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.     

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.     

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.     

Diffusion barrier coating using a newly developed blowing coating method for a thermally stable Pd membrane deposited on porous stainless-steel support

In this study, we present an intermetallic diffusion barrier coating using a newly developed blowing coating method for a thermally stable Pd-based composite membrane on porous stainless steel (PSS). A tubular PSS sample with 1/2 inch (12.7 mm) in diameter and 450 mm in length was used for the support. The support was welded with a stainless-steel cap and a 450-mm-long stainless-steel tube for each end. Before the diffusion barrier coating, the large-sized entrance pores were gradually blocked with sub-micron (～500 nm) and nano (50–80 nm) yttria stabilized zirconia (YSZ). 8YSZ, i.e., 8wt.% YSZ, was used for the interdiffusion barrier material and dispersed on the surface of the pre-treated PSS using the blowing coating method. The blowing coating method has 4 steps: (i) spraying the 17 wt. % 8YSZ paste on the surface of the PSS tube, (ii) blowing the paste using compressed air, (iii) drying at room temperature, and (iv) heat treatment at 923 K for 2 h in air. Steps (i) and (ii) were repeated 3 times to have a ～240 nm thick 8YSZ layer. A thin palladium layer (～3 μm) was deposited on the pre-treated PSS using electroless plating, and the membrane stability was tested at 673–773 K for ～ 200 h. A hydrogen permeation flux of 9.86 × 10^?2 mol m^?2 s^?1 and an H₂/N₂ selectivity of 595 were obtained at 773 K and a transmembrane pressure difference of 20 kPa. The surface and cross-sectional SEM/EDX analysis confirmed that the 8YSZ layer sufficiently prevented the interdiffusion between Pd and PSS elements, such as Fe, Cr and Ni.     

Methane steam reforming using a membrane reactor equipped with a Pd-based composite membrane for effective hydrogen production

Herein, a methane steam reforming (MSR) reaction was carried out using a Pd composite membrane reactor packed with a commercial Ru/Al₂O₃ catalyst under mild operating conditions, to produce hydrogen with CO₂ capture. The Pd composite membrane was fabricated on a tubular stainless steel support by the electroless plating (ELP) method. The membrane exhibited a hydrogen permeance of 2.26 × 10^?3 mol m² s^?1 Pa^?0.5, H₂/N₂ selectivity of 145 at 773 K, and pressure difference of 20.3 kPa. The MSR reaction, which was carried out at steam to carbon ratio (S/C) = 3.0, gas hourly space velocity (GHSV) = 1700 h^?1, and 773 K, showed that methane conversion increased with the pressure difference and reached 79.5% at ΔP = 506 kPa. This value was ～1.9 time higher than the equilibrium value at 773 K and 101 kPa. Comparing with the previous studies which introduced sweeping gas for low hydrogen partial pressure in the permeate stream, very high pressure difference (2500–2900 kPa) for increase of hydrogen recovery and very low GHSV (<150) for increase hydraulic retention time (HRT), our result was worthy of notice. The gas composition monitored during the long-term stability test showed that the permeate side was composed of 97.8 vol% H₂, and the retentate side contained 67.8 vol% CO₂ with 22.2 vol% CH₄. When energy was recovered by CH₄ combustion in the retentate streams, pre-combustion carbon capture was accomplished using the Pd-based composite membrane reactor.     

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.     

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.     

Preparation and performance of thin-layered PdAu/ceramic composite membranes

Preparation of 3–5 μm thick, hydrogen-selective PdAu layers via sequential electroless plating of Pd and Au onto ceramic microfiltration membranes was investigated employing a cyanide-free Au plating bath. The Au deposition rate was strongly dependent on bath temperature and alkalinity reaching an optimum at 333 K and pH 10. Homogenous alloying of the separate metal layers under atmospheric H₂ proved to be a protracted process and required approximately a week at 873 K for a PdAu layer as thin as 3 μm. After 300 h annealing at 823 K the 5 μm thick PdAu layer of a composite membrane still exhibited a Au gradient declining from 7.4 at.% at the top surface to 5.5 at.% at the support interface despite that the H₂ permeation rate had become stable. Nonetheless, the membrane exhibited a very high H₂ permeability of e.g. 1.3 × 10⁻⁸ mol m m⁻² s⁻¹ Pa^−0.5 at 673 K, but it decreased much faster with temperature below 573 K than above, likely due to a change from bulk H diffusion-controlled to H₂ adsorption or desorption-limited transport. The composite membrane withstood cycling between 523 and 723 K in H₂ well showing that differing thermal expansion of the joined metallic and ceramic materials stayed within the tolerance range up to 723 K.     

Kinetic investigation on butanol steam reforming over Ru/Al2O3 catalyst

Steam reforming of biomass-derived oxygenates is an attractive technique for the renewable production of hydrogen (H₂). In this work, steam reforming of n-butanol – a representative of bio-oxygenates – was studied over commercial 5% Ru/Al₂O₃ catalyst in a fixed-bed reactor. Kinetics of butanol reforming was investigated between temperatures 623 and 773 K at steam/carbon (S/C) ratio equal to 33.3 mol/mol. The W/F_A0 ratio (W: mass of catalyst, F_A0: molar flow rate of butanol in feed) was varied between 3.3 and 16.7 g h/mol. At T = 773 K, butanol conversion and H₂ yield were 93.4% and 0.61 mol/mol. Evaluation of the kinetic data showed that reaction order with respect to butanol was unity. The activation energy for the investigated reaction was 78 kJ/mol. Finally, a Langmuir-Hinshelwood model that assumed the surface reaction between the adsorbed reactants as rate-determining was used to describe the kinetic data.     

Porous stainless steel support for hydrogen separation Pd membrane; fabrication by metal injection molding and simple surface modification

We prepared a disc-shaped porous stainless steel (PSS) support for hydrogen separation Pd membrane via metal injection molding (MIM) method to facilitate the mass production of porous substrates. MIMed PSS supports obtained in a batch showed relatively higher apparent porosity (from 32.75% to 39.28%) than that reported for commercially available PSS substrate. In addition, the surface morphologies of the MIMed PSS, surface roughness of 1.119 μm and pore depth of 8.6 μm, indicate its suitability as a membrane support than the commercially available one. Pd membrane prepared over MIMed PSS, which was modified by a simple axial pressing method to control the surface morphologies, had a thinner Pd layer, 2.94 μm, and showed an extremely higher ideal H₂/N₂ selectivity with a hydrogen permeation flux of 21.3 ml/min/cm² at del-P = 1 bar and 400 °C, compared with Pd membrane over MIMed PSS modified with conventional surface modification.     

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.     

Steam reforming of model bio-oil compounds 2-butanone, 1-methoxy-2-propanol,ethyl acetate and butyraldehyde over Ni/Al2O3

Oil derived from fast pyrolysis of biomass (or bio-oil) is a candidate renewable feedstock for producing hydrogen (H₂). In this work, the steam reforming of model oxygenates present in the bio-oil aqueous fraction was studied in a fixed-bed reactor. Using Ni/Al₂O₃ catalyst, the reactions with 2-butanone, 1-methoxy-2-propanol, ethyl acetate and butyraldehyde were studied. To study the efficacy of the chosen catalyst for H₂ production, experiments were performed in the 623–773 K range using varying steam/carbon ratios in feed (15–25 mol/mol). The conversion of the various feeds was of the order: butyraldehyde > ethyl acetate > 1-methoxy-2-propanol > 2-butanone. The catalyst was characterized using SEM, XRD, TPR/TPD and TGA methods. It showed high stability for 7 h of time-on-stream.     

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.     

Coating the porous Al2O3 substrate with a natural mineral of Nontronite-15A for fabrication of hydrogen-permeable palladium membranes

Substrate surface modification is a key pretreatment during fabrication of composite palladium membranes for hydrogen purification in hydrogen energy applications. The suspension of a natural porous material, Nontronite-15A mineral, without any organic additives was employed in dip-coating of the porous Al₂O₃ substrate. The Nontronite-15A mineral was characterized by SEM, XRD, TG−DSC and granulometry analysis. The surface and cross-section of the coated porous Al₂O₃ tubes were observed by SEM, and their pore size distribution and nitrogen flux were also measured. Palladium membranes were fabricated over the coated Al₂O₃ tubes by a suction-assisted electroless plating. The optimal loading amount of the Nontronite-15A mineral is just to fill in and level up the surface cavities of the Al₂O₃ substrate rather than to form an extra continuous layer. A thin and selective palladium membrane was successfully obtained, and its permeation performances were tested. The kinetic analyses on the hydrogen flux indicate that the hydrogen permeation behavior exhibits typical characteristics for most of the palladium membranes. During the stability test at 450 °C for 192 h, no membrane damage was detected, and the hydrogen flux increased slightly.     

Hydrogen production by steam methane reforming in a membrane reactor equipped with a Pd composite membrane deposited on a porous stainless steel

With the aim of producing hydrogen at low cost and with a high conversion efficiency, steam methane reforming (SMR) was carried out under moderate operating conditions in a Pd-based composite membrane reactor packed with a commercial Ru/Al₂O₃ catalyst. A Pd-based composite membrane with a thickness of 4–5 μm was prepared on a tubular stainless steel support (diameter of 12.7 mm, length of 450 mm) using electroless plating (ELP). The Pd-based composite membrane had a hydrogen permeance of 2.4 × 10^?3 mol m^?1 s^?1 Pa^?0.5 and an H₂/N₂ selectivity of 618 at a temperature of 823 K and a pressure difference of 10.1 kPa. The SMR test was conducted at 823 K with a steam-to-carbon ratio of 3.0 and gas hourly space velocity of 1000 h^?1; increasing the pressure difference resulted in enhanced methane conversion, which reached 82% at a pressure difference of 912 kPa. To propose a guideline for membrane design, a process simulation was conducted for conversion enhancement as a function of pressure difference using Aspen HYSYS^®. A stability test for SMR was conducted for ～120 h; the methane conversion, hydrogen production rate, and gas composition were monitored. During the SMR test, the carbon monoxide concentration in the total reformed stream was <1%, indicating that a series of water gas shift reactors was not needed in our membrane reactor system.     

Production strategies of asymmetric BaCe0.65Zr0.20Y0.15O3-δ – Ce0.8Gd0.2O2-δ membrane for hydrogen separation

Mixed proton and electron conductor ceramic composites are among the most promising materials for hydrogen separation membrane technology especially if designed in an asymmetrical configuration (thin membrane supported onto a thicker porous substrate). However a precise processing optimization is needed to effectively obtain planar and crack free asymmetrical membranes with suitable microstructure and composition without affecting their hydrogen separation efficiency. This work highlights for the first time the most critical issues linked to the tape casting process used to obtain BaCe_0.65Zr_0.20Y_0.15O_3-δ – Ce_0.8Gd_0.2O_2-δ (BCZY-GDC) asymmetrical membranes for H₂ separation. The critical role of the co-firing process, sintering aid and atmosphere was critically investigated. The optimization of the production strategy allowed to obtain asymmetric membranes constituted by a dense 20 μm-thick ceramic-ceramic composite layer supported by a porous (36%) 750 μm-thick BCZY-GDC substrate. The asymmetric membranes here reported showed H₂ fluxes (0.47 mL min⁻¹ cm⁻² at 750 °C) among the highest obtained for an all-ceramic membrane.     

Membrane reformer module with Ni-foam catalyst for pure hydrogen production from methane: Experimental demonstration and modeling

Results of experiments and modeling of a compact (800 cm³) membrane reformer module for the production of 0.25–0.30 Nm³/h hydrogen by methane steam reforming are reported. The module consists of a two-sided composite membrane disc with a 50 μm PdAg layer and two adjacent 4 mm thick Ni foam discs (60 ppi). A nickel catalyst and a porous support were deposited on the foam discs to give the final composition of 10%Ni/10%MgO/Ni-foam. Membrane permeability by pure hydrogen was investigated, and coefficients of transverse hydrogen transport across the Ni foam to the membrane in the case of inlet binary N₂H₂ mixture were refined in order to account for concentration polarization effect into the model. Activity of the catalytic discs was measured in a differential laboratory scale reactor at a pressure of 1 bar and temperature of 400–600 °C. Modules were tested at a 8–13 bar pressure of the mixture in the reforming zone and at 1 bar of pure hydrogen under the membrane, H₂O/C = 2.5–3 and a module temperature of 550–680 °C (with and without hydrogen removal). Two modifications of the module were tested: consecutive (I-type) and parallel (II-type) flow of the reaction mixture around two sides of the membrane disc. In order to optimize construction of the module, calculations were made for revealing the effect of thickness of the PdAg membrane layer (5–50 μm), thickness of the Ni foam discs (0.5–8 mm) and temperature (600–700 °C) on the hydrogen output of the module. A comparison of the values obtained in our experiments (>1 MW/m³ and >0.7 kg(H₂)/h/m²) with the literature data reported by other authors showed that the developed modules are promising for practical application as components of a fuel processor section for mobile applications.     

Preparation of a novel Pd/layered double hydroxide composite membrane for hydrogen filtration and characterization by thermal cycling

A layered double hydroxide (LDH) layer was grown directly on a porous stainless steel (PSS) surface to reduce the pore opening of the PSS and to be a middle layer retarding Pd/Fe interdiffusion. A thin Pd film (∼7.85 μm) was plated on the modified PSS tube by an electroless plating method. A helium leak test proved that the thin Pd on the LDH-modified PSS substrate was free of defects. The membrane had a H₂ flux of 28–36 m³/(m² h) and H₂/He selectivity larger than 2000 at a pressure difference of 1 bar. Thermal cycling between room temperature and 673 K was performed and showed that the membrane exhibited good permeance and selectivity. Long-term evaluation (1500 h) of the membrane at 673 K showed static results of H₂ flux (∼30 m³/(m² h)) and H₂/He selectivity (∼2000) over the 1500 h test period.     

Stability and hydrogen permeation behavior of supported platinum membranes in presence of hydrogen sulfide

Chemical stability for hydrogen sulfide of a platinum composite membrane, consisting of a platinum layer supported on a porous alumina tube by a CVD technique, was evaluated in comparison with a palladium composite membrane. These composite membranes gave high fluxes comparable to that of a reported palladium composite membrane prepared by an electroless-plating technique, as well as high ideal permselectivity for hydrogen over nitrogen, typically 240 for palladium and 210 for platinum at 773 K. When these composite membranes were in contact with gas stream including hydrogen sulfide, their hydrogen permeability declined rapidly. Many cracks were formed on the surface metallic layer of the palladium composite membrane, so that other gases besides hydrogen permeated mainly through the cracks formed. On the other hand, cracks were hardly formed for the platinum composite membrane. It was reported that the lattice constant of palladium was expanded from 0.39 to 0.65 nm by sulfidation of the metallic layer, but that of platinum was slightly changed from 0.39 to 0.35 nm. The difference in the expansion of lattice constant may affect structural change and rupture phenomena of these composite membranes. After the sulfurized platinum composite membrane was treated with pure oxygen flow, the hydrogen permeability was recovered up to 50% of that of the fresh membrane.     

Development of a H2-permeable Pd60Cu40-based composite membrane using a reverse build-up method

A new reverse build-up method is developed to fabricate an economical H₂-permeable composite membrane. Sputtering and electroplating are used for the formation of a membrane comprised of a 3.7-μm-thick Pd₆₀Cu₄₀ (wt.%) alloy layer and a 13-μm-thick porous Ni support layer, respectively. The H₂-permeation measurements are performed under the flow of a gaseous mixture of H₂ and He at 300–320 °C and 50–100 kPa of H₂ partial pressure. The H₂/He selectivity values exceed 300. The activation energy at 300–320 °C is 10.9 kJ mol⁻¹. The H₂ permeability of the membrane is 1.25 × 10⁻⁸ mol m⁻¹ s⁻¹ Pa^−0.5 at 320 °C after 448 h. The estimated Pd cost of the proposed membrane is approximately 1/8 of the cost for a pure Pd₆₀Cu₄₀ membrane. This study demonstrates that the proposed method allows the facile production of low-cost, Pd-based membranes for H₂ separation.