The Master’s thesis is focused on a study of the effect of increased content of heavy metals present in a raw meal on the formation and properties of prepared clinker and acquired cement. Main attention is devoted to changes on the physical, mechanical, microstructural and hydration properties. The theoretical part contains an overview of clinker minerals occurring in Portland cement including the possibility of incorporation of heavy metals into their structure and affecting the properities of the cement. In the experimental part, there is compared the effect of heavy metal oxides on the composition and hydration properties of portland clinker and physical-mechanical and microstructural properities of cement pastes prepared from this clinker.

Depuis la fin du 20ème siècle, notre société a pris conscience que la protection de l’environnement et le développement durable sont nécessaires à notre épanouissement futur. Des directives ont contraint les pouvoirs publics, les collectivités, ainsi que les industriels à réagir notamment en s’impliquant dans la recherche. Les cimentiers sont aussi concernés. La fabrication du ciment nécessite énormément de matières premières.L’objectif principal de cette thèse est donc de valoriser les sous-produits industriels en matériaux cimentaires. Le contexte et la problématique des déchets sont abordés, ainsi que la possibilité de valorisation par les ciments. La méthodologie mise en place et son originalité sont expliqués. Dans un premier temps, le protocole de caractérisation des déchets minéraux a été développé et les résultats en laboratoire sont prometteurs pour le remplacement du calcaire et de l’argile dans le cru d’un ciment. Les cuissons en laboratoire ont permis d’obtenir un ciment comportant les 4 phases d’un Portland. La synthèse en plus grande quantité d’une formulation en laboratoire a mis en évidence de bonnes performances mécaniques sur mortiers au jeune âge. Dans un deuxième temps, les meilleures formulations ont été testées à l’échelle industrielle, dans le four de ARF. Le cru, malaxé par trémies agitatrices, a été une réussite. Enfin, l’immobilisation des polluants dans une matrice cimentaire des résidus de combustion, provenant des combustibles secondaires de ARF a permis de déclasser le déchet stabilisé/solidifié par réduction granulométrique du matériau avant tabilisation/solidification. / Since 20th century’s end, our society started to take conscience of environmental protection and sustainable development are required to our future blooming. Directives have obliged public authorities, communities, such as industry to be reacted particularly while being implied in research. The cement-manufacturers are also concerned. The process cement-manufacturer requires large quantities of raw materials. The main objective of the thesis is to value industrial by-products by cementitious materials. Context and problem of wastes were discussed, as well as the possibility of valorization such as the cements. The methodology set up for the thesis and its originality are explained. First, the protocol of characterization of mineral wastes was developed. The results in laboratory are promising for the replacement of limestone and clay in the cement’s raw meal and different formulations. The cookings in laboratory allowed obtaining a cement containing 4 phases of Portland. The synthesis in bigger quantity of a formulation in laboratory highlighted good mechanical performances on mortars at the young age. In a second stage, the best formulations were tested on an industrial scale in the ARF’s kiln. The raw meal, mixed by hoppers agitators, was a success. Finally, immobilization of pollutants in a cement matrix of the residues after combustion, resulting from secondary fuels of ARF, was studied to be able to downgrade the waste stabilized/solidified by grading reduction of the material before stabilization/solidification.

The dissertation is focused on the applied technical and economic analysis of the influence separation of transport air from raw meal on the economy clinker/cement production, in specific cement production. The analysis is performed on the basis of a detailed understanding and analysis of the function of each component of the technology of cement production, which are affected by separation of transport air from raw meal, mainly the dosing and preheat system of the raw meal. The results of the analysis show a significant effect (impact) separation of transport air on the production costs.

Η παρακάτω διπλωματική εργασία περιλαμβάνει την περιγραφή των εργασιών που πραγματοποιήθηκαν κατά τον εκσυγχρονισμό του συστήματος αυτοματισμού των σιλό φαρίνας Δ και Ε. Αρχικά περιγράφεται περιληπτικά η διαδικασία παραγωγής του τσιμέντου και ο ρόλος των σιλό φαρίνας Δ και Ε στη γραμμή παραγωγής. Στη συνέχεια αναλύεται η μετάβαση από τον κλασσικό αυτοματισμό στη χρήση Προγραμματιζόμενου Λογικού Ελεγκτή (PLC) και αναφέρονται οι σημαντικότερες αλλαγές που συνέβησαν. Το επόμενο κομμάτι της εργασίας αναφέρεται στο διάγραμμα ροής του συγκροτήματος φαρίνας ΠΚ4 και ΠΚ5 όπου παρατίθεται σχετικό σχεδιάγραμμα με τη ροή του υλικού ενώ επιπροσθέτως περιγράφεται η λειτουργία όλων των μηχανών που περιλαμβάνονται σ’ αυτό. Έπειτα γίνεται μετάβαση στη λογική αυτοματισμού που αναπτύχθηκε από τους μηχανικούς αυτοματισμού του εργοστασίου όπου περιγράφονται όλες οι είσοδοι και οι έξοδοι του PLC, το πρόγραμμα που χρησιμοποιήθηκε και ο κώδικας προγράμματος που δημιουργήθηκε. Αμέσως μετά γίνεται ξεχωριστή αναφορά στο μιμητικό διάγραμμα (SCADA) με παράθεση των εικόνων που το αποτελούν και επεξήγηση όλων των ενδείξεων και επιλογών που περιλαμβάνει. Στη συνέχεια αναφέρονται τα δίκτυα που χρησιμοποιήθηκαν για τον έλεγχο της μονάδας των σιλό Δ και Ε, δηλαδή το βιομηχανικό δίκτυο Profibus και το δίκτυο Ethernet, όπου περιγράφεται ο τρόπος επικοινωνίας των χειριστών της μονάδας με τις μηχανές της διεργασίας. Το τελευταίο τμήμα της εργασίας περιλαμβάνει την βήμα προς βήμα περιγραφή των εργασιών ως την ολοκλήρωση του έργου, τη διαδικασία του τελικού ελέγχου του έργου καθώς και μια σύντομη αναφορά στη συμμετοχή του φοιτητή σε τμήμα των παραπάνω εργασιών. Η διπλωματική εργασία κλείνει με την παράθεση των πηγών καθώς και ορισμένων συμπληρωματικών παραρτημάτων. / The following thesis includes a description of the work carried out during the modernization of the automation system of raw meal silo D and E. Firstly it is described briefly the production process of cement and the role of raw meal silo D and E on the production line. Afterwards the transition from classical automation to the use of a Programmable Logic Controller (PLC) and some of the most significant changes occurred are analyzed. In the next chapter it is reported the complex flow of raw meal PK4 and PK5 citing a diagram with the flow of material and furthermore the operation of all machinery therein is described. Following there is a shift in the automation logic developed by automation engineers of the factory describing all inputs and outputs of the PLC, the program used and the program code created. A separate reference to mimetic diagram (SCADA) follows including the images that constitute it and an explanation of all the indications and options included. The next chapter includes the networks used for the control unit of the silo D and E, which are the Profibus industrial network and the network Ethernet, where it is described the way in which the operator of the plant contacts with the machinery of the process. The last part of the thesis includes step-by-step the description of the works as the project is completed, the process of final verification of the project and a brief reference to the student’s involvement. The thesis concludes with a statement of sources and some additional annexes.

Under detta arbete studeras en av Europas mest moderna cementfabriker med kapacitet att producera runt 2,6 miljoner ton cement per år. Syftet med examensarbetet är att beskriva variationen i utfallen av råmjöl och identifiera vilka orsaker till variation som är möjliga att minska. Oavsiktliga variationer av kvalitet i råmjölet kan resultera i bristande klinkerkvalitet, som i sin tur kan medföra en betydande intäktsförlust. Arbetet utgår från teorier om offensiv kvalitetsutveckling, Six sigma, processledning och cementproduktion. En metodkombination av kvantitativa och kvalitativa metoder har tillämpats för datainsamling och dataanalys, där den kvantitativa datainsamlingen baserats på historiska data från referensorganisationen. De slutsatser som redogörs för, är att processen som studeras har möjlighet till att prestera i världsklass. Huvudsakliga bidragande orsaken är metoden för styrning där systemet saknar styrgränser som leder till överstyrning. Även materialvariation vid byten av råmaterialslimpor är en betydande orsak till variansen i råmjölet. Förutsatt att styrsystemet kopplas på för tidigt efter ett genomfört limpbyte kan effekten av ett limpbyte förvärras. Vidare tyder resultaten på att 80% av den totala variationen i råmjölets kalkmättnad skapas av limpbyten. / During this work, one of Europe's most modern cement factories is studied, with the capacity to produce around 2.6 million tons of cement per year. The purpose of the thesis is to describe the variation in the outcome of raw meal and identify which causes of variation are possible to reduce. Involuntary variations in the quality of the input raw meal can result in a lack of clinker quality, which in turn can result in a significant loss of revenue. The work is based on theories relating to Total Quality Management, process management and cement production. A method combination of quantitative and qualitative methods has been applied for data collection and data analysis, where the quantitative data collection is based on historical data gathered from the reference organization. The conclusions outlined are that the process being studied has the opportunity to perform world-class. The main contributing factor is the method for control where the system lacks control limits that lead to over compensation. Also, material variation in the case of changes of raw material piles is a significant cause of the variance in the raw meal. Provided that the control system is switched on prematurely after a raw material pile change has been carried out, the effect of the change can be worsened. Furthermore, the results indicate that 80% of the total variation in the raw meal’s lime saturation is created by raw material pile changes.

Portland clinker is thanks to its large-scale production a continuously studied topic. Clinker, or Portland cement, is used for construction purposes, or for insulation and special applications. One of these special applications could be shielding of different types of radiation by making use of the content of barium ions. The present master’s thesis examines the influence of barium oxide on the formation and properties of Portland clinker, which could be, by incorporation of barium ions into the system, used as a binder for buildings resistant to various types of radiation. Barium sulfate and barium carbonate were added to the raw meal in order to prepare clinkers with different content of barium oxide. The effect of barium on the formation of clinker phases was studied (by XRD – Rietveld analysis and by the microscopic point integration), as well as the effects on the variations of temperature of the phase formation (TG-DTA) and the rate of alite formation under isothermal conditions. Furthermore, the ability of barium to become a part of clinker minerals was studied by SEM with EDS, and the solubility of barium phases by ICP-OES. The hydration of clinker minerals containing barium was studied by isothermal calorimetry.