Modelos de estimativa de radiação solar para elaboração de mapas solarimétricos

O objetivo fundamental desta dissertação foi desenvolver modelos de estimativa da radiação solar no intuito de complementar a base de dados visando o traçado de mapas de radiação solar para o Rio Grande do Sul. Inicialmente foi realizada uma pesquisa na literatura sobre as metodologias desenvolvidas para a estimativa da radiação solar para locais onde inexistem dados medidos desta variável. Foi feito um levantamento das técnicas estatísticas utilizadas na previsão de valores de variáveis. As metodologias pesquisadas foram aplicadas ao banco de dados SAMSON (Solar and Meteorological Surface Observational Network). Entre as variáveis deste banco de dados estão a radiação solar, a umidade relativa, a temperatura, a latitude, a altitude e a nebulosidade. A metodologia dos modelos de estimativa aplicada neste trabalho baseia-se no Método dos Mínimos Quadrados. Foram realizadas correlações mensais e anuais entre as variáveis acima citadas e seus resultados validados através de validação cruzada. Resultou apropriada, na disponibilidade de dados climatológicos, a aplicação de modelos com parâmetros mensais de regressão linear múltipla envolvendo as variáveis explicativas: insolação, temperatura média e umidade relativa. Este modelo, entre outros, foi aplicado aos dados do Rio Grande do Sul. A metodologia acima descrita aplicada aos dados medidos no Rio Grande do Sul, resultou eficaz. Foram pesquisadas técnicas de interpolação para traçado de mapas e estabelecidas regras para o traçado dos mesmos. Foram utilizados dados periféricos para a Argentina, Uruguai e Santa Catarina. Foram feitos mapas mensais de médias mensais de radiação solar global horizontal diária bem como um mapa da média anual de radiação solar global horizontal diária. Observou-se que o modelo de Ångström–Prescott apresenta bons resultados quando se dispõe apenas da insolação Os mapas serão úteis para a pesquisa e implementação de sistemas empregando Energia Solar no Estado do Rio Grande do Sul. Finalmente, a principal conclusão é a de que modelos de correlações obtidos com dados de cada mês e produzindo parâmetros mensais são mais adequados do que um único modelo de correlação com parâmetros de validade anual utilizado nas estimativas mensais.

Novel catalyst systems based on Ni(II), Ti(IV), and Cr(III) complexes for oligo-and polymerization of ethylene

The complex of Brookhart Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6- diisopropylphenyl)-acenaphthenediimine) has been characterized after impregnation on silica (S1) and MAO-modified silicas (4.0, 8.0 and 23.0 wts.% Al/SiO2 called S2, S3 and S4, respectively). The treatment of these heterogeneous systems with MAO produces some active catalysts for the polymerization of the ethylene. A high catalytic activity has been gotten while using the system supported 1/S3 (196 kg of PE/mol[Ni].h.atm; toluene, Al/Ni = 1000, 30ºC, 60 min and atmospheric pressure of ethylene). The effects of polymerization conditions have been tested with the catalyst supported in S2 and the best catalytic activity has been gotten with solvent hexane, MAO as cocatalyst, molar ratio Al/Ni of 1000 and to the temperature of 30°C (285 kg of PE/mol[Ni].h.atm). When the reaction has been driven according to the in situ methodology, the activity practically doubled and polymers showed some similar properties. Polymers products by the supported catalysts showed the absence of melting fusion, results similar to those gotten with the homogeneous systems by DSC analysis. But then, polymers gotten with the transplanted system present according to the GPC’s curves the polydispersity (MwD) varies between 1.7 and 7.0. A polyethylene blend (BPE/LPE) was prepared using the complex Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {TpMs*}TiCl3 (2) (TpMs* = hydridobis(3-mesitylpyrazol-1-yl)(5-mesitylpyrazol-1-yl)) supported in situ on MAO-modified silica (4.0 wts. -% Al/SiO2, S2). Reactions of polymerization of ethylene have been executed in the toluene in two different temperatures (0 and 30°C), varying the molars fraction of nickel (xNi), and using MAO as external cocatalyst. To all temperatures, the activities show a linear variation tendency with xNi and indicate the absence of the effect synergic between the species of nickel and the titanium. The maximum of activity have been found at 0°C. The melting temperature for the blends of polyethylene produced at 0 °C decrease whereas xNi increases indicating a good compatibility between phases of the polyethylene gotten with the two catalysts. The melting temperature for the blends of polyethylene showed be depend on the order according to which catalysts have been supported on the MAO-modified silica. The initial immobilization of 1 on the support (2/1/S2) product of polymers with a melting temperature (Tm) lower to the one of the polymer gotten when the titanium has been supported inicially (1/2/S2). The observation of polyethylenes gotten with the two systems (2/1/S2 and 1/2/S2) by scanning electron microscopy (SEM) showed the spherical polymer formation showing that the spherical morphology of the support to been reproduced. Are described the synthesis, the characterization and the catalytic properties for the oligomerization of the ethylene of four organometallics compounds of CrIII with ligands ([bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine] chromium (III) chloride (3a), [bis[2-(3,5- dimethyl-l-pyrazolyl)ethyl]benzylamine] chromium (III) chloride (3b), [bis[2-(3,5-dimethyl-lpyrazolyl) ethyl]ether] chromiun(III)chloride (3c), [bis[2-(3-phenyl-lpyrazolyl) ethyl]ether]chromiun(III)chloride (3d)). In relation of the oligomerization, at exception made of the compounds 3a, all complex of the chromium showed be active after activation with MAO and the TOF gotten have one effect differentiated to those formed with CrCl3(thf)3. The coordination of a tridentate ligand on the metallic center doesn't provoke any considerable changes on the formation of the C4 and C6, but the amount of C8 are decrease and the C10 and C12+ have increased. The Polymers produced by the catalyst 3a to 3 and 20 bar of ethylene have, according to analyses by DSC, the temperatures of fusion of 133,8 and 136ºC respectively. It indicates that in the two cases the production of high density polyethylene. The molar mass, gotten by GPC, is 46647 g/mols with MwD = 2,4 (3 bar). The system 3c/MAO showed values of TOF, activity and selectivity to different α-olefins according to the pressure of ethylene uses. Himself that shown a big sensibility to the concentration of ethylene solubilized.