A series of iron, cobalt and nickel transition metal phosphides was synthesized by means of temperature-programmed reduction (TPR) of the corresponding phosphates. The same materials, Fe₂P, CoP and Ni₂P, were also prepared on a silica (SiO₂) support. The phase purity of these catalysts was established by x-ray diffraction (XRD), and the surface properties were determined by N₂ BET specific surface area (Sg) measurements and CO chemisorption. The activities of the silica-supported catalysts were tested in a three-phase trickle bed reactor for the simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene using a model liquid feed at realistic conditions (30 atm, 370 °C). The reactivity studies showed that the nickel phosphide (Ni₂P/SiO₂) was the most active of the catalysts. Compared with a commercial Ni-Mo-S/g-Al₂O₃ catalyst at the same conditions, Ni₂P/silica had a substantially higher HDS activity (100 % vs. 76 %) and HDN activity (82 % vs. 38 %). Because of their good hydrotreating activity, an extensive study of the preparation of silica supported nickel phosphides, Ni₂P/SiO₂, was carried out. The parameters investigated were the phosphorus content and the weight loading of the active phase. The most active composition was found to have a starting synthesis Ni/P ratio close to 1/2, and the best loading of this sample on silica was observed to be 18 wt.%. Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES) measurements were employed to determine the structures of the supported samples. The main phase before and after reaction was found to be Ni₂P, but some sulfur was found to be retained after reaction. A comprehensive scrutiny of the HDN reaction mechanism was also made over the Ni₂P/SiO₂ sample (Ni/P = 1/2) by comparing the HDN activity of a series of piperidine derivatives of different structure. It was found that piperidine adsorption involved an a-H activation and nitrogen removal proceeded mainly by means of a b-H activation though an elimination (E2) mechanism. The relative elimination rates depended on the type and number of b-hydrogen atoms. Elimination of b-H atoms attached to tertiary carbon atoms occurred faster than those attached to secondary carbon atoms. Also, the greater the number of the b-H atoms, the higher the elimination rates. The nature of the adsorbed intermediates was probed by Fourier transform infrared spectroscopy (FTIR) and temperature-programmed desorption (TPD) of the probe molecule, ethylamine. This measurement allowed the determination of the likely steps in the hydrodenitrogenation reaction. / Ph. D.

Orientador: José Roberto Môro / Banca: Cícero Beserra de Menezes / Banca: Robert Eugene Schaffert / Banca: Dilermando Perecin / Banca: Rinaldo César de Paula / Resumo: O trabalho objetivou identificar e classificar linhagens de sorgo, eficientes e ineficientes ao P avaliadas em ambientes com estresse e sem estresse de P, identificar a importância relativa da eficiência de aquisição e a eficiência de utilização em relação à eficiência de uso de P, obter as estimativas dos coeficientes de correlação genética e fenotípica, realizar análise de trilha e identificar os componentes principais. Avaliou-se 243 linhagens de sorgo e duas testemunhas adicionais divididas em três látices 9x9 com três repetições. Avaliaram-se as seguintes características nos ambientes com e sem estresse de P: florescimento, altura de plantas e produtividade de grãos. As características teor de fósforo nos grãos, eficiência de aquisição, eficiência de utilização interna de P, eficiência de uso de P, índice de colheita de P e quociente de utilização, foram avaliadas somente no ambiente com estresse de P. Foram identificadas e classificadas 107 linhagens eficientes ao P e 138 linhagens ineficientes avaliadas em ambientes com e sem estresse de P. Na importância relativa das eficiências o índice eficiência de aquisição foi o que melhor se relacionou com a eficiência uso de fósforo. De acordo com os resultados das correlações fenotípicas e genotípicas o índice de eficiência de uso de fósforo pode ser avaliado indiretamente, pela avaliação da produtividade de grãos em ambiente com estresse de P. Dentre as variáveis explicativas na análise de trilha, o teor de P total na planta foi a que melhor explicou os efeitos diretos nas variáveis básicas de eficiência de aquisição e uso de P. Foram identificados três componentes principais (PCA 1, 2 e 3), que juntos explicaram 81% da variação original dos dados / Abstract: This study aimed to identify and classify sorghum lines for P efficiency in environments with high and low P, to identify the relative importance of acquisition efficiency and utilization efficiency in relation to P use efficiency, to obtain the estimates of correlation coefficients and evaluate genetic and phenotypic path analyzes through the development of the direct and indirect effects of independent variables on the dependent variables, and identify the major components. Two hundred forty-three sorghum lines and two additional controls divided into three 9x9 lattices with three replications. Flowering, plant height and grain yield were evaluated in low and high P environments. Phosphorus content in the grain, P acquisition efficiency, P utilization efficiency of internal P, P use efficiency, harvest index and P utilization quotient were evaluated in the low P environment. One hundred and seven lines were identified and classified as P efficient and 138 lines as P inefficient. The relative efficiency of the P acquisition index was the most highly correlated with the efficiency of phosphorus use. These results suggest that the phenotypic correlation index of phosphorus use efficiency can be evaluated indirectly by the assessment of grain yield in P environments total P content in plant was the variable that best explained the direct effects, in the path analysis, of variables in the basic efficiency of acquisition and use. Three main components; 1, 2 and 3, together explained 81% of the variation of the original data / Doutor

Made available in DSpace on 2014-06-11T19:32:16Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-06-05Bitstream added on 2014-06-13T20:43:09Z : No. of bitstreams: 1 silva_la_dr_jabo.pdf: 667095 bytes, checksum: f07b680dee9ab27fcd76f2d412bb2029 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O trabalho objetivou identificar e classificar linhagens de sorgo, eficientes e ineficientes ao P avaliadas em ambientes com estresse e sem estresse de P, identificar a importância relativa da eficiência de aquisição e a eficiência de utilização em relação à eficiência de uso de P, obter as estimativas dos coeficientes de correlação genética e fenotípica, realizar análise de trilha e identificar os componentes principais. Avaliou-se 243 linhagens de sorgo e duas testemunhas adicionais divididas em três látices 9x9 com três repetições. Avaliaram-se as seguintes características nos ambientes com e sem estresse de P: florescimento, altura de plantas e produtividade de grãos. As características teor de fósforo nos grãos, eficiência de aquisição, eficiência de utilização interna de P, eficiência de uso de P, índice de colheita de P e quociente de utilização, foram avaliadas somente no ambiente com estresse de P. Foram identificadas e classificadas 107 linhagens eficientes ao P e 138 linhagens ineficientes avaliadas em ambientes com e sem estresse de P. Na importância relativa das eficiências o índice eficiência de aquisição foi o que melhor se relacionou com a eficiência uso de fósforo. De acordo com os resultados das correlações fenotípicas e genotípicas o índice de eficiência de uso de fósforo pode ser avaliado indiretamente, pela avaliação da produtividade de grãos em ambiente com estresse de P. Dentre as variáveis explicativas na análise de trilha, o teor de P total na planta foi a que melhor explicou os efeitos diretos nas variáveis básicas de eficiência de aquisição e uso de P. Foram identificados três componentes principais (PCA 1, 2 e 3), que juntos explicaram 81% da variação original dos dados / This study aimed to identify and classify sorghum lines for P efficiency in environments with high and low P, to identify the relative importance of acquisition efficiency and utilization efficiency in relation to P use efficiency, to obtain the estimates of correlation coefficients and evaluate genetic and phenotypic path analyzes through the development of the direct and indirect effects of independent variables on the dependent variables, and identify the major components. Two hundred forty-three sorghum lines and two additional controls divided into three 9x9 lattices with three replications. Flowering, plant height and grain yield were evaluated in low and high P environments. Phosphorus content in the grain, P acquisition efficiency, P utilization efficiency of internal P, P use efficiency, harvest index and P utilization quotient were evaluated in the low P environment. One hundred and seven lines were identified and classified as P efficient and 138 lines as P inefficient. The relative efficiency of the P acquisition index was the most highly correlated with the efficiency of phosphorus use. These results suggest that the phenotypic correlation index of phosphorus use efficiency can be evaluated indirectly by the assessment of grain yield in P environments total P content in plant was the variable that best explained the direct effects, in the path analysis, of variables in the basic efficiency of acquisition and use. Three main components; 1, 2 and 3, together explained 81% of the variation of the original data

Made available in DSpace on 2014-08-20T14:36:58Z (GMT). No. of bitstreams: 1 Tese_Magali_de_Avila_Fortes.pdf: 728610 bytes, checksum: fd451b6ee0f901a627e0fe08c27afe84 (MD5) Previous issue date: 2009-03-20 / The general objective of this study was to evaluate the effect of the phosphorus fertilization and the availability of the phosphorus forms in irrigated rice under no tillage in Albaqualf soil cultivated on dryland crops mulch. The experiments installed in 2003 were conducted under a randomized blocks design with four replications. The treatments were disposed in 2 x 2 factorial (triple superphosphate - TSP) and Arad rock phosphate (ARP), with and without annual replication of P with TSF). Additionally, it was conducted a treatment under natural condition (without the application of the phosphorus fertilization). The soils collected from the layers: 0 - 10 cm and 0 - 20 cm were analyzed using the Mehlich-1 and anion-exchange resin methods. Soils collected from 0.0 - 2.5; 2.5 - 5.0 and 5.0 - 15.0 cm was used to evaluate the P fractions. Analysis of P concentration in flag leaves and shoot (leaves stalk and grain) were also evaluated. Total P accumulated was calculated from the shoot P concentration in relation to the dry matter. For the future analysis, the rice harvest was done when the plants were in physiological maturity stage. The phosphorus fertilization did not affect the production of rice grains; even though with initial P soil level below of the critical level (< 6.0 mg dm-3). The phosphorus fertilization applied to the dryland crops (maize and soybean) presented a residual effect to subsequent irrigated rice, even after four years of experiment under notillage management. For the irrigated rice no differences were shown between the results of P availability using the Mehlich-1 and anion-exchange resin methods. The P concentrations from the soils, using these two methods, presented significant correlations with the P accumulated in plants. The ARP presented similar performance as TSP regarding to the P nutrition in irrigated rice in rotation with dryland crops under no tillage. The P inorganic fractions that predominate in Albaqualf soil cultivated with maize and soybean under no tillage are extracted with 0.1 NaOH and 0.5 NaOH mol L-1. The fertilizations carried out annually with TSP and ARP had increased all the P inorganic fractions in soil. The organic fractions were not much affected by the phosphate fertilization. The P accumulated in shoot of rice plants was better correlated with the labile P fractions (anion-exchange resin, NaHCO3 and 0.1 NaOH mol L-1), mainly in the superficial layer (0.0 - 2.5 cm). / O objetivo geral deste estudo foi avaliar o efeito da adubação fosfatada e a disponibilidade das formas de fósforo para o arroz irrigado cultivado em Planossolo no sistema plantio direto, após o cultivo de culturas de sequeiro. Os experimentos foram conduzidos desde 2003, delineados em blocos ao acaso com quatro repetições e os tratamentos foram dispostos em um fatorial 2 x 2 (superfosfato triplo - SFT) e fosfato natural de Arad - FNA), com e sem reaplicação anual de P com SFT) mais um tratamento adicional testemunha sem a aplicação da adubação fosfatada. Foram coletadas amostras de solo em duas profundidades (0 - 10 cm e 0 - 20 cm), analisadas pelo método Mehlich-1 e resina de troca aniônica (RTA), e amostras de 0,0 - 2,5; 2,5 - 5,0 e 5,0 - 15,0 cm, analisadas pelo fracionamento de P. Nas plantas fez-se determinação da concentração de fósforo nas folhas bandeira e parte aérea (folhas, colmo e grãos) e quantidade total acumulada de P nas plantas, calculada a partir da concentração de fósforo na parte aérea em relação à massa de matéria seca. Foi realizada a colheita dos grãos após a maturação fisiológica para análise de rendimento. O rendimento de grãos de arroz não respondeu à adubação fosfatada, mesmo com teores inicias de P no solo abaixo do nível crítico (< 6,0 mg dm-3). A adubação fosfatada realizada nas culturas de sequeiro (milho e soja) apresentou um efeito residual para o arroz irrigado mesmo após quatro anos de cultivos destas, no sistema plantio direto. Os extratores Mehlich-1 e resina de troca aniônica foram igualmente eficientes na avaliação da disponibilidade de P para o arroz irrigado. Os teores de P extraídos do solo pelos dois métodos apresentaram correlações significativas com o P acumulado nas plantas. O fosfato natural de Arad apresenta desempenho semelhante ao superfosfato triplo no que se refere à nutrição por fósforo em arroz irrigado em rotação com culturas de sequeiro no sistema plantio direto. As frações de fósforo inorgânico que predominam em um Planossolo cultivado com as culturas de milho e soja em sistema plantio direto são as extraídas com NaOH 0,1 e NaOH 0,5 mol L-1. As adubações realizadas anualmente com superfosfato triplo e fosfato natural de Arad aumentaram todas as frações inorgânicas de fósforo no solo, desde as mais lábeis até as menos lábeis. As frações orgânicas apresentam-se pouco sensíveis à adubação fosfatada. As quantidades de fósforo acumuladas na parte aérea das plantas de arroz melhor se correlacionaram com as frações de fósforo mais lábeis (RTA, NaHCO3 e NaOH 0,1 mol L-1), principalmente na profundidade de 0,0 - 2,5 cm.