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%.     

Characterization of an ammonia decomposition process by means of a multifunctional catalytic membrane reactor

Ammonia decomposition was studied in a multifunctional catalytic membrane reactor filled with Ruthenium catalyst and equipped with palladium-coated membranes. To characterize the system we measured NH₃ conversion, H₂ yield and its partial pressure, the internal and external temperatures of the reactor shell and the electric consumption under several NH₃ flow and pressure conditions. Experimental results showed that the combined effect of Ruthenium catalyst and palladium membranes allowed the reaction to reach the equilibrium in all the conditions we tested. At 450 °C the ammonia conversion resulted the most stationary, while at 7 bar the hydrogen yield was almost independent of both the ammonia flow and temperature. In addition, the experimental system used in this work showed high values of NH₃ conversion and H₂ permeation also without heating the ammonia tank and therefore renouncing to control the feeding gas pressure. When ultra-pure hydrogen is needed at a distal site, a reactor like this can be considered for in situ hydrogen production.     

Preparation of a novel bimodal catalytic membrane reactor and its application to ammonia decomposition for COx-free hydrogen production

A novel bimodal catalytic membrane reactor (BCMR) consisting of a Ru/γ-Al₂O₃/α-Al₂O₃ bimodal catalytic support and a silica separation layer was proposed. The catalytic activity of the support was successfully improved due to enhanced Ru dispersion by the increased specific surface area for the γ-Al₂O₃/α-Al₂O₃ bimodal structure. The silica separation layer was prepared via a sol–gel process, showing a H₂ permeance of 2.6 × 10⁻⁷ mol Pa⁻¹ m⁻² s⁻¹, with H₂/NH₃ and H₂/N₂ permeance ratios of 120 and 180 at 500 °C. The BCMR was applied to NH₃ decomposition for CO_x-free hydrogen production. When the reaction was carried out with a NH₃ feed flow rate of 40 ml min⁻¹ at 450 °C and the reaction pressure was increased from 0.1 to 0.3 MPa, NH₃ conversion decreased from 50.8 to 35.5% without H₂ extraction mainly due to the increased H₂ inhibition effect. With H₂ extraction, however, NH₃ conversion increased from 68.8 to 74.4% due to the enhanced driving force for H₂ permeation through the membrane.     

Study on a catalytic membrane reactor for hydrogen production from ethanol steam reforming

Ethanol steam reforming in a membrane reactor with catalytic membranes was investigated to achieve important aims in one process, such as improvement in ethanol conversion and hydrogen yield, high hydrogen recovery and CO reduction. In order to confirm the efficiency of reaction and CO reduction, an ethanol reforming-catalytic membrane reactor with water–gas shift reaction (ECRW) in the permeate side was compared with a conventional reactor (CR) and an ethanol reforming-catalytic membrane reactor (ECR). In comparison with the CR, ethanol conversion improvement of 11.9–19% and high hydrogen recovery of 78–87% were observed in the temperature range of 300–600 °C in the ECRW. Compared with CR and ECR, the hydrogen yield of ECRW increased up to 38% and 30%, respectively. Particularly, the ECRW showed higher hydrogen yield at high temperature, because Pt/Degussa P25 loaded in the permeate side showed catalytic activity for the methane steam reforming as well as WGS reaction. Moreover, CO concentration was reduced under 1% by the WGS reaction in the permeate side in the temperature range of 300–500 °C.     

Performance assessment and evaluation of catalytic membrane reactor for pure hydrogen production via steam reforming of methanol

The steam reforming of methanol was investigated in a catalytic Pd–Ag membrane reactor at different operating conditions on a commercial Cu/ZnO/Al₂O₃ catalyst. A comprehensive two-dimensional non-isothermal stationary mathematical model has been developed. The present model takes into account the main chemical reactions, heat and mass transfer phenomena in the membrane reactor with hydrogen permeation across the PdAg membrane in radial direction. Model validation revealed that the predicted results satisfy the experimental data reasonably well under the different operating conditions. Also the impact of different operating parameters including temperature, pressure, sweep ratio and steam ratio on the performance of reactor has been examined in terms of methanol conversion and hydrogen recovery. The modeling results have indicated the high performance of the membrane reactor which is related to continuous removal of hydrogen from retentate side through the membrane to shift the reaction equilibrium towards formation of hydrogen. The obtained results have confirmed that increasing the temperature improves the kinetic properties of the catalyst and increase in the membrane's H₂ permeance, which results in higher methanol conversion and hydrogen production. Also it is inferred that the hydrogen recovery is favored at higher temperature, pressure, sweep ratio and steam ratio. The model prediction revealed that at 573 K, 2 bar and sweep ratio of 1, the maximum hydrogen recovery improves from 64% to 100% with increasing the steam ratio from 1 to 4.     

Analysis of ammonia decomposition reactor to generate hydrogen for fuel cell applications

In this paper, reaction engineering principles are utilized to analyze process conditions for producing sufficient hydrogen in an ammonia decomposition reactor for generating net power of 100 W in a fuel cell. It is shown that operating the reactor adiabatically results in a sharp decrease in temperature due to endothermic reaction, which results in low conversion of ammonia. For this reason, the reactor is heated electrically to provide heat for the endothermic reactions. It is observed that when the reactor is operated non-adiabatically, it is possible to get over 99.5% conversion of ammonia. The weight of absorbent to reduce ammonia to ppb levels is calculated. An energy balance on the reactor exit gas indicates that there is sufficient heat available to vaporize enough water to achieve 100% relative humidity in the fuel cell. A suitable fuel cell stack is designed and it is shown that this stack is able to provide the necessary power to electrically heat the reactor and produce net power of 100 W.     

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.     

Performance and economics of a Pd-based planar WGS membrane reactor for coal gasification

Conceptual 300 tonne per day (tpd) H₂-from-coal plants have been the subject of several major costing exercises in the past decade. Incorporating conventional high- and low-temperature water-gas-shift (WGS) reactors, amine-based CO₂ removal and PSA-based H₂ purification systems, these studies provide a benchmark against which alternative H₂-from-coal technologies can be compared. The catalytic membrane reactor (CMR), combining a WGS catalyst and hydrogen-selective metal membrane, can potentially replace the multiple shift and separation stages of a plant based on conventional technology. CMR-based shift and separation offers several major advantages over the conventional approach, including greater-than-equilibrium WGS conversion, the containment of the CO₂ at high-pressure and a reduction in the number of unit processes.     

Semi-continuous hydrogen production from catalytic methane decomposition using a fluidized-bed reactor

Non-oxidative, catalytic decomposition of hydrocarbons is an alternative, one-step process to produce pure hydrogen with no production of carbon oxides or higher hydrocarbons. Carbon produced from the decomposition reaction, in the form of potentially valuable carbon nanotubes, remains anchored to the active catalyst sites in a fixed bed. To facilitate periodical removal of this carbon from the reactor and to make hydrogen production continuous, a fluidized-bed reactor was envisioned. The hypothesis that the tumbling and inter-particle collisions of bed material would efficiently separate nanotubes anchored to the active catalyst sites of the bed particles was tested and shown to be invalid. However, a switching mode reaction system for the semi-continuous production of hydrogen and carbon nanotubes by periodic removal and replenishment of the catalytic bed material has been successfully demonstrated.     

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.     

Enhancement of pure hydrogen production through the use of a membrane reactor

Pure hydrogen production is of great interest as it is an energy carrier which can be used in PEM fuel cells for power production. Methane Steam Reforming (MSR) is commonly used for hydrogen production although the produced hydrogen is not free of other components. Membrane Reactors (MR) enable a pure hydrogen product stream and allows the reaction to take place at significantly lower temperatures (lower than 550 °C) than in conventional reactors (greater than 800 °C) with comparable methane conversion. This is achieved by hydrogen removal through a permselective Pd–Ag based membrane that cause a favorable shift in chemical equilibrium towards hydrogen production. In the present study, a two-dimensional, nonlinear, and pseudo-homogeneous mathematical model of a catalytic fixed-bed membrane reactor for methane steam reforming over a nickel-based foam supported catalyst is presented. Simulated results referring to the distribution of species, methane conversion, temperature and hydrogen flowrate along the reactor for different radial positions are obtained and analyzed. The performance of structured catalyst and catalyst supported on foam configurations under the same operating conditions is also studied. Experimental results for the membrane facilitate the identification of suitable operating conditions.     

Application of catalytic membrane reactor for pure hydrogen production by flare gas recovery as a novel approach

In the present study, application of catalytic membrane reactor as a novel approach for the flare gas recovery is proposed. A comprehensive two-dimensional non-isothermal model has been constructed to evaluate the performance of flare gas recovery process in the membrane reactor. The model is developed by taking into accounts the main chemical kinetics, heat and mass transfer phenomena and hydrogen permeation in the radial direction across a Pd–Ag membrane. The model predictions are validated based on different experimental results reported in literature. The impact of reactor operating conditions on the recovery process such as temperature and pressure, feed molar ratio and sweep gas ratio are investigated and discussed. The modeling results confirm that the flare gas conversion and hydrogen recovery improves with increasing the operating temperature, pressure and sweep ratio as a consequence of increasing the driving force for H₂ permeation through membrane. The environmental consideration revealed that by application of catalytic membrane reactor for the flare gas recovery of Asalouyeh gas processing plant (Iran), not only the equivalent mass of greenhouse gases emission reduces from 2179 kg/s to 36 kg/s, but also, 12.7 kg/s pure hydrogen will be produced by flare gas recovery at 750 K, 5 bar, sweep ratio of 5 and feed molar ratio of 4.     

COx-free hydrogen production from ammonia decomposition over sepiolite-supported nickel catalysts

Sepiolite, a clay mineral, was utilized as a support for nickel-based catalysts for CO_x-free hydrogen production from ammonia decomposition. First, the physical and chemical properties of sepiolite were changed by calcining it at temperatures varying from 500 to 1000 °C, then nickel was impregnated on these calcined supports and tested for ammonia decomposition at various temperatures following reduction at 650 °C. Results indicated that even though the catalysts contained almost the same amount of nickel, they showed different hydrogen production performance. Detailed characterization of the catalysts before and after reaction illustrated that the support obtained by calcining sepiolite at 700 °C shows good basic properties with a high surface area offering a high degree of nickel dispersion. These properties lead to promising hydrogen production rates which are on par, if not higher, than most of the nickel-based catalysts prepared on supports, which are either not cheap or require tedious preparation procedures.     

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

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

Supported Ni catalysts prepared from hydrotalcite-like compounds for the production of hydrogen by ammonia decomposition

Ni catalysts with high surface areas were prepared from Mg–Al hydrotalcite-like compounds containing Ni with different Mg-to-Al ratios for the production of hydrogen via ammonia decomposition. At atomic ratios of Mg-to-Al from 3:1 to 6:1, Ni reduction was greater than 90%, and the amounts of Ni⁰ exposed were kept at more than 200 μmol g^?1. With the increase in Mg-to-Al ratio, turnover frequency was increased due to an increase in the basicity of the support. Of the catalysts examined, Ni_MgAl(6:1) exhibited the highest NH₃ conversion, which was attributed to its relatively high basicity and large amount of Ni⁰ exposed.     

Structure and catalytic properties of Ni/MWCNTs and Ni/AC catalysts for hydrogen production via ammonia decomposition

The structure and catalytic properties of nickel catalysts supported on multi-wall carbon nanotubes (MWCNTs) and on three different types of activated carbon (AC) were studied. The surface areas of AC carriers were defining the size of supported nickel particles. Large surface area of AC led to small Ni nanoparticles and high Ni dispersion. Turnover frequency (TOF_NH3) of ammonia decomposition decreased with decreasing of Ni particle size. The highest degree of ammonia conversion was observed on Ni/AC prepared by using of AC support with largest surface area. The catalytic activity of Ni/MWCNTs was much higher than catalytic activity of the studied Ni/AC catalysts. The synergic nickel-support interaction and special electronic conductivity properties of MWCNTs were responsible for high catalytic activity of Ni/MWCNTs catalyst.     

Influence of basic dopants on the activity of Ru/Pr6O11 for hydrogen production by ammonia decomposition

Basic oxides such as alkali metal oxides, alkaline earth metal oxides, and rare earth oxides were added to Ru/Pr₆O₁₁, and the activity of the catalysts with respect to hydrogen production by ammonia decomposition was investigated. Ru/Pr₆O₁₁ doped with alkali metal oxides, except for Li₂O, achieved higher NH₃ conversions than bare Ru/Pr₆O₁₁. Cs₂O, the most basic of the alkali metal oxides, was the most effective dopant. In contrast, other dopants with lower basicity than the alkali metal oxides achieved lower NH₃ conversions than bare Ru/Pr₆O₁₁. Changing the Cs/Ru molar ratio revealed that the best Cs/Ru ratio was 0.5–2; the reaction was effectively promoted without negative effects from coverage of the Ru surface by the Cs₂O. Varying the order of loading the Ru and Cs₂O onto Pr₆O₁₁ revealed that loading Ru onto Cs₂O/Pr₆O₁₁ was an effective way to enhance NH₃ conversion, and coverage of the Ru surface was reduced.     

Pure hydrogen production via autothermal reforming of ethanol in a fluidized bed membrane reactor: A simulation study

In this paper the production of ultra-pure hydrogen via autothermal reforming of ethanol in a fluidized bed membrane reactor has been studied. The heat needed for the steam reforming of ethanol is obtained by burning part of the hydrogen recovered via the hydrogen perm-selective membrane thereby integrating CO₂ capture. Simulation results based on a phenomenological model show that it is possible to obtain overall autothermal reforming of ethanol while 100% of hydrogen can in principle be recovered at relatively high temperatures and at high reaction pressures. At the same operating conditions, ethanol is completely converted, while the methane produced by the reaction is completely reformed to CO, CO₂ and H₂.     

Production of hydrogen from purge gases of ammonia plants in a catalytic hydrogen-permselective membrane reactor

The present study investigates hydrogen production in a hydrogen-permselective membrane reactor from purge gases of an ammonia plant. Hydrogen which initially exists in the purge gases and hydrogen that is produced from decomposition of ammonia on nickel–Alumina catalyst bed simultaneously permeate from reaction side to shell side through a thin layer of palladium–silver membrane. A sweep gas can be used in the shell side for increasing driving force. The amount of hydrogen that can be gained annually and effect of pressure, temperature, thickness of Pd–Ag layer, configuration of flow in the membrane reactor and sweep gas flow ratio have been studied. This study shows that the countercurrent mode is better than co-current mode of operation. The rate of hydrogen permeation increases with increasing of temperature, pressure and sweep gas flow rate. This approach produces and separates large amounts of hydrogen and decreases environmental impacts owing to ammonia emission.     

DDR zeolite membrane reactor for enhanced HI decomposition in IS thermochemical process

The third section of closed loop Iodine Sulphur (IS) thermochemical cycle, dealing with HI_x processing, suffers from low equilibrium decomposition of HI to hydrogen with a conversion value of only ～22% at 700 K. Here, we report a significant enhancement in conversion of HI into hydrogen (up to ～95%) using a zeolite membrane reactor for the first time. The all silica DDR (deca dodecasil rhombohedral) zeolite membrane with dense, interlocked structure was synthesized on the seeded clay alumina substrate by sonication mediated hydrothermal process. The synthesized membranes along with seed crystals were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and energy dispersive X-ray spectroscopy (EDX). Corrosion studies were carried out by exposing the membrane samples to simulated HI decomposition reaction environment (at 450 °C) for different durations of time upto 200 h. The FESEM, EDX and XRD analyses indicated that no significant changes occurred in the morphology, composition and structure of the membranes. Iodine adsorption on to the membrane surface was observed which got increased with the exposure duration as confirmed by secondary ion mass spectrometry studies. A packed bed membrane reactor (PBMR) assembly was fabricated with integration of in-house synthesized zeolite membrane and Pt-alumina catalyst for carrying out HI decomposition studies. The tube side was chosen as reaction zone and the shell side as the permeation zone. The HI decomposition experiments were carried out for different values of temperature and feed flow rates. DDR zeolite based PBMR was found to enhance the single-pass conversion of HI up to ～95%. The results indicate that for achieving optimal performance of PBMR, it should be operated with space velocities of 0.2–0.3 s^?1 and temperature in the range of 650 K–700 K with permeate side vacuum of 0.12 kg/cm². It is believed that the in-house developed zeolite PBMR shall be a potential technology augmentation in making the IS thermochemical cycle energy efficient.