Electrochemical Treatment of Wastewaters

Electrocoagulation is a process in which wastewater is treated under electrical current. Coagulant is formed during the process through the metal anode dissolution to respective ions which react with hydroxyl ions released in cathode. These metal hydroxides form complexes with pollutant ions. Pollutants are removed among metal hydroxide precipitates. This study was concentrated on describing chemistry and device structures in which electrochemical treatment operations are based on. Studied pollutants were nitrogen compounds, sulphate, trivalent and pentavalent arsenic, heavy metals, phosphate, fluoride, chloride, and bromide. In experimental part, removal of ammonium, nitrate, and sulphate during electrochemical treatment was studied separately. Main objective of this study was to find suitable metal plate material for ammonium, nitrate, and sulphate removal, respectively. Also other parameters such as pH of solution, concentration of pollutant and sodium chloride, and current density were optimized. According to this study the most suitable material for ammonium and sulphate removal by electrochemical treatment was stainless steel. Respectively, iron was the optimum material for nitrate removal. Rise in the pH of solution at the final stage of electrochemical treatment of ammonium, nitrate, and sulphate was detected. Conductivities of solutions decreased during ammonium removal in electrochemical processes. When nitrate and sulphate were removed electrochemically conductivities of solutions increased. Concentrations of residual metals in electrochemically treated solutions were not significant. Based on this study electrochemical treatment processes are recommended to be used in treatment of industrial wastewaters. Treatment conditions should be optimized for each wastewater matrix.

Comparison of Biomass Gasification Technologies for Natural Gas Substitution in Iron Ore Pelletizing Plants

The iron ore pelletizing process consumes high amounts of energy, including nonrenewable sources, such as natural gas. Due to fossil fuels scarcity and increasing concerns regarding sustainability and global warming, at least partial substitution by renewable energy seems inevitable. Gasification projects are being successfully developed in Northern Europe, and large-scale circulating fluidized bed biomass gasifiers have been commissioned in e.g. Finland. As Brazil has abundant biomass resources, biomass gasification is a promising technology in the near future. Biomasses can be converted into product gas through gasification. This work compares different technologies, e.g. air, oxygen and steam gasification, focusing on the use of the product gas in the indurating machine. The use of biosynthetic natural gas is also evaluated. Main parameters utilized to assess the suitability of product gas were adiabatic flame temperature and volumetric flow rate. It was found that low energy content product gas could be utilized in the traveling grate, but it would require burner’s to be changed. On the other hand, bio-SGN could be utilized without any adaptions. Economical assessment showed that all gasification plants are feasible for sizes greater than 60 MW. Bio-SNG production is still more expensive than natural gas in any case.

Manifestation of the pairing symmetry in the vortex core structure in iron-based superconductors

The superconducting gap is a basic character of a superconductor. While the cuprates and conventional phonon-mediated superconductors are characterized by distinct d- and s-wave pairing symmetries with nodal and nodeless gap distributions respectively, the superconducting gap distributions in iron-based superconductors are rather diversified. While nodeless gap distributions have been directly observed in Ba1–xKxFe2As2, BaFe2–xCoxAs2, LiFeAs, KxFe2–ySe2, and FeTe1–xSex, the signatures of a nodal superconducting gap have been reported in LaOFeP, LiFeP, FeSe, KFe2As2, BaFe2–xRuxAs2, and BaFe2(As1–xPx)2. Due to the multiplicity of the Fermi surface in these compounds s± and d pairing states can be both nodeless and nodal. A nontrivial orbital structure of the order parameter, in particular the presence of the gap nodes, leads to effects in which the disorder is much richer in dx2–y2-wave superconductors than in conventional materials. In contrast to the s-wave case, the Anderson theorem does not work, and nonmagnetic impurities exhibit a strong pair-breaking influence. In addition, a finite concentration of disorder produces a nonzero density of quasiparticle states at zero energy, which results in a considerable modification of the thermodynamic and transport properties at low temperatures. The influence of order parameter symmetry on the vortex core structure in iron-based pnictide and chalcogenide superconductors has been investigated in the framework of quasiclassical Eilenberger equations. The main results of the thesis are as follows. The vortex core characteristics, such as, cutoff parameter, ξh, and core size, ξ2, determined as the distance at which density of the vortex supercurrent reaches its maximum, are calculated in wide temperature, impurity scattering rate, and magnetic field ranges. The cutoff parameter, ξh(B; T; Г), determines the form factor of the flux-line lattice, which can be obtained in _SR, NMR, and SANS experiments. A comparison among the applied pairing symmetries is done. In contrast to s-wave systems, in dx2–y2-wave superconductors, ξh/ξc2 always increases with the scattering rate Г. Field dependence of the cutoff parameter affects strongly on the second moment of the magnetic field distributions, resulting in a significant difference with nonlocal London theory. It is found that normalized ξ2/ξc2(B/Bc2) dependence is increasing with pair-breaking impurity scattering (interband scattering for s±-wave and intraband impurity scattering for d-wave superconductors). Here, ξc2 is the Ginzburg-Landau coherence length determined from the upper critical field Bc2 = Φ0/2πξ2 c2, where Φ0 is a flux quantum. Two types of ξ2/ξc2 magnetic field dependences are obtained for s± superconductors. It has a minimum at low temperatures and small impurity scattering transforming in monotonously decreasing function at strong scattering and high temperatures. The second kind of this dependence has been also found for d-wave superconductors at intermediate and high temperatures. In contrast, impurity scattering results in decreasing of ξ2/ξc2(B/Bc2) dependence in s++ superconductors. A reasonable agreement between calculated ξh/ξc2 values and those obtained experimentally in nonstoichiometric BaFe2–xCoxAs2 (μSR) and stoichiometric LiFeAs (SANS) was found. The values of ξh/ξc2 are much less than one in case of the first compound and much more than one for the other compound. This is explained by different influence of two factors: the value of impurity scattering rate and pairing symmetry.

Towards sustainable Iron- and steelmaking with economic optimization

The iron and steelmaking industry is among the major contributors to the anthropogenic emissions of carbon dioxide in the world. The rising levels of CO2 in the atmosphere and the global concern about the greenhouse effect and climate change have brought about considerable investigations on how to reduce the energy intensity and CO2 emissions of this industrial sector. In this thesis the problem is tackled by mathematical modeling and optimization using three different approaches. The possibility to use biomass in the integrated steel plant, particularly as an auxiliary reductant in the blast furnace, is investigated. By pre-processing the biomass its heating value and carbon content can be increased at the same time as the oxygen content is decreased. As the compression strength of the preprocessed biomass is lower than that of coke, it is not suitable for replacing a major part of the coke in the blast furnace burden. Therefore the biomass is assumed to be injected at the tuyere level of the blast furnace. Carbon capture and storage is, nowadays, mostly associated with power plants but it can also be used to reduce the CO2 emissions of an integrated steel plant. In the case of a blast furnace, the effect of CCS can be further increased by recycling the carbon dioxide stripped top gas back into the process. However, this affects the economy of the integrated steel plant, as the amount of top gases available, e.g., for power and heat production is decreased. High quality raw materials are a prerequisite for smooth blast furnace operation. High quality coal is especially needed to produce coke with sufficient properties to ensure proper gas permeability and smooth burden descent. Lower quality coals as well as natural gas, which some countries have in great volumes, can be utilized with various direct and smelting reduction processes. The DRI produced with a direct reduction process can be utilized as a feed material for blast furnace, basic oxygen furnace or electric arc furnace. The liquid hot metal from a smelting reduction process can in turn be used in basic oxygen furnace or electric arc furnace. The unit sizes and investment costs of an alternative ironmaking process are also lower than those of a blast furnace. In this study, the economy of an integrated steel plant is investigated by simulation and optimization. The studied system consists of linearly described unit processes from coke plant to steel making units, with a more detailed thermodynamical model of the blast furnace. The results from the blast furnace operation with biomass injection revealed the importance of proper pre-processing of the raw biomass as the composition of the biomass as well as the heating value and the yield are all affected by the pyrolysis temperature. As for recycling of CO2 stripped blast furnace top gas, substantial reductions in the emission rates are achieved if the stripped CO2 can be stored. However, the optimal recycling degree together with other operation conditions is heavily dependent on the cost structure of CO2 emissions and stripping/storage. The economical feasibility related to the use of DRI in the blast furnace depends on the price ratio between the DRI pellets and the BF pellets. The high amount of energy needed in the rotary hearth furnace to reduce the iron ore leads to increased CO2 emissions.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

Quantitative Magnetic Resonance Imaging of the Liver and Heart In Iron Overload

Systemic iron overload (IO) is considered a principal determinant in the clinical outcome of different forms of IO and in allogeneic hematopoietic stem cell transplantation (alloSCT). However, indirect markers for iron do not provide exact quantification of iron burden, and the evidence of iron-induced adverse effects in hematological diseases has not been established. Hepatic iron concentration (HIC) has been found to represent systemic IO, which can be quantified safely with magnetic resonance imaging (MRI), based on enhanced transverse relaxation. The iron measurement methods by MRI are evolving. The aims of this study were to implement and optimise the methodology of non-invasive iron measurement with MRI to assess the degree and the role of IO in the patients. An MRI-based HIC method (M-HIC) and a transverse relaxation rate (R2*) from M-HIC images were validated. Thereafter, a transverse relaxation rate (R2) from spin-echo imaging was calibrated for IO assessment. Two analysis methods, visual grading and rSI, for a rapid IO grading from in-phase and out-of-phase images were introduced. Additionally, clinical iron indicators were evaluated. The degree of hepatic and cardiac iron in our study patients and IO as a prognostic factor in patients undergoing alloSCT were explored. In vivo and in vitro validations indicated that M-HIC and R2* are both accurate in the quantification of liver iron. R2 was a reliable method for HIC quantification and covered a wider HIC range than M-HIC and R2*. The grading of IO was able to be performed rapidly with the visual grading and rSI methods. Transfusion load was more accurate than plasma ferritin in predicting transfusional IO. In patients with hematological disorders, the prevalence of hepatic IO was frequent, opposite to cardiac IO. Patients with myelodysplastic syndrome were found to be the most susceptible to IO. Pre-transplant IO predicted severe infections during the early post-transplant period, in contrast to the reduced risk of graft-versus-host disease. Iron-induced, poor transplantation results are most likely to be mediated by severe infections.

Iron(III) as Lewis acid catalyst in organosilicon and carbonyl chemistry

Iron is one of the most common elements in the earth’s crust and thus its availability and economic viability far exceed that of metals commonly used in catalysis. Also the toxicity of iron is miniscule, compared to the likes of platinum and nickel, making it very desirable as a catalyst. Despite this, prior to the 21st century, the applicability of iron in catalysis was not thoroughly investigated, as it was considered to be inefficient and unselective in desired transformations. In this doctoral thesis, the application of iron catalysis in combination with organosilicon reagents for transformations of carbonyl compounds has been investigated together with insights into iron catalyzed chlorination of silanes and silanols. In the first part of the thesis, the synthetic application of iron(III)-catalyzed chlorination of silanes (Si-H) and the monochlorination of silanes (SiH2) using acetyl chloride as the chlorine source is described. The reactions proceed under ambient conditions, although some compounds need to be protected from excess moisture. In addition, the mechanism and kinetics of the chlorination reaction are briefly adressed. In the second part of this thesis a versatile methodology for transformation of carbonyl compounds into three different compound classes by changing the conditions and amounts of reagents is discussed. One pot reductive benzylation, reductive halogenation and reductive etherification of ketones and aldehydes using silanes as the reducing agent, halide source or cocatalyst, were investigated. Also the reaction kinetics and mechanism of the reductive halogenation of acetophenone are briefly discussed.

Mechanical design and optics simulation of the illuminated Volvo Iron mark

Utilization of light and illumination systems in automotive industry for different purposes has been increased significantly in recent years. Volvo as one of the leading companies in manufacturing of luxury cars has found the great capacity in this area. The performance of such an illumination systems is one of the challenges that engineers in this industry are facing with. In this study an effort has been made to design a system to make the iron mark of Volvo being illuminated and the system is being evaluated by optics simulation in software using Ray optics method. At the end, results are assessed and some optimizations are carried out. Different kind of light guides, front side of the iron mark and some possible arrangement for LED also evaluated and different materials tested. The best combination from uniformity, color and amount of luminance aspect selected as a possible solution for this special project which can be used as a base for further studies in Volvo.

Marks of Fire, Value and Faith. Swords with Ferrous Inlays in Finland during the Late Iron Age (ca. 700–1200 AD)

This study explores swords with ferrous inlays found in Finland and dating from the late Iron Age, ca. 700–1200 AD. These swords reflect profound changes not only in styles and fashion but also in the technology of hilts and blades. This study explores how many of these kinds of swords are known from Finland, how they were made and where, what their status was in Late Iron Age Finland, and where the Finnish finds stand in accordance with other areas of Europe. The various methods included measuring of the finds and statistics. The main method of revealing the inlaid marks was radiography due to its non-destructive nature. In cases where inlays were visible without radiography, their details were inspected via microscopy. To study the materials and manufacture of inlaid swords, a sample of them was metallographically analysed to determine the forging technologies and nature of used materials. Furthermore, the manufacture was also studied with experimental approaches. As a result, a catalogue of 151 swords with ferrous inlays was created. This number is relatively high compared with other European countries, although systematic studies have been conducted in only some countries. The inlaid motifs were classified into five distinct categories to help the classification. To summarize, almost every documented inlaid sword was unique in some respect including measurements, inlaid motifs and materials of blades and inlays. Technological variation was also present, some blades being poorer and some of higher quality in spite of the inlaid motifs. Misspelt inscriptions as well as letter-like marks were common in Finland and also in Scandinavia. Furthermore, the provenance of iron and steel used in some blades hints at Scandinavian ores. The above observations, along with the experimental results indicating the existence of multiple alternative techniques of inlaying, suggest that these swords were manufactured locally in Scandinavia, most likely in imitation of Continental European models. Inlaid swords were valued partly for their assumed functionality in combat, as evidenced by damage on some examined blades, or they were valued for their inlays, which could have had fashionable or symbolical meanings bound to local beliefs.