Síntese e aplicação de catalisadores à base de óxidos de cério, tungstênio e HZSM-5 para a produção do biodiesel

This work presents a study on the production of biodiesel by esterification reaction of oleic acid with methanol using batch reactor and different catalysts based on CeO2 and WO3 and HZSM-5. Acid treatment was performed in order to increase the catalytic activity. Different characterization techniques were performed, among them X-ray diffraction (XRD), Thermogravimetric analysis TGA/DTA, Spectroscopy in the Region in Fourier Transform Infrared (FTIR) and X-ray fluorescence (XRF). The effects of independent variables: temperature, molar ratio of oil: alcohol and the amount of catalyst and their interactions on the dependent variable (conversion of oleic acid to the corresponding ester). Overall, through the results obtained in the characterization was observed that the applied treatments were efficient, however the XRF technique, indicated that tungsten oxide leaching could occur during the preparation of the materials. The treatments performed on HZSM-5 caused no significant changes in the structure indicating that the zeolite was quite resistant to the treatments used. It was evaluated using complete 23 factorial design. For the catalysts investigated, the best reaction conditions were obtained when using higher levels of the independent variables temperature and amount of catalyst. However, for the variable molar ratio the lowest level showed significant yields for most of the synthesized catalyst, obtaining maximum conversion to the OC (67.97%), OW (74.37%), HZSM-5 (61.16%) OC-OW 1 (75.93%), OC-OW 2 (82.57%), OC-OW 3 (79.15%), S/OC-OW 1 (86.90%), S/OC-OW 2 (91.04%), S/OC-OW 3 (88.60%), S/OC-OW/H 1 (92.34%), S/OC-OW/H 2 (100%) and S/OC-OW/H 3 (98.16%). According to the experimental design, the temperature has the biggest influence on the reaction variable for all the synthesized catalysts. Among the catalysts investigated S/OC-OW/H 2 e S/OC-OW/H 3 were more effective. Reuse tests showed that the catalyst activity decreased after each cycle, indicating that the regeneration process was effective. The leaching test indicated that the catalysts are heterogeneous in the evaluated operating range. The catalysts investigated showed themselves promising for the production of biodiesel.

Regressão Simplex aplicada a delineamentos de mistura e utilização do Algoritmo Boosting

In the composition of this work are present two parts. The first part contains the theory used. The second part contains the two articles. The first article examines two models of the class of generalized linear models for analyzing a mixture experiment, which studied the effect of different diets consist of fat, carbohydrate, and fiber on tumor expression in mammary glands of female rats, given by the ratio mice that had tumor expression in a particular diet. Mixture experiments are characterized by having the effect of collinearity and smaller sample size. In this sense, assuming normality for the answer to be maximized or minimized may be inadequate. Given this fact, the main characteristics of logistic regression and simplex models are addressed. The models were compared by the criteria of selection of models AIC, BIC and ICOMP, simulated envelope charts for residuals of adjusted models, odds ratios graphics and their respective confidence intervals for each mixture component. It was concluded that first article that the simplex regression model showed better quality of fit and narrowest confidence intervals for odds ratio. The second article presents the model Boosted Simplex Regression, the boosting version of the simplex regression model, as an alternative to increase the precision of confidence intervals for the odds ratio for each mixture component. For this, we used the Monte Carlo method for the construction of confidence intervals. Moreover, it is presented in an innovative way the envelope simulated chart for residuals of the adjusted model via boosting algorithm. It was concluded that the Boosted Simplex Regression model was adjusted successfully and confidence intervals for the odds ratio were accurate and lightly more precise than the its maximum likelihood version.

Análise energética da madeira e do carvão de híbridos entre Corymbia citriodora (Hook.) K.D. Hill & L.A.S. Johnson e Corymbia torelliana (F. Muell.) K.D. Hill & L.A.S. Johnson

This research aimed to evaluate the wood and charcoal quality of hybrids clone of the crossing C. citriodora with C. torelliana in two different locations for charcoal production. Seven with 3,75 years old clones, planted at country of Itamarandiba – MG, and six 6,42 years old clones, planted in Dionísio – MG, were studied. For wood and charcoal quality analysis, samples were collected along the stem of the trees until the commercial height. Properties study of the wood was done by chemical analysis, basic density, superior heat power, and thermogravimetric analysis. The wood samples were carbonized in laboratory conditions with heating rate of 1.67 0 C.min -1 , starting at 100 0 C until 450 0 C and keeping on this temperature for 30 minutes. It were determined the carbonizations gravimetric yield, all in dry basis. The wood quality was evaluated based on the chemical immediate analysis, relative apparent density, and gross heating value. The experiment was installed according to the completely randomized design, with five repetitions. The collected data were submitted to analysis of variance and, when the evaluated effects were significant by “F” test, was applied the Scott-Knott test at 5% probability for multiple comparisons. For correlation analysis, Pearson correlation coefficient, tested by the "t" test at 5% probability was used. Results showed variability of wood between the genetic materials evaluated in relation to place and plant crossing. The thermal analysis of the wood showed significant variation between clones and it was possible to differentiate two stages of degradation (hemicelluloses and cellulose). The majority of the clones presented satisfactory properties for the charcoal production, while, clone 3, planted in Itamarandiba, obtained the best performance due it have the higher yield and energetic efficiency, thus, achieving the best potential for charcoal production. However, clone 9, planted in Dionísio, was the less indicated for charcoal production since it presented the lowest energetic efficiency, gravimetric yield, and densities.