L'objectif général de cette thèse est de transformer les déchets ultimes et dangereux contenant des métaux lourds, en matières minérales chimiquement stables. L'augmentation de la production des ordures ménagères (OM) est un problème qui concerne et préoccupe le monde entier. Parmi les différentes méthodes de traitement des déchets municipaux, l'incinération est une technologie qui peut fournir une solution efficace et respectueuse pour l'environnement. Le problème de ce traitement est la production de REFIOM. Les REFIOM peuvent contenir de grandes quantités de composés métalliques toxiques et est considéré comme un déchet dangereux ce qui oblige à les mettre en décharges classées. Trois types de matériaux pour l'immobilisation du plomb et du cadmium ont été étudiés : les vitrocéramiques, les céramiques frittées et les géopolymères. Nous sommes parvenus à synthétiser une base de vitrocéramique à partir de cendres incinérées purs et nous avons diminué sa volatilisation lors de sa production. Des résultats prometteurs ont été obtenus pour la vitrocéramique Ca-Mg-Si-O qui a incorporé durablement une quantité élevée de cadmium dans les structures cristallines et le plomb dans la structure amorphe. La phase cristalline est plus résistante à l'attaque acide en raison de son incorporation dans une matrice vitreuse qui génère une double protection. Ses travaux ouvrent la possibilité de créer cette matrice en ajoutant des oxydes commerciaux aux résidus d'incinération. Nous avons étudié la céramique frittée à base du système Ba-Mg-Ti-O. Nous avons obtenu les trois phases minérales présentées dans la céramique SYNROC (hollandite, pérovskite et rutile) où le cadmium substitue le magnésium tandis que le plomb a occupé le site appartenant au baryum. La céramique frittée est satisfaisante en termes d'immobilisation des métaux lourds avec de bonnes propriétés physiques. Pour produire des géopolymères résistants à partir de REFIOM, il est avantageux d'utiliser un rapport L/S = 1,2 et de les sécher à température ambiante. Il a été observé que le frittage influence le taux de réorganisation structurelle avec l'apparition de la phase sodalite ( Na4Si3Al3O12Cl), qui se compose de tunnels où les métaux lourds peuvent être incorporés. Le plomb et le cadmium restent largement en dessous de la limite des normes TCLP. Le traitement thermique à plus de 500°C augmente la densité de l'échantillon. Lorsque les REFIOM sont mélangés avec d'autres types de déchets tels que des MIOM ou du calcin, il est possible d'augmenter la résistance chimique et mécanique. Nous avons conclu que les trois matrices de stockages étudiées offrent de bonne perspective pour l'immobilisation du plomb et du cadmium / The overall objective of this thesis is to transform ultimate and hazardous waste containing heavy metals, into chemically stable mineral materials. The increasing municipal solid waste (MSW) generation is a problem ranging to global concern. Among various MSW treatment methods, incineration is a technology, which may provide an efficient and environmental friendly solution. Problem of this treatment is the production of fly ash. Fly ash may contain large amounts of toxic metal compounds and is considered as hazardous waste with obligation of final disposal into specialized landfills. Three types of materials for immobilization of lead and cadmium have been investigated: glass ceramics, sintered ceramics and geopolymers. We manage to synthetize a glass-ceramic based purely on the incinerated ashes and to decrease the volatilization during its production. Promising results have been obtained for Ca-Mg-Si-O bearing glass-ceramic with high sustainable incorporation of cadmium into crystalline structures and lead into an amorphous structure. Crystalline structure was evaluated being more resistant against acid attack because of its embedding into a glass matrix that generates a double protection. The future research should be done on possibility obtaining this phase by addition of commercial oxides into fly ash. Sintered ceramic investigated was based on Ba-Mg-Ti-O system. We obtained three mineral phases presented in SYNROC (hollandite, perovskite and rutile) where cadmium substituted the site of magnesium while lead occupied the site belonging to barium. The sintered ceramic is satisfactory in terms of toxic elements incorporation and of chemical and mechanical resistance. For production of resistant geopolymer from fly ashes, it is favorable to use ratio L/S =1.2 and drying at room temperature. It was observed that sintering affects the rate of structural reorganization with apparition of sodalite phase (Na4Si3Al3O12Cl), which consists of tunnels where heavy metals can be incorporated. Lead and cadmium stay mainly below the limit of TCLP standards. The heat treatment over 500°C increases density of the sample. When fly ash mixed with other types of waste such as bottom ash or waste glass powder, it is possible to obtain a more resistant. It was found that all three matrices are a good prospect for a stabilization technique with respect to the major pollutants lead (Pb) and cadmium (Cd)

Ce travail est basé sur la synthèse d’un liant aluminosilicaté de type géopolymère à partir de différentes argiles tunisiennes. Afin de comprendre les mécanismes de géopolymérisation, une première étape a concerné la caractérisation des matières premières argileuses par différentes méthodes d’analyses ainsi que leur comportement vis-à-vis du traitement thermique. La faisabilité des matériaux consolidés a été étudiée afin de comprendre le rôle des minéraux associés et la granulométrie de l’argile, en présence d’une solution de référence et de sources aluminosilicatées connues, sur les produits synthétisés. Afin d’identifier le rôle de la solution alcaline, de nouvelles formulations ont été élaborées et comparées aux précédentes en présence des argiles tunisiennes. Plusieurs techniques ont été réalisées pour évaluer les matériaux au cours de leur formation par spectroscopie infrarouge et après consolidation par diffraction des rayons X, microscopie électronique à balayage et analyse thermique. Leurs propriétés mécaniques ont été testées par compression. / This work is based on the synthesis of geopolymers from different Tunisian clays. In order to understand the geoplymerization mechanisms two steps are established. The first is relate to the characterization of the raw clays materials through different analyzes and their behavior with thermal treatment. The second involve around the study of geopolymers feasibility in order to understand the role of associated minerals and particle size, in the presence of a reference solution and aluminosilicate sources, on the synthesized products. To identify the role of the alkaline solution, new formulations have been developed and compared with previous one in the presence of Tunisian clays. Several techniques are used to characterize the materials during their formation: Infrared Spectroscopy, X ray diffraction, Scanning Electron Microscopy analysis and Thermal analysis. Their mechanical properties were tested by compression.

Presented thesis deals with monitoring of the properties of the interface between opening materials and geopolymer binder using three quartz and four non quartz opening materials. There is observed mainly the type of destruction of connective bridges. The theoretical part of the thesis briefly summarizes commonly used methods in foundries and monitors experience with implementation of geopolymers in different foundries. The practical part monitors shape of the grains of the chosen opening materials. There are writed down the results from the measurement of the bending strength and workability and there is observed the type of destruction of connective bridges.

La finalidad de este trabajo de investigación es producir cemento geopolímero para la elaboración de shotcrete o concreto lanzado a partir de la activación alcalina de relaves mineros, el cual pueda mejorar sus propiedades físicas y mecánicas, principalmente la resistencia a la compresión. Para llevar a cabo este proceso se utilizarán activadores alcalinos como el silicato de sodio (Na₂SiO₃) e hidróxido de sodio (NaOH). Por otro lado, para la validación de esta investigación se realizará el ensayo normalizado para la determinación de la resistencia a la compresión de concreto en muestras cilíndricas, con el objetivo de analizar las propiedades mecánicas alcanzadas por el shotcrete producido a base de cemento geopolímero de 12 y 15M de concentración de NaOH. Los principales resultados indican que es posible obtener concreto ecoeficiente con una resistencia a la compresión de hasta 19 MPa a los 28 días de curado. Asimismo, es una alternativa sostenible, porque utiliza los relaves y presenta una reducción de un 73% en emisiones de CO2 en comparación con la producción del cemento Portland. En síntesis, este trabajo se centra en desarrollar cemento geopolímero sostenible, el cual se utilizará como material para la elaboración de shotcrete. / The purpose of this research work is to produce geopolymer cement for the manufacture of shotcrete or shotcrete from the alkaline activation of mining tailings, which can improve its physical and mechanical properties, mainly its resistance to compression. To carry out this process, alkaline activators such as sodium silicate (Na₂SiO₃) and sodium hydroxide (NaOH) will be used. On the other hand, for the validation of this research, the standardized test will be carried out to determine the compressive strength of concrete in cylindrical samples, with the aim of analyzing the mechanical properties achieved by the shotcrete produced from 12 and 15M NaOH concentration. The main results indicate that it is possible to obtain eco-efficient concrete with a compressive strength of up to 19 MPa after 28 days of curing. It is also a sustainable alternative, because it uses tailings and presents a 73% reduction in CO2 emissions compared to the production of Portland cement. In summary, this work focuses on developing sustainable geopolymer cement, which will be used as a material to produce shotcrete. / Trabajo de investigación

Cette étude a pour but de documenter la relation qui existe entre les propriétés de transfert d’un matériau (répartition en taille de pores, porosité totale accessible à l’eau, saturation en eau), et son coefficient de diffusion. Pour cela, des matériaux ayant une porosité quasi-monomodale sont utilisés : verres Vycor® et géopolymères ; ainsi que des matériaux ayant une porosité complexe : pâtes de ciment CEM V. L’utilisation des verres Vycor® et des géopolymère permet de quantifier la diffusion gazeuse, en fonction de la saturation en eau, de matériaux ayant des pores de même dimension, ou du moins, de même ordre de grandeur. L’utilisation des pâtes de ciment permet quant à elle, de vérifier s’il est possible de décomposer le coefficient de diffusion d’un matériau dont la porosité est complexe, en un assemblage de coefficients de diffusion de matériaux dont la porosité est quasi-monomodale. Pour cela, on s’attachera à particulièrement à étudier l’impact de l’agencement du réseau poreux sur le coefficient de diffusion.Les travaux se décomposent en trois parties :• Etude des caractéristiques géométriques du réseau poreux des matériaux étudiés. Il sera utilisé la porosimétrie par intrusion de mercure, la porosimétrie à eau, des essais de sorption / désorption d’azote, et des essais de désorption d’eau.• Mesure expérimentale du coefficient de diffusion des matériaux, en fonction de leur humidité relative de stockage et de leur saturation en eau.• Modélisation du coefficient de diffusion des matériaux utilisés, et étude de l’impact de l’agencement de leur réseau poreux (tortuosité, connexion des pores entre eux) / This work documents the relationship that exists between the transfer properties of a material (pore size distribution, total porosity accessible to water, water saturation degree), and its diffusion coefficient. For this sake, materials having a quasi mono modal porosity are used: Vycor® glasses and geopolymers. We also use materials having a complex porosity: CEM V cement pastes. The use of Vycor® glasses and geopolymers allows quantifying the gas diffusion coefficient through materials having known pores size, as a function of their water saturation degree. The use of cement pastes allows checking if it is possible to decompose the diffusion coefficient of a complex porosity material, in an assembling of diffusion coefficients of quasi mono modal porosity materials. For this sake, the impact of pore network arrangement on the diffusion coefficient is studied in great details. This study is divided into three parts:• Measurement of the geometric characteristics of materials porous network by means of the mercury intrusion porosimetry, water porosimetry, isotherms of nitrogen sorption / desorption, and water desorption tests.• Measurement of the materials diffusion coefficient, as a function of their relative humidity storage, and their water saturation degree.• Modeling the diffusion coefficient of the materials, and study the impact of the pore network (tortuosity, pores connection)

Abstract This thesis examines three different areas of water treatment technology: the application of organic peracids in wastewater treatment; the removal of organic residues from boiler make-up water; and the use of geopolymers as sorbents. The main advantages of peracids as alternative wastewater disinfectants are their effective antimicrobial properties and high oxidation power, as well the absence of harmful disinfection by-products after their use. Performic, peracetic and perpropionic acids were compared in laboratory-scale disinfection, oxidation and corrosion experiments. From the techno-economical point of view, performic acid proved to be the most effective disinfectant against E. coli and fecal enterococci. However, in the bisphenol-A oxidation experiments, no advantages compared to hydrogen peroxide use were observed. It was also determined that corrosion rates on stainless steel 316L were negligible, while carbon steel seemed unsuitable in terms of corrosion for use with peracids even in low concentrations. Organic compounds in the boiler plant water-steam cycle thermally decompose and form potentially corrosive species. Activated carbon filtration was confirmed to be a suitable method for the removal of organic residue from deionized boiler make-up water. No significant differences in terms of treatment efficiency between commercial activated carbons were observed. However, acid washing as a pre-treatment reduced the leaching of impurities from new carbon beds. Nevertheless, a mixed-bed ion exchanger was required to remove leached impurities, such as silica and sodium. Geopolymers, or amorphous analogues of zeolites, can be used as sorbents in the treatment of wastewater. Metakaolin and blast-furnace-slag geopolymers showed positive potential in the treatment of landfill leachate (NH4+ ) and mine effluent (Ni, As, Sb). / Tiivistelmä Tämä väitöskirja käsittelee kolmea erillistä vedenkäsittelyteknologian osa-aluetta: orgaanisten perhappojen käyttöä jäteveden käsittelyssä, orgaanisten jäämien poistoa suolavapaasta kattilalaitoksen lisävedestä ja geopolymeerien sovelluksia vedenkäsittelysorbentteina. Orgaanisten perhappojen pääasialliset edut verrattuna kilpaileviin tekniikoihin ovat hyvä desinfiointiteho, korkea hapetuspotentiaali ja desinfioinnin sivutuotteiden muodostumattomuus. Permuurahais-, peretikka- ja perpropaanihapon vertailu osoitti permuurahaishapon olevan kemikaaleista tehokkain E. coli - ja enterokokkibakteerien inaktivoinnissa kustannus- ja teknisistä näkökulmista. Hapetuksessa, jossa käytettiin bisfenoli-A:ta malliaineena, ei kuitenkaan havaittu etua verrattuna edullisempaan vetyperoksidiin. Ruostumattoman teräksen (316L) pinnalla ei havaittu merkittävää korroosiota, kun taas hiiliteräs ei sovellu käytettäväksi perhappojen kanssa. Orgaaniset jäämät kattilalaitoksen vesi-höyrykierrossa hajoavat termisesti pienen moolimassan hapoiksi ja aiheuttavat korroosioriskin. Aktiivihiilisuodatuksen todettiin olevan soveltuva menetelmä orgaanisten jäämien poistoon lisävedestä. Aktiivihiililaatujen välillä ei havaittu merkittäviä eroja, mutta happopesu aktiivihiilen esikäsittelynä vähensi hiilestä liukenevien epäpuhtauksien määrää. Geopolymeerit ovat zeoliittien amorfisia analogeja ja niiden ioninvaihtokykyä voidaan hyödyntää vedenkäsittelysovelluksissa. Metakaoliini- ja masuunikuonapohjaisten geopolymeerien todettiin olevan lupaavia materiaaleja malliliuosten, kaatopaikan suotoveden ja kaivoksen purkuveden käsittelyssä poistettaessa ammoniumia, nikkeliä, arseenia ja antimonia.

Abstract The main aim of the European Union’s waste legislation and the corresponding Finnish waste legislation is to reduce the production of waste. Further, the aims of the European Union’s growth strategy are to reduce the production of greenhouse gases, increase the use of renewable energy, and improve energy efficiency. According to the renewed Waste Tax Act, a waste tax has to be paid on all fly ashes that are deposited in landfills in Finland. A large amount of wood- and peat-based fly ashes are formed annually in Finland, and the amount is likely to increase in the future due to the increasing use of renewable energy. Previously, these ashes have mainly been deposited in industrial landfills, but the need to utilize the fly ashes has increased recently due to changes in waste legislation. In this thesis, several issues related to the utilization of wood- and peat-based fly ash were studied, with the general objective of improving the utilization potential of such ashes. As the first stage of this research, the suitability of willow ash for use as a fertilizer was studied. Willow ash would be well suited for use as a fertilizer due to its very high nutrient content. However, cadmium, a heavy metal, was found to be enriched in the ashes of the studied willow species. Due to this, special attention should be paid when choosing willow species for energy production. In the second stage of the research, the possibility of improving the strength development of wood- and peat-based fly ashes, as well as the possibility of stabilizing fly ash containing high amounts of heavy metals via the addition of cement and/or alkali activation, was investigated. Strength development was found to be dependent on the amount of reactive calcium and the ratio between that amount of reactive calcium and the sum of the reactive silicon, aluminum, and sulfur (Ca/(Si + Al + S)). The studied methods performed well in terms of stabilizing barium, copper, lead, and zinc. During the next stage, the effect of different chemical digestion methods, which are regulated by the Finnish waste legislation, on the utilization potential of fly ash was studied. The digestion method had a significant impact on the results of the potassium content analysis, which could affect the possibility of using fly ash as a fertilizer. As the final stage of the research, the co-granulation of ash with sewage sludge and lime was studied. From a technical point of view, the co-granulation was successful, although the compressive strength of the granules was low. Additionally, an insufficient nitrogen content was achieved with a sludge addition of 20-40 weight%. / Tiivistelmä Euroopan unionin jätelainsäädännön ja sitä vastaavan suomalaisen lainsäädännön tavoitteena on ehkäistä jätteiden muodostumista. Euroopan Unionin kasvustrategian tavoitteena on vähentää kasvihuonekaasupäästöjä, lisätä uusiutuvan energian käyttöä ja parantaa energiatehokkuutta. Uudistetun jäteverolain mukaan kaikista kaato-paikoille sijoitetuista lentotuhkista tulee Suomessa maksaa jäteveroa. Suomessa puu- ja turveperäisiä lentotuhkia muodostuu vuosittain suuria määriä ja määrä tulee vielä kasvamaan uusiutuvan energiankäytön lisääntyessä. Aiemmin nämä tuhkat ovat päätyneet pääasiassa läjitykseen teollisuuden kaatopaikoille, mutta muuttuneen jätelainsäädännön seurauksena tarve hyödyntää lentotuhkia on lisääntynyt. Tässä väitöstyössä tutkittiin puu- ja turveperäisten tuhkien hyödyntämiseen liittyviä kysymyksiä. Työn yleistavoitteena oli parantaa tuhkien hyödyntämis-mahdollisuuksia. Tutkimuksen ensimmäisessä vaiheessa tutkittiin pajutuhkan soveltuvuutta lannoitteeksi. Pajutuhka soveltuisi hyvin lannoitteeksi erittäin hyvien ravinne-pitoisuuksien ansiosta. Raskasmetalleista kadmiumin havaittiin kuitenkin rikastuvan tutkittujen pajulajien tuhkiin. Tähän tulisi kiinnittää erityishuomiota, kun pajulajeja valitaan energiantuotantoa varten. Tutkimuksen toisessa vaiheessa selvitettiin mahdollisuutta parantaa turpeen ja puun lentotuhkien lujittumista sekä raskasmetallipitoisen lentotuhkan stabiloimista sementtilisäyksen ja/tai alkaliaktivoinnin avulla. Lujuuden kehitys riippui reaktiivisen kalsiumin määrästä sekä reaktiivisen kalsiumin määrän ja reaktiivisten piin, alumiinin ja rikin määrien summan välisestä suhteesta (Ca/(Si + Al + S)). Tutkitut menetelmät toimivat hyvin bariumin, kuparin, lyijyn ja sinkin stabiloinnissa. Seuraavassa vaiheessa selvitettiin Suomen lainsäädännössä määritettyjen kemiallisten hajotusmenetelmien vaikutusta tuhkan hyödyntämispotentiaaliin. Hajotusmenetelmällä oli suuri merkitys kaliumin pitoisuutta määritettäessä, mikä voi vaikuttaa lentotuhkan hyödynnettävyyteen lannoitteena. Viimeisessä vaiheessa tutkittiin tuhkan yhteisrakeistusta lietteen ja kalkin kanssa. Teknisesti yhteisrakeistus onnistui hyvin, mutta rakeiden puristuslujuus oli alhainen. Lisäksi 20 - 40 paino% lietelisäyksellä ei rakeisiin saatu riittävän korkeaa typpipitoisuutta.

Preparation of geopolymer composites from industrial wastes of energy power stations and metalurgy.

This thesis explores the posibility of using of foundry filter ash for production of inorganic composite materials, that could be used primary in the construction industry. The thesis is divided into theoretical and experimental section, where theoretical section contain literature review of used materials and the experimental section summarizes the results of laboratory tests performed on tested mixture based on portland and alumina cement with various content of foundry filter ash. For comparison was also used another foundry waste - foundry sand. Prepared test bodies with dimension of 40 x 40x 160 mm was subjected to mechanical strength tests and the influence of amount of foundry waste on the strenght of the prepared mixtures was monitored. Next the thesis deals with possibilities of alkaline activation of foundry waste, where sodium water glass, sodium hydroxide and commercially supplied baucis L 160 component B were used as alkaline activator. These test mixtures were also subjected to mechanical strenght tests and the influence of amount of foundry waste on the strenght was observed too. The analysis of input materials were performed by XRF, TG – DTA – EGA and XRD powder diffraction methods. All strength tests were tested by testing equipment desttest 4310.

In der vorliegenden Arbeit sind One-part Geopolymere, hergestellt aus drei verschiedenen Silikatquellen und Natriumaluminat, mit Hilfe der Festkörper-Kernspinresonanz-Spektroskopie (NMR) charakterisiert worden. Die Methode erlaubt neben der Untersuchung von kristallinen auch die von amorphen Phasen, was einen der Hauptvorteile der NMR gegenüber der Röntgendiffraktometrie darstellt. Unter der Verwendung von Reisschalenasche konnte ein vollständig amorphes Material hergestellt werden, während Microsilica und ein siliciumreiches Nebenprodukt aus der Chlorsilan-Herstellung zur Bildung von Geopolymer-Zeolith-Kompositen führte. Zeolith Na-A ist bei diesen der kristalline Hauptbestandteil und je nach Ausgangszusammensetzung variiert die Stoffmenge dieser Phase. Die Bildung von Zeolithen ist für herkömmliche Two-part Geopolymere mit kleinem Si/Al-Verhältnis hinreichend bekannt hier für One-part Geopolymere untersucht worden. Verschiedene Methoden der NMR-Spektroskopie wurden eingesetzt. So konnten mehrere Wasser-Spezies in den Geopolymer-Zeolith-Kompositen durch die Verwendung von Einzelpuls-, Kreuzpolarisations- und rotor-synchronisierten Spin-Echo-Experimenten unterschieden werden. Wiederholungsmessungen nach mehr als 500 Tagen konnten keine relevanten Alterungseffekte nachweisen und bestätigten die chemische Stabilität der Komposite. Weiterführend sind REDOR- (rotational-echo double-resonance) und TRAPDOR (transfer of population in double resonance) MAS NMR Experimente durchgeführt worden. Die beiden Faujasith-ähnlichen Zeolithe Na-X und Na-Y wurden als Modellsubstanzen genutzt, um das 29Si-27Al TRAPDOR-Verhalten von Q4(mAl)-Einheiten in Alumosilikaten zu analysieren. Zusätzliche quantitative 29Si MAS NMR Messungen (qNMR) konnten den Reaktionsgrad der Silikatquellen bestimmen und diesen in Relation zu den mechanischen Eigenschaften der Materialien setzen. Durch Kombination der erzielten Ergebnisse konnte der Reaktionsprozess von One-part Geopolymeren illustriert werden. / One-part geopolymers produced from three different silica sources and sodium aluminate were characterized using solid-state nuclear magnetic resonances (NMR) spectroscopy. The method allows the investigation of crystalline as well as amorphous phases in the materials. The latter is one of the main advantages of NMR over X-ray diffraction. The use of rice husk ash produced a fully amorphous material. On the contrary, microsilica and a silica-rich industrial byproduct from chlorosilane production led to the formation of geopolymer-zeolite composites. Zeolite Na-A was found as major crystalline phase in these composites. Depending on the starting composition, the relative amounts of this phase varied. The formation of zeolites is well known for conventional two-part geopolymers with low Si/Al-ratios and was investigated in this study for one-part mixes. Different solid-state NMR spectroscopic methods were applied. Various water species could be distinguished in the composites using single pulse, cross polarisation and rotor-synchronised spin echo measurements. Measurements after more than 500 days revealed no significant aging effects of the composites, which confirm their chemical stability. REDOR (rotational-echo double-resonance) and TRAPDOR (transfer of population in double resonance) MAS NMR experiments were conducted. Two faujasite-type zeolites - Na-X and Na-Y - were used as model systems to analyse the 29Si-27Al TRAPDOR behaviour of different Q4(mAl) sites in alumosilicates. Additionally, quantitative 29Si MAS NMR measurements were used to investigate the degree of reaction of the silica feedstocks, showing relations to the mechanical properties of the hardened materials. Combining the findings gained in the present study, the reaction process of one-part geopolymers could be illustrated.