Oxidação úmida de fenóis com catalisadores de ferro suportado em argilominerais em reator de leito de lama (slurry)

The wet oxidation of organic compounds with CO2 and H2O has been demonstrated to be an efficient technique for effluent treatment. This work focuses on the synthesis, characterization and catalytic performance of Fe-MnO2/CeO2, K-MnO2/CeO2/ palygorskite and Fe/ palygorskite toward the wet oxidative degradation of phenol. The experiments were conducted in a sludge bed reactor with controlled temperature, pressure and stirring speed and sampling of the liquid phase. Experiments were performed on the following operating conditions: temperature 130 ° C, pressure 20.4 atm, catalyst mass concentration of 5 g / L initial concentration of phenol and 0.5 g / L. The catalytic tests were performed in a slurry agitated reactor provided with temperature, pressure and agitation control and reactor liquid sampling. The influences of iron loaded on the support (0.3; 7 and 10%, m/m) and the initial pH of the reactant medium (3.1; 6.8; 8.7) were studied. The iron dispersion on the palygorskite, the phase purity and the elemental composition of the catalyst were evaluated by X-Ray Difraction (XRD), Scanning Electron Microscopy (SEM) and X-Ray Flourescence (XRF). The use of palygorskite as support to increase the surface area was confirmed by the B.E.T. surface results. The phenol degradation curves showed that the Fe3+ over palygorskite when compared with the other materials tested has the best performance toward the (Total Organic carbonic) TOC conversion. The decrease in alkalinity of the reaction medium also favors the conversion of TOC. The maximum conversion obtained from the TOC with the catalyst 3% Fe / palygorskite was around 95% for a reaction time of 60 minutes, while reducing the formation of acids, especially acetic acid. With products obtained from wet oxidation of phenol, hydroquinone, p-benzoquinone, catechol and oxalic acid, identified and quantified by High Performance Liquid Chromatography was possible to propose a reaction mechanism of the process where the phenol is transformed into the homogeneous and heterogeneous phase in the other by applying a kinetic model, Langmuir-Hinshelwood type, with evaluation of kinetic constants of different reactions involved.

Síntese e caracterização de aluminofosfato impregnado com molibdênio/zinco visando a dessulfurização por adsorção

Discussions about pollution caused by vehicles emission are old and have been developed along the years. The search for cleaner technologies and frequent weather alterations have been inducing industries and government organizations to impose limits much more rigorous to the contaminant content in fuels, which have an direct impact in atmospheric emissions. Nowadays, the quality of fuels, in relation to the sulfur content, is carried out through the process of hydrodesulfurization. Adsorption processes also represent an interesting alternative route to the removal of sulfur content. Both processes are simpler and operate to atmospheric temperatures and pressures. This work studies the synthesis and characterization of aluminophosphate impregnate with zinc, molybdenum or both, and its application in the sulfur removal from the gasoline through the adsorption process, using a pattern gasoline containing isooctane and thiophene. The adsorbents were characterized by x-ray diffraction, differential thermal analysis (DTG), x-ray fluorescence and scanning electron microscopy (SEM). The specific area, volume and pore diameter were determined by BET (Brunauer- Emmet-Teller) and the t-plot method. The sulfur was quantified by elementary analysis using ANTEK 9000 NS. The adsorption process was evaluated as function of the temperature variation and initial sulfur content through the adsorption isotherm and its thermodynamic parameters. The parameters of entropy (ΔS), enthalpy variation (ΔH) and free Gibbs energy (ΔG) were calculated through the graph ln(Kd) versus 1/T. Langmuir, Freundlich and Langmuir-Freundlich models were adjusted to the experimental data, and the last one had presented better results. The thermodynamic tests were accomplished in different temperatures, such as 30, 40 and 50ºC, where it was concluded the adsorption process is spontaneous and exothermic. The kinetic of adsorption was studied by 24 h and it showed that the capability adsorption to the adsorbents studied respect the following order: MoZnPO > MoPO > ZnPO > AlPO. The maximum adsorption capacity was 4.91 mg/g for MoZnPO with an adsorption efficiency of 49%.

Conversão catalítica de clorometano em hidrocarbonetos

Amorphous silica-alumina and modified by incipient impregnation of iron, nickel, zinc and chromium were synthetized in oxide and metal state and evaluated as catalysts for the chloromethane conversion reaction. With known techniques their textural properties were determined and dynamics techniques in programmed temperature were used to find the acid properties of the materials. A thermodynamic model was used to determine the adsorption and desorption capacity of chloromethane. Two types of reactions were studied. Firstly the chloromethane was catalytically converted to hydrocarbons (T = 300 450 oC e m = 300 mg) in a fixed bed reactor with controlled pressure and flow. Secondly the deactivation of the unmodified support was studied (at 300 °C and m=250 g) in a micro-adsorver provided of gravimetric monitoring. The metal content (2,5%) and the chloromethane percent of the reagent mixture (10% chloromethane in nitrogen) were fixed for all the tests. From the results the chloromethane conversion and selectivity of the gaseous products (H2, CH4, C3 and C4) were determined as well as the energy of desorption (75,2 KJ/mol for Ni/Al2O3-SiO2 to 684 KJ/mol for the Zn/Al2O3-SiO2 catalyst) considering the desorption rate as a temperature function. The presence of a metal on the support showed to have an important significance in the chloromethane condensation. The oxide class catalyst presented a better performance toward the production of hydrocarbons. Especial mention to the ZnO/Al2O3-SiO2 that, in a gas phase basis, produced C3 83 % max. and C4 63% max., respectively, in the temperature of 450 oC and 20 hours on stream. Hydrogen was produced exclusively in the FeO/Al2O3-SiO2 catalysts (15 % max., T = 550 oC and 5,6 h on stream) and Ni/SiO2-Al2O3 (75 % max., T = 400 oC and 21,6 h on stream). All the catalysts produced methane (10 à 92 %), except for Ni/Al2O3-SiO2 and CrO/Al2O3-SiO2. In the deactivation study two models were proposed: The parallel model, where the product production competes with coke formation; and the sequential model, where the coke formation competes with the product desorption dessorption step. With the mass balance equations and the mechanism proposed six parameters were determined. Two kinetic parameters: the hydrocarbon formation constant, 8,46 10-4 min-1, the coke formation, 1,46 10-1 min-1; three thermodynamic constants (the global, 0,003, the chloromethane adsorption 0,417 bar-1, the hydrocarbon adsorption 2,266 bar-1), and the activity exponent of the coke formation (1,516). The model was reasonable well fitted and presented a satisfactory behavior in relation with the proposed mechanism

Estudo da reidratação do feijão verde (Vigna unguiculata L. Walp) desidratado por micro-ondas com e sem pré-tratamento osmótico

The green bean has organoleptic and nutritional characteristics that make it an important food source in tropical regions such as the Northeast of Brazil. It is a cheap source of protein and important for nutrition of rural population contributing significantly in subsistence farming of the families from Brazil s northeast. It is consumed in entire region and together with the dry meat and other products composes the menu of typical restaurants, being characterized as an important product for economy of Northeast. The green bean is consumed freshly harvested and has short cycle, being characterized as a very perishable food, which hampers your market. The drying method is an alternative to increase the lifetime and provide a reduction volume of this product making easier your transportation and storage. However is necessary to search ways of drying which keep the product quality not only from the nutritional standpoint but also organoleptic. Some characteristics may change with the drying process such as the coloring, the rehydration capacity and the grains cooking time. The decrease of drying time or of exposure of the grains to high temperature minimizes the effects related with the product quality loss. Among the techniques used to reduce the drying time and improve some characteristics of the product, stands out the osmotic dehydration, widely used in combined processes such as the pretreatment in drying food. Currently the use of the microwaves has been considered an alternative for drying food. The microwave energy generates heat inside of materials processed and the heating is practically instantaneous, resulting in shorter processing times and product quality higher to that obtained by conventional methods. Considering the importance of the green beans for the Northeast region, the wastefulness of production due to seasonality of the crop and your high perishability, the proposal of this thesis is the study of drying grain by microwaves with and without osmotic pretreatment, focusing on the search of conditions of processes which favor the rehydration of the product preserving your organoleptic characteristics. Based on the analysis of the results of osmotic dehydration and dielectric properties was defined the operating condition to be used in pretreatment of the green bean, with osmotic concentration in saline solution containing 12,5% of sodium chloride, at 40°C for 20 minutes. The drying of green bean by microwave was performed with and without osmotic pretreatment on the optimized condition. The osmotic predehydration favored the additional drying, reducing the process time. The rehydration of dehydrated green bean with and without osmotic pretreatment was accomplished in different temperature conditions and immersion time according to a factorial design 22, with 3 repetitions at the central point. According to results the better condition was obtained with the osmotically pretreated bean and rehydrated at a temperature of 60°C for 90 minutes. Sensory analysis was performed comparing the sample of the green bean in natura and rehydrated in optimized conditions, with and without osmotic pretreatment. All samples showed a good acceptance rate regarding the analyzed attributes (appearance, texture, color, odor and taste), with all values above 70%. Is possible conclude that the drying of green bean by microwave with osmotic pretreatment is feasible both in respect to technical aspects and rehydration rates and sensory quality of the product

Utilização de microemulsões como agentes modificadores de superfícies para remoção de íons metálicos

The heavy metals are used in many industrial processes and when discharged to the environment can cause harmful effects to human, plants and animals. The adsorption technology has been used as an effective methodology to remove metallic ions. The search for new adsorbents motivated the development of this research, accomplished with the purpose of removing Cr (III) from aqueous solutions. Diatomite, chitosan, Filtrol 24TM and active carbon were used as adsorbents. To modify the adsorbent surface was used a bicontinuous microemulsion composed by water (25%), kerosene (25%), saponified coconut oil (10%) and as co-surfactant isoamyl or butyl alcohols (40%). With the objective of developing the best operational conditions the research started with the surfactant synthesis and after that the pseudo-ternary diagrams were plotted. It was decided to use the system composed with isoamyl alcohol as co-surfactant due its smallest solubility in water. The methodology to impregnate the microemulsion on the adsorbents was developed and to prepare each sample was used 10 g of adsorbent and 20 mL of microemulsion. The effect of drying time and temperature was evaluated and the best results were obtained with T = 65 ºC and t = 48 h. After evaluating the efficiency of the tested adsorbents it was decided to use chitosan and diatomite. The influence of the agitation speed, granule size, heavy metal synthetic solution concentration, pH, contact time between adsorbent and metal solution, presence or not of NaCl and others metallic ions in the solution (copper and nickel) were evaluated. The adsorption isotherms were obtained and Freundlich and Langmuir models were tested. The last one correlated better the data. With the purpose to evaluate if using a surfactant solution would supply similar results, the adsorbent surface was modified with this solution. It was verified that the adsorbent impregnated with a microemulsion was more effective than the one with a surfactant solution, showing that the organic phase (kerosene) was important in the heavy metal removal process. It was studied the desorption process and verified that the concentrated minerals acids removed the chromium from the adsorbent surface better than others tested solutions. The treatment showed to be effective, being obtained an increase of approximately 10% in the chitosan s adsorption capacity (132 mg of Cr3+ / g adsorbent), that was already quite efficient, and for diatomite, that was not capable to remove the metal without the microemulsion treatment, it was obtained a capacity of 10 mg of Cr3+ / g adsorbent, checking the applied treatment effectiveness

Concepção de um secador rotatório para secagem do cefalotórax do camarão

The present work has as objective the knowledge of the process of drying of the cephalothorax of shrimp to give support the industry to make possible the use of this byproduct. In this sense, the process conditions in this tray dryer and spouted bed were analyzed. With these results, it was projected and constructs a dryer with specific characteristics for the drying of the cephalothorax. The desorption isotherms were obtained by the dynamic method in the temperatures of 20, 35 and 50º C and in the interval of 10-90% of relative humidity. It was observed that the product in form of powder can be conserved with larger stability for lower relative humidity to 40%. The curves of drying of the dryer of fixed bed were adjusted for the models: single exponential, biparametric exponential and Page. The model biparametric exponential more adequately described all the drying conditions studied. The tests carry out in spouted bed showed high drying rate for the material in the paste form in beds active dynamicly-fluid, provely the necessity of a feeding in shorter intervals of time to increase the thermal efficiency of the process. The projected dryer, be considered the obtained results, it was a rotary dryer with inert bed, feed co-current, discharge in cyclone to take place the separation gas-solid, and feed carry out in intervals of 2 minutes. The optimization of the equipment projected it was accomplished used the complete factorial experimental design 24, this had as independent variables temperature velocity of the air, feed flow rate and encapsulated concentration (albumin), as variables answers the thermal efficiency, the moisture content of obtained powder, total time of test and the efficiency of production of powder in several points of processing. The results showed that the rotary dryer with inert bed can present, also, good results if applied industrially

Eutrofização do Reservatório Cruzeta na bacia representativa do rio Seridó RN

Eutrophication has been listed as one of the main problems of water pollution on a global level. In the Brazilian semi-arid areas this problem takes even greater proportions due to characteristical water scarcity of the region. It is extremely important to the predictive eutrophication models development and to the reservoirs management in the semi-arid region, studies that promotes understanding of the mechanisms responsible for the expansion and control of algae blooms, essential for improving the water quality of these environments. The present study had as its main aims, evaluate the temporal pattern of trophic state, considering the influence of nutrients (N and P) and the light availability in the water column in the development of phytoplankton biomass, and perform the mathematical modelling of changes in phosphorus and chlorophyll a concentrations in the Cruzeta man-made lake located on Seridó, a typical semi-arid region of Rio Grande do Norte. To this, a fortnightly monitoring was performed in the reservoir in 05 stations over the months of March 2007 to May 2008. Were measured the concentrations of total phosphorus, total organic nitrogen, chlorophyll a, total, fixed and volatile suspended solids, as well as the measure of transparency (Secchi) and the profiles of photosynthetic active radiation (PAR), temperature, pH, dissolved oxygen and electrical conductivity in the water column. Measurements of vertical profiles have shown some periods of chemical and thermal stratification, especially in the rainy season, due to increased water column depth, however, the reservoir can be classified as warm polimitic. During the study period the reservoir was characterized as eutrophic considering the concentrations of phosphorus and most of the time as mesotrophic, based on the concentrations of chlorophyll a, according to the Thornton & Rast (1993) classification. The N:P relations suggest N limitation, conversely, significant linear relationship between the algae biomass and nutrients (N and P) were not observed in our study. However, a relevant event was the negative and significant correlation presented by Kt and chlorophyll a (r ² = 0.83) at the end of the drought of 2007 and the rainy season of 2008, and the algal biomass collapse observed at the end of the drought season (Dec/07). The equation used to simulate the change in the total phosphorus was not satisfactory, being necessary inclusion of parameters able to increase the power of the model prediction. The chlorophyll a simulation presented a good adjustment trend, however there is a need to check the calibrated model parameters and subsequent equation validation

Caracterização do conteúdo de fossas e tanques sépticos na cidade de Natal

Only 32% of the population of Natal is attended by sewage, while the remaining population use pits and septic tanks. The characterization of the contents of septic tanks and pits contributes to the performance of such system and may guide the decision on treatment of these contents. The main of this research is to characterize the contents of interior residential pits and septic tanks in the greater Natal, with the following specific goals: to develop and manufacture a sampler capable of collecting a representative sample of the entire column (the surface scum, the clarified liquid and sludge bottom); to compare the contents of the tanks with the pits; to compare the contents of the septage from vacuum trucks; to relate the composition content with socioeconomic characteristics of households; to compare the content in both chambers of the septic tanks in series; to assess the situation of the content before and six months after the cleanness; and ultimately propose a pilot scale plant for treatment of septage. Once the sampler was developed, samples were collected within 14 septic tanks and 10 pits in many districts of Natal. Medians of the 24 systems were obtained: temperature, pH, conductivity, oil and grease, total solids, total suspended solids and sediments of 28.0 °C, 6.95; 882 mS/cm, 75.2 mg/L; 10,169 mg/L, 6,509 mg/L and 175 mL/L respectively; 111.0 mgN/L for ammonia, 130.5 mgN/ L for organic nitrogen, 0.2 mgN/L for nitrite, 0.4 mg/L for nitrate; 8935 mgO2/L for COD, 29.2 mgP/L for total phosphorus, thermotolerant coliforms from 9.95 E +06 CFU/100mL helminth eggs and 9.2 eggs/L with a maximum concentration of 688 eggs/L and minimum of 0 eggs/L. Medians of organic nitrogen and TKN were significantly different between groups of tanks and pits. The systems with cleanness gap from 11 and 20 years presented the higher concentrations for most variables. The effluent from the toilets and bathrooms participate more effectively in contributing fractions of solids, alkalinity, nitrogen, COD, total phosphorus, thermotolerant coliforms and helminth eggs. The systems used by socioeconomics class with income from R$ 3,700.00 to R$ 7,600.00, presented higher concentrations for COD, nitrogen, solids and helminth eggs. The first of the two chambers had always presented higher concentrations over the second compartment. The analysis of variance for most variables, showed that the values of septic tanks, pits and septage from vacuum trucks belong to the same group. In the samples taken after cleanness, the median of pH and temperature increased, while alkalinity, COD, organic nitrogen, total phosphorus, ammonia and helminth eggs decreased. The oils and greases and thermotolerant coliforms had slightly varied due to the continuous release of sewage into the systems that maintained their steady state concentrations.

Remoção de matéria orgânica em sistemas de lagoas de estabilização no Nordeste brasileiro

Stabilization pond is the main technology used for treatment wastewater, in northeast Brazil, due to lower cost of deployment, operation and maintenance compared to other technologies. Most systems of stabilization ponds has been in operation for some time, on average 10 years of operation, receiving high organic loads and do not have good removal efficiencies of the main parameters for which have been designed. Therefore it is necessary to work to quantify the efficiency of current systems. This study evaluated the biodegradability of organic matter in raw sewage, the removal of organic matter in reactors and determination of the kinetic constant removal of organic matter (k), both in reactors and in raw sewage, based on the analysis made in the laboratory and through mathematical methods proposed in the literature, in nine systems stabilization ponds, located in Rio Grande do Norte. In relation the degradation kinetics in stabilization ponds, it was observed that many papers published in the literature were obtained in pilot-scale systems, which often, due to the action of external factors such as wind and temperature, these can t be considered as a reference in the analysis of the kinetic constant K, so the need for more research into systems of scale. This study had three distinct phases and simultaneous, routine monitoring, study of the daily cycle and the determination of kinetic constant of degradation of organic matter (K). The monitoring showed that the removal efficiencies of organic matter on most systems were lower than suggested by the literature, the best efficiencies of around 76% (BOD) and 72% (COD) and the worst of the order of 48% (BOD) and 55% (COD). The calculation of K in raw sewage (Ke) was within the range of variation expected in the literature (0.35 to 0.60 days-1). Already for the results obtained for K in the reactors (Kr), there were well below the values recommended in the literature (0.25 to 0.40 d-1 for complete mix and from 0.13 to 0.17 d-1 for flow dispersed), in line with the overloads that organic systems are subject

Avaliação da eficiência da remoção de matéria orgânica e microbiológica de três sistemas de lagoas de estabilização em série na Grande Natal-RN: Beira Rio, Jardim Lola I e Jardim Lola II

Waste stabilization ponds are the main technology in use for domestic sewage treatment in Rio Grande do Norte State (RN), northeast Brazil. The are around 80 systems, constructed mainly by municipal city halls, being series comprised by a primary facultative pond followed by two maturation ponds the most used configuration. Due to problems related with the production and destination of sludge and generation of bad odors, the designers have avoided the use of anaerobic lagoons. The majority of systems are rarely monitored to verify their efficiencies and to get new project parameters for future designing. This work has as purpose to make a diagnosis of efficiency of three series of waste stabilization pond series (WSPS) of Jardim Lola 1, Jardim Lola 2 and Beira Rio, located in the North Zone of the city of the Natal/RN, treating domestic raw sewage, on the removal of organic matter and thermotolerant coliform, comparing the operational conditions of the systems this inside of the bands foreseen in the project, through parameters BOD5, QOD, thermotolerant coliforms, dissolved oxygen, pH, temperature, ammoniac nitrogen, total and suspended solids. The work was carried through in the WSPS, all constituted by a primary facultative pond followed by two maturation ponds. Socioeconomic characteristics of population are predominantly low and all the plants are very near of the contributing basins. The series were monitored from of May the November of 2002, totalizing 20 collections of grab samples of raw sewage and ponds effluents between 8:00 and 9:50 h. The main aspect to be detached by the results was the great concentration of organic matter (BOD and COD) and microorganisms the raw sewage which were around two times more concentrated than those values foreseen one in project. Considering all series the highest removals of organic matter were observed in system Beira Rio (84 and 78% of BOD and COD, respectively), which presented high hydraulic detention time (TDH = 89 days). On the other hand, Jardim Lola 1 and Jardim Lola 2 presented a much lower values of HDT (36 days and 18 days respectively) and their removals of BOD and COD were the same (76% and 60%, respectively). The Beira Rio WSPS, was the most efficient verified in relation to solids and ammonia, proving the great influence of the operational variables such as HDT and applied surface organic loadings on the performance of pond series. Although the treatment plants have reached efficiencies of thermotolerant coliforms around 99,999%, the concentrations in the final effluent can be considered very high for launching in aquatic bodies, particularly those produced by Jardim Lola 1 and Jardim Lola 2 series

Elaboração e aplicação de uma estratégia de ensino sobre os conceitos de calor e de temperatura

This piece of work has investigated the alternative conceptions shown by students of secondary school, concerned to the concepts of warmth and temperature, aiming the elaboration and application of a learning strategy as of the diagnose risen from the conceptions present in students. The learning strategy was built up by a sequence of activities that involve History of Science and experiments, put in a course that had as a base the proposal of the Group of Redevelopment of Physics Teaching (GREF). We have used as the conductor wire of our research the development of thermo dynamics since the development of the first thermo machines, passing by the Industrial Revolution and the evolution of concepts of warmth and temperature. The learning strategy was applied to a group of second grade of secondary school in a public school in Mossoró (RN). By doing these activities we tried to become the concepts, which are part of thermo dynamics, more meaningful to the students. We have estimated that the application of the strategy has represented some profits to the students of the group, concerning to learning of laws and concepts of thermo dynamics (specifically the concepts of warmth and temperature), as well as what it is referred to the overcoming of its initial conceptions

Assimilação do IWV-GPS no Brasil: otimização das estimativas do atraso zenital troposférico em tempo real

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

Avaliação das previsões do atraso zenital troposférico para a América do Sul, obtidas usando modelo de previsão numérica de tempo com alta resolução espacial

A Center for Weather Forecast and Climatic Studies of National Institute for Space Research (CPTEC/INPE) has provided to the Brazilian Geodetic community, since 2004, an alternative to correct the GNSS observables from the tropospheric refraction. Numerical Weather Prediction (NWP) Model is used to generate Zenital Tropospheric Delay (ZTD). For the version 1, it was developed a model with horizontal resolution of 100 km, which was updated with Eta model, with resolution of 20 km. This paper provides the most significative details of the current version, as well an evaluation of its quality, using for such ZTD estimates from GPS data collect at RBMC. Comparing to the old version, considerable improvement could be observed from the new model, mainly in Brasilia and Curitiba, reaching up to 55% improvement. When all stations were used in the quality control, almost null bias and RMS of about 4 to 5 cm could be observed.

Caracterização mecânica e térmica da borracha natural formulada e vulcanizada dos clones: GT 1, IAN 873, PB 235 e RRIM 600

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

Comportamento elétrico a alta temperatura de termistor cerâmico alfa-Fe2O3 com coeficiente de temperatura negativo

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