Experimental study on sulfur trioxide decomposition in a volumetric solar receiver–reactor

Process conditions for the direct solar decomposition of sulfur trioxide have been investigated and optimized by using a receiver–reactor in a solar furnace. This decomposition reaction is a key step to couple concentrated solar radiation or solar high‐temperature heat into promising sulfur‐based thermochemical cycles for solar production of hydrogen from water. After proof‐of‐principle a modified design of the reactor was applied. A separated chamber for the evaporation of the sulfuric acid, which is the precursor of sulfur trioxide in the mentioned thermochemical cycles, a higher mass flow of reactants, an independent control and optimization of the decomposition reactor were possible. Higher mass flows of the reactants improve the reactor efficiency because energy losses are almost independent of the mass flow due to the predominant contribution of re‐radiation losses. The influence of absorber temperature, mass flow, reactant initial concentration, acid concentration, and residence time on sulfur trioxide conversion and reactor efficiency has been investigated systematically. The experimental investigation was accompanied by energy balancing of the reactor for typical operational points. The absorber temperature turned out to be the most important parameter with respect to both conversion and efficiency. When the reactor was applied for solar sulfur trioxide decomposition only, reactor efficiencies of up to 40% were achieved at average absorber temperature well below 1000°C. High conversions almost up to the maximum achievable conversion determined by thermodynamic equilibrium were achieved. As the re‐radiation of the absorber is the main contribution to energy losses of the reactor, a cavity design is predicted to be the preferable way to further raise the efficiency. Copyright © 2009 John Wiley & Sons, Ltd.     

A distributed energy system integrating SOFC-MGT with mid-and-low temperature solar thermochemical hydrogen fuel production

Solar thermochemical hydrogen production with energy level upgraded from solar thermal to chemical energy shows great potential. By integrating mid-and-low temperature solar thermochemistry and solid oxide fuel cells, in this paper, a new distributed energy system combining power, cooling, and heating is proposed and analyzed from thermodynamic, energy and exergy viewpoints. Different from the high temperature solar thermochemistry (above 1073.15 K), the mid-and-low temperature solar thermochemistry utilizes concentrated solar thermal (473.15–573.15 K) to drive methanol decomposition reaction, reducing irreversible heat collection loss. The produced hydrogen-rich fuel is converted into power through solid oxide fuel cells and micro gas turbines successively, realizing the cascaded utilization of fuel and solar energy. Numerical simulation is conducted to investigate the system thermodynamic performances under design and off-design conditions. Promising results reveal that solar-to-hydrogen and net solar-to-electricity efficiencies reach 66.26% and 40.93%, respectively. With the solar thermochemical conversion and hydrogen-rich fuel cascade utilization, the system exergy and overall energy efficiencies reach 59.76% and 80.74%, respectively. This research may provide a pathway for efficient hydrogen-rich fuel production and power generation.     

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.     

Energy and exergy analysis of hydrogen production from ammonia decomposition systems using non-thermal plasma

In the current study, the energy and exergy efficiencies of three hydrogen production systems from ammonia decomposition using dielectric barrier discharge plasma (DBD) were comparatively evaluated. The hydrogen gas was separated in a cylindrical plasma membrane reactor (PMR) using the Pd–Cu40% membrane with a thickness of 20 μm. The pre-catalytic reactor (CR) is added to the second system (CR-PMR), additionally, the CR is filled with the catalytic material type of 2%Ru/Al₂O₃ and the CR temperature is raised to 450 °C. Furthermore, the zeolite material type of SA-600 A was added to the PMR in the third H₂ production system (PMR) to enhance the hydrogen permeation through the Pd–Cu membrane. The hydrogen production rate was enhanced by combining the plasma and zeolite material in the third system (CR-CPMR). Moreover, the maximum obtained hydrogen production rates were 2.66, 81.6, and 96.6% in PMR, CR-PMR, and CR-CPMR or catalytic PMR, respectively. Also, it was observed that the energy efficiency increased by adding the CR to the system, while, the exergy efficiency values of all ammonia decomposition systems were still low due to the effect of system irreversibility. Additionally, the maximum energy efficiencies values were 0.8, 16.1, 44.1%, while the maximum exergy efficiencies values were 0.156, 4.91, and 6.344% for PMR, CR-PMR, and CR-CPMR, respectively. The exergy destruction rate of all NH₃ decomposition systems was still high although using the modified systems. The depletion factor is enhanced with the feeding ammonia flow rate increased while the sustainability index decreased at the same flow rates. Moreover, it was seen that the depletion factor results of PMR only were higher than other systems due to the exergy destruction rate was high.     

Enhancing the ammonia to hydrogen (ATH) energy efficiency of alternating current arc discharge

In order to enhance the ammonia to hydrogen (ATH) energy efficiency, systematic study was carried out with atmospheric pressure alternating current arc discharge reactor (using a pair of stainless steel (SS) tube electrodes). Results showed that, using small-diameter SS tube electrodes with small discharge gaps forced more ammonia molecules to go through the effective plasma volume and obtained high electrodes temperature. Adopting low discharge frequency increased the discharge time, the effective plasma volume and the electrode temperature. These changes can enhance both the gas-phase plasma decomposition and the electrode-surface catalytic decomposition of ammonia. Insulating the reactor significantly increased the electrode temperature in small-diameter reactor, so as to enhance the electrode-surface catalytic decomposition of ammonia. In large-diameter reactors, however, the electrodes temperature increased less rapidly and more ammonia bypass of the effective plasma volume occurred. A 12.5 mol/kW h ATH energy efficiency was reached when ammonia was completely converted under the conditions of electrode diameter 3 mm, electrode gap 4 mm, discharge frequency 5 kHz, reactor diameter 8 mm, NH₃ flow rate 150 ml/min and input power 48 W. The ATH energy efficiency was further enhanced under similar conditions when incomplete ammonia conversion was allowed.     

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%.     

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.     

Integration of direct carbon and hydrogen fuel cells for highly efficient power generation from hydrocarbon fuels

In view of impending depletion of hydrocarbon fuel resources and their negative environmental impact, it is imperative to significantly increase the energy conversion efficiency of hydrocarbon-based power generation systems. The combination of a hydrocarbon decomposition reactor with a direct carbon and hydrogen fuel cells (FC) as a means for a significant increase in chemical-to-electrical energy conversion efficiency is discussed in this paper. The data on development and operation of a thermocatalytic hydrocarbon decomposition reactor and its coupling with a proton exchange membrane FC are presented. The analysis of the integrated power generating system including a hydrocarbon decomposition reactor, direct carbon and hydrogen FC using natural gas and propane as fuels is conducted. It was estimated that overall chemical-to-electrical energy conversion efficiency of the integrated system varied in the range of 49.4–82.5%, depending on the type of fuel and FC used, and CO₂ emission per kW_elh produced is less than half of that from conventional power generation sources.     

Ammonia decomposition reaction to produce COx-free hydrogen using carbon supported cobalt catalysts in microwave heated reactor system

In this study, COx-free hydrogen production via decomposition of ammonia was investigated in the microwave reactor using carbon supported cobalt-containing catalysts. Two different carbon sources, namely mesoporous carbon and activated carbon, were utilized and catalysts were successfully synthesized following an impregnation procedure. Different characterization techniques, such as ICP-OES, X-Ray Diffraction (XRD), Nitrogen Physisorption, Transmission Electron Microscopy (TEM), Raman Spectroscopy were applied to determine the structural properties of the catalysts. Total conversion of ammonia was achieved over carbon supported cobalt catalysts at about 350–400 °C under pure ammonia flow (GHSV_NH3 of 36,000 ml/g_cat.h). Significantly higher conversion values could be achieved in microwave reactor due to the its superior properties, such as selective heating, compared to conventional reactor. Microwave energy would probably facilitate the recombinative desorption of bonded N atoms from cobalt active species during ammonia decomposition reaction resulted in higher conversion values comparatively lower reaction temperature.     

Thermodynamic analysis of a multigeneration system using solid oxide cells for renewable power-to-X conversion

A hybrid renewable-based integrated energy system for power-to-X conversion is designed and analyzed. The system produces several valuable commodities: Hydrogen, electricity, heat, ammonia, urea, and synthetic natural gas (SNG). Hydrogen is produced and stored for power generation from solar energy by utilizing solid oxide electrolyzers and fuel cells. Ammonia, urea, and synthetic natural gas are produced to mitigate hydrogen transportation and storage complexities and act as energy carriers or valuable chemical products. The system is analyzed from a thermodynamic perspective, the exergy destruction rates are compared, and the effects of different parameters are evaluated. The overall system's energy efficiency is 56%, while the exergy efficiency is 14%. The highest exergy destruction occurs in the Rankine cycle with 48 MW. The mass flow rates of the produced chemicals are 0.064, 0.088, and 0.048 kg/s for ammonia, urea, and SNG, respectively.     

Preparation of Ru–Cs catalyst and its application on hydrogen production by ammonia decomposition

Ammonia can be a hydrogen source for many applications including fuel cells. Using Ru or Cs–Ru as the catalyst, hydrogen is generated from ammonia by decomposition reaction. These catalysts are deposited on carbon powder by either chemical reduction or precipitation method in this study. Different carbon powder pre-treatment solutions and catalyst deposition conditions are evaluated. Nitric acid pre-treatment followed by precipitation at pH of 6 produces the highest catalyst loading from solution with given concentration of catalyst precursor. Hydrogen generation rate is measured at different catalyst compositions, ammonia inlet flow rates, decomposition temperatures, amount of catalyst packing, and ratio of Cs/Ru. The optimal condition for the ammonia decomposition reaction is Cs/Ru weight ratio at 3, ammonia inlet flow at 6 ml min⁻¹, reaction temperature at 400 °C. At this condition, the ammonia conversion rate reaches 90% and hydrogen generation rate reaches 29.8 mmol/min-g_cat.     

A thermochemical reactor design with better thermal management and improved performance for methane/carbon dioxide dry reforming

A solar thermochemical reactor with better thermal management is proposed to improve the performance for dry reforming of methane. Conical cavity is introduced in the thermochemical reactor to adjust incident solar radiation distribution. Preheating area is adopted to recover sensible heat from gas outlet. Multiphysical model is presented for analyzing the overall performance of the reactor under different inlet flow rates. Also, local ideal reaction temperature required for maximizing local hydrogen production is analyzed according to the reaction kinetics. It is shown that better synergy between real temperature distribution and ideal temperature requirement can be achieved in this new reactor. Compared with conventional reactor, the present reactor exhibits the better performance in terms of reactant conversion, energy storage efficiency and hydrogen yield. Particularly, hydrogen yield is increased by 4.31%–17.12% at inlet flow rates between 6 and 12 L min^?1.     

基于太阳能热驱动甲烷重整制氢的燃料电池发电系统性能研究

该文采用Aspen Plus软件建立膜反应器重整制氢及燃料电池模型,根据拉萨某日太阳能直接辐射强度（DNI）变化计算太阳能可供使用的能量,作为外热源输入重整系统,并分析反应温度、水碳比（S/C）及DNI对该系统各性能指标的影响,性能指标包括甲烷转化率、H₂收率、电池功率及电压、太阳能转换为氢能的效率。结果表明：反应温度为500 ℃,S/C为2.5时有利于太阳能甲烷湿重整反应;系统日性能结果显示在某日10:00—20:00时,电池输出功率120 kW,太阳能-化学能转化效率0.368,系统发电效率0.225。     

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.     

Hydrogen production from methane using vanadium-based catalytic membrane reactors

The application of vanadium-based membranes as the hydrogen separation membrane for a catalytic membrane reactor system was investigated for the direct production of hydrogen from methane. The methane conversion and hydrogen production rates of the catalytic membrane reactor system with Pd-coated 100 μm-thick vanadium-based membranes were comparable with the reactor using 50 μm-thick Pd–Ag alloy membrane at all temperatures examined. The methane conversion rates of the catalytic membrane reactor with the Pd-coated vanadium-based membranes were approximately 35% and 62% at 623 K and 773 K, respectively. The hydrogen production rates were around 660  μmol min⁻¹ at 623 K, and reached over 1710  μmol min⁻¹ at 773 K. The relationship between the methane conversion rates and hydrogen permeation fluxes of the catalytic membrane reactor confirmed that the removal of hydrogen from the reaction site enhances the methane decomposition reaction. Further, the vanadium based membrane exhibited good stability against Fe in a hydrogen containing atmosphere.     

A bifunctional electrochemical flow cell integrating ammonia production and electricity generation for renewable energy conversion and storage

Renewable energy has rapidly advanced in the global energy system, triggering the visible development of energy storage technologies in recent decades. Among them, the electricity-fuel-electricity approach is an effective way for the storage and utilization of renewable power. In this work, a bifunctional electrochemical flow cell integrating both ammonia production and electricity generation modes is developed for renewable energy conversion and storage. Ammonia, a hydrogen carrier having a high hydrogen content of 17.6 wt %, is relatively easier to convert to liquid phase for large-scale storage. The long-distance ammonia transport can reliably depend on the established infrastructure. In addition, as a carbon-free fuel beneficial for achieving the goal of carbon-neutrality, ammonia is considered as an environmentally benign and cost-effective mediator fuel. This flow cell is able to operate via two modes, i.e., an ammonia-production mode for energy storage in the form of ammonia (via nitrogen reduction reaction) and an electricity-generation mode for energy conversion in the form of electricity (via ammonia oxidation reaction). This flow cell is constituted by a PtAu/C-coated nickel-foam electrode for nitrogen and oxygen reduction reactions, a Pt/C-coated nickel-foam electrode for water and ammonia oxidation reactions, and an alkaline anion exchange membrane for charge-carrier migration. Charging this flow cell with the supply of nitrogen results in a Faradaic efficiency of 2.70% and an ammonia production rate as high as 9.34 × 10^?10 mol s^?1 cm^?2 at 23 °C. Moreover, energizing this flow cell with ammonia results in an open-circuit voltage of 0.59 V and a peak power density of 3.31 mW cm^?2 at 23 °C. A round-trip efficiency of 25.7% is realized with the constant-electrode mode.     

Influence of process parameters on direct solar-thermal hydrogen and graphite production via methane pyrolysis

Current hydrogen and carbon production technologies emit massive amounts of CO₂ that threaten Earth's climate stability. Here, a new solar-thermal methane pyrolysis process involving flow through a fibrous carbon medium to produce hydrogen gas and high-value graphitic carbon product is presented and experimentally quantified. A 10 kW_e solar simulator is used to instigate the methane decomposition reaction with direct irradiation in a custom solar reactor. From localized solar heating of fibrous medium, the process reaches steady-state thermal and chemical operation from room temperature within the first minute of irradiation. Additionally, no measurable carbon deposition occurs outside the fibrous medium, leaving the graphitic product in a form readily extractable from the solar reactor. Parametric variations of methane inlet flow rate (10–2000 sccm), solar power (0.92–2.49 kW) and peak flux (1.3–3.5 MW/m²), operating pressure (1.33–40 kPa), and medium thickness (0.36–9.6 mm) are presented, with methane conversion varying from 22% to 96%.     

Techno-economic analysis and life cycle assessment for electrochemical ammonia production using proton conducting membrane

Green ammonia production is facing increasing interest on a global scale as a hydrogen carrier for power generation as well as fertilizer for food production. The conventional Haber-Bosch method for ammonia synthesis is energy demanding, requires high purity hydrogen, and is based on fossil fuels. A preliminary techno-economic model for electrochemical ammonia synthesis at near ambient pressure using feed rates of 32 metric ton/day for hydrogen and 135 metric ton/day for nitrogen is presented in this study. Various pathways using different methods for nitrogen generation and hydrogen production were investigated to gain insight into added energy savings per metric ton of ammonia. Electrochemical synthesis using electrolysis for hydrogen and cryogenic nitrogen was found to be a potentially viable pathway for green ammonia. The profitability metrics including discounted cash flow rate of return, net present value and discounted payback period were estimated to be 8%, $40 MM, and 4–6 years respectively for this pathway. The cost of electricity, conversion rate, and conversion efficiency dominate the tonnage cost of ammonia and were used to assess the feasibility of the model. A life cycle assessment was also conducted to assess the environmental impact of a well to product ammonia process.     

A novel combined biomass and solar energy conversion-based multigeneration system with hydrogen and ammonia generation

In the present study, an innovative multigeneration plant for hydrogen and ammonia generation based on solar and biomass power sources is suggested. The proposed integrated system is designed with the integration of different subsystems that enable different useful products such as power and hydrogen to be obtained. Performance evaluation of designed plant is carried out using different techniques. The energetic and exergetic analyses are applied to investigate and model the integrated plant. The plant consists of the parabolic dish collector, biomass gasifier, PEM electrolyzer and hydrogen compressor unit, ammonia reactor and ammonia storage tank unit, Rankine cycle, ORC cycle, ejector cooling unit, dryer unit and hot water production unit. The biomass gasifier unit is operated to convert biomass to synthesis gaseous, and the concentrating solar power plant is utilized to harness the free solar power. In the proposed plant, the electricity is obtained by using the gas, Rankine and ORC turbines. Additionally, the plant generates compressed hydrogen, ammonia, cooling effect and hot water with a PEM electrolyzer and compressed plant, ammonia reactor, ejector process and clean-water heater, respectively. The plant total electrical energy output is calculated as 20,125 kW, while the plant energetic and exergetic effectiveness are 58.76% and 55.64%. Furthermore, the hydrogen and ammonia generation are found to be 0.0855 kg/s and 0.3336 kg/s.     

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.