Energia- ja ilmastotoimenpiteiden käynnistäminen pk-yrityksissä

Tämän diplomityön tarkoituksena oli kehittää toimintamalli pk-yritysten energia- ja ilmastotoimenpiteiden käynnistämiseksi HINKU-kunnissa. Esimerkkiyrityksenä työssä toimi Tehomet Oy:n Parikkalan tehdas. Työssä tutustuttiin ensimmäisenä erilaisiin jo olemassa oleviin toimintamalleihin, hiilijalanjäljen laskentastandardeihin sekä erilaisiin mahdollisuuksiin hiilineutraaliuden saavuttamiseksi. Lisäksi Tehomet Oy:n Parikkalan tehtaalta kerättiin tarvittavaa tietoa yrityksen ja tuotteen hiilijalanjälkien laskentaa varten. Kerätyn tiedon ja jo olemassa olevien standardien ja toimintamallien pohjalta kehitettiin toimintamalli, johon sisältyy laskentataulukko, jonka avulla yritykset voivat laskea hiilijalanjälkensä ja tunnistaa kasvihuonekaasupäästöjen merkittävyyden liiketoimintansa kehittämisen näkökulmasta. Tehomet Oy:n valmistaman puupylvään hiilijalanjälki pieneni merkittävästi, kun laskennassa huomioitiin hiilen sitoutuminen tuotteeseen sekä tuotteen käytöstä poisto. Parikkalan tehtaan tapauksessa suurin yksittäinen kasvihuonekaasujen päästölähde on sähkönkulutus. Energiankulutuksen kannalta merkittävin säästökohde olisi mitä todennäköisimmin teholtaan liian suuresta kompressorista luopuminen. Kasvihuonekaasupäästöjen hiilineutraaliksi saattamiseksi mahdolliset toimenpiteet olisivat tässä tapauksessa hiilivapaan sähkön ostaminen tai päästöjen kompensoiminen ostamalla päästöoikeuksia. Toimintamallin todellinen toimivuus nähdään tulevaisuudessa, kun sitä päästään testaamaan laajemmalti eri aloilla toimiviin yrityksiin.

Production of magnesium carbonates from serpentinites for CO2 mineral sequestration : optimisation towards industrial application

Global warming is one of the most alarming problems of this century. Initial scepticism concerning its validity is currently dwarfed by the intensification of extreme weather events whilst the gradual arising level of anthropogenic CO2 is pointed out as its main driver. Most of the greenhouse gas (GHG) emissions come from large point sources (heat and power production and industrial processes) and the continued use of fossil fuels requires quick and effective measures to meet the world’s energy demand whilst (at least) stabilizing CO2 atmospheric levels. The framework known as Carbon Capture and Storage (CCS) – or Carbon Capture Utilization and Storage (CCUS) – comprises a portfolio of technologies applicable to large‐scale GHG sources for preventing CO2 from entering the atmosphere. Amongst them, CO2 capture and mineralisation (CCM) presents the highest potential for CO2 sequestration as the predicted carbon storage capacity (as mineral carbonates) far exceeds the estimated levels of the worldwide identified fossil fuel reserves. The work presented in this thesis aims at taking a step forward to the deployment of an energy/cost effective process for simultaneous capture and storage of CO2 in the form of thermodynamically stable and environmentally friendly solid carbonates. R&D work on the process considered here began in 2007 at Åbo Akademi University in Finland. It involves the processing of magnesium silicate minerals with recyclable ammonium salts for extraction of magnesium at ambient pressure and 400‐440⁰C, followed by aqueous precipitation of magnesium in the form of hydroxide, Mg(OH)2, and finally Mg(OH)2 carbonation in a pressurised fluidized bed reactor at ~510⁰C and ~20 bar PCO2 to produce high purity MgCO3. Rock material taken from the Hitura nickel mine, Finland, and serpentinite collected from Bragança, Portugal, were tested for magnesium extraction with both ammonium sulphate and bisulphate (AS and ABS) for determination of optimal operation parameters, primarily: reaction time, reactor type and presence of moisture. Typical efficiencies range from 50 to 80% of magnesium extraction at 350‐450⁰C. In general ABS performs better than AS showing comparable efficiencies at lower temperature and reaction times. The best experimental results so far obtained include 80% magnesium extraction with ABS at 450⁰C in a laboratory scale rotary kiln and 70% Mg(OH)2 carbonation in the PFB at 500⁰C, 20 bar CO2 pressure for 15 minutes. The extraction reaction with ammonium salts is not at all selective towards magnesium. Other elements like iron, nickel, chromium, copper, etc., are also co‐extracted. Their separation, recovery and valorisation are addressed as well and found to be of great importance. The assessment of the exergetic performance of the process was carried out using Aspen Plus® software and pinch analysis technology. The choice of fluxing agent and its recovery method have a decisive sway in the performance of the process: AS is recovered by crystallisation and in general the whole process requires more exergy (2.48–5.09 GJ/tCO2sequestered) than ABS (2.48–4.47 GJ/tCO2sequestered) when ABS is recovered by thermal decomposition. However, the corrosive nature of molten ABS and operational problems inherent to thermal regeneration of ABS prohibit this route. Regeneration of ABS through addition of H2SO4 to AS (followed by crystallisation) results in an overall negative exergy balance (mainly at the expense of low grade heat) but will flood the system with sulphates. Although the ÅA route is still energy intensive, its performance is comparable to conventional CO2 capture methods using alkanolamine solvents. An energy‐neutral process is dependent on the availability and quality of nearby waste heat and economic viability might be achieved with: magnesium extraction and carbonation levels ≥ 90%, the processing of CO2‐containing flue gases (eliminating the expensive capture step) and production of marketable products.

Power Consumption in Carbon Capture and Storage Systems (CCS) and Possibilities to Reduce Power Consumption with Variable Speed Drives

The aim of this master´s thesis is to study which processes increase the auxiliary power consumption in carbon capture and storage processes and if it is possible to reduce the auxiliary power consumption with variable speed drives. Also the cost of carbon capture and storage is studied. Data about auxiliary power consumption in carbon capture is gathered from various studies and estimates made by various research centres. Based on these studies a view is presented how the power auxiliary power consumption is divided between different processes in carbon capture processes. In a literary study, the operation of three basic carbon capture systems is described. Also different methods to transport carbon dioxide and carbon dioxide storage options are described in this section. At the end of the thesis processes that consume most of the auxiliary power are defined and possibilities to reduce the auxiliary power consumption are evaluated. Cost of carbon capture, transport and storage are also evaluated at this point and in the case that the carbon capture and storage systems are fully deployed. According to the results, it can be estimated what are the processes are where variable speed drives can be used and what kind of cost and power consumption reduction could be achieved. Results also show how large a project carbon capture and storage is if it is fully deployed.

Kinetics of selective oxidation of lactose to lactobionic acid over Pd-active carbon catalyst

Laktoosi eli maitosokeri on tärkein ainesosa useimpien nisäkkäiden tuottamassa maidossa. Sitä erotetaan herasta, juustosta ja maidosta. Laktoosia käytetään elintarvike- ja lääketeollisuuden raaka-aineena monissaeri tuotteissa. Lääketeollisuudessa laktoosia käytetään esimerkiksi tablettien täyteaineena. Hapettamalla laktoosia voidaan valmistaa laktobionihappoa, 2-keto-laktobionihappoa ja laktuloosia. Laktobionihappoa käytetään biohajoavien pintojen ja kosmetiikkatuotteiden valmistuksessa, sekä sisäelinten säilöntäliuoksissa, joissa laktobionihappo estää happiradikaalien aiheuttamien kudosvaurioiden syntymistä. Tässä työssä laktoosia hapetettiin laktobionihapoksi sekoittimella varustetussa laboratoriomittakaavaisessa panosreaktorissa käyttäenkatalyyttinä palladiumia aktiivihiilellä. Muutamissa kokeissa katalyytin promoottorina käytettiin vismuttia, joka hidastaa katalyytin deaktivoitumista. Työn tarkoituksena oli saada lisää tietoa laktoosin hapettamisen kinetiikasta. Laktoosin hapettumisessa laktobionihapoksi havaittiin selektiivisyyteen vaikuttavan muunmuassa reaktiolämpötila, paine, pH ja käytetyn katalyytin määrä. Katalyyttiä kierrättämällä eri kokeiden välillä saatiin paremmat konversiot, selektiivisyydet ja saannot. Parhaat koetulokset saatiin hapetettaessa synteettisellä ilmalla 60 oC lämpötilassa ja 1 bar paineessa. Tehdyissä kokeissa pH:n säätö tehtiin manuaalisesti, joten pH ei pysynyt koko ajan haluttuna. Laktoosin konversio oli parhaimmillaan 95 %. Laktobionihapon suhteellinen selektiivisyys oli 100% ja suhteellinen saanto 100 %. Kinetiikan matemaattinen mallinnus tehtiin Modest-ohjelmalla käyttäen kokeista saatuja mittaustuloksia.Ohjelman avulla estimoitiin parametreja ja saatiin matemaattinen malli reaktorille. Tässä työssä tehtiin kineettinen mallinnus myös ravistelureaktorissa tehdyille laktoosin hapetuskokeille, missä pH pysyi koko ajan haluttuna 'in-situ' titrauksen avulla. Työn yhteydessä selvitettiin myös mahdollisuutta käyttää monoliittikatalyyttejä laktoosin hapetusreaktiossa.

Model based study of a calcium oxide looping process for post-combustion carbon dioxide capture

Calcium oxide looping is a carbon dioxide sequestration technique that utilizes the partially reversible reaction between limestone and carbon dioxide in two interconnected fluidised beds, carbonator and calciner. Flue gases from a combustor are fed into the carbonator where calcium oxide reacts with carbon dioxide within the gases at a temperature of 650 ºC. Calcium oxide is transformed into calcium carbonate which is circulated into the regenerative calciner, where calcium carbonate is returned into calcium oxide and a stream of pure carbon dioxide at a higher temperature of 950 ºC. Calcium oxide looping has proved to have a low impact on the overall process efficiency and would be easily retrofitted into existing power plants. This master’s thesis is done in participation to an EU funded project CaOling as a part of the Lappeenranta University of Technology deliverable, reactor modelling and scale-up tools. Thesis concentrates in creating the first model frame and finding the physically relevant phenomena governing the process.

Modelling of calciner in post-combustion carbon capture process

Climate change has given an impetus to research and developed new technologies to reduce significantly carbon dioxide emissions in energy production in the developed countries. The major pollution source, fossil fuels, will be used as an energy source for many decades, which provides the demand for carbon capture and storage technologies. Over recent years many new technologies has been developed and one of the most promising is calcium-looping in post-combustion carbon capture process, which use carbonation-calcination cycle to capture carbon dioxide from the flue gas of a combustion process. First pilot plant for calcium-looping process has been built in Oviedo, Spain. In this study, a three-dimensional model has been created for the calciner, which is one of the two fluidized bed reactors needed for the process. The calciner is a regenerator where the captured carbon dioxide is removed from the calcium material and then collected after the reactor. Thesis concentrates in creating the calciner 3D-model frame with CFB3D-program and testing the model with two different example cases. Used input parameters and calciner geometry are Oviedo pilot plant design parameters. The calculation results give information about the process and show that pilot plant calciner should perform as planned. This Master’s Thesis is done in participation to EU FP7 project CaOling.

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.

Carponate precipitation with carbon dioxide gas

The aim of this thesis research work focused on the carbonate precipitation of magnesium using magnesium hydroxide Mg(OH)2 and carbon dioxide (CO2) gas at ambient temperature and pressure. The rate of dissolution of Mg(OH)2 and precipitation kinetics were investigated under different operating conditions. The conductivity and pH of the solution were inline monitored by a Consort meter and the solid samples gotten from the precipitation reaction were analysed by a laser diffraction analyzer Malvern Mastersizer to obtain particle size distributions (PSD) of crystal samples. Also the Mg2+ concentration profiles were determined from the liquid phase of the precipitate by ion chromatography (IC) analysis. Crystal morphology of the obtained precipitates were also investigated and discussed in this work. For the carbonation reaction of magnesium hydroxide in the present work, it was found that magnesium carbonate trihydrate (nesquehonite) was the main product and its formation occurred at a pH of around 7-8. The stirrer speed has a significant effect on the dissolution rate of Mg(OH)2. The highest obtained Mg2+ concentration level was 0.424 mol L-l for the 470 rpm and 0.387 mol L-1 for the 560 rpm which corresponded to the processing time of 45 mins and 40 mins respectively. The particle size distribution shows that the average particle size keeps increasing during the reaction as the CO2 is been fed to the system. The carbonation process is kinetically favored and simple as nesquehonite formation occurs in a very short time. It is a thermodynamically and chemically stable solid product, which allows for a long-term storage of CO2. Since the carbonation reaction is a complex system which includes dissolution of magnesium hydroxide particles, absorption of CO2, chemical reaction and crystallization, the dissolution of magnesium hydroxide was studied in hydrochloric acid (HCl) solvent with and without nitrogen (N2) inert gas. It was found on the dissolution part that the impeller speed had effect on the dissolution rate. The higher the impeller speed the higher the pH of the solution, although for the highest speed of 650rpm it was not the case. Therefore, it was concluded that the optimum speed of the stirrer was 560rpm. The influence of inert gas N2 on the dissolution rate of Mg(OH)2 particles could be seen based on measured pH, electric conductivity and Mg2+ concentration curves.

Variation in soil organic carbon and thickness of soil horizons within a boreal forest stand - effect of trees and implications for sampling

Summary

Carbon Reservoirs in Peatlands and Forests in the Boreal Regions of Finland

Summary