Search results for: heterogeneous catalytic ozonation

Authors: Ligang Wang, Theodoros Damartzis, Stefan Diethelm, Jan Van Herle, François Marechal

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Biogas production from anaerobic digestion of organic sludge from wastewater treatment as well as various urban and agricultural organic wastes is of great significance to achieve a sustainable society. Two upgrading approaches for cleaned biogas can be considered: (1) direct H₂ injection for catalytic CO₂ methanation and (2) CO₂ separation from biogas. The first approach usually employs electrolysis technologies to generate hydrogen and increases the biogas production rate; while the second one usually applies commercially-available highly-selective membrane technologies to efficiently extract CO₂ from the biogas with the latter being then sent afterward for compression and storage for further use. A straightforward way of utilizing the captured CO₂ is on-site catalytic CO₂ methanation. From the perspective of system complexity, the second approach may be questioned, since it introduces an additional expensive membrane component for producing the same amount of methane. However, given the circumstance that the sustainability of the produced biogas should be retained after biogas upgrading, renewable electricity should be supplied to drive the electrolyzer. Therefore, considering the intermittent nature and seasonal variation of renewable electricity supply, the second approach offers high operational flexibility. This indicates that these two approaches should be compared based on the availability and scale of the local renewable power supply and not only the technical systems themselves. Solid-oxide electrolysis generally offers high overall system efficiency, and more importantly, it can achieve simultaneous electrolysis of CO₂ and H₂O (namely, co-electrolysis), which may bring significant benefits for the case of CO₂ separation from the produced biogas. When taking co-electrolysis into account, two additional upgrading approaches can be proposed: (1) direct steam injection into the biogas with the mixture going through the SOE, and (2) CO₂ separation from biogas which can be used later for co-electrolysis. The case study of integrating SOE to a wastewater treatment plant is investigated with wind power as the renewable power. The dynamic production of biogas is provided on an hourly basis with the corresponding oxygen and heating requirements. All four approaches mentioned above are investigated and compared thermo-economically: (a) steam-electrolysis with grid power, as the base case for steam electrolysis, (b) CO₂ separation and co-electrolysis with grid power, as the base case for co-electrolysis, (c) steam-electrolysis and CO₂ separation (and storage) with wind power, and (d) co-electrolysis and CO₂ separation (and storage) with wind power. The influence of the scale of wind power supply is investigated by a sensitivity analysis. The results derived provide general understanding on the economic competitiveness of SOE for sustainable biogas upgrading, thus assisting the decision making for biogas production sites. The research leading to the presented work is funded by European Union’s Horizon 2020 under grant agreements n° 699892 (ECo, topic H2020-JTI-FCH-2015-1) and SCCER BIOSWEET.

Keywords: biogas upgrading, solid-oxide electrolyzer, co-electrolysis, CO₂ utilization, energy storage

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Authors: Shrikaant Kulkarni, Akshata Naik Nimbalkar

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In this worki a method protocol has been developed for the synthesis of innovative Co3O4 material by using a method of chemical synthesis followed by calcination. The effect of calcination temperature on the morphology, structure and catalytic performance on material in question is investigated by using characterization tools like scanning electron microscopy (SEM), X-ray diffraction (XRD) spectroscopy and electrochemical techniques. The SEM images reveal that the morphology of the Co3O4 material undergoes a change from the rod to a beadlike shape on calcination at temperature of 700 °C. The XRD image shows that although the morphology of synthesized Co3O4 material exhibits a cubic phase but it differs in crystallinity depending upon morphology. Similarly spherical beadlike Co3O4 material has exhibited better activity than its rodlike counterpart which is reflected from electrochemical findings. Further, its performance in terms of bifunctional nature and hlods a lot much of promise as a excellent electrode material in the next generation batteries and fuel cells.

Keywords: bifunctional, next generation material, Co3O4, XRD

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Authors: Y. C. Bhattacharyulu, Amit J. Agrawal, Vikram S. Chatake, Ketan S. Desai

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In recent years, the improper disposal of waste polymeric materials like plastics, rubber, liquid containers, daily household materials, etc. is posing a grave problem by polluting the environment. On the other hand fluctuations in the oil market and limited stocks of fossil fuels have diverted the interest of researchers to study the production of fuels and hydrocarbons from alternative sources. Hence, to study the production of fuels from waste plastic is the need of hour at present. Effect of alkali solutions of different concentrations with copper comprising catalyst on depolymerisation reactions was studied here. The present study may become a preliminary method for obtaining valuable hydrocarbons from waste plastics and an effective way for depolymerising or degrading waste plastics for their safe disposal without causing any environmental problems.

Keywords: catalyst, depolymerisation, disposal, hydrocarbon liquids, waste plastic

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Authors: Sarmistha Baruah, Akshai Kumar, Nageswara Rao Peela

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The global energy crisis due to the dependence on fossil fuels and its limited reserves as well as environmental pollution are key concerns to the research communities. However, the implementation of alcohol-based fuel cells such as methanol is anticipated as a reliable source of future energy technology due to their high energy density, environment friendliness, ease of storage, transportation, etc. To drive the anodic methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs), an active and long-lasting catalyst is necessary for efficient energy conversion from methanol. Recently, transition metal-zeolite-based materials have been considered versatile catalysts for a variety of industrial and lab-scale processes. Large specific surface area, well-organized micropores, and adjustable acidity/basicity are characteristics of zeolites that make them excellent supports for immobilizing small-sized and highly dispersed metal species. Significant advancement in the production and characterization of well-defined metal clusters encapsulated within zeolite matrix has substantially expanded the library of materials available, and consequently, their catalytic efficacy. In this context, we developed bimetallic Ni-Co catalysts encapsulated within LTA (also known as 4A) zeolite via a method combined with the in-situ encapsulation of metal species using hydrothermal treatment followed by a chemical reduction process. The prepared catalyst was characterized using advanced characterization techniques, such as X-ray diffraction (XRD), field emission transmission electron microscope (FETEM), field emission scanning electron microscope (FESEM), energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of the catalyst for MOR was carried out in an alkaline medium at room temperature using techniques such as cyclic voltammetry (CV), and chronoamperometry (CA). The resulting catalyst exhibited better catalytic activity of 12.1 mA cm-2 at 1.12 V vs Ag/AgCl and retained remarkable stability (~77%) even after 1000 cycles CV test for the electro-oxidation of methanol in alkaline media without any significant microstructural changes. The high surface area, better Ni-Co species integration in the zeolite, and the ample amount of surface hydroxyl groups contribute to highly dispersed active sites and quick analyte diffusion, which provide notable MOR kinetics. Thus, this study will open up new possibilities to develop a noble metal-free zeolite-based electrocatalyst due to its simple synthesis steps, large-scale fabrication, improved stability, and efficient activity for DMFC application.

Keywords: alkaline media, bimetallic, encapsulation, methanol oxidation reaction, LTA zeolite.

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Authors: Izabela L. Ciesielska-Wrόbel

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This paper presents finite element models of the fingertip skin which have been created to simulate the contact of textile objects with the skin to gain a better understanding of the perception of textiles through the skin, so-called Hand of Textiles (HoT). Many objective and subjective techniques have been developed to analyze HoT, however none of them provide exact overall information concerning the sensation of textiles through the skin. As the human skin is a complex heterogeneous hyperelastic body composed of many particles, some simplifications had to be made at the stage of building the models. The same concerns models of woven structures, however their utilitarian value was maintained. The models reflect only friction between skin and woven textiles, deformation of the skin and fabrics when “touching” textiles and heat transfer from the surface of the skin into direction of textiles.

Keywords: fingertip skin models, finite element models, modelling of textiles, sensation of textiles through the skin

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Authors: W. Y. Zhu, X. L. Yan, Y. Zhou

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Sulfonamides (SAs) are extensively used antibiotics; photocatalysis is an effective, way to remove the SAs from water driven by solar energy. Here we used WO3 nanoplates and their Ag heterogeneous as photocatalysts to investigate their photodegradation efficiency against sulfanilamide (SAM) which is the precursor of SAs. Results showed that WO3/Ag composites performed much better than pure WO3 where the highest removal rate was 96.2% can be achieved under visible light irradiation. Ag as excellent antibacterial agent also endows certain antibacterial efficiency to WO3, and 100% removal efficiency could be achieved in 2 h under visible light irradiation for all WO3/Ag composites. Generally, WO3/Ag composites are very effective photocatalysts with potentials in practical applications which mainly use cheap, clean and green solar energy as energy source.

Keywords: antibacterial, photocatalysis, semiconductor, sulfanilamide

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Authors: Lucie Speyer, Vincent Lecocq, Séverine Humbert, Antoine Hugon

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Mesoporous alumina is commonly used as a catalyst support for the hydrotreating of heavy petroleum cuts. The process of fabrication usually involves: the synthesis of the boehmite AlOOH precursor, a kneading-extrusion step, and a calcination in order to obtain the final alumina extrudates. Alumina is described as a complex porous medium, generally agglomerates constituted of aggregated nanocrystallites. Its porous texture directly influences the active phase deposition and mass transfer, and the catalytic properties. Then, it is easy to figure out that each step of the fabrication of the supports has a role on the building of their porous network, and has to be well understood to optimize the process. The synthesis of boehmite by precipitation of aluminum salts was extensively studied in the literature and the effect of various parameters, such as temperature or pH, are known to influence the size and shape of the crystallites and the specific surface area of the support. The calcination step, through the topotactic transition from boehmite to alumina, determines the final properties of the support and can tune the surface area, pore volume and pore diameters from those of boehmite. However, the kneading extrusion step has been subject to a very few studies. It generally consists in two steps: an acid, then a basic kneading, where the boehmite powder is introduced in a mixer and successively added with an acid and a base solution to form an extrudable paste. During the acid kneading, the induced positive charges on the hydroxyl surface groups of boehmite create an electrostatic repulsion which tends to separate the aggregates and even, following the conditions, the crystallites. The basic kneading, by reducing the surface charges, leads to a flocculation phenomenon and can control the reforming of the overall structure. The separation and reassembling of the particles constituting the boehmite paste have a quite obvious influence on the textural properties of the material. In this work, we are focused on the influence of the kneading step on the alumina catalysts supports. Starting from an industrial boehmite, extrudates are prepared using various kneading conditions. The samples are studied by nitrogen physisorption in order to analyze the evolution of the textural properties, and by synchrotron small-angle X-ray scattering (SAXS), a more original method which brings information about agglomeration and aggregation of the samples. The coupling of physisorption and SAXS enables a precise description of the samples, as same as an accurate monitoring of their evolution as a function of the kneading conditions. These ones are found to have a strong influence of the pore volume and pore size distribution of the supports. A mechanism of evolution of the texture during the kneading step is proposed and could be attractive in order to optimize the texture of the supports and then, their catalytic performances.

Keywords: alumina catalyst support, kneading, nitrogen physisorption, small-angle X-ray scattering

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Authors: Yameen Ahmed, Jamshid Hussain, Farman Ullah, Sohaib Asif

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The investigation aims at the synthesis of copper oxide and cobalt oxide nanoparticles using Spinacia oleracea leaf extract. These nanoparticles have many properties and applications. They possess antimicrobial catalytic properties and also they can be used in energy storage materials, gas sensors, etc. The Spinacia oleracea leaf extract behaves as a reducing agent in nanoparticle synthesis. The plant extract was first prepared and then treated with copper and cobalt salt solutions to get the precipitate. The salt solutions used for this purpose are copper sulfate pentahydrate (CuSO₄.5H₂O) and cobalt chloride hexahydrate (CoCl₂.6H₂O). The UV-Vis, XRD, EDX, and SEM techniques are used to find the optical, structural, and morphological properties of copper oxide and cobalt oxide nanoparticles. The UV absorption peaks are at 326 nm and 506 nm for copper oxide and cobalt oxide nanoparticles.

Keywords: cobalt oxide, copper oxide, green synthesis, nanoparticles

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Authors: K. Piórkowska

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The overarching aim of the paper is to incorporate the micro-foundations perspective in strategic management and offering possibilities to bridge the macro–micro divide, to review the concept of habits, as well as to propose research findings and directions in terms of further exploring the habit construct and its impact on higher epistemological level phenomena (for instance organizational routines, which is a domain inherently multilevel in nature). To realize this aim, the following sections have been developed: (1) habits’ origins, (2) habits – cognitive constellations, (3) interrelationships between habits and mental representations, intentions, (4) habits and organizational routines, and (5) habits and routines linkages with adaptation. The conclusions that have been made support recent and current studies linking the level of individual heterogeneous agents with the level of macro (organizational) outcomes.

Keywords: behaviorism, habits, micro-foundations, routines

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Authors: Carolin Schulze

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Characterized by a positive interdependence of learners, cooperative learning (CL) is one possibility of successfully dealing with the increasing heterogeneity of students. Various positive effects of CL on the mental, physical and social health of students have already been documented. However, this structure is still rarely used in physical education (PE). Moreover, there is a lack of information about factors that determine the successful implementation of CL in PE. Therefore, the objective of the current study was to find out factors that determine the successful implementation of CL in PE using a digital questionnaire that was conducted from November to December 2022. In addition to socio-demographic data (age, gender, teaching experience, and education level), frequency of using CL, implementation strategies (theory-led, student-centred), and positive and negative effects of CL were measured. Furthermore, teachers were asked to rate the success of implementation on a 6-point rating scale (1-very successful to 6-not successful at all). For statistical analysis, multiple linear regression was performed, setting the success of implementation as the dependent variable. A total of 224 teachers (mean age=44.81±10.60 years; 58% male) took part in the current study. Overall, 39% of participants stated that they never use CL in their PE classes. Main reasons against the implementations of CL in PE were no time for preparation (74%) or for implementation (61%) and high heterogeneity of students (55%). When using CL, most of the reported difficulties are related to uncertainties about the correct procedure (54%) and the heterogeneous performance of students (54%). The most frequently mentioned positive effect was increased motivation of students (42%) followed by an improvement of psychological abilities (e.g. self-esteem, self-concept; 36%) and improved class cohesion (31%). Reported negative effects were unpredictability (29%), restlessness (24%), confusion (24%), and conflicts between students (17%). The successful use of CL is related to a theory-based preparation (e.g., heterogeneous formation of groups, use of rules and rituals) and a flexible implementation tailored to the needs and conditions of students (e.g., the possibility of individual work, omission of CL phases). Compared to teachers who solely implemented CL theory-led or student-adapted, teachers who switched from theory-led preparation to student-centred implementation of CL reported more successful implementation (t=5.312; p<.001). Neither frequency of using CL in PE nor the gender, age, the teaching experience, or the education level of the teacher showed a significant connection with the successful use of CL. Corresponding to the results of the current study, it is advisable that teachers gather enough knowledge about CL during their education and to point out the need to adapt the learning structure according to the diversity of their students. In order to analyse implementation strategies of teachers more deeply, qualitative methods and guided interviews with teachers are needed.

Keywords: diversity, educational technology, physical education, teaching styles

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Authors: Shreya Bokare, Sanjay Pawar, Shika Nema

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Growth in cloud applications is generating the tremendous amount of data, building load on traditional storage management systems. Software Defined Storage (SDS) is a new storage management concept becoming popular to handle this large amount of data. CoprHD is one of the open source SDS controller, available for experimentation and development in the storage industry. In this paper, the storage management techniques provided by CoprHD to manage heterogeneous storage platforms are experimented and analyzed. Various storage management parameters such as time to provision, storage capacity measurement, and heterogeneity are experimentally evaluated along with the theoretical expression to prove the completeness of CoprHD controller for storage management.

Keywords: software defined storage, SDS, CoprHD, open source, SMI-S simulator, clarion, Symmetrix

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Authors: Ebrahim Taherzadeh, Helmi Z. M. Shafri, Kaveh Shahi

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One of the most important tasks in urban area remote sensing is detection of impervious surface (IS), such as building roof and roads. However, detection of IS in heterogeneous areas still remains as one of the most challenging works. In this study, detection of concrete roof using an object-oriented approach was proposed. A new rule-based classification was developed to detect concrete roof tile. The proposed rule-based classification was applied to WorldView-2 image. Results showed that the proposed rule has good potential to predict concrete roof material from WorldView-2 images with 85% accuracy.

Keywords: object-based, roof material, concrete tile, WorldView-2

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Authors: Nikolay E. Dubinin

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Pair-interaction approximations allow to consider a different states of condensed matter from a single position. At the same time, description of an effective pair interaction in transition metal is a hard task since the d-electron contribution to the potential energy in this case is non-pairwise in principle. There are a number of models for transition-metal effective pair potentials. Here we use the Wills-Harrison (WH) approach to calculate pair potentials for Fe, Co, and Ni in crystalline, liquid, and nano states. Last is especially interesting since nano particles of pure transition metals immobilized on the dielectric matrices are widely used in different fields of advanced technologies: as carriers and transmitters of information, as an effective catalytic materials, etc. It is found that the minimum of the pair potential is deeper and oscillations are stronger in nano crystalline state in comparison with the liquid and crystalline states for all metals under consideration.

Keywords: effective pair potential, nanocrystalline state, transition metal, Wills-Harrison approach

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Authors: Ilqar Ramazanli

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The matrix completion problem has been studied broadly under many underlying conditions. The problem has been explored under adaptive or non-adaptive, exact or estimation, single-phase or multi-phase, and many other categories. In most of these cases, the observation cost of each entry is uniform and has the same cost across the columns. However, in many real-life scenarios, we could expect elements from distinct columns or distinct positions to have a different cost. In this paper, we explore this generalization under adaptive conditions. We approach the problem under two different cost models. The first one is that entries from different columns have different observation costs, but within the same column, each entry has a uniform cost. The second one is any two entry has different observation cost, despite being the same or different columns. We provide complexity analysis of our algorithms and provide tightness guarantees.

Keywords: matroid optimization, matrix completion, linear algebra, algorithms

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Authors: Katya Milenova, Penko Nikolov, Irina Stambolova, Plamen Nikolov, Vladimir Blaskov

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In the recent article, a comparison was made between Cu and TiO2 supported catalysts on activated carbon for ozone decomposition reaction. The activated carbon support in the case of TiO2/AC sample was prepared by physicochemical pyrolysis and for Cu/AC samples the supports are chemically modified carbons. The prepared catalysts were synthesized by impregnation method. The samples were annealed in two different regimes-in air and under vacuum. To examine adsorption efficiency of the samples BET method was used. All investigated catalysts supported on chemically modified carbons have higher specific surface area compared to the specific surface area of TiO2 supported catalysts, varying in the range 590÷620 m2/g. The method of synthesis of the precursors had influenced catalytic activity.

Keywords: activated carbon, adsorption, copper, ozone decomposition, TiO2

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Authors: Tayo P. Ogundunmade, Adedayo A. Adepoju

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Terrorist attacks in liberal democracies bring about a few pessimistic results, for example, sabotaged public support in the governments they target, disturbing the peace of a protected environment underwritten by the state, and a limitation of individuals from adding to the advancement of the country, among others. Hence, seeking for techniques to understand the different factors involved in terrorism and how to deal with those factors in order to completely stop or reduce terrorist activities is the topmost priority of the government in every country. This research aim is to develop an efficient deep learning-based predictive model for the prediction of future terrorist activities in Nigeria, addressing low-quality prediction accuracy problems associated with the existing solution methods. The proposed predictive AI-based model as a counterterrorism tool will be useful by governments and law enforcement agencies to protect the lives of individuals in society and to improve the quality of life in general. A Heterogeneous Bayesian Neural Network (HETBNN) model was derived with Gaussian error normal distribution. Three primary transfer functions (HOTTFs), as well as two derived transfer functions (HETTFs) arising from the convolution of the HOTTFs, are namely; Symmetric Saturated Linear transfer function (SATLINS ), Hyperbolic Tangent transfer function (TANH), Hyperbolic Tangent sigmoid transfer function (TANSIG), Symmetric Saturated Linear and Hyperbolic Tangent transfer function (SATLINS-TANH) and Symmetric Saturated Linear and Hyperbolic Tangent Sigmoid transfer function (SATLINS-TANSIG). Data on the Terrorist activities in Nigeria gathered through questionnaires for the purpose of this study were used. Mean Square Error (MSE), Mean Absolute Error (MAE) and Test Error are the forecast prediction criteria. The results showed that the HETFs performed better in terms of prediction and factors associated with terrorist activities in Nigeria were determined. The proposed predictive deep learning-based model will be useful to governments and law enforcement agencies as an effective counterterrorism mechanism to understand the parameters of terrorism and to design strategies to deal with terrorism before an incident actually happens and potentially causes the loss of precious lives. The proposed predictive AI-based model will reduce the chances of terrorist activities and is particularly helpful for security agencies to predict future terrorist activities.

Keywords: activation functions, Bayesian neural network, mean square error, test error, terrorism

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Authors: Prozorkevitch D., Mishurov A., Sokolov K., Karsakov L., Pestrikova L.

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The current body of knowledge about the marine environment and the dynamics of marine ecosystems includes a huge amount of heterogeneous data collected over decades. It generally includes a wide range of hydrological, biological and fishery data. Marine researchers collect these data and analyze how and why the ecosystem changes from past to present. Based on these historical records and linkages between the processes it is possible to predict future changes. Multivariate analysis of trends and their interconnection in the marine ecosystem may be used as an instrument for predicting further ecosystem evolution. A wide range of information about the components of the marine ecosystem for more than 50 years needs to be used to investigate how these arrays can help to predict the future.

Keywords: barents sea ecosystem, abiotic, biotic, data sets, trends, prediction

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Authors: Sam Rasoulzadeh, Atefeh Mousavi

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Fluidized bed reactors are known as highly exothermic and endothermic according to uniformity in temperature as a safe and effective mean for catalytic reactors. In these reactors, a wide range of catalyst particles can be used and by using a continuous operation proceed to produce in succession. Providing optimal conditions for the operation of these types of reactors will prevent the exorbitant costs necessary to carry out laboratory work. In this regard, a hydrodynamic analysis was carried out with heat transfer in the solid-gas fluidized bed reactor for solar thermal applications. The results showed that in the fluid flow the input of the reactor has a lower temperature than the outlet, and when the fluid is passing from the reactor, the heat transfer happens between cylinder and solar panel and fluid. It increases the fluid temperature in the outlet pump and also the kinetic energy of the fluid has been raised in the outlet areas.

Keywords: heat transfer, solar reactor, fluidized bed reactor, CFD, computational fluid dynamics

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Authors: Aryan Azad, Sun Jae Kim

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Cotton fabric is particularly prone to wrinkling. BTCA has been confirmed as the most effective reagent with sodium hypophosphite (SHP) as catalyst for decreasing the wrinkle issue. Using nano TiO2 as aco-catalyst could improve the catalytic reaction of the BTCA as well. In this study, the effect of dying process using reactive/disperse on the cotton/polyester blended fabric (65/35%) which is previously treated by nano TiO2 and BTCA, were investigated. Results were compared by samples which were not treated by nano TiO2 and BTCA by scanning electronic microscopy (SEM). Results showed, samples which were treated by mixing nano TiO2 and BTCA have not absorbed dye as much as untreated samples.

Keywords: cotton/polyester, dyeing process, nano titanium dioxide (TiO2), sodium hypophosphite (SHP), Tetra carboxylic acid (BTCA)

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Authors: Jae Moon Lee

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In general, algorithms to find continuous k-nearest neighbors have been researched on the location based services, monitoring periodically the moving objects such as vehicles and mobile phone. Those researches assume the environment that the number of query points is much less than that of moving objects and the query points are not moved but fixed. In gaming environments, this problem is when computing the next movement considering the neighbors such as flocking, crowd and robot simulations. In this case, every moving object becomes a query point so that the number of query point is same to that of moving objects and the query points are also moving. In this paper, we analyze the performance of the existing algorithms focused on location based services how they operate under gaming environments.

Keywords: flocking behavior, heterogeneous agents, similarity, simulation

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Authors: Karim Hrratha, Khaled Essalahb, Christophe Morellc, Henry Chermettec, Salima Boughdiria

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Among the carbon-carbon bond formation types, allylation of active methylene compounds with cyclic Baylis-Hillman (BH) alcohols is a reliable and widely used method. This reaction is a very attractive tool in organic synthesis of biological and biodiesel compounds. Thus, in view of an insistent and peremptory request for an efficient and straightly method for synthesizing the desired product, a thorough analysis of various aspects of the reaction processes is an important task. The product afforded by the reaction of active methylene with BH alcohols depends largely on the experimental conditions, notably on the catalyst properties. All experiments reported that catalysis is needed for this reaction type because of the poor ability of alcohol hydroxyl group to be as a suitable leaving group. Within the catalysts, several transition- metal based have been used such as palladium in the presence of acid or base and have been considered as reliable methods. Furthemore, acid catalysts such as BF3.OEt2, BiX3 (X= Cl, Br, I, (OTf)3), InCl3, Yb(OTf)3, FeCl3, p-TsOH and H-montmorillonite have been employed to activate the C-C bond formation through the alkylation of active methylene compounds. Interestingly a report of a smoothly process for the ability of 4-imethyaminopyridine(DMAP) to catalyze the allylation reaction of active methylene compounds with cyclic Baylis-Hillman (BH) alcohol appeared recently. However, the reaction mechanism remains ambiguous, since the C- allylation process leads to an unexpected product (noted P1), corresponding to a direct allylation instead of conjugate allylation, which involves the most electrophilic center according to the electron withdrawing group CO effect. The main objective of the present theoretical study is to better understand the role of the DMAP catalytic activity as well as the process leading to the end- product (P1) for the catalytic reaction of a cyclic BH alcohol with active methylene compounds. For that purpose, we have carried out computations of a set of active methylene compounds varying by R1 and R2 toward the same alcohol, and we have attempted to rationalize the mechanisms thanks to the acid–base approach, and conceptual DFT tools such as chemical potential, hardness, Fukui functions, electrophilicity index and dual descriptor, as these approaches have shown a good prediction of reactions products.The present work is then organized as follows: In a first part some computational details will be given, introducing the reactivity indexes used in the present work, then Section 3 is dedicated to the discussion of the prediction of the selectivity and regioselectivity. The paper ends with some concluding remarks. In this work, we have shown, through DFT method at the B3LYP/6-311++G(d,p) level of theory that: The allylation of active methylene compounds with cyclic BH alcohol is governed by orbital control character. Hence the end- product denoted P1 is generated by direct allylation.

Keywords: DFT calculation, gas phase pKa, theoretical mechanism, orbital control, charge control, Fukui function, transition state

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Authors: Li Na Zhao, Arieh Warshel

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The design of enzymes is an extremely challenging task, and this is also true for metalloenzymes. In the case of naturally evolved enzymes, one may consider the active site residues as the musicians in the enzyme orchestra, while the metal can be considered as their concertmaster. Together they catalyze reactions as if they performed a masterpiece written by nature. The Lactonase can be thought as a member of the amidohydrolase family, with two concertmasters, Fe and Zn, at its active site. It catalyzes the quorum sensing signal- N-acyl homoserine lactones (AHLs or N-AHLs)- by hydrolyzing the lactone ring. This process, known as quorum quenching, provides a strategy in the treatment of infectious diseases without introducing selection pressure. However, the activity of lactonase is metal-dependent, and this dependence hampers the clinic usage. In our study, we use the empirical valence bond (EVB) approach to evaluate the catalytic contributions decomposing them to electrostatic and other components.

Keywords: enzyme redesign, empirical valence bond, lactonase, quorum quenching

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Authors: Karine B. de Oliveira, Carina F. Dorneles

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The structure level matching is the problem of combining elements of a structure, which can be represented as entities, classes, XML elements, web forms, and so on. This is a challenge due to large number of distinct representations of semantically similar structures. This paper describes a structure-based matching method applied to search for different representations in data sources, considering the similarity between elements of two structures and the data source context. Using real data sources, we have conducted an experimental study comparing our approach with our baseline implementation and with another important schema matching approach. We demonstrate that our proposal reaches higher precision than the baseline.

Keywords: context, data source, index, matching, search, similarity, structure

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Authors: Iris Vural Gursel, Andrea Ramirez

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Effective utilization of lignin is an important mean for developing economically profitable biorefineries. Current literature suggests that large amounts of lignin will become available in second generation biorefineries. New conversion technologies will, therefore, be needed to carry lignin transformation well beyond combustion to produce energy, but towards high-value products such as chemicals and transportation fuels. In recent years, significant progress on catalysis has been made to improve transformation of lignin, and new catalytic processes are emerging. In this work, a techno-economic assessment of two of these novel conversion routes and comparison with more established lignin pyrolysis route were made. The aim is to provide insights into the potential performance and potential hotspots in order to guide the experimental research and ease the commercialization by early identifying cost drivers, strengths, and challenges. The lignin conversion routes selected for detailed assessment were: (non-catalytic) lignin pyrolysis as the benchmark, direct hydrodeoxygenation (HDO) of lignin and hydrothermal lignin depolymerisation. Products generated were mixed oxygenated aromatic monomers (MOAMON), light organics, heavy organics, and char. For the technical assessment, a basis design followed by process modelling in Aspen was done using experimental yields. A design capacity of 200 kt/year lignin feed was chosen that is equivalent to a 1 Mt/y scale lignocellulosic biorefinery. The downstream equipment was modelled to achieve the separation of the product streams defined. For determining external utility requirement, heat integration was considered and when possible gasses were combusted to cover heating demand. The models made were used in generating necessary data on material and energy flows. Next, an economic assessment was carried out by estimating operating and capital costs. Return on investment (ROI) and payback period (PBP) were used as indicators. The results of the process modelling indicate that series of separation steps are required. The downstream processing was found especially demanding in the hydrothermal upgrading process due to the presence of significant amount of unconverted lignin (34%) and water. Also, external utility requirements were found to be high. Due to the complex separations, hydrothermal upgrading process showed the highest capital cost (50 M€ more than benchmark). Whereas operating costs were found the highest for the direct HDO process (20 M€/year more than benchmark) due to the use of hydrogen. Because of high yields to valuable heavy organics (32%) and MOAMON (24%), direct HDO process showed the highest ROI (12%) and the shortest PBP (5 years). This process is found feasible with a positive net present value. However, it is very sensitive to the prices used in the calculation. The assessments at this stage are associated with large uncertainties. Nevertheless, they are useful for comparing alternatives and identifying whether a certain process should be given further consideration. Among the three processes investigated here, the direct HDO process was seen to be the most promising.

Keywords: biorefinery, economic assessment, lignin conversion, process design

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Authors: Patrizia Frontera, Anastasia Macario, Sebastiano Candamano, Fortunato Crea, Pierluigi Antonucci

Abstract:

The increasing of the world energy demand makes today biomass an attractive energy source, based on the minimizing of CO2 emission and on the global warming reduction purposes. Recently, COP-21, the international meeting on global climate change, defined the roadmap for sustainable worldwide development, based on low-carbon containing fuel. Hydrogen is an energy vector able to substitute the conventional fuels from petroleum. Ethanol for hydrogen production represents a valid alternative to the fossil sources due to its low toxicity, low production costs, high biodegradability, high H2 content and renewability. Ethanol conversion to generate hydrogen by a combination of partial oxidation and steam reforming reactions is generally called auto-thermal reforming (ATR). The ATR process is advantageous due to the low energy requirements and to the reduced carbonaceous deposits formation. Catalyst plays a pivotal role in the ATR process, especially towards the process selectivity and the carbonaceous deposits formation. Bimetallic or trimetallic catalysts, as well as catalysts with doped-promoters supports, may exhibit high activity, selectivity and deactivation resistance with respect to the corresponding monometallic ones. In this work, NiMoCo/GDC, NiMoCu/GDC and NiMoRe/GDC (where GDC is Gadolinia Doped Ceria support and the metal composition is 60:30:10 for all catalyst) have been prepared by impregnation method. The support, Gadolinia 0.2 Doped Ceria 0.8, was impregnated by metal precursors solubilized in aqueous ethanol solution (50%) at room temperature for 6 hours. After this, the catalysts were dried at 100°C for 8 hours and, subsequently, calcined at 600°C in order to have the metal oxides. Finally, active catalysts were obtained by reduction procedure (H2 atmosphere at 500°C for 6 hours). All sample were characterized by different analytical techniques (XRD, SEM-EDX, XPS, CHNS, H2-TPR and Raman Spectorscopy). Catalytic experiments (auto-thermal reforming of ethanol) were carried out in the temperature range 500-800°C under atmospheric pressure, using a continuous fixed-bed microreactor. Effluent gases from the reactor were analyzed by two Varian CP4900 chromarographs with a TCD detector. The analytical investigation focused on the preventing of the coke deposition, the metals sintering effect and the sulfur poisoning. Hydrogen productivity, ethanol conversion and products distribution were measured and analyzed. At 600°C, all tri-metallic catalysts show the best performance: H2 + CO reaching almost the 77 vol.% in the final gases. While NiMoCo/GDC catalyst shows the best selectivity to hydrogen whit respect to the other tri-metallic catalysts (41 vol.% at 600°C). On the other hand, NiMoCu/GDC and NiMoRe/GDC demonstrated high sulfur poisoning resistance (up to 200 cc/min) with respect to the NiMoCo/GDC catalyst. The correlation among catalytic results and surface properties of the catalysts will be discussed.

Keywords: catalysts, ceria, ethanol, gadolinia, hydrogen, Nickel

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Authors: Soukaina Oujana, Peggy Zwolinski

Abstract:

Fines are heterogeneous residues created during the shredding of non-hazardous waste. They are one of the most challenging issues faced by recyclers, because they are at the present time considered as non-sortable and non-reusable mixtures destined to landfill. However, fines contain a large amount of recoverable materials that could be recycled or reused for the production of solid recovered fuel. This research is conducted in relation to a project named ValoRABES. The aim is to characterize fines and establish a suitable sorting process in order to extract the materials contained in the mixture and define their suitable recovery paths. This paper will highlight the importance of a good sampling and will propose a sampling methodology for fines characterization. First results about the characterization will be also presented.

Keywords: fines, non-hazardous waste, recovery, shredding residues, waste characterization, waste sampling

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Authors: M. Hemam, M. Djezzar, T. Djouad

Abstract:

We are interested in the problem of building an ontology in a heterogeneous organization, by taking into account different viewpoints and different terminologies of communities in the organization. Such ontology, that we call multi-viewpoint ontology, confers to the same universe of discourse, several partial descriptions, where each one is relative to a particular viewpoint. In addition, these partial descriptions share at global level, ontological elements constituent a consensus between the various viewpoints. In order to provide response elements to this problem we define a multi-viewpoints knowledge model based on viewpoint and ontology notions. The multi-viewpoints knowledge model is used to formalize the multi-viewpoints ontology in description logics language.

Keywords: description logic, knowledge engineering, ontology, viewpoint

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Authors: Abas Mohsenzadeh, Mina Arya, Kim Bolton

Abstract:

Catalytic combustion of hydrocarbons is an important technology developed to produce energy with minimum pollutant formation. The catalyst plays a key role in this process which operates at lower temperatures compared to conventional flame combustion. The energetics of the direct combustion of hydrocarbons (CH → C + H) on a series of metal surfaces including Ag, Au, Al, Cu, Rh, Pt, Pd, Ni, Fe and Co were investigated using density functional theory (DFT). Brønsted-Evans-Polanyi (BEP) and transition state scaling (TSS) correlations were proposed based on DFT calculations on the Ag, Au, Al, Cu, Rh, Pt and Pd surfaces. These correlations were then used to estimate the energetics on Fe, Ni and Co surfaces. Results showed that the estimated reaction and activation energies by BEP and TSS correlations on Fe, Ni and Co surfaces are in an excellent agreement with those obtained by DFT calculations. Therefore these correlations can be efficiently used to predict energetics of similar reactions on these surfaces without doing computationally costly transition state calculations. It was found that the activation barrier for CH dissociation follows the order Ag ˃ Au ˃ Al ˃ Cu ˃ Pt ˃ Pd ˃ Ni > Co > Rh > Fe. Also, BEP (with R2 value of 0.96) and TSS correlations (with R2 value of 0.99) support the results.

Keywords: BEP, DFT, hydrocarbon combustion, metal surfaces, TSS

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Authors: Brenda Cecilia Ledesma, Andrea Beltramone

Abstract:

This work deals with the bio-waste valorization approach for catalyst development, the use of products derived from biomass as raw material and the obtaining of biofuels. In this research, activated carbons were synthesized from the orange peel using different synthesis conditions. With the activated carbons obtained with the best structure and texture, PtIr bimetallic catalysts were prepared. Carbon activation was carried out through a chemical process with phosphoric acid as an activating agent, varying the acid concentration, the ratio substrate/activating agent and time of contact between them. The best support was obtained using a carbonization time of 1 h, the temperature of carbonization of 470oC, the phosphoric acid concentration of 50 wt.% and a BET area of 1429 m2/g. Subsequently, the metallic nanoparticles were deposited in the activated carbon to use the solid as a catalytic material for the hydrogenation of HMF to 2,5-DMF. The catalyst presented an excellent performance for biofuels generation.

Keywords: orange peel, bio-waste valorization, platinum, iridium, 5-hydroxymethylfurfural

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Authors: Amit Gill, Lalith Wijerathne, Sebastian Poledna

Abstract:

This research presents the details of the implementation of high performance computing (HPC) extension of agent-based economic models (ABEMs) to simulate hundreds of millions of heterogeneous agents. ABEMs offer an alternative approach to study the economy as a dynamic system of interacting heterogeneous agents, and are gaining popularity as an alternative to standard economic models. Over the last decade, ABEMs have been increasingly applied to study various problems related to monetary policy, bank regulations, etc. When it comes to predicting the effects of local economic disruptions, like major disasters, changes in policies, exogenous shocks, etc., on the economy of the country or the region, it is pertinent to study how the disruptions cascade through every single economic entity affecting its decisions and interactions, and eventually affect the economic macro parameters. However, such simulations with hundreds of millions of agents are hindered by the lack of HPC enhanced ABEMs. In order to address this, a scalable Distributed Memory Parallel (DMP) implementation of ABEMs has been developed using message passing interface (MPI). A balanced distribution of computational load among MPI-processes (i.e. CPU cores) of computer clusters while taking all the interactions among agents into account is a major challenge for scalable DMP implementations. Economic agents interact on several random graphs, some of which are centralized (e.g. credit networks, etc.) whereas others are dense with random links (e.g. consumption markets, etc.). The agents are partitioned into mutually-exclusive subsets based on a representative employer-employee interaction graph, while the remaining graphs are made available at a minimum communication cost. To minimize the number of communications among MPI processes, real-life solutions like the introduction of recruitment agencies, sales outlets, local banks, and local branches of government in each MPI-process, are adopted. Efficient communication among MPI-processes is achieved by combining MPI derived data types with the new features of the latest MPI functions. Most of the communications are overlapped with computations, thereby significantly reducing the communication overhead. The current implementation is capable of simulating a small open economy. As an example, a single time step of a 1:1 scale model of Austria (i.e. about 9 million inhabitants and 600,000 businesses) can be simulated in 15 seconds. The implementation is further being enhanced to simulate 1:1 model of Euro-zone (i.e. 322 million agents).

Keywords: agent-based economic model, high performance computing, MPI-communication, MPI-process

Procedia PDF Downloads 130