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

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.

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

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)

Remoção de óleo da água de produção por flotação em coluna utilizando tensoativos de origem vegetal

In the petroleum industry, water is always present in the reservoir formation together with petroleum and natural gas and this fact provokes the production of water with petroleum, resulting in a great environmental impact. Several methods can be applied for treatment of oily waters, such as: gravitational vases, granulated media filtration systems, flotation process, centrifugation process and the use of hydrocyclones, which can also be used in a combined way. However, the flotation process has showed a great efficiency as compared with other methods, because these methods do not remove great part of the emulsified oil. In this work was investigated the use of surfactants derived from vegetable oils, OSS and OGS, as collectors, using the flotation process in a glass column with a porous plate filter in its base for the input of the gaseous steam. For this purpose, oil/water emulsions were prepared using mechanical stirring, with concentrations around 300 ppm. The air flow rate was set at 700 cm3/min and the porous plate filter used for the generation of the air bubbles has pore size varying from 16 to 40 Pm. The column operated at constant volume (1500mL). A new methodology has been developed to collect the samples, where, instead of collecting the water phase, it was collected the oil phase removed by the process in the top of the flotation column. It has been observed that it is necessary to find an optimum surfactant concentration to achieve enhanced removal efficiency. Being for OSS 1.275 mmol/L and for OGS 0.840 mmol/L, with removal efficiencies of 93% and 99%, respectively, using synthetic solutions. For the produced water, the removal in these concentrations was 75% for OSS and 65% for OGS. It is possible to remove oil from water in a flotation process using surfactants of high HLB, fact that is against the own definition of HLB (Hydrophile-Lipophile Balance). The interfacial tension is an important factor in the oil removal process using a flotation process, because it has direct interference in the coalescence of the oil drops. The spreading of the oil of the air bubble should be considered in the process, and for the optimum surfactant concentrations it reached a maximum value. The removal kinetics for the flotation process using surfactants in the optimum concentration has been adjusted according to a first order model, for synthetic water as for the produced water.

Eficiência do processo de obtenção do biodiesel de girassol usando o catalisador KNO3/Al2O3

It is known that the head office world energetics is leaning in the fossil fuels. However, the world panorama is changing quickly, for linked reasons to three of the humanity's great concerns in that century beginning: environment, global economy and energy. The biodiesel production is based on the transesterificação of vegetable oils or animal fats, using catalysts homogeneous or heterogeneous. The process of heterogeneous transesterificação presents lower conversions in comparison with the homogeneous, however, it doesn't present corrosion problems and it reduces to the occurrence of parallel reactions as saponification. In this sense, this work has for purpose the synthesis of a heterogeneous catalyst, KNO3/Al2O3, that soon afterwards was used in the reaction of transesterificação of the oil of the Helianthus annuus L. (sunflower). The solid materials (it supports and catalyst) they were analyzed by diffraction of ray-X (XRD) and electronic microscope of sweeping (MEV). After the analysis of Al2O3, a structure monophase amorphous tetragonal was verified, with characteristic patterns of that material, what could not be visualized in the difratograma of the catalyst. The biodiesel obtained with 4% wt. of KNO3/Al2O3 it was what obtained a better cinematic viscosity 8,3 mm2/s, comparing with the norms of ANP, and it also presented the best conversion tax in ethyl ésteres, in accordance with the quantitative measure starting from TG, that was of 60%. While the biodiesel with 6% wt. and with 8% wt. of KNO3/Al2O3 it was it that no transesterificou, because it was observed in the analysis termogravimétrica of those two materials, a single thermal event, that it corresponds the decomposition or volatilization of the triglycerides

Avaliação térmica dos resíduos da destilação atmosférica das blendas - biodiesel/diesel

The worldwide concern regarding the use of sustainable energy and preserving the environment are determining factors in the search for resources and alternative sources of energy and therefore fuel less aggressive nature. In response to these difficulties Biodiesel has emerged as a good solution because it is produced from renewable sources, produces burns cleaner and is easily reproducible. This work was synthesized with biodiesel oil, sunflower via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the blends BX (a proportion of biodiesel X = 5, 10, 15 and 20 %). Atmospheric distillation of the analysis, performed in blends with and without BHT were collected residue generated by each sample and performed a study heat from the thermogravimetric analysis at a heating rate of 10 °C*min-1, nitrogen atmosphere and heating to 600 °C. According to the specifications of Resolution N 7/2008 for biodiesel, it was found that the synthesized material was in accordance with the specifications. For blends showed that the samples are in accordance with the Resolution of ANP N 42/2009. From the TG / DTG curves of the samples of biodiesel, blends and waste can be seen that these show a single loss of thermal decomposition concerning constituents present in each sample. The blends without BHT with ratios of 5%, 10% and 15% biodiesel showed a lower amount of waste (1,07%; 1,09% e 1,10%) to mineral diesel (1,15%). Therefore, it is concluded that the addition of biodiesel with diesel mineral can improve some physico-chemical parameters, but also, depending on the added amount, decreasing the amount of waste generated. This fact is of great importance because the carbonaceous residue can cause problems in mechanical equipment and parts for vehicles, causing more frequent maintenance, and this is not desirable

Desenvolvimento de emulsões contendo óleos vegetais para uso cosmético

The fat acid esters and tocopherolic derivatives are of great economic interest in many industries. The sunflower oil, which had its rich constitution in these composites, is a very interesting raw material source for the job in some sectors as bio-carburants, bio-lubrificants, bio-surfactants, dispersing agents, food industries, medicines and cosmetics. A system emulsified steady from this oil can wide be used in the therapeutical one, therefore it is of easy acceptance for the patient, for being pharmaceutical forms that allow a better medicine administration. The chemical composition characteristics, rich in unsaturad fat acid and tocopherolic derivatives, the sunflower oil, make of the emulsified systems contend this oil a proposal promising for formularizations of pharmaceutical and cosmetic use with antirust and photoprotection. The general objective of this work was to apply the HLB beddings to determine the sunflower oil critical HLB and, from this, to be able to evaluate the ideal mixture of the constituent of this system through the study of the ternary diagrams for the determination of the ratio of constituent that will generate the emulsion most steady

Tratamento de água de produção de petróleo visando o aproveitamento na obtenção de barrilha

The petroleum production is associated to the produced water, which has dispersed and dissolved materials that damage not only the environment, but also the petroleum processing units. This study aims at the treatment of produced water focusing mainly on the removal of metals and oil and using this treated water as raw material for the production of sodium carbonate. Initially, it was addressed the removal of the following divalent metals: calcium, magnesium, barium, zinc, copper, iron, and cadmium. For this purpose, surfactants derived from vegetable oils, such as coconut oil, soybean oil, and sunflower oil, were used. The investigation showed that there is a stoichiometric relationship between the metals removed from the produced water and the surfactants used in the process of metals removal. It was also developed a model that correlates the hydrolysis constant of saponified coconut oil with the metal distribution between the resulting stages of the proposed process, flocs and aqueous phases, and relating the results with the pH of the medium. The correlation coefficient obtained was 0.963. Next, the process of producing washing soda (prefiro soda ahs ou sodium carbonate) started. The resulting water from the various treatment approaches from petroleum production water was used. During this stage of the research, it was observed that the surfactant assisted in the produced water treatment, by removing some metals and the dispersed oil entirety. The yield of sodium carbonate production was approximately 80%, and its purity was around 95%. It was also assessed, in the production of sodium carbonate, the influence of the type of reactor, using a continuous reactor and a batch reactor. These tests showed that the process with continuous reactor was not as efficient as the batch process. In general, it can be concluded that the production of sodium carbonate from water of oil production is a feasible process, rendering an effluent that causes a great environmental impact a raw material with large scale industrial use

Hidróxidos duplos lamelares aplicados à obtenção de biodiesel

In this paper, the Layered Double Hydroxides (LDH s) type hydrotalcite were synthesized, characterized and tested as basic heterogeneous catalysts for the production of biodiesel by transesterification of sunflower oil with methanol. The synthesis of materials Layered Double Hydroxides (LDH s) by co-precipitation method from nitrates of magnesium and aluminum, and sodium carbonate. The materials were submitted to the variation in chemical composition, which is the amount of Mg2+ ions replaced by Al3+. This variation affects the characteristic physico-chemical and reaction the solid. The molar ratio varied in the range of 1:1 and 3:1 magnesium / aluminum, and their values between 0.2 and 0.33. This study aims to evaluate the influence of variation of molar ratio of mixed oxides derived from LDH s and the influence of impregnation of a material with catalytic activity, the KI, the rate of conversion of sunflower oil into methyl esters (biodiesel) through transesterification by heterogeneous catalysis. .The catalysts were calcined at 550 ° C and characterized by X-ray diffraction (XRD), scanning electron microscopy and energy dispersive spectroscopy of X-ray (SEM / EDS), thermogravimetric analysis (TG) and test basicity. The transesterification reaction was performed for reflux is a mixture of sunflower oil and methanol with a molar ratio of 15:1, a reaction time of 4h and a catalyst concentration of 2% by weight. The physical-chemical characterization of sunflower oil and biodiesel obtained by the route methyl submitted according NBR, EN, ASTM. Subsequently, it was with the chromatographic and thermogravimetric characterizations of oils. The results of chromatographic analysis showed that the catalysts were effective in converting vegetable oil into biodiesel, in particular the type hydrotalcite KI-HDL-R1, with a conversion of 99.2%, indicating the strong influence of the chemical composition of the material, in special due to presence of potassium in the structure of the catalyst

Síntese e caracterização de óxidos de zinco e de magnésio suportados em A1SBA-15 para produção de biodiesel

To overcome the challenge of meeting growing energy demand in a sustainable way, biodiesel has shown very promising as alternative energy can replace fossil fuels, even partially. Industrially, the biodiesel is produced by homogeneous transesterification reaction of vegetable oils in the presence of basic species used as catalysts. However, this process is the need for purification of the esters obtained and the removal of glycerin formed after the reaction. This context, the alternative catalysts have that can improve the process of biodiesel production, aiming to reduce costs and facilitate its production. In this study, the AlSBA-15 support with Si / Al ratio = 50 was synthesized, as like as the heterogeneous catalysts of zinc oxide and magnesium supported on mesoporous AlSBA-15 silica, in the concentrations of 5, 10, 15 and 30 %, relative to the support. The textural properties and structural characterization of catalysts and supports were determined by techniques: X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) coupled to the chemical analyzer, adsorption / desorption of N2, thermal analysis (TG / DTG), absorption spectroscopy in the infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). Characterization results indicated that the support AlSBA-15 retained the hexagonal ordered after the incorporation of zinc oxide and magnesium oxide in the holder. For heterogeneous catalysts, ZnO-AlSBA-15, that was observed the presence of zinc oxide nanoparticles dispersed in the surface and interior channels of the mesoporous and microporous support. The catalytic activity was evaluated by the transesterification reaction of sunflower oil via methylic route, and some reaction parameters were optimized with the most active catalyst in biodiesel production by sunflower oil. For the series of heterogeneous catalysts, the sample with 30 % ZnO supported on AlSBA-15 showed a better conversion of triglyceride to methyl esters, about 95.41 % of reaction conditions: temperature 175 °C, with molar ratio of 42:1, stirring at 200 rpm and under a pressure of 14 bar for 6 h. The catalyst MgO-AlSBA-15 showed no catalytic activity in the studied reactions