Silver coating on porous stainless steel substrate and preparation of H2-permeable palladium membranes

The H₂-permeable palladium membranes based on porous stainless steel (PSS) substrate are important for development of various hydrogen energy systems. To improve the surface of the PSS, a microporous silver layer was deposited successively by a coating with a suspension of silver powder in polyvinyl alcohol (PVA) solution, a heating under nitrogen at 500 °C for carbonization of PVA, an air treatment and a hydrogen reduction. The formation of carbon from PVA helps to maintain the porosity and integrity of the silver layer. After an activation of the resulting Ag/PSS surface through galvanic-cell reaction, palladium membranes with a thickness around 4 μm were successfully prepared by a suction-assisted electroless plating. SEM, EDS, metallography and porometry analyzes were conducted for material characterizations. The prepared Pd/Ag/PSS membrane is permeable and selective as compared with similar those reported in literature. The permeation tests were carried out at 350, 400, 450 and 500 °C for 48, 48, 48 and 60 h, respectively, and the membrane was found to be unstable at 500 °C due to the presence of pinholes. No significant intermetallic diffusion between the silver and palladium layers was observed.     

Pre-activation of SBA-15 intermediate barriers with Pd nuclei to increase thermal and mechanical resistances of pore-plated Pd-membranes

Thermal and mechanical resistances of palladium composite membranes prepared by Electroless Pore-Plating (ELP-PP) and containing SBA-15 as intermediate layer were improved by doping the silica material with Pd nuclei before its incorporation on the composite membrane. Textural properties of synthesized SBA-15 materials (both raw and doped ones) were analyzed by XRD, N₂ adsorption-desorption at 77 K and TEM, while the main properties of the composite membrane were determined by SEM and gravimetric analyses. Moreover, membrane permeation tests were also carried out with pure gases, hydrogen and nitrogen, and binary mixtures of them at temperature of 400 °C and pressure driving forces in the range of 0.5–2.5 bar. The use of bare SBA-15 intermediate layer leads to the appearance of cracks on the Pd layer during permeation experiments at high temperature. In contrast, the use of Pd-doped SBA-15 particles avoids this problem, thus improving both thermal and mechanical resistances of the composite ELP-PP Pd-membrane. Following this preparation method, an estimated Pd thickness of 7.1 μm was obtained, reaching a hydrogen permeance of 3.81·10^?4 mol s^?1 m^?2 Pa^?0.5 and ensuring an ideal H₂/N₂ separation factor higher than 2550 at 400 °C.     

Novel non-alloy Ru/Pd composite membrane fabricated by electroless plating for hydrogen separation

This study presents a new non-alloy Ru/Pd composite membrane fabricated by electroless plating for hydrogen separation. It shows that palladium and ruthenium can be deposited on an aluminum-oxide-modified porous Hastalloy by using our new EDTA-free plating bath at room temperature and 358 K, respectively. A 6.8 μm thick non-alloy Ru/Pd membrane film could be plated and helium leak test confirmed that the membrane was free of defects. Hydrogen permeation test showed that the membrane had a hydrogen permeation flux of 4.5 × 10⁻¹ mol m⁻² s⁻¹ at a temperature of 773 K and a pressure difference of 100 kPa. The hydrogen permeability normalized value with thickness of the membrane was 1.4 times higher than our pure Pd membrane having similar structure. The EDX profiles of the front and back side membrane, cross-sectional EDX line scanning and XRD profile show that there was no alloying progress between the palladium and ruthenium layer after hydrogen permeation test at 773 K.     

Aluminizing and oxidation treatments on the porous stainless steel substrate for preparation of H2-permeable composite palladium membranes

Composite palladium membranes based on porous stainless steel (PSS) substrate are idea hydrogen separators and purifiers for hydrogen energy systems, and the surface modification of the PSS is of key importance. In this work, the macroporous PSS tubes were aluminized through pack cementation at 850 °C in argon, followed by an oxidation with air at 600 °C. Palladium membranes were prepared by electroless plating. Their permeation performances were tested, and the hydrogen permeation kinetics was discussed. The substrate materials and the palladium membranes were characterized by means of scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD). An Al₂O₃-enriched surface layer with small pore size was created through aluminizing and oxidation treatments, which greatly improves the membrane integrity. The intermetallic diffusion between the palladium membranes and the PSS substrate material was not observed after a heat-treatment at 500 °C under hydrogen for 200 h. However, the aluminizing and oxidation treatments still need to be further optimized in order to improve the membrane permeability and selectivity, and particularly, the high diffusion resistance of the substrate materials greatly limited the hydrogen flux.     

Improved hydrogen permeation through thin Pd/Al2O3 composite membranes with graphene oxide as intermediate layer

Here we proposed the decreasing in the roughness of asymmetric alumina (Al₂O₃) hollow fibers by the deposition of a thin graphene oxide (GO) layer. GO coated substrates were then used for palladium (Pd) depositions and the composite membranes were evaluated for hydrogen permeation and hydrogen/nitrogen selectivity. Dip coating of alumina substrates for 45, 75 and 120 s under vacuum reduced the surface mean roughness from 112.6 to 94.0, 87.1 and 62.9 nm, respectively. However, the thicker GO layer (deposited for 120 s) caused membrane peel off from the substrate after Pd deposition. A single Pd layer was properly deposited on the GO coated substrates for 45 s with superior hydrogen permeance of 24 × 10⁻⁷ mol s⁻¹m⁻² Pa⁻¹ at 450 °C and infinite hydrogen/nitrogen selectivity. Activation energy for hydrogen permeation through the Al₂O₃/GO/Pd composite membrane was of 43 kJ mol⁻¹, evidencing predominance of surface rate-limiting mechanisms in hydrogen transport through the submicron-thick Pd membrane.     

Hydrogen sorption by Pd77Ag23 metallic membranes. Role of hydrogen content, temperature and sample microstructure

Permeation across metallic membranes is a process used in the industry for purifying hydrogen. In conventional technology, a few tens of micrometers thick metallic membranes made of palladium alloys are used in the 400-600 °C temperature range, using a driving force of several bars for enhanced kinetics. In stationary conditions of flow, the diffusion-controlled transport of atomic hydrogen across the membrane is usually rate-determining. When thin (sub-micron thick) membranes are used, surface rate contributions become more significant. To optimize permeation performances, there is therefore a need for separately measuring surface and bulk rate contributions. In this communication, we report on the kinetics of hydrogen permeation across Pd₇₇Ag₂₃ metallic membranes using pneumato-chemical impedance spectroscopy. The role of different operating parameters (temperature, surface state, membrane microstructure) on the kinetics of permeation is analyzed and discussed.     

Influence of the type of siliceous material used as intermediate layer in the preparation of hydrogen selective palladium composite membranes over a porous stainless steel support

In this work, several composite membranes were prepared by Pd electroless plating over modified porous stainless steel tubes (PSS). The influence of different siliceous materials used as intermediate layers was analyzed in their hydrogen permeation properties. The addition of three intermediate siliceous layers over the external surface of PSS (amorphous silica, silicalite-1 and HMS) was employed to reduce both roughness and pore size of the commercial PSS supports. These modifications allow the deposition of a thinner and continuous layer of palladium by electroless plating deposition. The technique used to prepare these silica layers on the porous stainless steel tubes is based on a controlled dip-coating process starting from the precursor gel of each silica material. The composite membranes were characterized by SEM, AFM, XRD and FT-IR. Moreover they were tested in a gas permeation set-up to determine the hydrogen and nitrogen permeability and selectivity. Roughness and porosity of original PSS supports were reduced after the incorporation of all types of silica layers, mainly for silicalite-1. As a consequence, the palladium deposition by electroless plating was clearly influenced by the feature of the intermediate layer incorporated. A defect free thin palladium layer with a thickness of ca. 5 μm over the support modified with silicalite-1 was obtained, showing a permeance of 1.423·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5 and a complete ideal permselectivity of hydrogen.     

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.     

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.     

Hydrogen permeation in asymmetric La28 − xW4 + xO54 + 3x/2 membranes

Asymmetric supported La_28 − xW_4 + xO_54 + 3x/2 (La/W ≈ 5.6) membranes were investigated for their hydrogen permeation properties as a function of temperature and feed gas conditions. Dense membranes of thickness 25–30 μm supported on substrates with 25 and 40 vol.% porosity were compared. Above 850 °C under dry conditions, the hydrogen permeation rate was approximately constant as a function of temperature due to low concentration of protons in the material at high temperatures. Under humid conditions and above 960 °C enhanced permeation rates were observed. A hydrogen permeation as high as 0.14 NmL min⁻¹ cm⁻² was recorded at 1000 °C with 10 vol.% H₂ (2.5 vol.% H₂O) as feed gas.     

Hydrogen permeation measurements of Pd and Pd-Cu membranes using dynamic pressure difference method

Hydrogen permeation across membranes is measured using a dynamic pressure difference method. In the method, a transient system for continuously monitoring hydrogen flux of a membrane is conducted. Three different membranes, consisting of two pure palladium (Pd) membranes with different thicknesses and one palladium-copper (Pd-Cu) membrane supported by porous stainless steel (PSS) tubes, are taken into account. Three different operating temperatures of 320, 350 and 380 °C as well as two different initial pressure differences of 5 and 10 atm are considered to evaluate the effects of the operating parameters upon the hydrogen permeation. The results suggest that a threshold of pressure difference is always exhibited at the end of the permeation process, regardless of which membrane is tested. The hydrogen permeation rate can be predicted well for the pressure exponent in the range of 0.1-1.0; however, the optimal pressure exponent is located between 0.5 and 0.8. The theoretical analysis indicates that the characteristic time of hydrogen permeation in the present system ranges from 245 to 460 s and the entire permeation period is longer than the characteristic time by an order of magnitude. In regard to the effect of membrane temperature on the permeation, the activation energies of the three membranes range from 11 to 18 kJ mol⁻¹.     

Proton exchange membrane water electrolysis with short-side-chain Aquivion membrane and IrO2 anode catalyst

A series of three membrane types has been screened for medium temperature solid polymer electrolyte water electrolysis in membrane electrode assemblies coated with 2 mg cm⁻² of iridium oxide as a catalyst for the oxygen evolution reaction, synthesised via a hydrolysis method from the hexachloroiridic acid precursor, and deposited on the membrane either directly by spray deposition or by decal transfer. The short-side-chain perfluorosulfonic acid Aquivion^® ionomer of equivalent weight 870 meq g⁻¹, in membranes of thickness 120 μm, gives higher water electrolysis performance at 120 °C than a composite membrane of Aquivion^® with zirconium phosphate, while a sulfonated ether-linked polybenzimidazole, sulfonated poly-[(1-(4,4′-diphenylether)-5-oxybenzimidazole)-benzimidazole], shows promising performance and no transport limitations up to 2 A cm⁻². The lowest cell voltage was observed at 120 °C for an MEA prepared using spray-coating directly on the Aquivion^® membrane, 1.57 V at 1 A cm⁻².     

Functional LSM-ScSZ/NiO-ScSZ dual-layer hollow fibres for partial oxidation of methane

In this study, a functional La_0.80Sr_0.20MnO_3−δ (LSM)-Scandia-Stabilized-Zirconia (ScSZ)/NiO-ScSZ dual-layer hollow fibre has been developed using a single-step co-extrusion and co-sintering process, and has been employed as a dual-layer hollow fibre membrane reactor for partial oxidation of methane. Oxygen permeation rate between 0.49 and 1.82 ml/min and methane conversion between 53.55% and 98.78% have been achieved when operating temperature is elevated from 920 to 1060 °C, together with a significant reduction in coke-deposition. Oxygen permeation through the outer LSM-ScSZ permeation layer (approximately 109.2 μm in thickness) is found to be the controlling step to methane conversion at the operating temperature below 990 °C, above which the excessive oxygen permeation results in formation of CO₂ and H₂O as by-products. The experimental results further suggest that the amount of NiO in the inner NiO-ScSZ layer should be optimised based on the factors such as catalytic activity/stability, porosity and mechanical strength in addition to the sintering behaviour which has to be matched to the outer LSM-ScSZ layer.     

On the long-term stability of Pd-membranes with TiO2 intermediate layers for H2 purification

This work addresses the use of TiO₂-based particles as an intermediate layer for reaching fully dense Pd-membranes by Electroless Pore-Plating for long-time hydrogen separation. Two different intermediate layers formed by raw and Pd-doped TiO₂ particles were considered. The estimated Pd-thickness of the composite membrane was reduced in half when the ceramic particles were doped with Pd nuclei before their incorporation onto the porous support by vacuum-assisted dip-coating. The real thickness of the top Pd-film was even lower (around 3 μm), as evidenced by the cross-section SEM images. However, a certain amount of palladium penetrates in some points of the porous structure of the support up to 50 μm in depth. In this manner, despite saving a noticeable amount of palladium during the membrane fabrication, lower H₂-permeance was found while permeating pure hydrogen from the inner to the outer surface of the membrane at 400 °C (3.55·10^?4 against 4.59·10^?4 mol m^?2 s^?1 Pa^?0.5). Certain concentration-polarization was found in the case of feeding binary H₂–N₂ mixtures for all the conditions, especially in the case of reaching the porous support before the Pd-film during the permeation process. Similarly, the effect of using sweep gas is more significant when applied on the side where the Pd-film is placed. Besides, both membranes showed good mechanical stability for around 200 h, obtaining a complete H₂/N₂ ideal separation factor for the entire set of experiments. At this point, this value decreased up to around 400 for the membrane prepared with raw TiO₂ particles as intermediate layer (TiO₂/Pd). At the same time, complete selectivity was maintained up to 1000 h in case of using doped TiO₂ particles (Pd–TiO₂/Pd). However, a specific decrease in the H₂-permeate flux was found while operating at 450 °C due to a possible alloy between palladium and titanium that is not formed at a lower temperature (400 °C). Therefore, Pd–TiO₂/Pd membranes prepared by Electroless Pore-Plating could be very attractive to be used under stable operation in either independent separators or membrane reactors in which moderate temperatures are required.     

H2 production via water gas shift in a composite Pd membrane reactor prepared by the pore-plating method

In this work, H₂ production via catalytic water gas shift reaction in a composite Pd membrane reactor prepared by the ELP “pore-plating” method has been carried out. A completely dense membrane with a Pd thickness of about 10.2 μm over oxidized porous stainless steel support has been prepared. Firstly, permeation measurements with pure gases (H₂ and N₂) and mixtures (H₂ with N_2, CO or CO₂) at four different temperatures (ranging from 350 to 450 °C) and trans-membrane pressure differences up to 2.5 bar have been carried out. The hydrogen permeance when feeding pure hydrogen is within the range 2.68–3.96·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5, while it decreases until 0.66–1.35·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5 for gas mixtures. Furthermore, the membrane has been also tested in a WGS membrane reactor packed with a commercial oxide Fe–Cr catalyst by using a typical methane reformer outlet (dry basis: 70%H₂–18%CO–12%CO₂) and a stoichiometric H₂O/CO ratio. The performance of the reactor was evaluated in terms of CO conversion at different temperatures (ranging from 350 °C to 400 °C) and trans-membrane pressures (from 2.0 to 3.0 bar), at fixed gas hourly space velocity (GHSV) of 5000 h⁻¹. At these conditions, the membrane maintained its integrity and the membrane reactor was able to achieve up to the 59% of CO conversion as compared with 32% of CO conversion reached with conventional packed-bed reactor at the same operating conditions.     

Preparation of palladium membrane on Pd/silicalite-1 zeolite particles modified macroporous alumina substrate for hydrogen separation

A palladium composite membrane was successfully fabricated by electroless plating on a macroporous alumina tube. Pd/silicalite-1 zeolite particles were employed to reduce the pore size of the alumina support and improve its surface roughness. Moreover, the Pd⁰ existed in the Sil-1 particle can avoid the time consuming sensitization and activation steps for palladium seeding. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS) and X-ray diffraction (XRD) analysis were conducted for analyzing the detailed microstructure of the palladium composite membrane. The hydrogen permeation performance of the resulting palladium membrane was investigated at temperatures of 623 K, 673 K, 723 K and 773 K. The hydrogen permeance of 1.95 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ with an H₂/N₂ ideal selectivity of 1165 for the palladium membrane was obtained at 773 K. Furthermore, the resulting palladium membrane was stable for a long-term operation of 15 days at 673 K.     

Thermal stability and effect of typical water gas shift reactant composition on H2 permeability through a Pd-YSZ-PSS composite membrane

This work comprises a study of hydrogen separation with a composite Pd-YSZ-PSS membrane from mixtures of H₂, N₂, CO and CO₂, typical of a water gas shift reactor. The Pd layer is extended over a tubular porous stainless steel support (PSS) with an intermediate layer of yttria-stabilized-zirconia (YSZ). YSZ and Pd layers were incorporated over the PSS using Atmospheric Plasma Spraying and Electroless Plating techniques, respectively. The Pd and YSZ thickness values are 13.8 and 100 μm, respectively, and the Pd layer is fully dense. Permeation measurements with pure, binary and ternary gases at different temperatures (350–450 °C), trans-membrane pressures (0–2.5 bar) and gas composition have been carried out. Moreover, thermal stability of the membrane was also checked by repeating permeation measurements after several cycles of heating and cooling the system. Membrane hydrogen permeances were calculated using Sieverts' law, obtaining values in the range of 4·10⁻⁵–4·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5. The activation energy of the permeance was also calculated using Arrhenius' equation, obtaining a value of 16.4 kJ/mol. In spite of hydrogen selectivity being 100% for all experiments, the hydrogen permeability was affected by the composition of feed gas. Thus, a significant depletion in H₂ permeate flux was observed when other gases were in the mixture, especially CO, being also more or less significant depending on gas composition.     

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.     

Stability of pore-plated membranes for hydrogen production in fluidized-bed membrane reactors

Pd-based membranes prepared by pore-plating technique have been investigated for the first time under fluidization conditions. A palladium thickness around 20 μm was achieved onto an oxidized porous stainless steel support. The stability of the membranes has been assessed for more than 1300 h in gas separation mode (no catalyst) and other additional 200 h to continuous fluidization conditions. Permeances in the order of 5·10⁻⁷ mol s⁻¹ m⁻² Pa⁻¹ have been obtained for temperatures in a range between 375 and 500 °C. During fluidization, a small decrease in permeance is observed, as consequence of the increased external (bed-to-wall) mass transfer resistances. Moreover, water gas shift (WGS) reaction cases have been carried out in a fluidized bed membrane reactor. It has been confirmed that the selective H₂ separation through the membranes resulted in CO conversions beyond the thermodynamic equilibrium (of conventional systems), showing the benefits of membrane reactors in chemical conversions.     

Composite cathodes based on Sm0.5Sr0.5CoO3−δ with porous Gd-doped ceria barrier layers for solid oxide fuel cells

Cobaltite-based perovskites based on Sm_0.5Sr_0.5CoO_3−δ (SSC) are attractive as a cathode material with a barrier layer for solid oxide fuel cells (SOFC) due to their high electrochemical activity and electrical conductivity. SSC, synthesized by a complex method, is used as a cathode material in a composite cathode with Gd-doped ceria (GDC). A porous GDC layer is fabricated as a barrier to resist reactions of SSC with yttria-stabilized zirconia (YSZ). The effects of the ratio of SSC on GDC in composite cathodes and the thickness of the GDC barrier are characterized in this study. An SOFC with an SSC7–GDC3 composite cathode on a 4 μm GDC layer at 0.8 V yields the highest fuel cell performance: 1.24 W cm⁻² and 0.61 W cm⁻² at 780 °C and 680 °C, respectively. Impedance analysis indicates that the ohmic resistances are more dependent upon the GDC barrier thickness than the cathode composition. The polarization resistances at 780 °C and 730 °C exhibit similar values, but with decreasing temperature, the polarization resistances change dramatically according to the composition and barrier thickness. The ohmic and polarization resistances show different trends in different temperature ranges, due to the different charge transfer mechanisms of SSC and GDC within those temperature ranges. To obtain higher fuel cell performance, the addition of GDC into the porous SSC is effective, and the compositions of the composite cathode as well as the thickness of the barrier layer need to be optimized.