This thesis has used medium- and high-resolution spectral data to derive elemental abundances, in particular light and heavy s-process elemental abundances, for groups of giant stars in the globular clusters 47 Tuc, NGC 6388 and NGC 362. These analyses were undertaken using both curve-of-growth and spectrum synthesis techniques. The techniques were calibrated with respect to the metal-poor giant star Arcturus in order to reduce systematic errors in the analysis process. A feasibility study was undertaken that compared synthetic spectra at different resolutions throughout the colour-magnitude diagram (CMD) of a metal-rich ([Fe/H] = -0.5 dex) globular cluster. This study identified where on the CMD light and heavy s-process elemental abundances could be derived at medium resolution (R ~ 10,000). Abundance analyses could be undertaken on the giant branches down to just below the horizontal branch and then again on the main sequence below Teff ~ 4500 K. At all other places on the CMD high-resolution spectra (R ~ 30,000) are required to derive these abundances. Performance verification data at R ~ 5,000$ was obtained using the Robert Stobie Spectrograph (RSS) on the Southern African Large Telescope (SALT) and showed that there were no large scale s-process elemental abundance variations in 47 Tuc giant branch stars. The level of precision in this preliminary data was [X/Fe] ~ 0.5dex. A resolution of R ~ 10,000 should be achievable with SALT RSS in the future which will improve this limit. The AAOmega survey of 47 Tuc stars at R ~ 6,500 was more promising in certain aspects of elemental abundance determination. The observed wavelengths included the key features of CN and CH molecular bands, and light (Z < 30) and heavy (38 < Z < 63) element spectral lines. CN indices were measured and calibrated to previous results. The well-known CN bimodality was observed in the 47 Tuc stars, as well as a radial gradient in CN strength. A preliminary subset of ten of the survey stars have undergone an abundance analysis for which the abundances of Fe, Si, and Ca were found to be homogeneous within this cluster. The Na abundances had a large range in values that were observed to correlate with CN strength. The s-process elemental abundance results were inconclusive. The Zr abundances showed little to no enhancement in the sample and the Ba abundances varied considerably due to strong lines of Ba II being extremely sensitive to microturbulence. Various high-resolution studies were carried out using spectra of giant stars in 47 Tuc, NGC 6388 and NGC 362 observed on the Australian National Observatory (ANO) 2.3 m echelle spectrograph and the Ultra-Violet Echelle Spectrograph (UVES) on the Very Large Telescope (VLT). The high-resolution analysis of 47 Tuc giant star Lee 2525 found an enhanced Zr abundance in this star which resolved a discrepancy between two previous 47 Tuc elemental abundance studies (Brown & Wallerstein 1992; Wylie et al. 2006). The stars in the VLT dataset that were analysed here included five giant branch stars in 47 Tuc, two in NGC 6388 and thirteen in NGC 362. The low temperatures and gravities of these stars caused departures from local thermodynamic equilibrium in low excitation potential neutral species, particularly Fe and Zr, that needed to be taken into account before reliable stellar parameters and elemental abundances could be determined for these stars. Veiling effects due to circumstellar dust were postulated to have produced artificially low metallicities for the infra-red excess stars in this sample, particularly for the 47 Tuc stars. The element abundance analyses of 47 Tuc, NGC 6388 and NGC 362 stars found the derived metallicities to be homogeneous for each cluster (<[Fe/H]>(47Tuc) = -0.88 +/- 0.09 dex; <[Fe/H]>(NGC6388) = -0.60 +/- 0.06 dex; <[Fe/H]>(NGC362) = -1.21 +/- 0.08 dex). The 47 Tuc sample included Lee 2525 and the five VLT stars. The derived metallicities were in reasonable agreement with previously reported values. The light (ls) and heavy (hs) s-process element abundances were enhanced and homogeneous in the stars of each cluster. The abundances determined for 47 Tuc and NGC 6388 were in good agreement, reflecting the similarity in metallicity of the stars in these two clusters (<[ls/Fe]>(47Tuc) = +0.53 +/- 0.02 dex; <[hs/Fe]>(47Tuc) = +0.40 +/- 0.06 dex; <[ls/Fe]>(NGC6388) = +0.58 +/- 0.13 dex; <[hs/Fe]>(NGC6388) = +0.39 +/- 0.07 dex). The more metal-poor cluster NGC 362 was less enhanced in ls elemental abundances and slightly more enhanced in hs elemental abundances (<[ls/Fe]>(NGC362) = +0.32 +/- 0.10 dex, <[hs/Fe]>(NGC362) = +0.46 +/- 0.09 dex). The clear enhancement in the s-process elemental abundances and homogeneity in the results for each globular cluster is evidence that these stars have been enhanced extrinsically in s-process elements. Pollution events in the history of each cluster has resulted in the abundance distribution in both the light elements and the heavy elements that has been observed in the stars analysed in this thesis. The enhancements in Na, ls and hs elemental abundances favours intermediate mass AGB stars as the source of the pollution.

This thesis has used medium- and high-resolution spectral data to derive elemental abundances, in particular light and heavy s-process elemental abundances, for groups of giant stars in the globular clusters 47 Tuc, NGC 6388 and NGC 362. These analyses were undertaken using both curve-of-growth and spectrum synthesis techniques. The techniques were calibrated with respect to the metal-poor giant star Arcturus in order to reduce systematic errors in the analysis process. A feasibility study was undertaken that compared synthetic spectra at different resolutions throughout the colour-magnitude diagram (CMD) of a metal-rich ([Fe/H] = -0.5 dex) globular cluster. This study identified where on the CMD light and heavy s-process elemental abundances could be derived at medium resolution (R ~ 10,000). Abundance analyses could be undertaken on the giant branches down to just below the horizontal branch and then again on the main sequence below Teff ~ 4500 K. At all other places on the CMD high-resolution spectra (R ~ 30,000) are required to derive these abundances. Performance verification data at R ~ 5,000$ was obtained using the Robert Stobie Spectrograph (RSS) on the Southern African Large Telescope (SALT) and showed that there were no large scale s-process elemental abundance variations in 47 Tuc giant branch stars. The level of precision in this preliminary data was [X/Fe] ~ 0.5dex. A resolution of R ~ 10,000 should be achievable with SALT RSS in the future which will improve this limit. The AAOmega survey of 47 Tuc stars at R ~ 6,500 was more promising in certain aspects of elemental abundance determination. The observed wavelengths included the key features of CN and CH molecular bands, and light (Z < 30) and heavy (38 < Z < 63) element spectral lines. CN indices were measured and calibrated to previous results. The well-known CN bimodality was observed in the 47 Tuc stars, as well as a radial gradient in CN strength. A preliminary subset of ten of the survey stars have undergone an abundance analysis for which the abundances of Fe, Si, and Ca were found to be homogeneous within this cluster. The Na abundances had a large range in values that were observed to correlate with CN strength. The s-process elemental abundance results were inconclusive. The Zr abundances showed little to no enhancement in the sample and the Ba abundances varied considerably due to strong lines of Ba II being extremely sensitive to microturbulence. Various high-resolution studies were carried out using spectra of giant stars in 47 Tuc, NGC 6388 and NGC 362 observed on the Australian National Observatory (ANO) 2.3 m echelle spectrograph and the Ultra-Violet Echelle Spectrograph (UVES) on the Very Large Telescope (VLT). The high-resolution analysis of 47 Tuc giant star Lee 2525 found an enhanced Zr abundance in this star which resolved a discrepancy between two previous 47 Tuc elemental abundance studies (Brown & Wallerstein 1992; Wylie et al. 2006). The stars in the VLT dataset that were analysed here included five giant branch stars in 47 Tuc, two in NGC 6388 and thirteen in NGC 362. The low temperatures and gravities of these stars caused departures from local thermodynamic equilibrium in low excitation potential neutral species, particularly Fe and Zr, that needed to be taken into account before reliable stellar parameters and elemental abundances could be determined for these stars. Veiling effects due to circumstellar dust were postulated to have produced artificially low metallicities for the infra-red excess stars in this sample, particularly for the 47 Tuc stars. The element abundance analyses of 47 Tuc, NGC 6388 and NGC 362 stars found the derived metallicities to be homogeneous for each cluster (<[Fe/H]>(47Tuc) = -0.88 +/- 0.09 dex; <[Fe/H]>(NGC6388) = -0.60 +/- 0.06 dex; <[Fe/H]>(NGC362) = -1.21 +/- 0.08 dex). The 47 Tuc sample included Lee 2525 and the five VLT stars. The derived metallicities were in reasonable agreement with previously reported values. The light (ls) and heavy (hs) s-process element abundances were enhanced and homogeneous in the stars of each cluster. The abundances determined for 47 Tuc and NGC 6388 were in good agreement, reflecting the similarity in metallicity of the stars in these two clusters (<[ls/Fe]>(47Tuc) = +0.53 +/- 0.02 dex; <[hs/Fe]>(47Tuc) = +0.40 +/- 0.06 dex; <[ls/Fe]>(NGC6388) = +0.58 +/- 0.13 dex; <[hs/Fe]>(NGC6388) = +0.39 +/- 0.07 dex). The more metal-poor cluster NGC 362 was less enhanced in ls elemental abundances and slightly more enhanced in hs elemental abundances (<[ls/Fe]>(NGC362) = +0.32 +/- 0.10 dex, <[hs/Fe]>(NGC362) = +0.46 +/- 0.09 dex). The clear enhancement in the s-process elemental abundances and homogeneity in the results for each globular cluster is evidence that these stars have been enhanced extrinsically in s-process elements. Pollution events in the history of each cluster has resulted in the abundance distribution in both the light elements and the heavy elements that has been observed in the stars analysed in this thesis. The enhancements in Na, ls and hs elemental abundances favours intermediate mass AGB stars as the source of the pollution.

Orientadores: Jose Vicente Hallak D'Angelo, Roger Josef Zem / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T20:34:11Z (GMT). No. of bitstreams: 1 Andrade_AlexandreAugustode_M.pdf: 1431250 bytes, checksum: 071f09bc36a20d1058f5dcaef7eb20e6 (MD5) Previous issue date: 2006 / Resumo: Na indústria de papel e celulose há uma grande preocupação sobre o consumo crescente de água fresca e também quanto ao volume de efluentes a serem tratados, pois estão estritamente ligados às limitações de expansões do processo, devido a restrições ambientais e capacidade da planta. O objetivo principal deste trabalho é estudar a viabilidade técnica de se usar o efluente gerado nas máquinas de papel, água branca, nas prensas de lavagem do branqueamento, visando uma redução no consumo de água fresca nestes equipamentos. Foi realizado um estudo de caso do processo de produção da Ripasa S.A. Celulose e Papel, uma indústria de papel e celulose localizada em Limeira (Estado de São Paulo). Nesse processo é gerada uma taxa de cerca de 700 m3/h de água branca e devido às propriedades físico-químicas deste efluente, especialmente seu conteúdo de matéria orgânica e sua alta dureza, não é possível a reutilização total dessa água na etapa de branqueamento sem causar problemas operacionais como incrustações em tubos e entupimento das telas. Assim, neste trabalho, um balanço de massa na unidade de branqueamento da Ripasa foi desenvolvido em uma planilha eletrônica, para avaliar a possibilidade de reduzir o consumo de água fresca usando-se uma fração do volume da água branca para a lavagem da polpa nessa etapa do processo. Para tanto algumas propriedades físico-químicas da corrente de água branca e de outras correntes do processo de branqueamento foram determinadas, tendo-se como a mais importante a análise de matéria orgânica. As concentrações máximas de alguns elementos não processáveis (NPE) como Si, Ca, Mn e Fe também foram determinados para estabelecer alguns parâmetros para permitir essa integração de processo, considerando-as como restrições operacionais. Os resultados obtidos mostraram que é possível reduzir aproximadamente 13% do consumo de água fresca, tendose como principais restrições a concentração de matéria orgânica seguida da concentração de Ca presentes na água branca. É importante dizer que esta integração de processo não só contribui para a redução no consumo de água fresca, mas também para a redução do volume dos efluentes gerados no processo / Abstract: In pulp and paper mills there is a great concern about the increasing consumption of fresh water and also the great volume of effluents that need to be treated, since they are represent limitations to new process expansions, due to environment restrictions and plant capacity. The aim of this work is to study the technical viability of using the effluent stream generated in the paper machines, called white water, in the washing presses of bleaching stages, seeking for a reduction in the consumption of fresh water in these equipments. A case study was performed, using industrial data of a real pulp and paper mil!. In its process, white water is produced at a rate of about 700 m3/h and the physical-chemical properties of this effluent, mainly its organic material content and hardness, do not allow its complete reuse in the bleaching process, without causing operational problems like fouling in tubes and clogging in the screens. So, in this work, a material balance of the bleaching unit was developed in an electronic spreadsheet in order to evaluate the possibility to reduce the consumption of fresh water in the washing presses, using a portion of the white water effluent stream. To accomplish the objective proposed, some physical-chemical properties of white water stream and other process streams were determined experimentally, and the most important one is organic material analysis. The maximum concentration of some non-process elements like Si, Ca, Mn and Fe that could accumulate in the process were also determined in order to establish some parameters to perform process integration, considering these concentrations as operational restrictions. The results obtained have shown that it is possible to reduce approximately 13% of fresh water consumption and the main restrictions to this reduction is organic material content and concentration of Ca in white water stream. It is also important to say that this process integration not only contributes to reduce fresh water consumption but also helps to reduce the volume of effluents generated in the process / Mestrado / Sistemas de Processos Quimicos e Informatica / Mestre em Engenharia Química

Modern chemical technology is an efficient tool for solving problems, particularly within the complex environment of the pulp and paper industry, and the combination of experimental studies, mill data and mass balance calculations are of fundamental importance to the development of the industry. In this study various examples are presented, whereby chemical technology is of fundamental importance. It is well documented that under normal conditions the molten salt mixture from the kraft recovery boiler flows down into the dissolving tank without problems. However, in the case of  alternatives to the kraft recovery boiler, knowledge of more precise data of the molten salts is required for the design calculations. In this study the viscosity for the case of sodium carbonate and 30 mole% sulphide has been measured and is of the magnitude 2 – 3 cP at temperatures relevant for a recovery boiler, i.e. similar to water at room temperature. The presence of non-process elements (NPE) in a typical pulp mill has been investigated. The main input is with regards to the wood, and anticipated problems include; deposits in evaporators, high dead-load in liquor streams, plugging of the upper part of the recovery boiler and decreasing efficiency in the causticization department. Efficient green liquor clarification is of the greatest importance as an efficient kidney for many NPE. Mill data and calculations show that the magnesium added in the oxygen delignification does not form a closed loop. Integration of a prehydrolysis kraft pulp mill producing dissolving pulp with a plant producing viscose textile fiber could be highly beneficial. The prehydrolysis liquor will contain both sugars and acetic acid. It is however not possible to fully replace the sulphuric acid of the viscose spinning bath with acetic acid of own production. The sulphuric chemicals from the viscose plant can be partly taken care of in the kraft recovery area as well as the viscose plant which can be supplied with alkali and sulphuric acid. Zinc-containing effluents from the viscose plant can be treated with green liquor to precipitate zinc sulphide. / Modern chemical technology is an extremely efficient tool for solving problems particularly in a complicated environment such as the pulp and paper industry. Here, examples are studied during which chemical technology is of fundamental importance. At normal conditions the molten salt mixture from the kraft recovery boiler flows down into the dissolving tank without hindrance. However, for certain kraft recovery boiler alternatives, knowledge of more precise data of the molten salts is required. The viscosity for the case of sodium carbonate and 30 mole% sulphide has been measured and is of the magnitude 2 – 3 cP at relevant temperatures. The main input of non-process elements (NPE) is down to the wood, and known problems include deposits in evaporators and decreasing efficiency in the causticization department. Green liquor clarification is an efficient kidney for many NPE. Magnesium added in the oxygen delignification does not form a closed loop. Integration of a prehydrolysis kraft pulp mill producing dissolving pulp with a plant producing viscose textile fiber could be of significant interest, as the handling of both alkali and sulphuric compounds can be integrated. Problems will however arise as the capacity of the pulping line and the chemical recovery has to be adjusted.