Aplicação da parafina e do óleo de linhaça como hidrofobizantes da vermiculita, para remoção de derivados de óleo diesel resentes em água produzida sintética

Produced water has lately aroused interest due to their high degree of salinity, suspended oil particles, chemicals added in various manufacturing processes, heavy metals and radioactivity sometimes. Along with oil and due to its high volume production, water production is one of the pollutants of most concern in the process of oil extraction. PAHs due to their ubiquity and their characteristics carcinogenic or mutagenic and teratogenic even have attracted the attention of every scientific society. Formed from the incomplete combustion of organic matter may be natural or anthropogenic. Some materials have been researched with the goal of cleaning up environmental matrices that may be contaminated by hydrocarbons. Among these materials researched various clays have been employed, of which highlights the vermiculite. The family of phyllosilicates, vermiculite for its potential and its high hydrophobic surface area has been a tool widely used in the decontamination of water in processes of oil spills. However, when it loses its capacity expanded hydrophobic having the necessity of using a hidrofobizante to make it organophilic. Among the numerous hidrofobizantes researched and used the linseed oil was the pioneer. In this study sought to evaluate the capacity of removal of PAHs using the vermiculite hydrofobized with linseed oil and wax also, for it was made use of the 24 full factorial design as the main tool for the experiments. We also evaluated the clay grain size (-20 +48 and -48 +80 #), the percentage of hidrofobizante applied (5 and 10%) and salinity of the water produced synthesized in our laboratory (35,000 and 55,000 ppm). The molecular fluorescence spectroscopy due to its sensitivity and speed was used to verify the adsorption capacity of clay, as well as gas chromatography served as an auxiliary technique to identify and quantify the PAHs in solution. In order to characterize the vermiculite was made use of X-ray fluorescence and X-ray diffraction. The infrared and thermogravimetry were essential to note hydrophobization and the amount of coating of clay. According to the fluorescence analysis showed that the test 12 was the best result in about 98% adsorption of fluorescent compounds, however the high salinity, the smallest particle size, the highest percentage of hidrofobizante and the use of linseed oil showed greater efficiency in the removal capacity of these hydrocarbons, in accordance with the trend followed by the analysis of the major factors of the factorial design. To verify the adsorption capacity of clay using a fixed volume of water produced synthetically, used as the test base 12, at their respective levels and factors. Thus, it was observed that after adding about 1 ½ liters of water solution produced synthetically, about 300 times its volume in mass, the vermiculite was able to adsorb 80% of fluorescent species present in solution

Síntese e caracterização do poli(ácido láctico) para potencial uso em sistemas de liberação controlada de fármacos

With the advances in medicine, life expectancy of the world population has grown considerably in recent decades. Studies have been performed in order to maintain the quality of life through the development of new drugs and new surgical procedures. Biomaterials is an example of the researches to improve quality of life, and its use goes from the reconstruction of tissues and organs affected by diseases or other types of failure, to use in drug delivery system able to prolong the drug in the body and increase its bioavailability. Biopolymers are a class of biomaterials widely targeted by researchers since they have ideal properties for biomedical applications, such as high biocompatibility and biodegradability. Poly (lactic acid) (PLA) is a biopolymer used as a biomaterial and its monomer, lactic acid, is eliminated by the Krebs Cycle (citric acid cycle). It is possible to synthesize PLA through various synthesis routes, however, the direct polycondensation is cheaper due the use of few steps of polymerization. In this work we used experimental design (DOE) to produce PLAs with different molecular weight from the direct polycondensation of lactic acid, with characteristics suitable for use in drug delivery system (DDS). Through the experimental design it was noted that the time of esterification, in the direct polycondensation, is the most important stage to obtain a higher molecular weight. The Fourier Transform Infrared (FTIR) spectrograms obtained were equivalent to the PLAs available in the literature. Results of Differential Scanning Calorimetry (DSC) showed that all PLAs produced are semicrystalline with glass transition temperatures (Tgs) ranging between 36 - 48 °C, and melting temperatures (Tm) ranging from 117 to 130 °C. The PLAs molecular weight characterized from Size Exclusion Chromatography (SEC), varied from 1000 to 11,000 g/mol. PLAs obtained showed a fibrous morphology characterized by Scanning Electron Microscopy (SEM)

Síntese do Poli (ácido láctico) por policondensação direta utilizando um planejamento fatorial

The environmental impact caused by the disposal of non-biodegradable polymer packaging on the environment, as well as the high price and scarcity of oil, caused increase of searches in the area of biodegradable polymers from renewable resources were developed. The poly (lactic acid) (PLA) is a promising polymer in the market, with a large availability of raw material for the production of its monomer, as well as good processability. The aimed of this study was synthesis PLA by direct polycondesation of lactic acid, using the tool of experimental design (DOE) (central composite rotatable design (CCRD)) to optimize the conditions of synthesis. The polymer obtained was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), viscosimetric analysis, differential scanning calorimeter (DSC) and size exclusion chromatography (SEC). The results confirmed the formation of a poly (lactic acid) semicrystalline in the syntheses performed. Through the central composite rotatable design was possible to optimize the crystallization temperature (Tc) and crystallinity degree (Xc). The crystallization temperature maximum was found for percentage of catalyst around the central point (0,3 (%W)) and values of time ranging from the central point (6h) to the upper level (+1) (8h). The crystallization temperature maximum was found for the total synthesis time of 4h (-1) and percentage of catalyst 0,1(W%) (-1). The results of size exclusion chromatography (SEC) showed higher molecular weights to 0,3 (W%) percent of catalyst and total time synthesis of 3,2h

Síntese enzimática de ésteres de açúcar: surfactantes e polímeros como novos materiais ambientalmente seguros

Sugar esters are substances which possess surfactant, antifungical and bactericidal actions and can be obtained through two renewable sources of raw materials: sugars and vegetable oils. Their excellent biodegradability, allied to lhe fact that they are non toxic, insipid, inodorous, biocompatible, no-ionic, digestible and because they can resist to adverse conditions of temperature, pH and salinity, explain lhe crescent use of these substances in several sections of lhe industry. The objective of this thesis was to synthesize and characterize surfactants and polymers containing sugar branched in their structures, through enzymatic transesterification of vinyl esters and sugars, using alkaline protease from Bacillus subtilis as catalyst, in organic medium (DMF).Three types of sugars were used: L-arabinose, D-glucose and sucrose and two types of vinyl esters: vinyl laurate and vinyl adipate. Aiming to reach high conversions from substrates to products for a possible future large scale industrial production, a serie of variables was optimized, through Design of Experiments (DOE), using Response Surface Methodology (RSM).The investigated variables were: (1) enzyme concentration; (2) molar reason of substrates; (3) water/solvent rale; (4) temperature and (5) time. We obtained six distinct sugar esters: 5-0-lauroyl L-arabinose, 6-0-lauroyl D-glucose, 1'-O-lauroyl sucrose, 5-0-vinyladipoyl L-arabinose, 6-0-vinyladipoyl D-glucose and 1 '-O-vinyladipoyl sucrose, being lhe last three polymerizable. The progress of lhe reaction was monitored by HPLC analysis, through lhe decrease of sugar concentration in comparison to lhe blank. Qualitative analysis by TLC confirmed lhe formation of lhe products. In lhe purification step, two methodologies were adopted: (1) chromatographic column and (2) extraction with hot acetone. The acylation position and lhe chemical structure were determined by 13C-RMN. The polymerization of lhe three vinyl sugar esters was possible, through chemical catalysis, using H2O2 and K2S2O8 as initiators, at 60°C, for 24 hours. IR spectra of lhe monomers and respective polymers were compared revealing lhe disappearance of lhe vinyl group in lhe polymer spectra. The molar weights of lhe polymers were determined by GPC and presented lhe following results: poly (5-0-vinyladipoyl L-arabinose): Mw = 7.2 X 104; PD = 2.48; poly (6-0-vinyladipoyl D-glucose): Mw = 2.7 X 103; PD = 1.75 and poly (1'-O-vinyladipoyl sucrose): Mw = 4.2 X 104; PD = 6.57. The six sugar esters were submitted to superficial tension tests for determination of the critical micelle concentrations (CMC), which varied from 122 to 167 ppm. Finally, a study of applicability of these sugar esters, as lubricants for completion fluids of petroleum wells was' accomplished through comparative analysis of lhe efficiency of these sugar esters, in relation to three commercial lubricants. The products synthesized in this thesis presented equivalent or superior action to lhe tested commercial products

Desgaste de polímeros estruturais de engenharia em contato de deslizamento com cilindro metálico

Present work proposed to map and features the wear mechanisms of structural polymers of engineering derived of the sliding contact with a metallic cylindrical spindle submitted to eccentricity due to fluctuations in it is mass and geometric centers. For this it was projected and makes an experimental apparatus from balancing machine where the cylindrical counterbody was supported in two bearings and the polymeric coupon was situated in a holder with freedom of displacement along counterbody. Thus, the experimental tests were standardized using two position of the two bearings (Fixed or Free) and seven different positions along the counterbody, that permit print different conditions to the stiffness from system. Others parameters as applied normal load, sliding velocity and distance were fixed. In this investigation it was used as coupon two structural polymers of wide quotidian use, PTFE (polytetrafluroethylene) and PEEK (poly-ether-ether-ketone) and the AISI 4140 alloy steel as counterbody. Polymeric materials were characterized by thermal analysis (thermogravimetric, differential scanning calorimetry and dynamic-mechanical), hardness and rays-X diffractometry. While the metallic material was submitted at hardness, mechanical resistance tests and metallographic analysis. During the tribological tests were recorded the heating response with thermometers, yonder overall velocity vibration (VGV) and the acceleration using accelerometers. After tests the wear surface of the coupons were analyzed using a Scanning Electronic Microscopy (SEM) to morphological analysis and spectroscopy EDS to microanalysis. Moreover the roughness of the counterbody was characterized before and after the tribological tests. It was observed that the tribological response of the polymers were different in function of their distinct molecular structure. It were identified the predominant wear mechanisms in each polymer. The VGV of the PTFE was smaller than PEEK, in the condition of minimum stiffness, in function of the higher loss coefficient of that polymer. Wear rate of the PTFE was more of a magnitude order higher than PEEK. With the results was possible developed a correlation between the wear rate and parameter (E/ρ)1/2 (Young modulus, E, density, ρ), proportional at longitudinal elastic wave velocity in the material.

Os Polímeros como Sistemas Complexos

Neste trabalho, através de simulações computacionais, identificamos os fenômenos físicos associados ao crescimento e a dinâmica de polímeros como sistemas complexos exibindo comportamentos não linearidades, caos, criticalidade auto-organizada, entre outros. No primeiro capítulo, iniciamos com uma breve introdução onde descrevemos alguns conceitos básicos importantes ao entendimento do nosso trabalho. O capítulo 2 consiste na descrição do nosso estudo da distribuição de segmentos num polímero ramificado. Baseado em cálculos semelhantes aos usados em cadeias poliméricas lineares, utilizamos o modelo de crescimento para polímeros ramificados (Branched Polymer Growth Model - BPGM) proposto por Lucena et al., e analisamos a distribuição de probabilidade dos monômeros num polímero ramificado em 2 dimensões, até então desconhecida. No capítulo seguinte estudamos a classe de universalidade dos polímeros ramificados gerados pelo BPGM. Utilizando simulações computacionais em 3 dimensões do modelo proposto por Lucena et al., calculamos algumas dimensões críticas (dimensões fractal, mínima e química) para tentar elucidar a questão da classe de universalidade. Ainda neste Capítulo, descrevemos um novo modelo para a simulação de polímeros ramificados que foi por nós desenvolvido de modo a poupar esforço computacional. Em seguida, no capítulo 4 estudamos o comportamento caótico do crescimento de polímeros gerados pelo BPGM. Partimos de polímeros criticamente organizados e utilizamos uma técnica muito semelhante aquela usada em transições de fase em Modelos de Ising para estudar propagação de danos chamada de Distância de Hamming. Vimos que a distância de Hamming para o caso dos polímeros ramificados se comporta como uma lei de potência, indicando um caráter não-extensivo na dinâmica de crescimento. No Capítulo 5 analisamos o movimento molecular de cadeias poliméricas na presença de obstáculos e de gradientes de potenciais. Usamos um modelo generalizado de reptação para estudar a difusão de polímeros lineares em meios desordenados. Investigamos a evolução temporal destas cadeias em redes quadradas e medimos os tempos característicos de transporte t. Finalizamos esta dissertação com um capítulo contendo a conclusão geral denoss o trabalho (Capítulo 6), mais dois apêndices (Apêndices A e B) contendo a fenomenologia básica para alguns conceitos que utilizaremos ao longo desta tese (Fractais e Percolação respectivamente) e um terceiro e ´ultimo apêndice (Apêndice C) contendo uma descrição de um programa de computador para simular o crescimentos de polímeros ramificados em uma rede quadrada

Influência de tensoativos não iônicos na destilação molecular de petróleo

The molecular distillation is show as an alternative for separation and purification of various kinds of materials. The process is a special case of evaporation at high vacuum, in the order from 0.001 to 0.0001 mmHg and therefore occurs at relatively lower temperatures, preserves the material to be purified. In Brazil, molecular distillation is very applied in the separation of petroleum fractions. However, most studies evaluated the temperature of the evaporator, condenser temperature and flow such variables of the molecular distillation oil. Then, to increase the degree of recovery of the fraction of the distillate obtained in the process of the molecular distillation was evaluated the use nonionic surfactants of the class of nonylphenol ethoxylate, molecules able to interact in the liquid-liquid and liquid-vapor interface various systems. In this context, the aim of this work was to verify the influence of commercial surfactant (Ultranex-18 an Ultranex-18-50) in the molecular distillation of a crude oil. The physicochemical characterization of the oil was realized and the petroleum shown an API gravity of 42°, a light oil. Initially, studied the molecular distillation without surfactant using star design experimental (2H ± ) evaluated two variables (evaporator temperature and condenser temperature) and answer variable was the percentage in distillate obtained in the process (D%). The best experimental condition to molecular distillation oil (38% distillate) was obtained at evaporator and condenser temperatures of 120 °C and 10 ° C, respectively. Subsequently, to determine the range of surfactant concentration to be applied in the process, was determined the critical micellar concentration by the technique of scattering X-ray small angle (SAXS). The surfactants Ultranex-18 an Ultranex-18-50 shown the critical micelle concentration in the range of 10-2 mol/L in the hydrocarbons studied. Then, was applied in the study of distillation a concentration range from 0.01 to 0.15 mol/L of the surfactants (Ultranex- 18 and 50). The use of the nonionic surfactant increased the percentage of hydrocarbons in the range from 5 to 9 carbons in comparison to the process carried out without surfactant, and in some experimental conditions the fraction of light compounds in the distilled was over 700% compared to the conventional process. The study showed that increasing the degree of ethoxylation of Ultranex18 to Ultranex-50, the compounds in the range of C5 to C9 reduced the percentage in the distilled, since the increase of the hydrophilic part of the surfactant reduces its solubility in the oil. Finally, was obtained an increase in the degree of recovery of light hydrocarbons, comparing processes with and without surfactant, obtained an increase of 10% and 4% with Ultranex-18 and Ultranex-50, respectively. Thus, it is concluded that the Ultranex- 18 surfactant showed a higher capacity to distillation compared with Ultranex-50 and the application of surfactant on the molecular distillation from petroleum allowed for a greater recovery of light compounds in distillate

Estudo paramétrico da injeção de polímeros em reservatórios de petróleo

Developing an efficient methodology for oil recovery is extremely important . Within the range of enh anced oil recovery, known as EOR, the injection of polymer solutions becomes effective in controlling the mobility of displacing fluid . This method consists of adding polymers to the injection water to increase its viscosity, so that more water diffuses in to the porous medium and increasing the sweep efficiency in the reservoir. This work is studied by numerical simulation , application of the injection polymer solution in a homogeneous reservoir , semisynthetic with similar characteristics to the reservoirs of the Brazilian Northeast , numerical simulations were performed using thermal simulator STARS from CMG (Computer Modelling Group ). The study aimed to analyze the influence of some parameters on the behavior of reservoir oil production, with the response to cumulative production. Simulations were performed to analyze the influence of water injection, polymer solution and alternating injection of water banks and polymer solution, comparing the results for each simulated condition. The primary outcomes were: oil viscosity, percentage of injected polymer, polymer viscosity and flow rate of water injection. The evaluation of the influence of variables consisted of a complete experimental design followed a Pareto analysis for the purpose of pointing out which va riables would be most influential on the response represented b y the cumulative oil production . It was found that all variables significantly influenced the recovery of oil and the injection of polymer solution on an ongoing basis is more efficient for the cumulative production compared to oil recovery by continuous water injection. The primary recovery show ed low levels of oil production , water injection significantly improves the pro duction of oil in the reservoir , but the injection of polymer solution em erges as a new methodology to increase the production of oil, increasing the life of the well and possible reduction of water produced.

Simulação da destilação molecular de filme descendente para o petróleo

The heavy part of the oil can be used for numerous purposes, e.g. to obtain lubricating oils. In this context, many researchers have been studying alternatives such separation of crude oil components, among which may be mentioned molecular distillation. Molecular distillation is a forced evaporation technique different from other conventional processes in the literature. This process can be classified as a special distillation case under high vacuum with pressures that reach extremely low ranges of the order of 0.1 Pascal. The evaporation and condensation surfaces must have a distance from each other of the magnitude order of mean free path of the evaporated molecules, that is, molecules evaporated easily reach the condenser, because they find a route without obstacles, what is desirable. Thus, the main contribution of this work is the simulation of the falling-film molecular distillation for crude oil mixtures. The crude oil was characterized using UniSim® Design and R430 Aspen HYSYS® V8.5. The results of this characterization were performed in spreadsheets of Microsoft® Excel®, calculations of the physicochemical properties of the waste of an oil sample, i.e., thermodynamic and transport. Based on this estimated properties and boundary conditions suggested by the literature, equations of temperature and concentration profiles were resolved through the implicit finite difference method using the programming language Visual Basic® (VBA) for Excel®. The result of the temperature profile showed consistent with the reproduced by literature, having in their initial values a slight distortion as a result of the nature of the studied oil is lighter than the literature, since the results of the concentration profiles were effective allowing realize that the concentration of the more volatile decreases and of the less volatile increases due to the length of the evaporator. According to the transport phenomena present in the process, the velocity profile tends to increase to a peak and then decreases, and the film thickness decreases, both as a function of the evaporator length. It is concluded that the simulation code in Visual Basic® language (VBA) is a final product of the work that allows application to molecular distillation of petroleum and other similar mixtures.

Uma nova proposta de fluidos de perfuração aquosos à base de polímeros vinílicos e bentonita para poços de alta temperatura e pressão

The advance of drilling in deeper wells has required more thermostable materials. The use of synthetic fluids, which usually have a good chemical stability, faces the environmental constraints, besides it usually generate more discharge and require a costly disposal treatment of drilled cuttings, which are often not efficient and require mechanical components that hinder the operation. The adoption of aqueous fluids generally involves the use of chrome lignosulfonate, used as dispersant, which provides stability on rheological properties and fluid loss under high temperatures and pressures (HTHP). However, due to the environmental impact associated with the use of chrome compounds, the drilling industry needs alternatives that maintain the integrity of the property and ensure success of the operation in view of the strong influence of temperature on the viscosity of aqueous fluids and polymers used in these type fluids, often polysaccharides, passives of hydrolysis and biological degradation. Therefore, vinyl polymers were selected for this study because they have predominantly carbon chain and, in particular, polyvinylpyrrolidone (PVP) for resisting higher temperatures and partially hydrolyzed polyacrylamide (PHPA) and clay by increasing the system's viscosity. Moreover, the absence of acetal bonds reduces the sensitivity to attacks by bacteria. In order to develop an aqueous drilling fluid system for HTHP applications using PVP, HPAM and clay, as main constituents, fluid formulations were prepared and determined its rheological properties using rotary viscometer of the Fann, and volume filtrate obtained by filtration HTHP following the standard API 13B-2. The new fluid system using polyvinylpyrrolidone (PVP) with high molar weight had higher viscosities, gels and yield strength, due to the effect of flocculating clay. On the other hand, the low molecular weight PVP contributed to the formation of disperse systems with lower values in the rheological properties and fluid loss. Both systems are characterized by thermal stability gain up to around 120 ° C, keeping stable rheological parameters. The results were further corroborated through linear clay swelling tests.

Uma nova proposta de fluidos de perfuração aquosos à base de polímeros vinílicos e bentonita para poços de alta temperatura e pressão

The advance of drilling in deeper wells has required more thermostable materials. The use of synthetic fluids, which usually have a good chemical stability, faces the environmental constraints, besides it usually generate more discharge and require a costly disposal treatment of drilled cuttings, which are often not efficient and require mechanical components that hinder the operation. The adoption of aqueous fluids generally involves the use of chrome lignosulfonate, used as dispersant, which provides stability on rheological properties and fluid loss under high temperatures and pressures (HTHP). However, due to the environmental impact associated with the use of chrome compounds, the drilling industry needs alternatives that maintain the integrity of the property and ensure success of the operation in view of the strong influence of temperature on the viscosity of aqueous fluids and polymers used in these type fluids, often polysaccharides, passives of hydrolysis and biological degradation. Therefore, vinyl polymers were selected for this study because they have predominantly carbon chain and, in particular, polyvinylpyrrolidone (PVP) for resisting higher temperatures and partially hydrolyzed polyacrylamide (PHPA) and clay by increasing the system's viscosity. Moreover, the absence of acetal bonds reduces the sensitivity to attacks by bacteria. In order to develop an aqueous drilling fluid system for HTHP applications using PVP, HPAM and clay, as main constituents, fluid formulations were prepared and determined its rheological properties using rotary viscometer of the Fann, and volume filtrate obtained by filtration HTHP following the standard API 13B-2. The new fluid system using polyvinylpyrrolidone (PVP) with high molar weight had higher viscosities, gels and yield strength, due to the effect of flocculating clay. On the other hand, the low molecular weight PVP contributed to the formation of disperse systems with lower values in the rheological properties and fluid loss. Both systems are characterized by thermal stability gain up to around 120 ° C, keeping stable rheological parameters. The results were further corroborated through linear clay swelling tests.

Concentração do óleo de girassol em compostos insaturados utilizando destilação molecular

Vegetable oils are characterized as important raw materials in the supplying of natural substances of interest pharmaceutical, food and cosmetic industry. Sunflower oil stands out for its important composition present in unsaturated fatty acids such as oleic acid (C18:1) and linoleic (C18:2), responsible for many health benefits. The main objective of this study is obtain enriched fractions in unsaturated compounds from refined sunflower oil. The oil used in this study was characterized by the determination of some properties, like iodine number, acid number and viscosity. A transesterification was done to transform the triglycerides into their corresponding methyl esters of fatty acids. These was submitted the molecular distillation process, for present as an efficient alternative to separation and purification of these substances, using high vacuum and low temperatures. Of the esters fractions that was obtained, were analyzed by gas chromatography. The experimental design technique was used to evaluate the influence of the temperature variation of evaporation and condensation system on the percentage obtained residue. The evaporator temperature proved to be the most influential variable on the studied response. The optimized conditions for the answer was studied at 100 °C for evaporator temperature and 10 °C for the condenser temperature. The graph of "split ratio" showed that for the lowest flow feed (1 mL/min) and higher evaporator temperature (110 °C) was obtained in the largest fraction of distillate. It also used the study of the influence of evaporator temperature on the concentration of unsaturated compounds. The best operating conditions for temperature was 90 °C reached 82.21 % of unsaturated compounds. Elimination curves of the unsaturated compounds present in the distillate stream were obtained. The simulation results of the molecular distillation process of sunflower oil showed the concentration profiles for three different feed flow rates. The speed, temperature and thickness profiles of the liquid film were obtained. The speed of the film increases as the fluid flows through the walls of the evaporator, reaching a maximum on length of 0.075 m. The film thickness decreases on the route, since many compounds are volatilized. The result of the temperature profile had to be consistent with the literature reproduced, being constant after reaching the maximum operating temperature in the length of 0.15 m. This study allowed characterizing and focusing, through experimental analysis, unsaturated compounds and observing the sunflower oil´s behavior through process simulation.

Concentração do óleo de girassol em compostos insaturados utilizando destilação molecular

Vegetable oils are characterized as important raw materials in the supplying of natural substances of interest pharmaceutical, food and cosmetic industry. Sunflower oil stands out for its important composition present in unsaturated fatty acids such as oleic acid (C18:1) and linoleic (C18:2), responsible for many health benefits. The main objective of this study is obtain enriched fractions in unsaturated compounds from refined sunflower oil. The oil used in this study was characterized by the determination of some properties, like iodine number, acid number and viscosity. A transesterification was done to transform the triglycerides into their corresponding methyl esters of fatty acids. These was submitted the molecular distillation process, for present as an efficient alternative to separation and purification of these substances, using high vacuum and low temperatures. Of the esters fractions that was obtained, were analyzed by gas chromatography. The experimental design technique was used to evaluate the influence of the temperature variation of evaporation and condensation system on the percentage obtained residue. The evaporator temperature proved to be the most influential variable on the studied response. The optimized conditions for the answer was studied at 100 °C for evaporator temperature and 10 °C for the condenser temperature. The graph of "split ratio" showed that for the lowest flow feed (1 mL/min) and higher evaporator temperature (110 °C) was obtained in the largest fraction of distillate. It also used the study of the influence of evaporator temperature on the concentration of unsaturated compounds. The best operating conditions for temperature was 90 °C reached 82.21 % of unsaturated compounds. Elimination curves of the unsaturated compounds present in the distillate stream were obtained. The simulation results of the molecular distillation process of sunflower oil showed the concentration profiles for three different feed flow rates. The speed, temperature and thickness profiles of the liquid film were obtained. The speed of the film increases as the fluid flows through the walls of the evaporator, reaching a maximum on length of 0.075 m. The film thickness decreases on the route, since many compounds are volatilized. The result of the temperature profile had to be consistent with the literature reproduced, being constant after reaching the maximum operating temperature in the length of 0.15 m. This study allowed characterizing and focusing, through experimental analysis, unsaturated compounds and observing the sunflower oil´s behavior through process simulation.

Síntese e caracterização do poli(ácido láctico) para potencial uso em sistemas de liberação controlada de fármacos

With the advances in medicine, life expectancy of the world population has grown considerably in recent decades. Studies have been performed in order to maintain the quality of life through the development of new drugs and new surgical procedures. Biomaterials is an example of the researches to improve quality of life, and its use goes from the reconstruction of tissues and organs affected by diseases or other types of failure, to use in drug delivery system able to prolong the drug in the body and increase its bioavailability. Biopolymers are a class of biomaterials widely targeted by researchers since they have ideal properties for biomedical applications, such as high biocompatibility and biodegradability. Poly (lactic acid) (PLA) is a biopolymer used as a biomaterial and its monomer, lactic acid, is eliminated by the Krebs Cycle (citric acid cycle). It is possible to synthesize PLA through various synthesis routes, however, the direct polycondensation is cheaper due the use of few steps of polymerization. In this work we used experimental design (DOE) to produce PLAs with different molecular weight from the direct polycondensation of lactic acid, with characteristics suitable for use in drug delivery system (DDS). Through the experimental design it was noted that the time of esterification, in the direct polycondensation, is the most important stage to obtain a higher molecular weight. The Fourier Transform Infrared (FTIR) spectrograms obtained were equivalent to the PLAs available in the literature. Results of Differential Scanning Calorimetry (DSC) showed that all PLAs produced are semicrystalline with glass transition temperatures (Tgs) ranging between 36 - 48 °C, and melting temperatures (Tm) ranging from 117 to 130 °C. The PLAs molecular weight characterized from Size Exclusion Chromatography (SEC), varied from 1000 to 11,000 g/mol. PLAs obtained showed a fibrous morphology characterized by Scanning Electron Microscopy (SEM)

Síntese do Poli (ácido láctico) por policondensação direta utilizando um planejamento fatorial

The environmental impact caused by the disposal of non-biodegradable polymer packaging on the environment, as well as the high price and scarcity of oil, caused increase of searches in the area of biodegradable polymers from renewable resources were developed. The poly (lactic acid) (PLA) is a promising polymer in the market, with a large availability of raw material for the production of its monomer, as well as good processability. The aimed of this study was synthesis PLA by direct polycondesation of lactic acid, using the tool of experimental design (DOE) (central composite rotatable design (CCRD)) to optimize the conditions of synthesis. The polymer obtained was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), viscosimetric analysis, differential scanning calorimeter (DSC) and size exclusion chromatography (SEC). The results confirmed the formation of a poly (lactic acid) semicrystalline in the syntheses performed. Through the central composite rotatable design was possible to optimize the crystallization temperature (Tc) and crystallinity degree (Xc). The crystallization temperature maximum was found for percentage of catalyst around the central point (0,3 (%W)) and values of time ranging from the central point (6h) to the upper level (+1) (8h). The crystallization temperature maximum was found for the total synthesis time of 4h (-1) and percentage of catalyst 0,1(W%) (-1). The results of size exclusion chromatography (SEC) showed higher molecular weights to 0,3 (W%) percent of catalyst and total time synthesis of 3,2h