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 2018-03-02T23:17:20Z No. of bitstreams: 1 AndersonDeAzevedoGomesSantiago_DISSERT.pdf: 24209731 bytes, checksum: 05db1a373581407b4becff19ecbe7250 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2018-03-13T18:12:44Z (GMT) No. of bitstreams: 1 AndersonDeAzevedoGomesSantiago_DISSERT.pdf: 24209731 bytes, checksum: 05db1a373581407b4becff19ecbe7250 (MD5) / Made available in DSpace on 2018-03-13T18:12:44Z (GMT). No. of bitstreams: 1 AndersonDeAzevedoGomesSantiago_DISSERT.pdf: 24209731 bytes, checksum: 05db1a373581407b4becff19ecbe7250 (MD5) Previous issue date: 2017-12-18 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Os molibdatos v?m sendo objeto de estudos devido as suas diversas aplica??es. Entre os molibdatos, o molibdato de b?rio (BaMoO4) e molibdato de zinco (ZnMoO4) t?m se destacado pelas suas interessantes propriedades fotoluminescentes, com emiss?es de luz na regi?o do azul, verde e laranja, e pelos seus diferentes m?todos de obten??o, como hidrotermal, sol-gel e coprecipita??o. P?s de Ba1-xZnxMoO4 (x=0; 0,25; 0,50; 0,75 e 1) foram sintetizados, em etapa ?nica, pelo m?todo de spray pir?lise ultrass?nico, utilizando temperaturas de 1000 ?C e 1100 ?C. O tempo para forma??o das part?culas dentro do reator foi de aproximadamente 1 min. As amostras foram caracterizadas estruturalmente pela t?cnica de difra??o de raios X e morfologicamente pela t?cnica de microscopia eletr?nica de varredura de emiss?o de campo (MEV-FEG). As propriedades ?pticas das amostras foram estudadas utilizando as espectroscopias de UV-vis?vel e de fotoluminesc?ncia (FL). Os padr?es de DRX mostraram que as amostras com x = 0 e x = 1 t?m estrutura cristalina scheelita tetragonal e tricl?nica, respectivamente, sem a presen?a de fases secund?rias. Por outro lado, as amostras com x = 0,25, 0,50 e 0,75 revelaram a forma??o de uma heteroestrutura tetragonal/tricl?nica, em que ocorre substitui??o at?mica de Ba2+ por Zn2+ na estrutura tetragonal do BaMoO4 e na estrutura tricl?nica do ZnMoO4 ocorrendo a substitui??o at?mica de Zn2+ por Ba2+. As micrografias de MEV-FEG demostraram que as part?culas obtidas t?m morfologia predominantemente esf?rica, com di?metros que variam entre 100 e 1500 nm. A energia de gap dos Ba1-xZnxMoO4 variou entre 4,56 eV ? 4,17 eV, com os p?s com x = 0 se obteve os valores mais elevados (4,54 eV e 4,56 eV) e os p?s com x = 1 os valores mais baixos (4,17 eV e 4,26 eV). Dessa forma, foi percebido que as energias de gap das amostras diminuem com o aumento do valor de x, ou seja, com aumento da substitui??o dos ?tomos de Ba2+ pelos de Zn2+. Os espetros fotoluminescentes (FL) das amostras apresentaram comportamento banda larga, com emiss?o predominante na regi?o laranja-vermelho e pequena contribui??o de emiss?o da regi?o azul-verde, com a amostra de x = 0,75 obtida ? 1000 ?C mostrando maior intensidade FL. As coordenadas de cromaticidade x e y mostraram que as amostras com x ? 0,75 apresentam emiss?o em laranja, entretanto, as amostras com x = 1 apresentaram emiss?o em branco, podendo ser um candidato promissor para aplica??es em diodos emissores de luz. / The molybdates have been the subject of studies due to their various applications. Among the molybdates, the barium molybdate (BaMoO4) and zinc molybdate (ZnMoO4) have been standing out by its interesting photoluminescent properties, with light emissions in the region of the blue, green and orange, and by its different methods of obtaining, such as hydrothermal, sol-gel and coprecipitation. Ba1-xZnxMoO4 (x = 0, 0.25, 0.50, 0.75 and 1) powders were synthesized, in a one-step, by the ultrasonic spray pyrolysis method, using temperatures of 1000 ?C and 1100 ?C. Time for particle formation within the reactor was approximately 1 min. The samples were structurally characterized by the X-ray diffraction and morphologically by the field emission scanning electron microscopy (FESEM). Optical properties of the samples were studied using UV-visible and photoluminescence (PL) spectroscopies. The DRX patterns showed that the samples with x = 0 and x = 1 have crystalline tetragonal scheelite and triclinic structure, respectively, without the presence of secondary phases. On the other hand, the samples with x = 0.25, 0.50 and 0.75 revealed the formation of a heterostructure tetragonal/triclinic, in which atomic substitution of Ba2+ by Zn2+ in the tetragonal structure of the BaMoO4 and triclinic structure of the ZnMoO4 occurring the atomic substitution of Zn2+ by Ba2+. FESEM micrographs showed that the particles obtained have predominantly spherical morphology with diameters ranging from 100 to 1500 nm. The gap energy of the Ba1-xZnxMoO4 ranged from 4.56 eV to 4.17 eV, with the powders with x = 0, obtaining the highest values (4.54 eV and 4.56 eV) and the powders with x = 1 the lowest values (4.17 eV and 4.26 eV). In this way, it was noticed that the gap energies of the samples decrease with the increase of the value of x, that is, with increasing substitution of the Ba2+ for the Zn2+ atoms. Photoluminescent (PL) spectra of the samples showed broad band behavior, with predominant emission in the orange-red region and small emission contribution of the blue-green region, with the sample of x = 0.75 obtained at 1000 ? C showing higher PL intensity. The chromaticity coordinates x and y showed that the samples with x ? 0.75 exhibit in orange emission, however, the samples with x = 1 presented white emission, can be a promising candidate for applications in light emitting diodes.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-03-17T19:32:34Z No. of bitstreams: 1 RegineideDeOliveiraLima_TESE.pdf: 4803577 bytes, checksum: 6d7e58376e418b1ba438c2b3c932552e (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-03-18T00:12:17Z (GMT) No. of bitstreams: 1 RegineideDeOliveiraLima_TESE.pdf: 4803577 bytes, checksum: 6d7e58376e418b1ba438c2b3c932552e (MD5) / Made available in DSpace on 2017-03-18T00:12:17Z (GMT). No. of bitstreams: 1 RegineideDeOliveiraLima_TESE.pdf: 4803577 bytes, checksum: 6d7e58376e418b1ba438c2b3c932552e (MD5) Previous issue date: 2016-07-26 / A ind?stria de petr?leo gera diferentes res?duos e as ze?litas possuem grande import?ncia no tratamento e beneficiamento dos res?duos da ind?stria de refino de petr?leo e petroqu?mica por apresentarem propriedades peculiares. Neste contexto, o presente trabalho relata o estudo de ze?litas ZSM-5 com estruturas hier?quicas de poros, sintetizadas utilizando como agente silanizante, o fenilaminopropiltrimetoxisilano (PHAPTMS) nas concentra??es de 15 mol%, 17 mol% e 20 mol%, visando aplica??o do melhor material na pir?lise termocatal?tica de res?duos gerados e derivados da ind?stria de petr?leo. As s?nteses das ZSM-5 tamb?m foram realizadas na aus?ncia de direcionador org?nico de estutura, assistido pelo m?todo de indu??o por semente na forma de p?, submetidas a 180 ?C, por 27 h, sendo os per?odos de interrup??o da cristaliza??o em 8, 12 e 16 h para adi??o do PHAPTMS. Os materiais foram sintetizados e caracterizados pelos m?todos de difra??o de raios X (DRX), espectroscopia na regi?o do infravermelho por transformada de Fourier (FTIR), an?lise t?rmica (TG/DTG), acidez superficial medidas atrav?s da dessor??o de n-butilamina por termogravimetria (TG) e FTIR, microscopia eletr?nica de varredura (MEV) e adsor??o de nitrog?nio. Ainda foi realizado um estudo do comportamento cin?tico atrav?s da termogravimetria dos RAT, PEAD e sobre os catalisadores. Atrav?s do modelo cin?tico model-free, utilizando as curvas integrais TG, foram estimados a energia de ativa??o, as taxas de convers?o e o tempo degrada??o dos res?duos em fun??o da temperatura. Notou-se que para os materiais sintetizados com 15 mol% de PHAPTMS nos per?odos de 8, 12 e 16 h apresentaram maiores concentra??es dos s?tios ativos, acidez superficial, tornando promissores na degrada??o de PEAD. O estudo cin?tico feito em PEAD pelo m?todo Vyazovkin revelou uma menor energia de ativa??o para o material HZ5 15 mol% no per?odo de 16 h. Tamb?m foi revelado um abaixamento da energia de ativa??o quando utilizou esse material no estudo cin?tico para o RAT. Na pir?lise t?rmica e termocatal?tica dos res?duos realizadas nas temperaturas de 500 ?C, 475 ?C, 450 ?C. Foi escolhido para aplica??o na pir?lise termocatal?tica, o material, (HZ5 15 mol% 16 h), por apresentar melhor acidez e menor energia requerida para a degrada??o de PEAD. Na pir?lise termocatal?tica sobre PEAD proporcionou seletividade de produtos com valores agregados, os quais podem ser utilizados na ind?stria petroqu?mica. Na pir?lise termocatal?tica de RAT este material potencializou as faixas de hidrocarbonetos de C1-C4; C5-C12, C13-C19 referentes ao GLP, gasolina e diesel. Proporcionando melhores cargas no processo e reduzindo os res?duos gerados durante o refino de petr?leo. / The petroleum industry generates different residues and zeolites are of great importance in the treatment and processing of residues of the petroleum refining and petrochemical industry for having peculiar properties. In this context, this paper reports the zeolites study ZSM-5 with hierarchically structures of pores, synthesized using as silanizante agent phenylaminopropyl trimethoxysilane (PHAPTMS) at concentrations of 15mol%, 17mol% and 20mol%, aiming at implementing the best material in thermo catalytic pyrolysis of the waste generated of the petroleum industry. The synthesis of ZSM-5 were also conducted without organic template, assisted by the seed induction method in the form of powder, subjected to 180 ?C for 27 h, the crystallization interrupt periods at 8, 12 and 16 h for addition of PHAPTMS. The materials were synthesized and characterized by the methods of X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermal analysis (TG / DTG), surface acidity measured by n-butylamine desorption thermogravimetric analysis (TG) and FTIR, scanning electron microscopy (SEM), nitrogen adsorption. The kinetic study by thermogravimetry of pure RAT and HDPE waste was performed with and without catalyst. Through model-free kinetic method using the integral curves TG, were estimated activation energy, conversion rates and time degradation of waste in function of temperature. It was noted that for the materials synthesized with 15mol% of PHAPTMS in periods of 8, 12 and 16h showed higher concentrations of the active sites, surface acidity, making promising in HDPE degradation. The kinetic study of HDPE by Vyazovkin method showed a lower activation energy for the HZ5 15mol% material in the 16 h period. Also a lowering of the activation energy was revealed when used this material in the kinetic study for the RAT. In the thermal pyrolysis and thermalcatalytic of waste carried out at temperatures of 500 ?C, 475 ?C, 450 ?C. It was chosen for use in thermalcatalytic pyrolysis, the material (HZ5 15mol% 16h) due to better acidity and lower energy required for the degradation of HDPE. In thermalcatalytic pyrolysis of HDPE selectivity afforded products with added values, which can be used in the petrochemical industry. In thermalcatalytic pyrolysis RAT This material potentiated C1-C4 hydrocarbon groups; C5-C12, C13-C19 regarding the LPG, gasoline and diesel. Providing better loads in the process and reducing the waste generated during petroleum refining.

Made available in DSpace on 2014-12-17T15:41:53Z (GMT). No. of bitstreams: 1 RicardoMO_DISSERT.pdf: 2015893 bytes, checksum: dea62cb9390752fd7430293c73c9a1dd (MD5) Previous issue date: 2011-12-06 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The catalytic cracking of triglycerides presents itself as a possible alternative to the production of biofuels with low emission of pollutants. In this work were synthesized the SAPO-5, the catalysts for the cracking reaction of soybean oil is presented. The solids were powder X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG) and infrared spectroscopy (FTIR). The analyses indicated that the synthesis method has employed to obtain materials with high surface area and high acid. The soybean 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. The products obtained in the cracking of soybean oil were analyzed by distillation, acid number, infra-red spectroscopy, density, viscosity, carbon residue, cetane number determination and characterization. The analysis of the products obtained in the presence and in the absence of the SAPO-5 permitted to conclude that all the solids tested presented catalytic activity in the deoxygenation of final products only at the second step of the cracking process / O craqueamento catal?tico de triacilglicer?deos se apresenta como uma alternativa vi?vel para a produ??o de biocombust?veis com baixa emiss?o de poluentes. Neste trabalho foi sintetizado o SAPO-5, o catalisador foi utilizado na rea??o de craqueamento do ?leo de Girassol. O s?lido foi caracterizado por difra??o de raios -X, an?lise termogravim?trica, espectroscopia no infravermelho. As an?lises indicaram que atrav?s do m?todo de s?ntese empregado foram obtidos materiais com elevada ?rea espec?fica e alta acidez. A partir do craqueamento t?rmico e termocatal?tico do ?leo de girassol, realizado desde a temperatura ambiente at? 450 oC em um sistema de destila??o simples, foram obtidas duas fra??es l?quidas, cada uma contendo duas fases, uma aquosa e outra org?nica. A primeira fra??o do l?quido org?nico obtido apresentou alto ?ndice de acidez, no processo de craqueamento t?rmico. Os produtos obtidos no craqueamento de ?leo de Girassol foram analisados por destila??o, ?ndice de acidez, espectroscopia no infravermelho, densidade, viscosidade e determina??o do ?ndice de cetano. A an?lise dos produtos obtidos na presen?a e na aus?ncia do SAPO-5, sintetizados permitiu concluir que todos os s?lidos testados apresentaram atividade catal?tica para a desoxigena??o dos produtos finais apenas na segunda etapa do processo de craqueamento

Made available in DSpace on 2014-12-17T14:08:46Z (GMT). No. of bitstreams: 1 AnelieseLF_DISSERT.pdf: 3198107 bytes, checksum: 808e93eb6952cb8e374d91afa53cabe1 (MD5) Previous issue date: 2011-07-01 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / This master thesis aims at developing a new methodology for thermochemical degradation of dry coconut fiber (dp = 0.25mm) using laboratory rotating cylinder reactor with the goal of producing bio-oil. The biomass was characterized by infrared spectroscopy with Fourier transform FTIR, thermogravimetric analysis TG, with evaluation of activation energy the in non-isothermal regime with heating rates of 5 and 10 ?C/min, differential themogravimetric analysis DTG, sweeping electron microscopy SEM, higher heating value - HHV, immediate analysis such as evaluated all the amounts of its main constituents, i.e., lignin, cellulose and hemicelluloses. In the process, it was evaluated: reaction temperature (450, 500 and 550oC), carrier gas flow rate (50 and 100 cm?/min) and spin speed (20 and 25 Hz) to condensate the bio-oil. The feed rate of biomass (540 g/h), the rotation of the rotating cylinder (33.7 rpm) and reaction time (30 33 min) were constant. The phases obtained from the process of pyrolysis of dry coconut fiber were bio-oil, char and the gas phase non-condensed. A macroscopic mass balance was applied based on the weight of each phase to evaluate their yield. The highest yield of 20% was obtained from the following conditions: temperature of 500oC, inert gas flow of 100 cm?/min and spin speed of 20 Hz. In that condition, the yield in char was 24.3%, non-condensable gas phase was 37.6% and losses of approximately 22.6%. The following physicochemical properties: density, viscosity, pH, higher heating value, char content, FTIR and CHN analysis were evaluated. The sample obtained in the best operational condition was subjected to a qualitative chromatographic analysis aiming to know the constituents of the produced bio-oil, which were: phenol followed by sirigol, acetovanilona and vinyl guaiacol. The solid phase (char) was characterized through an immediate analysis (evaluation of moisture, volatiles, ashes and fixed carbon), higher heating value and FTIR. The non-condensing gas phase presented as main constituents CO2, CO and H2. The results were compared to the ones mentioned by the literature. / O presente trabalho tem como objetivo o desenvolvimento de uma metodologia de degrada??o termoqu?mica da fibra do coco seco (dp = 0,25 mm) utilizando reator de cilindro rotativo em escala de laborat?rio, visando a produ??o de bio-?leo. A biomassa foi caracterizada por an?lise elementar (C, H, N), espectroscopia no infravermelho com transformada de Fourier - IVTF, an?lise termogravim?trica ATG, com avalia??o da energia de ativa??o no regime n?o isot?rmico com taxas de aquecimento de 5 e 10 oC/min, an?lise diferencial termogravim?trica - DTG, microscopia eletr?nica de varredura - MEV, poder calor?fico superior - PCS, an?lise imediata (avalia??o da umidade, materiais vol?teis, cinzas e carbono fixo) bem como avalia??o dos teores dos principais constituintes, ou seja, lignina, celulose e hemicelulose. No processo de pir?lise os seguintes par?metros foram estudados: temperatura da rea??o (450, 500 e 550 ?C), vaz?o do g?s de arraste (50 e 100 cm?/min) e velocidade de centrifuga??o para condensa??o do bio-?leo (20 e 25 Hz). O fluxo de alimenta??o da biomassa (540 g/h), a rota??o do cilindro rotativo (33,7 rpm) e o tempo de rea??o (30 33 min) foram mantidos constantes. Os produtos obtidos no processo da pir?lise da fibra do coco seco foram o bio-?leo, os finos de carv?o e a fase gasosa n?o condensada. Um balan?o de massa macrosc?pico aplicado tendo como base o peso de cada produto permitiu obter o rendimento dessas fases. O melhor rendimento de 18,1 % em bio-?leo foi obtido nas seguintes condi??es: temperatura de 500 ?C, vaz?o de g?s inerte 100 cm?/min e velocidade de centrifuga??o de 20 Hz. Nessas condi??es, o rendimento em finos de carv?o foi de 21,7 %, fase gasosa n?o condens?vel 37,6 % e perdas da ordem de 22,6 %. Algumas propriedades f?sicas do bio-?leo foram avaliadas, a saber, a densidade, viscosidade, pH, poder calor?fico superior, teor de finos de carv?o, an?lise por IVTF e CHN. A an?lise cromatogr?fica do bio-?leo mostrou que os principais constituintes de sua composi??o foram o fenol seguido do sirigol, aceto vanilona e vinil guaiacol. A fase s?lida (finos de carv?o) obtida foi caracterizada por an?lise imediata, poder calor?fico superior e IVTF. A fase gasosa n?o condensada apresentou como principais constituintes o CO2, CO e H2. Os resultados foram comparados com dados da literatura.

Made available in DSpace on 2014-12-17T14:09:12Z (GMT). No. of bitstreams: 1 LucioAOF_TESE.pdf: 1700370 bytes, checksum: e23b516b6b57629ea655b3a1c24fcf35 (MD5) Previous issue date: 2011-05-27 / The demand for alternative sources of energy drives the technological development so that many fuels and energy conversion processes before judged as inadequate or even non-viable, are now competing fuels and so-called traditional processes. Thus, biomass plays an important role and is considered one of the sources of renewable energy most important of our planet. Biomass accounts for 29.2% of all renewable energy sources. The share of biomass energy from Brazil in the OIE is 13.6%, well above the world average of participation. Various types of pyrolysis processes have been studied in recent years, highlighting the process of fast pyrolysis of biomass to obtain bio-oil. The continuous fast pyrolysis, the most investigated and improved are the fluidized bed and ablative, but is being studied and developed other types in order to obtain Bio-oil a better quality, higher productivity, lower energy consumption, increased stability and process reliability and lower production cost. The stability of the product bio-oil is fundamental to designing consumer devices such as burners, engines and turbines. This study was motivated to produce Bio-oil, through the conversion of plant biomass or the use of its industrial and agricultural waste, presenting an alternative proposal for thermochemical pyrolysis process, taking advantage of particle dynamics in the rotating bed that favors the right gas-solid contact and heat transfer and mass. The pyrolyser designed to operate in a continuous process, a feeder containing two stages, a divisive system of biomass integrated with a tab of coal fines and a system of condensing steam pyrolytic. The prototype has been tested with sawdust, using a complete experimental design on two levels to investigate the sensitivity of factors: the process temperature, gas flow drag and spin speed compared to the mass yield of bio-oil. The best result was obtained in the condition of 570 oC, 25 Hz and 200 cm3/min, temperature being the parameter of greatest significance. The mass balance of the elementary stages presented in the order of 20% and 37% liquid pyrolytic carbon. We determined the properties of liquid and solid products of pyrolysis as density, viscosity, pH, PCI, and the composition characterized by chemical analysis, revealing the composition and properties of a Bio-oil. / A demanda por fontes alternativas de energia impulsiona o desenvolvimento tecnol?gico de tal forma que muitos combust?veis e processos de convers?o energ?tica, antes julgada como inadequados ou mesmo invi?veis, s?o agora concorrentes de combust?veis e processos ditos tradicionais. Assim, a biomassa exerce um papel relevante, sendo considerada uma das fontes de energia renov?vel mais importante de nosso planeta. A biomassa contribui com 29,2 % de todas as fontes renov?veis de energia. A participa??o de energia de biomassa do Brasil na OIE ? de 13,6 %, sendo bem superior a m?dia mundial de participa??o. V?rios tipos de processos de pir?lise v?m sendo estudados nos ?ltimos anos, destacando-se o processo de pir?lise r?pida de biomassa para obten??o de Bio-?leo. Os processos cont?nuos de pir?lise r?pida, mais investigados e aprimorados s?o os de leito fluidizado e leito ablativo, entretanto vem sendo estudados e desenvolvidos outros tipos, visando obter um bio-?leo de melhor qualidade, com maior produtividade, menor consumo de energia, maior estabilidade e confiabilidade de processo e menor custo de produ??o. A estabilidade do produto Bio-?leo ? fundamental para a concep??o de dispositivos consumidores, tais como queimadores, motores de pist?o e turbinas. O presente estudo foi motivado para a produ??o de Bio-?leo, atrav?s da convers?o da biomassa vegetal ou do aproveitamento de seus res?duos industriais e agr?colas, sendo apresentada uma proposta alternativa de processo de pir?lise termoqu?mica, aproveitando a vantagem din?mica das part?culas no leito rotativo o que favorece a raz?o de contato g?s-s?lido e a transfer?ncia de calor e massa. O pirolisador foi projetado para operar em processo cont?nuo, contendo um alimentador de dois est?gios, um sistema desagregador da biomassa integrado com um separador de finos de carv?o e um sistema de condensa??o de vapores pirol?ticos. O Prot?tipo foi submetido a ensaios com serragem de madeira, utilizando um planejamento experimental completo em dois n?veis para investigar a sensibilidade dos fatores: temperatura do processo, fluxo de g?s de arraste e velocidade de centrifuga??o em rela??o ao rendimento m?ssico de Bio-?leo. O melhor resultado foi obtido na condi??o de 570 oC, 25 Hz e 200 cm3/min, sendo a temperatura o par?metro de maior signific?ncia. O balan?o Tese de Doutorado PPGCEP/UFRN L?cio ?ngelo de Oliveira Fontes vi de massa elementar das fases apresentou da ordem de 20 % liquidos pirol?ticos e 37 % de carv?o. Foram determinadas as propriedades dos produtos l?quidos e s?lidos da pir?lise como densidade, viscosidade, pH, PCI, sendo a composi??o caracterizada atrav?s an?lise qu?mica, revelando as propriedades e composi??o de um Bio-?leo.

Made available in DSpace on 2014-12-17T14:09:14Z (GMT). No. of bitstreams: 1 RenataMB_TESE.pdf: 1339744 bytes, checksum: 24902b1b3636b97bbd787863d62c1f99 (MD5) Previous issue date: 2012-08-09 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc / A pir?lise r?pida da biomassa lignocelul?sica ? um processo de convers?o termoqu?mica para produ??o de energia que vem se tornando muito atratativo devido ao aproveitamento energ?tico de seus produtos: g?s (CO, CO2, H2, CH4, etc), l?quido (bio-?leo) e carv?o vegetal. O bio-?leo ? o principal produto da pir?lise r?pida, sendo a sua composi??o e caracter?sticas finais intrinsecamente relacionadas ? qualidade da biomassa (elimina??o de cinzas, teor de umidade, teor de celulose, hemicelulose e lignina) bem como ? efici?ncia da remo??o dos compostos oxigenados que causam caracter?sticas indesej?veis como aumento da viscosidade, instabilidade, corrosividade e baixo poder calor?fico. Os compostos oxigenados s?o originados no processo de pir?lise convencional da biomassa onde o uso de catalisadores s?lidos, em geral, permite a minimiza??o destes produtos melhorando a qualidade do produto final, o bio-?leo. O presente trabalho teve como objetivo avaliar os produtos da pir?lise catal?tica do capim elefante (Pennisetum purpureum Schum) utilizando catalisadores s?lidos, ?xidos a base de tungst?nio, suportados ou n?o em materiais mesoporosos do tipo MCM-41, derivados da s?lica da casca do arroz, visando ? redu??o de compostos oxigenados produzidos na pir?lise. O tratamento da biomasssa atrav?s da lavagem com ?gua aquecida (CEL) ou lavagem com solu??o ?cida (CELix), bem como a aplica??o de catalisadores a base de tungst?nio nos vapores provenientes do processo de pir?lise, teve a finalidade de melhorar a qualidade dos produtos da pir?lise. A pir?lise convencional e catal?tica da biomassa foram realizadas em um micro pirolisador, Py-5200, acoplado ao GC/MS. Os catalisadores sintetizados foram caracterizados por Difra??o de raios X, Espectroscopia na regi?o do infravermelho, Fluoresc?ncia de Raios X, Redu??o por Temperatura Programada e An?lise termogravim?trica. Estudos cin?ticos aplicando o modelo de Flynn Wall foram realizados com a finalidade de avaliar a energia de ativa??o aparente da decomposi??o t?rmica da holoceluloce nas amostras de capim elefante (CE, CEL e CELix). Os resultados mostraram a efici?ncia do processo de tratamento, reduzindo o teor de cinzas, como tamb?m foi observada a diminui??o na energia de ativa??o aparente dessas amostras. O processo de pir?lise catal?tica converteu a maioria dos produtos oxigenados do CE em arom?ticos como benzeno, tolueno, etilbenzeno, etc

Made available in DSpace on 2014-12-17T14:09:17Z (GMT). No. of bitstreams: 1 CiceroSL_TESE.pdf: 5334902 bytes, checksum: 41714ced8f45a82dbc84b8d2449a7bee (MD5) Previous issue date: 2014-03-21 / The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery / A borra oleosa (BO) de petr?leo ? uma mistura complexa de hidrocarbonetos, impurezas org?nicas, inorg?nicas e ?gua. Um dos grandes problemas encontrados atualmente na ind?stria de petr?leo ? o gerenciamento (acondicionamento, armazenamento, transporte e destino) de res?duos. Os nanomateriais (catalisadores) mesoporosos e microporosos s?o considerados promissores em processos de refino de petr?leo e como adsorventes para prote??o ambiental. O objetivo deste trabalho foi estudar a BO de petr?leo oriunda do processamento prim?rio (bruta e tratada) e res?duo de v?cuo, com aplica??o de an?lise termogravim?trica, t?cnica de pir?lise t?rmica e catal?tica com nanomateriais, visando a produ??o de derivado de petr?leo. As borras extra?das em um equipamento soxhlet foram analisadas por an?lise elementar, cromatografia em camada fina, termogravimetria (TG) e pir?lise acoplado a um cromatogr?fico gasoso/espectro de massa (Py-GC/MS). Os catalisadores AlMCM-41 e AlSBA-15 foram sintetizados com uma raz?o molar de s?licio/alum?nio de 50 (Si/Al = 50), usando tetraetilortossilicato (TEOS) como fonte de sil?cio e pseudobuhemita (AlOOH) como a fonte de alum?nio. Os catalisadores indicam que os materiais apresentaram estrutura hexagonal, ?rea espec?fica de 783,6 m2/g para o AlMCM-41, 600 m2/g para o AlSBA-15.1 e 377 m2/g para o AlSBA-15.2). A BO extra?da apresentou de 65 a 95% de componentes org?nicos (?leo), de 5 a 35% de componentes inorg?nicos (sais e ?xidos) e diferentes composi??es dos derivados. Os catalisadores tipo AlSBA-15 apresentaram melhor desempenho na obten??o dos derivados de petr?leo, aumentando em 20% a produ??o de querosene e gas?leo leve. O potencial energ?tico da BO foi elevado, pois ela pode ser utilizada como combust?vel e processada com outras cargas pesadas do petr?leo para a produ??o de diferentes derivados de petr?leo

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 2014-12-17T15:01:31Z (GMT). No. of bitstreams: 1 MayaraOL_DISSERT.pdf: 2406797 bytes, checksum: e542f1e52029a933cac4b8af8d311ef3 (MD5) Previous issue date: 2012-12-27 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / This work depicts a study of the adsorption of carbon dioxide on zeolite 13X. The activities were divided into four stages: study batch adsorption capacity of the adsorbent with synthetic CO2 (4%), fixed bed dynamic evaluation with the commercial mixture of gases (4% CO2, 1.11% CO, 1 2% H2, 0.233% CH4, 0.1% C3, 0.0233% C4 argon as inert closing balance), fixed bed dynamic modeling and evaluation of the breakthrough curve of CO2 originated from the pyrolysis of sewage sludge. The sewage sludge and the adsorbent were characterized by analysis TG / DTA, SEM, XRF and BET. Adsorption studies were carried out under the following operating conditions: temperature 40 ?C (for the pyrolysis of the sludge T = 600 ?C), pressures of 0.55 to 5.05 bar (batch process), flow rate of the gaseous mixture between 50 - 72 ml/min and the adsorbent masses of 10, 15 and 20 g (fixed bed process). The time for the adsorption batch was 7 h and on the fixed bed was around 180 min. The results of this study showed that in batch adsorption process step with zeolite 13X is efficient and the mass of adsorbed CO2 increases with the increases pressure, decreases with temperature increases and rises due the increase of activation temperature adsorbent. In the batch process were evaluated the breakthrough curves, which were compared with adsorption isotherms represented by the models of Langmuir, Fre?ndlich and Toth. All models well adjusted to the experimental points, but the Langmuir model was chosen in view of its use in the dynamic model does not have implications for adsorption (indeterminacy and larger number of parameters such as occurred with others) in solving the equation. In the fixed bed dynamic study with the synthetic gas mixture, 20 g of mass adsorbent showed the maximum adsorption percentage 46.7% at 40 ?C temperature and 50 mL/min of flow rate. The model was satisfactorily fitted to the three breakthrough curves and the parameters were: axial dispersion coefficient (0.0165 dm2/min), effective diffusivity inside the particle (dm2/min 0.0884) and external transfer coefficient mass (0.45 dm/min). The breakthrough curve for CO2 in the process of pyrolysis of the sludge showed a fast saturation with traces of aerosols presents in the gas phase into the fixed bed under the reaction process / O presente trabalho retrata um estudo da adsor??o de di?xido de carbono em ze?lita comercial do tipo 13X. As atividades desenvolvidas foram divididas em quatro etapas: estudo em batelada da capacidade de adsor??o do adsorvente com o CO2 sint?tico (4%), avalia??o din?mica em leito fixo com a mistura sint?tica de gases (4% CO2, 1,11% CO, 1,2% H2, 0,233% CH4, 0,1% C3, 0,0233% C4 e arg?nio como inerte fechando o balan?o), modelagem din?mica em leito fixo e avalia??o em leito fixo da curva de ruptura do CO2 com o g?s de pir?lise do lodo de esgoto. O lodo e o adsorvente foram caraterizados por an?lises TG/DTA, MEV, FRX e BET. Os estudos de adsor??o foram realizados nas seguintes condi??es operat?rias: temperatura de 40 ?C (para a pir?lise do lodo T = 600 ?C), press?o de 0,55 5,05 bar (processo batelada), vaz?o da mistura gasosa entre 50 72 mL/min e massa de adsorvente igual a 10, 15 e 20 g (processo em leito fixo). O tempo do processo de adsor??o em batelada foi de 7h e em leito fixo foi em torno de 180 min. Os resultados obtidos nesta etapa mostraram que no estudo batelada o processo de adsor??o com a ze?lita 13X ? eficiente e que a massa adsorvida do CO2 aumenta com o crescimento da press?o, diminui com o aumento da temperatura e se eleva com a temperatura de ativa??o do adsorvente. No processo din?mico foram avaliadas as curvas de rupturas, as quais foram comparadas ?s isotermas de adsor??o representadas pelos modelos de Langmuir, Fre?ndlich e Toth. Todos os modelos se ajustaram bem aos pontos experimentais, por?m o modelo de Langmuir foi o escolhido tendo em vista sua utiliza??o no modelo din?mico de adsor??o n?o apresentar implica??es (indetermina??o e maior n?mero de par?metros como ocorreu com os demais) na resolu??o da equa??o. No estudo din?mico em leito fixo com a mistura de gases sint?ticos e diferentes massas de adsorvente, a massa de 20 g apresentou maior percentual de adsor??o 46,7% na temperatura de 40 oC e vaz?o da mistura gasosa de 50 mL/min. O modelo se ajustou satisfatoriamente para as tr?s curvas de ruptura e os par?metros avaliados foram: coeficiente de dispers?o axial (0,0165 dm2/min), difusividade efetiva no interior da part?cula (0,0884 dm2/min) e coeficiente externo de transfer?ncia de massa (0,45 dm/min). A curva de ruptura para o CO2 constru?da no processo de pir?lise do lodo mostrou uma r?pida satura??o do leito proveniente de tra?os de aeross?is, presentes na fase gasosa, decorrentes do processo reacional