Search results for: hydrogen ion

Authors: Dirk Zapf, Bastian Leuger

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For several years, natural gas and crude oil have been stored in salt caverns in Germany and also worldwide. The dimensioning concepts have been continuously developed from a rock mechanics point of view. In addition to the possibilities of realizing large numerical calculation models based on real survey data nowadays, especially the consideration of mechanical processes such as damage and healing played a role in the development of adequate material laws. In addition, thermodynamic aspects have had to be considered for some years in the operation of a gas storage cavern since temperature changes have a significant influence on the stress states in the vicinity of a storage cavern. The possibility of thermally induced fracturing processes is also investigated in the context of rock mechanics dimensioning. In recent years, the energy crisis and the finite nature of fossil fuel use have led to increased discussion of the use of salt caverns for hydrogen storage. In this paper, state of the art is presented, the current research work is described, and an outlook is given as to which questions still need to be answered from a rock mechanics point of view in connection with large-scale storage of hydrogen in salt caverns.

Keywords: cavern design, hydrogen, rock salt, thermomechanical coupled calculations

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Authors: Esther Acha, Jose Cambra, De Chen

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Hydrogen is considered an important energy vector for the 21st century. Nowadays there are some difficulties for hydrogen economy implantation, and one of them is the high purity required for hydrogen. This energy vector is still being mainly produced from fuels, from wich hydrogen is produced as a component of a mixture containing other gases, such as CO, CO2 and H2O. A forthcoming sustainable pathway for hydrogen is steam-reforming of bio-oils derived from biomass, e.g. via fast pyrolysis. Bio-oils are a mixture of acids, alcohols, aldehydes, esters, ketones, sugars phenols, guaiacols, syringols, furans, multi-functional compounds and also up to a 30 wt% of water. The sorption enhanced steam reforming (SESR) process is attracting a great deal of attention due to the fact that it combines both hydrogen production and CO2 separation. In the SESR process, carbon dioxide is captured by an in situ sorbent, which shifts the reversible reforming and water gas shift reactions to the product side, beyond their conventional thermodynamic limits, giving rise to a higher hydrogen production and lower cost. The hydrogen containing mixture has been obtained from the SESR of bio-oil type compounds. Different types of catalysts have been tested. All of them contain Ni at around a 30 wt %. Two samples have been prepared with the wet impregnation technique over conventional (gamma alumina) and non-conventional (olivine) supports. And a third catalysts has been prepared over a hydrotalcite-like material (HT). The employed sorbent is a commercial dolomite. The activity tests were performed in a bench-scale plant (PID Eng&Tech), using a stainless steel fixed bed reactor. The catalysts were reduced in situ in the reactor, before the activity tests. The effluent stream was cooled down, thus condensed liquid was collected and weighed, and the gas phase was analysed online by a microGC. The hydrogen yield, and process behavior was analysed without the sorbent (the traditional SR where a second purification step will be needed but that operates in steady state) and the SESR (where the purification step could be avoided but that operates in batch state). The influence of the support type and preparation method will be observed in the produced hydrogen yield. Additionally, the stability of the catalysts is critical, due to the fact that in SESR process sorption-desorption steps are required. The produced hydrogen yield and hydrogen purity has to be high and also stable, even after several sorption-desorption cycles. The prepared catalysts were characterized employing different techniques to determine the physicochemical properties of the fresh-reduced and used (after the activity tests) materials. The characterization results, together with the activity results show the influence of the catalysts preparation method, calcination temperature, or can even explain the observed yield and conversion.

Keywords: CO2 sorbent, enhanced steam reforming, hydrogen

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Authors: Jeong-Hyun Yoo, Hanjung Kwon, Sung-Wook Cho

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Fused salt electrolysis was studied to make the high purity rare-earth metals using domestic rare-earth ore. The target metals of the fused salt electrolysis were Mm (Misch metal), La, Ce, Nd, etc. Fused salt electrolysis was performed with the supporting salt such as chloride and fluoride at the various temperatures and ampere. The metals made by fused salt electrolysis were analyzed to identify the phase and composition using the methods of XRD and ICP. As a result, the acquired rare-earth metals were the high purity ones which had more than 99% purity. Also, VIM (vacuum induction melting) was studied to make the kg level rare-earth alloy for the use of secondary battery and hydrogen storage. In order to indentify the physicochemical properties such as phase, impurity gas, alloy composition and hydrogen storage, the alloys were investigated. The battery characteristics were also analyzed through the various tests in the real production line of a battery company.

Keywords: domestic rare-earth ore, fused salt electrolysis, rare-earth materials, hydrogen storage alloy, secondary battery

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Authors: Hendrick Maxil Zárate Rocha, Ricardo da Silva Pereira, Manoel Fernandes Martins Nogueira, Carlos R. Pereira Belchior, Maria Emilia de Lima Tostes

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This study investigates experimentally the effects of hydrogen addition in the intake manifold of a diesel generator operating with a 7% biodiesel-diesel oil blend (B7). An experimental apparatus setup was used to conduct performance and emissions tests in a single cylinder, air cooled diesel engine. This setup consisted of a generator set connected to a wirewound resistor load bank that was used to vary engine load. In addition, a flowmeter was used to determine hydrogen volumetric flowrate and a digital anemometer coupled with an air box to measure air flowrate. Furthermore, a digital precision electronic scale was used to measure engine fuel consumption and a gas analyzer was used to determine exhaust gas composition and exhaust gas temperature. A thermopar was installed near the exhaust collection to measure cylinder temperature. In-cylinder pressure was measured using an AVL Indumicro data acquisition system with a piezoelectric pressure sensor. An AVL optical encoder was installed in the crankshaft and synchronized with in-cylinder pressure in real time. The experimental procedure consisted of injecting hydrogen into the engine intake manifold at different mass concentrations of 2,6,8 and 10% of total fuel mass (B7 + hydrogen), which represented energy fractions of 5,15, 20 and 24% of total fuel energy respectively. Due to hydrogen addition, the total amount of fuel energy introduced increased and the generators fuel injection governor prevented any increases of engine speed. Several conclusions can be stated from the test results. A reduction in specific fuel consumption as a function of hydrogen concentration increase was noted. Likewise, carbon dioxide emissions (CO2), carbon monoxide (CO) and unburned hydrocarbons (HC) decreased as hydrogen concentration increased. On the other hand, nitrogen oxides emissions (NOx) increased due to average temperatures inside the cylinder being higher. There was also an increase in peak cylinder pressure and heat release rate inside the cylinder, since the fuel ignition delay was smaller due to hydrogen content increase. All this indicates that hydrogen promotes faster combustion and higher heat release rates and can be an important additive to all kind of fuels used in diesel generators.

Keywords: diesel engine, hydrogen, dual fuel, combustion analysis, performance, emissions

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Authors: Sivakumar Kottapalli, Abdesselam Abdelouas, Christoph Hartnack

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Spent nuclear fuel generates a mixed field of ionizing radiation to the water. This radiation field is generally dominated by gamma rays and a limited flux of fast neutrons. The fuel cladding effectively attenuates beta and alpha particle radiation. Small fraction of the spent nuclear fuel exhibits some degree of fuel cladding penetration due to pitting corrosion and mechanical failure. Breaches in the fuel cladding allow the exposure of small volumes of water in the cask to alpha and beta ionizing radiation. The safety of the transport of radioactive material is assured by the package complying with the IAEA Requirements for the Safe Transport of Radioactive Material SSR-6. It is of high interest to avoid generation of hydrogen inside the cavity which may to an explosive mixture. The risk of hydrogen production along with other radiation gases should be analyzed for a typical spent fuel for safety issues. This work aims to perform a realistic study of the production of hydrogen by radiolysis assuming most penalizing initial conditions. It consists in the calculation of the radionuclide inventory of a pellet taking into account the burn up and decays. Westinghouse 17X17 PWR fuel has been chosen and data has been analyzed for different sets of enrichment, burnup, cycles of irradiation and storage conditions. The inventory is calculated as the entry point for the simulation studies of hydrogen production by radiolysis kinetic models by MAKSIMA-CHEMIST. Dose rates decrease strongly within ~45 μm from the fuel surface towards the solution(water) in case of alpha radiation, while the dose rate decrease is lower in case of beta and even slower in case of gamma radiation. Calculations are carried out to obtain spectra as a function of time. Radiation dose rate profiles are taken as the input data for the iterative calculations. Hydrogen yield has been found to be around 0.02 mol/L. Calculations have been performed for a realistic scenario considering a capsule containing the spent fuel rod. Thus, hydrogen yield has been debated. Experiments are under progress to validate the hydrogen production rate using cyclotron at > 5MeV (at ARRONAX, Nantes).

Keywords: radiolysis, spent fuel, hydrogen, cyclotron

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Authors: Matteo Nicoli, Gianvito Colucci, Valeria Di Cosmo, Daniele Lerede, Laura Savoldi

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The transport sector is currently responsible for approximately 1/3 of greenhouse gas emissions in Europe. In the wider context of achieving carbon neutrality of the global energy system, different alternatives are available to decarbonizethe transport sector. In particular, while electricity is already the most consumed energy commodity in rail transport, battery electric vehicles are one of the zero-emissions options on the market for road transportation. On the other hand, hydrogen-based fuel cell vehicles are available for road and non-road vehicles. The European Commission is strongly pushing toward the integration of hydrogen in the energy systems of European countries and its widespread adoption as an energy vector to achieve the Green Deal targets. Furthermore, the Italian government is defining hydrogen-related objectives with the publication of a dedicated Hydrogen Strategy. The adoption of energy system optimization models to study the possible penetration of alternative zero-emitting transport technologies gives the opportunity to perform an overall analysis of the effects that the development of innovative technologies has on the entire energy system and on the supply-side, devoted to the production of energy carriers such as hydrogen and electricity. Using an open-source modeling framework such as TEMOA, this work aims to compare the role of hydrogen and electric vehicles in the decarbonization of the transport sector. The analysis investigates the advantages and disadvantages of adopting the two options, from the economic point of view (costs associated with the two options) and the environmental one (looking at the emissions reduction perspectives). Moreover, an analysis on the profitability of the investments in hydrogen and electric vehicles will be performed. The study investigates the evolution of energy consumption and greenhouse gas emissions in different transportation modes (road, rail, navigation, and aviation) by detailed analysis of the full range of vehicles included in the techno-economic database used in the TEMOA model instance adopted for this work. The transparency of the analysis is guaranteed by the accessibility of the TEMOA models, based on an open-access source code and databases.

Keywords: battery electric vehicles, decarbonization, energy system optimization models, fuel cell vehicles, hydrogen, open-source modeling, TEMOA, transport

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Authors: Mohamed Ayoub

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The structures and energetics of various isomeric hydrogen bonded dimers, such as (FH…OC, FH…CO), (FH…CNH, FH…NCH), (FH…N2O, FH…ON2), and (FH…NHCO, FH…OCNH) have been investigated using DFT B3LYP with aug-cc-pVTZ basis set and by natural bond orbital (NBO) analysis. For each isomeric pair we calculated: H-bond energy (ΔEB…H), charge-transfer (QCT), where B is atom bearing lone-pairs in CO, CNH, NCH, N2O, and NHCO, H-bond distances (RB…H), the elongation of HF bond (ΔRHF) and the red-shift of HF stretching frequency (ΔVHF). We conclude that the principle difference in the relative stability between each isomeric pair is attributed to distinctive interaction of carbon and oxygen lone pairs of CO, carbon and nitrogen lone-pairs of CNH and NCH, and nitrogen and oxygen lone pairs of N2O and NHCO into the unfilled antibond on HF (σ*HF).

Keywords: charge transfer, computational chemistry, isomeric hydrogen bond, natural bond orbital

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Authors: Juan Alfredo Guevara Carrio, Swamy Toolahalli Thipperudra, Riddhi Naik Dharmeshbhai, Sergio Graniero Echeverrigaray, Jose Vitorio Emiliano, Antonio Helio Castro

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In order to advance the hydrogen economy, several industrial sectors can potentially benefit from the trillions of stimulus spending for post-coronavirus. Blending hydrogen into natural gas pipeline networks has been proposed as a means of delivering it during the early market development phase, using separation and purification technologies downstream to extract the pure H₂ close to the point of end-use. This first step has been mentioned around the world as an opportunity to use existing infrastructures for immediate decarbonisation pathways. Among current technologies used to extract hydrogen from mixtures in pipelines or liquid carriers, membrane separation can achieve the highest selectivity. The most efficient approach for the separation of H₂ from other substances by membranes is offered from the research of 2D layered materials due to their exceptional physical and chemical properties. Graphene-based membranes, with their distribution of pore sizes in nanometers and angstrom range, have shown fundamental and economic advantages over other materials. Their combination with the structure of ceramic and geopolymeric materials enabled the synthesis of nanocomposites and the fabrication of membranes with long-term stability and robustness in a relevant range of physical and chemical conditions. Versatile separation modules have been developed for hydrogen separation, which adaptability allows their integration in industrial prototypes for applications in heavy transport, steel, and cement production, as well as small installations at end-user stations of pipeline networks. The developed membranes and prototypes are a practical contribution to the technological challenge of supply pure H₂ for the mentioned industries as well as hydrogen energy-based fuel cells.

Keywords: graphene nano-composite membranes, hydrogen separation and purification, separation modules, indsutrial prototype

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Authors: A. K. R. Gobinath, He Jianzhong, Kun-Lin Yang

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Fruit waste was used as a feedstock to produce biohydrogen in this study. Fruit waste used in this study was collected from several fruit juice stalls in Singapore. Based on our observation, the fruit waste contained 35-40% orange, 10-20% watermelon, 10-15% apple, 10-15% pineapple, 1-5% mango. They were mixed with water (1:1 ratio based on wet biomass) and blended to attain homogenous mixtures. Later, fruit waste was subjected to one of the following pretreatments: autoclave (121 °C for 20min), microwave (20min) or both. After pretreatment, the total sugar concentration in the hydrolysate was high (>12g/l) when both autoclave and microwave were applied. In contrast, samples without pretreatment measured only less than 2g/l of sugar. While using these hydrolysates as carbon sources, Clostridium strain BOH3 produces 2526-3126 ml/l of hydrogen after 72h of anaerobic fermentation. The hydrogen yield was 295-300 ml/g of sugar which is close to the hydrogen yields from glucose (338 ml/gm) and xylose (330 ml/gm). Our HPLC analysis showed that fruit waste hydrolysate contained oligosugars (25-27%), sucrose (18-23%), fructose (25-30%), glucose (10-15%) and mannose (2-5%). Additionally, pretreatment led to the release of free amino acids (160-512 mg/l), calcium (7.8-12.9 ppm), magnesium (4.32-6.55 ppm), potassium (5.4-65.1 ppm) and sodium (0.4-0.5 ppm) into the hydrolysate. These nutrients were able to support strain-BOH3 to grow and produce high level of hydrogen. Notably, unlike other pretreatment methods (with strong acids and bases), these pretreatment techniques did not generate any inhibitors (e.g. furfural and phenolic acids) to suppress the hydrogen production. Interestingly, strain BOH3 can also ferment pretreated fruit waste slurry and produce hydrogen with a high yield (156-343 ml/gm fruit waste). While fermenting pretreated fruit waste slurry, strain-BOH3 excreted several saccharolytic enzymes majorly xylanase (1.84U/ml), amylase (1.10U/ml), pectinase (0.36U/ml) and cellulase (0.43U/ml). Due to expressions of these enzymes, strain BOH3 was able to directly utilize pretreated fruit waste hydrolysate and produces high-level of hydrogen.

Keywords: autoclave pretreatment, biohydrogen production, clostridial fermentation, fruit waste, and microwave pretreatment

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Authors: Talal Hasan, Akram Mohammad

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Carbon-free combustion has great attention in today’s research for its unlimited benefits regarding various factors, and ammonia is considered a potential carbon-free alternative gas despite its flame characteristics. The Shrestha mechanism and Chemkin-Pro software will be used for numerical data. Firstly, experimental and numerical results should show good agreement to move for studying the laminar flame speed of ammonia under various conditions. Ammonia flame speed will be investigated under normal conditions (298 K, 1 atm) as well as under the influence of a range of equivalence ratios (0.6-1.8), elevated temperatures (298,323,373,423, and 473), elevated pressures (1 atm- 70 atm) and finally at varying hydrogen content (0-100%). Therefore, this work will understand the ammonia laminar flame speed characteristics and how and to what extent hydrogen can improve ammonia combustion intensity.

Keywords: laminar burning velocity, ammonia, hydrogen, combustion

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Authors: Dongju Kim, Youngjoo Suh, Hyojin Kim, Gyeongyeong Kim

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Acoustic Emission Testing (AET) is widely used to test the structural integrity of an operational hydrogen storage container, and clustering algorithms are frequently used in pattern recognition methods to interpret AET results. However, the interpretation of AET results can vary from user to user as the tuning of the relevant parameters relies on the user's experience and knowledge of AET. Therefore, it is necessary to use a deep learning model to identify patterns in acoustic emission (AE) signal data that can be used to classify defects instead. In this paper, a deep learning-based model for classifying the types of defects in hydrogen storage tanks, using AE sensor waveforms, is proposed. As hydrogen storage tanks are commonly constructed using carbon fiber reinforced polymer composite (CFRP), a defect classification dataset is collected through a tensile test on a specimen of CFRP with an AE sensor attached. The performance of the classification model, using one-dimensional convolutional neural network (1-D CNN) and synthetic minority oversampling technique (SMOTE) data augmentation, achieved 91.09% accuracy for each defect. It is expected that the deep learning classification model in this paper, used with AET, will help in evaluating the operational safety of hydrogen storage containers.

Keywords: acoustic emission testing, carbon fiber reinforced polymer composite, one-dimensional convolutional neural network, smote data augmentation

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Authors: Ratnakumar V. Kappagantula, Gordon D. Ingram, Hari B. Vuthaluru

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This paper analyzes a three reactor chemical looping process for hydrogen production from natural gas, allowing for carbon dioxide capture through chemical looping technology. An oxygen carrier is circulated to separate carbon dioxide, to reduce steam for hydrogen production and to supply oxygen for combustion. In this study, the emphasis is placed on the steam conversion in the steam reactor by investigating the hydrogen efficiencies of the complete system at steam conversions of 15.8% and 50%. An Aspen Plus model was developed for a Three Reactor Chemical Looping process to study the effects of operational parameters on hydrogen production is investigated. Maximum hydrogen production was observed under stoichiometric conditions. Different conversions in the steam reactor, which was modelled as a Gibbs reactor, were found when Gibbs-identified products and user identified products were chosen. Simulations were performed for different oxygen carriers, which consist of an active metal oxide on an inert support material. For the same metal oxide mass flowrate, the fuel reactor temperature decreased for different support materials in the order: aluminum oxide (Al2O3) > magnesium aluminate (MgAl2O4) > zirconia (ZrO2). To achieve the same fuel reactor temperature for the same oxide mass flow rate, the inert mass fraction was found to be 0.825 for ZrO2, 0.7 for MgAl2O4 and 0.6 for Al2O3. The effect of poisoning of the oxygen carrier was also analyzed. With 3000 ppm sulfur-based impurities in the feed gas, the hydrogen product energy rate of the process were found to decrease by 0.4%.

Keywords: aspen plus, chemical looping combustion, inert support balls, oxygen carrier

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Authors: Indra Gonzalez Ojeda, Tatiana Quinones, Manuel Rosario, Igor Lednev, Juan Lopez Garriga

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Amyloid fibrils are stable aggregates of misfolded protein associated with many neurodegenerative disorders. It has been shown that hydrogen sulfide (H2S), inhibits the fibrillation of lysozyme through the formation of trisulfide (S-S-S) bonds. However, the overall mechanism remains elusive. Here, the concentration dependence of H2S effect was investigated using Atomic force microscopy (AFM), non-resonance Raman spectroscopy, Deep-UV Raman spectroscopy and circular dichroism (CD). It was found that small spherical aggregates with trisulfide bonds and a unique secondary structure were formed instead of amyloid fibrils when adding concentrations of 25 mM and 50 mM of H2S. This could indicate that H2S might serve as a protecting agent for the protein. However, further characterization of these aggregates and their trisulfide bonds is needed to fully unravel the function H2S has on protein fibrillation.

Keywords: amyloid fibrils, hydrogen sulfide, protein folding, raman spectroscopy

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Authors: Juan A. G. Carrio, Prasad Talluri, Sergio G. Echeverrigaray, Antonio H. Castro Neto

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Hydrogen as a fuel and environmentally pleasant energy carrier is part of this transition towards low-carbon systems. The extensive deployment of hydrogen production, purification and transport infrastructures still represents significant challenges. Independent of the production process, the hydrogen generally is mixed with light hydrocarbons and other undesirable gases that need to be removed to obtain H₂ with the required purity for end applications. In this context, membranes are one of the simplest, most attractive, sustainable, and performant technologies enabling hydrogen separation and purification. They demonstrate high separation efficiencies and low energy consumption levels in operation, which is a significant leap compared to current energy-intensive options technologies. The unique characteristics of 2D laminates have given rise to a diversity of research on their potential applications in separation systems. Specifically, it is already known in the scientific literature that graphene oxide-based membranes present the highest reported selectivity of H₂ over other gases. This work explores the potential of a new type of 2D materials-based membranes in separating H₂ from CO₂ and CH₄. We have developed nanostructured composites based on 2D materials that have been applied in the fabrication of membranes to maximise H₂ selectivity and permeability, for different gas mixtures, by adjusting the membranes' characteristics. Our proprietary technology does not depend on specific porous substrates, which allows its integration in diverse separation modules with different geometries and configurations, looking to address the technical performance required for industrial applications and economic viability. The tuning and precise control of the processing parameters allowed us to control the thicknesses of the membranes below 100 nanometres to provide high permeabilities. Our results for the selectivity of new nanostructured 2D materials-based membranes are in the range of the performance reported in the available literature around 2D materials (such as graphene oxide) applied to hydrogen purification, which validates their use as one of the most promising next-generation hydrogen separation and purification solutions.

Keywords: membranes, 2D materials, hydrogen purification, nanocomposites

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Authors: Muhammad Syahir Aminuddin, Zakaria Man, Mohamad Azmi Bustam Khalil

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In order to identify the best possible reaction media for performing H₂S conversion, a total number of 300 different ILs from a combination of 20 cations and 15 anions were screened via COSMO-RS model simulations. By COSMO-RS method, thermodynamic and physicochemical properties of 300 ILs, such as Henry's law constants, activity coefficient, selectivity, capacity, and performance index, are obtained and analyzed. Thus, by comparing the performance of ILs via COSMO-RS, a series of TSILs containing cation of [P66614] with metal chloride anions such as Fe, Ga, and Al were chosen and selected for synthesis based on their performance predicted by COSMO-RS and their economic values. Consequently, the physiochemical properties such as density, viscosity, thermal properties, as well as H₂S absorptive oxidation performances in those TSILs will be systematically investigated.

Keywords: conversion of hydrogen sulfide, hydrogen sulfide, H₂S, sour natural gas, task specific ionic liquids

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Authors: Athanasios A. Tountas, Geoffrey A. Ozin, Mohini M. Sain

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Renewable hydrogen (H₂) carriers such as methanol (MeOH), dimethyl ether (DME), oxymethylene dimethyl ethers (OMEs), and conceivably ammonia (NH₃) can be reformed back into H₂ and are fundamental chemical conversions for the long-term viability of the H₂ economy due to their higher densities and ease of transportability compared to H₂. MeOH is an especially important carrier as it is a simple C1 chemical that can be produced from green solar-PV-generated H₂ and direct-air-captured CO₂ with a current commercially practical solar-to-fuel efficiency of 10% from renewable solar energy. MeOH steam reforming (MSR) in stationary systems next to H₂ fuel-cell filling stations can eliminate the need for onboard mobile reformers, and the former systems can be more robust in terms of attaining strict H₂ product specifications, and MeOH is a safe, lossless, and compact medium for long-term H₂ storage. Both thermal- and photo-catalysts are viable options for achieving the stable, long-term performance of stationary MSR systems.

Keywords: fuel-cell vehicle filling stations, methanol steam reforming, hydrogen transport and storage, stationary reformer, liquid hydrogen carriers

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Authors: D. Amaranatha Reddy

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Highly efficient and stable co-catalysts materials is of great important for boosting photo charge carrier’s separation, transportation efficiency, and accelerating the catalytic reactive sites of semiconductor photocatalysts. As a result, it is of decisive importance to fabricate low price noble metal free co-catalysts with high catalytic reactivity, but it remains very challenging. Considering this challenge here, dual metal organic frame work derived N-Doped Fe3C nanocages have been rationally designed and decorated with ultrathin ZnIn2S4 nanosheets for efficient photocatalytic hydrogen generation. The fabrication strategy precisely integrates co-catalyst nanocages with ultrathin two-dimensional (2D) semiconductor nanosheets by providing tightly interconnected nano-junctions and helps to suppress the charge carrier’s recombination rate. Furthermore, constructed highly porous hybrid structures expose ample active sites for catalytic reduction reactions and harvest visible light more effectively by light scattering. As a result, fabricated nanostructures exhibit superior solar driven hydrogen evolution rate (9600 µmol/g/h) with an apparent quantum efficiency of 3.6 %, which is relatively higher than the Pt noble metal co-catalyst systems and earlier reported ZnIn2S4 based nanohybrids. We believe that the present work promotes the application of sulfide based nanostructures in solar driven hydrogen production.

Keywords: photocatalysis, water splitting, hydrogen fuel production, solar-driven hydrogen

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Authors: I. Wiemann, N. Weiß, E. Schlücker, M. Wensing

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A very promising alternative to compression or cryogenics is the chemical storage of hydrogen by liquid organic hydrogen carriers (LOHC). These carriers enable high energy density and allow, at the same time, efficient and safe storage under ambient conditions without leakage losses. Another benefit of this storage medium is the possibility of transporting it using already available infrastructure for the transport of fossil fuels. Efficient use of LOHC is related to precise process control, which requires a number of sensors in order to measure all relevant process parameters, for example, to measure the level of hydrogen loading of the carrier. The degree of loading is relevant for the energy content of the storage carrier and simultaneously represents the modification in the chemical structure of the carrier molecules. This variation can be detected in different physical properties like permittivity, viscosity, or density. E.g., each degree of loading corresponds to different viscosity values. Conventional measurements currently use invasive viscosity measurements or near-line measurements to obtain quantitative information. This study investigates permittivity changes resulting from changes in hydrogenation degree (chemical structure) and temperature. Based on calibration measurements, the degree of loading and temperature of LOHC can thus be determined by comparatively simple permittivity measurements in a cavity resonator. Subsequently, viscosity and density can be calculated. An experimental setup with a heating device and flow test bench was designed. By varying temperature in the range of 293,15 K -393,15 K and flow velocity up to 140 mm/s, corresponding changes in the resonation frequency were determined in the hundredths of the GHz range. This approach allows inline process monitoring of hydrogenation of the liquid organic hydrogen carrier (LOHC).

Keywords: hydrogen loading, LOHC, measurement, permittivity, viscosity

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Authors: Belyayev P. E., Makeyeva I. R., Mastyuk D. A., Pigasov E. E.

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Previously, the phrase ”hydrogen safety” was often used in terms of NPP safety. Due to the rise of interest to “green” and, particularly, hydrogen power engineering, the problem of hydrogen safety at industrial facilities has become ever more urgent. In Russia, the industrial production of hydrogen is meant to be performed by placing a chemical engineering plant near NPP, which supplies the plant with the necessary energy. In this approach, the production of hydrogen involves a wide range of combustible gases, such as methane, carbon monoxide, and hydrogen itself. Considering probable incidents, sudden combustible gas outburst into open space with further ignition is less dangerous by itself than ignition of the combustible mixture in the presence of many pipelines, reactor vessels, and any kind of fitting frames. Even ignition of 2100 cubic meters of the hydrogen-air mixture in open space gives velocity and pressure that are much lesser than velocity and pressure in Chapman-Jouguet condition and do not exceed 80 m/s and 6 kPa accordingly. However, the space blockage, the significant change of channel diameter on the way of flame propagation, and the presence of gas suspension lead to significant deflagration acceleration and to its transition into detonation or quasi-detonation. At the same time, process parameters acquired from the experiments at specific experimental facilities are not general, and their application to different facilities can only have a conventional and qualitative character. Yet, conducting deflagration and detonation experimental investigation for each specific industrial facility project in order to determine safe infrastructure unit placement does not seem feasible due to its high cost and hazard, while the conduction of numerical experiments is significantly cheaper and safer. Hence, the development of a numerical method that allows the description of reacting flows in domains with complex geometry seems promising. The base for this method is the modification of Kuropatenko method for calculating shock waves recently developed by authors, which allows using it in Eulerian coordinates. The current work contains the results of the development process. In addition, the comparison of numerical simulation results and experimental series with flame propagation in shock tubes with orifice plates is presented.

Keywords: CFD, reacting flow, DDT, gas explosion

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Authors: Kamyar Maleki Bagherabadi, Torstein Aarseth Bø, Truls Flatberg, Olve Mo

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Hydrogen fuel cells and batteries are one of the promising solutions aligned with carbon emission reduction goals for the marine sector. However, the higher installation and operation costs of hydrogen-based systems compared to conventional diesel gensets raise questions about the appropriate hydrogen tank size, energy, and fuel consumption estimations. Ship designers need methodologies and tools to calculate energy and fuel consumption for different component sizes to facilitate decision-making regarding feasibility and performance for retrofits and design cases. The aim of this work is to compare three alternative modeling approaches for the estimation of energy and fuel consumption with various hydrogen tank sizes, battery capacities, and load-sharing strategies. A fishery vessel is selected as an example, using logged load demand data over a year of operations. The modeled power system consists of a PEM fuel cell, a diesel genset, and a battery. The methodologies used are: first, an energy-based model; second, considering load variations during the time domain with a rule-based Power Management System (PMS); and third, a load variations model and dynamic PMS strategy based on optimization with perfect foresight. The errors and potentials of the methods are discussed, and design sensitivity studies for this case are conducted. The results show that the energy-based method can estimate fuel and energy consumption with acceptable accuracy. However, models that consider time variation of the load provide more realistic estimations of energy and fuel consumption regarding hydrogen tank and battery size, still within low computational time.

Keywords: fuel cell, battery, hydrogen, hybrid power system, power management system

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Authors: Heba M. Gobara, Ahmed A. M. El-Naggar, Rasha S. El-Sayed, Amal A. AlKahlawy

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In this study, metal organic framework (Cr-MIL-101) and TiO₂ nanoparticles were utilized as two semiconductors for water splitting process. The coupling of both semiconductors in order to improve the photocatalytic reactivity for the hydrogen production in presence of methanol as a hole scavenger under visible light (sunlight) has been performed. The forementioned semiconductors and the collected samples after water splitting application are characterized by several techniques viz., XRD, N₂ adsorption-desorption, TEM, ED, EDX, Raman spectroscopy and the total content of carbon. The results revealed an efficient yield of H₂ production with maximum purity 99.3% with the in-situ formation of graphene oxide nanosheets and multiwalled carbon nanotubes coated over the surface of the physically mixed Cr-MIL-101–TiO₂ system. The amount of H₂ gas produced was stored when using Cr-MIL-101 catalyst individually. The obtained data in this work provides promising candidate materials for pure hydrogen production as a clean fuel acquired from the water splitting process. In addition, the in-situ production of graphene nanosheets and carbon nanotubes is counted as promising advances for the presented process.

Keywords: hydrogen production, water splitting, photocatalysts, Graphene

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Authors: Annapurna Basavaraju, Arianna Mastrodonato, Franz Heitmeir

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The Advisory Council for Aeronautics Research in Europe (ACARE) is creating awareness for the overall reduction of NOx emissions by 80% in its vision 2020. Hence this promotes the researchers to work on novel technologies, one such technology is the use of alternative fuels. Among these fuels hydrogen is of interest due to its one and only significant pollutant NOx. The influence of NOx formation due to hydrogen combustion depends on various parameters such as air pressure, inlet air temperature, air to fuel jet momentum ratio etc. Appropriately, this research is motivated to investigate the impact of the air to fuel jet momentum ratio onto the NOx formation in a hydrogen combustion chamber for aircraft engines. The air to jet fuel momentum is defined as the ratio of impulse/momentum of air with respect to the momentum of fuel. The experiments were performed in an existing combustion chamber that has been previously tested for methane. Premix of the reactants has not been considered due to the high reactivity of the hydrogen and high risk of a flashback. In order to create a less rich zone of reaction at the burner and to decrease the emissions, a forced internal recirculation flow has been achieved by integrating a plate similar to honeycomb structure, suitable to the geometry of the liner. The liner has been provided with an external cooling system to avoid the increase of local temperatures and in turn the reaction rate of the NOx formation. The injected air has been preheated to aim at so called flameless combustion. The air to fuel jet momentum ratio has been inspected by changing the area of fuel inlets and keeping the number of fuel inlets constant in order to alter the fuel jet momentum, thus maintaining the homogeneity of the flow. Within this analysis, promising results for a flameless combustion have been achieved. For a constant number of fuel inlets, it was seen that the reduction of the fuel inlet diameter resulted in decrease of air to fuel jet momentum ratio in turn lowering the NOx emissions.

Keywords: combustion chamber, hydrogen, jet momentum, NOx emission

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Authors: Alessandro Balbo, Gianvito Colucci, Matteo Nicoli, Laura Savoldi

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Hydrogen is expected to become a game changer in the energy transition, especially enabling sector coupling possibilities and the decarbonization of hard-to-abate end-uses. The Italian National Recovery and Resilience Plan identifies hydrogen as one of the key elements of the ecologic transition to meet international decarbonization objectives, also including it in several pilot projects for the early development in Italy. This matches the European energy strategy, which aims to make hydrogen a leading energy carrier of the future, setting ambitious goals to be accomplished by 2030. The huge efforts needed to achieve the announced targets require to carefully investigate of their feasibility in terms of economic expenditures and technical aspects. In order to quantitatively assess the hydrogen potential within the Italian context and the feasibility of the planned investments and projects, this work uses the TEMOA-Italy energy system model to study pathways to meet the strict objectives above cited. The possible hydrogen development has been studied both in the supply-side and demand-side of the energy system, also including storage options and distribution chains. The assessment comprehends alternative hydrogen production technologies involved in a competition market, reflecting the several possible investments declined by the Italian National Recovery and Resilience Plan to boost the development and spread of this infrastructure, including the sector coupling potential with natural gas through the currently existing infrastructure and CO2 capture for the production of synfuels. On the other hand, the hydrogen end-uses phase covers a wide range of consumption alternatives, from fuel-cell vehicles, for which both road and non-road transport categories are considered, to steel, and chemical industries uses and cogeneration for residential and commercial buildings. The model includes both high and low TRL technologies in order to provide a consistent outcome for the future decades as it does for the present day, and since it is developed through the use of an open-source code instance and database, transparency and accessibility are fully granted.

Keywords: decarbonization, energy system optimization models, hydrogen, open-source modeling, TEMOA

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Authors: Wojciech J. Nowak, Natalia Maciaszek, Marcin Drajewicz

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A constant requirement to reduce greenhouse gas emissions in combination with the desire to increase gas turbine efficiency results in a continuous trend to increase the operating temperature of gas turbines. An increase in operating temperature will result in lower fuel consumption, and a higher combustion temperature will result in lower pollution release. Moreover, there is a strong trend for hydrogen to be used as an alternative and clean fuel. However, using hydrogen or hydrogen-rich fuel results in a higher combustion temperature, as well as an increase in the water vapor content in the exhaust gases. Commonly used Ni-base alloys have their limits. Moreover, the presence of water vapor worsens the oxidation behavior of Ni-based alloys at a high temperature. Therefore, a new brand of materials is demanded to be used in gas turbines operated with hydrogen-rich fuel. High-entropy alloys (HEAs) seem to be very promising materials to replace commonly used Ni-based alloys. HEAs are the group of materials consisting of at least five main equiatomic elements. These alloys can be doped by other elements in amounts less than 5 at. % in total. Thus, in the present study, NiCoCrAlFe-X alloys are studied in terms of oxidation behavior during exposure to dry and wet atmospheres up to 1000 h. NiCoCrAlFe-X alloys are doped with minor alloying elements in amounts ranging from 1-5 at.%. The effect of the chemical composition on oxidation resistance in dry and wet atmospheres will be shown and discussed.

Keywords: high entropy alloys, oxidation resistance, hydrogen fuel, water vapor

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Authors: Vera Marcantonio, Marcello De Falco, Mauro Capocelli, Álvaro Amado-Fierro, Teresa A. Centeno, Enrico Bocci

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Concerns about energy security, energy prices, and climate change led scientific research towards sustainable solutions to fossil fuel as renewable energy sources coupled with hydrogen as an energy vector and carbon capture and conversion technologies. Among the technologies investigated in the last decades, biomass gasification acquired great interest owing to the possibility of obtaining low-cost and CO₂ negative emission hydrogen production from a large variety of everywhere available organic wastes. Upstream and downstream treatment were then studied in order to maximize hydrogen yield, reduce the content of organic and inorganic contaminants under the admissible levels for the technologies which are coupled with, capture, and convert carbon dioxide. However, studies which analyse a whole process made of all those technologies are still missing. In order to fill this lack, the present paper investigated the coexistence of hydrothermal carbonization (HTC), sorption enhance gasification (SEG), hot gas cleaning (HGC), and CO₂ conversion by dielectric barrier discharge (DBD) plasma reactor for H₂ production from biomass waste by means of Aspen Plus software. The proposed model aimed to identify and optimise the performance of the plant by varying operating parameters (such as temperature, CaO/biomass ratio, separation efficiency, etc.). The carbon footprint of the global plant is 2.3 kg CO₂/kg H₂, lower than the latest limit value imposed by the European Commission to consider hydrogen as “clean”, that was set to 3 kg CO₂/kg H₂. The hydrogen yield referred to the whole plant is 250 gH₂/kgBIOMASS.

Keywords: biomass gasification, hydrogen, aspen plus, sorption enhance gasification

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Authors: Palash Kumar Mollick, Leire Olazar, Laura Santamaria, Pablo Comendador, Gartzen Lopez, Martin Olazar

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Average calorific value of a mixure of waste plastic is approximately 38 MJ/kg. Present work aims to extract maximum possible energy from a mixure of waste plastic using a DC thermal plasma in a spouted bed reactor. Plasma pyrolysis and steam reforming process has shown a potential to generate hydrogen from plastic with much below of legal limit of producing dioxins and furans as the carcinogenic gases. A spouted bed pyrolysis rector can continuously process plastic beads to produce organic volatiles, which later react with steam in presence of catalyst to results in syngas. lasma being the fourth state of matter, can carry high impact electrons to favour the activation energy of any chemical reactions. Computational Fluid Dynamic (CFD) simulation using COMSOL Multiphysics software has been performed to evaluate performance of a plasma spouted bed reactor in producing contamination free hydrogen as a green energy from waste plastic beads. The simulation results will showcase a design of a plasma spouted bed reactor for converting plastic waste into green hydrogen in a single step process. The high temperature hydrodynamics of spouted bed with plastic beads and the corresponding temperature distribution inside the reaction chamber will be critically examined for it’s near future installation of demonstration plant.

Keywords: green hydrogen, plastic waste, synthetic gas, pyrolysis, steam reforming, spouted bed, reactor design, plasma, dc palsma, cfd simulation

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Authors: Mohammed Kamil, M. M. Rahman, Rosli A. Bakar

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Modeling of hydrogen fueled engine (H₂ICE) injection system is a very important tool that can be used for explaining or predicting the effect of advanced injection strategies on combustion and emissions. In this paper, a common rail injection system (CRIS) is proposed for 4-strokes 4-cylinders hydrogen fueled engine with port injection feeding system (PIH₂ICE). For this system, a numerical one-dimensional gas dynamic model is developed considering single injection event for each injector per a cycle. One-dimensional flow equations in conservation form are used to simulate wave propagation phenomenon throughout the CR (accumulator). Using this model, the effect of common rail on the injection system characteristics is clarified. These characteristics include: rail pressure, sound velocity, rail mass flow rate, injected mass flow rate and pressure drop across injectors. The interaction effects of operational conditions (engine speed and rail pressure) and geometrical features (injector hole diameter) are illustrated; and the required compromised solutions are highlighted. The CRIS is shown to be a promising enhancement for PIH₂ICE.

Keywords: common rail, hydrogen engine, port injection, wave propagation

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Authors: Priya Ruban, Thirunavoukkarasu Manikkannan, Sakthivel Ramasamy

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Sulfide is one of the major pollutants of tannery effluent which is mainly generated during the process of unhairing. Recovery of Hydrogen green fuel from sulfide wastewater using photocatalysis is a ‘Cleaner Production Method’, since renewable solar energy is utilized. It has triple advantages of the generation of H2, waste minimization and odor or pollution control. Designing of safe and green photocatalysts and developing suitable solar photoreactor is important for promoting this technology to large-scale application. In this study, green photocatalyst i.e., spinach derived carbon dots (SCDs 5 wt % and 10 wt %)/TiO2 nanocomposite was synthesized for generation of H2 from sulfide wastewater using lab-scale solar photocatalytic reactor. The physical characterization of the synthesized solar light responsive nanocomposites were studied by using DRS UV-Vis, XRD, FTIR and FESEM analysis. The absorption edge of TiO2 nanoparticles is extended to visible region by the incorporation of SCDs, which was used for converting noxious pollutant sulfide into eco-friendly solar fuel H2. The SCDs (10 wt%)-TiO2 nanocomposite exhibits enhanced photocatalytic hydrogen production i.e. ~27 mL of H2 (180 min) from simulated sulfide wastewater under LED visible light irradiation which is higher as compared to SCDs. The enhancement in the photocatalytic generation of H2 is attributed to combining of SCDs which increased the charge mobility. This work may provide new insights to usage of naturally available and cheap materials to design novel nanocomposite as a visible light active photocatalyst for the generation of H2 from sulfide containing wastewater.

Keywords: carbon dots, hydrogen fuel, hydrogen sulfide, photocatalysis, sulfide wastewater

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Authors: Saud Hamdan Alshammari

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Photocatalytic water splitting to produce hydrogen (H₂) has obtained significant attention as an environmentally friendly technology. This process, which produces hydrogen from water and sunlight, represents a renewable energy source. Titanium dioxide (TiO₂) plays a critical role in photocatalytic hydrogen production due to its chemical stability, availability, and low cost. Nevertheless, TiO₂'s wide band gap (3.2 eV) limits its visible light absorption and might affect the effectiveness of the photocatalytic. Coupling TiO₂ with other semiconductors is a strategy that can enhance TiO₂ by narrowing its band gap and improving visible light absorption. This paper studies the modification of TiO₂ by coupling it with another semiconductor such as CdS nanoparticles using a reflux reactor and autoclave reactor that helps form a core-shell structure. Characterization techniques, including TEM and UV-Vis spectroscopy, confirmed successful coating of TiO₂ on CdS core, reduction of the band gap from 3.28 eV to 3.1 eV, and enhanced light absorption in the visible region. These modifications are attributed to the heterojunction structure between TiO₂ and CdS.The essential goal of this study is to improve TiO₂ for use in photocatalytic water splitting to enhance hydrogen production. The core-shell TiO₂@CdS nanoparticles exhibited promising results, due to band gap narrowing and improved light absorption. Future work will involve adding Pt as a co-catalyst, which is known to increase surface reaction activity by enhancing proton adsorption. Evaluation of the TiO₂@CdS@Pt catalyst will include performance assessments and hydrogen productivity tests, considering factors such as effective shapes and material ratios. Moreover, the study could be enhanced by studying further modifications to the catalyst and displaying additional performance evaluations. For instance, doping TiO₂ with metals such as nickel (Ni), iron (Fe), and cobalt (Co) and non-metals such as nitrogen (N), carbon (C), and sulfur (S) could positively influence the catalyst by reducing the band gap, enhancing the separation of photogenerated electron-hole pairs, and increasing the surface area, respectively. Additionally, to further improve catalytic performance, examining different catalyst morphologies, such as nanorods, nanowires, and nanosheets, in hydrogen production could be highly beneficial. Optimizing photoreactor design for efficient photon delivery and illumination will further enhance the photocatalytic process. These strategies collectively aim to overcome current challenges and improve the efficiency of hydrogen production via photocatalysis.

Keywords: hydrogen production, photocatalytic, water spliiting, semiconductor, nanoparticles

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Authors: A. Alkattib, M. Boumaza

Abstract:

Steam reforming is industrially important as it is incorporated in several major chemical processes including the production of ammonia, methanol, hydrogen and ox alcohols. Due to the strongly endothermic nature of the process, a large amount of heat is supplied by fuel burning (commonly natural gas) in the furnace chamber. Reaction conversions, tube catalyst life, energy consumption and CO2 emission represent the principal factors affecting the performance of this unit and are directly influenced by the high operating temperatures and pressures. This study presents a simulation of the performance of the reforming of methane in a primary reformer, through a developed empirical relation which enables to investigate the effects of operating parameters such as the pressure, temperature, steam to carbon ratio on the production of hydrogen, as well as the fraction of non-converted methane. It appears from this analysis that the exit temperature Te, the operating pressure as well the steam to carbon ratio has an important effect on the reforming of methane.

Keywords: reforming, methane, performance, hydrogen, parameters

Procedia PDF Downloads 226