864 resultados para Fixed bed reactor


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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Fluidization consists in a bed of solid particles acquire fluid behavior by using a fluid (in this case air) flowing through the solid particles. Because of this, it can be a good mix of these materials, as well as to show increased rates of heat and mass transport. The fluid flowing through the spaces between the particles gives an interstitial velocity, that if is too low does not cause movement of the particulates. The gradual increase in speed will generate small vibrations between the particles promotes its fluidization. Our study focus in the fluid state of solid bed , when the fluid velocity reaches a state where the drag forces are sufficient to support the weight of the solid particles making these solids behave like fluids . Knowledge of the minimum velocity required to fluidize that particles is of great importance since below this speed there is no fluidization, and far above it, the solids are carried out of the bed. The fluidized bed reactor is widely used in physics and engineering, particularly in gas-solid fluidization, with emphasis on thermochemical processes

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Brazil has one of the largest cattle herds in the world, so the cattle slaughter is one of the most important economic activities in the Brazilian market. But this activity requires a high demand of water, resulting in serious problems about the correct disposal of wastewater generated in the process. This effluent has a high pollution load, becoming its receiving bodies (streams and rivers) unfit for various activities such as public water supply, recreation, fisheries. To minimize the environmental impacts of its industrial wastewater and fallow the local environmental legislation, refrigerators must make the treatment of these effluents. This study aimed to verify the efficiency of a enzymatic reactor, when occur hydrolysis of lipids present in the effluent industrial of an cattle slaughter industry. The treatment system used was composed of two separate reactors: one being the anaerobic fluidized bed reactor (AFBR), inoculated with immobilized enzymes on the matrix support, and the other by sequential batch reactor (SBR) inoculated with activated sludge. Whereas, the reactors have been developed and installed at the Wastewater Treatment Laboratory, Faculdade de Ciências e Tecnologia, UNESP, campus Presidente Prudente. The procedure operating occurred differently for each reactor: preparation and inoculation of enzyme granules, filling the reactor, hydrolysis, and AFBR emptying, filling, aerobic reaction, sedimentation, and emptying the SBR. We performed three experimental stages, with the first and second stage of the work were done reactor analyzes separately, and the third step of the analysis were made with the interconnected reactors... (Complete abstract electronic access below)

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Pós-graduação em Agronomia (Energia na Agricultura) - FCA

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The effect of ultrasound and osmotic dehydration pretreatments on papaya drying kinetics was investigated. The ultrasound pretreatment was carried out in an ultrasonic bath at 30 A degrees C. The osmotic pretreatment in sucrose solution was carried out in an incubator at 34 A degrees C and agitation of 80 rpm for 210 min. The drying process was conducted in a fixed bed dryer at 70 A degrees C. Experimental data were fitted successfully using the Page model for dried fresh and pretreated fruits, with coefficient of determination greater than 0.9992 and average relative error lower that 14.4 %. The diffusional model was used to describe the moisture transfer, and the effective water diffusivity was identified in the order of 10(-9) m(2) s(-1). It was found that drying rates of osmosed fruits were the lowest due to the presence of infused solutes, while the ultrasound pretreatment contributed to faster drying rates. Evaluation of the dried fruit was performed by means of total carotenoids retention. Ultrasound treatments in distilled water prior to air-drying gave rise to dried papayas with retention of carotenoids in the range 30.4-39.8 % and the ultrasonic-assisted osmotic dehydration of papayas showed carotenoids retention values up to 64.9 %, whereas the dried fruit without pretreatment showed carotenoids retention lower than 24 %.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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The removal of Pb2+ from aqueous solution by two Brazilian rocks that contain zeolites-amygdaloidal dacite (ZD) and sandstone (ZS)-was examined by batch experiments. ZD contains mordenite and ZS, stilbite. The effects of contact time, concentration of metal in solution and capacity of Na+ to recover the adsorbed metals were evaluated at room temperature (20A degrees C). The sorption equilibrium was reached in the 30 min of agitation time. Both materials removed 100% of Pb2+ from solutions at concentrations up to 50 mg/L, and at concentrations larger than 100 mg/L of Pb2+, the adsorption capacity of sandstone was more efficient than that of amygdaloidal dacite due to the larger quantities and the type of zeolites (stilbite) in the cement of this rock. All adsorbed Pb2+ was easily replaced by Na+ in both samples. The analysis of the adsorption models using nonlinear regression revealed that the Sips and the Freundlich isotherms provided the best fit for the ZS and ZD experimental data, respectively, indicating the heterogeneous adsorption surfaces of these zeolites.

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Selective oxidation is one of the simplest functionalization methods and essentially all monomers used in manufacturing artificial fibers and plastics are obtained by catalytic oxidation processes. Formally, oxidation is considered as an increase in the oxidation number of the carbon atoms, then reactions such as dehydrogenation, ammoxidation, cyclization or chlorination are all oxidation reactions. In this field, most of processes for the synthesis of important chemicals used vanadium oxide-based catalysts. These catalytic systems are used either in the form of multicomponent mixed oxides and oxysalts, e.g., in the oxidation of n-butane (V/P/O) and of benzene (supported V/Mo/O) to maleic anhydride, or in the form of supported metal oxide, e.g., in the manufacture of phthalic anhydride by o-xylene oxidation, of sulphuric acid by oxidation of SO2, in the reduction of NOx with ammonia and in the ammoxidation of alkyl aromatics. In addition, supported vanadia catalysts have also been investigated for the oxidative dehydrogenation of alkanes to olefins , oxidation of pentane to maleic anhydride and the selective oxidation of methanol to formaldehyde or methyl formate [1]. During my PhD I focused my work on two gas phase selective oxidation reactions. The work was done at the Department of Industrial Chemistry and Materials (University of Bologna) in collaboration with Polynt SpA. Polynt is a leader company in the development, production and marketing of catalysts for gas-phase oxidation. In particular, I studied the catalytic system for n-butane oxidation to maleic anhydride (fluid bed technology) and for o-xylene oxidation to phthalic anhydride. Both reactions are catalyzed by systems based on vanadium, but catalysts are completely different. Part A is dedicated to the study of V/P/O catalyst for n-butane selective oxidation, while in the Part B the results of an investigation on TiO2-supported V2O5, catalyst for o-xylene oxidation are showed. In Part A, a general introduction about the importance of maleic anhydride, its uses, the industrial processes and the catalytic system are reported. The reaction is the only industrial direct oxidation of paraffins to a chemical intermediate. It is produced by n-butane oxidation either using fixed bed and fluid bed technology; in both cases the catalyst is the vanadyl pyrophosphate (VPP). Notwithstanding the good performances, the yield value didn’t exceed 60% and the system is continuously studied to improve activity and selectivity. The main open problem is the understanding of the real active phase working under reaction conditions. Several articles deal with the role of different crystalline and/or amorphous vanadium/phosphorous (VPO) compounds. In all cases, bulk VPP is assumed to constitute the core of the active phase, while two different hypotheses have been formulated concerning the catalytic surface. In one case the development of surface amorphous layers that play a direct role in the reaction is described, in the second case specific planes of crystalline VPP are assumed to contribute to the reaction pattern, and the redox process occurs reversibly between VPP and VOPO4. Both hypotheses are supported also by in-situ characterization techniques, but the experiments were performed with different catalysts and probably under slightly different working conditions. Due to complexity of the system, these differences could be the cause of the contradictions present in literature. Supposing that a key role could be played by P/V ratio, I prepared, characterized and tested two samples with different P/V ratio. Transformation occurring on catalytic surfaces under different conditions of temperature and gas-phase composition were studied by means of in-situ Raman spectroscopy, trying to investigate the changes that VPP undergoes during reaction. The goal is to understand which kind of compound constituting the catalyst surface is the most active and selective for butane oxidation reaction, and also which features the catalyst should possess to ensure the development of this surface (e.g. catalyst composition). On the basis of results from this study, it could be possible to project a new catalyst more active and selective with respect to the present ones. In fact, the second topic investigated is the possibility to reproduce the surface active layer of VPP onto a support. In general, supportation is a way to improve mechanical features of the catalysts and to overcome problems such as possible development of local hot spot temperatures, which could cause a decrease of selectivity at high conversion, and high costs of catalyst. In literature it is possible to find different works dealing with the development of supported catalysts, but in general intrinsic characteristics of VPP are worsened due to the chemical interaction between active phase and support. Moreover all these works deal with the supportation of VPP; on the contrary, my work is an attempt to build-up a V/P/O active layer on the surface of a zirconia support by thermal treatment of a precursor obtained by impregnation of a V5+ salt and of H3PO4. In-situ Raman analysis during the thermal treatment, as well as reactivity tests are used to investigate the parameters that may influence the generation of the active phase. Part B is devoted to the study of o-xylene oxidation of phthalic anhydride; industrially, the reaction is carried out in gas-phase using as catalysts a supported system formed by V2O5 on TiO2. The V/Ti/O system is quite complex; different vanadium species could be present on the titania surface, as a function of the vanadium content and of the titania surface area: (i) V species which is chemically bound to the support via oxo bridges (isolated V in octahedral or tetrahedral coordination, depending on the hydration degree), (ii) a polymeric species spread over titania, and (iii) bulk vanadium oxide, either amorphous or crystalline. The different species could have different catalytic properties therefore changing the relative amount of V species can be a way to optimize the catalytic performances of the system. For this reason, samples containing increasing amount of vanadium were prepared and tested in the oxidation of o-xylene, with the aim of find a correlations between V/Ti/O catalytic activity and the amount of the different vanadium species. The second part deals with the role of a gas-phase promoter. Catalytic surface can change under working conditions; the high temperatures and a different gas-phase composition could have an effect also on the formation of different V species. Furthermore, in the industrial practice, the vanadium oxide-based catalysts need the addition of gas-phase promoters in the feed stream, that although do not have a direct role in the reaction stoichiometry, when present leads to considerable improvement of catalytic performance. Starting point of my investigation is the possibility that steam, a component always present in oxidation reactions environment, could cause changes in the nature of catalytic surface under reaction conditions. For this reason, the dynamic phenomena occurring at the surface of a 7wt% V2O5 on TiO2 catalyst in the presence of steam is investigated by means of Raman spectroscopy. Moreover a correlation between the amount of the different vanadium species and catalytic performances have been searched. Finally, the role of dopants has been studied. The industrial V/Ti/O system contains several dopants; the nature and the relative amount of promoters may vary depending on catalyst supplier and on the technology employed for the process, either a single-bed or a multi-layer catalytic fixed-bed. Promoters have a quite remarkable effect on both activity and selectivity to phthalic anhydride. Their role is crucial, and the proper control of the relative amount of each component is fundamental for the process performance. Furthermore, it can not be excluded that the same promoter may play different role depending on reaction conditions (T, composition of gas phase..). The reaction network of phthalic anhydride formation is very complex and includes several parallel and consecutive reactions; for this reason a proper understanding of the role of each dopant cannot be separated from the analysis of the reaction scheme. One of the most important promoters at industrial level, which is always present in the catalytic formulations is Cs. It is known that Cs plays an important role on selectivity to phthalic anhydride, but the reasons of this phenomenon are not really clear. Therefore the effect of Cs on the reaction scheme has been investigated at two different temperature with the aim of evidencing in which step of the reaction network this promoter plays its role.

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Die Ziele der vorliegenden Arbeit waren 1) die Entwicklung und Validierung von sensitiven und substanz-spezifischen Methoden für die quantitative Bestimmung von anionischen, nichtionischen und amphoteren Tensiden und deren Metaboliten in wässrigen Umweltproben unter Einsatz leistungsfähiger, massenspektrometrischer Analysengeräte,2) die Gewinnung von aeroben, polaren Abbauprodukten aus Tensiden in einem die realen Umweltbedingungen simulierenden Labor-Festbettbioreaktor (FBBR), dessen Biozönose oberflächenwasserbürtig war,3) zur Aufklärung des Abbaumechanismus von Tensiden neue, in 2) gewonnene Metabolite zu identifizieren und massenspektrometrisch zu charakterisieren ebenso wie den Primärabbau und den weiteren Abbau zu verfolgen,4) durch quantitative Untersuchungen von Tensiden und deren Abbauprodukten in Abwasser und Oberflächenwasser Informationen zu ihrem Eintrag und Verhalten bei unterschiedlichen hydrologischen und klimatischen Bedingungen zu erhalten,5) das Verhalten von persistenten Tensidmetaboliten in Wasserwerken, die belastetes Oberflächenwasser aufbereiten, zu untersuchen und deren Vorkommen im Trinkwasser zu bestimmen,6) mögliche Schadwirkungen von neu entdeckten Metabolite mittels ökotoxikologischer Biotests abzuschätzen,7) durch Vergleich der Felddaten mit den Ergebnissen der Laborversuche die Umweltrelevanz der Abbaustudien zu belegen. Die Auswahl der untersuchten Verbindungen erfolgte unter Berücksichtigung ihres Produktionsvolumens und der Neuheit auf dem Tensidmarkt. Sie umfasste die Waschmittelinhaltsstoffe lineare Alkylbenzol-sulfonate (LAS), welches das Tensid mit der höchsten Produktionsmenge darstellte, die beiden nichtionischen Tenside Alkylglucamide (AG) und Alkylpolyglucoside (APG), ebenso wie das amphotere Tensid Cocamidopropylbetain (CAPB). Außerdem wurde der polymere Farbübertragungsinhibitor Polyvinylpyrrolidon (PVP) untersucht.

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This work presents the preliminary study of new carbonaceous materials (CMs) obtained from exhausted sludge, their use in the heterogeneous anaerobic process of biodecolorization of azo dyes and the comparison of their performance with one commercial active carbon. The preparation of carbonaceous materials was conducted through chemical activation and carbonization. Chemical activation was carried out through impregnation of sludge-exhausted materials with ZnCl2 and the activation by means of carbonization at different temperatures (400, 600 and 800°C). Their physicochemical and surface characteristics were also investigated. Sludge based carbonaceous (SBC) materials SBC400, SBC600 and SBC800 present values of 13.0, 111.3 and 202.0m(2)/g of surface area. Biodecolorization levels of 76% were achieved for SBC600 and 86% for SBC800 at space time (τ) of 1.0min, similar to that obtained with commercial activated carbons in the continuous anaerobic up-flow packed bed reactor (UPBR). The experimental data fit well to the first order kinetic model and equilibrium data are well represented by the Langmuir isotherm model. Carbonaceous materials show high level of biodecolorization even at very short space times. Results indicate that carbonaceous materials prepared from sludge-exhausted materials have outstanding textural properties and significant degradation capacity for treating textile effluents.