A novel phosphorus (P) adsorbent, ferrihydrite-modified diatomite (FHMD) was developed and characterized in this study. The FHMD was made through surface modification treatments, including NaOH treatment and ferrihydrite deposition on raw diatomite. In the NaOH treatment, surface SiO2 was partially dissolved in the NaOH solution. The dissolved Si contributed to form stable 2-line ferrihydrite, which deposited into the larger mesopores and macropores of the diatomite. The 2-line ferrihydrite not only deposited into the pores of the diatomite but also aggregated on the surface. Filling the larger mesopores and macropores of the diatomite and aggregation on the diatomite surface with 0.24 g Fe/g of 2-line ferrihydrite resulted in a specific surface area of 211.1 m2/g for the FHMD, which is an 8.5-fold increase over the raw diatomite (24.77 m2/g). The surface modification also increased the point of zero charge (pHPZC) values to 10 for the FHMD from 5.8 for the raw diatomite.<p> Effects of the formation process parameters such as concentrations of FeCl2, NaOH, and drying temperature on the formation mechanism and crystalline characteristics of FHMD were studied by using X-ray absorption near-edge structure (XANES) spectroscopy. The spectra were recorded in both the total electron yield (TEY) and the fluorescence yield (FY) modes to investigate the chemical nature of Fe and Si on the surface and in the bulk of ferrihydrite-modified diatomite, respectively. It was found that only the surface SiO2 was partially dissolved in the NaOH solution with stirring and heating, whereas the bulk of diatomite seemed to be preserved. The dissolved Si was incorporated into the structure of ferrihydrite to form the 2-line Si-containing ferrihydrite. The crystalline degree of ferrihydrite increased with the increasing FeCl2 concentration and the Brunauer-Emmett-Teller (BET) specific surface area of FHMD decreased with the increasing FeCl2 concentration. The NaOH solution of higher concentration partially dissolved more surface SiO2 and the crystalline degree of ferrihydrite decreased with the increase in NaOH concentration. The dehydroxylation on the surface of FHMD occurred in the high temperature calcination, causing an energy shift in the Si L-edge spectra to the high energy side and an increase in the crystalline degree of ferrihydrite. In this study, the optimal synthesis conditions for the FHMD with the least crystalline degree and the highest surface area were found to be as the follows: 100 mL of 0.5M FeCl2 solution, 6M NaOH solution and the drying temperature of 50 ºC.<p> Phosphorus adsorption behavior and adsorption mechanism of FHMD were investigated in the research. The Langmuir model best described the P adsorption data for FHMD. Because of increased surface area and surface charge, the maximum adsorption capacity of FHMD at pH 4 and pH 8.5 was increased from 10.2 mg P/g and 1.7 mg P/g of raw diatomite to 37.3 mg P/g and 13.6 mg P/g, respectively. Phosphorus showed the best affinity of adsorption onto FHMD among common anions. K-edge P XANES spectra demonstrate that P is not precipitated with Fe (III) of FHMD, but adsorbed on the surface layer of FHMD.<p> Phosphorus removal from lake water and limiting phosphorus release from sediment by FHMD was examined. Phosphorus removal from lake water proceeded primarily through P adsorption onto the surface of FHMD. When a dose of FHMD of 250 mg/L was applied to lake water, a total phosphorus (TP) removal efficiency of 88% was achieved and a residual TP concentration was 17.0 µg/L which falls within the oligotrophic TP range (3.0-17.7 µg/L). FHMD settled down to the bottom of the 43 cm high cylinder within 6 hours, which suggested that retention time of FHMD in the 5.5 m of Jackfish lake water column was close to the equilibrium time of P adsorption onto FHMD (72 hours). During the 30-day anoxic incubation period, TP concentrations in lake water treated by 400, 500 and 600 mg/L of FHMD showed a slight decrease and maximum TP concentrations remained at levels lower than 15 µg/L. The addition of FHMD resulted in a marked increase in Fe-P fraction, a pronounced decrease in labile-P and organic-P fractions, and stable Al-P, Ca-P and residual-P fractions. The effect of FHMD on limiting P release was comparable with those of the combination of FHMD and alum solutions with logarithmic ratios of Al to mobile P of 0.5 and 0.8. FHMD not only can effectively remove P from lake water but also keep a strong P-binding capacity under anoxic conditions and competition for P with alum at high amounts.<p> The role of gypsum on stabilizing sediment and the optimum dose of gypsum were investigated. The effectiveness of gypsum in stabilizing sediment was proved by the fact that at the same agitation speed, turbidities and soluble reactive P (SRP) concentrations of samples treated with gypsum were much lower than those of sample without gypsum. The optimal thickness of the gypsum layer was found to be 0.8 cm.<p> Combined application of FHMD and gypsum to P control was investigated in the research. It was found in the 30-day incubation of lake water and sediment treated by FHMD and gypsum that no P release seemed to occur regardless of oxic or anoxic conditions. In order to investigate the 120-day effects of FHMD and gypsum on the P control under anoxic and agitation conditions a lab-scale artificial aquarium was established in an environmental chamber. Daily oscillation of a metal grid did not yield the sediment resuspension due to the gypsum stabilization. The combined application of FHMD and gypsum resulted in a 1 g/L increase in the SO42- concentration in the 120-day aquarium compared with that in the control aquarium; however it did not affect the total kjeldahl nitrogen (TKN) concentrations in both the control aquarium and the 120-day aquarium. The addition of FHMD and gypsum enhanced total alkalinity in the 120-day aquarium, thereby improving buffering capacity of lake water. Under anoxic conditions and sediment resuspension conditions, relative to a large increase in total P (TP) concentrations in the control aquarium, TP concentrations in the 120-day aquarium stayed relatively stable, fluctuating within the range of 9.1-13.3 µg/L. Relative to control sediment, Fe-P was significantly enhanced during the 60-day incubation; however, Fe-P did not appear to increase significantly in the second 60-day incubation. Labile-P and organic-P decreased with sediment depths in both control aquarium and test aquariums; however, Al-P, Ca-P and residue-P increased with sediment depth. Lower Al-P is observed in treatment aquariums than in control sediment.<p> As an effective P adsorbent, FHMD showed a high adsorption capacity as well as a significantly higher affinity for P than other anions. A combined application of FHMD and gypsum effectively reduced sediment resuspension and maintained TP levels within the oligotrophic range under anoxic conditions in the laboratory-scale artificial aquarium.

A novel phosphorus (P) adsorbent, ferrihydrite-modified diatomite (FHMD) was developed and characterized in this study. The FHMD was made through surface modification treatments, including NaOH treatment and ferrihydrite deposition on raw diatomite. In the NaOH treatment, surface SiO2 was partially dissolved in the NaOH solution. The dissolved Si contributed to form stable 2-line ferrihydrite, which deposited into the larger mesopores and macropores of the diatomite. The 2-line ferrihydrite not only deposited into the pores of the diatomite but also aggregated on the surface. Filling the larger mesopores and macropores of the diatomite and aggregation on the diatomite surface with 0.24 g Fe/g of 2-line ferrihydrite resulted in a specific surface area of 211.1 m2/g for the FHMD, which is an 8.5-fold increase over the raw diatomite (24.77 m2/g). The surface modification also increased the point of zero charge (pHPZC) values to 10 for the FHMD from 5.8 for the raw diatomite.<p> Effects of the formation process parameters such as concentrations of FeCl2, NaOH, and drying temperature on the formation mechanism and crystalline characteristics of FHMD were studied by using X-ray absorption near-edge structure (XANES) spectroscopy. The spectra were recorded in both the total electron yield (TEY) and the fluorescence yield (FY) modes to investigate the chemical nature of Fe and Si on the surface and in the bulk of ferrihydrite-modified diatomite, respectively. It was found that only the surface SiO2 was partially dissolved in the NaOH solution with stirring and heating, whereas the bulk of diatomite seemed to be preserved. The dissolved Si was incorporated into the structure of ferrihydrite to form the 2-line Si-containing ferrihydrite. The crystalline degree of ferrihydrite increased with the increasing FeCl2 concentration and the Brunauer-Emmett-Teller (BET) specific surface area of FHMD decreased with the increasing FeCl2 concentration. The NaOH solution of higher concentration partially dissolved more surface SiO2 and the crystalline degree of ferrihydrite decreased with the increase in NaOH concentration. The dehydroxylation on the surface of FHMD occurred in the high temperature calcination, causing an energy shift in the Si L-edge spectra to the high energy side and an increase in the crystalline degree of ferrihydrite. In this study, the optimal synthesis conditions for the FHMD with the least crystalline degree and the highest surface area were found to be as the follows: 100 mL of 0.5M FeCl2 solution, 6M NaOH solution and the drying temperature of 50 ºC.<p> Phosphorus adsorption behavior and adsorption mechanism of FHMD were investigated in the research. The Langmuir model best described the P adsorption data for FHMD. Because of increased surface area and surface charge, the maximum adsorption capacity of FHMD at pH 4 and pH 8.5 was increased from 10.2 mg P/g and 1.7 mg P/g of raw diatomite to 37.3 mg P/g and 13.6 mg P/g, respectively. Phosphorus showed the best affinity of adsorption onto FHMD among common anions. K-edge P XANES spectra demonstrate that P is not precipitated with Fe (III) of FHMD, but adsorbed on the surface layer of FHMD.<p> Phosphorus removal from lake water and limiting phosphorus release from sediment by FHMD was examined. Phosphorus removal from lake water proceeded primarily through P adsorption onto the surface of FHMD. When a dose of FHMD of 250 mg/L was applied to lake water, a total phosphorus (TP) removal efficiency of 88% was achieved and a residual TP concentration was 17.0 µg/L which falls within the oligotrophic TP range (3.0-17.7 µg/L). FHMD settled down to the bottom of the 43 cm high cylinder within 6 hours, which suggested that retention time of FHMD in the 5.5 m of Jackfish lake water column was close to the equilibrium time of P adsorption onto FHMD (72 hours). During the 30-day anoxic incubation period, TP concentrations in lake water treated by 400, 500 and 600 mg/L of FHMD showed a slight decrease and maximum TP concentrations remained at levels lower than 15 µg/L. The addition of FHMD resulted in a marked increase in Fe-P fraction, a pronounced decrease in labile-P and organic-P fractions, and stable Al-P, Ca-P and residual-P fractions. The effect of FHMD on limiting P release was comparable with those of the combination of FHMD and alum solutions with logarithmic ratios of Al to mobile P of 0.5 and 0.8. FHMD not only can effectively remove P from lake water but also keep a strong P-binding capacity under anoxic conditions and competition for P with alum at high amounts.<p> The role of gypsum on stabilizing sediment and the optimum dose of gypsum were investigated. The effectiveness of gypsum in stabilizing sediment was proved by the fact that at the same agitation speed, turbidities and soluble reactive P (SRP) concentrations of samples treated with gypsum were much lower than those of sample without gypsum. The optimal thickness of the gypsum layer was found to be 0.8 cm.<p> Combined application of FHMD and gypsum to P control was investigated in the research. It was found in the 30-day incubation of lake water and sediment treated by FHMD and gypsum that no P release seemed to occur regardless of oxic or anoxic conditions. In order to investigate the 120-day effects of FHMD and gypsum on the P control under anoxic and agitation conditions a lab-scale artificial aquarium was established in an environmental chamber. Daily oscillation of a metal grid did not yield the sediment resuspension due to the gypsum stabilization. The combined application of FHMD and gypsum resulted in a 1 g/L increase in the SO42- concentration in the 120-day aquarium compared with that in the control aquarium; however it did not affect the total kjeldahl nitrogen (TKN) concentrations in both the control aquarium and the 120-day aquarium. The addition of FHMD and gypsum enhanced total alkalinity in the 120-day aquarium, thereby improving buffering capacity of lake water. Under anoxic conditions and sediment resuspension conditions, relative to a large increase in total P (TP) concentrations in the control aquarium, TP concentrations in the 120-day aquarium stayed relatively stable, fluctuating within the range of 9.1-13.3 µg/L. Relative to control sediment, Fe-P was significantly enhanced during the 60-day incubation; however, Fe-P did not appear to increase significantly in the second 60-day incubation. Labile-P and organic-P decreased with sediment depths in both control aquarium and test aquariums; however, Al-P, Ca-P and residue-P increased with sediment depth. Lower Al-P is observed in treatment aquariums than in control sediment.<p> As an effective P adsorbent, FHMD showed a high adsorption capacity as well as a significantly higher affinity for P than other anions. A combined application of FHMD and gypsum effectively reduced sediment resuspension and maintained TP levels within the oligotrophic range under anoxic conditions in the laboratory-scale artificial aquarium.

Cette thèse s’inscrit dans le cadre d’un projet GREENANONANO né d’un partenariat entre le Luxembourg Institute of Science and Technology (LIST), Goodyear et l’Université de Lorraine dans le but de relever un défi technologique concernant l’augmentation des performances des propriétés viscoélastiques de la gomme utilisée dans les pneumatiques. Cette gomme est un composite constitué d’un élastomère (caoutchouc naturel) renforcé par la silice et le noir de carbone. La dispersion de ces charges n’est pas optimale et tend à dégrader les propriétés mécaniques et électrostatiques et donc les performances des pneus. Faces à ces limitations industrielles, l’utilisation d’autres types de renforts tels que les nanotubes de carbone devient une alternative crédible. Etant donné que les nanotubes de carbone (NTCs) ont tendance à s’organiser en fagots, le problème de la dispersion reste à résoudre. Nous proposons dans cette thèse la mise en place d’un matériau biphasé constitué de silice mésoporeuse naturelle, appelée diatomite, sur laquelle ont été synthétisés des NTCs. La grande surface spécifique de la diatomite offre la possibilité d’y faire croître une grande densité de NTCs et d’accroître significativement la surface de contact avec la matrice polymère. Cette thèse multidisciplinaire a débuté par la synthèse de nanoparticules métalliques par ALD pour la croissance de NTCs, suivie d’un développement du procédé de croissance de NTCs sur la diatomite. L’intégration réussie des charges biphasées obtenues au sein de matrices polymériques (élastomère, thermoplastique) a permis de mesurer les propriétés mécaniques, thermiques et électriques des nanocomposites ainsi fabriqués / This thesis is part of the GREENANONANO project ensuing from a partnership between the Luxembourg Institute of Science and Technology (LIST), Goodyear Company and Université de Lorraine, in order to address a technological challenge for increasing tires performances. The latter are directly related to the viscoelastic properties of the rubber used in tires. This gum is a composite material made by mixing an elastomeric matrix (natural rubber) and fillers (silica and carbon black). Nowadays, the filler dispersion is not optimal, which degrades the mechanical and electrostatic properties and therefore performances of tires. All these industrial limitations require the use of other types of reinforcing agents such as carbon nanotubes. Since carbon nanotubes tend to be organized into bundles, the dispersion problem still exists. We therefore propose in this thesis the synthesis of a biphased material composed by diatomite particles (natural mesoporous silica) on which are grown carbon nanotubes (CNTs). The high surface area of diatomite offers the possibility of growing a high density of CNTs, increasing the contact area with the polymer matrix. This multidisciplinary thesis started with the synthesis of metal nanoparticles by Atomic Layer Deposition (ALD) to catalyse the growth of CNTs and then a process was developed to grow CNTs on diatomite particles. The successful integration of the resulting biphased particles in polymer matrices (elastomer, thermoplastic) allowed to measure the mechanical, thermal and electrical properties of the nanocomposites thus produced

In Santa Barbara County, Santa Maria Pacific (an exploration and production company) is expanding their cyclic steam project in a diatomite reservoir. The hilly or mountainous topography and cut and fill restrictions have interfered with the company's ideal development plan. The steep hillsides prevent well pad development for about 22 vertical well locations in the 110 well expansion plan. Conventional production performs poorly in the area because the combination of relatively low permeability (1-10 md) and high viscosity (~220 cp) at the reservoir temperature. Cyclic steam injection has been widely used in diatomite reservoirs to take advantage of the diatomite rocks unique properties and lower the viscosity of the oil. Some companies used deviated wells for cyclic steam injection, but Santa Maria Pacific prefers the use only vertical wells for the expansion. Currently, the inability to create well pads above 22 vertical well target locations will result in an estimated $60,000,000 of lost revenue over a five year period. The target locations could be developed with unstimulated deviated or horizontal wells, but expected well rates and expenses have not been estimated. In this work, I use a thermal reservoir simulator to estimate production based on five potential development cases. The first case represents no development other than the cyclic wells. This case is used to calibrate the model based on the pilot program performance and serves as a reference point for the other cases. Two of the cases simulate a deviated well with and without artificial lift next to a cyclic well, and the final two cases simulate a horizontal well segment with and without artificial lift next to a cyclic well. The deviated well with artificial lift results in the highest NPV and profit after five years. The well experienced pressure support from the neighboring cyclic well and performed better with the cyclic well than without it. Adding 22 deviated wells with artificial lift will increase the project's net profit by an estimated $7,326,000 and NPV by $2,838,000 after five years.

The aim of the present work was to develop synthesis routes to produce synthetic zeolites with industrial attractiveness from non-expensive Bolivian raw materials, such as clays and diatomite. In particular, the work was focused on the synthesis of low-silica zeolites with the LTA and FAU structures. The raw materials as well as intermediate and final zeolite products were structurally characterized by different techniques, namely scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen gas adsorption, inductively coupled plasma mass spectrometry (ICP-MS). Besides, the final properties were evaluated for intended applications i.e. brightness by UV-VIS spectroscopy for LTA-type zeolite A in detergents and the CO2 breakthrough adsorption of FAU-type zeolite X for gas separation.   The first part of this study deals with the synthesis of low silica zeolite A from Bolivian montmorillonite clay (Paper I). The clay was fused at high temperature with NaOH to render the material more reactive. The raw montmorillonite had a SiO2/Al2O3 ratio of 4 and sodium aluminate was added to the mixture to decrease this ratio to 2. An optimization of the synthesis time was performed. For the sake of comparison, the same treatment was applied to commercial kaolin. The final zeolite product from Bolivian montmorillonite exhibited high brightness despite the presence of iron in appreciable amount in the starting material and the final product. It was concluded that magnesium, present in the raw material, exerted a masking effect on iron. The latter was incorporated into extraneous magnesium aluminosilica compounds, thereby increasing brightness and strongly decreasing the overall yellowness. This simple method appears as a promising alternative to the complex and costly techniques suggested to reduce the iron content in natural raw materials, especially kaolin.   The second part of the study addresses the synthesis, characterization and evaluation of FAU-type zeolites i.e. Y and X from diatomite and chemical grade reagents, respectively. With regard to the synthesis of zeolite Y, the diatomite was leached in sulfuric acid to remove impurities prior to synthesis, this step also resulted in dealumination, which rendered possible the synthesis of ZSM-5 zeolite (Paper II). However, extra aluminum had to be added in the form of aluminum sulfate for the synthesis of zeolite Y (Paper III). In this case, the raw materials were reacted hydrothermally at 100°C in aqueous medium with sodium hydroxide. Variations in parameters such as the Na2O/SiO2 ratio and synthesis time were investigated. As a result, micro-sized crystals of zeolite Y were obtained at a Na2O/SiO2 ratio of 0.9, which produced zeolite Y with a SiO2/Al2O3 ratio of 3.9. Also, zeolite Y with a SiO2/Al2O3 ratio of 5.3 in low yield at a Na2O/SiO2 ratio of 0.6 was achieved. In this way, diatomite behaved similarly to colloidal silica in traditional syntheses having a high degree of polymerization. Zeolite Y with a SiO2/Al2O3 ratio of 5.3 might be useful for the production of ultra-stable zeolite Y for use as FCC catalyst. Addition of NaCl to this system was also found to completely inhibit the formation of zeolite P and to retard the effects of overrunning by a synergic effect of Na and Cl ions (Paper IV).   As an innovate application, FAU-type zeolite X films were growth on steel monoliths as structured adsorbent for CO2 removal (Paper V). Thicknesses 3 and 10 µm on steel monoliths of 1600 cells per square inches (c.p.s.i.) were investigated. The produced structured adsorbents showed reasonable CO2 adsorption capacity but with a very low pressure drop compared with traditional packed beds of zeolite beads. The CO2 breakthrough fronts were very sharp and the mass transfer resistance was very low compensating the presence of less adsorbing material by reducing cycle time and increased cycle frequency to increase throughput.     To summarize, zeolites with promising characteristics were successfully synthesized from Bolivian raw materials in this thesis work. However, further characterization is required to qualify these products for industrial applications. Moreover, this study might help the development of poor regions of the Bolivian Altiplano and open up for large scale production, since the methods developed in this work are simple and non-expensive. / Characterisation of clays and feldspars from the Altiplano and development of methods for conversion of these materials to valuable zeolites and evaluation in applications

O presente trabalho trata do desenvolvimento um novo material, diatomita modificada por ferro, como ativador dos oxidantes persulfato de sódio e peróxido de hidrogênio para degradar poluentes prioritários (fenantreno e antraceno), diesel e o poluente emergente ácido perfluoroctanóico (PFOA). Os objetivos deste estudo foram comparar esse novo método com métodos convencionais de ativação para esses oxidantes; e estudar, estatisticamente, a relação ótima entre a quantidade deste material e a concentração de oxidante para a degradação dos contaminantes. A diatomita bruta e as diatomitas modificadas (CAT-5 e CAT-20) foram caracterizadas por diferentes técnicas. Os principais resultados da caracterização mostraram que os materiais são amorfos e que a concentração de ferro foi 4%, 17% e 25% para diatomita bruta, CAT-5 e CAT-20, respectivamente. Os resultados mostraram que os materiais modificados apresentaram significativa atividade catalítica para ativar os oxidantes e degradar os poluentes, sendo a CAT-5 a mais reativa. Resultados satisfatórios foram obtidos utilizando 45 g L-1 de persulfato de sódio com 2,5 g de diatomita modificada (CAT-5), com degradação de 87% e 96% de fenantreno e antraceno, respectivamente, em 168 horas de tratamento. Para o tratamento de solo arenoso contaminado com diesel, os melhores resultados foram obtidos utilizando 41 g L-1 de persulfato de sódio e 1,56 g de CAT-5, obtendo decaimento de 91% de carbono total em 146 horas. A eficiência da decomposição de PFOA mostra que a reatividade dos sistemas seguiu a ordem: peróxido de hidrogênio em altas concentrações > peróxido de hidrogênio em paralelo com persulfato > persulfato alcalino, ambos ativados com CAT-5, atingindo 86%, 69% e 48%, respectivamente, após 6 horas de reação. / The present work deals with the development of a new materials, modified diatomite by iron, as an activator of the oxidants sodium persulfate and hydrogen peroxide to degrade priority pollutants (phenantherene and anthracene), diesel and emerging pollutant perfluorooctanoic acid (PFOA). The aims of this study were to compare this new method with traditional activation method for these oxidants; and to study, statistically, the optimal ratio between the quantity of the material and the concentration of oxidant to the degradation of contaminants. The raw and modified materials were characterized by different techniques. The main characterization results showed that materials are amorphous, and that the iron concentrations were 4,78%, 17,65% and 25% for the raw diatomite, CAT-5 and CAT-20, respectively. The results showed that the modified material showed significant catalytic activity to activate the oxidants and to degrade pollutants, with CAT-5 being the most reactive. Satisfactory results were obtained using 2,5 g of modified diatomite (CAT-%) with sodium persulfate at 45 g L-1, with degradation of 87% and 96% of phenanthrene and anthracene, respectively, in 168 hours of treatment. For the treatment of sandy soil contaminated with diesel, the best result was obtained using 41 g L-1 of sodium persulfate sodium and 1,56 g of CAT-5, resulting in a decrease of 91% of total carbon present in diesel. The PFOA decomposition efficiency for the systems shows that hydrogen peroxide at high concentrations > hydrogen peroxide-activated persulfate > alkaline-activated persulfate, both with CAT-5, achieving 83%, 69% and 48% , respectively, after 6 hours of reaction.

O presente trabalho trata do desenvolvimento um novo material, diatomita modificada por ferro, como ativador dos oxidantes persulfato de sódio e peróxido de hidrogênio para degradar poluentes prioritários (fenantreno e antraceno), diesel e o poluente emergente ácido perfluoroctanóico (PFOA). Os objetivos deste estudo foram comparar esse novo método com métodos convencionais de ativação para esses oxidantes; e estudar, estatisticamente, a relação ótima entre a quantidade deste material e a concentração de oxidante para a degradação dos contaminantes. A diatomita bruta e as diatomitas modificadas (CAT-5 e CAT-20) foram caracterizadas por diferentes técnicas. Os principais resultados da caracterização mostraram que os materiais são amorfos e que a concentração de ferro foi 4%, 17% e 25% para diatomita bruta, CAT-5 e CAT-20, respectivamente. Os resultados mostraram que os materiais modificados apresentaram significativa atividade catalítica para ativar os oxidantes e degradar os poluentes, sendo a CAT-5 a mais reativa. Resultados satisfatórios foram obtidos utilizando 45 g L-1 de persulfato de sódio com 2,5 g de diatomita modificada (CAT-5), com degradação de 87% e 96% de fenantreno e antraceno, respectivamente, em 168 horas de tratamento. Para o tratamento de solo arenoso contaminado com diesel, os melhores resultados foram obtidos utilizando 41 g L-1 de persulfato de sódio e 1,56 g de CAT-5, obtendo decaimento de 91% de carbono total em 146 horas. A eficiência da decomposição de PFOA mostra que a reatividade dos sistemas seguiu a ordem: peróxido de hidrogênio em altas concentrações > peróxido de hidrogênio em paralelo com persulfato > persulfato alcalino, ambos ativados com CAT-5, atingindo 86%, 69% e 48%, respectivamente, após 6 horas de reação. / The present work deals with the development of a new materials, modified diatomite by iron, as an activator of the oxidants sodium persulfate and hydrogen peroxide to degrade priority pollutants (phenantherene and anthracene), diesel and emerging pollutant perfluorooctanoic acid (PFOA). The aims of this study were to compare this new method with traditional activation method for these oxidants; and to study, statistically, the optimal ratio between the quantity of the material and the concentration of oxidant to the degradation of contaminants. The raw and modified materials were characterized by different techniques. The main characterization results showed that materials are amorphous, and that the iron concentrations were 4,78%, 17,65% and 25% for the raw diatomite, CAT-5 and CAT-20, respectively. The results showed that the modified material showed significant catalytic activity to activate the oxidants and to degrade pollutants, with CAT-5 being the most reactive. Satisfactory results were obtained using 2,5 g of modified diatomite (CAT-%) with sodium persulfate at 45 g L-1, with degradation of 87% and 96% of phenanthrene and anthracene, respectively, in 168 hours of treatment. For the treatment of sandy soil contaminated with diesel, the best result was obtained using 41 g L-1 of sodium persulfate sodium and 1,56 g of CAT-5, resulting in a decrease of 91% of total carbon present in diesel. The PFOA decomposition efficiency for the systems shows that hydrogen peroxide at high concentrations > hydrogen peroxide-activated persulfate > alkaline-activated persulfate, both with CAT-5, achieving 83%, 69% and 48% , respectively, after 6 hours of reaction.

Made available in DSpace on 2014-12-17T14:07:07Z (GMT). No. of bitstreams: 1 AlexandreFMC_DISSERT.pdf: 2018035 bytes, checksum: dd77e9d37e80465172d8dc362ca0200a (MD5) Previous issue date: 2011-11-25 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The synthesis of zeolites from natural sources of silicon and aluminum are promising alternative routes to obtain porous or zeolite MCM family. Such materials are typically used in catalytic processes and / or adsorption is to obtain new products or for separation and purification processes thereof. Environmental legislation is becoming stricter and requires the use of materials more efficient, aiming to achieve pollution prevention, by gas or liquid contaminants in the environment. In order to obtain a material with environmentally friendly features, this study aimed at the synthesis of zeolite A, from an amorphous sediment, diatomite, which is found in abundance in the northeast region of Brazil, may be substituted for conventional products the production of zeolite, involving higher costs. The methodology for obtaining the "Zeolite A" using as a source of silica and alumina diatomite is simple, since this is a source of silicon, not requiring therefore a structural driver, but also by heat treatment, only drying conventional to remove water. The "zeolite A" was obtained from diatomite, but as an intermediate step we obtained the sodalite. The characterization was made by the following techniques: EDX, XRD, FT-IR, SEM and determining a specific area by the BET method and the BJH method for checking the diameter of pores. By characterization of the obtained material was first demonstrated the achievement of sodalite and after modification of the same, there was obtained zeolite A / A s?ntese de ze?litas a partir de fontes naturais de Sil?cio e Alum?nio s?o rotas alternativas promissoras para a obten??o de materiais porosos da fam?lia MCM ou ze?litas. Tais materiais normalmente s?o usados em processos catal?ticos e/ou adsortivos seja para obten??o de novos produtos ou para processos de purifica??o e separa??o dos mesmos. A legisla??o ambiental ? cada vez mais rigorosa e exige o uso de materiais cada vez mais eficientes, com intuito de realizar preven??o de polui??o, por gases ou a l?quidos contaminantes do meio ambiente. Visando a obten??o de um material com caracter?sticas ambientalmente corretos, esse estudo teve como objetivo a s?ntese de ze?lita A, a partir de um sedimento amorfo, diatomita, o qual ? encontrado em abund?ncia na regi?o nordeste do Brasil, podendo vir a substituir produtos convencionais para a produ??o de ze?lita, envolvendo custos mais altos. A metodologia utilizada para obten??o da ze?lita A usando como fonte de s?lica e alumina a diatomita ? simples, uma vez que esta ? uma fonte de sil?cio, n?o necessitando, portanto de um direcionador estrutural, como tamb?m de um tratamento t?rmico, apenas secagem convencional para retirada da ?gua. A ze?lita A foi obtida a partir da diatomita, por?m como etapa intermedi?ria obteve-se a sodalita. As caracteriza??es foram feitas pelas seguintes t?cnicas: EDX, DRX, FT-IR, MEV e determina??o de ?rea espec?fica pelo m?todo BET e o m?todo BJH para verifica??o do di?metro de poros. Atrav?s da caracteriza??o do material obtido comprovou-se primeiramente a obten??o da sodalita e ap?s modifica??o da mesma, obteve-se a ze?lita A

Made available in DSpace on 2014-12-17T14:57:56Z (GMT). No. of bitstreams: 1 ValtencirLLG_TESE.pdf: 4119375 bytes, checksum: d0d468830e58c2ece8cde326af6db203 (MD5) Previous issue date: 2013-12-27 / The mortar is a type of adhesive products used in large scale in construction, it is a function of its variety and ease of application . Although industrialized product and endowed with technology in its production is very frequent occurrence of the same pathology , which causes frequent damage and losses in the construction industry. Faced with this real market situation , the technical and scientific study of the effects of the addition of diatomite on the rheological and mechanical behavior of adhesive mortars are needed. This work back as a suggestion the use of diatomite as a mineral additive in formulations of adhesive mortars for partial replacement of cellulose based additives . The choice of using this mineral occurs through physical, chemical and rheological properties that justify its use in this product line , and is a raw material abundant in our region and can thus contribute positively to the minimization of direct costs cellulose -based additives . Industrial adhesive mortar used for comparison , was type AC1 . Formulations of adhesive mortar with diatomite held constant dosed quantities of sand, cement and the water / cement (w / c ) , or adhesive mortar formulations were developed with levels 10, 20, 30 and 40% of diatomite substituting part of the cellulose -based additives . These mortars were subjected to the following tests that define and evaluate the rheological and mechanical behavior of this type of mortar. The results attest the best performance of the adhesive mortar type AC1 with partial replacement of 30 % of the cellulose-based additive for diatomite / As argamassas do tipo colante ? um dos produtos utilizados em grande escala na constru??o civil, isso se d? em fun??o da sua variedade e da facilidade de aplica??o. Embora seja produto industrializado e dotado de tecnologia em sua produ??o ? muito frequente a ocorr?ncia de patologias nas mesmas, o que ocasiona danos e preju?zos frequentes na ind?stria da constru??o civil. Frente a esta situa??o real de mercado, se fazem necess?rios o estudo t?cnico e cient?fico dos efeitos da adi??o de diatomita no comportamento reol?gico e mec?nico de argamassas colantes. Este trabalho tr?s como sugest?o a utiliza??o da diatomita como um aditivo mineral nas formula??es das argamassas colantes em substitui??o parcial dos aditivos a base de celulose. A op??o do uso deste mineral se d? pelas suas propriedades f?sicas, qu?micas e reol?gicas que justificam seu uso nesta linha de produto, al?m de ser uma mat?ria prima abundante em nossa regi?o, podendo desta forma contribuir de maneira positiva para a minimiza??o dos custos diretos com aditivos a base de celulose. A argamassa colante industrial utilizada, para efeito de compara??o, foi a do tipo AC1. As formula??es das argamassas colantes dosadas com diatomita mantiveram constantes as quantidades de cimento, areia e a rela??o ?gua/cimento (a/c), ou seja, foram desenvolvidas formula??es de argamassas colantes com teores 10, 20, 30 e 40% de diatomita em substitui??o parcial dos aditivos a base de celulose. Essas argamassas foram submetidas aos seguintes ensaios que definem e avaliam o comportamento reol?gico e mec?nico deste tipo de argamassa. Os resultados obtidos atestaram o melhor desempenho das argamassas colantes tipo AC1 com substitui??o parcial de 30% do aditivo a base de celulose pela diatomita

Programa Internacional de Becas da FundaÃÃo Ford / O processamento de materiais cerÃmicos, que envolve a queima de tijolos e demais produtos das indÃstrias cerÃmicas vermelhas, està associado à liberaÃÃo de componentes gasosos e material particulado que em fortes concentraÃÃes podem prejudicar o meio-ambiente e principalmente a saÃde humana, uma vez que os gases emitidos por estas indÃstrias, na maioria das vezes, nÃo sÃo tratados antes de serem lanÃados à atmosfera. O escopo desta pesquisa foi desenvolver um suporte cerÃmico visando, principalmente, à remoÃÃo de material particulado da indÃstria cerÃmica vermelha. Para sua obtenÃÃo foi usado resÃduo de terra diatomÃcea, ignimbrita (Sillar), e como aglomerante a bentonita, as quais possuem aproximadamente 70% a 80% de sÃlica. A sÃlica apresentando-se sob duas formas cristalinas: quartzo e cristobalita. O resÃduo, terra diatomÃcea, coletado em uma indÃstria cervejeira, foi submetido a um tratamento tÃrmico para a eliminaÃÃo da matÃria orgÃnica absorvida durante a etapa de filtraÃÃo. As matÃrias-primas foram submetidas a uma anÃlise quÃmica e mineralÃgica mediante FluorescÃncia de raios X e DifraÃÃo de raios X. Para a fabricaÃÃo do suporte cerÃmico foram preparadas espumas cerÃmicas pelo mÃtodo da replica. As espumas polimÃricas foram imersas na suspensÃo (diatomita, ignimbrita, bentonita e Ãgua), secas e tratadas termicamente. A eliminaÃÃo da espuma cerÃmica polimÃrica ocorreu a 400ÂC e, em seguida, o corpo cerÃmico foi sinterizado a 1100ÂC, em um intervalo de tempo compreendido de 45 e 60 min. Foram testadas quatro formulaÃÃes com duas variÃveis: tamanho de grÃo e composiÃÃo. A formulaÃÃo quatro (10% de diatomita e 16% de ignimbrita), foi a mais Ãtima, com uma resistÃncia mecÃnica à compresao de 0,8 MPa e uma porosidade de 81%. A reduÃÃo de material particulado, apÃs o uso do suporte cerÃmico, foi de aproximadamente 84% e de 72% de monÃxido de carbono, estando dentro dos padrÃes estabelecido pela ResoluÃÃo nÂ382/2006 do CONAMA. / The processing of ceramic materials which involves burning of the bricks and other ceramic product red ceramic industries is associated with the release of gaseous components and particulate material in high concentrations that affect the environment and human health, considering that the gases emitted by these industries are not mostly treated before being released to the atmosphere. The purpose of this research was to develop a ceramic support with the main objective of the removal of particulate matter. Was used diatomaceous earth residue, ignimbrita (Sillar) and the bentonite as a binder, which possess a high amount of silica. The silica exists in two crystalline forms: quartz, cristobalite. The residue, diatomaceous earth, collected in a beer industry, was submitted to a thermal treatment for the elimination organic matter absorbed during filtration. The raw materials were subjected to chemical and mineralogical analysis by XRF and XRD. Were processed by the replication method. The Polymeric foams were immersed in the ceramic suspension (diatomite, ignimbrita, bentonite and water), and then dried and heat-treated for consolidation. The polymer foam was burned out at 400 ÂC and sintering was carried out at 1100 ÂC for 45 - 60 min. We&#8223;re working four formulations with two variables, grain size and composition. The four formulations (10% diatomite and 16% ignimbrita) was more excellent, mechanical strength compresao of 0,8MPa and porosity of 81%. The reduction of particulate matter after using the ceramic support was approximately 84% and carbon monoxide was 72% is within the standards established by the Resolution nÂ382/2006 do CONAMA.