Management of Metals in the Pulping Process

Diplomityön tarkoituksena oli löytää keino korkean mangaanipitoisuuden hallintaan ECF-valkaisussa. Kirjallisuusosassa käsiteltiin eri metallien ja kuidun vuorovaikutuksia sekä niiden vaikutuksia prosessiin. Lisäksi käytiin läpi sellunvalmituksen yleisimpiä metallienhallintamenetelmiä. Työn kokeellisessa osassa tehtiin esikokeina laboratoriokokeita, jotta löydettiin oikeat kelatointistrategiat tehdasmittakaavan koeajoille. Laboratoriovalkaisut suoritettiin kuudella eri kemikaalilla käyttäen DD3-pesurin jälkeistä massaa ja samanlaisia parametrejä kuin tehdasvalkaisussa. Kolmesta eri valkaisusekvenssistä paras tulos saavutettiin D0-QEP-sekvenssillä. Tehdasmittakaavan koeajojen tavoitteena oli saavuttaa alle 1 mg/kg jäännösmangaanipitoisuus valkaistussa massassa ja korkeampi vaaleus EOP-vaiheessa pienemmällä klooridioksidin kulutuksella. Koeajoissa käytettiinDTPA:ta ja EDTA:ta kahdeksassa eri koepisteessä. Pienimpiin jäännöspitoisuuksiin päästiin koepisteissä, joissa kelatointiaine annosteltiin ennen valkaisun viimeistä pesuvaihetta tai sen jälkeen. Samanlaisia tuloksia saavutettiin koepisteissä, joissa kelatointiaine lisättiin suoraan EOP-vaiheeseen. Tällöin kelatointiaineen käyttö johti myös korkeampaan vaaleuteen EOP-vaiheessa pienemmällä kappakertoimella kuin referenssissä. Säästöt klooridioksidin kulutuksessa eivät olleet kuitenkaan tarpeeksi suuret kattaakseen kelatointiaineiden käytön kustannuksia. Kustannustehokkain tapa kontrolloida jäännösmangaanipitoisuutta oli EDTA:n annostelu D2 DD-pesurin jälkeen. Haittapuolena tälläisessä kelatoinnissa oli metallikompleksien palautuminen valkaisuun kuivauskoneen kiertoveden mukana. Tärkeimmät onnistuneeseen kelatointiin vaikuttavat parametrit olivat lajittelussa käytetyn rikkihapon annos, D0-vaiheen pH ja D0 DD-pesurin pesutehokkuus.

Utilization of non ferrous metals in boiler combustion environment

The made research is focused on possibility of application of non ferrous metals in boiler pressure parts as a substitute of currently used ferrous-base alloys. The main issue was to define resistive ability of some perspective non ferrous metals to chlorine induced corrosion. Experimental study was performed using simultaneous thermal analysis (STA) in the temperature range of 400-700 °C. The chloride induced corrosion was simulated by mixtures of metal samples with potassium chloride treated by synthetic air. The advantage of synergetic effect of non ferrous alloys compare to single metals is shown due to the obtained data from conducted thermal balance tests.

Formation and Control of Trace Metal Emissions in Co-Firing of Biomass, Peat, and Wastes in Fluidised Bed Combustors

Environmentally harmful consequences of fossil fuel utilisation andthe landfilling of wastes have increased the interest among the energy producers to consider the use of alternative fuels like wood fuels and Refuse-Derived Fuels, RDFs. The fluidised bed technology that allows the flexible use of a variety of different fuels is commonly used at small- and medium-sized power plants ofmunicipalities and industry in Finland. Since there is only one mass-burn plantcurrently in operation in the country and no intention to build new ones, the co-firing of pre-processed wastes in fluidised bed boilers has become the most generally applied waste-to-energy concept in Finland. The recently validated EU Directive on Incineration of Wastes aims to mitigate environmentally harmful pollutants of waste incineration and co-incineration of wastes with conventional fuels. Apart from gaseous flue gas pollutants and dust, the emissions of toxic tracemetals are limited. The implementation of the Directive's restrictions in the Finnish legislation is assumed to limit the co-firing of waste fuels, due to the insufficient reduction of the regulated air pollutants in the existing flue gas cleaning devices. Trace metals emission formation and reduction in the ESP, the condensing wet scrubber, the fabric filter, and the humidification reactor were studied, experimentally, in full- and pilot-scale combustors utilising the bubbling fluidised bed technology, and, theoretically, by means of reactor model calculations. The core of the model is a thermodynamic equilibrium analysis. The experiments were carried out with wood chips, sawdust, and peat, and their refuse-derived fuel, RDF, blends. In all, ten different fuels or fuel blends were tested. Relatively high concentrations of trace metals in RDFs compared to the concentrations of these metals in wood fuels increased the trace metal concentrations in the flue gas after the boiler ten- to hundred-folds, when RDF was co-fired with sawdust in a full-scale BFB boiler. In the case of peat, lesser increase in trace metal concentrations was observed, due to the higher initial trace metal concentrations of peat compared to sawdust. Despite the high removal rate of most of the trace metals in the ESP, the Directive emission limits for trace metals were exceeded in each of the RDF co-firing tests. The dominat trace metals in fluegas after the ESP were Cu, Pb and Mn. In the condensing wet scrubber, the flue gas trace metal emissions were reduced below the Directive emission limits, whenRDF pellet was used as a co-firing fuel together with sawdust and peat. High chlorine content of the RDFs enhanced the mercuric chloride formation and hence the mercury removal in the ESP and scrubber. Mercury emissions were lower than theDirective emission limit for total Hg, 0.05 mg/Nm3, in all full-scale co-firingtests already in the flue gas after the ESP. The pilot-scale experiments with aBFB combustor equipped with a fabric filter revealed that the fabric filter alone is able to reduce the trace metal concentrations, including mercury, in the flue gas during the RDF co-firing approximately to the same level as they are during the wood chip firing. Lower trace metal emissions than the Directive limits were easily reached even with a 40% thermal share of RDF co-firing with sawdust.Enrichment of trace metals in the submicron fly ash particle fraction because of RDF co-firing was not observed in the test runs where sawdust was used as the main fuel. The combustion of RDF pellets with peat caused an enrichment of As, Cd, Co, Pb, Sb, and V in the submicron particle mode. Accumulation and release oftrace metals in the bed material was examined by means of a bed material analysis, mass balance calculations and a reactor model. Lead, zinc and copper were found to have a tendency to be accumulated in the bed material but also to have a tendency to be released from the bed material into the combustion gases, if the combustion conditions were changed. The concentration of the trace metal in the combustion gases of the bubbling fluidised bed boiler was found to be a summary of trace metal fluxes from three main sources. They were (1) the trace metal flux from the burning fuel particle (2) the trace metal flux from the ash in the bed, and (3) the trace metal flux from the active alkali metal layer on the sand (and ash) particles in the bed. The amount of chlorine in the system, the combustion temperature, the fuel ash composition and the saturation state of the bed material in regard to trace metals were discovered to be key factors affecting therelease process. During the co-firing of waste fuels with variable amounts of e.g. ash and chlorine, it is extremely important to consider the possible ongoingaccumulation and/or release of the trace metals in the bed, when determining the flue gas trace metal emissions. If the state of the combustion process in regard to trace metals accumulation and/or release in the bed material is not known,it may happen that emissions from the bed material rather than the combustion of the fuel in question are measured and reported.

Surface Studies of Thiolate Adsorbates on Some Metals

The results and discussions in this thesis are based on my studies about selfassembled thiol layers on gold, platinum, silver and copper surfaces. These kinds of layers are two-dimensional, one molecule thick and covalently organized at the surface. They are an easy way to modify surface properties. Self-assembly is today an intensive research field because of the promise it holds for producing new technology at nanoscale, the scale of atoms and molecules. These kinds of films have applications for example, in the fields of physics, biology, engineering, chemistry and computer science. Compared to the extensive literature concerning self-assembled monolayers (SAMs) on gold, little is known about the structure and properties of thiolbased SAMs on other metals. In this thesis I have focused on thiol layers on gold, platinum, silver and copper substrates. These studies can be regarded as a basic study of SAMs. Nevertheless, an understanding of the physical and chemical nature of SAMs allows the correlation between atomic structure and macroscopic properties. The results can be used as a starting point for many practical applications. X-ray photoelectron spectroscopy (XPS) and synchrotron radiation excited high resolution photoelectron spectroscopy (HR-XPS) together with time-offlight secondary ion mass spectrometry (ToF-SIMS) were applied to investigate thin organic films formed by the spontaneous adsorption of molecules on metal surfaces. Photoelectron spectroscopy was the main method used in these studies. In photoelectron spectroscopy, the sample is irradiated with photons and emitted photoelectrons are energy-analyzed. The obtained spectra give information about the atomic composition of the surface and about the chemical state of the detected elements. It is widely used in the study of thin layers and is a very powerful tool for this purpose. Some XPS results were complemented with ToF-SIMS measurements. It provides information on the chemical composition and molecular structure of the samples. Thiol (1-Dodecanethiol, CH3(CH2)11SH) solution was used to create SAMs on metal substrates. Uniform layers were formed on most of the studied metal surfaces. On platinum, surface aligned molecules were also detected in investigations by XPS and ToF-SIMS. The influence of radiation on the layer structure was studied, leading to the conclusion that parts of the hydrocarbon chains break off due to radiation and the rest of the layer is deformed. The results obtained showed differences depending on the substrate material. The influence of oxygen on layer formation was also studied. Thiol molecules were found to replace some of the oxygen from the metal surfaces.

Element speciation and behaviour in metal-rich Boreal river and estuarine systems using ultrafiltration and chemical modelling

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations, but is to a great extent determined by their chemical form. Consequently, knowledge of aqueous metal species is essential in investigating potential metal toxicity and mobility. The overall aim of this thesis is, thus, to determine the species of major and trace elements and the size distribution among the different forms (e.g. ions, molecules and mineral particles) in selected metal-enriched Boreal river and estuarine systems by utilising filtration techniques and geochemical modelling. On the basis of the spatial physicochemical patterns found, the fractionation and complexation processes of elements (mainly related to input of humic matter and pH-change) were examined. Dissolved (<1 kDa), colloidal (1 kDa-0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic carbon (OC) and 44 metals/metalloids were investigated in the extremely acidic Vörå River system and its estuary in W Finland, and in four river systems in SW Finland (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), largely affected by soil erosion and acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these investigated waters. One of the most important findings of this study is that the very large amounts of metals known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si, U and the lanthanoids) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and especially dissolved Al is expected to have acute effects on fish and other organisms, but also other potentially toxic dissolved elements (e.g. Cd, Cu, Mn and Ni) can have fatal effects on the biota in these environments. In upstream areas that are generally relatively forested (higher pH and contents of OC) fewer bioavailable elements (including Al, Cu, Ni and U) may be found due to complexation with the more abundantly occurring colloidal OC. In the rivers in SW Finland total metal concentrations were relatively high, but most of the elements occurred largely in a colloidal or particulate form and even elements expected to be very soluble (Ca, K, Mg, Na and Sr) occurred to a large extent in colloidal form. According to geochemical modelling, these patterns may only to a limited extent be explained by in-stream metal complexation/adsorption. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of AS soils, known to exist in the catchment, could be clearly distinguished in the Sirppujoki River as it had very high concentrations of a metal sequence typical of AS soils in a dissolved form (Ba, Br, Ca, Cd, Co, K, Mg, Mn, Na, Ni, Rb and Sr). In the Paimionjoki River, metal concentrations (including Ba, Cs, Fe, Hf, Pb, Rb, Si, Th, Ti, Tl and V; not typical of AS soils in the area) were high, but it was found that the main cause of this was erosion of metal bearing phyllosilicates and thus these metals occurred dominantly in less toxic colloidal and particulate fractions. In the two nearby rivers (Laajoki and Mynäjoki) there was influence of AS soils, but it was largely masked by eroded phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high background metal concentrations due to erosion. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring, or geochemical modelling based on such data, can lead to a great overestimation of the water toxicity in this environment. The potentially toxic elements that are of concern in AS soil areas will ultimately be precipitated in the recipient estuary or sea, where the acidic metalrich river water will gradually be diluted/neutralised with brackish seawater. Along such a rising pH gradient Al, Cu and U will precipitate first together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides together with elements such as Ba, Cd, Co, Cu and Ni. Iron oxides, on the contrary, are not important scavengers of metals in the estuary, they are predicted to be associated only with As and PO4.

Hydrometallurgical recovery of valuable metals from secondary raw materials

Wastes and side streams in the mining industry and different anthropogenic wastes often contain valuable metals in such concentrations their recovery may be economically viable. These raw materials are collectively called secondary raw materials. The recovery of metals from these materials is also environmentally favorable, since many of the metals, for example heavy metals, are hazardous to the environment. This has been noticed in legislative bodies, and strict regulations for handling both mining and anthropogenic wastes have been developed, mainly in the last decade. In the mining and metallurgy industry, important secondary raw materials include, for example, steelmaking dusts (recoverable metals e.g. Zn and Mo), zinc plant residues (Ag, Au, Ga, Ge, In) and waste slurry from Bayer process alumina production (Ga, REE, Ti, V). From anthropogenic wastes, waste electrical and electronic equipment (WEEE), among them LCD screens and fluorescent lamps, are clearly the most important from a metals recovery point of view. Metals that are commonly recovered from WEEE include, for example, Ag, Au, Cu, Pd and Pt. In LCD screens indium, and in fluorescent lamps, REEs, are possible target metals. Hydrometallurgical processing routes are highly suitable for the treatment of complex and/or low grade raw materials, as secondary raw materials often are. These solid or liquid raw materials often contain large amounts of base metals, for example. Thus, in order to recover valuable metals, with small concentrations, highly selective separation methods, such as hydrometallurgical routes, are needed. In addition, hydrometallurgical processes are also seen as more environmental friendly, and they have lower energy consumption, when compared to pyrometallurgical processes. In this thesis, solvent extraction and ion exchange are the most important hydrometallurgical separation methods studied. Solvent extraction is a mainstream unit operation in the metallurgical industry for all kinds of metals, but for ion exchange, practical applications are not as widespread. However, ion exchange is known to be particularly suitable for dilute feed solutions and complex separation tasks, which makes it a viable option, especially for processing secondary raw materials. Recovering valuable metals was studied with five different raw materials, which included liquid and solid side streams from metallurgical industries and WEEE. Recovery of high purity (99.7%) In, from LCD screens, was achieved by leaching with H2SO4, extracting In and Sn to D2EHPA, and selectively stripping In to HCl. In was also concentrated in the solvent extraction stage from 44 mg/L to 6.5 g/L. Ge was recovered as a side product from two different base metal process liquors with Nmethylglucamine functional chelating ion exchange resin (IRA-743). Based on equilibrium and dynamic modeling, a mechanism for this moderately complex adsorption process was suggested. Eu and Y were leached with high yields (91 and 83%) by 2 M H2SO4 from a fluorescent lamp precipitate of waste treatment plant. The waste also contained significant amounts of other REEs such as Gd and Tb, but these were not leached with common mineral acids in ambient conditions. Zn was selectively leached over Fe from steelmaking dusts with a controlled acidic leaching method, in which the pH did not go below, but was held close as possible to, 3. Mo was also present in the other studied dust, and was leached with pure water more effectively than with the acidic methods. Good yield and selectivity in the solvent extraction of Zn was achieved by D2EHPA. However, Fe needs to be eliminated in advance, either by the controlled leaching method or, for example, by precipitation. 100% Pure Mo/Cr product was achieved with quaternary ammonium salt (Aliquat 336) directly from the water leachate, without pH adjustment (pH 13.7). A Mo/Cr mixture was also obtained from H2SO4 leachates with hydroxyoxime LIX 84-I and trioctylamine (TOA), but the purities were 70% at most. However with Aliquat 336, again an over 99% pure mixture was obtained. High selectivity for Mo over Cr was not achieved with any of the studied reagents. Ag-NaCl solution was purified from divalent impurity metals by aminomethylphosphonium functional Lewatit TP-260 ion exchange resin. A novel preconditioning method, named controlled partial neutralization, with conjugate bases of weak organic acids, was used to control the pH in the column to avoid capacity losses or precipitations. Counter-current SMB was shown to be a better process configuration than either batch column operation or the cross-current operation conventionally used in the metallurgical industry. The raw materials used in this thesis were also evaluated from an economic point of view, and the precipitate from a waste fluorescent lamp treatment process was clearly shown to be the most promising.

Environmental Challenges in the Joint Border Area of Norway, Finland and Russia

This report examines the human impact on the subarctic environment of the joint border area of Norway, Finland and Russia. The aim is to present the current state and recent changes that have taken place in the region. The main threat to the environment is the Pechenganikel mining and metallurgical industrial combine in the towns of Nikel and Zapolyarny in the Kola Peninsula. Emissions from this complex include high levels of heavy metals, persistent organic pollutants and sulfur dioxide. Pollution, along with climate change, water level regulation and other anthropogenic effects, has affected the aquatic ecosystems in the joint border area. The main heavy metals in the area are copper and nickel, the highest concentrations of which are measured near the combine. Direct discharge of sewage into the river continues and airborne heavy metal particles are also deposited to areas farther away. Climate changeinduced increase in temperature and precipitation in the Kola Peninsula is evident. Water level regulation with seven hydropower plants in the Pasvik River have changed it into a series of lakes and lake-like reservoirs. This report discusses modelling, which was enabled to estimate the effect of climate change on Lake Inarijärvi and the Pasvik River hydrology, water level fluctuation and ecology and to follow the sulfur dioxide emissions emitted from the Pechenganikel. Effects of pollution on the nature and concentrations of the main pollutants were studied and climate change in the border area and its effects on the ecology were estimated. Also the effects of water level regulation on the ecological status of the aquatic ecosystems were addressed.

The role of metal ions in selective and sustainable processes

Sustainability and recycling are core values in today’s industrial operations. New materials, products and processes need to be designed in such a way as to consume fewer of the diminishing resources we have available and to put as little strain on the environment as possible. An integral part of this is cleaning and recycling. New processes are to be designed to improve the efficiency in this aspect. Wastewater, including municipal wastewaters, is treated in several steps including chemical and mechanical cleaning of waters. Well-cleaned water can be recycled and reused. Clean water for everyone is one of the greatest challenges we are facing today. Ferric sulphate, made by oxidation from ferrous sulphate, is used in water purification. The oxidation of ferrous sulphate, FeSO4, to ferric sulphate in acidic aqueous solutions of H2SO4 over finely dispersed active carbon particles was studied in a vigorously stirred batch reactor. Molecular oxygen was used as the oxidation agent and several catalysts were screened: active carbon, active carbon impregnated with Pt, Rh, Pd and Ru. Both active carbon and noble metal-active carbon catalysts enhanced the oxidation rate considerably. The order of the noble metals according to the effect was: Pt >> Rh > Pd, Ru. By the use of catalysts, the production capacities of existing oxidation units can be considerably increased. Good coagulants have a high charge on a long polymer chain effectively capturing dirty particles of the opposite charge. Analysis of the reaction product indicated that it is possible to obtain polymeric iron-based products with good coagulation properties. Systematic kinetic experiments were carried out at the temperature and pressure ranges of 60B100°C and 4B10 bar, respectively. The results revealed that both non-catalytic and catalytic oxidation of Fe2+ to Fe3+ take place simultaneously. The experimental data were fitted to rate equations, which were based on a plausible reaction mechanism: adsorption of dissolved oxygen on active carbon, electron transfer from Fe2+ ions to adsorbed oxygen and formation of surface hydroxyls. A comparison of the Fe2+ concentrations predicted by the kinetic model with the experimentally observed concentrations indicated that the mechanistic rate equations were able to describe the intrinsic oxidation kinetics of Fe2+ over active carbon and active carbon-noble metal catalysts. Engineering aspects were closely considered and effort was directed to utilizing existing equipment in the production of the new coagulant. Ferrous sulphate can be catalytically oxidized to produce a novel long-chained polymeric iron-based flocculent in an easy and affordable way in existing facilities. The results can be used for modelling the reactors and for scale-up. Ferric iron (Fe3+) was successfully applied for the dissolution of sphalerite. Sphalerite contains indium, gallium and germanium, among others, and the application can promote their recovery. The understanding of the reduction process of ferric to ferrous iron can be used to develop further the understanding of the dissolution mechanisms and oxidation of ferrous sulphate. Indium, gallium and germanium face an ever-increasing demand in the electronics industry, among others. The supply is, however, very limited. The fact that most part of the material is obtained through secondary production means that real production quota depends on the primary material production. This also sets the pricing. The primary production material is in most cases zinc and aluminium. Recycling of scrap material and the utilization of industrial waste, containing indium, gallium and geranium, is a necessity without real options. As a part of this study plausible methods for the recovery of indium, gallium and germanium have been studied. The results were encouraging and provided information about the precipitation of these valuables from highly acidic solutions. Indium and gallium were separated from acidic sulphuric acid solutions by precipitation with basic sulphates such as alunite or they were precipitated as basic sulphates of their own as galliunite and indiunite. Germanium may precipitate as a basic sulphate of a mixed composition. The precipitation is rapid and the selectivity is good. When the solutions contain both indium and gallium then the results show that gallium should be separated before indium to achieve a better selectivity. Germanium was separated from highly acidic sulphuric acid solutions containing other metals as well by precipitating with tannic acid. This is a highly selective method. According to the study other commonly found metals in the solution do not affect germanium precipitation. The reduction of ferric iron to ferrous, the precipitation of indium, gallium and germanium, and the dissolution of the raw materials are strongly depending on temperature and pH. The temperature and pH effect were studied and which contributed to the understanding and design of the different process steps. Increased temperature and reduced pH improve the reduction rate. Finally, the gained understanding in the studied areas can be employed to develop better industrial processes not only on a large scale but also increasingly on a smaller scale. The small amounts of indium, gallium and germanium may favour smaller and more locally bound recovery.

Optimal Recycling Combination of Ash in South-East Finland

The present world energy production is heavily relying on the combustion of solid fuels like coals, peat, biomass, municipal solid waste, whereas the share of renewable fuels is anticipated to increase in the future to mitigate climate change. In Finland, peat and wood are widely used for energy production. In any case, the combustion of solid fuels results in generation of several types of thermal conversion residues, such as bottom ash, fly ash, and boiler slag. The predominant residue type is determined by the incineration technology applied, while its composition is primarily relevant to the composition of fuels combusted. An extensive research has been conducted on technical suitability of ash for multiple recycling methods. Most of attention was drawn to the recycling of the coal combustion residues, as coal is the primary solid fuel consumed globally. The recycling methods of coal residues include utilization in a cement industry, in concrete manufacturing, and mine backfilling, to name few. Biomass combustion residues were also studied to some extent with forest fertilization, road construction, and road stabilization being the predominant utilization options. Lastly, residues form municipal solid waste incineration attracted more attention recently following the growing number of waste incineration plants globally. The recycling methods of waste incineration residues are the most limited due to its hazardous nature and varying composition, and include, among others, landfill construction, road construction, mine backfilling. In the study, environmental and economic aspects of multiple recycling options of thermal conversion residues generated within a case-study area were studied. The case-study area was South-East Finland. The environmental analysis was performed using an internationally recognized methodology — life cycle assessment. Economic assessment was conducted applying a widely used methodology — cost-benefit analysis. Finally, the results of the analyses were combined to enable easier comparison of the recycling methods. The recycling methods included the use of ash in forest fertilization, road construction, road stabilization, and landfill construction. Ash landfilling was set as a baseline scenario. Quantitative data about the amounts of ash generated and its composition was obtained from companies, their environmental reports, technical reports and other previously published literature. Overall, the amount of ash in the case-study area was 101 700 t. However, the data about 58 400 t of fly ash and 35 100 t of bottom ash and boiler slag were included in the study due to lack of data about leaching of heavy metals in some cases. The recycling methods were modelled according to the scientific studies published previously. Overall, the results of the study indicated that ash utilization for fertilization and neutralization of 17 600 ha of forest was the most economically beneficial method, which resulted in the net present value increase by 58% compared to ash landfilling. Regarding the environmental impact, the use of ash in the construction of 11 km of roads was the most attractive method with decreased environmental impact of 13% compared to ash landfilling. The least preferred method was the use of ash for landfill construction since it only enabled 11% increase of net present value, while inducing additional 1% of negative impact on the environment. Therefore, a following recycling route was proposed in the study. Where possible and legally acceptable, recycle fly and bottom ash for forest fertilization, which has strictest requirements out of all studied methods. If the quality of fly ash is not suitable for forest fertilization, then it should be utilized, first, in paved road construction, second, in road stabilization. Bottom ash not suitable for forest fertilization, as well as boiler slag, should be used in landfill construction. Landfilling should only be practiced when recycling by either of the methods is not possible due to legal requirements or there is not enough demand on the market. Current demand on ash and possible changes in the future were assessed in the study. Currently, the area of forest fertilized in the case-study are is only 451 ha, whereas about 17 600 ha of forest could be fertilized with ash generated in the region. Provided that the average forest fertilizing values in Finland are higher and the area treated with fellings is about 40 000 ha, the amount of ash utilized in forest fertilization could be increased. Regarding road construction, no new projects launched by the Center of Economic Development, Transport and the Environment in the case-study area were identified. A potential application can be found in the construction of private roads. However, no centralized data about such projects is available. The use of ash in stabilization of forest roads is not expected to increased in the future with a current downwards trend in the length of forest roads built. Finally, the use of ash in landfill construction is not a promising option due to the reducing number of landfills in operation in Finland.

DSA-elektrodien testaaminen kulumisen arvioimiseksi

Työn tavoitteena oli tutkia eri mittausmenetelmillä metallipinnoitettujen elektrodien kulumista kulumiskokeiden aikana. Mittausmenetelminä olivat käytössä syklinen voltammetria, polarisaatiokäyrän määritys ja sähkökemiallinen impedanssispektrometria, jotka olivat offline-mittausmenetelmiä. Näiden menetelmien avulla pystyttiin seuraamaan yksittäisten elektrodien kulumista ajon aikana. Elektrodin pinnoitteen alkuaineiden pitoisuuksia tutkittiin myös elektronimikroskoopin röntgenspektrometrin avulla. Työn aikana tehdyissä kulumiskokeista havaittiin elektrodin kuluvan sitä nopeammin mitä suurempi on virrantiheys. Työssä tehtyjen elektronimikroskooppikokeiden avulla havaittiin, että harvinaisten metallien seostaminen pinnoitteeseen pidentää metallipinnoitetun elektrodin käyttöikää. Syklisen voltammetrian avulla pystyttiin seuraamaan elektrodin pinta-alan muuttumista ajon aikana. Työssä käytettyjen kulumiskokeiden avulla ei suoranaisesti pystytty määrittämään elektrodin jäljellä olevaa elinikää.

Ilmaan johdettavien epäpuhtauksien päästökartoitus Porvoon öljynjalostamolla

Työn tarkoituksena oli laatia suunnitelma ilmaan johdettavien epäpuhtauksien päästökartoitukselle Porvoon öljynjalostamolla. Raskasmetallien, metaanin, fluorivetyhapon, rikkivedyn ja ammoniakin merkittävät päästöpaikat ja -tarkkailumenetelmät kartoitettaisiin tulevaa päästöraportointia varten. Tarkkailun alaisten komponenttien muodostuminen, kulkeutuminen ja merkittävät päästöpaikat Porvoon jalostamolla selvitettiin kirjallisuuslähteiden, jalostamon toimintajärjestelmän ohjeiden sekä työntekijöiden haastattelujen perusteella. Merkittäviä häiriöpäästötilanteita kartoitettiin ja arvioitiin jalostamon poikkeamatilastojen ja haastattelujen avulla. Normaalitoiminnan aikana tarkkailun alaisista epäpuhtauksista vapautuu ilmaan merkittäviä määriä ainoastaan metaania ja raskasmetalleja. Metaania vapautuu ilmaan polttoprosesseissa sekä hajapäästönä. Raskasmetallipäästöjä syntyy pohjaöljyn poltossa energialaitoksella sekä leijukatalyyttisessä krakkauksessa. Rikkilaitosten häiriötilanteista aiheutuu rikkivety- ja ammoniakkipäästöjä pääasiassa soihtujärjestelmän kautta. Alkylointiyksikön vuodoissa voi vapautua fluorivetyhappoa ilmaan. Päästömääriä arvioidaan pääosin laskennallisesti. Päästökartoitussuunnitelma on kokonaisuudessaan tämän työn liitteenä. Näyttäisi siltä, että TRS-yhdisteiden, ammoniakin ja fluorivetyhapon ilmapäästöt eivät ole merkittäviä Porvoon öljynjalostamolla. Uuden pohjaöljy-yksikön käyttöönotto on vähentänyt myös raskasmetallipäästöjä energialaitoksella. Metaanipäästö vaikuttaa kartoitukseen sisällytettävistä epäpuhtauksista merkityksellisimmältä Porvoon öljynjalostamolla.

Epäpuhtausmetallien talteenotto sinkkiprosessissa

There are small amounts of valuable metals, such as indium, gallium and germanium, in zinc process solutions. Their solvent extraction was studied in this work in sulphate solutions containing zinc and other metals present in industrial solutions. It was discovered, that a commercial bis(2-ethylhexyl)phosphate (D2EHPA) extractant can be used to extract indium and gallium. Indium was extracted separately at a higher acid concentration than gallium. Zinc was co-extracted faster than gallium and almost as much as gallium at the same pH. However, the scrubbing of zinc was possible using a dilute sulphuric acid and a short contact time while gallium losses were small. Both indium and gallium were stripped with sulphuric acid. Germanium was extracted with 5,8-diethyl-7-hydroxydodecane-6-oxime with the commercial name of LIX 63. Unlike other metals in the solution the extraction of germanium increased with different extractants as the acidity increased. Germanium extraction isotherm was measured for a 125 g/L sulfuric acid solution. The loaded organic phase was washed with pure water. It removed the co-extracted acid and part of the germanium and extracted impurities such as iron and copper. Germanium was stripped using a NaOH solution. A process model utilizing own experimentally determined extraction, scrubbing and stripping isotherms was made with HSC Sim software developed by Outotec Oyj. The model based on McCabe–Thiele diagrams was used in sizing the necessary amount of stages and phase ratios in a recovery process. It was concluded, that indium, gallium and germanium can be recovered in the process from a feed where their concentrations are low (<300 ppm). In an example case the feed contained also more than 20 g/L zinc and 2–8 g/L iron, aluminium and copper. The recoveries of indium, gallium and germanium were more than 90 % when 1–3 stages were used in each extraction, scrubbing and stripping section. Since the number of stages is small mixer-settlers would be well suited for this purpose.

Jatkuvatoiminen ioninvaihto ja kompleksoituvien metallien sorptio kloridiympäristössä

Työn tarkoituksena oli tutkia kompleksoituvien metallien erotusta kloridiliuoksesta ioninvaihdolla. Kirjallisessa osassa perehdyttiin metallikompleksien muodostumiseen, ja erityisesti hopean, kalsiumin, magnesiumin, lyijyn ja sinkin muodostamiin komplekseihin kloridin ja nitraatin kanssa. Kirjallisessa osassa käsiteltiin myös metallien erottamista kiintopetikolonneissa jatkuvatoimisilla ioninvaihtomenetelmillä. Tässä työssä jatkuvatoimisen ioninvaihdon prosessivaihtoehdot jaoteltiin pyöriviin ja paikallaan pysyviin kolonneihin, sekä tarkasteltiin eri prosessivaihtoehtoja kolonnien kytkentöjen suhteen. Työn kokeellisessa osassa tutkittiin kahdenarvoisten metallien erottamista yhdenarvoisista metalleista sekä luotiin koedataa vastaavanlaisen erotusprosessin simulointiin. Kokeissa käytettiin anioninvaihtohartsia ja kelatoivaa selektiivistä ioninvaihtohartsia. Kahdenarvoisen kalsiumin, magnesiumin, lyijyn ja sinkin adsorptiota hartseihin tutkittiin tasapaino-, kinetiikka- ja kolonnikokeilla. Anioninvaihtohartsilla tehtyjen tasapaino- ja kolonnikokeiden tulokset osoittivat, että hartsi adsorboi tehokkaasti sinkkiä kloridiliuoksista, koska sinkki muodostaa stabiileja anionisia klorokomplekseja. Muiden tutkittujen kahdenarvoisten metallien adsorptio hartsiin oli huomattavasti vähäisempää. Tulosten perusteella tutkittu anioninvaihtohartsi on hyvä vaihtoehto sinkin erottamiseen muista tutkituista kahdenarvoisista metalleista kloridiympäristössä. Kelatoivalla hartsilla tehdyt tasapaino- ja kolonnikokeet osoittivat, että hartsi adsorboi kloridiliuoksista hyvin kahdenarvoista kalsiumia, magnesiumia, lyijyä ja sinkkiä, mutta ei adsorboi yhdenarvoista hopeaa. Tulosten perusteella kahdenarvoisten metallien erottaminen yhdenarvoisista metalleista voidaan toteuttaa kokeissa käytetyllä kelatoivalla ioninvaihtohartsilla.