Asymmetric synthesis and catalysis is one of the leading research areas in chemistry society, for its versatility and efficiency in obtaining chiral molecules that found the vast majority in natural active compounds and synthetic drugs. Developing asymmetric catalytic methodology is at the frontier in both industrial and academic research laboratories. Enantioselective organocatalysis has emerged as a powerful synthetic tool that is complementary to metal-catalyzed transformations. The development of chiral phosphoric acid and metal phosphate as catalysts has been a breakthrough in recent years. Chiral phosphoric acids have been shown to be powerful catalysts in many organic transformations. Moreover, chiral metal phosphates, which formed by simply replacing the proton in phosphoric acid with metals, have introduced new catalytic activations and broaden the scope of phosphoric acids. This thesis details new highly enantioselective chiral phosphoric acid-catalyzed Pinacol rearrangement and robust alkaline phosphates catalytic system, which utilizes novel carbonyl activation. The Pinacol rearrangement has long been known to be difficult to control in terms of regioselectivity and stereoselectivity. The initial studies found that indolyl-diol compounds can be treated with chiral phosphoric acids to afford the Pinacol rearrangement with high regio- and enantioselectivity. Over 16 chiral phosphoric acids were screened, and it was found an H8-BINOL-phosphoric acid variant with 1-naphthyl groups at 3 and 3' position was the excellent catalyst. This asymmetric transformation is tolerant toward variety of substituents both on the indole ring and migrating groups. During the study, it was found that different ways to generate the catalyst had critical effect on this catalytic transformation. Only those phosphoric acids washed with HCl after column chromatography afforded the rearrangement products with high enantioselectivity. And those without treating with HCl were found contaminated by alkaline metals. These "contamination" catalysts were also found active with carbonyl activations. A highly enantioselective catalytic hetero-Diels-Alder reaction of alpha-keto esters has been developed with chiral alkaline metal phosphates. A calcium 1-naphthyl-BINOL phosphate was found to be the optimum catalyst. A large range of alpha-keto esters as well as isatins can be applied in this alkaline phosphates catalytic system with high efficiency and selectivity. The structure of the catalyst is detailed for the first time by X-ray crystal structure analysis. A proposed Transition state model is provided based on the catalyst crystal structure and Raman spectroscopy analysis. This methodology was further developed with an asymmetric Mukaiyama-Michael addition of beta,gamma-unsaturated alpha-keto ester. The best catalyst was found to be a magnesium chiral phosphate. And the transformation was found capable of tolerating a wide variety of beta,gamma-unsaturated alpha-keto esters.

In this study production and characterization of activated carbon from an agricultural waste, pistachio-nut shells, was investigated. To determine optimum production conditions by chemical activation method, effect of tempreature (300, 500, 700 and 900 oC) and effect of impregnation ratio (1:1, 2:1 and 3:1 as activation agent:sample) were investigated by applying two different methods (raw material activation and char activation) and with two different activation agents (phosphoric acid and potassium hydroxide). To produce activated carbon, all the impregnated samples were heated to the final activation temperature under a continuous nitrogen flow (100 cm3/min) and at a heating rate of 10 oC/min and were held at that temperature for 1 hour. Pore structures of activated carbons were determined by N2 adsorption and micro-mesopore analysis was made by &ldquo / Non-local Density Functional Theory&rdquo / and &ldquo / Monte Carlo Simulation&rdquo / method (NLDFT-Monte Carlo Simulation Method). BET surface areas of produced activated carbons were found from N2 adsorption data in the relative pressure range of 0.01 to 0.15. BET surface areas of phosphoric acid activated carbons by raw material activation method were found between 880 and 1640 m2/g. The highest value of the BET surface area was obtained in the case of the activated carbon which was produced with an impregnation ratio of 3/1 (g H3PO4/g raw material), at an activation temperature of 500 oC. The repeatibility was also investigated on phosphoric acid activated carbons which were produced with conventional raw matererial activation method. Results showed that, both the BET surface area values and pore size distributions were consistent among themselves. On the other hand char activation experiments with phosphoric acid produced activated carbons having lower BET surface areas than the ones obtained with raw material activation method by creating mesoporous structure. When the same char activation method was tried with potassium hydroxide, it was concluded that elevated temperatures could help in producing activated carbons with high BET surface areas by creating microporous structure. Results also showed that properties of activated carbon such as ash content, slurry pH value, true density, elemental composition, methylene blue number and surface morphology were strongly affected by both production conditions and production method, as pore structure was affected considerably.

Die Nutzung von Kraftstoffen auf der Basis von Biodiesel erlaubt es, konventionelle, etablierte Antriebstechniken mit Nachhaltigkeit zu kombinieren. Daher kann in den nächsten Jahren mit einer weiteren weltweiten Steigerung der Biodieselproduktion gerechnet werden. Damit verbunden ist jedoch auch ein Anstieg der anfallenden Menge an Glycerol, das bei der Herstellung von Biodiesel als Koppelprodukt entsteht. Da traditionelle Märkte für Glycerol kaum mehr Wachstum zeigen, müssen neue Wege zur effizienten Verwertung von Glycerol gefunden werden. Die vorliegende Arbeit beschäftigt sich mit der heterogen-katalysierten Umsetzung von Glycerol zu Acrolein. Unter Verwendung von ZSM-5-Katalysatorproben mit unterschiedlichem Si/Al-Verhältnis und phosphorsäure-modifizierten Katalysatorproben konnte die Existenz von Synergieeffekten zwischen den texturellen, strukturellen und aciden Eigenschaften in der heterogen-katalysierten Glyceroldehydratisierung zu Gunsten der Acroleinselektivität eindeutig nachgewiesen werden. Eine selektive Umsetzung von Glycerol zu Acrolein wird daher an solchen Katalysatorproben ermöglicht, die ausgewogene texturelle, strukturelle und acide Eigenschaften aufweisen.

Magister Scientiae - MSc (Chemistry) / The anode catalyst is one of the important parts of the direct alcohol fuel cell (DAFC); it is responsible for the alcohol oxidation reaction (AOR) takes place at the anode side. Pd has been reported to have good alcohol oxidation reactions and good stability in alkaline solution. Better stability and activity has been reported for Pd alloyed catalysts when compared to Pd. Choosing a suitable alcohol also has an effect on the activity and stability of the catalyst. This study investigates the best catalyst with better AOR and the best stability and also looks at the better alcohol to use between glycerol and ethanol for the five in-house catalysts (20% Pd, PdNi, PdNiO, PdMn3O4 and PdMn3O4NiO on multi walled carbon nanotubes) using cyclic voltammetry (CV), linear sweep voltammetry (LSV), electrochemical impedance spectrometry (EIS) and chronoamperometry. HR-TEM and XRD techniques were used to determine the particle size and average particle size, respectively while EDS used to determine elemental composition and ICP was used to determine catalyst loading. It was observed from LSV that PdNiO was the most active catalyst for both ethanol and glycerol oxidation, and it was the most stable in ethanol while PdMn3O4 proved to be the most stable catalyst in glycerol observed using chronoamperometry. The best alcohol in this study was reported to be glycerol having given the highest current densities for all the inhouse catalysts compared to ethanol observed using LSV. From XRD and HR-TEM studies, particle sizes were in the range of 0.97 and 2.69 nm for XRD 3.44 and 7.20 nm for HR-TEM with a little agglomeration for PdMn3O4 and PdMn3O4NiO.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Composting of pig slurry (DLS) is an important strategy to mitigate the environmental damage of intensive pig farms. Despite being a promising strategy, one of the problems from composting is still the losses of nitrogen (N) by volatilization of ammonia (NH3). Acidification of DLS before to addition to the piles, reducing the pH and thus, the piles, may be a possibility to circumvent this problem. However, little is known about the effect of acidification of DLS, not only on emissions of (NH3) as with respect to emissions of greenhouse gases (GEE) (CO2, CH4 e N2O) during the process, especially in automated systems where the addition of manure and mixing of piles are frequent. This study was conducted with the objective of evaluating the effect of acidification of pig slurry on ammonia and greenhouse gases emissions during an automated composting process. The study was conducted at the Federal University of Santa Maria, RS, during 154 days in compost piles containing the mixture of wood shavings and sawdust as substrate, with weekly additions of DLS, followed by two revolving piles during the first 106 days. Between 107 and 154 days were made only weekly turnings piles. Two treatments were tested, one with manure acidification with H3PO4 to pH around 6.0 and another without acidification. The evaluation of emissions of NH3 was carried out in semi-open static chambers, while the GEE was performed in static chambers. The pH of DLS was reduced on average 0.87 units with acidification compared to the original values and the average value of all applications was 5.84. In compost piles, the pH decreased from 8.11 to 6.72 on average during all period of the experiment. The concentrations of NH4+ at the end of the experiment were, on an average of two evaluated layers, 102.98 mg kg-1 in the pile without acidification and 398.81 mg kg-1 in the pile with acidification, while the levels of NO3- were 13.37 mg kg-1 in the pile without acidification and 1371.04 mg kg-1 in the pile with acidification. The cumulative emission of NH3 in the treatment with acidification was 32.6 g m-2, 70% lower than the treatment without acidification (107.8 g m-2). Acidification of DLS also reduced the cumulative CO2 emissions to the atmosphere of 91.65 kg m-2 to 69.05 kg m-2 (25%) and the CH4 of 639.97 g m-2 to 227.13 g m-2 (65%). On the other hand, acidification of DLS at the time of addition to the substrate increased the cumulative emission of N2O by 30.4 g N-N2O m-2 (130%) at 154 days of composting. / A compostagem de dejetos líquidos de suínos (DLS) é uma importante estratégia para mitigar o passivo ambiental da suinocultura intensiva. Apesar de ser uma estratégia promissora, um dos problemas decorrentes da compostagem são, ainda, as perdas de nitrogênio (N) por volatilização de amônia (NH3). A acidificação dos DLS previamente a adição às pilhas, reduzindo seu pH e, consequentemente, das pilhas, pode ser uma possibilidade para contornar esse problema. Todavia, pouco se conhece sobre o efeito da acidificação dos DLS, não somente sobre as emissões de NH3 como no que tange às emissões de gases de efeito estufa (GEE) (CO2, CH4 e N2O) durante o processo, sobretudo, em sistemas automatizados, onde a adição de dejetos e o revolvimento das pilhas são frequentes. Esse trabalho foi conduzido com o objetivo de avaliar o efeito da acidificação de dejetos líquidos de suínos sobre as emissões de amônia e gases de efeito estufa durante um processo de compostagem automatizada. O trabalho foi conduzido na Universidade Federal de Santa Maria, RS, durante 154 dias, em pilhas de compostagem contendo a mistura de maravalha e serragem como substrato, com adições semanais de DLS, seguidas de dois revolvimentos das pilhas durante os primeiros 106 dias. No período entre 107 e 154 dias foram efetuados apenas revolvimentos semanais das pilhas. Foram testados dois tratamentos, sendo um com acidificação dos dejetos com H3PO4 até pH próximo a 6,0 e outro sem acidificação. A avaliação das emissões de NH3 foi realizada em câmaras estáticas semi-abertas, enquanto a de GEE foi realizada em câmaras estáticas. O pH dos DLS foi reduzido em média 0,87 unidades com a acidificação em relação aos valores originais, sendo o valor médio de todas as aplicações de 5,84. Nas pilhas de compostagem, o pH reduziu de 8,11 para 6,72 na média de todo período de condução do experimento. Os teores de NH4+ ao final do experimento foram, na média das duas camadas avaliadas, de 102,98 mg kg-1 na pilha sem acidificação e 398,81 mg kg-1 na pilha com acidificação, enquanto os teores de NO3- foram de 13,37 mg kg-1 na pilha sem acidificação e 1371,04 mg kg-1 na pilha com acidificação. A emissão acumulada de NH3 no tratamento com acidificação foi de 32,6 g m-2, 70% inferior ao tratamento sem acidificação (107,8 g m-2). A acidificação dos DLS reduziu, também, as emissões acumuladas de CO2 para a atmosfera de 91,65 kg m-2 para 69,05 kg m-2 (25%) e CH4 de 639,97 g m-2 para 227,13 g m-2 (65%). Por outro lado, a acidificação dos DLS no momento da sua adição ao substrato aumentou a emissão acumulada de N2O em 30,4 g N-N2O m-2 (130%) em 154 dias de compostagem.

Made available in DSpace on 2014-10-09T12:46:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:01:34Z (GMT). No. of bitstreams: 1 07438.pdf: 5655413 bytes, checksum: f397d4eeed4467ace8cd509f912632a0 (MD5) / Dissertacao (Mestrado Profissionalizante em Lasers em Odontologia) / IPEN/D-MPLO / Intituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP; Faculdade de Odontologia, Universidade de Sao Paulo

Orientadores: Rubens Maciel Filho, Aline Carvalho da Costa / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-16T07:08:40Z (GMT). No. of bitstreams: 1 Gomez-Rueda_SandraMarcela_M.pdf: 7950373 bytes, checksum: c7f5e37417de9cac03256c3918348b65 (MD5) Previous issue date: 2010 / Resumo: Neste trabalho foi estudada a produção de açúcares fermentescíveis a partir de bagaço de cana-de-açúcar pré-tratado com os ácidos sulfúrico (H2SO4) e fosfórico (H3PO4) diluídos e deslignificado com hidróxido de sódio (NaOH). Planejamentos fatoriais 23 foram realizados para avaliar a influência do tempo de pré-tratamento (h), temperatura (°C) e concentração de H2SO4 ou H3PO4. Depois do pré-tratamento ácido, o bagaço foi deslignificado por 1h a 100°C com 1%p/v. Os resultados mostraram que ambos pré-tratamentos podem levar a altos rendimentos de glicose na hidrólise enzimática. Os melhores resultados para o ácido fosfórico foram obtidos quando o bagaço foi pré-tratado a 140°C, 120 min e 0,5%p/v H3PO4. Após deslignificação com NaOH e hidrólise enzimática com 15 FPU/g de bagaço pré-tratado e 7,5 CBU/g de bagaço pré-tratado houve liberação de 367 mg de glicose/g bagaço sem pré-tratar, que corresponde a um rendimento de 88%. Quando o ácido sulfúrico foi usado, os melhores resultados foram obtidos para pré-tratamentos a 100°C por 15 min e com 0,5%p/v de H2SO4. Após deslignificação e hidrólise enzimática nas mesmas condições usadas para o bagaço pré-tratado com ácido fosfórico, o bagaço apresentou liberação de 380,6 mg de glicose/g bagaço sem pré-tratar, que corresponde a rendimento de 92%. Devido aos bons resultados obtidos usando ácido fosfórico sendo este pré-tratamento menos estudado do que o pré-tratamento com ácido sulfúrico, o pré-tratamento com este ácido foi escolhido para a etapa posterior. Nesta etapa foram feitos ensaios para determinar a influência das concentrações das enzimas celulase e ?-glicosidase no rendimento de glicose. O bagaço foi pré-tratado com ácido fosfórico diluído nas melhores condições determinadas, deslignificado com NaOH e hidrolisado com concentrações de celulase e ?-glicosidase variando segundo um planejamento composto central. Trabalhando-se com concentrações de celulase de 30 FPU/g e de ?-glicosidade de 25 CBU/g foi possível obter rendimento de 97,1%. Rendimento de 95,10% apenas um pouco mais baixo, foi obtido com 25,85 FPU/g de celulase e 7,33 CBU/g de ?-glicosidade / Abstract: In this work the production of fermentable sugars from sugar cane bagasse pretreated with diluted sulfuric acid and phosphoric acid and delignified with NaOH was estudied. 23 Factorial designs were performed to evaluate the influence of pretreatment time (h), temperature (°C) and acid concentration (H2SO4 or H3PO4). After pretreatment bagasse was delignified for 1 hour at 100 ° C with 1% p/v NaOH. The results have shown that both pre-treatments can lead to high glucose yields at enzymatic hydrolysis. The best results for the pretreatment with phosphoric acid was when bagasse was pretreated at 140 ° C, 120 min and 0.5% p/v H3PO4. After delignification with NaOH and enzymatic hydrolysis with 15 FPU/g of cellulase and 7,5 CBU/g of ?-glicosidase, 367 mg glucose/g untreated bagasse were released, corresponding to a 88% yield. When sulfuric acid was used, the best results were obtained for pretreatment at 100°C, for 15 min and with 0,5%p/v of H2SO4. After delignification and hydrolysis at the same conditions used in the phosporic acid pretreatment, glucose release was of 380,6 mg glucose/g non pretreated bagasse, corresponding to a 92% yield. Due to the good results obtained using phosphoric acid and because pretreatment with this acid is less studied than with sulfuric acid, it was chosen for the posterior stages of the study. In this stage experimental assays were performed to determine the influence of cellulase and ?-glucosidase loads on glucose yield at hydrolysis. Bagasse was pretreated with diluted phosphoric acid at the best conditions, delignified with NaOH and hydrolysed with cellulase and ?-glucosidase loads varying according to a central composite factorial design. Yield of 97.17% was obtained with 30 FPU/g of cellulase and 25 CBU/g of ?- glucosidase. Yield of 95.10%, only a little lower, was obtained with 25.85 FPU/g of cellulase and 7.33 CBU/g of ?-glucosidase / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Made available in DSpace on 2014-10-09T12:46:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:01:34Z (GMT). No. of bitstreams: 1 07438.pdf: 5655413 bytes, checksum: f397d4eeed4467ace8cd509f912632a0 (MD5) / Dissertacao (Mestrado Profissionalizante em Lasers em Odontologia) / IPEN/D-MPLO / Intituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP; Faculdade de Odontologia, Universidade de Sao Paulo

Ce travail vise à montrer l'intérêt de valoriser des phosphates d'origine animale, après une étape de calcination qui produit des cendres minérales constituées essentiellement d'hydroxyapatite : Ca10(PO4)6(OH)2. Elles constituent une matière première renouvelable, riche en phosphore. Plusieurs voies de valorisations sont examinées. La première est la fabrication d'un acide phosphorique très pur, de pureté supérieure à celui produit industriellement à partir de phosphates géologiques. Les propriétés des hydroxyapatites font que ces cendres pourraient être utilisées comme des barrières chimiques pour fixer des éléments polluants contenus dans un sol, un effluent ou une nappe. L'étude de la fixation de divers éléments polluants a montré les grandes capacités de fixation de ces matériaux. / Natural phosphorus sources are drastically decreasing, and it is necessary to find new phosphorus sources. Ashes obtained from calcination of bone meals are mainly hydroxyapatite: Ca10(PO4)6(OH)2. Thus, they can be used as phosphorus-rich raw material. Several valorization ways were evaluated. Bone ashes can be used for the synthesis of a pure phosphoric acid without metallic elements, mainly cadmium and uranium. Hydroxyapatite properties suggest that bone meals ashes can be used for remediation of soils, sludge, effluents and groundwater. Experiments with different metallic elements (Cr, Pb, La...) showed the high sorption properties of this material.

This thesis deals with refractory concrete binding system based on aluminous cement and phosphoric acid. The prepared refractory concretes were fired at 1 000 °C. Various effects on compressive strength of refractory concrete were studied. The influence of aluminous cement content and phosphoric acid content, the influence of various admixtures, the influence of plasticizers and the influence of time and method of sample storage were studied. Simultaneous thermogravimetry and differential thermal analysis of the basic unfired sample were performed. Finally, selected refractory concretes were fired at 110, 200, 400, 600, 800, 900, 1 000 and 1 100 °C. The compressive strength of these samples was measured and powder X ray diffraction analysis was performed. The compressive strength of refractory concretes under intermediate temperatures (800–1 100 °C) was most increased in samples with metakaolin and gray microsilica.