Search results for: hydrogen embrittlement

Authors: Joelle Penniston, E. B. Gueguim-Kana

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Biohydrogen has been identified as a promising alternative to the use of non-renewable fossil reserves, owing to its sustainability and non-polluting nature. pH is considered as a key parameter in fermentative biohydrogen production processes, due to its effect on the hydrogenase activity, metabolic activity as well as substrate hydrolysis. The present study assesses the influence of regulating pH on dark fermentative biohydrogen production. Four experimental hydrogen production schemes were evaluated. Two were implemented using suspended cells under regulated pH growth conditions (Sus_R) and suspended and non-regulated pH (Sus_N). The two others regimes consisted of alginate immobilized cells under pH regulated growth conditions (Imm_R) and immobilized and non-pH regulated conditions (Imm_N). All experiments were carried out at 37.5°C with glucose as sole source of carbon. Sus_R showed a lag time of 5 hours and a peak hydrogen fraction of 36% and a glucose degradation of 37%, compared to Sus_N which showed a peak hydrogen fraction of 44% and complete glucose degradation. Both suspended culture systems showed a higher peak biohydrogen fraction compared to the immobilized cell system. Imm_R experiments showed a lag phase of 8 hours, a peak biohydrogen fraction of 35%, while Imm_N showed a lag phase of 5 hours, a peak biohydrogen fraction of 22%. 100% glucose degradation was observed in both pH regulated and non-regulated processes. This study showed that biohydrogen production in batch mode with suspended cells in a non-regulated pH environment results in a partial degradation of substrate, with lower yield. This scheme has been the culture mode of choice for most reported studies in biohydrogen research. The relatively lower slope in pH trend of the non-regulated pH experiment with immobilized cells (Imm_N) compared to Sus_N revealed that that immobilized systems have a better buffering capacity compared to suspended systems, which allows for the extended production of biohydrogen even under non-regulated pH conditions. However, alginate immobilized cultures in flask systems showed some drawbacks associated to high rate of gas production that leads to increased buoyancy of the immobilization beads. This ultimately impedes the release of gas out of the flask.

Keywords: biohydrogen, sustainability, suspended, immobilized

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Authors: Ana M. Antolín, Sandra Contreras, Francesc Medina, Didier Tichit

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Introduction: High levels of nitrates (> 50 ppm NO3-) in drinking water are potentially risky to human health. In the recent years, the trend of nitrate concentration in groundwater is rising in the EU and other countries. Conventional catalytic nitrate reduction processes into N2 and H2O lead to some toxic intermediates and by-products, such as NO2-, NH4+, and NOx gases. Alternatively, photocatalytic nitrate removal using solar irradiation and heterogeneous catalysts is a very promising and ecofriendly technique. It has been scarcely performed and more research on highly efficient catalysts is still needed. In this work, different nanocatalysts supported on Aeroxide Titania P25 (P25) have been prepared varying: 0.5-4 % wt. Ag); Pt (2, 4 % wt.); Pt precursor (H2PtCl6/K2PtCl6); and impregnation order of both metals. Pt was chosen in order to increase the selectivity to N2 and decrease that to NO2-. Catalysts were characterized by nitrogen physisorption, X-Ray diffraction, UV-visible spectroscopy, TEM and X Ray-Photoelectron Spectroscopy. The aim was to determine the influence of the composition and the preparation method of the catalysts on the conversion and selectivity in the nitrate reduction, as well as going through an overall and better understanding of the process. Nanocatalysts synthesis: For the mono and bimetallic catalysts preparation, wise-drop wetness impregnation of the precursors (AgNO3, H2PtCl6, K2PtCl6) followed by a reduction step (NaBH4) was used to obtain the metal colloids. Results and conclusions: Denitration experiments were performed in a 350 mL PTFE batch reactor under inert standard operational conditions, ultraviolet irradiations (λ=254 nm (UV-C); λ=365 nm (UV-A)), and presence/absence of hydrogen gas as a reducing agent, contrary to most studies using oxalic or formic acid. Samples were analyzed by Ionic Chromatography. Blank experiments using respectively P25 (dark conditions), hydrogen only and UV irradiations without hydrogen demonstrated a clear influence of the presence of hydrogen on nitrate reduction. Also, they demonstrated that UV irradiation increased the selectivity to N2. Interestingly, the best activity was obtained under ultraviolet lamps, especially at a closer wavelength to visible light irradiation (λ = 365 nm) and H2. 2% Ag/P25 leaded to the highest NO3- conversion among the monometallic catalysts. However, nitrite quantities have to be diminished. On the other hand, practically no nitrate conversion was observed with the monometallics based on Pt/P25. Therefore, the amount of 2% Ag was chosen for the bimetallic catalysts. Regarding the bimetallic catalysts, it is observed that the metal impregnation order, amount and Pt precursor highly affects the results. Higher selectivity to the desirable N2 gas is obtained when Pt was firstly added, especially with K2PtCl6 as Pt precursor. This suggests that when Pt is secondly added, it covers the Ag particles, which are the most active in this reaction. It could be concluded that Ag allows the nitrate reduction step to nitrite, and Pt the nitrite reduction step toward the desirable N2 gas.

Keywords: heterogeneous catalysis, hydrogenation, nanocatalyst, nitrate removal, photocatalysis

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Authors: Maria Fontenele, Claude-Gilles Dussap, Vincent Dumouilla, Baptiste Boit

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Roquette Frères is a producer of plant-based ingredients that employs many processes to extract relevant molecules and often transforms them through chemical and physical processes to create desired ingredients with specific functionalities. In this context, Roquette encounters numerous multi-component complex systems in their processes, including fibers, proteins, and carbohydrates, in an aqueous environment. To develop, control, and optimize both new and old processes, Roquette aims to develop new in silico tools. Currently, Roquette uses process modelling tools which include specific thermodynamic models and is willing to develop computational methodologies such as molecular dynamics simulations to gain insights into the complex interactions in such complex media, and especially hydrogen bonding interactions. The issue at hand concerns aqueous mixtures of polyols with high dry matter content. The polyols mannitol and sorbitol molecules are diastereoisomers that have nearly identical chemical structures but very different physicochemical properties: for example, the solubility of sorbitol in water is 2.5 kg/kg of water, while mannitol has a solubility of 0.25 kg/kg of water at 25°C. Therefore, predicting liquid-solid equilibrium properties in this case requires sophisticated solution models that cannot be based solely on chemical group contributions, knowing that for mannitol and sorbitol, the chemical constitutive groups are the same. Recognizing the significance of solvation phenomena in polyols, the GePEB (Chemical Engineering, Applied Thermodynamics, and Biosystems) team at Institut Pascal has developed the COSMO-UCA model, which has the structural advantage of using quantum mechanics tools to predict formation and phase equilibrium properties. In this work, we use molecular dynamics simulations to elucidate the behavior of polyols in aqueous solution. Specifically, we employ simulations to compute essential metrics such as radial distribution functions and hydrogen bond autocorrelation functions. Our findings illuminate a fundamental contrast: sorbitol and mannitol exhibit disparate hydrogen bond lifetimes within aqueous environments. This observation serves as a cornerstone in elucidating the divergent physicochemical properties inherent to each compound, shedding light on the nuanced interplay between their molecular structures and water interactions. We also present a methodology to predict the physicochemical properties of complex solutions, taking as sole input the three-dimensional structure of the molecules in the medium. Finally, by developing knowledge models, we represent some physicochemical properties of aqueous solutions of sorbitol and mannitol.

Keywords: COSMO models, hydrogen bond, molecular dynamics, thermodynamics

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Authors: Alaa Y. Ali, Natalie P. Holmes, John Holdsworth, Warwick Belcher, Paul Dastoor, Xiaojing Zhou

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Multi-layered graphene has been produced under low temperature chemical vapour deposition (CVD) growth conditions by utilizing an organic solvent and polymer film source. Poly(methylmethacrylate) (PMMA) was dissolved in chlorobenzene solvent and used as a drop-cast film carbon source on a quartz slide. A source temperature (T_source) of 180 °C provided sufficient carbon to grow graphene, as identified by Raman spectroscopy, on clean copper foil catalytic surfaces.  Systematic variation of hydrogen gas (H₂) flow rate from 25 standard cubic centimeters per minute (sccm) to 100 sccm and CVD temperature (T_growth) from 400 to 800 °C, yielded graphene films of varying quality as characterized by Raman spectroscopy. The optimal graphene growth parameters were found to occur with a hydrogen flow rate of 75 sccm sweeping the 180 °C source carbon past the Cu foil at 600 °C for 1 min. The deposition at 600 °C with a H₂ flow rate of 75 sccm yielded a 2D band peak with ~53.4 cm^-1 FWHM and a relative intensity ratio of the G to 2D bands (I_G/I_2D) of 0.21. This recipe fabricated a few layers of good quality graphene.

Keywords: graphene, chemical vapor deposition, carbon source, low temperature growth

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Authors: Ahmed Elreedy, Ahmed Tawfik

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This investigation aims to assess the effect of inoculum to substrate ratio (ISR) and nitrogen to phosphorous balance on simultaneous biohydrogen and methane production from anaerobic decomposition of mono-ethylene glycol (MEG). Different ISRs were applied in the range between 2.65 and 13.23 gVSS/gCOD, whereas the tested N/P ratios were changed from 4.6 to 8.5; both under thermophilic conditions (55°C). The maximum obtained methane and hydrogen yields (MY and HY) of 151.86±10.8 and 22.27±1.1 mL/gCODinitial were recorded at ISRs of 5.29 and 3.78 gVSS/gCOD, respectively. Unlikely, the ammonification process, in terms of net ammonia produced, was found to be ISR and COD/N ratio dependent, reaching its peak value of 515.5±31.05 mgNH4-N/L at ISR and COD/N ratio of 13.23 gVSS/gCOD and 11.56. The optimum HY was enhanced by more than 1.45-fold with declining N/P ratio from 8.5 to 4.6; whereas, the MY was improved (1.6-fold), while increasing N/P ratio from 4.6 to 5.5 with no significant impact at N/P ratio of 8.5. The results obtained revealed that the methane production was strongly influenced by initial ammonia, compared to initial phosphate. Likewise, the generation of ammonia was markedly deteriorated from 535.25±41.5 to 238.33±17.6 mgNH4-N/L with increasing N/P ratio from 4.6 to 8.5. The kinetic study using Modified Gompertz equation was successfully fitted to the experimental outputs (R2 > 0.9761).

Keywords: mono-ethylene glycol, biohydrogen and methane, inoculum to substrate ratio, nitrogen to phosphorous balance, ammonification

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Authors: Chris Miskelly, Eoin Cunningham, Beatrice Smyth, John. D. Holbrey, Gosia Swadzba-Kwasny, Emily L. Byrne, Yoan Delavoux, Mantian Li.

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Recently, the use of ionic liquids (ILs) for the preparation of lignocellulose derived cellulosic materials as alternatives to petrochemical feedstocks has been the focus of considerable research interest. While the technical viability of IL-based lignocellulose treatment methodologies has been well established, the high cost of reagents inhibits commercial feasibility. This work aimed to assess the technoeconomic viability of the preparation of cellulose rich materials (CRMs) using protic ionic liquids (PILs) synthesized from low cost alkylamines and sulphuric acid. For this purpose, the tertiary alkylamines, triethylamine, and dimethylbutylamine were selected. Bulk scale production cost of the synthesized PILs, triethylammonium hydrogen sulphate and dimetheylbutylammonium hydrogen sulphate, was reported as $0.78 kg-1 to $1.24 kg-1. CRMs were prepared through the treatment of common wheat (Triticum aestivum) straw with these PILs. By controlling treatment parameters, CRMs with a cellulose content of ≥ 80 wt% were prepared. This was achieved using a T. aestivum straw to PIL loading ratio of 1:15 w/w, a treatment duration of 180 minutes, and ethanol as a cellulose antisolvent. Infrared spectra data and decreased onset degradation temperature of CRMs (ΔTONSET ~ 70 °C) suggested the formation of cellulose sulphate esters during treatment. Chemical derivatisation can aid the dispersion of prepared CRMs in non-polar polymer/ composite matrices, but act as a barrier to thermal processing at temperatures above 150 °C. It was also shown that treatment increased the crystallinity of CRMs (ΔCrI ~ 40 %) without altering the native crystalline structure or crystallite size (~ 2.6 nm) of cellulose; peaks associated with the cellulose I crystalline planes (110), (200), and (004) were observed at Bragg angles 16.0 °, 22.5 ° and 35.0 ° respectively. This highlighted the inability of assessed PILs to dissolve crystalline cellulose and was attributed to the high acidity (pKa ~ - 1.92 to - 6.42) of sulphuric acid derived anions. Electron micrographs revealed that the stratified multilayer tissue structure of untreated T. aestivum straw was significantly modified during treatment. T. aestivum straw particles were disassembled during treatment, with prepared CRMs adopting a golden-brown film-like appearance. This work demonstrated the degradation of non-cellulosic fractions of lignocellulose without dissolution of cellulose. It is the first to report on the derivatisation of cellulose during treatment with protic hydrogen sulphate ionic liquids, and the potential implications of this with reference to biopolymer feedstock preparation.

Keywords: cellulose, extraction, protic ionic liquids, esterification, thermal stability, waste valorisation, biopolymer feedstock

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Authors: Shah Sufaid, Hussain Shahid, Tianyan You, Liu Guiwu, Qiao Guanjun

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Nickel oxide (NiO) is an optimal material for precise detection of hydrogen (H₂) gas due to its high catalytic activity and low resistivity. However, the gas response kinetics of H₂ gas molecules with the surface of NiO concurrence limitation imposed by its solid structure, leading to a diminished gas response value and slow electron-hole transport. Herein, NiO@CuO NFs with porous sharp-tip and nanospheres morphology were successfully synthesized by using a metal-organic framework (MOFs) as a precursor. The fabricated porous 2 wt% NiO@CuO NFs present outstanding selectivity towards H₂ gas, including a high sensitivity of a response value (170 to 20 ppm at 150 °C) higher than that of porous Ni-MOF (6), low detection limit (300 ppb) with a notable response (21), short response and recovery times at (300 ppb, 40/63 s and 20 ppm, 100/167 s), exceptional long-term stability and repeatability. Furthermore, an understanding of NiO@CuO sensor functioning in an actual environment has been obtained by using the impact of relative humidity as well. The boosted hydrogen sensing properties may be attributed due to synergistic effects of numerous facts including p-p heterojunction at the interface between NiO and CuO nanoflowers. Particularly, a porous Ni-MOF structure combined with the chemical sensitization effect of NiO with the rough surface of CuO nanosphere, are examined. This research presents an effective method for development of Ni-MOF derived metal oxide semiconductor (MOS) heterostructures with rigorous morphology and composition, suitable for gas sensing application.

Keywords: NiO@CuO NFs, metal organic framework, porous structure, H₂, gas sensing

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Authors: Z. N. Ali, O. A. Babatunde, S. Garba, H. M. S. Haruna

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The potency of modified and unmodified activated carbons prepared from shells of Cocos nucifera (coconut shell), straws of Pennisetum glaucum (millet) and Sorghum bicolor (sorghum) for adsorption of hydrogen sulphide gas were investigated using an adsorption apparatus (stainless steel cylinder) at constant temperature (ambient temperature). The adsorption equilibria states were obtained when the pressure indicated on the pressure gauge remained constant. After modification with nitric acid, results of the scanning electron microscopy of the unmodified and modified activated carbons showed that HNO3 greatly improved the formation of micropores and mesopores on the activated carbon surface. The adsorption of H2S gas was found to be highest in modified Cocos nucifera activated carbon with maximum monolayer coverage of 28.17 mg/g, and the adsorption processes were both physical and chemical with the physical process being predominant. The adsorption data were well fitted into the Langmuir isotherm model with the adsorption capacities of the activated carbons in the order modified Cocos nucifera > modified Pennisetum glaucum > modified Sorghum bicolor > unmodified Cocos nucifera > unmodified Pennisetum glaucum > unmodified Sorghum bicolour.

Keywords: activated carbon adsorption, hydrogen sulphide, nitric acid, modification, stainless steel cylinder

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Authors: Wen Cai Ng, Saman Ilankoon, Meng Nan Chong

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The vast increase in global energy demand, coupled with the growing concerns on environmental issues, has triggered the search for cleaner alternative energy sources. In view of this, the photoelectrochemical (PEC) water splitting offers a sustainable hydrogen (H2) production route that only requires solar energy, water, and PEC system operating in an ambient environment. However, the current advancement of PEC water splitting technologies is still far from the commercialization benchmark indicated by the solar-to-H2 (STH) efficiency of at least 10 %. This is largely due to the shortcomings of photoelectrodes used in the PEC system, such as the rapid recombination of photogenerated charge carriers and limited photo-responsiveness in the visible-light spectrum. Silver orthophosphate (Ag3PO4) possesses many desirable intrinsic properties for the fabrication into photoanode used in PEC systems, such as narrow bandgap of 2.4 eV and low valence band (VB) position. Hence, in this study, a highly efficient Ag3PO4-based photoanode was synthesized and characterized. The surface of the Ag foil substrate was directly oxidized to fabricate a top layer composed of {111}-bound Ag3PO4 tetrahedrons layer with a porous structure, forming the dual-layer Ag/Ag3PO4 photoanode. Furthermore, the key synthesis parameters were systematically investigated by varying the concentration ratio of capping agent-to-precursor (R), the volume ratio of hydrogen peroxide (H2O2)-to-water, and reaction period. Results showed that the optimized dual-layer Ag/Ag3PO4 photoanode achieved a photocurrent density as high as 4.19 mA/cm2 at 1 V vs. Ag/AgCl for the R-value of 4, the volume ratio of H2O2-to-water of 3:5 and 20 h reaction period. The current work provides a solid foundation for further nanoarchitecture modification strategies on Ag3PO4-based photoanodes for more efficient PEC water splitting applications. This piece of information needs to be backed up by evidence; therefore, you need to provide a reference. As the abstract should be self-contained, all information requiring a reference should be removed. This is a fact known to the area of research, and not necessarily required a reference to support.

Keywords: solar-to-hydrogen fuel, photoelectrochemical water splitting, photoelectrode, silver orthophosphate

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Authors: Wilmer Esteban Vallejo Narváez, Serguei Fomine

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The theoretical investigation of Si-doped graphene nanoflakes (NFs) was conducted to understand their catalytic impact on CO₂ reduction using molecular hydrogen at the Density Functional Theory (DFT) level. The introduction of silicon by substituting carbon induces defects in the NF structure, resulting in a polyradical ground state. This silicon defect significantly boosts reactivity towards substrates, making Si-doped graphene NFs more catalytically active in CO₂ reduction to formic acid compared to silicene. Notably, Si-doped graphene demonstrates a preference for formic acid over carbon monoxide, mirroring the behavior of silicene. Furthermore, investigations into formic acid-to-formaldehyde and formaldehyde-to-methanol conversions reveal instances where Si-doped graphene outperforms silicene in terms of efficacy. In the final reduction step, the methanol-to-methane reaction unfolds in four stages, with the rate-determining step involving hydrogen transfer from silicon to methyl. Notably, the activation energy for this step is lower in Si-doped graphene compared to silicene. Consequently, Si-doped graphene NFs emerge as superior catalysts with lower activation energies overall. Remarkably, throughout these catalytic processes, Si-doped graphene maintains environmental stability, further highlighting its enhanced catalytic activity without compromising graphene's inherent stability.

Keywords: silicon-doped graphene, CO₂ reduction, DFT, catalysis

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Authors: Suhadiyana Hanapi, Alhassan Salami Tijani, W. A. N Wan Mohamed

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In this paper, a prototype PEM fuel cell vehicle integrated with a 1 kW air-blowing proton exchange membrane fuel cell (PEMFC) stack as a main power sources has been developed for a lightweight cruising vehicle. The test vehicle is equipped with a PEM fuel cell system that provides electric power to a brushed DC motor. This vehicle was designed to compete with industrial lightweight vehicle with the target of consuming least amount of energy and high performance. Individual variations in driving style have a significant impact on vehicle energy efficiency and it is well established from the literature. The primary aim of this study was to assesses the power and fuel consumption of a hydrogen fuel cell vehicle operating at three difference driving technique (i.e. 25 km/h constant speed, 22-28 km/h speed range, 20-30 km/h speed range). The goal is to develop the best driving strategy to maximize performance and minimize fuel consumption for the vehicle system. The relationship between power demand and hydrogen consumption has also been discussed. All the techniques can be evaluated and compared on broadly similar terms. Automatic intelligent controller for driving prototype fuel cell vehicle on different obstacle while maintaining all systems at maximum efficiency was used. The result showed that 25 km/h constant speed was identified for optimal driving with less fuel consumption.

Keywords: prototype fuel cell electric vehicles, energy efficient, control/driving technique, fuel economy

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Authors: Zohreh Derikvand, Hadis Cheraghi, Azadeh Azadbakht, Vaclav Eigner, Michal Dusek

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Two new one and two dimensional metal organic coordination polymers of Cu(II), [Cu(3-nph)2(H2O)2pz]n (1) and Ag(I), {[Ag(3-nph)pz].H2O}n (2) with pyrazine (pz) and 3- nitrophthalic acid (3-nph) have been synthesized and characterized by elemental analysis, spectral (IR, UV-Vis), thermal (TG/DTG) analysis and single crystal X-ray diffraction. We used these compounds to preparation modified electrode with Au/Pt nanosparticles in order to investigation electrochemistry and electrocatalysis activities. The surface structure and composition of the sensor were characterized by scanning electron microscopy (SEM). The Ag(I) coordination polymer shows a 2D layer structure constructed from dinuclear silver (I) building blocks in which two crystallographically Ag+ ions are connected to each other by a covalent bond. The pyrazine ligands adopt μ2 bridging modes, linking the metal centers into a one and two -dimensional coordination framework in 1 and 2. The two AgI cations are surrounded by pyrazine and 3-nitrophthalate mono anions and indicate distorted tetrahedral geometry. In the crystal structures of Ag(I) complex there are non-classical hydrogen bonding arrangements, C–O•••π and π–π stacking interactions. In Cu(II) coordination polymer, the coordination geometry around Cu(II) atom is a distorted octahedron. Interestingly, the structural analysis illustrates that the strong and weak hydrogen bond accompanied with C–H•••π and C–O•••π stacking interactions assemble the crystal structure of 1 and 2 into fascinating 3D supramolecular architecture.

Keywords: 3-nithrophethalic acid, crystal structure, coordination polymer, electrocatalysis

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Authors: Luis F. Bianchessi, Gustavo G. Shimamoto, Matthieu Tubino

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The use of biodiesel has been diffused in Brazil and all over the world by the trading of biodiesel (B100). In Brazil, the diesel oil currently being sold is a blend, containing 7% biodiesel (B7). In this context, it is necessary to develop methods capable of identifying this blend composition, especially regarding the biodiesel quality used for making these blends. In this study, hydrogen nuclear magnetic resonance spectra (1H-NMR) are proposed as a form of identifying and confirming the quality of type B10 blends (10% of biodiesel and 90% of diesel). Furthermore, the presence of vegetable oils, which may be from fuel adulteration or as an evidence of low degree of transesterification conversion during the synthesis of B100, may also be identified. Mixtures of diesel, vegetable oils and their respective biodiesel were prepared. Soybean oil and macauba kernel oil were used as raw material. The diesel proportion remained fixed at 90%. The other proportion (10%) was varied in terms of vegetable oil and biodiesel. The 1H-NMR spectra were obtained for each one of the mixtures, in order to find a correlation between the spectra and the amount of biodiesel, as well as the amount of residual vegetable oil. The ratio of the integral of the methylenic hydrogen H-2 of glycerol (exclusive of vegetable oil) with respect to the integral of the olefinic hydrogens (present in vegetable oil and biodiesel) was obtained. These ratios were correlated with the percentage of vegetable oil in each mixture, from 0% to 10%. The obtained correlation could be described by linear relationships with R2 of 0.9929 for soybean biodiesel and 0.9982 for macauba kernel biodiesel. Preliminary results show that the technique can be used to monitor the biodiesel quality in commercial diesel-biodiesel blends, besides indicating possible adulteration.

Keywords: biodiesel, diesel, biodiesel quality, adulteration

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Authors: Shiying Fan, Xinyong Li

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The development of highly efficient multifunctional catalytic materials towards HER, ORR and Photo-fuel cell applications in terms of combined electrochemical and photo-electrochemical principles have currently confronted with dire challenges. In this study, novel palladium (Pd) and ruthenium (Ru) Bimetal Quantum Dots (BQDs) co-anchored on Titania nanotube (NTs) arrays electrodes have been successfully constructed by facial two-step electrochemical strategy. Double Schottky junctions with superior performance in electrocatalytic (EC) hydrogen generations and solar fuel cell energy conversions (PE) have been found. Various physicochemical techniques including UV-vis spectroscopy, TEM/EDX/HRTEM, SPV/TRV and electro-chemical strategy including EIS, C-V, I-V, and I-T, etc. were chronically utilized to systematically characterize the crystal-, electronic and micro-interfacial structures of the composites with double Schottky junction, respectively. The characterizations have implied that the marvelous enhancement of separation efficiency of electron-hole pairs generations is mainly caused by the Schottky-barriers within the nanocomposites, which would greatly facilitate the interfacial charge transfer for H₂ generations and solar fuel cell energy conversions. Moreover, the DFT calculations clearly indicated that the oriented growth of Ru and Pd bimetal atoms at the anatase (101) surface is mainly driven by the interaction between Ru/Pd and surface atoms, and the most active site for bimetal Ru and Pd adatoms on the perfect TiO₂ (101) surface is the 2cO-6cTi-3cO bridge sites and the 2cO-bridge sites with the highest adsorption energy of 9.17 eV. Furthermore, the electronic calculations show that in the nanocomposites, the number of impurity (i.e., co-anchored Ru-Pd BQDs) energy levels near Fermi surface increased and some were overlapped with original energy level, promoting electron energy transition and reduces the band gap. Therefore, this work shall provide a deeper insight for the molecular design of Bimetal Quantum Dots (BQDs) assembled onto Tatiana NTs composites with superior performance for electrocatalytic hydrogen productions and solar fuel cell energy conversions (PE) simultaneously.

Keywords: eletrocatalytic, Ru-Pd bimetallic quantum dots, titania nanotube arrays, double Schottky junctions, hydrogen production

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Authors: A. V. Samokhin, A. A. Fadeev, M. A. Sinaiskii, N. V. Alekseev, A. V. Kolesnikov

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Composite materials where metal matrix is reinforced by ceramic or metal particles are of great interest for use in the manufacturing of electrical contacts. Significant improvement of the composite physical and mechanical properties as well as increase of the performance parameters of composite-based products can be achieved if the nanoscale structure in the composite materials is obtained by using nanosized powders as starting components. The results of nanosized composite powders synthesis (Ag-SnO2, W-Cu and Cu-C) in the DC thermal plasma flows are presented in this paper. The investigations included the following processes: - Recondensation of micron powder mixture Ag + SnO2 in a nitrogen plasma; - The reduction of the oxide powders mixture (WO3 + CuO) in a hydrogen-nitrogen plasma; - Decomposition of the copper formate and copper acetate powders in nitrogen plasma. The calculations of equilibrium compositions of multicomponent systems Ag-Sn-O-N, W-Cu-O-H-N and Cu-O-C-H-N in the temperature range of 400-5000 K were carried to estimate basic process characteristics. Experimental studies of the processes were performed using a plasma reactor with a confined jet flow. The plasma jet net power was in the range of 2 - 13 kW, and the feedstock flow rate was up to 0.35 kg/h. The obtained powders were characterized by TEM, HR-TEM, SEM, EDS, ED-XRF, XRD, BET and QEA methods. Nanocomposite Ag-SnO2 (12 wt. %). Processing of the initial powder mixture (Ag-SnO2) in nitrogen thermal plasma stream allowed to produce nanopowders with a specific surface area up to 24 m2/g, consisting predominantly of particles with size less than 100 nm. According to XRD results, tin was present in the obtained products as SnO2 phase, and also as intermetallic phases AgxSn. Nanocomposite W-Cu (20 wt .%). Reduction of (WO3+CuO) mixture in the hydrogen-nitrogen plasma provides W-Cu nanopowder with particle sizes in the range of 10-150 nm. The particles have mainly spherical shape and structure tungsten core - copper shell. The thickness of the shell is about several nanometers, the shell is composed of copper and its oxides (Cu2O, CuO). The nanopowders had 1.5 wt. % oxygen impurity. Heat treatment in a hydrogen atmosphere allows to reduce the oxygen content to less than 0.1 wt. %. Nanocomposite Cu-C. Copper nanopowders were found as products of the starting copper compounds decomposition. The nanopowders primarily had a spherical shape with a particle size of less than 100 nm. The main phase was copper, with small amount of Cu2O and CuO oxides. Copper formate decomposition products had a specific surface area 2.5-7 m2/g and contained 0.15 - 4 wt. % carbon; and copper acetate decomposition products had the specific surface area 5-35 m2/g, and carbon content of 0.3 - 5 wt. %. Compacting of nanocomposites (sintering in hydrogen for Ag-SnO2 and electric spark sintering (SPS) for W-Cu) showed that the samples having a relative density of 97-98 % can be obtained with a submicron structure. The studies indicate the possibility of using high-intensity plasma processes to create new technologies to produce nanocomposite materials for electric contacts.

Keywords: electrical contact, material, nanocomposite, plasma, synthesis

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Authors: I. V. Palamarchuk, N. V. Zaichko

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Background and Aims: Galectin-3 is a marker of subclinical cardiac injury and is elevated in individuals with type 2 diabetes mellitus; while hydrogen sulfide (H₂S), metabolite of sulfur-containing amino acids, is considered having antifibrogenic effects. This study was designed to investigate whether metformin and its combination with NaHS can influence plasma galectin-3 and cystathionine-γ-lyase/hydrogen sulfide (CSE/H₂S) system in diabetic rat’s heart. Methods: 32 healthy male rats (180-250 g) were divided into 4 groups. To induct diabetes, rats (group 2-4) were injected with streptozotocin (STZ, 40 mg/kg/i.p., 0.1 M citrate buffer (pH 4.5). Rats from 3d (STZ+Metf) and 4th (STZ+Metf+NaHS) groups were given metformin (500 mg/kg/day) orally, and rats from 4th (STZ+Metf+NaHS) group were injected sodium hydrosulfide (NaHS, 3 mg/kg/i.p.) once per day starting from 3 to 28 day after streptozotocin injection. Rats of first group (control) were administered the equivalent volumes of 0.9% NaCl. Plasma galectin-3 was measured by ELISA. Rats’ hearts were sampled for determination of H2S by reaction with N,N-Dimethyl-p-phenylenediamine. Determination of CSE gene expression was performed in real time using PCR in the presence of SYBR Green I, using DT-Light detecting amplifier ('DNA-technology', Russia). Results: Induction of streptozotocin diabetes (STZ-diabetes, group 2) was followed by low myocardial H2S concentration and CSE expression (by 35%, p < 0.05 and 60.5%, p < 0.001 respectively, than that in controls), while plasma galectin-3 in this group was significantly higher than in controls (by 3.8 times, p < 0.05). Administration of metformin (group 3) resulted in significantly higher H₂S concentration (by 28.5%, p < 0.05), whereas CSE expression was only by 6% more than that in STZ-diabetes, as well as plasma galectin-3 was only by 14.8% lower in comparison with untreated diabetic rats. The inhibition of H₂S generation and CSE activity by diabetes was greatly attenuated in STZ+Metf+NaHS group. The combination of metformin with NaHS significantly stimulated H₂S production (by 48%, p < 0.05 and 15%, p < 0.05 more than STZ-diabetes and STZ+Metf respectively) and CSE gene expression (by 64.8%, p < 0.05 compared to STZ-diabetes and by 55.4%,p < 0.05 compared to STZ+Metf). Besides, plasma galectin-3 in rats receiving metformin and NaHS was significantly lower by 42%, p < 0.05 and 32.5%, p < 0.05 compared to STZ-diabetes and STZ+Metf groups respectively. Conclusions: To summarize, dysfunction of CSE/H2S system and galectin-3 stimulation was found in streptozotocin-induced diabetic rats. Metformin and its combination with exogenous H2S effectively prevented the development of metabolic changes induced by diabetes. These findings suggest that CSE/H₂S system can be integrated into pathogenesis of diabetic complications through modulation of pro-inflammatory and pro-fibrogenic mediator galectin-3.

Keywords: cystathionine-γ-lyase, diabetic heart, galectin-3, hydrogen sulfide, metformin, sodium hydrosulfide

Procedia PDF Downloads 226

Authors: Rocio López, Miriam Tena, Montserrat Pérez, Rosario Solera

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Biotransformation of organic waste into biogas is considered an interesting alternative for the production of clean energy from renewable sources by reducing the volume and organic content of waste Anaerobic digestion is considered one of the most efficient technologies to transform waste into fertilizer and biogas in order to obtain electrical energy or biofuel within the concept of the circular economy. Currently, three types of anaerobic processes have been developed on a commercial scale: (1) single-stage process where sludge bioconversion is completed in a single chamber, (2) two-stage process where the acidogenic and methanogenic stages are separated into two chambers and, finally, (3) temperature-phase sequencing (TPAD) process that combines a thermophilic pretreatment unit prior to mesophilic anaerobic digestion. Two-stage processes can provide hydrogen and methane with easier control of the first and second stage conditions producing higher total energy recovery and substrate degradation than single-stage processes. On the other hand, co-digestion is the simultaneous anaerobic digestion of a mixture of two or more substrates. The technology is similar to anaerobic digestion but is a more attractive option as it produces increased methane yields due to the positive synergism of the mixtures in the digestion medium thus increasing the economic viability of biogas plants. The present study focuses on the energy recovery by anaerobic co-digestion of sewage sludge and waste from the aquaculture-fishing sector. The valorization is approached through the application of a temperature sequential phase process or TPAD technology (Temperature - Phased Anaerobic Digestion). Moreover, two-phase of microorganisms is considered. Thus, the selected process allows the development of a thermophilic acidogenic phase followed by a mesophilic methanogenic phase to obtain hydrogen (H₂) in the first stage and methane (CH₄) in the second stage. The combination of these technologies makes it possible to unify all the advantages of these anaerobic digestion processes individually. To achieve these objectives, a sequential study has been carried out in which the biochemical potential of hydrogen (BHP) is tested followed by a BMP test, which will allow checking the feasibility of the two-stage process. The best results obtained were high total and soluble COD yields (59.8% and 82.67%, respectively) as well as H₂ production rates of 12LH₂/kg SVadded and methane of 28.76 L CH₄/kg SVadded for TPAD.

Keywords: anaerobic co-digestion, TPAD, two-phase, BHP, BMP, sewage sludge, fish waste

Procedia PDF Downloads 156

Authors: Bastien Sanglard, Simon Cayez, Guillaume Viau, Thomas Blon, Julian Carrey, Sébastien Lachaize

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The need to develop clean production processes is a key challenge of any industry. Steel and iron industries are particularly concerned since they emit 6.8% of global anthropogenic greenhouse gas emissions. One key step of the process is the high-temperature reduction of iron ore using coke, leading to large amounts of CO2 emissions. One route to decrease impacts is to get rid of fossil fuels by changing both the heat source and the reducer. The present work aims at investigating experimentally the possibility to use concentrated solar energy and carbon-free reducing agents. Two sets of experimentations were realized. First, in situ X-ray diffraction on pure and industrial powder of hematite was realized to study the phase evolution as a function of temperature during reduction under hydrogen and ammonia. Secondly, experiments were performed on industrial iron ore pellets, which were reduced by NH3 or H2 into a “solar furnace” composed of a controllable 1600W Xenon lamp to simulate and control the solar concentrated irradiation of a glass reactor and of a diaphragm to control light flux. Temperature and pressure were recorded during each experiment via thermocouples and pressure sensors. The percentage of iron oxide converted to iron (called thereafter “reduction ratio”) was found through Rietveld refinement. The power of the light source and the reduction time were varied. Results obtained in the diffractometer reaction chamber show that iron begins to form at 300°C with pure Fe2O3 powder and 400°C with industrial iron ore when maintained at this temperature for 60 minutes and 80 minutes, respectively. Magnetite and wuestite are detected on both powders during the reduction under hydrogen; under ammonia, iron nitride is also detected for temperatures between400°C and 600°C. All the iron oxide was converted to iron for a reaction of 60 min at 500°C, whereas a conversion ratio of 96% was reached with industrial powder for a reaction of 240 min at 600°C under hydrogen. Under ammonia, full conversion was also reached after 240 min of reduction at 600 °C. For experimentations into the solar furnace with iron ore pellets, the lamp power and the shutter opening were varied. An 83.2% conversion ratio was obtained with a light power of 67 W/cm2 without turning over the pellets. Nevertheless, under the same conditions, turning over the pellets in the middle of the experiment permits to reach a conversion ratio of 86.4%. A reduction ratio of 95% was reached with an exposure of 16 min by turning over pellets at half time with a flux of 169W/cm2. Similar or slightly better results were obtained under an ammonia reducing atmosphere. Under the same flux, the highest reduction yield of 97.3% was obtained under ammonia after 28 minutes of exposure. The chemical reaction itself, including the solar heat source, does not produce any greenhouse gases, so solar metallurgy represents a serious way to reduce greenhouse gas emission of metallurgy industry. Nevertheless, the ecological impact of the reducers must be investigated, which will be done in future work.

Keywords: solar concentration, metallurgy, ammonia, hydrogen, sustainability

Procedia PDF Downloads 138

Authors: Hosein Faramarzpour

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This work presents the optimum operational conditions for a hydrogen-based micro-scale power source, using a verified mathematical model including fluid dynamics and reaction kinetics. Thereafter the stable operational flame regime is pursued as a key factor in optimizing the design of micro-combustors. The results show that with increasing velocities, four H2 flame regimes develop in the micro-combustor, namely: 1) periodic ignition-extinction regime, 2) steady symmetric regime, 3) pulsating asymmetric regime, and 4) steady asymmetric regime. The first regime that appears in 0.8 m/s inlet velocity is a periodic ignition-extinction regime which is characterized by counter flows and tulip-shape flames. For flow velocity above 0.2 m/s, the flame shifts downstream, and the combustion regime switches to a steady symmetric flame where temperature increases considerably due to the increased rate of incoming energy. Further elevation in flow velocity up to 1 m/s leads to the pulsating asymmetric flame formation, which is associated with pulses in various flame properties such as temperature and species concentration. Further elevation in flow velocity up to 1 m/s leads to the pulsating asymmetric flame formation, which is associated with pulses in various flame properties such as temperature and species concentration. Ultimately, when the inlet velocity reached 1.2 m/s, the last regime was observed, and a steady asymmetric regime appeared.

Keywords: thermophotovoltaic generator, micro combustor, micro power generator, combustion regimes, flame dynamic

Procedia PDF Downloads 102

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

Procedia PDF Downloads 302

Authors: Hamad Almohamadi, Nabeel Alharthi, Majed Alamoudi

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Biphasic electrodes featuring CuSx/NiSx electrodeposited on nickel foam have been investigated for their electrocatalytic activity in water splitting. The study investigates the impacts of an S-vacancy induced biphasic design on the overpotential and Tafel slope. According to the findings, the NiSx/CuSx/NF electrode with S-vacancy defects displays stronger oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) activity with lower overpotential and a steeper Tafel slope than the non-defect sample. NiSx/CuSx/NF exhibits the lowest overpotential value of 212 mV vs reversible hydrogen electrode (RHE) for OER and −109 mV vs RHE for HER at 10 mA cm−2. Tafel slope of 25.4 mV dec−1 for OER and −108 mV dec−1 for OER found of that electrode. The electrochemical surface area (ECSA) and diffusion impedance of the electrode is calculated. The maximum ECSA, lowest series resistance and lowest charge transfer resistance are found in the *NiSx/CuSx/NF sample with S-vacancy defects, showing increased electrical conductivity and quick charge transfer kinetics. The *NiSx/CuSx/NF electrode was found to be stable for 80 hours in pure water splitting and 20 hours in sea-water splitting. The investigation comes to the conclusion that the enhanced water splitting activity and electrical conductivity of the electrode are caused by S-vacancy defects resulting in improved water splitting performance.

Keywords: water splitting, electrocatalyst, biphasic design, electrodeposition

Procedia PDF Downloads 74

Authors: Angga Pratama Herman, Muhammad Shahbaz, Suzana Yusup

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Bottom ash is a solid waste from thermal power plant and it is usually disposed of into landfills and ash ponds. These disposal methods are not sustainable since new lands need to be acquired as the landfills and ash ponds are fill to its capacity. Bottom ash also classified as hazardous material that makes the disposal methods may have contributed to the environmental effect to the area. Hence, more research needs to be done to explore the potential of recycling the bottom ash as more useful product. The objective of this research is to explore the potential of utilizing bottom ash as catalyst in biomass steam gasification. In this research, bottom ash was used as catalyst in gasification of Palm Kernel Shell (PKS) using Thermo Gravimetric Analyzer coupled with mass spectrometry (TGA/MS). The effects of temperature (650 – 750 °C), particle size (0.5 – 1.0 mm) and bottom ash percentage (2 % - 10 %) were studied with and without steam. The experimental arrays were designed using expert method of Central Composite Design (CCD). Results show maximum yield of hydrogen gas was 34.3 mole % for gasification without steam and 61.4 Mole % with steam. Similar trend was observed for syngas production. The maximum syngas yield was 59.5 mole % for without steam and it reached up to 81.5 mole% with the use of steam. The optimal condition for both product gases was temperature 700 °C, particle size 0.75 mm and cool bottom ash % 0.06. In conclusion, the use of bottom ash as catalyst is possible for biomass steam gasification and the product gases composition are comparable with previous researches, however the results need to be validated for bench or pilot scale study.

Keywords: bottom ash, biomass steam gasification, catalyst, lab scale

Procedia PDF Downloads 298

Authors: Virag Vass, Ilona Bereczki, Erzsebet Szabo, Nora Debreczeni, Aniko Borbas, Pal Herczegh, Arpad Tosaki

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Hydrogen sulfide (H₂S) is a toxic gas, but it is produced by certain tissues in a small quantity. According to earlier studies, ibuprofen and H₂S has a protective effect against damaging heart tissue caused by ischemia-reperfusion. Recently, we have been investigating the effect of a new water-soluble H₂S releasing ibuprofen molecule administered after artificially generated ischemia-reperfusion on isolated rat hearts. The H₂S releasing property of the new ibuprofen derivative was investigated in vitro in medium derived from heart endothelial cell isolation at two concentrations. The ex vivo examinations were carried out on rat hearts. Rats were anesthetized with an intraperitoneal injection of ketamine, xylazine, and heparin. After thoracotomy, hearts were excised and placed into ice-cold perfusion buffer. Perfusion of hearts was conducted in Langendorff mode via the cannulated aorta. In our experiments, we studied the dose-effect of the H₂S releasing molecule in Langendorff-perfused hearts with the application of gradually increasing concentration of the compound (0- 20 µM). The H₂S releasing ibuprofen derivative was applied before the ischemia for 10 minutes. H₂S concentration was measured with an H₂S detecting electrochemical sensor from the coronary effluent solution. The 10 µM concentration was chosen for further experiments when the treatment with this solution was occurred after the ischemia. The release of H₂S is occurred by the hydrolyzing enzymes that are present in the heart endothelial cells. The protective effect of the new H₂S releasing ibuprofen molecule can be confirmed by the infarct sizes of hearts using the Triphenyl-tetrazolium chloride (TTC) staining method. Furthermore, we aimed to define the effect of the H₂S releasing ibuprofen derivative on autophagic and apoptotic processes in damaged hearts after investigating the molecular markers of these events by western blotting and immunohistochemistry techniques. Our further studies will include the examination of LC3I/II, p62, Beclin1, caspase-3, and other apoptotic molecules. We hope that confirming the protective effect of new H₂S releasing ibuprofen molecule will open a new possibility for the development of more effective cardioprotective agents with exerting fewer side effects. Acknowledgment: This study was supported by the grants of NKFIH- K-124719 and the European Union and the State of Hungary co- financed by the European Social Fund in the framework of GINOP- 2.3.2-15-2016-00043.

Keywords: autophagy, hydrogen sulfide, ibuprofen, ischemia, reperfusion

Procedia PDF Downloads 140

Authors: Frea Van Steenweghen, Lander Hollevoet, Johan A. Martens

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Compared to other hydrogen (H₂) carriers, ammonia (NH₃) is one of the most promising carriers as it contains 17.6 wt% hydrogen. It is easily liquefied at ≈ 9–10 bar pressure at ambient temperature. More importantly, NH₃ is a carbon-free hydrogen carrier with no CO₂ emission at final decomposition. Ammonia has a well-defined regulatory framework and a good track record regarding safety concerns. Furthermore, the industry already has an existing transport infrastructure consisting of pipelines, tank trucks and shipping technology, as ammonia has been manufactured and distributed around the world for over a century. While NH₃ synthesis and transportation technological solutions are at hand, a missing link in the hydrogen delivery scheme from ammonia is an energy-lean and efficient technology for cracking ammonia into H₂ and N₂. The most explored option for ammonia decomposition is thermo-catalytic cracking which is, by itself, the most energy-efficient approach compared to other technologies, such as plasma and electrolysis, as it is the most energy-lean and robust option. The decomposition reaction is favoured only at high temperatures (> 300°C) and low pressures (1 bar) as the thermocatalytic ammonia cracking process is faced with thermodynamic limitations. At 350°C, the thermodynamic equilibrium at 1 bar pressure limits the conversion to 99%. Gaining additional conversion up to e.g. 99.9% necessitates heating to ca. 530°C. However, reaching thermodynamic equilibrium is infeasible as a sufficient driving force is needed, requiring even higher temperatures. Limiting the conversion below the equilibrium composition is a more economical option. Thermocatalytic ammonia cracking is documented in scientific literature. Among the investigated metal catalysts (Ru, Co, Ni, Fe, …), ruthenium is known to be most active for ammonia decomposition with an onset of cracking activity around 350°C. For establishing > 99% conversion reaction, temperatures close to 600°C are required. Such high temperatures are likely to reduce the round-trip efficiency but also the catalyst lifetime because of the sintering of the supported metal phase. In this research, the first focus was on catalyst bed design, avoiding diffusion limitation. Experiments in our packed bed tubular reactor set-up showed that extragranular diffusion limitations occur at low concentrations of NH₃ when reaching high conversion, a phenomenon often overlooked in experimental work. A second focus was thermocatalyst development for ammonia cracking, avoiding the use of noble metals. To this aim, candidate metals and mixtures were deposited on a range of supports. Sintering resistance at high temperatures and the basicity of the support were found to be crucial catalyst properties. The catalytic activity was promoted by adding alkaline and alkaline earth metals. A third focus was studying the optimum process configuration by process simulations. A trade-off between conversion and favorable operational conditions (i.e. low pressure and high temperature) may lead to different process configurations, each with its own pros and cons. For example, high-pressure cracking would eliminate the need for post-compression but is detrimental for the thermodynamic equilibrium, leading to an optimum in cracking pressure in terms of energy cost.

Keywords: ammonia cracking, catalyst research, kinetics, process simulation, thermodynamic equilibrium

Procedia PDF Downloads 66

Authors: Kai Zhang, Xi Jiang

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Effect of fuel variabilities on premixed combustion of bio-syngas mixtures is of great importance in bio-syngas utilisation. The uncertainties of concentrations of fuel constituents such as H2, CO and CH4 may lead to unpredictable combustion performances, combustion instabilities and hot spots which may deteriorate and damage the combustion hardware. Numerical modelling and simulations can assist in understanding the behaviour of bio-syngas combustion with pre-defined species concentrations, while the evaluation of variabilities of concentrations is expensive. To be more specific, questions such as ‘what is the burning velocity of bio-syngas at specific equivalence ratio?’ have been answered either experimentally or numerically, while questions such as ‘what is the likelihood of burning velocity when precise concentrations of bio-syngas compositions are unknown, but the concentration ranges are pre-described?’ have not yet been answered. Uncertainty quantification (UQ) methods can be used to tackle such questions and assess the effects of fuel compositions. An efficient probabilistic UQ method based on Polynomial Chaos Expansion (PCE) techniques is employed in this study. The method relies on representing random variables (combustion performances) with orthogonal polynomials such as Legendre or Gaussian polynomials. The constructed PCE via Galerkin Projection provides easy access to global sensitivities such as main, joint and total Sobol indices. In this study, impacts of fuel compositions on combustion (adiabatic flame temperature and laminar flame speed) of bio-syngas fuel mixtures are presented invoking this PCE technique at several equivalence ratios. High-pressure effects on bio-syngas combustion instability are obtained using detailed chemical mechanism - the San Diego Mechanism. Guidance on reducing combustion instability from upstream biomass gasification process is provided by quantifying the significant contributions of composition variations to variance of physicochemical properties of bio-syngas combustion. It was found that flame speed is very sensitive to hydrogen variability in bio-syngas, and reducing hydrogen uncertainty from upstream biomass gasification processes can greatly reduce bio-syngas combustion instability. Variation of methane concentration, although thought to be important, has limited impacts on laminar flame instabilities especially for lean combustion. Further studies on the UQ of percentage concentration of hydrogen in bio-syngas can be conducted to guide the safer use of bio-syngas.

Keywords: bio-syngas combustion, clean energy utilisation, fuel variability, PCE, targeted uncertainty reduction, uncertainty quantification

Procedia PDF Downloads 276

Authors: Ayman M. Arfaj, Jose Lauro M. Llamas, Saleh Y Qahtani

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Sulfur Loading Operation (SLO) is an operation that poses risk of exposure to toxic gases such as Hydrogen Sulfid and Sulfur Dioxide during molten sulfur loading operation. In this operation molten sulfur is loaded into a truck tanker in a liquid state and the temperature of the tanker must maintain liquid sulfur within a 43-degree range — between 266 degrees and 309 degrees Fahrenheit in order for safe loading and unloading to occur. Accordingly, in this study, the e potential risk of occupational exposure to the airborne toxic gases was assessed at three sulfur loading facilities. The concentrations of toxic airborne substances such as Hydrogen Sulfide (H2S) and Sulfur Dioxide (SO2), were monitored during operations at the different locations within the sulfur loading operation facilities. In addition to extensive real-time monitoring, over one hundred and fifty samples were collected and analysed at internationally accredited laboratories. The concentrations of H2S, and SO2 were all found to be well below their respective occupational exposure limits. Very low levels of H2S account for the odours observed intermittingly during mixing and application operations but do not pose a considerable health risk and hence these levels are considered a nuisance. These results were comparable to those reported internationally. Aside from observing the usual general safe work practices such as wearing safety glasses, there are no specific occupational health related concerns at the examined sulfur loading facilities.

Keywords: exposure assessment, sulfur loading operation, health risk study, molten sulfur, toxic airborne substances, air contaminants monitoring

Procedia PDF Downloads 79

Authors: Sahar Ehsani, David James, Vernon Hodge

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In this experimental study, total selenium in solution was measured with Graphite Furnace Atomic Absorption Spectroscopy, GFAAS, then chemical reactions with sodium borohydride were used to reduce selenite to hydrogen selenide. Hydrogen selenide was then stripped from the solution by purging the solution with nitrogen gas. Since the two main speciations in oxic waters are usually selenite, Se(IV) and selenate, Se(VI), it was assumed that after Se(IV) is removed, the remaining total selenium was Se(VI). Total selenium measured after stripping gave Se(VI) concentration, and the difference of total selenium measured before and after stripping gave Se(IV) concentration. An additional step of reducing Se(VI) to Se(IV) was performed by boiling the stripped solution under acidic conditions, then removing Se(IV) by a chemical reaction with sodium borohydride. This additional procedure of removing Se(VI) from the solution is useful in rare cases where the water sample is reducing and contains selenide speciation. In this study, once Se(IV) and Se(VI) were both removed from the water sample, the remaining total selenium concentration was zero. The method was tested to determine Se(IV) and Se(VI) in both purified water and synthetic irrigation water spiked with Se(IV) and Se(VI). Average recovery of spiked samples of diluted synthetic irrigation water was 99% for Se(IV) and 97% for Se(VI). Detection limits of the method were 0.11 µg L⁻¹ and 0.32 µg L⁻¹ for Se(IV) and Se(VI), respectively.

Keywords: Analytical Method, Graphite Furnace Atomic Absorption Spectroscopy, Selenate, Selenite, Selenium Speciations

Procedia PDF Downloads 142

Authors: Hyun-Jong Choi, Minjun Kwak, Doo-Won Seo, Sang-Kuk Woo, Sun-Dong Kim

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Solid Oxide Cell(SOC) systems can contribute to the transition to the hydrogen society by utilized as a power and hydrogen generator by the electrochemical reaction with high efficiency at high operation temperature (>750 ℃). La1-xSrxCo1-yFeyO3, which is an air electrode, is occurred stability degradations due to reaction and delamination with yittria stabilized zirconia(YSZ) electrolyte in a water electrolysis mode. To complement this phenomenon SOCs need gadolinium doped ceria(GDC) buffer layer between electrolyte and air electrode. However, GDC buffer layer requires a high sintering temperature and it causes a reaction with YSZ electrolyte. This study carried out low temperature sintering of GDC layer by applying Cu-oxide as a sintering aid. The effect of a copper additive as a sintering aid to lower the sintering temperature for the construction of solid oxide fuel cells (SOFCs) was investigated. GDC buffer layer with 0.25-10 mol% CuO sintering aid was prepared by reacting GDC power and copper nitrate solution followed by heating at 600 ℃. The sintering of CuO-added GDC powder was optimized by investigating linear shrinkage, microstructure, grain size, ionic conductivity, and activation energy of CuO-GDC electrolytes at temperatures ranging from 1100 to 1400 ℃. The sintering temperature of the CuO-GDC electrolyte decreases from 1400 ℃ to 1100 ℃ by adding the CuO sintering aid. The ionic conductivity of the CuO-GDC electrolyte shows a maximum value at 0.5 mol% of CuO. However, the addition of CuO has no significant effects on the activation energy of GDC electrolyte. GDC-LSCF layers were co-sintering at 1050 and 1100 ℃ and button cell tests were carried out at 750 ℃.

Keywords: Co-Sintering, GDC-LSCF, Sintering Aid, solid Oxide Cells

Procedia PDF Downloads 245

Authors: Jian Yu

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Carbo dioxide (CO2) from fossil fuel combustion is a prime green-house gas emission. It can be mitigated by microalgae through conventional photosynthesis. The algal oil is a feedstock of biodiesel, a carbon neutral liquid fuel for transportation. The conventional CO2 fixation, however, is quite slow and affected by the intermittent solar irradiation. It is also a technical challenge to reform the bio-oil into a drop-in liquid fuel that can be directly used in the modern combustion engines with expected performance. Here, an artificial photosynthesis system is presented to produce a biopolyester and liquid fuels from CO2, water, and solar power. In this green process, solar energy is captured using photovoltaic modules and converted into hydrogen as a stable energy source via water electrolysis. The solar hydrogen is then used to fix CO2 by Cupriavidus necator, a hydrogen-oxidizing bacterium. Under the autotrophic conditions, CO2 was reduced to glyceraldehyde-3-phosphate (G3P) that is further utilized for cell growth and biosynthesis of polyhydroxybutyrate (PHB). The maximum cell growth rate reached 10.1 g L-1 day-1, about 25 times faster than that of a typical bio-oil-producing microalga (Neochloris Oleoabundans) under stable indoor conditions. With nitrogen nutrient limitation, a large portion of the reduced carbon is stored in PHB (C4H6O2)n, accounting for 50-60% of dry cell mass. PHB is a biodegradable thermoplastic that can find a variety of environmentally friendly applications. It is also a platform material from which small chemicals can be derived. At a high temperature (240 - 290 oC), the biopolyester is degraded into crotonic acid (C4H6O2). On a solid phosphoric acid catalyst, PHB is deoxygenated via decarboxylation into a hydrocarbon oil (C6-C18) at 240 oC or so. Aromatics and alkenes are the major compounds, depending on the reaction conditions. A gasoline-grade liquid fuel (77 wt% oil) and a biodiesel-grade fuel (23 wt% oil) were obtained from the hydrocarbon oil via distillation. The formation routes of hydrocarbon oil from crotonic acid, the major PHB degradation intermediate, are revealed and discussed. This work shows a novel green process from which biodegradable plastics and high-grade liquid fuels can be directly produced from carbon dioxide, water and solar power. The productivity of the green polyester (5.3 g L-1 d-1) is much higher than that of microalgal oil (0.13 g L-1 d-1). Other technical merits of the new green process may include continuous operation under intermittent solar irradiation and convenient scale up in outdoor.

Keywords: bioplastics, carbon dioxide fixation, drop-in liquid fuels, green process

Procedia PDF Downloads 189

Authors: Cheng Shen, LaiHong Shen

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Ammonia is an important carrier of hydrogen energy, with the characteristics of high hydrogen content density and no carbon dioxide emission. Ammonia synthesis by the Haber process is the main method for industrial ammonia synthesis, but the conversion rate of ammonia per pass is only about 12%, while the conversion rate of biomass synthesis ammonia is as high as 56%. Therefore, safe and efficient ammonia capture for ammonia synthesis from biomass is an important way to alleviate the energy crisis and solve the energy problem. Metal chloride has a chemical adsorption effect on ammonia, and can be desorbed at high temperature to obtain high-concentration ammonia after combining with ammonia, which has a good development prospect in ammonia capture and separation technology. In this paper, the ammonia adsorption properties of CuCl₂ were measured, and the composite adsorbents were prepared by using silicon and multi-walled carbon nanotubes respectively to support CuCl₂, and the ammonia adsorption properties of the composite adsorbents were studied. The study found that the ammonia adsorption capacity of the three adsorbents decreased with the increase in temperature, so metal chlorides were more suitable for the low-temperature adsorption of ammonia. Silicon and multi-walled carbon nanotubes have an enhanced effect on the ammonia adsorption of CuCl₂. The reason is that the porous material itself has a physical adsorption effect on ammonia, and silicon can play the role of skeleton support in cupric chloride particles, which enhances the pore structure of the adsorbent, thereby alleviating sintering.

Keywords: ammonia, adsorption properties, metal chloride, silicon, MWCNTs

Procedia PDF Downloads 112