Le ciment Portland est de loin le liant hydraulique le plus connu et utilisé depuis de très nombreuses années tant dans le secteur de la construction civile qu’au niveau du stockage des déchets (barrières ouvragées ou matériau de confinement). Le processus industriel qui donne naissance au clinker, constituant de base du ciment Portland, n’a pas subi de modifications depuis des décennies. Par ailleurs, au cours de ces dernières années, certaines considérations telles que le réchauffement climatique et le développement durable ont mis à mal les industries qui émettent des gaz à effets de serre et qui sont grosses consommatrices d’énergie. Or, la production de ciment Portland n’est pas uniquement consommatrice de calcaires, d’argiles, de marnes et de combustibles fossiles, elle produit et libère ces gaz à effets de serre tels que le dioxyde de carbone (CO2) et l’hémioxyde nitreux (N2O). Le dioxyde de soufre (SO2), l’acide chlorhydrique (HCl) ainsi que d’autres oxydes d’azote (NOx) sont également émis lors du processus de fabrication du clinker. Le secteur des matériaux de construction contribue de façon importante aux émissions de CO2, le principal responsable du réchauffement climatique. La problématique majeure de l’industrie cimentière provient d’un simple processus chimique de transformation : la décarbonatation du calcaire ou de la craie, débutant vers 550°C, qui forme de la chaux (CaO) et qui libère du dioxyde de carbone selon la réaction suivante : CaCO3 = CaO + CO2 Cette transformation est responsable de la majeure partie des émissions de CO2 liée au processus de clinkérisation. Or, ce carbonate de calcium constitue la matière première essentielle nécessaire à la fabrication du ciment. La combustion des énergies fossiles est l’autre source principale des émissions de gaz à effets de serre. Le développement de l’industrie cimentière est donc fortement lié à une stratégie qui permet de limiter ces émissions de gaz et de participer au développement durable. A l’heure actuelle, l’industrie cimentière se voit contrainte d’explorer certaines voies exploitables pour réduire ses émissions de CO2. Parmi elles, l'utilisation de matériaux de substitution, d'origine industrielle, est la voie la plus importante et intéressante en terme de réduction des émissions. Elle permet d’éviter les émissions de CO2 liées à la décarbonatation du calcaire. L'amélioration de l'efficacité énergétique est également une voie à exploiter grâce aux réductions des émissions pouvant être obtenues grâce à un renouvellement ou à une modernisation des fours de cimenteries. Les déperditions de chaleur par rayonnement tout au long de ces fours sont très importantes et peuvent être limitées en améliorant l’isolation du four. Cette amélioration contribue à l’augmentation du rendement des combustibles et donc, indirectement, à une réduction des émissions. Parmi ces deux voies, la première est plus facilement exploitable, moins coûteuse et permet d’apporter certains avantages non négligeables en terme de performance, de qualité et d’utilisation du produit fini, c’est-à-dire du ciment. Les matériaux de substitution les plus couramment utilisés depuis de nombreuses années sont les laitiers de haut-fourneau et les cendres volantes silicoalumineuses ou sulfocalciques. Le laitier de haut-fourneau est un sous-produit de l’industrie sidérurgique qui peut être valorisé soit comme ajout au ciment (liant hydraulique), lorsqu’il est vitrifié et granulé, soit comme granulat, agrégat lorsqu’il est cristallisé. Quant aux cendres volantes, elles sont issues de la combustion du charbon dans les centrales thermiques. Elles peuvent être valorisées soit comme matière première dans le cru soit, également, comme ajout au ciment. L’utilisation la plus valorisante de ces ajouts reste toutefois leur incorporation dans le ciment qui met à profit leurs propriétés pouzzolaniques (cendres volantes) et/ou hydrauliques latentes (laitier). Au point de vue de cette incorporation, seul le laitier peut être substitué, au ciment Portland, dans des proportions maximales puisqu’elles peuvent atteindre plus de 95% en poids du ciment. A ce niveau de substitution, la valorisation, en terme de limitations d’émissions directes de CO2, est maximale. De plus, si les ciments au laitier sont « respectueux » de l’environnement lors de leur production, ils possèdent également des propriétés physico-chimiques et des applications avantageuses telles que leur haute résistance aux attaques des sulfates, une faible, voire très faible, perméabilité, un bon comportement en milieu chimiquement agressif (utilisation en station d’épuration), une faible chaleur d’hydratation (utilisation dans des bétons de masse), une bonne résistance au gel, une excellente durabilité,… Cependant, malgré ces avantages plus qu’indéniables, le laitier granulé de haut-fourneau et le ciment Portland possèdent des propriétés hydrauliques qui diffèrent, de manière appréciable, au niveau de leur degré et leurs mécanismes de réactions avec l’eau. C’est essentiellement en raison de leur composition chimique et de leur structure différente que leur hydraulicité varie. Dans la réalité, ces différences se traduisent par des cinétiques de réactions d’hydratation du laitier plus lentes et, donc, par une prise du ciment et un développement des résistances mécaniques initiales plus lents. En conclusion, si les cinétiques de réactions d’hydratation sont plus lentes pour un ciment lorsque la température diminue, elles le sont d’autant plus pour un ciment au laitier. Ce comportement implique que l’utilisation de ce ciment, pour certaines applications qui nécessitent des résistances mécaniques initiales élevées (ex : usine de préfabrication de béton), n’est pas adaptée. Afin de ne pas hypothéquer l’utilisation hivernale des ciments au laitier, les principaux acteurs de la construction font appels à des adjuvants. Ces adjuvants correspondent à une classe d’additifs autre que l'eau, les granulats et le ciment qui est utilisée comme ajout au mélange de béton. Cet ingrédient peut être ajouté au mélange, avant ou pendant les opérations de malaxage. Aujourd’hui, un grand nombre de composés, organiques et inorganiques existent dans le domaine des adjuvants. Ils peuvent avoir plusieurs fonctions dont celles d’accélérer la prise et le durcissement. Cependant, le recours à ce genre d’additifs est fort coûteux et, s’ils améliorent certaines propriétés des bétons et/ou mortiers, ils peuvent en détériorer d’autres. Parmi les adjuvants utilisés commercialement, le CHLORURE DE CALCIUM est le plus répandu. Il possède un faible coût et une efficacité largement reconnue. Mais, le recours au CaCl2 lors de la fabrication des bétons est aujourd’hui proscrit par une norme pour des raisons de CORROSION D’ARMATURES MÉTALLIQUES dans les bétons et pour des RAISONS ENVIRONNEMENTALES. Cette situation entraîne donc la nécessité de développer de « nouveaux » adjuvants (accélérateurs de prise et durcissement) non chlorurés dont l’efficacité doit être prouvée, notamment vis-à-vis de : - l’hydratation du laitier et du clinker dans le ciment, - des temps de prise, - du développement des résistances mécaniques initiales, - de la température, - et son coût raisonnable. L’OBJECTIF DE CE TRAVAIL a donc été de développer un « nouvel » adjuvant qui a permi d’améliorer le durcissement et la résistance des ciments au laitier (CEM III/A, B et C) à court terme et à basse température.

L’objectif de cette étude est de réaliser la synthèse d’un ciment riche en phases réactives, obtenu par cuisson à une température inférieure ou égale à 1300°C d’un cru constitué de vase de barrage et d’un complément de chaux et utilisant du sulfate de zinc comme minéralisateur. Cette étude donne les caractéristiques minéralogiques et les propriétés physico- mécaniques du ciment synthétisé. L’analyse qualitative et quantitative par diffraction des rayons X a été utilisée pour caractériser les matériaux bruts et les minéraux du ciment. L’évolution du durcissement des pâtes de ce ciment a été suivie et quantifiée par calorimétrie isotherme, DTG, diffraction des rayons X et au moyen d’essais mécaniques en compression sur éprouvettes de pâte pure. Les résistances obtenues à 7 et 28 jours permettent de viser une classification CEM II 32,5 N. / The objective of this study is the synthesis of a cement rich in reactive phases, obtained by burning, at a temperature lower than or equal to 1300 °C, a raw material composed of sludge from a dam with a complement of lime, and using zinc sulphate as a mineralizer. This study gives the mineralogical, physical and mechanical characteristics and properties of the synthesized cement. Qualitative and quantitative X-ray diffraction analysis was used to characterize the raw materials and the minerals of the cement. The evolution of its hardening was monitored and quantified by isothermal calorimetry, DTG, X-ray diffraction and mechanical compression tests on pure paste samples. The strengths obtained at 7 and 28 days make it possible to aim at a CEM II 32.5 N classification.

A geração de resíduos sólidos é inerente ao desenvolvimento humano. O concreto armado é um dos materiais mais utilizados pelo homem e tem o cimento Portland como seu principal constituinte, o qual é produzido pela moagem de clínquer e gesso. O clínquer pode ser definido como um mineral artificial, obtido a partir das reações físico-químicas de calcário, argila e corretivos a altas temperaturas, em forno rotativo industrial, mediante a queima de combustíveis fósseis. No início da década de 70 foram realizadas as primeiras experiências de substituição de combustíveis fósseis por resíduos industriais nos Estados Unidos e países europeus, através da técnica denominada co-processamento, resultando na manufatura de um produto ao mesmo tempo em que os resíduos eram eliminados. O co-processamento se baseia na recuperação da energia disponível nos resíduos, substituindo parte daquela fornecida pelos combustíveis tradicionais ou na substituição de matérias-primas por resíduos com características químicas semelhantes àquelas normalmente empregadas na produção do clínquer. No estado de São Paulo as primeiras iniciativas para a utilização de resíduos industriais em fornos de clínquer ocorreram no início da década de 90. A partir de 1997 os órgãos ambientais de alguns estados brasileiros normatizaram procedimentos de licenciamento da atividade que foi, posteriormente, uniformizada por norma em âmbito federal. No ano de 1995 a Companhia de Cimento Ribeirão Grande/SP, Brasil, iniciou os procedimentos visando a substituição parcial dos combustíveis utilizados nos fornos rotativos por uma mistura de resíduos industriais. No período de 1995 a 2002 foram realizadas campanhas de amostragens em chaminés para avaliação das emissões atmosféricas dos dois fornos de produção de clínquer. A análise dos resultados obtidos associada às demais informações disponíveis de monitoramento das características das matérias-primas e combustíveis utilizados, bem como dos produtos finais, clínquer e cimento, não evidenciou alterações significativas nos níveis de emissões atmosféricas, sobretudo de material particulado e óxidos de enxofre, que pudessem ser associadas à utilização dos resíduos. Foram confirmadas as baixas emissões de inorgânicos e evidenciado o papel representado pelos resíduos no aporte dessas substâncias no sistema-forno, concluindo-se que esse aporte pode ser tão ou mais importante pela via da alimentação da farinha, cujos teores estão associados às características das jazidas minerais utilizadas. Foi também confirmada a alta eficiência do sistema-forno na destruição e remoção dos compostos orgânicos perigosos alimentados durante os testes de queima. / The production of industrial residues in inherent to the human development. The cement concrete is one of the most used material, manly the type portland cement, which is constituted by grinding clinker and gypsum together. Clinker can be defined as an artificial mineral obtained by applying physico-chemical reactions, at very high temperatures, to an appropriated mixture of limestone, clay, and some other materials in a rotating industrial kiln wich burns fossil fuels. In the early 1970 decade occurred the first experiences substituting fossil fuels by organic residues in USA and Europe through a technique named co-processing that results the production of certain manufacture while eliminates residues. Co-processing is based in the recovery of thermal energy and/or the mass of some constituents from some residues, with the same chemical characteristics of normal sources of energy, then economizing fuels and mass constituents and making better use of residues, otherwise useless and environmentally polluters. In the state of São Paulo this practice began in early 1990 decade and by 1997 it was started the standardization of the rules for its use in some units of the federation. Later this activity was regulated by nationally approved standard rules. In 1995 the industry Companhia de Cimento Ribeirão Grande (CCRG), a cement plant located in the city of Ribeirão Grande, São Paulo state, Brazil, started procedures searching the partial substitution of the normal fuels by a mixture of industrial residues in its two rotating kilns. The gaseous emissions from the chimneys of these two clinker kilns were studied from 1995 to 2002 about the use of residues as part of the fuel. Analyses of the final results associated with other informations concerning to the quality of raw minerals, fuels and products did not show significant alterations in atmospheric emissions, mainly for particulate material and sulfur oxides, related with the use of residues. The emissions of inorganic continued to be low and not significantly altered by the presence of residues. It was possible to conclude that the alterations in inorganic emissions depend more from the quality of the raw minerals feed in the kilns, which is more difficult to control, than from the presence of residues being burn with the fuel. It was shown a high efficiency in the destruction of dangerous organic compounds feed in the cement kilns, under test conditions.

En raison de l'épuisement des combustibles fossiles et en raison de son coût croissant, les déchets ont été utilisés comme combustibles alternatifs dans les fours rotatifs à ciment pendant plusieurs années. Afin de répondre aux exigences de protection de l'environnement et de qualité du produit final, il est nécessaire de comprendre et de quantifier les différents processus intervenant dans le four. Dans le cadre de cette thèse, nous nous sommes intéressés à la substitution partielle des déchets (pneus usés et Refuse Derived Fuel « RDF ») et biomasse (résidus d’agriculture) dans les fours tournants de production de ciment à un taux de 50 % d’apport énergétique. Le présent projet de thèse a été financé par la République Démocratique Congo, porté par l’Université Kongo (UK), dans le cadre du renfoncement des capacités des universités congolaises. Les travaux de recherche ont été réalisés au sein du Laboratoire de Thermique, Energétique et Procédés (LaTEP) de l’Ecole Nationale Supérieure en Génie de Technologies Industrielles (ENSGTI)/Université de Pau et des Pays de l’Adour (France), dans le but d’étudier et de comprendre les phénomènes thermochimiques se déroulant dans les fours tournants de production de ciments, dans le cas de substitution partielle des combustibles fossiles par des combustibles alternatifs. Pour cela, un modèle mathématique à deux sous-modèles a été établi : - Le modèle monodimensionnel stationnaire du lit de solides et de l’enveloppe du four, caractérisé dans sa première partie par le mélange de la farine de ciment, de déchets et/ou biomasse, et de gaz, et alors que dans sa deuxième partie par les échanges thermiques. Le travail de modélisation est effectué à l'aide du langage de programmation Fortran 90 dans lequel sont implémentées les équations de conservations de la masse, des espèces et de l’énergie, l’équation de transport de la charge, ainsi que les équations algébriques. - Le modèle tridimensionnel instationnaire, repose sur l’utilisation de la mécanique des fluides numérique, et l’outil commercial Fluent a été retenu pour représenter les processus se déroulant au-dessus de la surface libre du lit.Le modèle complet est le couplage entre les deux sous modèles, étant donné les échanges qui s’y effectuent.Deux grands groupes de simulations ont été réalisés dans cette thèse : le cas monodimensionnel et le cas global (couplage Modèle 1D-Modèle 3D). Dans les deux situations, les simulations ont été effectuées dans le cas de fonctionnement au fuel lourd seul, puis dans celui du fonctionnement avec substitution partielle du combustible fossile par les combustibles alternatifs. Pour le modèle monodimensionnel, les simulations ont été effectuées en imposant les flux de chaleur dans la surface libre du lit et dans la paroi découverte. Alors que pour le modèle global, les simulations ont été effectuées en considérant les densités de flux de chaleur associées aux phénomènes physico-chimiques (combustion du fuel lourd, rayonnement, turbulence) se déroulant dans le volume de gaz situé au-dessus de la surface libre du lit.Les résultats ainsi obtenus nous ont permis de conclure sur l’importance de mener en amont une étude expérimentale dans un four tournant à l’échelle pilote afin de pouvoir disposer des ordres de grandeur des différents flux de chaleur au sein du four tournant. Les résultats obtenus nous ont également permis de nous rendre compte de la nécessité de disposer de la géométrie exacte (emplacement) du brûleur dans le four tournant. / Because of the depletion of fossil fuels and because of its increasing cost, waste has been used as alternative fuels in cement rotary kilns for several years. In order to fulfill the requirements of environmental protection and quality of the final product, it is necessary to understand and quantify the different processes occurring in the kiln.As part of this thesis, we focused on the partial substitution of waste (used tires and Refuse Derived Fuel "RDF") and biomass (agricultural residues) in rotary kilns producing cement at a rate of 50 % of energy supply. This thesis project was funded by the Democratic Republic of Congo, led by Kongo University (UK), as part of the capacity building of Congolese universities. The research work was carried out within the Laboratory of Thermal, Energy and Processes (LaTEP) of the National School of Engineering in Industrial Technologies (ENSGTI) /University of Pau, with the aim of to study and understand the thermochemical phenomena taking place in rotary kilns for the production of cement, in the case of partial substitution of fossil fuels by alternative fuels. For this, a mathematical model with two sub-models has been established:- The stationary one-dimensional model of the bed of solids and furnace casing, characterized in its first part by the mixing of cement flour, waste and / or biomass, and gas, and while in its second part by thermal exchanges. The modeling work is performed using the Fortran 90 programming language in which the conservation equations for mass, species and energy, the load transport equation, and the algebraic equations are implemented.- The unsteady three-dimensional model relies on the use of digital fluid mechanics, and the Fluent commercial tool has been retained to represent the processes taking place above the free surface of the bed.The complete model is the coupling between the two sub models, because of the exchanges that take place there.Two large groups of simulations have been realized in this thesis: the one-dimensional case and the global case (Model 1D-3D model coupling). In both situations, the simulations were carried out in the case of operation with heavy fuel oil alone, then in the case of operation with partial substitution of the fossil fuel by alternative fuels. For the one-dimensional model, the simulations were performed by imposing the heat flux in the free surface of the bed and in the exposed wall. Whereas for the global model, the simulations were performed considering the heat flux densities associated with physico-chemical phenomena (combustion of heavy fuel oil, radiation, turbulence) taking place in the volume of gas located above the free surface of the bed.The results thus obtained allowed us to conclude on the importance of carrying out an experimental study in a pilot scale furnace in order to be able to have orders of magnitude of the different heat flows within the rotating furnace. The results obtained also allowed us to realize the necessity to model the exact geometry (location) of the burner in the rotary kiln.

A geração de resíduos sólidos é inerente ao desenvolvimento humano. O concreto armado é um dos materiais mais utilizados pelo homem e tem o cimento Portland como seu principal constituinte, o qual é produzido pela moagem de clínquer e gesso. O clínquer pode ser definido como um mineral artificial, obtido a partir das reações físico-químicas de calcário, argila e corretivos a altas temperaturas, em forno rotativo industrial, mediante a queima de combustíveis fósseis. No início da década de 70 foram realizadas as primeiras experiências de substituição de combustíveis fósseis por resíduos industriais nos Estados Unidos e países europeus, através da técnica denominada co-processamento, resultando na manufatura de um produto ao mesmo tempo em que os resíduos eram eliminados. O co-processamento se baseia na recuperação da energia disponível nos resíduos, substituindo parte daquela fornecida pelos combustíveis tradicionais ou na substituição de matérias-primas por resíduos com características químicas semelhantes àquelas normalmente empregadas na produção do clínquer. No estado de São Paulo as primeiras iniciativas para a utilização de resíduos industriais em fornos de clínquer ocorreram no início da década de 90. A partir de 1997 os órgãos ambientais de alguns estados brasileiros normatizaram procedimentos de licenciamento da atividade que foi, posteriormente, uniformizada por norma em âmbito federal. No ano de 1995 a Companhia de Cimento Ribeirão Grande/SP, Brasil, iniciou os procedimentos visando a substituição parcial dos combustíveis utilizados nos fornos rotativos por uma mistura de resíduos industriais. No período de 1995 a 2002 foram realizadas campanhas de amostragens em chaminés para avaliação das emissões atmosféricas dos dois fornos de produção de clínquer. A análise dos resultados obtidos associada às demais informações disponíveis de monitoramento das características das matérias-primas e combustíveis utilizados, bem como dos produtos finais, clínquer e cimento, não evidenciou alterações significativas nos níveis de emissões atmosféricas, sobretudo de material particulado e óxidos de enxofre, que pudessem ser associadas à utilização dos resíduos. Foram confirmadas as baixas emissões de inorgânicos e evidenciado o papel representado pelos resíduos no aporte dessas substâncias no sistema-forno, concluindo-se que esse aporte pode ser tão ou mais importante pela via da alimentação da farinha, cujos teores estão associados às características das jazidas minerais utilizadas. Foi também confirmada a alta eficiência do sistema-forno na destruição e remoção dos compostos orgânicos perigosos alimentados durante os testes de queima. / The production of industrial residues in inherent to the human development. The cement concrete is one of the most used material, manly the type portland cement, which is constituted by grinding clinker and gypsum together. Clinker can be defined as an artificial mineral obtained by applying physico-chemical reactions, at very high temperatures, to an appropriated mixture of limestone, clay, and some other materials in a rotating industrial kiln wich burns fossil fuels. In the early 1970 decade occurred the first experiences substituting fossil fuels by organic residues in USA and Europe through a technique named co-processing that results the production of certain manufacture while eliminates residues. Co-processing is based in the recovery of thermal energy and/or the mass of some constituents from some residues, with the same chemical characteristics of normal sources of energy, then economizing fuels and mass constituents and making better use of residues, otherwise useless and environmentally polluters. In the state of São Paulo this practice began in early 1990 decade and by 1997 it was started the standardization of the rules for its use in some units of the federation. Later this activity was regulated by nationally approved standard rules. In 1995 the industry Companhia de Cimento Ribeirão Grande (CCRG), a cement plant located in the city of Ribeirão Grande, São Paulo state, Brazil, started procedures searching the partial substitution of the normal fuels by a mixture of industrial residues in its two rotating kilns. The gaseous emissions from the chimneys of these two clinker kilns were studied from 1995 to 2002 about the use of residues as part of the fuel. Analyses of the final results associated with other informations concerning to the quality of raw minerals, fuels and products did not show significant alterations in atmospheric emissions, mainly for particulate material and sulfur oxides, related with the use of residues. The emissions of inorganic continued to be low and not significantly altered by the presence of residues. It was possible to conclude that the alterations in inorganic emissions depend more from the quality of the raw minerals feed in the kilns, which is more difficult to control, than from the presence of residues being burn with the fuel. It was shown a high efficiency in the destruction of dangerous organic compounds feed in the cement kilns, under test conditions.

This thesis investigates sustainability measures for quicklime and cement clinker production. It is the aim of this thesis to contribute to the effort of creating a more sustainable modus of industrial production. The methods used comprises process simulations through multicomponent chemical equilibrium calculations, fuel characterization and raw materials characterization through dynamic rate thermogravimetry. The investigated measures relate to alternative fuels, co-combustion, oxygen enrichment, oxyfuel combustion, mineral carbonation and optimizing raw material mixes based on thermal decomposition characteristics. The predictive multicomponent chemical equilibrium simulation tool developed has been used to investigate new process designs and combustion concepts. The results show that fuel selection and oxygen enrichment influence energy efficiency, and that oxyfuel combustion and mineral carbonation could allow for considerable emission reductions at low energy penalty, as compared to conventional post-combustion carbon dioxide capture technologies. Dynamic rate thermogravimetry, applied to kiln feed limestone, allows for improved feed analysis with a deeper understanding of how mixing of different feed materials will affect the production processes. The predictive simulation tool has proven to be of practical value when planning and executing production and full scale campaigns, reducing costs related to trial and error. The main conclusion of this work is that several measures are available to increase the sustainability of the industry.

Zeolites are among the least-known products for environmental pollution control, separation science and technology. Due to their unique porous properties, they are used in various applications in petrochemical cracking, ion-exchange and separation and removal of gases and solvents. The preparation of synthetic zeolites from chemical reagents is expensive. Therefore, in order to reduce costs, zeolite researchers are seeking cheaper aluminosilicate bearing raw materials, such as clay minerals, to produce synthetic zeolites. This research concerns the synthesis of zeolites and zeotypes derived from low-cost materials like kaolinite (KAO), natural clinker (NC) and fly ash (FA). The motivation for using these sources as the starting materials in zeolite synthesis is driven by factors, such as they are cheap and available in bulk quantities, are currently under-utilized, have high workability, and require less water (or solution) for activation. The raw materials were activated by two different routes: (1) classic alkaline hydrothermal synthesis and (2) alkaline fusion prior to hydrothermal synthesis. In the first method, the synthesis of zeolitic materials was carried out generally in alkaline media, although KAO or its calcination product, metakaolinite (MTK), was also activated in the presence or absence of structure directing agents (SDAs) and additional silica (precipitated SiO2), with the last one determining the SiO2/Al2O3 ratio of the reaction mixture and the time given for zeolitization. Synthesis in fluoride- and calcium-bearing media was also used to activate kaolinite. The process of synthesis was optimized by applying a wide range of experimental conditions with a wide range of reaction temperature, time, mineralizer concentration and solid/solution ratio. In the second approach, an alkaline fusion step was conducted prior to hydrothermal treatment, because it plays an important role in enhancing the hydrothermal conditions for zeolite synthesis. On the other hand, this approach was adopted because it can dissolve more aluminosilicates. The main synthesis products obtained after activation of KAO in NaOH solutions included zeolite LTA (LTA), sodalite (SOD), cancrinite (CAN), faujasite (FAU), zeolite Na-P1 (GIS), JBW-type zeolite (JBW), analcime (ANA), whereas the activation of KAO in KOH solutions produced chabazite (CHA), zeolite Barrer-KF, phillipsite (PHI) and K-feldspar. The hydrothermal conversion of kaolinite in fluoride media did not produce successful results, although traces of FAU, GIS, CHA, SOD and CAN crystallized. The activation of KAO in the system CaO-SiO2-Al2O3-H2O promoted the formation of different calcium silicate hydrate (C-S-H) phases, including hydrogarnet (HYD) and tobermorite (TOB). Following the fusion approach, the main zeolitic phases obtained using NaOH as mineralizer were LTA and CAN. The main as-synthesized zeolites obtained from NC by the conventional hydrothermal treatment method include PHI, SOD and CAN. Using the fusion approach, FAU and LTA were obtained with NaOH as an activator, whereas non-zeolitic material crystallized when KOH was used. The main as-synthesized zeolitic materials obtained by hydrothermal reaction of FA include PHI, zeolite Barrer-KF, CHA and SOD with traces of TOB, ANA, zeolite LTF (LTF) and herschelite (HER), appearing occasionally. By the fusion approach, FAU was obtained with NaOH as activator, whereas no zeolitic material crystallized using KOH. Experimental results indicate that the method, mineralizer, concentration and time have strong effects on the type and degree of crystallinity of the synthesis products. On the other hand, the type and chemical composition of the as-synthesized products are strongly dependent on the chemical composition of the starting material. The chemistry of zeolite synthesis was subject to perturbations caused by the presence of impurities in the raw materials, which may remain insoluble during crystallization and cause undesired species to nucleate, developing mixtures of different types of zeolites. However, other physicochemical factors may play a very important role in the thermodynamics and kinetics of zeolite formation. The raw materials have very high contents of SiO2 and Al2O3, with SiO2/Al2O3 ratios appropriate for the synthesis of low-Si zeolitic materials with high crystallinity and cation exchange capacity (CEC). However, although zeolites’ CEC represents a very important characteristic quality in the removal of undesired species from polluted effluents, it is not the deciding factor in determining zeolite performance during ion exchange processes, since numerous other factors also need to be considered. Finally, the potential application of the raw materials and their as-synthesized products as low-cost sorbents in the remediation of metal ions and ammonium from wastewater effluents was investigated. PHI showed a lower efficiency than FAU. Selectivity of FAU for metal removal was, in decreasing order, Fe>As>Pb>Zn>Cu>Ni>Cr. Based on these results, the use of these materials has the potential to provide improved methods for the treatment of contaminated effluents.

O presente trabalho consiste na detalhada caracterização geológica da Mina de Vallemí no Paraguai, utilizada para fabricação de cimento Portland pela Industria Nacional de Cemento (INC), seguida da caracterização das matérias-primas, por petrografia e análises químicas e mineralógicas, e posteriores testes de queimabilidade de seis farinhas experimentais, elaboradas com misturas das matérias-primas disponíveis. As farinhas foram sinterizadas e avaliadas qualitativamente, por microscopia do clínquer, e quantificadas por difração de raios-X (DRX) e método de Rietveld. A geologia da mina consiste em metapelitos, por vezes em alternâncias rítmicas, com metacalcários (metaritmito) da Formação Vallemí, basal, sobrepostos por metacalcários puros, com intercalações de metadolomito, da Formação Camba Jhopo, ambas do Grupo Itapucumí (Ediacarano), dispostas em dobra isoclinal com flanco invertido (Faixa de Dobramentos Vallemí). Dada à diversidade litológica e complexidade tectônica, o estudo requereu mapeamento geológico detalhado (escala 1:2000), com coleta de amostras e análise química concomitante, no laboratório de qualidade da indústria, e atualização da topografia e modelagem 3D. Foram individualizados nove litotipos: 1) Litotipo Misto (Itá jopara); 2) Litotipo Ritmito Verde (Itá hovy?); 3) Litotipo Ritmito Vermelho (Itá pytã); 4) Litotipo Calcário Cinza (Itá hungy); 5) Litotipo Calcrete (Itá manduvi sa\'yju); 6) Litotipo Dolomito (Itá pytãngy); 7) Litotipo Arenito Vermelho (Itá atã pytã); 8) Litotipo Lamprofiro (Itá h?); 9) Litotipo Vulcânica Básica (Itá kui sa\'yju), sendo os cincos primeiros apropriados para fabricação de cimento. O Litotipo Dolomito é apropriado se usado em misturas e os demais são materiais estéreis. Foram realizadas seis diferentes misturas de litotipos, além da normalmente empregada na indústria, utilizada como referência, com avaliação do índice de queimabilidade (IQ) nos laboratórios da Associação Brasileira de Cimento Portland (ABCP). As farinhas D1, D3 e D4 foram classificados como fácil de queimar, e as demais, D2, D5b e D6b, com queimabilidade normal. Pode-se dizer que todas apresentam índices de queimabilidade compatíveis com os padrões exigidos para a produção de cimento Portland, destacando que a melhor mistura foi obtida com a farinha D4 (composta por Litotipo Ritmito Vermelho 83,07%, Litotipo Ritmito Verde 14,45% e mineral de ferro 1,48%), e a de menor desempenho a D5b (composta por Litotipo Calcrete 50,17%, Litotipo Misto 48,32% e mineral de ferro 1,52%), o que foi possível também corroborar na quantificação das fases do clínquer. / The present work deals with a detailed geological characterization of the Vallemí Mine in Paraguay, explored to manufacture of Portland cement by the National Cement Industry (INC), followed by the characterization of the raw materials, by petrography, chemical and mineralogical analyzes, and subsequent burnability tests of six experimental raw mixtures, prepared with mixtures of available raw materials. The flours were sintered and evaluated qualitatively by clinker microscopy and quantified by X-ray diffraction (XRD) and Rietveld method. The geology of the mine includes metapelites, sometimes in rhythmic alternations, with metalimestone of the Vallemí Formation, basal, overlapped by pure metalimestone, with intercalation of metadolomite, of the Camba Jhopo Formation, both of the Itapucumí Group (Ediacaran), arranged in fold isoclinal with inverted flank (Vallemí Folding Belt). Due to the lithological diversity and tectonic complexity, the study required detailed geological mapping (scale 1: 2000), with sample collection and concomitant chemical analysis, in the industrial quality laboratory, and updating the topography and 3D modeling. Nine lithotypes were individualized: 1) Litotipo Misto (Itá jopara); 2) Litotipo Ritmito Verde (Itá hovy?); 3) Litotipo Ritmito Vermelho (Itá pytã); 4) Litotipo Calcário Cinza (Itá hungy); 5) Litotipo Calcrete (Itá manduvi sa\'yju); 6) Litotipo Dolomito (Itá pytãngy); 7) Litotipo Arenito Vermelho (Itá atã pytã); 8) Litotipo Lamprofiro (Itá h?); 9) Litotipo Vulcânica Básica (Itá kui sa\'yju), the first five suitable for manufacturing cement. Litotipo Dolomito is applicable if used in mixtures. The others lithotype are sterile materials. Six different mixtures of lithotypes were carried out, besides the one normally used in industry, used as reference, with evaluation of the burnability index (IQ) in the laboratories of the Assocciação Brasileira de Cimento Portland (ABCP). Flours D1, D3 and D4 were classified as easy to burn, and the others, D2, D5b and D6b, with normal burning. It is possible to say that all of them have a comparable burnability index compatible with the standards required for Portland cement production, the best mixture was obtained with the raw mixture D4 (composed by Litotipo Ritmito Vermelho 83,07%, Litotipo Ritmito Verde 14,45% and iron ore 1,48%) and the D5b (composed by Litotipo Calcrete 50,17%, Litotipo Misto 48,32% and iron ore 1,52%) appear as the worst, which were corroborated in the quantification of clinker phases.

O presente trabalho consiste na detalhada caracterização geológica da Mina de Vallemí no Paraguai, utilizada para fabricação de cimento Portland pela Industria Nacional de Cemento (INC), seguida da caracterização das matérias-primas, por petrografia e análises químicas e mineralógicas, e posteriores testes de queimabilidade de seis farinhas experimentais, elaboradas com misturas das matérias-primas disponíveis. As farinhas foram sinterizadas e avaliadas qualitativamente, por microscopia do clínquer, e quantificadas por difração de raios-X (DRX) e método de Rietveld. A geologia da mina consiste em metapelitos, por vezes em alternâncias rítmicas, com metacalcários (metaritmito) da Formação Vallemí, basal, sobrepostos por metacalcários puros, com intercalações de metadolomito, da Formação Camba Jhopo, ambas do Grupo Itapucumí (Ediacarano), dispostas em dobra isoclinal com flanco invertido (Faixa de Dobramentos Vallemí). Dada à diversidade litológica e complexidade tectônica, o estudo requereu mapeamento geológico detalhado (escala 1:2000), com coleta de amostras e análise química concomitante, no laboratório de qualidade da indústria, e atualização da topografia e modelagem 3D. Foram individualizados nove litotipos: 1) Litotipo Misto (Itá jopara); 2) Litotipo Ritmito Verde (Itá hovy?); 3) Litotipo Ritmito Vermelho (Itá pytã); 4) Litotipo Calcário Cinza (Itá hungy); 5) Litotipo Calcrete (Itá manduvi sa\'yju); 6) Litotipo Dolomito (Itá pytãngy); 7) Litotipo Arenito Vermelho (Itá atã pytã); 8) Litotipo Lamprofiro (Itá h?); 9) Litotipo Vulcânica Básica (Itá kui sa\'yju), sendo os cincos primeiros apropriados para fabricação de cimento. O Litotipo Dolomito é apropriado se usado em misturas e os demais são materiais estéreis. Foram realizadas seis diferentes misturas de litotipos, além da normalmente empregada na indústria, utilizada como referência, com avaliação do índice de queimabilidade (IQ) nos laboratórios da Associação Brasileira de Cimento Portland (ABCP). As farinhas D1, D3 e D4 foram classificados como fácil de queimar, e as demais, D2, D5b e D6b, com queimabilidade normal. Pode-se dizer que todas apresentam índices de queimabilidade compatíveis com os padrões exigidos para a produção de cimento Portland, destacando que a melhor mistura foi obtida com a farinha D4 (composta por Litotipo Ritmito Vermelho 83,07%, Litotipo Ritmito Verde 14,45% e mineral de ferro 1,48%), e a de menor desempenho a D5b (composta por Litotipo Calcrete 50,17%, Litotipo Misto 48,32% e mineral de ferro 1,52%), o que foi possível também corroborar na quantificação das fases do clínquer. / The present work deals with a detailed geological characterization of the Vallemí Mine in Paraguay, explored to manufacture of Portland cement by the National Cement Industry (INC), followed by the characterization of the raw materials, by petrography, chemical and mineralogical analyzes, and subsequent burnability tests of six experimental raw mixtures, prepared with mixtures of available raw materials. The flours were sintered and evaluated qualitatively by clinker microscopy and quantified by X-ray diffraction (XRD) and Rietveld method. The geology of the mine includes metapelites, sometimes in rhythmic alternations, with metalimestone of the Vallemí Formation, basal, overlapped by pure metalimestone, with intercalation of metadolomite, of the Camba Jhopo Formation, both of the Itapucumí Group (Ediacaran), arranged in fold isoclinal with inverted flank (Vallemí Folding Belt). Due to the lithological diversity and tectonic complexity, the study required detailed geological mapping (scale 1: 2000), with sample collection and concomitant chemical analysis, in the industrial quality laboratory, and updating the topography and 3D modeling. Nine lithotypes were individualized: 1) Litotipo Misto (Itá jopara); 2) Litotipo Ritmito Verde (Itá hovy?); 3) Litotipo Ritmito Vermelho (Itá pytã); 4) Litotipo Calcário Cinza (Itá hungy); 5) Litotipo Calcrete (Itá manduvi sa\'yju); 6) Litotipo Dolomito (Itá pytãngy); 7) Litotipo Arenito Vermelho (Itá atã pytã); 8) Litotipo Lamprofiro (Itá h?); 9) Litotipo Vulcânica Básica (Itá kui sa\'yju), the first five suitable for manufacturing cement. Litotipo Dolomito is applicable if used in mixtures. The others lithotype are sterile materials. Six different mixtures of lithotypes were carried out, besides the one normally used in industry, used as reference, with evaluation of the burnability index (IQ) in the laboratories of the Assocciação Brasileira de Cimento Portland (ABCP). Flours D1, D3 and D4 were classified as easy to burn, and the others, D2, D5b and D6b, with normal burning. It is possible to say that all of them have a comparable burnability index compatible with the standards required for Portland cement production, the best mixture was obtained with the raw mixture D4 (composed by Litotipo Ritmito Vermelho 83,07%, Litotipo Ritmito Verde 14,45% and iron ore 1,48%) and the D5b (composed by Litotipo Calcrete 50,17%, Litotipo Misto 48,32% and iron ore 1,52%) appear as the worst, which were corroborated in the quantification of clinker phases.

La volonté de préservation de l'environnement est de plus en plus présente dans nos sociétés. C'est la mise en place de la recherche de ce que l'on appelle le développement durable qui traduit cette volonté à tous les niveaux. Afin de s'inscrire dans cette démarche de développement durable, les autorités soumettent les industries à une pression sans cesse croissante afin de réduire les diverses pollutions qu'elles peuvent engendrer. Dans le cas de l'industrie cimentière, ce sont les émissions de CO2 et la consommation des matières premières qui sont essentiellement visées afin de réduire son impact sur l'environnement. Le développement des ciments avec ajouts minéraux, le plus souvent issus de procédés industriels, constitue une voie de réduction de la quantité de clinker contenue dans le ciment portland et donc de diminution des émissions. De tels ciments existent déjà et utilisent entre autre des laitiers de haut fourneau, fumées de silice ou cendres volantes. D'autre part, les ciments avec ajouts sont intéressants car ils possèdent aussi des propriétés spécifiques différentes du ciment Portland de type CEM I. C'est sur le dernier point des propriétés spécifiques des ciments avec ajouts associé à la pression croissante du développement durable que se fonde cette thèse. Notre travail vise à mettre au point une méthodologie de développement des ciments avec ajouts minéraux plus basée sur une approche numérique qu'expérimentale. Une telle méthodologie permettrait à l'industrie cimentière de développer de nouveaux produits tout en s'inscrivant dans le cadre du développement durable en valorisant des sous-produits d'autres industries. L'originalité de la présente méthodologie repose sur l'utilisation maximale d'outils informatiques et de la simulation en remplacement de l'expérimental qui constitue actuellement l'essentiel des études visant à développer de tels ciments. Ceci présente en effet comme intérêts majeurs une réduction des coûts et surtout des temps de développement des ciments qui peuvent durer des dizaines d'années notamment vis-à-vis des essais de durabilité. Le travail de thèse réalisé a tout d'abord consisté à donner une réalité fonctionnelle à la méthodologie qui se décompose en trois étapes successives de tests pour la sélection de la pertinence d'un sous-produit industriel en tant qu'ajout dans un ciment. Pour cela, trois logiciels ont été choisis : • CHESS, code de calcul géochimique, utilisé pour la première étape • VCCTL, code de génération de microstructure de pâte de ciment, utilisé pour la deuxième étape. • HYTEC, code de simulation de transport réactif, utilisé pour la troisième étape. Il a donc fallu adapter ces logiciels à leur utilisation dans le cadre de la méthodologie afin de pouvoir établir une synergie de fonctionnement entre eux. Cette adaptation nous a notamment conduit à une modification conséquente du code source du VCCTL afin de pouvoir étendre ses capacités à la prise en compte d'ajouts inconnus. Le travail s'est ensuite porté sur la validation pratique de la méthodologie en la confrontant à des résultats d'études expérimentales. Cette validation pratique s'est tout d'abord portée sur un CEM I puis sur des mélanges de ciment avec soit un laitier HF soit une cendre volante de lit fluidisé circulant (CVLFC). Les résultats obtenus confirment l'intérêt de l'approche en laissant toutefois entrevoir les limitations actuelles principalement dues aux outils informatiques.