545 resultados para MICROPOROUS CARBONS
Resumo:
A preocupação com o meio ambiente, nomeadamente na descarga de águas residuais, consumo de água excessivo e produção de resíduos industriais, está cada vez mais presente no quotidiano. Devido a estas problemáticas, efetuou-se a avaliação de impacte ambiental (AIA) do processo produtivo das rolhas de cortiça naturais, tratamento das águas de cozedura da cortiça (estudo da possível reutilização do efluente tratado) e valorização de subprodutos – resíduo sólido (raspa de cortiça), sendo estes os objetivos propostos para a realização da presente dissertação. Na AIA, efetuada no decorrer das fases da Análise do Ciclo de Vida (ACV), foram selecionadas 8 categorias de impacte – aquecimento global, acidificação, dessecação, toxicidade e ecotoxicidade, eutrofização, consumo de recursos não renováveis e oxidação foto-química. A água de cozedura caracterizou-se por uma elevada carga poluente, apresentando elevada concentração de cor, Carência Química de Oxigénio (CQO), taninos e lenhina e Sólidos Suspensos Totais (SST). O processo de tratamento proposto consistiu num pré-tratamento por ultrafiltração (UF), com membranas de 30.000 e 20.000 MWCO, seguido de adsorção por carvão ativado (comercial e produzido a partir de raspa de cortiça). No tratamento por UF, utilizando uma membrana de 30.000 MWCO, foram obtidas percentagens de remoção para a primeira amostra de água de cozedura de 74,8 % para a cor, 33,1 % para a CQO e para a segunda amostra de 85,2 % para a cor e 41,8 % para a CQO. Posteriormente, apenas para a segunda amostra de água de cozedura e com uma membrana de 20.000 MWCO, as percentagens de remoção obtidas foram superiores, de 93% para a cor, 68,9 % para a CQO, 88,4 % para taninos e lenhina e 43,0 % para azoto total. No tratamento por adsorção com carvão ativado estudou-se o tempo de equilíbrio do carvão ativado comercial e do carvão ativado produzido a partir de aparas de cortiça, seguindo-se o estudo das isotérmicas de adsorção, no qual foram analisados os parâmetros da cor e CQO para cada solução. Os ajustes dos modelos teóricos aos pontos experimentais demonstraram que ambos os modelos (Langmuir e Freundlich) poderiam ser considerados, uma vez que apresentaram ajustes idênticos. Relativamente ao tratamento de adsorção em contínuo do permeado, obtido por UF com membrana de 20.000 MWCO, constatou-se que ambos os carvões ativados (comercial e produzido) não ficaram saturados, tendo em consideração os tempos de saturação estimados pela capacidade máxima de adsorção (determinada para a isotérmica de Langmuir) e as representações gráficas dos valores experimentais obtidos para cada ensaio. No ensaio de adsorção com carvão ativado comercial verificou-se que o efluente tratado poderia ser descarregado no meio hídrico ou reutilizado no processo industrial (considerando os parâmetros analisados), uma vez que até aos 11 minutos de ensaio a concentração da solução à saída foi de 111,50 mg/L O2, para a CQO, e incolor, numa diluição de 1:20. Em relação à adsorção em contínuo com carvão ativado produzido verificou-se no ensaio 4 que o efluente resultante apresentou uma concentração de CQO de 134,5 mg/L O2 e cor não visível, numa diluição de 1:20, ao fim de 1h22 min de ensaio. Assim, concluiu-se que os valores obtidos são inferiores aos valores limite de emissão (VLE) presentes no Decreto-Lei n.º 236/98 de 1 de Agosto. O carvão ativado produzido apresentou elevada área superficial específica, com 870 m2/g, comparativamente ao carvão comercial que foi de 661 m2/g. O processo de extração da suberina a partir de raspa de cortiça isenta de extraíveis, efetuado através da metanólise alcalina, apresentou percentagens de extração superiores aos restantes métodos. No processo efetuado em scale-up, por hidrólise alcalina, obteve-se uma extração de 3,76 % de suberina. A aplicação da suberina no couro demonstrou que esta cera apresenta enormes potencialidades, uma vez que a sua aplicação confere ao couro um aspeto sedoso, com mais brilho e um efeito de “pull-up”.
Resumo:
The applicability of the n-nonane pre-adsorption method for characterising the porosity in clays is presented. Na-SD, a Na+-exchanged purified bentonite, and materials obtained by Al3+-exchange and acid treatments of Na-SD and SAz-1 were used. Nitrogen adsorption isotherms, at -196 ºC, were determined before and after n-nonane pre-adsorption on each of the samples. In all materials, n-nonane remained adsorbed in ultramicropores after outgassing at 25 ºC. Outgassing at higher temperatures (50, 75 and 200 ºC) removed nonane and ultramicropores became available for nitrogen adsorption. All treatments on Na-SD led to increase in micropore volume. Larger ultramicropore and supermicropore volumes were obtained for Na-SD acid activated with HCl at 95 ºC than for treatments at 25 ºC with HCl or following Al3+-exchange (Al-SD), and increased with increasing acid concentration to 3 M. Activation with 4 M HCl led to the largest pore volume with contribution from mesopores. However, the specific external surface area was the same as that obtained for Na-SD, Al-SD and for most of the other acid activated samples. Treatments at 95 ºC with 1 M and 6 M HCl promoted increase in specific external surface area. The micropore volumes and specific external surface area for SAz-1 treated with 1 M HCl at 95 ºC were larger than those of Al-SAz-1, but lower than those obtained for corresponding materials derived from Na-SD. The n-nonane pre-adsorption method enabled micropore volumes and specific external surface areas to be obtained for all samples.
Resumo:
heterogeneous catalyst such as a silicoaluminophosphate, molecular sieve with AEL (Aluminophosphate eleven) structure such as SAPO-11, was synthesized through the hydrothermal method starting from silica, pseudoboehmite, orthophosphoric acid (85%) and water, in the presence of a di-isopropylamine organic template. For the preparation of SAPO-11 in a dry basis it was used as reactants: DIPA; H3PO4; SiO4; Pseudoboehmite and distilled water. The crystallization process occurred when the reactive hydrogel was charged into a vessel and autoclaved at 200ºC for a period of 72 hours under autogeneous pressure. The obtained material was washed, dried and calcined to remove the molecular sieves of DIPA. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), nitrogen adsorption (BET) and thermal analysis (TG/DTG). The acidic properties were determined using adsorption of nbutylamine followed by programmed thermodessorption. This method revealed that SAPO-11 shows an acidity that ranges from weak to moderate. However, a small quantity of strong acid sites could be detected there. The deactivation of the catalysts was conducted by artificial coking followed by the cracking of the n-hexane in a fixed bed with a continuous flow micro-reactor coupled on line to a gas chromatograph. The main products obtained were: ethane, propane, isobutene, n-butane, n-pentane and isopentane. The Vyazovkin (model-free) kinetics method was used to determine the regeneration and removal of the coke
Resumo:
We have examined the effect of the uncharged species of lidocaine (LDC) and etidocaine (EDC) on the acyl chain moiety of egg phosphatidylcholine liposomes. Changes in membrane organization caused by both anesthetics were detected through the use of EPR spin labels (5, 7 and 12 doxyl stearic acid methyl ester) or fluorescence probes (4, 6, 10, 16 pyrene-fatty acids). The disturbance caused by the LA was greater when the probes were inserted in more external positions of the acyl chain and decreased towards the hydrophobic core of the membrane. The results indicate a preferential insertion of LDC at the polar interface of the bilayer and in the first half of the acyl chain, for EDC. Additionally, 2 H NMR spectra of multilamellar liposomes composed by acyl chain-perdeutero DMPC and EPC (1:4 mol%) allowed the determination of the segmental order (S-mol) and dynamics (T-1) of the acyl chain region. In accordance to the fluorescence and EPR results, changes in molecular orientation and dynamics are more prominent if the LA preferential location is more superficial, as for LDC while EDC seems to organize the acyl chain region between carbons 2-8, which is indicative of its positioning. We propose that the preferential location of LDC and EDC inside the bilayers creates a "transient site", which is related to the anesthetic potency since it could modulate the access of these molecules to their binding site(s) in the voltage-gated sodium channel. (C) 2007 Elsevier B.V. All rights reserved.
Resumo:
The present work has as objective the development of ceramic pigments based in iron oxides and cobalt through the polymeric precursor method, as well as study their characteristics and properties using methods of physical, chemical, morphological and optical characterizations.In this work was used iron nitrate, and cobalt citrate as precursor and nanometer silica as a matrix. The synthesis was based on dissolving the citric acid as complexing agent, addition of metal oxides, such as chromophores ions and polymerization with ethylene glycol. The powder obtained has undergone pre-ignition, breakdown and thermal treatments at different calcination temperatures (700 °C, 800 °C, 900 °C, 1000 °C and 1100 °C). Thermogravimetric analyzes were performed (BT) and Differential Thermal Analysis (DTA), in order to evaluate the term decomposition of samples, beyond characterization by techniques such as BET, which classified as microporous materials samples calcined at 700 ° C, 800 º C and 900 º C and non-porous when annealed at 1000 ° C and 1100 º C, X-ray diffraction (XRD), which identified the formation of two crystalline phases, the Cobalt Ferrite (CoFe2O4) and Cristobalite (SiO2), Scanning Electron Microscopy (SEM) revealed the formation of agglomerates of particles slightly rounded;and Analysis of Colorimetry, temperature of 700 °C, 800 °C and 900 °C showed a brown color and 1000 °C and 1100 °C violet
Resumo:
Structural changes in waste for zeolites synthesis are subject of many studies carried out in the synthesis of molecular sieves. These materials are named molecular sieves because they have well defined pore sizes and they have the capacity of select molecules by its size. In this work, it was studied the synthesis processes of two types of molecular sieves: pillared acid clays using as starting material one natural montmorillonite clay and the synthesis of zeolites from a silico-aluminous residue. This residue is a byproduct of the extraction of lithium -spodumene. The preparation of pillared acid clays was performed in two steps: 1° acid treatment of clay samples (time and temperature studies) and 2°pilarization of them with Al13 (Keggin ion). The temperature and acid concentration affect the removal of cations in the structure and porosity of the material obtained. The analysis of X-ray diffraction (XRD) and infrared spectroscopy (IR), showed that increasing the severity of the acid treatment compromises the structural material. Also the pore size distribution is approximately uniform. Despite presenting a structural disorganization, the samples were pillared. As evidenced by XRD increasing the basal spacing, specific area and uniform porosity by adsorption of N2. Regarding the microporous molecular sieves were synthesized zeolites A and NaP1 from a silico-aluminous residue, a byproduct of extracting lithium. The temperature and time of agitation during the synthesis were the most important factors for obtaining zeolite A. The aging of the gel and the highest crystallization time promoted the formation of zeolite NaP1 using a Si / Al ratio = 3.2
Resumo:
The change in the carbonaceous skeleton of nanoporous carbons during their activation has received limited attention, unlike its counterpart process in the presence of an inert atmosphere. Here we adopt a multi-method approach to elucidate this change in a poly(furfuryl alcohol)-derived carbon activated using cyclic application of oxygen saturation at 250 °C before its removal (with carbon) at 800 °C in argon. The methods used include helium pycnometry, synchrotron-based X-ray diffraction (XRD) and associated radial distribution function (RDF) analysis, transmission electron microscopy (TEM) and, uniquely, electron energy-loss spectroscopy spectrum-imaging (EELS-SI), electron nanodiffraction and fluctuation electron microscopy (FEM). Helium pycnometry indicates the solid skeleton of the carbon densifies during activation from 78% to 93% of graphite. RDF analysis, EELS-SI, and FEM all suggest this densification comes through an in-plane growth of sp2 carbon out to the medium range without commensurate increase in order normal to the plane. This process could be termed ‘graphenization’. The exact way in which this process occurs is not clear, but TEM images of the carbon before and after activation suggest it may come through removal of the more reactive carbon, breaking constraining cross-links and creating space that allows the remaining carbon material to migrate in an annealing-like process.
Resumo:
We show here that a physical activation process that is diffusion-controlled yields an activated carbon whose chemistry – both elemental and functional – varies radially through the particles. For the ∼100 μm particles considered here, diffusion-controlled activation in CO2 at 800 °C saw a halving in the oxygen concentration from the particle periphery to its center. It was also observed that this activation process leads to an increase in keto and quinone groups from the particle periphery towards the center and the inverse for other carbonyls as well as ether and hydroxyl groups, suggesting the two are formed under CO2-poor and -rich environments, respectively. In contrast to these observations, use of physical activation processes where diffusion-control is absent are shown to yield carbons whose chemistry is radially invariant. This suggests that a non-diffusion limited activation processes should be used if the performance of a carbon is dependent on having a specific optimal pore surface chemical composition.
Resumo:
This study describes a new synthesis route for bone chars using a CO2 atmosphere and their behavior as adsorbent for fluoride removal from water. Specifically, we have performed a detailed analysis of the adsorption properties of bone char samples obtained at different carbonization conditions and a comparative study with samples of bone char obtained via pyrolysis under nitrogen. Experimental results show that the nature of the gas atmosphere (CO2 versus N2) and the carbonization temperature play a major role to achieve an effective bone char for water defluoridation. In particular, the best adsorption properties of bone char for fluoride removal are obtained with those samples synthesized at 700 °C. Carbonization temperatures above 700 °C under CO2 atmosphere cause the dehydroxylation of the hydroxyapatite in the bone char, thus reducing its fluoride adsorption capacity. The maximum fluoride adsorption capacity for the bone char obtained in this study under CO2 atmosphere (i.e., 5.92 mg/g) is higher than those reported for commercial bone chars.
Resumo:
Fixed-bed thermodynamic CO2 adsorption tests were performed in model flue-gas onto Filtrasorb 400 and Nuchar RGC30 activated carbons (AC) functionalized with [Hmim][BF4] and [Emim][Gly] ionic liquids (IL). A comparative analysis of the CO2 capture results and N2 porosity characterization data evidenced that the use of [Hmim][BF4], a physical solvent for carbon dioxide, ended up into a worsening of the parent AC capture performance, due to a dominating pore blocking effect at all the operating temperatures. Conversely, the less sterically-hindered and amino acid-based [Emim][Gly] IL was effective in increasing the AC capture capacity at 353 K under milder impregnation conditions, the beneficial effect being attributed to both its chemical affinity towards CO2 and low pore volume reduction. The findings derived in this work outline interesting perspectives for the application of amino acid-based IL supported onto activated carbons for CO2 separation under post-combustion conditions, and future research efforts should be focused on the search for AC characterized by optimal pore size distribution and surface properties for IL functionalization.
Resumo:
One of the main concerns in the technological application of several metal–organic frameworks (MOFs) relates to their structural instability under pressure (after a conforming step). Here we report for the first time that mechanical instability can be highly improved via nucleation and growth of MOF nanocrystals in the confined nanospace of activated carbons.
Resumo:
A novel synthesis method for ordered mesoporous carbons is presented. The inverse replication of a silica template was achieved using the carbonization of sucrose within mesoporous KIT-6. Instead of liquid acid etching, as in classical nanocasting, a novel dry chlorine etching procedure for template removal is presented for the first time. The resultant ordered mesostructured carbon material outperforms carbons obtained by conventional hard templating with respect to high specific micro- and mesopore volumes (0.6 and 1.6 cm3 g−1, respectively), due to the presence of a hierarchical pore system. A high specific surface area of 1671 m2 g−1 was achieved, rendering this synthesis route a highly convenient method to produce ordered mesoporous carbons.
Resumo:
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
Resumo:
In this project we developed conductive thermoplastic resins by adding varying amounts of three different carbon fillers: carbon black (CB), synthetic graphite (SG) and multi–walled carbon nanotubes (CNT) to a polypropylene matrix for application as fuel cell bipolar plates. This component of fuel cells provides mechanical support to the stack, circulates the gases that participate in the electrochemical reaction within the fuel cell and allows for removal of the excess heat from the system. The materials fabricated in this work were tested to determine their mechanical and thermal properties. These materials were produced by adding varying amounts of single carbon fillers to a polypropylene matrix (2.5 to 15 wt.% Ketjenblack EC-600 JD carbon black, 10 to 80 wt.% Asbury Carbons’ Thermocarb TC-300 synthetic graphite, and 2.5 to 15 wt.% of Hyperion Catalysis International’s FIBRILTM multi-walled carbon nanotubes) In addition, composite materials containing combinations of these three fillers were produced. The thermal conductivity results showed an increase in both through–plane and in–plane thermal conductivities, with the largest increase observed for synthetic graphite. The Department of Energy (DOE) had previously set a thermal conductivity goal of 20 W/m·K, which was surpassed by formulations containing 75 wt.% and 80 wt.% SG, yielding in–plane thermal conductivity values of 24.4 W/m·K and 33.6 W/m·K, respectively. In addition, composites containing 2.5 wt.% CB, 65 wt.% SG, and 6 wt.% CNT in PP had an in–plane thermal conductivity of 37 W/m·K. Flexural and tensile tests were conducted. All composite formulations exceeded the flexural strength target of 25 MPa set by DOE. The tensile and flexural modulus of the composites increased with higher concentration of carbon fillers. Carbon black and synthetic graphite caused a decrease in the tensile and flexural strengths of the composites. However, carbon nanotubes increased the composite tensile and flexural strengths. Mathematical models were applied to estimate through–plane and in–plane thermal conductivities of single and multiple filler formulations, and tensile modulus of single–filler formulations. For thermal conductivity, Nielsen’s model yielded accurate thermal conductivity values when compared to experimental results obtained through the Flash method. For prediction of tensile modulus Nielsen’s model yielded the smallest error between the predicted and experimental values. The second part of this project consisted of the development of a curriculum in Fuel Cell and Hydrogen Technologies to address different educational barriers identified by the Department of Energy. By the creation of new courses and enterprise programs in the areas of fuel cells and the use of hydrogen as an energy carrier, we introduced engineering students to the new technologies, policies and challenges present with this alternative energy. Feedback provided by students participating in these courses and enterprise programs indicate positive acceptance of the different educational tools. Results obtained from a survey applied to students after participating in these courses showed an increase in the knowledge and awareness of energy fundamentals, which indicates the modules developed in this project are effective in introducing students to alternative energy sources.
Resumo:
Les zéolithes étant des matériaux cristallins microporeux ont démontré leurs potentiels et leur polyvalence dans un nombre très important d’applications. Les propriétés uniques des zéolithes ont poussé les chercheurs à leur trouver constamment de nouvelles utilités pour tirer le meilleur parti de ces matériaux extraordinaires. Modifier les caractéristiques des zéolithes classiques ou les combiner en synergie avec d’autres matériaux se trouvent être deux approches viables pour trouver encore de nouvelles applications. Dans ce travail de doctorat, ces deux approches ont été utilisées séparément, premièrement avec la modification morphologique de la ZSM-12 et deuxièmement lors de la formation des matériaux de type coeur/coquille (silice mésoporeuses@silicalite-1). La ZSM-12 est une zéolithe à haute teneur en silice qui a récemment attiré beaucoup l’attention par ses performances supérieures dans les domaines de l’adsorption et de la catalyse. Afin de synthétiser la ZSM-12 avec une pureté élevée et une morphologie contrôlée, la cristallisation de la zéolithe ZSM-12 a été étudiée en détail en fonction des différents réactifs chimiques disponibles (agent directeur de structure, types de silicium et source d’aluminium) et des paramètres réactionnels (l’alcalinité, ratio entre Na, Al et eau). Les résultats présentés dans cette étude ont montré que, contrairement à l’utilisation du structurant organique TEAOH, en utilisant un autre structurant, le MTEAOH, ainsi que le Al(o-i-Pr)3, cela a permis la formation de monocristaux ZSM-12 monodisperses dans un temps plus court. L’alcalinité et la teneur en Na jouent également des rôles déterminants lors de ces synthèses. Les structures de types coeur/coquille avec une zéolithe polycristalline silicalite-1 en tant que coquille, entourant un coeur formé par une microsphère de silice mésoporeuse (tailles de particules de 1,5, 3 et 20-45 μm) ont été synthétisés soit sous forme pure ou chargée avec des espèces hôtes métalliques. Des techniques de nucléations de la zéolithe sur le noyau ont été utilisées pour faire croitre la coquille de façon fiable et arriver à former ces matériaux. C’est la qualité des produits finaux en termes de connectivité des réseaux poreux et d’intégrité de la coquille, qui permet d’obtenir une stéréosélectivité. Ceci a été étudié en faisant varier les paramètres de synthèse, par exemple, lors de prétraitements qui comprennent ; la modification de surface, la nucléation, la calcination et le nombre d’étapes secondaires de cristallisation hydrothermale. En fonction de la taille du noyau mésoporeux et des espèces hôtes incorporées, l’efficacité de la nucléation se révèle être influencée par la technique de modification de surface choisie. En effet, les microsphères de silice mésoporeuses contenant des espèces métalliques nécessitent un traitement supplémentaire de fonctionnalisation chimique sur leur surface externe avec des précurseurs tels que le (3-aminopropyl) triéthoxysilane (APTES), plutôt que d’utiliser une modification de surface avec des polymères ioniques. Nous avons également montré que, selon la taille du noyau, de deux à quatre traitements hydrothermaux rapides sont nécessaires pour envelopper totalement le noyau sans aucune agrégation et sans dissoudre le noyau. De tels matériaux avec une enveloppe de tamis moléculaire cristallin peuvent être utilisés dans une grande variété d’applications, en particulier pour de l’adsorption et de la catalyse stéréo-sélective. Ce type de matériaux a été étudié lors d’une série d’expériences sur l’adsorption sélective du glycérol provenant de biodiesel brut avec des compositions différentes et à des températures différentes. Les résultats obtenus ont été comparés à ceux utilisant des adsorbants classiques comme par exemple du gel de sphères de silice mésoporeux, des zéolithes classiques, silicalite-1, Si-BEA et ZSM-5(H+), sous forment de cristaux, ainsi que le mélange physique de ces matériaux références, à savoir un mélange silicalite-1 et le gel de silice sphères. Bien que le gel de sphères de silice mésoporeux ait montré une capacité d’adsorption de glycérol un peu plus élevée, l’étude a révélé que les adsorbants mésoporeux ont tendance à piéger une quantité importante de molécules plus volumineuses, telles que les « fatty acid methyl ester » (FAME), dans leur vaste réseau de pores. Cependant, dans l’adsorbant à porosité hiérarchisée, la fine couche de zéolite silicalite-1 microporeuse joue un rôle de membrane empêchant la diffusion des molécules de FAME dans les mésopores composant le noyau/coeur de l’adsorbant composite, tandis que le volume des mésopores du noyau permet l’adsorption du glycérol sous forme de multicouches. Finalement, cette caractéristique du matériau coeur/coquille a sensiblement amélioré les performances en termes de rendement de purification et de capacité d’adsorption, par rapport à d’autres adsorbants classiques, y compris le gel de silice mésoporeuse et les zéolithes.