Fluoriditasetarkastelu ja päästöjen hallinta ferrokromi- ja terästeollisuudessa

Työn alkuosassa kartoitettiin AvestaPolarit –yhtiöiden Tornion tehtaiden keskeiset fluoridilähteet kuten fluspaatti, valukuonat, valupulverit ja fluorivetyhappo. Valupulverien ja kuonien haihtumis- ja liukoisuuskäyttäytymistä valaistiin kotimaisten ja kansainvälisten tutkimusten avulla. Tutkimustuloksia sovellettiin pääpiirteittäin Tornion tehtaiden tilanteeseen ottamalla huomioon tekijät, jotka saattoivat lieventää tai vahvistaa fluoridien vaikutusta ympäristöön. Yleisesti fluoridien ympäristö- ja terveysvaikutukset arvioitiin vähäisiksi. Työn kokeellisessa osassa määritettiin Tornion tehtaiden ferrokromitehtaan, terässulaton, kuumavalssaamon ja kylmävalssaamon fluoriditaseet. Jokaisen osastojen syötteiden fluoridipitoisuudet selvitettiin tuottajien ilmoittamien tuotekoostumuksien, spesifikaatioiden ja fluoridianalyysien perusteella. Fluoridien kokonaismäärät laskettiin jokaiselle syötteelle ja ne suhteutettiin kunkin osaston vuoden 2001 tuotantotasoon. Tasetarkastelussa suurimpina fluoridisyötteinä nousivat odotetusti esiin terässulaton käyttämä kuonanmuodostaja-aine fluspaatti (CaF2) ja kylmävalssaamon peittaushappo, 70 prosenttinen fluorivetyhappo (HF). Lisäksi muita merkittäviä syötteitä olivat kylmävalssaamon käyttämä kalkkipitoinen sekakuona ja ferrokromitehtaan sulatuskoksi. Tuotoksien eli päästöjen fluoridipitoisuudet saatiin selville päästömittauksin. Jätevesistä otettiin pääosin viikoittaisia kokoomanäytteitä, jotka analysoitiin tehtaan laboratoriossa. Kaasumaiset tuotokset oli määritetty kertamittauksien perusteella. Kiinteiden tuotoksien eli sakkojen ja kuonien fluoridimittaukset suoritettiin 3 sulatuksen kuonanäytteistä ja sakan vuosinäytteestä. Tuotoksista suurimmat ominaispäästökertoimet olivat juuri terässulaton AOD-konvertterin ja senkkauunin kuonilla ja kylmävalssaamon neutraloidulla regenerointisakalla ja neutralointisakoilla. Näistä ei aiheutunut varsinaista päästöä lähiympäristöön, koska sakat ja kuonat loppusijoitetaan tehtaan kaatopaikalle tai niitä käytetään liukenemattomassa muodossa. Tornion tehtaiden fluoridisyötteiden ja -tuotoksien mittausepätarkkuudet vaikuttivat fluoriditaseeseen. Ferrokromitehtaan fluoridisyötteet olivat kokonaismäärältään selvästi suurempia kuin tuotokset. Terässulaton fluoriditaseen tuotokset olivat suurempia kuin syötteet ja kylmävalssaamon syötteet sekä tuotokset olivat karkeasti arvioiden samaa suuruusluokkaa. Kuumavalssaamon fluoridisyötteet ja -tuotokset olivat mitättömiä. Fluoriditaseen epävarmuustekijöitä voidaan vähentää suorittamalla esimerkiksi useita fluoridimittauksia kaasumaisista päästöistä.

Commodity Price Driven Risk Management from Viewpoint of High Grade Steel Alloys

The study of price risk management concerning high grade steel alloys and their components was conducted. This study was focused in metal commodities, of which nickel, chrome and molybdenum were in a central role. Also possible hedging instruments and strategies for referred metals were studied. In the literature part main themes are price formation of Ni, Cr and Mo, the functioning of metal exchanges and main hedging instruments for metal commodities. This section also covers how micro and macro variables may affect metal prices from the viewpoint of short as well as longer time period. The experimental part consists of three sections. In the first part, multiple regression model with seven explanatory variables was constructed to describe price behavior of nickel. Results were compared after this with information created with comparable simple regression model. Additionally, long time mean price reversion of nickel was studied. In the second part, theoretical price of CF8M alloy was studied by using nickel, ferro-chrome and ferro-molybdenum as explanatory variables. In the last section, cross hedging possibilities for illiquid FeCr -metal was studied with five LME futures. Also this section covers new information concerning possible forthcoming molybdenum future contracts as well. The results of this study confirm, that linear regression models which are based on the assumption of market rationality, are not able to reliably describe price development of metals at issue. Models fulfilling assumptions for linear regression may though include useful information of statistical significant variables which have effect on metal prices. According to the experimental part, short futures were found to incorporate the most accurate information concerning the price movements in the future. However, not even 3M futures were able to predict turning point in the market before the faced slump. Cross hedging seemed to be very doubtful risk management strategy for illiquid metals, because correlations coefficients were found to be very sensitive for the chosen time span.

Magnetic and transport properties of II-V diluted magnetic semiconductors doped with manganese and nickel

This thesis is devoted to investigations of three typical representatives of the II-V diluted magnetic semiconductors, Zn1-xMnxAs2, (Zn1-xMnx)3As2 and p-CdSb:Ni. When this work started the family of the II-V semiconductors was presented by only the compounds belonging to the subgroup II3-V2, as (Zn1-xMnx)3As2, whereas the rest of the materials mentioned above were not investigated at all. Pronounced low-field magnetic irreversibility, accompanied with a ferromagnetic transition, are observed in Zn1-xMnxAs2 and (Zn1-xMnx)3As2 near 300 K. These features give evidence for presence of MnAs nanosize magnetic clusters, responsible for frustrated ground magnetic state. In addition, (Zn1-xMnx)3As2 demonstrates large paramagnetic response due to considerable amount of single Mn ions and small antiferromagnetic clusters. Similar paramagnetic system existing in Zn1-xMnxAs2 is much weaker. Distinct low-field magnetic irreversibility, accompanied with a rapid saturation of the magnetization with increasing magnetic field, is observed near the room temperature in p- CdSb:Ni, as well. Such behavior is connected to the frustrated magnetic state, determined by Ni-rich magnetic Ni1-xSbx nanoclusters. Their large non-sphericity and preferable orientations are responsible for strong anisotropy of the coercivity and saturation magnetization of p- CdSb:Ni. Parameters of the Ni1-xSbx nanoclusters are estimated. Low-temperature resistivity of p-CdSb:Ni is governed by a hopping mechanism of charge transfer. The variable-range hopping conductivity, observed in zero magnetic field, demonstrates a tendency of transformation into the nearest-neighbor hopping conductivity in non-zero magnetic filed. The Hall effect in p-CdSb:Ni exhibits presence of a positive normal and a negative anomalous contributions to the Hall resistivity. The normal Hall coefficient is governed mainly by holes activated into the valence band, whereas the anomalous Hall effect, attributable to the Ni1-xSbx nanoclusters with ferromagnetically ordered internal spins, exhibits a low-temperature power-law resistivity scaling.

De metallorum quamvis infimo, omnium tamen fere utilissimo, ferro et chalybe

Invocatio: KREIKKAA Alpha, omega.

Amicitia magnetis cum ferro

Dedicatio: Johannes Keckonius, Matthias Rungius, Ericus Thomaeus, Gustavus Salonius.

Ammonia regeneration in nickel matte chloride leaching

Ammonia can be used as a pH controller in chloride-based metal recovery processes. In chloride conditions, ammonia reacts to ammonium chloride which can be regenerated back to ammonia with lime. Although the regeneration process itself has been known for a long time, the concentrations, non-reacting species, conditions, and even goals are different when comparing the ammonia regeneration process in different industries. The main objective of this thesis was to study the phenomena, equipment, and challenges in ammonia regeneration in the nickel process and to make a preliminary process design. The study concentrated on the regeneration and recovery units. The thesis was made by process simulation and laboratory tests using the current processes as initial information. The results were combined from all of the information obtained during the studies to provide a total process solution, which can be used as a basis when designing an ammonia regeneration process to be used in industry. In particular, it was possible to determine ammonia recovery with a stripping column and the achievement of the desired ammonia water product within the scope of this thesis. The required mass flows and process conditions were also determined. The possible challenges and solutions or further studies to overcome them were provided as well to ease the prediction and design of the ammonia regeneration process in the future. On the basis of the results of this thesis, the ammonia regeneration process can be developed further and implemented in the nickel chloride leaching process.