Conversão térmica e termocatalítica à baixa temperatura do óleo de girassol para obtenção de bio-óleo

The use of biofuels remotes to the eighteenth century, when Rudolf Diesel made the first trials using peanut oil as fuel in a compression ignition engine. Based on these trials, there was the need for some chemical change to vegetable oil. Among these chemical transformations, we can mention the cracking and transesterification. This work aims at conducting a study using the thermocatalytic and thermal cracking of sunflower oil, using the Al-MCM-41 catalyst. The material type mesoporous Al-MCM-41 was synthesized and characterized by Hydrothermical methods of X-ray diffraction, scanning electron microscopy, nitrogen adsorption, absorption spectroscopy in the infrared and thermal gravimetric analysis (TG / DTG).The study was conducted on the thermogravimetric behavior of sunflower oil on the mesoporous catalyst cited. Activation energy, conversion, and oil degradation as a function of temperature were estimated based on the integral curves of thermogravimetric analysis and the kinetic method of Vyazovkin. The mesoporous material Al-MCM-41 showed one-dimensional hexagonal formation. The study of the kinetic behavior of sunflower oil with the catalyst showed a lower activation energy against the activation energy of pure sunflower oil. Two liquid fractions of sunflower oil were obtained, both in thermal and thermocatalytic pyrolisis. The first fraction obtained was called bio-oil and the second fraction obtained was called acid fraction. The acid fraction collected, in thermal and thermocatalytic pyrolisis, showed very high level of acidity, which is why it was called acid fraction. The first fraction was collected bio-called because it presented results in the range similar to petroleum diesel

Extração e pirólise do óleo de girassol (Helianthus annus l.) visando a produção de biocombustíveis

Nowadays, the growing environmental worry leads research the focus the application of alternative materials from renewable resources on the industrial process. The most common vegetable oil extractant using around the world is the hexane, a petroleum derived, toxic and flammable. Based on this fact, the goal of this work was to test vegetable oil extractions from sunflower seeds cultivated on the Rio Grande do Norte State using two extraction process, the mechanical expelling and solvent extraction, this one using hexane and ethanol as a alternative solvent. The solvent extractions were carried out in the Soxhlet extractor in three different extraction times (4, 6, and 8 hours). The effect of solvent and extraction time was evaluated. The mechanical extraction was carried out in a expeller and the sunflower oil obtained was characterized by its physical-chemical properties and compared with sunflower refinery oil. Furthermore this work also explored the pyrolysis reaction carried out by thermogravimetry measurement as alternative route to obtain biofuel. For this purpose the oil samples were heated to ambient temperature until 900°C in heating rate of 5, 10, 20ºC min-1 with the objective evaluated the kinetics parameters such activation energy and isoconversion. The TG/DTG curves show the thermal profile decomposition of triglycerides. The curves also showed that antioxidant presents on the refinery oil not influence on the thermal stability of sunflower oil. The total yield of the extraction s process with hexane and ethanol solvent were compared, and the results indicated that the extraction with ethanol were more efficient. The pyrolysis reaction results indicated that the use of unpurified oil required less energy to obtain the bio-oil

Craqueamento termocatalítico de óleo de girassol na presença da peneira molecular SAPO-5

The catalytic cracking of triglycerides presents itself as a possible alternative to the production of biofuels with low emission of pollutants. In this work were synthesized the SAPO-5, the catalysts for the cracking reaction of soybean oil is presented. The solids were powder X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG) and infrared spectroscopy (FTIR). The analyses indicated that the synthesis method has employed to obtain materials with high surface area and high acid. The soybean oil thermal and thermal catalytic cracking, realized from the room temperature to 450 ºC in a simple distillation system, has allowed obtaining two liquid fractions, each consisting of two phases, one aqueous and another organic, organic liquid (OL). The OL obtained from first fractions has shown high acid index, even in the thermal catalytic process. The products obtained in the cracking of soybean oil were analyzed by distillation, acid number, infra-red spectroscopy, density, viscosity, carbon residue, cetane number determination and characterization. The analysis of the products obtained in the presence and in the absence of the SAPO-5 permitted to conclude that all the solids tested presented catalytic activity in the deoxygenation of final products only at the second step of the cracking process

Craqueamento térmico e termocatalítico do óleo de girassol (Hellianthus annus L.) sobre materiais micro e mesoporosos

Microporous materials zeolite type Beta and mesoporous type MCM-41 and AlMCM-41 were synthesized hydrothermally and characterized by methods of X-ray diffraction, Fourier transform infrared, scanning electron microscopy, surface acidity, nitrogen adsorption, thermal analysis TG / DTG. Also we performed a kinetic study of sunflower oil on micro and mesoporous catalysts. The microporous material zeolite beta showed a lower crystallinity due to the existence of smaller crystals and a larger number of structural defects. As for the mesoporous materials MCM-41 and AlMCM-41 samples showed formation of hexagonal one-dimensional structure. The study of kinetic behavior of sunflower oil with zeolite beta catalysts, AlMCM-41 and MCM-41 showed a lower activation energy in front of the energy of pure sunflower oil, mainly zeolite beta. In the thermal cracking and thermocatalytic of sunflower oil were obtained two liquid fractions containing an aqueous phase and another organic - organic liquid fraction (FLO). The FLO first collected in both the thermal cracking as the thermocatalytic, showed very high level of acidity, performed characterizations of physicochemical properties of the second fraction in accordance with the specifications of the ANP. The second FLO thermocatalytic collected in cracking of sunflower oil presented results in the range of diesel oil, introducing himself as a promising alternative for use as biofuel liquid similar to diesel, either instead or mixed with it

Avaliação do óleo de girassol adicionado de antioxidantes sob estocagem

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

COMPORTAMENTO do ÓLEO DE GIRASSOL COM ALTO TEOR DE ÁCIDO OLÉICO em TERMOXIDAÇÃO E FRITURA

Óleos de sementes de girassol com diferentes níveis de ácido oléico foram utilizados sob condições de termoxidação e fritura para avaliar o comportamento do óleo de girassol com alto teor de ácido oléico quanto ao seu grau de insaturação quando comparado com o óleo de girassol convencional. Os métodos analíticos aplicados incluíram a determinação de compostos polares totais, quantificação de compostos glicerídicos menores, quantificação da composição triglicerídica, período de indução a 100oC e níveis de a -tocoferol. Os resultados para compostos polares totais apresentaram menores valores em óleo de girassol com alto teor de ácido oléico quando comparados com óleo de girassol convencional. Quanto à distribuição dos compostos glicerídicos menores, verificou-se, de modo geral, que o aumento dos compostos polares totais estava relacionado essencialmente aos compostos de maior peso molecular, isto é, polímeros, dímeros e triglicerídios oxidados, os quais são representantes das alterações térmica e oxidativa. Já os diglicerídios e ácidos graxos, indicativos da alteração hidrolítica, permaneceram praticamente nos níveis originais; uma vez que a umidade não se encontrava presente no meio. A perda quantitativa da composição triglicerídica dependeu do grau de insaturação do triglicerídio, sendo mais elevada em triglicerídios que contêm duas ou três moléculas de ácido linoléico. em todos os casos, o óleo de girassol convencional teve uma maior tendência à polimerização, um maior grau de alteração total e uma maior perda de triglicerídios majoritários que o óleo de girassol com alto teor de ácido oléico. Assim, dentre os óleos utilizados neste estudo, os resultados mostraram um excelente comportamento do óleo de girassol com alto teor de ácido oléico em relação à termoxidação, independente do tipo de aquecimento e à fritura descontínua. Tais resultados demonstraram que sua resistência à alteração termoxidativa estava relacionada com seu baixo teor em ácidos graxos polinsaturados e alto teor em ácido oléico e trioleína.

Desempenho e características de carcaça de cordeiros alimentados com fontes de carboidratos associadas ao óleo de girassol

This work was carried out with the objective to evaluate the effect of different carbohydrate sources associated with sunflower oil on performance, carcass characteristics and cuts yields of feedlot sheep. Twenty four lambs were assigned to a completely randomized design with a 2 × 2 factorial arrangement with two sources of neutral detergent soluble carbohydrate, starch or neutral detergent soluble fiber, with and without the inclusion of 4.2% sunflower oil. The treatments consisted of diets containing high content of soluble fiber (17.14% DM) without adding oil, high in soluble fiber (16.35% DM) with inclusion of 4.2% sunflower oil, high starch (30.14% DM) without adding oil and high starch (28.21% DM) with addition of 4.2% of sunflower oil. The animals were feedlot with average initial of 17.7 kg and when reached 35 kg body weight were slaughtered. The different sources of carbohydrate and oil inclusion in the diet not influence the days on feedlot in the dry matter intake and average daily weight gain, but higher feed conversion was observed for the diet with a high percentage of neutral detergent soluble fiber compared to diet high in starch. The carcass weights and yields as well as the commercial cuts were not affected by diets. The performance and quantitative characteristics and carcass cuts of lamb are not affected by different carbohydrate sources and their association with 4.2% sunflower oil.

Derivados da extração do óleo de girassol para vacas leiteiras

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Consumo, digestibilidade e balanço de nitrogênio de cordeiros alimentados com alto teor de amido ou fibra solúvel em detergente neutro associados ao óleo de girassol

The aim of this study was to evaluate the effect of different carbohydrate sources associated with sunflower oil on intake, digestibility of nutrients and nitrogen balance in diets of lambs. Twenty lambs were used, assigned in a completely randomized design with a 2 x 2 factorial arrangement of treatments with two sources of neutral detergent soluble carbohydrate, starch and neutral detergent soluble fiber, with and without the inclusion of 4.2% sunflower oil. The dry matter intake was not affected by carbohydrate sources and the inclusion of oil. Diets with a high percentage of starch provided higher digestibility of dry matter, starch and ether extract. The different sources of carbohydrates had no interference on digestibility of organic matter, crude protein, neutral detergent soluble fiber, nonfiber carbohydrates, neutral detergent fiber, hemicellulose and acid detergent fiber. The addition of oil in the diets increased the digestibility of ether extract. The combination of 4.2% oil in the diet high in soluble neutral detergent fiber had no influence on the nutrient digestibility, otherwise, the addition of oil at high starch diet caused a significant reduction in the digestibility of organic matter, neutral detergent fiber, hemicellulose and nonfiber carbohydrates. The quantities of nitrogen intake, absorbed and retained, did not differ as sources of carbohydrates and oil inclusion in the diet. The association of 4.2 % sunflower oil to the different sources of carbohydrates in the diet does not affect consumption and nitrogen metabolism in lambs. The addition of 4.2 % oil in the diet with high starch (28% of DM diet) promotes reduction in digestibility of organic matter, of fibrous and nonfibrous carbohydrate in the diet.

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.

Avaliação de alguns parâmetros da qualidade da anchoita (Engraulis anchoita) enlatada em óleo de girassol e em molho de tomate

O consumo de pescado no Brasil cresceu 40% nos últimos 7 anos passando de 6,46 para 9,03 kg/habitante/ano, valor que se aproxima do recomendado pela Organização Mundial de Saúde. A razão está relacionada com a subutilização de determinadas espécies e a falta de diversificação da indústria processadora para a produção de alimentos com maior valor agregado. Considerando o esgotamento de determinadas espécies com a utilização da sobrepesca, é possível o emprego da anchoita na forma de conservas através da utilização de meios de cobertura como molho de tomate e óleo comestível. Este trabalho teve como objetivo elaborar conservas de anchoita (Engraulis anchoita) com a utilização de 2 meios de cobertura: molho de tomate e óleo de girassol, submetidas a tempos de salmouragem diferenciados, 2 e 5 min e com o emprego ou não de pré-cozimento. De acordo com os padrões estabelecidos, as amostras de pescado fresco utilizadas para a execução dos enlatados apresentaram resultados físico químicos adequados comprovando o frescor do pescado envolvido no processo, ou sejam: 16,29 mg/100 g amostra para N-BVT, 7,90 mg/100 g amostra para N-TMA e pH 6,5. As conservas em molho de tomate submetidas a operação de salmouragem durante 2 min, com e sem pré-cozimento apresentaram, respectivamente, 16,57 e 16,24% proteínas, 3,94 e 4,66% lipídios, 73,0 e 73,28% umidade, 3,22 e 3,67% cinzas, 0,17 e 0,19% de cloretos (NaCl). As conservas com molho de tomate, utilizando anchoita eviscerada salmourada por 5 min, com e sem pré-cozimento, apresentaram respectivamente, 15,94 e 15,31% proteínas, 3,15 e 4,90 lipídios%, 73,70 e 73,98% umidade, 3,80 e 4,10% cinzas, 0,21 e 0,24% cloretos (NaCl). Para as conservas de anchoita em óleo de girassol, utilizando tempo de salmouragem de 2 min, com e sem pré-cozimento, apresentaram 16,97 e 16,76% proteínas, 7,68 e 5,70% lipídios, 65,87 e 68,74% umidade, 3,16 e 3,28% cinzas, 0,10 e 0,12% cloretos (NaCl), respectivamente. As conservas utilizando o pescado previamente submetido a salmouragem por 5 min e posteriormente enlatado com a adição de óleo de girassol, com e sem pré-cozimento apresentaram respectivamente, 15,97 e 15,89% proteínas, 7,91 e 5,19% lipídios, 66,26 e 68,23% umidade, 3,78 e 3,87% cinzas, 0,13 e 0,21% NaCl. As análises microbiológicas das conservas submetidas aos diferentes tratamentos mostraram ausência de Salmonella spp, Staphylococcus coagulase positiva e Clostridium sulfito-redutor, resultados estes, de acordo com o estabelecido pela legislação higiênico-sanitária brasileira. Nos testes de esterilidade comercial não foram constatadas alterações visíveis nos enlatados submetidos a incubação por 5 dias a 36 ± 1°C (determinação de micro-organismos aeróbios viáveis) e a 7-10 dias a 55 ± 1°C (termófilos). Considerando as quantidades de pescado enlatado (80, 90 e 100g), o rendimento para todas as amostras apresentaram, no mínimo, 50% de pescado em relação ao peso líquido. A avaliação sensorial realizada por teste de ordenação para a avaliação da preferência não apresentou diferenças significativas entre as amostras.

Conversão térmica e termocatalítica à baixa temperatura do óleo de girassol para obtenção de bio-óleo

The use of biofuels remotes to the eighteenth century, when Rudolf Diesel made the first trials using peanut oil as fuel in a compression ignition engine. Based on these trials, there was the need for some chemical change to vegetable oil. Among these chemical transformations, we can mention the cracking and transesterification. This work aims at conducting a study using the thermocatalytic and thermal cracking of sunflower oil, using the Al-MCM-41 catalyst. The material type mesoporous Al-MCM-41 was synthesized and characterized by Hydrothermical methods of X-ray diffraction, scanning electron microscopy, nitrogen adsorption, absorption spectroscopy in the infrared and thermal gravimetric analysis (TG / DTG).The study was conducted on the thermogravimetric behavior of sunflower oil on the mesoporous catalyst cited. Activation energy, conversion, and oil degradation as a function of temperature were estimated based on the integral curves of thermogravimetric analysis and the kinetic method of Vyazovkin. The mesoporous material Al-MCM-41 showed one-dimensional hexagonal formation. The study of the kinetic behavior of sunflower oil with the catalyst showed a lower activation energy against the activation energy of pure sunflower oil. Two liquid fractions of sunflower oil were obtained, both in thermal and thermocatalytic pyrolisis. The first fraction obtained was called bio-oil and the second fraction obtained was called acid fraction. The acid fraction collected, in thermal and thermocatalytic pyrolisis, showed very high level of acidity, which is why it was called acid fraction. The first fraction was collected bio-called because it presented results in the range similar to petroleum diesel

Síntese e caracterização de biodiesel obtido via catálises homogênea e heterogênea de óleo extraído de sementes de Helianthus annuus

O biodiesel é definido como um mono alquil éster de ácidos graxos de cadeia longa derivado de fontes renováveis tais como óleos vegetais e gorduras animais. Sua importância esta associada ao uso como um combustível alternativo para motores do ciclo Diesel podendo ser utilizado puro ou em misturas com o diesel representando economia de petróleo e menor poluição ambiental. Em geral é obtido por meio da reação de transesterificação na qual os triacilgliceróis, principais constituintes dos óleos e gorduras reagem com álcool, em presença de um catalisador ácido ou básico, produzindo ésteres de ácidos graxos e glicerol. A transesterificação pode ser conduzida por catálise homogênea ou heterogênea. O grande desafio da indústria é otimizar o processo a fim de alcançar um produto e uma rota de produção tecnologicamente eficiente e ambientalmente correta. O objetivo desta pesquisa foi estudar a síntese do biodiesel utilizando o processo de transesterificação do óleo de girassol por catálises homogênea e heterogênea. Foram realizadas reações de transesterificação via rotas metílica e etílica, empregando como catalisador homogêneo alcóxido de potássio e como catalisador heterogêneo a resina comercial de troca iônica Amberlyst 26

Análise da lubricidade do biodiesel brasileiro de ésteres etílicos de soja e girassol

Fuel is a material used to produce heat or power by burning, and lubricity is the capacity for reducing friction. The aim of this work is evaluate the lubricity of eight fossil and renewable fuels used in Diesel engines, by means of a HFRR tester, following the ASTM D 6079-04 Standard. In this conception, a sphere of AISI 52100 steel (diameter of 6,000,05 mm, Ra 0,050,005 μm, E = 210 GPa, HRC 624, HV0,2 63147) is submitted to a reciprocating motion under a normal load of 2 N and 50 Hz frequency to promote a wear track length of 1.10.1mm in a plan disc of AISI 52100 steel (HV0,05 18410, Ra 0,020,005 μm). The testing extent time was 75 minutes, 225,000 cycles. Each one test was repeated six times to furnish the results, by means of intrinsic signatures from the signals of the lubricant film percentage, friction coefficient, contact heating, Sound Pressure Level, SPL [dB]. These signal signatures were obtained by two thermocouples and a portable decibelmeter coupled to a data acquisition system and to the HFRR system. The wettability of droplet of the diesel fuel in thermal equilibrium on a horizontal surface of a virgin plan disc of 52100 steel, Ra 0,02  0,005 μm, were measured by its contact angle of 7,0  3,5o, while the results obtained for the biodiesel B5, B20 and B100 blends originated by the ethylic transesterification of soybean oil were, respectively, 7,5  3,5o, 13,5  3,5o e 19,0  1,0o; for the distilled water, 78,0  6,0o; the biodiesel B5, B20 and B100 blends originated by the ethylic transesterification of sunflower oil were, respectively, 7,0  4,0o, 8,5  4,5o e 19,5  2,5o. Different thickness of lubricant film were formed and measured by their percentage by means of the contact resistance technique, suggesting several regimes, since the boundary until the hydrodynamic lubrication. All oils analyzed in this study promoted the ball wear scars with diameters smaller than 400 μm. The lowest values were observed in the scar balls lubricated by mixtures B100, B20 and B5 of sunflower and B20 and B5 of soybean oils (WSD < 215 μm)