Search results for: hydrogen evolution reaction

Authors: Hamadi Cherif, Christophe Coquelet, Paolo Stringari, Denis Clodic, Laura Pellegrini, Stefania Moioli, Stefano Langè

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Biogas is a promising technology which can be used as a vehicle fuel, for heat and electricity production, or injected in the national gas grid. It is storable, transportable, not intermittent and substitutable for fossil fuels. This gas produced from the wastewater treatment by degradation of organic matter under anaerobic conditions is mainly composed of methane and carbon dioxide. To be used as a renewable fuel, biogas, whose energy comes only from methane, must be purified from carbon dioxide and other impurities such as water vapor, siloxanes and hydrogen sulfide. Purification of biogas for this application particularly requires the removal of hydrogen sulfide, which negatively affects the operation and viability of equipment especially pumps, heat exchangers and pipes, causing their corrosion. Several methods are available to eliminate hydrogen sulfide from biogas. Herein, reactive absorption in structured packed column by means of chemical absorption in aqueous sodium hydroxide solutions is considered. This study is based on simulations using Aspen Plus™ V8.0, and comparisons are done with data from an industrial pilot plant treating 85 Nm3/h of biogas which contains about 30 ppm of hydrogen sulfide. The rate-based model approach has been used for simulations in order to determine the efficiencies of separation for different operating conditions. To describe vapor-liquid equilibrium, a γ/ϕ approach has been considered: the Electrolyte NRTL model has been adopted to represent non-idealities in the liquid phase, while the Redlich-Kwong equation of state has been used for the vapor phase. In order to validate the thermodynamic model, Henry’s law constants of each compound in water have been verified against experimental data. Default values available in Aspen Plus™ V8.0 for the properties of pure components properties as heat capacity, density, viscosity and surface tension have also been verified. The obtained results for physical and chemical properties are in a good agreement with experimental data. Reactions involved in the process have been studied rigorously. Equilibrium constants for equilibrium reactions and the reaction rate constant for the kinetically controlled reaction between carbon dioxide and the hydroxide ion have been checked. Results of simulations of the pilot plant purification section show the influence of low temperatures, concentration of sodium hydroxide and hydrodynamic parameters on the selective absorption of hydrogen sulfide. These results show an acceptable degree of accuracy when compared with the experimental data obtained from the pilot plant. Results show also the great efficiency of sodium hydroxide for the removal of hydrogen sulfide. The content of this compound in the gas leaving the column is under 1 ppm.

Keywords: biogas, hydrogen sulfide, reactive absorption, sodium hydroxide, structured packed column

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Authors: Said Alshukri, Mazhar Hussain Malik

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Green hydrogen is hydrogen produced using renewable energy sources. In the last few years, Oman aimed to reduce its dependency on fossil fuels. Recently, the hydrogen economy has become a global trend, and many countries have started to investigate the feasibility of implementing this sector. Oman created an alliance to establish the policy and rules for this sector. With motivation coming from both global and local interest in green hydrogen, this paper investigates the potential of producing hydrogen from wind and solar energies in three different locations in Oman, namely Duqm, Salalah, and Sohar. By using machine learning-based software “WEKA” and local metrological data, the project was designed to figure out which location has the highest wind and solar energy potential. First, various supervised models were tested to obtain their prediction accuracy, and it was found that the Random Forest (RF) model has the best prediction performance. The RF model was applied to 2021 metrological data for each location, and the results indicated that Duqm has the highest wind and solar energy potential. The system of one wind turbine in Duqm can produce 8335 MWh/year, which could be utilized in the water electrolysis process to produce 88847 kg of hydrogen mass, while a solar system consisting of 2820 solar cells is estimated to produce 1666.223 MWh/ year which is capable of producing 177591 kg of hydrogen mass.

Keywords: green hydrogen, machine learning, wind and solar energies, WEKA, supervised models, random forest

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Authors: Ajay Dwivedi, M. Suresh Kumar, A. N. Vaidya

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The problem of fruit and vegetable waste management is a grave one and with ever increasing need to feed the exponentially growing population, more and more solid waste in the form of fruit and vegetables waste are generated and its management has become one of the key issues in protection of environment. Energy generation from fruit and vegetables waste by dark anaerobic fermentation is a recent an interesting avenue effective management of solid waste as well as for generating free and cheap energy. In the present study 17 vegetables were characterized for their physical as well as chemical properties, these characteristics were used to determine the hydrogen and methane potentials of vegetable from various models, and also lab scale batch experiments were performed to determine their actual hydrogen and methane production capacity. Lab scale batch experiments proved that vegetable waste can be used as effective substrate for bio hydrogen and methane production, however the expected yield of bio hydrogen and methane was much lower than predicted by models, this was due to the fact that other vital experimental parameters such as pH, total solids content, food to microorganism ratio was not optimized.

Keywords: vegetable waste, physico-chemical characteristics, hydrogen, methane

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Authors: K. Digheche, K. Saadi, Z. Boumerzoug

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Welding is one of the most important technological processes used in many branches of industry such as industrial engineering, shipbuilding, pipeline fabrication among others. Generally, welding is the preferred joining method and most common steels are weldable. This investigation is a contribution to scientific work of welding of low carbon steel. This work presents the results of the isothermal heat treatment effect at 200, 400 and 600 °C on microstructural evolution in weld region of X70 pipeline steel. The welding process has been realized in three passes by industrial arc welding. We have found that the heat treatments cause grain growth reaction.

Keywords: heat treatments, low carbon steel, microstructures, welding

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Authors: Abdulla Rahil, Rupert Gammon, Neil Brown

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The rapid growth of renewable energy sources and their integration into the grid have been motivated by the depletion of fossil fuels and environmental issues. Unfortunately, the grid is unable to cope with the predicted growth of renewable energy which would lead to its instability. To solve this problem, energy storage devices could be used. Electrolytic hydrogen production from an electrolyser is considered a promising option since it is a clean energy source (zero emissions). Choosing flexible operation of an electrolyser (producing hydrogen during the off-peak electricity period and stopping at other times) could bring about many benefits like reducing the cost of hydrogen and helping to balance the electric systems. This paper investigates the price of hydrogen during flexible operation compared with continuous operation, while serving the customer (hydrogen filling station) without interruption. The optimization algorithm is applied to investigate the hydrogen station in both cases (flexible and continuous operation). Three different scenarios are tested to see whether the off-peak electricity price could enhance the reduction of the hydrogen cost. These scenarios are: Standard tariff (1 tier system) during the day (assumed 12 p/kWh) while still satisfying the demand for hydrogen; using off-peak electricity at a lower price (assumed 5 p/kWh) and shutting down the electrolyser at other times; using lower price electricity at off-peak times and high price electricity at other times. This study looks at Derna city, which is located on the coast of the Mediterranean Sea (32° 46′ 0 N, 22° 38′ 0 E) with a high potential for wind resource. Hourly wind speed data which were collected over 24½ years from 1990 to 2014 were in addition to data on hourly radiation and hourly electricity demand collected over a one-year period, together with the petrol station data.

Keywords: hydrogen filling station off-peak electricity, renewable energy, off-peak electricity, electrolytic hydrogen

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Authors: Ravi Prakash

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The effects of Zr addition on kinetics and hydrogen absorption characteristics of BCC alloy 52Ti-12V-36Cr doped with x wt% of Zr (x = 0, 4, 8 & 12) was investigated. The samples have been characterized by X-ray diffraction, and activation study were made at four different temperatures- 100 oC, 200 oC, 300 oC and 400 oC. First hydrogenation kinetics of alloys were studied at 20 bar of hydrogen pressure and room temperature after giving heat treatment at different temperatures for 6 hours. Among the various Zr doped alloys studied, the composition 52Ti-12V-36Cr + 4wt% Zr shows maximum hydrogen storage capacity of 3.6wt%. Small amount of Zr shows advantageous effects on kinetics of alloy. It was also found out that alloys with the higher Zr concentration can be activated by giving heat treatment at lower temperatures. There is reduction in hydrogen storage capacity with increasing Zr content in the alloy primarily due to increasing abundance of secondary phase as established by X-Ray Diffraction and Scanning Electron Microscope results.

Keywords: hydrogen storage, metal hydrides, bcc alloy, heat treatment

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Authors: Dajana Gašo-Sokač, Valentina Bušić

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Deep eutectic solvents (DES) are liquids composed of two or three safe, inexpensive components, often interconnected by noncovalent hydrogen bonds which produce eutectic mixture whose melting point is lower than that of each component. No data in literature have been found on the quaternization reaction in DES. The use of DES have several advantages: they are environmentally benign and biodegradable, easy for purification and simple for preparation. An environmentally sustainable method for preparing quaternary salts of izonicotinamide and substituted 2-bromoacetophenones was demonstrated here using choline chloride-based DES. The quaternization reaction was carried out by three synthetic approaches: conventional method, microwave and ultrasonic irradiation. We showed that the highest yields were obtained by the microwave method.

Keywords: deep eutectic solvents, izonicotinamide salts, microwave synthesis, ultrasonic irradiation

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Authors: Premrudee Promdet, Fan Cui, Gi Byoung Hwang, Ka Chuen To, Sanjayan Sathasivam, Claire J. Carmalt, Ivan P. Parkin

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A novel single-step fabrication of Cu nanoparticle embedded ZnO (Cu.ZnO) thin films was developed by aerosol-assisted chemical vapor deposition for stable and efficient hydrogen production in Photoelectrochemical (PEC) cell. In this approach, the Cu.ZnO nanoplate thin films were grown by using acetic acid to promote preferential growth and enhance surface active sites, where Cu nanoparticles can be formed under chemical deposition by reduction of Cu salt. Studies using photoluminescence spectroscopy indicate the enhanced photocatalytic performance is attributed to hot electron generated from SPR. The Cu metal in the composite material is functioning as a sensitizer to supply electrons to the semiconductor resulting in enhanced electron density for redox reaction. This work not only describes a way to obtain photoanodes with high photocatalytic activity but also suggests a low-cost route towards production of photocatalysts for hydrogen production. This work also supports a vital need to understand electron transfer between photoexcited semiconductor materials and metals, a requirement for tailoring the properties of semiconductor/metal composites.

Keywords: photocatalysis, photoelectrochemical cell (PEC), aerosol-assisted chemical vapor deposition (AACVD), surface plasmon resonance (SPR)

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Authors: Ebru Kaymaz, Aslı İlbay Hamamcı, Yakup Enes Garip, Samet Ay

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The use of hydrogen as a fuel is important for decreasing carbon emissions. For the steel industry, reducing carbon emissions is one of the most important agendas of recent times globally. Because of the Paris Agreement requirements, European steel industry studies on green steel production. Although many literature reviews have analyzed this topic from technological and hydrogen based ironmaking, there are very few studies focused on patents of decarbonize parts of the steel industry. Hence, this study focus on technological progress of hydrogen based ironmaking and on understanding the main trends through patent data. All available patent data were collected from Questel Orbit. The trend analysis of more than 900 patent documents has been carried out by using Questel Orbit Intellixir to analyze a large number of data for scientific intelligence.

Keywords: hydrogen based ironmaking, DRI, direct reduction, carbon emission, steelmaking, patent analysis

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Authors: H. Rezzouk, M. Hatti, H. Rahmani, S. Atoui

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This paper discusses the design and analysis of a hybrid PV-Fuel cell energy system destined to power a DC load. The system is composed of a photovoltaic array, a fuel cell, an electrolyzer and a hydrogen tank. HOMER software is used in this study to calculate the optimum capacities of the power system components that their combination allows an efficient use of solar resource to cover the hourly load needs. The optimal system sizing allows establishing the right balance between the daily electrical energy produced by the power system and the daily electrical energy consumed by the DC load using a 28 KW PV array, a 7.5 KW fuel cell, a 40KW electrolyzer and a 270 Kg hydrogen tank. The variation of powers involved into the DC bus of the hybrid PV-fuel cell system has been computed and analyzed for each hour over one year: the output powers of the PV array and the fuel cell, the input power of the elctrolyzer system and the DC primary load. Equally, the annual variation of stored hydrogen produced by the electrolyzer has been assessed. The PV array contributes in the power system with 82% whereas the fuel cell produces 18%. 38% of the total energy consumption belongs to the DC primary load while the rest goes to the electrolyzer.

Keywords: electrolyzer, hydrogen, hydrogen fueled cell, photovoltaic

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Authors: Ruchi Jain, Chinnakonda S. Gopinath

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The CO oxidation is a primary reaction in heterogeneous catalysis due to its potential to overcome the air pollution caused by various reasons. Indeed, in the study of sustainable catalysis, the role played by water is very important. The present work is focused on studying the effect of moisture on the sustainability of Co3O4 NR catalyst for CO oxidation reaction at ambient temperature. The catalytic activity, electronic structure and the mechanistic aspects of spinel Co3O4 nanorod surfaces have been explored in dry and wet atmosphere by near-ambient pressure photoelectron spectroscopic techniques (NAP-PES) with conventional x-ray (Al kα) and ultraviolet sources (He-I).Comparative NAPPES studies have been employed to understand the elucidation of the catalytic reaction pathway and the evolution of various surface species. The presence of water with CO+O2 plummet the catalytic activity due to the change in electronic nature from predominantly oxidic (without water in the feed) to few intermediates covered Co3O4 surface. However, ≥ 375 K Co3O4 surface recovers and regain oxidation activity, at least partially, even in the presence of water. Above mentioned observations are fully supported by the changes observed in the work function of Co3O4 in the presence of wet (H2O+CO+O2) compared to dry (CO+O2) conditions. Various type of surface species, such as CO(ads), carbonate, formate, are found to be on the catalyst surface depending on the reaction conditions. Under dry condition, CO couples with labile O atoms to form CO2, however under wet conditions it also interacts with surface OH groups results in the formation carbonate and formate intermediate. The carbonate acts at reaction inhibitor at room temperature, however proves as active intermediate at temperature 375 K or above. On the other hand, formate has proved to be reaction spectator due to its high stability. The intrinsic role of these species to suppress the oxidation has been demonstrated through a possible reaction mechanism under different reaction conditions.

Keywords: heterogeneous catalysis, surface chemistry, photoelectron spectroscopy, ambient oxidation

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Authors: Doo Ki Lee, Kumaresh Selvakumar, Man Young Kim

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Catalytic combustion is an environmentally friendly technique to combust fuels in gas turbines. In this paper, the behavior of surface reaction rate on catalytic combustion is studied with respect to the heterogeneous oxidation of methane-air mixture in a catalytic reactor. Plug flow reactor (PFR), the simplified single catalytic channel assists in investigating the catalytic combustion phenomenon over the Pt catalyst by promoting the desired chemical reactions. The numerical simulation with multi-step elementary surface reactions is governed by the availability of free surface sites onto the catalytic surface and thereby, the catalytic combustion characteristics are demonstrated by examining the rate of the reaction for lean fuel mixture. Further, two different surface reaction mechanisms are adopted and compared for surface reaction rates to indicate the controlling heterogeneous reaction for better fuel conversion. The performance of platinum catalyst under heterogeneous reaction is analyzed under the same temperature condition, where the catalyst with the higher kinetic rate of reaction would have a maximum catalytic activity for enhanced methane catalytic combustion.

Keywords: catalytic combustion, heterogeneous reaction, plug flow reactor, surface reaction rate

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Authors: Jianliang Xu, Zhenghua Dai, Zhongjie Shen, Haifeng Liu, Fuchen Wang

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In an entrained flow gasifier, the combustible components are converted into the gas phase, and the mineral content is converted into ash. Most of the ash particles or droplets are deposited on the refractory or membrane wall and form a slag layer that flows down to the quenching system. The captured particle reaction process and slag flow and phase transformation play an important role in gasifier performance and safe and stable operation. The reaction characteristic of captured char particles on the molten slag had been studied by applied a high-temperature stage microscope. The gasification process of captured chars with CO2 on the slag surface was observed and recorded, compared to the original char gasification. The particle size evolution, heat transfer process are discussed, and the gasification reaction index of the capture char particle are modeled. Molten slag layer promoted the char reactivity from the analysis of reaction index, Coupled with heat transfer analysis, shrinking particle model (SPM) was applied and modified to predict the gasification time at carbon conversion of 0.9, and results showed an agreement with the experimental data. A comprehensive model with gas-particle-slag flow and reaction models was used to model the different industry gasifier. The carbon conversion information in the spatial space and slag layer surface are investigated. The slag flow characteristic, such as slag velocity, molten slag thickness, slag temperature distribution on the membrane wall and refractory brick are discussed.

Keywords: char, slag, numerical simulation, gasification, wall reaction, membrane wall

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Authors: M. Heidari, A. Safekordi, A. Zamaniyan, E. Ganji Babakhani, M. Amanipour

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Perovskite-type membrane Ba_0.5Sr_0.5Ce_0.9Y_0.1O_3-δ (BSCY) was successfully synthesized by liquid citrate method. The hydrogen permeation and stability of BSCY perovskite-type membranes were studied at high temperatures. The phase structure of the powder was characterized by X-ray diffraction (XRD). Scanning electron microscopy (SEM) was used to characterize microstructures of the membrane sintered under various conditions. SEM results showed that increasing in sintering temperature, formed dense membrane with clear grains. XRD results for BSCY membrane that sintered in 1150 °C indicated single phase perovskite structure with orthorhombic configuration, and SEM results showed dense structure with clear grain size which is suitable for permeation tests. Partial substitution of Sr with Ba in SCY structure improved the hydrogen permeation flux through the membrane due to the larger ionic radius of Ba²⁺. BSCY membrane shows high hydrogen permeation flux of 1.6 ml/min.cm² at 900 °C and partial pressure of 0.6.

Keywords: hydrogen separation, perovskite, proton conducting membrane.

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Authors: Zeynep Yilmazer Hitit, Patrick C. Hallenbeck

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Fuel reserve requirements due to depletion of fossil fuels have increased interest in biohydrogen since the 1990’s. In fermentative hydrogen production, pure, mixed, and co-cultures can be used to produce hydrogen. Several previous studies have evaluated hydrogen production by pure cultures of Clostridium butyricum or Enterobacter aerogenes. Evaluating hydrogen production by co-culture of these microorganisms is an interestıng approach since E. aerogenes is a facultative microorganism with resistance to oxygen in contrast to the strict anaerobe C. butyricum, and therefore has the ability to maintain anaerobic conditions. It was found that using co-cultures of facultative E. aerogenes (as a reducing agent and H2 producer) and the obligate anaerobe C. butyricum for producing hydrogen increases the yield of hydrogen by about 50% compared to C. butyricum by itself. Also, using different types of microorganisms for hydrogen production eliminates the need to use expensive reducing agents. C. butyricum strain pre-cultured anaerobically at 37 0C for 15h by inoculating 100 mL of GP medium (pH 6.8) consisting of 1% glucose, 2% polypeptone, 0.2% KH2PO4, 0.05% yeast extract, 0.05% MgSO4. 7H2O and E. aerogenes strain was pre-cultured aerobically at 30 0C, 150 rpm for 9 h by inoculating 100 mL of TGY medium (pH 6.8), consisting of 0.1% glucose, 0.5% tryptone, 0.1% K2HPO4, 0.5% yeast extract. All duplicate batch experiments were conducted in 100 mL bottles with different inoculum ratios of Clostridium butyricum and Enterobater aerogenes (C:E) using 5x diluted rich media (GP) consisting of 2 g/L glucose, 4g/L polypeptone, 0.4 g/L KH2PO4, 0.1 g/L yeast extract, 0.1 MgSO4.7H2O. The range of inoculum ratio of C. butyricum to E. aerogenes were 2:1,4:1,8:1, 1:2,1:4, 1:8, 1:0, 0:1. Using glucose as a carbon source aided in the observation of microbial behavior as well as making the effect of inoculum ratio more evident. Nearly all the glucose in the medium was used to produce hydrogen, except at a 1:0 ratio of inoculum (i.e. containing only C. butyricum). Low glucose consumption leads to a higher hydrogen yield due to cumulative hydrogen production and consumption of glucose, but not as much as C:E, 8:1. The lowest hydrogen yield was achieved in 1:8 inoculum ratio of C:E, 71.9 mL, 1.007±0.01 mol H2/mol glucose and the highest cumulative hydrogen, hydrogen yield and dry cell weight were achieved in 8:1 inoculum ratio of C:E, 117.4 mL, 2.035±0.082 mol H2/mol glucose, 0.4 g/L respectively. In this study effect of inoculum ratio on dark fermentative biohydrogen production using C. butyricum and E. aerogenes was investigated. The maximum hydrogen yield of 2.035mol H2/mol glucose was obtained using 2g/L glucose, an initial pH of 6 and an inoculum ratio of C. butyricum to E. aerogenes of 8:1. Results showed that inoculum ratio is an important parameter on hydrogen production due to competition between the two microorganisms in using substrate for growth and production of by-products. The results presented here could be of great significance for further waste management studies using co-culture hydrogen production.

Keywords: biohydrogen, Clostridium butyricum, dark fermentation, Enterobacter aerogenes, inoculum ratio in biohydrogen production

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Authors: H. M. Ferreira, H. Cockings, D. F. Gordon

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Climate change is driving a transition in the energy sector, with low-carbon energy sources such as hydrogen (H2) emerging as an alternative to fossil fuels. However, the successful implementation of a hydrogen economy requires an expansion of hydrogen production, transportation and storage capacity. The costs associated with this transition are high but can be partly mitigated by adapting the current oil and natural gas networks, such as pipeline, an important component of the hydrogen infrastructure, to transport pure or blended hydrogen. Steel pipelines are designed to withstand fatigue, one of the most common causes of pipeline failure. However, it is well established that some materials, such as steel, can fail prematurely in service when exposed to hydrogen-rich environments. Therefore, it is imperative to evaluate how defects (e.g. inclusions, dents, and pre-existing cracks) will interact with hydrogen under cyclic loading and, ultimately, to what extent hydrogen induced failure will limit the service conditions of steel pipelines. This presentation will explore how the exposure of API 5L X65 to a hydrogen-rich environment and cyclic loads will influence its susceptibility to hydrogen induced failure. That evaluation will be performed by a combination of several techniques such as hydrogen permeation testing (ISO 17081:2014), fatigue crack growth (FCG) testing (ISO 12108:2018 and AFGROW modelling), combined with microstructural and fractographic analysis. The development of a FCG test setup coupled with an electrochemical cell will be discussed, along with the advantages and challenges of measuring crack growth rates in electrolytic hydrogen environments. A detailed assessment of several electrolytic charging conditions will also be presented, using hydrogen permeation testing as a method to correlate the different charging settings to equivalent hydrogen concentrations and effective diffusivity coefficients, not only on the base material but also on the heat affected zone and weld of the pipelines. The experimental work is being complemented with AFGROW, a useful FCG modelling software that has helped inform testing parameters and which will also be developed to ultimately help industry experts perform structural integrity analysis and remnant life characterisation of pipeline steels under representative conditions. The results from this research will allow to conclude if there is an acceleration of the crack growth rate of API 5L X65 under the influence of a hydrogen-rich environment, an important aspect that needs to be rectified instandards and codes of practice on pipeline integrity evaluation and maintenance.

Keywords: AFGROW, electrolytic hydrogen charging, fatigue crack growth, hydrogen, pipeline, steel

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Authors: Mohammed W. Abdulrahman

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The thermochemical copper-chlorine (Cu-Cl) cycle is considered as a sustainable and efficient technology for a hydrogen production, when linked with clean-energy systems such as nuclear reactors or solar thermal plants. In the Cu-Cl cycle, water is decomposed thermally into hydrogen and oxygen through a series of intermediate reactions. This paper investigates the thermal scale up analysis of the three phase oxygen production reactor in the Cu-Cl cycle, where the reaction is endothermic and the temperature is about 530 ^oC. The paper focuses on examining the size and number of oxygen reactors required to provide enough heat input for different rates of hydrogen production. The type of the multiphase reactor used in this paper is the continuous stirred tank reactor (CSTR) that is heated by a half pipe jacket. The thermal resistance of each section in the jacketed reactor system is studied to examine its effect on the heat balance of the reactor. It is found that the dominant contribution to the system thermal resistance is from the reactor wall. In the analysis, the Cu-Cl cycle is assumed to be driven by a nuclear reactor where two types of nuclear reactors are examined as the heat source to the oxygen reactor. These types are the CANDU Super Critical Water Reactor (CANDU-SCWR) and High Temperature Gas Reactor (HTGR). It is concluded that a better heat transfer rate has to be provided for CANDU-SCWR by 3-4 times than HTGR. The effect of the reactor aspect ratio is also examined in this paper and is found that increasing the aspect ratio decreases the number of reactors and the rate of decrease in the number of reactors decreases by increasing the aspect ratio. Finally, a comparison between the results of heat balance and existing results of mass balance is performed and is found that the size of the oxygen reactor is dominated by the heat balance rather than the material balance.

Keywords: sustainable energy, clean energy, Cu-Cl cycle, heat transfer, hydrogen, oxygen

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Authors: S. Jaikeaw, S. Chavadej

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The objective of this study was to determine the effects of COD loading rate on hydrogen and methane production and micronutrient transportation using a two-stage upflow anaerobic sludge blanket (UASB) system under mesophilic temperature (37°C) with a constant recycle ratio of 1:1 (final effluent flow rate: feed flow rate). The first (hydrogen) UASB unit having 4 L liquid holding volume was controlled at pH 5.5 but the second (methane) UASB unit having 24 L liquid holding volume had no pH control. The two-stage UASB system operated at different COD loading rates from 8 to 20 kg/m³d based on total UASB working volume. The results showed that, at the optimum COD loading rate of 13 kg/m³d, the produced gas from the hydrogen UASB unit contained 1.5% H₂, 16.5% CH₄, and 82% CO₂ with H₂S of 252 ppm and also provided a hydrogen yield of 1.66 mL/g COD removed (or 0.56 mL/g COD applied) and a specific hydrogen production rate of 156.85 ml H₂/LRd (or 5.12 ml H₂/g MLVSS d). Under the optimum COD loading rate, the produced gas from the methane UASB unit mainly contained methane and carbon dioxide without hydrogen of 74 and 26%, respectively with hydrogen sulfide of 287 ppm and the system also provided a maximum methane yield of 407.00 mL/g COD removed (or 263.23 mL/g COD applied) and a specific methane production rate of 2081.44 ml CH₄/LRd (or 99.75 ml CH₄/g MLVSS d). Under the optimum COD loading rate, all micronutrients markedly dropped by the sulfide precipitation reactions. The reduction of micronutrients mostly appeared in the methane UASB unit. Under the studied conditions, both Co and Ni were found to be greatly precipitated out, causing the deficiency to microbial activity. It is hypothesized that an addition of both Co and Ni can improve the methanogenic activity.

Keywords: hydrogen and methane production, ethanol wastewater, a two-stage upflow anaerobic blanket (UASB) system, mesophillic temperature, microbial concentration (MLVSS), micronutrients

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Authors: J. Alcisto, M. Papakyriakou, J. Guerra, A. Dominguez, M. Miller, J. Foyos, E. Jones, N. Ula, M. Hahn, L. Zeng, Y. Li, O. S. Es-Said

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Current methods of testing for hydrogen charging are slow and time consuming. The objective of this paper was to determine if hydrogen charging can be detected quantitatively through the use of Charpy Impact (CI) testing. CI is a much faster and simpler process than current methods for detecting hydrogen charging. Steel plates were Electro Discharge Machined (EDM) into ninety-six 4340 steel CI samples and forty-eight tensile bars. All the samples were heat treated at 900°C to austentite and then rapidly quenched in water to form martensite. The samples were tempered at eight different target strengths/target temperatures (145, 160, 170, 180, 190, 205, 220, to 250KSI, thousands of pounds per square inch)/(1100, 1013, 956, 898, 840, 754, 667, 494 degrees Celsius). After a tedious process of grinding and machining v-notches to the Charpy samples, they were divided into four groups. One group was kept as received baseline for comparison while the other three groups were sent to Alcoa (Fasteners) Inc. in Torrance to be cadmium coated. The three groups were coated with three thicknesses (2, 3 and 5 mils). That means that the samples were charged with ascending hydrogen levels. The samples were CI tested and tensile tested, and the data was tabulated and compared to the baseline group of uncharged samples of the same material. The results of this study were successful and indicated that CI testing was able to quantitatively detect hydrogen charging.

Keywords: Charpy impact toughness, hydrogen charging, 4340 steel, Electro Discharge Machined (EDM)

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Authors: Ali Zazi, Ouiza Cherifi

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The Catalysts materials Ni-SiO₂, Ni-Co-SiO₂ and Ni-Ce-SiO₂ were synthetized by classical method impregnation and supported by silica. This involves combing the silica with an adequate rate of the solution of nickel nitrates, or nickel nitrate and cobalt nitrate, or nickel nitrate and cerium nitrate, mixed, dried and calcined at 700 ° c. These catalysts have been characterized by different physicochemical analysis techniques. The atomic absorption spectrometry indicates that the real contents of nickel, cerium and cobalt are close to the theoretical contents previously assumed, which let's say that the nitrate solutions have impregnated well the silica support. The BET results show that the surface area of the specific surfaces decreases slightly after impregnation with nickel nitrates or Co and Ce metals and a further slight decrease after the reaction. This is likely due to coke deposition. X-ray diffraction shows the presence of the different SiO₂ and NiO phases for all catalysts—theCoO phase for that promoted by Co and the Ce₂O₂ phase for that promoted by Ce. The methane steam reforming reaction was carried out on a quartz reactor in a fixed bed. Reactants and products of the reaction were analyzed by a gas chromatograph. This study shows that the metal addition of Cerium or Cobalt improves the majority of the catalytic performance of Ni for the steam reforming reaction of methane. And we conclude the classification of our Catalysts in order of decreasing activity and catalytic performances as follows: Ni-Ce / SiO₂ >Ni-Co / SiO₂> Ni / SiO₂ .

Keywords: cerium, cobalt, heterogeneous catalysis, hydrogen, methane, steam reforming, synthesis gas

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Authors: Rafayel K. Kostanyan

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The opportunities of use of metallic magnesium as a generator of hydrogen gas, as well as thermal and electric energy is presented in the paper. Various schemes of magnesium application are discussed and power characteristics of corresponding devices are presented. Economic estimation of hydrogen price obtained by different methods is made, including the use of magnesium as a source of hydrogen for transportation in comparison with gasoline. Details and prospects of our new inexpensive technology of magnesium production from magnesium hydroxide and magnesium bearing rocks (which are available worldwide and in Armenia) are analyzed. It is estimated the threshold cost of Mg production at which application of this metal in power engineering is economically justified.

Keywords: energy, electrodialysis, magnesium, new technology

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Authors: Dake Xiong, Ben Hankamer, Ian Ross

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The most urgent challenge of our time is to replace the depleting resources of fossil fuels by sustainable environmentally friendly alternatives. Hydrogen is a promising CO2-neutral fuel for a more sustainable future especially when produced photo-biologically. Hydrogen can be photosynthetically produced in unicellular green alga like Chlamydomonas reinhardtii, catalysed by the inducible highly active and bidirectional [FeFe]-hydrogenase enzymes (HydA). However, evolutionary and physiological constraints severely restrict the hydrogen yield of algae for industrial scale-up, mainly due to its competition among other metabolic pathways on photosynthetic electrons. Among them, a major challenge to be resolved is the inferior competitiveness of hydrogen production (catalysed by HydA) with NADPH production (catalysed by ferredoxin-NADP+-reductase (FNR)), which is essential for cell growth and takes up ~95% of photosynthetic electrons. In this work, the in vivo hydrogen production efficiency of mutants with ferredoxin-hydrogenase (Fd*-HydA1*) fusion protein construct, where the electron donor ferredoxin (Fd*) is fused to HydA1* and expressed in the model organism C. reinhardtii was investigated. Once Fd*-HydA1* fusion gene is expressed in algal cells, the fusion enzyme is able to draw the redistributed photosynthetic electrons and use them for efficient hydrogen production. From preliminary data, mutants with Fd*-HydA1* transgene showed a ~2-fold increase in the photosynthetic hydrogen production rate compared with its parental strain, which only possesses the native HydA in vivo. Therefore, a solid method of having more efficient hydrogen production in microalgae can be achieved through the expression of the synthetic enzymes.

Keywords: Chlamydomonas reinhardtii, ferredoxin, fusion protein, hydrogen production, hydrogenase

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Authors: Hristina Šalipur, Jasmina Dostanić, Davor Lončarević, Matej Huš

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Photocatalytic water splitting/alcohol photoreforming has been used for the conversion of sunlight energy in the process of hydrogen production due to its sustainability, environmental safety, effectiveness and simplicity. Titanate nanotubes are frequently studied materials since they combine the properties of photo-active semiconductors with the properties of layered titanates, such as the ion-exchange ability. Platinum (Pt) doping into titanate structure has been considered an effective strategy in better separation efficiency of electron-hole pairs and lowering the overpotential for hydrogen production, which results in higher photocatalytic activity. In our work, Pt doped titanate catalysts were synthesized via simple alkaline hydrothermal treatment, incipient wetness impregnation method and temperature-programmed reduction. The structural, morphological and optical properties of the prepared catalysts were investigated using various characterization techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 physisorption, and diffuse reflectance spectroscopy (DRS). The activities of the prepared Pt-doped titanate photocatalysts were tested for hydrogen production via photocatalytic water splitting/alcohol photoreforming process under simulated solar light irradiation. Characterization of synthesized Pt doped titanate catalysts showed crystalline anatase phase, preserved nanotubular structure and high specific surface area. The result showed enhancement of activity in photocatalytic water splitting/alcohol photoreforming in the following order 2-butanol>1-butanol>tert-butanol, with obtained maximal hydrogen production rate of 7.5, 5.3 and 2 mmol g-1 h-1, respectively. Different possible factors influencing the hole scavenging ability, such as hole scavenger redox potential and diffusivity, adsorption and desorption rate of the hole scavenger on the surface and stability of the alcohol radical species generated via hole scavenging, were investigated. The theoretical evaluation using density functional theory (DFT) further elucidated the reaction kinetics and detailed mechanism of photocatalytic water splitting/alcohol photoreforming.

Keywords: hydrogen production, platinum, semiconductor, water splitting, density functional theory

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Authors: V. Viswanathan, Md. Irshad Ahmad, Prashant K. Singh, Nayeem Ahmad, Pradeep Sharma, Sujata Sharma, Tej P Singh

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Lactoperoxidase (LPO) is a heme containing mammalian enzyme which uses hydrogen peroxide (H2O2) to catalyze the conversion of substrates into oxidized products. LPO is found in body fluids and tissues such as milk, saliva, tears, mucosa and other body secretions. The previous structural studies have shown that LPO converts substrates, thiocyanate (SCN‾) and iodide (I‾) ions into oxidized products, hypothiocyanite (OSCN‾) and hypoiodite (IO‾) ions, respectively. We report here a new structure of the complex of LPO with an oxidized product, nitrite (NO2‾). This product was generated from NO using the two step reaction of LPO by adding hydrogen peroxide (H2O2) in the solution of LPO in 0.1M phosphate buffer at pH 6.8 as the first step. In the second step, NO gas was added to the above mixture. This was crystallized using 20% (w/v) PEG-3350 and 0.2M ammonium iodide at pH 6.8. The structure determination showed the presence of NO2‾ ion in the distal heme cavity of the substrate binding site of LPO. The structure also showed that the propionate group, which is linked to pyrrole ring D of the heme moiety, was disordered. Similarly, the side chain of Asp108, which is covalently linked to heme moiety, was also split into two components. As a result of these changes, the conformation of the side chain of Arg255 was altered, allowing it to form new interactions with the disordered carboxylic group of propionate moiety. These structural changes are indicative of an intermediate state in the catalytic reaction pathway of LPO.

Keywords: lactoperoxidase, structure, nitric oxide, nitrite ion, intermediate, complex

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Authors: Nadeem Bashir, Ghulam Mustafa Peerzada

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The present study pertains to the nonlinear behavior of acetaminophen based uncatalyzed Belousov-Zhabotinsky (BZ) oscillator and its dynamics in the presence of Ferroin as the catalyst. The role of free metal ions as catalysts was examined and the results compared with corresponding complexed catalysts. Free metal ions were found to be sluggish with respect to the evolution of the oscillatory regime as compared to complexed ones. Effect of change of the ligand moiety of the catalyst complex on the oscillatory parameters was monitored. Since ethanol potentiates the hepatotoxicity caused by acetaminophen in-vivo, it is thought to understand this interaction by virtue of causing perturbation of the acetaminophen based oscillator with different concentrations of the ethanol with and without ferroin as the catalyst. Another dimension to the ethanol effect was added by perturbation of the system with ethanol at different stages of the reaction so as to get an idea whether it is acetaminophen or some reactive intermediate generated in the reaction system which reacts with ethanol. Further, the ferroin-catalyzed oscillator is taken as a prototype inorganic model of the acetaminophen-ethanol syndrome, as ferroin and HOBr were inorganic replacements to Cyt P450 and NADPH in the alcohol metabolism.

Keywords: Belousov-Zhabotinsky reaction, ferroin, Paracetamol-Ethanol syndrome, kinetics

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Authors: Ferid Hammami

Abstract:

The molecular geometries of the possible conformations of pyruvic acid-water complexes (PA-(H₂O)ₙ = 1- 4) have been fully optimized at DFT/B3LYP/6-311G ++ (d, p) levels of calculation. Among several optimized molecular clusters, the most stable molecular arrangements obtained when one, two, three, and four water molecules are hydrogen-bonded to a central pyruvic acid molecule are presented in this paper. Apposite topological and geometrical parameters are considered as primary indicators of H-bond strength. Atoms in molecules (AIM) analysis shows that pyruvic acid can form a ring structure with water, and the molecular structures are stabilized by both strong O-H...O and C-H...O hydrogen bonds. In large clusters, classical O-H...O hydrogen bonds still exist between water molecules, and a cage-like structure is built around some parts of the central molecule of pyruvic acid. The electrostatic potential energy map (MEP) and the HOMO-LUMO molecular orbital (highest occupied molecular orbital-lowest unoccupied molecular orbital) analysis has been performed for all considered complexes.

Keywords: pyruvic acid, PA-water complex, hydrogen bonding, DFT, AIM, MEP, HOMO-LUMO

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Authors: L. K. Nivedha, V. Maruthapandian, R. Kothandaraman

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Rechargeable zinc-air batteries (ZAB) are gaining significant research attention owing to their high energy density and copious zinc resources worldwide. However, the unsolved obstacles such as dendrites, passivation, depth of discharge and the lack of an efficient cathode catalyst restrict their practical application1. By and large, non-noble transition metal-based catalysts are well-reputed materials for catalysing oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with greater stability in alkaline medium2. Herein, we report the synthesis and application of Mn₃O4-NiFeLDH/Carbon composite as a cathode catalyst for rechargeable ZAB. The synergetic effects of the mixed transition metals (Mn/Ni/Fe) have aided in catalysing ORR and OER in alkaline electrolyte with a shallow potential gap of 0.7 V. The composite, by its distinctive physicochemical characteristics, shows an excellent OER activity with a current density of 1.5 mA cm⁻² at a potential of 1.6 V and a superior ORR activity with an onset potential of 0.8 V when compared with their counterparts. Nevertheless, the catalyst prefers a two-electron pathway for the electrochemical reduction of oxygen which results in a limiting current density of 2.5 mA cm⁻². The bifunctional activity of the Mn₃O₄-NiFeLDH/Carbon composite was utilized in developing rechargeable ZAB. The fully fabricated ZAB delivers an open circuit voltage of 1.4 V, a peak power density of 70 mW cm⁻², and a specific capacity of 800 mAh g⁻¹ at a current density of 20 mA cm⁻² with an average discharge voltage of 1 V and the cell is operable upto 50 mA cm-2. Rechargeable ZAB demonstrated over 110 h at 10 mA cm⁻². Further, the cause for the diminished charge-discharge performance experienced beyond the 100th cycle was investigated, and carbon corrosion was testified using Infrared spectroscopy.

Keywords: rechargeable zinc-air battery, oxygen evolution reaction, bifunctional catalyst, alkaline medium

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Authors: A. Azizi, M. Toubane, L. Chetibi

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Differential scanning calorimetry (DSC) is a widely used technique for the study of phase transformations, particularly in the study of precipitation. The kinetic of the precipitation and dissolution is always related to the concept of activation energy Ea. The determination of the activation energy gives important information about the kinetic of the precipitation reaction. In this work, we were interested in the study of the isothermal and non-isothermal treatments on the decomposition of the supersaturated solid solution in the alloy AZ91 (Mg-9 Al-Zn 1-0.2 Mn. mass fraction %), using Differential Calorimetric method. Through this method, the samples were heat treated up to 425° C, using different rates. To calculate the apparent activation energies associated with the formation of precipitated phases, we used different isoconversional methods. This study was supported by other analysis: X-ray diffraction and microhardness measurements.

Keywords: calorimetric, activation energy, AZ91 alloys, microstructural evolution

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Authors: John Olorunfemi Abe, Olawale Muhammed Popoola, Abimbola Patricia Idowu Popoola

Abstract:

Hydrogen is an appealing alternative to fossil fuels because of its abundance, low weight, high energy density, and relative lack of contaminants. However, its low density presents a number of storage challenges. Therefore, this work studies the influence of refractory nitride additives consisting of 5 wt. % each of hexagonal boron nitride (h-BN), titanium nitride (TiN), and aluminum nitride (AlN) on hydrogen storage and electrochemical characteristics of Ti6Al4V-based materials produced by spark plasma sintering. The microstructure and phase constituents of the sintered materials were characterized using scanning electron microscopy (in conjunction with energy-dispersive spectroscopy) and X-ray diffraction, respectively. Pressure-composition-temperature (PCT) measurements were used to assess the hydrogen absorption/desorption behavior, kinetics, and storage capacities of the sintered materials, respectively. The pure Ti6Al4V alloy displayed a two-phase (α+β) microstructure, while the modified composites exhibited apparent microstructural modifications with the appearance of nitride-rich secondary phases. It is found that the diffusion process controls the kinetics of the hydrogen absorption. Thus, a faster rate of hydrogen absorption at elevated temperatures ensued. The additives acted as catalysts, lowered the activation energy and accelerated the rate of hydrogen sorption in the composites relative to the monolithic alloy. Ti6Al4V-5 wt. % h-BN appears to be the most promising candidate for hydrogen storage (2.28 wt. %), followed by Ti6Al4V-5 wt. % TiN (2.09 wt. %), whereas Ti6Al4V-5 wt. % AlN shows the least hydrogen storage performance (1.35 wt. %). Accordingly, the developed hydride system (Ti6Al4V-5h-BN) may be competitive for use in applications involving short-range continuous vehicles (~50-100km) as well as stationary applications such as electrochemical devices, large-scale storage cylinders in hydrogen production locations, and hydrogen filling stations.

Keywords: hydrogen storage, Ti6Al4V hydride system, pressure-composition-temperature measurements, refractory nitride additives, spark plasma sintering, Ti6Al4V-based materials

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Authors: T. Nozu, K. Hibi, T. Nishiie

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This paper discusses the applicability of the numerical model for a damage prediction method of the accidental hydrogen explosion occurring in a hydrogen facility. The numerical model was based on an unstructured finite volume method (FVM) code “NuFD/FrontFlowRed”. For simulating unsteady turbulent combustion of leaked hydrogen gas, a combination of Large Eddy Simulation (LES) and a combustion model were used. The combustion model was based on a two scalar flamelet approach, where a G-equation model and a conserved scalar model expressed a propagation of premixed flame surface and a diffusion combustion process, respectively. For validation of this numerical model, we have simulated the previous two types of hydrogen explosion tests. One is open-space explosion test, and the source was a prismatic 5.27 m3 volume with 30% of hydrogen-air mixture. A reinforced concrete wall was set 4 m away from the front surface of the source. The source was ignited at the bottom center by a spark. The other is vented enclosure explosion test, and the chamber was 4.6 m × 4.6 m × 3.0 m with a vent opening on one side. Vent area of 5.4 m2 was used. Test was performed with ignition at the center of the wall opposite the vent. Hydrogen-air mixtures with hydrogen concentrations close to 18% vol. were used in the tests. The results from the numerical simulations are compared with the previous experimental data for the accuracy of the numerical model, and we have verified that the simulated overpressures and flame time-of-arrival data were in good agreement with the results of the previous two explosion tests.

Keywords: deflagration, large eddy simulation, turbulent combustion, vented enclosure

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