Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2018-04-11T19:34:25Z No. of bitstreams: 1 JulianaElionaraBezerraCosta_TESE.pdf: 2543108 bytes, checksum: 556e8d7316f4202efa7113ded946013c (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2018-04-12T22:40:15Z (GMT) No. of bitstreams: 1 JulianaElionaraBezerraCosta_TESE.pdf: 2543108 bytes, checksum: 556e8d7316f4202efa7113ded946013c (MD5) / Made available in DSpace on 2018-04-12T22:40:16Z (GMT). No. of bitstreams: 1 JulianaElionaraBezerraCosta_TESE.pdf: 2543108 bytes, checksum: 556e8d7316f4202efa7113ded946013c (MD5) Previous issue date: 2017-12-18 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Alguns res?duos, provenientes das mais variadas atividades, podem ser reaproveitados, diminuindo o efeito dos impactos ambientais ocasionados pela m? disposi??o dos mesmos no meio ambiente. Os res?duos classificados com biomassa lignocelul?sica, podem ser convertidos em produtos qu?micos e combust?veis a partir da pir?lise r?pida convencional, gerando como produto principal o bio-?leo com caracter?sticas diretamente ligadas as caracter?sticas da biomassa de origem que podem ser melhoradas a partir do uso de catalisadores. Neste trabalho foram sintetizados catalisadores do tipo ZSM-5 e HZSM-5, utilizando res?duos de p? de granito, p? de vidro, diatomita e cinza da casca do arroz como fontes alternativas e tamb?m um catalisador utilizando fonte convencional de S?lica e Alum?nio. O objetivo da s?ntese desses materiais ? utiliz?-los como catalisador na pir?lise da fibra do coco visando a obten??o de produtos com maior valor agregado, reduzindo a produ??o de compostos oxigenados. A biomassa utilizada foi caracterizada por an?lise imediata, densidade, an?lise elementar, Teor de Celulose, hemicelulose e lignina, Poder calor?fico, TG/DTG, DRX, FT-IR e FRX afim de analisar o potencial energ?tico da mesma. Os precursores de S?lica e Alum?nio foram submetidos a an?lises de FRX, DRX, e os catalisadores foram caracterizados por TG/DTG, DRX, FT-IR, MEV e BET. Nos resultados de pir?lise convencional da fibra do coco observou a grande produ??o de produtos oxigenados, a maior parte deles fen?is e nos resultados das pir?lise catal?tica foi poss?vel observar a diminui??o desses produtos, provando a efici?ncia dos catalisadores utilizados. / Some waste, from the most varied activities, can be reused, reducing the effect of these impacts, usually caused by poor disposal in the environment. The residues classified with lignocellulosic biomass can be converted into chemical products and fuels from the conventional fast pyrolysis, generating as main product the bio-oil. This generally presents some undesirable characteristics directly linked to the characteristics of the source biomass, which decrease its energy efficiency. The use of catalysts allows the reduction of these undesirable products and improves the final quality of the bio oil. As a result, ZSM-5 and HZSM-5 catalysts were synthesized using granite powder, glass powder, diatomite and rice husk ash as alternative sources of silica and aluminum; was also synthesized using a conventional silica and aluminum source, serving as a standard for the others. . The objective of the synthesis of these materials is to use them as a catalyst in the pyrolysis of coconut fiber in order to obtain products with higher added value, reducing the production of oxygenated compounds. The biomass used was characterized by immediate analysis, density, elemental analysis, cellulose content, hemicellulose and lignin, calorific power, TG / DTG, XRD, FT-IR and FRX in order to analyze the energy potential of the same. Silica and Aluminum precursors were subjected to FRX, XRD analyzes, and the catalysts were characterized by TG / DTG, DRX, FT-IR, MEV and BET. In the results of conventional pyrolysis of the coconut fiber, it was observed the great production of oxygenated products, most of them phenols and in the results of the catalytic pyrolysis it was possible to observe the decrease of these products, proving the efficiency of the catalysts used.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-09-19T19:40:40Z No. of bitstreams: 1 ElaniaMariaFernandesSilva_TESE.pdf: 3393670 bytes, checksum: 8755f5c2f474b6b328f5f50e212e7e18 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-09-19T23:05:55Z (GMT) No. of bitstreams: 1 ElaniaMariaFernandesSilva_TESE.pdf: 3393670 bytes, checksum: 8755f5c2f474b6b328f5f50e212e7e18 (MD5) / Made available in DSpace on 2017-09-19T23:05:55Z (GMT). No. of bitstreams: 1 ElaniaMariaFernandesSilva_TESE.pdf: 3393670 bytes, checksum: 8755f5c2f474b6b328f5f50e212e7e18 (MD5) Previous issue date: 2017-07-25 / Catalisadores de alto desempenho v?m sendo bastante investigados com o objetivo de aumentar o rendimento dos processos de reforma a seco do metano (RSM). Alguns metais de transi??o, em especial o n?quel, s?o amplamente estudados para essa aplica??o. Por possu?rem propriedades catal?ticas, estabilidade t?rmica e qu?mica, os ?xidos com estrutura do tipo perovsquita s?o materiais promissores como precursores catal?ticos em processos de RSM. O objetivo deste estudo ? avaliar a efici?ncia de ?xidos do tipo perovsquita como catalisadores m?ssicos e como suportes catal?ticos na reforma a seco de metano (RSM). Assim, ?xidos tipo perovsquita ABO3 foram sintetizados pelo m?todo de combust?o assistida por micro-ondas usando ureia como combust?vel. Os materiais foram calcinados a 900 ?C por 2h. Ap?s a calcina??o todos os ?xidos preparados foram impregnados com 20 % (m/m) de n?quel e calcinados novamente a 600 ?C por 2h. As amostras foram caracterizadas por: difra??o de raios X (DRX), redu??o ? temperatura programada (RTP) e microscopia eletr?nica de varredura com espectroscopia de energia dispersiva (MEV-EDS). Testes de reforma de metano com CO2 foram realizados para avalia??o desses materiais como catalisadores na produ??o de g?s de s?ntese. Ap?s os testes de reforma, os catalisadores foram submetidos novamente a caracteriza??es para investiga??o da exist?ncia de carbono nas superf?cies dos ?xidos. De acordo com os difratogramas de raios X, fases secund?rias de ?xidos de n?quel foram formadas ap?s a impregna??o do n?quel nos p?s. Os mapeamentos obtidos atrav?s de EDS mostraram que a metodologia de impregna??o resultou numa dispers?o homog?nea das part?culas de ?xido de n?quel na superf?cie das perovsquitas. Os testes catal?ticos foram realizados a 750 ?C durante 10 horas. Os catalisadores avaliados apresentaram melhores desempenhos, tanto de convers?es como de estabilidade, ap?s a impregna??o de n?quel, mostrando que as perovsquitas podem ser potenciais suportes catal?ticos para reforma a seco do metano. / High-performance catalysts have been widely researched in order to increase the yield in methane dry reforming processes (DRM). Some transition metals, especially nickel, are largely studied for this purpose. Due to its catalysts? properties, thermal and chemical stability, perovskite-type oxides ABO3 are promising materials as catalytic precursors in DRM processes. The objective of this study is to evaluate the efficiency of perovskite type oxides as catalysts and as supports in dry reforming of methane (DRM). Perovskite-type oxides ABO3 were synthesized by microwave assisted combustion using urea as fuel and calcinated at 900 ?C for 2h. After the calcination, all the prepared oxides were impregnated with 20% (w/w) of nickel and calcinated again at 600?C for 2h. The samples were characterized by the following techniques: x-ray diffraction (XRD), temperature programmed reduction (TPR), and dispersive energy scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS). Methane reforming tests with CO2 were performed for evaluation of these materials as catalysts in the production of syngas. After the reforming tests, the catalysts were submitted once again to characterizations for the evaluation of the existence of carbon in the oxides? surface. According to the X-ray diffractograms, secondary phases of nickel oxides were formed after the nickel impregnation in the powders. The mapping by EDS showed that the impregnation methodology resulted in a homogeneous dispersion of the nickel oxide particles on the perovskite?s surface. The catalytic tests were performed at 750 ? C for 10 hours. The catalysts showed better performances, conversions and stability, after nickel impregnation, showing that the perovskites may be potential catalytic supports for dry reforming methane.

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No description available.

Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-05-15T11:16:01Z No. of bitstreams: 1 2016 - Maria Clara Adum de paiva.pdf: 2279180 bytes, checksum: d1de128b3d5f5984c844a68538cd255e (MD5) / Made available in DSpace on 2017-05-15T11:16:01Z (GMT). No. of bitstreams: 1 2016 - Maria Clara Adum de paiva.pdf: 2279180 bytes, checksum: d1de128b3d5f5984c844a68538cd255e (MD5) Previous issue date: 2016-08-04 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / The demand for electricity production, and the need for thermoelectric use as power generating units, makes it necessary to search for less polluting matrices. In this search the catalytic combustion of methane, both from natural gas and other sources (residue disposal, for example) have shown promising. It is known the use of cobalt oxides is an alternative to the use of catalysts based on noble metals which has shown high performance. In order to potentiate the activity of the cobalt based catalyst, thus reducing both the ignition temperature and the temperature of total burning of methane, this work proposes the production of cobalt-based precursors using different types of layered double hydroxides (LDHs). Cobalt based catalysts partially substituted in layered double hydroxides (LDH Mg, Al and CO32-) were prepared by co-precipitation and impregnation with a nominal content of 9% CoII in LDH, or by impregnating a commercial hydrotalcite (HT). The LDH precursors were characterized by X-ray powder diffraction (XRD) and infrared absorption spectroscopy (FTIR). The XRD patterns indicated a LDH of 3R polytype. XRD showed the presence of Gibbisite in the HT precursor. The infrared spectra of precursor LDHs presented bands related to ?1, ?2 and ?3 vibrations of the carbonate anion, and interlayer water characteristic bands, thus in line with the XRD data. Analysis by XRD of the catalysts after calcination at 800 ?C showed the presence of periclase and spinel phases. Infrared spectra showed bands ascribed to the Mg-O and Co-O stretching in tetrahedral and octahedral sites as well as bands attributed to the Mg-O-Al bond and the cobalt spinel. The catalytic activity of these materials was investigated in the catalytic combustion of methane under kinetic regime, using predetermined reaction conditions to avoid diffusional limitations, resulting in a significant decrease in the combustion temperature, with the higher activity observed for the catalyst prepared by impregnating a commercial HT. Scanning electron microscopy (SEM) and quantitative chemical analysis (EDS) of catalysts with improved performance show both the homogeneous dispersion of the components in the sample surface and the higher aluminum content of the sample supported on HT. / A demanda de produ??o de energia el?trica, e a necessidade do uso de termel?tricas como unidades geradoras de energia, fazem com que seja necess?ria a busca por matrizes menos poluentes. Nessa busca a combust?o catal?tica do metano, tanto proveniente do g?s natural como de outras fontes (res?duo do tratamento de lixo, por exemplo), tem se mostrado promissora. Sabidamente o uso de ?xidos de cobalto ? uma alternativa, que vem mostrando alto desempenho, ao uso de catalisadores a base de metais nobres. Com o intuito de potencializar a atividade do catalisador a base de cobalto, reduzindo assim tanto a temperatura de igni??o quanto a de queima total do metano, esse trabalho prop?e sua produ??o utilizando como precursor diferentes tipos de hidr?xidos duplos lamelares (HDLs). Catalisadores ? base de cobalto parcialmente substitu?dos em hidr?xidos duplos lamelares (HDL de Mg, Al e CO32-) foram preparados por co-precipita??o e impregna??o num teor nominal de 9% de CoII em HDL, ou por impregna??o em hidrotalcita comercial (HT). Os HDLs precursores foram caracterizados por difra??o de raios?X pelo m?todo de p? (DRX) e por espectroscopia de absor??o no infravermelho (FTIR). Os difratogramas indicaram a obten??o de um HDL de politipo 3R. Por meio do DRX foi identificada a presen?a de Gibbisita no suporte de HT. Os espectros de infravermelho dos HDLs precursores presentaram bandas referentes ?s vibra??es ?1, ?2 e ?3 do ?nion carbonato, al?m de bandas caracter?sticas de ?gua interlamelar, estando portanto de acordo com os dados de DRX. A an?lise por difra??o de raios-X dos catalisadores ap?s calcina??o a 800?C mostrou apenas as fases espin?lio e pericl?sio. Os espectros de infravermelho apresentaram bandas atribu?das aos estiramentos Mg?O e Co?O em s?tios tetra?dricos e octa?dricos, assim como bandas caracter?sticas de Mg?O?Al e de Co3O4. A atividade catal?tica desses materiais foi investigada na combust?o catal?tica do metano, em regime cin?tico, empregando-se condi??es reacionais preestabelecidas de forma a evitar limita??es difusionais, obtendo-se uma significativa diminui??o na temperatura de combust?o, sendo que a maior atividade foi observada para o catalisador preparado por impregna??o em HT comercial. Foi realizada microscopia eletr?nica de varredura (MEV) e an?lise qu?mica quantitativa (EDS) para os catalisadores com melhor desempenho, mostrando tanto a dispers?o homog?nea dos componentes na superf?cie das amostras como o maior teor de alum?nio presente na amostra suportada em HT.

Made available in DSpace on 2014-12-17T14:07:15Z (GMT). No. of bitstreams: 1 MariaSBF_TESE.pdf: 2706042 bytes, checksum: e909d3cb5ee177d47cc6917725b38335 (MD5) Previous issue date: 2013-05-17 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In recent years, the area of advanced materials has been considerably, especially when it comes to materials for industrial use, such as is the case with structured porosity of catalysts suitable for catalytic processes. The use of catalysts combined with the fast pyrolysis process is an alternative to the oxygenate production of high added value, because, in addition to increasing the yield and quality of products, allows you to manipulate the selectivity to a product of interest, and therefore allows greater control over the characteristics of the final product. Based on these arguments, in this work were prepared titanium catalysts supported on MCM-41 for use in catalytic pyrolysis of biomass, called elephant grass. The reactions of pyrolysis of biomass were performed in a micro pyrolyzer, Py-5200, coupled to GC / MS, the company CDS Corporation, headquartered in the United States. The catalysts Ti-MCM-41 in different molar ratios were characterized by XRD, TG / DTG, FT-IR, SEM, XRF, UV-visible adsorption of nitrogen and the distribution of particle diameter and specific surface area measurement by the BET method. From the catalytic tests it was observed that the catalysts synthesized showed good results for the pyrolysis reaction.The main products were obtained a higher yield of aldehydes, ketones and furan. It was observed that the best reactivity is a direct function of the ratio Si/Ti, nature and concentration of the active species on mesoporous supports. Among the catalysts Ti-MCM-41 (molar ratio Si / Ti = 25 and 50), the ratio Si / Ti = 25 (400 ? C and 600 ? C) favored the cracking of oxygenates such as acids , aldehydes, ketones, furans and esters. Already the sample ratio Si / Ti = 50 had the highest yield of aromatic oxygenates / Nos ?ltimos anos, a ?rea de materiais tem avan?ado consideravelmente, principalmente, quando se trata de materiais para uso industrial, como ? o caso de catalisadores estruturados com porosidade adequada para os processos catal?ticos. O uso de catalisadores combinados ao processo de pir?lise r?pida ? uma alternativa para a produ??o de compostos oxigenados de alto valor agregado, pois, al?m de elevar o rendimento e qualidade dos produtos, permite manipular a seletividade para um produto de interesse e, portanto, permite um maior controle sobre as caracter?sticas do produto final. Com base nesses argumentos, neste trabalho foram preparados catalisadores de tit?nio suportados em MCM-41 para uso em pir?lise catal?tica da biomassa, denominada de capim elefante. As rea??es de pir?lise da biomassa foram realizadas em um micro pirolisador, Py-5200, acoplado ao GC/MS, da empresa CDS Corporation, sediada nos Estados Unidos. Os catalisadores Ti-MCM-41, em diferentes raz?es molares, foram caracterizados por DRX, TG/DTG, FT-IR, MEV, FRX, UV-Vis?vel, adsor??o de nitrog?nio, distribui??o de di?metro de part?culas e medidas de ?rea espec?fica pelo m?todo BET. A partir dos testes catal?ticos foi poss?vel observar que os catalisadores sintetizados apresentaram bons resultados para a rea??o de pir?lise. Entre os catalisadores Ti-MCM-41 (raz?es molares Si/Ti = 25 e 50), o de raz?o Si/Ti=25 (temperatura de 400?C e 600?C) favoreceu o craqueamento de compostos oxigenados, tais como, ?cidos, alde?dos, cetonas, furanos e ?steres. J? a amostra de raz?o Si/Ti = 50 apresentou maior rendimento de arom?ticos oxigenados

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-08-26T23:16:09Z No. of bitstreams: 1 MonickarlaTeixeiraPegadoDaSilva_DISSERT.pdf: 2972749 bytes, checksum: 333ef217ee5461818b38fff8de7cfdeb (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-08-31T00:12:48Z (GMT) No. of bitstreams: 1 MonickarlaTeixeiraPegadoDaSilva_DISSERT.pdf: 2972749 bytes, checksum: 333ef217ee5461818b38fff8de7cfdeb (MD5) / Made available in DSpace on 2016-08-31T00:12:48Z (GMT). No. of bitstreams: 1 MonickarlaTeixeiraPegadoDaSilva_DISSERT.pdf: 2972749 bytes, checksum: 333ef217ee5461818b38fff8de7cfdeb (MD5) Previous issue date: 2016-02-23 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Suportes catal?ticos ? base de ?xido de alum?nio foram sintetizados pelo m?todo e esferas h?bridas utilizando carboximetilcelulose (CMC) como precursor org?nico (template) e nitrato de alum?nio como precursor inorg?nico. As caracteriza??es foram realizadas por an?lises de termogravimetria (TG), difra??o de raios-X (DRX), espectroscopia no infravermelho por transformada de fourier (FTIR), microscopia eletr?nica de varredura (MEV) e fisissor??o N2. Os materiais sintetizados foram testados na rea??o de convers?o do glicerol em fase g?s. Os estudos da s?ntese indicaram que as caracter?sticas do biopol?mero (grau de substitui??o e de polimeriza??o) influenciam diretamente no valor m?ximo da rela??o entre o precursor org?nico e inorg?nico para a forma??o das esferas h?bridas. As propriedades f?sico-qu?micas do material final (cristalinidade, porosidade, ?rea espec?fica e morfologia) mostraram uma depend?ncia direta com as propriedades do biopol?mero (grau de substitui??o e de polimeriza??o), indicando a versatilidade desta rota s?ntese. Os espectros de FTIR confirmaram a forma??o de um material h?brido quando se compara o espectro da CMC pura com os s?lidos obtidos ap?s a secagem. Os resultados de DRX mostraram um perfil de material amorfo para algumas amostras. Para alguns s?lidos foi poss?vel identificar a forma??o de uma fase cristalina relacionada com a alumina hidratada, ?xido de alum?nio e ?xido de cobre. As imagens obtidas por MEV indicaram a forma??o de um material com morfologia semelhante a uma esponja ap?s a calcina??o, caracter?stico de um s?lido altamente poroso. O perfil de adsor??o/dessor??o de N2 confirma a forma??o de materiais contendo micro-mesoporos com uma ?rea espec?fica entre 50-162 m2.g-1 para os suportes e 112-303 m2.g-1 para os catalisadores com cobre, indicando um aumento ?rea ap?s a adi??o do Cu por impregna??o devido a redissolu??o e recristaliza??o da fase alumina. Testes catal?ticos indicaram que os ?xidos s?o ativos e seletivos para a convers?o do glicerol (92-15%) a bioprodutos de alto maior valor agregado, confirmando a viabilidade do m?todo de s?ntese. / Catalytic supports based on aluminum oxide were synthesized by the method of hybrid spheres using carboxymethylcellulose (CMC) as organic precursor (template) and aluminum nitrate as inorganic precursor. The characterizations were performed by thermal chemical analysis (TGA), X-Ray diffraction (XRD), fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and N2 physisorption. The study of synthesis indicated that the characteristics of the biopolymer (degree of substitution and polymerization) directly influence on the maximum value of the ratio between the organic and inorganic precursor for the formation of hybrid spheres. The physicochemical properties of the final material (crystallinity, porosity, surface area and morphology) showed a direct dependence on the biopolymer properties (degree of substitution and polymerization), indicating the versatility of this synthesis route. The FTIR spectra confirm the formation of a hybrid material when comparing the pure CMC spectrum with the obtained solids after drying. The XRD results show a profile of amorphous and crystalline material for the different samples. For some solids were possible to identify the formation of a crystalline phase related to the hydrated alumina, aluminium oxide and copper oxide. The images obtained by SEM analysis showed the formation of a material with sponge-like morphology after calcination, characteristic of highly porous solid. The N2 adsorption/desorption isotherm profile confirms the formation of micro-mesoporous materials with a specific surface area between 50-162 m2.g-1 for the supports and 112-303 m2.g-1 for the copper-based catalysts, indicating an increase in the area after the addition of Cu by impregnation due to redissolution and recrystallization of alumina phase. Catalytic tests were tested in the glycerol conversion reaction (92-15%) to added value products in order to confirm their real viability.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-09-19T19:40:39Z No. of bitstreams: 1 CassiaCarvalhoDeAlmeida_TESE.pdf: 6857436 bytes, checksum: 5d930402b569e88da7eb76c2ad9e091d (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-09-19T22:52:56Z (GMT) No. of bitstreams: 1 CassiaCarvalhoDeAlmeida_TESE.pdf: 6857436 bytes, checksum: 5d930402b569e88da7eb76c2ad9e091d (MD5) / Made available in DSpace on 2017-09-19T22:52:56Z (GMT). No. of bitstreams: 1 CassiaCarvalhoDeAlmeida_TESE.pdf: 6857436 bytes, checksum: 5d930402b569e88da7eb76c2ad9e091d (MD5) Previous issue date: 2017-05-26 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Nos ?ltimos anos os processos de reforma para a produ??o de hidrog?nio como um vetor energ?tico vem sendo bastante estudados, em fun??o do aumento da demanda por tecnologias alternativas de gera??o de energia, apresentando uma boa rela??o custo/benef?cio quando comparados a outras tecnologias de produ??o de hidrog?nio. Al?m disso, possuem vantagens do ponto de vista ambiental, n?o contribuindo com o aumento da concentra??o de CO2 na atmosfera. No entanto, a produ??o de hidrog?nio atrav?s dos processos de reforma, embora promissora, ainda apresenta muitos gargalos tecnol?gicos, necessitando de avan?os em novos materiais com propriedades catal?ticas. Dentro desta proposta, este trabalho teve como objetivo obter materiais catal?ticos com alta reatividade e seletividade para produtos frente ?s rea??es de reforma a vapor do etanol (RVE) e reforma a seco do metano (RSM). Desta maneira, catalisadores a base de n?quel e cobalto suportado em SBA-15 foram preparados pelo m?todo de impregna??o via ?mida e caracterizados antes e ap?s os testes catal?ticos, pelas t?cnicas: An?lise Termogravim?trica (TGA), Espectroscopia na Regi?o do Infravermelho (IR), Difra??o de Raios X (DRX), An?lise de Redu??o ? Temperatura Programada (RTP), Adsor??o e Dessor??o de Nitrog?nio, Difra??o de Raios X in situ (DRX in situ) e Microscopia Eletr?nica por Varredura (MEV) com Espectroscopia de Energia Dispersiva (EDS), visando ? compreens?o dos mecanismos envolvidos nas rea??es de reforma e tamb?m respons?veis pela deposi??o de carbono sobre os catalisadores. Os catalisadores testados frente ? rea??o a vapor do etanol durante 6 horas a 500 ?C apresentaram convers?o inicial em torno de 80-100 %, com produ??o de H2 (60-70 %), CO2 (18-23 %) e com apenas tra?os de CO (0,5-10 %). No entanto, estes catalisadores sofreram r?pida desativa??o nas primeiras horas de teste, sendo mais promissores frente ? rea??o de reforma a seco do metano, os quais apresentaram boa atividade catal?tica e estabilidade durante 10 horas de rea??o a 700 ?C, com convers?es (CH4 e CO2) e rendimentos a H2 acima de 80 % e baixa deposi??o de carbono. / In the last years, the processes of reform for the production of hydrogen as an energetic vector have been well studied because of the increase of the demand for alternative technologies of energy generation, showing a good relation cost/benefit when compared to other technologies of hydrogen production. In addition, they have advantages from an environmental point of view, not contributing to the increase of CO2 concentration in the atmosphere. However, hydrogen production through reform processes, while promising, still presents many technological bottlenecks, requiring advances in new materials with catalytic properties. In this proposal, the goal of this work is to obtain catalytic materials with high reactivity and selectivity for products in the face of reactions of steam reforming of ethanol (SRE) and dry reforming of methane (DRM). Catalysts based on nickel and cobalt supported on SBA-15 were prepared by wet impregnation method and characterized before and after the catalytic tests by several techniques: Thermogravimetric Analysis (TGA), Fourier Transformer Infrared Spectroscopy (FT- IR), X-ray diffraction (XRD), Temperature Programmed Reduction (TPR), Nitrogen Adsorption and Desorption, X-ray Diffraction in situ (XRD in situ), and Scanning Electron Microscopy (SEM) with Energy Spectroscopy (ES) to understanding the mechanisms involved in the reforming reactions and also responsible for the deposition of carbon on the catalysts. The catalysts tested against the steam reaction of ethanol for 6 hours at 500 ?C presented an initial conversion around 80-100 %, with H2 (60-70 %), CO2 (18-23 %) and only traces of CO (0.5-10 %), but they suffered a rapid deactivation in the first hours of test, being more promising in the dry reforming reaction of methane, which showed good activity and stability during 10 hours of reaction at 700 ?C with conversions (CH4 and CO2) and H2 yields above 80 % and low carbon deposition.

Made available in DSpace on 2014-12-17T15:42:09Z (GMT). No. of bitstreams: 1 SolangeAQ_TESE.pdf: 2741616 bytes, checksum: ad21da6882b166123a02d610e3d096ef (MD5) Previous issue date: 2009-08-06 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The nanostructured molecular sieve SBA-15 was synthesized by the hydrothermal method, and modified with lanthanum with Si/La molar ratios of 25, 50, 75 and 100. The materials were evaluated as catalysts for the cracking of n-hexane model reaction. Type SBA- 15 and LaSBA-15 mesoporous materials were synthesized using tetraetilortosilicato as a source of silica, hydrochloric acid, heptahydrate lanthanum chloride and distilled water. Pluronic P123 triblock. polymer was used as structure template. The syntheses were carried out by 72 hours. The obtained SBA-15 samples were previously analyzed by thermogravimetry, in order to check the conditions of calcination for removal of organic template. Then, the calcined materials were characterized by X-ray diffraction, infrared spectroscopy, adsorption and desorption of nitrogen, scanning electron microscopy and X-ray microanalysis by dispersive energy. The acidity of the samples was determined using adsorption of n-bulinamina and desorption followed by thermogravimetry. It was found that the hydrothermal synthesis method was suitable for the synthesis of the SBA-15 mesoporous materials, with an excellent degree of hexagonal ordering. The reactions of catalytic cracking of n-hexane were carried out using a fixed bed continuous flow microreactor, coupled on-line to a gas chromatograph. From the catalytic evaluation, it was observed that the mesoporous materials containing lanthanum showed different results for the reaction of cracking of nhexane compared to the unmodified mesoporous material SBA-15. As a result of cracking was obtained as main products hydrocarbons in the range of C1 to C5. The catalyst that showed better properties in relation to the acidity and catalytic activity was LaSBA-15 with the ratio Si/La = 50 / A peneira molecular nanoestruturada SBA-15 foi sintetizada pelo m?todo hidrot?rmico, e modificada com lant?nio com raz?es molares Si/La de 25, 50, 75 e 100. Os materiais obtidos foram avaliados como catalisador para a rea??o modelo de craqueamento de n-hexano. Os materiais mesoporosos tipo SBA-15 e LaSBA-15 foram sintetizados utilizando tetraetilortosilicato, como fonte de s?lica, ?cido clor?drico, cloreto de lant?nio heptahidratado e ?gua destilada. Como direcionador estrutural foi utilizado copol?mero tribloco Pluronic P123. As s?nteses foram realizadas durante 72 horas. As amostras de SBA-15 modificadas foram avaliadas por termogravimetria para verificar as condi??es de calcina??o para remo??o do direcionador org?nico. Ap?s a retirada do direcionador as amostras de SBA-15 modificadas com diversas raz?es Si/La (25, 50, 75 e 100) foram caracterizadas por an?lises por difra??o de raios-X, espectroscopia na regi?o do infravermelho, adsor??o e dessor??o de nitrog?nio, microscopia eletr?nica de varredura e microan?lise de raios X por energia dispersiva. A acidez das amostras foi determinada utilizando adsor??o de n-bulinamina seguido de dessor?ao por termogravimetria. Verificou-se que o m?todo de s?ntese hidrot?rmica foi adequado ? s?ntese dos materiais mesoporosos modificados com excelente grau de ordena??o hexagonal. As rea??es de craqueamento catal?tico do n-hexano foram realizadas em um microreator catal?tico de leito fixo com fluxo cont?nuo acoplado em linha com um cromat?grafo a g?s. A partir da avalia??o catal?tica, foi observado que os materiais mesoporosos contendo lant?nio foram mais ativos que o SBA-15, para a rea??o de craqueamento do n-hexano, obtendo-se como produto hidrocarbonetos na faixa de C1 a C5. O catalisador que apresentou melhores propriedades, em rela??o ? acidez e a atividade catal?tica foi o sintetizado com a raz?o Si/La=50

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-12-12T18:02:43Z No. of bitstreams: 1 GilvanPereiraDeFigueredo_TESE.pdf: 4395902 bytes, checksum: dcc65d04331c39ac75781ca0d55044db (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-12-13T18:29:41Z (GMT) No. of bitstreams: 1 GilvanPereiraDeFigueredo_TESE.pdf: 4395902 bytes, checksum: dcc65d04331c39ac75781ca0d55044db (MD5) / Made available in DSpace on 2017-12-13T18:29:41Z (GMT). No. of bitstreams: 1 GilvanPereiraDeFigueredo_TESE.pdf: 4395902 bytes, checksum: dcc65d04331c39ac75781ca0d55044db (MD5) Previous issue date: 2017-08-11 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / Os materiais cer?micos apresentam diversas aplica??es, principalmente por sua versatilidade e propriedades. V?rias metodologias foram consolidadas para a s?ntese destes materiais, mas algumas desvantagens limitam sua aplicabilidade em cat?lise. Assim, h? muitas pesquisas concentradas no estudo de m?todos de s?ntese de catalisadores e suportes catal?ticos que sejam simples, r?pidos, de baixo custo, ecol?gicos e que produzam materiais adequados. Nos ?ltimos anos algumas rotas alternativas de s?ntese t?m atra?do bastante aten??o, mas a obten??o do espin?lio MgAl2O4 pelo m?todo da gelatina e da perovskita LaAlO3 via rea??o de combust?o assistida por microondas tem sido pouco explorada. O MgAl2O4 ? bastante utilizado na reforma a seco do metano (RSM), mas estudos de RSM usando LaAlO3 como suporte s?o muito limitados. Neste contexto, os objetivos deste trabalho foram: sintetizar MgAl2O4 usando gelatina como precursor org?nico; preparar a perovskita LaAlO3 via rea??o de combust?o assistida por microondas; e, comparar o desempenho em reforma a seco do metano de dois catalisadores preparados com n?quel suportado no LaAlO3 e na ?-Al2O3 comercial. Pelo m?todo da gelatina foi poss?vel obter MgAl2O4 puro, nanom?trico e com cristalinidade de at? 90,40%. Um aumento brusco no tamanho dos cristalitos foi observado para temperatura de calcina??o acima de 900 ?C. Na s?ntese por microondas, a perovskita LaAlO3 monof?sica e nanom?trica foi obtida. Os perfis de RTP-H2 mostram que as vac?ncias de oxig?nio presentes na superf?cie da perovskita exerceram um forte efeito sobre a temperatura de redu??o e a redutibilidade das nanopart?culas de NiO, resultando em fraca intera??o Ni0/LaAlO3. Os resultados dos testes de 10 h com GHSV de 18 L g-1 h-1 mostram que o catalisador Ni/LaAlO3 ? 7,8 e 11,5 % mais est?vel do que o Ni/?-Al2O3 nas convers?es de CH4 e CO2, respectivamente. A maior estabilidade e atividade do Ni/LaAlO3 est? diretamente relacionada ? presen?a de NiO (3,38 %p) ap?s a ativa??o, que promoveu a forma??o de nanotubos de carbono (NTC), aumentando a dispers?o da fase met?lica. Mesmo em condi??es severas de ativa??o e rea??o (alta GHSV), como no teste a longo prazo (20 h), o catalisador Ni/LaAlO3 revelou um rendimento em H2 de 37,2% a mais que o Ni/?-Al2O3. As an?lises por Microscopia Eletr?nica de Transmiss?o (MET) revelam que o catalisador Ni/?-Al2O3 desativou por sinteriza??o. Assim, a presen?a de defeitos estruturais e de superf?cies ricas em vac?ncias de oxig?nio tornam a perovskita LaAlO3 um potencial suporte para aplica??o em processos de reforma catal?tica do metano. / Ceramic materials have several applications, mainly due to their versatility and properties. Several methodologies have been consolidated for the synthesis of these materials, but some disadvantages limit their applicability in catalysis. Thus, much research is concentrated on the study of catalyst synthesis methods that are simple, fast, low cost, ecofriendly and produce suitable materials. In recent years, some alternative synthesis routes have attracted great attention, however the obtainment of MgAl2O4 spinel by the gelatin method and perovskite LaAlO3 via microwave assisted combustion method has been little explored. MgAl2O4 is widely used in the dry reforming of methane (DRM), but DRM studies using LaAlO3 as support are very limited. In this context, the aims of this work were: to synthesize MgAl2O4 using gelatin as an organic precursor; to prepare LaAlO3 perovskite via microwave assisted combustion reaction; and to compare the methane dry reforming performance of two nickel catalysts supported on LaAlO3 and commercial ?-Al2O3. By the gelatin method it was possible to obtain pure and nano-sized MgAl2O4 with crystallinity of up to 90.40%. An abrupt increase in crystallite size was observed for calcination temperatures above 900 ?C. In the microwave synthesis, a monophasic and nano-sized LaAlO3 perovskite was obtained. The TPR-H2 profiles show that the oxygen vacancies present on the perovskite surface exerted a strong effect on the reduction temperature and the reducibility of NiO nanoparticles, resulting in poor Ni0/LaAlO3 interaction. The results of the 10 h catalytic tests with GHSV of 18 L g-1 h-1 show that the Ni/LaAlO3 catalyst is 7.8 and 11.5% more stable than Ni/?-Al2O3 for CH4 and CO2 conversions, respectively. The higher stability and activity of Ni/LaAlO3 is directly related to the presence of NiO (3.38% p) after activation, which promoted the formation of carbon nanotubes (CNT), increasing the dispersion of the metal phase. Even under severe activation and reaction conditions (high GHSV) as in the long-term test (20 h), Ni/LaAlO3 catalyst showed a H2 yield of 37.2% higher than Ni/?-Al2O3. Transmission Electron Microscopy (MET) analyzes revealed that the Ni/?-Al2O3 catalyst deactivated by sintering. Thus, the presence of structural defects and surfaces rich in oxygen vacancies makes the LaAlO3 perovskite a potential support for application in processes of catalytic reforming of methane.