Submitted by Kilvya Braga (kilvyabraga@hotmail.com) on 2018-04-19T12:49:52Z No. of bitstreams: 1 ANTUSIA DOS SANTOS BARBOSA - TESE (PPGEQ) 2015.pdf: 4188064 bytes, checksum: b6d46e877c5fce328aa4e68c61e9dcb9 (MD5) / Made available in DSpace on 2018-04-19T12:49:52Z (GMT). No. of bitstreams: 1 ANTUSIA DOS SANTOS BARBOSA - TESE (PPGEQ) 2015.pdf: 4188064 bytes, checksum: b6d46e877c5fce328aa4e68c61e9dcb9 (MD5) Previous issue date: 2015 / As membranas zeolíticas têm despertado interesse nos pesquisadores em processos de separação e catálise, uma vez que elas apresentam elevada estabilidade térmica e química, são altamente seletivas, devido ao potencial no peneiramento molecular. A inovação deste estudo se dá na síntese da membrana zeolítica Y/ɣ-alumina para separação óleo/água. Este trabalho teve como objetivos: preparar a zeólita Y via síntese hidrotérmica, ɣ-alumina pelas decomposições do sulfato de alumínio e acetato de alumínio e membranas zeolíticas utilizando 3 métodos distintos: transporte a vapor e crescimento secundário: dip-coating e rubbing. Os produtos obtidos foram caracterizados por DRX, Adsorção Física de Nitrogênio, MEV, ATD e TG, FRX-ED e Porosimetria de Mercúrio. Além da síntese e caracterização, numa segunda etapa as membranas zeolíticas foram avaliadas no processo de remoção óleo/água de um efluente sintético, utilizando uma coluna de separação por membrana. Os ensaios foram realizados nas condições de concentração inicial do óleo 500 mg.L-1, Temperatura igual a 25 °C e Pressão atmosférica, permitindo observar a variação da concentração do permeado em (mg.L-1) e o coeficiente de rejeição (R%). Para síntese da alumina foram utilizadas os precursores sulfato de alumínio e acetato de alumínio, utilizando temperaturas de decomposição de 1000 ºC e 850 °C, respectivamente. Foi selecionada a alumina que obteve menor custo operacional, ou seja, ɣ-alumina oriunda da decomposição térmica do sulfato de aluminio. A zeólita Y e as membranas zeolíticas Y/ɣ-alumina foram preparadas em condições hidrotérmica, com temperatura de 90 ºC, durante 7 horas. Foram realizadas modificações térmicas (500, 600, 700, 750, 800, 900, 950, 1000 e 1100 °C) por período de 1 e 2 horas no sulfato de alumínio (após moagem, conformação e compactação). Baseado nos resultados de DRX pode-se concluir que: (i) os materiais de partida (sulfato de alumínio e acetato de alumínio), evoluem termicamente, resultando como produto final em ɣ-alumina; (ii) é possível obter a zeólita Y; observou-se também a formação dos suportes cerâmicos ɣ-alumina, após sinterização. O estudo térmico realizado no suporte cerâmico (DTSA) evidenciou que a temperatura ótima deve limitar-se em valores entre 700-750 °C/1h. O maior valor de cristalinidade foi observada para o suporte tratado a 700 °C/1h. O mesmo foi classificado como um material mesoporoso podendo ser utilizados em processos de ultrafiltração (UF). Os resultados obtidos por caracterização das membranas zeolíticas evidenciaram que as mesmas foram obtidas com sucesso independente do método utilizado. Dos testes de separação da emulsão óleo/água pode-se concluir que a inserção da zeólita (Y) ao suporte cerâmico (ɣ-alumina) melhorou o processo de separação da emulsão óleo/água. Como conclusão geral, as membranas zeolíticas obtidas utilizadas em coluna de separação por membrana são bastante promissoras no processo de separação emulsão óleo/agua. / The zeolite membranes have attracted attention of researchers in separation processes and catalysts since they have high thermal and chemical stability, are highly selective because of the potential on the molecular sieve. The innovation of this study gives the synthesis of zeolite membrane Y/ɣ-alumina for oil/water separation. This study aimed to: prepare the zeolite Y via hydrothermal synthesis, ɣalumina by decomposition of aluminum sulfate and ethyl aluminum and zeolite membranes using three different methods: steam transportation and secondary growth: dip-coating and rubbing. The products obtained were characterized by XRD, nitrogen adsorption of Physics, SEM, DTA and TG, ED-XRF and Porosimetry Mercury. In addition to the synthesis and characterization in a second step the zeolite membranes were evaluated in the process of removing oil/water of a synthetic effluent using a column separation membrane. Assays were performed under the conditions of the initial oil concentration 500 mg.L-1, temperature of 25 °C and atmospheric pressure, allowing to observe the change in concentration of the permeate (mg.L-1) and the rejection coefficient ( R%). For synthesis of the precursors used were alumina aluminum sulfate and aluminum acetate using decomposition temperatures of 1000 °C and 850 °C respectively. Was selected alumina which had lower operating costs, so, ɣ-alumina originating from the thermal decomposition of aluminum sulfate. The zeolite Y and zeolite membranes Y/ɣ-alumina were prepared in hydrothermal conditions, with a temperature of 90 for 7 hours. Thermal changes were performed (500, 600, 700, 750, 800, 900, 950, 1000 and 1100 °C) per period of 1 hour and 2 hours in aluminum sulphate (after milling, shaping and compacting). Based on the XRD results it can be concluded that: (i) the starting materials (aluminum sulphate and aluminum acetate) to evolve heat, resulting in a finished product ɣ alumina; (ii) it can get the zeolite Y; It also noted the formation of ɣ-alumina ceramic brackets after sintering. Thermal study on ceramic support (DTSA) showed that the optimum temperature should be limited to values between 700-750 °C/1h. The greatest amount of crystallinity was observed for material treated at 700 °C/1h. The same was classified as a mesoporous materials can be used in ultrafiltration process (UF). The results of the characterization of the zeolite membranes showed that they were obtained with successful independent of the method used. From tests separation of the emulsion oil/water can be concluded that the insertion of zeolite (Y) to the ceramic support (ɣ-alumina) improved separation process of the oil/water emulsion. As a general conclusion, the obtained zeolite membranes used in membrane separation column are very promising in the separation process oil / water emulsion.

The thesis deals with possibilities of FBC fly ash utilization for composite cements. It focuses on thermodynamic stability of ettringite, which is produced during composite cements hydration. Specific tasks are dedicated to observation of influence of outdoor environment and influence of calciumhydrosilicate environment to stability of ettringite.

In this research, five different coagulants were evaluated to determine their effectiveness at removing turbidity, color and dissolved organic carbon (DOC) from a surface water in Sarasota County, Florida. Bench-scale jar tests that simulated conventional coagulation, flocculation, and sedimentation processes were used. Iron-based coagulants (ferric chloride and ferric sulfate) and aluminum-based coagulants (aluminum sulfate, polyaluminum chloride (PACl) and aluminum chlorohydrate (ACH)) were used to treat a highly organic surface water supply (DOC ranging between 10 and 30 mg/L), known as the Cow Pen Slough, located within central Sarasota County, Florida. Isopleths depicting DOC and color removal efficiencies as a function of both pH and coagulant dose were developed and evaluated. Ferric chloride and ACH were observed to obtain the highest DOC (85% and 70%, respectively) and color (98% and 97%, respectively) removals at the lowest dose concentrations (120 mg/L and 100 mg/L, respectively). Ferric sulfate was effective at DOC removal but required a higher concentration of coagulant and was the least effective coagulant at removing color. The traditional iron-based coagulants and alum had low turbidity removals and they were often observed to add turbidity to the water. PACl and ACH had similar percent removals for color and turbidity achieving consistent percent removals of 95% and 45%, respectively, but PACl was less effective than ACH at removing organics. Sludge settling curves, dose-sludge production ratios, and settling velocities were determined at optimum DOC removal conditions for each coagulant. Ferric chloride was found to have the highest sludge settling rate but also produced the largest sludge quantities. Total trihalomethane formation potential (THMFP) was measured iv for the water treated with ferric chloride and ACH. As with DOC removal, ferric chloride yielded a higher percent reduction with respect to THMFP.

Lead is a known toxin, with the ability to accumulate in the human body from as early as fetal development. Lead exposure is known to cause a myriad of health effects which are more prominent among children. Health effects upon exposure can range from renal and heart disease or potentially cancer in adults to neurotoxicity in children. The continued presence of old lead service lines and plumbing in distribution systems as well as lead-containing solders and brass fixtures in homes may contribute lead to drinking water. Recent studies have highlighted the importance of a predictor known as the chloride-to-sulfate mass ratio (CSMR) in controlling lead release. A ratio above 0.5 – 0.6 theoretically increases the aggressiveness of lead leaching in galvanic settings, while a lower ratio controls lead corrosion. A switch in coagulant type could significantly alter the ratio. However, a coagulant switch could also trigger changes in finished water turbidity and organics, including disinfection by-product (DBP) precursors, as well as impact sludge production. Anecdotal evidence from an Ontario water treatment utility suggested the potential applicability of a newly formulated polymer, cationic activated silica (CAS), in improving DBP precursor removal when used in concurrence with a primary coagulant. No previous scientific research had been dedicated to testing of the polymer. The present research had three primary objectives: The first was to investigate the effect of conventional coagulation with six different coagulants on the chloride-to-sulfate mass ratio as it pertains to lead corrosion in two Ontario source waters of differing quality. Additionally, the effect of coagulant choice on pH, turbidity, and organics removal was investigated. The second objective was aimed at testing potential reductions in CSMR and organics that could be brought about by the use of two polymers, cationic and anionic activated silica (CAS and AAS, respectively), as flocculant aids. Finally, the performance of a high-rate sand-ballasted clarification process was simulated at bench-scale to gauge its performance in comparison with conventional coagulation simulation techniques. The first series of jar-tests investigated the effectiveness of CAS as a primary coagulant on Lake Ontario water. In comparison with the conventional coagulants aluminum sulfate and polyaluminum chloride, CAS did not offer any apparent advantage with respect to turbidity and organics removal. Testing of CAS and AAS as flocculant aids was also conducted. Results from a full factorial experiment focused on CAS testing on Lake Ontario water showed that coagulant dose is the most significant contributor to CSMR, turbidity, DOC removal, and THM control. Generally, improvements resulting from CAS addition were of small magnitude (<15%). Reductions in CSMR were attributed to the presence of the sulfate-containing chemicals alum and sulfuric acid in the CAS formulation. Testing of sulfuric acid-activated AAS on Grand River water showed that pairing of AAS with polyaluminum chloride provides better results than with alum with respect to DOC removal (39% and 27% respectively at 60 mg/L coagulant dose). Highest turbidity removals (>90%) with both coagulants were achieved at the tested coagulant and AAS doses of 10 mg/L and 4 mg/L respectively. CSMR reductions in the presence of AAS were also attributable to sulfate contribution from sulfuric acid. Bench-scale simulation of a high-rate sand-ballasted clarification process on Grand River water showed comparable removal efficiencies for turbidity (80 – 90% at 10 mg/L), and DOC (30 – 40% at 50 mg/L). Finally, six different coagulants were tested on the two source waters for potential applicability in CSMR adjustment in the context of lead corrosion. The two chloride-containing coagulants polyaluminum chloride and aluminum chlorohydrate increased CSMR in proportion to the coagulant dose added, as would be expected. Average chloride contribution per 10 mg/L coagulant dose was 2.7 mg/L and 2.0 mg/L for polyaluminum chloride and aluminum chlorohydrate, respectively. Sulfate-contributing coagulants aluminum sulfate, ferric sulfate, pre-hydroxylated aluminum sulfate, and polyaluminum silicate sulfate reduced CSMR as coagulant dose increased, also as would be expected. The highest sulfate contributors per 10 mg/L dose were pre-hydroxylated aluminum sulfate (6.2 mg/L) and ferric sulfate (6.0 mg/L). The lowest CSMR achieved was 0.6 in Lake Ontario water at a 30 mg/L dose and 0.8 in Grand River water at a 60 mg/L dose. Highest DOC removals were achieved with the chloride-containing coagulants in both waters (35 – 50%) with aluminum chlorohydrate showing superiority in that respect. DOC removals with sulfate-containing coagulants were less, generally in the range of 22 – 41%. Specificity of critical CSMR values to source water needs to be investigated. Additionally, long term effects of sustained high or low CSMR values in distribution systems need to be further looked into. Finally, the effect of interventions to alter CSMR on other water quality parameters influencing lead corrosion such as pH and alkalinity still represent a research deficit.

Lead is a known toxin, with the ability to accumulate in the human body from as early as fetal development. Lead exposure is known to cause a myriad of health effects which are more prominent among children. Health effects upon exposure can range from renal and heart disease or potentially cancer in adults to neurotoxicity in children. The continued presence of old lead service lines and plumbing in distribution systems as well as lead-containing solders and brass fixtures in homes may contribute lead to drinking water. Recent studies have highlighted the importance of a predictor known as the chloride-to-sulfate mass ratio (CSMR) in controlling lead release. A ratio above 0.5 – 0.6 theoretically increases the aggressiveness of lead leaching in galvanic settings, while a lower ratio controls lead corrosion. A switch in coagulant type could significantly alter the ratio. However, a coagulant switch could also trigger changes in finished water turbidity and organics, including disinfection by-product (DBP) precursors, as well as impact sludge production. Anecdotal evidence from an Ontario water treatment utility suggested the potential applicability of a newly formulated polymer, cationic activated silica (CAS), in improving DBP precursor removal when used in concurrence with a primary coagulant. No previous scientific research had been dedicated to testing of the polymer. The present research had three primary objectives: The first was to investigate the effect of conventional coagulation with six different coagulants on the chloride-to-sulfate mass ratio as it pertains to lead corrosion in two Ontario source waters of differing quality. Additionally, the effect of coagulant choice on pH, turbidity, and organics removal was investigated. The second objective was aimed at testing potential reductions in CSMR and organics that could be brought about by the use of two polymers, cationic and anionic activated silica (CAS and AAS, respectively), as flocculant aids. Finally, the performance of a high-rate sand-ballasted clarification process was simulated at bench-scale to gauge its performance in comparison with conventional coagulation simulation techniques. The first series of jar-tests investigated the effectiveness of CAS as a primary coagulant on Lake Ontario water. In comparison with the conventional coagulants aluminum sulfate and polyaluminum chloride, CAS did not offer any apparent advantage with respect to turbidity and organics removal. Testing of CAS and AAS as flocculant aids was also conducted. Results from a full factorial experiment focused on CAS testing on Lake Ontario water showed that coagulant dose is the most significant contributor to CSMR, turbidity, DOC removal, and THM control. Generally, improvements resulting from CAS addition were of small magnitude (<15%). Reductions in CSMR were attributed to the presence of the sulfate-containing chemicals alum and sulfuric acid in the CAS formulation. Testing of sulfuric acid-activated AAS on Grand River water showed that pairing of AAS with polyaluminum chloride provides better results than with alum with respect to DOC removal (39% and 27% respectively at 60 mg/L coagulant dose). Highest turbidity removals (>90%) with both coagulants were achieved at the tested coagulant and AAS doses of 10 mg/L and 4 mg/L respectively. CSMR reductions in the presence of AAS were also attributable to sulfate contribution from sulfuric acid. Bench-scale simulation of a high-rate sand-ballasted clarification process on Grand River water showed comparable removal efficiencies for turbidity (80 – 90% at 10 mg/L), and DOC (30 – 40% at 50 mg/L). Finally, six different coagulants were tested on the two source waters for potential applicability in CSMR adjustment in the context of lead corrosion. The two chloride-containing coagulants polyaluminum chloride and aluminum chlorohydrate increased CSMR in proportion to the coagulant dose added, as would be expected. Average chloride contribution per 10 mg/L coagulant dose was 2.7 mg/L and 2.0 mg/L for polyaluminum chloride and aluminum chlorohydrate, respectively. Sulfate-contributing coagulants aluminum sulfate, ferric sulfate, pre-hydroxylated aluminum sulfate, and polyaluminum silicate sulfate reduced CSMR as coagulant dose increased, also as would be expected. The highest sulfate contributors per 10 mg/L dose were pre-hydroxylated aluminum sulfate (6.2 mg/L) and ferric sulfate (6.0 mg/L). The lowest CSMR achieved was 0.6 in Lake Ontario water at a 30 mg/L dose and 0.8 in Grand River water at a 60 mg/L dose. Highest DOC removals were achieved with the chloride-containing coagulants in both waters (35 – 50%) with aluminum chlorohydrate showing superiority in that respect. DOC removals with sulfate-containing coagulants were less, generally in the range of 22 – 41%. Specificity of critical CSMR values to source water needs to be investigated. Additionally, long term effects of sustained high or low CSMR values in distribution systems need to be further looked into. Finally, the effect of interventions to alter CSMR on other water quality parameters influencing lead corrosion such as pH and alkalinity still represent a research deficit.