A Simple and Fast Method for the Production and Characterization of Methylic and Ethylic Biodiesels from Tucum Oil via an Alkaline Route

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Metodologia experimental para avaliação de custos de produção e utilização de biodiesel: estudo de caso de quatro ésteres metílicos e óleo diesel comercial

Considerando que o Brasil detém uma vasta gama de matérias-primas para produção de biodiesel, e também que há a possibilidade de produção em pequena escala, prima-se por estudos de cunho econômico a partir de metodologias de fácil execução. O objetivo do trabalho foi demonstrar uma metodologia e sua aplicação para avaliação dos custos inseridos dentro do processo produtivo e de utilização do biodiesel. A metodologia foi aplicada a biodieseis originários de óleo de soja, girassol, frango e sebo bovino, dos quais se avaliaram economicamente os custos fixos e variáveis para conversão química dos óleos e gorduras em ésteres metílicos, em uma planta de produção experimental. Os custos de produção para cada uma das quatro citadas são distintos em função do valor inicial por litro de cada uma. Também fora avaliado o custo específico e o consumo específico de cada um dos biodieseis, a fim de determinar a diferença em relação ao óleo diesel comercial. No estudo de caso, os resultados mostraram vantagens para o óleo diesel, tanto no custo quanto no consumo. Comparando-se os biodieseis, o de sebo bovino apresentou-se com o menor custo de produção e o menor consumo.

Direct analysis of biodiesel microemulsions using an inductively coupled plasma mass spectrometry

An analytical procedure for direct introduction of biodiesel samples into an inductively coupled plasma mass spectrometer (ICP-MS) by using microemulsion for sample preparation was developed here. Cadmium, Co, Cu, Mn, Ni, Pb, Ti, and Zn were determined in biodiesel microemulsified samples prepared from different oleaginous sources (African palm, castor beans, palm, soybeans and an unknown oleaginous). Microemulsions were prepared using 0.25 mL Triton X-100, 0.25 mL 20% v v(-1) HNO(3), 0.50 mL biodiesel sample and 4.0 mL n-propanol. Argon-oxygen mixture was added to the plasma as auxiliary gas for correcting matrix effects caused by the high carbon load due to biodiesel microemulsions. The oxygen gas flow rate was set in 37.5 mL min(-1). The accuracy of the developed procedure was evaluated by applying addition-recovery experiments for biodiesel samples from different sources. Recoveries varied from 76.5 to 116.2% for all analytes but Zn in castor beans biodiesel sample (65.0 to 76.2%). Recoveries lower than 86.6% were obtained for palm biodiesel sample, probably due to matrix effects. Detection limits calculated by using oxygen in the composition of the auxiliary gas added to the plasma were higher than those calculated without using it, probably due to the highest formation of oxides. Despite oxides formation, best analytical performance was reached by using oxygen as auxiliary gas and by proper correction of transport interferences. The developed procedure based on microemulsion formation was suitable for direct introduction of biodiesel samples in ICP-MS. (C) 2010 Elsevier B.V. All rights reserved.

Influence of vegetable oil in the viscosity of biodiesel-a review

Viscosity is a measure fluid resistance to flowing, affecting the fuel spray in the combustion chamber and, by this way, thus the formation of carbon deposits. The analysis of the influence of vegetable oil viscosity in biodiesel seems appropriate, because biodiesel viscosity is a function of vegetable oil. The increase of the fuel viscosity, promoted by biodiesel, has a major impact on the dynamics of jet fuel, increasing its speed and distance of penetration, obtaining therefore an increase in the amount of turbulent movement of the jet and thus an increase in the rate of preparation of the mixture, air-fuel, when adding biodiesel to diesel oil. The negative effect of this higher fuel viscosity is the increase of the wear of the train of gears, cam shaft, and valve push rod of all the injection pumps due to the higher pressure of injection. The viscosity of biodiesel is influenced by the size of its molecule and by the increase of molecule insaturations, is directly related with its origin vegetable oil or fat. This study is a review of the influence of vegetable oils in viscosity of biodiesel. Copyright © 2008 SAE International.

A preliminary physicochemical, exergetic and economic study of hydrogen production utilizing glycerol

This work has as objective to demonstrate technical and economic viability of hydrogen production utilizing glycerol. The volume of this substance, which was initially produced by synthetic ways (from oil-derived products), has increased dramatically due mainly to biodiesel production through transesterification process which has glycerol as main residue. The surplus amount of glycerol has been generally utilized to feed poultry or as fuel in boilers, beyond other applications such as production of soaps, chemical products for food industry, explosives, and others. The difficulty to allocate this additional amount of glycerol has become it in an enormous environment problem, in contrary to the objective of biodiesel chain, which is to diminish environmental impact substituting oil and its derivatives, which release more emissions than biofuels, do not contribute to CO2-cycle and are not renewable sources. Beyond to utilize glycerol in combustion processes, this material could be utilized for hydrogen production. However, a small quantity of works (theoretical and experimental) and reports concerning this theme could be encountered. Firstly, the produced glycerol must be purified since non-reacted amounts of materials, inclusively catalysts, contribute to deactivate catalysts utilized in hydrogen production processes. The volume of non-reacted reactants and non-utilized catalysts during transesterification process could be reutilized. Various technologies of thermochemical generation of hydrogen that utilizes glycerol (and other fuels) were evaluated and the greatest performances and their conditions are encountered as soon as the most efficient technology of hydrogen production. Firstly, a physicochemical analysis must be performed. This step has as objective to evaluate the necessary amount of reactants to produce a determined volume of hydrogen and determine thermodynamic conditions (such as temperature and pressure) where the major performances of hydrogen production could be encountered. The calculations are based on the process where advance degrees are found and hence, fractions of products (especially hydrogen, however, CO2, CO, CH4 and solid carbon could be also encountered) are calculated. To produce 1 Nm3/h of gaseous hydrogen (necessary for a PEMFC - Proton Exchange Membrane Fuel Cell - containing an electric efficiency of about 40%, to generate 1 kWh), 0,558 kg/h of glycerol is necessary in global steam reforming, 0,978 kg/h of glycerol in partial oxidation and cracking processes, and 0,782 kg/h of glycerol in autothermal reforming process. The dry reforming process could not be performed to produce hydrogen utilizing glycerol, in contrary to the utilization of methane, ethanol, and other hydrocarbons. In this study, steam reforming process was preferred due mainly to higher efficiencies of production and the need of minor amount of glycerol as cited above. In the global steam reforming of glycerine, for one mole of glycerol, three moles of water are necessary to produce three moles of CO2 and seven moles of H2. The response reactions process was utilized to predict steam reforming process more accurately. In this mean, the production of solid carbon, CO, and CH4, beyond CO2 and hydrogen was predicted. However, traces of acetaldehyde (C2H2), ethylene (C2H4), ethylene glycol, acetone, and others were encountered in some experimental studies. The rates of determined products obviously depend on the adopted catalysts (and its physical and chemical properties) and thermodynamic conditions of hydrogen production. Eight reactions of steam reforming and cracking were predicted considering only the determined products. In the case of steam reforming at 600°C, the advance degree of this reactor could attain its maximum value, i.e., overall volume of reactants could be obtained whether this reaction is maintained at 1 atm. As soon as temperature of this reaction increases the advance degree also increase, in contrary to the pressure, where advance degree decrease as soon as pressure increase. The fact of temperature of reforming is relatively small, lower costs of installation could be attained, especially cheaper thermocouples and smaller amount of thermo insulators and materials for its assembling. Utilizing the response reactions process in steam reforming, the predicted volumes of products, for the production of 1 Nm3/h of H2 and thermodynamic conditions as cited previously, were 0,264 kg/h of CO (13% of molar fraction of reaction products), 0,038 kg/h of CH4 (3% of molar fraction), 0,028 kg/h of C (3% of molar fraction), and 0,623 kg/h of CO2 (20% of molar fraction). Through process of water-gas shift reactions (WGSR) an additional amount of hydrogen could be produced utilizing mainly the volumes of produced CO and CH4. The overall results (steam reforming plus WGSR) could be similar to global steam reforming. An attention must to be taking into account due to the possibility to produce an additional amount of CH4 (through methanation process) and solid carbon (through Boudouard process). The production of solid carbon must to be avoided because this reactant diminishes (filling the pores) and even deactivate active area of catalysts. To avoid solid carbon production, an additional amount of water is suggested. This method could be also utilized to diminish the volume of CO (through WGSR process) since this product is prejudicial for the activity of low temperature fuel cells (such as PEMFC). In some works, more three or even six moles of water are suggested. A net energy balance of studied hydrogen production processes (at 1 atm only) was developed. In this balance, low heat value of reactant and products and utilized energy for the process (heat supply) were cited. In the case of steam reforming utilizing response reactions, global steam reforming, and cracking processes, the maximum net energy was detected at 700°C. Partial oxidation and autothermal reforming obtained negative net energy in all cited temperatures despite to be exothermic reactions. For global steam reforming, the major value was 114 kJ/h. In the case of steam reforming, the highest value of net energy was detected in this temperature (-170 kJ/h). The major values were detected in the cracking process (up to 2586 kJ/h). The exergetic analysis has as objective, associated with physicochemical analysis, to determine conditions where reactions could be performed at higher efficiencies with lower losses. This study was performed through calculations of exergetic and rational efficiencies, and irreversibilities. In this analysis, as in the previously performed physicochemical analysis, conditions such as temperature of 600°C and pressure of 1 atm for global steam reforming process were suggested due to lower irreversibility and higher efficiencies. Subsequently, higher irreversibilities and lower efficiencies were detected in autothermal reforming, partial oxidation and cracking process. Comparing global reaction of steam reforming with more-accurate steam reforming, it was verified that efficiencies were diminished and irreversibilities were increased. These results could be altered with introduction of WGSR process. An economic analysis could be performed to evaluate the cost of generated hydrogen and determine means to diminish the costs. This analysis suggests an annual period of operation between 5000-7000 hours, interest rates of up to 20% per annum (considering Brazilian conditions), and pay-back of up to 20 years. Another considerations must to be take into account such as tariffs of utilized glycerol and electricity (to be utilized as heat source and (or) for own process as pumps, lamps, valves, and other devices), installation (estimated as US$ 15.000 for a plant of 1 Nm3/h) and maintenance cost. The adoption of emission trading schemes such as carbon credits could be performed since this is a process with potential of mitigates environment impact. Not considering credit carbons, the minor cost of calculated H2 was 0,16288 US$/kWh if glycerol is also utilized as heat sources and 0,17677 US$/kWh if electricity is utilized as heat sources. The range of considered tariff of glycerol was 0-0,1 US$/kWh (taking as basis LHV of H2) and the tariff of electricity is US$ 0,0867 US$/kWh, with demand cost of 12,49 US$/kW. The costs of electricity were obtained by Companhia Bandeirante, localized in São Paulo State. The differences among costs of hydrogen production utilizing glycerol and electricity as heat source was in a range between 0,3-5,8%. This technology in this moment is not mature. However, it allows the employment generation with the additional utilization of glycerol, especially with plants associated with biodiesel plants. The produced hydrogen and electricity could be utilized in own process, increasing its final performance.

Using the electrochemical impedance spectroscopy to characterize carbon steel in biodiesel medium

Electrochemical impedance spectroscopy measurements using two carbon steel electrodes in soybean biodiesel medium, produced by methylic route, were performed in an electrochemical cell that allows positioning the two electrodes face-to-face. To retain the biodiesel between the electrodes and prevent its leakage a porous membrane soaked in biodiesel was used. The amplitude of the AC potential and the area of the electrodes were varied. The linearity between disturbance and response signals was observed for tests when the amplitude of the AC potential was lower than 1500 mV (rms). The electrical resistance of biodiesel dominates the global response and carbon steel presents low corrosion, which is observed only at low frequency, and was confirmed by chemical tests performed in the membrane. In conclusion the electrical resistance of biodiesel can be estimated using electrochemical impedance spectroscopy with two electrodes set up. ©The Electrochemical Society.

Determination of Mg (II) in biodiesel by adsorptive stripping voltammetry at a mercury film electrode in the presence of sodium thiopentone

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

Effect of Hot Air Drying on Ultrastructure of Crambe Seeds

This study was conducted to evaluate the morphologic modifications in tissues of the fruit and seed of the crambe (Crambe abyssinica Hochst. Ex R.E. Fr.) after drying at different temperatures. Fruits with a water content of 0.38 kg water/kg dry matter were harvested and manually homogenized. Drying was accomplished at 35, 45, 60, 75, and 90°C and at 21,9,7,5, and 2% relative humidity, respectively. After drying, the structure of the pericarp and tegument of the seed were evaluated and the embryo was removed from the fruit/seed for morphological analysis (structural and ultrastructural and the histolocalization of reserve substances). Drying at different temperatures did not affect the cellular structure of the tissues composing the pericarp of the fruits, but it disorganized the structure of the seed tegument. The cells of the tegument and cotyledons presented a contraction in their volumes. The lowest contractions in the cellular volumes of both the tegument and cotyledons occurred after drying at 35 and 45°C. The cytoplasm of the cotyledon cells contains oil drops and the protein bodies contain protein granules and starch grains. There were no changes in the cellular walls of the embryos of the fruits dried at different temperatures; however, ungluing of the medium lamella occurred. This damage occurred with greater intensity after drying at temperatures above 60°C. The form of the oil drops in the cytoplasm of the cotyledon cells was altered after drying. At temperatures above 60°C, the drops broke up and coalesced. After drying at 45 and 60°C, the form of some protein bodies was altered, whereas at 75 and 90°C coalescence of the protein bodies occurred in some cells. It was concluded that the identified alterations can affect the physiologic quality of crambe seeds. © 2013 Copyright Taylor and Francis Group, LLC.

Nutrição e produtividade do crambe em razão da adubação de semeadura na safrinha

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Determination of Glycerol in Biodiesel Using a Nickel(II) Oxyhydroxide Chemically Modified Electrode by Cyclic Voltammetry

A glassy carbon electrode chemically modified with nickel oxyhydroxide from a nickel hexacyanoferrate (NiHCF) film was used to determine glycerol in biodiesel by cyclic voltammetry. The modified electrode exhibited a linear response to glycerol concentration in the range from 0.05 to 0.35mmol L-1, and a detection limit of 0.030mmol L-1. The glycerol concentration found in the biodiesel sample was 0.156mmol L-1. The method developed in this study showed a recovery of (100.3±5.0)%. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Glycerol: Production, consumption, prices, characterization and new trends in combustion

The demand for petroleum has been rising rapidly due to increasing industrialization and modernization. This economic development has led to a huge demand for energy, most of which is derived from fossil fuel. However, the limited reserve of fossil fuel has led many researchers to look for alternative fuels which can be produced from renewable feedstock. Increasing fossil fuel prices have prompted the global oil industry to look at biodiesel, which is from renewable energy sources. Biodiesel is produced from animal fats and vegetable oils and has become more attractive because it is more environmentally friendly and is obtained from renewable sources. Glycerol is the main by-product of biodiesel production; about 10% of the weight of biodiesel is generated in glycerol. The large amount of glycerol generated may become an environmental problem, since it cannot be disposed of in the environment. In this paper, an attempt has been made to review the different approaches and techniques used to produce glycerol (hydrolysis, transesterification, refining crude glycerol). The world biodiesel/glycerol production and consumption market, the current world glycerin and glycerol prices as well as the news trends for the use of glycerol mainly in Brazil market are analyzed. The technological production and physicochemical properties of glycerol are described, as is the characterization of crude glycerol obtained from different seed oil feedstock. Finally, a simple way to use glycerol in large amounts is combustion, which is an advantageous method as it does not require any purification. However, the combustion process of crude glycerol is not easy and there are technological difficulties. The news and mainly research about the combustion of glycerol was also addressed in this review. © 2013 Elsevier Ltd.

Genetic diversity among progenies of Crambe abyssinica Hochst for seed traits

Crambe is an important biofuel crop and its oil has unique traits such as high erucic acid content which can be used as industrial lubricant, corrosion inhibitor as well as ingredient in synthetic rubber manufacturing. Genetic diversity among 70 progenies of Crambe abyssinica Hochst selected from a population of FMS Brilhante cultivar was quantified by multivariate analysis for traits related to germination, thousand grain weight and oil content. There were significant differences among progenies for all traits studied. Estimation of genetic variance and heritability coefficients showed that the variability found in the progeny is more genetic than environmental which enables genetic gains with selection. Heritability coefficient varied from 68 to 79%, except for oil content and number of dead seedlings. Simple correlation analysis showed that germination and vigor were positively correlated, and thousand grain weight and oil content were not correlated with any of the seed traits. Based on multivariate analysis, the progenies could be grouped into 26 clusters. Clusters 1, 2 and 3 had the highest number of progeny with 7, 8 and 6 lineages, respectively. Clusters 21-26 had higher dissimilarity within the cluster with one in each progeny. The trait that most contributed to the cluster was the germination (36.2%) and less contributed was the number of seedlings killed (1.1%). The progenies indicate genetic diversity for seed traits and the selection of superior progenies is possible considering the studied traits. © 2013.

Estudo comparativo do estresse oxidativo entre tilápias (Oreochromis niloticus) e cascudos (Pterygoplichthys anisitsi) expostos a óleo diesel e a biodiesel

Pós-graduação em Biologia Animal - IBILCE

Biodiesel de mamona em trator agrícola na operação de preparo do solo

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização do óleo de frutos de tucumã (Astrocaryum aculeatum) para produção de biodiesel

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)