A modelling evaluation of an ammonia-fuelled microchannel reformer for hydrogen generation

Hydrogen production from an ammonia-fuelled microchannel reactor is simulated in a three-dimensional (3D) model implemented via Comsol Multiphysics™. The work described in this paper endeavours to obtain a mathematical framework that provides an understanding of reaction-coupled transport phenomena within the microchannel reactor. The transport processes and reactor performance are elucidated in terms of velocity, temperature, and species concentration distributions, as well as local reaction rate and NH₃ conversion profiles. The baseline case is first investigated to comprehend the behaviour of the microchannel reactor, then microstructural design and operating parameters are methodically altered around the baseline conditions to explore the optimum values. The simulation results show that an optimum NH₃ space velocity (GHSV) of 65,000 Nml g_cat⁻¹ h⁻¹ yields 99.1% NH₃ conversion and a power density of 32 kW_e L⁻¹ at the highest operating temperature of 973 K. It is also shown that a 40-μm-thick porous washcoat is most desirable at these optimum conditions. Finally, a low channel hydraulic diameter (225 μm) is observed to contribute to high NH₃ conversion. Mass transport limitations in the porous-washcoat and gas-phase are negligible as depicted by the Damköhler and Fourier numbers, respectively. The experimental microchannel reactor yields 98.2% NH₃ conversion and a power density of 30.8 kW_e L⁻¹ when tested at the optimum operating conditions established by the model. Good agreement with experimental data is observed, so the integrated experimental-modelling approach developed in this paper may well provide an incisive step toward the efficient design of ammonia-fuelled microchannel reformers.     

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.     

A performance study of methanol steam reforming in an A-type microchannel reactor

The methanol steam reforming (MSR) performance in a microchannel reactor is directly related to the flow pattern design of the microchannel reactor. Hydrogen production improvements can be achieved by optimal design of the flow pattern. In this study, an A-type microchannel reactor with a flow pattern design of one inlet and two outlets was applied to conduct the MSR for hydrogen production. The MSR performance of the A-type microchannel reactor was investigated through numerical analysis by establishing a three-dimensional simulation model and compared with that of the conventional Z-type microchannel reactor. Experiments were also conducted to test the MSR performance and validate the accuracy of the simulation model. The results showed that compared with the conventional Z-type microchannel reactor, the species distributions in the A-type microchannel reactor were more homogeneous. In addition, compared with the Z-type microchannel reactor, the A-type microchannel reactor was shown to effectively increase the methanol conversion rate by up to 8% and decrease the pressure drop by about 20%, regardless of a slightly higher CO mole fraction. It was also noted that with various quantities of microchannels and microchannel cross sections, the A-type microchannel reactor was still more competitive in terms of a higher methanol conversion rate and a lower pressure drop.     

Further development of a microchannel steam reformer for diesel fuel

This paper presents results from the ongoing optimisation of a microchannel steam reformer for diesel fuel which is developed in the framework of the development of a PEM fuel cell system for vehicular applications. Four downscaled reformers with different catalytic coatings of precious metal were operated in order to identify the most favourable catalyst formulation. Diesel surrogate was processed at varying temperatures and steam to carbon ratios (S/C). The reformer performance was investigated considering hydrogen yield, reformate composition, fuel conversion, and deactivation from carbon formation. Complete fuel conversion is obtained with several catalysts. One catalyst in particular is less susceptible to carbon formation and shows a high selectivity.     

Demonstration of a scaled-down autothermal membrane methane reformer for hydrogen generation

A novel concept for hydrogen generation by methane steam reforming in a thermally coupled catalytic fixed bed membrane reformer is experimentally demonstrated. The reactor, built from three concentric compartments, indirectly couples the endothermic methane steam reforming with the exothermic methane oxidation, while hydrogen is separated by a permselective Pd membrane. The study focuses on the determination of the key operation parameters and understanding their influence on the reactor performance. It has been shown that the reactor performance is mainly defined by the dimensionless ratio of the methane steam reforming feed flow rate to the hydrogen maximal membrane flow rate and by the ratio of the oxidation and steam reforming methane feed flow rates.     

A physico-chemical study of an NH3BH3-based reactive composition for hydrogen generation

In order to reduce the use of fossil energies, the development of new technologies, such as those concerning fuel cells, is required. However, fuel cells currently involve issues of storing and generating hydrogen. Borohydride materials, like ammonia borane (NH₃BH₃), seem to present an interesting solution to these problems. In fact, NH₃BH₃ contains 19.6 wt.% of hydrogen, of which a high percentage can easily be released by moderate heating. Understanding and controlling the behaviour of ammonia borane would allow the development of a safe, lightweight and compact hydrogen storage system. The final purpose would consist in having a device that is able to be integrated in nomad applications such as GSM, PDA; or in thermal accumulators. The present study reports on thermal decompositions of ammonia borane doped with various percentages of NH₄NO₃. Differential scanning calorimetry (DSC) permitted an understanding of the thermal behaviour of the material, and the detection of released hydrogen was examined by evolved gas analysis on a thermo-gravimetric analyser (TGA) coupled to a mass spectrometer (MS). Finally, in order to avoid fuel cell malfunctioning due to pollutant gases, an identification of the decomposition products was carried out.     

Experiments on hydrogen production from methanol steam reforming in the microchannel reactor

The entire experiments were conducted for microchannel methanol steam reforming, by which, the selection of catalyst, the operating parameters and the configuration of microchannels were discussed thoroughly. It was found that the higher the Cu concentration is, the more the corresponding active surface area of Cu will be, thereby improving the catalytic activity. The Cu-to-Zn ratio in Cu/ZnO/Al₂O₃ catalyst should be set at 1:1. The impacts of reaction temperature, feed flow rate, mixture temperature, and H₂O-to-CH₃OH molar ratio on the methanol conversion rate were also revealed and discussed. Characteristics of micro-reactors with various microchannels, including that 20 mm and 50 mm in length, as well as non-parallel microchannels, were investigated. It was found that the increase of microchannel length can improve the methanol conversion rate significantly. Besides, non-parallel microchannels help to maintain flow and temperature distribution uniformity, which can improve the performance of micro-reactor. In the present experiments, the presence of CO was under the condition that the methanol conversion rate was above 70%.     

Design of experiment to predict the time between hydrogen purges for an air-breathing PEM fuel cell in dead-end mode in a closed environment

Fuel cells are promising technologies for zero-emission energy conversion. They are used in several applications such as power plants, cars and even submarines. Hydrogen supply is crucial for such systems and using Proton Exchange Membrane Fuel Cell in dead-end mode is a solution to save hydrogen. Since water and impurities accumulate inside the stack, purging is necessary. However, the importance of operating parameters is not well known for fuel cells working in closed environments. A Design of Experiment approach, studying time between two purges and cell performance, was conducted on an air-breathing stack in a closed environment. The most influential parameters on the time between two purges are the relative humidity and the current load. Convection in the closed environment can decrease the stability of the fuel cell. A linear model with interactions between these last three parameters was found to accurately describe the studied responses.     

Modeling and analysis of flow distribution in an A-type microchannel reactor

Flow distribution among microchannels is a fatal factor affecting the performance of laminated microchannel reactors for hydrogen production. Homogeneous flow strongly depends on the structural design of the microchannel reactor. The present work concentrates on improving the flow distribution in microchannel reactors for hydrogen production by optimization of the structural design. An innovative A-type microchannel reactor for hydrogen production with one inlet/two outlets was developed and analyzed. The equivalent electrical resistance network model was used to calculate the flow distribution in the microchannel reactor which was validated by computational fluid dynamics (CFD). The influences of structural parameters on flow distribution in the A-type were investigated quantitatively. The calculated results showed that longer microchannels with a higher aspect ratio and a small side length in the manifolds were beneficial for attaining uniform flow distribution in the A-type microchannel reactor. Furthermore, it was found that flow distributions among the microchannels in the A-type were much more uniform than those in the conventional Z-type microchannel reactor with one inlet/one outlet. Finally, an optimization strategy was proposed to optimize the manifold geometries to obtain a comparatively even flow distribution among microchannels.     

Noble-metal-free Co@Co2P/N-doped carbon nanotube polyhedron as an efficient catalyst for hydrogen generation from ammonia borane

Developing an efficient catalyst for hydrogen (H₂) generation from hydrolysis of ammonia borane (AB) to significantly improve the activity for the hydrogen generation from AB is important for its practical application. Herein, we report a novel hybrid nanostructure composed of uniformly dispersed Co@Co₂P core-shell nanoparticles (NPs) embedded in N-doped carbon nanotube polyhedron (Co@Co₂P/N–CNP) through a carbonization-phosphidation strategy derived from ZIF-67. Benefiting from the electronic effect of P doping, high dispersibility and strong interfacial interaction between Co@Co₂P and N-CNTs, the Co@Co₂P/N–CNP catalyst exhibits excellent catalytic performance towards the hydrolysis of AB for hydrogen generation, affording a high TOF value of 18.4 mol H₂ mol metal^?1 min^?1 at the first cycle. This work provides a promising lead for the design of efficient heterogeneous catalysts towards convenient H₂ generation from hydrogen-rich substrates in the close future.     

The impact of ammonia feed distribution on the performance of a fixed bed membrane reactor for ammonia decomposition to ultra-pure hydrogen

In this study, the influence of distribution of ammonia feed along the height of a fixed bed membrane reactor (FBMR) for ammonia decomposition to hydrogen is investigated to understand the leverage of this approach. A rigorous heterogeneous model with verified kinetics is implemented to simulate the reactor. The simulation results indicate that the application of a distributed ammonia feed with equal distribution of injection points resulted in a 17.45% improvement in hydrogen production rate at a low temperature of 800.0 K over a FBMR without feed distribution. In the parameter space of this study, it has been shown that the ammonia conversion is sensitive to the number of distribution points and has an optimal value. It is found that the implication of the optimum number of injection points can substantially reduce the length of the reactor by 75.0% to achieve 100.0% ammonia conversion. The hydrogen reversal permeation phenomenon is observed at a low pressure and the upper part of the reactor. A novel configuration of a FBR and a FBMR with feed distribution is proposed for efficient production of ultra-pure hydrogen at a relatively low pressure. The critical reactor length ratio has been provided for this configuration.     

Dehydrogenation of perhydro-dibenzyltoluene for hydrogen production in a microchannel reactor

A preliminary study regarding the dehydrogenation of perhydro-dibenzyltoluene as a liquid organic hydrogen carrier with switching from a stirred tank reactor to a continuous flow microchannel reactor is presented. The hydrogen production percentage in the case of a continuous flow microchannel reactor was found greater when compared to that of a stirred tank reactor. The hydrogen production was increased from 64.1% to 82.2% with the increase in bottom plate temperature from 260 to 320 °C for 0.01 mL/min flow rate. A maximum of 88% of hydrogen was generated for a 40 hours of operation, at a bottom wall temperature of 290 °C. The kinetic model for the microchannel reactor dehydrogenation was presented with a pre-exponential factor of 3.272 s^?1 and activation energy of 13.79 kJ/mol. The results revealed that a continuous microchannel reactor can be an appropriate technology for the dehydrogenation of perhydro-dibenzyltoluene.     

A thermal performance evaluation of a new integrated gas turbine-based multigeneration plant with hydrogen and ammonia production

In this study, a new combined system driving a gas turbine cycle has been proposed for seven useful outputs of power, hydrogen, ammonia, heating-cooling, drying and hot water. The proposed integrated plant mainly consists of the gas turbine cycle, Rankine cycle, two organic Rankine cycles, ejector-based cooling, hydrogen production and liquefaction, ammonia production and storage, drying and hot water generation sub-systems. In order to demonstrate that the designed system is an efficient and environmentally plant, the performance analysis was performed by using a software package. Before performing the performance assessment of the plant, the mathematical model of the integrated plant is prepared in accordance with thermodynamic equations. Basic equilibrium equations are used for the thermodynamic equations used. Obtaining multiple useful outputs from the system also have the positive effect on the system effectiveness. The energetic effectiveness of integrated plant for multigeneration with hydrogen and ammonia production is computed to be 62.18% and exergetic efficiency is 58.37%. In addition, the energetic and exergetic effectiveness of hydrogen production and liquefaction process are 57.92% and 54.23%, respectively.     

Conceptual design of a novel ammonia-fuelled portable solid oxide fuel cell system

A novel portable electric power generation system, fuelled by ammonia, is introduced and its performance is evaluated. In this system, a solid oxide fuel cell (SOFC) stack that consists of anode-supported planar cells with Ni-YSZ anode, YSZ electrolyte and YSZ-LSM cathode is used to generate electric power. The small size, simplicity, and high electrical efficiency are the main advantages of this environmentally friendly system. The results predicted through computer simulation of this system confirm that the first-law efficiency of 41.1% with the system operating voltage of 25.6 V is attainable for a 100 W portable system, operated at the cell voltage of 0.73 V and fuel utilization ratio of 80%. In these operating conditions, an ammonia cylinder with a capacity of 0.8 l is sufficient to sustain full-load operation of the portable system for 9 h and 34 min. The effect of the cell operating voltage at different fuel utilization ratios on the number of cells required in the SOFC stack, the first- and second-law efficiencies, the system operating voltage, the excess air, the heat transfer from the SOFC stack, and the duration of operation of the portable system with a cylinder of ammonia fuel, are also studied through a detailed sensitivity analysis. Overall, the ammonia-fuelled SOFC system introduced in this paper exhibits an appropriate performance for portable power generation applications.     

Design of compact methanol reformer for hydrogen with low CO for the fuel cell power generation

The effect of the heat transfer area and the thermal conductivity of the reactor materials are evaluated with three identical structured reactors having multiple columned-catalyst bed and using three different reactor materials, aluminum alloy, brass and stainless steel. A series of compact methanol reformers are then designed and fabricated with the use of large reactor surface area in catalyst beds and high heat transfer constant to produce hydrogen fuel with 2–4 ppm of CO for the fuel cell (FC) power generation. The same design principle is successfully used for easy scale up of the reactor capacity from 250 L/h to 10,000 L/h. This low CO hydrogen (68–70%) used as the fuel for the fuel cell power generation provides a very competitive cost of hydrogen and electric power, $0.20–0.23/m³ of H₂ and $0.196/KWh, respectively.     

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.     

Analysis of heptane autothermal reformer to generate hydrogen for fuel cell applications

In this paper, reaction engineering principles are utilized to analyze process conditions for producing sufficient hydrogen in a heptane autothermal reformer for generating 1 kW of power in a fuel cell. It is shown that operating the reformer adiabatically results in a sharp decrease in temperature due to endothermic reactions, which results in low conversion of heptane. For this reason, a heating jacket is added to the reformer where heptane is combusted to provide heat for the endothermic reactions. It is observed that when the reactor is operated non-isothermally, it is possible to get complete conversion of heptane and produce sufficient hydrogen to generate 1 kW of power via a fuel cell.     

Cold-start performance of an ammonia-fueled spark ignition engine with an on-board fuel reformer

This work demonstrated the first-ever cold-start operation of an ammonia (NH₃)-fueled four-cylinder spark ignition engine with an on-board fuel reformer, applying autothermal reforming. In this system, an electrically heated NH₃-air mixture was provided to a reforming catalyst and approximately 3 s was found to elapse between the start of engine rotation and the onset of combustion. Stable fast idle operation in conjunction with a cold start was realized with a H₂-to-NH₃ molar ratio of 2:1. Nearly zero NH₃ emissions were achieved during cold start and fast idle until the engine warmed up, by adsorbing unburned NH₃ passing through a three-way catalyst before the catalyst was sufficiently warmed up. The NH₃ adsorption capacity of this system could be regenerated during the engine warm-up when the engine was running under lean conditions.     

A techno-economic evaluation of the hydrogen production for energy generation using an ethanol fuel processor

The techno-economic analysis of a process to convert ethanol into H₂ to be used as a fuel for PEM fuel cells of H₂-powered cars was done. A plant for H₂ production was simulated using experimental results obtained on monolith reactors for ethanol steam reforming and WGS steps. The steam reforming (Rh/CeSiO₂) and WGS (Pt/ZrO₂) monolith catalysts remained quite stable during long-term startup/shut down cycles, with no carbon deposition. The H₂ production cost was significantly affected by the ethanol price. The monolith catalyst costs contribution was lower than that of conventional reactors. The H₂ production cost obtained using the expensive Brazilian ethanol price (0.81 US$/L ethanol) was US$ 8.87/kg H₂, which is lower than the current market prices (US$ 13.44/kg H₂) practiced at H₂ refueling stations in California. This result showed that this process is economically feasible to provide H₂ as a fuel for H₂-powered cars at competitive costs in refueling stations.     

Highly efficient Co/NC catalyst derived from ZIF-67 for hydrogen generation through ammonia decomposition

Small-size cobalt nanoparticles (NPs) distributed on nitrogen doped carbon support (Co/NC-X) were prepared by pyrolysis of ZIF-67 at various temperatures (X = 500, 600,700 and 800 °C) in nitrogen atmosphere and utilized as catalysts for hydrogen production through ammonia decomposition. Characterizations of the catalysts including XRD, HRTEM, XPS, H₂-TPR, CO₂-TPD, etc., were conducted for structure analysis. The N–C plate obtained from pyrolysis was coated with Co NPs to hinder its aggregation, which made the Co NPs dispersed evenly and increased their dispersion. The calcination temperature and the strong base of the support can adjust the strength of Co–N bond. The activity of the Co/NC-X catalysts is attributed to the high content of Co⁰ and the moderate Co–N bond strength. The ammonia decomposition activity of Co/NC-X catalysts in this paper is higher than many reported Co-based catalysts. Co/NC-600 catalyst demonstrates an ammonia conversion of 80% at 500 °C with a space velocity of 30,000 ml g_cat^?1 h^?1, corresponding to a hydrogen production rate of 26.8 mmol H₂ g_cat^?1 min^?1. The work provides insight for the development of highly active cobalt-based catalysts for hydrogen production through ammonia decomposition.