IEA Bioenergy Task 40 “Sustainable International Bioenergy Trade: Securing supply and demand” Country report of Finland 2008

This study considered the current situation of biofuels markets in Finland. The fact that industry consumes more than half of the total primary energy, widely applied combined heat and power production and a high share of solid biomass fuels in the total energy consumption are specific to the Finnish energy system. Wood is the most important source of bioenergy in Finland, representing 21% of the total energy consumption in 2006. Almost 80% of the wood-based energy is recovered from industrial by-products and residues. Finland has commitment itself to maintaining its greenhouse gas emissions at the 1990 level, at the highest, during the period 2008–2012. The energy and climate policy carried out in recent years has been based on the National Energy and Climate introduced in 2005. The Finnish energy policy aims to achieve the target, and a variety of measures are taken to promote the use of renewable energy sources and especially wood fuels. In 2007, the government started to prepare a new long-term (up to the year 2050) climate and energy strategy that will meet EU’s new targets for the reduction of green house gas emissions and the promotion of renewable energy sources. The new strategy will be introduced during 2008. The international biofuels trade has a substantial importance for the utilisation of bioenergy in Finland. In 2006, the total international trading of solid and liquid biofuels was approximately 64 PJ of which import was 61 PJ. Most of the import is indirect and takes place within the forest industry’s raw wood imports. In 2006, as much as 24% of wood energy was based on foreignorigin wood. Wood pellets and tall oil form the majority of export streams of biofuels. The indirect import of wood fuels increased almost 10% in 2004–2006, while the direct trade of solid and liquid biofuels has been almost constant.

Market of biomass fuels in Finland : IEA Bioenergy Task 40 and EUBIONET III - Country report of Finland 2009

This study considered the current situation of solid and liquid biomass fuels in Finland. The fact that industry consumes more than half of the total primary energy, widely applied combined heat and power production and a high share of solid biomass fuels in the total energy consumption are specific to the Finnish energy system. Wood is the most important source of bioenergy in Finland, representing 20% of the total energy consumption in 2007. Almost 80% of the woodbased energy is recovered from industrial by-products and residues. As a member of the European Union, Finland has committed itself to the Union’s climate and energy targets, such as reducing its overall emissions of green house gases to at least 20% below 1990 levels by 2020, and increasing the share of renewable energy in the gross final consumption. The renewable energy target approved for Finland is 38%. The present National Climate and Energy Strategy was introduced in November 2008. The strategy covers climate and energy policy measures up to 2020, and in brief thereafter, up to 2050. In recent years, the actual emissions have exceeded the Kyoto commitment and the trend of emissions is on the increase. In 2007, the share of renewable energy in the gross final energy consumption was approximately 25% (360 PJ). Without new energy policy measures, the final consumption of renewable energy would increase to 380 PJ, which would be approximately only 31% of the final energy consumption. In addition, green house gas emissions would exceed the 1990 levels by 20%. Meeting the targets will need the adoption of more active energy policy measures in coming years. The international trade of biomass fuels has a substantial importance for the utilisation of bioenergy in Finland. In 2007, the total international trading of solid and liquid biomass fuels was approximately 77 PJ, of which import was 62 PJ. Most of the import is indirect and takes place within the forest industry’s raw wood imports. In 2007, as much as 21% of wood energy was based on foreign-origin wood. Wood pellets and tall oil form the majority of export streams of biomass fuels. The indirect import of wood fuels peaked in 2006 to 61 PJ. The foreseeable decline in raw wood import to Finland will decrease the indirect import of wood fuels. In 2004– 2007, the direct trade of solid and liquid biomass fuels has been on a moderate growth path. In 2007, the import of palm oil and export of bio-diesel emerged, as a large, 170 000 t/yr biodiesel plant came into operation in Porvoo.

Etelä- ja Länsi-Suomen jätesuunnittelun toteutumisen 1. väliarvio

Jätehuollon tavoitetilana Etelä- ja Länsi-Suomessa vuonna 2020 on, että jätemäärä on vähentynyt, hyödyntäminen lisääntynyt ja jätehuolto muuttunut suunnitelmalliseksi. Jätehuoltoa kehitetään yhteistyössä sidosryhmien kanssa. Tässä ensimmäisessä väliarviossa tarkastellaan Etelä- ja Länsi-Suomen jätesuunnitelman sekä Keski-Suomen jätesuunnitelman toteutumista ja vaikuttavuutta. Väliarvio sisältää seurantatiedot jätemääristä ja tietoa toimenpiteistä jätehuollon kehittämiseksi. Tarkastelu kattaa Etelä-Pohjanmaan, Hämeen, Kaakkois-Suomen, Keski-Suomen, Pirkanmaan, Uudenmaan ja Varsinais-Suomen ELY-keskusten toiminta-alueet. Jätesuunnitelmissa vuonna 2009 asetetut tavoitteet ovat edenneet osittain. Painopisteet biohajoavat jätteet sekä yhdyskunta- ja haja-asutuslietteet ovat lähteneet edistymään parhaiten. Haastavimmat teemat, jotka eivät ole edenneet odotetusti, ovat pilaantuneita maita sekä jätehuoltoa poikkeuksellisissa tilanteissa koskevat painopisteet. Lähiaikoina kehittämistä vaativat teemat ovat painopisteet rakentamisen ateriaalitehokkuus sekä tuhkat ja kuonat. Näissä teemoissa on konkreettisia toteutumismahdollisuuksia ja useita kiinnostuneita toimijoita. Uusiomateriaalien kuten tuhkien ja kuonien, teollisuuden sivutuotteiden ja jätemateriaalien käyttöä on mahdollisuus lisätä luonnon kiviainesten sijaan. Rakentamisen materiaalitehokkuutta voidaan ennakoida suunnitelmallisuudella, resurssitehokkuudella ja säästävällä purkamisella. Väliarviossa on esitetty jatkotoimenpiteitä, jotka mahdollistavat jätesuunnitelmien toteutumisen. Asetetuista keskeisistä painopisteistä rakentamisen materiaalitehokkuus sekä tuhkat ja kuonat edellyttävät eniten jatkotoimenpiteitä. Lisäksi yhdyskuntajätteiden kierrätystä tulisi lisätä.

Possibilities and challenges in utilization of information provided by Industrial Internet applications

Global digitalization has affected also industrial sector. A trend called Industrial Internet has been present for some years and established relatively steady position in businesses. Industrial Internet is also referred with the terminology Industry 4.0 and in consumer businesses IoT (Internet of Things). Eventually, trend consists of many traditionally proven technologies and concepts, such as condition monitoring, remote services, predictive maintenance and Internet customer portals. All these technologies and information related to them are estimated to change the rules of business in industrial sector. This may result even a new industrial revolution. This research has its focus on Industrial Internet products, services and applications. The study analyses four case companies and their digital service offerings. According to this analysis the comparison of these services is done to find out if there is still space for companies to gain competitive advantage through differentiation with these state of the art solutions. One of the case companies, Case Company Ltd., is working as a primary case company and a subscriber of this particular research. The research and results are analyzed primarily from this company’s perspective and need. In empirical part, the research clarifies how Case Company Ltd. has allocated its development resources through last five years. These allocations in certain categories are then compared to other case companies’ current customer offering and conclusions are made how the approach of different companies differ from each other. Existing theoretical knowledge of Industrial Internet is about to find its shape. In this research we take a look how the case company analysis and findings correlate with the existing knowledge and literature of the topic.

Development of an environmentally friendly method of starch oxidation by hydrogen peroxide and a complex water-soluble Iron catalyst

Oxidized starch is a key component in the paper industry, where it is used as both surfacing sizer and filler. Large quantities are annually used for this purpose; however, the methods for the oxidation are not environmentally friendly. In our research, we have studied the possibility to replace the harmful oxidation agents, such as hypochlorite or iodates and transition metal catalysts, with a more environmentally friendly oxidant, hydrogen peroxide (H2O2), and a special metal complex catalyst (FePcS), of which only a small amount is needed. The work comprised batch and semi-batch studies by H2O2, ultrasound studies of starch particles, determination of low-molecular by-products and determination of the decomposition kinetics of H2O2 in the presence of starch and the catalyst. This resulted in a waste-free oxidation method, which only produces water and oxygen as side products. The starch oxidation was studied in both semi-batch and batch modes in respective to the oxidant (H2O2) addition. The semi-batch mode proved to yield a sufficient degree of substitution (COOH groups) for industrial purposes. Treatment of starch granules by ultrasound was found to improve the reactivity of starch. The kinetic results were found out to have a rather complex pattern – several oxidation phases were observed, apparently due to the fact that the oxidation reaction in the beginning only took place on the surface, whereas after a prolonged reaction time, partial degradation of the solid starch granules allowed further reaction in the interior parts. Batch-mode experiments enabled a more detailed study of the mechanisms of starch in the presence of H2O2 and the catalyst, but yielded less oxidized starch due to rapid decomposition of H2O2 due to its high concentrations. The effect of the solid-liquid (S/L) ratio in the reaction system was studied in batch experiments. These studies revealed that the presence of the catalyst and the starch enhance the H2O2 decomposition.

Potential utilization ways of recovered chemical products from digestate

The study evaluates the potential application of chemical substances, obtained from biogas plants` by-products. Through the anaerobic digestion process with biogas the large amount of digestate is produced. This digestate mainly consists on the organic matter with the high concentration of nutrients such as nitrogen and phosphorus. During ammonia stripping and phosphorus precipitation the products- ammonia water, ammonium sulfate, ammonium nitrate, ferrous phosphate, aluminum phosphate, calcium phosphate and struvite can be recovered. These chemicals have potential application in different industrial sectors. According to Finnish market and chemicals properties, the most perspective industrial applications were determined. Based on the data, obtained through the literature review and market study, the ammonia water was recognized as a most perspective recovered substances. According to interview provided among Finnish companies, ammonia water is used for flue gas treatment in SNCR technology. This application has a large scale in the framework of Finnish industrial sectors. As well nitrogen with phosphorous can be used as a source of nutrients in the biological wastewater treatment plants of paper mills.

Reporting of Green Supply Chain Management and Industrial Symbiosis

The purpose of this thesis is to examine how the reporting of operations related to green supply chain management and industrial symbiosis has evolved in UPM, Fortum and Kemira within the last ten years. The focus is on the improved operations, which are studied based on annual reports of these companies. The study provides a deeper understanding of the nature of green supply chain management and industrial symbiosis as well as the possibilites that their combination offers. The research is part of the DemaNET research project The study indicates that the environmental regulations and reporting standards have forced the studied companies to report their operations related to green supply chain management and industrial symbiosis more in detail during the last ten years. The operations related to green supply chain management in the studied companies are more common compared to operations related to industrial symbiosis. Often these two operations were also partially integrated, indicating a hybrid model. Even though firms often used hybrid models they still focused mainly on greening the internal operations rather than finding alternative ways for symbiosis outside the organization. The integration of green supply chain management and industrial symbiosis is most likely to occur when mutually beneficial relationships align the interests of all parties, thus resulting in the co-creation of value. The findings suggest that identifying mutual benefits and the flow of by-products are the ones that companies should give more attention to.

Levyteollisuuden energia-, kustannus- ja ympäristövaikutukset

Kuluvien vuosien aikana ei ole tehty kattavia tutkimuksia levyteollisuuden sähkönkulutuksista, joten on aika selvittää suurimpien sähkökäyttöjen kulutukset sekä muodostaa tutkittaville tehtaille energiataseet. Tutkittavia tehtaita ovat OSB- ja lastulevytehtaat. Yksittäisten sähkömoottoreiden kulutukset saadaan selville käyttämällä hyväksi teoreettisia lähteitä, kenttä-ja laboratoriotutkimusta. Ympäristölainsäädäntö ja siihen kiinteästi liittyvä lupakäytäntö muodostavat levyteollisuudelle yhden viimeaikojen suurimmista haasteista. Tulevaisuudessa lainsäädäntö tulee vielä entisestäänkin kiristymään. Euroopan ympäristölainsäädäntö perustuu pitkälti yhtenäislupadirektiiviin eli IPPC-direktiiviin. Direktiivin keskeinen osa on ympäristöluvan hankkiminen, koska teollista toimintaa ei voi harjoittaa ilman hyväksyttyä viranomaisen lupaa. Lupa myös velvoittaa toiminnanharjoittajan käyttämään parasta käyttökelpoista tekniikkaa päästöjen kontrolloinnissa. Yhdysvalloissa parhaan käyttökelpoisen tekniikan (BAT) vaatimus on sisälletty ympäristövirasto EPA:n MACT-standardeihin. Levyteollisuuden tehtaista syntyvät päästöt ovat hyvin samankaltaisia. Tehtaista on helposti erotettavissa kaksi suurta päästölähdettä, joita ovat kuivaus ja kuumapuristus. Merkittävimpiä päästöjä ovat haihtuvat orgaaniset yhdisteet, hiukkaset, typen oksidit, hiilimonoksidi ja rikkidioksidit. Työn loppuosa on varattu tuotantojen kustannusvaikutusten ja tunnuslukujen tarkasteluille. Saatavilla tiedoilla on keskeinen rooli tehtaiden jokapäiväisessä toiminnassa. Analysoinnin tarpeeseen vaikuttaa osaltaan nykyisen toimintaympäristön muutosherkkyys ja levymarkkinoiden kireä kilpailutilanne.

Paikalliset elinkeinot ja ilmastonmuutos Kaakkois-Suomen alueella

Kasvihuonekaasujen vähentäminen on lähitulevaisuudessa välttämätöntä ilmastonmuutoksen torjunnassa. Tämä tosiasia tulisi nähdä niin yrityksissä kuin kunnissakin mahdollisuutena, johon liittyvillä toimenpiteillä voitaisiin kehittää myös alueen liiketoimintaa ja elinkeinoelämää. Tämän tutkimuksen tavoitteena oli löytää Kaakkois- Suomen kannalta tehokkaimmat keinot ja toimintamallit alueen liiketoiminnan edistämiseksi kasvihuonekaasupäästöjä hillitsevään suuntaan. Työssä on käsitelty erityisesti kunnan toimintaan liittyviä vaikutusmahdollisuuksia tavoitteiden saavuttamisessa. Tutkimus on toteutettu osana Suomen Kuntaliitto Ry:n koordinoimaa kuntienilmastonsuojelukampanjaa. Tutkimus on luonteeltaan kirjallisuuden pohjalta tehty esiselvitys. Työhön sisältyvien esimerkkitapausten osalta on tietoa hankittu myös haastattelemalla alueen yrityksiä. Tutkimuksen alkuvaiheessa on kartoitettu Kaakkois-Suomen alueellisia erityispiirteitä ja potentiaaleja. Työssä on arvioitu esimerkiksi uusiutuvien energialähteiden lisäämispotentiaalien käyttöönottamisella saavutettavat kasvihuonekaasupäästöjen vähenemät sekä työllisyysvaikutukset Kaakkois-Suomen alueella. Potentiaalien luoman pohjan perusteella on selvitetty mahdollisuuksia kehittää alueen elinkeinorakenteeseen soveltuvaa liiketoimintaa. Kasvihuonekaasuja vähentävän liiketoiminnan edistämiseksi on selvitetty keinoja sekä olemassa olevien yritysten kilpailukyvyn parantamiseen että uuden liiketoiminnan kehittämiseen liittyen. Näiden tavoitteiden saavuttamisessa nähtiin yritysten verkostoitumisen olevan eräs tärkeä keino, jolla voidaan parantaa mm. alueen lukuisten pienten yritysten mahdollisuuksia suurten kokonaistoimitusten tuottamisessa. Työssä on esitetty kunnan toimintaan soveltuva toimintamalli yritysten verkostoimiseksi. Jätteiden ja sivutuotteiden osalta työssä on esitetty materiaalivirtojen hyötykäyttöön ohjaamiseen erikoistunutta liiketoimintaa niin sanotun materiaalipörssin muodossa. Myös koulutuksen, tutkimuksen ja rahoituksen tarjontaa kasvihuonekaasuja vähentävän liiketoiminnan kehittämisen tueksi on selvitetty Kaakkois-Suomen alueella. Tutkimuksen sisällössä ovat esimerkkitapaukset keskeisessä asemassa. Niiden puitteissa on haastateltu paikallisen alueen yrityksiä ja viranomaisia. Esimerkkitapauksissa on selvitetty materiaalipörssin, lämpöyrittäjyyden sekä erään yrityksen verkostoimiseen liittyviä tekijöitä ja keinoja. Haastatteluista ja kirjallisuudesta saatuihin tietoihin perustuen on ehdotettu toimintavaihtoehtoja toiminnan kehittämiseksi. Tutkimuksen tulosten perusteella on lopuksi esitetty suunnitelma jatkotoimenpiteistä, joilla tuloksia lähdetään viemään käytännön tasolle.

Reduction and Analysis Methods of Indigo

Throughout history indigo was derived from various plants for example Dyer’s Woad (Isatis tinctoria L.) in Europe. In the 19th century were the synthetic dyes developed and nowadays indigo is mainly synthesized from by-products of fossil fuels. Indigo is a so-called vat dye, which means that it needs to be reduced to its water soluble leucoform before dyeing. Nowadays, most of the industrial reduction is performed chemically by sodium dithionite. However, this is considered environmentally unfavourable because of waste waters contaminating degradation products. Therefore there has been interest to find new possibilities to reduce indigo. Possible alternatives for the application of dithionite as the reducing agent are biologically induced reduction and electrochemical reduction. Glucose and other reducing sugars have recently been suggested as possible environmentally friendly alternatives as reducing agents for sulphur dyes and there have also been interest in using glucose to reduce indigo. In spite of the development of several types of processes, very little is known about the mechanism and kinetics associated with the reduction of indigo. This study aims at investigating the reduction and electrochemical analysis methods of indigo and give insight on the reduction mechanism of indigo. Anthraquinone as well as it’s derivative 1,8-dihydroxyanthraquinone were discovered to act as catalysts for the glucose induced reduction of indigo. Anthraquinone introduces a strong catalytic effect which is explained by invoking a molecular “wedge effect” during co-intercalation of Na+ and anthraquinone into the layered indigo crystal. The study includes also research on the extraction of plant-derived indigo from woad and the examination of the effect of this method to the yield and purity of indigo. The purity has been conventionally studied spectrophotometrically and a new hydrodynamic electrode system is introduced in this study. A vibrating probe is used in following electrochemically the leuco-indigo formation with glucose as a reducing agent.

Teollisuuden sivutuotteiden hyödyntäminen ekstruusion raaka-aineena

Ilmaston lämpeneminen ja luonnonvarojen ehtyminen ovat nostaneet ympäristöasiat erittäin ajankohtaisiksi ja kierrättämisen merkitys korostuu entisestään. Tässä diplomityössä on käsitelty teollisuuden jätteiden ja sivutuotteiden kierrättämistä puumuovikomposiitin raaka-aineeksi. Työssä on tutkittu Kaakkois-Suomessa olevia tärkeimpiä teollisuuden sivuainevirtoja puumuovikomposiitin kannalta sekä valmistettu puumuovikomposiittia hyödyntämällä kahta kaatopaikalle päätyvää jätettä. Kaakkois-Suomen teollisuuden jätteitä selvitettäessä löytyi paljon puumuovikomposiitin valmistamiseen soveltuvia jätteitä. Mekaanisen metsäteollisuuden sivutuotteita käytetään yleisesti puumuovikomposiitin valmistamiseen. Muita potentiaaliseksi havaittuja raakaaineita ovat mm. lentotuhka, lasikuitujäte, pakkauskartonki, muovijätteet ja vuorivillan valmistuksessa syntyvät jätteet. Koemateriaaleiksi valittiin puunpoltosta peräisin oleva lentotuhka ja vuorivillan valmistamisessa syntyvä vuorivillapöly. Materiaaleilla korvattiin puuta puumuovikomposiitissa ja valmistetulle komposiitille suoritettiin kokeita mekaanisten ominaisuuksien selvittämiseksi. Molempien materiaalien kohdalla ominaisuuksien havaittiin parantuneen ilman täyteainetta valmistettuun komposiittiin verrattuna.

Determination of sugars and organic acids in pulp samples by capillary electrophoresis with UV detection

This MSc work was done in the project of BIOMECON financed by Tekes. The prime target of the research was, to develop methods for separation and determination of carbohydrates (sugars), sugar acids and alcohols, and some other organic acids in hydrolyzed pulp samples by capillary electrophoresis (CE) using UV detection. Aspen, spruce, and birch pulps are commonly used for production of papers in Finland. Feedstock components in pulp predominantly consist of carbohydrates, organic acids, lignin, extractives, and proteins. Here in this study, pulps have been hydrolyzed in analytical chemistry laboratories of UPM Company and Lappeenranta University in order to convert them into sugars, acids, alcohols, and organic acids. Foremost objective of this study was to quantify and identify the main and by-products in the pulp samples. For the method development and optimization, increased precision in capillary electrophoresis was accomplished by calculating calibration data of 16 analytes such as D-(-)-fructose, D(+)-xylose, D(+)-mannose, D(+)-cellobiose, D-(+)-glucose, D-(+)-raffinose, D(-)-mannitol, sorbitol, rhamnose, sucrose, xylitol, galactose, maltose, arabinose, ribose, and, α-lactose monohydratesugars and 16 organic acids such as D-glucuronic, oxalic, acetic, propionic, formic, glycolic, malonic, maleic, citric, L-glutamic, tartaric, succinic, adipic, ascorbic, galacturonic, and glyoxylic acid. In carbohydrate and polyalcohol analyses, the experiments with CE coupled to direct UV detection and positive separation polarity was performed in 36 mM disodium hydrogen phosphate electrolyte solution. For acid analyses, CE coupled indirect UV detection, using negative polarity, and electrolyte solution made of 2,3 pyridinedicarboxylic acid, Ca2+ salt, Mg2+ salts, and myristyltrimethylammonium hydroxide in water was used. Under optimized conditions, limits of detection, relative standard deviations and correlation coefficients of each compound were measured. The optimized conditions were used for the identification and quantification of carbohydrates and acids produced by hydrolyses of pulp. The concentrations of the analytes varied between 1 mg – 0.138 g in liter hydrolysate.

Developing markets of energy biomass – local and global perspectives

The thesis explores global and national-level issues related to the development of markets for biomass for energy. The thesis consists of five separate papers and provides insights on selected issues. The aim of Paper I was to identify methodological and statistical challenges in assessing international solid and liquid biofuels trade and provide an overview of the Finnish situation with respect to the status of international solid and liquid biofuels trade. We found that, for the Finnish case, it is possible to qualify direct and indirect trade volumes of biofuels. The study showed that indirect trade of biofuels has a highly significant role in Finland and may be a significant sector also in global biofuels trade. The purpose of Paper II was to provide a quantified insight into Finnish prospects for meeting the national 2020 renewable energy targets and concurrently becoming a largescale producer of forest-biomass-based second-generation biofuels for feeding increasing demand in European markets. We found that Finland has good opportunities to realise a scenario to meet 2020 renewable energy targets and for large-scale production of wood-based biofuels. The potential net export of transport biofuels from Finland in 2020 would correspond to 2–3% of European demand. Paper III summarises the global status of international solid and liquid biofuels trade as illuminated by several separate sources. International trade of biofuels was estimated at nearly 1 EJ for 2006. Indirect trade of biofuels through trading of industrial roundwood and material by-products comprises the largest proportion of the trading, with a share of about two thirds. The purpose of Paper IV was to outline a comprehensive picture of the coverage of various certification schemes and sustainability principles relating to the entire value-added chain of biomass and bioenergy. Regardless of the intensive work that has been done in the field of sustainability schemes and principles concerning use of biomass for energy, weaknesses still exist. The objective of Paper V was to clarify the alternative scenarios for the international biomass market until 2020 and identify the underlying steps needed toward a wellfunctioning and sustainable market for biomass for energy purposes. An overall conclusion drawn from this analysis concerns the enormous opportunities related to the utilisation of biomass for energy in the coming decades.

Bio-ethanol valorization towards C4s including 1-butanol over metal modified alumina and zeolite catalysts

Bio-ethanol has been used as a fuel additive in modern society aimed at reducing CO2-emissions and dependence on oil. However, ethanol is unsuitable as fuel supplement in higher proportions due to its physico-chemical properties. One option to counteract the negative effects is to upgrade ethanol in a continuous fixed bed reactor to more valuable C4 products such as 1-butanol providing chemical similarity with traditional gasoline components. Bio-ethanol based valorization products also have other end-uses than just fuel additives. E.g. 1-butanol and ethyl acetate are well characterised industrial solvents and platform chemicals providing greener alternatives. The modern approach is to apply heterogeneous catalysts in the investigated reactions. The research was concentrated on aluminium oxide (Al2O3) and zeolites that were used as catalysts and catalyst supports. The metals supported (Cu, Ni, Co) gave very different product profiles and, thus, a profound view of different catalyst preparation methods and characterisation techniques was necessary. Additionally, acidity and basicity of the catalyst surface have an important role in determining the product profile. It was observed that ordinary determination of acid strength was not enough to explain all the phenomena e.g. the reaction mechanism. One of the main findings of the thesis is based on the catalytically active site which originates from crystallite structure. As a consequence, the overall evaluation of different by-products and intermediates was carried out by combining the information. Further kinetic analysis was carried out on metal (Cu, Ni, Co) supported self-prepared alumina catalysts. The thesis gives information for further catalyst developments aimed to scale-up towards industrially feasible operations.

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.