Search results for: hydrogen sulphide

Authors: Anubha Kaushik, Raman Preet

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

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

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Authors: Sushil Kumar Saraswat, K. K. Pant

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

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

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

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

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

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

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

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

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

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

Keywords: adsorption, mathematical modeling, nanocarbons, numerical analysis

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Authors: Volker Wannack

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

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

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Authors: G. Balaji, R. Balasundaraprabhu, S. Prasanna, M. D. Kannan, K. Sivakumaran, David Mcilroy

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Copper Zin tin sulphide (Cu2ZnSnS4 or CZTS) is found to be better alternative to Copper Indium gallium diselenide as absorber layers in thin film based solar cells due to the utilisation of earth-abundant materials in the midst of lower toxicity. In the present study, Cu2ZnSnS4 thin films were prepared on soda lime glass using (CuS, ZnS, SnS) targets and were deposited by three different stacking orders, using RF Magnetron sputtering. The substrate temperature was fixed at 300 °C during the depositions. CZTS thin films were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and UV-Vis-NIR spectroscopy. All the samples exhibited X-ray peaks pertaining to (112) kesterite phase of CZTS, along with the presence of a predominant wurtzite CZTS phase. X-ray photoelectron spectroscopy revealed the presence of all the elements in all the samples. The change in stacking order clearly shows that it affects the structural and phase properties of the films. Relative atomic concentrations of Zn, Cu, Sn and S, which are determined by high-resolution XPS core level spectra integrated peak areas revealed that the CZTS films exhibit inhomogeneity in both stoichiometry and elemental composition. Raman spectroscopy studies on the film showed the presence of CZTS phase. The energy band gap of the CZTS thin films was found to be in the range of 1.5 eV to 1.6 eV. The films were then annealed at 450 °C for 5 hrs and it was found that the predominant nature of the X-ray peaks has transformed from Wurtzite to Kesterite phase which is highly desirable for absorber layers in thin film solar cells. The optimized CZTS layer was used as an absorber layer in thin film solar cells. ZnS and CdS were used as buffer layers which in turn prepared by Hot wall epitaxy technique. Gallium doped Zinc oxide was used as a transparent conducting oxide. The solar cell structure Glass/Mo/CZTS/CdS or ZnS/GZO has been fabricated, and solar cell parameters were measured.

Keywords: earth-abundant, Kesterite, RF sputtering, thin film solar cells

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

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

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

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

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

Keywords: blast furnace, CO₂ mitigation, DRI, hydrogen

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

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

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

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Authors: K. Sushma Varma, Rajesh Singh

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Non-engineered landfills cause serious environmental damage due to toxic emissions and mobilization of persistent pollutants, organic and inorganic contaminants, as well as soluble metal ions. The available treatment technologies for landfill leachate and solid waste are not effective from an economic, environmental, and social standpoint. The present study assesses the potential of the bioelectrochemical system (BES) integrated with sulfate-reducing bacteria (SRB) in the sustainable treatment and decontamination of landfill wastes. For this purpose, solid waste and landfill leachate collected from different landfill sites were evaluated for long-term treatment using the integrated SRB-BES anaerobic designed bioreactors after pre-treatment. Based on periodic gas composition analysis, physicochemical characterization of the leachate and solid waste, and metal concentration determination, the present system demonstrated significant improvement in volumetric hydrogen production by suppressing methanogenesis. High reduction percentages of Be, Cr, Pb, Cd, Sb, Ni, Cr, COD, and sTOC removal were observed. This mineralization can be attributed to the synergistic effect of ammonia-assisted pre-treatment complexation and microbial sulphide formation. Despite being amended with 0.1N ammonia, the treated leachate level of NO³⁻ was found to be reduced along with SO₄²⁻. This integrated SRB-BES system can be recommended as an eco-friendly solution for landfill reclamation. The BES-treated solid waste was evidently more stabilized, as shown by a five-fold increase in surface area, and potentially useful for leachate immobilization and bio-fortification of agricultural fields. The vector arrangement and magnitude showed similar treatment with differences in magnitudes for both leachate and solid waste. These findings support the efficacy of SRB-BES in the treatment of landfill leachate and solid waste sustainably, inching a step closer to our sustainable development goals. It utilizes low-cost treatment, and anaerobic SRB adapted to landfill sites. This technology may prove to be a sustainable treatment strategy upon scaling up as its outcomes are two-pronged: landfill waste treatment and energy recovery.

Keywords: bio-electrochemical system, leachate /solid waste treatment, landfill leachate, sulfate-reducing bacteria

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

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

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

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

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

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

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Authors: Gómez Romero Jacob, García Peña Elvia Inés

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

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

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Authors: Mandeep Kaur, Jitendra K. Bera

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

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

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

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

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

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Authors: Premrudee Promdet, Fan Cui, Gi Byoung Hwang, Ka Chuen To, Sanjayan Sathasivam, Claire J. Carmalt, Ivan P. Parkin

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A novel single-step fabrication of Cu nanoparticle embedded ZnO (Cu.ZnO) thin films was developed by aerosol-assisted chemical vapor deposition for stable and efficient hydrogen production in Photoelectrochemical (PEC) cell. In this approach, the Cu.ZnO nanoplate thin films were grown by using acetic acid to promote preferential growth and enhance surface active sites, where Cu nanoparticles can be formed under chemical deposition by reduction of Cu salt. Studies using photoluminescence spectroscopy indicate the enhanced photocatalytic performance is attributed to hot electron generated from SPR. The Cu metal in the composite material is functioning as a sensitizer to supply electrons to the semiconductor resulting in enhanced electron density for redox reaction. This work not only describes a way to obtain photoanodes with high photocatalytic activity but also suggests a low-cost route towards production of photocatalysts for hydrogen production. This work also supports a vital need to understand electron transfer between photoexcited semiconductor materials and metals, a requirement for tailoring the properties of semiconductor/metal composites.

Keywords: photocatalysis, photoelectrochemical cell (PEC), aerosol-assisted chemical vapor deposition (AACVD), surface plasmon resonance (SPR)

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Authors: Zeinab Sanaee, Hossein Jafaripour

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

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

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Authors: Annapurna Basavaraju, Andreas Marn, Franz Heitmeir

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The Advisory Council for Aeronautics Research in Europe (ACARE) is cognizant for the overall reduction of NOx emissions by 80% in its vision 2020. Moreover small turbo engines have higher fuel specific emissions compared to large engines due to their limited combustion chamber size. In order to fulfill these requirements, novel combustion concepts are essential. This motivates to carry out the research on the current state of art, catalytic stabilized combustion chamber using hydrogen in small jet engines which are designed and investigated both numerically and experimentally during this project. Catalytic combustion concepts can also be adopted for low caloric fuels and are therefore not constrained to only hydrogen. However, hydrogen has high heating value and has the major advantage of producing only the nitrogen oxides as pollutants during the combustion, thus eliminating the interest on other emissions such as Carbon monoxides etc. In the present work, the combustion chamber is designed based on the ‘Rich catalytic Lean burn’ concept. The experiments are conducted for the characteristic operating range of an existing engine. This engine has been tested successfully at Institute of Thermal Turbomachinery and Machine Dynamics (ITTM), Technical University Graz. One of the facts that the efficient combustion is a result of proper mixing of fuel-air mixture, considerable significance is given to the selection of appropriate mixer. This led to the design of three diverse configurations of mixers and is investigated experimentally and numerically. Subsequently the best mixer would be equipped in the main combustion chamber and used throughout the experimentation. Furthermore, temperatures and pressures would be recorded at various locations inside the combustion chamber and the exhaust emissions will also be analyzed. The instrumented combustion chamber would be inspected at the engine relevant inlet conditions for nine different sets of catalysts at the Hot Flow Test Facility (HFTF) of the institute.

Keywords: catalytic combustion, gas turbine, hydrogen, mixer, NOx emissions

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Authors: Haidy N. Salem, Nada O. Kamel, Shahinaz N. Hassan, Sherif M. Elhefnawy

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Aim: to assess the effect of using turmeric powder extract on changes of tooth color with extra-coronal and intra-coronal bleaching methods. Methods: Turmeric powder extract was weighted and mixed with two different hydrogen peroxide concentrations (3% and 6%) to be used as a bleaching agent. Thirty teeth were allocated into three groups (n=10): Group A: Bleaching agent (6%) was applied on the labial surface, Group B: Bleaching agent (3%) was applied inside the pulp chamber and Group C: Extra and intra-coronal bleaching techniques were used (6% and 3% respectively). A standardized access cavity was opened in the palatal surface of each tooth in both Groups B and C. Color parameters were measured using a spectrophotometer. Results: A statistically significant difference in color difference values (∆E*) and enamel brightness (∆L*) was found between Group C and each of Groups A and B. There was no statistically significant difference in (∆E*) and (∆L*) between Group A and Group B. The highest mean value of (∆E*) and (∆L*) was found in Group C, while the least mean value was found in Group B. Conclusion: Bleaching the external and internal tooth structure with low concentrations of hydrogen peroxide solution mixed with turmeric extract has a promising effect in color enhancement.

Keywords: bleaching, hydrogen peroxide, spectrophotometer, turmeric

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Authors: Wei-Jing Li, Ren-Xuan Yang, Kui-Hao Chuang, Ming-Yen Wey

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Nowadays, plastic product and utilization are extensive and have greatly improved our life. Yet, plastic wastes are stable and non-biodegradable challenging issues to the environment. Waste-to-energy strategies emerge a promising way for waste management. This work investigated the co-production of hydrogen and carbon nanotubes from the syngas which was from the gasification of polypropylene. A nickel-silica core-shell catalyst was applied for syngas reaction from plastic waste gasification in a fixed-bed reactor. SiO2 were prepared through various synthesis solvents by Stöber process. Ni plays a role as modified SiO2 support, which were synthesized by deposition-precipitation method. Core-shell catalysts have strong interaction between active phase and support, in order to avoid catalyst sintering. Moreover, Fe or Co metal acts as promoter to enhance catalytic activity. The effects of calcined atmosphere, second metal addition, and reaction temperature on hydrogen production and carbon yield were examined. In this study, the catalytic activity and carbon yield results revealed that the Ni/SiO2 catalyst calcined under H2 atmosphere exhibited the best performance. Furthermore, Co promoted Ni/SiO2 catalyst produced 3 times more than Ni/SiO2 on carbon yield at long-term operation. The structure and morphological nature of the calcined and spent catalysts were examined using different characterization techniques including scanning electron microscopy, transmission electron microscopy, X-ray diffraction. In addition, the quality and thermal stability of the nano-carbon materials were also evaluated by Raman spectroscopy and thermogravimetric analysis.

Keywords: plastic wastes, hydrogen, carbon nanotube, core-shell catalysts

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Authors: Mihir Hota, Namita Jena, S. N. Sahu

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LEEH (L-cysteine ethyl ester hydrochloride) capped CdS semiconductor nanocrystals are grown at 800C using a simple chemical route. Photoluminescence (PL), Optical absorption (UV) and Transmission Electron Microscopy (TEM) have been carried out to evaluate the structural and optical properties of the nanocrystal. Optical absorption studies have been carried out to optimize the sample. XRD and TEM analysis shows that the nanocrystal belongs to FCC structure having average size of 3nm while a bandgap of 2.84eV is estimated from Photoluminescence analysis. The nanocrystal emits bluish light when excited with 355nm LASER.

Keywords: cadmium sulphide, nanostructures, luminescence, optical properties

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Authors: Chetna Mohabeer, Luis Reyes, Lokmane Abdelouahed, Bechara Taouk

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In the transition to sustainability and the increasing use of renewable energy, hydrogen will play a key role as an energy carrier. Biomass has the potential to accelerate the realization of hydrogen as a major fuel of the future. Pyro-gasification allows the conversion of organic matter mainly into synthesis gas, or “syngas”, majorly constituted by CO, H2, CH4, and CO2. A second, condensable fraction of biomass pyro-gasification products are “tars”. Under certain conditions, tars may decompose into hydrogen and other light hydrocarbons. These conditions include two types of cracking: homogeneous cracking, where tars decompose under the effect of temperature ( > 1000 °C), and heterogeneous cracking, where catalysts such as olivine, dolomite or biochar are used. The latter process favors cracking of tars at temperatures close to pyro-gasification temperatures (~ 850 °C). Pyro-gasification of biomass coupled with water-gas shift is the most widely practiced process route for biomass to hydrogen today. In this work, an innovating solution will be proposed for this conversion route, in that all the pyro-gasification products, not only methane, will undergo processes that aim to optimize hydrogen production. First, a heterogeneous cracking step was included in the reaction scheme, using biochar (remaining solid from the pyro-gasification reaction) as catalyst and CO2 and H2O as gasifying agents. This process was followed by a catalytic steam methane reforming (SMR) step. For this, a Ni-based catalyst was tested under different reaction conditions to optimize H2 yield. Finally, a water-gas shift (WGS) reaction step with a Fe-based catalyst was added to optimize the H2 yield from CO. The reactor used for cracking was a fluidized bed reactor, and the one used for SMR and WGS was a fixed bed reactor. The gaseous products were analyzed continuously using a µ-GC (Fusion PN 074-594-P1F). With biochar as bed material, it was seen that more H2 was obtained with steam as a gasifying agent (32 mol. % vs. 15 mol. % with CO2 at 900 °C). CO and CH4 productions were also higher with steam than with CO2. Steam as gasifying agent and biochar as bed material were hence deemed efficient parameters for the first step. Among all parameters tested, CH4 conversions approaching 100 % were obtained from SMR reactions using Ni/γ-Al2O3 as a catalyst, 800 °C, and a steam/methane ratio of 5. This gave rise to about 45 mol % H2. Experiments about WGS reaction are currently being conducted. At the end of this phase, the four reactions are performed consecutively, and the results analyzed. The final aim is the development of a global kinetic model of the whole system in a multi-stage fluidized bed reactor that can be transferred on ASPEN PlusTM.

Keywords: multi-staged fluidized bed reactor, pyro-gasification, steam methane reforming, water-gas shift

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Authors: Rihana Hadjeb, Djamel Barkat

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Schiff bases derived from o-hydroxybenzaldehyde has attracted a great interest not only for its promising applications towards linear and non-linear optical properties, biological activity and technological applications but also used as model compounds for the theory of hydrogen bonding. Due to its intramolecular hydrogen bonding, depending on the position of proton in the hydrogen bond o-hydroxy salicylidene Schiff bases exhibit two tautomeric forms, enol-imine (E-form) and keto-enamine (K-form) both in solution and in crystalline state. A zwitterionic structure also appears due to a proton transfer in enol – imine and keto – amine tautomer. These classes of compounds also exhibit thermochromic and photochromic behavior. We undertook in this study the synthesis of ten compounds of hydroxy Schiff bases from the condensation of salicylic aldehyde and aniline substituted in the ortho, meta and para by the methyl, chloro and nitro groups. To study the keto-enol equilibrium of the compounds; UV-VIS spectra were studied in different polarity solvents. The compounds were in tautomeric equilibrium (enol imine O–H•••N, keto-amine O•••H–N forms). For some derivatives of salicylideneanilines the keto-amine form was observed in both ethanol and dioxane. IR results showed that all Schiff bases studied favor the enol-imine form over the keto form.

Keywords: salicylideneaniline, tautomerism, keto-enol equilibrium, UV-VIS spectroscopy, solvent effect

Procedia PDF Downloads 355

Authors: Marita Pigłowska, Beata Kurc, Paweł Daszkiewicz

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Railway vehicles are divided into two groups: traction (powered) vehicles and wagons. The traction vehicles include locomotives (line and shunting), railcars (sometimes referred to as railbuses), and multiple units (electric and diesel), consisting of several or a dozen carriages. In vehicles with diesel traction, fuel energy (petrol, diesel, or compressed gas) is converted into mechanical energy directly in the internal combustion engine or via electricity. In the latter case, the combustion engine generator produces electricity that is then used to drive the vehicle (diesel-electric drive or electric transmission). In Poland, such a solution dominates both in heavy linear and shunting locomotives. The classic diesel drive is available for the lightest shunting locomotives, railcars, and passenger diesel multiple units. Vehicles with electric traction do not have their own source of energy -they use pantographs to obtain electricity from the traction network. To determine the competitiveness of the hydrogen propulsion system, it is essential to understand how it works. The basic elements of the construction of a railway vehicle drive system that uses hydrogen as a source of traction force are fuel cells, batteries, fuel tanks, traction motors as well as main and auxiliary converters. The compressed hydrogen is stored in tanks usually located on the roof of the vehicle. This resource is supplemented with the use of specialized infrastructure while the vehicle is stationary. Hydrogen is supplied to the fuel cell, where it oxidizes. The effect of this chemical reaction is electricity and water (in two forms -liquid and water vapor). Electricity is stored in batteries (so far, lithium-ion batteries are used). Electricity stored in this way is used to drive traction motors and supply onboard equipment. The current generated by the fuel cell passes through the main converter, whose task is to adjust it to the values required by the consumers, i.e., batteries and the traction motor. The work will attempt to construct a fuel cell with unique electrodes. This research is a trend that connects industry with science. The first goal will be to obtain hydrogen on a large scale in tube furnaces, to thoroughly analyze the obtained structures (IR), and to apply the method in fuel cells. The second goal is to create low-energy energy storage and distribution station for hydrogen and electric vehicles. The scope of the research includes obtaining a carbon variety and obtaining oxide systems on a large scale using a tubular furnace and then supplying vehicles. Acknowledgments: This work is supported by the Polish Ministry of Science and Education, project "The best of the best! 4.0", number 0911/MNSW/4968 – M.P. and grant 0911/SBAD/2102—B.K.

Keywords: railway, hydrogen, fuel cells, hybrid vehicles

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Authors: Longkui Zhu, Zhengcao Li

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High temperature gas-cooled reactors (HTGRs) are considered as one of the next-generation advanced nuclear reactors, in which porous nuclear graphite is used as neutron moderators, reflectors, structure materials, and cooled by inert helium. Radioactive tritium and ¹⁴C are generated in terms of reactions of thermal neutrons and ⁶Li, ¹⁴N, ¹⁰B impurely within nuclear graphite and the coolant during HTGRs operation. Currently, hydrogen and nitrogen diffusion behavior together with nuclear graphite microstructure evolution were investigated to minimize the radioactive waste release, using thermogravimetric analysis, X-ray computed tomography, the BET and mercury standard porosimetry methods. It is found that the peak value of graphite weight loss emerged at 573-673 K owing to nitrogen diffusion from graphite pores to outside when the system was subjected to vacuum. Macropore volume became larger while porosity for mesopores was smaller with temperature ranging from ambient temperature to 1073 K, which was primarily induced by coalescence of the subscale pores. It is suggested that the porous nuclear graphite should be first subjected to vacuum at 573-673 K to minimize the nitrogen and the radioactive 14°C before operation in HTGRs. Then, results on hydrogen diffusion show that the diffusible hydrogen and tritium could permeate into the coolant with diffusion coefficients of > 0.5 × 10⁻⁴ cm²·s⁻¹ at 50 bar. As a consequence, the freshly-generated diffusible tritium could release quickly to outside once formed, and an effective approach for minimizing the amount of radioactive tritium is to make the impurity contents extremely low in nuclear graphite and the coolant. Besides, both two- and three-dimensional observations indicate that macro and mesopore volume along with total porosity decreased with temperature at 50 bar on account of synergistic effects of applied compression strain, sharpened pore morphology, and non-uniform temperature distribution.

Keywords: advanced high temperature gas-cooled reactor, hydrogen and nitrogen diffusion, microstructure evolution, nuclear graphite, radioactive waste management

Procedia PDF Downloads 286

Authors: Gabriel Wosiak, Felipe Staciaki, Eryka Nobrega, Ernesto Pereira

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Hydrogen is an energy carrier with potential applications in various industries. Alkaline electrolysis is a commonly used method for hydrogen production; however, its energy cost remains relatively high compared to other methods. This is due in part to interfacial pH changes that occur during the electrolysis process. Interfacial pH changes refer to the changes in pH that occur at the interface between the cathode electrode and the electrolyte solution. These changes are caused by the electrochemical reactions at both electrodes, which consume or produces hydroxide ions (OH-) from the electrolyte solution. This results in an important change in the local pH at the electrode surface, which can have several impacts on the energy consumption and durability of electrolysers. One impact of interfacial pH changes is an increase in the overpotential required for hydrogen production. Overpotential is the difference between the theoretical potential required for a reaction to occur and the actual potential that is applied to the electrodes. In the case of water electrolysis, the overpotential is caused by a number of factors, including the mass transport of reactants and products to and from the electrodes, the kinetics of the electrochemical reactions, and the interfacial pH. An increase in the interfacial pH at the anode surface in alkaline conditions can lead to an increase in the overpotential for hydrogen production. This is because the lower local pH makes it more difficult for the hydroxide ions to be oxidized. As a result, there is an increase in the required energy to the process occur. In addition to increasing the overpotential, interfacial pH changes can also lead to the degradation of the electrodes. This is because the lower pH can make the electrode more susceptible to corrosion. As a result, the electrodes may need to be replaced more frequently, which can increase the overall cost of water electrolysis. The method presented in the paper addresses the issue of interfacial pH changes by using a cell design with a different cell design, introducing the electrode asymmetry. This design helps to mitigate the pH gradient at the anode/electrolyte interface, which reduces the overpotential and improves the energy efficiency of the electrolyser. The method was tested using a multivariate approach in both laboratory and industrial current density conditions and validated the results with numerical simulations. The results demonstrated a clear improvement (11.6%) in energy efficiency, providing an important contribution to the field of sustainable energy production. The findings of the paper have important implications for the development of cost-effective and sustainable hydrogen production methods. By mitigating interfacial pH changes, it is possible to improve the energy efficiency of alkaline electrolysis and make it a more competitive option for hydrogen production.

Keywords: electrolyser, interfacial pH, numerical simulation, optimization, asymmetric cell

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Authors: Lounes Aouane, Omar Bouledroua

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Sonatrach uses 24,000 kilometers of pipelines to transport gas and oil. Over time, these pipes run the risk of bursting due to corrosion inside and/or outside the pipeline. For this reason, a check must be made with the help of an equipped scraper. This intelligent tool provides a detailed picture of all errors in the pipeline. Based on the ERF values, these wear defects are divided into two parts: acceptable defect and unacceptable defect. The objective of this work is to conduct a comparative study of the different methods of calculating the marginal pressure found in the literature (DNV RP F-101, SHELL, P-CORRC, NETTO and CSA Z662). This comparison will be made from a database of 329 burst tests published in the literature. Finally, we will propose a new approach based on the finite element method using the commercial software ANSYS.

Keywords: hydrogen embrittlement, pipelines, hydrogen, transient flow, cyclic pressure, fatigue crack growth

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Authors: K. Kefif, Y. Bouizem, A. Belfedal, D. J. Sib, K. Zellama, l. Chahed

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Hydrogenated microcrystalline silicon (μc-Si:H) thin films were prepared by radio frequency magnetron sputtering at relatively low growth temperatures (Ts=100 °C). The films grown on glass substrate in order to use the new generation of substrates sensitive to elevated temperatures. Raman spectroscopy was applied to investigate the effect of the argon gas diluted in hydrogen, on the structural properties and the evolution of the micro structure in the films. Raman peak position, intensity and line width were used to characterize the quality and the percentage of the crystallites in the films. The results of this investigation suggest the existence of a threshold dilution around a gas mixture of argon (40%) and hydrogen (60%) for which the crystallization occurs, even at low deposition temperatures. The difference between the amorphous and the crystallized structures is well confirmed by spectroscopic ellipsometry (SE) technique.

Keywords: Silicon, Thin films, Structural properties, Raman spectroscopy, Ellipsometry

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Authors: Neera Singh, Devendra Kumar, Om Parkash

Abstract:

We have synthesized nanocrystalline Fe-Ni alloy powders where Ni varies as 10, 30 and 50 mole% by a wet chemical route (sol-gel auto-combustion) followed by reduction in hydrogen atmosphere. The ratio of citrate to nitrate was maintained at 0.3 where citric acid has worked as a fuel during combustion. The reduction of combusted powders was done at 700°C/1h in hydrogen atmosphere using an atmosphere controlled quartz tube furnace. Phase and microstructure analysis has shown the formation of α-(Fe,Ni) and γ-(Fe,Ni) phases after reduction. An increase in Ni concentration resulted in more γ-(Fe,Ni) formation where complete γ-(Fe,Ni) formation was achieved at 50 mole% Ni concentration. Formation of particles below 50 nm size range was confirmed using Scherrer’s formula and Transmission Electron Microscope. The work is aimed at the effect of Ni concentration on phase, microstructure and magnetic properties of synthesized alloy powders.

Keywords: combustion, microstructure, nanocrystalline, reduction

Procedia PDF Downloads 149