Thesis (Ph.D.) - University of Queensland, 2003. / Includes bibliography.

Thesis (doctoral)--University of Oulu, 1992. / Includes bibliographical references.

Thesis (M.Sc.)--Memorial University of Newfoundland, 2004. / Restricted until October 2005. Bibliography: leaves 135-154.

Thesis (Ph.D.)--York University, 2009. Graduate Programme in Chemistry. / Typescript. Includes bibliographical references. Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:NR51666

Made available in DSpace on 2014-06-11T19:35:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2013-06-24Bitstream added on 2014-06-13T19:05:22Z : No. of bitstreams: 1 perujo_sd_dr_ilha.pdf: 3975409 bytes, checksum: 20915b5dadee73e9b64313a155116ba3 (MD5) / Neste trabalho, primeiramente foi sintetizado o octa (3-cloropropil) silsesquioxano (OCS), por meio da condensação hidrolítica do 3-Cloropropil trietoxisilano. Na sequência, foram preparados dois adsorventes a partir da organofuncionalização do OCS com os ligantes 2- mercaptopirimidina (2-MCP) e o 2-amino-1,3,4-tiadiazol (ATD), resultando os materiais: octa (2-mercaptopirimidinapropil) silsesquioxano (2-MCP-SSQ) e o octa (2-amino-1,3,4- tiadiazolpropil) silsesquioxano (ATD-SSQ). Em seguida estes materiais foram caracterizados por meio das técnicas de FTIR, NMR 13 C, NMR 29 Si, SEM, análise elementar e análise termogravimétrica. A análise elementar do nitrogênio indicou um teor de funcionalização de 4,4 e 3,6 mmol g-1 para o 2-MCP-SSQ e o ATD-SSQ, respectivamente. Estes nanoadsorventes foram aplicados na adsorção dos íons metálicos CuX2, CoX2 e NiX2 (X= Cl-, Br- e ClO4-) em soluções aquosas, etanólicas e cetônicas, pelo método de “Batch” (batelada). O tempo de equilíbrio de adsorção para os dois adsorventes estudados foi de aproximadamente 40 minutos para os íons metálicos em todos os solventes estudados. Foi observado que as capacidades máximas de adsorção (Nfmáx) nos solventes estudados obedeceram a ordem cetônico > etanólico >> aquoso. Nos meios etanólico e cetônico a adsorção obedece a seguinte ordem: Cu2+ > Co2+ > Ni2+ e em meio aquoso: Ni2+ > Co2+ > Cu2+. As isotermas de adsorção foram ajustadas aos modelos de Langmuir, Freundlich, Temkin e Dubinin-Radushkevich (D-R). Foram aplicados os modelos cinéticos de adsorção de pseudo-primeira-ordem, pseudo-segunda-ordem e Elovich, e os modelos de difusão de Boyd & Reichenberg e de difusão intrapartícula. Os modelos de Langmuir, pseudo-segunda- ordem e de Boyd & Reichenberg foram os mais apropriados para... / In this work, first the octa (3-chloropropyl) silsesquioxane (OCS) was synthesized by hydrolytic condensation of the 3-chloropropyl triethoxysilane. In the following, two adsorventes were prepared from the OCS organofunctionalization with the ligands 2- mercaptopyrimidine (2-MCP) and 2-amino-1,3,4-thiadiazole (ATD), resulting the materials octa (2-mercaptopyrimidinepropyl) silsesquioxane (2-MCP-SSQ) and octa (2-amino-1,3,4- tiadiazolpropyl) silsesquioxane (ATD-SSQ). Then the material was characterized by the techniques of FTIR, 13 C-NMR, 29 Si-NMR, SEM, elemental analysis and thermogravimetric analysis. The nitrogen elemental analysis indicated a degree of functionalization of 4.4 and 3.6 mmol g-1 for the 2-MCP-SSQ and ATD-SSQ, respectively. These nanoadsorventes were applied to the adsorption of metal ions CuX2, CoX2 and NiX2 (X = Cl-, Br- and ClO4-) in aqueous, ethanolic and ketone solutions by the batch method. The time of adsorption equilibrium for the two adsorbents studied was approximately 40 minutes for all solvents and metal ions. It was observed that the maximum adsorption capacity (Nfmáx) in the solvents studied obeyed the order ketone > ethanolic > > aqueous. In ethanol and ketone media the adsorption obeys the following order: Cu2+ > Co2+ > Ni2+ and aqueous: Ni2+ > Co2+ > Cu2+. The adsorption isotherms were fitted to Langmuir, Freundlich, Temkin and Dubinin- Radushkevich (D-R). It were applied the kinetic models of adsorption pseudo-first-order, pseudo-second-order and Elovich and diffusion models of Boyd & Reichenberg and intraparticle diffusion. The Langmuir, pseudo-second-order and Boyd & Reichenberg models were the most appropriate to describe the data of adsorption, kinetics and diffusion, respectively. The thermodynamic parameters ΔG, ΔH and ΔS were... (Complete abstract click electronic access below)

Thesis (MTech (Chemical Engineering)--Cape Technikon, Cape Town, 1998 / Ion exchange resins are widely used to remove or concentrate heavy metals from aqueous solutions or slurries.This thesis attempts to properly evaluate the interaction between ion exchange resins and heavy metals at trace metal concentrations.The durability of the resins and their effectiveness in real slurries were also investigated. In this study, a chelating resin, as well as a cation, and anion exchange resin was contacted with aqueous solutions of heavy metals in both free and complexed form. Zinc, nickel and copper cyanide complexes were adsorbed onto the anion exchange resin, while the chelating and cation exchange resins were contacted with zinc and nickel nitrates, and cupric sulphate. All the tests were conducted in batch stirred tank reactors. All the metal cyanide complexes behaved in a similar manner when contacted with the anion exchange resins. These tests were p~rf0nned under variations in temperature, stirring speed, pH., ionic strength and . initial metal 90E~entrations. Fitting of a dual resistance model to the profiles for thetlptllk:e" of the complexes, show that both film diffusion and intraparticle diffusion rates were improved with an increase in temperature, and that film diffusion rates improved with an increase in stirring speed. A high ionic strength negatively affected equilibrium loading as well as diffusional rates.It was found that at these low concentrations, the diffusional rates improves with a decrease in the external metal concentration. A comparative study involving the chelating and cation·exchange resins were performed, during which the resins were contacted with the metals in free fonn. It was found that at high metal concentrations, the chelating resin induced a rate limiting effect, but at trace concentrations, this effect is virtually negated. Whereas the cation exchange resin exhibited little selectivity in adsorbing the metals, it was found that the chelating resin prefers the metals in the eu > Ni > Zn. The chelating resin proved to be no less durable then the cation exchange resin, and both slightly lost their ability to adsorb the metal cations as a result of the effects of an inert coarse sand slurry.Tests performed with a real ore leachate, showed the cation exchange resin to be efficient at a low pH , but also relatively non selective, since the adsorption of copper from the leachate was greatly reduced due to the presence of other heavy metals.

Orientador: Roberto Alves Oliveira / Coorientador: Allynson Takehiro Fujita / Banca: Mariana Carina Frigieri / Banca: Luciano dos Santos Rodrigues / Resumo: Reatores contínuos com leito de lodo biológico anaeróbio, in natura e seco em estufa, foram utilizados para a remoção de metais (Cu+2, Mn+2 e Zn+2) em solução aquosa. Com o lodo in natura avaliou-se o efeito conjunto da bioacumulação e biossorção; e com o lodo seco em estufa o efeito exclusivo da biossorção. Foram utilizadas baixas concentrações de Cu+2, Mn+2 e Zn+2 (0,01 a 5,00 mg L-1), tendo em vista que para a ocorrência de bioacumulação devem ser mantidas condições não tóxicas para os micro-organismos. Portanto, os resultados poderão ser aplicados para o pós-tratamento de efluentes com concentrações remanescentes desses metais, que necessitem de polimento para a disposição final, atendendo aos limites legais de qualidade de água do corpo receptor. Os lodos utilizados foram coletados de reatores anaeróbios horizontal (RAH) e de fluxo ascendente com manta de lodo (UASB) utilizados no tratamento de águas residuárias de suinocultura. A temperatura foi controlada a 20°C em todos os ensaios. Foram avaliadas vazões de 5, 10 e 15 mL min-1, valores de pH 4,0 e 6,0 e concentrações de 0,01, 0,5 e 1,0 mg L-1 de Cu2+ e Mn2+, e de 0,05; 2,5 e 5,0 mg L-1 de Zn2+. O pH ótimo para a remoção de Mn2+ e Zn2+ foi 4,0 e para o Cu2+ não foi verificada diferença. A maior eficiência foi encontrada quando utilizou-se os menores valores de concentração e fluxo para os três biossorventes avaliados. Foi verificado que os valores de concentração de metais utilizados demonstraram não serem tóxicos para... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Continuous reactors with anaerobic biological sludge bed, in nature and dry in an oven, were used for removal of metals (Cu+2, Mn+2 and Zn+2 ) in aqueous solution. With the sludge in natura it was evaluated the combined effect of bioaccumulation and biosorption; and the dry sludge in greenhouse sole effect of biosorption. It was used lower concentrations of Cu+2, Mn+2 and Zn+2 (0.01 to 5.00 mg L -1 ), considering that for bioaccumulation occurring should be kept non-toxic conditions for the micro-organisms. Therefore, the results can be applied to the posttreatment of effluents with remaining concentrations of these metals, which require polishing to final disposal, meeting the legal limits of quality of the receiving water body. The used sludges were collected from horizontal anaerobic reactors (RAH) and ascendant upflow sludge blanket (UASB) used in the treatment of swine wastewater. The temperature was controlled at 20°C in all tests. It was analyzed outputs of 5, 10 and 15 ml min-1, pH values 4.0 and 6.0 and concentrations of 0.01, 0.5 and 1.0 mg L- 1 Cu+2 and Mn+2, and 0.05; 2.5 and 5.0 mg L -1 Zn+2 . The optimum pH for the removal of Mn+2 and Zn+2 was 4.0 and the Cu+2 it was not verified difference. The highest efficiency was found when it was used the lowest values of concentration and flux for all three reviews biosorbents. It has been found that the metals concentration values used proved not to be toxic to cells of microorganisms present in the sludge in nature,... (Complete abstract click electronic access below) / Mestre

The selective recovery of rhodium from wastewaters, in which the metal would be otherwise lost, would be highly profitable if the process were suitably low-cost. Current recovery processes are generally high maintenance and high-cost, whereas biological processes can be engineered to run with little external input in terms of cost and maintenance. Three emerging technologies were chosen based on their reported efficiency when removing base metals from wastewaters. The first technology screened, the sulphide-extraction membrane bioreactor (SEMB), consists of a sulphate-reducing prokaryote (SRP) anaerobic digester, in which a silicone membrane is submerged. Wastewater is passed through the membrane and metal ions are precipitated as metal sulphides by the hydrogen sulphide gas, which is capable of permeating the membrane. The second technology screened was a fluidized sand bed reactor in which metal ions are removed from solution via induction of nucleated precipitation by sodium carbonate onto the sand grains. The third, and most well established removal technology screened was a biosorption system using immobilized Saccharomyces cerevisiae biomass as the biosorbent. Experimental trials with each technology highlighted drawbacks with each; the SEMB system proved to be largely ineffective when challenged with the removal of rhodium from the wastewater as the rhodium precipitate fouled the membrane within hours, the fluidized bed system seemed unable to overcome the acidity of the wastewater and thus could not precipitate out the rhodium metal, and the efficiency of the biosorption process was hampered by the diversity of rhodium species present in the wastewater, which reduced the amount recovered. The outcomes of the trials with each technology indicated that further optimization of the technology or pretreatment of the wastewater is necessary before any of these options can be implemented. It could be concluded, however, that despite further optimization, both the SEMB and the fluidized bed system were not applicable in this case as precipitation would be non-specific, resulting in the necessity for further steps in order to purify the rhodium ions. Hence, the biosorption system was shown to be most applicable, and further optimization of the system could yield a highly efficient rhodium recovery process.

A Ni(II)-dimethylglyoxime ion imprinted polymer {Ni(II)-DMG IIP} was synthesized by the trapping method using the bulk polymerisation format. The structures of the imprinted and non-imprinted polymer were evaluated by infrared spectroscopy and the morphology was observed by scanning electron microscopy. The Ni(II)-DMG IIP was optimised for pH, mass, time and by the uniform design experimental method for the molar ratios of monomer to crosslinker to porogen and template to ligands as well as keeping these parameters constant and varying the quantities of initiator, 2,2'-azobisisobutyronitrile (AIBN). The optimum pH was 8.5, optimum mass was 50 mg, optimum time was 1 min and the optimum molar ratios of crosslinker to monomer, monomer to template and nickel(II) sulfate hexahydrate (NiSO₄.6H₂O) to 4-vinylpyridine to dimethylglyoxime were found to be 3.3:1.0, 0.6:1.0 and 1.0:0.6:3.6 respectively with 30 mg and 8 mL as the optimum amounts of initiator and porogen respectively. Through this optimisation, recovery of Ni(II) was increased from 98 to 100%. Selectivity of the ion imprinted polymer was evaluated by analysing, using an inductively coupled plasma-optical emission spectrometer, for Ni(II) ions that were spiked with varying concentrations of Co(II), Cu(II), Zn(II), Pd(II), Fe(II), Ca(II), Mg(II), Na(I) and K(I) in aqueous samples. Selectivity studies also confirmed that the ion imprinted polymer had very good selectivity characterised by % RSD of less than 5 %. Co(II) was the only ion found to slightly interfere with the determination of Ni(II). The limits of detection and quantification were found to be 3x10⁻⁴ μg/mL and 9x10⁻⁴ μg/mL respectively. The method was evaluated by a custom solution of ground water certified reference material (SEP-3) and sandy soil reference material (BCR-142R) and the concentrations of Ni(II) obtained were not significantly different to the certified ones. The Ni(II)-DMG IIP was then evaluated in aqueous and soil samples where recoveries of 93 to 100% and 98 to 99% respectively were obtained with enrichment factors ranging from 2 to 18 in aqueous and 27 to 40 in soil samples. Finally, the Ni(II)-DMG IIP was used to analyse mine tailings samples and Ni(II) recovery of 99% was obtained with an enrichment factor of 2.

Orientador: Newton Luiz Dias Filho / Banca: Devaney Ribeiro do Carmo / Banca: Ezequiel Costa Siqueira / Banca: Cesar Ricardo Teixeira Tarley / Banca: Luciana Camargo de Oliveira / Resumo: Neste trabalho, primeiramente foi sintetizado o octa (3-cloropropil) silsesquioxano (OCS), por meio da condensação hidrolítica do 3-Cloropropil trietoxisilano. Na sequência, foram preparados dois adsorventes a partir da organofuncionalização do OCS com os ligantes 2- mercaptopirimidina (2-MCP) e o 2-amino-1,3,4-tiadiazol (ATD), resultando os materiais: octa (2-mercaptopirimidinapropil) silsesquioxano (2-MCP-SSQ) e o octa (2-amino-1,3,4- tiadiazolpropil) silsesquioxano (ATD-SSQ). Em seguida estes materiais foram caracterizados por meio das técnicas de FTIR, NMR 13 C, NMR 29 Si, SEM, análise elementar e análise termogravimétrica. A análise elementar do nitrogênio indicou um teor de funcionalização de 4,4 e 3,6 mmol g-1 para o 2-MCP-SSQ e o ATD-SSQ, respectivamente. Estes nanoadsorventes foram aplicados na adsorção dos íons metálicos CuX2, CoX2 e NiX2 (X= Cl-, Br- e ClO4-) em soluções aquosas, etanólicas e cetônicas, pelo método de "Batch" (batelada). O tempo de equilíbrio de adsorção para os dois adsorventes estudados foi de aproximadamente 40 minutos para os íons metálicos em todos os solventes estudados. Foi observado que as capacidades máximas de adsorção (Nfmáx) nos solventes estudados obedeceram a ordem cetônico > etanólico >> aquoso. Nos meios etanólico e cetônico a adsorção obedece a seguinte ordem: Cu2+ > Co2+ > Ni2+ e em meio aquoso: Ni2+ > Co2+ > Cu2+. As isotermas de adsorção foram ajustadas aos modelos de Langmuir, Freundlich, Temkin e Dubinin-Radushkevich (D-R). Foram aplicados os modelos cinéticos de adsorção de pseudo-primeira-ordem, pseudo-segunda-ordem e Elovich, e os modelos de difusão de Boyd & Reichenberg e de difusão intrapartícula. Os modelos de Langmuir, pseudo-segunda- ordem e de Boyd & Reichenberg foram os mais apropriados para... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work, first the octa (3-chloropropyl) silsesquioxane (OCS) was synthesized by hydrolytic condensation of the 3-chloropropyl triethoxysilane. In the following, two adsorventes were prepared from the OCS organofunctionalization with the ligands 2- mercaptopyrimidine (2-MCP) and 2-amino-1,3,4-thiadiazole (ATD), resulting the materials octa (2-mercaptopyrimidinepropyl) silsesquioxane (2-MCP-SSQ) and octa (2-amino-1,3,4- tiadiazolpropyl) silsesquioxane (ATD-SSQ). Then the material was characterized by the techniques of FTIR, 13 C-NMR, 29 Si-NMR, SEM, elemental analysis and thermogravimetric analysis. The nitrogen elemental analysis indicated a degree of functionalization of 4.4 and 3.6 mmol g-1 for the 2-MCP-SSQ and ATD-SSQ, respectively. These nanoadsorventes were applied to the adsorption of metal ions CuX2, CoX2 and NiX2 (X = Cl-, Br- and ClO4-) in aqueous, ethanolic and ketone solutions by the batch method. The time of adsorption equilibrium for the two adsorbents studied was approximately 40 minutes for all solvents and metal ions. It was observed that the maximum adsorption capacity (Nfmáx) in the solvents studied obeyed the order ketone > ethanolic > > aqueous. In ethanol and ketone media the adsorption obeys the following order: Cu2+ > Co2+ > Ni2+ and aqueous: Ni2+ > Co2+ > Cu2+. The adsorption isotherms were fitted to Langmuir, Freundlich, Temkin and Dubinin- Radushkevich (D-R). It were applied the kinetic models of adsorption pseudo-first-order, pseudo-second-order and Elovich and diffusion models of Boyd & Reichenberg and intraparticle diffusion. The Langmuir, pseudo-second-order and Boyd & Reichenberg models were the most appropriate to describe the data of adsorption, kinetics and diffusion, respectively. The thermodynamic parameters ΔG, ΔH and ΔS were... (Complete abstract click electronic access below) / Doutor