Deoxygenation of fatty acids for production of fuels and chemicals

The decreasing fossil fuel resources combined with an increasing world energy demand has raised an interest in renewable energy sources. The alternatives can be solar, wind and geothermal energies, but only biomass can be a substitute for the carbon–based feedstock, which is suitable for the production of transportation fuels and chemicals. However, a high oxygen content of the biomass creates challenges for the future chemical industry, forcing the development of new processes which allow a complete or selective oxygen removal without any significant carbon loss. Therefore, understanding and optimization of biomass deoxygenation processes are crucial for the future bio–based chemical industry. In this work, deoxygenation of fatty acids and their derivatives was studied over Pd/C and TiO2 supported noble metal catalysts (Pt, Pt–Re, Re and Ru) to obtain future fuel components. The 5 % Pd/C catalyst was investigated in semibatch and fixed bed reactors at 300 °C and 1.7–2 MPa of inert and hydrogen–containing atmospheres. Based on extensive kinetic studies, plausible reaction mechanisms and pathways were proposed. The influence of the unsaturation in the deoxygenation of model compounds and industrial feedstock – tall oil fatty acids – over a Pd/C catalyst was demonstrated. The optimization of the reaction conditions suppressed the formation of by–products, hence high yields and selectivities towards linear hydrocarbons and catalyst stability were achieved. Experiments in a fixed bed reactor filled with a 2 % Pd/C catalyst were performed with stearic acid as a model compound at different hydrogen–containing gas atmospheres to understand the catalyst stability under various conditions. Moreover, prolonged experiments were carried out with concentrated model compounds to reveal the catalyst deactivation. New materials were proposed for the selective deoxygenation process at lower temperatures (~200 °C) with a tunable selectivity to hydrodeoxygenation by using 4 % Pt/TiO2 or decarboxylation/decarbonylation over 4 % Ru/TiO2 catalysts. A new method for selective hydrogenation of fatty acids to fatty alcohols was demonstrated with a 4 % Re/TiO2 catalyst. A reaction pathway and mechanism for TiO2 supported metal catalysts was proposed and an optimization of the process conditions led to an increase in the formation of the desired products.

Testing FCM technique for the wind energy scenarios in Finland

In the latter days, human activities constantly increase greenhouse gases emissions in the atmosphere, which has a direct impact on a global climate warming. Finland as European Union member, developed national structural plan to promote renewable energy generation, pursuing the aspects of Directive 2009/28/EC and put it on the sharepoint. Finland is on a way of enhancing national security of energy supply, increasing diversity of the energy mix. There are plenty significant objectives to develop onshore and offshore wind energy generation in country for a next few decades, as well as another renewable energy sources. To predict the future changes, there are a lot of scenario methods developed and adapted to energy industry. The Master’s thesis explored “Fuzzy cognitive maps” approach in scenarios developing, which captures expert’s knowledge in a graphical manner and using these captures for a raw scenarios testing and refinement. There were prospects of Finnish wind energy development for the year of 2030 considered, with aid of FCM technique. Five positive raw scenarios were developed and three of them tested against integrated expert’s map of knowledge, using graphical simulation. The study provides robust scenarios out of the preliminary defined, as outcome, assuming the impact of results, taken after simulation. The thesis was conducted in such way, that there will be possibilities to use existing knowledge captures from expert panel, to test and deploy different sets of scenarios regarding to Finnish wind energy development.

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.

Working fluid selection and design of small-scale waste heat recovery systems based on organic Rankine cycles

Demand for the use of energy systems, entailing high efficiency as well as availability to harness renewable energy sources, is a key issue in order to tackling the threat of global warming and saving natural resources. Organic Rankine cycle (ORC) technology has been identified as one of the most promising technologies in recovering low-grade heat sources and in harnessing renewable energy sources that cannot be efficiently utilized by means of more conventional power systems. The ORC is based on the working principle of Rankine process, but an organic working fluid is adopted in the cycle instead of steam. This thesis presents numerical and experimental results of the study on the design of small-scale ORCs. Two main applications were selected for the thesis: waste heat re- covery from small-scale diesel engines concentrating on the utilization of the exhaust gas heat and waste heat recovery in large industrial-scale engine power plants considering the utilization of both the high and low temperature heat sources. The main objective of this work was to identify suitable working fluid candidates and to study the process and turbine design methods that can be applied when power plants based on the use of non-conventional working fluids are considered. The computational work included the use of thermodynamic analysis methods and turbine design methods that were based on the use of highly accurate fluid properties. In addition, the design and loss mechanisms in supersonic ORC turbines were studied by means of computational fluid dynamics. The results indicated that the design of ORC is highly influenced by the selection of the working fluid and cycle operational conditions. The results for the turbine designs in- dicated that the working fluid selection should not be based only on the thermodynamic analysis, but requires also considerations on the turbine design. The turbines tend to be fast rotating, entailing small blade heights at the turbine rotor inlet and highly supersonic flow in the turbine flow passages, especially when power systems with low power outputs are designed. The results indicated that the ORC is a potential solution in utilizing waste heat streams both at high and low temperatures and both in micro and larger scale appli- cations.

Alueellisen lämmitysjärjestelmän valinta hankesuunnitteluvaiheessa

Työn lähtökohtana oli tarkastella hankesuunnitteluvaiheen lämmitysjärjestelmän valintaa ja siihen vaikuttavia tekijöitä. Työssä käytettiin Case-tarkasteluna Espoon Finnoon aluetta. Rakennusosakeyhtiö Hartela voitti Espoon Finnoon ensimmäisen (Finnoo I) asemakaava-alueen suunnittelu ja toteuttamisen ideakilpailun vuoden 2012 lopussa. Finnoo I alueelle rakennettaan noin 155 000 kerrosmetriä eli huoneistot noin 4000 asukkaalle. Alueen ra-kennukset suunnitellaan energiatehokkaaksi, sekä lämmityksessä ja sähkössä on tarkoitus käyttää uusiutuvaa energiaa. Työssä käsiteltiin alueellista lämmitysjärjestelmää ja sen vaihtoehtoetoja. Työssä tutkittiin myös aurinkosähkön käytön mahdollisuutta alueella. Ensin työssä mitoitettiin rakennusten energiankulutuksen muodostuminen alustavien suunnitelmien ja arvioitujen ominaiskulu-tusten avulla. Sen jälkeen käytiin läpi mahdolliset lämmitysjärjestelmät, joita alueella voi-daan käyttää ja arvioitiin niiden aiheuttamat elinkaarikustannukset koko laskenta-ajan jak-solla. Elinkaarilaskentaan valittiin viisi toteutuskelpoisinta järjestelmää ja niistä laskettiin elinkaarikustannukset. Lisäksi laskettiin järjestelmien hiilidioksidipäästöt vuosittain. Työn tulosten pohjalta voidaan olettaa, että kokonaisvaltaisesti yhtä ainoata parasta lämmi-tysjärjestelmää alueelle ei ole, vaan kaukolämpöä, maalämpöä ja hybridijärjestelmiä tulisi käyttää alueella sekaisin. Lisäksi alue on mahdollista rakentaa niin, että alue käyttäisi nolla-lämpöalueen periaatetta, niin että rakennukset, jotka tuottavat lämpöä liikaa myisivät ne sitä rakennuksille jotka tarvitsevat sitä. Aurinkosähkön potentiaali alueella on hyvä ja sitä käyttämällä voidaan rakennusten E-lukua ja hiilidioksidipäästöjä laskea.

Potential for synthetic gas in Finnish industry

Finland, other Nordic countries and European Union aim to decarbonize their energy production by 2050. Decarbonization requires large scale implementation of non-emission energy sources, i.e. renewable energy and nuclear power. Stochastic renewable energy sources present a challenge to balance the supply and demand for energy. Energy storages, non-emissions fuels in mobility and industrial processes are required whenever electrification is not possible. Neo-Carbon project studies the decarbonizing the energy production and the role of synthetic gas in it. This thesis studies the industrial processes in steel production, oil refining, cement manufacturing and glass manufacturing, where natural gas is already used or fuel switch to SNG is possible. The technical potential for fuel switching is assessed, and economic potential is necessary after this. All studied processes have potential for fuel switching, but total decarbonization of steel production, oil refining requires implementation of other zero-emission technologies.

Review of water electrolysis technologies and design of renewable hydrogen production systems

An electric system based on renewable energy faces challenges concerning the storage and utilization of energy due to the intermittent and seasonal nature of renewable energy sources. Wind and solar photovoltaic power productions are variable and difficult to predict, and thus electricity storage will be needed in the case of basic power production. Hydrogen’s energetic potential lies in its ability and versatility to store chemical energy, to serve as an energy carrier and as feedstock for various industries. Hydrogen is also used e.g. in the production of biofuels. The amount of energy produced during hydrogen combustion is higher than any other fuel’s on a mass basis with a higher-heating-value of 39.4 kWh/kg. However, even though hydrogen is the most abundant element in the universe, on Earth most hydrogen exists in molecular forms such as water. Therefore, hydrogen must be produced and there are various methods to do so. Today, the majority hydrogen comes from fossil fuels, mainly from steam methane reforming, and only about 4 % of global hydrogen comes from water electrolysis. Combination of electrolytic production of hydrogen from water and supply of renewable energy is attracting more interest due to the sustainability and the increased flexibility of the resulting energy system. The preferred option for intermittent hydrogen storage is pressurization in tanks since at ambient conditions the volumetric energy density of hydrogen is low, and pressurized tanks are efficient and affordable when the cycling rate is high. Pressurized hydrogen enables energy storage in larger capacities compared to battery technologies and additionally the energy can be stored for longer periods of time, on a time scale of months. In this thesis, the thermodynamics and electrochemistry associated with water electrolysis are described. The main water electrolysis technologies are presented with state-of-the-art specifications. Finally, a Power-to-Hydrogen infrastructure design for Lappeenranta University of Technology is presented. Laboratory setup for water electrolysis is specified and factors affecting its commissioning in Finland are presented.

Legitimacy Building in Public Disclosures on Strategic Energy Investments

Renewable energy investments play a key role in energy transition. While studies have suggested that social acceptance may form a barrier for renewable energy investments, the ways in which companies perceive and attempt to gain the acceptance have received little attention. This study aims to fill the gap by exploring how large electric utilities justify their strategic investments in their press releases and how do the justifications differ between renewable and non-renewable energy investments. The study bases on legitimacy theory and aims at contributing to the research on legitimation in institutional change. As its research method, the study employs an inductive mixed method content analysis. The study has two parts: a qualitative content analysis that explores and identifies the themes and legitimation strategies of the press releases and a quantitative computer-aided analysis that compares renewable and non-renewable energy investments. The sample of the study consists of 396 press releases representing the strategic energy investments of 34 electric utilities from the list of the world’s 250 largest and financially most successful energy companies. The data is collected from the period of 2010–2014. The study reveals that most important justifications for strategic energy investments are fit with the strategy and environmental and social benefits. Justifications address especially the expectations of market. Investments into non-renewable energy are justified more and they use more arguments addressing the proprieties and performance of power plants whereas renewable energy investments are legitimized by references to past actions and commonly accepted morals and norms. The findings support the notion that validity-addressing and propriety-addressing legitimation strategies are used differently in stable and unstable institutional settings.

Integrated energy storage tank for large scale power-to-gas applications

The global interest towards renewable energy production such as wind and solar energy is increasing, which in turn calls for new energy storage concepts due to the larger share of intermittent energy production. Power-to-gas solutions can be utilized to convert surplus electricity to chemical energy which can be stored for extended periods of time. The energy storage concept explored in this thesis is an integrated energy storage tank connected to an oxy-fuel combustion plant. Using this approach, flue gases from the plant could be fed directly into the storage tank and later converted into synthetic natural gas by utilizing electrolysis-methanation route. This work utilizes computational fluid dynamics to model the desublimation of carbon dioxide inside a storage tank containing cryogenic liquid, such as liquefied natural gas. Numerical modelling enables the evaluation of the transient flow patterns caused by the desublimation, as well as general fluid behaviour inside the tank. Based on simulations the stability of the cryogenic storage and the magnitude of the key parameters can be evaluated.

Carbon sources for Power-to-Gas applications in the Finnish energy system

This thesis is done as a part of the NEOCARBON project. The aim of NEOCARBON project is to study a fully renewable energy system utilizing Power-to-Gas or Power-to-Liquid technology for energy storage. Power-to-Gas consists of two main operations: Hydrogen production via electrolysis and methane production via methanation. Methanation requires carbon dioxide and hydrogen as a raw material. This thesis studies the potential carbon dioxide sources within Finland. The different sources are ranked using the cost and energy penalty of the carbon capture, carbon biogenity and compatibility with Power-to-Gas. It can be concluded that in Finland there exists enough CO2 point sources to provide national PtG system with sufficient amounts of carbon. Pulp and paper industry is single largest producer of biogenic CO2 in Finland. It is possible to obtain single unit capable of grid balancing operations and energy transformations via Power-to-Gas and Gas-to-Power by coupling biogas plants with biomethanation and CHP units.

Electrical Safety of Island Operated Low Voltage DC Network

Today, renewable energy technologies and modern power electronics have made it feasible to implement low voltage direct current (LVDC) microgrids (MGs) ca-pable to island operation. Such LVDC networks are particularly useful in remote areas. However, there are still pending issues in island operated LVDC MGs like electrical safety and controlled operation, which should be addressed before wide-scale implementation. This thesis is focused on the overall protection of an island operated LVDC network concept, including protection against electrical shocks, mains equipment protection and protection of photovoltaic (PV) power sources and battery energy storage systems (BESSs). The topic is approached through ex-amination of the safety hazards and the appropriate methods to protect against them, comprising considerations for earthing system selection and realisation of the protection system.

The legal framework for energy provisions in the European Union – With special regard to providing of energy provisions within the scope of Article 194(2) TFEU

The thesis interprets the caveat of Article 194(2) TFEU in order to assess the use of the Article as a legal basis for energy provisions provided by the European Union. The research subject is the Energy Title in the Treaty of the Functioning of the European Union and the possibilities of the application of the legal basis provided therein. The purpose is analysis of the possibilities for providing of provisions within the scope of the caveat found in Article 194(2) TFEU with special regard to the possibilities of providing renewable energy legislation. The purpose of the thesis is on one hand to provide an overview of the premises for providing of energy provisions in the EU, and on the other hand to analyse the Treaty text in order to determine the legal basis for energy provisions. The ultimate objective is to determine the correct legal basis for renewable energy provisions, aimed at the mitigation of climate change. According to Article 194(2) TFEU, the practice of the shared legislative powers in the field of energy are restricted by the retention of certain energy matters within the power of the Member States. The wording of the caveat containing the restrictions is open to interpretation and has been a subject of extensive discussion. Many scholars have argued that the caveat in Article 194(2) TFEU might obstruct decision-making in energy matters. This argument is contested, and the factual impact of the codification of the energy competences is analysed. The correct legal basis for energy provisions depends on the final interpretation of the text of the caveat and the level of significance of the effect of the measure. The use of Article 194(2) TFEU as a legal basis might not be the only option. There is a possibility that the legal bases within the Environmental Title might be used as legal bases for energy provisions in addition to Article 194(2) TFEU.

The legal framework for energy provisions in the European Union – With special regard to providing of energy provisions within the scope of Article 194(2) TFEU

The thesis interprets the caveat of Article 194(2) TFEU in order to assess the use of the Article as a legal basis for energy provisions provided by the European Union. The research subject is the Energy Title in the Treaty of the Functioning of the European Union and the possibilities of the application of the legal basis provided therein. The purpose is analysis of the possibilities for providing of provisions within the scope of the caveat found in Article 194(2) TFEU with special regard to the possibilities of providing renewable energy legislation. The purpose of the thesis is on one hand to provide an overview of the premises for providing of energy provisions in the EU, and on the other hand to analyse the Treaty text in order to determine the legal basis for energy provisions. The ultimate objective is to determine the correct legal basis for renewable energy provisions, aimed at the mitigation of climate change. According to Article 194(2) TFEU, the practice of the shared legislative powers in the field of energy are restricted by the retention of certain energy matters within the power of the Member States. The wording of the caveat containing the restrictions is open to interpretation and has been a subject of extensive discussion. Many scholars have argued that the caveat in Article 194(2) TFEU might obstruct decision-making in energy matters. This argument is contested, and the factual impact of the codification of the energy competences is analysed. The correct legal basis for energy provisions depends on the final interpretation of the text of the caveat and the level of significance of the effect of the measure. The use of Article 194(2) TFEU as a legal basis might not be the only option. There is a possibility that the legal bases within the Environmental Title might be used as legal bases for energy provisions in addition to Article 194(2) TFEU.

Potential of energy and nutrient recovery from biodegradable waste by co-treatment in Lithuania

Biodegradable waste quantities in Lithuania and their potential for the co-treatment in renewable energy and organic fertilizer production are investigated. Two scenarios are formulated to study the differences of the amounts of obtainable energy and fertilizers between different ways of utilization. In the first scenario, only digestion is used, and in the second scenario, other materials than straw are digested, and straw and the solid fraction of sewage sludge digestate are combusted. As a result, the amounts of heat and electricity, as well as the fertilizer amounts in the counties are obtained for both scenarios. Based on this study, the share of renewable energy in Lithuania could be doubled by the co-treatment of different biodegradable materials.

Improvement of Energy Efficiency in a Gold Mining Industry: Case Study of a Russian Gold Mining Company

The issue of energy efficiency is attracting more and more attention of academia, business and policy makers worldwide due to increasing environmental concerns, depletion of non-renewable energy resources and unstable energy prices. The significant importance of energy efficiency within gold mining industry is justified by considerable energy intensity of this industry as well as by the high share of energy costs in the total operational costs. In the context of increasing industrial energy consumption energy efficiency improvement may provide significant energy savings and reduction of CO2 emission that is highly important in order to contribute to the global goal of sustainability. The purpose of this research is to identify the ways of energy efficiency improvement relevant for a gold mining company. The study implements single holistic case study research strategy focused on a Russian gold mining company. The research involves comprehensive analysis of company’s energy performance including analysis of energy efficiency and energy management practices. This study provides following theoretical and managerial contributions. Firstly, it proposes a methodology for comparative analysis of energy performance of Russian and foreign gold mining companies. Secondly, this study provides comprehensive analysis of main energy efficiency challenges relevant for a Russian gold mining company. Finally, in order to overcome identified challenges this research conceives a guidance for a gold mining company for implementation of energy management system based on the ISO standard.