Made available in DSpace on 2014-10-09T12:25:53Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:29Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:26:48Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:13Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

nÃo hà / Os altos nÃveis de emissÃo de CO2 neste Ãltimo sÃculo tÃm gerado alerta e preocupaÃÃo Ãs autoridades a nÃvel mundial. Incentivos para desenvolver tecnologias de captura e armazenamento de CO2 ganham destaque nesse cenÃrio. Dentre as alternativas viÃveis para captura do referido gÃs està o processo de adsorÃÃo. A literatura à vasta nos estudos experimentais de adsorÃÃo de CO2 em diversos materiais impregnados, entretanto poucos trabalhos se dedicam ao entendimento dos fenÃmenos em nÃvel atÃmico. O presente estudo objetiva investigar a adsorÃÃo de CO2 em faujasitas do tipo X e carbonos ativados impregnados com monoetanolamina (MEA), mediante o uso de simulaÃÃo molecular. Para isso, modelos de MEA, CO2, faujasita e carbono ativado foram elaborados. Para a faujasita, construiu-se a estrutura com base nos dados cristalogrÃficos reportados na literatura. No carbono ativado, os poros foram representados pelo modelo de placas paralelas de grafeno e realizou-se o estudo em trÃs tamanhos caracterÃsticos (8,9, 18,5, 30,9 Ã) de modo a representar distintas regiÃes de adsorÃÃo e tambÃm permitir correlacionar dados com o carvÃo comercial WV-1050. A molÃcula de CO2 foi construÃda com os modelos de 3 centros (ensaios em faujasitas) e de 1 centro (ensaios em carbonos ativados). Os adsorventes foram carregados com quantidades crescentes de MEA e o impacto desta adiÃÃo foi avaliado atravÃs do levantamento de novas isotermas de CO2 utilizando-se o mÃtodo de Monte Carlo no ensemble Grande CanÃnico (GCMC). Com o modelo proposto faujasita/MEA/CO2, foi possÃvel reproduzir a tendÃncia experimental de reduÃÃo de adsorÃÃo de CO2 com aumento da concentraÃÃo de MEA, em concordÃncia com resultados experimentais apresentados na literatura. Em carbonos ativados, observou-se que os valores de CO2 adsorvidos a alta pressÃo (acima de 4 bar) sempre decaÃam com o carregamento de MEA para ambos os poros, como foi evidenciado experimentalmente em carbonos reais. No entanto, a simulaÃÃo revelou que as quantidades adsorvidas a baixa pressÃo (abaixo de 1 bar) sÃo maiores quando se adiciona monoetanolamina ao material carbonoso. Os resultados, com base nas tÃcnicas aplicadas nesse estudo, indicam que os sistemas NaX e carbono ativado modificados com MEA sÃo pouco viÃveis para captura de CO2 no que diz respeito ao critÃrio isolado de capacidade de adsorÃÃo / The high levels of CO2 emissions over the last century have generated concern and alert worldwide. Incentives to promote technologies for CO2 capture and storage are highlighted in this situation. Among the viable alternatives to capture that gas is the adsorption process. The literature contains many experimental studies of CO2 adsorption in various impregnated materials, despite that, few papers are devoted to the understanding of such phenomena at the atomic level. This study investigates the CO2 adsorption in X-faujasites and activated carbons impregnated with monoethanolamine (MEA) using molecular simulation. Thus, models of MEA, CO2, faujasite and activated carbon were proposed. For faujasite, the structure was modeled based on the crystallographic data reported in the literature. For activated carbon, the pores were represented by the slit pores model of graphene and the study was conducted in three pore sizes (8.9, 18.5, 30.9 Ã) to represent different regions of the adsorption and also allow for data correlation with the commercial activated carbon WV-1050. The CO2 molecule was modeled in the three-centers (faujasites tests) and one-center (carbons tests) models. The adsorbents were loaded with increasing amounts of monoethanolamine and the impact of this addition was evaluated through a set of simulated CO2 isotherms using the Grand Canonical Monte Carlo (GCMC) method. With the model faujasite/MEA/CO2, it was possible to reproduce the decreasing experimental CO2 adsorption with increased MEA concentration. In carbons, it was observed that the values of adsorbed CO2 at high pressure (above 4 bar) always decrease with MEA increasing loadings for both pores, as verified experimentally in real carbons. However, the simulation has shown that the amount adsorbed at low pressures (below 1 bar) is enhanced with monoethanolamine concentration in carbonaceous material. These results, considering the techniques used in this study, indicate that the activated carbon and NaX systems modified with monoethanolamine are unfeasible for capturing CO2 if adsorption capacity is the only criterion to take into account

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Os corantes sintÃticos sÃo um dos poluentes mais comuns e frequentemente encontrados na indÃstria tÃxtil. A destinaÃÃo de esgoto contendo corantes para corpos de Ãgua à extremamente importante do ponto de vista ambiental, jà que mesmo em baixas concentraÃÃes os corantes podem ser altamente tÃxicos para sistemas aquÃticos. A elevada toxicidade à um dos grandes problemas de Ãguas residuais contendo corantes. Este estudo examinou como adsorventes nanoporosos trÃs materiais sendo um HidrÃxido Duplo Lamelar (HDL â Mg/Al), uma argila pilarizada (Al-PILC) e um carbono ativado comercial (GAC-Norit 1240) avaliando seus comportamentos na remoÃÃo dos corantes Reativo Preto 5 (RP5), Azul de Metileno (AM) e Ãcido Azul 25 (AA25). Os materiais baseados em argilas naturais e sintetizadas em laboratÃrio, assim como o carbono ativado, foram caracterizados por difraÃÃo de raios X, BET e FTIR, a fim de se obter informaÃÃo sobre suas caracteristicas estruturais e texturais. Experimentos em batelada utilizando um sistema de tanques agitados foram realizados para averiguar o efeito do pH do meio, da concentraÃÃo inicial de corante, do tempo de contato e da forÃa iÃnica do meio na adsorÃÃo dos corantes. Para o sistema de tanques agitados foram utilizados um agitador rotatÃrio orbital e tubos de acrÃlico contendo 20 mL de soluÃÃes de corantes em contato com 0,015 g dos adsorventes. As concentraÃÃes de equilÃbrio de cada corante foram determinadas em espectrofotÃmetro UV/Vis. A fim de descrever o comportamento das isotermas de adsorÃÃo, os dados de equilÃbrio foram correlacionados com o modelo de Langmuir (L). A contribuiÃÃo dos parÃmetros de transferÃncia de massa na cinÃtica de adsorÃÃo dos corantes RP5, AA25 e AM em carbono ativado tambÃm foi investigada. Estes dados fundamentais forneceram uma melhor compreensÃo dos mecanismos de transferÃncia de massa e dinÃmica difusional do sistema. O comportamento do pH e da forÃa iÃnica do meio foi de suma importÃncia para o entendimento dos processos de adsorÃÃo nos respectivos materiais para cada corante analisado. O pH das soluÃÃes aquosas foi bastante diferenciado, o qual foi dependente das caracterÃsitcas aniÃnicas e catiÃnicas dos materiais e dos corantes. De acordo com a anÃlise estatÃstica, o modelo de Langmuir foi adequado para representar os dados de adsorÃÃo dos corantes comprovado pela combinaÃÃo das constantes de ligaÃÃo do modelo, evidenciando uma forte interaÃÃo adsorvente-adsorbato. Pode-se notar que as cinÃticas de adsorÃÃo de corantes seguem um comportamento semelhante, com uma queda brusca da concentraÃÃo inicial de corante no sobrenadante nos primeiros momentos de contato, atingindo o equilÃbrio em aproximadamente 60 minutos, do que se pode inferir uma difusÃo molecular intrapartÃcula. As quantidades adsorvidas dos trÃs materiais indicaram um melhor desempenho obtido para o carbono ativado. / Synthetic dyes are one of the most common pollutants and often found in the textile industry. The disposal of wastewater containing dyes on water bodies is extremely important from an environmental standpoint, since the dyes even at low concentrations can be highly toxic to aquatic systems. The high stability and toxicity are the major problem in the treatment of wastewater containing dyes. This study examined three nanoporous adsorbents materials: a lamellar double hydroxide (LDH-Mg/Al), pillared clay (Al-PILC) and a commercial activated carbon (Norit GAC-1240), assessing hair performance in the removal of dyes Reactive Black 5 (RB5), Methylene Blue (MB) and Acid Blue 25 (AB25) used in the textile industry. The materials based on natural clays synthesized in the laboratory, and activated carbons were characterized by XRD, BET and FTIR, in order to obtain information about their structural and textural characteristics. Experiments using a batch stirred tank system were performed to investigate the effect of pH, the initial concentration of dye, contact time and ionic strength through adsorption of the dyes. For the system of stirred tanks a rotary shaker and acrylic tubes were used containing 20 mL of dye solutions in contact with 0.015 g of adsorbent. The equilibrium concentration of each dye was determined with a spectrophotometer UV/Vis. In order to describe the behavior of adsorption isotherms, the equilibrium data were correlated with the Langmuir model (L). The contribution of mass transfer parameters on the kinetics of adsorption of dyes RP5, AB25 and MB on activated carbon was also investigated. These data provide a basic understanding of mechanisms of mass transfer and dynamic diffusional system. The behavior of pH and ionic strength of the medium was very important for understanding of adsorption processes in the respective materials for each dye examined. The pH of the aqueous solutions was greatly different, which was dependent on characteristics anionic and cationic materials and colorants. According to statistical analysis, the Langmuir model was adequate to represent the data of adsorption of dyes shown. It may be noted that the kinetics of adsorption of dyes follow a similar behavior, with a sharp drop of the dye initial concentration in the supernatant in the first moments of contact, reaching the equilibrium in approximately 100 minutes. The adsorbed amounts of the three materials showed a revealed better performance obtained for activated carbon.

Made available in DSpace on 2014-10-09T12:49:16Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:32Z (GMT). No. of bitstreams: 1 09809.pdf: 7318754 bytes, checksum: 166979fe7dbb592b70e1bc5fb8417a96 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:25:53Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:29Z (GMT). No. of bitstreams: 0 / A magnetita, também chamada de ferrita de ferro, é um minério conhecido como imã natural e encontrada em depósitos de ferro. Além desse comportamento intrínseco, a magnetita possui a capacidade de remover os íons metálicos do meio aquoso por fenômenos de adsorção. O seu caráter fortemente magnético a distingue de outros tipos de adsorventes, visto que, é facilmente removida da solução por separação magnética. Neste trabalho estudou-se a adsorção de urânio(VI), na forma de íons UO22+, de solução nítrica pela magnetita sintética. Esta foi preparada por precipitação simultânea adicionando-se uma solução de NaOH à solução contendo os íons Fe2+ e Fe3+. A magnetita sintética, na forma de um pó preto, exibiu uma resposta magnética de atração intensa na presença de um campo magnético, sem contudo tornar-se magnética, um comportamento típico de material superparamagnético constatado por medidas de magnetização. Estudou-se a influência dos parâmetros de adsorção de íons UO22+ tais como o pH, a dose do adsorvente, tempo de contato e a isoterma de equilíbrio. A máxima adsorção de urânio foi encontrada no intervalo de pH entre 4 e 5. Verificou-se que quanto maior a dose de magnetita menor a capacidade de adsorção e maior a remoção de U. Da relação entre adsorção e tempo de contato verificou-se que a remoção aumentou rapidamente com o tempo e atingiu-se a condição de equilíbrio em 30 min. Os resultados da isoterma de equilíbrio apresentaram maior concordância com o modelo de Langmuir, o qual permitiu a determinação da capacidade teórica de saturação da magnetita para o urânio. A interação entre os íons UO22+ e a magnetita foi caracterizada como uma adsorção química e espontânea. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:26:48Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:13Z (GMT). No. of bitstreams: 0 / Dentre os vários radioisótopos existentes, o 99mTc e o 188Re apresentam propriedades físicoquímicas bastante específicas que os qualificam para utilização em Medicina Nuclear nas áreas de diagnóstico e terapia, respectivamente. Além disso, estes radiofármacos podem ser distribuídos à classe médica sob a forma de sistemas geradores de 99Mo-99mTc e 188W-188Re, garantindo autonomia e praticidade em sua utilização. O presente projeto de mestrado tem por objetivo determinar a capacidade de alguns materiais adsorvedores para retenção de molibdênio e tungstênio, visando o preparo de sistemas geradores de 99Mo-99mTc e de 188W- 188Re com características adequadas para aplicação em Medicina Nuclear. Quantidades conhecidas, em massa, de molibdênio (Mo) e tungstênio (W) foram adicionadas às soluções carga previamente preparadas, com valores de pH ajustados entre 1 e 7, e estas por sua vez foram então percoladas ao longo de diferentes dispositivos contendo em seu interior alumina, resina ou composto de poli-zircônio também denominado PZC. As eluições foram realizadas com um intervalo de tempo de aproximadamente 24 horas entre uma outra para os sistemas geradores de 99Mo-99mTc e de cerca de 48 horas para os sistemas geradores de 188W-188Re em função da diferença da meia-vida física existente entre os elementos pai e filho envolvidos em ambas as reações. As amostras eluídas dos sistemas geradores contendo tanto 99mTc quanto 188Re foram submetidas a testes de controle de qualidade visando-se determinar o grau de pureza radionuclídica, radioquímica e química de cada uma delas, mas nenhuma contaminação significativa por 99Mo, 188W, tecnécio ou rênio nos estados coloidais assim como zircônio foi detectada tanto nas soluções carga eluídas quanto nas soluções extraídas com solução salina para qualquer valor de pH estudado. Os cartuchos comerciais de alumina do tipo Sep Pak Ácida retiveram de maneira mais eficiente o molibdênio presente nas soluções carga eluídas quando comparados aos demais dispositivos comerciais de retenção utilizados. Entretanto, quando esta comparação estende-se as colunas cromatográficas de alumina, conclui-se que o emprego da alumina ácida como adsorvedor é ainda mais eficaz do que a utilização dos cartuchos do tipo Sep Pak Ácida e da própria alumina calcinada convencional, porém ainda assim não supera a performance apresentada pelo PZC. Os experimentos realizados com tungstênio, os quais envolveram a utilização de cartuchos comerciais de retenção de Sep Pak Ácida, assim como o emprego de alumina sob as formas calcinada convencional e ácida, revelaram que a alumina ácida constitui o melhor material adsorvedor. Quanto ao pH das soluções carga, observou-se que este deve ser ajustado de modo a ser mantido sempre que possível por volta de 5 (pH ácido) para as soluções preparadas contendo molibdênio sob a forma não radioativa como carregador, enquanto que para as soluções carga preparadas com tungstênio o pH deve ser neutro. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Fossil based energy resources are dominating the world’s primary energy consumption for the last century. However, with decreasing crude oil reservoirs and the role they play in global warming by emitting greenhouse gases, the focus has been turned towards improved utilization of renewable resources and the need for new, sustainable fuels and chemicals is more urgent than ever. Biomass is a carbon neutral resource that can be used to produce biofuels and other useful chemicals. One such chemical is 1-butanol (or simply butanol), which has great potential as a gasoline substitute because of its favorable fuel properties. Butanol can be produced from acetone, butanol and ethanol (ABE) fermentation using e.g. Clostridium acetobutylicum. However, the concentration of butanol in fermentation in the resulting broth is limited to ca. 20 g/L due to its toxicity for microorganisms. Butyric acid is a precursor to butanol, which is produced prior to butanol in ABE fermentation. Butyric acid is an important industrial chemical, which can be further converted into a number of commercial compounds e.g. acetate butyrate, butyl acetate and butanol. Arginine is a semi-essential amino acid that has vast applications in the field of pharmaceutical and food industry. In addition, arginine can replace inorganic nitrogen as nitrogen source in fertilizers. It can be produced via fermentation of sugars using engineered microorganism like E. Coli, but like butanol its concentration is restricted to approximately 12 g/L. Due to low concentration of these useful chemicals in the resulting fermentation broths recovery of these chemicals remain challenging with today’s options and therefore  novel recovery process should be developed. In this study, zeolite adsorbents were used to recover butanol, butyric acid and arginine from model and real fermentation broths. Zeolite MFI adsorbent efficiently adsorbed butanol from model solutions with a saturation loading of 0.11 g/g- zeolite. On the other hand, adsorption of butyric acid was found to be strongly pH dependent, with high adsorption below and little adsorption above the pKa value of the acid. A structured adsorbent in the form of steel monolith coated with a silicalite-1 film was also used and performance was evaluated by performing breakthrough experiments at room temperature using model ABE fermentation broths and the results were compared with those obtained using traditional adsorbent sin the form of beads. Desorption studies showed that a high quality butanol product with purity up to 95.2% for butanol-water system and 88.5% for the ABE system can be recovered with the structured silicalite-1 adsorbent. Further, zeolite X adsorbents in the form of powder and extrudates was used to recover arginine from a real fermentation broth and also from aqueous model solutions. To the best of our knowledge, this is the first time recovery of arginine from real fermentation broths using any type of adsorbent is reported. Arginine loading of 0.15 g/g was observed at pH 11 using zeolite X powder. The selectivity for arginine over ammonia and alanine from the fermentation broth at pH 11 was 1.9 and 8.3, respectively, for powder and 1.0 and 4.1, respectively, for extrudates. Synthesis gas (CO + H2) can be produced e.g.by gasification of lignocellulose biomass. This synthesis gas can be used to produce methanol, which subsequently may be converted into gasoline using zeolite ZSM-5 catalyst. However, during Methanol to Gasoline (MTG) process, undesirable carbon residue (coke) is formed that gradually reduces the activity of catalyst. It was hypothesized that intracrystalline defects in the zeolite formed during conventional synthesis may accelerate the deactivation rate by coke formation. In this work, a novel ZSM-5 zeolite catalyst essentially free of intracrystalline defects was synthesized and evaluated in the  MTG reaction,. The novel catalyst showed significantly higher resistance towards deactivation by coke formation as compared to a reference catalyst containing defects.

Magister Scientiae - MSc / The current study investigated application of natural adsorbents in brine treatment. Brines are hypersaline waters generated in power stations and mining industries rich in Mg2+, K+, Ca2+, Na+, SO4 2- , Cl- and traces of heavy metals, thus there is a need for these brines to be treated to recover potable water and remove problematic elements. Natural adsorbents have been successfully used in waste water treatment because of their high surface area and high adsorptive properties when they are conditioned with acid or base. The investigation of pH showed that natural adsorbents did not perform well at low pH of 4 and 6. The adsorbents were able to work efficiently at the natural pH of 8.52 of the brine solution. These results show that natural adsorbents hold great potential to remove cationic major components and selected heavy metal species from industrial brine waste water. Heterogeneity of natural adsorbents samples, even when they have the same origin, could be a problem when wastewater treatment systems utilizing natural clinoptilolite and bentonite are planned to be developed. Therefore, it is very important to characterize the reserves fully in order to make them attractive in developing treatment technologies. / South Africa

>Magister Scientiae - MSc / Studies involving the use of natural clays such as bentonite, montmorillonite and natural zeolite clinoptilolite in water treatment have been reported. Researchers suggested cost effective processes, such as ion-exchange and adsorption for the removal of heavy metals from waste waters by using naturally occurring and synthetic materials. The current study investigated application of natural adsorbents in brine treatment. Brines are hypersaline waters generated in power stations and mining industries rich in Mg2+, K+, Ca2+,Na+, so,': cr and traces of heavy metals, thus there is a need for these brines to be treated to recover potable water and remove problematic elements. Natural adsorbents have been successfully used in waste water treatment because of their high surface area and high adsorptive properties when they are conditioned with acid or base. The natural adsorbents used in this study were obtained from Ecca Holdings company (Cape bentonite mine) Western Cape in South Africa, comprising bentonite clay and natural zeolite (clinoptilolite) and another clinoptilolite sample was obtained from Turkey. These adsorbents were investigated in their natural and pretreated form for removal of toxic elements in brine water. The pretreatment was aimed at removing Na+, K+, Ca2+, Mg2+ from the clinoptilolite as well as the bentonite and replacing these cations with the H+ cation to activate the materials. The cation exchange capacity (CEC) of natural zeolite from South Africa was found to be 2.14 meq/ g, Turkish Clinoptilolite was 2.98 meq/ g while South African bentonite was 1.73 meq/g. at 25°C using ammonium acetate (pH 8.2) method. Characterization of these natural adsorbents was done prior to pretreatment and after the treatment. ICP-AES analysis was used for determination of toxic elements in brines before and after sorption. The morphology of clays was characterized by X-ray diffraction (XRD), Brunauer Emmett Teller (N2-BET) and Scanning electron microscopy (SEM) for confirmatory purposes and X-ray Fluorescent spectroscopy (XRF) was used for the composition analysis of the natural adsorbent. The results from batch experiments prior to pretreatment of the natural adsorbents showed that these natural adsorbents contained Mg2+, K+, Ca2+, Na+ in their structures as charge balancing cations, thus needed pretreatment to remove the cations. The natural adsorbents were pre-treated with 0.02M HCI. After the pretreatment of natural adsorbents it was possible to enhance the percentage removal of the major cations from brine, and the Na+ and Mg2+ removal achieved (86 % and 85% respectively) from brine was more than C02+ (70% ) the SC was the adsorbent one that gave highest removal of cations in the brines. Trace elements removal was high with Cu2+and Zn2+ being the highest of toxic elements in brine. The optimum contact for the toxic element removal was found to be 30 min for the Turkish clinoptilolite and 1 hr for the South African clinoptilolite and South African bentonite clay. Leaching of Ae+ and Si4+ during adsorption was also investigated and it was found that less than 1 ppm of A13+ and Si4+ were leached into the solution during adsorption experiments indicating that these materials were stable. The investigation of pH showed that natural adsorbents did not perform well at low pH of 4 and 6. The adsorbents were able to work efficiently at the natural pH of 8.52 of the brine solution. These results show that natural adsorbents hold great potential to remove cationic major components and selected heavy metal species from industrial brine wastewater. Heterogeneity of natural adsorbents samples, even when they have the same origin, could be a problem when wastewater treatment systems utilizing natural clinoptilolite and bentonite are planned to be developed. Therefore, it is very important to characterize the reserves fully in order to make them attractive in developing treatment technologies.