José R. Zamian

Determination of the oxidative stability by DSC of vegetable oils from the Amazonian area

Differential scanning calorimetry (DSC) and a Rancimat method apparatus were applied to evaluate the oxidative stability of buriti pulp oil (Mauritia flexuosa Mart), rubber seed oil (Hevea brasiliensis), and passion fruit oil (Passiflora edulis). The Rancimat measurements taken for the oxidative induction times were performed under isothermal conditions at 100°C and in an air atmosphere. The DSC technique involved the oxidation of oil samples in an oxygen-flow DSC cell. The DSC cell temperature was set at five different isothermal temperatures: 100, 110, 120, 130 and 140°C. During the oxidation reaction, an increase in heat was observed as a sharp exothermic curve. The value T(0) represents the oxidative induction time, which is determined from the downward extrapolated DSC oxidative curve verses the time axis. These curves indicate a good correlation between the DSC T(0) and oxidative stability index (OSI) values. The DSC method is useful because it consumes less time and less sample.

Conversion of waste produced by the deodorization of palm oil as feedstock for the production of biodiesel using a catalyst prepared from waste material.

The distillate produced by deodorization of palm oil (DDPO) is a waste that corresponds to 4% of the product formed in this process. DDPO is 83% free of fatty acids (FFA), making it a good material for biodiesel production. In this paper, a catalyst prepared from a waste material, Amazon flint kaolin, was used for the esterification of DDPO with methanol. Leached metakaolin treated at 950°C and activated with 4M sulfuric acid (labeled as MF9S4) offered maximum esterification activity (92.8%) at 160°C with a DDPO:methanol molar ratio of 1:60 and a 4-h reaction time. The influences of reaction parameters, such as the molar ratio of the reactants, alcohol chain length, temperature, time and the presence of glycerides and unsaponifiable matter, have also been investigated. Based on the catalytic results, esterification of DDPO using MF9S4 can be a cheaper alternative for production of sustainable fuels.

Characterization, thermal properties and phase transitions of amazonian vegetable oils

Thermal profiles of buriti pulp oil (Mauritia flexuosa Mart.), tucumã pulp and kernel oils (Astrocarium vulgare Mart.), rubber seed oil (Hevea brasiliensis), passion fruit oil (Passiflora edulis) and ucuúba butter (Virola surinamensis) were analyzed by thermogravimetry (TG/DTG) and differential scanning calorimetry (DSC). Gas chromatography and calculated iodine values were performed to determine the fatty acid profile and to measure the degree of unsaturation in these oils, respectively. The TG curves showed three steps of mass loss, which can be attributed to the degradation of polyunsaturated, monounsaturated and saturated fatty acids. The DSC crystallization and melting curves are reported and depended on the fatty acid composition. Usually, oil samples with a high degree of saturation showed crystallization and melting profiles at higher temperatures than the oils with a high degree of unsaturation. The data obtained by physicochemical analysis of oil samples were analyzed by principal component analysis and hierarchical cluster analysis to increase understanding of the data set, examining the presence or absence of natural groupings between samples.

Soybean biodiesel methyl esters, free glycerin and acid number quantification by 1H nuclear magnetic resonance spectroscopy.

Production of alternative fuels, such as biodiesel, from transesterification of vegetable oil driven by heterogeneous catalysts is a promising alternative to fossil diesel. However, achieving a successful substitution for a new renewable fuel depends on several quality parameters. 1H NMR spectroscopy was used to determine the amount of methyl esters, free glycerin and acid number in the transesterification of soybean oil with methanol in the presence of hydrotalcite‐type catalyst to produce biodiesel. Reaction parameters, such as temperature and time, were used to evaluate soybean oil methyl esters rate conversion. Temperatures of 100 to 180 °C and times of 20 to 240 min were tested on a 1 : 12 molar ratio soybean oil/methanol reaction. At 180 °C/240 min conditions, a rate of 94.5 wt% of methyl esters was obtained, where free glycerin and free fatty acids were not detected. Copyright

Ethanolysis optimisation of jupati (Raphia taedigera Mart.) oil to biodiesel using response surface methodology.

In this work, the transesterification of jupati (Raphia taedigera Mart.) oil using ethanol and acid catalyst was examined. The production of biodiesel was performed using a central composite design (CCD). A range of values for catalyst concentration (1 to 4.21%), temperature (70-80 °C), and the molar ratio of alcohol to oil (6:1-13.83:1) were tested, and ester content, viscosity, and yield were the response variables. The synthesis process was optimised using response surface methodology (RSM), resulting in the following optimal conditions for the production of jupati ethyl esters: a catalyst concentration of 3.85% at 80 °C and an alcohol-to-oil molar ratio of 10:1.

Functionalization of Bentonite and Vermiculite after the Creation of Structural Defects through an Acid Leaching Process

The synthesis and use of functionalized materials is growing every year. Thus, this work presents a methodology for the functionalization of bentonite and vermiculite after the acid leaching of the raw materials. Leaching was performed with sulfuric acid (H2SO4), and the functionalization was performed with (3-mercaptopropyl)trimethoxysilane (MPTS), which was oxidized after being anchored to the support. Compared to the results in the literature for directly functionalized raw bentonite, the materials had a greater number of anchored propyl sulfonic acid groups, and the greatest number of these groups led to an increase in the acidity of the raw materials. The raw and functionalized bentonite and vermiculite were characterized by X-ray diffraction (XRD), energy dispersive X-ray (EDX), thermogravimetric analysis (TGA), N2 adsorption and the surface acidity was determined by acid-base titration.

Thermal decomposition and stability in a series of heterobimetallic carbonyl compounds of the type [Fe(CO)4(HgX)2] (X=Cl, Br, I)

Heterobimetallic carbonyl compounds of the type [Fe(CO)4(HgX)2] (X= Cl, Br, I), which have metal-metal bonds, have been prepared in order to study their thermal stabilities as a function of the halogen coordinated to mercury atoms. The characterization of the above complexes was carried out by elemental analysis, IR and NMR spectroscopies. Their thermal behaviour has been investigated and the final product was identified by IR spectroscopy and by X-ray powder diffractogram.

Investigação espectroscópica dos carbonilos heterobimetálicos cis-[Fe(CO)4(HgX)2], X = Cl, Br,I

The series of compounds cis-[Fe(CO)4(HgX)2], X=Cl,Br,I shows an octahedral geometry around the iron atom with the two HgX groups cis to each other. In this paper the assignment for the carbonyl stretching modes and the calculation of their force constants were performed on the basis of the Cotton-Krainhanzel model. Taking into account all the data from the IR, 199Hg NMR and UV-vis spectra it is possible to verify the influence of X on the electronic densities at the metallic centers.

Determination of Carbon Microresidue at Mixtures of Diesel/Biodiesel

This study proposes to evaluate the influence of the addition of biodiesel to diesel in relation the combustion quality of Diesel/Biodiesel mixtures by monitoring the carbon residue. Biodiesel methyl and ethyl esters were synthesized from soybean oil using KOH as catalyst. The diesel and the methyl and ethyl esters were characterized according to official methods. The mixtures were obtained in proportions of 5 %, 10 %, 15 %, 20% and 25% of biodiesel in diesel and were evaluated by analyzes of microresidue carbon, higher heating value and kinematic viscosity. The results show an increase of the carbon residue with the content of biodiesel and also with the increase of the chain of the methyl ester (biodiesel methyl to ethyl biodiesel) which may indicate a greater possibility of carbon residue deposits in the injection system and the engine pistons.

Síntese de éster de cadeia longa via catálise básica heterogênea

Um ester de cadeia longa foi sintetizado pela transesterificacao do palmitato de metila com alcoois de cadeia longa usando oxido de magnesio como catalisador. Esses foram preparados pela decomposicao termica de diferentes precursores, buscando estabelecer relacoes entre propriedades estruturais e atividades. Temperatura e quantidade de catalisador foram variados para se avaliar o rendimento do ester em funcao do precursor utilizado na preparacao do oxido.