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

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

Palladium based membranes and membrane reactors for hydrogen production and purification: An overview of research activities at Tecnalia and TU/e

In this paper, the main achievements of several European research projects on Pd based membranes and Pd membrane reactors for hydrogen production are reported. Pd-based membranes have received an increasing interest for separation and purification of hydrogen. In addition, the integration of such membranes in membrane reactors has been widely studied for enhancing the efficiency of several dehydrogenation reactions. The integration of reaction and separation in one multifunctional reactor allows obtaining higher conversion degrees, smaller reactor volumes and higher efficiencies compared with conventional systems. In the last decade, much thinner dense Pd-based membranes have been produced that can be used in membrane reactors. However, the thinner the membranes the higher the flux and the higher the effect of concentration polarization in packed bed membrane reactors. A reactor concept that can circumvent (or at least strongly reduce) concentration polarization is the fluidized bed membrane reactor configuration, which improves the heat transfer as well. Tecnalia and TU/e are involved in several European projects that are related to development of fluidized bed membrane reactors for hydrogen production using thin Pd-based (<5 μm) supported membranes for different application: In DEMCAMER project a water gas shift (WGS) membrane reactor was developed for high purity hydrogen production. ReforCELL aims at developing a high efficient heat and power micro-cogeneration system (m-CHP) using a methane reforming fluidized membrane reactor. The main objective of FERRET is the development of a flexible natural gas membrane reformer directly linked to the fuel processor of the micro-CHP system. FluidCELL aims the Proof-of-Concept of a m-CHP system for decentralized off-grid using a bioethanol reforming membrane reactor. BIONICO aims at applying membrane reactors for biogas conversion to hydrogen. The fluidized bed system allows operating at a virtually uniform temperature which is beneficial in terms of both membrane stability and durability and for the reaction selectivity and yield.     

Carbon molecular sieve membranes supported on non-modified ceramic tubes for hydrogen separation in membrane reactors

Supported carbon membranes have been regarded as more competitive than traditional gas separation materials due to the versatile combination of different pyrolyzable polymers and supports which in turn leads to high separation factors and mechanical stability. In order to determine the extent to which supported carbon membranes are more competitive, the transport mechanism of supported carbon membranes was investigated in the range 32–150 °C and 1–2.5 bar. Polyimide (Matrimid 5218) material was coated and pyrolyzed under N₂ atmosphere on TiO₂-ZrO₂ macroporous tubes (Tami) that had not been structurally modified in any way. The supported carbon membrane was studied to determine its permeation for low molecular weight gases such as H₂, CH₄, CO, N₂ and CO₂. For these gases, the permeance of the composite supported carbon membranes obtained after pyrolysis at 550 °C increased with inverse square root of molecular weight. The temperature dependence of the permeance was described using an Arrhenius law with the negative activation energies for hydrogen, carbon dioxide and nitrogen providing evidence of a non-activated process. The ideal separation selectivity computed from single gas measurements leads to values slightly lower than the Knudsen because of the influence of viscous flow. The coexistence of more than one transport mechanism in the composite membrane was confirmed. After plugging the possible defects with Polydimethylsiloxane (PDMS), the supported carbon membranes obtained at a pyrolysis temperature of 650 °C showed evidence of a molecular sieving mechanism. This paper shows the separation properties of a crack-free supported carbon membrane obtained using a simple fabrication method that does not require modification of the mesoporous support. The permeance and selectivity values were compared with those of other hydrogen selective materials. Finally, the membranes were applied to methanol steam reforming (MSR).     

Tube-wall catalytic membrane reactor for hydrogen production by low-temperature ammonia decomposition

Ammonia has attracted great interest as a chemical hydrogen carrier. However, ammonia decomposition is limited kinetically rather than thermodynamically below 400 °C. We developed a tube-wall catalytic membrane reactor that could decompose ammonia with high conversion even at temperatures below 400 °C. The reactor had excellent heat transfer characteristics, and thus nearly 100% conversion for an NH3 feed of 10 mL/min at 375 °C was achieved with a 2-μm-thick palladium composite membrane, and hydrogen removal from the decomposition side resulted in a large kinetic acceleration.     

Ultra-pure hydrogen production via ammonia decomposition in a catalytic membrane reactor

In this work two alternatives are presented for increasing the purity of hydrogen produced in a membrane reactor for ammonia decomposition. It is experimentally demonstrated that either increasing the thickness of the membrane selective layer or using a small purification unit in the permeate of the membranes, ultra-pure hydrogen can be produced. Specifically, the results show that increasing the membrane thickness above 6 μm ultra-pure hydrogen can be obtained at pressures below 5 bar. A cheaper solution, however, consists in the use of an adsorption bed downstream the membrane reactor. In this way, ultra-pure hydrogen can be achieved with higher reactor pressures, lower temperatures and thinner membranes, which result in lower reactor costs. A possible process diagram is also reported showing that the regeneration of the adsorption bed can be done by exploiting the heat available in the system and thus introducing no additional heat sources.     

Steam reforming of propane in a fluidized bed membrane reactor for hydrogen production

Steam reforming of propane was carried out in a fluidized bed membrane reactor to investigate a feedstock other than natural gas for production of pure hydrogen. Close to equilibrium conditions were achieved inside the reactor with fluidized catalyst due to the very fast steam reforming reactions. Use of hydrogen permselective Pd₇₇Ag₂₃ membrane panels to extract pure hydrogen shifted the reaction towards complete conversion of the hydrocarbons, including methane, the key intermediate product. Irreversible propane steam reforming is limited by the reversibility of the steam reforming of this methane. To assess the performance improvement due to pure hydrogen withdrawal, experiments were conducted with one and six membrane panels installed along the height of the reactor. The results indicate that a compact reformer can be achieved for pure hydrogen production for a light hydrocarbon feedstock like propane, at moderate operating temperatures of 475–550 °C, with increased hydrogen yield.     

Equilibrium shift of methylcyclohexane dehydrogenation in a thermally stable organosilica membrane reactor for high-purity hydrogen production

A high-performance organosilica membrane was prepared via sol–gel processing for use in methylcyclohexane (MCH) dehydrogenation to produce high-purity hydrogen. The membrane showed a high H₂ permeance of 1.29 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹, with extremely high H₂/C₃H₈ and H₂/SF₆ selectivities of 6680 and 48,900, respectively, at 200 °C. The extraction of hydrogen from the membrane reactor led to the MCH conversion higher than the thermodynamic equilibrium, with almost pure hydrogen obtained in the permeate stream without considering the effect of carrier gas and sweep gas in the membrane reactor, and the organosilica membrane reactor was very stable under the reaction conditions employed.     

Mathematical modeling of hydrogen production using methanol steam reforming in the coupled membrane reactor when the output materials of the reformer section is used as feed for the combustion section

Hydrogen is one of the most abundant elements on Earth's surface. It is not in nature in its pure form, but it can produce by various methods such as methanol steam reforming, partial oxidation, electrolysis, etc. In the present study, using the mass and energy conservation law, hydrogen production in coupled membrane reactors has been modeled using the methanol steam reforming process using two different methods in the coupled membrane reactor. A separate (fresh) methanol is used as feed for the combustion section in the first method. While in the second method, the reformer reactor's output material is used as feed for the combustion section. After simplifying using the required assumptions, the governing equations solved using the ode45 (shooting method) numerical method using MATLAB software. The results of this study show that the conversion of methanol in the coupled membrane reactor when separate methanol is used as feed in the combustion reactor, while in the same reactor, the output material of the reformer section used as feed in the combustion section, is 92% and 88.5% respectively. In this study, the effect of different parameters on the methanol conversion rate is investigated. Finally, it found that with increasing temperature and pressure and decreasing membrane thickness in coupled membrane reactors, methanol conversion rate increases. The percentage of hydrogen recovery in the two coupled membrane reactors is almost equal to 92%.     

Hydrogen-based membrane biofilm reactors for nitrate removal from water and wastewater

H₂-based membrane biofilm reactor (MBfR), a kind of autotrophic denitrification system, is a novel and special membrane bioreactor using hydrogen as inorganic electron donor to reduce nitrate and nitrite in water and wastewater. In this paper, the state of the art of recent research on denitrification through H₂-based MBfRs is reviewed, including theoretical fundamentals, key influencing factors, possible problems and applications. Hydrogen/nitrate counter-diffusion has been described as Dual substrates limitations. The denitrifying bacteria in H₂-based MBfR were summarized. The key factors affecting the performance of H₂-based MBfR were listed in terms of substrate concentrations, membrane materials, reactor types, biofilm management and operation conditions. The pH value, salinity, dissolved oxygen, HRT (hydraulic retention time) and carbon source have been identified as main operational conditions affecting H₂-MBfR performance. Furthermore, membrane fouling in H₂-based MBfRs was emphasized. H₂-MBfR was proved excellent in denitrification based on its high performance for groundwater, IX brine and aquaculture wastewater treatment. Several aspects may be considered in future works were proposed.     

Characterization of mechanical strength and hydrogen permeability of a PdCu alloy film prepared by one-step electroplating for hydrogen separation and membrane reactors

A single phase, dense PdCu alloy film was prepared by one-step electroplating. The electroplated film was easily delaminated from the SUS electrode by cutting around the edge, and the single alloy film was thus collectable. The phase structure, surface morphologies, and alloy compositions were determined by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron probe microanalysis (EPMA). The plated film before and after hydrogen permeation tests consisted of a single face-centered cubic α phase and an ordered body-centered cubic β phase, respectively. The atomic ratios of Pd and Cu were 49 and 51 at%, respectively; the Pd and Cu contents were slightly higher and lower than Pd₄₇Cu₅₃, which shows the highest hydrogen permeability among Pd-Cu systems. The as-plated film exhibited high mechanical strength, and its load force at break point and displacement were 3 and 1.7 times those of the as-rolled Pd₄₇Cu₅₃ films. The hydrogen permeability of the plated film with the β phase was almost the same as that of the rolled film and the values reported in literature.     

A process dynamic modeling and control framework for performance assessment of Pd/alloy-based membrane reactors used in hydrogen production

In the present study a comprehensive, insightful and practical process dynamic modeling framework is developed in order to analyze and characterize the transient behavior of a Pd/alloy-based (Pd/Au or Pd/Cu) water-gas shift (WGS) membrane reactor. Furthermore, simple process control ideas are proposed aiming at enhancing process system performance by inducing the desirable dynamic characteristics in the response of the controlled process during start-up as well as in the presence of unexpected adverse disturbances (process upset episodes) or operationally favorable set-point changes that reflect new hydrogen production requirements. Finally, the proposed methods are evaluated through detailed simulation studies in an illustrative example involving a Pd/alloy-based WGS membrane reactor that exhibits complex dynamic behavior and is currently used for lab-scale pure hydrogen production and separation.     

RuRh based catalysts for hydrogen production via methanol steam reforming in conventional and membrane reactors

Results of hydrogen production study in methanol steam reforming (MSR) process with the use of Ru_0.5–Rh_0.5 catalysts supported on different carbon materials: synthetic graphite-like material Sibunit, carbon black Ketjenblack EC600DJ, detonation nanodiamonds (DND) and ZrO₂-based material with fluorite structure, doped with ceria, have been described. The samples have been tested in conventional flow reactor and membrane (MR) reactor, containing Pd-based membranes with different composition, thickness and surface architecture. It has been shown that the catalytic activity of the composites depends on the support nature. The RuRh/DND catalyst exhibits the highest activity, whereas RuRh/Ce_0.1Zr_0.9O_2–δ is the most selective. The use of PdAg (23%) foil with the surface modified by palladium black showed great advantages comparing to the smooth dense membrane. The use of the MR with the PdAg membrane improves the MSR reaction and provides almost 50% increase in the hydrogen yield. The hydrogen produced with the use of the MR is ultra pure.     

Parametric study of membrane reactors for hydrogen production via high-temperature water gas shift reaction

This study presents numerical studies of hydrogen production performance via water gas shift reaction in membrane reactor. The pre-exponential factor in describing the hydrogen permeation flux is used as the main parameter to account for the membrane permeance variation. The operating pressure, temperature and H₂O/CO molar ratio are chosen in the 1–20 atm, 400–600 °C and 1–3 ranges, respectively. Based on the numerical simulation results three distinct CO conversion regimes exist based on the pre-exponential factor value. For low pre-exponential factors corresponding to low membrane permeance, the CO conversion approaches to that obtained from a conventional reactor without hydrogen removal. For high pre-exponential factor, high CO conversion and H₂ recovery with constant values can be obtained. For intermediate pre-exponential factor range both CO conversion and H₂ recovery vary linearly with the pre-exponential factor. In the high membrane permeation case CO conversion and H₂ recovery approach limiting values as the operating pressure increases. Increasing the H₂O/CO molar ratio results in an increase in CO conversion but decrease in H₂ recovery due to hydrogen permeation driving force reduction. As the feed rate increases in the reaction side both the CO conversion and hydrogen recovery decrease because of decreased reactant residence time. The sweep gas flow rate has a significant effect on hydrogen recovery. Low sweep gas flow rate results in low CO conversion H₂ recovery while limiting CO conversion and hydrogen recovery can be reached for the high membrane permeance and high sweep gas flow rate cases.     

La1−xSrxMO3 (M = Mn, Fe) perovskites as materials for thermochemical hydrogen production in conventional and membrane reactors

La_1−xSr_xMO₃ (M = Mn, Fe) perovskites are investigated as potential redox materials for the thermochemical production of hydrogen. Thermogravimetric oxidation/reduction experiments indicated that the materials are able to lose and uptake oxygen reversibly from their lattice up to 5.5 wt.% for La_1−xSr_xMnO₃ with x = 1 and up to 1.7 wt.% for La_1−xSr_xFeO₃ with x = 0. Pulse reaction experiments indicated that the materials can be used as redox catalysts in a redox process where water is dissociated giving rise to the production of pure hydrogen during the oxidation step. The oxidation and reduction steps can be combined in a membrane reactor constructed from dense perovskite membranes towards a continuous and isothermal operation. The system is also able to operate on partial pressure-based desorption without the need of a carbon-containing reductant, so that a process towards hydrogen production, based only on renewable hydrogen source such as water, can be established. At steady state and 900 ^°C, 25 ± 7 cm³ (STP) H₂ m⁻² min⁻¹ is produced in purified state.     

3D simulation of hydrogen production by ammonia decomposition in a catalytic membrane reactor

Ammonia decomposition in an integrated Catalytic Membrane Reactor for hydrogen production was studied by numerical simulation. The process is based on anhydrous NH₃ thermal dissociation inside a small size reactor (30 cm³), filled by a Ni/Al₂O₃ catalyst. The reaction is promoted by the presence of seven Pd coated tubular membranes about 203 mm long, with an outer diameter of 1.98 mm, which shift the NH₃ decomposition towards the products by removing hydrogen from the reaction area. The system fluid-dynamics was implemented into a 2D and 3D geometrical model. Ammonia cracking reaction over the Ni/Al₂O₃ catalyst was simulated using the Temkin-Pyzhev equation.Introductory 2D simulations were first carried out for a hypothetic system without membranes. Because of reactor axial symmetry, different operative pressures, temperatures and input flows were evaluated. These introductory results showed an excellent ammonia conversion at 550 °C and 0.2 MPa for an input flow of 1.1 mg/s, with a residual NH₃ of only a few ppm. 3D simulations were then carried out for the system with membranes. Hydrogen adsorption throughout the membranes has been modeled using the Sievert’s law for the dissociative hydrogen flux. Several runs have been carried out at 1 MPa changing the temperature between 500 °C and 600 °C to point out the conditions for which the permeated hydrogen flux is the highest. With temperatures higher than 550 °C we obtained an almost complete ammonia conversion already before the membrane area. The working temperature of 550 °C resulted to be the most suitable for the reactor geometry. A good matching between membrane permeation and ammonia decomposition was obtained for an NH₃ input flow rate of 2.8 mg/s. Ammonia reaction shift due to the presence of H₂ permeable membranes in the reactor significantly fostered the dissociation: for the 550 °C case we obtained a conversion rate improvement of almost 18%.     

Photocatalytic membrane reactors for hydrogen production from water

Hydrogen is considered today a promising environmental friendly energy carrier for the next future, since it produces no air pollutants or greenhouse gases when it burns in air, and it possesses high energy capacity. In the last decades great attention has been devoted to hydrogen production from water splitting by photocatalysis. This technology appears very attractive thanks to the possibility to work under mild conditions producing no harmful by-products with the possibility to use renewable solar energy. Besides, it can be combined with the technology of membrane separations making the so-called photocatalytic membrane reactors (PMRs) where the chemical reaction, the recovery of the photocatalyst and the separation of products and/or intermediates simultaneously occur. In this work the basic principles of photocatalytic hydrogen generation from water splitting are reported, giving particular attention on the use of modified photocatalysts able to work under visible light irradiation. Several devices to achieve the photocatalytic hydrogen generation are presented focusing on the possibility to obtain pure hydrogen employing membrane systems and visible light irradiation. Although many efforts are still necessary to improve the performance of the process, membrane photoreactors seem to be promising for hydrogen production by overall water splitting in a cost-effective and environmentally sustainable way.     

Modeling of fluidized bed membrane reactors for hydrogen production from steam methane reforming with Aspen Plus

Hydrogen production via steam methane reforming with in situ hydrogen separation in fluidized bed membrane reactors was simulated with Aspen Plus. The fluidized bed membrane reactor was divided into several successive steam methane sub-reformers and membrane sub-separators. The Gibbs minimum free energy sub-model in Aspen Plus was employed to simulate the steam methane reforming process in the sub-reformers. A FORTRAN sub-routine was integrated into Aspen Plus to simulate hydrogen permeation through membranes in the sub-separator based on Sieverts' law. Model predictions show satisfactory agreement with experimental data in the literature. The influences of reactor pressure, temperature, steam-to-carbon ratio, and permeate side hydrogen partial pressure on reactor performances were investigated with the model. Extracting hydrogen in situ is shown to shift the equilibrium of steam methane reactions forward, removing the thermodynamic bottleneck, and improving hydrogen yield while neutralizing, or even reversing, the adverse effect of pressure.     

Performance of gas-phase photocatalytic reactors on hydrogen production

Three types of high-performance photocatalytic reactors were developed for gas-phase photocatalytic hydrogen (H₂) production from hydrogen sulphide (H₂S) and effective photocatalytic decomposition of gaseous H₂S at a very low concentration is investigated. In this paper, three lab-scale photocatalytic reactors viz., packed bed photocatalytic reactor, catalyst coated fixed bed photocatalytic reactor and catalyst dispersed photocatalytic reactors were developed to study the performance of reactors on hydrogen production. The novel photocatalyst (CdS + ZnS)/Fe₂O₃ and the optimized catalyst dosage, H₂S gas flow rate, pollutant concentration, light irradiations were used. The experimental result indicates that packed bed photocatalytic reactor can effectively splits the H₂S into hydrogen (i.e. 98%) and rapidly decompose H₂S toward zero concentration than the other two reactors. Hence the bench-scale photocatalytic reactor was fabricated in packed bed reactor and the maximum hydrogen conversion achieved from hydrogen sulphide was found to be 98%.