Search results for: heterogeneous catalytic hydroesterification

Authors: M. Shopska, D. Paneva, G. Kadinov, Z. Cherkezova-Zheleva, I. Mitov

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The iron containing materials are used as catalysts in different processes. The chemical methods of their synthesis use toxic and expensive chemicals; sophisticated devices; energy consumption processes that raise their cost. Besides, dangerous waste products are formed. At present time such syntheses are out of date and wasteless technologies are indispensable. The bioinspired technologies are consistent with the ecological requirements. Different microorganisms participate in the biomineralization of the iron and some phytochemicals are involved, too. The methods for biogenic production of iron containing materials are clean, simple, nontoxic, realized at ambient temperature and pressure, cheaper. The biogenic iron materials embrace different iron compounds. Due to their origin these substances are nanosized, amorphous or poorly crystalline, porous and have number of useful properties like SPM, high magnetism, low toxicity, biocompatibility, absorption of microwaves, high surface area/volume ratio, active sites on the surface with unusual coordination that distinguish them from the bulk materials. The biogenic iron materials are applied in the heterogeneous catalysis in different roles - precursor, active component, support, immobilizer. The application of biogenic iron oxide materials gives rise to increased catalytic activity in comparison with those of abiotic origin. In our study we investigated the catalytic behavior of biomasses obtained by cultivation of Leptothrix bacteria in three nutrition media – Adler, Fedorov, and Lieske. The biomass composition was studied by Moessbauer spectroscopy and transmission IRS. Catalytic experiments on CO oxidation were carried out using in situ DRIFTS. Our results showed that: i) the used biomasses contain α-FeOOH, γ-FeOOH, γ-Fe2O3 in different ratios; ii) the biomass formed in Adler medium contains γ-FeOOH as main phase. The CO conversion was about 50% as evaluated by decreased integrated band intensity in the gas mixture spectra during the reaction. The main phase in the spent sample is γ-Fe2O3; iii) the biomass formed in Lieske medium contains α-FeOOH. The CO conversion was about 20%. The main phase in the spent sample is α-Fe2O3; iv) the biomass formed in Fedorov medium contains γ-Fe2O3 as main phase. CO conversion in the test reaction was about 19%. The results showed that the catalytic activity up to 200°C resulted predominantly from α-FeOOH and γ-FeOOH. The catalytic activity at temperatures higher than 200°C was due to the formation of γ-Fe2O3. The oxyhydroxides, which are the principal compounds in the biomass, have low catalytic activity in the used reaction; the maghemite has relatively good catalytic activity; the hematite has activity commensurate with that of the oxyhydroxides. Moreover it can be affirmed that catalytic activity is inherent in maghemite, which is obtained by transformation of the biogenic lepidocrocite, i.e. it has biogenic precursor.

Keywords: nanosized biogenic iron compounds, catalytic behavior in reaction of CO oxidation, in situ DRIFTS, Moessbauer spectroscopy

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Authors: S. Totong, P. Daorattanachai, N. Laosiripojana

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Lignin depolymerization into phenolic-based chemicals is an interesting process for utilizing and upgrading a benefit and value of lignin. In this study, the depolymerization reaction was performed to convert alkaline lignin into smaller molecule compounds. Fumed SiO₂ was used as a catalyst to improve catalytic activity in lignin decomposition. The important parameters in depolymerization process (i.e., reaction temperature, reaction time, etc.) were also investigated. In addition, gas chromatography with mass spectrometry (GC-MS), flame-ironized detector (GC-FID), and Fourier transform infrared spectroscopy (FT-IR) were used to analyze and characterize the lignin products. It was found that fumed SiO₂ catalyst led the good catalytic activity in lignin depolymerization. The main products from catalytic depolymerization were guaiacol, syringol, vanillin, and phenols. Additionally, metal supported on fumed SiO₂ such as Cu/SiO₂ and Ni/SiO₂ increased the catalyst activity in terms of phenolic products yield.

Keywords: alkaline lignin, catalytic, depolymerization, fumed SiO₂, phenolic-based chemicals

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Authors: Jianwen Li, Hongfang Ma, Haitao Zhang, Qiwen Sun, Weiyong Ying

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Catalytic cracking of butene to propylene was carried out in a continuous-flow fixed-bed reactor over HZSM-5 catalysts modified by nickel and phosphorus. The structure and acidity of catalysts were measured by N2 adsorption, NH3-TPD and XPS. The results revealed that surface area and strong acid sites both decreased with increasing phosphorus loadings. The increment of phosphorus loadings reduced the butene conversion but enhanced the propylene selectivity and catalyst stability.

Keywords: butene, catalytic cracking, HZSM-5, modification

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Authors: Khaled Alshammari

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A facile approach to synthesizing highly active and stable Au/NiO catalysts for the hydrogenation of nitro-aromatics is reported. Preformed gold nanoparticles have been immobilized onto NiO using a colloidal method. In this article, the reduction of 4-nitrophenol with NaBH4 has been used as a model reaction to investigate the catalytic activity of synthesized Au/NiO catalysts. In addition, we report a systematic study of the reduction kinetics and the influence of specific reaction parameters such as (i) temperature, (ii) stirring rate, (iii) sodium borohydride concentration and (iv) substrate/metal molar ratio. The reaction has been performed at a substrate/metal molar ratio of 7.4, a ratio significantly higher than previously reported. The reusability of the catalyst has been examined, with little to no decrease in activity observed over 5 catalytic cycles. Systematic variation of Au loading reveals the successful synthesis of low-cost and efficient Au/NiO catalysts at very low Au content and using high substrate/metal molar ratios.

Keywords: nonochemistry, catalyst, nanoparticles supported, characterization of materials, colloidal nanoparticles

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Authors: Srinivasapriyan Vijayan

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Phenol is one of the most vital chemical in industry. Nowadays, phenol production is based upon the three-step cumene process, which involves a hazardous cumene hydroperoxide intermediate and produces nearly equimolar amounts of acetone as a coproduct. An attractive route in phenol production is the direct one-step selective hydroxylation of benzene using eco-friendly oxidants such as O2, N2O, and H2O2. In particular, the direct hydroxylation of benzene to form phenol with O2 has recently attracted extensive research attention because this process is green clean and eco-friendly. However, most of the catalytic systems involving O2 have a low rate of hydroxylation because the direct introduction of hydroxyl functionality into benzene is challenging. Almost all the developed catalytic systems require an elevated temperature and suffer from low conversion because of the notoriously low reactivity of aromatic C–H bonds. Moreover, increased reactivity of phenol relative to benzene makes the selective oxidation of benzene to phenol very difficult, especially under heating conditions. Hollow spheres, a very fascinating class of materials with good permeation and low density, highly monodisperse MOF hollow sandwich spheres have been rationally synthesized using monodisperse polystyrene (PS) nanoparticles as templates through a versatile step-by-step self-assembly strategy. So, our findings could pave the way toward highly efficient nonprecious catalysts for low-temperature oxidation reactions in heterogeneous catalysis. Because it is easy post-reaction separation, its cheap, green and recyclable.

Keywords: benzene hydroxylation, Fe-based metal organic frameworks, molecular oxygen, phenol

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Authors: Y. J. Song, Q. S. Xu, X. C. Wang, H. Wang, C. Q. Li

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The catalyst of copper oxide loaded on HZSM-5 was developed for nitrous oxide (N₂O) direct decomposition. The kinetic of nitrous oxide decomposition was studied for CuO/HZSM-5 catalyst prepared by incipient wetness impregnation method. The external and internal diffusion of catalytic reaction were considered in the investigation. Experiment results indicated that the external diffusion was basically eliminated when the reaction gas mixture gas hourly space velocity (GHSV) was higher than 9000h⁻¹ and the influence of the internal diffusion was negligible when the particle size of the catalyst CuO/HZSM-5 was small than 40-60 mesh. The experiment results showed that the kinetic of catalytic decomposition of N₂O was a first-order reaction and the activation energy and the pre-factor of the kinetic equation were 115.15kJ/mol and of 1.6×109, respectively.

Keywords: catalytic decomposition, CuO/HZSM-5, kinetic, nitrous oxide

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Authors: Liang-Yi Lin, Hsunling Bai

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In this work, transition metal (metal= Co, Fe, Ni, Cu, and Mn) modified cerium oxide catalysts supported on mesoporous aluminosilicate particles (Ce/Al-MSPs) were prepared using waste silicate as the precursors through aerosol-assisted flow process, and their catalytic performances were investigated for acetone incineration. Tests on the bimetallic Ce/Al-MSPs and Mn/Al-MSPs and trimetallic Mn-Ce, Fe-Ce, Co-Ce, Ni-Ce, and Cu-Ce/Al-MSPs in the temperature range of 100-300 oC demonstrated that Ce was the main active metal while Mn acted as a suitable promoter in acetone incineration reactions. Among tested catalysts, Mn-Ce/Al-MSPs with a Mn/Ce molar ratio of 2/1 exhibited the highest acetone catalytic activity. Moreover, the synergetic effect was observed for trimetallic Mn-Ce/Al-MSPs on the acetone removal as compared to the bimetallic Ce/Al-MSPs or Mn/Al-MSPs catalysts.

Keywords: acetone, catalytic oxidation, cerium oxide, mesoporous silica

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Authors: Tappei Yotsumoto, Atsushi Nomura, Kozo Tanigawa, Kenichi Takahashi, Takao Kawamura, Kazunori Sugahara

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In a human tracking system, expanding a monitoring range of one system is complicating the management of devices and increasing its cost. Therefore, we propose a method to realize a wide-range human tracking by connecting small systems. In this paper, we examined an agent deploy method and information contents across the heterogeneous human tracking systems. By implementing the proposed method, we can construct a human tracking system across heterogeneous systems, and the system can track a target continuously between systems.

Keywords: human tracking system, mobile agent, monitoring, heterogeneous systems

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Authors: Serges Mendomo Meye, Li Guowei, Shen Zhenzhong, Gan Lei, Xu Liqun

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Due to the characteristics of high-heap and large-volume, the complex layers of waste and the high-water level of leachate, environmental pollution, and slope instability are easily produced. It is therefore of great significance to research the heterogeneous seepage field and stability of landfills. This paper focuses on the heterogeneous characteristics of the landfill piles and analyzes the seepage field and slope stability of the landfill using statistical and numerical analysis methods. The calculated results are compared with the field measurement and literature research data to verify the reliability of the model, which may provide the basis for the design, safe, and eco-friendly operation of the landfill. The main innovations are as follows: (1) The saturated-unsaturated seepage equation of heterogeneous soil is derived theoretically. The heterogeneous landfill is regarded as composed of infinite layers of homogeneous waste, and a method for establishing the heterogeneous seepage model is proposed. Then the formation law of the stagnant water level of heterogeneous landfills is studied. It is found that the maximum stagnant water level of landfills is higher when considering the heterogeneous seepage characteristics, which harms the stability of landfills. (2) Considering the heterogeneity weight and strength characteristics of waste, a method of establishing a heterogeneous stability model is proposed, and it is extended to the three-dimensional stability study. It is found that the distribution of heterogeneous characteristics has a great influence on the stability of landfill slope. During the operation and management of the landfill, the reservoir bank should also be considered while considering the capacity of the landfill.

Keywords: heterogeneous characteristics, leachate levels, saturated-unsaturated seepage, seepage field, slope stability

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Authors: Ts. Lazarova, V. Tumbalev, S. Atanacova-Vladimirova, G. Ivanov, A. Naydenov, D. Kovacheva

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Methane is a major Greenhouse Gas (GHG) that accounts for 14% of the world’s total amount of GHG emissions, originating mainly from agriculture, Coal mines, land fields, wastewater and oil and gas facilities. Nowadays the problem caused by the methane emissions has been a subject of an increased concern. One of the methods for neutralization of the methane emissions is it's complete catalytic oxidation. The efforts of the researchers are focused on the development of new types of catalysts and optimizing the existing catalytic systems in order to prevent the sintering of the palladium, providing at the same time a sufficient activity at temperatures below 500oC. The aim of the present work is to prepare mixed Cu-Ag-Pd oxide catalysts supported on alumina and to test them for methane complete catalytic oxidation. Cu-Ag-Pd/Al2O3 were prepared on a γ-Al2O3 (BET surface area = 220 m2/g) by the incipient wetness method using the corresponding metal nitrates (Cu:Ag = 90:10, Cu:Pd =97:3, Cu:Ag:Pd= 87:10:3) as precursors. A second set of samples were prepared with addition of urea to the metal nitrate solutions with the above mentioned ratios assuming increased dispersivity of the catalysts. The catalyst samples were dried at 100°C for 3 hours and calcined at 550°C for 30 minutes. Catalysts samples were characterized using X-ray diffraction (XRD), low temperature adsorption of nitrogen (BET) and scanning electron microscopy (SEM). The catalytic activity tests were carried out in a continuous flow type of reactor at atmospheric pressure. The effect of catalyst aging at 500 oC for 120 h on the methane combustion activity was also investigated. The results clearly indicate the synergetic effect of Ag and Pd on the catalytic activity.

Keywords: catalysts, XRD, BET, SEM, catalytic oxidation

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Authors: Sungho Kim, Dae Shik Kim, Jong Min Lee

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Fluid catalytic cracking (FCC) process is one of the most important process in modern refinery indusrty. This paper focuses on the fluid catalytic cracking (FCC) process. As the FCC process is difficult to model well, due to its nonlinearities and various interactions between its process variables, rigorous process modeling of whole FCC plant is demanded for control and plant-wide optimization of the plant. In this study, a process design for the FCC plant includes riser reactor, main fractionator, and gas processing unit was developed. A reactor model was described based on four-lumped kinetic scheme. Main fractionator, gas processing unit and other process units are designed to simulate real plant data, using a process flowsheet simulator, Aspen PLUS. The custom reactor model was integrated with the process flowsheet simulator to develop an integrated process model.

Keywords: fluid catalytic cracking, simulation, plant data, process design

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Authors: O. P. Yadav

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Nano-size Ag-N co-doped ZnO/CuO composite photo-catalyst has been synthesized by chemical method and characterized using XRD, TEM, FTIR, AAS and UV-Vis spectroscopic techniques. Photo-catalytic activity of as-synthesized nanomaterial has been studied using degradation of methyl orange as a probe under UV as well as visible radiations. Ag-N co-doped ZnO/CuO composite showed higher photo-catalytic activity than Ag- or N-doped ZnO and undoped ZnO-CuO composite photo-catalysts. The observed highest activity of Ag-N co-doped ZnO-CuO among the studied photo-catalysts is attributed to the cumulative effects of lowering of band-gap energy and decrease of recombination rate of photo-generated electrons and holes owing to doped N and Ag, respectively. Effects of photo-catalyst load, pH and substrate initial concentration on degradation of methyl orange have also been studied. Photo-catalytic degradation of methyl orange follows pseudo first order kinetics.

Keywords: degradation, nanocomposite, photocatalyst, spectroscopy, XRD

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Authors: Caroline Alice Rouget-Virbel, F. Dean Toste

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Heterobimetallic systems have been precedented in a wide array of bioinorganic and heterogeneous catalytic settings, in which cooperative bond-breaking and bond-forming events mediated by neighboring metal sites have been proposed but are challenging to study and characterize. Heterodinuclear transition-metal catalysis has recently emerged as a promising strategy to tackle challenging chemical transformations, including C−C and C−X couplings as well as small molecule activation. It has been shown that these reactions can traverse nontraditional mechanisms, reactivities, and selectivities when homo- and heterobimetallic systems are employed. Moreover, stoichiometric studies of transmetallation from gold complexes have demonstrated that R transfer from PPh3–Au(I)R to Cp- and Cp*-ligated group 8/9 complexes is a viable elementary step. With these considerations in mind, we hypothesized that heterobimetallic Au–M complexes could serve as a viable and tunable catalyst platform to explore mechanisms and reactivity. In this work, heterobimetallic complexes containing Au(I) centers tethered to Ir(III) and Rh(III) piano stool moieties were synthesized and characterized. Preliminary application of these complexes to a catalytic allylic arylation reaction demonstrates bimetallic cooperativity relative to their monomeric metal components.

Keywords: heterobimetallic, catalysis, gold, rhodium

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Authors: Ieva Gaide, Violeta Makareviciene

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Increasing environmental pollution is caused by various factors, including the usage of vehicles. Legislation is focused on the increased usage of renewable energy sources for fuel production. Electric car usage is also important; however, it is relatively new and expensive transport. It is necessary to increase the amount of renewable energy in the production of diesel fuel, whereas many agricultural machineries are powered by diesel, as are water vehicles. For this reason, research on biodiesel production is relevant. The majority of studies globally are related to the improvement of conventional biofuel production technologies by applying the transesterification process of oil using alcohol and catalyst. Some of the more recent methods to produce biodiesel are based on heterogeneous catalysis, which has the advantage of easy separation of catalyst from the final product. It is known that a large amount of eggshells is treated as waste; therefore, it is eliminated in landfills without any or with minimal pre-treatment. CaO, which is known as a good catalyst for biodiesel synthesis, is a key component of eggshells. In the present work, we evaluated the catalytic efficiency of eggshells and determined the optimal transesterification conditions to obtain biodiesel that meets the standards. Content CaO in eggshells was investigated. Response surface methodology was used to determine the optimal reaction conditions. Three independent variables were investigated: the molar ratio of alcohol to oil, the amount of the catalyst, and the duration of the reaction. It was obtained that the optimum transesterification conditions when the methanol and eggshells as a heterogeneous catalyst are used and the process temperature is 64°C are the following: the alcohol-to-oil molar ratio 10.93:1, the reaction duration 9.48 h, and the catalyst amount 6.80 wt%. Under these conditions, 97.79 wt% of the ester yield was obtained.

Keywords: heterogeneous catalysis, eggshells, biodiesel, oil

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Authors: Yiwei Li, Mingyu Gao

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Integrating hybrid memories with heterogeneous processors could leverage heterogeneity in both compute and memory domains for better system efficiency. To ensure performance isolation, we introduce Hydrogen, a hardware architecture to optimize the allocation of hybrid memory resources to heterogeneous CPU-GPU systems. Hydrogen supports efficient capacity and bandwidth partitioning between CPUs and GPUs in both memory tiers. We propose decoupled memory channel mapping and token-based data migration throttling to enable flexible partitioning. We also support epoch-based online search for optimized configurations and lightweight reconfiguration with reduced data movements. Hydrogen significantly outperforms existing designs by 1.21x on average and up to 1.31x.

Keywords: hybrid memory, heterogeneous systems, dram cache, graphics processing units

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Authors: Faezeh Aghazadeh

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The catalytic activity of Pt/γ-Al₂O₃ and Pt-Fe/γ-Al₂O₃ catalysts was investigated to bring about the complete oxidation of 2-Propanol. Among them, Pt-Fe/γ-Al₂O₃ was found to be the most promising catalyst based on activity. The catalysts were characterized by (XRD), (SEM), (TEM) and ICP-AES techniques. Iron loadings on Pt/γ-Al₂O₃ had a great effect on catalytic activity, and Pt-Fe/γ-Al₂O₃ (1.75 wt% Fe) catalyst at calcination temperature 300°C was observed to be the most active, which might be contributed to the favorable synergetic effects between Pt and Fe, high activity and the well-dispersed bimetallic phase. The combustion of 2-Propanol in the vapor phase was carried out in a conventional flow U-shape glass reactor used in the differential mode at atmospheric pressure. 2-Propanol was analyzed by a gas chromatograph VARIAN 3800 CX equipped with an FID. As observed, better performance and activity were observed for Pt-Fe/Al₂O₃ bimetallic catalyst. These results indicate that the high dispersion on support gives a positive effect on catalytic activity.

Keywords: volatile organic compounds, bimetallic catalyst, catalytic activity, low temperature

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Authors: S. F. H. Tasfy, N. A. M. Zabidi, M.-S. Shaharun

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Utilization of CO2 as a carbon source to produce valuable chemicals is one of the important ways to reduce the global warming caused by increasing CO2 in the atmosphere. Supported metal catalysts are crucial for the production of clean and renewable fuels and chemicals from the stable CO2 molecules. The catalytic conversion of CO2 into methanol is recently under increased scrutiny as an opportunity to be used as a low-cost carbon source. Therefore, series of the bimetallic Cu/ZnO-based catalyst supported by SBA-15 were synthesized via impregnation technique with different total metal loading and tested in the catalytic hydrogenation of CO2 to methanol. The morphological and textural properties of the synthesized catalysts were determined by transmission electron microscopy (TEM), temperature programmed desorption, reduction, oxidation and pulse chemisorption (TPDRO), and N2-adsorption. The CO2 hydrogenation reaction was performed in microactivity fixed-bed system at 250 °C, 2.25 MPa, and H2/CO2 ratio of 3. Experimental results showed that the catalytic structure and performance was strongly affected by the loading of the active site. Where, the catalytic activity, methanol selectivity as well as the space-time yield increased with increasing the metal loading until it reaches the maximum values at a metal loading of 15 wt% while further addition of metal inhibits the catalytic performance. The higher catalytic activity of 14 % and methanol selectivity of 92 % were obtained over Cu/ZnO-SBA-15 catalyst with total bimetallic loading of 15 wt%. The excellent performance of 15 wt% Cu/ZnO-SBA-15 catalyst is attributed to the presence of well disperses active sites with small particle size, higher Cu surface area, and lower catalytic reducibility.

Keywords: hydrogenation of carbon dioxide, methanol synthesis, metal loading, Cu/ZnO-SBA-15 catalyst

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Authors: Supakorn Tantisriyanurak, Hussaya Maneesuwan, Thanyalak Chaisuwan, Sujitra Wongkasemjit

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TUD-1 is a siliceous mesoporous material with a three-dimensional amorphous structure of random, interconnecting pores, large pore size, high surface area (400-1000 m2/g), hydrothermal stability, and tunable porosity. However, the significant disadvantage of the mesoporous silicates is few catalytic active sites. In this work, a series of bimetallic Fe and Ti incorporated into TUD-1 framework is successfully synthesized by sol–gel method. The synthesized Fe,Ti-TUD-1 is characterized by various techniques. To study the catalytic activity of Fe, Ti–TUD-1, phenol hydroxylation was selected as a model reaction. The amounts of residual phenol and oxidation products were determined by high performance liquid chromatography coupled with UV-detector (HPLC-UV).

Keywords: iron, phenol hydroxylation, titanium, TUD-1

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Authors: J. Franco Macías, E. Montes Alba, A. López Vásquez

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The growing development in the poultry industry has generated a strong and adverse impact on quality and availability of water resources. Inside this industry, is finding out the treatment of by-products such as feathers, viscera and blood demanding highly water consumption, generating contaminant discharges as well. As one of current of treatment of by-products is the effluent of cooking condensate steam that has contaminant organic load; therefore, it is necessary to implement removal treatments before discharging it toward water sources. The photo catalysis appears as a promising alternative of treatment due to the different advantages it has, among others, includes low cost, easily operation, high efficiency and elimination of a wide variety of contaminants in a watery environment. This study has evaluated a heterogeneous photo catalytic treatment for removal contaminant organic load. This process was developed in oxidation and reduction conditions. It was analyzed the effect of factors such as pH, catalyst and sacrifice agent concentration. Finally, good conditions to removal contaminant organic load were achieved to determine percentage of contaminant organic load by means of response surface methodology.

Keywords: poultry industry, advanced oxidation process, photocatalysis, photodegradation, TiO2

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Authors: Sungho Kim, Dae Shik Kim, Jong Min Lee

Abstract:

Fluid catalytic cracking (FCC) process is one of the most important process in modern refinery industry. This paper focuses on the fluid catalytic cracking (FCC) process. As the FCC process is difficult to model well, due to its non linearities and various interactions between its process variables, rigorous process modeling of whole FCC plant is demanded for control and plant-wide optimization of the plant. In this study, a process design for the FCC plant includes riser reactor, main fractionator, and gas processing unit was developed. A reactor model was described based on four-lumped kinetic scheme. Main fractionator, gas processing unit and other process units are designed to simulate real plant data, using a process flow sheet simulator, Aspen PLUS. The custom reactor model was integrated with the process flow sheet simulator to develop an integrated process model.

Keywords: fluid catalytic cracking, simulation, plant data, process design

Procedia PDF Downloads 491

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

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In this paper, we propose a new packing strategy to find free resources for run-time mapping of application tasks on NoC-based Heterogeneous MPSoCs. The proposed strategy minimizes the task mapping time in addition to placing the communicating tasks close to each other. To evaluate our approach, a comparative study is carried out. Experiments show that our strategy provides better results when compared to latest dynamic mapping strategies reported in the literature.

Keywords: heterogeneous MPSoCs, NoC, dynamic mapping, routing

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Authors: Agnieszka S. Dzielendziak, Lindsay-Marie Armstrong, Matthew E. Potter, Robert Raja, Pier J. A. Sazio

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Reducing carbon dioxide, CO₂, is one of the greatest global challenges. Conversion of CO₂ for utilisation across synthetic fuel, pharmaceutical, and agrochemical industries offers a promising option, yet requires significant research to understanding the complex multiscale processes involved. To experimentally understand and optimize such processes at that catalytic sites and exploring the impact of the process at reactor scale, is too expensive. Computational methods offer significant insight and flexibility but require a more detailed multi-scale approach which is a significant challenge in itself. This work introduces a computational approach which incorporates detailed catalytic models, taken from experimental investigations, into a larger-scale computational flow dynamics framework. The reactor-scale species transport approach is modified near the catalytic walls to determine the influence of catalytic clustering regions. This coupling approach enables more accurate modelling of velocity, pressures, temperatures, species concentrations and near-wall surface characteristics which will ultimately enable the impact of overall reactor design on chemical conversion performance.

Keywords: catalysis, CCU, CO₂, multi-scale model

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Authors: Silviya Todorova, Anton Naydenov, Ralitsa Velinova, Alexander Larin

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Catalytic combustion of methane has been extensively investigated for emission control and power generation during the last decades. The alumina-supported palladium catalyst is widely accepted as the most active catalysts for catalytic combustion of methane. The activity of Pd/Al₂O₃ decreases during the time on stream, especially underwater vapor. The following order of activity in the reaction of complete oxidation of methane was established: Co₃O₄> CuO>NiO> Mn₂O₃> Cr₂O₃. It may be expected that the combination between Pd and these oxides could lead to the promising catalysts in the reaction of complete methane. In the present work, we investigate the activity of Pd/Al₂O₃ catalysts promoted with other metal oxides (MOx; M= Ni, Co, Ce). The Pd-based catalysts modified by metal oxide were prepared by sequential impregnation of Al₂O₃ with aqueous solutions of Me(NO₃)₂.6H₂O and Pd(NO₃)₂H₂O. All samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). An improvement of activity was observed after modification with different oxides. The results demonstrate that the Pd/Al₂O₃ catalysts modified with Co and Ce by impregnation with a common solution of respective salts, exhibit the most promising catalytic activity for methane oxidation. Most probably, the presence of Co₃O₄ and CeO₂ on catalytic surface increases surface oxygen and therefore leads to the better reactivity in methane combustion.

Keywords: methane combustion, palladium, Co-Ce, Ni-Ce

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Authors: Mariam Alsharifi, Hussein Znad, Ming Ang

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Considering the environmental issues and the shortage in the conventional fossil fuel sources, biodiesel has gained a promising solution to shift away from fossil based fuel as one of the sustainable and renewable energy. It is synthesized by transesterification of vegetable oils or animal fats with alcohol (methanol or ethanol) in the presence of a catalyst. This study focuses on synthesizing a high efficient Li/TiO2 heterogeneous catalyst for biodiesel production from canola oil. In this work, lithium immobilized onto TiO2 by the simple impregnation method. The catalyst was evaluated by transesterification reaction in a batch reactor under moderate reaction conditions. To study the effect of Li concentrations, a series of LiNO3 concentrations (20, 30, 40 wt. %) at different calcination temperatures (450, 600, 750 ºC) were evaluated. The Li/TiO2 catalysts are characterized by several spectroscopic and analytical techniques such as XRD, FT-IR, BET, TG-DSC and FESEM. The optimum values of impregnated Lithium nitrate on TiO2 and calcination temperature are 30 wt. % and 600 ºC, respectively, along with a high conversion to be 98 %. The XRD study revealed that the insertion of Li improved the catalyst efficiency without any alteration in structure of TiO2 The best performance of the catalyst was achieved when using a methanol to oil ratio of 24:1, 5 wt. % of catalyst loading, at 65◦C reaction temperature for 3 hours of reaction time. Moreover, the experimental kinetic data were compatible with the pseudo-first order model and the activation energy was (39.366) kJ/mol. The synthesized catalyst Li/TiO2 was applied to trans- esterify used cooking oil and exhibited a 91.73% conversion. The prepared catalyst has shown a high catalytic activity to produce biodiesel from fresh and used oil within mild reaction conditions.

Keywords: biodiesel, canola oil, environment, heterogeneous catalyst, impregnation method, renewable energy, transesterification

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Authors: Yalçın Kılıç, İbrahim Kani

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The conversion of hydrocarbons to carbonyl compounds by oxidation reaction is one of the most important reactions in the synthesis of fine chemicals. As a result of the oxidation of hydrocarbons containing aliphatic sp3-CH groups in their structures, aldehydes, ketones or carboxylic acids can be obtained. In this study, OSSO-type 2,2'-[1,4-butanedylbis(thio)]bis-benzoic acid (tsabutH2) ligand and [Zn(µ-tsabut)(phen)]n complex (where phen = 1,10-phenantroline) were synthesized and their structures were characterized by single crystal x-ray diffraction method. The catalytic efficiency of the complex in the catalytic oxidation studies of organic compounds such as cyclohexane, ethylbenzene, diphenylmethane, and p-xylene containing sp3-C-H in its structure was investigated.

Keywords: metal complex, OSSO-type ligand, catalysis, oxidation

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Authors: Naime Boudemagh

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In this work, we aim to improve the detection performances of radar systems. To this end, we propose and analyze a novel censoring technique of undesirable samples, of priori unknown positions, that may be present in the environment under investigation. Therefore, we consider heterogeneous backgrounds characterized by the presence of some irregularities such that clutter edge transitions and/or interfering targets. The proposed detector, termed automatic censoring constant false alarm (AC-CFAR), operates exclusively in a Gaussian background. It is built to allow the segmentation of the environment to regions and switch automatically to the appropriate detector; namely, the cell averaging CFAR (CA-CFAR), the censored mean level CFAR (CMLD-CFAR) or the order statistic CFAR (OS-CFAR). Monte Carlo simulations show that the AC-CFAR detector performs like the CA-CFAR in a homogeneous background. Moreover, the proposed processor exhibits considerable robustness in a heterogeneous background.

Keywords: CFAR, automatic censoring, heterogeneous environments, radar systems

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Authors: Luqman Ali Shah, Murtaza Sayed, Mohammad Siddiq

Abstract:

Three-dimensional cross-linked polymer microgels with temperature responsive N-isopropyl acrylamide (NIPAM) and pH-sensitive methacrylic acid (MAA) were successfully synthesized by free radical emulsion polymerization with different amount of MAA. Silver and gold nanoparticles with size of 6.5 and 3.5 nm (±0.5 nm) respectively were homogeneously reduced inside these materials by chemical reduction method at pH 2.78 and 8.36 for the preparation of hybrid materials. The samples were characterized by FTIR, DLS and TEM techniques. The catalytic activity of the hybrid materials was investigated for the reduction of 4-nitrophenol (4- NP) using NaBH4 as reducing agent by UV-visible spectroscopy. The hybrid polymer network synthesized at pH 8.36 shows enhanced catalytic efficiency compared to catalysts synthesized at pH 2.78. In this study, it has been explored that catalyst activity strongly depends on amount of MAA, synthesis pH and type of metal nanoparticles entrapped.

Keywords: cross-linked polymer microgels, free radical polymerization, metal nanoparticles, catalytic activity, comparative study

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Authors: Thidarat Imyen, Paisan Kongkachuichay

Abstract:

Cu-Zn/core-shell Al-MCM-41 catalyst with various copper species, prepared by a combination of three methods—substitution, ion-exchange, and impregnation, was studied for the selective catalytic reduction (SCR) of NO with NH3 at 300 °C for 150 min. In order to investigate the effects of Zn introduction on the nature of the catalyst, Cu/core-shell Al-MCM-41 and Zn/core-shell Al-MCM-41 catalysts were also studied. The roles of Zn promoter in the acidity and the NOx adsorption properties of the catalysts were investigated by in situ Fourier transform infrared spectroscopy (FTIR) of NH3 and NOx adsorption, and temperature-programmed desorption (TPD) of NH3 and NOx. The results demonstrated that the acidity of the catalyst was enhanced by the Zn introduction, as exchanged Zn(II) cations loosely bonded with Al-O-Si framework could create Brønsted acid sites by interacting with OH groups. Moreover, Zn species also provided the additional sites for NO adsorption in the form of nitrite (NO2–) and nitrate (NO3–) species, which are the key intermediates for SCR reaction. In addition, the effect of Zn on the nature of copper was studied by in situ FTIR of CO adsorption and in situ X-ray adsorption near edge structure (XANES). It was found that Zn species hindered the reduction of Cu(II) to Cu(0), resulting in higher Cu(I) species in the Zn promoted catalyst. The Cu-Zn/core-shell Al-MCM-41 exhibited higher catalytic activity compared with that of the Cu/core-shell Al-MCM-41 for the whole reaction time, as it possesses the highest amount of Cu(I) sites, which are responsible for SCR catalytic activity. The Cu-Zn/core-shell Al-MCM-41 catalyst also reached the maximum NO conversion of 100% with the average NO conversion of 76 %. The catalytic performance of the catalyst was further improved by using Zn promoter in the form of ZnO instead of reduced Zn species. The Cu-ZnO/core-shell Al-MCM-41 catalyst showed better catalytic performance with longer working reaction time, and achieved the average NO conversion of 81%.

Keywords: Al-MCM-41, copper, nitrogen oxide, selective catalytic reduction, zinc

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Authors: Arne Koschel

Abstract:

This article discusses event monitoring options for heterogeneous event sources as they are given in nowadays heterogeneous distributed information systems. It follows the central assumption, that a fully generic event monitoring solution cannot provide complete support for event monitoring; instead, event source specific semantics such as certain event types or support for certain event monitoring techniques have to be taken into account. Following from this, the core result of the work presented here is the extension of a configurable event monitoring (Web) service for a variety of event sources. A service approach allows us to trade genericity for the exploitation of source specific characteristics. It thus delivers results for the areas of SOA, Web services, CEP and EDA.

Keywords: event monitoring, ECA, CEP, SOA, web services

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Authors: Abdel Ghany F. Shoair, Mai M. A. H. Shanab

Abstract:

The basic aqueous systems NiSO4.6H₂O / K₂S₂O₈ (PH= 14) or NiSO₄.6H₂O / KBrO₃ (PH = 11.5) were ‎investigated ‎for the ‎catalytic conversion benzyl alcohol and ‎some para-substituted benzyl ‎alcohols to their ‎corresponding ‎acids in 75-97 % yield at room ‎temperature. The active species ‎was isolated and characterized by scanning ‎electron ‎microscopy (SEM), ‎‎transmission electron microscopy (TEM), X-ray ‎powder diffraction, EDX and ‎‎FT-IR ‎techniques and identified as NiO₂ nanoparticles (NPNPs). The SEM and ‎TEM images of nickel peroxide samples show a fine spherical-like ‎aggregation of ‎NiO₂ molecules with a nearly homogeneous partial size and confirm the ‎aggregation's size ‎to ‎be in the range of 2-3 nm. The yields, turnover (TO) and turn ‎over frequencies (TOF) were calculated. ‎It was noticed ‎that the aromatic alcohols ‎containing para-substituted electron donation groups gave better ‎‎yields than ‎those having electron-withdrawing groups. The optimum conditions for this ‎‎catalytic reaction ‎were studied using benzyl alcohol as a model. The mechanism ‎of the ‎catalytic conversion reaction was ‎suggested, in which the produced ‎(NPNPs) convert alcohols ‎to acids in two steps through the formation of the ‎‎corresponding aldehyde. The produced ‎NiO, because of this conversion, is ‎converted again to (NPNPs) by ‎an excess of K₂S₂O₈ or KBrO₃. This ‎catalytic cycle continues ‎until all the substrate is oxidized.

Keywords: Nickel, oxidation, catalysts, benzyl alcohol

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