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Adsorption and Desorption of Mercury Chloride on Sulfur-impregnated Activated Carbon by Thermogravimetric Analysis (TGA)Syue, Sheng-Han 27 August 2008 (has links)
This study investigated the adsorptive and desorption capacity of HgCl2 onto powdered activated carbon derived from carbon black of pyrolyzed waste tires (CPBAC) via thermogravimetric analysis (TGA).
Due to incomplete classification and recycling of municipal solid wastes (MSW), they still mix with a lot of hazardous materials, which unfortunately can not be removed by incinerators and air pollution control devices(APCDs). Among them, mercury and its pollutants attract more attention by people. Mercury and its pollutants emitted from the incineration of municipal solid wastes could cause severely adverse effects on human health and ecosystem since they exist mainly in vapor phase due to high vapor pressure. If they can not be remove by the air pollution control devices, they will be emitted to the atmosphere and cause serious effects on environmental ecology via various routes.
Activated carbon has been widely applied to the treatment of organic compounds and heavy metals in wastewater and waste gas stream. However, the adsorptive capacity of activated carbon decreases with adsorption temperature. The low adsorptive capacity of activated carbon at high temperature (>150 oC) can be overcome by impregnated activated carbons. Previous study reported that sulfur impregnated powdered activated carbons could effectively remove the vapor-phase elemental mercury (Hgo) emitted from MSW incinerators and utility power plants. However, the impregnated typically used is sulfur (S) which is solely applied for the adsorption of elemental mercury (Hgo). Besides, these studies seldom investigate the distribution of impregnated sulfur in the inner pores of activated carbon and its effects on the specific surface area and pore size distribution. Thus, this study was to investigate the fundamental mechanisms for the adsorption/desorption of HgCl2 by/from sulfur impregnated PAC.
Experimental results indicated that the sulfur content of sulfur impregnated CBPAC decreased with increasing impregnation temperatures form 400 to 650 oC; while the surface area of sulfur impregnated CBPAC increased with impregnation temperatures. In this study, TGA was applied to obtain the adsorptive capacity of HgCl2 onto CBPAC with adsorption temperature (150oC) and influent HgCl2 concentration (100~500 £gg/m3). Experimental results indicated that the adsorptive capacity of CBPAC increased with the increase of influent HgCl2 concentration and surface area of the activated carbon. This study revealed that the impregnation of sulfur on CBPAC could increase its adsorption capacity at high temperatures.
Desorption experimental parameters included desorption temperature (400, 500, and 600 oC), heating rate (10, 15, and 20 oC /min) and regeneration cycle (1~7 cycles). In probing into the regeneration efficiency of CBPAC, experiments were conducted at the desorption times of 60 and 30 min. The results suggested the regeneration efficiency of carbon under 30 min was generally highter than that under 60 min. Because the desorption time was more longer and the sulfur content was lesser. Therefore, the regeneration times was reduce. Experimental results indicated that the mechanism of HgCl2 desorption from the spent CPBAC was strongly affected by desorption temperature. Both the desorption efficiency and the desorption rate of HgCl2 increased dramatically with desorption temperature. The desorption heat of HgCl2 (823 KJ/mole) was much higher than the vaporization heat of HgCl2 (59.2 KJ/mole), indicating that the adsorption of HgCl2 on sulfur impregnated CBPAC was chemical adsorption. Consequently, raising desorption temperature could enhance the desorption of HgCl2 and shorten the duration for HgCl2 desorption. Moreover, the formation of HgS during the desorption of HgCl2 from activated carbons can be proved by the surface characteristics of sulfur impregnated activated carbons. Results obtained from the regeneration of sulfur impregnated activated carbons indicated that the regeneration cycles decreased as the desorption duration increased. It was attributed to the potential desorption of sulfur from actived carbons, which thus decreased the adsorptive capacity and the regeneration cycles.
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Removal of organic micropollutants and trace metal from water using modified activated carbonsChingombe, Purazen January 2006 (has links)
Pollution of water by herbicides and heavy metals has caused world wide concern because of the adverse effects of these pollutants on the environment, humans and wildlife. This has resulted in tighter legislation being imposed on the levels of these pollutants in drinking water. For example, the European Union (EU) has set the legislation in the drinking water Directive Admissible Concentration for a single herbicide to a maximum of 0.1 ppb. Despite the tight environmental pollution controls, isolated cases of pollutants exceeding their limits are still encountered. This would suggest that research towards the efficient and effective removal of these pollutants will be an on-going process. In this study, sorption of copper and some selected herbicides e.g. atrazine, benazolin and 2,4-dichlorophenoxyacetic acid (2,4-D) was undertaken on a conventional activated carbon and its modified series. A low level detection method was developed using High Performance Liquid Chromatography (HPLC) and this system was used to quantify the sorption capacity of the herbicides. In order to understand the sorption mechanism of the targeted pollutants, physical and chemical characterisation of the adsorbents was undertaken using a variety of techniques. These include, Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared (FT-IR) method, pore size distribution and surface area measurements, elemental analysis, sodium capacity determination, zeta potential and pH titration. The sorption data were presented and analysed by conventional adsorption isotherms. Sorption of the herbicides was favoured on carbon samples with least oxygen content while the uptake of copper was strongest in oxidised carbons. Kinetic experimental data were analysed by a pseudo second order model and the Boyd kinetic model. Molecular structural configurations and the physico-chemical properties of the adsorbent played a crucial role in the sorption behaviour of the herbicides.
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Estudo do desempenho de carbonos ativados para a remoção de H2S do biogásMenezes, Randreanne Lybine da Costa Bandeira 16 February 2017 (has links)
MENEZES, R. L. C. B. Estudo do desempenho de carbonos ativados para a remoção de H2S do biogás. 2017. 85 f. Dissertação (Mestrado em Engenharia Química) - Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2017. / Submitted by Marlene Sousa (mmarlene@ufc.br) on 2017-04-07T18:34:44Z
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Previous issue date: 2017-02-16 / The use of biogas as a source of energy represents an alternative to the use of fossil fuels. However, this gas mixture presents contaminants in its composition, among them the hydrogen sulfide (H2S), which causes harmful effects to health and corrosion in equipment. Thus, the removal of H2S from the biogas is usually conducted by means of conventional absorption processes in amine solutions, which usually have a rather onerous regeneration step. In this context, the adsorption in porous materials, especially activated carbons, has been shown as an attractive alternative for the removal process. The objective of this work was to study the performance of three commercial activated carbons, one of them being the base matrix and the other impregnated with sodium hydroxide and iron oxide, for the removal of H2S in fixed bed. The adsorbents were characterized by X-ray fluorescence, pH measurement and removal of N2 isotherms at -196 °C and CO2 at 0 °C. From the characterization tests, it was observed that all the samples presented specific surface areas and high microporosity. In relation to H2S adsorption, the results showed that sodium impregnated carbon was the one with the highest H2S removal capacity due to its high alkalinity and percentage of ultramicropores, detected in the characterization. This suggests that the presence of the metals and the modification of the porous structure due to the impregnation process are the determinant factors to obtain a high capacity of H2S retention. The results for tests carried out at different temperatures showed that the dominant mechanism is for the impregnated samples. However, the regenerability study showed that the samples are not suitable for use in cyclic adsorption processes, since there is a significant loss of H2S adsorption capacity during the cycles. This loss is due to the mechanism involved, whereby H2S molecules form covalent bonds with the surface, making them more difficult to remove during regeneration. In spite of having a more moderate adsorption capacity, the matrix sample (not impregnated) maintained its capacity after the second cycle of use and regeneration, indicating predominance of physical adsorption mechanism and better potential for use in cyclic processes. / A utilização do biogás como fonte de energia representa uma alternativa ao uso dos combustíveis fósseis. No entanto, esta mistura gasosa apresenta contaminantes em sua composição, dentre eles o sulfeto de hidrogênio (H2S), que causa efeitos danosos à saúde e corrosão em equipamentos. Assim, a remoção do H2S do biogás é usualmente conduzida por meio de processos convencionais de absorção em soluções de aminas, que costumam apresentar uma etapa de regeneração bastante onerosa. Neste contexto, a adsorção em materiais porosos, com destaque para carbonos ativados, vem se mostrando como uma alternativa atrativa para o processo de remoção. Desta forma, esse trabalho teve por objetivo estudar o desempenho de três carbonos ativados comerciais, sendo um deles a matriz base e os demais impregnados com hidróxido de sódio e óxido de ferro, para a remoção do H2S em leito fixo. Os adsorventes foram caracterizados através de fluorescência de raios X, medição de pH e levantamento de isotermas de N2 a -196 °C e de CO2 a 0 °C. A partir dos ensaios de caracterização, observou-se que todas as amostras apresentaram áreas superficiais específicas e microporosidade elevadas. Em relação à adsorção de H2S, os resultados mostraram que o carbono impregnado com sódio foi o que apresentou maior capacidade de remoção de H2S, devido a sua elevada alcalinidade e percentagem de ultramicroporos, detectadas na caracterização. Isso sugere que a presença dos metais e a modificação da estrutura porosa devido ao processo de impregnação são os fatores determinante para obtenção de uma elevada capacidade de retenção de H2S. Os resultados para testes realizados em diferentes temperaturas mostraram que o mecanismo dominante é de quimissorção para as amostras impregnadas. Já o estudo de regenerabilidade mostrou que as amostras não são indicadas para serem utilizadas em processos cíclicos de adsorção, uma vez que ocorre perda significativa da capacidade de adsorção de H2S no decorrer dos ciclos. Essa perda é decorrente do mecanismo envolvido, através do qual as moléculas de H2S formam ligações covalentes com a superfície, tornando-as mais difíceis de serem removidas durante a regeneração. Já a amostra matriz (não impregnada), apesar de ter apresentado capacidade de adsorção mais moderada, manteve sua capacidade depois do segundo ciclo de uso e de regeneração, indicando predominância de mecanismo de adsorção física e melhor potencial para uso em processos cíclicos.
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Diffusion of n-paraffins in carbonaceous materials / Diffusion of n-paraffins in carbonaceous materialsFederico Leandro Greco Melo 26 November 2015 (has links)
FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / A profunda compreensÃo dos mecanismos difusivos em sÃlidos porosos à essencial para o desenvolvimento de vÃrios processos envolvendo catÃlise heterogÃnea. A impregnaÃÃo de metais em suporte poroso Ã, geralmente, uma forma eficaz de aumentar a eficiÃncia do catalisador. No entanto, os efeitos de tal procedimento sobre as propriedades de transporte ainda sÃo pouco conhecidos. ZeÃlitas, sÃlicas e aluminas sÃo os suportes mais frequentemente utilizados para catalisadores heterogÃneos. Atualmente, utilizam-se tambÃm carbonos ativados (AC) como suportes, porÃm, apesar das vÃrias vantagens potenciais (por exemplo, Ãreas de superfÃcie bastante especÃficas), pouco tem sido estudado em relaÃÃo ao comportamento difusivo nestes materiais. A SÃntese de Fischer-Tropsch (FTS) à um processo que pode ser beneficiado com a utilizaÃÃo de materiais à base de carbono impregnados. Dessa forma, o mÃtodo Zero Length Column (ZLC) foi aplicado neste estudo para avaliar a difusÃo de n-heptano e n-octano, produtos relevantes do FTS, em materiais à base de carbono antes e apÃs a impregnaÃÃo com Fe com o objetivo de investigar a cinÃtica sob as condiÃÃes normais de temperatura de FTS e determinar se os produtos do processo apresentam uma resistÃncia significativa para o processo. / A deep understanding of the diffusion mechanisms in porous solids is essential to the development of many processes involving heterogeneous catalysis. The impregnation of metals on porous supports is generally an effective way of increasing the catalyst efficiency, but the effects of such procedure on the transport properties are poorly known. Zeolite, silica and alumina are most frequently used as supports for heterogeneous catalysts. Despite the several potential advantages of using activated carbon (AC) as supports (e.g. high specific surface areas), little has been studied regarding diffusion behavior in these materials. The Fischer-Tropsch Synthesis (FTS) is a process which could benefit from the use of carbon-based impregnated materials. The Zero Length Column (ZLC) method was applied in this study to evaluate the diffusion of n-heptane and n-octane, relevant products of the FTS, in carbon-based materials before and after impregnation with Fe. The aim was to investigate the kinetics under the usual temperature conditions of the FTS and determine if the products diffusion poses a significant resistance for the process.
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Systematic development of predictive molecular models of high surface area activated carbons for the simulation of multi-component adsorption processes related to carbon captureDi Biase, Emanuela January 2015 (has links)
Adsorption in porous materials is a promising technology for CO2 capture and storage. Particularly important applications are adsorption separation of streams associated with the fossil fuel power plants operation, as well as natural gas sweetening. High surface area activated carbons are a promising family of materials for these applications, especially in the high pressure regimes. As the streams under consideration are generally multi-component mixtures, development and optimization of adsorption processes for their separation would substantially benefit from predictive simulation models. In this project we combine experimental data and molecular simulations to systematically develop a model for a high surface area carbon material, taking activated carbon Maxsorb MSC-30 as a reference. Our study starts from the application of the well-established slit pore model, and then evolves through the development of a more realistic model, based on a random packing of small graphitic fragments. In the construction of the model, we introduce a number of constraints, such as the value of the accessible surface area, concentration of the surface groups and pore volume, to bring the properties of the model structure close to the reference porous material. Once a plausible model is developed, its properties are further tuned through comparison between simulated and experimental results for carbon dioxide and methane. The model is then validated by predictions for the same species at different conditions and by prediction of other species involved in the carbon capture processes. The model is applied to simulate the separations involved in pre and post combustion capture processes and sweetening of sour natural gas, using realistic conditions and compositions for the multicomponent mixtures. Finally, it is used to explore the effect of water in pre and post combustion separations.
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Application of Thermogravimetric Analysis (TGA) Technique on Adsorption Capacity and Adsorption and Desorption Kinetics of Sulfur-impregenated Activated Carbon Saturated with Gaseous Mercury ChlorideChen, Wei-chin 09 July 2010 (has links)
The objective of this study is to investigate the influence of sulfur compounds (S and Na2S) for powdered activated carbon derived from carbon black of pyrolyzed waste tires (CPBAC). Besides, this study investigated the distribution of impregnated sulfur in the inner pores of activated carbon and its effected on the specific surface area and pore size distribution. This study investigated the fundamental mechanisms by analysis of thermodynamic properties and to establish the kinetic models for the adsorption/desorption of HgCl2 by/from sulfur impregnated CBPAC. Furthermore, this study investigated the adsorptive and desorption capacity of HgCl2 onto CPBAC via thermogravimetric analysis (TGA).
Experimental results indicated that the specific surface area of sulfur impregnated CBPAC with elemental S (S0) was larger than sulfur impregnated CBPAC with Na2S. Besides, the sulfur content of sulfur impregnated CBPAC increased with increasing the surface area of CBPAC under the same impregnated temperature. And, the adsorptive capacity of CBPAC increased with the increase of influent HgCl2 concentration and surface area of the activated carbon. According to the experimental results of the adsorption capacity under the differential sulfur content, its indicated that the affection of sulfur content for adsorption capacity of HgCl2 was much than HgCl2 concentration and surface area of the activated carbon.
The desorption energys were 266 and 282 kJ/mole for HgCl2 desorption from saturated CBPAC-S0 and CBPAC-Na2S, respectively. The results showed the process of HgCl2 adsorption onto CBPAC was in favor of a physisorbed state of HgCl2 at the adsorption temperature of 150 oC but the process of HgCl2 adsorption onto CBPAC which impregated was in favor of a chemisorbed state of HgCl2 at the adsorption of 150 oC. The value of ∆G for CBPAC at the adsorption temperature of 30 ~150 oC were ranged from -15.28 kJ/mole to -26.63 kJ/mole. The value of ∆G for CBPAC-S0 at the adsorption temperature of 30~150 oC ranged from -23.45 kJ/mole to -32.09 kJ/mole. The value of ∆G for CBPAC-Na2S at the adsorption temperature of 30~150 oC ranged from -22.84 kJ/mole to -32.72 kJ/mole. The results showed negative values of ∆G confirmed the feasibility of adsorption process and the spontaneous nature for the adsorption of HgCl2. The value of ∆H for CBPAC at the adsorption temperature of 30 ~150 oC ranged from -35.58 kJ/mole to -35.82 kJ/mole. The value of ∆H for CBPAC-S0 at the adsorption temperature of 30 ~150 oC ranged from -38.07 kJ/mole to -52.49 kJ/mole. The value of ∆H for CBPAC-Na2S at the adsorption temperature of 30~150 oC was -37.45 kJ/mole to -53.12 kJ/mole. A negative ∆H suggested that the adsorption of HgCl2 is an exothermic process. Besides, the adsorptive behavior of HgCl2 for two activated carbons (CBPAC-Na2S and CBPAC-S0) at high temperature (110 ¢J and 150 ¢J ) was the same chemical reaction mechanism due to the same ∆H. Besides, the results of model simulation indicated that modified adsorption kinetic model based on pore diffusion scheme developed in this study could successfully simulate the transport and adsorption of HgCl2 by considering the chemical reaction within the inner pores of carbon grains at 150 oC.
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Préparation et modification de carbones activés pour l'adsorption de polluants organiques émergents : molécules pharmaceutiques et liquides ioniques / Preparation and modification of activated carbons for adsorption of organic pollutants emerging : pharmaceutical molecules and ionic liquidsGuedidi, Hanen 16 February 2015 (has links)
Dans ce travail, nous avons modifié deux carbones activés (grain AC et tissu T0) par divers traitements chimique (H2O2, NaOCl et un traitement thermique sous azote) et par des traitements ultrasonores à 20 et 500 kHz en présence de différents solvants (eau ultrapure, peroxyde d'hydrogène et acide formique). Ces carbones (bruts et modifiés) ont été caractérisés du point de vue de leur chimie de surface et de leur texture. Nous avons étudié l'adsorption d'ibuprofène (IBP) aux différents pH et températures. Le processus d'adsorption de l'IBP sur (AC ou T0) est avéré endothermique à pH 3. L'oxydation par NaOCl crée des groupes phénoliques qui défavorisent l'adsorption d'IBP tandis que l'oxydation par H2O2 augmente la teneur en groupe carbonyles et carboxyles responsable d'une contribution à l'adsorption de l'IBP. Le traitement ultrasonore de AC a augmenté son adsorption d'IBP par rapport au charbon brut. La cinétique d'adsorption de deux liquides ioniques synthétisés (LI1 : bromure de 4-tertiobutyl-1-propylpyridinium et LI2 : bromure de 4-tertiobutyl-1(2-carboxy-ethyl)pyridinium ) sur T0 est beaucoup plus rapide que la cinétique d'adsorption de l'IBP à pH 7,5. La compétition d'adsorption sur T0 entre les trois molécules (IBP et les deux liquides ioniques) a montré que l'IBP s'adsorbe en plus grande quantité sur le T0 que le LI1 et le LI2. / In this work, two activated carbons (granular AC and fabric T0) were modified either by chemical treatment (H2O2, NaOCl and thermal treatment under N2) or by ultrasonic irradiation at 20 kHz or 500 kHz in different solvents (UHQ water, H2O2 and HCOOH). The raw and modified materials were characterized by different methods. We studied the ibuprofen (IBP) adsorption at different pH and temperatures. The adsorption of IBP by (AC or T0) was an endothermic process at pH 3. Oxidation with NaOCl creates phenol groups that led to a decrease of the adsorption uptake while oxidation by H2O2 increases the carbonyl group content and carboxyl that induce an increase in the adsorption of IBP. The ultrasonic treatment of AC increases the adsorption capacity of ibuprofen in comparison with the raw AC. The adsorption of the two ionic liquids (LI1 : the 4(tert-butyl)-1propylpyridinium bromide and LI2 : 4(tert-butyl)-1(2-carboxy-ethyl)pyridinium bromide ) onto T0 was found much faster than the adsorption kinetic of IBP at pH 7.5. The competitive adsorption of mixture of IBP and the two ionic liquids showed that IBP is the most adsorbed by T0.
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Molecular simulation studies of adsorption of fuel components and their mixtures in engine depositsHarrison, Alexander James January 2016 (has links)
Carbonaceous deposits accumulate on the majority of the inner surfaces of internal combustion engines. The presence of these deposits is known to cause impaired engine performance. This is manifested as increased knocking, higher fuel consumption, higher emissions and other adverse effects. One of the proposed mechanisms for this behaviour is the adsorption and desorption of fuel components in the pores within the deposit. The porous nature of the deposits promotes this behaviour, altering the fuel composition and reducing the amount of fuel entering the combustion chamber. Previous research in this area was aimed at determining the porous structure of the deposits by combining experimental procedures with molecular simulations to investigate adsorption interactions with fuel components. Using a characterisation procedure regularly applied to activated carbons, a molecular model was developed that was able to provide new insights into the deposit structure. This model enabled predictions to be made for the single-component adsorption of normal heptane and iso-octane, two species commonly used as a gasoline reference fuel. Results showed significant adsorption of both species, and highlighted the impact of adsorption into the internal porous structure of the engine deposits. The aim of this thesis is to further investigate adsorption in engine deposits by expanding the studies to more complex systems. We develop a model to predict the adsorption of normal heptane, iso-octane, toluene and their mixtures in deposits of different origins and under different conditions. The study of multi-component mixtures provides insight into selectivity effects of adsorption under confinement, while at the same time bringing the systems under consideration closer to realistic multi-component mixtures that better represent fuel blends. The study also considers for the first time adsorption of aromatic species, both as a single component and in mixtures, since aromatics have a high presence in gasoline fuel. We explore the influence of molecular structure of adsorbing species, composition of the bulk mixture and temperature on the uptake and selectivity behaviour of the engine deposits. We demonstrate that under equilibrium conditions, deposits can adsorb substantial amounts of hydrocarbon species of all types. However, selectivity behaviour in engine deposits was found to be a subtle and complex property, highly sensitive to both pore size and system pressure.
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Catalisadores heterogêneos para produção de chalconas: reação de condensação de Claisen-Schmidt / Heterogeneous catalysts for chalcones production: Claisen-Schmidt condensation reactionWinter, Caroline 07 March 2016 (has links)
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Previous issue date: 2016-03-07 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The members of flavonoids and chalcones family have attracted great interest because of their pharmacological applications as antibacterial, anti-inflammatory and anticarcinogenicagents, and are commonly synthesized by Claisen-Schmidt condensation between acetophenone and benzaldehyde derivatives. This reaction is usually catalyzed under homogeneous conditions which present, however, several drawbacks such as catalyst recovery and waste disposal problems. This work proposes the use of a variety of heterogeneous catalysts to achieve good results for condensation Claisen-Schmidt reaction in terms of conversion and chalcones selectivity, when compared to the homogeneous catalysis. Two groups of catalysts were tested: metal oxides and activated carbons. Magnesium oxide catalysts were prepared by hydrothermal treatment and magnesium, niobium, lanthanum and titanium oxides by rehydration of commercial precursors, all methods followed and not followed by cesium impregnation. The activated carbons used as catalysts were Babassu, Bahia Coconut, ox bone and Dendê, raw and treated with sodium hydroxide. The catalysts were characterized by scanning and transmission electron microscopy, thermogravimetric analysis, differential thermal analysis, determination of the specific superficial area by the adsorption/desorption of N2 at 77 K method, infrared spectroscopy, X-ray diffraction and temperature-programmed desorption of CO2 and NH3. The basic sites of carbons were quantified by Boehm Method. Finally, the performance of the catalysts was evaluated on the Claisen-Schmidt reaction between Acetophenone and 4-nitrobenzaldehyde, and the conversion was quantified by high performance liquid chromatography. The best catalyst was treated babassu activated carbon, whose conversion achieved was 92,38%. / Os membros da família das chalconas e flavonóides têm despertado um grande interesse devido às suas aplicações como agentes farmacológicos, antibacterianos, anti-inflamatórios e anticarcinogênicos, sendo comumente sintetizados via condensação de Claisen-Schmidt entre derivados de acetofenona e de benzaldeído. Esta reação é catalisada normalmente sob condições homogêneas, que apresentam, no entanto, vários inconvenientes, tais como a recuperação do catalisador e problemas de destinação de resíduos. Neste trabalho foi proposto o uso de uma série de catalisadores heterogêneos para se alcançar bons resultados para a reação de condensação de Claisen-Schmidt, em termos de conversão e seletividade de derivados de chalconas, quando comparados à catálise homogênea. Foram testados dois grupos de catalisadores: óxidos metálicos e carvões ativados. Prepararam-se catalisadores de óxido de magnésio por tratamento hidrotérmico e óxidos de magnésio, nióbio, lantânio e titânio por reidratação de precursores comerciais, todos os métodos seguidos e não seguidos por impregnação de césio. Os carvões ativados utilizados como catalisadores foram de babaçu, coco da Bahia, osso de boi e dendê brutos e tratados com hidróxido de sódio. Os catalisadores foram caracterizados por microscopia eletrônica de varredura e transmissão, análise termogravimétrica, análise térmica diferencial, determinação de área superficial específica por análise textural de adsorção/dessorção de N2 a 77 K, espectroscopia de infravermelho, difração de raios X e dessorção à temperatura programada de CO2 e NH3. Os sítios básicos dos carvões foram quantificados pelo método de Boehm. Finalmente, o desempenho dos catalisadores foi avaliado na reação de Claisen-Schmidt entre Acetofenona e 4-Nitrobenzaldeído, sendo a conversão quantificada por cromatografia líquida de alta eficiência. O melhor catalisador foi o de carvão de babaçu tratado, cuja conversão alcançada foi de 92,38%.
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Remoção de compostos ácidos do petróleo em diferentes tipos de carvão ativado / Acid compounds removal from oil crude in different types of activated carbonsAraújo, Anderson Barros Caixeta 29 February 2016 (has links)
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Previous issue date: 2016-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The naphthenic acids comprise a complex mixture of carboxylic acids that are present in
petroleum. They are directly responsible for the oil acidity and its corrosiveness in liquid phase
during the refining process. Such compounds are also presents in the derivatives, causing several
problems to product quality. A possible way of removing these acids from those oil fractions is
using the adsorption process in porous solids, as activated carbons. There are few studies about the
removal of naphthenic acids on coals. For this reason, we chose four types of activated carbons for
adsorption tests, and they coal babassu, palm kernel, coconut and of Bahia ox bone. In order to
assess the possibility of further removing acidic compounds, the four carbons were subjected to a
chemical treatment with concentrated sodium hydroxide. Physical and chemical analyzes were
performed in order to promote the characterization of all adsorbents, showing that the treatment
previously mentioned was leading to an increase in the adsorption capacity of the coals. The
adsorption experiments with commercial batch naphthenic acid solution showed that the treated ox
bone char had the highest retention efficiency, which is the adsorbent used to construct the
adsorption isotherms. The isotherms were better adjusted by Langmuir model, revealing the
chemisorption of character adsorptive process. The thermodynamic data showed that the process is
spontaneous and endothermic, is favored by increasing the temperature. Regarding the crude oil
sample, batch adsorption experiments were conducted in such a way as to determine the removal
efficiency of class O2 and reducing the Total Acid Number (IAT). The results spectrometry FTICR
ix MS Pasta, they showed that all coals chemically treated were able to remove more acidic
compounds in relation to their untreated related. The raw coals babassu oil, palm oil and coconut
Bahia showed a potential for adsorption of nitrogen compounds from oil, given that there was a
decrease in its class in the class chart. As a final analysis, all the coals were evaluated for their
ability to lower oil IAT, it was found that the ox bone char treated again achieved the best result,
reducing by 70% the value of the IAT. / Os ácidos naftênicos correspondem à complexa mistura de ácidos carboxílicos presentes no petróleo, responsáveis diretamente pela sua acidez e pela sua corrosividade em fase líquida durante o refino. Tais compostos também estão presentes nas frações destiladas do petróleo, causando diversos problemas na qualidade final do produto. Uma alternativa para a remoção desses ácidos das frações destiladas é por meio da adsorção em materiais porosos, como os carvões ativados. Poucos são os estudos a respeito da remoção de ácidos naftênicos em carvões. Por esta razão, foram escolhidos quatro tipos de carvões ativados para os ensaios de adsorção, sendo eles carvão de babaçu, dendê, coco da Bahia e osso de boi. A fim de avaliar a possibilidade de uma maior
remoção de compostos ácidos, os quatro carvões foram submetidos a um tratamento químico com
solução concentrada de hidróxido de sódio. Análises físico-químicas foram realizadas com o
intuito de promover a caracterização de todos os adsorventes, revelando que o tratamento
anteriormente citado foi preponderante para um aumento na capacidade adsortiva dos carvões. Os
ensaios de adsorção em batelada com solução comercial de ácidos naftênicos mostraram que o
carvão de osso de boi tratado apresentou a maior eficiência de retenção, sendo este o adsorvente
utilizado para a construção das isotermas de adsorção. As isotermas foram melhor ajustadas pelo
Modelo de Langmuir, revelando o caráter de quimiossorção do processo adsortivo. Os dados
termodinâmicos mostraram que o processo é espontâneo e endotérmico, sendo mais favorecido
pelo aumento da temperatura. Em relação à amostra de petróleo bruto, ensaios de adsorção em
batelada foram conduzidos de tal forma a averiguar a eficiência na remoção da classe O2 e na
redução do Índice de Acidez Total (IAT). Os resultados de Espectrometria de Massas FT-ICR MS,
mostraram que todos os carvões tratados quimicamente conseguiram remover mais compostos
ácidos em relação a seus correlatos não tratados. Os carvões brutos de babaçu, dendê e coco da
Bahia apresentaram uma potencialidade para adsorção de compostos nitrogenados do petróleo, haja
vista que houve a diminuição desta classe no gráfico de classes. Como análise final, todos os
carvões foram avaliados quanto suas capacidades de redução do IAT do petróleo, em que foi
constatado que o carvão de osso de boi tratado novamente conseguiu o melhor resultado, reduzindo
em 70% o valor do IAT.
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