The depletion of stocks of fossil fuels and the environment protection requirements increase the significance of hydrogen as a future energy carrier. The present research is focused on the development of new safe methods of production, transport and storage of hydrogen. The paper presents an analysis of problems related to the assessment of the effects of failure of hydrogen transporting pipelines. Scenarios of hazardous events connected with an uncontrollable leakage of hydrogen are discussed. The sizes of heat radiation and pressure wave hazard zones are determined.
On May 17, 2018, the National Center for Research and Development announced the initiation of a new procedure within the Hydrogen Storage Program. The objective was to develop a Hydrogen Storage System for use with fuel cells and its demonstration in a Mobile Facility. This is to create an alternative to the use of fossil fuels and create a field for competition in creating solutions in the field of access to “clean” energy. The National Center for Research and Development is responsible for the development of assumptions, regulations and implementation. The analysis presents the main assumptions of the program is correlated to the current legal situation related to the financing of Research and Development. An in-depth study concerns the ways of using innovative partnership and its placement in the system of European Union legal acts. The idea of the pre-commercial procurement procedure (Pre-Commercial Procurement), which was developed to support the implementation of prototypes of solutions – resulting from research and development – with a high potential for possible commercialization, was described in details. This procedure is characterized by ensuring the financing of a product or service at an early stage of development. Although this creates the risk of failure of the project, it stimulates technological development.
A detailed comparison of catalytic properties of two different ruthenium-based catalysts in the reaction of homogeneous hydrogenation of acetophenone was performed. Additionally, methods of synthesis of both catalysts were tested and optimized in order to achieve the best possible quality and purity of the final catalysts. NMR analysis was used to analyze and identify the composition of ruthenium compounds and gas chromatography was used to analyze the conversion rate of hydrogenation reactions. It was determined that RuCl2(PPh3)3 obtained with a modified method described by Shaw’s group (Shawet al., 2007) had the best catalytic properties in the reaction performed under conditions described in Liang Wang’s publication (Wang et al., 2014). It was also determined that for concentration ratio of substrate to RuCl2(PPh3)3 amounting to 250:1 the conversion rate was much higher than that of the reaction performed with a double dose of the catalyst. Results of experiments also show that samples of the post-reaction solution should be analyzed right after the reaction, because even if they are stored in low temperature the amount of product can change up to 3–5% compared to the base sample and this change is not predictable. These findings have significant implications for further research of the reaction of homogeneous transfer hydrogenation of ketones. With the right catalysts and methods of their synthesis other parameters of this reaction can be optimized. The most important one is a change of solvent from isopropyl alcohol to a less toxic substance like water. This may increase the value of the reaction in green chemistry and chemical industry.
The paper describes a fuel cell based system and its performance. The system is based on two fuel cell units, DC/DC converter, DC/AC inverter, microprocessor control unit, load unit, bottled hydrogen supply system and a set of measurement instruments. In the study presented in the paper a dynamic response of the proton exchange membrane (PEM) fuel cell system to unit step change load as well as to periodical load changing cycles in the form of semi-sinusoidal and trapezoidal signals was investigated. The load was provided with the aid of an in-house-developed electronic load unit, which was fully PC controlled. The apparatus was commissioned by testing the steady-state operation of the module. The obtained efficiency of the fuel cell shows that the test apparatus used in the study provides data in substantial agreement with the manufacturer’s data.
Energy from different sources is fundamental to the economy of each country. Bearing in mind the limited reserves of non-renewable energy sources and the fact that their production from new deposits is becoming less economically viable, attention is paid to alternative energy sources, particularly those that are readily available or require no substantial financial investment. One possible solution may be to generate hydrogen, which will then be used for heat (energy) production using other methods. At the same time, these processes will be characterized by low emission levels compared to conventional energy sources. In recent years, more and more emphasis has been placed on the use of clean energy from renewable sources. New, more technically and economically efficient technologies are being developed. The energy use worldwide comes mostly from fossil fuel processing. It can be observed that the share of RES in global production is growing every year. At the end of the 1990s, the share of renewable energy sources was at 6–7%. Global trends indicate the increasing demand for renewable energy due to its form. Global hydrogen resources are practically inexhaustible, but the problem is its availability in molecular form. The article analyzed the use of hydrogen as a fuel. The basic problem is the inexpensive and easy extraction of hydrogen from its compounds; attention has been paid to water, which can easily be electrolytically decomposed to produce oxygen and hydrogen. Hydrogen generated by electrolysis can be stored, but due to its physicochemical properties, it is a costly process; therefore, a decision was made that it is better to store it with natural gas or use it for further reaction. In addition, hydrogen can be used as a substrate for binding and converting the increasingly problematic carbon dioxide, thus reducing its content in the atmosphere.
Titania nanotube (TNT) arrays fabricated by anodizing of titanium foil in organic (ethylene glycol) and inorganic (phosphoric acid) electrolytes and thermally modified in argon revealed much improved properties to detect hydrogen peroxide. Horseradish peroxidase and acetate thionine co-absorbed by a dip coating on the TNT electrode were used to detect hydrogen peroxide in phosphate buffered saline. The morphology and electrochemical properties of TNT arrays were studied by scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry. Well defined oxidation and reduction peaks for potassium ferricyanide have been observed for TNT formed in ethylene glycol and annealed in argon. TNT arrays formed in organic electrolyte and annealed in argon indicated more favorable adsorption and electrochemical properties what was confirmed by detection of hydrogen peroxide towards analyte in phosphorate buffered saline solution.
Passive autocatalytic recombiners (PAR) is the only used method for hydrogen removal from the containment buildings in modern nuclear reactors. Numerical models of such devices, based on the CFD approach, are the subject of this paper. The models may be coupled with two types of computer codes: the lumped parameter codes, and the computational fluid dynamics codes. This work deals with 2D numerical model of PAR and its validation. Gaseous hydrogen may be generated in water nuclear reactor systems in a course of a severe accident with core overheating. Therefore, a risk of its uncontrolled combustion appears which may be destructive to the containment structure.
Gaseous hydrogen may be generated in a nuclear reactor system as an effect of the core overheating. This creates a risk of its uncontrolled combustion which may have a destructive consequences, as it could be observed during the Fukushima nuclear power plant accident. Favorable conditions for hydrogen production occur during heavy loss-of-coolant accidents. The author used an own computer code, called HEPCAL, of the lumped parameter type to realize a set of simulations of a large scale loss-of-coolant accidents scenarios within containment of second generation pressurized water reactor. Some simulations resulted in high pressure peaks, seemed to be irrational. A more detailed analysis and comparison with Three Mile Island and Fukushima accidents consequences allowed for withdrawing interesting conclusions.
The paper describes factors influencing the development of electricity storage technologies. The results of the energy analysis of the electric energy storage system in the form of hydrogen are presented. The analyzed system consists of an electrolyzer, a hydrogen container, a compressor, and a PEMFC fuel cell with an ion-exchange polymer membrane. The power curves of an electrolyzer and a fuel cell were determined. The analysis took the own needs of the system into account, i.e. the power needed to compress the produced hydrogen and the power of the air compressor supplying air to the cathode channels of the fuel cell stack. The characteristics describing the dependence of the efficiency of the energy storage system in the form of hydrogen as a function of load were determined. The costs of electricity storage as a function of storage capacity were determined. The energy aspects of energy accumulation in lithium-ion cells were briefly characterized and described. The efficiency of the charge/discharge cycle of lithium-ion batteries has been determined. The graph of discharge of the lithium-ion battery depending on the current value was presented. The key parameters of battery operation, i.e. the Depth of Discharge (DoD) and the State of Charge (SoC), were determined. Based on the average market prices of the available lithium-ion batteries for the storage of energy from photovoltaic cells, unit costs of electrochemical energy storage as a function of the DoD parameter were determined.
This paper proposes a new, simple and an efficient method for methanol formation under the cavitation influence of hydrogen-peroxide using a dynamic cavitation reactor. The process involves the reaction of the generated hydroxyl radical with propanebutane gas (C3–C4) to form propyl and butyl radicals which decompose into methyl radicals and alkenes, followed by the subsequent yield of methanol (via the interaction of methyl-radical with hydroxyl radical). Technological process parameters employed in this investigation are quite achievable for industrial production.
This article presents a critical mini-review of research conducted on bioelectrochemical reactors with emphasis placed on microbial fuel cells (MFC) and microbial electrolysis cells (MEC). The principle of operation and typical constructions of MFCs and MECs were presented. The types of anodes and cathodes, ion-selective membranes and microorganisms used were discussed along with their limitations.
Substitution of fossil fuels with alternative energy carriers has become necessary due to climate change and fossil fuel shortages. Fermentation as a way of producing biohydrogen, an attractive and environmentally friendly future energy carrier, has captured received increasing attention in recent years because of its high H2 production rate and a variety of readily available waste substrates used in the process. This paper discusses the state-of-the-art of fermentative biohydrogen production, factors affecting this process, as well as various bioreactor configurations and performance parameters, including H2 yield and H2 production rate.
A passive autocatalytic hydrogen recombiner (PAR) is a self-starting device, without operator action or external power input, installed in nuclear power plants to remove hydrogen from the containment building of a nuclear reactor. A new mechanistic model of PAR has been presented and validated by experimental data and results of Computational Fluid Dynamics (CFD) simulations. The model allows to quickly and accurately predict gas temperature and composition, catalyst temperature and hydrogen recombination rate. It is assumed in the model that an exothermic recombination reaction of hydrogen and oxygen proceeds at the catalyst surface only, while processes of heat and mass transport occur by assisted natural and forced convection in non-isothermal and laminar gas flow conditions in vertical channels between catalyst plates. The model accounts for heat radiation from a hot catalyst surface and has no adjustable parameters. It can be combined with an equation of chimney draft and become a useful engineering tool for selection and optimisation of catalytic recombiner geometry.
This paper reviews research at the Institute of Materials Science and Engineering, Poznań University of Technology, on the synthesis of nanocrystalline hydride electrode materials. Nanocrystalline materials have been synthesized by mechanical alloying (MA) followed by annealing. Examples of the mate2-, LaNi5 and Mg2Ni-type phases. Details on the process used and the enhancement of properties due to the nanoscale structures are presented. The synthesized alloys were used as negative electrode materials for Ni-MH battery. The properties of hydrogen host materials can be modi?ed substantially by alloying to obtain the desired storage characteristics. For example, it was found that the respective replacement of Fe in TiFe by Ni and/or by Cr, Co, Mo improved not only the discharge capacity but also the cycle life of these electrodes. The hydrogen storage properties of nanocrystalline ZrV2- and LaNi5-type powders prepared by mechanical alloying and annealing show no big di?erence with those of melt casting (polycrystalline) alloys. On the other hand, a partial substitution of Mg by Mn orAl in Mg2Ni alloy leads to an increase in discharge capacity, at room temperature. Furthermore, the e?ect of the nickel and graphite coating on the structure of some nanocrystalline alloys and the electrodes characteristics were investigated. In the case of Mg2Ni-type alloy mechanical coating with graphite e?ectively reduced the degradation rate of the studied electrode materials. The combination of a nanocrystalline TiFe-, ZrV2- and LaNi5-type hydride electrodes and a nickel positive electrode to form a Ni-MH battery, has been successful.
Paper presents the concept of energy storage system based on power-to-gas-to-power (P2G2P) technology. The system consists of a gas turbine co-ﬁring hydrogen, which is supplied from a distributed electrolysis installations, powered by the wind farms located a short distance from the potential construction site of the gas turbine. In the paper the location of this type of investment was selected. As part of the analyses, the area of wind farms covered by the storage system and the share of the electricity production which is subjected storage has been changed. The dependence of the changed quantities on the potential of the hydrogen production and the operating time of the gas turbine was analyzed. Additionally, preliminary economic analyses of the proposed energy storage system were carried out.
The organo-inorganic commercial binder Albertine F/1 (Hüttenes-Albertus) constituting the starch-aluminosilicate mixture was directed to structural studies. The paper presents a detailed structural analysis of the binder before and after exposure to physical curing agents (microwaves, high temperature) based on the results of infrared spectroscopy studies (FTIR). An analysis of structural changes taking place in the binder system with the quartz matrix was also carried out. Based on the course of the obtained IR spectra, it was found that during the exposure on physical agents there are structural changes within the hydroxyl groups in the polymeric starch chains and silanol groups derived from aluminosilicate as well as in the quartz matrix (SiO2). The curing of the molding sand takes place due to the evaporation of the solvent water and the formation of intramolecular and intermolecular cross-linking hydrogen bonds. Type and amount of hydrogen bonds presence in cured molding sand have an impact on selected properties of molding sand. Results indicates that for molding sand with Albertine F/1 during conventional heating a more extensive network of hydrogen bonds is created.
Changes of gas pressure in the moulding sand in the zone adjacent to mould cavity were analysed during pouring of cast iron. No significant effect of pressure on the surface quality of castings was observed. In the second series of tests, the concentration of hydrogen in the gas atmosphere was measured. It has been found that the value of this concentration depends on metal composition and is particularly high in cast iron containing magnesium. This is due to the reduction of water vapour with the element that has high affinity to oxygen. The presence of hydrogen causes the formation of gas-induced defects on the casting surface.
Hydrogen is the fuel of the future, therefore many hydrogen production methods are developed. At present, fuel cells are of great interest due to their energy efficiency and environmental benefits. A brief review of effective formation methods of hydrogen was conducted. It seems that hydrogen from steam reforming of methanol process is the best fuel source to be applied in fuel cells. In this process Cu-based complex catalysts proved to be the best. In presented work kinetic equations from available literature and catalysts are reported. However, hydrogen produced even in the presence of the most selective catalysts in this process is not pure enough for fuel cells and should be purified from CO. Currently, catalysts for hydrogen production are not sufficiently active in oxidation of carbon monoxide. A simple and effective method to lower CO level and obtain clean H2 is the preferential oxidation of monoxide carbon (CO-PROX). Over new CO-PROX catalysts the level of carbon monoxide can be lowered to a sufficient level of 10 ppm.
It is known that external diffusional resistances are significant in immobilized enzyme packed-bed reactors, especially at large scales. Thus, the external mass transfer effects were analyzed for hydrogen peroxide decomposition by immobilized Terminox Ultra catalase in a packed-bed bioreactor. For this purpose the apparent reaction rate constants, kP, were determined by conducting experimental works at different superficial velocities, U, and temperatures. To develop an external mass transfer model the correlation between the Colburn factor, JD, and the Reynolds number, Re, of the type JD = K Re(n-1) was assessed and related to the mass transfer coefficient, kmL. The values of K and n were calculated from the dependence (am kp-1 - kR-1) vs. Re-1 making use of the intrinsic reaction rate constants, kR, determined before. Based on statistical analysis it was found that the mass transfer correlation JD = 0.972 Re-0.368 predicts experimental data accurately. The proposed model would be useful for the design and optimization of industrial-scale reactors.
A layered sensor structure of metal-free phthalocyanine H2Pc (~160 nm) with a very thin film of palladium (Pd ~20 nm) on the top, has been studied for hydrogen gas-sensing application at relatively low temperatures of about 30°C and about 40°C. The layered structure was obtained by vacuum deposition (first the phthalocyanine Pc and than the Pd film) onto a LiNbO3Y- cut Z-propagating substrate, making use of the Surface Acoustic Wave method, and additionally (in this same technological processes) onto a glass substrate with a planar microelectrode array for simultaneous monitoring of the planar resistance of the layered structure. In such a layered structure we can detect hydrogen in a medium concentration range (from 0.5 to 3% in air) even at about 30°C. At elevated temperature up to about 40°C the differential frequency increases proportionally (almost linearly) to the hydrogen concentration and the response reaches its steady state very quickly. The response times are about 18 s at the lowest 0.5% hydrogen concentration to about 42 s at 4% (defined as reaching 100% of the steady state). In the case of the investigated layered structure a very good correlation has been observed between the two utilized methods - the frequency changes in the SAW method correlate quite well with the decreases of the layered structure resistance.
HY2SEPS was an EU-funded project directed at the reduction of CO2 emissions. The principal objective of the project was to develop a hybrid membrane-adsorptive H2/CO2 separation technique that would form an integral element of the pre-combustion process. Specific tasks included the derivation of simplified mathematical models for the membrane separation of H2/CO2 mixtures. In the present study one of the developed models is discussed in detail, namely that with the countercurrent plug flow of the feed and the permeate. A number of simulations were carried out concerning the separation of binary mixtures that may appear following steam conversion of methane. The numerical results were then compared with the experimental data obtained by FORTH/ICEHT. The estimated fluxes of pure CO2, H2, CH4 and N2 are shown alongside those measured experimentally as a function of temperature and CO2 partial pressure in Figs 2 - 7. It is concluded that, in general, CO2 flux increases monotonically with both temperature and CO2 partial pressure. It is also found that the fluxes of hydrogen, methane and nitrogen reach a minimum at a temperature slightly above 323 K. Overall, a good agreement was obtained between the simulations and experiments.
The aeronautical industry is a sector constantly looking for new materials and equipment because of its tendency to expand quickly. The Ti6Al4V titanium alloy is used frequently in the aeronautic, aerospace, automobile, chemical and medical industry because it presents high strength combined with low density (approximately 4.5 g/cm3), good creep resistance (up to 550°C), excellent corrosion resistance, high flexibility, good fatigue and biocompatibility. As a result of these properties, this titanium alloy is considered an excellent material for manufacturing structural parts in the aircraft industry for modern aeronautic structures, especially for airframes and aero-engines. But its use is also problematic because the Ti6Al4V titanium alloy manifests hydrogen embrittlement, by means of hydrides precipitation in the metal. The Ti6Al4V alloy becomes brittle and fractures because of hydrogen diffusion into metal and because titanium hydrides appear and create pressure from within the metal, thus generating corrosion. Because of titanium hydrides, the titanium alloy suffers from reduced ductility, tensile strength and toughness, which can result in fractures of aeronautical parts. This poses a very serious problem for aircrafts. In this paper, rapid hydrogen embrittlement is presented along with XRD, SEM and TEM analysis. Its goal is to detect the presence of titanium hydrides and to spot the initial cracks in the metallic material.
Energy efficiency improvement and ecological safety of heat power plants are urgent problems, which require scientifically grounded approaches and solutions. These problems can be solved partly within the presented heat-and-power cycles by including contact energy exchange equipment in the circuits of existing installations. A significant positive effectis obtained in the contact energy exchange installations, such as gas-steam installation ‘Aquarius’ and the contact hydrogen heat generator that also can use hydrogen as a fuel. In these plants, the efficiency increases approximately by 10–12% in comparison with traditional installations, and the concentration of toxic substances, such as nitrogen oxides and carbon monoxide in flue gas can be reduced to 30 mg/m3and to 5 mg/m3, respectively. Moreover, the plants additionally ‘generate’ the clean water, which can be used for technical purposes.
The new investigation method of the kinetics of the gas emission from moulding sands used for moulds and cores is presented in this paper. The gas evolution rate is presented not only as a function of heating time but also as a function of instantaneous temperatures. In relation to the time and heating temperature the oxygen and hydrogen contents in evolving gases was also measured. This method was developed in the Laboratory of Foundry Moulds Technology, Faculty of Foundry Engineering, AGH. Gas amounts which are emitted from the moulding sand at the given temperature recalculated to the time unit (kinetics) are obtained in investigations. Results of investigations of moulding sand with furan resin are presented - as an example - in the paper.
Reduction of three industrial nickel oxides (Goro, Tokyo and Sinter 75) with a hydrogen bearing gas was revisited in the temperature interval from 523 to 673 K (250 to 400°C). A pronounced incubation period is observed in the temperature interval tested. This period decreases as the reduction temperature increases. Thermogravimetric data of these oxides were fitted using the Avrami-Erofeyev kinetic model. The reduction of these oxides is controlled by a nucleation and growth mechanism of metallic nickel over the oxides structure. Rate kinetic constants were re-evaluated and the activation energy for the reduction of these oxides was re-calculated.