Ligniinin hienojauhatus planeettamyllyllä

Kirjallisuusosassa tarkastellaan ligniiniä luonnon polymeerinä sekä sen kemiallisia perustietoja. Aiheena on myös sen tuotanto ja käyttö uusiutuvana raaka-ainelähteenä energian-, materiaali- ja kemikaalituotantoon sekä niiden mahdolliset tulevaisuudennäkymät. Mekaanisten prosessien osalta keskitytään kiintoaineen hienontamiseen. Lisäksi perehdytään planeettamyllyn toiminnan teoriaan sekä tuoreimpiin tutkimuksiin planeettamyllyjauhatukseen liittyen. Työn kokeellisen osan tarkoituksena oli tutkia ligniinin jauhautuvuutta, sillä partikkelien pienentämisellä voidaan kasvattaa ligniininijauheen ominaisalaa ja tasoittaa sen kokojakaumaa. Jauhautuvuuden avulla voidaan esimerkiksi arvioida ligniinille tehtävän hienojauhatuksen kannattavuutta jatkoprosesseja varten. Tutkimuskysymyksinä oli ”kuinka hyvin ligniini jauhautuu planeettamyllyllä?”, ”onko kylmäkäsittelyllä vaikutusta jauhatustulokseen?”, ”miten eri parametrit (jauhatusaika, kuulakoko ja kierrosnopeus) vaikuttavat jauhatustulokseen?” sekä ”muuttaako hienojauhatus ligniinin kemiallista koostumusta?”. Tutkittavana materiaalina oli kaupallinen kraft-ligniini ja koelaitteena käytettiin planeettamyllyä. Syötölle ja kaikille jauhatustuotteille suoritettiin partikkelikokoanalyysi, ja lisäksi syötölle ja erittäin hienoksi jauhetulle tuotteelle suoritettiin FTIR-analyysi. Kokeiden mukaan ligniini oli hyvin jauhautuvaa, eikä kylmäkäsittelyllä ollut merkittävää vaikutusta jauhatukseen. Kuulakoon pienentäminen sekä jauhatusajan ja kierrosnopeuden kasvattaminen alensivat ligniininjauheen partikkelikokoa. Lisäksi hienojauhatuksen ei todettu muuttaneen ligniinin kemiallista koostumusta.

Modeling of fireside deposit formation in two industrial furnaces

Fireside deposits can be found in many types of utility and industrial furnaces. The deposits in furnaces are problematic because they can reduce heat transfer, block gas paths and cause corrosion. To tackle these problems, it is vital to estimate the influence of deposits on heat transfer, to minimize deposit formation and to optimize deposit removal. It is beneficial to have a good understanding of the mechanisms of fireside deposit formation. Numerical modeling is a powerful tool for investigating the heat transfer in furnaces, and it can provide valuable information for understanding the mechanisms of deposit formation. In addition, a sub-model of deposit formation is generally an essential part of a comprehensive furnace model. This work investigates two specific processes of fireside deposit formation in two industrial furnaces. The first process is the slagging wall found in furnaces with molten deposits running on the wall. A slagging wall model is developed to take into account the two-layer structure of the deposits. With the slagging wall model, the thickness and the surface temperature of the molten deposit layer can be calculated. The slagging wall model is used to predict the surface temperature and the heat transfer to a specific section of a super-heater tube panel with the boundary condition obtained from a Kraft recovery furnace model. The slagging wall model is also incorporated into the computational fluid dynamics (CFD)-based Kraft recovery furnace model and applied on the lower furnace walls. The implementation of the slagging wall model includes a grid simplification scheme. The wall surface temperature calculated with the slagging wall model is used as the heat transfer boundary condition. Simulation of a Kraft recovery furnace is performed, and it is compared with two other cases and measurements. In the two other cases, a uniform wall surface temperature and a wall surface temperature calculated with a char bed burning model are used as the heat transfer boundary conditions. In this particular furnace, the wall surface temperatures from the three cases are similar and are in the correct range of the measurements. Nevertheless, the wall surface temperature profiles with the slagging wall model and the char bed burning model are different because the deposits are represented differently in the two models. In addition, the slagging wall model is proven to be computationally efficient. The second process is deposit formation due to thermophoresis of fine particles to the heat transfer surface. This process is considered in the simulation of a heat recovery boiler of the flash smelting process. In order to determine if the small dust particles stay on the wall, a criterion based on the analysis of forces acting on the particle is applied. Time-dependent simulation of deposit formation in the heat recovery boiler is carried out and the influence of deposits on heat transfer is investigated. The locations prone to deposit formation are also identified in the heat recovery boiler. Modeling of the two processes in the two industrial furnaces enhances the overall understanding of the processes. The sub-models developed in this work can be applied in other similar deposit formation processes with carefully-defined boundary conditions.

Model based analysis of the post-combustion calcium looping process for carbon dioxide capture

This thesis presents a one-dimensional, semi-empirical dynamic model for the simulation and analysis of a calcium looping process for post-combustion CO2 capture. Reduction of greenhouse emissions from fossil fuel power production requires rapid actions including the development of efficient carbon capture and sequestration technologies. The development of new carbon capture technologies can be expedited by using modelling tools. Techno-economical evaluation of new capture processes can be done quickly and cost-effectively with computational models before building expensive pilot plants. Post-combustion calcium looping is a developing carbon capture process which utilizes fluidized bed technology with lime as a sorbent. The main objective of this work was to analyse the technological feasibility of the calcium looping process at different scales with a computational model. A one-dimensional dynamic model was applied to the calcium looping process, simulating the behaviour of the interconnected circulating fluidized bed reactors. The model incorporates fundamental mass and energy balance solvers to semi-empirical models describing solid behaviour in a circulating fluidized bed and chemical reactions occurring in the calcium loop. In addition, fluidized bed combustion, heat transfer and core-wall layer effects were modelled. The calcium looping model framework was successfully applied to a 30 kWth laboratory scale and a pilot scale unit 1.7 MWth and used to design a conceptual 250 MWth industrial scale unit. Valuable information was gathered from the behaviour of a small scale laboratory device. In addition, the interconnected behaviour of pilot plant reactors and the effect of solid fluidization on the thermal and carbon dioxide balances of the system were analysed. The scale-up study provided practical information on the thermal design of an industrial sized unit, selection of particle size and operability in different load scenarios.

Effect of additives, precursors and process conditions on particle morphology

The objective of the thesis was to develop methods to manufacture and control calcium carbonate crystal nucleation and growth in precipitation process. The work consists of experimental part and literature part that addresses theory of nucleation, crystallization and precipitation. In the experimental part calcium carbonate was precipitated using carbonization reaction. Precipitation was carried out in presence of known morphology controlling agents (anionic polymers and sodium silicate) and by using different operation conditions. Formed material was characterized using SEM images, and its thermal stability was assessed. This work demonstrates that carbon dioxide feeding rate and concentrations of calcium hydroxide and additives can be used to control size, shape and amount of precipitating calcium carbonate.

Greenhouse gas emissions from peat and biomass-derived fuels, electricity and heat — Estimation of various production chains by using LCA methodology

More discussion is required on how and which types of biomass should be used to achieve a significant reduction in the carbon load released into the atmosphere in the short term. The energy sector is one of the largest greenhouse gas (GHG) emitters and thus its role in climate change mitigation is important. Replacing fossil fuels with biomass has been a simple way to reduce carbon emissions because the carbon bonded to biomass is considered as carbon neutral. With this in mind, this thesis has the following objectives: (1) to study the significance of the different GHG emission sources related to energy production from peat and biomass, (2) to explore opportunities to develop more climate friendly biomass energy options and (3) to discuss the importance of biogenic emissions of biomass systems. The discussion on biogenic carbon and other GHG emissions comprises four case studies of which two consider peat utilization, one forest biomass and one cultivated biomasses. Various different biomass types (peat, pine logs and forest residues, palm oil, rapeseed oil and jatropha oil) are used as examples to demonstrate the importance of biogenic carbon to life cycle GHG emissions. The biogenic carbon emissions of biomass are defined as the difference in the carbon stock between the utilization and the non-utilization scenarios of biomass. Forestry-drained peatlands were studied by using the high emission values of the peatland types in question to discuss the emission reduction potential of the peatlands. The results are presented in terms of global warming potential (GWP) values. Based on the results, the climate impact of the peat production can be reduced by selecting high-emission-level peatlands for peat production. The comparison of the two different types of forest biomass in integrated ethanol production in pulp mill shows that the type of forest biomass impacts the biogenic carbon emissions of biofuel production. The assessment of cultivated biomasses demonstrates that several selections made in the production chain significantly affect the GHG emissions of biofuels. The emissions caused by biofuel can exceed the emissions from fossil-based fuels in the short term if biomass is in part consumed in the process itself and does not end up in the final product. Including biogenic carbon and other land use carbon emissions into the carbon footprint calculations of biofuel reveals the importance of the time frame and of the efficiency of biomass carbon content utilization. As regards the climate impact of biomass energy use, the net impact on carbon stocks (in organic matter of soils and biomass), compared to the impact of the replaced energy source, is the key issue. Promoting renewable biomass regardless of biogenic GHG emissions can increase GHG emissions in the short term and also possibly in the long term.

Mitigation possibilities to Greenhouse gas emissions from power production in India

Global warming is assertively the greatest environmental challenge for humans of 21st century. It is primarily caused by the anthropogenic greenhouse gas (GHG) that trap heat in the atmosphere. Because of which, the GHG emission mitigation, globally, is a critical issue in the political agenda of all high-profile nations. India, like other developing countries, is facing this threat of climate change while dealing with the challenge of sustaining its rapid economic growth. India’s economy is closely connected to its natural resource base and climate sensitive sectors like water, agriculture and forestry. Due to Climate change the quality and distribution of India’s natural resources may transform and lead to adverse effects on livelihood of its people. Therefore, India is expected to face a major threat due to the projected climate change. This study proposes possible solutions for GHG emission mitigation that are specific to the power sector of India. The methods discussed here will take Indian power sector from present coal dominant ideology to a system, centered with renewable energy sources. The study further proposes a future scenario for 2050, based on the present Indian government policies and global energy technologies advancements.

Particle model for simulating limestone reactions in novel fluidised bed energy applications

The development of carbon capture and storage (CCS) has raised interest towards novel fluidised bed (FB) energy applications. In these applications, limestone can be utilized for S02 and/or CO2 capture. The conditions in the new applications differ from the traditional atmospheric and pressurised circulating fluidised bed (CFB) combustion conditions in which the limestone is successfully used for SO2 capture. In this work, a detailed physical single particle model with a description of the mass and energy transfer inside the particle for limestone was developed. The novelty of this model was to take into account the simultaneous reactions, changing conditions, and the effect of advection. Especially, the capability to study the cyclic behaviour of limestone on both sides of the calcination-carbonation equilibrium curve is important in the novel conditions. The significances of including advection or assuming diffusion control were studied in calcination. Especially, the effect of advection in calcination reaction in the novel combustion atmosphere was shown. The model was tested against experimental data; sulphur capture was studied in a laboratory reactor in different fluidised bed conditions. Different Conversion levels and sulphation patterns were examined in different atmospheres for one limestone type. The Conversion curves were well predicted with the model, and the mechanisms leading to the Conversion patterns were explained with the model simulations. In this work, it was also evaluated whether the transient environment has an effect on the limestone behaviour compared to the averaged conditions and in which conditions the effect is the largest. The difference between the averaged and transient conditions was notable only in the conditions which were close to the calcination-carbonation equilibrium curve. The results of this study suggest that the development of a simplified particle model requires a proper understanding of physical and chemical processes taking place in the particle during the reactions. The results of the study will be required when analysing complex limestone reaction phenomena or when developing the description of limestone behaviour in comprehensive 3D process models. In order to transfer the experimental observations to furnace conditions, the relevant mechanisms that take place need to be understood before the important ones can be selected for 3D process model. This study revealed the sulphur capture behaviour under transient oxy-fuel conditions, which is important when the oxy-fuel CFB process and process model are developed.

Weed management boosts yield in fine rice under system of rice intensification

The system of rice intensification has emerged as a promising rice production package but weed infestation could lead to incomplete benefits from the system. A two-year field study was performed to determine an appropriate method of weed management in SRI. Weed management treatments were manual hoeing 20, 40 and 60 days after transplanting (DAT), hoeing with rotary hoe at 20, 40 and 60 DAT, hoeing with rotary hoe at 20 DAT + spray with sorghum and sunflower water extracts at 15 L ha-1 40 DAT, manual hoeing 20 DAT + spray with sorghum and sunflower water extracts, both in equal amount, at 15 L ha-1 40 DAT, orthosulfamuron at 145 g a.i. ha-1 7 DAT, weedy check and weed free. Manual hoeing at 20, 40 and 60 DAT was the treatment that exhibited the maximum kernel yield i.e. 5.34 and 4.99 t ha-1., which was 8.4 and 7.2% higher than orthosulfamuron and 61.0 and 64.9% higher than weedy check, during both years of study, respectively. The highest weed suppression was also achieved by manual hoeing at 20, 40 and 60 DAT with weed control efficiency of 87.89 and 82.32% during 2010 and 2011, respectively. Manual hoeing at 20, 40 and 60 DAT is an eco-friendly, non-chemical weed control method to increase kernel yield of fine rice under SRI.

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.

Carta particolare dell fine del Mare Baltico in sino all narue : la longitudine comincia da l'isola di Picho d'Asores [i.e. Pico Azores] : di Europa carta XXXXII

Julkaisussa: Dell' arcano del mare di Ruberto Dudleo ... parte seconda del tomo terzo contenente il libro sesto. Vol III

Minimizing Conducted RF-Emissions in Switch Mode Power Supplies Using Spread-Spectrum Techniques

Switching power supplies are usually implemented with a control circuitry that uses constant clock frequency turning the power semiconductor switches on and off. A drawback of this customary operating principle is that the switching frequency and harmonic frequencies are present in both the conducted and radiated EMI spectrum of the power converter. Various variable-frequency techniques have been introduced during the last decade to overcome the EMC problem. The main objective of this study was to compare the EMI and steady-state performance of a switch mode power supply with different spread-spectrum/variable-frequency methods. Another goal was to find out suitable tools for the variable-frequency EMI analysis. This thesis can be divided into three main parts: Firstly, some aspects of spectral estimation and measurement are presented. Secondly, selected spread spectrum generation techniques are presented with simulations and background information. Finally, simulations and prototype measurements from the EMC and the steady-state performance are carried out in the last part of this work. Combination of the autocorrelation function, the Welch spectrum estimate and the spectrogram were used as a substitute for ordinary Fourier methods in the EMC analysis. It was also shown that the switching function can be used in preliminary EMC analysis of a SMPS and the spectrum and autocorrelation sequence of a switching function correlates with the final EMI spectrum. This work is based on numerous simulations and measurements made with the prototype. All these simulations and measurements are made with the boost DC/DC converter. Four different variable-frequency modulation techniques in six different configurations were analyzed and the EMI performance was compared to the constant frequency operation. Output voltage and input current waveforms were also analyzed in time domain to see the effect of the spread spectrum operation on these quantities. According to the results presented in this work, spread spectrum modulation can be utilized in power converter for EMI mitigation. The results from steady-state voltage measurements show, that the variable-frequency operation of the SMPS has effect on the voltage ripple, but the ripple measured from the prototype is still acceptable in some applications. Both current and voltage ripple can be controlled with proper main circuit and controller design.

Biogas production in regional integrated biodegradable waste treatment – Possibilities for improving energy performance and reducing GHG emissions

The greatest threat that the biodegradable waste causes on the environment is the methane produced in landfills by the decomposition of this waste. The Landfill Directive (1999/31/EC) aims to reduce the landfilling of biodegradable waste. In Finland, 31% of biodegradable municipal waste ended up into landfills in 2012. The pressure of reducing disposing into landfills is greatly increased by the forthcoming landfill ban on biodegradable waste in Finland. There is a need to discuss the need for increasing the utilization of biodegradable waste in regional renewable energy production to utilize the waste in a way that allows the best possibilities to reduce GHG emissions. The objectives of the thesis are: (1) to find important factors affecting renewable energy recovery possibilities from biodegradable waste, (2) to determine the main factors affecting the GHG balance of biogas production system and how to improve it and (3) to find ways to define energy performance of biogas production systems and what affects it. According to the thesis, the most important factors affecting the regional renewable energy possibilities from biodegradable waste are: the amount of available feedstock, properties of feedstock, selected utilization technologies, demand of energy and material products and the economic situation of utilizing the feedstocks. The biogas production by anaerobic digestion was seen as the main technology for utilizing biodegradable waste in agriculturally dense areas. The main reason for this is that manure was seen as the main feedstock, and it can be best utilized with anaerobic digestion, which can produce renewable energy while maintaining the spreading of nutrients on arable land. Biogas plants should be located close to the heat demand that would be enough to receive the produced heat also in the summer months and located close to the agricultural area where the digestate could be utilized. Another option for biogas use is to upgrade it to biomethane, which would require a location close to the natural gas grid. The most attractive masses for biogas production are municipal and industrial biodegradable waste because of gate fees the plant receives from them can provide over 80% of the income. On the other hand, directing gate fee masses for small-scale biogas plants could make dispersed biogas production more economical. In addition, the combustion of dry agricultural waste such as straw would provide a greater energy amount than utilizing them by anaerobic digestion. The complete energy performance assessment of biogas production system requires the use of more than one system boundary. These can then be used in calculating output–input ratios of biogas production, biogas plant, biogas utilization and biogas production system, which can be used to analyze different parts of the biogas production chain. At the moment, it is difficult to compare different biogas plants since there is a wide variation of definitions for energy performance of biogas production. A more consistent way of analyzing energy performance would allow comparing biogas plants with each other and other recovery systems and finding possible locations for further improvement. Both from the GHG emission balance and energy performance point of view, the energy consumption at the biogas plant was the most significant factor. Renewable energy use to fulfil the parasitic energy demand at the plant would be the most efficient way to reduce the GHG emissions at the plant. The GHG emission reductions could be increased by upgrading biogas to biomethane and displacing natural gas or petrol use in cars when compared to biogas CHP production. The emission reductions from displacing mineral fertilizers with digestate were seen less significant, and the greater N2O emissions from spreading digestate might surpass the emission reductions from displacing mineral fertilizers.

Catalytic upgrading of biomass extractives to fine chemicals over supported ionic liquid catalysts (SILCAs)

Behovet av förnyelsebar energi ökar ständigt eftersom det finns en strävan att minska beroendet av fossila bränslen. Dessutom är tillgångar av fossila bränslen begränsade. Miljövänliga processer för bioraffinaderier erbjuder en stor möjlighet för produktion av energi, bränslen och kemikalier. Den finska och svenska skogsindustrin har en lång tradition i utnyttjandet av skogsbiomassor. Bioraffinaderier som integreras med pappers- och cellulosaindustrin kan frambringa både ekonomiska och ekologiska fördelar i framställning av traditionella och biobaserade produkter. I doktorsarbetet studerades omvandling av extraktivämnen till finkemikalier som kan användas t.ex. av läkemedelsindustrin. Extraktivämnen fås ur biomassa. I forskningsarbetet framställdes biobaserade finkemikalier med hjälp av katalysatorer som baserar sig på joniska vätskor. Biomassan består av cellulosa, hemicellulosa, lignin och extraktivämnen, vilka huvudsakligen är terpener, vaxer och fettsyror. Extraktivämen är vedens komponenter, som kan separeras ur vedmaterialet med hjälp av neutrala lösningsmedel. Joniska vätskekatalysatorer som var immobiliserade på fasta bärare utnyttjades för isomerisering av α,β-pinenoxider samt hydrogenering citral. Inverkan av joniska vätskor på katalysatorns aktivitet och reaktionernas produktfördelning undersöktes under varierande reaktionsbetingelser. Kinetiska modeller för pinenoxidens isomeriseringsreaktioner beskrev väl experimentellt upptäckta skillnader mellan olika katalysatorer. --------------------------------------------------- Uusiutuvan energian tarve on kasvussa, koska riippuvuutta fossiilisista polttoaineista pyritään vähentämään. Tämän lisäksi fossiilisten polttoaineiden varannot ovat rajalliset. Ympäristöystävälliset biojalostusprosessit ovat näin ollen suuri mahdollisuus energian, polttoaineiden ja kemikaalien tuotannossa. Suomen ja Ruotsin metsäteollisuudella on pitkät perinteet metsäbiomassojen hyödyntämisessä. Paperi- ja selluteollisuuden yhteyteen integroiduilla biojalostamoilla voidaan luoda taloudellisia ja ympäristöllisiä etuja sekä perinteisten että biopohjaisten tuotteiden valmistuksessa. Väitöstyössä on tutkittu biomassan uuteaineiden kemiallista muuntamista hienokemikaaleiksi, joita voidaan käyttää esimerkiksi lääkeaineteollisuudessa. Biopohjaisia hienokemikaaleja on valmistettu biomassan uuteaineista ionisiin nesteisiin perustuvilla katalyyteillä. Biomassa koostuu selluloosasta, hemiselluloosasta, ligniinistä sekä uuteaineista, jotka ovat pääosin terpeenejä, vahoja tai rasvahappoja. Uuteaineet ovat puun komponentteja, jotka voidaan erottaa puusta neutraalien liuottimien avulla. Kiinteän kantajan päälle immobilisoituja ionisia nestekatalyyttejä (Supported Ionic Liquid Catalyst) hyödynnettiin α,β-pineenioksidien isomerisointireaktioissa sekä sitraalin vedytysreaktioissa. Ionisten nesteiden vaikutusta katalyyttien aktiivisuuteen sekä reaktioiden tuotejakaumaan tutkittiin erilaisissa reaktio-olosuhteissa. Pineenioksidien isomerisointireaktioiden kineettiset mallit kuvasivat hyvin kokeellisesti todettuja katalyyttien eroavaisuuksia.

Reduction of nitrogen oxide emissions in lime kiln

Different nitrogen oxide removal technologies for rotary lime kiln are studied in this thesis, the main focus being in commercial technologies. Post-combustion methods are investigated in more detail as potential possible NOx removal with combustion methods in rotary lime kiln is more limited or primary methods are already in use. However, secondary methods as NOx scrubber, SNCR or SCR technologies are not listed as the Best Available Technologies defined by European Union. BAT technologies for NOx removal in lime kiln are (1) Optimised combustion and combustion control, (2) Good mixing of fuel and air, (3) Low-NOx burner and (4) Fuel selection/low-N fuel. SNCR method is the most suitable technique for NOx removal in lime kiln when NOx removal from 50 % to 70 % is required in case primary methods are already in use or cannot be applied. In higher removal cases ammonia slip is an issue in SNCR. By using SCR better NOx reduction can be achieved but issues with catalyst materials are expected to arise because of the dust and sulphur dioxide which leads to catalyst poison formation in lower flue gas temperatures. NOx scrubbing has potential when simultaneous NOx and SO2 removal is required. The challenge is that NO cannot be scrubbed directly, but once it is oxidized to NO2 or further scrubbing can be performed as the solubility of NO2 is higher. Commercial installations have not been made regarding SNCR, SCR or NOx scrubbing regarding rotary lime kiln. For SNCR and SCR the closest references come from cement industry.