Dewatering fine coal is needed in many applications but has remained a great challenge. The hydrophobic-hydrophilic separation (HHS) method is a powerful technology to address this problem. However, organic solvents in solvent-coal slurries produced during HHS must be recovered for the method to be economically viable. Here, the experimental studies of recovering solvents from pentane-coal and hexane-coal slurries by combining liquid-solid filtration and in-situ vaporization and removing the solvent by a carrier gas (i.e., drying) are reported. The filtration behaviors are studied under different solid mass loading and filtration pressure. It is shown that using pressure filtration driven by 20 psig nitrogen, over 95% of solvents by mass in the slurries can be recovered, and filtration cakes can be formed in 60 s. The drying behavior was studied using nitrogen and steam at different temperatures and pressures. It is shown that residual solvents in filtration cakes can be reduced below 1400 ppm within 10 s by 15 psig steam superheated to 150C, while other parameter combinations are far less effective in removing solvents. Physical processes involved in drying and the structure of solvent-laden filtration cakes are analyzed in light of these results. / Master of Science / Coal particles below a certain size are discarded to waste tailing ponds as there is no economically viable method for processing them. However, a new process called hydrophobic-hydrophilic separation offers a solution to this problem. A hydrophobic solvent is used to displace water from a coal-water slurry, and it is then easier and cheaper to filter and dry this new coal-solvent slurry. In this work experimental studies of recovering solvents from pentane-coal and hexane-coal slurries by combining filtration and drying are reported. The filtration behaviors are studied under different solid mass loading and filtration pressures. It is shown that using pressure filtration driven by 20 psig nitrogen, over 95% of solvents by mass in the slurry can be recovered, and filtration cakes can be formed in 60 s. The drying behavior was studied using nitrogen and steam at different temperatures and pressures to evaporate any remaining solvents. It is shown that the remaining solvents in filtration cakes can be reduced below 1400 ppm within 10 s by using 15 psig steam superheated to 150C as a drying medium, while other parameter combinations are far less effective in removing solvents. Physical processes involved in drying and the structure of solvent-laden filtration cakes are analyzed in light of these results.

Beneficiation of fine coal (+500 μm –2000 μm) is a worldwide problem in the mining industry, especially dry beneficiation of fine coal. Coal beneficiation can be divided primarily into two methods, namely wet- and dry beneficiation. Wet beneficiation methods are utilized more in today‘s industry because of the sharp separation efficiency that can be achieved. These processes include wet jigging, dense medium cyclones, spiral beneficiation etc. Due to the lack of a sufficient water supply in some regions around the world including South Africa, dry beneficiation methods are becoming more popular. Recent mechanized mining methods caused the fraction of fines from coal mines to increase over the years. However, due to old inefficient technologies, coal fines contained in slurry ponds could not be beneficiated and had to be discarded. One new dry beneficiation technology that has been used and researched extensively is the fluidized dense medium bed (FDMB) technology. The purpose of this study is to determine whether fine coal can be successfully beneficiated with a FDMB. It also has to be determined whether adding magnetite and introducing a jigging (pulse) motion to the air feed will increase the separation efficiency of the fluidization process. Witbank seam 4 and a Waterberg coal was used in experiments during this study. A coarse (+1180 μm –2000 μm), fine (+500 μm –1180 μm) and a mix of the two samples were prepared and tested. It was found that adding magnetite to the feed of the fluidized bed did not increase the separation efficiency. However, previous studies indicated the opposite results with regards to magnetite addition. The difference in results obtained could be prescribed to the ultrafine nature of the magnetite and the small coal particles size range used. If the presence of fine particles in the bed increases, the stability of fluidization decreases. In turn, the separation efficiency of the process decreases. Subjecting the feed air flow to a pulsating motion did not have a significant effect on separation. Good results were still obtained with jigging experiments, although not better than with normal fluidization. Stratification of coal particles according to quality was evident by the results obtained during experiments. The quality of coal increases from the bottom to the top of the bed. Overall the fluidized bed, in the absence of magnetite, was found to be a sufficient de-ashing process and further research on this technology could be very beneficial to the coal industry. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2014

Beneficiation of fine coal (+500 μm –2000 μm) is a worldwide problem in the mining industry, especially dry beneficiation of fine coal. Coal beneficiation can be divided primarily into two methods, namely wet- and dry beneficiation. Wet beneficiation methods are utilized more in today‘s industry because of the sharp separation efficiency that can be achieved. These processes include wet jigging, dense medium cyclones, spiral beneficiation etc. Due to the lack of a sufficient water supply in some regions around the world including South Africa, dry beneficiation methods are becoming more popular. Recent mechanized mining methods caused the fraction of fines from coal mines to increase over the years. However, due to old inefficient technologies, coal fines contained in slurry ponds could not be beneficiated and had to be discarded. One new dry beneficiation technology that has been used and researched extensively is the fluidized dense medium bed (FDMB) technology. The purpose of this study is to determine whether fine coal can be successfully beneficiated with a FDMB. It also has to be determined whether adding magnetite and introducing a jigging (pulse) motion to the air feed will increase the separation efficiency of the fluidization process. Witbank seam 4 and a Waterberg coal was used in experiments during this study. A coarse (+1180 μm –2000 μm), fine (+500 μm –1180 μm) and a mix of the two samples were prepared and tested. It was found that adding magnetite to the feed of the fluidized bed did not increase the separation efficiency. However, previous studies indicated the opposite results with regards to magnetite addition. The difference in results obtained could be prescribed to the ultrafine nature of the magnetite and the small coal particles size range used. If the presence of fine particles in the bed increases, the stability of fluidization decreases. In turn, the separation efficiency of the process decreases. Subjecting the feed air flow to a pulsating motion did not have a significant effect on separation. Good results were still obtained with jigging experiments, although not better than with normal fluidization. Stratification of coal particles according to quality was evident by the results obtained during experiments. The quality of coal increases from the bottom to the top of the bed. Overall the fluidized bed, in the absence of magnetite, was found to be a sufficient de-ashing process and further research on this technology could be very beneficial to the coal industry. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2014

Dense medium separation (DMS) plants are typically used to beneficiate run-of-mine (ROM) coal in coal metallurgy. These plants normally make use of a dense medium cyclone as the primary processing unit. Because of the deviations in the ROM quality, the production yield and quality become difficult to maintain. A control system could benefit such operations to maintain and increase product throughput and quality. There are many different methods for developing a control system in a metallurgical operation; however, what is most fundamental is the use of a mathematical model to design a controller. For this reason, a first principle dynamic mathematical model has been developed for a DMS circuit. Each unit operation is modelled individually, then integrated together to form the complete system. The developed DMS circuit dynamic model is then used to simulate the process. It is also found that most models developed for DMS operations typically make use of steady-sate analysis and that very little literature is available on dynamic models of this kind. Difficulties that arise when validating a model in metallurgical processes are insufficient measurement points or the challenges in measuring certain variables, such as physical properties (e.g. particle size) or chemical components (e.g. ash percentage). This paper also explains how the Runge-Kutta approximation can be used in simulating DMS unit processes with intermediate online measurements that may be available. This can ultimately assist in verifying the accuracy of the simulation. One of the other problems that can occur when developing models from first principles is the estimation of model parameters. Specifically when non-linear state-space relationships are developed, one must ensure that there is a unique solution for the parameters in question. A method employing parameter identifiability is also presented in this dissertation to illustrate its use. In addition the process of estimating parameters is explained and illustrated. Copyright / Dissertation (MEng)--University of Pretoria, 2010. / Electrical, Electronic and Computer Engineering / unrestricted

A presença de elevada carga nitrogenada em corpos hídricos pode causar sérios impactos ambientais como a eutrofização e a toxicidade do meio. Um dos processos que possibilitam a remoção de nitrogênio de efluentes é a adsorção, na qual o uso de adsorventes alternativos tem sido aplicado para o aproveitamento de resíduos e redução dos custos no processo. Dentro deste contexto, o processo de extração e beneficiamento do carvão fóssil na Região Sul do Brasil produz um rejeito (RB) com características que possibilitam sua aplicação na síntese de zeólitas, as quais podem ser utilizadas como adsorventes. Assim, o objetivo da presente tese foi avaliar a remoção do íon amônio de soluções aquosas por adsorção utilizando-se zeólitas naturais e sintetizadas a partir do rejeito RB. Em um primeiro momento, experimentos de adsorção foram conduzidos utilizando-se zeólita Na-clinoptilolita para conhecimento dos parâmetros termodinâmicos e da capacidade de regeneração do material. Posteriormente, a síntese de zeólitas utilizando rejeito RB foi realizada variando-se a fonte de alumínio, o emprego da agitação do meio durante a síntese e temperatura de calcinação do rejeito. A caracterização dos materiais foi feita através das técnicas de Difração de Raios X (DRX), Microscopia Eletrônica de Varredura acoplada a Espectroscopia por Dispersão em Energia (MEV-EDS), Potencial Zeta (PZ), Fluorescência de Raios X (FRX), Porosimetria de Nitrogênio (BET), Espectroscopia no Infravermelho por Transformada de Fourier (FTIR) e Capacidade de Troca Catiônica (CTC). Por fim, experimentos de adsorção de amônio foram feitos para o material que apresentou o maior conteúdo de íons sódio em sua composição. Quanto aos estudos com a Na-clinoptilolita, o estudo termodinâmico demostrou que a constante de equilíbrio (K0) da adsorção da zeólita estimada por diferentes métodos pode apresentar variação de até 105 de um método para outro. O estudo em questão também revelou que o método de Gaines e Thomas é o mais adequado para a estimativa dos parâmetros termodinâmicos. Nos testes de regeneração da zeólita utilizando-se solução NaCl de 0,5 a 3,0 M foram obtidos valores acima de 76% de regeneração para toda faixa de concentração avaliada, sem o reuso da solução de NaCl. Os testes feitos com o reuso da solução salina na etapa da dessorção permitiram concluir que é possível tratar até 160 mL de efluente utilizando-se somente 20 mL de solução NaCl 1,0 M, mantendo-se uma capacidade de adsorção equivalente a 80% da capacidade original da zeólita. Através da aplicação de diferentes condições de síntese utilizando o rejeito RB, foram obtidos sete diferentes materiais. O material que apresentou maior conteúdo de Na+ em sua composição foi obtido utilizando-se: pré-tratamento do rejeito com calcinação a 800 °C, síntese sem agitação do meio reacional e sem adição de fonte de alumínio. As análises do material indicaram formação de zeólitas dos tipos SOD e LTA. Quanto à adsorção de íons amônio, o mesmo apresentou capacidade de adsorção (qe) equivalente a 6,8 mg·g-1 (a 25ºC), que corresponde a 34 % do valor obtido para a Na-clinoptilolita, indicando que a síntese ainda necessita de melhoramentos para tornar o material mais competitivo frente à zeólita natural comercializada. / The presence of high nitrogen loading in water bodies can cause serious environmental impacts, such as eutrophication and toxicity of the medium. One of the process that enables nitrogen removal from effluents is adsorption, in which the use of alternative adsorbents have been applied in order to reuse wastes from other production processes and for lowering costs. Within this context, the coal mining and beneficiation in southern Brazil generates a waste with features that allow its application in zeolite synthesis. Thus, the objective of this thesis was to evaluate the removal of ammonium from aqueous solutions by adsorption using a natural zeolite and a zeolite synthesized from coal beneficiation tailings. Firstly, adsorption experiments were conducted using the natural zeolite Na-clinoptilolite in order to understand the thermodynamics and regeneration of process. Then, zeolite synthesis experiments using coal beneficiation tailings (RB) were conducted by varying the source of aluminum, stirring during crystallization step, and the calcination temperature applied to RB. The characterization of materials was made through the techniques of X-Ray Diffraction (XRD), Scanning Electron Microscopy coupled to Energy Dispersive Spectroscopy (SEM-EDS), Zeta Potential (ZP), X-rays Fluorescence (XRF), Porosimetry of Nitrogen (BET), Infrared Spectroscopy Fourier Transform (FTIR) and Cation Exchange Capacity (CEC). Finally, a test of ammonium adsorption was made with the material that had the highest content of Na+ in its composition. Regarding the studies with Na-clinoptilolite, the thermodynamic study showed that the equilibrium constant (K0) to adsorption process estimated through different approaches can present variation of up to 105 from one method to another. This study also revealed that the Gaines and Thomas method was the most adequate to the estimative of thermodynamic parameters. In the Na-clinoptilolite regeneration tests using NaCl solution from 0.5 to 3.0 M were obtained values above 76% regeneration to whole concentration range evaluated, without the reuse of NaCl solution. Tests made with the reuse of saline solution in the desorption step showed that it is possible to treat up to 160 mL of effluent using only 20 mL of NaCl solution, maintaining an adsorption capacity of 80 % of zeolite original capacity. By applying different synthesis conditions using the by-product of coal processing, seven different materials were obtained. The material with the highest content of Na+ was obtained using: calcination at 800°C as a thermal pretreatment applied to the waste, no stirring of the reaction during crystallization step and no additional aluminum source. The analysis of this material indicated formation of zeolites SOD and LTA. This same material was tested for the adsorption of ammonium, resulting in adsorption capacity (qe) of 6.8 m2·g-1, under the same conditions as the test with Na-clinoptilolite (at 25 ºC), which corresponds to 34 % of Na-clinoptilolite capacity, indicating that the synthesis still need some improvement in order to make the synthetic material competitive faced with the natural one.

Considerando a crescente demanda por energia e tendo em vista uma matriz diversificada, faz-se necessário o estudo das jazidas carboníferas não exploradas, como é o caso da Jazida de Morungava, em cujas últimas pesquisas datam da década de 1980. A jazida situa-se no nordeste do estado do Rio Grande do Sul, com uma área de abrangência de cerca de 250km2. Realizou-se um poço exploratório para estudar o carvão e avaliar a economicidade da jazida, por meio de caracterização petrográfica, química e tecnológica das camadas obtidas no poço CBM 001-MO-RS, que atingiu a profundidade de 387,70m, uma espessura cumulativa de carvão de 9,22m. Identificou-se 6 camadas de carvão, das quais obteve-se 27 amostras. Para caracterizar as amostras, realizou-se: descrições de litotipos do carvão, refletância da vitrinita, contagem de macerais, análises imediatas, poder calorífico superior, enxofre total, difração de raios-X e teste de beneficiamento. O litotipo carvão fosco é predominante nas amostras, com um rank variando de carvão betuminoso alto volátil A à antracito.As amostras, estão afetadas progressivamente por intrusão vulcânica sotoposta. O grupo maceral vitrinita predomina nos carvões na porção inferior, enquanto inertinita predomina na superior. Matéria mineral apresenta uma tendência de aumento da base para o topo. Os carvões apresentaram altos teores de cinza (>50%m.b.s.), matéria volátil (6,04-30,69%m.b.s), enxofre (0,20-2,88%m) e poder calorífico superior (777-4.732Kcal/Kg). Ocorre um predomínio mineralógico de quartzo, caulinita, e illita. A maioria das camadas são classificadas como rocha carbonosa (>50% cinza/b.s.). Em ensaios de beneficiamento foi observado um baixo rendimento (<7%vol.), na obtenção de produtos nobres. / Considering the growing demand for energy and with a view to a diverse energy matrix, it is necessary to study the coal deposits not or little exploited, such as the Morungava coalfield, where the latest research is dating back to the 1980s. The Coalfield is located in the northeast of Rio Grande do Sul State, Brazil. The present study characterizes coal seams obtained from borehole CBM 001-MO-RS, which reached a depth of 387,70 m. 6 coal seams were identified, with a cumulative coal thickness of 9,22 m, from which 27 coal samples were taken for analyses. The following methods were applied: lithotype description, vitrinite reflectance measurement, maceral analyses, proximate analysis, calorific value analysis, sulphur determination, x-ray diffraction and beneficiation tests. The lithotype dull coal is prevalent in the samples. Coal rank ranges from high volatile bituminous A coal to anthracite, with samples progressively affected by an overlying volcanic intrusion. The vitrinite maceral group dominates the coals in the lower portion, whereas inertinite prevails at the top. The coals show high ash content (> 40 wt.% d.f.). Volatile matter ranges from 6.04 to 30.69 wt.% d.f,,sulfur ranges from 0.20 to 2.88 wt.%, and gross calorific values range from 777 - 4732 Kcal/kg). There is a predominance of quartz, kaolinite and illite in the mineral fraction. Beneficiation tests indicate a very low yield in better quality, low ash coal. Most of the coal seams are classified as carbonaceous rock (> 50% Ash/d.f.).

A presença de elevada carga nitrogenada em corpos hídricos pode causar sérios impactos ambientais como a eutrofização e a toxicidade do meio. Um dos processos que possibilitam a remoção de nitrogênio de efluentes é a adsorção, na qual o uso de adsorventes alternativos tem sido aplicado para o aproveitamento de resíduos e redução dos custos no processo. Dentro deste contexto, o processo de extração e beneficiamento do carvão fóssil na Região Sul do Brasil produz um rejeito (RB) com características que possibilitam sua aplicação na síntese de zeólitas, as quais podem ser utilizadas como adsorventes. Assim, o objetivo da presente tese foi avaliar a remoção do íon amônio de soluções aquosas por adsorção utilizando-se zeólitas naturais e sintetizadas a partir do rejeito RB. Em um primeiro momento, experimentos de adsorção foram conduzidos utilizando-se zeólita Na-clinoptilolita para conhecimento dos parâmetros termodinâmicos e da capacidade de regeneração do material. Posteriormente, a síntese de zeólitas utilizando rejeito RB foi realizada variando-se a fonte de alumínio, o emprego da agitação do meio durante a síntese e temperatura de calcinação do rejeito. A caracterização dos materiais foi feita através das técnicas de Difração de Raios X (DRX), Microscopia Eletrônica de Varredura acoplada a Espectroscopia por Dispersão em Energia (MEV-EDS), Potencial Zeta (PZ), Fluorescência de Raios X (FRX), Porosimetria de Nitrogênio (BET), Espectroscopia no Infravermelho por Transformada de Fourier (FTIR) e Capacidade de Troca Catiônica (CTC). Por fim, experimentos de adsorção de amônio foram feitos para o material que apresentou o maior conteúdo de íons sódio em sua composição. Quanto aos estudos com a Na-clinoptilolita, o estudo termodinâmico demostrou que a constante de equilíbrio (K0) da adsorção da zeólita estimada por diferentes métodos pode apresentar variação de até 105 de um método para outro. O estudo em questão também revelou que o método de Gaines e Thomas é o mais adequado para a estimativa dos parâmetros termodinâmicos. Nos testes de regeneração da zeólita utilizando-se solução NaCl de 0,5 a 3,0 M foram obtidos valores acima de 76% de regeneração para toda faixa de concentração avaliada, sem o reuso da solução de NaCl. Os testes feitos com o reuso da solução salina na etapa da dessorção permitiram concluir que é possível tratar até 160 mL de efluente utilizando-se somente 20 mL de solução NaCl 1,0 M, mantendo-se uma capacidade de adsorção equivalente a 80% da capacidade original da zeólita. Através da aplicação de diferentes condições de síntese utilizando o rejeito RB, foram obtidos sete diferentes materiais. O material que apresentou maior conteúdo de Na+ em sua composição foi obtido utilizando-se: pré-tratamento do rejeito com calcinação a 800 °C, síntese sem agitação do meio reacional e sem adição de fonte de alumínio. As análises do material indicaram formação de zeólitas dos tipos SOD e LTA. Quanto à adsorção de íons amônio, o mesmo apresentou capacidade de adsorção (qe) equivalente a 6,8 mg·g-1 (a 25ºC), que corresponde a 34 % do valor obtido para a Na-clinoptilolita, indicando que a síntese ainda necessita de melhoramentos para tornar o material mais competitivo frente à zeólita natural comercializada. / The presence of high nitrogen loading in water bodies can cause serious environmental impacts, such as eutrophication and toxicity of the medium. One of the process that enables nitrogen removal from effluents is adsorption, in which the use of alternative adsorbents have been applied in order to reuse wastes from other production processes and for lowering costs. Within this context, the coal mining and beneficiation in southern Brazil generates a waste with features that allow its application in zeolite synthesis. Thus, the objective of this thesis was to evaluate the removal of ammonium from aqueous solutions by adsorption using a natural zeolite and a zeolite synthesized from coal beneficiation tailings. Firstly, adsorption experiments were conducted using the natural zeolite Na-clinoptilolite in order to understand the thermodynamics and regeneration of process. Then, zeolite synthesis experiments using coal beneficiation tailings (RB) were conducted by varying the source of aluminum, stirring during crystallization step, and the calcination temperature applied to RB. The characterization of materials was made through the techniques of X-Ray Diffraction (XRD), Scanning Electron Microscopy coupled to Energy Dispersive Spectroscopy (SEM-EDS), Zeta Potential (ZP), X-rays Fluorescence (XRF), Porosimetry of Nitrogen (BET), Infrared Spectroscopy Fourier Transform (FTIR) and Cation Exchange Capacity (CEC). Finally, a test of ammonium adsorption was made with the material that had the highest content of Na+ in its composition. Regarding the studies with Na-clinoptilolite, the thermodynamic study showed that the equilibrium constant (K0) to adsorption process estimated through different approaches can present variation of up to 105 from one method to another. This study also revealed that the Gaines and Thomas method was the most adequate to the estimative of thermodynamic parameters. In the Na-clinoptilolite regeneration tests using NaCl solution from 0.5 to 3.0 M were obtained values above 76% regeneration to whole concentration range evaluated, without the reuse of NaCl solution. Tests made with the reuse of saline solution in the desorption step showed that it is possible to treat up to 160 mL of effluent using only 20 mL of NaCl solution, maintaining an adsorption capacity of 80 % of zeolite original capacity. By applying different synthesis conditions using the by-product of coal processing, seven different materials were obtained. The material with the highest content of Na+ was obtained using: calcination at 800°C as a thermal pretreatment applied to the waste, no stirring of the reaction during crystallization step and no additional aluminum source. The analysis of this material indicated formation of zeolites SOD and LTA. This same material was tested for the adsorption of ammonium, resulting in adsorption capacity (qe) of 6.8 m2·g-1, under the same conditions as the test with Na-clinoptilolite (at 25 ºC), which corresponds to 34 % of Na-clinoptilolite capacity, indicating that the synthesis still need some improvement in order to make the synthetic material competitive faced with the natural one.

A presença de elevada carga nitrogenada em corpos hídricos pode causar sérios impactos ambientais como a eutrofização e a toxicidade do meio. Um dos processos que possibilitam a remoção de nitrogênio de efluentes é a adsorção, na qual o uso de adsorventes alternativos tem sido aplicado para o aproveitamento de resíduos e redução dos custos no processo. Dentro deste contexto, o processo de extração e beneficiamento do carvão fóssil na Região Sul do Brasil produz um rejeito (RB) com características que possibilitam sua aplicação na síntese de zeólitas, as quais podem ser utilizadas como adsorventes. Assim, o objetivo da presente tese foi avaliar a remoção do íon amônio de soluções aquosas por adsorção utilizando-se zeólitas naturais e sintetizadas a partir do rejeito RB. Em um primeiro momento, experimentos de adsorção foram conduzidos utilizando-se zeólita Na-clinoptilolita para conhecimento dos parâmetros termodinâmicos e da capacidade de regeneração do material. Posteriormente, a síntese de zeólitas utilizando rejeito RB foi realizada variando-se a fonte de alumínio, o emprego da agitação do meio durante a síntese e temperatura de calcinação do rejeito. A caracterização dos materiais foi feita através das técnicas de Difração de Raios X (DRX), Microscopia Eletrônica de Varredura acoplada a Espectroscopia por Dispersão em Energia (MEV-EDS), Potencial Zeta (PZ), Fluorescência de Raios X (FRX), Porosimetria de Nitrogênio (BET), Espectroscopia no Infravermelho por Transformada de Fourier (FTIR) e Capacidade de Troca Catiônica (CTC). Por fim, experimentos de adsorção de amônio foram feitos para o material que apresentou o maior conteúdo de íons sódio em sua composição. Quanto aos estudos com a Na-clinoptilolita, o estudo termodinâmico demostrou que a constante de equilíbrio (K0) da adsorção da zeólita estimada por diferentes métodos pode apresentar variação de até 105 de um método para outro. O estudo em questão também revelou que o método de Gaines e Thomas é o mais adequado para a estimativa dos parâmetros termodinâmicos. Nos testes de regeneração da zeólita utilizando-se solução NaCl de 0,5 a 3,0 M foram obtidos valores acima de 76% de regeneração para toda faixa de concentração avaliada, sem o reuso da solução de NaCl. Os testes feitos com o reuso da solução salina na etapa da dessorção permitiram concluir que é possível tratar até 160 mL de efluente utilizando-se somente 20 mL de solução NaCl 1,0 M, mantendo-se uma capacidade de adsorção equivalente a 80% da capacidade original da zeólita. Através da aplicação de diferentes condições de síntese utilizando o rejeito RB, foram obtidos sete diferentes materiais. O material que apresentou maior conteúdo de Na+ em sua composição foi obtido utilizando-se: pré-tratamento do rejeito com calcinação a 800 °C, síntese sem agitação do meio reacional e sem adição de fonte de alumínio. As análises do material indicaram formação de zeólitas dos tipos SOD e LTA. Quanto à adsorção de íons amônio, o mesmo apresentou capacidade de adsorção (qe) equivalente a 6,8 mg·g-1 (a 25ºC), que corresponde a 34 % do valor obtido para a Na-clinoptilolita, indicando que a síntese ainda necessita de melhoramentos para tornar o material mais competitivo frente à zeólita natural comercializada. / The presence of high nitrogen loading in water bodies can cause serious environmental impacts, such as eutrophication and toxicity of the medium. One of the process that enables nitrogen removal from effluents is adsorption, in which the use of alternative adsorbents have been applied in order to reuse wastes from other production processes and for lowering costs. Within this context, the coal mining and beneficiation in southern Brazil generates a waste with features that allow its application in zeolite synthesis. Thus, the objective of this thesis was to evaluate the removal of ammonium from aqueous solutions by adsorption using a natural zeolite and a zeolite synthesized from coal beneficiation tailings. Firstly, adsorption experiments were conducted using the natural zeolite Na-clinoptilolite in order to understand the thermodynamics and regeneration of process. Then, zeolite synthesis experiments using coal beneficiation tailings (RB) were conducted by varying the source of aluminum, stirring during crystallization step, and the calcination temperature applied to RB. The characterization of materials was made through the techniques of X-Ray Diffraction (XRD), Scanning Electron Microscopy coupled to Energy Dispersive Spectroscopy (SEM-EDS), Zeta Potential (ZP), X-rays Fluorescence (XRF), Porosimetry of Nitrogen (BET), Infrared Spectroscopy Fourier Transform (FTIR) and Cation Exchange Capacity (CEC). Finally, a test of ammonium adsorption was made with the material that had the highest content of Na+ in its composition. Regarding the studies with Na-clinoptilolite, the thermodynamic study showed that the equilibrium constant (K0) to adsorption process estimated through different approaches can present variation of up to 105 from one method to another. This study also revealed that the Gaines and Thomas method was the most adequate to the estimative of thermodynamic parameters. In the Na-clinoptilolite regeneration tests using NaCl solution from 0.5 to 3.0 M were obtained values above 76% regeneration to whole concentration range evaluated, without the reuse of NaCl solution. Tests made with the reuse of saline solution in the desorption step showed that it is possible to treat up to 160 mL of effluent using only 20 mL of NaCl solution, maintaining an adsorption capacity of 80 % of zeolite original capacity. By applying different synthesis conditions using the by-product of coal processing, seven different materials were obtained. The material with the highest content of Na+ was obtained using: calcination at 800°C as a thermal pretreatment applied to the waste, no stirring of the reaction during crystallization step and no additional aluminum source. The analysis of this material indicated formation of zeolites SOD and LTA. This same material was tested for the adsorption of ammonium, resulting in adsorption capacity (qe) of 6.8 m2·g-1, under the same conditions as the test with Na-clinoptilolite (at 25 ºC), which corresponds to 34 % of Na-clinoptilolite capacity, indicating that the synthesis still need some improvement in order to make the synthetic material competitive faced with the natural one.

Considerando a crescente demanda por energia e tendo em vista uma matriz diversificada, faz-se necessário o estudo das jazidas carboníferas não exploradas, como é o caso da Jazida de Morungava, em cujas últimas pesquisas datam da década de 1980. A jazida situa-se no nordeste do estado do Rio Grande do Sul, com uma área de abrangência de cerca de 250km2. Realizou-se um poço exploratório para estudar o carvão e avaliar a economicidade da jazida, por meio de caracterização petrográfica, química e tecnológica das camadas obtidas no poço CBM 001-MO-RS, que atingiu a profundidade de 387,70m, uma espessura cumulativa de carvão de 9,22m. Identificou-se 6 camadas de carvão, das quais obteve-se 27 amostras. Para caracterizar as amostras, realizou-se: descrições de litotipos do carvão, refletância da vitrinita, contagem de macerais, análises imediatas, poder calorífico superior, enxofre total, difração de raios-X e teste de beneficiamento. O litotipo carvão fosco é predominante nas amostras, com um rank variando de carvão betuminoso alto volátil A à antracito.As amostras, estão afetadas progressivamente por intrusão vulcânica sotoposta. O grupo maceral vitrinita predomina nos carvões na porção inferior, enquanto inertinita predomina na superior. Matéria mineral apresenta uma tendência de aumento da base para o topo. Os carvões apresentaram altos teores de cinza (>50%m.b.s.), matéria volátil (6,04-30,69%m.b.s), enxofre (0,20-2,88%m) e poder calorífico superior (777-4.732Kcal/Kg). Ocorre um predomínio mineralógico de quartzo, caulinita, e illita. A maioria das camadas são classificadas como rocha carbonosa (>50% cinza/b.s.). Em ensaios de beneficiamento foi observado um baixo rendimento (<7%vol.), na obtenção de produtos nobres. / Considering the growing demand for energy and with a view to a diverse energy matrix, it is necessary to study the coal deposits not or little exploited, such as the Morungava coalfield, where the latest research is dating back to the 1980s. The Coalfield is located in the northeast of Rio Grande do Sul State, Brazil. The present study characterizes coal seams obtained from borehole CBM 001-MO-RS, which reached a depth of 387,70 m. 6 coal seams were identified, with a cumulative coal thickness of 9,22 m, from which 27 coal samples were taken for analyses. The following methods were applied: lithotype description, vitrinite reflectance measurement, maceral analyses, proximate analysis, calorific value analysis, sulphur determination, x-ray diffraction and beneficiation tests. The lithotype dull coal is prevalent in the samples. Coal rank ranges from high volatile bituminous A coal to anthracite, with samples progressively affected by an overlying volcanic intrusion. The vitrinite maceral group dominates the coals in the lower portion, whereas inertinite prevails at the top. The coals show high ash content (> 40 wt.% d.f.). Volatile matter ranges from 6.04 to 30.69 wt.% d.f,,sulfur ranges from 0.20 to 2.88 wt.%, and gross calorific values range from 777 - 4732 Kcal/kg). There is a predominance of quartz, kaolinite and illite in the mineral fraction. Beneficiation tests indicate a very low yield in better quality, low ash coal. Most of the coal seams are classified as carbonaceous rock (> 50% Ash/d.f.).

Considerando a crescente demanda por energia e tendo em vista uma matriz diversificada, faz-se necessário o estudo das jazidas carboníferas não exploradas, como é o caso da Jazida de Morungava, em cujas últimas pesquisas datam da década de 1980. A jazida situa-se no nordeste do estado do Rio Grande do Sul, com uma área de abrangência de cerca de 250km2. Realizou-se um poço exploratório para estudar o carvão e avaliar a economicidade da jazida, por meio de caracterização petrográfica, química e tecnológica das camadas obtidas no poço CBM 001-MO-RS, que atingiu a profundidade de 387,70m, uma espessura cumulativa de carvão de 9,22m. Identificou-se 6 camadas de carvão, das quais obteve-se 27 amostras. Para caracterizar as amostras, realizou-se: descrições de litotipos do carvão, refletância da vitrinita, contagem de macerais, análises imediatas, poder calorífico superior, enxofre total, difração de raios-X e teste de beneficiamento. O litotipo carvão fosco é predominante nas amostras, com um rank variando de carvão betuminoso alto volátil A à antracito.As amostras, estão afetadas progressivamente por intrusão vulcânica sotoposta. O grupo maceral vitrinita predomina nos carvões na porção inferior, enquanto inertinita predomina na superior. Matéria mineral apresenta uma tendência de aumento da base para o topo. Os carvões apresentaram altos teores de cinza (>50%m.b.s.), matéria volátil (6,04-30,69%m.b.s), enxofre (0,20-2,88%m) e poder calorífico superior (777-4.732Kcal/Kg). Ocorre um predomínio mineralógico de quartzo, caulinita, e illita. A maioria das camadas são classificadas como rocha carbonosa (>50% cinza/b.s.). Em ensaios de beneficiamento foi observado um baixo rendimento (<7%vol.), na obtenção de produtos nobres. / Considering the growing demand for energy and with a view to a diverse energy matrix, it is necessary to study the coal deposits not or little exploited, such as the Morungava coalfield, where the latest research is dating back to the 1980s. The Coalfield is located in the northeast of Rio Grande do Sul State, Brazil. The present study characterizes coal seams obtained from borehole CBM 001-MO-RS, which reached a depth of 387,70 m. 6 coal seams were identified, with a cumulative coal thickness of 9,22 m, from which 27 coal samples were taken for analyses. The following methods were applied: lithotype description, vitrinite reflectance measurement, maceral analyses, proximate analysis, calorific value analysis, sulphur determination, x-ray diffraction and beneficiation tests. The lithotype dull coal is prevalent in the samples. Coal rank ranges from high volatile bituminous A coal to anthracite, with samples progressively affected by an overlying volcanic intrusion. The vitrinite maceral group dominates the coals in the lower portion, whereas inertinite prevails at the top. The coals show high ash content (> 40 wt.% d.f.). Volatile matter ranges from 6.04 to 30.69 wt.% d.f,,sulfur ranges from 0.20 to 2.88 wt.%, and gross calorific values range from 777 - 4732 Kcal/kg). There is a predominance of quartz, kaolinite and illite in the mineral fraction. Beneficiation tests indicate a very low yield in better quality, low ash coal. Most of the coal seams are classified as carbonaceous rock (> 50% Ash/d.f.).