According to the waste-to-energy (WTE) valorization and circular economy principles, the use of waste oil and grease (WOG) for obtaining biofuels shows the tendency towards sustainability, makes the interest in green chemistry, and the development of environmentally friendly processes grow. Three different fatty wastes (from the fat trap of a sewage station, lard waste, and frying oil) were analyzed and this work showed they have no potentially toxic metals. The frying oil sample and residual lard waste showed a higher percentage of triacylglycerides resulting in higher biodiesel conversion. The samples showed physical and chemical properties (density, viscosity, and ash) within the limits established by current regulations. Bio-oil samples formed a mixture of carboxylic acids, with high acidity. However, the parameters that deviated from the maximum permitted by the standard could be adjusted blending with petroleum diesel, replacing partially the fossil energy carriers with biomass-derived energy carriers which could bring positive impacts from multiple perspectives, i.e., economic, environmental, and health.

This work reports the characterization of a vegetable oil extracted from pequi seeds, an agroindustrial residue, and its biodiesel production using ethanol and heterogeneous catalysis. The pequi seeds showed 40.73 wt.% of extractive content, which represents a large amount of the biomass composition. The crude oil extracted from the pequi seeds with ethanol as solvent presented a high content of free fatty acids (FFAs), mainly oleic (54.14%) and palmitic (36.71%) acids, resulting in an acidity value of 13.8 ± 0.1 mg KOH g-1. The esterification/transesterification process was performed using two ion exchange resins as heterogeneous catalysts, a commercial protonic form (assigned as PR) and a zirconium-exchanged (assigned as PRZr). Conversions of 87.1 and 91.4% were achieved for PR and PRZr as catalysts, respectively, at optimal conditions (1:6 oil-to-alcohol molar ratio, 25 wt.% of catalyst, 100 ºC and 1 h). These results indicated that heterogeneous acid catalysts can be successfully applied in biodiesel production from fatty acid-rich oils, such as the one extracted from pequi seeds. Also, a simultaneous process involving both oil extraction and biodiesel production was tested using PRZr as catalyst (25 wt.% of catalyst and 100 ºC), but due to the greater amount of ethanol necessary for the oil extraction (1:16 oil to alcohol mass ratio) the conversion reached only 51.5% after 5 h. For that reason, this work proposes a two stage system for biodiesel production that integrates oil extraction (stage one) and the esterification/transesterification reaction (stage two) to achieve a greener process, waste-to-bioenergy.

The main objective of this work was to design an innovative method to prepare heterogeneous heteropolyacid catalysts. The heteropolyacid H3PW12O40 (HPW) was modified with tin(II) by two methodologies: a conventional aqueous ion-exchange (CS) and a redox solid-state (SS). In both cases, Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) measurements evidenced that Keggin structure was preserved. All materials were active in the esterification of lactic acid with several alcohols and a mechanism was proposed. The best results were obtained for octanol and benzyl alcohol, where higher conversion values were obtained. The catalytic activity (turnover frequency, TON) showed an efficient performance for the materials prepared with 4 h of calcination (CS4h and SS4h). However, the catalyst prepared by the SS method was in accordance with the development of environmentally friendly processes.

This work deals with preparation and characterization of H3PW12O40 (H3PW) supported on silica-alumina. Impregnation of H3PW (15, 20, 30 and 40 wt.%) on commercial silica-alumina support in acidic aqueous solution is effective for preparing this catalyst keeping its Keggin structure, according to different methods of characterization. The catalysts were tested in a model reaction of acetic acid with ethanol and 30 wt.% H3PW/SiO2-Al2O3 had the highest activity under the conditions: catalyst calcination at 300 ºC, temperature of 100 ºC, acetic acid:ethanol molar ratio of 2:1 and catalyst:acetic acid mass ratio of 10 wt.%. The reaction yield was 79 and 100% selectivity for ethyl acetate over three reutilizations, for reaction time of 2 h. The calculated total acid site distribution was 0.299 mmol g-1 (97% of the theoretical probed by pyridine), and most of these (0.236 mmol g-1) were Brønsted weak-medium strength (pyridine desorption between 300 and 500 ºC).

Simple synthetic procedures have been applied to obtain luminescent carbon quantum dots, also referred as C-dots, from an abundant carbon source, that is, from the brewing industry waste. The synthetic procedures have been conducted aiming to investigate the effects of the oxidation stage on the properties of the nanomaterial. C-dots down- and up-conversion properties, as well as their potential for cellular imaging experiments in live (and adhered) cells, are disclosed herein.

Soybean oil transesterification with ethanol was carried out in a batch reactor using USY zeolites modified with barium and strontium (15 wt.%) as catalysts. A series of three catalytic cycles were performed for each zeolite without any loss of activity. The biodiesel product was analyzed by HPLC and FT-Raman, and the catalysts by pyridine and CO2 adsorption. Ba/USY provided higher conversions (> 97%) than Sr/USY (< 75%). The increased catalytic activity of Ba/USY was attributed to two different effects: a larger number of basic sites; and a lower interaction between barium species and HUSY BrØnsted sites.

Este trabalho descreve detalhadamente o efeito da quantidade de cério na estrutura e morfologia da zeólita NH4USY. Ce-USY (2-25% m/m de CeO2) foi obtido por impregnação úmida de CeCl3 seguida de calcinação a 550ºC por 8 h. Em quantidades baixas (2-10%), foi observado que as espécies de cério encontram-se nas posições de troca iônica na rede, enquanto em maiores teores (15-25%) pequenos agregados formaram-se na superfície da HUSY. Difratometria de raios X (XRD) mostrou apenas reflexões relacionadas à HUSY, confirmando a alta dispersão das espécies de cério, porém as análises por espectroscopia Raman com transformada de Fourier (FT-Raman) detectaram CeOx para os materiais acima de 10%. A reação do CeCl3 com NH4USY produziu NH4Cl, o qual se decompõe em HCl, ocasionando a desaluminização da rede. Os materiais apresentaram um aumento da razão Lewis/Brønsted com o aumento da quantidade de cério, devido a interação do excesso de cério com os grupos OH da USY e consequente formação de espécies CeOx.

This work describes comprehensibly the effect of cerium loading on the structure and morphology of NH4USY zeolite. The Ce-USY (2-25 wt.% of CeO2) was obtained by wet impregnation of CeCl3 followed by calcination at 550ºC for 8 h. At low loadings (2-10%), cerium species are mainly located at ion exchange positions in the framework, whereas at higher loadings (15-25%), small aggregates were formed on the HUSY surface. X-ray diffractograms (XRD) exhibited only the reflections related to HUSY, demonstrating the high dispersion of cerium species, but Fourier transform Raman spectroscopy (FT-Raman) detected CeOx for the materials above 10%. Reaction of CeCl3 with NH4USY produced NH4Cl, which decomposed to form HCl, leading to framework dealumination. The materials showed an increased Lewis/Brønsted ratio with increasing cerium loadings due to the interaction between the excess cerium and the OH groups of USY, and the consequent formation of CeOx species.