Intensification of Hydrogen production:Pd-Ag Membrane on Tailored Hastelloy X Filter for Membrane-Assisted Steam Methane Reforming

H2 production via membrane-assisted steam methane reforming (MA-SMR) can ensure higher energy efficiency and lower emissions compared to conventional reforming processes (SMR). Ceramic-supported Pd–Ag membranes have been extensively investigated for membrane-assisted steam methane reforming applications, with outstanding performance. However, costs, sealings for integration in the reactor structure, and resistance to solicitations remain challenging issues. In this work, the surface quality of a low-cost, porous Hastelloy-X filter is improved by asymmetric filling with α-Al2O3 of decreasing size and deposition of γ-Al2O3 as an interdiffusion barrier. On the modified support, a thin Pd–Ag layer was deposited via electroless plating (ELP), resulting in a membrane with H2/N2 selectivity >10,000. The permeation characteristics of the membrane were studied, followed by testing for membrane-assisted methane steam reforming. The results showed the ability of the membrane reactor to overcome thermodynamic conversion of the conventional process for all explored operating conditions, as well as ensuring 99.3% H2 purity in the permeate stream at 500 °C and 4 bar

Hydrogen permeation studies of composite supported alumina-carbon molecular sieves membranes: Separation of diluted hydrogen from mixtures with methane

One alternative for the storage and transport of hydrogen is blending a low amount of hydrogen (up to 15 or 20%) into existing natural gas grids. When demanded, hydrogen can be then separated, close to the end users using membranes. In this work, composite alumina carbon molecular sieves membranes (Al-CMSM) supported on tubular porous alumina have been prepared and characterized. Single gas permeation studies showed that the H2/CH4 separation properties at 30 °C are well above the Robeson limit of polymeric membranes. H2 permeation studies of the H2–CH4 mixture gases, containing 5–20% of H2 show that the H2 purity depends on the H2 content in the feed and the operating temperature. In the best scenario investigated in this work, for samples containing 10% of H2 with an inlet pressure of 7.5 bar and permeated pressure of 0.01 bar at 30 °C, the H2 purity obtained was 99.4%.This project received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant agreement N700355 (Hygrid). This Joint Undertaking receives support fromthe European Union’s Horizon 2020 Research and InnovationProgramme, Hydrogen Europe and N. ERGH

Intensification of Hydrogen production:Pd-Ag Membrane on Tailored Hastelloy X Filter for Membrane-Assisted Steam Methane Reforming

H2 production via membrane-assisted steam methane reforming (MA-SMR) can ensure higher energy efficiency and lower emissions compared to conventional reforming processes (SMR). Ceramic-supported Pd–Ag membranes have been extensively investigated for membrane-assisted steam methane reforming applications, with outstanding performance. However, costs, sealings for integration in the reactor structure, and resistance to solicitations remain challenging issues. In this work, the surface quality of a low-cost, porous Hastelloy-X filter is improved by asymmetric filling with α-Al2O3 of decreasing size and deposition of γ-Al2O3 as an interdiffusion barrier. On the modified support, a thin Pd–Ag layer was deposited via electroless plating (ELP), resulting in a membrane with H2/N2 selectivity >10,000. The permeation characteristics of the membrane were studied, followed by testing for membrane-assisted methane steam reforming. The results showed the ability of the membrane reactor to overcome thermodynamic conversion of the conventional process for all explored operating conditions, as well as ensuring 99.3% H2 purity in the permeate stream at 500 °C and 4 bar

Ultra-Selective CMSMs Derived from Resorcinol-Formaldehyde Resin for CO2 Separation

A resorcinol-formaldehyde precursor was synthesized to fabricate the CO2 selective Carbon Molecular Sieve Membranes (CMSMs) developed in this study. The degree of polymerization (DP) was analyzed via Gel Permeation Chromatography (GPC) and its effect on the CO2/N2 perm-selectivity and CO2 permeance was investigated. The membrane that was polymerized at 80 °C (named R80) was selected as the best performing CMSM after a preliminary test. The post treatment with oxidative atmosphere was performed to increase the CO2 permeance and CO2/N2 perm-selectivity on membrane R80. The gas permeation results and Pore Size Distribution (PSD) measurements via perm-porometry resulted in selecting the membrane with an 80 °C polymerization temperature, 100 min of post treatment in 6 bar pressure and 120 °C with an oxygen concentration of 10% (named R80T100) as the optimum for enhancing the performance of CMSMs. The 3D laser confocal microscopy results confirmed the reduction in the surface roughness in post treatment on CMSMs and the optimum timing of 100 min in the treatment. CMSM R80T100 exhibiting CO2/N2 ideal selectivity of 194 at 100 °C with a CO2 permeability of 4718 barrier was performed higher than Robeson’s upper bound limit for polymeric membranes and also the other CMSMs fabricated in this work.The research has been carried out within the TTW Perspectief Program “Microsync” project number P16-10

Comparison between carbon molecular sieve and Pd-Ag membranes in H2-CH4 separation at high pressure

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.This project has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant agree-ment No 700355. This Joint Undertaking receives support fromthe European Union’s Horizon 2020 research and innovation

Development of selective Pd–Ag membranes on porous metal filters

Metallic supports with sufficient surface quality to achieve highly selective thin Pd–Ag membranes require specific pre-treatments, are not readily available on the market and are generally very expensive. To reduce costs, rough and large media grade Hastelloy X filters have been acquired and pre-treated via polishing and chemical etching. The loss in gas permeance given by the polishing treatment proved fully recovered after chemical etching. A method to fill the large pores of the filters via aspiration of α-Al2O3 water-powder suspension has been applied and characterized via imaging of the filled pores, inferential statistics, and capillary flow porometry measurements. The most suitable filler particle size for pore size distribution reduction has been identified as 18 μm, while a 5 μm filler proved optimal for further pore morphology improvement. The wide pore size distribution of the filters has thus been reduced up to 200 nm by filling with α-Al2O3 particles of decreasing size, similarly to the ceramic supports used for thin Pd–Ag membranes deposition. A boehmite based interdiffusion barrier has been deposited, achieving further surface roughness reduction. A highly H2 selective membrane has been obtained via simultaneous Pd–Ag plating on the pre-treated filter

Vapor/gas separation through carbon molecular sieve membranes: Experimental and theoretical investigation

The separation of H2O vapor from (hydrogen-rich) gaseous streams is a topic of increasing interest in the context of CO2 valorisation, where the in situ water removal increases product yield and catalyst stability. In this work, composite alumina carbon molecular sieve membranes (Al-CMSM) were prepared from phenolic resin solutions loaded with hydrophilic boehmite (γ-AlO(OH)) nanosheets (0.4–1.4 wt. % in solution) which partially transform to γ-Al2O3 nanosheets upon thermal decomposition of the resin, improving the hydrophilicity and thus the adsorption-diffusion contribution of the H2O permeation. The γ-Al2O3 nanosheets showed no influence on the pore size distribution of the membranes in the range of micropores, but they increased the membrane hydrophilicity. In addition, the use of boehmite in the resin solution causes an increase in the viscosity and thus an increase in the carbon layers thickness deposited on the porous α-Al2O3 support (from 1 to 3.3 μm). Furthermore, the alumina sheets introduce defects in the carbon matrix, increasing the tortuosity of the active layer, as concluded via phenomenological modelling and parametric fitting of the experimental results. As a consequence, the water permeability exhibits a maximum (1.3ꞏ10−6 molꞏs−1 Pa−1 m−1 at 150 °C) with boehmite/alumina content of ca. 0.8 wt. %, as the combined effects of increasing hydrophilicity (which favour H2O permeability) and increasing thickness and tortuosity (which hamper permeability) upon increasing boehmite loading. Similarly, the H2O/gas perm-selectivity is optimum at 1.2 wt. % boehmite loading. We further investigated the H2O permeation mechanism by modelling the mono- and multi-layer adsorption and capillary condensation of water in microporous media, which result as the main transport mechanisms in the explored conditions.This project has received funding from the European Union’s Horizon 2020 research and innovation programme undergrant agreement No 838014 (C2Fuelproject)

Carbon molecular sieve membranes for water separation in CO₂ hydrogenation reactions:Effect of the carbonization temperature

Carbon membranes are a potentially attractive candidate for the in-situ removal of water vapor in CO2 hydrogenation reactions. Their hydrophilicity and pore structure can be tuned by properly adjusting the synthesis procedure. Herein, we assess the effect of the carbonization temperature (450–750 °C) on the performance of supported CMSM in terms of vapor/gas separation, in correlation with changes in their surface functionality and porous structure. FTIR spectra showed that the nature of the functional groups changes with the evolution of the carbonization step, leading to a gradual loss in hydrophilicity (i.e., OH stretching disappears at Tcarb ≥ 600 °C). The extent of water adsorption displays an optimum at Tcarb of 500 °C, with the membrane carbonized at 650 °C being the least hydrophilic. We found that the pore size distribution strongly influences the water permeance. At all Tcarb, adsorption-diffusion (AD) is the dominant transport mechanisms. However, as soon as ultra-micropores appear (Tcarb: 600–700 °C) molecular sieving (MS) contributes to an increase in the water permeance, despites a loss in hydrophilicity. At Tcarb ≥ 750 °C, MS pores disappear, causing a drop in the water permeance. Finally, the permeance of different gases (N2, H2, CO, CO2) is mostly affected by the pore size distribution, with MS being the dominant mechanism over the AD, except for CO2. However, the extent and mechanism of gas permeation drastically change as a function of the water content in the feed, indicating that gas/vapor molecules need to compete to access the pores of the membranes.</p

Water Adsorption Effect on Carbon Molecular Sieve Membranes in H2-CH4 Mixture at High Pressure

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.This project has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant Agreement no. 700355. This Joint Undertaking receves support from the European Union´s Horizon 2020 research

Recent Advances on Carbon Molecular Sieve Membranes (CMSMs) and Reactors

Carbon molecular sieve membranes (CMSMs) are an important alternative for gas separation because of their ease of manufacture, high selectivity due to molecular sieve separation, and high permeance. The integration of separation by membranes and reaction in only one unit lead to a high degree of process integration/intensification, with associated benefits of increased energy, production efficiencies and reduced reactor or catalyst volume. This review focuses on recent advances in carbon molecular sieve membranes and their applications in membrane reactors