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%.     

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.     

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.     

Ammonia decomposition kinetics over LiOH-promoted, α-Al2O3-supported Ru catalyst

A LiOH-promoted Ru-based catalyst was recently reported to have a high TOF of 17.7 s⁻¹ at 623 K, compared to 2.7 s⁻¹ for an un-promoted Ru-based catalyst, and has been reproduced for this study to develop further understanding of the catalyst activity under a range of conditions. The kinetic values were calculated using a Temkin-Pyzhev-like power law rate expression model. Reaction orders, pre-exponential factors (A) and activation energies (E) were calculated for two temperature ranges, 623–748 K, and 748–873 K. The TOF of this catalyst at 623 K is not similar to that previously reported, being only 1.6 s⁻¹ in this study. A follow-up CFD analysis supports the fact that the kinetic model effectively describes performance of the catalyst at a range of temperatures and pressures, and can be used in the future on similar catalysts. H₂ partial pressure has an inhibitory effect on the rate of decomposition of NH₃ at all temperatures, not just near or below 673 K as previously proposed in the literature, however equilibrium decomposition is still possible with sufficient catalyst loading.     

Experimental performance evaluation of an ammonia-fuelled microchannel reformer for hydrogen generation

Microchannel reactors appear attractive as integral parts of fuel processors to generate hydrogen (H₂) for portable and distributed fuel cell applications. The work described in this paper evaluates, characterizes, and demonstrates miniaturized H₂ production in a stand-alone ammonia-fuelled microchannel reformer. The performance of the microchannel reformer is investigated as a function of reaction temperature (450–700 °C) and gas-hourly-space-velocity (6520–32,600 Nml g_cat⁻¹ h⁻¹). The reformer operated in a daily start-up and shut-down (DSS)-like mode for a total 750 h comprising of 125 cycles, all to mimic frequent intermittent operation envisaged for fuel cell systems. The reformer exhibited remarkable operation demonstrating 98.7% NH₃ conversion at 32,600 Nml g_cat⁻¹ h⁻¹ and 700 °C to generate an estimated fuel cell power output of 5.7 W_e and power density of 16 kW_e L⁻¹ (based on effective reactor volume). At the same time, reformer operation yielded low pressure drop (<10 Pa mm⁻¹) for all conditions considered. Overall, the microchannel reformer performed sufficiently exceptional to warrant serious consideration in supplying H₂ to fuel cell systems.     

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.     

Hydrogen production from the methanolysis of ammonia borane by Pd-Co/Al2O3 coated monolithic catalyst

The aim of this study is to enable high hydrogen production yield from catalytic methanolysis of ammonia borane (AB) in the presence of a cordierite type ceramic monolithic. The monolithic channel surfaces were coated with Al₂O₃ by wash-coating method and then this layer was impregnated with 1 wt%Pd-2 wt%Co bimetallic catalyst. SEM-EDX and multi-point BET analysis were used in order to characterize the catalyst. The experimental studies were conducted in a continuous flow type reactor, which was used for the first time in this study. The reactions were carried on low temperature (40 °C), and with various AB feed concentrations and flow rates. It was found that the highest hydrogen production yield (88.5%) was obtained from AB flow rate of 3.3 mL/min, and AB feed concentration of 0.1 wt%. It was concluded that Pd-Co/Al₂O₃ coated monolithic, which is a stable, active and low-cost catalyst, was a very promising catalyst for on-board hydrogen production from the methanolysis of ammonia borane.     

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.     

Hydrogen production via ammonia decomposition catalyzed by Ni/M–Mo–N (M = Ni,Co) bimetallic nitrides

This study demonstrates the significant improvement in NH₃ decomposition using Ni-decorated M–Mo–N-based catalysts (M = Co and Ni) compared with conventional catalysts. Catalysts are prepared using a mixture of the corresponding metal salts and hexamethylenetetramine, and the impregnation method is used to decorate the Ni-particles on the catalysts. Among all the samples, 10 wt% Ni-decorated Co₃Mo₃N exhibits the highest NH₃ conversion rate (71%) at 500 °C, and the performance remains stable for 30 h of long-term testing. According to the gas chromatography measurements, the H₂/N₂ ratio is approximately 3 in all cases, which is consistent with the theoretical value. X-ray photoelectron spectroscopy results show that Co₃Mo₃N possesses the highest NH₃ conversion efficiency because of the weaker binding energy of Mo–N. Furthermore, Co₃Mo₃N exhibits a stronger Lewis acidity and higher NH₃ decomposition, which is attributed to the easy breaking of the N–H bond on the Co₃Mo₃N surface.     

Effect of preparation methods on the catalyst performance of Co/MgLa mixed oxide catalyst for COx-free hydrogen production by ammonia decomposition

This work deals with the effect of catalyst preparation method of the mixed Co, Mg and La oxide catalysts on their structure and catalytic properties for ammonia decomposition. Two methods are used for catalysts preparations impregnation and co-precipitation (in air and in pure O₂ atmosphere), The Mg/La = 2 molar ratio and 5 wt% of cobalt content was maintained same in all catalysts. The catalyst performance was evaluated in the temperature range 300–550 °C at atmospheric pressure. The prepared catalysts were characterized by BET, XRD, TPR, XPS, CO₂-TPD and SEM techniques. No pronounced differences were observed in BET among the catalysts. It was found that the 5CML-OXY (5 wt%Co over MgLa catalyst prepared by co-precipitation method in oxygen atmosphere) has superior activity among the other catalysts. This could be attributed to availability of easily reducible cobalt species determined by TPR studies and enhanced interaction between Mg and La determined by SEM and XPS. The moderate basic site density determined by CO₂-TPD results was also increased in 5CML–OXY catalysts compared with other catalysts. These consequences are might be one of the reasons for enhanced activity of 5CML–OXY catalyst compared to other catalysts. Hence catalyst preparation by co-precipitation in oxygen atmosphere is the best method which might be one of the parameters that influenced on catalytic properties of the cobalt on MgOLa₂O₃ system, for ammonia decomposition.     

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.