Modeling study of limestone reactions in fluidized bed conditions

Traditionally limestone has been used for the flue gas desulfurization in fluidized bed combustion. Recently, several studies have been carried out to examine the use of limestone in applications which enable the removal of carbon dioxide from the combustion gases, such as calcium looping technology and oxy-fuel combustion. In these processes interlinked limestone reactions occur but the reaction mechanisms and kinetics are not yet fully understood. To examine these phenomena, analytical and numerical models have been created. In this work, the limestone reactions were studied with aid of one-dimensional numerical particle model. The model describes a single limestone particle in the process as a function of time, the progress of the reactions and the mass and energy transfer in the particle. The model-based results were compared with experimental laboratory scale BFB results. It was observed that by increasing the temperature from 850 °C to 950 °C the calcination was enhanced but the sulfate conversion was no more improved. A higher sulfur dioxide concentration accelerated the sulfation reaction and based on the modeling, the sulfation is first order with respect to SO2. The reaction order of O2 seems to become zero at high oxygen concentrations.

Kaukolämpöverkon paluuveden hyödyntäminen lämmityksessä

Tässä diplomityössä on määritetty paluuvesilämmityksen mahdollisuudet Savon Voima Oyj:n kaukolämpöpaikkakunnilla. Työssä tarkasteltiin paluuvesilämmityksen tuoman paremman kaukolämpöveden jäähtymän vaikutuksia kaukolämpöverkkoon ja energiantuotantoon sekä laskettiin esimerkkipaikkakunnilla kaukolämmön paluuveden lämpötilan alentumisen tuomat rahalliset hyödyt. Lisäksi tarkasteltiin paluuvesilämmityksen taloudellisuutta esimerkkipaikkakunnilla. Laskennassa saatiin paluuvesilämmityksen tuomaksi jäähtymähyödyksi pumppauskustannuksissa 0,7 – 0,8 €/MWh ja lämpöhäviöissä 1,5 – 2,9 €/MWh. Iisalmessa sähköntuotannon lisääntymisestä saadaan hyötyä 0,7 €/MWh. Suurin hyöty saadaan Pielaveden ja Suonenjoen biolämpökeskusten lämmöntalteenotolla varustetuista savukaasupesureista. Pielavedellä tämä hyöty on 6,4 €/MWh ja Suonenjoella 6,1 €/MWh. Paluuvesilämmityksen kannattavuus asuinkiinteistöissä vaatii lämmöntuotannon yhteydessä olevan savukaasupesurin tuoman rahallisen hyödyn. Esimerkiksi Iisalmessa asiakkaalle myönnettävissä oleva jäähtymähyvitys paluuvesilämmöstä ei riitä kattamaan paluuvesilämmityksen suurempia investointikuluja. Myös pesuripaikkakunnilla kannattavuus vaatii suuren vuosittaisen lämmönkäytön. Tavoiteltaessa 8 vuoden korollista takaisinmaksuaikaa vaatii kannattavuus kohteelta Pielavedellä 250 MWh:n ja Suonejoella 300 MWh:n vuosittaisen lämmönkäytön. Myös asiakkaan sijainnin sopivuus kaukolämpöverkossa paluuvesilämmitykseen täytyy tarkastella tapauskohtaisesti. Paluuvesilämmitys ei tule työn tulosten perusteella tulevaisuudessa yleisesti käyttöön, mutta yksittäisiä asiakkaita siihen voidaan liittää.

Soodakattilan lentotuhkan uudentyyppisen analysaattorin arviointi

RBDA (Recovery Boiler Dust Analyzer) on soodakattilan savukaasujen hiukkasten määrää mittaava laite. Yksi laitteen mahdollisista sovelluskohteista on soodakattilan nuohouksen optimointi. Tämän työn tarkoituksena oli parantaa RBD-analysaattorin toimintaa ja erityisesti tutkia laitteen toimivuutta soodakattilan nuohouksen optimoinnis-sa. Soodakattilan nuohouksen optimoinnilla voidaan vähentää nuohoukseen kuluneen höyryn määrää ja näin saavuttaa taloudellisia säästöjä. RBD-analysaattorin toimivuutta testattiin toimivan soodakattilan avulla. Tutkimuksen tueksi testeissä käytetyn soodakattilan savukaasujen lämpötilat ja tuhkan tarttumisomi-naisuudet selvitettiin. Laitteen toimivuutta testattiin vertaamalla RBDA:n mittaustulosta standardin mukaiseen savukaasujen hiukkasmittausmenetelmään. Mittajärjestelmän soveltuvuutta soodakattilan nuohouksen optimointiin tutkittiin ajamalla nuohoimia käsin eri seisonta-aikojen jälkeen sekä mittaamalla soodakattilan normaalia nuohousjärjes-tystä. Mittausten perusteella todettiin, että RBDA havaitsee savukaasujen pölypitoisuuden ja sen muutokset luotettavasti. Nuohouksen optimointiin RBDA:n todettiin soveltuvan ny-kyisessä mallissaan vain vedenesilämmittimien osalta. Keittopinnan ja tulistimien nuo-hointen optimointiin ei saatu riittävän luotettavia mittaustuloksia. RBDA:n kehittäminen jatkotutkimuksilla todettiin mahdolliseksi.

Puupelletin hybridipoltto

Diplomityö on tehty osana laajempaa kehitysprojektia. Kehitysprojektin tavoitteena on kehittää poltin jossa polttoaineena käytetään kevyt polttoöljyä ja puupellettiä. Työ on jaettu kahteen osioon, kirjallisuus- ja tutkimusosioon. Kirjallisuusosiossa on käsitelty kehitystyön pohjana käytettyä teoriatietoa. Tutkimusosassa esitellään laitteistolle tehdyt savukaasumittaukset.

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.

Limestone Reactions in a Fluidized Bed Heat Exchanger of an Oxy-fuel Circulating Fluidized Bed Boiler

Oxy-fuel combustion in a circulating fluidized bed (CFB) boiler appears to be a promising option for capturing CO2 in power plants. Oxy-fuel combustion is based on burning of fuel in the mixture of oxygen and re-circulated flue gas instead of air. Limestone (CaCO3) is typically used for capturing of SO2 in CFB boilers where limestone calcines to calcium oxide (CaO). Because of high CO2 concentration in oxy-fuel combustion, calcination reaction may be hindered or carbonation, the reverse reaction of calcination, may occur. Carbonation of CaO particles can cause problems especially in the circulation loop of a CFB boiler where temperature level is lower than in the furnace. The aim of the thesis was to examine carbonation of CaO in a fluidized bed heat exchanger of a CFB boiler featuring oxy-fuel combustion. The calculations and analyzing were based on measurement data from an oxy-fuel pilot plant and on 0-dimensional (0D) gas balance of a fluidized bed heat exchanger. Additionally, the objective was to develop a 1-dimensional (1D) model of a fluidized bed heat exchanger by searching a suitable pre-exponential factor for a carbonation rate constant. On the basis of gas measurement data and the 0D gas balance, it was found that the amount of fluidization gas decreased as it flew through the fluidized bed heat exchanger. Most likely the reason for this was carbonation of CaO. It was discovered that temperature has a promoting effect on the reaction rate of carbonation. With the 1D model, a suitable pre-exponential factor for the equation of carbonation rate constant was found. However, during measurements there were several uncertainties, and in the calculations plenty of assumptions were made. Besides, the temperature level in the fluidized bed heat exchanger was relatively low during the measurements. Carbonation should be considered when fluidized bed heat exchangers and the capacity of related fans are designed for a CFB boiler with oxy-fuel combustion.

Soodakattilalaitosten energiantuotannon lisääminen

The aim of this thesis is to study different methods to increase the energy production of recovery boilers. This improvement is encouraged by the current energy policy and the rapid rise in energy prices, especially in electricity. In addition, the energy efficiency of the power plants is intended to be improved. There are several methods to increase the energy production. The methods taken into more accurate study are lower pressure steam for soot blowing and flue gas coolers. Energy balances are made for these two cases to check a plausible addition of power generation of turbo-generator of the steam turbine. Also, the viability issues are studied. Solvo Power Plant Simulation program is used for the energy balance research. Two case power plants are simulated to solve the balances. To solve the addition of power generation with the flue gas coolers, basic balance calculation is performed. The viabilities are also taken into account, especially the payback times of these alternatives. On the basis of the results, installing the system to the process is viable in both cases. By installing the lowest possible pressure steam system for the soot blowing, the advantages are the most significant. The investment costs are the highest but the payback time is less than 1,5 years and the profit in the next 20 years is the greatest. In the case of flue gas coolers, the results did not entirely agree with past studies. Nevertheless, installing the flue gas coolers into the process also seems to be significant and profitable.

Sorbent characterization for circulating fluidized bed scrubbers

Harmful sulfur dioxide (SO2) emissions from power plants have increasingly been restricted since the 1970’s. Circulating fluidized bed (CFB) scrubber is a dry flue gas desulfurization method of absorbing SO2 out of the flue gas with sorbent. In current commercial plants, the used sorbent is commercial or on-site hydrated calcium hydroxide. The CFB scrubber process is characterized by a close but adequate approach to the flue gas saturation temperature that is achieved by spraying water to the absorber followed by a particulate control device. Very high SO2 removal is achieved along with a dry byproduct that is continuously recirculated back to the absorber for enhanced sorbent utilization. The aim of this work is to develop a method that would characterize the reactivity of sorbents used in CFB scrubbers and to conclude how different process parameters and sorbent properties affect the sulfur absorption. The developed characterization method is based on a fixed bed of sorbent and inert silica sand, through which an SO2 containing gas mixture is led. The reaction occurs in the bed and the SO2 concentration in the outlet as a function of time, a breakthrough curve, is obtained from the analyzer. Reactivity of the sorbents are evaluated by the absorbed sulfur amount. Results suggest that out of process parameters, lower SO2 concentration, lower temperature and higher moisture content enhance the desulfurization. Between different sorbents, specific surface area seems to be the most significant parameter. Large surface area linearly leads to more efficient desulfurization. Overall, the solid conversion levels in the tests were very low creating uncertainty to the validity of the results. New desing is being planned to overcome the problems of the device.

Potential utilization ways of recovered chemical products from digestate

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

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.

Surface studies of limestones and dolostones : characterisation using various techniques and batch dissolution experiments with hydrochloric acid solutions

In this thesis, stepwise titration with hydrochloric acid was used to obtain chemical reactivities and dissolution rates of ground limestones and dolostones of varying geological backgrounds (sedimentary, metamorphic or magmatic). Two different ways of conducting the calculations were used: 1) a first order mathematical model was used to calculate extrapolated initial reactivities (and dissolution rates) at pH 4, and 2) a second order mathematical model was used to acquire integrated mean specific chemical reaction constants (and dissolution rates) at pH 5. The calculations of the reactivities and dissolution rates were based on rate of change of pH and particle size distributions of the sample powders obtained by laser diffraction. The initial dissolution rates at pH 4 were repeatedly higher than previously reported literature values, whereas the dissolution rates at pH 5 were consistent with former observations. Reactivities and dissolution rates varied substantially for dolostones, whereas for limestones and calcareous rocks, the variation can be primarily explained by relatively large sample standard deviations. A list of the dolostone samples in a decreasing order of initial reactivity at pH 4 is: 1) metamorphic dolostones with calcite/dolomite ratio higher than about 6% 2) sedimentary dolostones without calcite 3) metamorphic dolostones with calcite/dolomite ratio lower than about 6% The reactivities and dissolution rates were accompanied by a wide range of experimental techniques to characterise the samples, to reveal how different rocks changed during the dissolution process, and to find out which factors had an influence on their chemical reactivities. An emphasis was put on chemical and morphological changes taking place at the surfaces of the particles via X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). Supporting chemical information was obtained with X-Ray Fluorescence (XRF) measurements of the samples, and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) measurements of the solutions used in the reactivity experiments. Information on mineral (modal) compositions and their occurrence was provided by X-Ray Diffraction (XRD), Energy Dispersive X-ray analysis (EDX) and studying thin sections with a petrographic microscope. BET (Brunauer, Emmet, Teller) surface areas were determined from nitrogen physisorption data. Factors increasing chemical reactivity of dolostones and calcareous rocks were found to be sedimentary origin, higher calcite concentration and smaller quartz concentration. Also, it is assumed that finer grain size and larger BET surface areas increase the reactivity although no certain correlation was found in this thesis. Atomic concentrations did not correlate with the reactivities. Sedimentary dolostones, unlike metamorphic ones, were found to have porous surface structures after dissolution. In addition, conventional (XPS) and synchrotron based (HRXPS) X-ray Photoelectron Spectroscopy were used to study bonding environments on calcite and dolomite surfaces. Both samples are insulators, which is why neutralisation measures such as electron flood gun and a conductive mask were used. Surface core level shifts of 0.7 ± 0.1 eV for Ca 2p spectrum of calcite and 0.75 ± 0.05 eV for Mg 2p and Ca 3s spectra of dolomite were obtained. Some satellite features of Ca 2p, C 1s and O 1s spectra have been suggested to be bulk plasmons. The origin of carbide bonds was suggested to be beam assisted interaction with hydrocarbons found on the surface. The results presented in this thesis are of particular importance for choosing raw materials for wet Flue Gas Desulphurisation (FGD) and construction industry. Wet FGD benefits from high reactivity, whereas construction industry can take advantage of slow reactivity of carbonate rocks often used in the facades of fine buildings. Information on chemical bonding environments may help to create more accurate models for water-rock interactions of carbonates.

Korkeasti kuormitetun soodakattilan likaantumisen ja päästöjen vähentäminen

Tässä työssä perehdytään korkeasti kuormitettujen soodakattiloiden tyypillisiin ongelmiin. Ongelmia ovat likaantuminen ja tukkeutuminen sekä liialliset päästöt. Työn teoriaosassa esitetään taustat likaantumiselle ja päästöjen muodostumiselle. Molemmat johtuvat suurelta osin tulipesän huonosta toiminnasta. Soodakattilan ilmajärjestelmä ja mustalipeän ruiskutus vaikuttavat tulipesän toimintaan. Usein tulipesän toimintaa voidaan parantaa ilmajärjestelmän ja lipeänruiskutuksen säätöjä muuttamalla. Suurempi muutos tulipesän toimintaan saadaan uusimalla perinteinen sekundääri-ilmajärjestelmä vertikaali-ilmajärjestelmäksi. Nykyaikainen vertikaali-ilmajärjestelmä sekoittaa savukaasut tehokkaasti ja saa aikaan tasaisemman virtauksen tulipesään. Myös mustalipeän korkea kloori- ja kaliumpitoisuus voivat aiheuttaa lämpöpintojen likaantumista. Oikea nuohointen sijainti on tärkeä tekijä kattilan puhtaana pysymisen kannalta. Työn kokeellisessa osassa selvitetään, kuinka erään eukalyptussellutehtaan korkeasti kuormitetun soodakattilan käytettävyyttä voidaan parantaa ja kapasiteettia nostaa soodakattilan toimintaa virittämällä. Kattilan nykyinen ajomalli ja ongelmat selvitettiin. Tulipesän toimintaa testattiin muuttamalla ilmajakoa primääri-, sekundääri- ja tertiääri-ilman välillä ja muuttamalla sekundääri-ilman syöttöä tulipesään. Testien ja kerätyn tiedon perusteella voitiin päätellä, miten soodakattilaa kannattaa modernisoida kapasiteetin nostamiseksi ja käytettävyyden parantamiseksi. Usein tulipesän toimintaa ja käytettävyyttä voidaan parantaa paljon jo pienilläkin muutostöillä. Kapasiteetin nostaminen vaatii tavallisesti suuremman investoinnin ja pidennetyn vuosihuoltoseisokin.

Leijukattilan savukaasujen loppulämpötilan hallinta

Nykyaikaista leijukattilaa voidaan ohjata ja säätää erilaisten säätöpiirien ja sekvenssien kautta erittäin tarkasti. Toiminnot on optimoitu parhaan hyötysuhteen saavuttamiseksi ja kunnossapitokustannusten minimoimiseksi. Tehokkaasta automaatiosta ja nykyaikaisista laitevalinnoista huolimatta leijukattiloissa on usein yksi osa-alue, jota ei pystytä hallitsemaan tehokkaasti. Useilla voimalaitoksilla savukaasu poistuu liian korkeassa lämpötilassa viimeiseltä lämpöpinnalta. Kun kattilahyötysuhdetta tarkastellaan epäsuoralla menetelmällä, savukaasuhäviö on merkittävin tekijä kaikista häviöstä. Tässä diplomityössä on etsitty mahdollisuuksia savukaasun loppulämpötilan hallintaan kattilan ajoarvojen muutoksella sekä lämpöpintoja muuttamalla. Tutkimus keskittyy Järvi-Suomen Voima Oy:n Ristiinan voimalaitokselle. Tutkimus on tehty yhteistyössä laitoksen omistajien Pohjolan Voima Oy:n, UPM-Kymmene Oyj:n sekä laitetoimittaja Valmet Oyj:n kanssa.

Optimal processing chain for waste power plant

This study is done to examine waste power plant’s optimal processing chain and it is important to consider from several points of view on why one option is better than the other. This is to insure that the right decision is made. Incineration of waste has devel-oped to be one decent option for waste disposal. There are several legislation matters and technical options to consider when starting up a waste power plant. From the tech-niques pretreatment, burner and flue gas cleaning are the biggest ones to consider. The treatment of incineration residues is important since it can be very harmful for the envi-ronment. The actual energy production from waste is not highly efficient and there are several harmful compounds emitted. Recycling of waste before incineration is not very typical and there are not many recycling options for materials that cannot be easily re-cycled to same product. Life cycle assessment is a good option for studying the envi-ronmental effect of the system. It has four phases that are part of the iterative study process. In this study the case environment is a waste power plant. The modeling of the plant is done with GaBi 6 software and the scope is from gate-to-grave. There are three different scenarios, from which the first and second are compared to each other to reach conclusions. Zero scenario is part of the study to demonstrate situation without the power plant. The power plant in this study is recycling some materials in scenario one and in scenario two even more materials and utilize the bottom ash more ways than one. The model has the substitutive processes for the materials when they are not recycled in the plant. The global warming potential results show that scenario one is the best option. The variable costs that have been considered tell the same result. The conclusion is that the waste power plant should not recycle more and utilize bottom ash in a number of ways. The area is not ready for that kind of utilization and production from recycled materials.

Kiertoleijupetikattilateknologia ja sen matemaattinen mallinnus energiantuotantoprosessissa

Työn teoreettisessa osuudessa tehdään katsaus kiertoleijupetiteknologian eri osa-alueisiin: leijupedin virtausdynamiikkaan, hiukkaserottimeen ja kiintoaineen palautusmekanismiin. Myös teknologian historiaa ja muita käyttötarkoituksia energiantuotannon ohella käydään läpi. Termodynamiikkaa sekä lämmönsiirron ja voimalaitosprosessien teoriaa käsitellään mallinnuksessa tarvittavilta osin. Mallinnusosiossa käydään läpi kiertoleijupetihöyrykattilan matemaattisen mallin tekoprosessia. Malli perustuu yleisesti saatavilla oleviin yhtälöihin ja korrelaatioihin. Mallintaminen koostuu höyrykattilan jakamisesta lämpöpintoihin ja niiden mitoittamisesta. Mallissa esitetään myös näkemys siitä, miten lämpö siirtyy savukaasuun ja miten petimateriaalin kierto tapahtuu tulipesässä.