Search results for: electrolytic hydrogen charging

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: Jean Paul Hategekimana, Josiane Irakoze, Eugene Niyonzima, Annick Ndekezi

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Cassava (Manihot esculenta Crantz) is a root crop comprising an anti-nutritive factor known as cyanide. The compound can be removed by numerous processing methods such as boiling, fermentation, blanching, and sun drying to avoid the possibility of cyanide poisoning. Inappropriate processing mean can lead to disease and death. Cassava-based dishes are consumed in different ways, where cassava is cultivated according to their culture and preference. However, they have been shown to be unsafe based on high cyanide levels. The current study targeted to resolve the problem of high cyanide in cassava consumed in Rwanda. This study was conducted to determine the effect of slicing, blanching, and soaking time to reduce the fermentation duration of cassava for hydrogen cyanide (HCN) in mg/g removal. Cassava was sliced into three different portions (1cm, 2cm, and 5cm). The first portions were naturally fermented for seven days, where each portion was removed every 24 hours from soaking tanks and then oven dried at a temperature of 60°C and then milled to obtain naturally fermented cassava flours. Other portions of 1cm, 2cm, and 5cm were blanched for 2, 5, 10 min, respectively, and each similarly dried at 60°C and milled to produce blanched cassava flour. Other blanched portions were used to follow the previous fermentation steps. The last portions, which formed the control, were simply chopped. Cyanide content and starch content in mg/100g were investigated. According to the conducted analysis on different cassava treatments for detoxification, found that usual fermentation can be used, but for sliced portions aimed to size reduction for the easy hydrogen cyanide diffuse out and it takes four days to complete fermentation, which has reduced at 94.44% with significantly different (p<0.05)of total hydrogen cyanide contained in cassava to safe level of consumption, and what is recommended as more effective is to apply blanching combined with fermentation due to the fact that, it takes three days to complete hydrogen cyanide removal at 95.56% on significantly different (p<0.05) of reduction to the safe level of consumption.

Keywords: cassava, cyanide, blanching, drying, fermentation

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Authors: Abdul Hadi Bin Abdol Rahim, Alhassan Salami Tijani

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Hydrogen produced by means of polymer electrolyte membrane electrolyzer (PEME) is one of the most promising methods due to clean and renewable energy source. In the process, some energy loss due to mass transfer through a PEM is caused by diffusion, electro-osmotic drag, and the pressure difference between the cathode channel and anode channel. In PEME water molecules and ionic particles transferred between the electrodes from anode to cathode, Extensive mixing of the hydrogen and oxygen at anode channel due to gases cross-over must be avoided. In recent times the consciousness of safety issue in high pressure PEME where the oxygen mix with hydrogen at anode channel could create, explosive conditions have generated a lot of concern. In this paper, the steady state and simulation analysis of gases crossover in PEME on the temperature and pressure effect are presented. The simulations have been analysis in MATLAB based on the well-known Fick’s Law of molecular diffusion. The simulation results indicated that as temperature increases, there is a significant decrease in operating voltage.

Keywords: diffusion, gases crosover, steady state, Fick’s law

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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: Boris M. Popović, Tatjana Jurić, Bojana Blagojević, Denis Uka, Ružica Ždero Pavlović

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Green solvents are environmentally friendly and greatly improve the sustainability of chemical processes. There is a growing interest in the green extraction of polyphenols from fruits. In this study, we consider three Natural Deep Eutectic Solvents (NADES) systems based on choline chloride as a hydrogen bond acceptor and malic acid, urea, and fructose as hydrogen bond donors. NADES systems were prepared by heating and stirring, ultrasound, and microwave (MW) methods. Sour cherry pomace was used as a natural source of polyphenols. Polyphenol extraction from cherry pomace was performed by ultrasound-assisted extraction and microwave-assisted extraction and compared with conventional heat and stirring method extraction. It was found that MW-assisted preparation of NADES was the fastest, requiring less than 30 s. Also, MW extraction of polyphenols was the most rapid, with less than 5 min necessary for the extract preparation. All three NADES systems were highly efficient for anthocyanin extraction, but the most efficient was the system with malic acid as a hydrogen bond donor (yield of anthocyanin content was enhanced by 62.33% after MW extraction with NADES compared with the conventional solvent).

Keywords: anthocyanins, green extraction, NADES, polyphenols

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Authors: Shashank Gupta, Shiva Garg

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The purpose of the present paper is to study the changes in the strength characteristics of autoclaved aerated concrete (AAC) and also the density when different expansion agents are used. The expansion agent so used releases air in the concrete thereby making it lighter by reducing its density. It also increases the workability of the concrete. The various air entraining agents used for this study are hydrogen peroxide, oleic acid, and olive oil. The addition of these agents causes the concrete to rise like cake but it reduces the strength of concrete due to the formation of air voids. The amount of agents chosen for concrete production are 0.5%, 1%, 1.5% by weight of cement.

Keywords: AAC, olive oil, hydrogen peroxide, oleic acid, steam curing

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Authors: Marcin Stasiulewicz, Sebastian Filipkowski, Aneta Panuszko

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Background: The hallmark of neurodegenerative diseases, including Alzheimer's and Parkinson's diseases, is an aggregation of the abnormal forms of peptides and proteins. Water is essential to functioning biomolecules, and it is one of the key factors influencing protein folding and misfolding. However, the hydration studies of proteins are complicated due to the complexity of protein systems. The use of model compounds can facilitate the interpretation of results involving larger systems. Objectives: The goal of the research was to characterize the properties of the hydration water surrounding the two three-residue K peptide fragments INS (Isoleucine - Asparagine - Serine) and NSR (Asparagine - Serine - Arginine). Methods: Fourier-transform infrared spectra of aqueous solutions of the tripeptides were recorded on Nicolet 8700 spectrometer (Thermo Electron Co.) Measurements were carried out at 25°C for varying molality of solute. To remove oscillation couplings from water spectra and, consequently, obtain narrow O-D semi-heavy water bands (HDO), the isotopic dilution method of HDO in H₂O was used. The difference spectra method allowed us to isolate the tripeptide-affected HDO spectrum. Results: The structural and energetic properties of water affected by the tripeptides were compared to the properties of pure water. The shift of the values of the gravity center of bands (related to the mean energy of water hydrogen bonds) towards lower values with respect to the ones corresponding to pure water suggests that the energy of hydrogen bonds between water molecules surrounding tripeptides is higher than in pure water. A comparison of the values of the mean oxygen-oxygen distances in water affected by tripeptides and pure water indicates that water-water hydrogen bonds are shorter in the presence of these tripeptides. The analysis of differences in oxygen-oxygen distance distributions between the tripeptide-affected water and pure water indicates that around the tripeptides, the contribution of water molecules with the mean energy of hydrogen bonds decreases, and simultaneously the contribution of strong hydrogen bonds increases. Conclusions: It was found that hydrogen bonds between water molecules in the hydration sphere of tripeptides are shorter and stronger than in pure water. It means that in the presence of the tested tripeptides, the structure of water is strengthened compared to pure water. Moreover, it has been shown that in the vicinity of the Asparagine - Serine - Arginine, water forms stronger and shorter hydrogen bonds. Acknowledgments: This work was funded by the National Science Centre, Poland (grant 2017/26/D/NZ1/00497).

Keywords: amyloids, K-peptide, hydration, FTIR spectroscopy

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Authors: Nuridayanti Che Khalib, Kaliyaperumal Thanigaimani, Suhana Arshad, Ibrahim Abdul Razak

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The 1:1 co-crystal of 2-amino-4-chloro-6-methylpyrimidine (2A4C6MP) with 4-methylbenzoic acid (4MBA) (I) has been prepared by slow evaporation method in methanol, which was crystallized in monoclinic C2/c space group, Z = 8, a = 28.431 (2) Å, b = 7.3098 (5) Å, c = 14.2622 (10) Å, and β = 109.618 (3)°. The presence of unionized –COOH functional group in co-crystal I was identified both by spectral methods (1H and 13C NMR, FTIR) and X-ray diffraction structural analysis. The 2A4C6MP molecule interact with the carboxylic group of the respective 4MBA molecule through N—H⋯O and O—H⋯N hydrogen bonds, forming a cyclic hydrogen –bonded motif R22(8). The crystal structure was stabilized by Npyrimidine-H⋯O=C and C=O-H⋯Npyrimidine types hydrogen bonding interactions. Theoretical investigations have been computed by HF and density function (B3LYP) method with 6-311+G(d,p) basis set. The vibrational frequencies together with 1H and 13C NMR chemical shifts have been calculated on the fully optimized geometry of co-crystal I. Theoretical calculations are in good agreement with the experimental results. Solvent-free formation of this co-crystal I is confirmed by powder X-ray diffraction analysis.

Keywords: supramolecular co-crystal, 2-amino-4-chloro-6-methylpyrimidine, Harthree-Fock and DFT studies, spectroscopic analysis

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

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Chemical storage of hydrogen by liquid organic hydrogen carriers (LOHC) is a very promising alternative to compression or cryogenics. These carriers have high energy density and allow at the same time efficient and safe storage of hydrogen under ambient conditions and without leakage losses. Another benefit of LOHC is the possibility to transport it using already available infrastructure for transport of fossil fuels. Efficient use of LOHC is related to a 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 represents simultaneously the modification in chemical structure of the carrier molecules. This variation can be detected in different physical properties like viscosity, permittivity or density. Thereby, each degree of loading corresponds to different viscosity values. Conventional measurements currently use invasive viscosity measurements or near-line measurements to obtain quantitative information. Avoiding invasive measurements has several severe advantages. Efforts are currently taken to provide a precise, non-invasive measurement method with equal or higher precision of the obtained results. This study investigates a method for determination of the viscosity of LOHC. Since the viscosity can retroactively derived from the degree of loading, permittivity is a target parameter as it is a suitable for determining the hydrogenation degree. This research analyses the influence of common physical properties on permittivity. The permittivity measurement system is based on a cavity resonator, an electromagnetic resonant structure, whose resonation frequency depends on its dimensions as well as the permittivity of the medium inside. For known resonator dimensions, the resonation frequency directly characterizes the permittivity. In order to determine the dependency of the permittivity on temperature and flow velocity, an experimental setup with 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 measured in the hundredths of the GHz range.

Keywords: liquid organic hydrogen carriers, measurement, permittivity, viscosity., temperature, flow process

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Authors: M. Cortés, E. Vera, M. Avella

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Corrosion is an imminent process in nature, which affects all types of materials. In sewerage systems, the corrosion process caused by microorganisms, also known as biogenic sulfuric acid attack, has been studied. This affects the structural integrity of the concrete drainage pipes and the sewage treatment plants. This article is a review of research which focuses on the study of how to reduce the production of hydrogen sulfide, how to improve the resistance of concrete through the use of additives and the implementation of antimicrobial techniques to reduce bacterial growth.

Keywords: bactericides, biogenic sulfuric acid, corrosion, concrete, hydrogen sulphide, nano materials, zeolites

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Authors: Anubha Kaushik, Raman Preet

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Distillery wastewater in the form of spent wash is a complex and strong industrial effluent, with high load of organic pollutants that may deplete dissolved oxygen on being discharged into aquatic systems and contaminate groundwater by leaching of pollutants, while untreated spent wash disposed on land acidifies the soil. Stringent legislative measures have therefore been framed in different countries for discharge standards of distillery effluent. Utilising the organic pollutants present in various types of wastes as food by mixed microbial populations is emerging as an eco-friendly approach in the recent years, in which complex organic matter is converted into simpler forms, and simultaneously useful gases are produced as renewable and clean energy sources. In the present study, wastewater from a rice bran based distillery has been used as the substrate in a dark fermenter, and native microbial consortium from the digester sludge has been used as the inoculum to treat the wastewater and produce hydrogen. After optimising the operational conditions in batch reactors, sequential batch mode and continuous flow stirred tank reactors were used to study the best operational conditions for enhanced and sustained hydrogen production and removal of pollutants. Since the rate of hydrogen production by the microbial consortium during dark fermentation is influenced by concentration of organic matter, pH and temperature, these operational conditions were optimised in batch mode studies. Maximum hydrogen production rate (347.87ml/L/d) was attained in 32h dark fermentation while a good proportion of COD also got removed from the wastewater. Slightly acidic initial pH seemed to favor biohydrogen production. In continuous stirred tank reactor, high H₂ production from distillery wastewater was obtained from a relatively shorter substrate retention time (SRT) of 48h and a moderate organic loading rate (OLR) of 172 g/l/d COD.

Keywords: distillery wastewater, hydrogen, microbial consortium, organic pollution, sludge

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Authors: H. Medjadji, A. Boulahouache, N. Salhi, A. Boudjemaa, M. Trari

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Hydrogen from renewable sources, such as solar, is referred to as green hydrogen. The splitting water process using semiconductors, such as photocatalysts, has attracted significant attention due to its potential application for solving the energy crisis and environmental pollution. Spinel ferrites of the MF₂O₄ type have shown broad interest in diverse energy conversion processes, including fuel cells and photo electrocatalytic water splitting. This work focuses on preparing nano-spinels based on iron AFe₂O₄ (A= Ca, Co, and Cu) as photocatalysts using the nitrate method. These materials were characterized both physically and optically and subsequently tested for hydrogen generation under visible light irradiation. Various techniques were used to investigate the properties of the materials, including TGA-DT, X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), UV-visible spectroscopy, Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDX) and X-ray Photoelectron Spectroscopy (XPS) was also undertaken. XRD analysis confirmed the formation of pure phases at 850°C, with crystalline sizes of 31 nm for CaFe₂O₄, 27 nm for CoFe₂O₄, and 40 nm for CuFe₂O₄. The energy gaps, calculated from recorded diffuse reflection data, are 1.85 eV for CaFe₂O₄, 1.27 eV for CoFe₂O₄, and 1.64 eV for CuFe₂O₄. SEM micrographs showed homogeneous grains with uniform shapes and medium porosity in all samples. EDX elemental analysis determined the absence of any contaminating elements, highlighting the high purity of the prepared materials via the nitrate route. XPS spectra revealed the presence of Fe3+ and O in all samples. Additionally, XPS analysis revealed the presence of Ca²⁺, Co²⁺, and Cu²⁺ on the surface of CaFe₂O₄ and CoFe₂O₄ spinels, respectively. The photocatalytic activity was successfully evaluated by measuring H₂ evolution through the water-splitting process. The best performance was achieved with CaFe₂O₄ in a neutral medium (pH ~ 7), yielding 189 µmol at an optimal temperature of ~50°C. The highest hydrogen production rates for CoFe₂O₄ and CuFe₂O₄ were obtained at pH ~ 12 with release rates of 65 and 85 µmol, respectively, under visible light irradiation at the same optimal temperature. Various conditions were investigated including the pH of the solution, the hole sensors utilization and recyclability.

Keywords: hydrogen, MFe₂O₄, nitrate route, spinel ferrite

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Authors: Sushil Kumar Saraswat, K. K. Pant

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Co metal supported on SiO2 and Al2O3 catalysts with a metal loading varied from 30 of 70 wt.% were evaluated for decomposition of methane to CO/CO2 free hydrogen and carbon nano materials. The catalytic runs were carried out from 550-800 oC under atmospheric pressure using fixed bed vertical flow reactor. The fresh and spent catalysts were characterized by BET surface area analyzer, TPR, XRD, SEM, TEM, and TG analysis. The data showed that 50% Co/Al2O3 catalyst exhibited remarkable higher activity and stability up to 10 h time-on-stream at 750 oC with respect to H2 production compared to rest of the catalysts. However, the catalytic activity and durability was greatly declined at a higher temperature. The main reason for the catalytic inhibition of Co containing SiO2 catalysts is the higher reduction temperature of Co2SiO4. TEM images illustrate that the carbon materials with various morphologies, carbon nanofibers (CNFs), helical-shaped CNFs, and branched CNFs depending on the catalyst composition and reaction temperature, were obtained. The TG data showed that a higher yield of MWCNTs was achieved over 50% Co/Al2O3 catalyst compared to other catalysts.

Keywords: carbon nanotubes, cobalt, hydrogen production, methane decomposition

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Authors: Bogale Tadesse, Krutik Parikh, Ndagha Mkandawire, Boris Albijanic, Nimal Subasinghe

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It is well established that the floatability and selectivity of mineral particles are highly dependent on the particle size. Generally, a particle size of 10 micron is considered as the critical size below which both flotation selectivity and recovery decline sharply. It is widely accepted that the majority of ultrafine particles, including highly liberated valuable minerals, will be lost in tailings during a conventional flotation process. This is highly undesirable particularly in the processing of finely disseminated complex and refractory ores where there is a requirement for fine grinding in order to liberate the valuable minerals. In addition, the continuing decline in ore grade worldwide necessitates intensive processing of low grade mineral deposits. Recent advances in comminution allow the economic grinding of particles down to 10 micron sizes to enhance the probability of liberating locked minerals from low grade ores. Thus, it is timely that the flotation of fine and ultrafine particles is improved in order to reduce the amount of valuable minerals lost as slimes. It is believed that the use of fine bubbles in flotation increases the bubble-particle collision efficiency and hence the flotation performance. Electroflotation, where bubbles are generated by the electrolytic breakdown of water to produce oxygen and hydrogen gases, leads to the formation of extremely finely dispersed gas bubbles with dimensions varying from 5 to 95 micron. The sizes of bubbles generated by this method are significantly smaller than those found in conventional flotation (> 600 micron). In this study, microbubbles generated by electrolysis of water were injected into a bench top flotation cell to assess the performance electroflotation in enhancing the flotation of fine and ultrafine pyrite particles of sizes ranging from 5 to 53 micron. The design of the cell and the results from optimization of the process variables such as current density, pH, percent solid and particle size will be presented at this conference.

Keywords: electroflotation, fine bubbles, pyrite, ultrafine particles

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Authors: Thamo Sutharssan, Diogo Montalvao, Wen-Chung Wang, Yong Chen, Claudia Pisac

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A combined heat and power (CHP) system is an efficient and clean way to generate power (electricity). Heat produced by the CHP system can be used for water and space heating. The CHP system which uses hydrogen as fuel produces zero carbon emission. Its’ efficiency can reach more than 80% whereas that of a traditional power station can only reach up to 50% because much of the thermal energy is wasted. The other advantages of CHP systems include that they can decentralize energy generation, improve energy security and sustainability, and significantly reduce the energy cost to the users. This paper presents the economic benefits of using a CHP system in the domestic environment. For this analysis, natural gas is considered as potential fuel as the hydrogen fuel cell based CHP systems are rarely used. UK government incentives for CHP systems are also considered as the added benefit. Results show that CHP requires a significant initial investment in return it can reduce the annual energy bill significantly. Results show that an investment may be paid back in 7 years. After the back period, CHP can run for about 3 years as most of the CHP manufacturers provide 10-year warranty.

Keywords: combined heat and power, clean energy, hydrogen fuel cell, economic analysis of CHP, zero emission

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Authors: Young Nam Chun, Mun Sup Lim, Byeo Ri Jeong

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Sewage sludge is regarded as the residue produced by the waste water treatment process, during which liquids and solids are being separated. Thermal treatments are interesting techniques to stabilize the sewage sludge for disposal. Among the thermal treatments, pyrolysis and/or gasification has been being applied to the sewage sludge. The final goal of our NRF research is to develop a microwave In-line Drying-Pyrolysis-Gasification (IDPG) technology for the dewatered sewage sludge for the bio-waste to energy conversion. As a first step, the pyrolysis characteristics in a bench scale electric furnace was investigated at 800℃ for the dewatered sludge and dried sludge samples of which moisture contents are almost 80% and 0%, respectively. Main components of producer gas are hydrogen and carbon dioxide. Particularly, higher hydrogen for the dewatered sludge is shown as 75%. The hydrogen production for the dewatered sludge and dried sludge are 56% and 32%, respectively. However, the pyrolysis for the dried sludge produces higher carbon dioxide and other gases, while higher methane and carbon dioxide are given to 74% and 53%, respectively. Tar also generates during the pyrolysis process, showing lower value for case of the dewatered sludge. Gravimetric tar is 195 g/m3, and selected light tar like benzene, naphthalene, anthracene, pyrene are 9.4 g/m3, 2.1 g/m3, 0.5 g/m3, 0.3 g/m3, respectively. After the pyrolysis process, residual char for the dewatered sludge and dried sludge remain 1g and 1.3g, showing weight reduction rate of 93% and 57%, respectively. Through the results, this could be known that the dewatered sludge can be used to produce a clean hydrogen-rich gas fuel without the drying process. Therefore, the IDPG technology can be applied effectively to the energy conversion for dewater sludge waste without a drying pretreatment. Acknowledgment: This work was supported by the National Research Foundation of Korea(NRF) grant funded by the Korea government(MSIP) (No. 2015R1A2A2A03003044).

Keywords: pyrolysis, gasification, sewage sludge, tar generation, producer gas, sludge char, biomass energy

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Authors: M. Ziółkowska, J. T. Duda, J. Milewska-Duda

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This paper describes an approach to the adsorption phenomena modeling aimed at specifying the adsorption mechanisms on localized or nonlocalized adsorbent sites, when applied to the nanocarbons. The concept comes from the fundamental thermodynamic description of adsorption equilibrium and is based on numerical calculations of the hydrogen adsorbed particles volume on the surface of selected nanocarbons: single-walled nanotube and nanocone. This approach enables to obtain information on adsorption mechanism and then as a consequence to take appropriate mathematical adsorption model, thus allowing for a more reliable identification of the material porous structure. Theoretical basis of the approach is discussed and newly derived results of the numerical calculations are presented for the selected nanocarbons.

Keywords: adsorption, mathematical modeling, nanocarbons, numerical analysis

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Authors: Volker Wannack

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Regional, national, and international strategies focusing on hydrogen (H₂) and blockchain are driving significant advancements in hydrogen and blockchain technology worldwide. These strategies lay the foundation for the groundbreaking "Blockchain Based Hydrogen Market (BBH₂)" project. The primary goal of this project is to develop a functional Blockchain Minimum Viable Product (B-MVP) for the hydrogen market. The B-MVP will leverage blockchain as an enabling technology with a common database and platform, facilitating secure and automated transactions through smart contracts. This innovation will revolutionize logistics, trading, and transactions within the hydrogen market. The B-MVP has transformative potential across various sectors. It benefits renewable energy producers, surplus energy-based hydrogen producers, hydrogen transport and distribution grid operators, and hydrogen consumers. By implementing standardized, automated, and tamper-proof processes, the B-MVP enhances cost efficiency and enables transparent and traceable transactions. Its key objective is to establish the verifiable integrity of climate-friendly "green" hydrogen by tracing its supply chain from renewable energy producers to end users. This emphasis on transparency and accountability promotes economic, ecological, and social sustainability while fostering a secure and transparent market environment. A notable feature of the B-MVP is its cross-border operability, eliminating the need for country-specific data storage and expanding its global applicability. This flexibility not only broadens its reach but also creates opportunities for long-term job creation through the establishment of a dedicated blockchain operating company. By attracting skilled workers and supporting their training, the B-MVP strengthens the workforce in the growing hydrogen sector. Moreover, it drives the emergence of innovative business models that attract additional company establishments and startups and contributes to long-term job creation. For instance, data evaluation can be utilized to develop customized tariffs and provide demand-oriented network capacities to producers and network operators, benefitting redistributors and end customers with tamper-proof pricing options. The B-MVP not only brings technological and economic advancements but also enhances the visibility of national and international standard-setting efforts. Regions implementing the B-MVP become pioneers in climate-friendly, sustainable, and forward-thinking practices, generating interest beyond their geographic boundaries. Additionally, the B-MVP serves as a catalyst for research and development, facilitating knowledge transfer between universities and companies. This collaborative environment fosters scientific progress, aligns with strategic innovation management, and cultivates an innovation culture within the hydrogen market. Through the integration of blockchain and hydrogen technologies, the B-MVP promotes holistic innovation and contributes to a sustainable future in the hydrogen industry. The implementation process involves evaluating and mapping suitable blockchain technology and architecture, developing and implementing the blockchain, smart contracts, and depositing certificates of origin. It also includes creating interfaces to existing systems such as nomination, portfolio management, trading, and billing systems, testing the scalability of the B-MVP to other markets and user groups, developing data formats for process-relevant data exchange, and conducting field studies to validate the B-MVP. BBH₂ is part of the "Technology Offensive Hydrogen" funding call within the research funding of the Federal Ministry of Economics and Climate Protection in the 7th Energy Research Programme of the Federal Government.

Keywords: hydrogen, blockchain, sustainability, innovation, structural change

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Authors: Mariam Jaber, Abdullah Yahya, Mohammad Alkhedher

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The shift toward sustainable energy solutions increasingly focuses on hydrogen, recognized for its potential as a clean energy carrier. Despite its benefits, hydrogen storage poses significant challenges, primarily due to its low energy density and high volatility. Among the various solutions, pressure vessels designed for hydrogen storage range from Type I to Type V, each tailored for specific needs and benefits. Notably, Type V vessels, with their all-composite, liner-less design, significantly reduce weight and costs while optimizing space and decreasing maintenance demands. This study focuses on optimizing Type V hydrogen storage tanks by examining how different shapes affect performance in drop tests—a crucial aspect of achieving ISO 15869 certification. This certification ensures that if a tank is dropped, it will fail in a controlled manner, ideally by leaking before bursting. While cylindrical vessels are predominant in mobile applications due to their manufacturability and efficient use of space, spherical vessels offer superior stress distribution and require significantly less material thickness for the same pressure tolerance, making them advantageous for high-pressure scenarios. However, spherical tanks are less efficient in terms of packing and more complex to manufacture. Additionally, this study introduces toroidal vessels to assess their performance relative to the more traditional shapes, noting that the toroidal shape offers a more space-efficient option. The research evaluates how different shapes—spherical, cylindrical, and toroidal—affect drop test outcomes when combined with various composite materials and layup configurations. The ultimate goal is to identify optimal vessel geometries that enhance the safety and efficiency of hydrogen storage systems. For our materials, we selected high-performance composites such as Carbon T-700/Epoxy, Kevlar/Epoxy, E-Glass Fiber/Epoxy, and Basalt/Epoxy, configured in various orientations like [0,90]s, [45,-45]s, and [54,-54]. Our tests involved dropping tanks from different angles—horizontal, vertical, and 45 degrees—with an internal pressure of 35 MPa to replicate real-world scenarios as closely as possible. We used finite element analysis and first-order shear deformation theory, conducting tests with the Abaqus Explicit Dynamics software, which is ideal for handling the quick, intense stresses of an impact. The results from these simulations will provide valuable insights into how different designs and materials can enhance the durability and safety of hydrogen storage tanks. Our findings aim to guide future designs, making them more effective at withstanding impacts and safer overall. Ultimately, this research will contribute to the broader field of lightweight composite materials and polymers, advancing more innovative and practical approaches to hydrogen storage. By refining how we design these tanks, we are moving toward more reliable and economically feasible hydrogen storage solutions, further emphasizing hydrogen's role in the landscape of sustainable energy carriers.

Keywords: hydrogen storage, drop test, composite materials, type V tanks, finite element analysis

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Authors: Munoz A. Tatiana, Solano R. Brandon, Montes C. Juan, Cierco G. Javier

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The hydrodynamic cavitation is a process in which the energy that the fluids have in the phase changes is used. From this energy, local temperatures greater than 5000 °C are obtained where thermal cracking of the fluid molecules takes place. The process applied to heavy oil affects variables such as viscosity, density, and composition, which constitutes an important improvement in the quality of crude oil. In this study, the need to design a software through mathematical integration models of mixing, cavitation, kinetics, and reactor, allows modeling changes in density, viscosity, and composition of a heavy oil crude, when the fluid passes through a hydrodynamic cavitation reactor. In order to evaluate the viability of this technique in the industry, a heavy oil of 18° API gravity, was simulated using naphtha as a hydrogen donor at concentrations of 1, 2 and 5% vol, where the simulation results showed an API gravity increase to 0.77, 1.21 and 1.93° respectively and a reduction viscosity by 9.9, 12.9 and 15.8%. The obtained results allow to have a favorable panorama on this technological development, an appropriate visualization on the generation of innovative knowledge of this technique and the technical-economic opportunity that benefits the development of the hydrocarbon sector related to heavy crude oil that includes the largest world oil production.

Keywords: hydrodynamic cavitation, thermal cracking, hydrogen donor, heavy oil upgrading, simulator

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Authors: Nils Mueller, Gregor Herz, Erik Reichelt, Matthias Jahn

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In the context of climate change, the reduction of greenhouse gas emissions in all economic sectors is considered to be an important factor in order to meet the demands of a sustainable energy system. The steel industry as one of the large industrial CO₂ emitters is currently highly dependent on fossil resources. In order to reduce coke consumption and thereby CO₂ emissions while still being able to further utilize existing blast furnaces, the possibility of including a direct reduction process (DRP) into a fully integrated steel mill was investigated. Therefore, a blast furnace model, derived from literature data and implemented in Aspen Plus, was used to analyze the impact of DRI in the blast furnace process. Furthermore, a state-of-the-art DRP was modeled to investigate the possibility of substituting the reducing agent natural gas with hydrogen. A sensitivity analysis was carried out in order to find the boundary percentage of hydrogen as a reducing agent without penalty to the DRI quality. Lastly, the two modeled process steps were combined to form a route of producing pig iron. By varying boundary conditions of the DRP while recording the CO₂ emissions of the two process steps, the overall potential for the reduction of CO₂ emissions was estimated. Within the simulated range, a maximum reduction of CO₂ emissions of 23.5% relative to typical emissions of a blast furnace could be determined.

Keywords: blast furnace, CO₂ mitigation, DRI, hydrogen

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Authors: Yang Gon Seo, Chang-Joon Kim, Dae Hyeok Kim

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It is estimated that 1.5 billion tires are produced worldwide each year which will eventually end up as waste tires representing a major potential waste and environmental problem. Pyrolysis has been great interest in alternative treatment processes for waste tires to produce valuable oil, gas and solid products. The oil and gas products may be used directly as a fuel or a chemical feedstock. The solid produced from the pyrolysis of tires ranges typically from 30 to 45 wt% and have high carbon contents of up to 90 wt%. However, most notably the solid have high sulfur contents from 2 to 3 wt% and ash contents from 8 to 15 wt% related to the additive metals. Upgrading tire pyrolysis products to high-value products has concentrated on solid upgrading to higher quality carbon black and to activated carbon. Hydrogen sulfide and ammonia are one of the common malodorous compounds that can be found in emissions from many sewages treatment plants and industrial plants. Therefore, removing these harmful gasses from emissions is of significance in both life and industry because they can cause health problems to human and detrimental effects on the catalysts. In this work, pyrolytic carbon black from waste tires was used to develop adsorbent with good adsorption capacity for removal of hydrogen and ammonia. Pyrolytic carbon blacks were prepared by pyrolysis of waste tire chips ranged from 5 to 20 mm under the nitrogen atmosphere at 600℃ for 1 hour. Pellet-type adsorbents were prepared by a mixture of carbon black, metal oxide and sodium hydroxide or hydrochloric acid, and their adsorption capacities were estimated by using the breakthrough curve of a continuous fixed bed adsorption column at ambient condition. The adsorbent was manufactured with a mixture of carbon black, iron oxide(III), and sodium hydroxide showed the maximum working capacity of hydrogen sulfide. For ammonia, maximum working capacity was obtained by the adsorbent manufactured with a mixture of carbon black, copper oxide(II), and hydrochloric acid.

Keywords: adsorbent, ammonia, pyrolytic carbon black, hydrogen sulfide, metal oxide

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Authors: Gi-Beom Park, Hyong-Gi Park, Seong-Yong Lee, Jaeho Choi, Seok Hong Min, Tae Kwon Ha

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The Nb silicide-based alloy has the excellent high-temperature strength and relatively lower density than the Ni-based superalloy; therefore, it has been receiving a lot of attention for the next generation high-temperature material. To enhance the high temperature creep property and oxidation resistance, Si was added to the Nb-based alloy, resulting in a multi-phase microstructure with metal solid solution and silicide phase. Since the silicide phase has a low machinability due to its brittle nature, it is necessary to fabricate components using the powder metallurgy. However, powder manufacturing techniques for the alloys have not yet been developed. In this study, we tried to fabricate Nb-based alloy powder by the hydrogenation-dehydrogenation reaction. The Nb-based alloy ingot was prepared by vacuum arc melting and it was annealed in the hydrogen atmosphere for the hydrogenation. After annealing, the hydrogen concentration was increased from 0.004wt% to 1.22wt% and Nb metal phase was transformed to Nb hydride phase. The alloy after hydrogenation could be easily pulverized into powder by ball milling due to its brittleness. For dehydrogenation, the alloy powders were annealed in the vacuum atmosphere. After vacuum annealing, the hydrogen concentration was decreased to 0.003wt% and Nb hydride phase was transformed back to Nb metal phase.

Keywords: Nb alloy, Nb metal and silicide composite, powder, hydrogenation-dehydrogenation reaction

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Authors: A. Odoom, A. Salama, H. Ibrahim

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Hydrogen is a clean source of energy for power production and transportation. The main source of hydrogen in this research is biodiesel. Glycerol also called glycerine is a by-product of biodiesel production by transesterification of vegetable oils and methanol. This is a reliable and environmentally-friendly source of hydrogen production than fossil fuels. A typical composition of crude glycerol comprises of glycerol, water, organic and inorganic salts, soap, methanol and small amounts of glycerides. Crude glycerol has limited industrial application due to its low purity thus, the usage of crude glycerol can significantly enhance the sustainability and production of biodiesel. Reforming techniques is an approach for hydrogen production mainly Steam Reforming (SR), Autothermal Reforming (ATR) and Partial Oxidation Reforming (POR). SR produces high hydrogen conversions and yield but is highly endothermic whereas POR is exothermic. On the downside, PO yields lower hydrogen as well as large amount of side reactions. ATR which is a fusion of partial oxidation reforming and steam reforming is thermally neutral because net reactor heat duty is zero. It has relatively high hydrogen yield, selectivity as well as limits coke formation. The complex chemical processes that take place during the production phases makes it relatively difficult to construct a reliable and robust numerical model. Numerical model is a tool to mimic reality and provide insight into the influence of the parameters. In this work, we introduce a finite volume numerical study for an 'in-house' lab-scale experiment of ATR. Previous numerical studies on this process have considered either using Comsol or nodal finite difference analysis. Since Comsol is a commercial package which is not readily available everywhere and lab-scale experiment can be considered well mixed in the radial direction. One spatial dimension suffices to capture the essential feature of ATR, in this work, we consider developing our own numerical approach using MATLAB. A continuum fixed bed reactor is modelled using MATLAB with both pseudo homogeneous and heterogeneous models. The drawback of nodal finite difference formulation is that it is not locally conservative which means that materials and momenta can be generated inside the domain as an artifact of the discretization. Control volume, on the other hand, is locally conservative and suites very well problems where materials are generated and consumed inside the domain. In this work, species mass balance, Darcy’s equation and energy equations are solved using operator splitting technique. Therefore, diffusion-like terms are discretized implicitly while advection-like terms are discretized explicitly. An upwind scheme is adapted for the advection term to ensure accuracy and positivity. Comparisons with the experimental data show very good agreements which build confidence in our modeling approach. The models obtained were validated and optimized for better results.

Keywords: autothermal reforming, crude glycerol, hydrogen, numerical model

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Authors: Gómez Romero Jacob, García Peña Elvia Inés

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The co-digestion process of crude cheese whey (CCW) with fruit vegetable waste (FVW) for biohydrogen production was investigated in batch and continuous systems, in stirred 1.8 L bioreactors at 37°C. Five different C/N ratios (7, 17, 21, 31, and 46) were tested in batch systems. While, in continuous system eight conditions were evaluated, hydraulic retention time (from 60 to 10 h) and organic load rate (from 21.96 to 155.87 g COD/L d). Data in batch tests showed a maximum specific biohydrogen production rate of 10.68 mmol H2/Lh and a biohydrogen yield of 449.84 mL H2/g COD at a C/N ratio of 21. In continuous co-digestion system, the optimum hydraulic retention time and organic loading rate were 17.5 h and 80.02 g COD/L d, respectively. Under these conditions, the highest volumetric production hydrogen rate (VPHR) and hydrogen yield were 11.02 mmol H2/L h, 800 mL H2/COD, respectively. A pyrosequencing analysis showed that the main acclimated microbial communities for co-digestion studies consisted of Bifidobacterium, with 85.4% of predominance. Hydrogen producing bacteria such as Klebsiella (9.1%), Lactobacillus (0.97%), Citrobacter (0.21%), Enterobacter (0.27%), and Clostridium (0.18%) were less abundant at this culture period. The microbial population structure was correlated with the lactate, acetate, and butyrate profiles obtained. Results demonstrated that the co-digestion of CCW with FVW improves biohydrogen production due to a better nutrient balance and improvement of the system’s buffering capacity.

Keywords: acclimatation, biohydrogen, co-digestion, microbial community

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Authors: Mandeep Kaur, Jitendra K. Bera

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The search for atom-economical and green synthetic methods for the synthesis of functionalized molecules has attracted much attention. Metal ligand cooperation (MLC) plays a pivotal role in organometallic catalysis to activate C−H, H−H, O−H, N−H and B−H bonds through reversible bond breaking and bond making process. Towards this goal, a bifunctional N─heterocyclic carbene (NHC) based pyridyl-functionalized amide ligand precursor, and corresponding dearomatized iridium complex was synthesized. The NMR and UV/Vis acid titration study have been done to prove the proton response nature of the iridium complex. Further, the dearomatized iridium complex explored as a catalyst on the platform of MLC via dearomatzation/aromatization mode of action towards atom economical α and β─alkylation of ketones and secondary alcohols by using primary alcohols through hydrogen borrowing methodology. The key features of the catalysis are high turnover frequency (TOF) values, low catalyst loading, low base loading and no waste product. The greener syntheses of quinoline, lactone derivatives and selective alkylation of drug molecules like pregnenolone and testosterone were also achieved successfully. Another structurally similar iridium complex was also synthesized with modified ligand precursor where a pendant amide unit was absent. The inactivity of this analogue iridium complex towards catalysis authenticated the participation of proton responsive imido sidearm of the ligand to accelerate the catalytic reaction. The mechanistic investigation through control experiments, NMR and deuterated labeling study, authenticate the borrowing hydrogen strategy.

Keywords: C-C bond formation, hydrogen borrowing, metal ligand cooperation (MLC), n-heterocyclic carbene

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Authors: Lei Zhao, Yi Song, Tim Dunne, Jiaxiang (Jason) Ren, Wenhan Yue, Lei Yang, Li Wen, Yu Liu

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Fasting dissolving magnesium (DM) alloy technology has contributed significantly to the “Shale Revolution” in oil and gas industry. This application requires DM downhole tools dissolving initially at a slow rate, rapidly accelerating to a high rate after certain period of operation time (typically 8 h to 2 days), a contradicting requirement that can hardly be addressed by traditional Mg alloying or processing itself. Premature disintegration has been broadly reported in downhole DM tool from field trials. To address this issue, “temporary” thin polymers of various formulations are currently coated onto DM surface to delay its initial dissolving. Due to conveying parts, harsh downhole condition, and high dissolving rate of the base material, the current delay coatings relying on pure polymers are found to perform well only at low temperature (typical < 100 ℃) and parts without sharp edges or corners, as severe geometries prevent high quality thin film coatings from forming effectively. In this study, a coating technology combining Plasma Electrolytic Oxide (PEO) coatings with advanced thin film deposition has been developed, which can delay DM complex parts (with sharp corners) in corrosive fluid at 150 ℃ for over 2 days. Synergistic effects between porous hard PEO coating and chemical inert elastic-polymer sealing leads to its delaying dissolution improvement, and strong chemical/physical bonding between these two layers has been found to play essential role. Microstructure of this advanced coating and compatibility between PEO and various polymer selections has been thoroughly investigated and a model is also proposed to explain its delaying performance. This study could not only benefit oil and gas industry to unplug their High Temperature High Pressure (HTHP) unconventional resources inaccessible before, but also potentially provides a technical route for other industries (e.g., bio-medical, automobile, aerospace) where primer anti-corrosive protection on light Mg alloy is highly demanded.

Keywords: dissolvable magnesium, coating, plasma electrolytic oxide, sealer

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Authors: M. Amanipour, J. Towfighi, E. Ganji Babakhani, M. Heidari

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Cylindrical alumina microfiltration membrane (GMITM Corporation, inside diameter=9 mm, outside diameter=13 mm, length= 50 mm) with an average pore size of 0.5 micrometer and porosity of about 0.35 was used as the support for membrane reactor. This support was soaked in boehmite sols, and the mean particle size was adjusted in the range of 50 to 500 nm by carefully controlling hydrolysis time, and calcined at 650 °C for two hours. This process was repeated with different boehmite solutions in order to achieve an intermediate layer with an average pore size of about 50 nm. The resulting substrate was then coated with a thin and dense layer of silica by counter current chemical vapour deposition (CVD) method. A boehmite sol with 10 wt.% of nickel which was prepared by a standard procedure was used to make the catalytic layer. BET, SEM, and XRD analysis were used to characterize this layer. The catalytic membrane reactor was placed in an experimental setup to evaluate the permeation and hydrogen separation performance for a steam reforming reaction. The setup consisted of a tubular module in which the membrane was fixed, and the reforming reaction occurred at the inner side of the membrane. Methane stream, diluted with nitrogen, and deionized water with a steam to carbon (S/C) ratio of 3.0 entered the reactor after the reactor was heated up to 500 °C with a specified rate of 2 °C/ min and the catalytic layer was reduced at presence of hydrogen for 2.5 hours. Nitrogen flow was used as sweep gas through the outer side of the reactor. Any liquid produced was trapped and separated at reactor exit by a cold trap, and the produced gases were analyzed by an on-line gas chromatograph (Agilent 7890A) to measure total CH₄ conversion and H₂ permeation. BET analysis indicated uniform size distribution for catalyst with average pore size of 280 nm and average surface area of 275 m².g^-1. Single-component permeation tests were carried out for hydrogen, methane, and carbon dioxide at temperature range of 500-800 °C, and the results showed almost the same permeance and hydrogen selectivity values for hydrogen as the composite membrane without catalytic layer. Performance of the catalytic membrane was evaluated by applying membranes as a membrane reactor for methane steam reforming reaction at gas hourly space velocity (GHSV) of 10,000 h⁻¹ and 2 bar. CH₄ conversion increased from 50% to 85% with increasing reaction temperature from 600 °C to 750 °C, which is sufficiently above equilibrium curve at reaction conditions, but slightly lower than membrane reactor with packed nickel catalytic bed because of its higher surface area compared to the catalytic layer.

Keywords: catalytic membrane, hydrogen, methane steam reforming, permeance

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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: Zeinab Sanaee, Hossein Jafaripour

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Copper is an excellent conductive material that is widely used in the energy devices such as Lithium-ion batteries and supercapacitors as the current collector. On the other hand, copper oxide nanowires have been used in these applications as potential electrode material. In this paper, nanowires of Copper and Copper oxide have been synthesized through a simple and time and cost-effective approach. The thermally grown Copper oxide nanowires have been converted into Copper nanowires through annealing in the Hydrogen atmosphere in a DC-PECVD system. To have a proper Copper nanostructure formation, an Au nanolayer was coated on the surface of Copper oxide nanowires. The results show the successful achievement of Copper nanowires without deformation or cracking. These structures have a great potential for Lithium-ion batteries and supercapacitors.

Keywords: Copper, Copper oxide, nanowires, Hydrogen annealing, Lithium ion battery

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