Pd Ag Membrane Research Articles

HYDROGEN GAS RECOVERY THROUGH THE PERMEATION MEMBRANE BASED BIMETALLIC PALLADIUM ALLOY

Generally, the H2 gas produced from the industrial processes is not in a pure state but is mixed with other compounds. For example, the off-gas produced in the oil refinery process still contains CH4, H2, and other gases. Thus, the process of separating as well as recovering the valuable H2 gas from other gas compounds is of essential process. Currently, the H2 separation process is being developed with relatively low costs with good efficiency, namely using the permeation membranes separation process, in which the compounds with high permeability tends to be more easily separated. Here we report the hydrogen recovery process from the mixed H2/N2 off-gas contains 61 % hydrogen and 39% balancing nitrogen, by using the bimetallic Pd-Ag membrane, where the effect of the gas feed pressure (1 and 2 bar) and operating temperature (373.15, 423.15, 473.15, and 523.15, 573.15 K) on the resulting permeate flux is comprehensively studied. We found that the flux and permeability increased with the increase in the gas feed pressure and temperature. Under the same gas temperature of 373.15 K, the permeation flux at the 2 bar gas feed pressure was found to be 2.047 mol.s-1.m-2, which was 166% greater than that of 1 bar pressure, i.e. 1.204 mol.s-1.m-2. Meanwhile, under the same gas feed pressure of 2 bar, the permeation flux at the operating temperature of 573.15 K was found to be 2.103 mol.s-1.m-2, which is 104,9% greater than that of 373.15 K operating temperature, i.e. 2.047 mol.s-1.m-2. These findings suggest the breakthrough advantages of the Pd-Ag alloy membrane for its high hydrogen permeability at low pressure.

Pre-pilot scale study of hydrogen production from biomass syngas via water-gas shift in Pd–Ag catalytic membrane reactor and dedicated hydrogen permeation unit

The water-gas shift reaction (WGS) was evaluated in two Pd–Ag membrane reactors operating in parallel and capable of processing 0.25 Nm3·h−1 of syngas. Various configurations, syngas compositions, and steam flow rates were explored within the temperature range of 300–350 °C and pressure range of 4–8bar. The performances were evaluated in a coupled configuration, consisting of a permeator and a membrane reactor operating in series, and single configuration of membrane reactor. Two syngas mixtures were fed and treated under different combinations of temperature, pressure, and steam/CO ratio. The syngas composition used was, in one case that typically produced by updraft gasifiers operated with air and having a content of H2 19.1 vol% and, in the second case, having content of 36.8 vol%, typically achievable by oxy-steam gasification. Carbon monoxide conversion, hydrogen permeation, and hydrogen permeability of membranes were determined. The use of these membranes effectively enhances the WGS reaction, overcoming the performances of a Gibbs reactor, and produces streams of ultrapure hydrogen. Competitive strong adsorption of CO was suggested from the permeability analysis and comparison with existing literature.

Reformer + Membrane separator plant for decarbonized hydrogen production from Biogas/Biomethane: An experimental study combined to energy efficiency and exergy analyses

Nowadays, the world energy production is still based on the exploitation of fossil fuels, mainly oil, coal, and natural gas, responsible for large greenhouse emissions in the environment. According to the measures proposed by the European Green Deal to meet the carbon neutrality by 2050, the decarbonisation of the global energy production processes represents a top priority. Hydrogen represents a carbon-free energy carrier, useful to drive the society toward a decarbonized-economy. The novelty of this work is represented by the experimental generation of clean hydrogen by a two stages plant constituted of a biogas/biomethane steam reformer and a Pd-Ag membrane separator, meanwhile applying on this simple case the methodology of the exergy analysis, identifying the main losses and suggesting improvements. Hence, it deals with the exergy analysis of the whole system with the process intensification operated by the membrane separator adopted instead of using several stages to separate/purify hydrogen − as conventionally done after the reforming stage (two water gas shift reactors, high and low temperature, followed by a pressure swing adsorption stage) − with the objective of recovering decarbonized hydrogen coming from the biogas/biomethane steam reformer, meeting the European targets indicated by the Clean Hydrogen Alliance. This approach allowed to understand the amount of irreversibilities present in such a system as well as how the thermal efficiency may be influenced by a number of parameters, constituting globally a baseline for the scaling up of this process technology from lab to bench/pilot scale. The best results of this work highlight that the utilization of biomethane in the feed stream to generate hydrogen resulted to be a better choice than biogas in terms of thermal efficiency (based on the lower heating value) of the whole system, equal to 73 % at 773 K, while the highest percentage of exergy destruction was concentrated in the condensation stage, with values varying between 76 % and 93 %, depending on the feed stream typology. The two stages system was able to meet the “decarbonized hydrogen production target 2027”, with a hydrogen recovery of 90 % and a purity of 99.9999 %. Last but not least, the overall exergy destroyed efficiency of the overall system in the two analyzed cases was 92 % (biomethane feed stream) and 88 % (biogas feed stream), respectively.

Hydrogen and NH3 co-adsorption on Pd–Ag membranes

Ammonia (NH3) represents a carbon-free hydrogen carrier that can be used as a zero-emission fuel in the maritime and heavy transport sector with hydrogen fuel cells. To use ammonia as feedstock, the hydrogen must be recovered through NH3 decomposition into H2 and N2. Ammonia decomposition by a membrane-enhanced reactor would inherently produce high-purity H2 through the membrane avoiding the need for a costly hydrogen separation/purification unit. Pd-based membrane reactors can obtain full ammonia decomposition and show significantly higher conversion than conventional reactors. However, the H2 permeability is found to be inhibited in the presence of NH3. A further fundamental understanding of the long-term stability and performance of the Pd-based membranes under exposure to NH3 is therefore required. In the current work, the adsorbate-adsorbate interactions during co-adsorption, the influence the presence of NH3 has on the hydrogen dissociation kinetics, and surface segregation effects in the presence of NH3 and/or hydrogen on the surface of Pd and Pd3Ag are investigated in detail using density functional theory calculations. We find that both the hydrogen surface coverage and dissociation kinetics are hindered by the presence of NH3 on the surface, and possible segregation of Ag towards the surface in the presence of NH3, which could explain the reduced hydrogen permeation in NH3.

Parametric and sensitive analysis of Pd-Ag membrane reactor performance in biogas reforming to generate decarbonized hydrogen by Computational Fluid Dynamic-Response Surface Methodology

The efficient production of hydrogen from renewable sources is pivotal for the development of sustainable energy systems. Biogas steam reforming (BSR) conducted in palladium-based membrane reactors (MRs) offers a pathway for high-purity H2 generation at lower temperatures compared to traditional processes. In this study, a computational fluid dynamics (CFD) model was developed to simulate the BSR process within a Pd-Ag MR. The CFD model has integrated comprehensive kinetics, mass transport, and hydrodynamics, and its accuracy was confirmed through validation against experimental data, demonstrating substantial agreement. As a novel approach, to optimize the BSR reaction conditions to get the best MR performance, the CFD model was coupled with response surface methodology (RSM), which has been employed to enable the identification of optimal values for key parameters such as reaction temperature, pressure, gas hour space velocity, feed molar ratio, and sweep gas ratio, where the temperature was found to have the most significant impact on the MR’s performance within the examined intervals of input parameters. The objective of RSM method applied to CFD modeling was to maximize with high accuracy CH4 conversion, H2 recovery, and reduce CO2 emissions. RSM models effectively established correlations between input parameters and responses. The determined optimal conditions for the BSR process were a temperature of 683 K, a reaction pressure of 6 bar, a GHSV of 3000 h−1, a H2O/CH4 ratio of 1.34, and a sweep ratio of 9. Under these conditions, the system achieved remarkable results with 100 % CH4 conversion, 43 % H2 recovery, and an 81 % reduction in CO2 emissions. This study underscores the effectiveness of integrating CFD with RSM for the precise modeling and optimization of MRs in BSR reactions. The synergy between these approaches provides a robust framework for advancing the efficiency and sustainability of hydrogen production processes from renewable sources.

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.

High-Performance Hydrogen-Selective Pd-Ag Membranes Modified with Pd-Pt Nanoparticles for Use in Steam Reforming Membrane Reactors.

A unique method for synthesizing a surface modifier for metallic hydrogen permeable membranes based on non-classic bimetallic pentagonally structured Pd-Pt nanoparticles was developed. It was found that nanoparticles had unique hollow structures. This significantly reduced the cost of their production due to the economical use of metal. According to the results of electrochemical studies, a synthesized bimetallic Pd-Pt/Pd-Ag modifier showed excellent catalytic activity (up to 60.72 mA cm-2), long-term stability, and resistance to COads poisoning in the alkaline oxidation reaction of methanol. The membrane with the pentagonally structured Pd-Pt/Pd-Ag modifier showed the highest hydrogen permeation flux density, up to 27.3 mmol s-1 m-2. The obtained hydrogen flux density was two times higher than that for membranes with a classic Pdblack/Pd-Ag modifier and an order of magnitude higher than that for an unmodified membrane. Since the rate of transcrystalline hydrogen transfer through a membrane increased, while the speed of transfer through defects remained unchanged, a one and a half times rise in selectivity of the developed Pd-Pt/Pd-Ag membranes was recorded, and it amounted to 3514. The achieved results were due to both the synergistic effect of the combination of Pd and Pt metals in the modifier composition and the large number of available catalytically active centers, which were present as a result of non-classic morphology with high-index facets. The specific faceting, defect structure, and unusual properties provide great opportunities for the application of nanoparticles in the areas of membrane reactors, electrocatalysis, and the petrochemical and hydrogen industries.

Investigating the effects of operating parameters on the performance of sorption-enhanced membrane reactor for ethanol steam reforming reaction using computational fluid dynamics method

In this study, the performance of a sorption-enhanced membrane reactor (SEMR) was examined using a Pd-Ag membrane during ethanol steam reforming (ESR). During this study, simultaneous ESR and CO2 adsorption concept was adopted and computational fluids dynamic (CFD) method (two-dimensional model) was developed to evaluate the SEMR performance during ESR reaction. The employed CFD model for the present study provided information about the molar fractions and pressures of components to analyze driving forces under unsteady state condition. Regarding validation, the experimental data related to the membrane reactor (MR) during ESR reaction showed good agreement with modeling outcomes and the application of adsorption reaction improved MR performance. The SEMR performance was investigated after model validation, and during this step, SEMR and MR were compared. Moreover, the effects of main operating parameters, such as gas hour space velocity (GHSV), reaction pressure, and temperature, were studied to compare the SEMR and MR performance during C2H5OH conversion and hydrogen recovery. CFD modeling results showed that SEMR had better performance and increased the ethanol conversion about 20% (SEMR: 70% and MR: 59%) by temperature enhancement at low pressures compared with the conventional membrane reactor. The relative error between numerical and experimental data obtained was 3% in this study.

On the applicability of PdAg membranes in propane dehydrogenation processes

The applicability of PdAg membranes in the propane dehydrogenation process has been evaluated in this work. The integration of membranes into the propane dehydrogenation process has the potential of making a significant step forward in energy and resource efficiency of the selective production of propylene. To assess the compatibility of the PdAg membrane with the process conditions of propane dehydrogenation, two double-skin PdAg membranes were exposed to the emulated process conditions of two cases: 1. A fully integrated membrane-reactor system (higher temperature) and 2. A cascade of catalyst and membrane separator units (lower temperature). The results of this study showed that at high temperature (475–500 °C) strong reduction of the hydrogen flux is observed during exposure to reactant and product containing mixtures. The reason for this is the deposition of carbonaceous species on the active sites of the membrane. Additionally, also the lifetime of the membrane (in terms of selectivity) was significantly lower due to the regeneration performed at high temperature in diluted air. The lower temperature experiments (300–350 °C) showed a much lower degree of deactivation and at the same time the membrane could be regenerated in air repeatedly without visible reduction of its selectivity. These findings show that the DS-PdAg membrane can be repeatedly exposed to reaction-regeneration cycles at acceptable activity and without significant loss of selectivity when operated in a cascade configuration at a temperature at or below 350 °C.

Use of Pd-Ag Membrane Reactors for Low-Temperature Dry Reforming of Biogas-A Simulation Study.

Biogas is a valuable renewable energy source that can help mitigate greenhouse emissions. The dry reforming of methane (DRM) offers an alternative hydrogen production route with the advantage of using two main greenhouse gases, CO2 and CH4. However, its real application is limited mainly due to catalyst deactivation by coke formation and the reverse water gas shift (RWGS) reaction that can occur in parallel. Additionally, the typical dry reforming temperature range is 700-950 °C, often leading to catalyst sintering. A low-temperature DRM process could be in principle achieved using a membrane reactor (MR) to shift the dry reforming equilibrium forward and inhibit the RWGS reaction. In this work, biogas reforming was investigated through the simulation of MRs with thin (3.4 µm) and thick (50 µm) Pd-Ag membranes. The effects of the feed temperature (from 450 to 550 °C), pressure (in the range of 2-20 bar), and biogas composition (CH4/CO2 molar ratios from 1/1 to 7/3) were studied for the thin membrane through the calculation and comparison of several process indicators, namely CH4 and CO2 conversions, H2 yield, H2/CO ratio and H2 recovery. Estimation of the CO-inhibiting effect on the H2 molar flux through the membrane was assessed for a thick membrane. Simulations for a thin Pd-Ag MR show that (i) CO2 and CH4 conversions and H2 yield increase with the feed temperature; (ii) H2 yield and average rate of coke formation increase for higher pressures; and (iii) increasing CH4/CO2 feed molar ratio leads to higher H2/CO ratios, but lower H2 yields. Moreover, simulations for a thick Pd-Ag MR showed that the average H2 molar flux decreases due to the CO inhibiting effect (ca. 15%) in the temperature range considered. In conclusion, this work showed that for the considered simulation conditions, the use of an MR leads to the inhibition of the RWGS reaction and improves H2 yield, but coke formation and CO inhibition on H2 permeation may pose limitations on its practical feasibility, for which proper strategies must be explored.

Experimental and Numerical Analysis of a Pd-Ag Membrane Unit for Hydrogen Isotope Recovery in a Solid Blanket.

The interest of the fusion community in Pd-Ag membranes has grown in the last decades due to the high value of hydrogen permeability and the possibility of continuous operation, making it a promising technology when a gaseous stream of hydrogen isotopes must be recovered and separated from other impurities. This is the case of the Tritium Conditioning System (TCS) of the European fusion power plant demonstrator, called DEMO. This paper presents an experimental and numerical activity aimed at (i) assessing the Pd-Ag permeator performance under TCS-relevant conditions, (ii) validating a numerical tool for scale-up purposes, and (iii) carrying out a preliminary design of a TCS based on Pd-Ag membranes. Experiments were performed by feeding the membrane with a He-H2 gas mixture in a specific feed flow rate ranging from 85.4 to 427.2 mol h-1 m-2. A satisfactory agreement between experiments and simulations was obtained over a wide range of compositions, showing a root mean squared relative error of 2.3%. The experiments also recognized the Pd-Ag permeator as a promising technology for the DEMO TCS under the identified conditions. The scale-up procedure ended with a preliminary sizing of the system, relying on multi-tube permeators with an overall number ranging between 150 and 80 membranes in lengths of 500 and 1000 mm each.

Metallic Supported Pd-Ag Membranes for Simultaneous Ammonia Decomposition and H2 Separation in a Membrane Reactor: Experimental Proof of Concept

The use of ammonia as a hydrogen carrier requires efficient cracking technology. A promising solution is the use of a membrane reactor (MR), which enables both ammonia decomposition and hydrogen separation to take place within the same device, providing advantages in terms of efficiency and compactness compared to conventional systems. The literature reports that ceramic-supported double-skinned Pd-Ag membranes show outstanding performance for hydrogen separation as well as good stability of the separation layer during ammonia decomposition. However, their sealing in the reactor may result in leakage increase, while their mechanical stability remains an unresolved issue. To circumvent these limitations, the use of metallic supported Pd-based membranes is recommended, due to their higher mechanical stability and ease of sealing and integration in the reactor. In this work, we propose the development of robust metallic supported hydrogen-selective membranes for integration in membrane reactors for ammonia cracking. A conventional Pd-Ag membrane was prepared on a low-cost porous Hastelloy X tubular filter, modified with α-Al2O3/γ-Al2O3 to reach the desired surface quality. The membrane was then tested for ammonia decomposition in a MR configuration, showing the ability to reach >99% NH3 conversion above 475 °C with H2 feed recovery >60%. The results achieved pave the way towards a possible substitute for the ceramic-supported alternatives.

An integrated two stages inorganic membrane-based system to generate and recover decarbonized H2: An experimental study and performance indexes analysis

This work focuses on the utilization of a two stages inorganic membrane-based system to generate and recover decarbonized hydrogen in order to meet the targets set by the European Clean Hydrogen Partnership under the Strategic Research & Innovation Agenda 2021–2027. In the first stage, a CH4:CO2 = 60:40 mixture simulating a biogas stream is used to generate a COx-free hydrogen via steam reforming reaction carried out in a tubular Pd-Ag membrane reformer, packed with a novel non-commercial 7 wt%Ni-0.5 wt%Ru/La0.3Y0.3Zr0.4Ox catalyst, prepared by solution combustion method. The catalyst was characterized by XRD, TPR and TEM techniques. The analyses reveal well-distributed active metal particles interacting differently with the support (weakly and strongly). In particular, the XRD pattern shows the formation of perovskite and nickel oxide in addition to the pyrochlore phase. This behaviour indicates a low solubility of Ni in the pyrochlore structure. Reaction measurements were carried out at a temperature of 673 K, in the total pressure range between 250 kPa ÷ 350 kPa, weight hourly space velocity (WHSV) of 0.2 h−1, H2O/CH4 feed molar ratio between 1.5 and 2, feeding N2-sweep gas in the permeated side. As best results of Stage 1, CH4 conversion equal to 99% (@ H2O/CH4 feed molar ratio = 2 and feed pressure of 250 kPa) and a COx-free H2 recovery of 40% were reached. In the second stage, the unpermeated stream of Stage 1 rich in hydrogen was fed to a supported Pd/Al2O3 membrane separator to further recover high grade hydrogen at the same temperature and total pressure set in Stage 1. The maximum hydrogen recovery equal to 67% was reached at 673 K and 350 kPa, with a purity of the recovered stream equal to 99.9%. The total hydrogen recovered in the permeate streams of Stage 1 and Stage 2 was equal to 80% of the total hydrogen produced during the steam reforming reaction, showing an average purity equal to 99.99%, which allowed to meet the established targets. The work further analized and discussed the experimental results of the integrated system by means of performance indexes.

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.

Improvement in Ammonia, Hydrogen, and Methyl Formate Synthesis Process by Employing Multiobjective Optimization of a Novel Multifunctional Membrane Reactor

This investigation analyzes the simultaneous production of hydrogen and ammonia as carbon-free energy carriers and methyl formate (MF) as a widely used chemical intermediate in a multifunctional membrane reactor (MFMR). The MFMR, based on Le Chatelier’s principle, has the advantage of changing the thermodynamic equilibrium by direct thermal coupling between ammonia synthesis and MF production and shifting the chemical equilibrium with the use of the Pd–Ag membrane. In the innovative configuration, the nitrogen conversion rate has been increased from 38.2 to 41.2% and the methanol conversion from 16.3 to 99.1%. Other benefits of the MFMR include providing the required energy for an endothermic reaction and eliminating a furnace and cooler in methanol dehydrogenation and ammonia synthesis reactors. Furthermore, it has been demonstrated that if the ammonia synthesis reaction is positioned at the center side of the MFMR, the nitrogen and methanol conversion are, respectively, 1.32 and 7.34% higher than when the reaction is located at the outer side of the MFMR. Likewise, the effect of operational process parameters such as inlet flow rates, inlet temperatures, and membrane thickness on the performance of each reaction has been studied. Utilizing multiobjective optimization (MOO), it has been observed that ammonia and MF production yields can reach 20.3 and 24.1%, respectively.

PROCESS INTENSIFICATION FOR HYDROGEN PRODUCTION FROM AMMONIA

Ammonia is presented as one of the main carriers for the transport and storage of hydrogen under mild conditions. In this context, the present work introduces the integration and intensification of an ultrapure hydrogen production process from ammonia as a feedstock. A production scale is set to satisfy the requirements of a typical hydrogen refueling station (200 kgH2/day). A multifunctional shell-and-tube reactor is designed to carry out the ammonia cracking reaction. The system operates at a moderate pressure (8 bar) and in a temperature range for the ammonia decomposition reaction between 300 °C and 650 °C. Total ammonia conversion is achieved due to the chemical equilibrium shift by H2 extraction through the incorporation of 100 % selective membranes. The Pd-Ag membranes provide a recovery of about 86 % of the hydrogen produced. The remaining hydrogen (i.e., the non-permeated stream) is catalytically combusted representing the only source of heat of the entire process.

Fluidized Bed Membrane Reactor for the Direct Dehydrogenation of Propane: Proof of Concept.

In this work, the fluidized bed membrane reactor (FBMR) technology for the direct dehydrogenation of propane (PDH) was demonstrated at a laboratory scale. Double-skinned PdAg membranes were used to selectively remove H2 during dehydrogenation tests over PtSnK/Al2O3 catalyst under fluidization. The performance of the fluidized bed membrane reactor was experimentally investigated and compared with the conventional fluidized bed reactor (FBR) by varying the superficial gas velocity over the minimum fluidization velocity under fixed operating conditions (i.e., 500 °C, 2 bar and feed composition of 30vol% C3H8-70vol% N2). The results obtained in this work confirmed the potential for improving the PDH performance using the FBMR system. An increase in the initial propane conversion of c.a. 20% was observed, going from 19.5% in the FBR to almost 25% in the FBMR. The hydrogen recovery factor displayed a decrease from 70% to values below 50%, due to the membrane coking under alkene exposure. Despites this, the hydrogen extraction from the reaction environment shifted the thermodynamic equilibrium of the dehydrogenation reaction and achieved an average increase of 43% in propylene yields.

Facile integration of core–shell catalyst and Pd-Ag membrane for hydrogen production from low-temperature dry reforming of methane

Dry reforming of methane (DRM) is an important way of conversion of CH4 and CO2, two greenhouse gases, for the production of hydrogen. In this study, a catalytic membrane reactor combining an ultra-thin Pd-Ag alloy membrane with a coke-resistant Ni-SiO2@CeO2 core–shell catalyst was developed for high yield hydrogen production from DRM. The performance of membrane in the presence of gases such as CO, CO2 and CH4 was evaluated, and very little reduction in H2 flux (∼2.5 %) was observed in the presence of these gases at the relevant reaction conditions. The catalyst was tested for DRM reaction in both fixed bed reactor (FBR) and catalytic membrane reactor (CMR) to evaluate its performance at different reaction conditions. In a catalytic membrane reactor, the removal of hydrogen resulted in 1.5 times higher methane conversion compared to the calculated conversion at thermodynamic equilibrium at the used reaction conditions when hydrogen is not removed from the reaction mixture. Around 70 % of the produced H2 was recovered from the reaction stream, by virtue of the high H2 flux through the ultra-thin Pd-Ag membrane. Further, the competing reverse water gas shift reaction, that consumes the produced H2, was drastically suppressed by using membrane reactor. The suppression of reverse water gas shift reaction (RWGS) in CMR was confirmed by analyzing downstream gases using gas chromatography mass spectrometer, the result showed significantly lower H2O content for CMR than FBR. Thus, the coupling of ultra-thin membrane with a core shell catalyst synergistically improved the performance of the dry reforming of methane.

Thermodynamic performance of solar-driven methanol steam reforming system for carbon capture and high-purity hydrogen production

• A solar MSR system via HPM reactor for high-purity hydrogen generation is proposed. • The conversion rate of methanol could exceed 99.9% between 150 and 250 °C. • The solar-to-fuel efficiency can reach 55.22% with 94.1% hydrogen separation. • Thermodynamic efficiencies of the system around a year is stable. • Standard coal saving rate is as high as 0.63 t/m 2 annually in this reactor. Solar energy storage via a thermochemical approach is a promising method to realize the efficient utilization of discontinuous sunlight. Traditional solar thermochemical conversion with the assistant of hydrocarbon requires the purification process of products, and a relatively high reaction temperature limits its thermodynamic efficiency. In this work, a thermodynamic study on solar-driven methanol steam reforming reaction in a Pd-Ag membrane reactor has been conducted. The partial pressure, conversion rate, and thermodynamic efficiency are studied and analyzed under different reaction temperatures (150–250 ˚C) and permeate pressures (10 −3 -1 bar). Via the membrane reactor, the equilibrium of reaction shifts forward and the conversion rate of methanol can reach as high as above 99.9% in 150–250 ˚C, and purified hydrogen and carbon dioxide can be collected separately. Under the optimized reaction temperature and pressure, the solar-to-fuel efficiency and exergy efficiency can reach as high as 55.2% and 74.79%, respectively. Due to the utilization of solar energy and membrane reactor, the annual coal saving rate and carbon dioxide reduction rate are predicted to be 0.63 t/m 2 and 1.53 t/m 2 , respectively. This thermodynamic research provides an efficient approach for solar energy conversion and storage without CO 2 emission.

Pd-based membranes performance under hydrocarbon exposure for propane dehydrogenation processes: Experimental and modeling

In this work, a novel Pd–Ag double-skinned (DS-) membrane is used for the first time in conditions typical of propane dehydrogenation (PDH). This membrane presents a protective layer on top of the H2-selective one, which acts as shield against chemical deactivation and mechanical erosion under reaction conditions. While the protective layer is already been proven as an efficient barrier against membrane erosion in fluidized beds, there is no validation yet under PDH reaction. The DS- membrane performance is compared with a conventional (C-) Pd–Ag membrane under alkane/alkene exposure, at 400–500 °C and 3 bar, to investigate whether the incorporation of the protective layer would be suited for H2 separation in PDH systems, and if coking rate would be affected. The novel membrane shows a H2 permeance of 2.28 × 10−6 mol∙m−2 s−1∙Pa−1 at 500 ᵒC and 4 bar of pressure difference, overcoming the performance of the conventional PdAg one (1.56x∙10−6 mol m−2 s−1∙Pa−1). Both membranes present a stable H2 flux under alkane exposure, while deactivation occurs under exposure to alkenes. A model able to describe the H2 flux through Pd-based membranes is presented to fit the experimental data and predict membrane performance. The model includes mass transfer limitations in the retentate and a corrective inhibition factor to account for the competitive adsorption of hydrocarbon species in the H2 selective layer. The experimental results obtained under alkene exposure deviates from model predictions; this can be attributed to carbon deposition on the surface of the selective layer, as further detected on the DS-membrane by Scanning Electron Microscopy (SEM)/Energy Dispersive X-Ray Analysis (EDX), which is the main factor for membrane deactivation.