Apesar de ser utilizado na indústria de Fosfato Bicácico (DCP) há vários anos, a microgranulação a partir de misturados horizontais de alto cisalhamento possui fundamentos pouco conhecidos, de maneira que as operações das unidades industriais sejam baseadas em conhecimentos empíricos. Este trabalho busca determinar os mecanismos de granulação associados com o processo de microgranulação de DCP e o perfil de crescimento dos grãos em função dos seguintes parâmetros operacionais: a quantidade de fase líquida, acidez do meio reacional e a velocidade de rotação do eixo central do granulador. Após a análise estatística de dados coletados a partir de um ano de operação em uma unidade industrial, conclui-se que a aglomeração do DCP em ambientes com alta umidade geram preferencialmente partículas grosseiras, que não contribuem para o aumento da eficiência de granulação. O processo de microgranulação de DCP deve ser controlado em uma estreita faixa de condições operacionais, balanceando a quantidade de fase líquida adicionada e a taxa de reciclo de material seco praticada. A redução na umidade de operação, aumenta a qualidade granulométrica do material produzido por este processo. / Despite being used by the Dicalcium Phosphate (DCP) Industry for many years, the fundaments of high shear horizontal mixer microgranulation are poorly known, so the industrial operations are based on empirical knowledge. The goal of this work was to determine the granulation mechanisms associated with the DCP microgranulation process and the particle size enlargement pattern, according with the following operational parameters: the amount of liquid phase, reaction media acidity and the mixer paddles` rotational speed. After statistically analysing one year operational data collected from an industrial facility, it was concluded that the agglomeration of DCP at a high moisture environment promotes preferable formation of coarse particles, which dont increase the overall granulation efficiency. The DCP microgranulated process has to be controlled in very narrow operational condition, balancing the liquid phase and the recycle material returned during the granulation process. The reduction of the process moisture increased the quality of physical quality of the material produced by this process route.

Brazil holds second place in world production of dicalcium phosphate, which represents the main source of phosphorus for complementing the mineral salt that makes up the daily feed for cattle, hogs and fowls. Considering the fact that the increase in consumption of phosphates due to the increased annual consumption of meat by the world population, development of the technology necessary to guarantee quality and productivity has become imperative in order to supply this competitive market. The requirement for BUNGE Fertilizantes S.A. to accompany the world trend, reflected by client suggestions for sales of bulk quantities, originated the search for a new technology to produce microgranulated dicalcium phosphate. Due to characteristics adverse to forming the microgranulated dicalcium phosphate grain (particle size, monocalcium phosphate and residual acidity), it has become necessary to apply a final product classification process to guarantee compliance with the physical specifications of the material at the moment of expediting to clients. The purpose of this dissertation is to perform a study of the classification system used for fluidization, seeking scale-up information for construction of an industrial unit to be installed at the Cajati Facilities of BUNGE Fertilizantes. Fluidization is utilized commercially in a wide range of processes such as: catalytic operations, cooling, drying, recovery, etc, it utilizes the elutriation effect in wich the relatively small components are entrained by the gas flow for physical classification of materials. Within this concept an effort was made to quantify the effects of operational and dimensional variables of the fluidized bed system: porosity of the distribuition screen, residence time and freeboard angle. In accordance with the main experimental results, a statistical analyses was made by multiple regression, thus obtaining parameters related to the isolated variables and the interactions among them. It was observed that the operational and dimensional conditions that promote the best Separation and Recovery efficiencies for the system were those for which the screen porosity was 11 %, the residence time was 5,34 minutes and the freeboard angle was 33,62o. On the basis of the optimum data obtained from the fluidization pilot system, an industrial system was designed for the Cajati Facilities, having classification capacity of microgranulated dicalcium phosphate of 100 Tons/h. The resultant Separation end Recovery efficiencies of the industrial system demonstrate an excellent application of technology for FBC (dicalcium phosphate) classification and the model obtained from the pilot project precisely predicts the efficiencies for industrial systems. Thus, the mathematic model obtained from the pilot plant can be used as a reference for design and scale-up of microgranulated dicalcium phosphate industrial classification units, having characteristics similar to those studied in this dissertation. / O Brasil ocupa o segundo lugar na produção de fosfato bicálcico, principal fonte de fósforo para complementação do sal mineral que integra a ração diária dos animais (bovinos, suínos e aves). Levando-se em consideração o crescimento do consumo de fósforo em decorrência do aumento anual do consumo de carne pela população mundial, torna-se imperativo o desenvolvimento de tecnologia para garantir qualidade e produtividade, visando atender a este mercado cada vez mais competitivo. A busca de uma nova tecnologia para a produção de fosfato bicálcico microgranulado originou-se da necessidade da BUNGE Fertilizantes S.A. acompanhar uma tendência mundial atendendo às sugestões de clientes para a venda a granel. Devido às características adversas para uma boa formação do grão do fosfato bicálcico microgranulado (diâmetro da partícula, fosfato monocálcico e acidez residual) faz-se necessário a aplicação de um processo de classificação do produto final para garantir o atendimento às especificações físicas do material no momento da expedição para os clientes. O objetivo deste trabalho é estudar um sistema de separação utilizando a fluidização, buscando informações de scale-up para o dimensionamento de uma unidade industrial a ser instalada no Complexo Industrial de Cajati da BUNGE Fertilizantes. A fluidização é usada comercialmente em uma grande variedade de processos, tais como: operações catalíticas, resfriamento, secagem, recobrimento, etc, e utiliza o efeito da elutriação, onde os componentes relativamente pequenos são arrastados pelo fluxo de gás, para a separação física dos materiais. Dentro deste conceito, busca-se quantificar os efeitos das variáveis operacionais e dimensionais de um sistema leito fluidizado: porosidade da placa distribuidora, tempo de residência e ângulo da zona de expansão. Conforme os principais resultados experimentais, foi feita uma análise estatística através de regressão múltipla obtendo-se os parâmetros relacionados às variáveis isoladas e interações entre elas. Observou-se que as condições operacionais e dimensionais que atingem as melhores eficiências de Separação e Recuperação para o sistema foram aquelas nas quais a porosidade da placa era de 11 %, o tempo de residência do material no leito de 5,34 minutos e o ângulo da zona de expansão (freeboard) de 33,62º. A partir dos dados ótimos obtidos no sistema piloto de fluidização foi dimensionado um sistema industrial para a Unidade da Bunge Fertilizantes em Cajati com capacidade de classificar 100 T/h de fosfato bicálcico microgranulado. Os resultados das eficiências de Separação e Recuperação do sistema industrial demonstram a excelente aplicação da tecnologia para classificação do FBC (fosfato bicálcico), e o modelo obtido no sistema piloto prevê, com uma boa precisão, as eficiências para sistemas industriais. Desta forma o modelo matemático levantado para o sistema piloto de leito fluidizado pode ser usado como referência para o dimensionamento ( scale-up ) de unidades industriais de classificação de fosfato bicálcico microgranulado, com características semelhantes ao estudado neste trabalho. / Mestre em Engenharia Química

The subject of this doctoral thesis was to elucidate the mechanism of reaction leading to the formation of dicalcium silicate (C2S), its solid solutions and other phosphatic calcium silicate phases using the sol-gel method of synthesis. SiO2 (Tosil A), CaO (calcium nitrate tetra-hydrate) and H3PO4 (as a source of P2O5) were used as starting materials. Series of samples with different content of P2O5 were synthesized. The characterization of Tosil A and samples was based on the following methods: DTA/TGA and EGA, XRD and SEM and EDS analy-ses. It is known, that phosphorous oxide can enter the structure of C2S and possibly form solid solutions and different phosphatic calcium silicate phases in C2SâC3P system. Depending on the P2O5 concentration in mixtures, three distinct phases are formed: larnite (2CaOâSiO2), Ca14,92(PO4)2,35(SiO4)5,65 and 5CaOâSiO2âP2O5, as detected by XRD. Local microanalysis de-monstrated the presence of calcium phosphate epicenters (C3P) containing SiO2, calcium sili-cate (C2S) zones with minimum content of P2O5 and intermediary areas of various phosphatic calcium silicates. The formation of two distinct islets of C2S and C3P is due the affinity of acid oxides (SiO2, P2O5) towards the basic one (CaO) during the sol-gel process. Then, the formation of various phosphatic calcium silicates results from the diffusion of P2O5 and SiO2 towards calcium silicate and calcium phosphate, respectively.

DIPLOMA THESIS IS DEVOTED TO THE STUDY OF PREPARATION OF PURE BELITE CLINKER FOR THE POTENTIAL INCREASE OF KINETICS OF THE HYDRATION PROCESS BY CHEMICAL ACTIVATION. THE THESIS OF THIS WORK IS BASED ON RESEARCH FINDINGS CONCERNING BELITE CLINKER AND RESEARCH AT THE INSTITUTE OF THD. THE THESIS AIMS TO DESIGN COMPOSITION OF THE RAW MEAL BURNING BELITE, FOLLOWING MODIFICATION BY SULPHATE AND POTASSIUM CARBONATE IN ORDER TO POTENTIALLY INCREASE THE REACTIVITY OF THE BURNT BELITE CLINKER AND THE LABORATORY FIRING OF PREPARED SAMPLES. THE LAST STEP WAS TO ASSESS THE MINERALOGICAL COMPOSITION OF BURNED SAMPLES XRD ANALYSIS AND FOLLOWING COMPARISON CELL PARAMETER OF BELITE WITH AND WITHOUT ADDED MODIFYING ADDITIVES.

This study aimed to evaluate the effect of the use of phytase exoenzyme and other mineral sources on the bioavailability of phosphorus , increased dietary energy and nutrient digestibility . The treatments were : sorghum with inorganic phosphate ( SFB ) , maize with inorganic phosphate ( MFB ) , sorghum meal, meat and bone meal ( SFco ) , sorghum with phytase ( SFV ) and without energy recovery and amino acids ( SFNV ) . 1400 birds were for performance reviews , which were determined feed intake , body weight , feed conversion real and traditional and viability . For the analysis of digestibility at 15 days were used 80 birds , which were subjected to total collection , now for carcass composition and mineralization of tibia were used 6 birds per treatment , where we proceeded to determine the dry matter , crude protein , ether extract , ash , gross energy housing , and calcium and phosphorus of tibia and carcass. Data were subjected to analysis of variance and means were compared by Tukey test at 5 % and viability Kruskal-Wallis test . There were no statistical differences in performance at 7 days of age and only 14 live weight was lower for the MFB , however at 42 days , body weight was greater for the SFB compared to the MFB . Digestibility at 15 days there was no statistical difference. For carcass composition, the SFV showed higher percentage of ether extract. The percentage of calcium MFB FCS and were lower compared with the SFNV and equal to SFco and SFV , and the phosphorus content of the SFV and SFNV showed higher values. The exogenous phytase enzyme is able to hydrolyze phytate and release phosphorus from vegetable source for assimilation by animals , thus acting as a substitute for vegetable sources of phosphorus. / Objetivou-se avaliar o efeito da utilização da exoenzima fitase e de outras fontes minerais sobre a biodisponibilização do fósforo, o incremento de energia da ração e a digestibilidade de nutrientes. Os tratamentos foram: Sorgo com fosfato bicálcico (SFB), milho com fosfato bicálcico (MFB), sorgo com farinha de carne e ossos (SFCO), sorgo com fitase com (SFV) e sem valorização de energia e aminoácidos (SFNV). Foram 1400 aves para as análises de desempenho determinou-se o consumo de ração, peso vivo, conversão alimentar real e tradicional e a viabilidade. Para as análises de digestibilidade aos 15 dias foram utilizadas 80 aves, que foram submetidas a coleta total de excretas, já para a composição de carcaça e mineralização das tíbias foram utilizadas 6 aves por tratamento, onde procedeu-se a determinação dos teores de matéria seca, proteína bruta, extrato etéreo, matéria mineral, energia bruta da carcaça, e cálcio e fósforo das tíbias e carcaça. Os dados foram submetidos a análise de variância e as médias comparadas pelo teste de Tukey 5% e a viabilidade pelo teste Kruskal-Wallis. Não houve diferenças estatísticas para o desempenho aos 7 dias de idade e aos 14 somente o peso vivo foi menor para o MFB, já aos 42 dias, o peso vivo foi maior para o SFB comparado com o MFB. A digestibilidade aos 15 dias não houve diferença estatística. Para a composição da carcaça, o SFV apresentou maior valor da porcentagem de extrato etéreo. A porcentagem de cálcio do SFB e MFB foram menores comparado com o SFNV e iguais para SFCO e SFV, e para o teor de fósforo, o SFV e SFNV apresentaram maiores valores. A enzima fitase exógena é capaz de hidrolisar o fitato de origem vegetal e liberar o fósforo para assimilação pelos animais, atuando assim como substituta de fontes vegetais de fósforo. / Mestre em Ciências Veterinárias

DIPLOMA THESIS IS FOCUSED ON THE PREPARATION AND PROPERTIE OF BELITE CLINKER. IT IS BASED ON THE STUDY OF SCIENTIFIC ARTICLES DEALING WITH THE ABOVE MENTIONED TOPIC AS WELL AS THE ANALYSIS OF THE BRNO THD INSTITUTE´S RESEARCH RESULTS. AS PART OF MY EXPERIMENTAL WORK, A PROPOSAL OF THE COMPOSITION OF RAW MEAL TO EXTRACT BELITE CLINKER IN THE PRESENCE OF POTASSIUMS CARBONATE AND SULPHATE WAS MADE TO MODIFY RAW MEAL. THE PURPOSE OF MODIFYING RAW MEAL IS A POTENTIAL INCREASE IN BELITE CLINKER REACTIVITY. FURTHER THE EXTRACTION OF BYPASS DUST FROM A LOCAL CEMENT PLANT WAS CONDUCTED. THE EVALUATION OF THIS RESEARCH WAS MADE BY THE X-RAY DIFFRACTION (XRD) ANALYSIS METHOD.

Roll compaction is a continuous process commonly used in the pharmaceutical industry for dry granulation of moisture and heat sensitive powder blends. It is intended to increase bulk density and improve flowability. Roll compaction is a complex process that depends on many factors, such as feed powder properties, processing conditions and system layout. Some of the variability in the process remains unexplained. Accordingly, modeling tools are needed to understand the properties and the interrelations between raw materials, process parameters and the quality of the product. It is important to look at the whole manufacturing chain from raw materials to tablet properties. The main objective of this thesis was to investigate the impact of raw materials, process parameters and system design variations on the quality of intermediate and final roll compaction products, as well as their interrelations. In order to do so, we have conducted a series of systematic experimental studies and utilized chemometric tools, such as design of experiments, latent variable models (i.e. PCA, OPLS and O2PLS) as well as mechanistic models based on the rolling theory of granular solids developed by Johanson (1965). More specifically, we have developed a modeling approach to elucidate the influence of different brittle filler qualities of mannitol and dicalcium phosphate and their physical properties (i.e. flowability, particle size and compactability) on intermediate and final product quality. This approach allows the possibility of introducing new fillers without additional experiments, provided that they are within the previously mapped design space. Additionally, this approach is generic and could be extended beyond fillers. Furthermore, in contrast to many other materials, the results revealed that some qualities of the investigated fillers demonstrated improved compactability following roll compaction. In one study, we identified the design space for a roll compaction process using a risk-based approach. The influence of process parameters (i.e. roll force, roll speed, roll gap and milling screen size) on different ribbon, granule and tablet properties was evaluated. In another study, we demonstrated the significant added value of the combination of near-infrared chemical imaging, texture analysis and multivariate methods in the quality assessment of the intermediate and final roll compaction products. Finally, we have also studied the roll compaction of an intermediate drug load formulation at different scales and using roll compactors with different feed screw mechanisms (i.e. horizontal and vertical). The horizontal feed screw roll compactor was also equipped with an instrumented roll technology allowing the measurement of normal stress on ribbon. Ribbon porosity was primarily found to be a function of normal stress, exhibiting a quadratic relationship. A similar quadratic relationship was also observed between roll force and ribbon porosity of the vertically fed roll compactor. A combination of design of experiments, latent variable and mechanistic models led to a better understanding of the critical process parameters and showed that scale up/transfer between equipment is feasible.

The present thesis gives a summary of results obtained through theoretical and experimental studies of systems with relevance to copper smelting and converting. Many chemical elements are involved in the copper production pro­cesses and a detailed experimental study would be very time- consuming and expensive. A complicating fact is also the corrosivity of the liquid phases towards container material. A powerful alternative is equilibrium calculations, in which models for the liquid phases as well as reliable basic thermodynamic data are needed. In the present thesis, a generalized structure based model for liquid silicates was developed and used in assessments of the sys­tems PbO-SiO2, Fe-O-SiO2, CuO0.5-SÌO2 and Cu-Fe-O-SiO2. In the model, the non-ideal silicate melt is treated as an ideal solu­tion but containing a few complexes. The PbO-Si02 melt could be described by introducing the complexes Pb3Si207, Pb4Si4010 and Pb13Si12O37 in addition to the components PbO and Pb2Si04. The species considered in the Fe-O-SiO2 melt were FeO, FeO1.5, Fe2Si04, Fe3Si207, Fe3Si6O15 and in the CUO0.5-SiO2 melt CuO0.5 ana CU4SiO4. Trie calculated phase diagrams, the activities of me­tal oxides and the oxygen partial pressures were all in good agreement with the published data. Two of the papers in this thesis concern the determination of Gibbs free energies for Cu2S(s,l) and Ca2Fe2O5(s) through emf measurements utilizing a solid electrolyte. Activities and termi­nal solubilities in the solid solution [Fet,Ca]0 were also deter­mined. The results obtained from the quantitative equilibrium calcula­tions for conventional copper smelting and converting were used to outline the overall reactions taking place and the outcome of changes in process parameters. Comparison with observed values, however, showed that the copper and magnetite contents in slag were calculated too low. These discrepancies could be completely explained by using a non-equilibrium approach in which the con­verter was assumed to consist of several segments with concentra­tion gradients between the segments. / digitalisering@umu.se