Uso da glicerina oriunda da síntese do biodiesel em sistemas microemulsionados visando aplicação de herbicidas

The program PROBIODIESEL from the Ministry of Science and Technology has substantially increased glycerine, obtained as a sub-product of biodiesel production process, making it necessary to seek alternatives for the use of this co-product. On the other hand, herbicides although play a role of fundamental importance in the agricultural production system in force, have been under growing concern among the various segments of society because of their potential environmental risk. In this work, we used glycerin in microemulsion systems for application of herbicides, to improve efficiency and lower environmental pollution caused by the loss of those products to the environment. To obtain the systems of microemulsinados were used Unitol L90 NP and Renex 40 as surfactants, butanol as co-surfactant, coconut oil as oil phase and aqueous phase as we used solutions of glycerin + water. Through the determination of phase diagrams, the microemulsion region was found in the system E (L90 Unitol, coconut oil and glycerin + water 1:1). Three points were chosen to the aqueous phase rich in characterization and application in the solubilization of glyphosate and atrazine. Three experiments were performed in Horta, Department of Plant Sciences, Plant Science Sector, UFERSA, Mossoró-RN. The first experiment was conducted in randomized complete blocks with 20 treatments and four replications. The treatments consisted of five doses of the herbicide glyphosate (0.0, 0.45, 0.9, 1.35 and 1.8 L ha-1) diluted with four sauces: C1, C2, C3 (microemulsions) and C4 (water). The phytotoxicity of Brachiaria brizantha was measured at 7, 14, 28 and 60 DAA (days after application). At 60 DAA, we evaluated the biomass of plants. The second experiment was developed in randomized complete blocks with 20 treatments and four repetitions. The treatments consisted of five doses of the herbicide atrazine (0.0, 0.4, 0.8, 1.6 and 2.4 L ha-1) diluted with four sauces: C1, C2, C3 (microemulsions) and C4 (water). The phytotoxicity on Zea mays and Talinum paniculatum was evaluated at 2, 7, 20 DAA. The experiment III was developed in randomized complete blocks with 16 treatments and three repetitions. The treatments consisted of 16 combinations among the constituents of the microemulsion: Unitol L90 surfactant (0.0, 1.66, 5.0, 15 %) and glycerin (0.0, 4.44, 13.33 and 40.0 %). The phytotoxicity on Zea mays was evaluated at 1, 7 and 14 DAA. At 14 DAA, we evaluated the biomass of plants. The control plants using the microemulsions was lower than in the water due to the poisoning caused by the initial microemulsions in the leaves of the plants, a fact that hinders the absorption and translocation of the herbicide. There was no toxicity in Zea mays plants caused by the herbicide, however, were highly intoxicated by microemulsions. T. paniculatum was better controlled in spraying with the microemulsions, regardless of the dose of the herbicide. The glycerine did not cause plant damage. Higher poisoning the plants are caused by tensoactive Unitol L90 and higher rates occur with the use of higher concentrations of surfactant and glycerin, or microemulsion. The microemulsions used hampered the action of glyphosate in controlling B. brizantha and caused severe poisoning in corn, and these poisonings attributed mainly to the action of surfactant

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

Obtenção de álcool alílico (PROP-2-EN-1-OL) a partir da glicerina derivada do biodiesel de óleo de mamona

In this work, biodiesel was produced from castor oil that was a byproduct glycerin. The molar ratio between oil and alcohol, as well as the use of (KOH) catalyst to provide the chemical reaction is based on literature. The best results were obtained using 1 mol of castor oil (260g) to 3 moles of methyl alcohol (138g), using 1.0% KOH as catalyst at a temperature of 260 ° C and shaken at 120 rpm. The oil used was commercially available, the process involves the reaction of transesterification of a vegetable oil with methyl alcohol. The product of this reaction is an ester, biodiesel being the main product and the glycerin by-product which has undergone treatment for use as raw material for the production of allyl alcohol. The great advantage of the use of glycerin to obtain allyl alcohol is that its use eliminates the large amount of waste of the biodiesel and various forms of insult to the environment. The reactions for the formation of allyl alcohol was conducted from formic acid and glycerin in a ratio 1/1, at a temperature of 260oC in a heater blanket, being sprayed by a spiral condenser for a period of 2 hours and the product obtained contains mostly the allylic alcohol .. The monitoring of reactions was performed by UV-Visible Spectrophotometer: FTIR Fourier transform, the analysis showed that these changes occur spectrometer indicating the formation of the product allylic alcohol (prop-2-en-1-ol) in the presence of water, This alcohol was appointed Alcohol GL. The absorption bands confirms that the reaction was observed in (υ C = C) 1470 -1600 cm -1 and (υ CO), 3610-3670 attributed to C = C groups and OH respectively. The thermal analysis was carried out in a thermogravimetric analyzer SDT Q600, where the mass and temperature are displayed against time, that allows checking the approximate rate of heating. The innovative methodology developed in the laboratory (LABTAM, UFRN), was able to treat the glycerine produced by transesterification of castor oil and used as raw material for production of allyl alcohol, with a yield of 80%, of alcohol, the same is of great importance in the manufacture of polymers, pharmaceuticals, organic compounds, herbicides, pesticides and other chemicals

Desenvolvimento de metodologias analíticas alternativas por cromatografia gasosa para análise de biodiesel

Since the beginning of the National Program for Production and Use of Biodiesel in Brazil, in 2004, different raw materials were evaluated for biodiesel production, trying to combine the agricultural diversity of the country to the desire to reduce production coasts. To determine the chemical composition of biodiesel produced from common vegetables oils, international methods have been used widely in Brazil. However, for analyzing biodiesel samples produced from some alternative raw materials analytical problems have been detected. That was the case of biodiesel from castor oil. Due the need to overcome these problems, new methodologies were developed using different chromatographic columns, standards and quantitative methods. The priority was simplifying the equipment configuration, realizing faster analyses, reducing the costs and facilitating the routine of biodiesel research and production laboratories. For quantifying free glycerin, the ethylene glycol was used in instead of 1,2,4-butanetriol, without loss of quality results. The ethylene glycol is a cheaper and easier standard. For methanol analyses the headspace was not used and the cost of the equipment used was lower. A detailed determination of the esters helped the deeper knowledge of the biodiesel composition. The report of the experiments and conclusions of the research that resulted in the development of alternative methods for quality control of the composition of the biodiesel produced in Brazil, a country with considerable variability of species in agriculture, are the goals of this thesis and are reported in the following pages

Os instrumentos de incentivo à produção e uso de biodiesel no Brasil: uma análise constitucional sob o princípio do desenvolvimento sustentável

The recent insertion of biodiesel derived from oily vegetables in the Brazilian energetic matrix calls for the study of some aspects that belong to it. The analysis of the carbonized energetic pattern concerns the paradigm of economic development that is constitutionally enshrined sustainable development which make environmental protection compatible with the needs of the economic rationality. This text is structured according to the ideas of modern hermeneutic that sees substantial value in the principles capable of create a harmonious relationship between law and society. The study of the constitutional principles to conduct a legal analysis about the National Program for Production and Use of Biodiesel - PNPB. The aim of the research is the study of PNPB ahead with the constitutional principles governing the economic order. To achieve this end we studied the sustainable development as a constitutional principle. We start with the notion that the thematic principles, and fundamental to understanding the dimension of sustainable development institute, since its concept is closely related to the applications of the principles enshrined in virtually all the constitutional order of the Western world. Then this was the National Energy Policy, initiating the approach by guiding principles of the National Energy Policy to develop the theme of public policy in the energy sector. Therefore, we studied the National Program of Biodiesel Production and Use - PNPB. From a technical introduction to the concept of biodiesel and a brief historical background, analyzing their advantages compared to fossil fuels predominantly used. Then it became a regulatory overview of the Brazilian legislation on the subject, central to understanding the plans and objectives pursued by the Brazilian government with encouraging the production of biodiesel. Finally discussed the tax incentives for production and use of biodiesel in Brazil. From the idea of federalism, characterized the tax as an instrument of state intervention in the economy. And finally it brought the tax incentives of Law No. 11.116/2005 in the face of the constitutional principles of economy and tax, and tax incentives from projects related to the Kyoto Protocol

Comportamento espacial da demanda energética em semeadura de amendoim em latossolo sob preparo convencional

A mecanização desempenha papel fundamental na produção agrícola e, consequentemente, na composição dos custos. Os adequados planejamento e gerenciamento dos sistemas mecanizados contribuem para a racionalização e redução dos gastos e melhoria do produto final. O objetivo deste trabalho foi estudar e caracterizar a variabilidade espacial da resistência mecânica do solo à penetração, da demanda energética e do desempenho operacional do conjunto trator-semeadora-adubadora em semeadura de amendoim, atuando com 5% de biodiesel etílico destilado de amendoim, em solo sob preparo convencional. As variáveis avaliadas neste estudo foram: força e potência requeridas na barra de tração, capacidade de campo efetiva, consumo de combustível, consumo de energia, patinhagem dos rodados e resistência mecânica do solo à penetração. Pelos resultados obtidos, concluiu-se que a variabilidade espacial das variáveis ligadas ao conjunto mecanizado depende principalmente da direção de deslocamento e que a resistência mecânica do solo à penetração não apresentou correlação com as outras variáveis. O consumo específico de combustível demonstrou correlação negativa com a força de tração, indicando que houve melhor aproveitamento da energia disponibilizada pelo combustível para maior exigência de tração.

Potential and costs for the production of electrolytic hydrogen in alcohol and sugar cane plants in the central and south regions of Brazil

This project verified the potential for the production of hydrogen via water electrolysis by using the exceeding electrical energy resultant from alcohol and sugar plants that use sugar cane bagasse as fuel. The studies were carried out in cogeneration plants authorized by the Electrical Energy National Agency (ANEEL). The processing history of sugar cane considered was based on the 2006/2007 harvests. The total bagasse produced, electrical energy generated and exceeding electrical energy in a year were calculated. It was obtained an average energy consumption value of 5.2 kWh Nm(-3) and the hydrogen production costs regarding the amount of sugar cane processed that ranged from US$ 0.50 to US$ 0.75 Nm(-3). The results pointed that the costs for the production of hydrogen via the bagasse exceeding energy are close to the production costs that use other sources of energy. As the energy generated from the bagasse is a renewable one, this alternative for the production of hydrogen is economical and environmentally viable. (C) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

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)

Estudo das propriedades físico-químicas do biodiesel e suas influências na deterioração dos elastômeros aplicados no sistema de injeção dos motores diesel

The biodiesel use has become important due to its renewable character and to reduce environmental impacts during the fuel burning. Theses benefit will be valid if the fuel shows good performance, chemistry stability and compatibility with engines. Biodiesel is a good fuel to diesel engines due to its lubricity. Then, the aimed of this study was to verify the physicalchemistry properties of biodiesel and their correlations with possible elastomers damage after biodiesel be used as fuel in an injection system. The methodology was divided in three steps: biodiesels synthesis by transesterification of three vegetable oil (soybean, palm and sunflower) and their physical-chemistry characterization (viscosity, oxidative stability, flash point, acidity, humidity and density); pressurized test of compatibility between elastomers (NBR and VITON) and biodiesel, and the last one, analyze of biodiesels lubricity by tribological test ball-plan( HFRR). Also, the effect of mixture of biodiesel and diesel in different concentrations was evaluated. The results showed that VITON showed better compatibility with all biodiesel blends in relation to NBR, however when VITON had contact with sunflower biodiesel and its blends the swelling degree suffer higher influences due to biodiesel humidity. For others biodiesels and theirs blends, this elastomer kept its mechanical properties constant. The better tribological performance was observed for blends with high biodiesel concentration, lower friction coefficient was obtained when palm biodiesel was used. The main mechanisms observed during the HFRR tests were abrasive and oxidative wear

Produção de biodiesel a partir de óleo de coco (Cocos nucifera L

The production of biodiesel has become an important and attractive process for the production of alternative fuels. This work presents a study of the biodiesel production from coconut oil (Cocos nucifera L.), by two routes: direct transesterification using NaOH as catalyst and esterification (with H2SO4) followed by basic transesterification. The reactor was built in pirex with 1L of capacity and was equipped with a jacket coupled with a thermostatic bath to temperature control, a mecanical stirring is also present in the reactor. The analysis of oil composition was carried out by gas chromatography and esters compounds were identified. The parameters of molar ratio oil/alcohol, reaction time and temperature were studied and their influence on the conversion products was evaluated using experimental planning (23). The molar ratio was the most significant variable by the statistical planning analysis. Conversions up to 85.3% where achived in the esterification/transesterification, with molar ratio 1:6 at 60ºC and 90 minutes of reaction. For the direct transesterification, route conversions up 87.4% eas obtained using 1:6.5 molar ratio at 80ºC and 60 minutes of reaction. The Coconut oil was characterized by their physic chemical properties and key constituents of the oil. The lauric acid was the main constituint and the oil showed high acidity. The biodiesel produced was characterized by its main physicochemical properties, indicating satisfactory results when compared to standard values of National Petroleum Agency. The work was supplemented with a preliminary assessment of the reaction kinetic

Avaliação da eficiência de catalisadores comerciais na obtenção de biodiesel de algodão (Gossipium hisutum L.)

The increasing demand for energy and the environment consequences derived from the use of fossil energy, beyond the future scarcity of the oil that currently is the main power plant of the world, it stimulated the research around the production of biodiesel. In this work the synthesis of biodiesel of cotton in the methyl route was carried through, for had been in such a way used catalyst commercial homogeneous, Na-Methylat and the K-Methylat, aiming to the evaluation of the efficiency of them. An experimental planning 23 was elaborated aiming to evaluate the influence of the variable (molar reason oil/alcohol, % of catalyst and temperature) in the process as well as indicating the excellent point of operation in each case. The biodiesel was analyzed by gaseous chromatography, indicating a conversion of 96,79% when used Na-Methylat® as catalytic, and 95,65% when the K-Methylat® was used. Optimum result found with regard to the conversion was obtained at the following conditions: molar reason oil/alcohol (1:8), temperature of 40°C and 1% of catalyst Na-Methylat, reaching a 96,79% conversion, being, therefore, above of the established for the European norm (96.5%). The analysis of regression showed that the only significant effect for a confidence level of 95%, was of the changeable temperature. The variance analysis evidenced that the considered model is fitted quite to the experimental response, being statistically significant; however it does not serve inside for make forecasts of the intervals established for each variable. The best samples were analyzed by infra-red (IR) that identified the strong bands of axial deformation C=O of methylic ester, characterized through analyses physicochemical that had indicated conformity with the norms of the ANP, that with the thermal and rheological analyses had together evidenced that biodiesel can be used as combustible alternative in substitution to diesel

Extração enzimática de óleo e produção in situ de biodiesel a partir da Moringa oleífera Lam

With the growth and development of modern society, arises the need to search for new raw materials and new technologies which present the "clean" characteristic, and do not harm the environment, but can join the energy needs of industry and transportation. The Moringa oleifera Lam, plant originating from India, and currently present in the Brazilian Northeast, presents itself as a multi-purpose plant, can be used as a coagulant in water treatment, as a natural remedy and as a feedstock for biodiesel production. In this work, Moringa has been used as a raw material for studies on the extraction and subsequently in the synthesis of biodiesel. Studies have been conducted on various techniques of Moringa oil extraction (solvents, mechanical pressing and enzymatic), being specially developed an experimental design for the aqueous extraction with the aid of the enzyme Neutrase© 0.8 L, with the aim of analyzing the influence variable pH (5.5-7.5), temperature (45-55°C), time (16-24 hours) and amount of catalyst (2-5%) on the extraction yield. In relation to study of the synthesis of biodiesel was initially carried out a conventional transesterification (50°C, KOH as a catalyst, methanol and 60 minutes reaction). Next, a study was conducted using the technique of in situ transesterification by using an experimental design variables as temperature (30-60°C), catalyst amount (2-5%), and molar ratio oil / ethanol (1:420-1:600). The extraction technique that achieved the highest extraction yield (35%) was the one that used hexane as a solvent. The extraction using 32% ethanol obtained by mechanical pressing and extraction reached 25% yield. For the enzymatic extraction, the experimental design indicated that the extraction yield was most affected by the effect of the combination of temperature and time. The maximum yield obtained in this extraction was 16%. After the step of obtaining the oil was accomplished the synthesis of biodiesel by the conventional method and the in situ technique. The method of conventional transesterification was obtained a content of 100% and esters by in situ technique was also obtained in 100% in the experimental point 7, with a molar ratio oil / alcohol 1:420, Temperature 60°C in 5% weight KOH with the reaction time of 1.5 h. By the experimental design, it was found that the variable that most influenced the ester content was late the percentage of catalyst. By physico-chemical analysis it was observed that the biodiesel produced by the in situ method fell within the rules of the ANP, therefore this technique feasible, because does not require the preliminary stage of oil extraction and achieves high levels of esters

Avaliação da produção de biodiesel de microalga Isochrysis galbana via transesterificação in situ

Microalgae are microscopic photosynthetic organisms that grow rapidly and in different environmental conditions due to their simple cellular structure. The cultivation of microalgae is a biological system capable of storing solar energy through the production of organic compounds via photosynthesis, and these species presents growth faster than land plants, enabling higher biomass yield. Thus, it is understood that the cultivation of these photosynthetic mechanisms is part of a relevant proposal, since, when compared to other oil producing raw materials, they have a significantly higher productivity, thus being a raw material able to complete the current demand by biodiesel . The overall aim of the thesis was to obtain biofuel via transesterification process of bio oil from the microalgae Isochrysis galbana. The specific objective was to estimate the use of a photobioreactor at the laboratory level, for the experiments of microalgae growth; evaluating the characteristics of biodiesel from microalgae produced by in situ transesterification process; studying a new route for disinfection of microalgae cultivation, through the use of the chemical agent sodium hypochlorite. The introduction of this new method allowed obtaining the kinetics of the photobioreactor for cultivation, besides getting the biomass needed for processing and analysis of experiments in obtaining biodiesel. The research showed acceptable results for the characteristics observed in the bio oil obtained, which fell within the standards of ANP Resolution No. 14, dated 11.5.2012 - 18.5.2012. Furthermore, it was demonstrated that the photobioreactor designed meet expectations about study culture growth and has contributed largely to the development of the chosen species of microalgae. Thus, it can be seen that the microalgae Isochrysis galbana showed a species with potential for biodiesel production

Equilíbrio líquido-líquido para o sistema biodiesel de óleo de semente de melão (Cucumis melo l.) + metanol + glicerina

Rio Grande do Norte, northeast state from Brazil, it is the greatest producer and exporter of yellow melon, well known as Spanish melon. Despite the consumption of this fruit to be mainly its pulp, melon seeds are an important source of lipids considered an industrial residue it has been discharge product. The use of oilseeds in order to produce biodiesel establishes an important raw material and the increase of its production promotes the national development of the agriculture. In this background, the aim of this work has been to use oil from seeds of yellow melon to produce biodiesel and to accomplish a study of the phase equilibrium of the system evolving biodiesel, methanol and glycerin. The biodiesel was obtained by oil transesterification through methylic route with molar ratio 1:9.7 (oil:alcohol) and with a mass of NaOH of 0.5% from the oil mass; the reaction time was 73 minutes at 55 °C. A yield of 84.94% in biodiesel was achieved. The equilibria data present a well-characterized behavior with a great region of two phases. The tie lines indicate that methanol has a best solubility in the phase that is rich in glycerin. Consistency of the experimental data was made based on Othmer-Tobias and Hand correlations which values above 0.99 were found to correlation coefficients, this fact confers a good thermodynamic consistency to the experimental data. NRTL and UNIQUAC models were employed to predict liquid-liquid equilibrium of this system. It was observed a better concordance of the results when NRTL was applied (standard deviation 1.25%) although the UNIQUAC model has presented a quite satisfactory result either (standard deviation 2.70%). The NRTL and UNIQUAC models were also used to evaluate the effect of temperature in the range of 328 K to 358 K, in which a little change in solubility with respect to the data obtained at 298 K was observed, thus being considered negligible the effect of temperature

Continuous ethanol production in a nonconventional five-stage system operating with yeast cell recycling at elevated temperatures

Three ranges of increasing temperatures (35-43, 37-45, 39-47degreesC) were sequentially applied to a five-stage system continuously operated with cell recycling so that differences of 2degreesC (between one reactor to the next) and 8degreesC (between the first reactor at the highest temperature and the fifth at the lowest temperature) were kept among the reactors for each temperature range. The entire system was fed through the first reactor. The lowest values of biomass and viability were obtained for reactor R-3 located in the middle of the system. The highest yield of biomass was obtained in the effluent when the system was operated at 35-43degreesC. This nonconventional system was set up to simulate the local fluctuations in temperature and nutrient concentrations that occur in different regions of the medium in an industrial bioreactor for fuel ethanol production mainly in tropical climates. Minimized cell death and continuous sugar utilization were observed at temperatures normally considered too high for Saccharomyces cerevisiae fermentations.