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

An Evaluation of Carbon Concentrations Associted with Biodiesel Particulate Matter in an Underground Metal Mine

Exposure to diesel particulate matter from diesel exhaust has been shown to have adverse health effects in humans. In 2012 The International Agency for Research on Cancer classified diesel exhaust as a group 1 know human carcinogen. Because of the associated health effects, there has been a strong push to reduce the amount of diesel exhaust present in the mining industry. Biodiesel is one to the more common and promising control options used to reduce the amount of diesel particulate matter that is generated during fuel combustion. The use of biodiesel over petroleum diesel has been shown to reduce not only particulate matter, but hydro carbon and carbon monoxide mass emissions as well. Personal and area samples were collected at an underground metal mine in the northwestern United States to evaluate the current blend of B70 biodiesel. The objective of this research was to evaluate the carbon levels associated with diesel particulate matter generated from the combustion of a B70 biodiesel. Data was also compared to past studies on which diesel particulate matter from petroleum diesel was evaluated. Samples were taken on four separate four day campaigns between March and October of 2014. Area samples were taken from 7 different areas in the mine and personal samples were taken from a 20 person cohort. The equipment used for sampling was compliant with the NIOSH 5040 method. Statistical analysis of the results was done using Minitab 17 software. The statistical analysis showed that the total carbon concentrations from biodiesel were well below the MSHA exposure limit. Results also showed that organic/elemental carbon ratios were consistent with past studies as the concentrations of organic carbon were significantly higher than those of elemental carbon.

ELECTROCATALYTIC PROCESSING OF RENEWABLE BIOMASS-DERIVED COMPOUNDS FOR PRODUCTION OF CHEMICALS, FUELS AND ELECTRICITY

The dual problems of sustaining the fast growth of human society and preserving the environment for future generations urge us to shift our focus from exploiting fossil oils to researching and developing more affordable, reliable and clean energy sources. Human beings had a long history that depended on meeting our energy demands with plant biomass, and the modern biorefinery technologies realize the effective conversion of biomass to production of transportation fuels, bulk and fine chemicals so to alleviate our reliance on fossil fuel resources of declining supply. With the aim of replacing as much non-renewable carbon from fossil oils with renewable carbon from biomass as possible, innovative R&D activities must strive to enhance the current biorefinery process and secure our energy future. Much of my Ph.D. research effort is centered on the study of electrocatalytic conversion of biomass-derived compounds to produce value-added chemicals, biofuels and electrical energy on model electrocatalysts in AEM/PEM-based continuous flow electrolysis cell and fuel cell reactors. High electricity generation performance was obtained when glycerol or crude glycerol was employed as fuels in AEMFCs. The study on selective electrocatalytic oxidation of glycerol shows an electrode potential-regulated product distribution where tartronate and mesoxalate can be selectively produced with electrode potential switch. This finding then led to the development of AEMFCs with selective production of valuable tartronate or mesoxalate with high selectivity and yield and cogeneration of electricity. Reaction mechanisms of electrocatalytic oxidation of ethylene glycol and 1,2-propanediol were further elucidated by means of an on-line sample collection technique and DFT modeling. Besides electro-oxidation of biorenewable alcohols to chemicals and electricity, electrocatalytic reduction of keto acids (e.g. levulinic acid) was also studied for upgrading biomass-based feedstock to biofuels while achieving renewable electricity storage. Meanwhile, ORR that is often coupled in AEMFCs on the cathode was investigated on non-PGM electrocatalyst with comparable activity to commercial Pt/C. The electro-biorefinery process could be coupled with traditional biorefinery operation and will play a significant role in our energy and chemical landscape.

Development of a 1-D Catalyzed Diesel Particulate Filter Model for Simulation of the Performance and the Oxidation of Particulate Matter and Nitrogen Oxides Using Passive Oxidation and Active Regeneration Engine Experimental Data

Back-pressure on a diesel engine equipped with an aftertreatment system is a function of the pressure drop across the individual components of the aftertreatment system, typically, a diesel oxidation catalyst (DOC), catalyzed particulate filter (CPF) and selective catalytic reduction (SCR) catalyst. Pressure drop across the CPF is a function of the mass flow rate and the temperature of the exhaust flowing through it as well as the mass of particulate matter (PM) retained in the substrate wall and the cake layer that forms on the substrate wall. Therefore, in order to control the back-pressure on the engine at low levels and to minimize the fuel consumption, it is important to control the PM mass retained in the CPF. Chemical reactions involving the oxidation of PM under passive oxidation and active regeneration conditions can be utilized with computer numerical models in the engine control unit (ECU) to control the pressure drop across the CPF. Hence, understanding and predicting the filtration and oxidation of PM in the CPF and the effect of these processes on the pressure drop across the CPF are necessary for developing control strategies for the aftertreatment system to reduce back-pressure on the engine and in turn fuel consumption particularly from active regeneration. Numerical modeling of CPF's has been proven to reduce development time and the cost of aftertreatment systems used in production as well as to facilitate understanding of the internal processes occurring during different operating conditions that the particulate filter is subjected to. A numerical model of the CPF was developed in this research work which was calibrated to data from passive oxidation and active regeneration experiments in order to determine the kinetic parameters for oxidation of PM and nitrogen oxides along with the model filtration parameters. The research results include the comparison between the model and the experimental data for pressure drop, PM mass retained, filtration efficiencies, CPF outlet gas temperatures and species (NO2) concentrations out of the CPF. Comparisons of PM oxidation reaction rates obtained from the model calibration to the data from the experiments for ULSD, 10 and 20% biodiesel-blended fuels are presented.

Examining the use of Simarouba glauca Seed Oil as a Feedstock for the Production of Biodiesel using a Small Scale Model Developed in India

Simarouba glauca, a non-edible oilseed crop native to South Florida, is gaining popularity as a feedstock for the production of biodiesel. The University of Agriculture Sciences in Bangalore, India has developed a biodiesel production model based on the principles of decentralization, small scales, and multiple fuel sources. Success of such a program depends on conversion efficiencies at multiple stages. The conversion efficiency of the field-level, decentralized production model was compared with the in-laboratory conversion efficiency benchmark. The study indicated that the field-level model conversion efficiency was less than that of the lab-scale set up. The fuel qualities and characteristics of the Simarouba glauca biodiesel were tested and found to be the standards required for fuel designation. However, this research suggests that for Simarouba glauca to be widely accepted as a biodiesel feedstock further investigation is still required.

Added value from biomass by broader utilization of fuels and CHP plants

The present work, where additional value-creating processes in existing combined heat and power (CHP) structures have been examined, is motivated by a political- and consumer-driven strive towards a bioeconomy and a stagnation for the existing business models in large parts of the CHP sector. The research is based on cases where the integration of flash pyrolysis for co-production of bio-oil, co-gasification for production of fuel gas and synthetic biofuels as well as leaching of extractable fuel components in existing CHP plants have been simulated. In particular, this work has focused on the CHP plants that utilize boilers of fluidized bed (FB) type, where the concept of coupling a separate FB reactor to the FB of the boiler forms an important basis for the analyses. In such dual fluidized bed (DFB) technology, heat is transferred from the boiler to the new rector that is operating with other fluidization media than air, thereby enabling other thermochemical processes than combustion to take place. The result of this work shows that broader operations at existing CHP plants have the potential to enable production of significant volumes of chemicals and/or fuels with high efficiency, while maintaining heat supply to external customers. Based on the insight that the technical preconditions for a broader operation are favourable, the motivation and ability among the incumbents in the Swedish CHP sector to participate in a transition of their operation towards a biorefinery was examined. The result of this assessment showed that the incumbents believe that a broader operation can create significant values for their own operations, the society and the environment, but that they lack both a strong motivation as well as important abilities to move into the new technological fields. If the concepts of broader production are widely implemented in the Swedish FB based CHP sector, this can substantially contribute in the transition towards a bioeconomy.

Production de biodiesel à partir de microalgues par catalyses homogène et hétérogène

Résumé : Au Canada, près de 80% des émissions totales, soit 692 Mt eq. CO[indice inférieur 2], des gaz à effet de serre (GES) sont produits par les émissions de dioxyde de carbone (CO[indice inférieur 2]) provenant de l’utilisation de matières fossiles non renouvelables. Après la Conférence des Nations Unies sur les changements climatiques, COP21 (Paris, France), plusieurs pays ont pour objectif de réduire leurs émissions de GES. Dans cette optique, les microalgues pourraient être utilisées pour capter le CO[indice inférieur 2] industriel et le transformer en biomasse composée principalement de lipides, de glucides et de protéines. De plus, la culture des microalgues n’utilise pas de terre arable contrairement à plusieurs plantes oléagineuses destinées à la production de biocarburants. Bien que les microalgues puissent être transformées en plusieurs biocarburants tels le bioéthanol (notamment par fermentation des glucides) ou le biométhane (par digestion anaérobie), la transformation des lipides en biodiesel pourrait permettre de réduire la consommation de diesel produit à partir de pétrole. Cependant, les coûts reliés à la production de biodiesel à partir de microalgues demeurent élevés pour une commercialisation à court terme en partie parce que les microalgues sont cultivées en phase aqueuse contrairement à plusieurs plantes oléagineuses, ce qui augmente le coût de récolte de la biomasse et de l’extraction des lipides. Malgré le fait que plusieurs techniques de récupération des lipides des microalgues n’utilisant pas de solvant organique sont mentionnées dans la littérature scientifique, la plupart des méthodes testées en laboratoire utilisent généralement des solvants organiques. Les lipides extraits peuvent être transestérifiés en biodiesel en présence d’un alcool tel que le méthanol et d’un catalyseur (catalyses homogène ou hétérogène). Pour la commercialisation du biodiesel à partir de microalgues, le respect des normes ASTM en vigueur est un point essentiel. Lors des essais en laboratoire, il a été démontré que l’extraction des lipides en phase aqueuse était possible afin d’obtenir un rendement maximal en lipides de 36% (m/m, base sèche) en utilisant un prétraitement consistant en une ébullition de la phase aqueuse contenant les microalgues et une extraction par des solvants organiques. Pour l’estérification, en utilisant une résine échangeuse de cations (Amberlyst-15), une conversion des acides gras libres de 84% a été obtenue à partir des lipides de la microalgue Chlorella protothecoïdes dans les conditions suivantes : température : 120°C, pression autogène, temps de réaction : 60 min, ratio méthanol/lipides: 0.57 mL/g et 2.5% (m/m) Amberlyst-15 par rapport aux lipides. En utilisant ces conditions avec une catalyse homogène (acide sulfurique) et une seconde étape alcaline avec de l’hydroxyde de potassium (température : 60°C ; temps de réaction : 22.2 min; ratio catalyseur microalgue : 2.48% (m/m); ratio méthanol par rapport aux lipides des microalgues : 31.4%), un rendement en esters méthyliques d’acides gras (EMAG) de 33% (g EMAG/g lipides) a été obtenu à partir des lipides de la microalgue Scenedesmus Obliquus. Les résultats démontrent que du biodiesel peut être produit à partir de microalgues. Cependant, basé sur les présents résultats, il sera necessaire de mener d’autre recherche pour prouver que les microalgues sont une matière première d’avenir pour la production de biodiesel.

Biodiesel production from waste cooking oil over sulfonated catalysts

Biodiesel production from waste cooking oil with methanol was carried out in the presence of poly(vinyl alcohol) with sulfonic acid groups (PVA-SO3H) and polystyrene with sulfonic acid groups (PS-SO3H), at 60°C. The PVA-SO3H catalyst showed higher catalytic activity than the PS-SO3H one. In order to optimize the reaction conditions, different parameters were studied. An increase of waste cooking oil conversion into fatty acid methyl esters with the amount of PVA-SO3H was observed. When the transesterification and esterification of WCO was carried out with ethanol over PVA-SO3H, at 60°C, a decrease of biodiesel production was also observed. The WCO conversion into fatty acid ethyl ester increased when the temperature was increased from 60 to 80°C. When different amounts of free fatty acids were added to the reaction mixture, a slight increase on the conversion was observed. The PVASO3H catalyst was reused and recycled with negligible loss in the activity.

Composites Chitosan/SBA-15 with sulfonic acid as heterogeneous catalysts for biodiesel production

Free fatty acids (palmitic, stearic and oleic acid) were converted into biodiesel with methanol over composites catalysts consisting in SBA-15 with sulfonic acid groups (SBA-15-SO3H) immobilized in Chitosan (CH), at 60ºC. It was observed that the catalytic activity increased with the amount of SBA-15-SO3H dispersed in CH. It was also observed that the catalytic activity decreased in the series: palmitic acid > stearic acid > oleic. The catalytic stability of [SBA-15-SO3H]3/CH composites was studied. A good stability was observed.

Cultivo de oleaginosas para produção de biodiesel como uma estratégia de mitigação às mudanças climáticas.

O aumento da concentração de Gases de Efeito Estufa (GEE) tem sido apontado como o principal agente das mudanças climáticas. O carbono é o principal GEE de origem antrópica. A redução das emissões de GEE para a atmosfera pode ser alcançada pela adoção de medidas mitigadoras, tais como o uso de biodiesel, em substituição aos combustíveis fósseis. Neste trabalho foram elaborados cenários de mitigação do uso de biodiesel produzido a partir do cultivo de oleaginosas por agricultores familiares do semiárido em substituição ao diesel mineral no setor de transporte rodoviário no Brasil. Os resultados apontam para o potencial de produção total de cerca de 0,9 a 2 bilhões de litros biodiesel em 2015, a partir do fornecimento de matéria -prima pelos agricultores familiares do semiárido, o que corresponde a uma redução de emissões de CO2 de até 7% no setor de transporte rodoviário. Na possibilidade de geração de créditos de carbono (Reduções Certificadas de Emissões - RCE) as emissões evitadas do uso desse biodiesel em substituição do diesel mineral, poderiam gerar entre 103 a 4.835 RCE ao ano, dependendo do cenário e do ano considerado. No caso da venda desses créditos a renda bruta equivale a cerca de U$5 a U$18,00 por metro cúbico (1000 litros) de biodiesel produzido, dependendo do cenário analisado e considerando o valor de venda de créditos de carbono igual a U$ 10,00/tCO2.

IMPACTO DE ESTABLECER JATROPHA CURCAS PARA PRODUCIR BIODIESEL, EN TRES COMUNIDADES DE MICHOACÁN, MÉXICO, ABORDADO A PARTIR DE DIFERENTES ESCALAS

México, a pesar de ser un país productor de petróleo, impulsa en el 2007 el “Programa Nacional de Introducción de Bioenergéticos”, sin que existan aportes reales al desarrollo del mercado interno de biodiesel. En Michoacán, la iniciativa privada y el gobierno local gestionaron infraestructura para obtener biodiesel sin que se tengan resultados; no obstante, varias comunidades en el Estado han plantado Jatropha curcas con ayuda de subsidios del gobierno Federal y el apoyo de la iniciativa privada. En el presente estudio se tiene como objetivo enmarcar la problemática de tres comunidades de Michoacán respecto a la situación Internacional, Nacional y Local, para determinar los impactos en los hogares, considerando la competencia de las plantaciones en su espacio de producción agrícola y las oportunidades de mercado, tomando en cuenta las visiones de los diferentes actores involucrados en la problemática.

REFLEXÕES SOBRE O ETANOL E O BIODIESEL NA MATRIZ ENERGÉTICA BRASILEIRA

A importância dada mundialmente para as fontes renováveis de energia se resulta das instabilidades relacionadas ao fornecimento de petróleo, ao cumprimento de tratados internacionais de redução de gases de efeito estufa, às exigências legais e a obrigação moral de promoção do Desenvolvimento Sustentável. No caso brasileiro, também se adota uma política voltada para a substituição de combustíveis de origem fóssil por combustíveis renováveis, dentre essas fontes tem recebido grande atenção a produção do etanol e do biodiesel. A proposta deste trabalho é discutir o cenário geral dessa nova aposta de produção de energia no país, elencando sutilmente algumas de suas condições, como as especulações financeiras e interesses particulares de alguns dos setores que incentivam a produção dos biocombustíveis. Em alguns casos, tais incentivos são baseados no discurso da viabilidade econômica, da sustentabilidade ambiental e da qualidade social, sendo esse, muitas vezes, interpretado de forma tendenciosa a apaziguar os impactos na cadeia produtiva de alimentos, no meio ambiente, na economia do país e para a sua população. Assim, antes mesmo do Brasil assumir o trabalho de produzir os combustíveis de que urgem as necessidades do mundo, no ritmo que o consumo e a acumulação do capital tanto impõem, é vital que se reflita para qual modelo de desenvolvimento se estará caminhando.