[pt] Compostos de boro são utilizados na indústria metalúrgica, microeletrônica, de vidros, na agricultura, etc. Esse elemento é um micronutriente essencial no desenvolvimento de microrganismos, plantas, animais e humanos. No entanto, pode ser tóxico em grandes concentrações e por isso necessita ser removido de águas e efluentes. No Brasil, o limite padrão é de 0,5mg/L para águas doces de classe I e II, estabelecido pela resolução do Conama 357/2005. Por sua vez, a resolução do Conama 430/2011 estabelece um padrão de lançamento de efluentes de 5mg/L. A presente dissertação tem como objetivo geral estudar a remoção de boro por eletrocoagulação para o tratamento de águas e efluentes contendo boro, utilizando uma célula com um arranjo de 4 eletrodos de alumínio (2 catodos e 2 anodos) monopolares em paralelo. Os resultados obtidos mostram que o processo de eletrocoagulação é uma alternativa viável para a remoção de boro, e alcança eficiências em torno de 70 por cento (em pH inicial igual à 4; densidade de corrente igual à 18,75mA/cm2 e tempo de eletrólise igual à 90min). O modelo cinético que melhor descreve a remoção de boro foi o de pseudo-primeira ordem. O modelo de Langmuir se ajustou muito bem aos dados experimentais obtidos. O valor de qm obtido pelo modelo de Langmuir refletiu a elevada capacidade de adsorção máxima (qm é igual à 334mg/g). Através das análises por Microscopia Eletrônica de Varredura (MEV) e por Espectroscopia de Energia Dispersiva (EDS) na superfície dos eletrodos, observou-se a presença de corrosão do tipo localizada nos catodos e a corrosão do tipo uniforme nos anodos. A morfologia do lodo produzido no processo de eletrocoagulação foi analisada por MEV, indicando a presença de uma morfologia heterogênea na superfície, enquanto que a análise por Difração de Raios-X (DRX) apresentou picos largos característicos de um material amorfo e a fase de alumínio predominante foi a boehmita, AlO(OH), finalmente, através da análise por Espectroscopia por Perda de Energia de Elétrons (EELS) foi possível a detecção do boro no lodo, além da detecção de alumínio e de oxigênio. Diante dos resultados obtidos no estudo de otimização a partir da Metodologia de Superfície de Resposta (RSM) constatou-se que o desenvolvimento de um modelo matemático por análise de regressão possibilitou a avaliação do efeito das variáveis independentes (densidade de corrente, pH inicial e tempo de eletrólise) e as suas interações na remoção de boro. / [en] Boron compounds are used in the metallurgical industry, microelectronics, glassware, agriculture, etc. This element is an essential micronutrient in the development of microorganisms, plants, animals and humans. However, it can be toxic in high concentrations and therefore needs to be removed from water and effluent. In Brazil, the standard limit is 0.5mg/L for Class I and II freshwaters, established by Conama Resolution 357/2005. In turn, the Conama 430/2011 resolution establishes an effluent discharge standard of 5mg/L. The present dissertation aims to study the removal of boron by electrocoagulation for the treatment of water and effluents containing boron, using a cell with an arrangement of 4 monopolar aluminum electrodes (2 cathodes and 2 anodes) in parallel. The results show that the electrocoagulation process is a viable alternative for the removal of boron and reaches efficiencies around 70 per cent (at initial pH equals to 4, current density equals to 18.75mA/cm2 and electrolysis time equals to 90min). The kinetic model that best describes the removal of boron was pseudo-first order. The Langmuir model fitted very well to the experimental data obtained. The value of qm obtained by the Langmuir model reflected the high maximum adsorption capacity (qm equals to 334mg/g). Through the analysis by Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) on the surface of the electrodes, it was observed the presence of pitting corrosion in the cathodes and uniform corrosion in the anodes. The morphology of the sludge produced in the electrocoagulation process was analyzed by SEM, indicating the presence of a heterogeneous surface morphology, while the X-ray diffraction (XRD) analysis showed broad peaks characteristic of an amorphous material and the predominant aluminum phase was boehmite, AlO(OH), finally, through the Electron Energy Loss Spectroscopy (EELS) analysis, it was possible to detect boron in the sludge, as well as aluminum and oxygen. In view of the results obtained in the optimization study from the Response Surface Methodology (RSM), it was verified that the development of a mathematical model by regression analysis made possible the evaluation of the effect of the independent variables (current density, initial pH and time of electrolysis) and their interactions in the removal of boron.

A degradação oxidativa dos lipídeos é um fator preponderante que limita a vida útil dos alimentos, reduzindo suas qualidades nutricionais e organolépticas. A utilização de antioxidantes durante o processo de fabricação pode diminuir consideravelmente a extensão da oxidação lipídica, desencadeada pela reação de radicais livres. A crescente preocupação pelo consumo de alimentos mais saudáveis e livres de aditivos sintéticos tem recebido maior atenção pelas indústrias, que atualmente tem procurado por alternativas mais naturais, como o uso de antioxidantes provenientes de especiarias, como uma forma promissora de substituição dos compostos sintéticos. O objetivo deste trabalho foi estudar as condições de obtenção de extratos hidroalcoólicos de cravo (Syzygium aromaticum), canela (Cinnamomum verum) e pimenta dedo-de-moça (Capsicum annuum) e sua aplicação em óleos de soja refinado, armazenado em embalagens de vidro, em comparação com amostras adicionadas de antioxidante sintético TBHQ e amostras livres de antioxidantes (controle), durante sete meses, simulando a comercialização em supermercados. Foram verificados também as propriedades antioxidantes dos extratos de especiarias produzidos nas condições selecionadas através das metodologias de DPPH e ABTS. O estudo do efeito da temperatura de extração e do grau de hidratação do etanol sobre o rendimento de compostos fenólicos totais dos extratos destas especiarias foi realizado com aplicação de planejamento experimental e metodologia de superfícies de resposta. As condições para uma extração eficiente dos compostos fenólicos do cravo, da canela e da pimenta foram o emprego de etanol a 49,5 % (v/v). As melhores temperaturas estiveram entre 45 a 50 °C para o cravo e canela, e 60 °C para a pimenta. Os extratos de cravo, canela e pimenta dedo-de-moça preparados nas condições otimizadas, foram adicionados nas proporções de 50 mg kg-1, 100 mg kg-1, 150 mg kg-1 e 200 mg kg-1 às amostras de óleo de soja refinado e submetido a um teste acelerado em estufa a 65 °C juntamente com amostras adicionadas nas mesmas proporções de TBHQ e amostras isentas de antioxidantes (controle), para verificação da concentração mais eficiente no retardar a oxidação. Em seguida, após os resultados do teste de estufa, os óleos adicionados de 100 mg kg-1 de extratos, TBHQ, e isento de antioxidantes foram acondicionados em embalagens de vidro transparente de 250 mL e armazenados sob condições de comercialização (incidência de luz fluorescente por 15 horas / 24 horas e 331,71 Lux). Os resultados de Índice de Peróxido, Acidez e Absortividade na faixa do ultravioleta evidenciaram que os extratos foram capazes de oferecer proteção antioxidante ao óleo de soja refinado em diferentes níveis, sendo que o tratamento adicionado de extrato de cravo foi o que mais se destacou na inibição da oxidação lipídica do óleo de soja, seguido do extrato adicionado de canela e pimenta (p<0,05). / Lipid deterioration is a major cause of shorter food shelf life, reducing its nutritional and organoleptical quality. The use of antioxidants during the manufacturing process can significantly decrease the extent of lipid oxidation reactions triggered by free radicals. The growing concern about the consumption of healthier foods and free from synthetic additives has received increased attention by the industry, which is currently looking for more natural alternatives, such as the use of antioxidants from herbs and spices, as a promising replacement of synthetic compounds. The objective of this work was to study the conditions for obtaining hydroalcoholic extracts of cloves (Syzygium aromaticum), cinnamon (Cinnamomum verum) and red pepper (Capsicum annuum) and its application in soybean oil refined, stored in glass containers, compared with samples added of synthetic antioxidant TBHQ and samples free antioxidant (control) during 7 months simulating marketing conditions in supermarkets. Extracts were analyzed by DPPH and ABTS methods. The study of the effect of extraction temperature and the degree of hydration of ethanol on the yield of total phenolic compounds of the extracts of these spices was carried out with application of experimental design and response surface methodology. The best solvent concentration for efficient extraction of phenolic compounds from clove, cinnamon and pepper was 49.5% ethanol (v / v). The best temperatures were between 45 and 50°C for cloves and cinnamon, and 60 ° C for pepper. The extracts of clove, cinnamon and red pepper prepared under optimized conditions were added in concentration of 50 mg kg-1 , 100 mg kg-1, 150 mg kg-1 and 200 mg kg-1 to samples of refined soybean oil and subjected to an accelerated storage test at 65°C with samples containing the same concentrations of TBHQ and samples free of antioxidant (control) in order to check the most efficient concentrations to slow the oxidation. The best extracts concentration 100 mg kg-1 from the Schaal oven test was added to oil packed in glass containers against oil with 100 mg kg-1 of TBHQ, and oils free of antioxidants and stored under normal commercialization conditions (fluorescence light exposure for 15 hours / 24 hours and 333,71 Lux). Peroxide, acid values and absorptivity in the ultraviolet range showed that the extracts were able to offer antioxidant protection to soybean oil at different levels. Clove extract, showed the best performance in the inhibition soybean oil oxidation, followed by cinnamon and pepper (p<0,05).

In this study, the effects of bioprocess parameters on glucose isomerase roduction by Bacillus thermoantarcticus (DSMZ 9572) were investigated. For his purpose, firstly, in laboratory scale shake-bioreactors, a defined medium was designed in terms of its carbon and nitrogen sources, to achieve the highest glucose isomerase activity. Optimum concentrations of medium components were determined by a statistical approach, namely Response Surface Methodology (RSM). RSM defined the relationship between the response, glucose isomerase activity and the independent variables, medium components. The highest glucose isomerase volumetric activity was obtained as 1630 U L-1 in the optimized medium containing 10.64 kg m-3 xylan, 5.66 kg m-3 yeast extract, 5.92 kg m-3 (NH4)2SO4, 0.25 kg m-3 MgSO4.7H2O, 0.001 kg m-3 FeSO4.7H2O, 0.001 kg m-3 ZnSO4.7H2O , 0.000075 kg m-3 MnSO4. H2O, and 0.00001 kg m-3 CuSO4.5H2O at conditions: pH0= 6.0, T=55&deg / C, N=200 min-1. Then by using the designed medium, pH and oxygen transfer conditions of the bioprocess were investigated in 3.0 dm3 pilot scale bioreactor. The effect of pH was analyzed at pH=6 uncontrolled and controlled operations with the following conditions: air inlet rate of Q0/VR=0.5 vvm and agitation rate of N=500 min-1. The effects of oxygen transfer parameters were examined, at pH=6 controlled condition, at an air inlet rate of Q0/VR=0.5 vvm and the agitation rates of N=300,500,750 min-1. The variations in glucose isomerase activity, cell, amino acid and organic acid concentrations with the cell cultivation time, specific cell growth rate, the oxygen uptake rate, the liquid phase coefficient by using the dynamic method, maintenance coefficient for oxygen and yield coefficients were determined. The highest glucose isomerase volumetric activity and cell concentration, 1838 U L-1 and 2.26 kg m-3 at the 24th of the cell cultivation were attained at 0.5 vvm, 500 min 1 and pH=6 uncontrolled operation.

The flapping path of a single airfoil and dual airfoils in a biplane configuration is optimized for maximum thrust and/or propulsive efficiency. Unsteady, low speed viscous flows are computed using a Navier-Stokes solver in a parallel computing environment. A gradient based algorithm and Response Surface Methodology (RSM) are employed for optimization. The evaluation of gradient vector components and the design of experiments for RSM, which require unsteady solutions, are also carried out in parallel. Parallel computations are performed using Parallel Virtual Machine (PVM) library. First, a single airfoil undergoing a combined sinusoidal or non-sinusoidal pitching and plunging motion is studied. The non-sinusoidal flapping motion is described using an elliptic curve or Non-Uniform Rational B-Splines (NURBS). It is shown that the thrust generation may significantly be increased in comparison to the sinusoidal flapping motion. For a high thrust, the airfoil stays at high effective angle of attack values during the upstroke and the downstroke, and the effective pitching occurs at minimum and maximum plunge positions. Secondly, the optimization of sinusoidal and non-sinusoidal flapping paths of dual airfoils is considered. Moving and deforming overset grids are used for computations. The deforming overset grids remove the restrictions on the flapping motion, and improve the optimization results obtained earlier. At low flapping frequencies, an airfoil in a biplane configuration produces more thrust than a single airfoil. Yet, at high frequencies the airfoil in biplane configuration produces less thrust at a significantly lower efficiency than the single airfoil.

A robust simulation-based optimization approach is proposed for truck-shovel systems in surface coal mines to maximize the expected value of revenue obtained from loading customer trains. To this end, a large surface coal mine in North America is considered as case study. A data-driven modeling framework is developed and then applied to automatically generate a highly detailed simulation model of the mine in Arena. The framework comprises a formal information model based on Unified Modeling Language (UML), which is used to input mine structural as well as production information. Petri net-based model generation procedures are applied to automatically generate the simulation model based on the whole set of simulation inputs. Then, factors encountered in material handling operations that may affect the robustness of revenue are then classified into 1) controllable; and 2) uncontrollable categories. While controllable factors are trucks locked to routes, uncontrollable factors are inverses of summation over truck haul, and shovel loading and truck-dumping times for each route. Historical production data of the mine contained in a data warehouse is used to derive probability distributions for the uncontrollable factors. The data warehouse is implemented in Microsoft SQL, and contains snapshots of historical equipment statuses and production outputs taken at regular intervals in each shift of the mine. Response Surface Methodology is applied to derive an expression for the variance of revenue as a function of controllable and uncontrollable factors. More specifically, 1) first order and second order effects for controllable factors, 2) first order effects for uncontrollable factors, and 3) two factor interactions for controllable and uncontrollable factors are considered. Latin Hypercube Sampling method is applied for setting controllable factors and the means of uncontrollable factors. Also, Common Random Numbers method is applied to generate the sequence of pseudo-random numbers for uncontrollable factors in simulation experiments for variance reduction between different design points of the metamodel. The variance of the metamodel is validated using leave-one-out cross validation. It is later applied as an additional constraint to the mathematical formulation to maximize revenue in the simulation model using OptQuest. The decision variables in this formulation are truck locks only. Revenue is a function of the actual quality of coal delivered to each customer and their corresponding quality specifications for premiums and penalties. OptQuest is an optimization add-on for Arena that uses Tabu search and Scatter search algorithms to arrive at the optimal solution. The upper bound on the variance as a constraint is varied to obtain different sets of expected value as well as variance of optimal revenue. After comparison with results using OptQuest with random sampling and without variance expression of metamodel, it has been shown that the proposed approach can be applied to obtain the decision variable set that not only results in a higher expected value but also a narrower confidence interval for optimum revenue. According to the best of our knowledge, there are two major contributions from this research: 1) It is theoretically demonstrated using 2-point and orthonormal k-point response surfaces that Common Random Numbers reduces the error in estimation of variance of metamodel of simulation model. 2) A data-driven modeling and simulation framework has been proposed for automatically generating discrete-event simulation model of large surface coal mines to reduce modeling time, expenditure, as well as human errors associated with manual development.

Lipases are widely researched enzyme group because of their ability to catalyze a wide range of synthesis reactions. The aim of this doctoral thesis was to study and optimize fatty acid ester synthesis using lipases. The influence of enzyme choice, its preparation (immobilization), choice of substrates and reaction conditions on fat hydrolysis, biodiesel and phenethyloctanoate (flavour ester) synthesis reaction course and yield was studied. Enterobacter aerogenes lipase, which was developed in Lithuania, was immobilized and its properties were determined for the first time. Commercial lipases were used for hydrolysis and synthesis reactions, the influence of reaction parameters was determined using response surface methodology, and so the yield was optimized. Silica gel was found to be a promising reaction additive for acyl group migration catalysis in biodiesel synthesis reaction. Different lipase specificities towards different acylglycerol classes and regioisomers varied greatly; on the basis of this knowledge two-step biodiesel synthesis catalysis was proposed. / Lipazių atranka ir taikymas riebalų rūgščių esterių sintezei Lipazės yra intensyviai tiriama fermentų grupė dėl jų gebos katalizuoti platų spektrą sintezės reakcijų. Disertacinio darbo tikslas buvo ištirti ir optimizuoti riebalų rūgščių esterių sintezės, panaudojant lipazes, būdus. Tirta fermento preparato paruošimo (imobilizavimo), fermento bei substratų pasirinkimo bei reakcijos sąlygų ir priedų įtaka riebalų hidrolizės, biodyzelino, fenetiloktanoato (kvapiojo esterio) sintezės reakcijų eigai ir išeigai. Pirmą kartą ištirtos Lietuvoje paruoštos Enterobacter aerogenes lipazės savybės, ji imobilizuota ant gamtinės kilmės nešiklių. Komercinių lipazių katalizuojamų reakcijų sąlygų įtakai nustatyti ir reakcijos išeigai optimizuoti naudota atsako paviršiaus metodologija. Tiriant reakcijos priedų įtaką acilgrupės migracijai ir biodyzelino sintezės reakcijai, nustatyta, kad perspektyvus priedas yra silikagelis. Lipazių specifiškumas ženkliai skiriasi skirtingoms acilglicerolių klasėms ir regioizomerams, šių žinių pagrindu buvo pasiūlyta dviejų etapų biodyzelino sintezės katalizė.

Lipazės yra intensyviai tiriama fermentų grupė dėl jų gebos katalizuoti platų spektrą sintezės reakcijų. Disertacinio darbo tikslas buvo ištirti ir optimizuoti riebalų rūgščių esterių sintezės, panaudojant lipazes, būdus. Tirta fermento preparato paruošimo (imobilizavimo), fermento bei substratų pasirinkimo bei reakcijos sąlygų ir priedų įtaka riebalų hidrolizės, biodyzelino, fenetiloktanoato (kvapiojo esterio) sintezės reakcijų eigai ir išeigai. Pirmą kartą ištirtos Lietuvoje paruoštos Enterobacter aerogenes lipazės savybės, ji imobilizuota ant gamtinės kilmės nešiklių. Komercinių lipazių katalizuojamų reakcijų sąlygų įtakai nustatyti ir reakcijos išeigai optimizuoti naudota atsako paviršiaus metodologija. Tiriant reakcijos priedų įtaką acilgrupės migracijai ir biodyzelino sintezės reakcijai, nustatyta, kad perspektyvus priedas yra silikagelis. Lipazių specifiškumas ženkliai skiriasi skirtingoms acilglicerolių klasėms ir regioizomerams, šių žinių pagrindu buvo pasiūlyta dviejų etapų biodyzelino sintezės katalizė. / Lipases are widely researched enzyme group because of their ability to catalyze a wide range of synthesis reactions. The aim of this doctoral thesis was to study and optimize fatty acid ester synthesis using lipases. The influence of enzyme choice, its preparation (immobilization), choice of substrates and reaction conditions on fat hydrolysis, biodiesel and phenethyloctanoate (flavour ester) synthesis reaction course and yield was studied. Enterobacter aerogenes lipase, which was developed in Lithuania, was immobilized and its properties were determined for the first time. Commercial lipases were used for hydrolysis and synthesis reactions, the influence of reaction parameters was determined using response surface methodology, and so the yield was optimized. Silica gel was found to be a promising reaction additive for acyl group migration catalysis in biodiesel synthesis reaction. Different lipase specificities towards different acylglycerol classes and regioisomers varied greatly; on the basis of this knowledge two-step biodiesel synthesis catalysis was proposed.

The purpose of this research was to determine the solubility of apricot (Prunus armeniaca L.) oil in supercritical carbon dioxide (SC-CO2), effects of parameters (particle size, solvent flow rate, pressure, temperature and co-solvent (ethanol) concentration) on extraction yield and to investigate the possibility of fractionation. Solubility, increased with pressure and increased with temperature above the crossover pressure, which was found between 200 and 300 bar, and decreased with temperature below the crossover pressure. Appropriate models were fitted to data. Extraction of apricot kernel oil occurred in two extraction periods as fast and slow extraction periods. Most of the oil was extracted in the fast extraction period and the oil recovered in the slow extraction period was negligible. Extraction yield increased with decrease in particle size and recovery of more than 99 % of the oil was possible if particle diameter decreased below 0.425 mm. Extraction rate increased with increase in flow rate, pressure, temperature and ethanol concentration. The volume mass transfer coefficient in the fluid phase changed between 0.6 and 3.7 /min, whereas the volume mass transfer coefficient in the solid phase changed between 0.00009 and 0.00048 /min. Extraction yield at 15 min for particle diameter smaller than 0.85 mm was formulated as a function of solvent flow rate, pressure, temperature, and ethanol concentration by using Response Surface Methodology. According to the model yield was highest (0.26 g /g) at 4 g/min flow rate, 60 oC, 450 bar and 3 % ethanol concentration. Fractionation was not possible at significant levels.

The main objective of this study was to optimize the processing conditions of breads baked in halogen lamp-microwave combination oven by using response surface methodology. It was also aimed to construct neural network models for the prediction of quality parameters of bread as a function of processing conditions. Different baking time and power combinations were used in order to find the optimum baking conditions of bread in halogen lamp-microwave combination oven. The independent variables were the baking time (4, 4.5, 5, 5.5, and 6 min), power of upper and lower halogen lamps (40, 50, 60, 70, and 80%), and power of the microwave (20, 30, 40, 50, and 60%). As control, breads baked in conventional oven at 200&ordm / C for 13 min were used. The measured quality parameters were the weight loss, color change, specific volume, porosity, and texture profile of the breads. Baking time, upper halogen lamp power, and microwave power were found to be significant on affecting most of the quality parameters. On the other hand, lower halogen lamp power was found to be an insignificant factor for all of the responses. For the optimization process, Response Surface Methodology (RSM) was used. The optimum baking conditions were determined as 5 min of baking time at 70% upper halogen lamp power, 50% lower halogen lamp power, and 20% microwave power. Breads baked at the optimum condition had comparable quality with conventionally baked ones. When halogen lamp-microwave combination oven was used, conventional baking time of breads was reduced by 60%. Artificial neural network models were developed for each of the quality parameters in order to observe the effects of the baking time and different oven conditions on the quality of the breads. High regression coefficients were calculated between the experimental data and predicted values showing that this method is capable in predicting quality parameters of breads during halogen lamp-microwave combination baking. In addition, the results were comparable to the RSM study.

The main objective of this study is to evaluate the effects of microwave frying process on the quality of potato slices and to optimize the process by using different statistical optimization techniques. Use of microwave frying for food products may be considered as a new way of improving the quality of the fried foods. In the first part of the study, the effects of microwaves on quality of fried potatoes (moisture content, oil content, color and hardness) were studied and the process was optimized by using Taguchi Technique. Microwave power level (400W, 550W and 700W), frying time (2.0, 2.5, 3.0 minutes) and oil type (sunflower, corn and hazelnut oil) were the parameters used in the study. Moisture content of potatoes decreased whereas oil content, hardness and &amp / #916 / E values of the potatoes increased with increasing frying time and microwave power level. The potatoes with the highest oil content were found to be the ones that were fried in the hazelnut oil. The optimum condition was found as frying at 550W microwave power level, for 2.5 minutes in sunflower oil. The potatoes that were fried at the optimum condition were determined to have lower oil contents compared to the ones fried conventionally.In the second part of the study, osmotic dehydration was applied prior to microwave frying process in order to reduce oil uptake and to evaluate the effect of osmotic dehydration with microwaves on quality of fried potatoes. The process was optimized by using both Taguchi Technique and Response Surface Methodology. Microwave power level (400W, 550W and 700W), frying time (1.5, 2.0, 2.5 minutes) and osmotic dehydration time (15, 30, 45 minutes) were the parameters used in the study. Osmotic dehydration treatment was conducted in a salt solution of 20 % (w/w) at 30oC. Moisture content decreased whereas oil content, hardness and &amp / #916 / E value of potatoes increased with increasing frying time and microwave power level. Dehydration of potatoes osmotically prior to frying reduced the oil content of fried potatoes. The optimum condition was found as frying at 400 W microwave power level for 1.5 min after 30 min of osmotic dehydration time according to Taguchi Technique. Microwave power level and frying time were the same as Taguchi Technique but osmotic dehydration time was 39 min for the optimum condition found using response surface methodology.