Catalysis is an important tool in obtaining a range of derivative products from renewable sources, such as ethanol. Solid-state dealumination using ammonium hexafluorosilicate on the BEA zeolite under the treatment at temperature of 190 °C, 70 mol% dealumination in the presence of humidity and washing with buffer solution at 25 °C generated larger pores. The absence of washing procedure for the same sample resulted in pore blockage. Ethanol dehydration reactions showed conversion of 72% (64% ethylene and 8% diethyl ether) for this sample at 300 °C and high weight hourly space velocity (WHSV, 3247 h-1), whereas, at the same temperature but at a low WHSV (57 h-1), the conversion was 88% (49% ethylene and 39% diethyl ether). Dealuminated BEA zeolite presented better diffusion conditions, higher hydrophobicity and generated larger pores. Impregnation with H3PW12O40, H4SiW12O40 and Nb2O5 explained the selectivity, showing that Lewis acid sites from Nb2O5 favored the diethyl ether production.

RESUMO O cultivo orgânico demanda a produção ou aquisição de sementes ou mudas certificadas a partir do mesmo sistema de cultivo, sendo imprescindível o estudo de cultivares de batata adaptadas ao sistema orgânico de produção. O objetivo deste trabalho foi estudar a viabilidade do aproveitamento de brotos de cultivares de batata, a multiplicação de sementes no campo e a produção comercial sem utilização de agroquímicos. Conduziu-se três experimentos, o primeiro sob cultivo protegido em Guarapuava-PR, de novembro de 2011 a fevereiro de 2012, o segundo em campo em Candói-PR, de maio a setembro de 2012, e o último em campo em Guarapuava-PR, de fevereiro a maio de 2013. O delineamento experimental foi de blocos casualizados com 3 repetições nos 3 experimentos. Avaliou-se nos 2 primeiros experimentos as cultivares: BRS Ana , BRS Clara , BRS Eliza , Cristal e Catucha e no último foram adicionados Agata , Bintje , Baronesa e BRSIPR Bel . As características analisadas foram: comprimento de haste principal, número de hastes, número de folhas, massa fresca e número de tubérculos, porcentagem de infecção por viroses, além de incidência de requeima nas folhas no segundo experimento, e no terceiro experimento ainda foi analisado, índice de área foliar (IAF), massa seca de tubérculos, folhas e hastes e severidade de requeima. No primeiro experimento as cultivares demonstraram diferença na altura de plantas e produção de minitubérculos, sendo a maior média observada nas cultivares BRS Ana e BRS Clara em altura de planta, e na cultivar BRS Clara na produção de minitubérculos. No segundo experimento houve diferença apenas na altura de plantas, com maior média final observada nas cultivares BRS Ana e BRS Clara. Observou-se baixa disseminação de viroses e isto não refletiu diretamente na produtividade. No terceiro experimento as cultivares com menor severidade de doença foram as indicadas para cultivo orgânico, em especial a BRS Clara e a Catucha ; esta segunda se destacou em IAF e produtividade, e demonstrou alta resistência à requeima, principal motivo que levou esta cultivar a atingir 13,8 t/ha de produtividade total.

ABSTRACT Organic farming requires the production or use of certified seeds from the same cultivation system and, the information of potato cultivars adapted to organic production system is important. The objective of this work was to study the feasibility of utilizing sprouts of different potato cultivars, seed multiplication and yield potential in field conditions without using agrochemicals. Three experiments were conducted: the first experiment using sprouts as seed under protected cultivation in Guarapuava, Paraná State, Brazil, from November 2011 to February 2012; the second experiment was field conducted in Candói, Paraná State, from May to September 2012 and the third experiment was field conducted in Guarapuava, Paraná State, from February to May 2013. The experimental design was a randomized block design with 3 replications in all 3 experiments. In the 2 first experiments the following cultivars were evaluated: BRS Ana, BRS Clara, BRS Eliza, Crystal and Catucha, and in the last experiment Agata, Bintje, Baronesa and BRSIPR Bel were included. The traits analyzed were length of main stem, number of stems, number of leaves, fresh weight and number of tubers, percentage of infection by viruses and in the second experiment the incidence of late blight on leaves. In the third experiment, leaf area index (LAI), tuber, leaves and stem dry weights and late blight severity were also analyzed. In the first experiment, the cultivars showed differences in plant height and minituber production, the highest value was observed in cultivars BRS Clara and BRS Ana for plant height and cultivar BRS Clara for minituber production. In the second experiment, there was difference only in plant height, the tallest cultivars were BRS Ana and BRS Clara . There was low spread of viruses and, it did not directly reflect in tuber yield. In the third experiment the cultivars with lower disease severity were those recommended to organic farming, especially BRS Clara and Catucha; this second cultivar had the higher LAI and tuber yield, as well as resistance to late blight, factors that might have contributed to the recorded highest total tuber yield (13.8 t/ha).

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).

Adsorventes ZSM-5 impregnados com Nb2O5 foram aplicados na remoção de enxofre sob a forma de tiofeno, substância refratária de difícil remoção dos combustíveis líquidos. Para tanto, foi preparado um combustível modelo contendo iso-octano contaminado com tiofeno nas concentrações de 877,5 a 1155 ppmw. As amostras foram caracterizadas por difratometria de raios X (XRD), espectroscopias no infravermelho (FTIR) e Raman (FT-Raman) por transformada de Fourier para confirmação dos adsorventes obtidos, sendo priorizado o estudo de adsorção com aquele contendo 5% de pentóxido de nióbio, que apresentou uma maior capacidade de remoção de tiofeno. Os melhores resultados de adsorção foram alcançados a 353 K, sendo observado um maior tempo para atingir o equilíbrio. Sob essas condições, o melhor ajuste cinético foi alcançado utilizando a equação de pseudo-segunda ordem, evidenciando o domínio do fenômeno de quimissorção. Por outro lado, sob menores temperaturas, o modelo de difusão apresentou uma melhor aproximação dos resultados experimentais. O aumento da temperatura também favoreceu os processos espontâneos.

ZSM-5 adsorbents impregnated with Nb2O5 were applied in the sulfur removal in the form of thiophene, refractory substance of difficult removal of liquid fuels. For this purpose, a model fuel containing iso-octane contaminated with thiophene in concentrations of 877.5 to 1155 ppmw was prepared. The samples were characterized by X-ray diffractometry (XRD), Fourier transform infrared (FTIR) and Fourier transform-Raman (FT-Raman) spectroscopies for confirmation of the adsorbents, being prioritized the adsorption study with that containing 5 wt.% of niobium pentoxide, because it showed a greater capacity for removal of thiophene. The best results of adsorption were achieved at 353 K, a longer time to reach equilibrium was observed. Under these conditions, the best kinetic fitting was achieved using the equation of pseudo-second order, demonstrating the domain of the phenomenon of chemisorption. While under lower temperatures, the diffusion model presented a better approximation of the experimental results. Also, the increasing of temperature did enhance spontaneous processes.

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.

Experimentos conduzidos em casa de vegetação, mediante condições controladas, e em campo, sob infestação natural, foram realizados com o objetivo de testar a transmissibilidade e a reação de genótipos de algodoeiro ao que se presume ser uma nova virose, afetando algodoais, notadamente, no Estado de Mato Grosso. Os testes demonstraram que a doença - denominada provisoriamente neste trabalho, "mosaico das nervuras atípico" - tem como vetor o pulgão do algodoeiro (Aphis gossypii Glover). Genótipos de algodoeiro, compreendendo cultivares e linhagens avançadas disponíveis no Brasil, diferiram notavelmente quanto à reação ao patógeno, enquadrando-se em grupos graduais de resistência/suscetibilidade. A inexistência de correlação positiva entre a resposta dos genótipos à virose em questão e ao mosaico das nervuras f. Ribeirão Bonito ("doença azul"), corrente na região, indica que patógenos diferentes podem ser responsáveis pelas duas doenças.

Greenhouse controlled experiments and field trials, under natural infestation, were carried out in order to verify the transmissibility and the reaction of cotton genotypes to a presumed new virus disease affecting cotton crops, mainly in Mato Grosso State, Brazil. The tests revealed that the disease, which is being tentatively named "atypical vein mosaic", has as a vector the cotton aphid (Aphys gossypii Glover). Cotton genotypes, comprising cultivars and advanced lineages available in Brazil, differed considerably with respect to reaction to the pathogen; they were put in graded groups of resistance/susceptibility. The lack of positive correlation between the genotypes' response to this disease, and to the vein mosaic viruses ("blue disease") currently present in this region, indicated that different pathogens could be responsible for these two diseases.

A method is presented for the choice of spectral regions when absorption measurements are coupled to chemometric tools to perform quantitative analyses. The method is based on the spectral distribution of the relative standard deviation of concentration (s c/c). It has been applied to the development of PLS-FTNIR calibration models for the determination of density and MON of gasoline, and ethanol content and density of ethanol fuel. The new method was also compared with the correlation (R²) method and has proved to generate PLS calibration models that present better accuracy and precision than those based on R².