Uma modelagem de sequestro e armazenamento de dióxido de carbono atmosférico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influência do aparelho fotoativador na resistência ao desgaste de compósitos restauradores

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Development of innovative catalysts for the hydrodechlorination to fluoroethers

In this work the hydrodechlorination of CF3OCFClCF2Cl to produce unsaturated CF3OCF=CF2 was studied over a series of supported metal catalysts. Currently this molecule is produced from the precursor CF3OCFClCF2Cl by dechlorination with zinc powder. An important cost on the economic and environmental balance is represents by the large amount of ZnCl2 produced and to be disposed of. A new approach, based on gas-phase hydrodechlorination over supported catalysts can lead to a new sustainable process. During the feasibility step of this project, substantially two kind of materials were studied: metals supported over activated carbon and Pd/Cu species supported over MCM-41 mesoporous silica. Observed catalytic performances were strongly dependent on the metal and support used. All carbon-supported Ru, Pd, and bimetallic catalysts are fairly active and yielded the target product CF3OCF=CF2, the higher selectivity being obtained with ruthenium- and palladium-based materials. Nevertheless, Ru-based catalysts showed poor stability and this deactivation may be attributed to the deposition of chlorinated organic species blocking the active sites. On the other hand, palladium-containing catalysts showed high stability. Ru/Pd and Pd/Cu bimetallic catalysts exhibited long-term selectivity and stability, highlighting the possibility for these materials to be employed in the CF3OCF=CF2 production process. During the second part of this thesis, a series of bimetallic meso-structured Pd/Cu MCM-41 catalysts were studies to overcome possible mass transfer limitations. The materials were obtained by different synthesis methods. The incorporation of Pd and Cu during MCM-41 synthesis, did not destroy the typical hexagonal array and ordered pore system of MCM-41. However, the calcination for the removal of the template provoked significant segregation of oxides. The impregnation leads to pore-occlusion and formation of Cu particles and large bimetallic PdCu species. Larger metal particles leads to lower CF3OCFClCF2Cl conversion, while the monometallic particles can decrease the selectivity to CF3OCF=CF2, fostering the dehalogenation to CF3OCH=CF2.

Planktonic foraminifera at DSDP Holes 72-516 and 72-518

Quantitative analysis was performed on the Quaternary planktonic foraminiferal fauna from Site 516, near the crest of the Rio Grande Rise, and Site 518, on the lower western flank of the Rise. From Hole 516, 46 samples were taken, and from Hole 518, 80 samples were taken. The mean interval between samples is 20 to 25 cm. About 50 species of Quaternary and Pliocene planktonic foraminifers were identified. Quaternary sediments, dated by the initial evolutionary appearance of Globorotalia truncatulinoides and other criteria, have thickness, of 9.8 m in Hole 516 and 16 m in Hole 518. The Globorotalia truncatulinoides Zone is subdivided into four subzones or biostratigraphic horizons (from lower to upper): (1) Globorotalia crassaformis viola, (2) Globorotalia crassaformis hessi, (3) Globigerina calida calida, and (4) Globigerinoides ruber (pink). Thickness of these horizons in Hole 516 establishes the age of the boundaries between them as 1.47, 0.81, and 0.28 Ma, respectively. All the Quaternary planktonic foraminiferal complexes sampled are subtropical. The region of the Rio Grande Rise, therefore, has been within the southern subtropical gyre continuously for the last 2 Ma. The average annual surface water temperatures were reconstructed for the Quaternary at both sites. A micropaleontologic method for the paleotemperature analysis of the thanatocoenosis registers an average Quaternary temperature of 21.2°C at Site 516 and 21.7°C at Site 518. The temperature fluctuations increase up to 3.5°C during the accumulation of the two last horizons (since 0.81 Ma). Temperature peaks are tentatively compared with oxygen isotopic stages and with continental glaciations. Levels at which planktonic foraminiferal species disappear correspond to coldwater intervals. In the Quaternary of Site 518, some layers show signs of dissolution. Corrosive to CaCO3, the northward flow of Antarctic Bottom Water through the Vema Channel increases during the cold periods. Site 518 has two layers of redeposited foraminiferal sand with Pliocene foraminifers. The average rate of the Quaternary sedimentation in Hole 516 is 0.52 cm per thousand years, and in Hole 518 it is 0.84 cm per thousand years.

A global budget for fine root biomass, surface area, and nutrient contents

Global biogeochemical models have improved dramatically in the last decade in their representation of the biosphere. Although leaf area data are an important input to such models and are readily available globally, global root distributions for modeling water and nutrient uptake and carbon cycling have not been available. This analysis provides global distributions for fine root biomass, length, and surface area with depth in the soil, and global estimates of nutrient pools in fine roots. Calculated root surface area is almost always greater than leaf area, more than an order of magnitude so in grasslands. The average C:N:P ratio in living fine roots is 450:11:1, and global fine root carbon is more than 5% of all carbon contained in the atmosphere. Assuming conservatively that fine roots turn over once per year, they represent 33% of global annual net primary productivity.

GCMC-surface area of carbonaceous materials with N-2 and Ar adsorption as an alternative to the classical BET method

In this paper we apply a new method for the determination of surface area of carbonaceous materials, using the local surface excess isotherms obtained from the Grand Canonical Monte Carlo simulation and a concept of area distribution in terms of energy well-depth of solid–fluid interaction. The range of this well-depth considered in our GCMC simulation is from 10 to 100 K, which is wide enough to cover all carbon surfaces that we dealt with (for comparison, the well-depth for perfect graphite surface is about 58 K). Having the set of local surface excess isotherms and the differential area distribution, the overall adsorption isotherm can be obtained in an integral form. Thus, given the experimental data of nitrogen or argon adsorption on a carbon material, the differential area distribution can be obtained from the inversion process, using the regularization method. The total surface area is then obtained as the area of this distribution. We test this approach with a number of data in the literature, and compare our GCMC-surface area with that obtained from the classical BET method. In general, we find that the difference between these two surface areas is about 10%, indicating the need to reliably determine the surface area with a very consistent method. We, therefore, suggest the approach of this paper as an alternative to the BET method because of the long-recognized unrealistic assumptions used in the BET theory. Beside the surface area obtained by this method, it also provides information about the differential area distribution versus the well-depth. This information could be used as a microscopic finger-print of the carbon surface. It is expected that samples prepared from different precursors and different activation conditions will have distinct finger-prints. We illustrate this with Cabot BP120, 280 and 460 samples, and the differential area distributions obtained from the adsorption of argon at 77 K and nitrogen also at 77 K have exactly the same patterns, suggesting the characteristics of this carbon.

Measurement and correlation of quaternary solubilities of dihydroxybenzene isomers in supercritical carbon dioxide

The equilibrium quaternary solubilities of dihydroxybenzene (resorcinol + pyrocatechol + hydroquinone + SCCO2) isomers were experimentally determined at 308, 318 and 328K over a pressure range of 9.8-15.7 MPa by using a saturation method. The effects of temperature, pressure and the components on each other have been thoroughly investigated. The selectivity of SCCO2 for ternary (resorcinol + pyrocatechol + SCCO2) and quaternary systems was discussed. A new model equation for quaternary solubilities of solids has been developed by accounting for non-idealities by combining the solution model with Wilson activity coefficient model. The model equation has five adjustable parameters and correlates the quaternary solubilities of current data along with two other quaternary data reported in the literature. (C) 2012 Elsevier B.V. All rights reserved.

Approaches to sesquiterpenes containing three contiguous quaternary carbon atoms. Synthesis of 3-methoxythapsene

Synthetic approach to 3-alkoxythapsane, comprising of the carbon framework of a small group of sesquiterpenes containing three contiguous quaternary carbon atoms has been described. A combination of alkylation, orthoester Claisen rearrangement and intramolecular diazoketone cyclopropanation has been employed for the creation of the three requisite contiguous quaternary carbon atoms.

Stereospecific construction of stereogenic vicinal quaternary carbon atoms. Enantiospecific synthesis of (+)-valerane

Stereo- and enantiospecific synthesis of (+)-valerane starting from R-carvone utilising orthoester Claisen rearrangement and intramolecular diazo ketone cyclopropanation reactions for the construction of the two vicinal quaternary carbon atoms is described. Copyright (C) 1996 Elsevier Science Ltd.

Rearrangement approaches to sesquiterpenes containing multiple contiguous quaternary carbon atoms. Total synthesis of (+/-)-myltayl-8(12)-ene and (+/-)-6-epijunicedranol

Details of the first total syntheses of the sesquiterpenes myltayl-8(12)-ene and 6-epijunicedran-8-ol are described. The aldehyde 13, obtained by Claisen rearrangement of cyclogeraniol, was transformed into the dienones 12 and 18. Boron trifluoride-diethyl ether mediated cyclization and rearrangement transformed the dienones 12 and 18 into the tricyclic ketones 16 and 17, efficiently creating three and four contiguous quaternary carbon atoms, respectively. Wittig methylenation of 16 furnished (+/-)-myltayl-8(12)-ene (11), whereas reduction of the ketone 17 furnished (+/-)-6-epijunicedranol (23).

Geochemical evidence for enhanced upwelling and organic productivity during the late Quaternary on the continental margin of northern California

EXTRACT (SEE PDF FOR FULL ABSTRACT): Laminated sediments are preserved in upper Pleistocene sections of cores collected on the continental slope at water depths within the present oxygen-minimum zone from at least as far north as the Klamath River and as far south as Point Sur. Comparison of sediment components in the laminae with those delivered to sediment traps as pelagic marine "snow" show the dark/light lamination couplets are indeed annual (varves). ... The presence of carbon-, sulfur-, and metal-rich sediments, as well as lack of bioturbation, all support the theory that the oxygen-minimum zone in the northeastern Pacific Ocean was more intense - in fact, anoxic - during the late Pleistocene in response to greater coastal upwelling and higher organic productivity.

Copolymerization of carbon dioxide and cyclohexene oxide catalyzed by aluminum porphyrin-quaternary ammonium salt in the presence of bulky lewis acid

Chloro( 5,10,15,20-tetraphenyl-porphyrinato)-aluminum/tetraethylammonium bromide ( Et4NBr) in combination with bulky Lewis acid was used for the copolymerization of CO2 and cyclohexene oxide ( CHO). Bulky Lewis acid having substituents at the ortho positions of the phenolate ligands, like methylaluminum bis(2,6-di-tert-butyl-4-methylphenolate), significantly shortened the induction period and raised the catalytic activity, the corresponding turnover frequency reached 44.9 h(-1) in 9 h, which was 23.8% higher than that from ( TPP)AlCl/Et4NBr binary catalyst. The resulting polycarbonate has carbonate linkage over 93% with number average molecular weight of ( 4.5-6.5) x 10(3) and polydispersity index below 1.10.