Wet Oxidation of Concentrated Wastewaters: Process Combination and Reaction Kinetic Modeling

The accumulation of aqueous pollutants is becoming a global problem. The search for suitable methods and/or combinations of water treatment processes is a task that can slow down and stop the process of water pollution. In this work, the method of wet oxidation was considered as an appropriate technique for the elimination of the impurities present in paper mill process waters. It has been shown that, when combined with traditional wastewater treatment processes, wet oxidation offers many advantages. The combination of coagulation and wet oxidation offers a new opportunity for the improvement of the quality of wastewater designated for discharge or recycling. First of all, the utilization of coagulated sludge via wet oxidation provides a conditioning process for the sludge, i.e. dewatering, which is rather difficult to carry out with untreated waste. Secondly, Fe2(SO4)3, which is employed earlier as a coagulant, transforms the conventional wet oxidation process into a catalytic one. The use of coagulation as the post-treatment for wet oxidation can offer the possibility of the brown hue that usually accompanies the partial oxidation to be reduced. As a result, the supernatant is less colored and also contains a rather low amount of Fe ions to beconsidered for recycling inside mills. The thickened part that consists of metal ions is then recycled back to the wet oxidation system. It was also observed that wet oxidation is favorable for the degradation of pitch substances (LWEs) and lignin that are present in the process waters of paper mills. Rather low operating temperatures are needed for wet oxidation in order to destruct LWEs. The oxidation in the alkaline media provides not only the faster elimination of pitch and lignin but also significantly improves the biodegradable characteristics of wastewater that contains lignin and pitch substances. During the course of the kinetic studies, a model, which can predict the enhancements of the biodegradability of wastewater, was elaborated. The model includes lumped concentrations suchas the chemical oxygen demand and biochemical oxygen demand and reflects a generalized reaction network of oxidative transformations. Later developments incorporated a new lump, the immediately available biochemical oxygen demand, which increased the fidelity of the predictions made by the model. Since changes in biodegradability occur simultaneously with the destruction of LWEs, an attempt was made to combine these two facts for modeling purposes.

Selective catalytic reduction of nitrogen oxides with ammonia in forced unsteady state reactors - Case based reasoning and mathematical model simulation reasoning

The application of forced unsteady-state reactors in case of selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3) is sustained by the fact that favorable temperature and composition distributions which cannot be achieved in any steady-state regime can be obtained by means of unsteady-state operations. In a normal way of operation the low exothermicity of the selective catalytic reduction (SCR) reaction (usually carried out in the range of 280-350°C) is not enough to maintain by itself the chemical reaction. A normal mode of operation usually requires supply of supplementary heat increasing in this way the overall process operation cost. Through forced unsteady-state operation, the main advantage that can be obtained when exothermic reactions take place is the possibility of trapping, beside the ammonia, the moving heat wave inside the catalytic bed. The unsteady state-operation enables the exploitation of the thermal storage capacity of the catalyticbed. The catalytic bed acts as a regenerative heat exchanger allowing auto-thermal behaviour when the adiabatic temperature rise is low. Finding the optimum reactor configuration, employing the most suitable operation model and identifying the reactor behavior are highly important steps in order to configure a proper device for industrial applications. The Reverse Flow Reactor (RFR) - a forced unsteady state reactor - corresponds to the above mentioned characteristics and may be employed as an efficient device for the treatment of dilute pollutant mixtures. As a main disadvantage, beside its advantages, the RFR presents the 'wash out' phenomena. This phenomenon represents emissions of unconverted reactants at every switch of the flow direction. As a consequence our attention was focused on finding an alternative reactor configuration for RFR which is not affected by the incontrollable emissions of unconverted reactants. In this respect the Reactor Network (RN) was investigated. Its configuration consists of several reactors connected in a closed sequence, simulating a moving bed by changing the reactants feeding position. In the RN the flow direction is maintained in the same way ensuring uniformcatalyst exploitation and in the same time the 'wash out' phenomena is annulated. The simulated moving bed (SMB) can operate in transient mode giving practically constant exit concentration and high conversion levels. The main advantage of the reactor network operation is emphasizedby the possibility to obtain auto-thermal behavior with nearly uniformcatalyst utilization. However, the reactor network presents only a small range of switching times which allow to reach and to maintain an ignited state. Even so a proper study of the complex behavior of the RN may give the necessary information to overcome all the difficulties that can appear in the RN operation. The unsteady-state reactors complexity arises from the fact that these reactor types are characterized by short contact times and complex interaction between heat and mass transportphenomena. Such complex interactions can give rise to a remarkable complex dynamic behavior characterized by a set of spatial-temporal patterns, chaotic changes in concentration and traveling waves of heat or chemical reactivity. The main efforts of the current research studies concern the improvement of contact modalities between reactants, the possibility of thermal wave storage inside the reactor and the improvement of the kinetic activity of the catalyst used. Paying attention to the above mentioned aspects is important when higher activity even at low feeding temperatures and low emissions of unconverted reactants are the main operation concerns. Also, the prediction of the reactor pseudo or steady-state performance (regarding the conversion, selectivity and thermal behavior) and the dynamicreactor response during exploitation are important aspects in finding the optimal control strategy for the forced unsteady state catalytic tubular reactors. The design of an adapted reactor requires knowledge about the influence of its operating conditions on the overall process performance and a precise evaluation of the operating parameters rage for which a sustained dynamic behavior is obtained. An apriori estimation of the system parameters result in diminution of the computational efforts. Usually the convergence of unsteady state reactor systems requires integration over hundreds of cycles depending on the initial guess of the parameter values. The investigation of various operation models and thermal transfer strategies give reliable means to obtain recuperative and regenerative devices which are capable to maintain an auto-thermal behavior in case of low exothermic reactions. In the present research work a gradual analysis of the SCR of NOx with ammonia process in forced unsteady-state reactors was realized. The investigation covers the presentationof the general problematic related to the effect of noxious emissions in the environment, the analysis of the suitable catalysts types for the process, the mathematical analysis approach for modeling and finding the system solutions and the experimental investigation of the device found to be more suitable for the present process. In order to gain information about the forced unsteady state reactor design, operation, important system parameters and their values, mathematical description, mathematicalmethod for solving systems of partial differential equations and other specific aspects, in a fast and easy way, and a case based reasoning (CBR) approach has been used. This approach, using the experience of past similarproblems and their adapted solutions, may provide a method for gaining informations and solutions for new problems related to the forced unsteady state reactors technology. As a consequence a CBR system was implemented and a corresponding tool was developed. Further on, grooving up the hypothesis of isothermal operation, the investigation by means of numerical simulation of the feasibility of the SCR of NOx with ammonia in the RFRand in the RN with variable feeding position was realized. The hypothesis of non-isothermal operation was taken into account because in our opinion ifa commercial catalyst is considered, is not possible to modify the chemical activity and its adsorptive capacity to improve the operation butis possible to change the operation regime. In order to identify the most suitable device for the unsteady state reduction of NOx with ammonia, considering the perspective of recuperative and regenerative devices, a comparative analysis of the above mentioned two devices performance was realized. The assumption of isothermal conditions in the beginningof the forced unsteadystate investigation allowed the simplification of the analysis enabling to focus on the impact of the conditions and mode of operation on the dynamic features caused by the trapping of one reactant in the reactor, without considering the impact of thermal effect on overall reactor performance. The non-isothermal system approach has been investigated in order to point out the important influence of the thermal effect on overall reactor performance, studying the possibility of RFR and RN utilization as recuperative and regenerative devices and the possibility of achieving a sustained auto-thermal behavior in case of lowexothermic reaction of SCR of NOx with ammonia and low temperature gasfeeding. Beside the influence of the thermal effect, the influence of the principal operating parameters, as switching time, inlet flow rate and initial catalyst temperature have been stressed. This analysis is important not only because it allows a comparison between the two devices and optimisation of the operation, but also the switching time is the main operating parameter. An appropriate choice of this parameter enables the fulfilment of the process constraints. The level of the conversions achieved, the more uniform temperature profiles, the uniformity ofcatalyst exploitation and the much simpler mode of operation imposed the RN as a much more suitable device for SCR of NOx with ammonia, in usual operation and also in the perspective of control strategy implementation. Theoretical simplified models have also been proposed in order to describe the forced unsteady state reactors performance and to estimate their internal temperature and concentration profiles. The general idea was to extend the study of catalytic reactor dynamics taking into account the perspectives that haven't been analyzed yet. The experimental investigation ofRN revealed a good agreement between the data obtained by model simulation and the ones obtained experimentally.

Puhdistetun jäteveden patogeenit ja desinfiointitarve

Turun seudulla kuuden kunnan jätevesien käsittely keskitetään Kakolanmäen kallion sisälle rakennettuun jätevedenpuhdistamoon, joka otetaan käyttöön vuoden 2008 lopulla. Kakolanmäen jätevedenpuhdistamolla on varauduttu tulevaisuudessa kiristyviin lupaehtoihin sekä mahdollisiin puhdistetun jäteveden hygieenistä laatua koskeviin lisämääräyksiin jättämällä tilavaraus puhdistetun jäteveden desinfioimiselle ultraviolettivalolla. Diplomityössä on selvitetty vuoden kestäneessä tutkimusjaksossa 1.9.2006- 31.8.2007 Turun kaupungin keskuspuhdistamolta mereen johdetun puhdistetun jäteveden ja esiselkeytetyn ohitusveden hygieenisen laadun vaihtelua. Jäteveden desinfiointitarvetta on arvioitu tarkastelemalla jätevedenpuhdistamon hygieenistä puhdistustulosta ja jätevesien vaikutusta purkuvesistön hygieeniseen tilaan. Tutkimuksen perusteella virtaama ei vaikuttanut merkittävästi jäteveden ulosteperäisten bakteerien määriin. Sen sijaan jäteveden bakteeripitoisuudet laskivat alhaisissa lämpötiloissa. Lämpötilan vaikutus näkyi selkeämmin esiselkeytetyssä kuin puhdistetussa jätevedessä eli bakteerien poistumiseen aktiivilietevaiheen aikana vaikuttavat muut tekijät. Mitä tehokkaammin aktiivilietevaihe toimi, sitä tehokkaammin myös bakteereja poistui. Taudinaiheuttajabakteerit selvisivät puhdistusprosessista paremmin viileän kauden aikana. Puhdistetun jäteveden hygieeninen laatu ei täyttänyt uimaveden tai kasteluveden laatuvaatimuksia, joten desinfiointitarve olisi perustelua. Jätevesien vaikutus Turun edustan merialueen hygieeniseen tilaan näkyi ajoittain korkeina bakteeripitoisuuksina purkupaikan lähistöllä. Vielä ei ole suoraa näyttöä siitä aiheuttavatko jätevedet purkupaikan lähistön uimarannoilla terveydellisiä riskejä. Jäteveden UV-desinfiointi kannattava toteuttaa vain jos hygieeninen puhdistusvelvoite määrätään. UV-desinfioinnin mitoituksessa Kakolanmäen jätevedenpuhdistamolla tulee ottaa huomioon suurin sallittu hydraulinen painehäviö. Mitoitus voidaan tehdä puhdistamon käyttöönoton jälkeen kun tarvitut prosessimittaustiedot ovat saatavilla.

Atomikerroskasvatuksen soveltaminen kemiantekniikassa

Tässä kirjallisuustyössä tutkittiin atomikerroskasvatuksen (ALD) soveltamista kemiantekniikassa. Työn alussa kerrottiin atomikerroskasvatuksesta, sen toimintaperiaatteista ja prosessitekniikasta. Tämän jälkeen tutkittiin viittä eri kemiantekniikan sovellusta, jotka olivat polymeerien pinnoittaminen, heterogeenisten katalyyttien syntetisointi, membraanien modifiointi, korroosionesto ja kaasunilmaisimet. ALD on ohutkalvotekniikka, jolla voidaan valmistaa nanometrin tai jopa Ångströmin (1 Å = 0.1 nm) tarkkuudella epäorgaanisia materiaalikerroksia, jotka yleensä ovat metallioksideja, kuten alumiinioksidi. ALD perustuu kaasu-kiintoainereaktioihin, joissa kaasumaiset kemialliset prekursorit reagoivat vuorotellen kasvualustan kanssa. Tyypilliset prekursorit ovat metalliligandi ja vesi, joka on yleisin hapen lähde ALD-reaktioissa. ALD−reaktiot suoritetaan yleensä matalassa paineessa (100−200 Pa) ja korkeassa lämpötilassa (200–400 °C) suljetussa reaktorikammiossa. ALD-prosesseissa voidaan hyödyntää myös plasmaa alentamaan reaktiolämpötiloja. Plasman avulla prekursoreista luodaan hyvin reaktiivisia radikaaleja, jotka voivat reagoida jopa huoneenlämmössä. Lämpöherkkiä polymeerejä voidaan pinnoittaa ohutkalvoilla, joilla voidaan lisätä esimerkiksi pakkausmateriaalien suojaa happea ja vesihöyryä vastaan. ALD:llä voidaan syntetisoida tarkasti nanomittakaavan heterogeenisiä katalyyttejä, joilla on korkea dispersio tukimateriaalin pinnalla. ALD:n avulla voidaan säästää katalyyttimateriaalia menettämättä katalyytin aktiivisuutta, mikä on tärkeää monien katalyyttisovellusten taloudellisuuden kannalta, esimerkiksi polttokennot. ALD soveltuu hyvin membraanien modifiointiin, koska kaasumaiset prekursorit leviävät tasaisesti membraanin huokosiin. Membraanien pinnoittamisella pyritään vaikuttamaan, selektiivisyyteen, hydrofiilisyyteen, liuotinkestävyyteen, huokoskokoon ja sen jakaumaan. Lisäksi membraaneja voidaan pinnoittaa katalyyttisillä ohutkalvoilla, mikä on tärkeää nanoreaktoreiden kehityksen kannalta. ALD:llä voidaan pinnoittaa esimerkiksi terästä, ja vähentää täten teräksen korroosiota. Puolijohtavia metallioksideja voidaan käyttää kaasunilmaisimina, joiden valmistuksessa ALD:n tarkkuudesta on suurta hyötyä.

Corrosion behaviour of boiler tube materials during combustion of fuels containing Zn and Pb

Många förbränningsanläggningar som bränner utmanande bränslen såsom restfraktioner och avfall råkar ut för problem med ökad korrosion på överhettare och/eller vattenväggar pga. komponenter i bränslena som är korrosiva. För att minimera problemen i avfallseldade pannor hålls ångparametrarna på en relativt låg nivå, vilket drastiskt minskar energiproduktionen. Beläggningarna i avfallseldade pannor består till största delen av element som är förknippade med högtemperaturkorrosion: Cl, S, alkalimetaller, främst K och Na, och tungmetaller som Pb och Zn, och det finns också indikationer av Br-förekomst. Det låga ångtrycket i avfallseldade pannor påverkar också stålrörens temperatur i pannväggarna i eldstaden. I dagens läge hålls temperaturen normalt vid 300-400 °C. Alkalikloridorsakad (KCl, NaCl) högtemperaturkorrosion har inte rapporterats vara relevant vid såpass låga temperaturer, men närvaro av Zn- och Pb-komponenter i beläggningarna har påvisats förorsaka ökad korrosion redan vid 300-400 °C. Vid förbränning kan Zn och Pb reagera med S och Cl och bilda klorider och sulfater i rökgaserna. Dessa tungmetallföreningar är speciellt problematiska pga. de bildar lågsmältande saltblandningar. Dessa lågsmältande gasformiga eller fasta föreningar följer rökgasen och kan sedan fastna eller kondensera på kallare ytor på pannväggar eller överhettare för att sedan bilda aggressiva beläggningar. Tungmetallrika (Pb, Zn) klorider och sulfater ökar risken för korrosion, och effekten förstärks ytterligare vid närvaro av smälta. Motivet med den här studien var att få en bättre insikt i högtemperaturkorrosion förorsakad av Zn och Pb, samt att undersöka och prediktera beteendet och motståndskraften hos några stålkvaliteter som används i överhettare och pannväggar i tungmetallrika förhållanden och höga materialtemperaturer. Omfattande laboratorie-, småskale- och fullskaletest utfördes. Resultaten kan direkt utnyttjas i praktiska applikationer, t.ex. vid materialval, eller vid utveckling av korrosionsmotverkande verktyg för att hitta initierande faktorer och förstå deras effekt på högtemperaturkorrosion.

Waste-to-Energy Scenarios in the China Context

Waste incineration plants are increasingly established in China. A low heating value and high moisture content, due to a large proportion of biowaste in the municipal solid waste (MSW), can be regarded as typical characteristics of Chinese MSW. Two incineration technologies have been mainly established in China: stoker grate and circular fluidized bed (CFB). Both of them are designed to incinerate mixed MSW. However, there have been difficulties to reach the sufficient temperature in the combustion process due to the low heating value of the MSW. That is contributed to the usage of an auxiliary fossil fuel, which is often used during the whole incineration process. The objective of this study was to design alternative Waste-to-energy (WTE) scenarios for existing WTE plants with the aim to improve the material and energy efficiency as well as the feasibility of the plants. Moreover, the aim of this thesis was to find the key factors that affect to the feasibility of the scenarios. Five different WTE plants were selected as study targets. The necessary data for calculation was gained from literature as well as received from the operators of the target WTE plants. The created scenarios were based on mechanical-biological treatment (MBT) technologies, in which the produced solid recovered fuel (SRF) was fed as an auxiliary fuel into a WTE plant replacing the fossil fuel. The mechanically separated biowaste was treated either in an anaerobic digestion (AD) plant, a biodrying plant, a thermal drying plant, or a combined AD plant + thermal drying plant. An interactive excel spreadsheet based computation tool was designed to estimate the viability of the scenarios in different WTE cases. The key figures of the improved material and energy efficiency, such as additional electricity generated and avoided waste for landfill, were got as results. Furthermore, economic indicators such as annual profits (or costs), payback period, and internal rate of return (IRR) were gained as results. The results show that the AD scenario was the most profitable in most of the cases. The current heating value of MSW and the tipping fee for the received MSW appeared as the most important factor in terms of feasibility.

Susteinable steelmaking by process integration

Environmental issues, including global warming, have been serious challenges realized worldwide, and they have become particularly important for the iron and steel manufacturers during the last decades. Many sites has been shut down in developed countries due to environmental regulation and pollution prevention while a large number of production plants have been established in developing countries which has changed the economy of this business. Sustainable development is a concept, which today affects economic growth, environmental protection, and social progress in setting up the basis for future ecosystem. A sustainable headway may attempt to preserve natural resources, recycle and reuse materials, prevent pollution, enhance yield and increase profitability. To achieve these objectives numerous alternatives should be examined in the sustainable process design. Conventional engineering work cannot address all of these substitutes effectively and efficiently to find an optimal route of processing. A systematic framework is needed as a tool to guide designers to make decisions based on overall concepts of the system, identifying the key bottlenecks and opportunities, which lead to an optimal design and operation of the systems. Since the 1980s, researchers have made big efforts to develop tools for what today is referred to as Process Integration. Advanced mathematics has been used in simulation models to evaluate various available alternatives considering physical, economic and environmental constraints. Improvements on feed material and operation, competitive energy market, environmental restrictions and the role of Nordic steelworks as energy supplier (electricity and district heat) make a great motivation behind integration among industries toward more sustainable operation, which could increase the overall energy efficiency and decrease environmental impacts. In this study, through different steps a model is developed for primary steelmaking, with the Finnish steel sector as a reference, to evaluate future operation concepts of a steelmaking site regarding sustainability. The research started by potential study on increasing energy efficiency and carbon dioxide reduction due to integration of steelworks with chemical plants for possible utilization of available off-gases in the system as chemical products. These off-gases from blast furnace, basic oxygen furnace and coke oven furnace are mainly contained of carbon monoxide, carbon dioxide, hydrogen, nitrogen and partially methane (in coke oven gas) and have proportionally low heating value but are currently used as fuel within these industries. Nonlinear optimization technique is used to assess integration with methanol plant under novel blast furnace technologies and (partially) substitution of coal with other reducing agents and fuels such as heavy oil, natural gas and biomass in the system. Technical aspect of integration and its effect on blast furnace operation regardless of capital expenditure of new operational units are studied to evaluate feasibility of the idea behind the research. Later on the concept of polygeneration system added and a superstructure generated with alternative routes for off-gases pretreatment and further utilization on a polygeneration system producing electricity, district heat and methanol. (Vacuum) pressure swing adsorption, membrane technology and chemical absorption for gas separation; partial oxidation, carbon dioxide and steam methane reforming for methane gasification; gas and liquid phase methanol synthesis are the main alternative process units considered in the superstructure. Due to high degree of integration in process synthesis, and optimization techniques, equation oriented modeling is chosen as an alternative and effective strategy to previous sequential modelling for process analysis to investigate suggested superstructure. A mixed integer nonlinear programming is developed to study behavior of the integrated system under different economic and environmental scenarios. Net present value and specific carbon dioxide emission is taken to compare economic and environmental aspects of integrated system respectively for different fuel systems, alternative blast furnace reductants, implementation of new blast furnace technologies, and carbon dioxide emission penalties. Sensitivity analysis, carbon distribution and the effect of external seasonal energy demand is investigated with different optimization techniques. This tool can provide useful information concerning techno-environmental and economic aspects for decision-making and estimate optimal operational condition of current and future primary steelmaking under alternative scenarios. The results of the work have demonstrated that it is possible in the future to develop steelmaking towards more sustainable operation.

Hydrogen Sensor Application of Anodic Titanium Oxide Nanostructures

Hydrogen (H2) fuel cells have been considered a promising renewable energy source. The recent growth of H2 economy has required highly sensitive, micro-sized and cost-effective H2 sensor for monitoring concentrations and alerting to leakages due to the flammability and explosiveness of H2 Titanium dioxide (TiO2) made by electrochemical anodic oxidation has shown great potential as a H2 sensing material. The aim of this thesis is to develop highly sensitive H2 sensor using anodized TiO2. The sensor enables mass production and integration with microelectronics by preparing the oxide layer on suitable substrate. Morphology, elemental composition, crystal phase, electrical properties and H2 sensing properties of TiO2 nanostructures prepared on Ti foil, Si and SiO2/Si substrates were characterized. Initially, vertically oriented TiO2 nanotubes as the sensing material were obtained by anodizing Ti foil. The morphological properties of tubes could be tailored by varying the applied voltages of the anodization. The transparent oxide layer creates an interference color phenomena with white light illumination on the oxide surface. This coloration effect can be used to predict the morphological properties of the TiO2 nanostructures. The crystal phase transition from amorphous to anatase or rutile, or the mixture of anatase and rutile was observed with varying heat treatment temperatures. However, the H2 sensing properties of TiO2 nanotubes at room temperature were insufficient. H2 sensors using TiO2 nanostructures formed on Si and SiO2/Si substrates were demonstrated. In both cases, a Ti layer deposited on the substrates by a DC magnetron sputtering method was successfully anodized. A mesoporous TiO2 layer obtained on Si by anodization in an aqueous electrolyte at 5°C showed diode behavior, which was influenced by the work function difference of Pt metal electrodes and the oxide layer. The sensor enabled the detection of H2 (20-1000 ppm) at low operating temperatures (50–140°C) in ambient air. A Pd decorated tubular TiO2 layer was prepared on metal electrodes patterned SiO2/Si wafer by anodization in an organic electrolyte at 5°C. The sensor showed significantly enhanced H2 sensing properties, and detected hydrogen in the range of a few ppm with fast response/recovery time. The metal electrodes placed under the oxide layer also enhanced the mechanical tolerance of the sensor. The concept of TiO2 nanostructures on alternative substrates could be a prospect for microelectronic applications and mass production of gas sensors. The gas sensor properties can be further improved by modifying material morphologies and decorating it with catalytic materials.

Ultimate capacity of stainless steel rectangular hollow section X- joints at low temperatures

Growing demand for stainless steel construction materials has increased the popularity of substitutive materials for austenitic stainless steels. The lean duplex grades have taken their place in building of structures exposed to corrosive environments. Since the duplex grades are relatively new materials, the current codes and norms do not fully cover the newest duplex grades. The joints tested in this thesis were designed and studied according to Eurocode 3, even though all the materials are not yet accepted to the standards. The main objective in this thesis was to determine the differences of the used materials in behaviour under loading at low temperatures. Tests in which the deformation and strength properties of the joints were determined were done at the temperature of -46°C, which is the requirement of temperature for structures designed according to Norsok standards. Results show that replacing the austenitic grade with the lean duplex grade is acceptable.

Feasibility Study and Market Review of Small Scale Bioenergy Heating Plants in North-West Russia

The paper is focused on feasibility study and market review of small scale bioenergy heating plants in the Russian North-West region. The main focus is effective and competitive usage of low-grade wood for heating purposes in the region. As example of economical feasibility estimation it was chosen the project of reconstruction of small scale boiler plant in Leningrad region that Brofta Oy is planning to implement the nearest time. It includes calculation the payback time with and without interest, the estimation of probable investments, the evaluation of possible risks and research on the potential of small scale heating plants projects. Calculations show that the profitability of this kind of projects is high, but payback time is not very short, because of high level of initial investments. Though, the development of small scale bioenergy heating plants in the region is considered to be the best way to solve the problems of heat supply in small settlements using own biomass resources.

Wet oxidation of recalcitrant lignin waters: Experimental and kinetic studies

The dissertation is based on four articles dealing with recalcitrant lignin water purification. Lignin, a complicated substance and recalcitrant to most treatment technologies, inhibits seriously pulp and paper industry waste management. Therefore, lignin is studied, using WO as a process method for its degradation. A special attention is paid to the improvement in biodegradability and the reduction of lignin content, since they have special importance for any following biological treatment. In most cases wet oxidation is not used as a complete ' mineralization method but as a pre treatment in order to eliminate toxic components and to reduce the high level of organics produced. The combination of wet oxidation with a biological treatment can be a good option due to its effectiveness and its relatively low technology cost. The literature part gives an overview of Advanced Oxidation Processes (AOPs). A hot oxidation process, wet oxidation (WO), is investigated in detail and is the AOP process used in the research. The background and main principles of wet oxidation, its industrial applications, the combination of wet oxidation with other water treatment technologies, principal reactions in WO, and key aspects of modelling and reaction kinetics are presented. There is also given a wood composition and lignin characterization (chemical composition, structure and origin), lignin containing waters, lignin degradation and reuse possibilities, and purification practices for lignin containing waters. The aim of the research was to investigate the effect of the operating conditions of WO, such as temperature, partial pressure of oxygen, pH and initial concentration of wastewater, on the efficiency, and to enhance the process and estimate optimal conditions for WO of recalcitrant lignin waters. Two different waters are studied (a lignin water model solution and debarking water from paper industry) to give as appropriate conditions as possible. Due to the great importance of re using and minimizing the residues of industries, further research is carried out using residual ash of an Estonian power plant as a catalyst in wet oxidation of lignin-containing water. Developing a kinetic model that includes in the prediction such parameters as TOC gives the opportunity to estimate the amount of emerging inorganic substances (degradation rate of waste) and not only the decrease of COD and BOD. The degradation target compound, lignin is included into the model through its COD value (CODligning). Such a kinetic model can be valuable in developing WO treatment processes for lignin containing waters, or other wastewaters containing one or more target compounds. In the first article, wet oxidation of "pure" lignin water was investigated as a model case with the aim of degrading lignin and enhancing water biodegradability. The experiments were performed at various temperatures (110 -190°C), partial oxygen pressures (0.5 -1.5 MPa) and pH (5, 9 and 12). The experiments showed that increasing the temperature notably improved the processes efficiency. 75% lignin reduction was detected at the lowest temperature tested and lignin removal improved to 100% at 190°C. The effect of temperature on the COD removal rate was lower, but clearly detectable. 53% of organics were oxidized at 190°C. The effect of pH occurred mostly on lignin removal. Increasing the pH enhanced the lignin removal efficiency from 60% to nearly 100%. A good biodegradability ratio (over 0.5) was generally achieved. The aim of the second article was to develop a mathematical model for "pure" lignin wet oxidation using lumped characteristics of water (COD, BOD, TOC) and lignin concentration. The model agreed well with the experimental data (R2 = 0.93 at pH 5 and 12) and concentration changes during wet oxidation followed adequately the experimental results. The model also showed correctly the trend of biodegradability (BOD/COD) changes. In the third article, the purpose of the research was to estimate optimal conditions for wet oxidation (WO) of debarking water from the paper industry. The WO experiments were' performed at various temperatures, partial oxygen pressures and pH. The experiments showed that lignin degradation and organics removal are affected remarkably by temperature and pH. 78-97% lignin reduction was detected at different WO conditions. Initial pH 12 caused faster removal of tannins/lignin content; but initial pH 5 was more effective for removal of total organics, represented by COD and TOC. Most of the decrease in organic substances concentrations occurred in the first 60 minutes. The aim of the fourth article was to compare the behaviour of two reaction kinetic models, based on experiments of wet oxidation of industrial debarking water under different conditions. The simpler model took into account only the changes in COD, BOD and TOC; the advanced model was similar to the model used in the second article. Comparing the results of the models, the second model was found to be more suitable for describing the kinetics of wet oxidation of debarking water. The significance of the reactions involved was compared on the basis of the model: for instance, lignin degraded first to other chemically oxidizable compounds rather than directly to biodegradable products. Catalytic wet oxidation of lignin containing waters is briefly presented at the end of the dissertation. Two completely different catalysts were used: a commercial Pt catalyst and waste power plant ash. CWO showed good performance using 1 g/L of residual ash gave lignin removal of 86% and COD removal of 39% at 150°C (a lower temperature and pressure than with WO). It was noted that the ash catalyst caused a remarkable removal rate for lignin degradation already during the pre heating for `zero' time, 58% of lignin was degraded. In general, wet oxidation is not recommended for use as a complete mineralization method, but as a pre treatment phase to eliminate toxic or difficultly biodegradable components and to reduce the high level of organics. Biological treatment is an appropriate post treatment method since easily biodegradable organic matter remains after the WO process. The combination of wet oxidation with subsequent biological treatment can be an effective option for the treatment of lignin containing waters.

Matalalämpötilaisen hukkalämmön hyödyntäminen kaukolämmön tuotannossa

Työ käsittelee tekniikoita, joilla voidaan hyödyntää matalalämpötilaisia hukkalämpöjä kaukolämmöntuotannossa. Työ esittelee lämpöpumpputekniikkaa, jolla hukkalämmön lähteestä tulevaa lämpöä voidaan lämpötilaltaan nostaa kaukolämpöverkon tarpeita vastaavaksi. Työssä käsitellään lämpöpumppujen kylmäaineita ja niiden soveltuvuutta eri lämpötila-alueisiin. Lisäksi käsitellään hyödyntämisen taloudellisuutta ja ympäristövaikutuksia. Taloudellisuudessa käsitellään investointi- ja käyttökustannukset ja pohditaan niiden pohjalta tuotteiden kaukolämpö- ja kaukokylmähinnoittelua asiakkaille. Työ myös tarkastelee hankkeen kokonaiskannattavuutta Mäntsälän Sähkölle. Kannattavuuslaskelmissa toteutetaan herkkyystarkastelu suurimpien muuttujien osalta. Työ tarkastelee yhdistetyn kylmän- ja lämmöntuotannon soveltuvuutta Mäntsälän keskustan kaukolämpöverkon ja Kapulin kaukolämpöverkon alueelle. Soveltuvuutta tarkastellaan Suomessa ja maailmalla toteutettujen referenssien pohjalta.

Simulation of wind powered hydraulic heating system

The objective of this master’s thesis was to design and simulate a wind powered hydraulic heating system that can operate independently in remote places where the use of electricity is not possible. Components for the system were to be selected in such a way that the conditions for manufacture, use and economic viability are the as good as possible. Savonius rotor was chosen for wind turbine, due to its low cut in speed and robust design. Savonius rotor produces kinetic energy in wide wind speed range and it can withstand high wind gusts. Radial piston pump was chosen for the flow source of the hydraulic heater. Pump type was selected due to its characteristics in low rotation speeds and high efficiency. Volume flow from the pump is passed through the throttle orifice. Pressure drop over the orifice causes the hydraulic oil to heat up and, thus, creating thermal energy. Thermal energy in the oil is led to radiator where it conducts heat to the environment. The hydraulic heating system was simulated. For this purpose a mathematical models of chosen components were created. In simulation wind data gathered by Finnish meteorological institute for 167 hours was used as input. The highest produced power was achieved by changing the orifice diameter so that the rotor tip speed ratio follows the power curve. This is not possible to achieve without using electricity. Thus, for the orifice diameter only one, the optimal value was defined. Results from the simulation were compared with investment calculations. Different parameters effecting the investment profitability were altered in sensitivity analyses in order to define the points of investment profitability. Investment was found to be profitable only with high average wind speeds.

Optimization of a dynamic district heating power plant

The purpose of this Thesis is to find the most optimal heat recovery solution for Wärtsilä’s dynamic district heating power plant considering Germany energy markets as in Germany government pays subsidies for CHP plants in order to increase its share of domestic power production to 25 % by 2020. Different heat recovery connections have been simulated dozens to be able to determine the most efficient heat recovery connections. The purpose is also to study feasibility of different heat recovery connections in the dynamic district heating power plant in the Germany markets thus taking into consideration the day ahead electricity prices, district heating network temperatures and CHP subsidies accordingly. The auxiliary cooling, dynamical operation and cost efficiency of the power plant is also investigated.