Search results for: heterogeneous catalytic ozonation

Authors: Talat Baran

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The Suzuki C(sp2)-C(sp2) coupling reaction is considered to be one of the best ways for the synthesis of biaryl compounds. There are many studies reporting the catalytic performance of palladium catalyst in Suzuki coupling reactions. Natural biopolymer (such as zeolite, carbon, silica, and chitosan) supporting catalysts have been lately attracted interest because of their low-cost, nontoxicity, and eco-friendliness. One of the most important natural biopolymer is cellulose, which is widely considered as an eco-friendly biopolymer due to its biodegradable, non-toxic and renewable nature. In this study, (1) cellulose supported Pd(II) catalyst was synthesized (2) its chemical structure was characterized by FT-IR, SEM/EDAX, XRD, TG-DTG, ICP-OES techniques (3) to investigate the performance of the catalyst in Suzuki coupling reactions by using microwave irradiation technique (4) reusability of the catalyst was done under optimum conditions. This cellulose supported Pd(II) catalyst exhibited high selectivity and efficiency in Suzuki coupling reactions under mild conditions (50°C). High TON and TOF values were recorded for the catalyst. Also, the reusability tests showed the catalysts could be used for several times in consequence of reusability tests.

Keywords: palladium, cellulose, Schiff base, reusability

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Authors: Shidrokh Goudarzi, Wan Haslina Hassan

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Heterogeneous wireless networks are converging towards an all-IP network as part of the so-called next-generation network. In this paradigm, different access technologies need to be interconnected; thus, vertical handovers or vertical handoffs are necessary for seamless mobility. In this paper, we conduct a review of existing vertical handover decision-making mechanisms that aim to provide ubiquitous connectivity to mobile users. To offer a systematic comparison, we categorize these vertical handover measurement and decision structures based on their respective methodology and parameters. Subsequently, we analyze several vertical handover approaches in the literature and compare them according to their advantages and weaknesses. The paper compares the algorithms based on the network selection methods, complexity of the technologies used and efficiency in order to introduce our vertical handover decision framework. We find that vertical handovers on heterogeneous wireless networks suffer from the lack of a standard and efficient method to satisfy both user and network quality of service requirements at different levels including architectural, decision-making and protocols. Also, the consolidation of network terminal, cross-layer information, multi packet casting and intelligent network selection algorithm appears to be an optimum solution for achieving seamless service continuity in order to facilitate seamless connectivity.

Keywords: heterogeneous wireless networks, vertical handovers, vertical handover metric, decision-making algorithms

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Authors: Sagir M. Yusuf, Chris Baber

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We describe issues bedeviling the coordination of heterogeneous (different sensors carrying agents) multi-agent missions such as belief conflict, situation reasoning, etc. We applied Bayesian and agents' presumptions inferential reasoning to solve the outlined issues with the heterogeneous multi-agent belief variation and situational-base reasoning. Bayesian Belief Network (BBN) was used in modeling the agents' belief conflict due to sensor variations. Simulation experiments were designed, and cases from agents’ missions were used in training the BBN using gradient descent and expectation-maximization algorithms. The output network is a well-trained BBN for making inferences for both agents and human experts. We claim that the Bayesian learning algorithm prediction capacity improves by the number of training data and argue that it enhances multi-agents robustness and solve agents’ sensor conflicts.

Keywords: distributed constraint optimization problem, multi-agent system, multi-robot coordination, autonomous system, swarm intelligence

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Authors: Tatyana T. Tabakova, Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Krasimir I. Ivanov, Yordanka G. Karakirova, Petya Cv. Petrova, Georgi V. Avdeev

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The catalytic oxidation of CO and volatile organic compounds (VOCs) is considered as one of the most efficient ways to reduce harmful emissions from various chemical industries. The effectiveness of gold-based catalysts for many reactions of environmental significance was proven during the past three decades. The aim of this work was to combine the favorable features of Au and Cu-Ce mixed oxides in the design of new catalytic materials of improved efficiency and economic viability for removal of air pollutants in waste gases from formaldehyde production. Supported oxides of copper and cerium with Cu: Ce molar ratio 2:1 and 1:5 were prepared by wet impregnation of g-alumina. Gold (2 wt.%) catalysts were synthesized by a deposition-precipitation method. Catalysts characterization was carried out by texture measurements, powder X-ray diffraction, temperature programmed reduction and electron paramagnetic resonance spectroscopy. The catalytic activity in the oxidation of CO, CH₃OH and (CH₃)₂O was measured using continuous flow equipment with fixed bed reactor. Both Cu-Ce/alumina samples demonstrated similar catalytic behavior. The addition of gold caused significant enhancement of CO and methanol oxidation activity (100 % degree of CO and CH₃OH conversion at about 60 and 140 ^oC, respectively). The composition of Cu-Ce mixed oxides affected the performance of gold-based samples considerably. Gold catalyst on Cu-Ce/γ-Al₂O₃ 1:5 exhibited higher activity for CO and CH₃OH oxidation in comparison with Au on Cu-Ce/γ-Al₂O₃ 2:1. The better performance of Au/Cu-Ce 1:5 was related to the availability of highly dispersed gold particles and copper oxide clusters in close contact with ceria.

Keywords: CO and VOCs oxidation, copper oxide, Ceria, gold catalysts

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Authors: Mir Hussain Nawaz, Lyudmila Nedyalkova, Haizhong Zhu, Wael M. Rabeh

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In this study, we aim to biochemically and structurally characterize the interactions of human HK2 with the mitochondria in addition to the role of its N-terminal domain in catalysis and stability of the full-length enzyme. Here, we solved the crystal structure of human HK2 in complex with glucose and glucose-6-phosphate (PDB code: 2NZT), where it is a homodimer with catalytically active N- and C-terminal domains linked by a seven-turn α-helix. Different from the inactive N-terminal domains of isozymes 1 and 3, the N- domain of HK2 not only capable to catalyze a reaction but it is responsible for the thermodynamic stabilizes of the full-length enzyme. Deletion of first α-helix of the N-domain that binds to the mitochondria altered the stability and catalytic activity of the full-length HK2. In addition, we found the linker helix between the N- and C-terminal domains to play an important role in controlling the catalytic activity of the N-terminal domain. HK2 is a major step in the regulation of glucose metabolism in cancer making it an ideal target for the development of new anticancer therapeutics. Characterizing the structural and molecular mechanisms of human HK2 and its role in cancer metabolism will accelerate the design and development of new cancer therapeutics that are safe and cancer specific.

Keywords: cancer metabolism, enzymology, drug discovery, protein stability

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Authors: Man Young Kim

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To reduce the NOx emission in a Diesel vehicle, such various after treatment systems as SCR, LNC, and LNT are frequently visited as promising systems. Among others, urea-based SCR systems are known to be stable, effective technologies that can reduce NOx emissions most efficiently from diesel exhaust systems. In this study, therefore, effect of urea injector installation angle on the evaporation and mixing characteristics is investigated to find optimum operation conditions. It can be found that the injection angle significantly affects the thermal behavior of the urea-water solution in the diesel exhaust gases.

Keywords: selective catalytic reduction (SCR), evaporation, thermolysis, urea-water solution (UWS), injector installation angle

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Authors: M. K. Benhaoua, A. K. Singh, A. E. H. Benyamina

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In this paper, we propose heuristic for dynamic communications mapping that considers the placement of communications in order to optimize the overall performance. The mapping technique uses a newly proposed Algorithm to place communications between the tasks. The placement we propose of the communications leads to a better optimization of several performance metrics (time and energy consumption). Experimental results show that the proposed mapping approach provides significant performance improvements when compared to those using static routing.

Keywords: Multi-Processor Systems-on-Chip (MPSoCs), Network-on-Chip (NoC), heterogeneous architectures, dynamic mapping heuristics

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Authors: Ali Zaker, Zhi Chen

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Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is the generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups, and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contains four obvious stages, and the main decomposition reaction occurred in the range of 200-600°C. The Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2, and 3 were in the range of 6.67-20.37 kJ for SS; 1.51-6.87 kJ for HZSM5; and 2.29-9.17 kJ for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1, and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with AC and HZSM5 were in the total range of C4-C17, with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds, while with the presence of AC and HZSM5 dropped to 13.02% and 7.3%, respectively. Meanwhile, the generation of benzene, toluene, and xylene (BTX) compounds was significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR, and TGA techniques. Overall, this research demonstrated AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.

Keywords: catalytic pyrolysis, sewage sludge, activated char, HZSM5, bio-oil

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Authors: Mulatu Kassie Birhanu

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Electrochemical reduction of CO₂ is an emerging and current issue for its conversion in to valuable product upon minimization of its atmospheric level for contribution of maintaining within the range of permissible limit. Among plenty of electro-catalysts gold and copper are efficient and effective catalysts, which are synthesized and applicable for this research work. The two metal catalysts were prepared in inert environment with different compositions through co-reduction process from their corresponding precursors and then by adding multi-walled carbon nano-tube as a supporter and enhanced the conductivity. The catalytic performance of CO₂ reduction for each composition was performed and resulted an outstanding catalytic activity with generation of high current density (70 mA/cm² at 0.91V vs. RHE) and relatively small onset potential. The catalytic performance, compositions, morphologies, structure and geometric arrangements were evaluated by electrochemical analysis (LSV, impedance, chronoamperometry & tafel plot), EDS, SEM and XAS respectively. The composite metals showed better selectivity of products and faradaic efficiencies due to the synergetic effects of the combined nano-particles in addition to the impact of grain size in reduction of CO₂. Carbon monoxide, hydrogen, formate and ethanol are the reduction products, which are detected and quantifiable by chromatographic techniques considering their physical state of each product.

Keywords: carbondioxide, faradaic efficiency, electrocatalyst, current density

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Authors: Houda Najeh, Mahendra Pratap Singh, Stéphane Ploix, Antoine Caucheteux, Karim Chabir, Mohamed Naceur Abdelkrim

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Building system is highly vulnerable to different kinds of faults and human misbehaviors. Energy efficiency and user comfort are directly targeted due to abnormalities in building operation. The available fault diagnosis tools and methodologies particularly rely on rules or pure model-based approaches. It is assumed that model or rule-based test could be applied to any situation without taking into account actual testing contexts. Contextual tests with validity domain could reduce a lot of the design of detection tests. The main objective of this paper is to consider fault validity when validate the test model considering the non-modeled events such as occupancy, weather conditions, door and window openings and the integration of the knowledge of the expert on the state of the system. The concept of heterogeneous tests is combined with test validity to generate fault diagnoses. A combination of rules, range and model-based tests known as heterogeneous tests are proposed to reduce the modeling complexity. Calculation of logical diagnoses coming from artificial intelligence provides a global explanation consistent with the test result. An application example shows the efficiency of the proposed technique: an office setting at Grenoble Institute of Technology.

Keywords: heterogeneous tests, validity, building system, sensor grids, sensor fault, diagnosis, fault detection and isolation

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Authors: Prathap S. Raghavendra, Mohamed S. Z. Shamshuddin, Thimmaraju N. Venkatesh

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The transesterification of dimethyl malonate (DMM) with phenol has been studied in vapour phase over cordierite honeycomb coated with solid acid catalysts such as ZrO2,Mo(VI)/ZrO2 and SO42-/ZrO2. The catalytic materials were prepared honeycomb coated and powder forms and characterized for their total surface acidity by NH3-TPD and crystalinity by powder XRD methods. Phenyl methyl malonate (PMM) and diphenyl malonate (DPM) were obtained as the reaction products. A good conversion of DMM (up to 82%) of MPM with 95% selectivity was observed when the reactions were carried out at a catalyst bed temperature of 200 °C and flow-rate of 10 mL/h in presence of Mo(VI)/ZrO2 as catalyst. But over SO42-/ZrO2 catalyst, the yield of DPM was found to be higher. The results have been interpreted based on the variation of acidic properties and powder XRD phases of zirconia on incorporation of Mo(VI) or SO42– ions. Transesterification reactions were also carried out over powder forms of the catalytic materials and the yield of the desired phenyl ester products were compared with that of the HC coated catalytic materials. The solid acids were found to be reusable when used for at least 5 reaction cycles.

Keywords: cordierite honeycomb, methyl phenyl malonate, vapour phase transesterification, zirconia

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Authors: Davyd Urbanas, Pranas Baltrenas

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It is well-known that, despite the constant increase of alternative energy sources usage, today combustible fuels are still widely used in power engineering. As a result of fuel combustion, significant amounts of nitrogen oxides (NOx) and carbon monoxide (CO is a product of incomplete combustion) are supplied to the atmosphere. Also, these pollutants are formed in industry (chemical production, refining, and metal production). In this work, the investigation of nitrogen oxides CO-selective catalytic reduction using new grain load-type catalysts was carried out. The catalysts containing the substrate and a thin active coating made of transition metal (Mn, Cu, and Nb) oxides were prepared with the use of electroless chemical deposition method. Chemical composition, chemical state, and morphology of the formed active coating were investigated using ICP-OES, EDX, SEM, and XPS techniques. The obtained results revealed that the prepared catalysts (Cu-Mn-oxide and Cu-Mn-Nb-oxide) have rough and developed surface and can be successfully used for the flue gas catalytic purification. The significant advantage of prepared catalysts is their suitability from technological application point of view, which differs this work from others dedicated to gas purification by SCR.

Keywords: flue gas, nitrogen oxides, selective catalytic reduction, transition metal oxides

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Authors: Tae Hyun Ahn, Gyo Woo Lee, Man Young Kim

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Because of high thermal efficiency and low CO2 emission, diesel engines are being used widely in many industrial fields although it makes many PM and NOx which give both human health and environment a negative effect. NOx regulations for diesel engines, however, are being strengthened and it is impossible to meet the emission standard without NOx reduction devices such as SCR (Selective Catalytic Reduction), LNC (Lean NOx Catalyst), and LNT (Lean NOx Trap). Among the NOx reduction devices, urea-SCR system is known as the most stable and efficient method to solve the problem of NOx emission. But this device has some issues associated with the ammonia slip phenomenon which is occurred by shortage of evaporation and thermolysis time, and that makes it difficult to achieve uniform distribution of the injected urea in front of monolith. Therefore, this study has focused on the mixing enhancement between urea and exhaust gases to enhance the efficiency of the SCR catalyst equipped in catalytic muffler by changing inlet gas temperature and spray conditions to improve the spray uniformity of the urea water solution. Finally, it can be found that various parameters such as inlet gas temperature and injector and injection angles significantly affect the evaporation and mixing of the urea water solution with exhaust gases, and therefore, optimization of these parameters are required.

Keywords: UWS (Urea-Water-Solution), selective catalytic reduction (SCR), evaporation, thermolysis, injection

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Authors: Yaxin Tang, Mingao Hou, Qian He, Guangfu Luo

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Bimetallic nanoparticles serve as a promising class of catalysts with tunable properties suitable for diverse catalytic reactions, yet a comprehensive understanding of their actual structures under operating conditions and the optimal design principles remains largely elusive. In this study, we unveil a prevalent surface segregation phenomenon in nearly 100 platinum-group-element-based bimetallic nanoparticles through first principles-based molecular dynamics simulations. Our findings highlight that two components in a nanoparticle with relatively lower surface energy tend to segregate to the surface. Motivated by this discovery, we propose a deliberate exploitation of surface segregation in designing bimetallic nanoparticle catalysts, aiming for heightened stability and reduced consumption of precious metals. To validate this strategy, we further investigate 36 platinum-based bimetallic nanoparticles for propane dehydrogenation catalysis. Through a systematic examination of catalytic sites on nanoparticles, we identify several systems as top candidates with Pt-enriched surfaces, remarkable thermal stability, and superior catalytic activity for propane dehydrogenation. The insights gained garnered from this study are anticipated to provide a valuable framework for the optimal design of other bimetallic nanoparticles.

Keywords: bimetallic nanoparticles, platinum-group element, catalysis, surface segregation, first-principles calculations

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Authors: Ali Noorian

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Crude oil contains various compounds of hydrocarbons but low concentrations of inorganic compounds or metals. Vanadium and Nickel are the most common metals in crude oil. These metals usually exist in solution in the oil and residual fuel oil in the refining process is condensed. Deleterious effects of metals in petroleum have been known for some time. These metals do not only contaminate the product but also cause intoxication and loss of catalyst and corrosion to equipment. In this study, removal of heavy metals and petroleum residues were investigated. These methods include physical, chemical and biological treatment processes. For example, processes such as solvent extraction and hydro-catalytic and catalytic methods are effective and practical methods, but typically often have high costs and cause environmental pollution. Furthermore, biological methods that do not cause environmental pollution have been discussed in recent years, but these methods have not yet been industrialized.

Keywords: removal, metal, heavy oil, nickel, vanadium

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Authors: Horiya Boukhatem, Lila Djouadi, Hussein Khalaf, Rufino Manuel Navarro Yerga, Fernando Vaquero Gonzalez

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Heterogeneous photo catalysis is an alternative method for the removal of organic pollutants in water. The photo excitation of a semi-conductor under ultra violet (UV) irradiation entails the production of hydroxyl radicals, one of the most oxidative chemical species. The objective of this study is the synthesis of nano materials based on montmorillonite and CuxCd1-xS with different Cu concentration (0.3 < x < 0.7) and their application in photocatalysis of a cationic dye: methylene blue. The synthesized nano materials and montmorillonite were characterized by fourier transform infrared (FTIR). Test results of photo catalysis of methylene blue under UV-Visible irradiation show that the photoactivity of nano materials montmorillonite/ CuxCd1-xS increase with the increasing of Cu concentration and it is significantly higher compared to that of sodium montmorillonite alone. The application of the kinetic model of Langmuir-Hinshelwood (L-H) to the photocatalytic test results showed that the reaction rate obeys to the first-order kinetic model.

Keywords: heterogeneous photo catalysis, methylene blue, montmorillonite, nano material

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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: M. K. Benhaoua, A. K. Singh, A. E. Benyamina, P. Boulet

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Mapping parallelized tasks of applications onto these MPSoCs can be done either at design time (static) or at run-time (dynamic). Static mapping strategies find the best placement of tasks at design-time, and hence, these are not suitable for dynamic workload and seem incapable of runtime resource management. The number of tasks or applications executing in MPSoC platform can exceed the available resources, requiring efficient run-time mapping strategies to meet these constraints. This paper describes a new Spiral Dynamic Task Mapping heuristic for mapping applications onto NoC-based Heterogeneous MPSoC. This heuristic is based on packing strategy and routing Algorithm proposed also in this paper. Heuristic try to map the tasks of an application in a clustering region to reduce the communication overhead between the communicating tasks. The heuristic proposed in this paper attempts to map the tasks of an application that are most related to each other in a spiral manner and to find the best possible path load that minimizes the communication overhead. In this context, we have realized a simulation environment for experimental evaluations to map applications with varying number of tasks onto an 8x8 NoC-based Heterogeneous MPSoCs platform, we demonstrate that the new mapping heuristics with the new modified dijkstra routing algorithm proposed are capable of reducing the total execution time and energy consumption of applications when compared to state-of-the-art run-time mapping heuristics reported in the literature.

Keywords: multiprocessor system on chip, MPSoC, network on chip, NoC, heterogeneous architectures, run-time mapping heuristics, routing algorithm

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Authors: Ramzi Farra, Detre Teschner, Marc Willinger, Robert Schlögl

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Introduction: The conventional approach of characterizing solid catalysts under static conditions, i.e., before and after reaction, does not provide sufficient knowledge on the physicochemical processes occurring under dynamic conditions at the molecular level. Hence, the necessity of improving new in situ characterizing techniques with the potential of being used under real catalytic reaction conditions is highly desirable. In situ Prompt Gamma Activation Analysis (PGAA) is a rapidly developing chemical analytical technique that enables us experimentally to assess the coverage of surface species under catalytic turnover and correlate these with the reactivity. The catalytic HCl oxidation (Deacon reaction) over bulk ceria will serve as our example. Furthermore, the in situ Transmission Electron Microscopy is a powerful technique that can contribute to the study of atmosphere and temperature induced morphological or compositional changes of a catalyst at atomic resolution. The application of such techniques (PGAA and TEM) will pave the way to a greater and deeper understanding of the dynamic nature of active catalysts. Experimental/Methodology: In situ Prompt Gamma Activation Analysis (PGAA) experiments were carried out to determine the Cl uptake and the degree of surface chlorination under reaction conditions by varying p(O2), p(HCl), p(Cl2), and the reaction temperature. The abundance and dynamic evolution of OH groups on working catalyst under various steady-state conditions were studied by means of in situ FTIR with a specially designed homemade transmission cell. For real in situ TEM we use a commercial in situ holder with a home built gas feeding system and gas analytics. Conclusions: Two complimentary in situ techniques, namely in situ PGAA and in situ FTIR were utilities to investigate the surface coverage of the two most abundant species (Cl and OH). The OH density and Cl uptake were followed under multiple steady-state conditions as a function of p(O2), p(HCl), p(Cl2), and temperature. These experiments have shown that, the OH density positively correlates with the reactivity whereas Cl negatively. The p(HCl) experiments give rise to increased activity accompanied by Cl-coverage increase (opposite trend to p(O2) and T). Cl2 strongly inhibits the reaction, but no measurable increase of the Cl uptake was found. After considering all previous observations we conclude that only a minority of the available adsorption sites contribute to the reactivity. In addition, the mechanism of the catalysed reaction was proposed. The chlorine-oxygen competition for the available active sites renders re-oxidation as the rate-determining step of the catalysed reaction. Further investigations using in situ TEM are planned and will be conducted in the near future. Such experiments allow us to monitor active catalysts at the atomic scale under the most realistic conditions of temperature and pressure. The talk will shed a light on the potential and limitations of in situ PGAA and in situ TEM in the study of catalyst dynamics.

Keywords: CeO2, deacon process, in situ PGAA, in situ TEM, in situ FTIR

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Authors: Muhammad Ayoub, Abrar Inayat, Bhajan Lal, Sintayehu Mekuria Hailegiorgis

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Biodiesel which comes from pure renewable resources provide an alternative fuel option for future because of limited fossil fuel resources as well as environmental concerns. The transesterification of vegetable oils for biodiesel production is a promising process to overcome this future crises of energy. The use of heterogeneous catalysts greatly simplifies the technological process by facilitating the separation of the post-reaction mixture. The purpose of the present work was to examine a heterogeneous catalyst, in particular, Mg-Al modified K-10 clay, to produce methyl esters of palm oil. The prepared catalyst was well characterized by different latest techniques. In this study, the transesterification of palm oil with methanol was studied in a heterogeneous system in the presence of Mg-Al modified K-10 clay as solid base catalyst and then optimized these results with the help of Design of Experiments software. The results showed that methanol is the best alcohol for this reaction condition. The best results was achieved for optimization of biodiesel process. The maximum conversion of triglyceride (88%) was noted after 8 h of reaction at 60 ̊C, with a 6:1 molar ratio of methanol to palm oil and 3 wt % of prepared catalyst.

Keywords: palm oil, transestrefication, clay, biodiesel, mesoporous clay, K-10

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Authors: Elitsa Kolentsova, Dimitar Dimitrov, Krasimir Ivanov

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The catalytic oxidation of methanol to formaldehyde is an important industrial process in which the waste gas in addition to CO contains methanol and dimethyl ether (DME). Evaluation of the possibility of removing the harmful components from the exhaust gasses needs a more complex investigation. Our previous work indicates that supported Cu-Mn oxide catalysts are promising for effective deep oxidation of these compounds. This work relates to the catalyst, comprising copper-manganese spinel, coated on carrier γ-Al₂O₃. The effect of preparation conditions on the active component composition and activity behavior of the catalysts is discussed. Different organometallic compounds on the base of four natural amino acids (Glycine, Alanine, Valine, Leucine) as precursors were used for the preparation of catalysts with Cu/Mn molar ratio 1:5. X-Ray and TEM analysis were performed on the catalyst’s bulk, and surface composition and the specific surface area was determined by BET method. The results obtained show that the activity of the catalysts increase up to 40% although there are some specific features, depending on the nature of the amino acid and the oxidized compound.

Keywords: Cu-Mn/γ-Al₂O₃, CO and VOCs oxidation, heterogeneous catalysis, amino acids

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Authors: Marlies Achenbach

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System competencies play a key role to ensure an effective and efficient improvement of production systems. Thus, there can be observed an increasing demand for developing system competencies in industry as well as in engineering education. System competencies consist of the following two main abilities: Evaluating the current state of a production system and developing a target state. The innovative course ‘multi-perspective learning in a real production plant (multi real)’ is developed to create a learning setting that supports the development of these system competencies. Therefore, the setting combines two innovative aspects: First, the Learning takes place in heterogeneous groups formed by students as well as professionals and managers from industry. Second, the learning takes place in a real production plant. This paper presents the innovative didactic concept of ‘multi real’ in detail, which will initially be implemented in October/November 2016 in the industrial engineering, logistics and mechanical master’s program at TU Dortmund University.

Keywords: experiential learning, heterogeneous groups, improving production systems, system competencies

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Authors: Elitsa Kolentsova, Dimitar Dimitrov, Vasko Idakiev, Tatyana Tabakova, Krasimir Ivanov

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Formaldehyde production by selective oxidation of methanol is an important industrial process. The main by-products in the waste gas are CO and dimethyl ether (DME). The idea of this study is to combine the advantages of both Cu-Mn and Cu-Co catalytic systems by obtaining a new mixed Cu-Mn-Co catalyst with high activity and selectivity at the simultaneous oxidation of CO, methanol, and DME. Two basic Cu-Mn samples with high activity were selected for further investigation: (i) manganese-rich Cu-Mn/γ–Al2O3 catalyst with Cu/Mn molar ratio 1:5 and (ii) copper-rich Cu-Mn/γ-Al2O3 catalyst with Cu/Mn molar ratio 2:1. Manganese in these samples was replaced by cobalt in the whole concentration region, and catalytic properties were determined. The results show a general trend of decreasing the activity toward DME oxidation and increasing the activity toward CO and methanol oxidation with the increase of cobalt up to 60% for both groups of catalyst. This general trend, however, contains specific features, depending on the composition of the catalyst and the nature of the oxidized gas. The catalytic activity of the sample with Cu/(Mn+Co) molar ratio of 2:1 is gradually changed with increasing the cobalt content. The activity of the sample with Cu/(Mn+Co) molar ratio of 1: 5 passes through a maximum at 60% manganese replacement by cobalt, probably due to the formation of highly dispersed Co-based spinel structures (Co3O4 and/or MnCo2O4). In conclusion, the present study demonstrates that the Cu-Mn-Co/γ–alumina supported catalysts have enhanced activity toward CO, methanol and DME oxidation. Cu/(Mn+Co) molar ratio 1:5 and Co/Mn molar ratio 1.5 in the active component can ensure successful oxidation of CO, CH3OH and DME. The active component of the mixed Cu-Mn-Co/γ–alumina catalysts consists of at least six compounds - CuO, Co3O4, MnO2, Cu1.5Mn1.5O4, MnCo2O4 and CuCo2O4, depending on the Cu/Mn/Co molar ratio. Chemical composition strongly influences catalytic properties, this effect being quite variable with regards to the different processes.

Keywords: Cu-Mn-Co catalysts, oxidation, carbon oxide, VOCs

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Authors: Ming-Jong Yao, Chin-Sum Shui, Chih-Han Wang

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This paper is developed based on a real-world decision scenario that an industrial gas company that applies the Vendor Managed Inventory model and supplies liquid oxygen with a self-operated heterogeneous vehicle fleet to hospitals in nearby cities. We name it as a Joint Replenishment and Heterogeneous Vehicle Routing Problem with Cyclical Schedule and formulate it as a non-linear mixed-integer linear programming problem which simultaneously determines the length of the planning cycle (PC), the length of the replenishment cycle and the dates of replenishment for each customer and the vehicle routes of each day within PC, such that the average daily operation cost within PC, including inventory holding cost, setup cost, transportation cost, and overtime labor cost, is minimized. A solution method based on genetic algorithm, embedded with an encoding and decoding mechanism and local search operators, is then proposed, and the hash function is adopted to avoid repetitive fitness evaluation for identical solutions. Numerical experiments demonstrate that the proposed solution method can effectively solve the problem under different lengths of PC and number of customers. The method is also shown to be effective in determining whether the company should expand the storage capacity of a customer whose demand increases. Sensitivity analysis of the vehicle fleet composition shows that deploying a mixed fleet can reduce the daily operating cost.

Keywords: cyclic inventory routing problem, joint replenishment, heterogeneous vehicle, genetic algorithm

Procedia PDF Downloads 51

Authors: Nathalie Elia, Samer Aouad, Jane Estephane, Christophe Poupin, Bilal Nsouli, Edmond Abi Aad

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Carbon dioxide is one of the main contributors to greenhouse effect and hence to climate change. As a result, the methanation reaction CO2(g) + 4H2(g) →CH4(g) + 2H2O (ΔH°298 = -165 kJ/mol), also known as Sabatier reaction, has received great interest as a process for the valorization of the greenhouse gas CO2 into methane which is a hydrogen-carrier gas. The methanation of CO2 is an exothermic reaction favored at low temperature and high pressure. However, this reaction requires a high energy input to activate the very stable CO2 molecule, and exhibits serious kinetic limitations. Consequently, the development of active and stable catalysts is essential to overcome these difficulties. Catalytic methanation of CO2 has been studied using catalysts containing Rh, Pd, Ru, Co and Ni on various supports. Among them, the Ni-based catalysts have been extensively investigated under various conditions for their comparable methanation activity with highly improved cost-efficiency. The addition of promoters are common strategies to increase the performance and stability of Ni catalysts. In this work, a small amount of Ru was used as a promoter for Ni catalysts supported on ceria and tested in the CO2 methanation reaction. The nickel loading was 5 wt. % and ruthenium loading is 0.5wt. %. The catalysts were prepared by successive impregnation method using Ni(NO3)2.6H2O and Ru(NO)(NO3)3 as precursors. The calcined support was impregnated with Ni(NO3)2.6H2O, dried, calcined at 600°C for 4h, and afterward, was impregnated with Ru(NO)(NO3)3. The resulting solid was dried and calcined at 600°C for 4 h. Supported monometallic catalysts were prepared likewise. The prepared solids Ru(0.5%)/CeO2, Ni(5%)/CeO2 and Ru(0.5%)-Ni(5%)/CeO2 were then reduced prior to the catalytic test under a flow of 50% H2/Ar (50 ml/min) for 4h at 500°C. Finally, their catalytic performances were evaluated in the CO2 methanation reaction, in the temperature range of 100–350°C by using a gaseous mixture of CO2 (10%) and H2 (40%) in Ar balanced at a total flow rate of 100 mL/min. The effect of pressure on the CO2 methanation was studied by varying the pressure between 1 and 10 bar. The various catalysts showed negligible CO2 conversion at temperatures lower than 250°C. The conversion of CO2 increases with increasing reaction temperature. The addition of Ru as promoter to Ni/CeO2 improved the CO2 methanation. It was shown that the CO2 conversion increases from 15 to 70% at 350°C and 1 bar. The effect of pressure on CO2 conversion was also studied. Increasing the pressure from 1 to 5 bar increases the CO2 conversion from 70% to 87%, while increasing the pressure from 5 to 10 bar increases the CO2 conversion from 87% to 91%. Ru–Ni catalysts showed excellent catalytic performance in the methanation of carbon dioxide with respect to Ni catalysts. Therefore the addition of Ru onto Ni catalysts improved remarkably the catalytic activity of Ni catalysts. It was also found that the pressure plays an important role in improving the CO2 methanation.

Keywords: CO2, methanation, nickel, ruthenium

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Authors: Safa'a M. Rasheed, Saba A. Gheni, Wadood T. Mohamed

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Phenolic compounds are the most carcinogenic pollutants in waste water in effluents of refineries and pulp industry. Catalytic wet air oxidation is an efficient industrial treatment process to oxidize phenolic compounds into unharmful organic compounds. Mode of flow of the fluid to be treated is a dominant factor in determining effectiveness of the catalytic process. The present study aims to obtain a mathematical model describing the conversion of phenolic compounds as a function of the process variables; mode of flow (trickling and pulsing), temperature, pressure, along with a high concentration of phenols and a platinum supported alumina catalyst. The model was validated with the results of experiments obtained in a fixed bed reactor. High pressure and temperature were employed at 8 bar and 140 °C. It has been found that conversion of phenols is highly influenced by mode of flow and the change is caused by changes occurred in hydrodynamic regime at the time of pulsing flow mode, thereby a temporal variation in wetting efficiency of platinum prevails; which in turn increases and/or decreases contact time with phenols in wastewater. The model obtained was validated with experimental results, and it is found that the model is a good agreement with the experimental results.

Keywords: wastewater, phenol, pulsing flow, wet oxidation, high pressure

Procedia PDF Downloads 111

Authors: Vaclav Heral

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Ideas about the mechanism of heterogeneous catalytic hydrogenation are diverse. The Horiuti-Polanyi mechanism is most often referred to, based on the idea of a semi-hydrogenated state. In our opinion, it does not represent a satisfactory explanation of the hydrogenation mechanism, because, for example: (1) It neglects the fact that the bond of atomic hydrogen to the metal surface is strongly polarized, (2) It does not explain why a surface deprived of atomic hydrogen (by thermal desorption or by alkyne) loses isomerization capabilities, but hydrogenation capabilities remain preserved, (3) It was observed that during the hydrogenation of 1-alkenes, the reaction can be of the 0th order to hydrogen and to the alkene at the same time, which is excluded during the competitive adsorption of both reactants on the catalyst surface. We offer an alternative mechanism that satisfactorily explains many of the ambiguities: It is the idea of an independent course of olefin isomerization, catalyzed by acidic atomic hydrogen bonded on the surface of the catalyst, in addition to the hydrogenation itself, in which a two-layer complex appears on the surface of the catalyst: olefin bound to the surface and molecular hydrogen bound to it in the second layer. The rate-determining step of hydrogenation is the conversion of this complex into the final product. We believe that the Horiuti-Polanyi mechanism is flawed and we naturally think that our two-layer theory better describes the experimental findings.

Keywords: acidity of hydrogenation catalyst, Horiuti-Polanyi, hydrogenation, two-layer hydrogenation

Procedia PDF Downloads 45

Authors: Nan Hu, Chao Wang, Xi Li, Xuehai Zhou

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The field-programmable gate array (FPGA) has been widely adopted in the high-performance computing domain. In recent years, the embedded system-on-a-chip (SoC) contains coarse granularity multi-core CPU (central processing unit) and mobile GPU (graphics processing unit) that can be used as general-purpose accelerators. The motivation is that algorithms of various parallel characteristics can be efficiently mapped to the heterogeneous architecture coupled with these three processors. The CPU and GPU offload partial computationally intensive tasks from the FPGA to reduce the resource consumption and lower the overall cost of the system. However, in present common scenarios, the applications always utilize only one type of accelerator because the development approach supporting the collaboration of the heterogeneous processors faces challenges. Therefore, a systematic approach takes advantage of write-once-run-anywhere portability, high execution performance of the modules mapped to various architectures and facilitates the exploration of design space. In this paper, A servant-execution-flow model is proposed for the abstraction of the cooperation of the heterogeneous processors, which supports task partition, communication and synchronization. At its first run, the intermediate language represented by the data flow diagram can generate the executable code of the target processor or can be converted into high-level programming languages. The instantiation parameters efficiently control the relationship between the modules and computational units, including two hierarchical processing units mapping and adjustment of data-level parallelism. An embedded system of a three-dimensional waveform oscilloscope is selected as a case study. The performance of algorithms such as contrast stretching, etc., are analyzed with implementations on various combinations of these processors. The experimental results show that the heterogeneous computing system with less than 35% resources achieves similar performance to the pure FPGA and approximate energy efficiency.

Keywords: FPGA-CPU-GPU collaboration, design space exploration, heterogeneous computing, intermediate language, parameterized instantiation

Procedia PDF Downloads 79

Authors: L. M. Ombaka, R. S. Oosthuizen, P. G. Ndungu, V. O. Nyamori

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Understanding the role of nitrogen species on the catalytic properties of nitrogen-doped carbon nanotubes (N-CNTs) as catalysts supports is critical as nitrogen species influence the support’s properties. To evaluate the influence of pyrrolic nitrogen on the physicochemical properties and catalytic activity of N-CNTs supported Pd (Pd/N-CNTs); N-CNTs containing varying pyrrolic contents were synthesized. The catalysts were characterised by the use of transmission electron microscope (TEM), scanning electron microscope, X-ray photoelectron spectroscopy (XPS), X-ray diffraction, Fourier transform infrared spectroscopy, and temperature programmed reduction. TEM analysis showed that the Pd nanoparticles were mainly located along the defect sites on N-CNTs. XPS analysis revealed that the abundance of Pd0 decreased while that of Pd2+ increased as the quantity of pyrrolic nitrogen increased. The increase of Pd2+ species was accredited to the formation of stable Pd-N coordination complexes which prevented further reduction of Pd2+ to Pd0 during synthesis. The formed Pd-N complexes increased the stability and dispersion of Pd2+ nanoparticles. The selective hydrogenation of nitrobenzophenone to aminobenzophenone over Pd/N-CNTs was compared to that of Pd on carbon nanotubes (Pd/CNTs). Pd/N-CNTs showed a higher catalytic activity and selectivity compared with Pd/CNTs. Pyrrolic nitrogen functional groups significantly promoted the selectivity towards aminobenzophenone formation.

Keywords: pyrrolic N-CNTs, hydrogenation reactions, chemical vapour deposition technique

Procedia PDF Downloads 332

Authors: Adewoyin O. Olusegun, Emmanuel O. Joshua, Marvel L. Akinyemi

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The heterogeneous nature of the subsurface requires the use of factual information to deal with rather than assumptions or generalized equations. Therefore, there is need to determine the actual rate of settlement possible in the soil before structures are built on it. This information will help in determining the type of foundation design and the kind of reinforcement that will be necessary in constructions. This paper presents a simplified and a faster approach for determining foundation settlement in any type of soil using real field data acquired from seismic refraction techniques and cone penetration tests. This approach was also able to determine the depth of settlement of each strata of soil. The results obtained revealed the different settlement time and depth of settlement possible.

Keywords: heterogeneous, settlement, foundation, seismic, technique

Procedia PDF Downloads 407