Authors:R. A. Candeia, F. S. M. Sinfrônio, T. C. Bicudo, N. Queiroz, A. K. D. Barros Filho, L. E. B. Soledade, I. M. G. Santos, A. L. Souza, and A. G. Souza
Biodiesel oxidation is a complex process widely influenced by the chemical composition of the biofuel and storage conditions. Several oxidation products can be formed from these processes, depending on type and amount of the unsaturated fatty acid esters. In this work, fatty acid methyl and ethyl esters were obtained by base-catalyzed transesterification of soybean oil and physicochemically characterized according to standards from ASTM, EN, and ABNT. The thermal and oxidative stabilities of biodiesel samples were investigated during the storage process by pressure differential scanning calorimetry (PDSC) and by viscosity measurements. Absolute viscosities of biodiesels after accelerated aging were also determined. The viscosity increased as the aging temperature and time were raised. The results showed that oxidation induction can occur during storage, decreasing the biodiesel stability. PDSC analysis showed that during storage under climate simulation the values of high-pressure oxidative induction times (HPOIT) were reduced for both FAEE and FAME.
Authors:M. L. A. Tavares, N. Queiroz, I. M. G. Santos, A. L. Souza, E. H. S. Cavalcanti, A. K. D. Barros, R. Rosenhaim, L. E. B. Soledade, and A. G. Souza
The higher is the degree of unsaturation in ester chain of a biodiesel, the smaller is its oxidation stability. Sunflower biodiesel obtained by the ethyl route possesses a high amount of unsaturated fatty acids, mainly oleic acid (C18:1) and linoleic acid (C18:2), thus being more prone to the oxidation process. In Brazil, with the purpose of meeting the specifications of the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP), antioxidant additives, from synthetic and natural origins, have been added to the biofuel. Antioxidants are an alternative to prevent the oxidative deterioration of the fatty acid derivatives, as they are substances able to reduce the oxidation rate. In this study, the oxidative stability of sunflower biodiesel, obtained by the ethyl route and additivated with different concentrations of the antioxidants butylated hydroxytoluene (BHT) and t-butylhydroquinone (TBHQ), was evaluated by means of Pressure differential scanning calorimetry (P-DSC) and the Accelerated oxidative stability test (Rancimat, Method EN 14112). The results obtained by the two techniques showed the same oxidation tendency. Thus, P-DSC can be used as an alternative to determine the oxidative stability of biodiesel. The antioxidant TBHQ, added to biodiesel at the concentrations of 2000 and 2500 mg kg−1, raised the oxidation induction time to a value higher than 6 h, the limit established by the Resolution ANP number 7/2008, thus being the best alternative among the studied antioxidants.
Authors:Rodrigo A. de Souza, Antonio E. Mauro, Adelino V. G. Netto, Gislaine A. da Cunha, and Eduardo T. de Almeida
Palladium(II) coordination compounds of general formula trans-[PdX2(isn)2], X = Cl− (1), N3− (2), SCN− (3), NCO− (4), isn = isonicotinamide; were synthesized and characterized in solid state by elemental analysis, infrared spectroscopy, and simultaneous TG–DTA. TG experiments reveal that the compounds 1–4 undergo thermal decomposition in three or four stages, yielding Pd0 as final residue, according to calculus and identification by X-ray powder diffraction.
Authors:M. L. S. De Melo, N. A. Santos, R. Rosenhaim, A. G. Souza, and P. F. Athayde Filho
Biodiesel has the advantage of being renewable and clean and for these reasons has been studied recently both academically and in industry. Research in this area is focused on developing new synthetic routes to obtain a purer product or to find new alternative sources of food to replace conventional oils. Papaya biodiesel is obtained from oily residues with a fatty acid composition similar to olive oil. It is generally discarded by the ton, considering that Brazil is the world’s largest producer of papaya with an annual output of 1,811 million tons, productivity of 52 t/hectare and domestic consumption at 86.5%. This study was designed by means of thermal analysis (TG, DSC, P-DSC, and MT-DSC), to verify the possibility of achieving high quality biodiesel, with oxidative stability and flow properties previously indicated by composition analysis of its fatty esters, physical–chemical properties (including oxidative stability) using classical methodology, recommended by ASTM D 6756.
Authors:F. L. Macedo, R. A. Candeia, L. L. M. Sales, M. B. Dantas, A. G. Souza, and M. M. Conceição
Searching for other alternative sources, which are not part of the food chain, and which are able to supply the biofuel market is a promising option. In this context, it has been searched to investigate the oiticica oil, approaching its availability to the biodiesel synthesis, as well as its thermal stability. Few works retreat parameters such as: the optimization of the biodiesel synthesis, its physical–chemical properties, and thermal parameters etc. The characterization results revealed that the oil showed very high kinematic viscosity, and acidity value around 13 mg KOH/g, requiring a pre-treatment. To reduce the acid in the oil, it has been done the esterification of oil, which was studied in different molar ratios oiticica oil/ethanol (1:9) and 2.0% catalyst, in order to get the best reduction the index of acidity. The lowest level of acidity of the oil obtained after the esterification was 4.4 mg KOH/g. The reaction rate for the synthesis of biodiesel, compared to the initial mass of oiticica oil ester was 85%. This income can be overcome by pursuing an even smaller reduction of acid value of biodiesel oiticica. The acid value of biodiesel was 1.8 mg KOH/g. The results have revealed that the oiticica oil and biodiesel are stable at 224 and 179 °C, respectively.
Authors:Alexandre G. S. Prado, Sheila M. Evangelista, Jurandir R. SouzaDe, Jeane G. S. Matos, Marco A. A. Souza, Denise A. Oliveira, and Claudio Airoldi
A microcalorimetric method was applied to study microbial soil activity of ornamental flower (Dahlia pinnata) plantations when irrigated with potable water and wastewaters. The samples were irrigated with potable water PW sample (reference) and treated wastewaters from Municipal Wastewater Treatment Station of Asa Norte in Brasilia City (Brazil). Three different water treatments were applied to irrigate soil samples, named TW1, TW2, and TW3 samples. The increase of the microbial soil activity observed in TW1 sample must have occurred because of the high amount of organic waste dissolved in wastewater used for irrigation. This rise indicates that the present treated wastewater can affect natural life cycle. However, only a low alteration in microbial soil activity was observed in the TW2 and TW3 samples, which suggests that these wastewater treatments can be normally used to irrigate soils without bringing environmental consequences, once they offer a great opportunity to upgrade and protect the environment.
Authors:N. A. Santos, R. Rosenhaim, M. B. Dantas, T. C. Bicudo, E. H. S. Cavalcanti, A. K. Barro, I. M. G. Santos, and A. G. Souza
Biodiesel is an increasingly attractive alternative to diesel fuel. The main component of Babassu biodiesel is lauric acid (C12:0), which is a saturated fatty acid with a high melting point. Controlling flow properties, such as viscosity and the cold filter plugging point, is critical because viscosity affects atomization, and crystal formation resulting from decreases in temperature can negatively affect engine starting and performance. To evaluate its flow characteristics more fully, the rheological properties of babassu biodiesel were analyzed, taking into account variations in temperature. The crystallization temperature was determined by modulated temperature differential scanning calorimetry (MT-DSC). The curve of biodiesel viscosity as a function of the biodiesel refrigeration temperature contained an inflection point (corresponding to a steep increase in viscosity) that was coincident with both the transition from a Newtonian-type flow to a pseudoplastic-type flow and the crystallization temperature obtained by MT-DSC, indicating that the appearance of crystals in the biodiesel increased its viscosity. The rheological properties of fatty acid methyl and ethyl mixtures (FAME and FAEE) with metropolitan diesel were also evaluated; a higher FAME percentage reduced viscosity in blends up to B100.