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  • Author or Editor: V. Fernandes Jr x
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Abstract  

In this work was studied the acid properties of a series of HZSM-12 zeolites with different Si/Al molar ratio. The samples of ZSM-12 were synthesized by the hydrothermal method starting from a gel with the following molar composition: 20MTEA:10Na2O:xAl2O3:100SiO2:200H2O, where: x=2, 1, 0.67 and 0.50, respectively. After the synthesis, the samples of ZSM-12 were ion-exchanged NH4Cl solution to obtain zeolite in the acid form (HZSM-12). The acid properties were evaluated by n-butylamine thermodesorption in a TG equipment at three different heating rates. The model-free kinetic model was applied in the TG integral curves to estimate the apparent activation energy (E a) of the n-butylamine desorption process. The results obtained showed that the HZSM-12 zeolite presents two kinds main of acid sites: one with E a in the range of 115-125 kJ mol-1 classified as weak and other kind with E a varying of 230-250 kJ mol-1 classified as strong.

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Journal of Thermal Analysis and Calorimetry
Authors: Nataly Santos, Marileide Tavares, R. Rosenhaim, F. Silva, V. Fernandes Jr, Iêda Santos, and A. Souza

Abstract  

The growing petroleum deficit requires the development of alternative fuel sources. Biodiesel is a good alternative, as it is a biodegradable and renewable product, which obeys the carbon cycle. In this work, the biodiesel from babassu was synthesized using the methanol route, and characterized by physico-chemical analyses in order to make able the investigated biodiesel to fulfill with its properties the requirements of Brazilian National Agency for Petroleum, Natural Gas and Biofuel (ANP). Besides gas chromatography, IR spectroscopy experiments and thermoanalytical measurements in air and in nitrogen were done to determine the main thermal decomposition processes and calorimetric events. The evaporation temperature of babassu biodiesel was similar in both atmospheres, started around 52 in air and around 60C in nitrogen.

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Journal of Thermal Analysis and Calorimetry
Authors: Marta Conceição, V. Fernandes Jr, A. Bezerra, M. Silva, Iêda Santos, F. Silva, and A. Souza

Abstract  

Diesel oil has an important role in the field of urban traffic as well as in the transportation of products. However, the amount of the non-renewable sources is continuously decreasing. This fact and the environmental requirements brought the necessity to search for other, renewable sources. This paper aimed the dynamic kinetic calculation of thermal decomposition of castor oil, methanol biodiesel and ethanol biodiesel using Coats–Redfern, Madhusudanan and Ozawa methods. On the base of the thermogravimetric curves the following thermal stability order could be established: castor oil>ethanol biodiesel>methanol biodiesel. Kinetic data presented coherent results. Methanol biodiesel presented lower activation energy than ethanol biodiesel, suggesting that methanol biodiesel has a better quality for combustion.

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Abstract  

Thermogravimetry (TG) and mass spectrometry (MS) combined techniques have been used to investigate the thermal degradation and catalytic decomposition of high-density polyethylene (HDPE) over solid acid catalysts as H-ZSM-5, Al-MCM-41 and a hybrid material with a bimodal pore size distribution (H-ZSM-5/Al-MCM-41). The silicon/aluminum ratio of all catalysts is 15. Both thermal and catalytic processes showed total conversion in a single mass loss step. Furthermore, the catalytic conversion presents average reduction of 27.4%, in the onset decomposition temperature. The kinetic parameters were calculated using non-isothermal method. These parameters do not indicate significant differences between the thermal and catalytic processes. Even though, the presence of the catalysts changes the reaction mechanism, from phase boundary controlled reaction to random nucleation mechanism. Important difference in distribution of evolved products was detected when several catalysts were used. However, in all cases the main products were alkanes (C2, C3 and C4), alkenes (C3 and C4), dienes (C4 and C5) and traces of aromatic compounds.

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Abstract  

The degradation kinetics of polycarbonate with flame retardant additive was investigated by means of thermogravimetric analysis. The samples were heated from 30 to 900C in nitrogen atmosphere, with three different heating rates: 5, 10 and 20C min–1. The Vyazovkin model-free kinetics method was applied to calculate the activation energy (E a) of the degradation process as a function of conversion and temperature. The results indicated that the polycarbonate without flame retardant additive starts to loose mass slightly over 380C and the polycarbonate with flame retardant additive, slightly over 390C (with heating rate of 5C min–1). The activation energy for flame retardant polycarbonate and normal polycarbonate were 190 and 165 kJ mol–1, respectively.

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Journal of Thermal Analysis and Calorimetry
Authors: A. M. Ramalho, M. M. Conceiçăo, V. J. Fernandes Jr., J. C. Machado, L. E. B. Soledade, and A. G. Souza
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Journal of Thermal Analysis and Calorimetry
Authors: M. Dantas, Marta Conceição, V. Fernandes Jr, Nataly Santos, R. Rosenhaim, Aldalea Marques, Iêda Santos, and A. Souza

Abstract  

This work evaluates the thermal and kinetic behaviour of corn biodiesel obtained by the methanol and ethanol routes. As to the TG curves, in air three thermal decomposition steps are for the methanol biodiesel and two steps are for the ethanol biodiesel. These steps are related to the evaporization and/or combustion of the methyl and ethyl esters, respectively. The corn oil presented four thermal decomposition steps in air, and only one step in nitrogen. These steps were attributed to the evaporization and/or decomposition of triglycerides. The TG and DTA profiles of the biodiesel approach the mineral diesel oil ones.

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Journal of Thermal Analysis and Calorimetry
Authors: M. Dantas, A. Almeida, Marta Conceição, V. Fernandes Jr, Iêda Santos, F. Silva, L. Soledade, and A. Souza

Abstract  

This work presents the characterization and the kinetic compensation effect of corn biodiesel obtained by the methanol and ethanol routes. The biodiesel was characterized by physico-chemical analyses, gas chromatography, nuclear magnetic resonance and thermal analysis. The physico-chemical properties indicated that the biodiesel samples meet the specifications of the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP) standards. The analyses by IR and 1H NMR spectroscopy indicated the ester formation. Gas chromatography indicated that biodiesel was obtained with an ester content above 97%. The kinetic parameters were determined with three different heating rates, and it was observed that both the methanol and ethanol biodiesel obeyed the kinetic compensation effect.

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