Caracterização de látices acrílicos em função da neutralização de seus grupos carboxilas

Latexes based on acrylic acid, acrylamide, ethyl methacrylate, and ethyl acrylate were synthesized via emulsion polymerization with different monomer compositions. The resultant latices were thickened with different molar ratios of NaOH to acrylic acid and were analyzed in terms of acid‐basis titrimetry, turbidimetry, rheology, and tensiometry. Titrimetry, turbidimetry, and rheometry were used to analyze factors such as carboxyl group availability and particle solubilization, tensiometry monitoring the influence of carboxyl neutralization on polymer‐surfactant interactions. For the acrylic acid content used in this work (20 wt%), the results indicated that as carboxyl groups distribution became more homogeneous, the process of latex thickening became more effective

Síntese, estudo cinético e análise microestrutural do sistema cério-níquel obtido pelo método pechini

The cerium oxide has a high potential for use in removing pollutants after combustion, removal of organic matter in waste water and the fuel-cell technology. The nickel oxide is an attractive material due to its excellent chemical stability and their optical properties, electrical and magnetic. In this work, CeO2-NiO- systems on molars reasons 1:1(I), 1:2(II) e 1:3(III) metal-citric acid were synthesized using the Pechini method. We used techniques of TG / DTG and ATD to monitor the degradation process of organic matter to the formation of the oxide. By thermogravimetric analysis and applying the dynamic method proposed by Coats-Redfern, it was possible to study the reactions of thermal decomposition in order to propose the possible mechanism by which the reaction takes place, as well as the determination of kinetic parameters as activation energy, Ea, pre-exponential factor and parameters of activation. It was observed that both variables exert a significant influence on the formation of complex polymeric precursor. The model that best fitted the experimental data in the dynamic mode was R3, which consists of nuclear growth, which formed the nuclei grow to a continuous reaction interface, it proposes a spherical symmetry (order 2 / 3). The values of enthalpy of activation of the system showed that the reaction in the state of transition is exothermic. The variables of composition, together with the variable temperature of calcination were studied by different techniques such as XRD, IV and SEM. Also a study was conducted microstructure by the Rietveld method, the calculation routine was developed to run the package program FullProf Suite, and analyzed by pseudo-Voigt function. It was found that the molar ratio of variable metal-citric acid in the system CeO2-NiO (I), (II), (III) has strong influence on the microstructural properties, size of crystallites and microstrain network, and can be used to control these properties

Influência das tensões tectônicas na permeabilidade da formação Açu - Bacia Potiguar

The behavior of the fluid flux in oil fields is influenced by different factors and it has a big impact on the recovery of hydrocarbons. There is a need of evaluating and adapting the actual technology to the worldwide reservoirs reality, not only on the exploration (reservoir discovers) but also on the development of those that were already discovered, however not yet produced. The in situ combustion (ISC) is a suitable technique for these recovery of hydrocarbons, although it remains complex to be implemented. The main objective of this research was to study the application of the ISC as an advanced oil recovery technique through a parametric analysis of the process using vertical wells within a semi synthetic reservoir that had the characteristics from the brazilian northwest, in order to determine which of those parameters could influence the process, verifying the technical and economical viability of the method on the oil industry. For that analysis, a commercial reservoir simulation program for thermal processes was used, called steam thermal and advanced processes reservoir simulator (STARS) from the computer modeling group (CMG). This study aims, through the numerical analysis, find results that help improve mainly the interpretation and comprehension of the main problems related to the ISC method, which are not yet dominated. From the results obtained, it was proved that the mediation promoted by the thermal process ISC over the oil recovery is very important, with rates and cumulated production positively influenced by the method application. It was seen that the application of the method improves the oil mobility as a function of the heating when the combustion front forms inside the reservoir. Among all the analyzed parameters, the activation energy presented the bigger influence, it means, the lower the activation energy the bigger the fraction of recovered oil, as a function of the chemical reactions speed rise. It was also verified that the higher the enthalpy of the reaction, the bigger the fraction of recovered oil, due to a bigger amount of released energy inside the system, helping the ISC. The reservoir parameters: porosity and permeability showed to have lower influence on the ISC. Among the operational parameters that were analyzed, the injection rate was the one that showed a stronger influence on the ISC method, because, the higher the value of the injection rate, the higher was the result obtained, mainly due to maintaining the combustion front. In connection with the oxygen concentration, an increase of the percentage of this parameter translates into a higher fraction of recovered oil, because the quantity of fuel, helping the advance and the maintenance of the combustion front for a longer period of time. About the economic analysis, the ISC method showed to be economically feasible when evaluated through the net present value (NPV), considering the injection rates: the higher the injection rate, the higher the financial incomes of the final project

Lógica Fuzzy para Controle de pH em um Processo Petrolífero

This work proposes the design, the performance evaluation and a methodology for tuning the initial MFs parameters of output of a function based Takagi-Sugeno-Kang Fuzzy-PI controller to neutralize the pH in a stirred-tank reactor. The controller is designed to perform pH neutralization of industrial plants, mainly in units found in oil refineries where it is strongly required to mitigate uncertainties and nonlinearities. In addition, it adjusts the changes in pH regulating process, avoiding or reducing the need for retuning to maintain the desired performance. Based on the Hammerstein model, the system emulates a real plant that fits the changes in pH neutralization process of avoiding or reducing the need to retune. The controller performance is evaluated by overshoots, stabilization times, indices Integral of the Absolute Error (IAE) and Integral of the Absolute Value of the Error-weighted Time (ITAE), and using a metric developed by that takes into account both the error information and the control signal. The Fuzzy-PI controller is compared with PI and gain schedule PI controllers previously used in the testing plant, whose results can be found in the literature.

Estudo do mecanismo de produção de oligossacarídeos com atividades nutracêuticas a partir da quitosana por hidrólise enzimática com processo fermentativo simultâneo

The obtaining of the oligosaccharides from chitosanase, has showed interest of the pharmaceutical area in the last years due their countless functional properties. Although, the great challenge founded out is how to keep a constant and efficient production. The alternative proposed by this present work was to study the viability to develop an integrated technology, with reduced costs. The strategy used was the obtaining of the oligomers through enzymatic hydrolysis using chitosanolitic enzymes obtained straight from the fermented broth, eliminating this way the phases involved in the enzymes purification. The two chitosanases producing strains chosen for the work, Paenibacillus chitinolyticus and Paenibacillus ehimensis, were evaluated according to the behavior in the culture medium with simple sugar and in relation to the pH medium variations. The culture medium for the chitosanases induction and production was developed through addition of soluble chitosan as carbon source. The soluble chitosan was obtained using hydrochloric acid solution 0.1 M and afterwards neutralization with NaOH 10 M. The enzymatic complexes were obtained from induction process in culture medium with 0.2% of soluble chitosan. The enzymes production was verified soon after the consumption of the simple sugars by the microorganisms and the maximum chitosanolitic activity obtained in the fermented broth by Paenibacillus chitinolyticus was 249 U.L-1 and by Paenibacillus ehimensis was 495U.L-1. These two enzymatic complexes showed stability when stored at 20°C for about 91 days. The enzymes in the fermented broth by Paenibacillus chitinolyticus, when exposed at temperature of 55°C and pH 6.0, where the activity is maximum, showed 50% lost of activity after 3 hours Meanwhile, for the complex produced by Paenibacillus ehimensis, after 6 days of exposure, it was detected 100% of the activity. The chito-oligosaccharides obtained by the hydrolysis of a 1% chitosan solution, using the enzymatic complex produced by Paenibacillus chitinolyticus showed larger quantity after 9 hours hydrolysis and using the complex produced by Paenibacillus ehimensis after 20 minutes was observed the chito-ligosacharides with polymerization degree between 3 and 6 units. Evaluating these results, it was verified that the production of chitosan-oligosaccharides is possible, using a simultaneous process

Flotação por ar dissolvido na clarificação de águas com baixa turbidez utilizando sulfato de alumínio e sementes de Moringa oleifera como coagulantes

This work aims to investigate the process of Dissolved air Flotation (DAF) for clarifying water samples with low turbidity using aluminum sulphate and Moringa oleifera seeds as coagulants. The experimental procedure was carried out in a bench scale flotation unit. The influences on the pre-treatment conditions (coagulant dosage and flocculation time) and flotation parameters (superficial application rate and recirculation rate) were evaluated considering the efficiency of the process. The efficiency was evaluated by determining the turbidity of the untreated and treated water samples. The results obtained showed that turbidity reduction can be obtained very efficiently by using DAF and the latter coagulant in low turbidity water. Using aluminum sulphate in pH´s 5.0 and 6.0 better efficiencies were obtained with low concentrations (15 mg/L), achieving values of 92% of turbidity reduction. In the case of use of Moringa oleifera better efficiencies of reduction of turbidity were reported when using a concentration of 50 mg/L in all range of pH´s, achieving 86% of reduction. The zeta potential was also determined, in an attempt to aid comprehension of the coagulation mechanisms involved. The coagulation mechanisms with Moringa oleifera seeds were shown to be adsorption and charge neutralization, as well as adsorption and bridging. Concerning aluminum sulphate, the predominant mechanisms are adsorption and charge neutralization and enmeshment in a precipitate. The results indicate that for low turbidity water, Moringa oleifera seeds could potentially be a viable substitute for aluminum sulphate

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%.

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

Caracterização de soluções de quitosana por espalhamento dinâmico de luz

Dynamic light scattering was used to monitor relaxation processes in chitosan solutions at concentrations within the semi-dilute and concentrated regimes, Kowhlrausch-Williams-Watts (KWW) equation being successfully fitted to intensity correlation function data. The dependence of KWW equation parameters on chitosan concentration indicated that an increase in concentration from semi-dilute to concentrated regimes resulted in narrowing the distribution of relaxation rates; temperature dependence indicated the relaxation process as described as an energy activated process, whose parameters were function of the interaction between chitosan chains (enthalpy of activation) and rigidity of chitosan conformations (pre-exponential factor)

Estudo teórico QTAIM e DFT dos compostos de coordenação: efeito quelato, titanocenos e ligação química

This work is a study of coordination compounds by quantum theory of atoms in molecules (QTAIM), based on the topological analysis of the electron density of molecular systems, both theoretically and experimentally obtained. The coordination chemistry topics which were studied are the chelate effect, bent titanocene and chemical bond in coordination complexes. The chelate effect was investigated according to topological and thermodynamic parameters. The exchange of monodentate ligands on polydentate ligands from same transition metal increases the stability of the complex both from entropy and enthalpy contributions. In some cases, the latter had a higher contribution to the stability of the complex in comparison with entropy. This enthalpic contribution is explained according to topological analysis of the M-ligand bonds where polidentate complex had higher values of electron density of bond critical point, Laplacian of electron density of bond critical point and delocalization index (number of shared electrons between two atoms). In the second chapter, was studied bent titanocenes with bulky cyclopentadienyl derivative π-ligand. The topological study showed the presence of secondary interactions between the atoms of π-ligands or between atoms of π-ligand and -ligand. It was found that, in the case of titanocenes with small difference in point group symmetry and with bulky ligands, there was an nearly linear relationship between stability and delocalization index involving the ring carbon atoms (Cp) and the titanium. However, the titanocene stability is not only related to the interaction between Ti and C atoms of Cp ring, but secondary interactions also play important role on the stability of voluminous titanocenes. The third chapter deals with the chemical bond in coordination compounds by means of QTAIM. The quantum theory of atoms in molecules so far classifies bonds and chemical interactions in two categories: closed shell interaction (ionic bond, hydrogen bond, van der Waals interaction, etc) and shared interaction (covalent bond). Based on topological parameters such as electron density, Laplacian of electron density, delocalization index, among others, was classified the chemical bond in coordination compounds as an intermediate between closed shell and shared interactions

Produção de filtrantes ativados a partir de aproveitamento de resíduos: uma proposta para a proteção respiratória ocupacional

A Proteção Respiratória Ocupacional é atualmente uma exigência legal do Ministério do Trabalho e Emprego para garantia da saúde e segurança de milhares de trabalhadores que labutam com exposição habitual a substâncias nocivas que possam ocasionar doenças ocupacionais por inalação de ar contaminado no local de trabalho, cuja principal via de penetração no organismo humano é o Sistema Respiratório. Carvões ativados são materiais obtidos a partir de fontes carbonáceas e utilizados como elemento tecnológico filtrante nos equipamentos destinados a proteção respiratória individual. Fomentada por esse contexto, e visando potencializar conceitos de eco-eficiência e sustentabilidade em produção de materiais, este trabalho destina-se a produção de carvão ativado com potencial filtrante a partir de um rejeito agrícola abundante na região Nordeste do Brasil através de uma rota que favorece carbonização e ativação simultâneas, seguido de neutralização térmica. A biomassa precursora foi caracterizada por Ensaios padrões para determinação do teor de umidade e cinzas, Análise Química Elementar, Análises Térmicas (TG e DSC) e Distribuição Granulométrica por difração a laser. As amostras de carvões ativos sintetizadas foram caracterizadas por Difração de Raios X (DRX), Medidas de área específica por BET, Microscopia Eletrônica de Varredura (MEV), Análise assistida com ultravioleta visível e Redução à Temperatura Programada (TPR) por Amônia. A rota empregada favorece uma tecnologia alternativa para o aproveitamento de resíduos e aplicável para a Proteção Respiratória Ocupacional. A atmosfera de queima influencia diretamente na produção. A temperatura de carbonização variou conforme a estabilidade térmica da amostra. A cristalinidade, morfologia, teor mineralógico, área superficial específica e a adsorção em fase líquida e gasosa variaram em função da interação do resíduo precursor com o tipo e concentração de ácido utilizado. Os ensaios de adsorção demonstraram a efetividade da ativação segundo a rota experimental proposta. O potencial catalítico dos materiais produzidos para uso em máscaras respiratórias foi evidenciado pelo ensaio de TPR. O processo de produção estudado se mostrou eficaz para obtenção dos carvões promovendo processamentos e aplicações mais nobres para materiais cujo uso tem sido restrito a meras aplicações primárias ou descarte, mas cujo potencial tecnológico é amplo, empreendedor, sustentável, viável em escala industrial e de baixo custo.

Síntese, estudo cinético e análise microestrutural do sistema cério-níquel obtido pelo método pechini

The cerium oxide has a high potential for use in removing pollutants after combustion, removal of organic matter in waste water and the fuel-cell technology. The nickel oxide is an attractive material due to its excellent chemical stability and their optical properties, electrical and magnetic. In this work, CeO2-NiO- systems on molars reasons 1:1(I), 1:2(II) e 1:3(III) metal-citric acid were synthesized using the Pechini method. We used techniques of TG / DTG and ATD to monitor the degradation process of organic matter to the formation of the oxide. By thermogravimetric analysis and applying the dynamic method proposed by Coats-Redfern, it was possible to study the reactions of thermal decomposition in order to propose the possible mechanism by which the reaction takes place, as well as the determination of kinetic parameters as activation energy, Ea, pre-exponential factor and parameters of activation. It was observed that both variables exert a significant influence on the formation of complex polymeric precursor. The model that best fitted the experimental data in the dynamic mode was R3, which consists of nuclear growth, which formed the nuclei grow to a continuous reaction interface, it proposes a spherical symmetry (order 2 / 3). The values of enthalpy of activation of the system showed that the reaction in the state of transition is exothermic. The variables of composition, together with the variable temperature of calcination were studied by different techniques such as XRD, IV and SEM. Also a study was conducted microstructure by the Rietveld method, the calculation routine was developed to run the package program FullProf Suite, and analyzed by pseudo-Voigt function. It was found that the molar ratio of variable metal-citric acid in the system CeO2-NiO (I), (II), (III) has strong influence on the microstructural properties, size of crystallites and microstrain network, and can be used to control these properties

Influência das tensões tectônicas na permeabilidade da formação Açu - Bacia Potiguar

The behavior of the fluid flux in oil fields is influenced by different factors and it has a big impact on the recovery of hydrocarbons. There is a need of evaluating and adapting the actual technology to the worldwide reservoirs reality, not only on the exploration (reservoir discovers) but also on the development of those that were already discovered, however not yet produced. The in situ combustion (ISC) is a suitable technique for these recovery of hydrocarbons, although it remains complex to be implemented. The main objective of this research was to study the application of the ISC as an advanced oil recovery technique through a parametric analysis of the process using vertical wells within a semi synthetic reservoir that had the characteristics from the brazilian northwest, in order to determine which of those parameters could influence the process, verifying the technical and economical viability of the method on the oil industry. For that analysis, a commercial reservoir simulation program for thermal processes was used, called steam thermal and advanced processes reservoir simulator (STARS) from the computer modeling group (CMG). This study aims, through the numerical analysis, find results that help improve mainly the interpretation and comprehension of the main problems related to the ISC method, which are not yet dominated. From the results obtained, it was proved that the mediation promoted by the thermal process ISC over the oil recovery is very important, with rates and cumulated production positively influenced by the method application. It was seen that the application of the method improves the oil mobility as a function of the heating when the combustion front forms inside the reservoir. Among all the analyzed parameters, the activation energy presented the bigger influence, it means, the lower the activation energy the bigger the fraction of recovered oil, as a function of the chemical reactions speed rise. It was also verified that the higher the enthalpy of the reaction, the bigger the fraction of recovered oil, due to a bigger amount of released energy inside the system, helping the ISC. The reservoir parameters: porosity and permeability showed to have lower influence on the ISC. Among the operational parameters that were analyzed, the injection rate was the one that showed a stronger influence on the ISC method, because, the higher the value of the injection rate, the higher was the result obtained, mainly due to maintaining the combustion front. In connection with the oxygen concentration, an increase of the percentage of this parameter translates into a higher fraction of recovered oil, because the quantity of fuel, helping the advance and the maintenance of the combustion front for a longer period of time. About the economic analysis, the ISC method showed to be economically feasible when evaluated through the net present value (NPV), considering the injection rates: the higher the injection rate, the higher the financial incomes of the final project