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The goal of the thesis is to evaluate if developed phase chemical process models for cement clinker and lime production processes are reliable to use as predictive tools in understanding the changes when introducing sustainability measures.

The thesis describes the development of process simulation models in the application of sustainability measures as well as the evaluation of these models. The motivation for developing these types of models arises from the need to predict the chemical and the process changes in the production process, the impact on the product quality and the emissions from the flue gas.

The main chemical reactions involving the major elements (calcium, silicon, aluminium and iron) are relatively well known. As for the minor elements, such as sodium and potassium metals, sulphur, chlorine, phosphorus and other trace elements, their influence on the main reactions and the formation of clinker minerals is not entirely known. When the concentrations of minor and trace elements increase due to the use of alternative materials and fuels, a model that can accurately predict their chemistry is invaluable. For example, the shift towards using less carbon intensive fuels and more biomass fuels often leads to an increased phosphorus concentration in the products.

One way to commit to sustainable development methods in cement clinker and lime production is to use new combustion technologies, which increase the ability to capture carbon dioxide. Introducing oxy-fuel combustion achieves this, but at the same time, the overall process changes in many other ways. Some of these changes are evaluated by the models in this work.

In this thesis, a combination of the software programs Aspen Plus™ and ChemApp™ constitutes the simulation model. Thermodynamic data from FACT are evaluated and adjusted to suit the chemistry of cement clinker and lime.

The resulting model has been verified for one lime and two cement industrial processes.

Simulated scenarios of co-combustion involving different fuels and different oxy-fuel combustion cases in both cement clinker and lime rotary kiln production are described as well as the influence of greater amounts of phosphorus on the cement clinker quality.

The methods used in this thesis work were a combination of computational and modeling based laboratory experiments.

Thermodynamic process modeling of the cement clinker process offers a tool for evaluating how changes in raw materials and process parameters affect the clinker quality. Work with finding suitable replacement raw materials involves investigating the chemical compatibility of potential alternative materials. Such replacement materials may be metallurgical slags, although there are some unsolved issues with the quantities of certain metals and particularly Mg in these materials.

For predicting the formation of clinker mineral phases, cooling calculations are used in order to reproduce the temperature history in the full scale process. A chemistry model including a solid solution phase based on C₂S and phosphate was developed along with the recommendation for continued work on clinker phases with solid solutions to include MgO. A thermodynamic database for phase chemistry calculations of clinkering reactions was created and evaluated. Suitable compounds and solution species were selected from the thermochemical database included in FactSage software. The extent and quality of the required thermodynamic data via available databases is generally satisfactory, except for certain properties of some of the main clinker phases. One example is the lack of a thermodynamic model for the alite solid solution. That is, the composition of the phase available in the database representing alite does not contain the minor elements Al, Fe and Mg. Therefore, it is difficult to predict the quantity and distribution of Mg in the clinker, with varying total content of MgO. Thus, one of the goals/objectives was to improve thethermodynamic model of alite as a solid solution of 3CaO-SiO₂-xAl₂O₃-yFe₂O₃-zMgO. To achieve this, it was assumed that a mix of compounds with adjusted Henrian coefficients representing the solid solution clinker phase alite was in equilibrium with the clinker melt.

The distribution of MgO was studied in synthetic clinker compositions with quantities ranging from 0.5 to 10 wt-%. Synthetic clinker mixes were heated to 1450°C and studied with Rietveld refinements of X-ray diffraction data and SEM-EDS analysis. In addition, the mechanisms of how slag and lime particles react facilitating the diffusion of MgO into the developing clinker melt and the formation of incipient belite were studied.

The calculated results provide a good prediction of the quantities and composition of the clinker phases formed during heating and non-equilibrium cooling. The solubility of MgO in the clinker and the quantity of periclase formed is in fair agreement with published data. Thus, this thesis work shows that using a mix of compounds with adjusted activities in alite together with available standard thermodynamic data and the Scheil cooling method had good potential for evaluating alternative raw materials.

Also, the work has identified weak points in the process modeling and suggest improvements to be made in future research work.