flux at a given feed pressure, is to increase the driving force of the process by feeding a sweep gas in the permeate side. This effect can however be significantly reduced if mass transfer limitations in the permeate side exist. The aim of this work is to study the mass transfer limitation that occurs in the permeate side in presence of sweep gas. A complete model for the hydrogen permeation through PdAg membranes has been developed, adding the effects of concentration polarization in retentate and permeate side and the presence of the porous support using the dusty gas model equation, which combines Knudsen diffusion, viscous flow and binary diffusion. By studying the influence of the sweep gas it has been observed that the reduction of the driving force is due to the stagnant sweep gas in the support pores while the concentration polarization in the permeate is negligible.     

Oxidative steam reforming of ethanol over a Pt/Al2O3 catalyst in a Pd-based membrane reactor

In this study, the ability of a Pd-Ag membrane reactor of producing ultrapure hydrogen via oxidative steam reforming of ethanol has been evaluated. A self supported Pd-Ag tube of wall thickness 60 μm has been filled with a commercial Pt-based catalyst and assembled into a membrane module in a finger-like configuration. In order to evaluate the hydrogen yield behavior under different operating conditions, experimental tests have been performed at temperatures of 400 and 450 °C and pressures of 150 and 200 kPa. The oxidative steam reforming of ethanol has been carried out by feeding the membrane reactor with a gas stream containing a dilute water-ethanol mixture and air. Different water/ethanol feed flow rates (5, 10, 15 g h⁻¹), several water/ethanol (4, 10, 13) and oxygen/ethanol (0.3, 0.5, 0.7) feed molar ratios have been tested. The results pointed out that the highest hydrogen yield (moles of permeated hydrogen per mole of ethanol fed) corresponding to almost 4.1 has been attained at 450 °C and 200 kPa of lumen pressure by using a water/ethanol/oxygen feed molar ratio of 10/1/0.5.The results of these tests have been compared with those reported for the ethanol steam reforming in a Pd-Ag membrane reactor filled with the same Pt-based catalyst. This comparison has shown a positive effect on the hydrogen yield of small oxygen addition in the feed stream.     

Preparation and characterization of palladium ceramic alumina membrane for hydrogen permeation

In this study, a tubular palladium membrane has been prepared by an electroless plating method using palladium II chloride as a precursor with the intent of not having a completely dense film since its application does not require high hydrogen selectivity. The support used was a 15 nm pore sized tubular ceramic alumina material that comprised of 77% alumina and 33% titania. It has dimensions of 7 mm inner and 10 mm outer diameters respectively. The catalyst was deposited on the outside tube surface using the electroless deposition process. The membrane was morphologically characterized using scanning electron microscopy/energy dispersive x-ray analysis (SEM/EDXA) and liquid nitrogen adsorption/desorption analysis (BET) to study the shape and nature of the palladium plating on the membrane. The catalytic membrane was then inserted into a tubular stainless-steel holder which was wrapped in heating tapes so as to enable the heating of the membrane in the reactor. The gases used for permeation tests comprised H₂, N₂, O₂ and He. Permeation tests were out at 573 K and at pressure range between 0.05 and 1 barg. The results showed that hydrogen displayed a higher permeation when compared to other gases that permeated through the membrane and its diffusion is also thought to include solution diffusion through the dense portions of the palladium in addition to Knudsen, convective and molecular sieving mechanisms occurring through cracks and voids along the grain boundaries. While high hydrogen selectivity is critically important in connection with hydrogen purification for fuel cells and in catalytic membrane reactors used to increase the yield of thermodynamically limited reactions such as methane steam reforming and water–gas shift reactions whereby the effective and selective removal of the H₂ produced from the reaction zone shifts the equilibrium, it is not so important in situations in which the membrane has catalytic activity such that it is possible to carryout the reaction in situations where the premixed reactants are forced-through the membrane on which the catalysts is attached. This type of catalytically active membranes is novel and has not been tested in gas-solid-liquid reactions and liquid-solid reactions before. With such a reactor configuration, it is possible to achieve good feed stream distribution and an optimal usage of the catalytic material. The preparation and characterization of such membrane catalysts has gained increased interest in the process industries because it can be adapted to carryout the chemical reactions if one of the reactants is present in low concentration and an optimal reactant distribution results in a better utilization of the active catalytic material. However, there are concerns in terms of the high cost of palladium membranes and research on how to fabricate membranes with a very low content of the palladium catalyst is still ongoing. Work is currently underway to deploy the Pd/Al₂O₃ membrane catalysts for the deoxygenating of water for downhole injection for pressure maintenance and in process applications.     

Fabrication of Pd/ceramic membranes for hydrogen separation based on low-cost macroporous ceramics with pencil coating

Increasing hydrogen energy utilization has greatly stimulated the development of the hydrogen-permeable palladium membrane, which is comprised of a thin layer of palladium or palladium alloy on a porous substrate. This work chose the low-cost macroporous Al₂O₃ as the substrate material, and the surface modification was carried out with a conventional 2B pencil, the lead of which is composed of graphite and clay. Based on the modified substrate, a highly permeable and selective Pd/pencil/Al₂O₃ composite membrane was successfully fabricated via electroless plating. The membrane was characterized by SEM (scanning electron microscopy), field-emission SEM and metallographic microscopy. The hydrogen flux and H₂/N₂ selectivity of the membrane (with a palladium thickness of 5 μm) under 1 bar at 723 K were 25 m³/(m² h) and 3700, respectively; the membrane was found to be stable during a time-on-stream of 330 h at 723 K.     

Study of low hydrogen flows into high-vacuum systems

A study is made of a scheme providing spectrally pure, low hydrogen flows into a high-vacuum chamber through the use of a palladium membrane with a working surface of 20 cm² and ethyl alcohol vapors (scheme combining the processes of hydrogen generation and admission). It is demonstrated that at an optimum alcohol vapor pressure and a membrane temperature of 973 K this scheme can provide specific hydrogen flows of about 5×10⁻² Torr.l⧸s cm². The hydrogen permeability is limited in this case by the processes occurring at the entrance surface of the Pd-membrane.     

Toward effective membranes for hydrogen separation: Multichannel composite palladium membranes

Composite palladium membranes can be used as a hydrogen separator because of their excellent permeability and permselectivity. The total membrane area in a hydrogen separator must be reasonably large for industrial use, and it is important that each membrane provides a large enough area. Such a demand can be well met by introducing multichannel composite membranes. In this work, a commercially available microporous ceramic filter with 19 channels was used as a membrane substrate, and the diameter of each channel was 4 mm. A uniform thin palladium layer was fabricated inside the narrow channels by using an electroless plating method, and the resulting membranes were highly permeable and selective. This membrane concept provides a high surface-to-volume ratio without causing significant pressure loss, making the hydrogen separator compact and capable. However, special attention should be paid to cleaning the membrane after electroless plating.     

Influence of the pre-reformer in steam reforming of dodecane using a Pd alloy membrane reactor

Dodecane, one of the main components in kerosene, was used as a model material to investigate reactions in a palladium membrane reactor for steam reforming of kerosene. The influence of pre-reforming on the performance of the membrane reactor was investigated. A decrease in hydrogen yield caused by coke formation was suppressed through pre-reforming by lowering the concentration of olefins, aromatics and unreacted dodecane in the feed to the membrane reactor. In addition, the proportion of total hydrogen production that permeated the membrane was clearly higher with pre-reforming compared with that without pre-reforming. Pre-reforming prevented deactivation of both the catalyst and the membrane, resulting in efficient separation of hydrogen from the reaction field and therefore achieving a higher hydrogen yield.     

Direct numerical simulation of laminar flame–wall interaction for a novel H2-selective membrane/injector configuration

Direct numerical simulations are performed to investigate the transient processes of laminar flame–wall interaction and quenching near a porous, permeable wall and compared against a reference case of a non-porous impermeable wall. A boundary condition formulation that models species (hydrogen in this case) transport through a permeable wall, driven by the fuel species partial pressure difference between the feed and the permeate side of a selective membrane, has been implemented in a high-order finite difference direct numerical simulation code for reactive flows (S3D) by Chen et al. (2009) [1]. The present results are obtained for lean, stoichiometric and rich initial mixture conditions on the permeate side of the permeable wall and indicate that the characteristic parameters of the flame–wall interaction (wall heat flux, quenching distance) are affected to a large extent by the presence of the membrane hydrogen flux. Concurrently, the hydrogen flux through the membrane is also strongly affected by the presence of the flame during the transient flame–wall interaction process, finally resulting in a strong feedback mechanism between the membrane hydrogen flux and the flame that greatly increases boundary layer flashback speeds at fuel lean conditions.     

General regularities of thermal decomposition of transition metal dihydrides in a medium with low hydrogen partial pressure

The results of the calorimetric studies of thermal dissociation of titanium, zirconium, magnesium, and palladium hydrides performed in recent years are presented. The multiplet character of thermal dissociation characteristic of all these hydrides is shown. A good correlation between the course of differential scanning calorimetry curves and the results of thermogravimetry has been demonstrated.The discrete nature of the decomposition processes is established. A sequence of mechanisms occurring during the heating of transition metal dihydrides in a medium with a low partial pressure of hydrogen has been proposed: rearrangement in the hydride phase; destruction of metal - hydrogen bonds to form a solid solution supersaturated with hydrogen; diffusion of hydrogen to the interface of solid phase - environment; molization of hydrogen at the exit from the solid phase.     

Rapid control of hydrogen permeation in Pd membrane reactor by magnetic-field-induced heating under microwave irradiation

A microwave (MW) heating system induced by a magnetic field was designed and applied for uniform heating of a Pd membrane selectively through hydrogen. This system aimed to control the temperature of the membrane and the hydrogen permeation rate. Although the conventional dielectric heating by MWs is not suitable for metal membranes because of the reflection of MWs, a magnetic field can excite the surface current (eddy current) and causes Joule heating. First, this was successfully achieved for thin metal films in a frequency-variable single-mode MW reactor system with a cylindrical cavity. The temperature of the surface was controlled precisely by a resonance frequency autotracking function. Then, for the control of the hydrogen permeation rate through the Pd membrane, this system was applied to a pore-filling-type Pd membrane where the Pd nanoparticles were filled in the nanospace void of the Al₂O₃ support tube, suggesting high durability. The temperature of Pd membrane could be quickly and precisely controlled due to direct heating by this MW system. Hydrogen permeation rate was well controlled associated with the temperature of the membrane.     

Theoretical modelling of porous silicon decorated with metal atoms for hydrogen storage

There is experimental evidence suggesting that metal adatoms enhance the physisorption of hydrogen molecules in porous silicon. However, theoretical reports about the physical properties for this material to be suitable for hydrogen storage are scarce. Thus, in this work we employ Density Functional Theory to study the effects of decoration with metals on the hydrogen-adsorption properties on hydrogen-passivated porous silicon. The results indicate that lithium and palladium decorating atoms are strongly bonded to the porous silicon—preventing the adverse effects of clusterization—while beryllium is not. Lithium and palladium exhibit physisorption capacity up to 5 and 4 hydrogen molecules per adatom, respectively. In contrast, adsorption of hydrogen molecules in beryllium is too weak as the adatom is not chemisorbed on the surface of the pore. The hydrogen passivation of the pore surface proves to be beneficial for a strong chemisorption of the decorating atoms.     

Dynamics of hydrogen permeation across metallic membranes

Thin and supported palladium membranes can be coupled to gas reformers to produce purified hydrogen. Such systems can potentially be used in the automotive industry to feed PEM fuel cells. However, for such applications, the membrane design must be optimized to meet some specific requirements, in particular to allow fast accelerations. The purpose of this paper is to take advantage of the possibility offered by pneumato-chemical impedance spectroscopy to analyze the dynamics of hydrogen permeation in transient conditions of flow, to determine the conditions for which shifts in rate-determining step (rds) between surface and bulk rate contributions are observed. Results reported in this paper have been obtained using a Pd₇₇Ag₂₃ metallic membrane. The gas-phase impedance of this 50 μm thick membrane has been measured. A model has been developed to evaluate separately surface and bulk rate contributions. It is shown that in a typical permeation experiment performed in transient conditions of flow, the surface step is rate-determining in the early stages of the experiment (highly transient conditions of flow) whereas the bulk diffusion step becomes rate-determining at longer time (quasi-stationary conditions of flow). The relationship between membrane characteristics, experimental conditions and the time at which the shift in rds is observed are determined, opening the way to the development of customized membranes for operation in transient conditions of flow.     

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.     

Effect of single atomic layer graphene film on the thermal stability and hydrogen permeation of Pd-coated Nb composite membrane

Pd coated Nb-base composite membranes are preferable in the fields of hydrogen permeation. However, the rapid reduction of hydrogen permeability caused by high-temperature interfacial diffusion of Pd and Nb atoms hinders their large-scale application. In this paper, a single atomic layer graphene film was used for improving the thermal stability of a hydrogen-permeable composite membrane comprising a Pd coating on the Nb substrate. First, the graphene film was transferred onto the surface of the “clean” niobium substrate. Then a thin palladium coating was deposited on it by magnetron sputtering to form the niobium/graphene/palladium (Nb/Gr/Pd) composite membrane. The interfacial stability was evaluated in the temperature range of 673–973 K under vacuum, and the hydrogen permeation behavior was studied by gas-driven permeation method at 573–823 K. The results show that the single atomic layer graphene film can effectively compress the interdiffusion of Pd coating and Nb substrate and achieve a good hydrogen permeability below 823 K. However, it would be broken due to the micro-deformation of Nb substrate, the high mobility of Pd atoms, and the grain growth at a higher temperature. Therefore, it is concluded that the single atomic layer graphene film is unsuitable as an intermediate hindering layer for Nb-based hydrogen-permeable membranes.