TECNALIA Publications Repository :: Browsing by Author "van Sint Annaland, Martin"

Browsing by Author "van Sint Annaland, Martin"

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Attrition-resistant membranes for fluidized-bed membrane reactors: Double-skin membranes: Double-skin membranes
(2018-10-01) Arratibel, Alba; Medrano, Jose Antonio; Melendez, Jon; Pacheco Tanaka, D. Alfredo; van Sint Annaland, Martin; Gallucci, Fausto; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS; Tecnalia Research & Innovation
Pd-Ag supported membranes have been prepared by coating a ceramic interdiffusion barrier onto a Hastelloy X (0.2 µm media grade) porous support followed by deposition of the hydrogen selective Pd-Ag (4–5 µm) layer by electroless plating. To one of the membranes an additional porous Al2O3-YSZ layer (protective layer with 50 wt% of YSZ) was deposited by dip-coating followed by calcination at 550 °C on top of the Pd-Ag layer, and this membrane is referred to as a double-skin membrane. Both membranes were integrated at the same time in a single reactor in order to assess and compare the performance of both membranes under identical conditions. The membranes have first been tested in an empty reactor with pure gases (H2 and N2) and afterwards in the presence of a catalyst (rhodium onto promoted alumina) fluidized in the bubbling regime. The membranes immersed in the bubbling bed were tested at 400 °C and 500 °C for 115 and 500 h, respectively. The effect of the protective layer on the permeation properties and stability of the membranes were studied. The double-skinned membraned showed a H2 permeance of 1.55·10−6 mol m−2 s−1 Pa−1 at 500 °C and 4 bar of pressure difference with an ideal perm-selectivity virtually infinite before incorporation of particles. This selectivity did not decay during the long term test under fluidization with catalyst particles.
Comparison between carbon molecular sieve and Pd-Ag membranes in H2-CH4 separation at high pressure
(2020-10-30) Nordio, Maria; Melendez, Jon; van Sint Annaland, Martin; Pacheco Tanaka, D. Alfredo; Llosa Tanco, Margot; Gallucci, Fausto; Tecnalia Research & Innovation; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
From a permeability and selectivity perspective, supported thin-film Pd–Ag membranes are the best candidates for high-purity hydrogen recovery for methane-hydrogen mixtures from the natural gas grid. However, the high hydrogen flux also results in induced bulk-to-membrane mass transfer limitations (concentration polarization) especially when working at low hydrogen concentration and high pressure, which further reduces the hydrogen permeance in the presence of mixtures. Additionally, Pd is a precious metal and its price is lately increasing dramatically. The use of inexpensive CMSM could become a promising alternative. In this manuscript, a detailed comparison between these two membrane technologies, operating under the same working pressure and mixtures, is presented. First, the permeation properties of CMSM and Pd–Ag membranes are compared in terms of permeance and purity, and subsequently, making use of this experimental investigation, an economic evaluation including capital and variable costs has been performed for a separation system to recover 25 kg/day of hydrogen from a methane-hydrogen mixture. To widen the perspective, also a sensitivity analysis by changing the pressure difference, membrane lifetime, membrane support cost and cost of Pd/Ag membrane recovery has been considered. The results show that at high pressure the use of CMSM is to more economic than the Pd-based membranes at the same recovery and similar purity.
Development of highly permeable ultra-thin Pd-based supported membranes
(2016-12-01) Fernandez, Ekain; Sanchez-Garcia, Jose Angel; Melendez, Jon; Spallina, Vincenzo; van Sint Annaland, Martin; Gallucci, Fausto; Pacheco Tanaka, D. A.; Prema, Radha; TECNOLOGÍAS DE HIDRÓGENO; Tecnalia Research & Innovation; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
This paper reports the preparation and characterization of ultra-thin (∼1 μm thick) Pd-based supported membranes for hydrogen purification. Ultra-thin membranes have been prepared by a combination of PVD magnetron sputtering and electroless plating techniques. The membranes have been characterized for single gas and mix gas permeation at temperatures between 350 and 500 °C and they have shown to exhibit very high hydrogen fluxes combined with a good perm-selectivity (H2/N2 ≈ 500). These results have been compared with the performance of highly permeable membranes reported in the literature. The influence of the morphology of the deposited Pd-based layers on the membrane performance has been investigated and discussed.
Development of Pd-based double-skinned membranes for hydrogen production in fluidized bed membrane reactors
(2018-03-15) Arratibel, Alba; Pacheco Tanaka, Alfredo; Laso, Iker; van Sint Annaland, Martin; Gallucci, Fausto; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
This paper reports the preparation and performance characterization of new PdAg supported membranes with a porous protecting layer to protect the membrane surface from particles in a fluidized bed membrane reactor. Supported membranes with a selective layer of 1 µm and a protective layer have been prepared. Outstanding H2 permeance (5·10−6 mol m−2 s−1 Pa−1) and H2/N2 perm-selectivity (over 25,000) were measured at 400 °C and 1 bar of pressure difference. One membrane has been tested for more than 750 h in the presence of fluidized glass beads showing a decay in the perm-selectivity to approximately 5000, mainly due to sealing leakage. However, the protective layer was removed during this long-term test. Another membrane has been tested for more than 2000 h in a fluidized bed membrane reactor with a Rh reforming catalyst supported on promoted alumina in the bubbling fluidization regime. During tests with binary mixtures mass transfer limitations toward the membrane were observed due to large H2 permeance of the membranes.
Effect of Au addition on hydrogen permeation and the resistance to H2S on Pd-Ag alloy membranes
(2017) Melendez, Jon; de Nooijer, Niek; Coenen, Kai; Fernandez, Ekain; Viviente, Jose Luis; van Sint Annaland, Martin; Arias, P. L.; Tanaka, D. A.Pacheco; Gallucci, Fausto; Tecnalia Research & Innovation; TECNOLOGÍAS DE HIDRÓGENO; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
In order to make a detailed comparison between Pd-Ag and Pd-Ag-Au membranes according to their H2 permeation properties and sulfide resistance Au was deposited by the electroless plating (ELP) technique onto one half of Pd-Ag membranes. Membranes' thicknesses are ranged between 2.45 and 3.13 µm. Permeation tests have been carried out from 400 to 600 °C under single gas conditions. The Pd91.7Ag4.8Au3.5 membrane has shown a H2 permeance of 4.71·10−3 mol s−1 m−2 Pa0.5 at 600 °C, which is one of the highest values ever reported in the literature, where the Pd-Ag-Au membranes have exhibited higher hydrogen permeation rates compared to their respective Pd-Ag membranes above 550 °C. The H2 permeation properties have been determined in terms of the degree of H2S inhibition, up to 17 ppm, and subsequent H2 flux recovery rate. Pd-Ag membranes alloyed with gold resisted 12.5 h of H2S exposure showing recovery rates of 85% and 83% for Pd91.5Ag4.7Au3.8 and Pd90.5Ag4.6Au4.9 membranes, respectively, whereas the hydrogen flux of non-gold membranes decreased below detectable values. H2/N2 ideal perm-selectivity of the Pd-Ag membrane was reduced to 18 after H2S tests (starting from > 1308) while Pd-Ag-Au membranes showed a better resistance to sulfur with H2/N2 selectivity values of 793 and 121 (starting from > 4115 and > 2557 respectively). No evidence of the formation of a crystalline sulfide phase on the Pd-Ag-Au alloy membrane surfaces was found in the XRD patterns after H2S exposure and also XPS characterization did not show important changes in the composition before and after the H2S exposure tests. However, SEM images showed a decrease in the thickness of the Pd-Ag membrane and signs of corrosion and roughening on its surface, while gold-alloyed membranes did not show any damage.
Fluidized Bed Membrane Reactors for Ultra Pure H2 Production - A Step forward towards Commercialization
(2016-03-19) Helmi, Arash; Fernandez, Ekain; Melendez, Jon; Pacheco Tanaka, David A.; Gallucci, Fausto; van Sint Annaland, Martin; TECNOLOGÍAS DE HIDRÓGENO; Tecnalia Research & Innovation; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
In this research the performance of a fluidized bed membrane reactor for high temperature water gas shift and its long term stability was investigated to provide a proof-of-concept of the new system at lab scale. A demonstration unit with a capacity of 1 Nm3/h of ultra-pure H2 was designed, built and operated over 900 h of continuous work. Firstly, the performance of the membranes were investigated at different inlet gas compositions and at different temperatures and H2 partial pressure differences. The membranes showed very high H2 fluxes (3.89E 6 mol m 2 Pa 1 s 1 at 400 C and 1 atm pressure difference) with a H2/N2 ideal perm-selectivity (up to 21,000 when integrating five membranes in the module) beyond the DOE 2015 targets. Monitoring the performance of the membranes and the reactor confirmed a very stable performance of the unit for continuous high temperature water gas shift under bubbling fluidization conditions. Several experiments were carried out at different temperatures, pressures and various inlet compositions to determine the optimum operating window for the reactor. The obtained results showed high hydrogen recovery factors, and very low CO concentrations at the permeate side (in average <10 ppm), so that the produced hydrogen can be directly fed to a low temperature PEM fuel cell.
Hydrogen production with integrated CO2 capture in a membrane assisted gas switching reforming reactor: Proof-of-Concept: Proof-of-Concept
(2018-03-22) Wassie, Solomon A.; Medrano, Jose A.; Zaabout, Abdelghafour; Cloete, Schalk; Melendez, Jon; Pacheco Tanaka, David A.; Amini, Shahriar; van Sint Annaland, Martin; Gallucci, Fausto; Tecnalia Research & Innovation; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
This paper presents a new membrane reactor concept for ultra-pure hydrogen production with integrated CO2 capture: the membrane-assisted gas switching reforming (MA-GSR). This concept integrates alternating exothermic and endothermic redox reaction stages in a single fluidized bed consisting of catalytically active oxygen-carrier particles, by switching the feed between air and methane/steam, where the produced hydrogen is selectively removed via Pd-based membranes. This concept results in overall autothermal conditions and allows easier operation at high pressure compared to alternative novel technologies. In this work, the MA-GSR concept is demonstrated at lab scale using four metallic supported membranes (Pd–Ag based) immersed into a fluidized bed consisting of a Ni-based oxygen carrier. The performance of the reactor has been tested under different experimental operating conditions and high methane conversions (>50%) have been obtained, well above the thermodynamic equilibrium conversion of a conventional fluidized bed as a result of the selective H2 extraction, with (ultra-pure) H2 recoveries above 20% at relatively low temperatures (<550 °C). These results could be further improved by working at elevated pressures or by integrating more membranes. Even though the concept has been successfully demonstrated, further research is required to develop suitable membranes since post-mortem membrane characterization has revealed defects in the membrane selective layer as a consequence of the frequent exposure to thermal cycles with alternating oxidative and reducing atmospheres.
Influence of H2S on the hydrogen flux of thin-film PdAgAu membranes
(2020-03-04) de Nooijer, Niek; Sanchez, Julio Davalos; Melendez, Jon; Fernandez, Ekain; Pacheco Tanaka, David Alfredo; van Sint Annaland, Martin; Gallucci, Fausto; Tecnalia Research & Innovation; TECNOLOGÍAS DE HIDRÓGENO; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
Pd-based membranes have the potential to be used for hydrogen purification and production in membrane reactors. However, the presence of impurities in the feedstock, such as H2S can poison the membrane, thus decreasing the hydrogen permeation by blocking and deactivating active sites of the Pd-alloy on the membrane surface. H2S at high concentrations can even destroy the membrane by the formation of Pd4S. It is known that alloying of Pd with Au enhances the membrane resistance to H2S. This work reports the performance of six PdAgAu/Al2O3 supported membranes, prepared by electroless plating combined with PVD under exposure to trace amounts (<2 ppm) of H2S. The Au content shows not to play a significant role at these low concentrations. Exposure results suggest a dual influence of physisorbed H2S and chemisorbed S species. A Langmuir description shows that the influence of the partial pressure of hydrogen is negligible on the flux inhibition. In the post characterization the absence of Pd4S was shown, however the surface was affected by the exposure to H2S.
Morphology and N2 Permeance of Sputtered Pd-Ag Ultra-Thin Film Membranes
(2016-02-10) Fernandez, Ekain; Sanchez-Garcia, Jose Angel; Viviente, J.L.; van Sint Annaland, Martin; Gallucci, Fausto; Pacheco Tanaka, David A.; Tecnalia Research & Innovation; TECNOLOGÍAS DE HIDRÓGENO; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
The influence of the temperature during the growth of Pd-Ag films by PVD magnetron sputtering onto polished silicon wafers was studied in order to avoid the effect of the support roughness on the layer growth. The surfaces of the Pd-Ag membrane films were analyzed by atomic force microscopy (AFM), and the results indicate an increase of the grain size from 120 to 250–270 nm and film surface roughness from 4–5 to 10–12 nm when increasing the temperature from around 360–510 K. After selecting the conditions for obtaining the smallest grain size onto silicon wafer, thin Pd-Ag (0.5–2-µm thick) films were deposited onto different types of porous supports to study the influence of the porous support, layer thickness and target power on the selective layer microstructure and membrane properties. The Pd-Ag layers deposited onto ZrO2 3-nm top layer supports (smallest pore size among all tested) present high N2 permeance in the order of 10−6 mol•m−2•s−1•Pa−1 at room temperature.
On concentration polarisation in a fluidized bed membrane reactor for biogas steam reforming: modelling and experimental validation: Modelling and experimental validation
(2018-09-15) de Nooijer, Niek; Gallucci, Fausto; Pellizzari, Emma; Melendez, Jon; Pacheco Tanaka, David A.; Manzolini, Giampaolo; van Sint Annaland, Martin; Tecnalia Research & Innovation; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
The production of pure hydrogen through the steam reforming of biogas in a fluidized bed membrane reactor has been studied. A phenomenological one-dimensional two-phase fluidized bed reactor model accounting for concentration polarisation with a stagnant film model has been developed and used to investigate the system performance. The validation of the model was performed with steam reforming experiments at temperatures ranging from 435 °C up to 535 °C, pressures between 2 to 5 bar and CO2/CH4 ratios up to 0.9. The permeation performance of the ceramic-supported PdAg thin-film membrane was first characterized separately for both pure gas and gas mixtures. Subsequently, the membrane was immersed into a fluidized bed containing Rh supported on alumina particles and the reactor performance, viz. the methane conversion, hydrogen recovery and hydrogen purity, was evaluated under biogas steam reforming conditions. The resulting hydrogen purity under biogas steam reforming conditions was up to 99.8%. The model results were in very good agreement with the experimental results, when assuming a thickness of the stagnant mass transfer boundary layer around the membrane equal to 0.54 cm. It is shown that the effects of concentration polarisation in a fluidized bed membrane reactor can be well described with the implementation of a film layer description in the two-phase model.
On the use of double-skinned membranes to prevent chemical interaction between membranes and catalysts
(2021-06-03) Arratibel, Alba; Pacheco Tanaka, Alfredo; van Sint Annaland, Martin; Gallucci, Fausto; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
This communication summarizes the use of double-skinned membranes for hydrogen separation in presence of TiO2 based catalyst (PtReCe/TiO2). The use of this type of membrane avoids the direct contact between catalyst particles and surface of the Pd-based hydrogen selective layer due to the presence of a mesoporous YSZ/γ-Al2O3 layer. The PdAg layer is protected by the mesoporous layer from direct contact with catalyst particles, avoiding erosion and possible chemical interactions. In comparison with a conventional PdAg membrane, the hydrogen flux of DS-membrane was observed not to be compromised during test carried out at 400 °C.
Pd-Based Membranes for High Temperature Applications: Current Status
(2016-03-29) Gallucci, Fausto; Fernandez, Ekain; Medrano, Jose Antonio; Pacheco Tanaka, David A.; van Sint Annaland, Martin; TECNOLOGÍAS DE HIDRÓGENO; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
Not available
Preparation and characterization of ceramic supported ultra-thin (~1 µm) Pd-Ag membranes
(2017) Melendez, Jon; Fernandez, Ekain; Gallucci, Fausto; van Sint Annaland, Martin; Arias, P. L.; Pacheco Tanaka, David A.; Tecnalia Research & Innovation; TECNOLOGÍAS DE HIDRÓGENO; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
This work reports the preparation and characterization of ultra-thin (~1 µm thick) Pd-Ag supported membranes for hydrogen purification. Ultra-thin membranes with different thicknesses (ranging from 0.46 to 1.29 µm) have been prepared by electroless plating (ELP) technique onto asymmetric tubular porous alumina supports. The membranes have been characterized by single gas and mixed gas permeation experiments at temperatures between 300 and 500 °C obtaining a correlation for the membrane permeation as a function of the activation energy and the membrane thickness. Hydrogen permeation results of the ultra-thin Pd-Ag membranes have been compared with other highly permeable membranes reported in the literature and they show some of the highest H2permeance values. A 1.29 µm thick membrane has been tested for 1000 h at 400 °C and has shown a stable H2permeance of 9.0−9.4×10−6mol m−2s−1Pa−1with a H2/N2perm-selectivity between 3300 and 2000 at 100 kPa transmembrane pressure difference. The same membrane has been tested with a feed gas mixture of H2/N2/CO with a 15% CO content and H2binary mixtures containing N2, CH4and CO2. When tested in a catalyst fluidization environment during 100 h, the 1.29 µm thick membrane showed stable H2permeance and H2/N2perm-selectivity.
Preparation and characterization of metallic supported thin Pd–Ag membranes for hydrogen separation
(2016-12-01) Fernandez, Ekain; Medrano, Jose Antonio; Melendez, Jon; Parco, Maria; Viviente, Jose Luis; van Sint Annaland, Martin; Gallucci, Fausto; Pacheco Tanaka, D. A.; TECNOLOGÍAS DE HIDRÓGENO; Tecnalia Research & Innovation; EXTREMAT; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
This paper reports the preparation and characterization of thin-film (4–5 μm thick) Pd–Ag metallic supported membranes for high temperature applications. Various thin film membranes have been prepared by depositing a ceramic interdiffusion barrier layer prior to the simultaneous Pd–Ag electroless plating deposition. Two deposition techniques for ceramic layers (made of zirconia and alumina) have been evaluated: Atmospheric Plasma Spraying and dip coating of a powder suspension. Initially, the prepared ceramic layers have been characterized for nitrogen permeation at room temperature and surface roughness for the selection of the appropriate type of ceramic layer. The most promising membranes have been tested at 400–600 °C for single gas permeation (H2 and N2), and have shown extremely high H2/N2 permselectivities (>200,000).
Recent advances on membranes and membrane reactors for hydrogen production
(2013-04-05) Gallucci, Fausto; Fernandez, Ekain; Corengia, Pablo; van Sint Annaland, Martin; TECNOLOGÍAS DE HIDRÓGENO; GENERAL
Membranes and membrane reactors for pure hydrogen production are widely investigated not only because of the important application areas of hydrogen, but especially because mechanically and chemically stable membranes with high perm-selectivity towards hydrogen are available and are continuously further improved in terms of stability and hydrogen flux. Membrane reactors are (multiphase) reactors integrating catalytic reactions (generally reforming and water gas shift reactions for hydrogen production) and separation through membranes in a single unit. This combination of process steps results in a high degree of process integration/intensification, with accompanying benefits in terms of increased process or energy efficiencies and reduced reactor or catalyst volume. The aim of this review is to highlight recent advances in hydrogen selective membranes (from palladium-based to silica and proton conductors) along with the advances for the different types of membrane reactors available (from packed bed to fluidized bed, from micro-reactors to bio-membrane reactors). In addition, the application of membrane reactors for hydrogen production from different feedstock is also discussed.
Unravelling the transport mechanism of pore-filled membranes for hydrogen separation
(2018-09-12) Arratibel, Alba; Pacheco Tanaka, David A.; Slater, Thomas J.A.; Burnett, Timothy L.; van Sint Annaland, Martin; Gallucci, Fausto; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
The permeation characteristics of palladium pore filled (PF) membranes have been investigated with gas permeation and structural characterization of the membranes. PF membranes have been prepared by filling with Pd the nanoporous γ-Al2O3/YSZ (or pure YSZ) layer supported onto porous α-Al2O3 and ZrO2. The number of nanoporous layers and the applied vacuum level during the electroless plating process have been studied. Gas permeation properties of the PF membranes have been determined in a temperature range of 300-550 °C. The measured hydrogen permeances have been found to be lower than previously reported for similar membranes. It has been found that the hydrogen fluxes do not depend on the thickness of the nanoporous layers (γ-Al2O3/YSZ or pure YSZ) or on the vacuum pump employed for filling with Pd. The physicochemical characterization performed showed that the palladium deposited does not form a percolated network across the mesoporous layer(s), leading to low hydrogen permeances and thus low H2/N2 perm-selectivities.
Water Adsorption Effect on Carbon Molecular Sieve Membranes in H2-CH4 Mixture at High Pressure
(2020-07) Nordio, Maria L. V.; Medrano, José A.; van Sint Annaland, Martin; Pacheco Tanaka, David Alfredo; Llosa Tanco, Margot; Gallucci, Fausto; Tecnalia Research & Innovation; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOS
Carbon molecular sieve membranes (CMSMs) are emerging as promising solution to overcome the drawbacks of Pd-based membranes for H2 separation since (i) they are relatively easy to manufacture; (ii) they have low production and raw material costs; (iii) and they can work at conditions where polymeric and palladium membranes are not stable. In this work CMSMs have been investigated in pure gas and gas mixture tests for a proper understanding of the permeation mechanism, selectivity and purity towards hydrogen. No mass transfer limitations have been observed with these membranes, which represents an important advantage compared to Pd-Ag membranes, which suffer from concentration polarization especially at high pressure and low hydrogen concentrations. H2, CH4, CO2 and N2 permeation at high pressures and different temperatures in presence of dry and humidified stream (from ambient and water vapour) have been carried out to investigate the effect of the presence of water in the feed stream. Diffusion is the main mechanism observed for hydrogen, while methane, nitrogen and especially carbon dioxide permeate through adsorption-diffusion at low temperatures and high pressures. Finally, H2 permeation from H2-CH4 mixtures in presence of water has been compared at different temperatures and pressure, which demonstrates that water adsorption is an essential parameter to improve the performance of carbon molecular sieve membranes, especially when working at high temperature. Indeed, a hydrogen purity of 98.95% from 10% H2—90% CH4 was achieved. The main aim of this work is to understand the permeation mechanisms of CMSMs in different operating conditions and find the best conditions to optimize the separation of hydrogen.

Browsing by Author "van Sint Annaland, Martin"

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