Made available in DSpace on 2014-12-17T15:01:35Z (GMT). No. of bitstreams: 1 ZanielSDP_DISSERT.pdf: 2717599 bytes, checksum: 57e9c7752ad1f265d12ad2b68b546c90 (MD5) Previous issue date: 2014-04-04 / Petr?leo Brasileiro SA - PETROBRAS / Microalgae are microscopic photosynthetic organisms that grow rapidly and in different environmental conditions due to their simple cellular structure. The cultivation of microalgae is a biological system capable of storing solar energy through the production of organic compounds via photosynthesis, and these species presents growth faster than land plants, enabling higher biomass yield. Thus, it is understood that the cultivation of these photosynthetic mechanisms is part of a relevant proposal, since, when compared to other oil producing raw materials, they have a significantly higher productivity, thus being a raw material able to complete the current demand by biodiesel . The overall aim of the thesis was to obtain biofuel via transesterification process of bio oil from the microalgae Isochrysis galbana. The specific objective was to estimate the use of a photobioreactor at the laboratory level, for the experiments of microalgae growth; evaluating the characteristics of biodiesel from microalgae produced by in situ transesterification process; studying a new route for disinfection of microalgae cultivation, through the use of the chemical agent sodium hypochlorite. The introduction of this new method allowed obtaining the kinetics of the photobioreactor for cultivation, besides getting the biomass needed for processing and analysis of experiments in obtaining biodiesel. The research showed acceptable results for the characteristics observed in the bio oil obtained, which fell within the standards of ANP Resolution No. 14, dated 11.5.2012 - 18.5.2012. Furthermore, it was demonstrated that the photobioreactor designed meet expectations about study culture growth and has contributed largely to the development of the chosen species of microalgae. Thus, it can be seen that the microalgae Isochrysis galbana showed a species with potential for biodiesel production / As microalgas s?o organismos microsc?picos fotossintetizantes que crescem rapidamente e em diferentes condi??es ambientais devido a sua simples estrutura celular. O cultivo de microalgas ? um sistema biol?gico capaz de armazenar energia solar, atrav?s da produ??o de compostos org?nicos via processo fotossint?tico, sendo que a maioria das esp?cies apresenta crescimento mais r?pido que as plantas terrestres, possibilitando maior rendimento de biomassa. Assim, compreende-se que o cultivo desses mecanismos fotossintetizantes se insere numa proposta relevante, uma vez que, quando comparados a outras mat?rias primas produtoras de ?leo, apresentam uma produtividade significativamente maior, sendo, portanto, uma mat?ria-prima capaz de completar a demanda atual de biodiesel. O objetivo geral da disserta??o foi a obten??o do biocombust?vel via processo de transesterifica??o do bio-?leo obtido a partir da microalga Isochrysis galbana. O estudo ainda teve por objetivos espec?ficos estimar o uso de um fotobiorreator em n?vel laboratorial, para realiza??o de experimentos de crescimento de microalgas; avaliar as caracter?sticas do biodiesel produzido por processo de transesterifica??o in situ da microalga; estudar uma nova rota para desinfec??o deste meio de cultura, por meio do uso do agente qu?mico hipoclorito de s?dio. Com a introdu??o deste novo m?todo foi poss?vel obter a cin?tica de crescimento do cultivo para o fotobiorreator, al?m de obter a biomassa necess?ria para transforma??o nos experimentos de an?lise e obten??o do biodiesel. A pesquisa apontou resultados aceit?veis para as caracter?sticas verificadas no bio-?leo obtido, o qual se enquadrou nos padr?es da resolu??o ANP N?14, de 11.5.2012 DOU 18.5.2012. Al?m disso, demonstrou-se que o fotobiorreator projetado atendeu ?s expectativas no que concerne ao crescimento do cultivo estudado e contribuiu amplamente para o desenvolvimento da esp?cie de microalga escolhida. Dessa maneira, pode-se constatar que a microalga Isochrysis galbana se mostrou uma esp?cie com potencial para a produ??o de biodiesel

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-12-04T21:01:21Z No. of bitstreams: 1 ZilianeMarquesDaSilva_DISSERT.pdf: 2916473 bytes, checksum: c662f03be19064cfeb67bce69176f1c3 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-12-07T23:37:11Z (GMT) No. of bitstreams: 1 ZilianeMarquesDaSilva_DISSERT.pdf: 2916473 bytes, checksum: c662f03be19064cfeb67bce69176f1c3 (MD5) / Made available in DSpace on 2017-12-07T23:37:11Z (GMT). No. of bitstreams: 1 ZilianeMarquesDaSilva_DISSERT.pdf: 2916473 bytes, checksum: c662f03be19064cfeb67bce69176f1c3 (MD5) Previous issue date: 2017-09-25 / O presente trabalho tem como objetivo analisar as pol?ticas p?blicas e programas nacionais de fomento ? produ??o brasileira de biocombust?veis, principalmente do etanol e do biodiesel, e suas inter-rela??es com o Direito Constitucional. A escolha da tem?tica se deu em virtude da produ??o brasileira ser considerada estrat?gica tanto nacional, quanto internacionalmente. Partindo de uma pesquisa bibliogr?fica somada a um estudo de caso da produ??o do biodiesel (um dos principais biocombust?veis da matriz energ?tica brasileira) proveniente do plantio de girassol no territ?rio do Mato Grande ? Rio Grande do Norte, realizada via Programa Nacional de Produ??o e Uso do Biodiesel (PNPB). Inicia-se um estudo trazendo os pilares do desenvolvimento econ?mico e do desenvolvimento sustent?vel afetos ? tem?tica da produ??o nacional de biocombust?veis, abordando o seu marco regulat?rio. Aprofunda-se, ainda, na correla??o entre a produ??o de biocombust?veis e as justi?as intra e intergeracional. As pol?ticas p?blicas na seara dos biocombust?veis s?o estudadas na perspectiva de um Estado constitucional em crise, trazendo ? reflex?o os alicerces e resultados obtidos com o Programa Nacional do ?lcool - PRO?LCOOL - e o Programa Nacional de Produ??o e Uso do Biodiesel - PNPB - em confronto com as pol?ticas atuais, ainda projetos de lei em tramita??o, a exemplo da Pol?tica Nacional de Biocombust?veis Florestais (Projeto de Lei n? 1.291/2015, aprovado pela Comiss?o de Minas e Energia da C?mara, em 25 de abril de 2017, e tramitando em car?ter conclusivo) e do Programa RENOVABIO (instaurando uma nova pol?tica nacional dos biocombust?veis em geral); verifica-se um descompasso entre o desenvolvimento nos moldes do texto constitucional de 1988 e as diretrizes das atuais pol?ticas, al?m de um lapso entre o vislumbrado pelas pol?ticas p?blicas e o seu resultado pr?tico, entre outros resultados e conclus?es. Finaliza-se o trabalho com sugest?es de altera??es ao texto das atuais pol?ticas, embasadas nas discuss?es proporcionadas. / The present work aims to analyze public policies and national programs to promote the Brazilian production of biofuels, mostly ethanol and biodiesel, and their interrelations with Constitutional Law. The theme choice occurred due to the Brazilian production was considered strategic both nationally and internationally. Based on a bibliographical research in addition to a case study of the biodiesel production (one of the main biofuels of the Brazilian energy matrix) from the sunflower in the Mato Grande territory ? Rio Grande do Norte? performed by Programa Nacional de Produ??o e Uso do Biodiesel (PNPB), this study is initiated bringing the pillars of economic development and sustainable development into the theme of biofuels national production, addressing its regulatory framework. It also explores the correlation between the biofuels production and the intra and intergenerational justice. Public politics in the exto of biofuels are studied in the constitutional perspective of the crisis state, bringing to results and foundations obtained with Programa Nacional do ?lcool ? PRO?LCOOL and Programa Nacional de Produ??o e Uso do Biodiesel ? PNPB in relation with Pol?tica Nacional de Biocombust?veis Florestais (Law n. 1.291/2015) and Programa Renovabio (establishing a new national biofuels politicy, with expected approval for this year); there is a mismatch between development along molds of the 1988 constitutional text and the guidelines of current politics, as well as a gap between what is envisioned by public politics and their practical results, among other results and conclusions. The paper ends with suggestions for changes to the 8exto f current politics, based on the discussions provided.

Data de aprova??o retirada da vers?o impressa do trabalho. / Incluir a Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM) como ag?ncia financiadora. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2017-12-13T16:15:41Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) alice_lopes_macedo.pdf: 5251789 bytes, checksum: e988c8abc173c91e128980414db14ef9 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2018-01-03T12:17:24Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) alice_lopes_macedo.pdf: 5251789 bytes, checksum: e988c8abc173c91e128980414db14ef9 (MD5) / Made available in DSpace on 2018-01-03T12:17:24Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) alice_lopes_macedo.pdf: 5251789 bytes, checksum: e988c8abc173c91e128980414db14ef9 (MD5) Previous issue date: 2017 / Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM) / A crescente demanda global por combust?veis l?quidos para transporte, gera??o de eletricidade, atividade industrial e produ??o agropecu?ria tem imposto planejamento de a??es direcionadas ao uso de fontes ambientalmente limpas de energia. Os derivados da biomassa s?o alternativas econ?mica e tecnicamente vi?veis aos de origem f?ssil, n?o renov?vel, ora dominantes na matriz energ?tica global. O biodiesel, l?quido formado por uma mistura de ?steres de ?cidos graxos, ? adequado ? opera??o em motores de combust?o interna de ciclo Diesel, em substitui??o ou em complemento ao petrodiesel, ou em outras m?quinas t?rmicas. O prop?sito central do presente trabalho foi o desenvolvimento de um catalisador s?lido economicamente vi?vel, quimicamente eficiente e ambientalmente limpo para a produ??o de biodiesel via processos de transesterifica??o de triacilglicer?is dos ?leos de maca?ba ou de soja, com metanol. Foi preparado o catalisador heterog?neo baseado em iodeto de pot?ssio impregnado em s?lica amorfa (SiO2; derivada de areia da constru??o civil) e misturada a um componente magn?tico sint?tico (maghemita, ?Fe2O3). As estruturas qu?mica, cristalogr?fica e hiperfina essenciais e as propriedades magn?ticas dos materiais precursores e do catalisador s?lido foram investigadas. O teor de ?steres e a composi??o dos biodieseis produzidos foram determinados por cromatografia de fase gasosa acoplada a espectr?metro de massa. A composi??o qu?mica do catalisador, verificada por espectroscopias de energia dispersiva sob feixe de el?trons e por fluoresc?ncia de raios X (FRX), confirmou a ocorr?ncia de Si, Fe, K, e I. As ?reas espec?ficas BET encontradas para os componentes individuais, SiO2, ?Fe2O3 e do catalisador SiO2/KI/?Fe2O3, foram 352, 102, e 19 m2 g-1, respectivamente. A significativa redu??o da ?rea espec?fica do catalisador aponta que os componentes foram efetivamente impregnados no suporte. A morfologia das part?culas visualizadas por microscopias eletr?nicas de varredura e de transmiss?o revela a textura esponjosa do catalisador SiO2/KI/?Fe2O3, similarmente ao suporte de s?lica; o ?xido de ferro magn?tico aparece como material altamente organizado, cristalino, disperso no suporte. Os dados M?ssbauer e da magnetometria do ?xido de ferro magn?tico puro e no catalisador confirmam ser a maghemita, resultando em uma magnetiza??o de satura??o do catalisador de 4,6 emu g-1. O catalisador SiO2/KI/?Fe2O3, usado na transesterifica??o de triacilglicer?is, na propor??o em massa em rela??o ao ?leo da am?ndoa de maca?ba de 4,5% e raz?o molar ?leo:metanol de 1:35, levou ? produ??o de 94,3 massa% de ?steres, ap?s 8 h de rea??o. Foi experimentalmente observado que a maghemita tem comportamento qu?mico-catal?tico sin?rgico com os demais componentes do catalisador. O SiO2/KI/?Fe2O3 foi reutilizado em seis rea??es consecutivas com ?leo de soja, na mesma propor??o do catalisador e raz?o molar ?leo:metanol de 1:35, com rendimentos de 94,5% e tempo reacional de 110 min, para o primeiro ciclo, e de 61,2% e 150 min, para o ?ltimo ciclo. O catalisador, antes e ap?s cada ciclo de reuso, e as al?quotas das rea??es foram analisados por FRX, que mostrou que n?o h? perda significativa dos componentes do catalisador. Os resultados demonstram uma perspectiva tecnol?gica que permite redu??o substantiva do volume de efluentes poluentes e utiliza??o de diferentes mat?rias-primas oleaginosas de alto potencial para a produ??o de biodiesel. / Tese (Doutorado) ? Programa de P?s-gradua??o em Biocombust?veis, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2017. / The global demand for liquid fuels destined to propel automobile motors and for all other types of transport has been growing significantly over the last decades in response to the needs of the population for mobility. These fuels are also necessary for the generation of electricity to support industrial and agricultural activities. However, the principal concern involved in the generation of mechanical work involves the threat that the effluents from burning fuels, particularly those from fossil origin, impart to the environment. Biomass-derived fuels are energetically, economically and environmentally interesting alternatives to the non-renewable fossil fuels, which still dominate the global energy matrix. Biodiesel, a liquid that is composed of a mixture of esters of fatty acids, is mainly suitable for use in Diesel-cycle internal combustion engines, totally replacing or partially complementing petrodiesel. The main purpose of the present work was the development of an economically viable, environmentally clean and chemically efficient solid catalyst for the production of biodiesel via the transesterification reaction of triacylglycerols from maca?ba or soybean oil with methanol. The proposed heterogeneous catalyst was based on potassium iodide-impregnated particles of amorphous silica (SiO2; derived from construction sand) mixed with a synthetic magnetic iron oxide (maghemite, ?Fe2O3). The essential chemical, crystallographic and hyperfine structures and magnetic properties of the starting materials and of the solid catalyst mixture were assessed by physical laboratory techniques. The ester content and the chemical composition of the biodiesel produced were determined by gas chromatography coupled with mass spectrometry. The chemical composition of the catalyst, as determined by electron energy dispersive and X-ray fluorescence (FRX) spectroscopies, confirmed the occurrence of Si, Fe, K, and I. Specific BET surface areas for the SiO2 and ?Fe2O3 components and for the SiO2/KI/?Fe2O3 catalyst were found to be 352; 102 and 19 m2 g-1, respectively. The significant reduction in the specific area of the catalyst indicates that the solid components were intimately mixed and that KI was indeed impregnated on the support. The morphology of the particles, as visualized from the scanning and transmission electron microscopy images, reveals the spongy texture of the SiO2/KI/?Fe2O3 catalyst, which was quite similar to that of the initial silica support. The atomic framework of the magnetic iron oxide appeared to be a highly organized, crystalline nano-material, relatively well dispersed on the silica support. The M?ssbauer and magnetometric data for the pure magnetic iron oxide and for the catalyst confirm that the component is essentially maghemite. The resulting saturation magnetization of the catalyst mixture was 4.6 emu g-1. From the chemical point of view, this maghemite was found to act synergically with the other components of the catalyst and to significantly improve its catalytic activity. The transesterification reaction of triacylglycerols using the SiO2/KI/?Fe2O3 catalyst at a mass ratio corresponding to 4.5 mass% relative to the maca?ba kernel oil and a methanol:oil molar ratio 30:1 yielded 94.3 mass% of esters after 8 h of reaction. The SiO2/KI/?Fe2O3 catalyst was reused for six consecutive transesterification reactions of triacylglicerols in soybean oil employing the same mass proportion of the catalyst and a methanol:oil molar ratio 35:1. A 94.5% yield of esters was obtained after 110 min of reaction in the first cycle, and a 61.2% yield was obtained in the last reaction cycle after 150 min. The compositions of the catalyst before and after each reaction cycle, along with detection of residual chemical elements in the liquid mixture of esters formed, were duly monitored by FRX. There was no significant leaching of the catalyst components during the reactions. These results open a perspective for (i) a substantial reduction in the volume of polluting effluents and (ii) the use bio-oils from native Brazilian flora (maca?ba) as raw materials for the industrial production of biodiesel.

Made available in DSpace on 2014-12-17T15:01:24Z (GMT). No. of bitstreams: 1 BrunaMEC_DISSERT.pdf: 1873830 bytes, checksum: 826b39ab376c52af03d9abc3c0b121dd (MD5) Previous issue date: 2010-12-21 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Global warming due to Greenhouse Gases (GHG) emissions, especially CO2, has been identified as one of the major problems of the twenty-first century, considering the consequences that could represent to planet. Currently, biological processes have been mentioned as a possible solution, especially CO2 biofixation due to association microalgae growth. This strategy has been emphasized as in addition to CO2 mitigation, occurs the production of biomass rich in compounds of high added value. The Microalgae show high photosynthetic capacity and growth rate higher than the superior plants, doubling its biomass in one day. Its culture does not show seasons, they grow in salt water and do not require irrigation, herbicides or pesticides. The lipid content of these microorganisms, depending on the species, may range from 10 to 70% of its dry weight, reaching 90% under certain culture conditions. Studies indicate that the most effective method to promote increased production of lipids in microalgae is to induce stress by limiting nitrogen content in the culture medium. These evidences justify research continuing the production of biofuels from microalgae. In this paper, it was studied the strategy of increasing the production of lipids in microalgae I. galbana with programmed nutritional stress, due to nitrogen limitation. The physiological responses of microalgae, grown in f / 2 with different concentrations of nitrogen (N: P 15,0-control, N: 5,0 P and N: P 2,5) were monitored. During exponential phase, results showed invariability in the studied conditions. However the cultures subjected to stress in stationary phase, showed lower biomass yields. There was an increase of 32,5% in carbohydrate content and 87.68% in lipids content at N: P ratio of 5,0 and an average decrease of 65% in protein content at N: P ratios of 5, 0 and 2.5. There were no significant variations in ash content, independently of cultivation and growth phase. Despite the limitation of biomass production in cultures with N: P smaller ratios, the increase of lipid accumulation highest lipids yields were observed as compared to the control culture. Given the increased concentration of lipids associated to stress, this study suggests the use of microalgae Isochrysis galbana as an alternative raw material for biofuel production / O aquecimento global decorrente da emiss?o dos gases geradores do Efeito Estufa (GEE), em especial o CO2, ? um dos problemas mais graves do s?culo XXI, tendo em vista as conseq??ncias que esse agravante pode trazer ao planeta. Atualmente, os processos biol?gicos v?m sendo apontados como uma poss?vel solu??o, principalmente a biofixa??o do CO2 por microalgas. Essa estrat?gia tem sido ressaltada, uma vez que, paralelamente a mitiga??o do CO2 ocorre ? produ??o de biomassa rica em compostos de alto valor econ?mico agregado. As microalgas possuem alta capacidade fotossint?tica e taxa de crescimento superior aos vegetais superiores, duplicam a sua biomassa em um dia. O seu cultivo n?o segue regime de safras, s?o cultivadas em meio salino simples e n?o exigem irriga??o, herbicidas ou pesticidas. O teor de lip?dios destes microrganismos, dependendo da esp?cie, varia de 1 a 70% do seu peso seco, podendo chegar a 90% em certas condi??es de cultivo. Estudos indicam que ? poss?vel aumentar a produ??o de lip?dios pelas microalgas atrav?s de estresses fisiol?gicos induzidos pela restri??o do nitrog?nio no meio de cultura. Essas evid?ncias justificam pesquisas envolvendo a produ??o de biocombust?veis a partir de microalgas. No presente trabalho, estudou-se a estrat?gia de aumentar a produ??o de lip?dios pela microalga I. galbana atrav?s de um estresse nutricional programado, ocasionado pela restrin??o do nitrog?nio. Foram acompanhadas as respostas fisiol?gicas desta esp?cie, cultivada em meio f/2 com diferentes concentra??es de nitrog?nio (raz?es m?ssica N:P 15,0-controle, N:P 5,0 e N:P 2,5). Durante a fase exponencial, as an?lises mostraram uma invariabilidade para os cultivos estudados. Por?m, na fase estacion?ria, os cultivos submetidos ao estresse, indicaram menores rendimentos em biomassa. Observou-se um amento de 32,5% nos n?veis de carboidratos e de 87,68% no teor de lip?deos na raz?o N:P 5,0 e uma redu??o m?dia de 65% de prote?na nas raz?es N:P 5,0 ou 2,5. N?o houve varia??es significativas no teor de cinzas, independente das condi??es de cultivo e fase de crescimento. Apesar da limita??o de biomassa, o aumento do ac?mulo de lip?dios pelas culturas estressadas, proporcionou maiores produtividades de lip?dios, conseq?entemente este estudo sugere a utiliza??o da microalga Isochrysis galbana como fonte alternativa para a produ??o de biocombust?vel

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-08-01T13:50:40Z No. of bitstreams: 1 MatheusSimoesNunes_DISSERT.pdf: 1513497 bytes, checksum: 8baee47339900a07d3bd07a91646af81 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-08-07T14:14:47Z (GMT) No. of bitstreams: 1 MatheusSimoesNunes_DISSERT.pdf: 1513497 bytes, checksum: 8baee47339900a07d3bd07a91646af81 (MD5) / Made available in DSpace on 2017-08-07T14:14:47Z (GMT). No. of bitstreams: 1 MatheusSimoesNunes_DISSERT.pdf: 1513497 bytes, checksum: 8baee47339900a07d3bd07a91646af81 (MD5) Previous issue date: 2015-08-18 / Ag?ncia Nacional do Petr?leo - ANP / Em se tratando da Economia, a ado??o de medidas protecionistas consiste em tem?tica que sempre desperta interesse e suscita pol?mica, especialmente pelo not?vel alcance da regula??o estatal no ?mbito da liberdade de mercado, haja vista o direcionamento do poder-dever estatal de administrar a inger?ncia do interesse p?blico na constru??o do processo de desenvolvimento. Diante da relev?ncia do estudo do controle da liberdade concorrencial no seio da Ind?stria brasileira do Petr?leo, G?s Natural e Biocombust?veis, o presente trabalho centraliza suas aten??es na avalia??o da efici?ncia econ?mica da Pol?tica de Conte?do Local adotada pelo Brasil nesse campo e sua contribui??o no processo de desenvolvimento do pa?s. A relev?ncia da tem?tica apresenta-se atrav?s da import?ncia cient?fica e pr?tica da investiga??o acerca dos reflexos da exig?ncia de aquisi??o local de bens e servi?os pelas empresas delegat?rias das atividades de Explora??o e Produ??o de petr?leo e g?s natural no Brasil. Pretende-se estudar, nessa abordagem jur?dico-econ?mica, se a mitiga??o da liberdade de mercado oriunda da inser??o das Clausulas de Conte?do Local contribui positivamente para a constru??o do desenvolvimento brasileiro. Nesse contexto, o modelo de regula??o adotado pelo Estado passa a constituir ferramenta basilar no que concerne ? atratividade dos interesses dos investidores no pa?s, servindo de refer?ncia para a verifica??o do potencial de concorr?ncia dos agentes do pa?s. Assim, em compasso com a proposta desta pesquisa, aborda-se a tem?tica ? luz dos sensos te?rico e pr?tico, de forma a promover, com enfoque no segmento de ?leo e g?s, uma an?lise sobre os reflexos da inser??o das Cl?usulas de Conte?do Local no cen?rio de mercado que se exige cada vez maior liberdade de atua??o dos agentes econ?micos a n?vel local e global. Para o trabalho em apre?o, utilizam-se como m?todos hipot?tico-dedutivo e funcionalista sist?mico para a abordagem, ao passo que a documenta??o indireta ? empregada no seio da pesquisa bibliogr?fica e documental. Uma vez empreendida a an?lise proposta, segundo a metodologia empregada para tal, conclui-se que a eleva??o da competitividade da ind?stria de hidrocarbonetos brasileira, imprescind?vel ao deslinde do processo de desenvolvimento, somente pode se realizar mediante a inser??o da inova??o no foco dessa din?mica. De igual forma, a efetividade da Pol?tica de Conte?do Local do pa?s, apesar de contribuir significativamente para o fortalecimento da cadeia produtiva nacional, deve constituir medida de cunho tempor?rio e receber rearranjo no sentido de afastar as barreiras anti-competitivas e minimizar os custos da produ??o. / Regarding economics, the adoption of protectionist measures consists on a theme that always arouses interest and raises polemics, especially by the notable range of state regulation in the free market's ambit, in view of the direction of state power and duty to manage the intervention of public interest in the construction of the development process. In the face of the importance of the competitive freedom's control study within the Brazilian Oil Industry, Natural Gas and Biofuels, this study centers its attention on evaluation of Local Content Policy economic efficiency adopted by Brazil in this area and its contribution in the country's development process. The theme's relevance presents through the scientific and practical importance of research concerning the requirement of local procurement of goods and services' reflects by represented companies of Exploration and Production of oil and natural gas' activities in Brazil. It is intended to study in this legal-economic approach, if its freedom market's mitigation from the insertion of Local Content Clauses contributes positively to the Brazilian development construction. In this context, the regulatory model adopted by the State becomes a fundamental tool concerning to the interests of investors' attractiveness in the country, used like reference for verification of potential competition from the country's agents. Therefore, in compass with this research's proposal, discusses with the theme in light of theoretical and practical senses, in order to promote, focused on oil and gas sector, an analysis about the impact of the Local Clauses Content's insertion in the market scenario what demands more freedom on the action of economic agents at local and global level. For the present work have been used hypothetical-deductive as methods and systemic functionalist as approach, while the indirect documentation is applied within bibliographical and documentary research. Once undertaken the proposed analysis, according the applied methods, it concludes that the competitivity elevation of the Brazilian hydrocarbons industry, essential to the development process conclusion, can only be done by inserting innovation in this dynamic focus. Likewise, the effectiveness of the country's Local Content Policy, although significantly contribute to the strengthening of national production chain, has to constitute a temporary measure and receive rearrangement in order to separate anti-competitive barriers and minimize production costs.

Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-05-30T17:17:07Z No. of bitstreams: 1 2015 - Than?zia Ferraz Santos.pdf: 1742658 bytes, checksum: 07706cbaaa52be04cb7ec04d0d453fa2 (MD5) / Made available in DSpace on 2017-05-30T17:17:07Z (GMT). No. of bitstreams: 1 2015 - Than?zia Ferraz Santos.pdf: 1742658 bytes, checksum: 07706cbaaa52be04cb7ec04d0d453fa2 (MD5) Previous issue date: 2015-08-28 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico - CNPq / In this work, potential energy surfaces for the reactions of hydroxyl radical and 2,5-dimethylfuran were studied using the Density Functional Theory. The stationary points, such as reactants, pre-barrier complex, transition states and products were located at BHandHLYP/aug-cc-pVDZ and M06-2X-cc-pVDZ levels by geometry optimization, followed by the calculations of vibrational frequencies. Single point calculations using CCSD(T) were also explored. Thermodynamics properties of enthalpy, entrophy and Gibbs free energies have been determinated at 298,15 K within the conventional equations of Statistical Thermodynamics. The results suggest different addition mechanisms, since an analysis of the potential energy surface (PES) in BHandHLYP/ aug-cc-pVDZ points to paths going through a pi-type intermediary, while in M06-2X/aug-cc-pVDZ the intermediary would have a sigma-type interaction. About the abstraction reactions, only the PES obtained in M06-2X/aug-cc-pVDZ level points to the formation of a pre-barrier complex. The rate coefficients have been determined on the basis of the Variational Transition State Theory, with the kcvt program. The coefficient obtained at CCSD(T)/aug-cc-pVDZ//BHandHLYP/aug-cc-pVDZ for the mechanism which includes the participation of ?-PC is ???????=48,4?10?11, cm? molec-1 s-1, approximately 4 times higher than the experimental rate coefficient. Deviations of this magnitude are considered satisfactory in theoretical calculation of kinetic parameters. Addition of OH should be the main degradation pathway for furan and its derivatives, during daytime. Moreover, it was possible to clarify the effect of the formation of pre-barrier complexes in the reactions between DMF and OH radicals and propose rate coefficients in the high temperature region, which can be applied in combustion studies / Neste trabalho, as superf?cies de energia potencial para as rea??es do radical hidroxila (OH) com o 2,5-dimetilfurano (DMF) foram estudadas em detalhes, utilizando a Teoria do Funcional de Densidade. Pontos estacion?rios como reagentes, complexos pr?-barreira, estados de transi??o e produtos foram localizados por procedimentos de otimiza??o de geometria, acompanhado do c?lculo das frequ?ncias vibracionais, em n?veis BHandHLYP/aug-cc-pVDZ e M06-2X/aug-cc-pVDZ. C?lculos single point a partir da metodologia coupled-cluster com simples e duplas excita??es com tratamento perturbativo das triplas conectadas, CCSD(T), tamb?m foi explorado. Propriedades termodin?micas de entalpia, entropia e energia livre de Gibbs foram calculadas a 298,15 K atrav?s das equa??es da Termodin?mica Estat?stica. Os resultados sugerem mecanismos de adi??o diferentes, j? que uma an?lise da superf?cie de energia potencial (SEP) em BHandHLYP/aug-cc-pVDZ aponta para caminhos passando por um intermedi?rio do tipo pi, enquanto em M06-2X/aug-cc-pVDZ o intermedi?rio seria do tipo sigma. Na abstra??o, apenas a SEP obtida em M06-2X/aug-cc-pVDZ aponta para a forma??o de um intermedi?rio pr?-barreira. Coeficientes de velocidade foram determinados com base na Teoria do Estado de Transi??o Variacional, com aux?lio do programa kcvt. O coeficiente CCSD(T)/aug-cc-pVDZ//BHandHLYP/aug-cc-pVDZ para o mecanismo que inclui a participa??o do ?-PC ? de ???????=48,4?10?11 cm? molec-1 s-1, superestimado em rela??o ao coeficiente experimental em aproximadamente 4 vezes. Desvios dessa magnitude s?o esperados em c?lculos te?ricos, especialmente quando envolvem mol?culas volumosas. Pode-se constatar que a adi??o de OH deve ser a principal rota de degrada??o para o furano e seus derivados durante o dia. Al?m disso, foi poss?vel esclarecer o efeito da forma??o de intermedi?rios pr?-barreira nas rea??es entre DMF e o radical OH.

Made available in DSpace on 2014-12-17T15:01:17Z (GMT). No. of bitstreams: 1 RobertaMP.pdf: 1074511 bytes, checksum: a2a332dc1724fb3abebb3c1cc5d53877 (MD5) Previous issue date: 2008-11-14 / The development of new fuels is an important field of scientific and technological activities, since much of the energy consumed in the world is obtained from oil, coal and natural gas, and these sources are limited and not renewable. Recently it has assessed the employment of microemulsions as an alternative for obtaining fuel isotropic between phases originally not miscible. Among many advantages, emphasizes the application of substances that provide the reduction of levels of emissions compared to fossil fuels. Thus, this work was a study of various microemulsified systems, aiming to check the performance of the winsor regions front of the use of surfactants: RENEX 18 → 150, UNITOL L-60 → L-100 and AMIDA 60, together with structure of esters from soybean and castor bean oils. From the results it were chosen four systems to physico-chemical analyzes: System I RENEX 60, Soil bean oil, methylic ester (EMOS) and water; System II RENEX 60/AMIDA 60, EMOS and water; System III RENEX 70, mamona oil methylic ester (EMOM) and water and System IV RENEX 95, EMOM and water. The tests of physico-chemical characterization and study of temperature increase were done with nine points with different compositions in a way to include the interest area (microemulsion W/O). After this study, was conducted a modeling to predict the viscosity, the property is more varied as function of compositions systems changes. The best results were the systems II and IV with a temperature stability above 60?C. The system I had its physico-chemical characterization very similar to a fossil fuel. The system II was the best one due to its corrosivity be stable. In the modeling the four systems had shown good, with an error that varied between 5 and 18%, showing to be possible the viscosity prediction from the composition of the system. The effects the microemulsion and the engine?s performance with the microemulsion were also avaliated. The tests were performed in a cycle-diesel engine. The potency and consumption were analysed. Results show a slight increase the rendiment fuel compared with the conventional as well as a decrease in specific consumption / O desenvolvimento de novos combust?veis constitui um importante campo de atividade cient?fica e tecnol?gica, uma vez que grande parte da energia consumida no mundo ? obtida do petr?leo, carv?o e do g?s natural, e estas s?o fontes limitadas e n?o renov?veis. Recentemente tem-se avaliado o emprego de microemuls?es como uma alternativa para obten??o de combust?veis isotr?picos entre fases originalmente n?o misc?veis. Dentre muitas vantagens, ressalta-se a aplica??o de subst?ncias que proporcionam a redu??o dos n?veis de emiss?es em compara??o aos combust?veis f?sseis. Desta forma, neste trabalho realizou-se um estudo de v?rios sistemas microemulsionados, visando verificar o comportamento das regi?es de Winsor frente ? utiliza??o dos tensoativos: RENEX 18 ? 150, UNITOL L-60 ? L-100 e AMIDA 60 em conjunto com a estrutura dos ?steres do ?leo de soja e de mamona. A partir dos resultados foram escolhidos quatro sistemas para an?lises fisico-qu?micas, sendo eles: Sistema I RENEX 60, ?ster Met?lico de ?leo de Soja (EMOS) e ?gua, Sistema II RENEX 60/AMIDA 60, EMOS e ?gua, Sistema III RENEX 70, ?ster Met?lico de ?leo de Mamona (EMOM) e ?gua e Sistema IV RENEX 95, EMOM e ?gua. Os ensaios de caracteriza??o f?sicoqu?mica e do estudo do aumento da temperatura foram realizados com nove pontos de composi??es diferentes de forma a melhor abranger a regi?o de interesse (microemuls?o A/O). Ap?s esse estudo, foi realizada uma modelagem para prever a viscosidade, a propriedade que mais variou em fun??o da mudan?a da composi??o dos sistemas. Os melhores resultados foram obtidos para os sistemas II e IV com estabilidade em temperaturas acima de 60?C. O sistema I apresentou propriedades f?sico-quimicas muito parecidas com um combust?vel f?ssil. O sistema II foi o melhor sistema obtido devido sua corrosividade ter se mantido est?vel, comparado ao diesel f?ssil. Na modelagem os quatro sistemas se mostraram bons com um erro que variou entre 5 e 18%, mostrando ser poss?vel a predi??o da viscosidade a partir da composi??o do sistema. Foram realizados alguns testes preliminares em um motor ciclo diesel, sendo analisado o consumo de combust?vel e a pot?ncia. Os resultados mostraram um ligeiro aumento no rendimento motor com o combust?vel microemulsionado em rela??o ao diesel convencional assim como uma diminui??o no consumo espec?fico

Made available in DSpace on 2014-12-17T15:01:21Z (GMT). No. of bitstreams: 1 IaraMSC_partes autorizadas.pdf: 1463501 bytes, checksum: e015bfe96823e1650378fba54b280954 (MD5) Previous issue date: 2009-12-03 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Nowadays, the growing environmental worry leads research the focus the application of alternative materials from renewable resources on the industrial process. The most common vegetable oil extractant using around the world is the hexane, a petroleum derived, toxic and flammable. Based on this fact, the goal of this work was to test vegetable oil extractions from sunflower seeds cultivated on the Rio Grande do Norte State using two extraction process, the mechanical expelling and solvent extraction, this one using hexane and ethanol as a alternative solvent. The solvent extractions were carried out in the Soxhlet extractor in three different extraction times (4, 6, and 8 hours). The effect of solvent and extraction time was evaluated. The mechanical extraction was carried out in a expeller and the sunflower oil obtained was characterized by its physical-chemical properties and compared with sunflower refinery oil. Furthermore this work also explored the pyrolysis reaction carried out by thermogravimetry measurement as alternative route to obtain biofuel. For this purpose the oil samples were heated to ambient temperature until 900?C in heating rate of 5, 10, 20?C min-1 with the objective evaluated the kinetics parameters such activation energy and isoconversion. The TG/DTG curves show the thermal profile decomposition of triglycerides. The curves also showed that antioxidant presents on the refinery oil not influence on the thermal stability of sunflower oil. The total yield of the extraction s process with hexane and ethanol solvent were compared, and the results indicated that the extraction with ethanol were more efficient. The pyrolysis reaction results indicated that the use of unpurified oil required less energy to obtain the bio-oil / Atualmente, o aumento da preocupa??o com o meio ambiente, incentiva as pesquisas que buscam a aplica??o de materiais alternativos provenientes de fontes renov?veis em processos industriais. O extratante de ?leo vegetal mais utilizado no mundo ? o hexano, um derivado de petr?leo t?xico e inflam?vel. Considerando este fato, o presente trabalho teve por objetivo realizar extra??es do ?leo das sementes de girassol cultivadas no Estado do Rio Grande do Norte usando dois processos de extra??o, a extra??o mec?nica e a extra??o com solventes, utilizando hexano e etanol como solvente alternativo. As extra??es com solvente foram realizadas em um extrator Soxhlet utilizando tr?s tempos de extra??o (4, 6 e 8 horas). O efeito do solvente no rendimento da extra??o foi avaliado. O ?leo de girassol obtido da extra??o mec?nica foi caracterizado em rela??o as suas propriedades fisico-qu?micas e comparadas com as propriedades do ?leo de girassol refinado. Al?m disso, o presente trabalho explora as rea??es de pir?lise do ?leo de girassol como uma rota alternativa para a obten??o de biocombust?veis realizadas em um analisador termogravim?trico. Com essa finalidade as amostras de ?leo foram aquecidas da temperatura ambiente at? 900?C em raz?es de aquecimento de 5, 10, 20 ?C min-1 com o objetivo de avaliar os par?metros cin?ticos tais como energia de ativa??o e isoconvers?o. As curvas TG/DTG mostram o perfil t?rmico de decomposi??o dos triglicer?deos. As curvas mostraram tamb?m que o antioxidante presente no ?leo refinado comercial, n?o influencia a estabilidade t?rmica do ?leo de girassol. O rendimento dos processos de extra??o com hexano e etanol foi comparado e os resultados indicaram que a extra??o com etanol foi mais eficiente. Os resultados das rea??es de pir?lise indicaram que o uso do ?leo bruto requer menos energia para a obten??o de biocombust?veis que o ?leo refinado

Made available in DSpace on 2014-12-17T15:42:08Z (GMT). No. of bitstreams: 1 Geraldo Eduardo da Luz Junior_TESE.pdf: 1318067 bytes, checksum: bc521809cc7c08b9ef99f31a1034f3a2 (MD5) Previous issue date: 2010-04-26 / In order to obtain a biofuel similar to mineral diesel, lanthanum-incorporated SBA- 15 nanostructured materials, LaSBA-15(pH), with different Si/La molar ratios (75, 50, 25), were synthesized in a two-steps hydrothermal procedure, with pH-adjusting of the synthesis gel at 6, and were used like catalytic solids in the buriti oil thermal catalytic cracking. These solids were characterized by X-ray fluorescence (XRF), powder X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), infrared spectroscopy (FTIR), nitrogen porosimetry and ethanol dehydration, aiming to active sites identify. Taken together, the analyses indicated that the synthesis method has employed to obtain materials highly ordered mesostructures with large average pore sizes and high surface area, besides suggested that the lanthanum was incorporated in the SBA-15 both into the framework as well as within the mesopores. Catalytic dehydration of ethanol over the LaSBA-15(pH) products has shown that they have weak Lewis acid and basic functionalities, indicative of the presence of lanthanum oxide in these samples, especially on the La75SBA-15(pH) sample, which has presented the highest selectivity to ethylene. The buriti oil thermal and thermal catalytic cracking, realized from the room temperature to 450 ?C in a simple distillation system, has allowed obtaining two liquid fractions, each consisting of two phases, one aqueous and another organic, organic liquid (OL). The OL obtained from first fractions has shown high acid index, even in the thermal catalytic process. One the other hand, OL coming from second ones, called green diesel (GD), have presented low acid index, particularly that one obtained from the thermal catalytic process realized over LaSBA-15(pH) samples. The acid sites presence in these samples, associated to their large average pore sizes and high surface areas, have allowed them, especially the La75SBA-15(pH), to present deoxygenating activity in the buriti oil thermal catalytic cracking, providing an oxygenates content reduction, particularly carboxylic acids, in the GD. Furthermore, the GD comes from the second liquid fraction obtained in the buriti oil thermal catalytic cracking over this latest solid sample has shown hydrocarbons composition and physic-chemical properties similar to that mineral diesel, beyond sulfur content low / Com o objetivo de obter um biocombust?vel semelhante ao diesel mineral, materiais nano-estruturados do tipo SBA-15 com lant?nio incorporado, LaSBA-15(pH), com raz?es molares Si/La = 75, 50 e 25, foram sintetizados em dois est?gios, com ajuste do pH do gel de s?ntese a 6, e utilizados como s?lidos catal?ticos no craqueamento termocatal?tico de ?leo de buriti. As amostras s?lidas foram caracterizadas por fluoresc?ncia de raios-X (FRX), difra??o de raios-X (DRX), an?lise termogravim?trica (TG/DTG), espectroscopia na regi?o do infravermelho (FTIR), adsor??o-dessor??o de nitrog?nio e desidrata??o de etanol, para identifica??o dos s?tios ativos. Os resultados destas caracteriza??es indicaram que o m?todo de s?ntese empregado proporcionou a obten??o de materiais mesoestruturados altamente ordenados com grande di?metro m?dio de poros e elevada ?rea superficial, al?m de sugerir que o lant?nio foi incorporado na SBA-15 tanto no interior das paredes, quanto dentro dos mesoporos. A desidrata??o catal?tica de etanol sobre os s?lidos LaSBA-15(pH) mostrou que eles apresentam s?tios ?cidos e b?sicos de Lewis, indicativo da presen?a de ?xido de lant?nio nestes, especialmente na amostra La75SBA-15(pH), que apresentou a maior seletividade para etileno. Os craqueamentos t?rmico e termocatal?ticos do ?leo de buriti, realizados da temperatura ambiente a 450 ?C em um sistema de destila??o simples, possibilitaram a obten??o de duas fra??es l?quidas, compostas por duas fases, uma aquosa e outra org?nica, l?quido org?nico (LO). O LO obtido a partir das primeiras fra??es apresentou ?ndice de acidez muito elevado, at? mesmo nos processos termocatal?ticos. Por outro lado, o LO oriundo das segundas fra??es, denominado de diesel verde (DV), apresentou baixo ?ndice de acidez, particularmente aquele obtido nos processos realizados sobre as amostras LaSBA-15(pH). Os s?tios ?cidos presentes nestas amostras, associados aos seus grandes di?metros m?dios de poros e ?s elevadas ?reas superficiais, permitiram que elas, especialmente a La75SBA-15(pH), apresentassem atividade desoxigenante no craqueamento temocatal?tico do ?leo de buriti, ocasionando uma diminui??o da concentra??o de oxigenados no DV, particularmente ?cidos carbox?licos. Al?m disso, o DV obtido sobre esta ?ltima amostra s?lida apresentou composi??o de hidrocarbonetos e propriedades f?sico-qu?micas semelhantes ?s do diesel mineral, al?m de um baixo teor de enxofre

Made available in DSpace on 2014-12-17T14:20:16Z (GMT). No. of bitstreams: 1 FranciscoNABN.pdf: 1571343 bytes, checksum: f30a0bcc5b0d576b24ed11dbd5f25df2 (MD5) Previous issue date: 2009-12-09 / This doctoral thesis presents an analysis of the production of bicarbonates and related regional development in Brazil. It is widely believed that one of Brazil s vocations lies in the agro-energy sector. However, current national agro-energy policies, together with the experience of Petrobras (the national oil company) in rural settlements in the state of Rio Grande do Norte, show that Brazil has fallen short of effectively including the North and Northeast regions of the country, let alone small-scale rural producers (residing in rural settlements or not), in the development process and related benefits from the country s participation in the current world energy grid. The methodology entails secondary research related to the theme, such as books, official documents, websites and statistical databases from diverse sources, in addition to an analysis of statements from interviews of Petrobras representatives and other important scientific, institutional and labor union authorities, in relation to agro-energy issues and the socio-economic participation of family-based agriculture in this process. Principal findings show a correlation between agro-energy and regional development, creating the potential for numerous opportunities and challenges. Findings demonstrate the possibility of reversing/reducing historically rooted indices of hunger and poverty that continue to devastate the North and Northeast regions. At the same time, the thesis points to a potentially catastrophic increase in regional disparities, should the present historic moment not be seized upon so as to include these regions. Classic examples of non-policy at the federal level are presented as evidence of the absence of a regionally focused agroenergy policy in the current government, reinforced by the experiences of Petrobras in the Rio Grande do Norte rural settlements. Finally, the thesis concludes that there is an urgent need to create a government-sponsored enterprise (with a structure similar to Petrobras) with the purpose of implementing a truly broad and inclusive development process for the bicarbonates production sector, while remaining attentive to Brazil s opportune and critical role in the world s current agro-energy scenario. / Analisa a rela??o entre a produ??o de biocarburantes e a quest?o regional. Acredita-se que a produ??o agroenerg?tica ? uma voca??o brasileira, contudo, a atual pol?tica nacional agoenerg?tica e a experi?ncia dos assentamentos rurais apoiados pela Petrobras, no Rio Grande do Norte, n?o incluem efetivamente as regi?es Norte e Nordeste do Brasil, tampouco os pequenos produtores rurais (assentados ou n?o) nos benef?cios decorrentes da atual mudan?a na matriz energ?tica mundial. A metodologia utilizada inclui a pesquisa secund?ria concernente ao tema, tais como livros, documentos oficiais, sites, bases estat?sticas entre as demais fontes, e ainda a an?lise de discurso tomando por base entrevistas realizadas junto ? Petrobras e com importantes autoridades cient?ficas, institucionais e sindicais relacionadas ? quest?o agroenerg?tica e a inclus?o s?cio-econ?mica da agricultura familiar neste processo. Os principais resultados indicam que a correla??o entre agroenergia e a quest?o regional apresenta in?meras potencialidades e desafios. Aponta para a possibilidade de revers?o/redu??o dos hist?ricos indicadores de fome e pobreza que assolam o Norte e o Nordeste. Contudo, tamb?m indica que a n?o pol?tica agroenerg?tica no atual governo federal, assim como experi?ncias da Petrobras nos assentamentos do Rio Grande do Norte s?o exemplos claros de n?o pol?tica que podem agravar o quadro de disparidades regionais de forma abissal, caso n?o haja aproveitamento deste momento hist?rico. Por fim conclui que urge a cria??o de uma empresa de economia mista (nos moldes da Petrobras) e integradora especializada na produ??o de biocarburantes, que trate desta quest?o com a urg?ncia e import?ncia que o Brasil ocupa no cen?rio agroenerg?tico mundial, numa perspectiva verdadeiramente includente e abrangente.