Hydrogen production system combined with a catalytic reactor and a plasma membrane reactor from ammonia

Ammonia is a 1promising raw material for hydrogen production because it may solve several problems related to hydrogen transport and storage. Hydrogen can be effectively produced from ammonia via catalytic thermal decomposition; however, the resulting residual ammonia negatively influences the fuel cells. Therefore, a high-purity hydrogen production system comprising a catalytic decomposition reactor and a plasma membrane reactor (PMR) has been developed in this work. Most of the ammonia is converted to hydrogen and nitrogen by the catalytic reactor. After the product gas containing unreacted ammonia is introduced to the PMR, unreacted ammonia is decomposed and hydrogen is separated in the PMR. Based on these processes, hydrogen with a purity of 99.99% is obtained at the output of the PMR. Optimal operation conditions maximizing the hydrogen production flow rate were investigated. The gap length of the PMR and the gas differential pressure and applied voltage of the plasma influence the flow rate. A pure hydrogen flow rate of ∼120 L/h was achieved using the current operating conditions. The maximum energy efficiency of the developed hydrogen production system is 28.5%.     

Transient thermodynamic analysis of a novel integrated ammonia production,storage and hydrogen production system

A transient thermodynamic analysis is reported of a novel chemical hydrogen storage system using energy and exergy approaches. The hydrogen is stored chemically in ammonia using the proposed hydrogen storage system and recovered via the electrochemical decomposition of ammonia through an ammonia electrolyzer. The proposed hydrogen storage system is based on a novel subzero ammonia production reactor. A single stage refrigeration system maintains the ammonia production reactor at a temperature of −10 °C. The energy and exergy efficiencies of the proposed system are 85.6% and 85.3% respectively. The proposed system consumes 34.0 kJ of work through the process of storing 1 mol of hydrogen and recovering it using the ammonia electrolyzer. The system is simulated for filling 30,000 L of ammonia at a pressure of 5 bar, and the system was able to store 7500 kg of ammonia in a liquid state (1% vapor) in 1500 s. The system consumes nearly 45.3 GJ of energy to store the 7500 kg of ammonia and to decompose it to reproduce the stored hydrogen during the discharge phase.     

An integrated system for ammonia production from renewable hydrogen: A case study

This study presents an analysis and assessment study of an integrated system which consists of cryogenic air separation unit, polymer electrolyte membrane electrolyzer and reactor to produce ammonia for a selected case study application in Istanbul, Turkey. A thermodynamic analysis of the proposed system illustrates that electricity consumption of PEM electrolyzer is 3410 kW while 585.4 kW heat is released from ammonia reactor. The maximum energy and exergy efficiencies of the ammonia production system which are observed at daily average irradiance of 200 W/m² are found as 26.08% and 30.17%, respectively. The parametric works are utilized to find out the impacts of inlet air conditions and solar radiation intensity on system performance. An increase in the solar radiation intensity results in a decrease of the efficiencies due to higher potential of solar influx. Moreover, the mass flow rate of inlet air has a substantial effect on ammonia production concerning the variation of generated nitrogen. The system has a capacity of 0.22 kg/s ammonia production which is synthesized by 0.04 kg/s H₂ from PEM electrolyzer and 0.18 kg/s N₂ from a cryogenic air separation unit. The highest exergy destruction rate belongs to PEM electrolyzer as 736.2 kW while the lowest destruction rate is calculated as 3.4 kW for the separation column.     

Hydrogen production from ammonia by the plasma membrane reactor

A new plasma membrane reactor (PMR) was developed to efficiently produce hydrogen from NH₃ with the use of atmospheric pressure plasma and a hydrogen separation membrane. The generation of high-purity hydrogen from NH₃ was also examined. First, hydrogen gas flowing into the PMR revealed the effect of the PMR on hydrogen separation. Hydrogen separation depends on the partial pressure of hydrogen gas supplied (P_{in, H2}) and permeated (P_{out, H2}) when P_{in, H2}^0.5 − P_{out, H2}^0.5 > 0. Second, NH₃ gas flowing into the PMR revealed its hydrogen production characteristics: the maximum hydrogen conversion rate of a typical plasma reactor (PR) is 13%, whereas the PMR converted 24.4%. Hydrogen obtained by hydrogen separation was approximately 100% pure. A hydrogen generation rate of 20 mL/min was stably obtained.     

Enhanced generation of hydrogen,power, and heat with a novel integrated photoelectrochemical system

Hydrogen is an essential component of power-to-gas technologies that are needed for a complete transition to renewable energy systems. Although hydrogen has zero GHG emissions at the end-use point, its production could become an issue if non-renewable, and pollutant energy and material resources are used in this step. Therefore, a crucial step for the fully developed hydrogen economy is to find alternative hydrogen production methods that are clean, efficient, affordable, and reliable. With this motivation, in this study, an integrated and continuous type of hydrogen production system is designed, developed, and investigated. This system has three components. There is a solar spectral splitting device (Unit I), which splits the incoming solar energy into two parts. Photons with longer wavelength is sent to the photovoltaic thermal hybrid solar collector, PV/T, (Unit II) and used for combined heat and power generation. Then the remaining part is transferred to the novel hybrid photoelectrochemical-chloralkali reactor (Unit III) for simultaneous H₂, Cl₂, and NaOH production. This system has only one energy input, which is the solar irradiation and five outputs, namely H₂, Cl₂, NaOH, heat, and electricity. Unlike most of the studies in the literature, this system does not use only PV or only a photoelectrochemical reactor. With this approach, solar energy utilization is maximized, and the wasted portion is minimized. By selecting PV/T rather than PV, the performance of the panels is maximized because recovering the by-product heat as a system output in addition to electricity, and the PV/T has less waste and higher efficiency. The present reactor does not use any additional electron donors, so the wastewater discharge is only depleted NaCl solution, which makes the system significantly cleaner than the ones available in the literature. The specific aim of this study is to demonstrate the optimum operating parameters to reach the maximum achievable production rates and efficiencies while keeping the exergy destruction as little as possible. In this study, there are four case studies, and in each case study, one decision variable is optimized to get the desired performance results. Within the selected operating parameter range, all performance criteria (except exergy destruction) are normalized and ranked for proper comparison. The maximum production rates and efficiencies with the least possible exergy destruction are observed at the operating temperature of 30 °C. At 30 °C, 4.18 g/h H₂, 127.55 g/h Cl₂, 151 W electricity, and 716 W heat are produced with an exergy destruction rate of 95.74 W and 78% and 30% energy and exergy efficiencies, respectively.     

Energy and exergy analyses and optimization study of an integrated solar heliostat field system for hydrogen production

In this paper, we propose an integrated system, consisting of a heliostat field, a steam cycle, an organic Rankine cycle (ORC) and an electrolyzer for hydrogen production. Some parameters, such as the heliostat field area and the solar flux are varied to investigate their effect on the power output, the rate of hydrogen produced, and energy and exergy efficiencies of the individual systems and the overall system. An optimization study using direct search method is also carried out to obtain the highest energy and exergy efficiencies and rate of hydrogen produced by choosing several independent variables. The results show that the power and rate of hydrogen produced increase with increase in the heliostat field area and the solar flux. The rate of hydrogen produced increases from 0.006 kg/s to 0.063 kg/s with increase in the heliostat field area from 8000 m² to 50,000 m². Moreover, when the solar flux is increased from 400 W/m² to 1200 W/m², the rate of hydrogen produced increases from 0.005 kg/s to 0.018 kg/s. The optimization study yields maximum energy and exergy efficiencies and the rate of hydrogen produced of 18.74%, 39.55% and 1571 L/s, respectively.     

Comparative assessments of two integrated systems with/without fuel cells utilizing liquefied ammonia as a fuel for vehicular applications

In the current study, two different integrated systems for vehicular applications are presented and thermodynamically analyzed. The first system consists of liquefied ammonia tank, dissociation and separation unit (DSC) for decomposition of ammonia and an internal combustion engine (ICE) to power the vehicle. The second system is a hybrid system consisting of liquefied ammonia tank, DSC unit, a small ICE and a fuel cell system. In the second system, the main power unit is fuel cell and a supplementary internal combustion engines is also utilized. The exhaust gasses emitted from the ICE are used to provide the required heat for the thermal decomposition process of ammonia. The ICE is fueled with a mix of ammonia and hydrogen generated from the DSC unit that is installed in the two systems. Hydrogen generated from DSC unit will be utilized to operate fuel cell installed in system 2. The proposed systems are analyzed and assessed both energetically and exergetically. A comprehensive parametric study is carried out for comparative assessments to determine the influence of altering design and operating parameters such as the amount of ammonia fuel supplied to the two systems on the performance of the two systems. The overall energy and exergy efficiencies for system 1 and system 2 are found to be 61.89%, 63.34%, 34.73% and 38.44% respectively. The maximum exergy destruction rate in the two systems occurred in the ICE.     

Exergoeconomic analysis and optimization of a concentrated sunlight-driven integrated photoelectrochemical hydrogen and ammonia production system

The study presented here concerns a comprehensive investigation on exergoeconomic analysis and optimization of an integrated system for photoelectrochemical hydrogen and electrochemical ammonia production. The present integrated system consists of a solar concentrator, spectrum-splitting mirrors, a photoelectrochemical hydrogen production reactor, a photovoltaic module, an electrochemical ammonia production reactor and support mechanisms. Detailed thermodynamic and exergoeconomic analyses are initially conducted to determine the performance of the integrated system namely; efficiency and total cost rate. The obtained performance parameters are then optimized to yield the minimum cost rate and maximum efficiency under given constraints of the experimental system. The highest capital cost rates are observed in the photoelectrochemical hydrogen and electrochemical ammonia production reactors because of high procurement costs and electricity inputs. The optimized values for exergy efficiency of the integrated system range from 5% to 9.6%. The photovoltaic and photoelectrochemical cell areas and solar light illumination mainly affect the overall system efficiencies. The optimum efficiencies are found to be 8.7% and 5% for the multi-objective optimization of hydrogen production and integrated ammonia production system, respectively. When the exergy efficiency of the integrated system is maximized and the total cost rate is minimized at the same time, the total cost rate of the system is calculated to be about 0.2 $/h. The cost sensitivity analysis results of the present study show that the total cost rate of the system is mostly affected by the interest rate and lifetime of the system.     

Exergy study of hydrogen cogeneration and seawater desalination coupled to the HTR-PM nuclear reactor

This work presents a novel integration system of the high-temperature gas-cooled reactor-pebble bed module project to a hydrogen production process using the iodine-sulfur cycle in cogeneration with seawater desalination. The current approach includes a Rankine cycle, a sulfur-iodine thermochemical cycle for hydrogen production and a multi-stage flash desalination process. The use of a catalyst that allows the H₂SO₄ decomposition reaction to being carried out at temperatures compatible with the nuclear reactor project is considered. The residual heat from the acid decomposition reactions is used to desalinate seawater through the multi-stage flash process. A chemical process simulator is used to create a computational model that allows estimates of global and local efficiencies of the proposed flow diagram. Some operating parameters were sized, and their influence on the efficiency is also reported. The proposed model for the sulfur-iodine cycle can produce 0.41 kg/s of hydrogen with partial energy and exergetic efficiency of 37.35% and 38.64%. The desalination process can process 40.70 kg/s with energy and exergy efficiencies of 58.78% and 82.66%, respectively. The higher exergy destruction share is obtained in the heat exchangers (36.55%), chemical reactors (16.56%) and separators (12.80%). The global system showed efficiencies of 40.13% and 52.04%, respectively.     

Hydrogen production through biomass gasification in supercritical water: A review from exergy aspect

Hydrogen production through supercritical water gasification (SWG) of biomass has been widely studied. This study reviews the main factors from exergy aspect, and these include feedstock characteristics, biomass concentration, gasification temperature, residence time, reaction catalyst, and reactor pressure. The results show that the exergy efficiencies of hydrogen production are mainly in the range of 0.04–42.05%. Biomass feedstock may affect hydrogen production by changing the H₂ yield and the heating value of biomass. Increases in biomass concentrations decrease the exergy efficiencies, increases in gasification temperatures generally increase the exergy efficiencies, and increases in residence times may initially increase and finally decrease the exergy efficiencies. Reaction catalysts also have positive effects on the exergy efficiencies, and the reviewed results show that the effects are followed KOH > K₂CO₃ > NaOH > Na₂CO₃. Reactor pressure may have positive, negative or negligible effects on the exergy efficiencies.     

Kinetic and thermodynamic analyses of mid/low-temperature ammonia decomposition in solar-driven hydrogen permeation membrane reactor

It is a promising method for hydrogen generation without carbon emitting by ammonia decomposition in a catalytic palladium membrane reactor driven by solar energy, which could also store and convert solar energy into chemical energy. In this study, kinetic and thermodynamic analyses of mid/low-temperature solar thermochemical ammonia decomposition for hydrogen generation in membrane reactor are conducted. Hydrogen permeation membrane reactor can separate the product and shift the reaction equilibrium forward for high conversion rate in a single step. The variation of conversion rate and thermodynamic efficiency with different characteristic parameters, such as reaction temperature (100–300 °C), tube length, and separation pressure (0.01–0.25 bar), are studied and analyzed. A near-complete conversion of ammonia decomposition is theoretically researched. The first-law thermodynamic efficiency, net solar-to-fuel efficiency, and exergy efficiency can reach as high as 86.86%, 40.08%, and 72.07%, respectively. The results of this study show the feasibility of integrating ammonia decomposition for hydrogen generation with mid/low-temperature solar thermal technologies.     

Thermodynamic and thermoeconomic assessment of hydrogen production employing an efficient multigeneration system based on rich fuel combustion

The recent development of distributed multigeneration energy systems is changing the focus of producing different energy vectors from large centralized plants to local energy systems. A novel multigeneration system is designed in the present work to supply domestic energy demands of power, hydrogen and heating. The proposed system mainly consists of a supercritical CO₂ cycle, a gas turbine equipped with a rich-fueled combustion chamber, a membrane for hydrogen separation and a water-gas shift reactor. Feeding the combustion chamber with a rich fuel mixture leads to the availability of a significant hydrogen amount in the products, which can be separated and stored. Thermodynamic analysis revealed that the highest irreversibility belongs to the combustion chamber, which is responsible for almost half of total exergy destruction. The cost of the produced hydrogen is estimated to be 2.2–6.8 $/kg for a natural gas price of 9.51 $/GJ and equivalence ratios of 2.9–1.65. The overall energy and exergy efficiencies, hydrogen production rate, total system cost rate, and cost of produced electricity are found to be 75.1%, 58.9%, 40.6 kg/h, 222 $/h and 51 $/MWh, respectively, assuming an equivalence ratio of 2.     

Exergy analysis of a simulation of the sulfuric acid decomposition process of the SI cycle for nuclear hydrogen production

This article details comprehensive energy and exergy analyses of the sulfuric acid decomposition process of the sulfur–iodine (SI) thermochemical cycle for hydrogen production. Energy and exergy efficiencies of the proposed process were evaluated over a variety of reaction temperatures and pressures. At an atmospheric temperature of 25 °C, the calculated values of exergy destruction of the H₂SO₄ decomposer ranged between 157 kJ/mol and 360 kJ/mol over reaction temperatures of 800–1000 °C and pressures between 1 and 50 atm. It was shown that the exergy efficiency of the H₂SO₄ decomposer improved with an increase in reaction temperature, while reaction pressure had a negative effect on exergy efficiency.     

Performance assessment of an electrochemical hydrogen production and storage system for solar hydrogen refueling station

This paper investigates the performance of a hydrogen refueling system that consists of a polymer electrolyte membrane electrolyzer integrated with photovoltaic arrays, and an electrochemical compressor to increase the hydrogen pressure. The energetic and exergetic performance of the hydrogen refueling station is analyzed at different working conditions. The exergy cost of hydrogen production is studied in three different case scenarios; that consist of i) off-grid station with the photovoltaic system and a battery bank to supply the required electric power, ii) on-grid station but the required power is supplied by the electric grid only when solar energy is not available and iii) on-grid station without energy storage. The efficiency of the station significantly increases when the electric grid empowers the system. The maximum energy and exergy efficiencies of the photovoltaic system at solar irradiation of 850 W m-2 are 13.57% and 14.51%, respectively. The exergy cost of hydrogen production in the on-grid station with energy storage is almost 30% higher than the off-grid station. Moreover, the exergy cost of hydrogen in the on-grid station without energy storage is almost 4 times higher than the off-grid station and the energy and exergy efficiencies are considerably higher.     

Direct high-purity hydrogen production from ammonia by using a membrane reactor combining V-10mol%Fe hydrogen permeable alloy membrane with Ru/Cs2O/Pr6O11 ammonia decomposition catalyst

The hydrogen production capabilities of the membrane reactor combining V-10 mol%Fe hydrogen permeable alloy membrane with Ru/Cs₂O/Pr₆O₁₁ ammonia decomposition catalyst are studied. The ammonia conversion is improved by 1.7 times compared to the Ru/Cs₂O/Pr₆O₁₁ catalyst alone by removing the produced hydrogen through the V-10mol%Fe alloy membrane during the ammonia decomposition. 79% of the hydrogen atoms contained in the ammonia gas are extracted directly as high-purity hydrogen gas. Both the Ru/Cs₂O/Pr₆O₁₁ catalyst and the V-10 mol% Fe alloy membrane are highly durable, and the initial performance of the hydrogen separation rate lasts for more than 3000 h. The produced hydrogen gas conforms to ISO 14687–2:2019 Grade D for fuel cell vehicles because the ammonia and nitrogen concentrations are less than 0.1 ppm and 100 ppm, respectively.     

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%.     

A review on biomass‐based hydrogen production and potential applications

In this paper, a detailed review is presented to discuss biomass‐based hydrogen production systems and their applications. Some optimum hydrogen production and operating conditions are studied through a comprehensive sensitivity analysis on the hydrogen yield from steam biomass gasification. In addition, a hybrid system, which combines a biomass‐based hydrogen production system and a solid oxide fuel cell unit is considered for performance assessment. A comparative thermodynamic study also is undertaken to investigate various operational aspects through energy and exergy efficiencies. The results of this study show that there are various key parameters affecting the hydrogen production process and system performance. They also indicate that it is possible to increase the hydrogen yield from 70 to 107 g H₂ per kg of sawdust wood. By studying the energy and exergy efficiencies, the performance assessment shows the potential to produce hydrogen from steam biomass gasification. The study further reveals a strong potential of this system as it utilizes steam biomass gasification for hydrogen production. To evaluate the system performance, the efficiencies are calculated at particular pressures, temperatures, current densities, and fuel utilization factors. It is found that there is a strong potential in the gasification temperature range 1023–1423 K to increase energy efficiency with a hydrogen yield from 45 to 55% and the exergy efficiency with hydrogen yield from 22 to 32%, respectively, whereas the exergy efficiency of electricity production decreases from 56 to 49.4%. Hydrogen production by steam sawdust gasification appears to be an ultimate option for hydrogen production based on the parametric studies and performance assessments that were carried out through energy and exergy efficiencies. Finally, the system integration is an attractive option for better performance. Copyright © 2012 John Wiley & Sons, Ltd.     

Development of a sustainable multi-generation system with re-compression sCO2 Brayton cycle for hydrogen generation

Current research aims to develop, design, and analyze a novel solar-assisted multi-purpose energy generation system for hydrogen production, electricity generation, refrigeration, and hot water preparation. The suggested system comprises a solar dish for supplying the necessary heat demand, a re-compression carbon dioxide-based Brayton cycle, a PEM electrolyzer for hydrogen generation, an ejector refrigeration system working with ammonia, and a hot water preparation system. The first law and exergy analyses are implemented to determine the performance of the multi-generation plant with various outputs. Besides, the exergo-environmental evaluation of the plant is conducted for the environmental impacts of the plant. Furthermore, parametric analyses are executed for investigating the system outputs, exergy destruction rate, and system efficiencies. According to the results, the rate of hydrogen generated by means of the multi-generation power plant is determined to be 0.062 g/s which corresponds to an hourly production of 0.223 kg. Besides, with the utilization of the supercritical closed Brayton cycle, a power generation rate of 74.86 kW is achieved. Furthermore, the irreversibility of the overall plant is estimated as 535.7 kW in which the primary contributor of this amount is the solar system with a destruction rate of 365.5 kW.     

Performance assessment of hydrogen production from a solar-assisted biomass gasification system

In this study, we investigate a solar-assisted biomass gasification system for hydrogen production and assess its performance thermodynamically using actual literature data. We also analyze the entire system both energetically and exergetically and evaluate its performance through both energy and exergy efficiencies. Three feedstocks, namely beech charcoal, sewage sludge and fluff, are considered as samples in the same reactor. While energy efficiencies vary from 14.14% to 27.29%, exergy efficiencies change from 10.43% to 23.92%. We use a sustainability index (SI), as a function of exergy efficiency, to calculate the impacts on sustainable development and environment. This index changes from 1.12 to 1.31 due to intensive utilization of solar energy. Also, environmental impact of these systems is evaluated through calculating the specific greenhouse gas (GHG) emissions. They are determined to be 17.97, 17.51 and 26.74 g CO₂/MJ H₂ for beech charcoal, sewage sludge and fluff, respectively.     

Development of a novel combined energy plant for multigeneration with hydrogen and ammonia production

In order to meet the energy and fuel needs of societies in a sustainable way and hence preserve the environment, there is a strong need for clean, efficient and low-emission energy systems. In this regard, it is aimed to generate cleaner energy outputs, such as electricity, hydrogen and ammonia as well as some additional useful commodities by utilizing both methane gas and the waste heat of an integrated unit to the whole system. In this paper, a novel multi-generation plant is proposed to generate power, hydrogen and ammonia as a chemical fuel, drying, freshwater, heating, and cooling. For this reason, the Brayton cycle as prime unit using methane gas is integrated into the s-CO₂ power cycle, organic Rankine cycle, PEM electrolyzer, freshwater production unit, cooling cycle and dryer unit. In order then to evaluate the designed integrated multigeneration system, thermodynamic analyses and parametric studies are performed, revealing that the energy and exergy efficiencies of the whole plant are found to be 69.08% and 65.42%. In addition, ammonia and hydrogen production rates have been found to be 0.2462 kg/s and 0.0631 kg/s for the methane fuel mass flow rate of 1.51 kg/s. Also, the effects of the reference temperature, pinch point temperature of superheater, combustion chamber temperature, gas turbine input pressure, and mass flow rate of fuel on numerous parameters and performance of the plant are investigated.