Recuperação e purificação de quitosanases usando adsorção em leito expandido com streamline DEAE com modelagem e simulação usando redes neurais

Expanded Bed Adsorption (EBA) is an integrative process that combines concepts of chromatography and fluidization of solids. The many parameters involved and their synergistic effects complicate the optimization of the process. Fortunately, some mathematical tools have been developed in order to guide the investigation of the EBA system. In this work the application of experimental design, phenomenological modeling and artificial neural networks (ANN) in understanding chitosanases adsorption on ion exchange resin Streamline® DEAE have been investigated. The strain Paenibacillus ehimensis NRRL B-23118 was used for chitosanase production. EBA experiments were carried out using a column of 2.6 cm inner diameter with 30.0 cm in height that was coupled to a peristaltic pump. At the bottom of the column there was a distributor of glass beads having a height of 3.0 cm. Assays for residence time distribution (RTD) revelead a high degree of mixing, however, the Richardson-Zaki coefficients showed that the column was on the threshold of stability. Isotherm models fitted the adsorption equilibrium data in the presence of lyotropic salts. The results of experiment design indicated that the ionic strength and superficial velocity are important to the recovery and purity of chitosanases. The molecular mass of the two chitosanases were approximately 23 kDa and 52 kDa as estimated by SDS-PAGE. The phenomenological modeling was aimed to describe the operations in batch and column chromatography. The simulations were performed in Microsoft Visual Studio. The kinetic rate constant model set to kinetic curves efficiently under conditions of initial enzyme activity 0.232, 0.142 e 0.079 UA/mL. The simulated breakthrough curves showed some differences with experimental data, especially regarding the slope. Sensitivity tests of the model on the surface velocity, axial dispersion and initial concentration showed agreement with the literature. The neural network was constructed in MATLAB and Neural Network Toolbox. The cross-validation was used to improve the ability of generalization. The parameters of ANN were improved to obtain the settings 6-6 (enzyme activity) and 9-6 (total protein), as well as tansig transfer function and Levenberg-Marquardt training algorithm. The neural Carlos Eduardo de Araújo Padilha dezembro/2013 9 networks simulations, including all the steps of cycle, showed good agreement with experimental data, with a correlation coefficient of approximately 0.974. The effects of input variables on profiles of the stages of loading, washing and elution were consistent with the literature

Determinação de dados de equilíbrio de fases para sistemas aquosos com eletrólitos

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer s ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

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

Equilíbrio líquido-líquido de sistemas aquosos com tensoativos polietoxilados: dados experimentais e modelagem

The nonionic surfactants when in aqueous solution, have the property of separating into two phases, one called diluted phase, with low concentration of surfactant, and the other one rich in surfactants called coacervate. The application of this kind of surfactant in extraction processes from aqueous solutions has been increasing over time, which implies the need for knowledge of the thermodynamic properties of these surfactants. In this study were determined the cloud point of polyethoxylated surfactants from nonilphenolpolietoxylated family (9,5 , 10 , 11, 12 and 13), the family from octilphenolpolietoxylated (10 e 11) and polyethoxylated lauryl alcohol (6 , 7, 8 and 9) varying the degree of ethoxylation. The method used to determine the cloud point was the observation of the turbidity of the solution heating to a ramp of 0.1 ° C / minute and for the pressure studies was used a cell high-pressure maximum ( 300 bar). Through the experimental data of the studied surfactants were used to the Flory - Huggins models, UNIQUAC and NRTL to describe the curves of cloud point, and it was studied the influence of NaCl concentration and pressure of the systems in the cloud point. This last parameter is important for the processes of oil recovery in which surfactant in solution are used in high pressures. While the effect of NaCl allows obtaining cloud points for temperatures closer to the room temperature, it is possible to use in processes without temperature control. The numerical method used to adjust the parameters was the Levenberg - Marquardt. For the model Flory- Huggins parameter settings were determined as enthalpy of the mixing, mixing entropy and the number of aggregations. For the UNIQUAC and NRTL models were adjusted interaction parameters aij using a quadratic dependence with temperature. The parameters obtained had good adjust to the experimental data RSMD < 0.3 %. The results showed that both, ethoxylation degree and pressure increase the cloudy points, whereas the NaCl decrease

Síntese e caracterização de tensoativos e estudo de equilíbrio de fase dos sistemas CnH2n+2/H2O/CnH2n+1COONa/But-OH

The growing utilization of surfactants in several different areas of industry has led to an increase on the studies involving solutions containing this type of molecules. Due to its amphiphilic nature, its molecule presents one polar part and one nonpolar end, which easily interacts with other molecules, being able to modify the media properties. When the concentration in which its monomers are saturated, the airliquid system interface is reached, causing a decrease in interfacial tension. The surfactants from pure fatty acids containing C8, C12 and C16 carbonic chains were synthesized in an alcoholic media using sodium hydroxide. They were characterized via thermal analysis (DTA and DTG) and via infrared spectroscopy, with the intention of observing their purity. Physical and chemical properties such as superficial tension, critical micelle concentration (c.m.c), surfactant excess on surface and Gibbs free energy of micellization were determined in order to understand the behaviour of these molecules with an aqueous media. Pseudo-ternary phase diagrams were obtained aiming to limit the Windsor equilibria conditions so it could be possible to understand how the surfactants carbonic chain size contributes to the microemulsion region. Solutions with known concentrations were prepared to study how the surfactants can influence the dynamic light scattering spectroscopy (DLS) and how the diffusion coefficient is influenced when the media concentration is altered. The results showed the variation on the chain size of the studied surfactant lipophilic part allows the conception of surfactants with similar interfacial properties, but dependent on the size of the lipophilic part of the surfactant. This variation causes the surfactant to have less tendency of microemulsionate oil in water. Another observed result is that the n-alcanes molecule size promoted a decrease on the microemulsion region on the obtained phase diagrams

Determinação de Dados de Equilíbrio Líquido-Vapor para Sistemas Hidrocarbonetos e Desenvolvimento de uma Nova Célula Dinâmica

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer's ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination Humberto Neves Maia de Oliveira Tese de Doutorado PPGEQ/PRH-ANP 14/UFRN of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Clássicos versus Keynes: a abordagem formal de David Champernowne

Este texto tem por objetivo ressaltar um aspecto que não tem sido tratado com a devida profundidade na literatura que estuda a formalização da Teoria Geral do Emprego, dos Juros e da Moeda de John Maynard Keynes (1936). Mais precisamente, o texto destaca a estratégia de formalização adotada por David G. Champernowne em seu artigo intitulado Unemployment, Basic and Monetary: the classical analysis and the keynesian, publicado em 1935-36 na Review of Economic Studies. Chamamos a atenção para o fato dele distinguir a teoria clássica da teoria de Keynes não apenas pelos pressupostos adotados por cada teoria, mas principalmente pela construção de subsistemas a partir de um sistema geral, com características recursivas (relações de causalidade) distintas. As explicações em prosa, a descrição algébrica das funções comportamentais e condições de equilíbrio e a ilustração por meio de diagramas, além da escolha de conjuntos específicos de variáveis para representar cada uma das teorias e suas diferentes versões são aspectos deste artigo de Champernowne que merecem uma análise mais minuciosa.

Refletindo dificuldades de aprendizagem de alunos do ensino médio no estudo do equilíbrio químico

This research intends to identify the main conceptual mistakes committed by High School students when studying Chemical Equilibrium and also how the didactic books can influence in their formation. For the data - collecting we applied 150 questionnaires with 11 open questions e 4 restricted ones. Students from three different private schools in Natal-RN were used in this survey. The questionary about the book analysis tried to understand how the subject has been boarded, making it easier or not for the knowledge building. The books were chosen by being usually the most used ones at the chemistry classes in the schools in town. On the didactic book analysis we evaluated 12 items that tried to identify the clarity with which the books would bring up the subjects, the contextualization of the exercises, the analogies used, the amount and the quality of exercises, the connections between the subjects, and the retaken of important concepts. The questionary given to the students tried to get their knowledge about the concepts related to Chemical Equilibrium. The main mistakes found were: the definition of the state of equilibrium in a chemical reaction, the constant, the double headed arrow, confusions between mass and concentration, the representation of a microscopic reaction in equilibrium, partial pressure and total pressure, and the function of the catalyser. The results demonstrated a lot of insecurity or lack of knowledge about the subject when it was realized that there was a big number of blank questions and a considerable percentage of questions with conceptual errors. We concluded that those errors could be eased or even avoided if the didactic books and the teachers boarded the contents in a more conceptual form with the application of a largest number of good quality exercices, watching the building of definitions by the students, avoiding this way the formation of wrong concepts

Formação de caudas maxwellianas no Contexto da rotação estelar

In this Thesis, we analyzed the formation of maxwellian tails of the distributions of the rotational velocity in the context of the out of equilibrium Boltzmann Gibbs statistical mechanics. We start from a unified model for the angular momentum loss rate which made possible the construction of a general theory for the rotational decay in the which, finally, through the compilation between standard Maxwellian and the relation of rotational decay, we defined the (_, _) Maxwellian distributions. The results reveal that the out of equilibrium Boltzmann Gibbs statistics supplies us results as good as the one of the Tsallis and Kaniadakis generalized statistics, besides allowing fittings controlled by physical properties extracted of the own theory of stellar rotation. In addition, our results point out that these generalized statistics converge to the one of Boltzmann Gibbs when we inserted, in your respective functions of distributions, a rotational velocity defined as a distribution

Teoria cinética não extensiva: efeitos físicos em gases e plasmas

The standard kinetic theory for a nonrelativistic diluted gas is generalized in the spirit of the nonextensive statistic distribution introduced by Tsallis. The new formalism depends on an arbitrary q parameter measuring the degree of nonextensivity. In the limit q = 1, the extensive Maxwell-Boltzmann theory is recovered. Starting from a purely kinetic deduction of the velocity q-distribution function, the Boltzmann H-teorem is generalized for including the possibility of nonextensive out of equilibrium effects. Based on this investigation, it is proved that Tsallis' distribution is the necessary and sufficient condition defining a thermodynamic equilibrium state in the nonextensive context. This result follows naturally from the generalized transport equation and also from the extended H-theorem. Two physical applications of the nonextensive effects have been considered. Closed analytic expressions were obtained for the Doppler broadening of spectral lines from an excited gas, as well as, for the dispersion relations describing the eletrostatic oscillations in a diluted electronic plasma. In the later case, a comparison with the experimental results strongly suggests a Tsallis distribution with the q parameter smaller than unity. A complementary study is related to the thermodynamic behavior of a relativistic imperfect simple fluid. Using nonequilibrium thermodynamics, we show how the basic primary variables, namely: the energy momentum tensor, the particle and entropy fluxes depend on the several dissipative processes present in the fluid. The temperature variation law for this moving imperfect fluid is also obtained, and the Eckart and Landau-Lifshitz formulations are recovered as particular cases

Estudos de modelos Estocásticos: processo de contato, séries aleatórias e processos difusivos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Propriedades críticas de sistemas fora do equilíbrio via simulação Monte Carlo

Conselho Nacional de Desenvolvimento Científico e Tecnológico

Efeitos do treinamento de dupla tarefa no controle do equilíbrio dinâmico e estático de idosas pré-frágeis: um estudo piloto

The increasing world population of older individuals has become a subject of growing research for prevention and reversibility of the frailty because it is a major risk factor for the occurrence of falls, especially when it involves everyday situations of dual task. Some rehabilitation programs have already used the methods of dual-task with general exercises for improving gait and postural control, but has been reported that these interventions have little specificity with limited success to improve certain aspects of static and dynamic position during the performance of functional tasks. This study aimed to verify the measures of postural control in a group of elderly women with fragility phenotype after physical therapy intervention program based on dual-task treadmill training. We selected six pre-frail elderly subjects, with a minimum age of 65, female, living in the community and randomly assigned to two groups. The survey was conducted twice a week for 45 minutes, for four weeks. The simple task intervention consisted only in training on a treadmill and the dual task consisted of in treadmill training associated with visual stimuli. The assessments were made with the use of the Berg Balance Scale (BBS) and the Balance Master® computerized posturography, static and dynamically. The effects of retention were observed after one month, using the same instruments earlier used. The results showed a tendency toward improvement or maintenance of the balance after training on a treadmill, especially with respect to static equilibrium. Both groups showed the most notable changes in the variables related to gait, as the length and speed. The BBS scores and the baropodometric variables showed that the experimental group could keep all values similar or better even one month after completion of training unlike the control group. We concluded that the dual-task performance had no additional value in relation to the improvement of balance in general, but we observed that the effectiveness of visual stimulation occurred in the maintenance of short term balancevariables

Efeito do método pilates no desempenho muscular e no equilíbrio corporal de mulheres idosas: ensaio clínico controlado randomizado

Background: The Pilates Method is a modality of exercise that has been growing in recent decades, but few researches has been conducted with elderly and little is known about its benefits in this population. Objective: To evaluate the effect of a program of Mat Pilates exercises in muscle performance and postural balance in elderly women. Materials and Method: This is a randomized controlled trial that evaluated the muscle performance (isokinetic dynamometer Biodex System 3 Pro®) and postural balance (Balance Master System®) of 33 women aged 65-80 years. The experimental group (EG) participated of a 12-week program of Mat Pilates exercises with two weekly sessions. Data normality was verified by the Shapiro - Wilk test and were adopted p value < 0.05 as significance level. Results: There were no differences between groups after training. However, the EG showed an increase in the values of extension and flexion average power to 60 ° / s after training (32.19 W to 37.04 W and 14.48 W to 17.56 W, respectively). Conclusion: The proposed exercise program was not effective in the total work and average power of flexor and extensor of the knee, as well as static and dynamic balance of participants

Comparação e mobilidade, equilíbrio corporal e desempenho muscular segundo a auto-eficácia para quedas em idosas

The aging process modifies various systems in the body, leading to changes in mobility, balance and muscle strength. This can cause a drop in the elderly, or not changing the perceived self-efficacy in preventing falls. Objective: To compare the mobility, body balance and muscle performance according to self-efficacy for falls in community-dwelling elderly. Methods: A cross-sectional comparative study with 63 older (65-80 years) community. Were evaluated for identification data and sociodemographic, cognitive screening using the Mini Mental State Examination (MMSE), effective for the fall of Falls Efficacy Scale International Brazil (FES-I-BRAZIL), Mobility through the Timed Up and Go Test , the balance Berg Balance Scale (BBS) and the Modified Clinical Test tests of Sensory Interaction on Balance (mCTSIB), tandem walk (TW) and Sit to Stand (STS) of the Balance Master® System. Finally, muscle performance by using isokinetic dynamometry. Statistical analysis was performed Student t test for comparison between groups, with p value ≤ 0.05. Results: Comparing the elderly with low-efficacy for falls with high-efficacy for falls, we found significant differences only for the variable Timed Up and Go Test (p = 0.04). With regard to data on balance tests were significant differences in the speed of oscillation firm surface eyes open modified Clinical Test of Sensory Interaction on Test of Balance (p = 0.01). Variables to isokinetic dynamometry were no significant differences in movement knee extension, as regards the variables peak torque (p = 0.04) and power (p = 0.03). Conclusion: The results suggest that, compared to older community with low-and high-efficacy for falls, we observed differences in variables related to mobility, balance and muscle function