Estudo de parâmetros físicoquímicos para a produção de argamassas utilizando resíduos industriais e da construção civil

As argamassas podem ser consideradas como a mistura de aglomerantes e agregados com água, possuindo capacidade de endurecimento e aderência. Como alternativa, é proposto produção de argamassas utilizando como agregado miúdo resíduos de construção civil (RCC), rico em silicoaluminatos, gerado nas obras de demolições e reformas, e cinza volante (CV) como material pozolânico, obtida a partir da combustão do carvão mineral em caldeiras de leitos fluidizados, em substituição parcial ao cimento Portland. Neste contexto, o resíduo de construção civil foi beneficiado e caracterizado pelas análises de espectrofotometria de raios- X e difração de raios-X, a cinza volante foi caracterizada pela análise granulométrica e espectrofotometria de raios-X. Para produção das argamassas formularam-se composições de RCC nas proporções de 95, 90, 85, 80, 75 e 70%; CV de 0, 5, 10, 15, 20 e 25% e 5% de cimento Portland CP II Z 32, sendo que em cada composição do traço de argamassa foi adicionado 0,8% em volume de água e para o ensaio reológico utilizou-se as mesmas proporções de resíduos (RCC e CV) com 35% em volume de água. Após a cura de 28 dias os corpos de prova foram submetidos a ensaios físicos de absorção, porosidade e massa específica aparente; ensaio mecânico de resistência à compressão e análise de difração de raios-X e microscopia eletrônica de varredura, cujos resultados obtidos mostraram-se ser viável a utilização da cinza volante e RCC na construção civil, na produção de argamassas.

Reaproveitamento de cinzas de carvão mineral na formulação de argamassas

Este trabalho tem como objetivo o estudo da incorporação de cinzas provenientes da combustão do carvão mineral em caldeiras de leito fluidizado, na produção de argamassas, em substituição parcial do cimento. Foram elaborados corpos de prova utilizando-se os cimentos Portland com as especificações CPII-E-32 de características normais e areia de classificação abaixo da malha 100. Foram preparadas misturas na proporção 4 partes de agregado e 1 parte de cimento, com a inserção de cinzas nas proporções 0, 10, 20, 30, 40 e 50%. A argamassa foi desenvolvida em misturador e a moldagem foi feita em moldes de 5 cm x 10 cm. Foi analisado o comportamento de resistência à compressão após 28 dias. A resistência diminui conforme o aumento da porcentagem de cinzas. Foram feitas análises complementares de difração de raios X e constatou-se que a substituição desse resíduo pode ser feita com sucesso em argamassas com teores de até 30%.

Estudo numérico de modelos de arrasto e do coeficiente de restituição no escoamento gás-sólido em leito fluidizado

Pós-graduação em Engenharia Mecânica - FEG

Aumento da oferta de eletricidade no setor sucroalcooleiro: incorporação de ciclo combinado associado à gaseificador de leito fluidizado

Pós-graduação em Engenharia Mecânica - FEG

Uso de invertase imobilizada em pó de sabugo de milho para produção de açúcar invertido

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo da fluidodinâmica de uma mistura de sólidos em um leito fluidizado gás-sólido

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

Estudo da secagem natural e forçada das folhas de Corymbia Citriodora a partir da extração de óleos essenciais

Essential oils are products from plants and can be located in parts or in its entirety. There are several methods for its extraction, where the most suitable depends on the plant or the use of the essence. The main species cultivated in Brazil are the Corymbia citriodora, Eucalyptus globulus and Eucalyptus staigeriana. The Corymbia citriodora is a species that was introduced in Brazil along with other species, with the initial objective of timber production. The yield of oil can range from 0.5 % to 3.0% according to the literature and this can be optimized by reducing the moisture content of the leaves. Studies show that the lower water content in the leaves allows the vapor stream generated in the extractor can drag, more efficiently, the volatiles stored in the cells as compared with the green material. The drying of the sheets is important for companies, so that there is transport of water, increasing the volume of the sheets to distillation and hence a greater volume of oil. The objective of this study was to compare the drying methods, analyzing the income of the essence and determine the best method to optimize the yield of essential oil. Experimental tests were performed natural drying 10, 15 and 20 days and fluidized with times of 60, 90 and 120 minutes and after drying were extractions of the oil. The results obtained for fresh leave yield was 1.20 % and the drying time which showed the highest yield was 15 and 20 days with 2.90 % and 2.70 % yield, respectively, with the lowest level humidity of 16%. The yields obtained in fluidized bed drying did not change as the natural drying to between 1.64% and 1.7%. It is concluded that the decreased level of the sheets increases the yield of oil and the temperature in the fluidized bed is essential for the removal of water from the leaves necessary to increase the yield

Tratamento de efluentes provenientes de abatedouro de bovinos por meio de reator enzimático seguido de reator aeróbio operado em bateladas sequenciais

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)

The calcium looping cycle study for capturing carbon dioxide applied to the energy generation

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

Desenvolvimento, implantação e avaliação do desempenho de biorreator anaeróbico de leito fluidizado e leito fixo com filtros biológicos em materiais diversos

This study aimed to develop, implement and evaluate the performance of a new type of bioreactor for anaerobic treatment of wastewater using different filling materials like trickling filters post-reactor. This bioreactor has mixed characteristics of the UASB reactors and horizontal flow from the point of view of removal of BOD (Biochemical Oxygen Demand) ssed (settled solids), TS (Total Solids), SS (Suspended Solid), SD (Dissolved Solids) and turbidity. The experimental model consists of a bioreactor with a volume of 12 m³, 2/3 filled by fluidized bed and 1/3 for fixed. The fluidized bed is made of polystyrene plates used as a system percolation and compartmentalized trickling filters, where each compartment was filled with a support medium with different characteristics (gravel number 4, plastic rings of polystyrene, PET and HDPE) . In addition, the output of a filter system was installed three entries filled with activated carbon. The bioreactor was installed in private residence in the city of Igarapava-SP (20° 02'40.18"S and 47° 45'01.36" W). The system was highly efficient as the removal of organic contaminant load 92% on average reducing the BOD, a significant result when compared to other anaerobic systems. For the other parameters, the mean reduction was 96% for turbidity, 99% ssed, 67.5% ST, 57% SD and 88% of SS. As for its operation the system was capable of operating in continuous flow without the need for maintenance during the entire period of evaluation and without energy, as it operates taking advantage of the natural slope of the terrain where it is installed. The environmental impacts were minimized due to the preservation of local vegetation allowing the ecosystem to remain unchanged beyond the prototype was completely sealed preventing exhalation of odors and therefore not causing inconvenience to neighboring populations. Given these facts it was concluded that the prototype is shown to be highly feasible deployed as a new alternative for treatment of sewage in rural and urban settings (individual homes, condos, farms, ranches, etc.) Due to ease of design and operability, and sustainability at all stages of execution.

Continuous enzymatic interesterification of milkfat with soybean oil produces a highly spreadable product rich in polyunsaturated fatty acids

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

Uso de reator aeróbio de leito fluidizado com circulação como dispositivo de pós-tratamento do efluente de um reator uasb compartimentado tratando esgotos sanitários

Pós-graduação em Engenharia Civil - FEIS

Investigation of the pore blockage of a Brazilian dolomite during the sulfation reaction

The influence of the temperature and reaction time on the sulfation process of a dolomite is investigated in this paper. The sulfation effectiveness was evaluated and correlated with changes in the physical characteristics of a Brazilian dolomite during the reactive process. Calcination and sulfation experiments were performed under isothermal conditions for dolomite samples with average particle sizes of 545 mu m at temperatures of 750 degrees C, 850 degrees C and 950 degrees C at different times of sulfation. Thermogravimetric tests were applied to establish the reactivity variation of the dolomite in function of the time in the sulfation reaction and evaluate the methodology of the samples preparation. Porosimetry tests were performed to study the pore blockage of dolomite during the sulfation reaction. The highest values of BET surface area were 25.55 m(2)/g, 29.55 m(2)/g and 12.62 m(2)/g for calcined samples and after their sulfation processes, conversions of 51.5%, 61.9% and 42.8% were obtained at 750 degrees C, 850 degrees C and 950 degrees C, respectively. Considering the process as a whole, the best fit was provided by a first-order exponential decay equation. Moreover, the results have shown that it is possible to quantify the decreasing in the dolomite reactivity for sulfur dioxide sorption and understand the changes in the behavior of the sulfation process of limestones when applied to technologies, as fluidized bed combustor, in which sulfur dioxide is present. (C) 2011 Elsevier B. V. All rights reserved.

In vitro drug permeation from chitosan pellets

The purpose of this study was to prepare and characterize coated pellets for controlled drug delivery. The influence of chitosan (CS) in pellets was evaluated by swelling, in vitro drug release and intestinal permeation assays. Pellets were coated with an enteric polymer, Kollicoat (R) MAE 30 DP, in a fluidized-bed apparatus and the coating formulations were based on a factorial design. Metronidazole (MT) released from coated and uncoated pellets were assessed by dissolution method using Apparatus I. Intestinal permeation was evaluated by everted intestinal sac model in rats, used to study the absorption of MT from coated pellets containing CS or not through the intestinal tissue. Although the film coating avoided drug dissolution in gastric medium, the overall drug release and intestinal permeation were dependent on the presence of CS. Thus, pellets containing CS show potential as a system for controlled drug delivery. (C) 2011 Elsevier Ltd. All rights reserved.

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).