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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
71

Determinação da cor do solo e sua utilização na predição dos teores de hematita. / Soil color determination and its use on the estimative of hematite contents.

Campos, Rogério Costa 21 January 2002 (has links)
Os objetivos do presente trabalho foram: (a) Determinar e avaliar a cor dos solos pelo método convencional e com equipamento colorímetro e sua implicação na classificação de solos: (b) Estimar teores de hematita a partir da cor do solo. O matiz de 80 amostras de solos foi determinado por cinco experientes pesquisadores pela comparação com a carta de Munsell e diretamente com um colorímetro. A cor de 15 amostras de solos pertencentes a diferentes regiões do Estado de São Paulo foi determinada utilizando um colorímetro e a partir de dados de reflectância obtidos por radiômetro. As cores foram determinadas no sistema L*a*b* e Munsell. Para cada amostra foram determinados os teores de hematita e calculados os índices de avermelhamento (IAV) a partir das cores obtidas. Os coeficientes de correlação, variando de 0,68 a 0,94 entre as determinações do matiz, constataram que os pedólogos produziram dados que validaram o estudo. No entanto, houve confirmação de que as medidas realizadas por pedólogos não coincidem, sendo difeprentes também das determinações feitas pelo colorímetro. Índices de precisão (IP) indicaram haver concordância em apenas 8,75 % das determinações em amostras úmidas e 17,5 % nas amostras secas, sendo constatado que as divergências resultariam em erros na classificação dos solos. Os IAVs apresentaram alta correlação com os teores de hematita das amostras, sendo maior para correlações com índices determinados a partir de cores no sistema L*a*b* do que no sistema Munsell. Modelos exponenciais mostraram-se mais adequados na predição dos teores de hematita. / The objectives of the present work were: (a) Determine and evaluate color by the conventional method, and its comparison with colormeter equipment and their implication with soil classification; (b) Estimate of hematite contents by using soil color data. The hue of 80 samples of soils was determined by five experienced soil scientists by the comparison with the Munsell’s soil color charts and by a colorimeter. Color of 15 soil samples from different sites of São Paulo State were determined by colorimeter and from reflectance data obtained with radiometer. The correlation coefficients, varying from 0,68 to 0,94 of hue determinations, showed that the soil scientists produced data that validated the study. However, there was confirmation that the measures accomplished by soil scientists were not coincident and also differed from the colormeter. The values of precision index (PI) indicated an agreement of only 8,75% in moist samples and 17,5% in the dry samples, which would result in mistakes in the soil classification. Colors were achieved by L*a*b* and Munsell systems. For each sample, hematite content were determinated and the redness indexes (RI) calculated. The RI presented high correlation with hematite contents, and higher correlations for colors obtained in L*a*b* than those obtained in Munsell system. Exponential models were more effective in predicting hematite contents.
72

Determinação da cor do solo e sua utilização na predição dos teores de hematita. / Soil color determination and its use on the estimative of hematite contents.

Rogério Costa Campos 21 January 2002 (has links)
Os objetivos do presente trabalho foram: (a) Determinar e avaliar a cor dos solos pelo método convencional e com equipamento colorímetro e sua implicação na classificação de solos: (b) Estimar teores de hematita a partir da cor do solo. O matiz de 80 amostras de solos foi determinado por cinco experientes pesquisadores pela comparação com a carta de Munsell e diretamente com um colorímetro. A cor de 15 amostras de solos pertencentes a diferentes regiões do Estado de São Paulo foi determinada utilizando um colorímetro e a partir de dados de reflectância obtidos por radiômetro. As cores foram determinadas no sistema L*a*b* e Munsell. Para cada amostra foram determinados os teores de hematita e calculados os índices de avermelhamento (IAV) a partir das cores obtidas. Os coeficientes de correlação, variando de 0,68 a 0,94 entre as determinações do matiz, constataram que os pedólogos produziram dados que validaram o estudo. No entanto, houve confirmação de que as medidas realizadas por pedólogos não coincidem, sendo difeprentes também das determinações feitas pelo colorímetro. Índices de precisão (IP) indicaram haver concordância em apenas 8,75 % das determinações em amostras úmidas e 17,5 % nas amostras secas, sendo constatado que as divergências resultariam em erros na classificação dos solos. Os IAVs apresentaram alta correlação com os teores de hematita das amostras, sendo maior para correlações com índices determinados a partir de cores no sistema L*a*b* do que no sistema Munsell. Modelos exponenciais mostraram-se mais adequados na predição dos teores de hematita. / The objectives of the present work were: (a) Determine and evaluate color by the conventional method, and its comparison with colormeter equipment and their implication with soil classification; (b) Estimate of hematite contents by using soil color data. The hue of 80 samples of soils was determined by five experienced soil scientists by the comparison with the Munsell’s soil color charts and by a colorimeter. Color of 15 soil samples from different sites of São Paulo State were determined by colorimeter and from reflectance data obtained with radiometer. The correlation coefficients, varying from 0,68 to 0,94 of hue determinations, showed that the soil scientists produced data that validated the study. However, there was confirmation that the measures accomplished by soil scientists were not coincident and also differed from the colormeter. The values of precision index (PI) indicated an agreement of only 8,75% in moist samples and 17,5% in the dry samples, which would result in mistakes in the soil classification. Colors were achieved by L*a*b* and Munsell systems. For each sample, hematite content were determinated and the redness indexes (RI) calculated. The RI presented high correlation with hematite contents, and higher correlations for colors obtained in L*a*b* than those obtained in Munsell system. Exponential models were more effective in predicting hematite contents.
73

The formation of cementite from hematite and titanomagnetite iron ore and its stability

Longbottom, Raymond James, Materials Science & Engineering, Faculty of Science, UNSW January 2005 (has links)
This project examined the reduction and formation of cementite from hematite and titanomagnetite ores and cementite stability. The aim of the project was to develop further understanding of cementite stability under conditions relevant to direct ironmaking and the mechanism of cementite decomposition. The reduction of hematite and ironsand by hydrogen-methane-argon gas mixtures was investigated from 600??C to 1100??C. Iron oxides were reduced by hydrogen to metallic iron, which was carburised by methane to form cementite. The hematite ore was reduced more quickly than the ironsand. Preoxidation of the ironsand accelerated its reduction. Hematite was converted to cementite faster than preoxidised ironsand. The decomposition of cementite formed from hematite was investigated from 500??C to 900??C. This cementite was most stable at temperatures 750-770??C. The decomposition rate increased with decreasing temperature between 750??C and 600??C and with increasing temperature above 770??C. The stability of cementite formed from pre-oxidised titanomagnetite was studied from 300??C to 1100??C. This cementite was most stable in the temperature range 700-900??C. The rate of decomposition of cementite increased with decreasing temperature between 700??C and 400??C and with increasing temperature above 900??C. Cementite formed from ironsand was more stable than cementite formed from hematite
74

Carbonate diagenesis and chemical weathering in the Southeastern United States: some implications on geotechnical behavior

Larrahondo-Cruz, Joan Manuel 15 November 2011 (has links)
The Savannah River Site (SRS) deposits in the Southeastern US between 30-45 m of depth are calcium carbonate-rich, marine-skeletal, Eocene-aged sediments with varying clastic content and extensive diagenetic alteration, including meter-sized caves that coexist with brittle and hard limestone. An experimental investigation including geotechnical (P- and S-wave velocities, tensile strength, porosity) and geochemical (EDS, XRD, SEM, N2-adsorption, stable isotopes, K-Ar age dating, ICP-assisted solubility, groundwater) studies highlighted the contrast between hard and brittle limestones, their relationship with cave formation, and allowed calculation of parameters for geochemical modeling. Results demonstrate that brittle and hard limestones bear distinct geochemical signatures whereby the latter exhibits higher crystallinity, lower clastic load, and freshwater-influenced composition. Results also reveal carbonate diagenesis pathways likely driven by geologic-time seawater/freshwater cycles, microorganism-driven micritization, and freshwater micrite lithification. The second section of this investigation dealt with SRS surface soils which are largely coarse-grained and rich in iron oxides with various degrees of maturity. These soils were simulated in the laboratory using Ottawa sands that were chemically coated with goethite and hematite. Surface (SEM, AFM, N2-adsorption) and geotechnical properties (fabric, small-strain stiffness, shear strength) were investigated on the resulting "soil analog". Results indicate that iron-oxide coated sands bear distinct inherent fabric and enhanced small-strain stiffness and critical state parameters when compared to uncoated sands. Contact mechanics analyses suggest that iron oxide coatings yield an increased number of grain-to-grain contacts, higher surface roughness, and interlocking, which are believed to be responsible for the observed properties.
75

Fluidized Bed Selective Oxidation and Sulfation Roasting of Nickel Sulfide Concentrate

Yu, Dawei 01 September 2014 (has links)
Selective oxidation and sulfation roasting of nickel concentrate followed by leaching was investigated as a novel route for nickel production. In the oxidation roasting stage, the iron species in the nickel concentrate was preferentially oxidized to form iron oxides, leaving non-ferrous metals (Ni, Cu, Co) as sulfides. The roasted product was then sulfation roasted to convert the sulfides of the latter metals into water-soluble sulfates. The sulfates were then leached into solution for further recovery and separation from iron oxides. The oxidation of nickel concentrate was firstly studied by means of thermogravimetric and differential thermal analysis over a wide temperature range. A reaction scheme was deduced, in which preferential oxidation of iron sulfide species occurred over a wide temperature range up to about 700 ºC, forming a Ni1-xS core with iron oxide shell. A batch fluidized bed roaster was then constructed to study the oxidation and sulfation roasting of nickel sulfide concentrate. Oxidation roasting tests were carried out at temperatures between 650 °C and 775 °C. It was found that low temperatures (e.g. 650 °C) are favorable for the preferential oxidation of iron sulfide species while minimizing the formation of nickeliferous oxides, i.e. trevorite and NiO. Several parameters were varied in the sulfation roasting experiments, including the sulfation gas flowrate, sulfation roasting temperature, the addition of Na2SO4, sulfation roasting time, and the oxidation roasting temperature. Under optimized conditions of sulfation gas composition (95% air, 5% SO2), temperature (700 °C), Na2SO4 addition (10 wt%) and time (150 min), the conversions to sulfates were 79% Ni, 91% Cu, and 91% Co. Only 5% Fe forms water-soluble sulfate. The residue from the leaching of calcine in water contained 49% Fe and 10% Ni, which is a suitable feedstock for the production of ferronickel alloys. Therefore, further studies were also conducted to evaluate the reduction behavior of the residue with CO, H2 and graphite.
76

Highly Efficient CIGS Based Devices for Solar Hydrogen Production and Size Dependent Properties of ZnO Quantum Dots

Jacobsson, T. Jesper January 2014 (has links)
Materials and device concepts for renewable solar hydrogen production, and size dependent properties of ZnO quantum dots are the two main themes of this thesis. ZnO particles with diameters less than 10 nm, which are small enough for electronic quantum confinement, were synthesized by hydrolysis in alkaline zinc acetate solutions. Properties investigated include: the band gap - particle size relation, phonon quantum confinement, visible and UV-fluorescence as well as photocatalytic performance. In order to determine the absolute energetic position of the band edges and the position of trap levels involved in the visible fluorescence, methods based on combining linear sweep voltammetry and optical measurements were developed. The large band gap of ZnO prevents absorption of visible light, and in order to construct devices capable of utilizing a larger part of the solar spectrum, other materials were also investigated, like hematite , Fe2O3, and CIGS, CuIn1-xGaxSe2. The optical properties of hematite were investigated as a function of film thickness on films deposited by ALD. For films thinner than 20 nm, a blue shift was observed for both the absorption maximum, the indirect band gap as well as for the direct transitions. The probability for the indirect transition decreased substantially for thinner films due to a suppressed photon/phonon coupling. These effects decrease the visible absorption for films thin enough for effective charge transport in photocatalytic applications. CIGS was demonstrated to be a highly interesting material for solar hydrogen production. CIGS based photocathodes demonstrated high photocurrents for the hydrogen evolution half reaction. The electrode stability was problematic, but was solved by introducing a modular approach based on spatial separation of the basic functionalities in the device. To construct devices capable of driving the full reaction, the possibility to use cells interconnected in series as an alternative to tandem devices were investigated. A stable, monolithic device based on three CIGS cells interconnected in series, reaching beyond 10 % STH-efficiency, was finally demonstrated. With experimental support from the CIGS-devices, the entire process of solar hydrogen production was reviewed with respect to the underlying physical processes, with special focus on the similarities and differences between various device concepts.
77

The formation of cementite from hematite and titanomagnetite iron ore and its stability

Longbottom, Raymond James, Materials Science & Engineering, Faculty of Science, UNSW January 2005 (has links)
This project examined the reduction and formation of cementite from hematite and titanomagnetite ores and cementite stability. The aim of the project was to develop further understanding of cementite stability under conditions relevant to direct ironmaking and the mechanism of cementite decomposition. The reduction of hematite and ironsand by hydrogen-methane-argon gas mixtures was investigated from 600??C to 1100??C. Iron oxides were reduced by hydrogen to metallic iron, which was carburised by methane to form cementite. The hematite ore was reduced more quickly than the ironsand. Preoxidation of the ironsand accelerated its reduction. Hematite was converted to cementite faster than preoxidised ironsand. The decomposition of cementite formed from hematite was investigated from 500??C to 900??C. This cementite was most stable at temperatures 750-770??C. The decomposition rate increased with decreasing temperature between 750??C and 600??C and with increasing temperature above 770??C. The stability of cementite formed from pre-oxidised titanomagnetite was studied from 300??C to 1100??C. This cementite was most stable in the temperature range 700-900??C. The rate of decomposition of cementite increased with decreasing temperature between 700??C and 400??C and with increasing temperature above 900??C. Cementite formed from ironsand was more stable than cementite formed from hematite
78

Σύνθεση και χαρακτηρισμός νανοσφαιρών οξειδίων σιδήρου : μελέτη μαγνητικών ιδιοτήτων αιματίτη και μαγγεμίτη / Synthesis and characterization of iron oxides nanospheres : study of the magnetic properties of hematite and maghemite

Ταπεινός, Χρήστος 24 January 2011 (has links)
Πολλοί από τους τομείς της επιστημονικής έρευνας, όπως χημεία, ενέργεια, βιομηχανία και ιατρική χρησιμοποιούν τη νανοτεχνολογία, με στόχο την παρασκευή υλικών, με καλύτερες και πιο εξειδικευμένες ιδιότητες σε σχέση με τα συμβατικά υλικά του μακρόκοσμου. Οι νανοσφαίρες λόγω των ποικίλων ιδιοτήτων που παρουσιάζουν, όπως οπτικές, μηχανικές, ηλεκτρικές κ.α., μπορούν να χρησιμοποιηθούν σε διάφορους τομείς της καθημερινής μας ζωής με μεγαλύτερο ενδιαφέρον στον τομέα της υγείας. Η παρούσα ερευνητική εργασία πραγματοποιήθηκε με στόχο τη σύνθεση και τη μελέτη νανοσφαιρών οξειδίων του σιδήρου. Πιο συγκεκριμένα παρασκευάσθηκαν νανοσφαίρες αιματίτη (α – Fe2O3) και μαγγεμίτη (γ – Fe2O3) και μελετήθηκαν οι μαγνητικές τους ιδιότητες. Στο πρώτο κεφάλαιο παρουσιάζεται μία εισαγωγή – ιστορική αναδρομή στο χώρο της νανοτεχνολογίας και των νανοσφαιρών. Γίνεται επίσης αναφορά στους τρόπους σύνθεσης των νανοσφαιρών και αναφέρονται εν συντομία κάποιες ιδιότητες και εφαρμογές αυτών. Στο δεύτερο κεφάλαιο αναφέρονται κάποιες βασικές έννοιες οι οποίες είναι απαραίτητες για την κατανόηση των ταχνικών που θα χρησιμοποιηθούν. Παρουσιάζονται αναλυτικά οι τρόποι με τους οποίους πραγματοποιείται η σύνθεση των νανοσφαιρών και περιγράφονται αναλυτικά, η μέθοδος λύματος – πηκτής (sol – gel) και η τεχνική του πολυμερισμού. Στο τρίτο κεφάλαιο αναφέρονται τα αντιδραστήρια καθώς επίσης και οι πειραματικές μέθοδοι που χρησιμοποιήθηκαν για το χαρακτηρισμό των νανοσφαιρών και τη μελέτη των ιδιοτήτων τους. Αναφέρονται επίσης τα όργανα που χρησιμοποιήθηκαν καθώς επίσης και οι βασικές αρχές λειτουργίας αυτών. Στο τέταρτο κεφάλαιο περιγράφεται αναλυτικά η πειραματική διαδικασία που πραγματοποιήθηκε και γίνεται συζήτηση των αποτελεσμάτων. Τέλος στο πέμπτο κεφάλαιο ανγράφονται τα συμπεράσματα και αναφέρονται μελλοντικοί στόχοι. / Nanotechnology is the study of the control of matter on an atomic and molecular scale and it’s main objective is the manufacture of new materials with better and more sophisticated properties. Nanotechnology is used in many different sciences like chemistry, physics and most of all in medicine. Nanospheres exhibit many diverse properties (electrical, optical etc) which render them the best solution for application such as drug delivery systems, Magnetic Resonance Imaging (MRI) agents, hyperthermia etc. The present work deals with the synthesis and characterization of magnetic nanospheres and more specifically in the study of magnetic properties of hematite (α – Fe2O3) and maghemite (γ – Fe2O3). The first chapter starts with a short introduction for nanospheres and nanotechnology . It reports also a quick historical review and some lines about new generation nanospheres, it’s properties and it’s applications. In the second chapter, polymerization and sol – gel techniques are described analytically. In the third chapter, reactants and experimental methods are described as well as some basic principles of the methods that were used to characterize the samples. The fourth chapter is the results and discussion session. Finally in the fifth chapter some conclusions and future targets are reported.
79

Efeito do agente precipitante nas propriedades de catalisadores de hematita contendo alumínio e cobre

Braga, Cláudio Taranto Lima 10 February 2014 (has links)
Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2014-09-09T17:09:12Z No. of bitstreams: 1 DISSERTAÇÃO - CLÁUDIO TARANTO.pdf: 18450159 bytes, checksum: 76f9d1c02e4cdba72b38d11a61fcc786 (MD5) / Approved for entry into archive by Fatima Cleômenis Botelho Maria (botelho@ufba.br) on 2014-09-09T17:15:00Z (GMT) No. of bitstreams: 1 DISSERTAÇÃO - CLÁUDIO TARANTO.pdf: 18450159 bytes, checksum: 76f9d1c02e4cdba72b38d11a61fcc786 (MD5) / Made available in DSpace on 2014-09-09T17:15:00Z (GMT). No. of bitstreams: 1 DISSERTAÇÃO - CLÁUDIO TARANTO.pdf: 18450159 bytes, checksum: 76f9d1c02e4cdba72b38d11a61fcc786 (MD5) / Considerando a busca por tecnologias mais limpas e sustentáveis, o hidrogênio surge como uma das fontes de energia mais práticas e sustentáveis do futuro. Esse combustível é obtido comercialmente pela reforma de gás natural, seguido de uma etapa de purificação, conhecida como conversão de monóxido a dióxido de carbono com vapor d’água (reação de HTS, High Temperature Shift). Os catalisadores comerciais empregados nessa reação são constituídos por hematita (-Fe2O3) contendo cromo hexavalente, um íon tóxico aos seres humanos e ao meio ambiente. Por essa razão, diversas pesquisas têm sido desenvolvidas visando a substituir o cromo nesses sólidos. Com o objetivo de otimizar as propriedades de catalisadores baseados em hematita contendo alumínio (Fe/Al=10) e cobre (Fe/Cu=10) para a reação de HTS, neste trabalho, estudou-se o efeito do agente precipitante sobre as propriedades desses sólidos. As amostras foram preparadas através do processo sol-gel, misturando-se soluções de nitrato férrico e nitrato de alumínio e usando diferentes agentes precipitantes (hidróxido de sódio e hidróxido de amônio), seguida de impregnação com solução alcoólica de cobre. Os sólidos foram caracterizados por termogravimetria, espectroscopia no infravermelho com transformada de Fourier, difração de raios X, medida de área superficial específica e de porosidade, redução à temperatura programada e espectroscopia Mössbauer. Os catalisadores foram avaliados na reação de HTS a 1 atm e 400 °C. Observou-se a formação da hematita e magnetita nos catalisadores antes e após a reação, respectivamente, não se detectando nenhuma outra fase. Os dopantes foram inseridos na rede do óxido de ferro, o que pode ser explicado pela similaridade dos raios iônicos das espécies Cu+2, Al+3 e Fe+3; esse processo foi facilitado pelo hidróxido de amônio. Quando presentes isoladamente, o alumínio e o cobre aumentaram a área superficial específica dos sólidos obtidos com hidróxido de amônio mas o hidróxido de sódio inibiu a ação textural do cobre e alumínio, juntos ou isoladamente. O hidróxido de amônio favoreceu o desenvolvimento de mesoporos interparticulares nos sólidos macroporosos obtidos. A redutibilidade da hematita foi alterada pela presença dos dopantes e pela natureza do agente precipitante; o alumínio dificultou a formação da magnetita (Fe3O4) e do ferro metálico enquanto o cobre e o hidróxido de amônio facilitaram esses processos. Dessa forma, a presença simultânea dos dopantes favoreceu a formação da fase ativa (magnetita) e a estabilidade do catalisador, retardando sua desativação pela formação de ferro metálico. Todos os catalisadores foram ativos na reação de HTS, mas aqueles contendo cobre, e obtidos com hidróxido de sódio, foram os mais ativos, devido a um aumento na atividade dos sítios ativos e à maior facilidade de formação da fase ativa (magnetita). O papel do alumínio foi relacionado ao aumento da resistência dos catalisadores à redução da fase ativa. O catalisador mais promissor foi aquele preparado com hidróxido de sódio, que apresentou elevada atividade (10,68 x 10-7 mol.s-1.g-1) e alta resistência à redução da fase ativa (magnetita), com a vantagem de não ser tóxico, podendo ser manuseado e descartado sem risco à saúde humana e ao meio ambiente. / Considering the search for cleaner and more sustainable technologies, hydrogen emerges as one of the most practical and sustainable energy source in the future. This fuel is commercially obtained by natural gas reforming, followed by a purification step known as the water gas shift reaction at high temperatures (HTS, High Temperature Shift). The commercial catalysts for this reaction are composed of hematite (-Fe2O3) containing hexavalent chromium, a toxic ion to humans and the environment. For this reason, many studies have been carried out aiming to replace chromium in these solids. In order to optimize the properties of catalysts based on hematite containing aluminum (Fe/Al= 10) and copper (Fe/Cu= 10) for the HTS reaction, the effect of precipitating agent on the properties of these solids was studied in this work. Samples were prepared by sol-gel process by mixing solutions of iron nitrate and aluminum nitrate and using different precipitating agents (sodium hydroxide and ammonium hydroxide) and impregnated with an alcoholic solution of copper. The solids were characterized by thermogravimetry, Fourier transform infrared spectroscopy, X-ray diffraction, specific surface area and porosity measurement, temperature programmed reduction and Mössbauer spectroscopy. The catalysts were evaluated in the HTS reaction at 1 atm and 400 °C. It was found hematite and magnetite in the catalysts before and after reaction, respectively and no other phase was detected. The dopants were found to be into the iron oxide lattice, a fact that was explained by the similarity of the ionic radii of Cu+2, Al+3 and Fe+3 species, this process being facilitated by ammonium hydroxide. Aluminum and copper alone increased the specific surface area of the solids obtained with ammonium hydroxide but sodium hydroxide inhibited the textural action of copper and aluminum, together or separately. Ammonium hydroxide favored the development of nterparticlemesopores in the macroporous solids obtained. The reducibility of hematite was changed by the dopants and by the kind of the precipitating agent, aluminum hindering the formation of magnetite (Fe3O4) and metallic iron while copper and ammonium hydroxide facilitated this process. Therefore, the dopants favored the formation of active phase (magnetite) and the catalyst stability, delaying its deactivation through the formation of metallic iron. All catalysts were active in HTS reaction, those containing copper and obtained with sodium hydroxide being the most active ones, due to increase in the activity of the active sites and the ease of formation of active phase (magnetite). The role of aluminum was related to increased resistance to reduction of the active phase. The most promising catalyst was the one prepared with sodium hydroxide, which showed high activity (10.68 x 10- 7 mol.s-1.g-1) and high resistance against the reduction of the active phase (magnetite), with the advantage of being non-toxic and can be handled and disposed without risk to human health and the environment.
80

Obtenção de catalisadores de óxidos de ferro contendo magnésio para a síntese de estireno

Oliveira, Soraia Jesus de January 2012 (has links)
Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2014-09-17T15:34:46Z No. of bitstreams: 1 _ TESE_ - Soraia Jesus de Oliveira - Versão Final com ficha catalográfica OK.pdf: 3092511 bytes, checksum: 4de5ad2f3ebfbeb60d029db00c51c206 (MD5) / Approved for entry into archive by Fatima Cleômenis Botelho Maria (botelho@ufba.br) on 2014-09-19T12:43:31Z (GMT) No. of bitstreams: 1 _ TESE_ - Soraia Jesus de Oliveira - Versão Final com ficha catalográfica OK.pdf: 3092511 bytes, checksum: 4de5ad2f3ebfbeb60d029db00c51c206 (MD5) / Made available in DSpace on 2014-09-19T12:43:31Z (GMT). No. of bitstreams: 1 _ TESE_ - Soraia Jesus de Oliveira - Versão Final com ficha catalográfica OK.pdf: 3092511 bytes, checksum: 4de5ad2f3ebfbeb60d029db00c51c206 (MD5) / FAPESB / A desidrogenação catalítica do etilbenzeno em presença de vapor d´água é, sem dúvida, a principal via de produção de estireno, um produto de alto valor comercial, amplamente utilizado na manufatura de borrachas e vários polímeros. Os catalisadores típicos comerciais são baseados em hematita (-Fe2O3) contendo óxido de cromo e óxido de potássio, que atuam como promotor textural e estrutural, respectivamente. Estes sistemas possuem diversas vantagens, tais como baixo custo e elevada resistência a venenos, mas apresentam algumas desvantagens, tais como a perda de potássio durante a reação, provocando a desativação do catalisador e a toxicidade do óxido de cromo. Visando a superar esses problemas, neste trabalho, foram preparados catalisadores de hematita dopada com magnésio, que foram avaliados na desidrogenação de etilbenzeno, a fim de obter sistemas isentos de cromo e de potássio para essa reação. Os catalisadores (Mg/Fe (molar)= 0; 0,01; 0,03; 0,06; 0,09 e 0,10) foram preparados por hidrólise simultânea de nitrato de ferro e de nitrato de magnésio, com hidróxido de amônio à temperatura ambiente, seguido de aquecimento a 600 °C. Os catalisadores foram caracterizados por análise química, espectroscopia no infravermelho com transformada de Fourier, difração de raios X, espectroscopia Mössbauer, medidas de área superficial específica, redução à temperatura programada e espectroscopia fotoeletrônica de raios X. Nas amostras com baixos teores de magnésio (Mg/Fe= 0,01 e 0,03) foram obtidos magnésia e cristais de hematita de 69 e 63 nm, respectivamente, enquanto na amostra com Mg/Fe= 0,06 foram produzidos cristais de hematita de 124 nm, co- existindo com ferrita de magnésio. Por outro lado, nas amostras mais ricas em magnésio (Mg/Fe= 0,09 e 0,1) foram obtidos cristais de hematita de 57 e 61 nm, respectivamente, co-existindo com magnésia e ferrita de magnésio. A adição de magnésio a catalisadores de hematita alterou a área superficial específica dos sólidos; a magnésia atua como um espaçador na produção de pequenos cristais de hematita. O magnésio também diminuiu a temperatura de redução da hematita mas não se observou uma tendência regular com o seu conteúdo. Em todos os catalisadores, o magnésio tende a depositar-se na superfície e este efeito aumenta com o seu teor, gerando superfícies sólidas parcialmente cobertas com magnésia e/ou ferrita de magnésio. Todos os catalisadores dopados com magnésio foram mais ativos que a hematita na desidrogenação de etilbenzeno, em presença de vapor d´água e seletiva ao estireno. A atividade e a seletividade da hematita variaram de forma irregular com o teor de magnésio, um fato que pode ser relacionado com as diferentes fases nos sólidos. Foi proposto que a magnésia atua como promotor textural, levando à produção de pequenos cristais de hematita, que são cataliticamente mais ativos, enquanto a ferrita de magnésio aumenta a atividade dos sítios de ferro devido às interações eletrônicas na estrutura do espinélio. A combinação destes efeitos conduz à formação do catalisador mais ativo (Mg/Fe= 0,9), consistindo de hematita parcialmente coberta por magnésia e ferrita de magnésio. Ele tem a vantagem de não ser tóxico, sendo promissor para aplicações comerciais. Além disso, o catalisador com o mais baixo teor de magnésio (Mg/Fe= 0,1), consistindo de hematita parcialmente coberta por magnésia, também é atrativo para aplicações comerciais, devido à sua elevada selectividade (quase 100%), o que pode evitar a reciclagem do etilbenzeno e as operações de separação, levando a uma redução nos custos operacionais / Catalytic ethylbenzene dehydrogenation in the presence of steam is by far the main route for the production of styrene, a high value chemical, widely used in the manufacture of several rubbers and polymers. The typical commercial catalysts are based on hematite (-Fe2O3) containing chromium oxide and potassium oxide which act as textural and structural promoter, respectively. These systems have several advantages such as low cost and high resistance to poisons but have some disadvantages such as potassium loss during reaction, leading to the catalyst deactivation and the toxicity of chromium oxide. In order to overcome these drawbacks, magnesium-doped hematite catalysts were prepared and evaluated in ethylbenzene dehydrogenation in this work, aiming to get chromium and potassium- free catalysts for the reaction. The catalysts (Mg/Fe (molar)= 0; 0.01, 0.03, 0.06, 0.09 and 0.10) were prepared by simultaneous hydrolysis of iron nitrate and magnesium nitrate with ammonium hydroxide at room temperature, followed by heating at 600 °C. The catalysts were characterized by chemical analysis, Fourier transform infrared spectroscopy, X-ray diffraction, Mössbauer spectroscopy, specific surface area measurements, temperature programmed reduction and X-ray photoelectronic spectroscopy. For the poorest-magnesium samples (Mg/Fe = 0.01 and 0.03) both magnesia and hematite crystals of 69 and 63 nm, respectively, were found while for the sample with Mg/Fe= 0.06 hematite crystals of around 124 nm were produced, coexisting with magnesium ferrite. Conversely, for the richest-magnesium samples (Mg/Fe = 0.09 and 0.1) hematite crystals of 57 and 61 nm, respectively, were found co-existing with magnesia and magnesium ferrite. The addition of magnesium to hematite-based catalysts changes the specific surface area of the solids, magnesia acts as a spacer to produce small crystals of hematite. Magnesium also decreases the reduction temperature of hematite but no regular tendency with its content was found. For all catalysts, magnesium tends to deposit on the surface, this effect increases with its amount, generating solid surfaces partially coated with magnesia and/or magnesium ferrite. All magnesium-doped catalysts were more active than pure hematite in ethylbenzene dehydrogenation in the presence of steam and selective to styrene. The activity and selectivity of hematite vary irregularly with magnesium content, a fact that can be related to the different phases in the solids. It was proposed that magnesia acts as textural promoter, leading to production of small crystals of hematite, which are catalytically more active while magnesium ferrite increases the activity of iron sites due to electronic interactions in the spinel structure. The combination of these effects leads to the most active catalyst (Mg/Fe = 0.9), consisting of hematite partially covered by magnesia and magnesium ferrite. It has the advantage of not being toxic and then is promising for commercial applications. In addition, the magnesium-poorest catalyst (Mg/Fe = 0.1), consisting of hematite partially covered by magnesia, is also attractive for commercial application due to its high selectivity (almost 100%), which could prevent ethylbenzene recycle and separation operations, leading to a reduction in operating costs.

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