Search results for: hydrogen based ironmaking

Authors: Yen-Ping Peng, Ku-Fan Chen, Ken-Lin Chang, Jian Sun

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In this study, palladium loaded titanium dioxide nanotube arrays (Pd/TNAs) was successfully synthesized by anodic oxidation etching method combined with microwave hydrothermal method, using tea or coffee as a green reductant. Pd/TNAs was employed as an electrode in a photoelectrochemcial (PEC) system to simultaneously remove azo-dye and to generate hydrogen in the anodic and cathodic chamber, respectively. The chemical and physical properties of as-synthesized Pd/TNAs were characterized by scanning electron microscopy (SEM), ultraviolet–visible spectroscopy (UV-vis), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). SEM image indicates the diameter and the length of Pd/TNAs were approximately 300 nm and 2.5 μm, respectively. XPS analyses indicate that 1.13% (atomic %) of Pd was loaded onto the surface of TNAs. UV-vis results show that the band gap of TNAs was reduced from 3.2 eV to 2.37 eV after Pd loading. In addition, the electrochemical performances of Pd/TNAs were investigated by photocurrent density test and electrochemical impedance spectroscopy (EIS). The photocurrent (4.0 mA/cm²) of Pd /TNAs was higher than that of the uncoated TNAs (1.4 mA/cm²) at a bias potential of 1 V (vs. Ag/AgCl), indicating that Pd/TNAs-C can effectively separate photogenerated electrons and holes. The mechanism of our PEC system was proposed and discussed in detail in this study.

Keywords: Pd/TNAs, photoelectrochemical, azo-dye degradation, hydrogen generation

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Authors: Aibek Kukpayev, Dhawal Shah

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Combustion of sour fuels containing high amount of sulfur leads to the formation of sulfur oxides, which adversely harm the environment and has a negative impact on human health. Considering this, several legislations have been imposed to bring down the sulfur content in fuel to less than 10 ppm. In recent years, novel deep eutectic solvents (DESs) have been developed to achieve deep desulfurization, particularly to extract thiophenic compounds from liquid fuels. These novel DESs, considered as analogous to ionic liquids are green, eco-friendly, inexpensive, and sustainable. We herein, using molecular dynamic simulation, analyze the interactions of metal-based DESs with model oil consisting of thiophenic compounds. The DES used consists of polyethylene glycol (PEG-200) as a hydrogen bond donor, choline chloride (ChCl) or tetrabutyl ammonium chloride (TBAC) as a hydrogen bond acceptor, and cobalt chloride (CoCl₂) as metal salt. In particular, the combination of ChCl: PEG-200:CoCl₂ at a ratio 1:2:1 and the combination of TBAC:PEG-200:CoCl₂ at a ratio 1:2:0.25 were simulated, separately, with model oil consisting of octane and thiophenes at 25ᵒC and 1 bar. The results of molecular dynamics simulations were analyzed in terms of interaction energies between different components. The simulations revealed a stronger interaction between DESs/thiophenes as compared with octane/thiophenes, suggestive of an efficient desulfurization process. In addition, our analysis suggests that the choice of hydrogen bond acceptor strongly influences the efficiency of the desulfurization process. Taken together, the results also show the importance of the metal ion, although present in small amount, in the process, and the role of the polymer in desulfurization of the model fuel.

Keywords: deep eutectic solvents, desulfurization, molecular dynamics simulations, thiophenes

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Authors: Qiming Wang

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Dynamic polymer networks (DPNs) crosslinked by dynamic bonds have received intensive attention because of their special crack-healing capability. Diverse DPNs have been synthesized using a number of dynamic bonds, including dynamic covalent bond, hydrogen bond, ionic bond, metal-ligand coordination, hydrophobic interaction, and others. Despite the promising success in the polymer synthesis, the fundamental understanding of their self-healing mechanics is still at the very beginning. Especially, a general analytical model to understand the interfacial self-healing behaviors of DPNs has not been established. Here, we develop polymer-network based analytical theories that can mechanistically model the constitutive behaviors and interfacial self-healing behaviors of DPNs. We consider that the DPN is composed of interpenetrating networks crosslinked by dynamic bonds. bonds obey a force-dependent chemical kinetics. During the self-healing process, we consider the The network chains follow inhomogeneous chain-length distributions and the dynamic polymer chains diffuse across the interface to reform the dynamic bonds, being modeled by a diffusion-reaction theory. The theories can predict the stress-stretch behaviors of original and self-healed DPNs, as well as the healing strength in a function of healing time. We show that the theoretically predicted healing behaviors can consistently match the documented experimental results of DPNs with various dynamic bonds, including dynamic covalent bonds (diarylbibenzofuranone and olefin metathesis), hydrogen bonds, and ionic bonds. We expect our model to be a powerful tool for the self-healing community to invent, design, understand, and optimize self-healing DPNs with various dynamic bonds.

Keywords: self-healing polymers, dynamic covalent bonds, hydrogen bonds, ionic bonds

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Authors: Igor Svishchev, Kashif Choudhry

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Progress in advanced energy technologies is not feasible without understanding how engineering materials perform under extreme environmental conditions. The corrosion behaviour of Fe-Ni-Cr and Zr alloys has been systematically examined under high-temperature and supercritical water flow conditions. The changes in elemental release rate and dissolved gas concentration provide valuable insights into the mechanism of passivation by forming oxide films. A non-intrusive method for monitoring the extent of surface oxidation based on hydrogen release rate has been developed. This approach can be used for the on-line monitoring corrosion behavior of reactor materials without the need to interrupt the flow and remove corrosion coupons. Surface catalysed thermochemical reactions may generate sufficient hydrogen to have an effect on the accumulation of oxidizing species generated by radiolytic processes in the heat transport systems of the supercritical water cooled nuclear reactor.

Keywords: high-temperature corrosion, non-intrusive monitoring, reactor materials, supercritical water

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Authors: Saba Didarataee, Abbas Ali Khodadadi, Yadollah Mortazavi, Fatemeh Mousavi

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Photocatalytic water splitting is one of the most attractive alternative methods for hydrogen evolution. A variety of nanoparticle engineering techniques were introduced to improve the activity of semiconductor photocatalysts. Among these methods, heterojunction formation is an appealing method due to its ability to effectively preventing electron-hole recombination and improving photocatalytic activity. Reaching an optimal ratio of the two target semiconductors for the formation of heterojunctions is still an open question. Considering environmental issues as well as the cost and availability, ZnS and ZnO are frequently studied as potential choices. In this study, first, the ZnS nanoparticle was synthesized in a hydrothermal process; the formation of ZnS nanorods with a diameter of 14-30 nm was confirmed by field emission scanning electron microscope (FESEM). Then two different methods, partial oxidation and chemical precipitation were employed to construct ZnS/ZnO core-shell heterojunction. X-ray diffraction (XRD), BET, and diffuse reflectance spectroscopy (DRS) analysis were carried out to determine crystallite phase, surface area, and bandgap of photocatalysts. Furthermore, the temperature of oxidation was specified by a temperature programmed oxidation (TPO) and was fixed at 510℃, at which mild oxidation occurred. The bandgap was calculated by the Kubelka-Munk method and decreased by increasing oxide content from 3.53 (pure ZnS) to 3.18 (pure ZnO). The optimal samples were determined by testing the photocatalytic activity of hydrogen evolution in a quartz photoreactor with side irradiation of UVC lamps with a wavelength of 254 nm. In both procedures, it was observed that the photocatalytic activity of the ZnS/ZnO composite was sensibly higher than the pure ZnS and ZnO, which is attributed to forming a type-II heterostructure. The best ratio of oxide to sulfide was 0.24 and 0.37 in partial oxidation and chemical precipitation, respectively. The highest hydrogen evolution was 1081 µmol/gr.h, gained from partial oxidizing of ZnS nanoparticles at 510℃ for 30 minutes.

Keywords: heterostructure, hydrogen, partial oxidation, photocatalyst, water splitting, ZnS

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Authors: Tumelo W. P. Seadira, Thabang Ntho, Cornelius M. Masuku, Michael S. Scurrell

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A ternary Cu/TiO2/rGO photocatalysts was prepared using solvothermal method. Firstly, pure anatase TiO2 hollow spheres were prepared with titanium butoxide, ethanol, ammonium sulphate, and urea via hydrothermal method; and Cu nanoparticles were subsequently loaded on the surface of the hollow spheres by wet impregnation. During the solvothermal process, the deposition and well dispersion of Cu-TiO2 hollow spheres composites onto the graphene oxide surface, as well as the reduction of graphene oxide to graphene were achieved. The morphological and structural properties of the prepared samples were characterized by Brunauer-Emmett-Tellet (BET), X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscopy (TEM), and UV-vis DRS, and photoelectrochemical. The activities of the prepared catalysts were tested for hydrogen production via simultaneous photocatalytic water-splitting and glycerol reforming under visible light irradiation. The excellent photocatalytic activity of the Cu-TiO2-hollow-spheres/rGO catalyst was attributed the rGO which acts as both storage and transferor of electrons generated at the Cu and TiO2 heterojunction, thus increasing the electron-hole pairs separation. This paper reports the preparation of photocatalyst which is highly active by coupling reduced graphene oxide with nano-structured TiO2 with high surface area that can efficiently harvest the visible light for effective water-splitting and glycerol photocatalytic reforming in order to achieve efficient hydrogen evolution.

Keywords: glycerol reforming, hydrogen evolution, graphene oxide, Cu/TiO2-hollow-spheres/rGO

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Authors: Heval Serhat Uluk, Sam M. Dakka, Kuldeep Singh, Richard Jefferson-Loveday

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The carbon footprint of the aviation sector in total measured 3.8% in 2017, and it is expected to triple by 2050. New combustion approaches and fuel types are necessary to prevent this. This paper will focus on using propane, methane, and hydrogen as fuel replacements for kerosene and implement a trapped vortex combustor design to increase efficiency. Reacting simulations were conducted for axisymmetric trapped vortex combustor to investigate the static pressure drop, combustion efficiency and pattern factor for various cavity aspect ratios for 0.3, 0.6 and 1 and air mass flow rates for 14 m/s, 28 m/s and 42 m/s. Propane, methane and hydrogen are used as alternative fuels. The combustion model was anchored based on swirl flame configuration with an emphasis on high fidelity of boundary conditions with favorable results of eddy dissipation model implementation. Reynolds Averaged Navier Stokes (RANS) k-ε model turbulence model for the validation effort was used for turbulence modelling. A grid independence study was conducted for the three-dimensional model to reduce computational time. Preliminary results for 24 m/s air mass flow rate provided a close temperature profile inside the cavity relative to the experimental study. The investigation will be carried out on the effect of air mass flow rates and cavity aspect ratio on the combustion efficiency, pattern factor and static pressure drop in the combustor. A comparison study among pure methane, propane and hydrogen will be conducted to investigate their suitability for trapped vortex combustors and conclude their advantages and disadvantages as a fuel replacement. Therefore, the study will be one of the milestones to achieving 2050 zero carbon emissions or reducing carbon emissions.

Keywords: computational fluid dynamics, aerodynamic, aerospace, propulsion, trapped vortex combustor

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Authors: Parth Mehta, Vedasri Bai Khavala, Prabhu Rajagopal, Tiju Thomas

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There is an increasing need for alternative clean fuels, and hydrogen (H₂) has long been considered a promising solution with a high calorific value (142MJ/kg). However, the storage of H₂ and expensive processes for its generation have hindered its usage. Sodium borohydride (NaBH₄) can potentially be used as an economically viable means of H₂ storage. Thus far, there have been attempts to optimize the life of NaBH₄ (half-life) in aqueous media by stabilizing it with sodium hydroxide (NaOH) for various pH values. Other reports have shown that H₂ yield and reaction kinetics remained constant for all ratios of H₂O to NaBH₄ > 30:1, without any acidic catalysts. Here we highlight the importance of pH and H₂O: NaBH₄ ratio (80:1, 40:1, 20:1 and 10:1 by weight), for NaBH₄ stabilization (half-life reaction time at room temperature) and corrosion minimization of H₂ reactor components. It is interesting to observe that at any particular pH>10 (e.g., pH = 10, 11 and 12), the H₂O: NaBH₄ ratio does not have the expected linear dependence with stability. On the contrary, high stability was observed at the ratio of 10:1 H₂O: NaBH₄ across all pH>10. When the H₂O: NaBH₄ ratio is increased from 10:1 to 20:1 and beyond (till 80:1), constant stability (% degradation) is observed with respect to time. For practical usage (consumption within 6 hours of making NaBH₄ solution), 15% degradation at pH 11 and NaBH₄: H₂O ratio of 10:1 is recommended. Increasing this ratio demands higher NaOH concentration at the same pH, thus requiring a higher concentration or volume of acid (e.g., HCl) for H₂ generation. The reactions are done with tap water to render the results useful from an industrial standpoint. The observed stability regimes are rationalized based on complexes associated with NaBH₄ when solvated in water, which depend sensitively on both pH and NaBH₄: H₂O ratio.

Keywords: hydrogen, sodium borohydride, stability optimization, H₂O:NaBH₄ ratio

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Authors: Kaewpradap Amornrat, Endo Takahiro, Kadowaki Satoshi

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The combustion of hydrogen-oxygen (H2-O2) mixtures was investigated to consider the reduction of carbon dioxide (CO2) and nitrogen oxide (NOx) as the greenhouse emission. Normally, the flame speed of combustion H2-O2 mixtures are very fast thus it is necessary to control the limit of mixtures with CO2 addition as H2-O2-CO2 combustion. The limit of hydrogen was set and replaced by CO2 with O2:CO2 ratio as 1:3.76, 1:4 and 1:5 for this study. In this study, the combustion of H2-O2 -CO2 on flat burner at equivalence ratio =0.5 was investigated for 10, 15 and 20 L/min of flow rate mixtures. When the ratio of CO2 increases, the power spectral density is lower, the size of attractor and cellular flame become larger because the decrease of hydrogen replaced by CO2 affects the diffusive-thermal instability. Moreover, the flow rate mixtures increases, the power spectral density increases, the size of reconstructed attractor and cell size become smaller due to decreasing of instability. The results show that the variation of CO2 and mixture flow rate affects the instability of cellular premixed flames on flat burner.

Keywords: instability, H2-O2-CO2 combustion, flat burner, diffusive-thermal instability

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Authors: Mohamed S. Sasi

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The research project aim is to study the hydrolysis of 8-diethylphosphate-1-naphthalenol with hydroxylamine in water. 8-diethylphosphate-1-naphthalenol, 1 was successfully synthesized and its rate of reaction with hydroxylamine was studied at 60°C. Pseudo first order behavior was observed. The rate of P-O cleavage of 1 at 60°C (7.43 x 10-3 M-1s-1) was found to be 178 fold and 7 fold slower than diethyl 8-dimethylamino-1-naphthyl phosphate, 3 at 60°C (1.32 M-1s-1) and diethyl 8-amino-1-naphthyl phosphate, 2 at 90 °C (5.5 x 10-2 M-1s-1) respectively. The rate of P-O cleavage of 1 with hydroxylamine was found to be faster than that of 4-chlorophenyl-1-cyclopropylphosphate triester, 5 where the reaction was too slow to observe at 60°C.

Keywords: phosphate esters, intramolecular hydrogen bonding

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Authors: E. A. Krasikov

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As the service life of an operating nuclear power plant (NPP) increases, the potential misunderstanding of the degradation of aging components must receive more attention. Integrity assurance analysis contributes to the effective maintenance of adequate plant safety margins. In essence, the reactor pressure vessel (RPV) is the key structural component determining the NPP lifetime. Environmentally induced cracking in the stainless steel corrosion-preventing cladding of RPV’s has been recognized to be one of the technical problems in the maintenance and development of light-water reactors. Extensive cracking leading to failure of the cladding was found after 13000 net hours of operation in JPDR (Japan Power Demonstration Reactor). Some of the cracks have reached the base metal and further penetrated into the RPV in the form of localized corrosion. Failures of reactor internal components in both boiling water reactors and pressurized water reactors have increased after the accumulation of relatively high neutron fluences (5´1020 cm–2, E>0,5MeV). Therefore, in the case of cladding failure, the problem arises of hydrogen (as a corrosion product) embrittlement of irradiated RPV steel because of exposure to the coolant. At present when notable progress in plasma physics has been obtained practical energy utilization from fusion reactors (FR) is determined by the state of material science problems. The last includes not only the routine problems of nuclear engineering but also a number of entirely new problems connected with extreme conditions of materials operation – irradiation environment, hydrogenation, thermocycling, etc. Limiting data suggest that the combined effect of these factors is more severe than any one of them alone. To clarify the possible influence of the in-service synergistic phenomena on the FR structural materials properties we have studied hydrogen-irradiated steel interaction including alternating hydrogenation and heat treatment (annealing). Available information indicates that the life of the first wall could be expanded by means of periodic in-place annealing. The effects of neutron fluence and irradiation temperature on steel/hydrogen interactions (adsorption, desorption, diffusion, mechanical properties at different loading velocities, post-irradiation annealing) were studied. Experiments clearly reveal that the higher the neutron fluence and the lower the irradiation temperature, the more hydrogen-radiation defects occur, with corresponding effects on the steel mechanical properties. Hydrogen accumulation analyses and thermal desorption investigations were performed to prove the evidence of hydrogen trapping at irradiation defects. Extremely high susceptibility to hydrogen embrittlement was observed with specimens which had been irradiated at relatively low temperature. However, the susceptibility decreases with increasing irradiation temperature. To evaluate methods for the RPV’s residual lifetime evaluation and prediction, more work should be done on the irradiated metal–hydrogen interaction in order to monitor more reliably the status of irradiated materials.

Keywords: hydrogen, radiation, stability, structural steel

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Authors: Nasrin Bakhshizadeh, Ashkan Forootan

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A major problem that affects the quality control of polymer in the industrial polymerization is the lack of suitable on-line measurement tools to evaluate the properties of the polymer such as melt and density indices. Controlling the polymerization in ordinary method is performed manually by taking samples, measuring the quality of polymer in the lab and registry of results. This method is highly time consuming and leads to producing large number of incompatible products. An online application for estimating melt index and density proposed in this study is a neural network based on the input-output data of the polyethylene production plant. Temperature, the level of reactors' bed, the intensity of ethylene mass flow, hydrogen and butene-1, the molar concentration of ethylene, hydrogen and butene-1 are used for the process to establish the neural model. The neural network is taught based on the actual operational data and back-propagation and Levenberg-Marquart techniques. The simulated results indicate that the neural network process model established with three layers (one hidden layer) for forecasting the density and the four layers for the melt index is able to successfully predict those quality properties.

Keywords: polyethylene, polymerization, density, melt index, neural network

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Authors: Hunmin Jung, Michael Hawkins, Seongmin Lee

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The exocyclic amines of nucleobases can undergo deamination by various DNA damaging agents such as reactive oxygen species, nitric oxide, and water. The deamination of guanine and adenine generates the promutagenic xanthine and hypoxanthine, respectively. The exocyclic amines of bases in DNA are hydrogen bond donors, while the carbonyl moiety generated by the base deamination acts as hydrogen bond acceptors, which can alter base pairing properties of the purines. Xanthine is known to base pair with both cytosine and thymine, while hypoxanthine predominantly pairs with cytosine to promote A to G mutations. Despite the known promutagenicity of the major deaminated purines, structures of DNA polymerase bypassing these lesions have not been reported. To gain insights into the deaminated-induced mutagenesis, we solved crystal structures of human DNA polymerase η (polη) catalyzing across xanthine and hypoxanthine. In the catalytic site of polη, the deaminated guanine (i.e., xanthine) forms three Watson-Crick-like hydrogen bonds with an incoming dCTP, indicating the O2-enol tautomer of xanthine involves in the base pairing. The formation of the enol tautomer appears to be promoted by the minor groove contact by Gln38 of polη. When hypoxanthine is at the templating position, the deaminated adenine uses its O6-keto tautomer to form two Watson-Crick hydrogen bonds with an incoming dCTP, providing the structural basis for the high promutagenicity of hypoxanthine.

Keywords: DNA damage, DNA polymerase, deamination, mutagenesis, tautomerization, translesion synthesis

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Authors: Hongfang Ma, Mingchuan Zhou, Haitao Zhang, Weiyong Ying

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One dimensional pseudo-homogenous modeling has been performed for methanol steam reforming reactor. The results show that the models can well predict the industrial data. The reactor had minimum temperature along axial because of endothermic reaction. Hydrogen productions and temperature profiles along axial were investigated regarding operation conditions such as inlet mass flow rate and mass fraction of methanol, inlet temperature of external thermal oil. Low inlet mass flow rate of methanol, low inlet temperature, and high mass fraction of methanol decreased minimum temperature along axial. Low inlet mass flow rate of methanol, high mass fraction of methanol, and high inlet temperature of thermal oil made cold point forward. Low mass fraction, high mass flow rate, and high inlet temperature of thermal oil increased hydrogen production. One dimensional models can be a guide for industrial operation.

Keywords: reactor, modeling, methanol, steam reforming

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

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

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

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Authors: R. F. Vieira, S. A. Figueiredo, O. M. Freitas, V. F. Domingues, C. Delerue-Matos

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The presence of sulphur compounds like hydrogen sulphide and mercaptans is one of the reasons for waste-water treatment and waste management being associated with odour emissions. In this context having a quantifying method for these compounds helps in the optimization of treatment with the goal of their elimination, namely biofiltration processes. The aim of this study was the development of a method for quantification of odorous gases in waste treatment plants air samples. A method based on head space solid phase microextraction (HS-SPME) coupled with gas chromatography - flame photometric detector (GC-FPD) was used to analyse H2S and Metil Mercaptan (MM). The extraction was carried out with a 75-μm Carboxen-polydimethylsiloxane fiber coating at 22 ºC for 20 min, and analysed by a GC 2010 Plus A from Shimadzu with a sulphur filter detector: splitless mode (0.3 min), the column temperature program was from 60 ºC, increased by 15 ºC/min to 100 ºC (2 min). The injector temperature was held at 250 ºC, and the detector at 260 ºC. For calibration curve a gas diluter equipment (digital Hovagas G2 - Multi Component Gas Mixer) was used to do the standards. This unit had two input connections, one for a stream of the dilute gas and another for a stream of nitrogen and an output connected to a glass bulb. A 40 ppm H2S and a 50 ppm MM cylinders were used. The equipment was programmed to the selected concentration, and it automatically carried out the dilution to the glass bulb. The mixture was left flowing through the glass bulb for 5 min and then the extremities were closed. This method allowed the calibration between 1-20 ppm for H2S and 0.02-0.1 ppm and 1-3.5 ppm for MM. Several quantifications of air samples from inlet and outlet of a biofilter operating in a waste management facility in the north of Portugal allowed the evaluation the biofilters performance.

Keywords: biofiltration, hydrogen sulphide, mercaptans, quantification

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Authors: Hugo Daneluzzo, Christelle Rabbat, Alan Jean-Marie

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Water electrolysis is one of the most advanced technologies for producing hydrogen and can be easily combined with electricity from different sources. Under the influence of electric current, water molecules can be split into oxygen and hydrogen. The production of hydrogen by water electrolysis favors the integration of renewable energy sources into the energy mix by compensating for their intermittence through the storage of the energy produced when production exceeds demand and its release during off-peak production periods. Among the various electrolysis technologies, anion exchange membrane (AEM) electrolyser cells are emerging as a reliable technology for water electrolysis. Modeling and simulation are effective tools to save time, money, and effort during the optimization of operating conditions and the investigation of the design. The modeling and simulation become even more important when dealing with multiphysics dynamic systems. One of those systems is the AEM electrolysis cell involving complex physico-chemical reactions. Once developed, models may be utilized to comprehend the mechanisms to control and detect flaws in the systems. Several modeling methods have been initiated by scientists. These methods can be separated into two main approaches, namely equation-based modeling and graph-based modeling. The former approach is less user-friendly and difficult to update as it is based on ordinary or partial differential equations to represent the systems. However, the latter approach is more user-friendly and allows a clear representation of physical phenomena. In this case, the system is depicted by connecting subsystems, so-called blocks, through ports based on their physical interactions, hence being suitable for multiphysics systems. Among the graphical modelling methods, the bond graph is receiving increasing attention as being domain-independent and relying on the energy exchange between the components of the system. At present, few studies have investigated the modelling of AEM systems. A mathematical model and a bond graph model were used in previous studies to model the electrolysis cell performance. In this study, experimental data from literature were simulated using OpenModelica using bond graphs and mathematical approaches. The polarization curves at different operating conditions obtained by both approaches were compared with experimental ones. It was stated that both models predicted satisfactorily the polarization curves with error margins lower than 2% for equation-based models and lower than 5% for the bond graph model. The activation polarization of hydrogen evolution reactions (HER) and oxygen evolution reactions (OER) were behind the voltage loss in the AEM electrolyzer, whereas ion conduction through the membrane resulted in the ohmic loss. Therefore, highly active electro-catalysts are required for both HER and OER while high-conductivity AEMs are needed for effectively lowering the ohmic losses. The bond graph simulation of the polarisation curve for operating conditions at various temperatures has illustrated that voltage increases with temperature owing to the technology of the membrane. Simulation of the polarisation curve can be tested virtually, hence resulting in reduced cost and time involved due to experimental testing and improved design optimization. Further improvements can be made by implementing the bond graph model in a real power-to-gas-to-power scenario.

Keywords: hydrogen production, anion-exchange membrane, electrolyzer, mathematical modeling, multiphysics modeling

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Authors: Harish Rajak, Preeti Patel

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The application of histone deacetylase inhibitors is a well-known strategy in prevention of cancer which shows acceptable preclinical antitumor activity due to its ability of growth inhibition and apoptosis induction of cancer cell. Molecular docking were performed using Histone Deacetylase protein (PDB ID:1t69) and prepared series of hydroxamic acid based HDACIs. On the basis of docking study, it was predicted that compound 1 has significant binding interaction with HDAC protein and three hydrogen bond interactions takes place, which are essential for antitumor activity. On docking, most of the compounds exhibited better glide score values between -8 to -10 which is close to the glide score value of suberoylanilide hydroxamic acid. The pharmacophore hypotheses were developed using e-pharmacophore script and phase module. The 3D-QSAR models provided a good correlation between predicted and actual anticancer activity. Best QSAR model showed Q2 (0.7974), R2 (0.9200) and standard deviation (0.2308). QSAR visualization maps suggest that hydrogen bond acceptor groups at carbonyl group of cap region and hydrophobic groups at ortho, meta, para position of R9 were favorable for HDAC inhibitory activity. We established structure activity correlation using docking, pharmacophore modeling and atom based 3D QSAR model for hydroxamic acid based HDACIs.

Keywords: HDACIs, QSAR, e-pharmacophore, docking, suberoylanilide hydroxamic acid

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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: T. Ghatauray, J. Ingram, P. Holborn

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The transition from a ‘carbon rich’ fossil fuel dependent to a ‘sustainable’ and ‘renewable’ hydrogen based society will see the deployment of hydrogen fuel cells (HFC) in transport applications and in the generation of heat and power for buildings, as part of a decentralised power network. Many deployments will be low power HFCs for domestic combined heat and power (CHP) and commercial ‘transportable’ HFCs for environmental situations, such as lighting and telephone towers. For broad commercialisation of small fuel cells to be achieved there needs to be significant confidence in their safety in both domestic and environmental applications. Low power HFCs are housed in protective steel enclosures. Standard enclosures have plain rectangular ventilation openings intended for thermal management of electronics and not the dispersion of a buoyant gas. Degradation of the HFC or supply pipework in use could lead to a low-level leak and a build-up of hydrogen gas in the enclosure. Hydrogen’s wide flammable range (4-75%) is a significant safety concern, with ineffective enclosure ventilation having the potential to cause flammable mixtures to develop with the risk of explosion. Mechanical ventilation is effective at managing enclosure hydrogen concentrations, but drains HFC power and is vulnerable to failure. This is undesirable in low power and remote installations and reliable passive ventilation systems are preferred. Passive ventilation depends upon buoyancy driven flow, with the size, shape and position of ventilation openings critical for producing predictable flows and maintaining low buoyant gas concentrations. With environmentally sited enclosures, ventilation openings with pressed horizontal and angled louvres are preferred to protect the HFC and electronics inside. There is an economic cost to adding louvres, but also a safety concern. A question arises over whether the use of pressed louvre vents impairs enclosure passive ventilation performance, when compared to same opening area plain vents. Comparison small enclosure (0.144m³) tests of same opening area pressed louvre and plain vents were undertaken. A displacement ventilation arrangement was incorporated into the enclosure with opposing upper and lower ventilation openings. A range of vent areas were tested. Helium (used as a safe analogue for hydrogen) was released from a 4mm nozzle at the base of the enclosure to simulate a hydrogen leak at leak rates from 1 to 10 lpm. Helium sensors were used to record concentrations at eight heights in the enclosure. The enclosure was otherwise empty. These tests determined that the use of pressed and angled louvre ventilation openings on the enclosure impaired the passive ventilation flow and increased helium concentrations in the enclosure. High-level stratified buoyant gas layers were also found to be deeper than with plain vent openings and were within the flammable range. The presence of gas within the flammable range is of concern, particularly as the addition of the fuel cell and electronics in the enclosure would further reduce the available volume and increase concentrations. The opening area of louvre vents would need to be greater than equivalent plain vents to achieve comparable ventilation flows or alternative schemes would need to be considered.

Keywords: enclosure, fuel cell, helium, hydrogen safety, louvre vent, passive ventilation

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Authors: Minjung Park, Jimin Park, Youngwoon Kim, Hyungseop Han, Myoungryul Ok, Hojeong Jeon, Hyunkwang Seok, Yuchan Kim

Abstract:

Magnesium is an essential element in human body and has unique characteristics such as bioabsorbable and biodegradable properties. Therefore, there has been much attention on studies on the implants based on magnesium to avoid subsequent surgery. However, high amount of hydrogen gas is generated by relatively severe corrosion of magnesium especially in aqueous condition with chloride ions. And it contributes to the causes of swelling of skin and causes consequent inflammation of soft tissue where is directly in contact with implants. Therefore, there is still concern about the safety of the using biodegradable magnesium alloys, which is limited to various applications. In this study, we analyzed the influence of coenzyme on corrosion behavior of magnesium. The analysis of corrosion rate was held by using Hanks’ balanced salt solution (HBSS) as a body stimulated fluid and in condition of 37°C. Thus, with deferring the concentration of the coenzyme used in this study, corrosion rates from 0.0654ml/ cm² to 0.0438ml/cm² were observed in immersion tests. Also, comparable results were obtained in electrochemical tests. Results showed that hydrogen gas produced from corrosion of magnesium can be controlled.

Keywords: biodegradable magnesium, biomaterials, coenzyme, corrosion

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Authors: Satyendra Mourya, Jyoti Jaiswal, Gaurav Malik, Brijesh Kumar, Ramesh Chandra

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Present work describes the fabrication and sensing characteristics of the Pd-Pt decorated nanostructured silicon carbide (SiC) thin films on anodized porous silicon (PSi) substrate by RF magnetron sputtering. The gas sensing performance of Pd-Pt/SiC/PSi sensing electrode towards H2 gas under low (10–400 ppm) detection limit and high operating temperature regime (25–600 °C) were studied in detail. The chemiresistive sensor exhibited high selectivity, good sensing response, fast response/recovery time with excellent stability towards H2 at high temperature. The selectivity measurement of the sensing electrode was done towards different oxidizing and reducing gases and proposed sensing mechanism discussed in detail. Therefore, the investigated Pd-Pt/SiC/PSi structure may be a highly sensitive and selective hydrogen gas sensing electrode for deployment in extreme environment applications.

Keywords: RF Sputtering, silicon carbide, porous silicon, hydrogen gas sensor

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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

Procedia PDF Downloads 365

Authors: Marcin Stasiulewicz, Sebastian Filipkowski, Aneta Panuszko

Abstract:

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

Abstract:

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: C. Hall, J. Ramos, V. Ramasamy

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Hydrocarbon-based fuel vehicles are a major contributor to air pollution due to harmful emissions produced, leading to a demand for cleaner fuel types. A leader in this pursuit is hydrogen, with its application in vehicles producing zero harmful emissions and the only by-product being water. To compete with the performance of conventional vehicles, hydrogen gas must be stored on-board of vehicles in cylinders at high pressures (35–70 MPa) and have a short refueling duration (approximately 3 mins). However, the fast-filling of hydrogen cylinders causes a significant rise in temperature due to the combination of the negative Joule-Thompson effect and the compression of the gas. This can lead to structural failure and therefore, a maximum allowable internal temperature of 85°C has been imposed by the International Standards Organization. The technological solution to tackle the issue of rapid temperature rise during the refueling process is to decrease the temperature of the gas entering the cylinder. Pre-cooling of the gas uses a heat exchanger and requires energy for its operation. Thus, it is imperative to determine the least amount of energy input that is required to lower the gas temperature for cost savings. A validated universal thermodynamic model is used to identify an energy-efficient pre-cooling strategy. The model requires negligible computational time and is applied to previously validated experimental cases to optimize pre-cooling requirements. The pre-cooling characteristics include the location within the refueling timeline and its duration. A constant pressure-ramp rate is imposed to eliminate the effects of rapid changes in mass flow rate. A pre-cooled gas temperature of -40°C is applied, which is the lowest allowable temperature. The heat exchanger is assumed to be ideal with no energy losses. The refueling of the cylinders is modeled with the pre-cooling split in ten percent time intervals. Furthermore, varying burst durations are applied in both the early and late stages of the refueling procedure. The model shows that pre-cooling in the later stages of the refuelling process is more energy-efficient than early pre-cooling. In addition, the efficiency of pre-cooling towards the end of the refueling process is independent of the pressure profile at the inlet. This leads to the hypothesis that pre-cooled gas should be applied as late as possible in the refueling timeline and at very low temperatures. The model had shown a 31% reduction in energy demand whilst achieving the same final gas temperature for a refueling scenario when pre-cooling was applied towards the end of the process. The identification of the most energy-efficient refueling approaches whilst adhering to the safety guidelines is imperative to reducing the operating cost of hydrogen refueling stations. Heat exchangers are energy-intensive and thus, reducing the energy requirement would lead to cost reduction. This investigation shows that pre-cooling should be applied as late as possible and for short durations.

Keywords: cylinder, hydrogen, pre-cooling, refueling, thermodynamic model

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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

Procedia PDF Downloads 444

Authors: Raina J. Olsen, Andrew K. Gillespie, John W. Taylor, Cristian I. Contescu, Peter Pfeifer, James R. Morris

Abstract:

While adsorbent surfaces such as graphite are known to increase the melting temperature of solid H2, this effect is normally rather small, increasing to 20 Kelvin (K) relative to 14 K in the bulk. An as-yet unidentified phase transition has been observed in a system of H2 adsorbed in a porous, locally graphitic, Saran carbon with sub-nanometer sized pores at temperatures (74-101 K) and pressures ( > 76 bar) well above the critical point of bulk H2 using hydrogen adsorption and neutron scattering experiments. Adsorption data shows a discontinuous pressure jump in the kinetics at 76 bar after nearly an hour of equilibration time, which is identified as an exothermic phase transition. This discontinuity is observed in the 87 K isotherm, but not the 77 K isotherm. At higher pressures, the measured isotherms show greater excess adsorption at 87 K than 77 K. Inelastic neutron scattering measurements also show a striking phase transition, with the amount of high angle scattering (corresponding to large momentum transfer/ large effective mass) increasing by up to a factor of 5 in the novel phase. During the course of the neutron scattering experiment, three of these reversible spectral phase transitions were observed to occur in response to only changes in sample temperature. The novel phase was observed by neutron scattering only at high H2 pressure (123 bar and 187 bar) and temperatures between 74-101 K in the sample of interest, but not at low pressure (30 bar), or in a control activated carbon at 186 bar of H2 pressure. Based on several of the more unusual observations, such as the slow equilibration and the presence of both an upper and lower temperature bound, a reasonable hypothesis is that this phase forms only in the presence of a high concentration of ortho-H2 (nuclear spin S=1). The increase in adsorption with temperature, temperatures which cross the lower temperature bound observed by neutron scattering, indicates that this novel phase is denser. Structural characterization data on the adsorbent shows that it may support a commensurate solid phase denser than those known to exist on graphite at much lower temperatures. Whatever this phase is eventually proven to be, these results show that surfaces can have a more striking effect on hydrogen phases than previously thought.

Keywords: adsorbed phases, hydrogen, neutron scattering, nuclear spin

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Authors: Peter Kus, Anna Ostroverkh, Yurii Yakovlev, Yevheniia Lobko, Roman Fiala, Ivan Khalakhan, Vladimir Matolin

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Hydrogen economy is a concept of low-emission society which harvests most of its energy from renewable sources (e.g., wind and solar) and in case of overproduction, electrochemically turns the excess amount into hydrogen, which serves as an energy carrier. Proton exchange membrane water electrolyzers (PEMWE) are the backbone of this concept. By fast-response electricity to hydrogen conversion, the PEMWEs will not only stabilize the electrical grid but also provide high-purity hydrogen for variety of fuel cell powered devices, ranging from consumer electronics to vehicles. Wider commercialization of PEMWE technology is however hindered by high prices of noble metals which are necessary for catalyzing the redox reactions within the cell. Namely, platinum for hydrogen evolution reaction (HER), running on cathode, and iridium for oxygen evolution reaction (OER) on anode. Possible way of how to lower the loading of Pt and Ir is by using conductive high-surface nanostructures as catalyst supports in conjunction with thin-film catalyst deposition. The presented study discusses unconventional technique of membrane electron assembly (MEA) preparation. Noble metal catalysts (Pt and Ir) were magnetron sputtered in very low loadings onto the surface of porous sublayers (located on gas diffusion layer or directly on membrane), forming so to say localized three-phase boundary. Ultrasonically sprayed corrosion resistant TiC-based sublayer was used as a support material on anode, whereas magnetron sputtered nanostructured etched nitrogenated carbon (CNx) served the same role on cathode. By using this configuration, we were able to significantly decrease the amount of noble metals (to thickness of just tens of nanometers), while keeping the performance comparable to that of average state-of-the-art catalysts. Complex characterization of prepared supported catalysts includes in-cell performance and durability tests, electrochemical impedance spectroscopy (EIS) as well as scanning electron microscopy (SEM) imaging and X-ray photoelectron spectroscopy (XPS) analysis. Our research proves that magnetron sputtering is a suitable method for thin-film deposition of electrocatalysts. Tested set-up of thin-film supported anode and cathode catalysts with combined loading of just 120 ug.cm⁻² yields remarkable values of specific current. Described approach of thin-film low-loading catalyst deposition might be relevant when noble metal reduction is the topmost priority.

Keywords: hydrogen economy, low-loading catalyst, magnetron sputtering, proton exchange membrane water electrolyzer

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Authors: Sushil Kumar Saraswat, K. K. Pant

Abstract:

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

Procedia PDF Downloads 321