Avfallsförbränning är process som producerar fjärrvärme och el som Tekniska Verken i Linköping AB levererar till närliggande områden i Linköping Kommun. Flygaska är en restprodukt som produceras vid rökgasreningen som krävs vid avfallsförbränningen. Flygaskan från avfallsförbränningen består i huvudsak av kalk, salter, svavelföreningar och aktivt kol, men innehåller också låga halter av skadliga ämnen som dioxiner och metaller. De höga halterna av lakbara ämnen som metaller och salter, orsakar att flygaskan inte får deponeras inom Sverige på grund av lakningskriterier för deponering, vilket gör att askan fraktas för behandling till Norge. Flygaskan som Tekniska Verken i Linköping AB producerar som restprodukt omhändertas av norska företaget NOAH AS som fraktar flygaskan till Langøya där den stabiliseras, vilket medför att de skadliga ämnena elimineras från samhällets resursomlopp. Examensarbetet är viktigt för att Tekniska Verken i Linköping AB ska kunna stabilisera och utvinna nyttiga ämnen från sin flygaska så att mindre internationella transporter krävs och fler ämnen stannar kvar inom samhällets resursomlopp för en ökad cirkularitet. Syftet med denna studie är att undersöka om Tekniska Verken i Linköping AB kan stabilisera minska urlakningshalterna ur sin flygaska med hjälp av befintliga resurser från processer inom företaget. Examensarbetet har fokuserat på att tvätta flygaska under basiska förhållanden med hänsyn till varierande parametrar som: tid under omrörning, temperatur och tvättmängd vatten. Examensarbetet använder sig av kemisk laboration, kemometri och kemisk analysteknik för att undersöka syftet. Resultatet visar att ämnena bly, klorid och zink kan tvättas ut ur flygaskan med vatten under basiska förhållanden för att minska urlakning vid deponi. Det leder till att Tekniska Verken i Linköping AB har en potential att kunna stabilisera och utvinna nyttiga ämnen från sin flygaska i framtiden. / Waste incineration is a process which produce district heating and electricity that Tekniska Verken i Linköping AB delivers to nearby areas in Linköping Municipality. Fly ash is a residual product which is produced during the flue gas purification needed in a waste incineration process. The fly ash from waste incineration mainly consists of lime, salts, sulfur compounds and activated carbon, but also contains low levels of harmful substances such as dioxins and metals. The high concentrations of leachable substances such as metals and salts prevent the fly ash from being landfilled in Sweden because of leaching criteria’s, therefore the fly ash is transported for treatment in Norway. The fly ash that Tekniska Verken i Linköping AB produces as a residual product is treated by the Norwegian company NOAH AS who transports the fly ash to Langøya island where it is stabilized, which eliminates the harmful substances from society’s resource cycle. This thesis is important for Tekniska Verken i Linköping AB so they can stabilize and extract useful substances from their fly ash so less international transport is needed and more vital substances stay within society’s resource cycle for increased circularity. The aim of this thesis is to examine whether Tekniska Verken i Linköping AB lower the leaching concentrations from their fly ash using existing resources from processes within the company. This thesis has focused on washing fly ash with consideration to various parameters such as stirring time, temperature, and amount of washing water. This thesis makes use of chemical laboratory work, chemometrics and chemical analysis techniques to examine the aim. The results show that the substances chloride, lead and zink can be washed out of the fly ash with water under basic condition to reduce leaching concentrations at the landfill. This shows that Tekniska Verken i Linköping AB has the potential to stabilize and extract useful substances from their fly ash in the future. / <p>Fysikhuset</p>

Expansion or swelling behavior of expansive soil has always created problems in the field of geotechnical engineering. When any construction has been carried out on expansive soil without pre-knowledge of their properties under various environmental conditions, the damage is severe. One of the methods to find out swelling potential of expansive soil is the expansive index (EI). The present study investigates the reduction of EI for the two commercially available expansive soils i.e., kaolinite and bentonite when mixed with Ottawa sand and Class C fly ash. The percentages of Ottawa sand and Class C fly ash mixed with kaolinite and bentonite were 0 to 50% by weight. The results show that there is a significant reduction in the swelling properties of expansive soil with the addition of Ottawa sand and Class C fly ash. The reduction in expansive index ranged approximately from 10 to 50% and 4 to 49% for kaolinite and bentonite, respectively. Also the maximum swelling pressure of kaolinite and bentonite soil decreased approximately 93% and 64%, respectively with the addition of various percentages of Ottawa sand and Class C fly ash. These results help to identify the swelling potential and swelling pressure of expansive soil with different percentages of sand and fly ash which will be beneficial to the geotechnical engineer. Standard index properties test such as liquid limit, plastic limit and shrinkage limit test was conducted to see the characteristic of expansive soil when mixed with less expansive sand and Class C fly ash. Also, for these expansive soils one dimensional (1-D) consolidation characteristics was studied with sand and Class C fly ash mixtures and the results were compared with pure kaolinite and bentonite soil. Pre-consolidation (Pc) behavior, compression index (Cc) and recompression or swelling index (Cs) properties were also studied for the different percentages of sand and Class C fly ash with expansive soil.

Σκοπός της παρούσας εργασίας είναι ο προσδιορισμός της ρύπανσης των ιζημάτων του Αλφειού ποταμού από στερεά σωματίδια, που προέρχονται από την εξόρυξη και την καύση του λιγνίτη Μεγαλόπολης. Βασικό αντικείμενο έρευνας αποτέλεσε η μικροσκοπική εξέταση του οργανικού μέρους, που είναι παρόν στα ιζήματα του Αλφειού ποταμού και η οργανική γεωχημική εξέταση επιλεγμένων δειγμάτων για την ανίχνευση πολυκυκλικών αρωματικών υδρογονανθράκων (polycyclic aromatic hydrocarbons, PAHs). Επιπλέον σε δείγματα λιγνίτη, ιπτάμενης τέφρας, τέφρας εστίας και τέφρας απόθεσης από το Λιγνιτικό Κέντρο Μεγαλόπολης πραγματοποιήθηκε μία σειρά εργαστηριακών προσδιορισμών, που περιέλαβε προσεγγιστική και άμεση ανάλυση, ανθρακοπετρογραφική εξέταση του λιγνίτη, καθώς και ορυκτολογικές και στοιχειακές αναλύσεις. Με βάση τις περιεκτικότητες του λιγνίτη και των παραπροϊόντων της καύσης του σε κύρια στοιχεία και ιχνοστοιχεία μπορεί να εκτιμηθεί η κινητικότητά τους κατά την καύση και το κατά πόσο αυτά διαφεύγουν στο περιβάλλον ή παραμένουν στο χώρο καύσης. Τα πιο ευκίνητα στοιχεία, που περιέχονται στο λιγνίτη Μεγαλόπολης, είναι τα Ba, Li, Mg, Rb και Sn, τα οποία μαζί με τα As και Pb, που συμμετέχουν στο λεπτόκοκκο τμήμα της ιπτάμενης τέφρας αποτελούν δυνητικούς ρυπαντές. Αντίθετα τα στοιχεία Ge, Mn, Th, Ti και Y είναι περιβαλλοντικά λιγότερο επικίνδυνα, καθώς συμμετέχουν στο τμήμα των παραπροϊόντων, που παραμένει στην τέφρα των ατμοηλεκτρικών σταθμών. Από μικροσκοπική παρατήρηση προέκυψε ότι το οργανικό υλικό, που είναι παρόν στα συγκεκριμένα ιζήματα αποτελείται κατά 78,4% κ.ό. από ανθρωπογενή σωματίδια, ενώ το υπόλοιπο 21,6% αποτελείται από φρέσκα φυτικά υπολείμματα. Το 81,5% κ.ό. του συνόλου των ανθρωπογενών σωματιδίων αποτελείται από κόκκους λιγνίτη και το 19,5% κ.ό. συνίσταται από εξανθρακώματα, που μεταφέρονται με την ιπτάμενη τέφρα και αποτίθενται στα ιζήματα. Τα ανθρακούχα σωματίδια στα ιζήματα του Αλφειού αντικατοπτρίζουν την ανθρακοπετρογραφική σύσταση του λιγνίτη Μεγαλόπολης, από την οποία εξαρτάται επίσης και η μορφή των εξανθρακωμάτων. Το επίπεδο των συγκεντρώσεων PAHs στα ιζήματα του Αλφειού είναι σχετικά χαμηλό (10-100 ng/g), ωστόσο η καύση του λιγνίτη συνεισφέρει σε ποσοστό 39,5% στην εκπομπή τους, ενώ το 23,5% προέρχεται από τον ίδιο το λιγνίτη. Η συμμετοχή των PAHs στα συγκεκριμένα ιζήματα φαίνεται να σχετίζεται ως ένα βαθμό με την παρουσία εξανθρακωμάτων, γεγονός που υποδεικνύει διεργασίες ρόφησης. Με την παρούσα εργασία αποδεικνύεται ότι η Οργανική Πετρολογία σε συνδυασμό με δεδομένα Οργανικής και Ανόργανης Γεωχημείας, μπορεί να αποτελέσει σημαντικό εργαλείο σε ό,τι αφορά στον προσδιορισμό της ρύπανσης ιζημάτων και εδαφών από την εκμετάλλευση γαιανθράκων. / The main target of the present study is the assessment of the contamination degree of Alfeios River sediments with solid particles deriving from mining and combustion of Megalopolis lignite. The objectives of the study were the microscopical examination of the organic matter present in these sediments, as well as the determination of the concentration of Polycyclic Aromatic Hydrocarbons (PAHs) in selected samples. Additionally in lignite, fly ash, bottom ash and ash deposit samples, were conducted a string of analyses including, proximate and ultimate analyses along with mineralogical and elemental determinations. The mobility of major and trace elements during the combustion of lignite can be estimated according to the concentration of these elements in bulk lignite and its combustion by-products. Based on these results the most mobile and thus more environmentally "sensitive" elements in Megalopolis lignite are As, Ba, Li, Mg, Pb, Rb and Sn, while Ge, Mn, Th, Ti and Y are the less mobile elements participating mostly in bottom ash. From the microscopical study of the organic matter present in Alfeios sediments it is evident that it consists of 78,4% of anthropogenic particles, while the remaining 21,6% consists of fresh plant remnants. The 81,5% of the anthropogenic particles consists of lignite particles deriving from mining and transportation processes and the remaining 19,5% consists of char particles transported and deposited as portion of the fly ash produced in Megalopolis Lignite Centre. The coal-petrographic composition of lignite particles is similar to the coal-petrographic composition of Megalopolis lignite. The latter is also responsible for the shape and texture of the char particles. The PAHs concentration level is rather low, ranging from 10-100 ng/g. Nevertheless lignite combustion along with the Megalopolis lignite itself are the main emission sources of such compounds accounting for 39,5% and 23,5% respectively. The presence of PAHs is related to the presence of char particles, probably via sortion procedures. The results of this study show that Organic Petrology can be a useful tool in environmental science and particularly in the field of contamination of soils and sediments from coal exploitation, if combined with Organic and Inorganic Geochemical data.

Pozzolanic reactions play a key role in improving the compressive strengths of compacted fly ash-lime specimens. Based on studies performed with cement amended fly ash (FA), activation of fly ash-lime pozzolanic reactions should accelerate the rate of strength development and mobilize larger compressive strengths facilitating improved engineering performance of fly ash amended materials. Further, use of phosphogypsum (PG) is a cause of environmental concern as the material is acidic (pH < 3.0) and contains considerable amounts of fluoride (0.86%). The main research objectives of the thesis are to activate lime-fly ash reactions by thermal and chemical activation process and examine the efficacy of fly ash pozzolanic reactions in controlling fluoride release by phosphogypsum. A comprehensive laboratory experimental program was performed to examine the influence of curing temperature (thermal activation) and calcined PG addition (chemical activation) on lime-fly ash reactions. The kinetics of fly ash-lime reactions are examined by monitoring the reacted lime content as function of curing period and temperature. The influence of variations in fly ash/lime content and dry density on the compressive strength developed by specimens is evaluated. The thermodynamic parameters for the fly ash-lime (FA-L) reactions have been delineated. Fly ash-lime-phosphogypsum (FA-L-G) mixes in slurry and compacted states were monitored for fluoride released as function of curing period The influence of curing temperature in activating fly ash-lime reactions is first examined. Specimens were cured at 25°C (termed RTC or room temperature cured) and at 80° (termed SC or steam cured) to understand thermal activation of fly ash-lime reactions. The rate of lime consumption by SC specimens classified as 2 stage process. The robust increase during stage 2 of steam curing suggested that the lime-solidification reactions did not reach equilibrium even after 4 days of curing at the elevated temperature. While only 3.1 to 3.3 % of added lime was consumed after 28 days of curing at room temperature, much larger amounts of lime ( 8.6-9.3%) were consumed after 4 days of steam-curing. Further, the lime-fly ash reactions were accelerated by 6 to 7 folds on curing the specimens at elevated temperature. The results indicated that activation of lime-fly ash reactions by curing at elevated temperature besides accelerating the rate of strength development also facilitated development of larger strength. Analysis of the free energy change values (ΔG°) indicated that the lime solidification reaction alters from dis-favored (less spontaneous) to favoured (spontaneous) state on curing at 80oC. The positive ΔH° (enthalpy change) values for the fly ash-lime reactions indicated that the reactions are endothermic in nature and are facilitated by increase in curing temperature. Gypsum activation was achieved by addition of 2.5 to 5% calcined phosphogypsum to fly ash lime mixes and curing the compacted specimens at room temperature (FA-L-G specimens). The rate of lime consumption by FA-L-G specimens appeared to be three stage process. The mass of lime consumed by FA-L-G specimens was about 1.5 to 3 folds higher than values of the RTC and SC specimens. Additional lime is consumed by FA-L-G specimens in ettringite formation. A similarity existed between rate of lime consumed and rate of strength developed by the FA-L-G specimens. It is proposed that besides lime solidification reactions, densification of the matrix by filling up of voids by fine gypsum particles and compaction of matrix by the growth of ettringite crystals also contribute to compressive strength of FA-L-G specimens; this additional mechanism of strength development accounts for their higher compressive strength in comparison to the SC and RTC specimens despite similar initial lime addition values. The trend of results suggests that activation of FA-L reactions by calcined PG addition is more effective than steam curing. Comparison of ΔG° values of RTC, SC and FA-L-G specimens revealed that the spontaneity of the lime solidification reactions is least for RTC specimens and improves with addition of phosphogypsum and further improves on curing at elevated temperature. Fly ash-lime pozzolanic reactions substantially reduced the fluoride released from the FA-L-G specimens. The marked reduction in fluoride released by PG amended with fly ash and lime is ascribed to entrapment of PG particles in the cemented matrix formed by fly ash-lime pozzolanic reactions together with consumption of fluoride in formation of insoluble fluoride bearing compounds. The thesis brings out that activation of fly ash-lime reactions leading to quicker and larger compressive strength development is achieved by curing the compacted fly ash-lime specimens at 80°C for 24 hr or by addition of 2.5 to 5% of calcined PG to fly ash-lime mix and curing the compacted specimens at room-temperature. As larger strengths are developed by PG addition than by curing at 80oC, it is recommended that FA-L-G technique be adopted for manufacture of building materials in the civil engineering industry. This technique is also sustainable as it does not require energy for heating which is needed in the steam-curing technique.

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