Harvinaisten metallien talteenotto epäorgaanisista jätevirroista

Taloudellisesti tärkeiden metallien varannot ja tuotanto eivät ole jakautuneet tasaisesti. Maantieteelliset alueet, joilla ei ole omia varantoja ovat riippuvaisia muualta tuoduista raaka-aineista. Euroopan komissio ja USA:n energiaministeriö ovat luokitelleet tietyt metallit kriittisiksi niiden taloudellisen merkittävyyden ja saatavuuteen liittyvien epävarmuustekijöiden johdosta. Tällaisten metallien saatavuutta voitaisiin mahdollisesti parantaa lisäämällä niiden talteenottoa jätteistä. Tutkimuksessa kartoitettiin Euroopan komission kriittiseksi luokittelemien metallien pitoisuuksia eräissä jätevirroissa. Kartoitetut jätteet olivat teollisissa poltto-prosesseissa syntyneitä polttojätteitä, prosessiteollisuuden jätesakkoja ja sähkö- ja elektroniikkajätteitä. Kartoituksen perusteella valittiin lupaavimmat jätteet ja suoritettiin niille talteenottokokeita. Talteenottokokeita suoritettiin kolmelle jätteelle. Yhdestä jätesakasta liuotettiin indiumia rikki- ja suolahapoilla. Kahden eri polttojätteen seoksesta liuotettiin galliumia rikkihapolla. Käytettyjen loisteputkien käsittelyprosessista peräisin olleesta sakasta liuotettiin maametalleja rikki- ja suolahapoilla sekä rikki- ja typpihapon seoksella. Indium liukeni heikosti (korkeintaan 25 %) huoneenlämmössä rikkihapolla. Suolahapolla se liukeni paremmin (68 %). Polttojätteen liuotuskokeissa galliumin talteenottoasteen todettiin riippuvan käytetyn liuottimen määrästä. Loisteputkijätesakasta liukeni yttriumia ja europiumia kaikilla käytetyillä happoliuoksilla noin 70–100 %. Käytetyillä happokonsentraatioilla ei havaittu suuria eroja yttriumin ja europiumin liukoisuuksissa. Näitä metalleja voitaisiin mahdollisesti ottaa talteen tämän tyyppisestä sakasta liuottamalla ne happoliuoksella ja saostamalla oksalaattina. Tarvittaessa liuokset voitaisiin puhdistaa tai metallit erottaa toisistaan neste–nesteuutolla, joka on tärkein maametallien tuotantoon käytetty hydrometallurginen menetelmä.

BIOMASS SUPPLY CHAIN ANALYSIS WITH DENSIFIED WASTE

ABSTRACT The possibility to vary the energy matrix, thus reducing the dependency on fossil fuels, has amplified the acceptance of biomass as an alternative fuel. Despite being a cheap and renewable option and the fact that Brazil is a major producer of waste from agriculture and forestry activities, the use of these materials has barriers due to its low density and low energetic efficiency, which can raise the costs of its utilization. Biomass densification has drawn attention due to its advantage in comparison to in natura biomass due to its better physical and combustion characteristics. The objective of this paper is to evaluate the impact of biomass densification in distribution and transport costs. To reach this objective, a mathematical model was used to represent decisions at a supply chain that coordinates the purchase and sale of forestry and wood waste. The model can evaluate the options to deliver biomass through the supply chain combining demand meeting and low cost. Results point to the possibility of an economy of 60% in transport cost and a reduction of 63% in the required quantity of trucks when densified waste is used. However, costs related to the densifying process lead to an increase of total supply costs of at least 37,8% in comparison to in natura waste. Summing up, the viability of biomass briquettes industry requires a cheaper densification process.

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.

Dieselsähköisen laivan pyörimisnopeussäädettyjen voimansiirtokonseptien mallinnus ja vertailu

Tässä työssä tutkitaan eri voimansiirtokonseptien vaikutusta referenssitapauksen polttomoottorivoimalaitoksen energiatehokkuuteen ja polttoaineenkulutukseen staattisessa tilan-teessa. Referenssitapaukseksi on valittu ulkomerellä toimiva huoltoalus. Työssä esitellään dieselsähköisen laivan voimansiirtokonseptien toteutusvaihtoehtoja ja luodaan katsaus valittuihin generaattoreihin sekä taajuusmuuttajiin. Voimansiirtokonseptien hankintahintaa arvioidaan saatujen hintatietojen ja aikaisempien tutkimusten avulla. Lisäksi konseptien energian- ja polttoaineenkulutusta arvioidaan vuositasolla staattisessa tilanteessa. Perinteiselle kiinteän pyörimisnopeuden toteutukselle löydettiin haastajia sekä konseptien kuluttaman energian, että polttoaineen kannalta tarkasteltuna. Lisäksi työssä muodostetaan referenssialusta vastaava yksinkertainen simulointimalli, jolla voidaan arvioida voimalaitoksen tehohäviöitä sekä polttoaineenkulutusta eri ajotavoilla. Simulointimallilla tutkitaan myös energiavaraston tuomia etuja lisäämällä energiavarasto malliin. Mallia simuloitiin paikoitusajossa ilman energiavarastoa, sekä sen kanssa. Energiavaraston avulla saavutettiin merkittävät polttoainesäästöt.

Lämmön- ja aineensiirto hiilipartikkelin palamisessa

Tässä tutkimusraportissa käsitellään yksittäisen hiilipartikkelin palamisen teoriaa. Tutkimusraportissa tullaan esittelemään palamisen kannalta olennaiset ilmiöt kuten lämmön- ja aineensiirto sekä palamiseen liittyvät reaktiot ja palamisen vaiheet. Lisäksi tarkastellaan eri aineominaisuuksien riippuvuutta eri parametreista. Käsitellyn teorian pohjalta luodaan palamista kuvaava malli, jonka avulla kuvataan aineensiirtoa ja lämpötilajakaumaa yksittäisessä partikkelissa. Tavoitteena on mallin avulla tarkastella partikkelikoon vaikutusta yllä esitettyihin ilmiöihin.

Biopolttoaineen rinnakkaispolton kannattavuustarkastelu hiilipölypolttokattilassa Martinlaakso 2:ssa

Euroopan unionin asettamat tavoitteet kasvihuonepäästöjen vähennykselle johtavat vih-reämpään teknologiaan. Tämä diplomityö on teoreettinen tutkimus, joka käsittelee biopolt-toaineen rinnakkaispolton kannattavuutta Vantaan Energian Martinlaakso 2:sen hiilipöly-polttokattilassa. Työssä perehdytään viiteen eri biopolttoainevaihtoehtoon, joita tarkastellaan viidessä eri skenaariossa, jotka vastaavat: 10, 20, 30, 40 ja 50 % biopolttoaineen osuutta kattilassa tuo-tetusta energiasta. Skenaarioissa on pohdittu tarvittavia investointikustannuksia ja muutos-töitä hiilipölypolttokattilassa. Tutkimuksessa on huomioitu myös uusi isojen laitosten pääs-töjä koskeva direktiivi, kattilan oletettava käyttöikä sekä biopolttoaineiden tuet. Saaduista arvioista on lopuksi laskettu vuosittainen polttoainekohtainen kustannusarvio ja investoin-nin kannattavuusarvio. Tuloksista voidaan päätellä, että sahanpurun mahdollisimman suuri hyötykäyttö on kannat-tavaa. Mikäli halutaan käyttää suuria määriä biopolttoainetta, (yli 20 % tuotetusta energias-ta) ei sahanpuru ole varteenotettava vaihtoehto huonon saatavuutensa johdosta. Tällöin hakkeen kaasutuslaitos olisi paras ratkaisu, mutta laitoksen kannattavuus riippuu tulevista energiatuista. Ilman energiatukia sahanpurun hyötykäyttö on ainoa kannattava investointi.

Puun ja turpeen seospolton vaikutus tuhkan hyötykäyttökohteisiin

Työn tavoitteena oli selvittää puun ja turpeen seospolton vaikutukset tuhkien hyötykäyttökohteiden valintaan laitoksella tehtävien koeajojen ja kustannus- sekä SWOT-analyysien avulla. Lisäksi tavoitteena oli selvittää lainsäädännön vaikutukset tuhkien hyötykäyttöön. Kustannusanalyysissä tarkasteltiin tuhkien hyödyntämisen nykytilan lisäksi rakeistuslaitosinvestointia ja selvitettiin eri hyötykäyttövaihtoehtojen etuja ja haittoja. Lainsäädäntö vaikuttaa oleellisesti tuhkien hyötykäyttöön. Hyötykäyttöä säädellään sekä kansallisella että EU-tasolta tulevalla lainsäädännöllä. Ympäristölainsäädännön ja etenkin jätelainsäädännön kokonaisuudistuksen myötä myös hyötykäyttöä koskevat lainsäädäntö uudistui. Energiantuotannon tuhkat tulivat jäteverolain piiriin ja lannoiteasetuksenuudistuksella pyrittiin helpottamaan tuhkien lannoitekäyttöä. Myös jäteluokittelu ja sen päättyminen tuhkien osalta vaikuttaa olennaisesti tuhkien käsittelymenetelmien ja hyödyntämisen kannattavuuteen. Jäteluokituksen päättyminen voi viedä tuhkat kemikaalilainsäädännön piiriin. Kustannus- ja SWOT-analyysissä selvitettiin tuhkien hyödyntämisen kannalta keskeiset kustannustekijät. Rakeistuslaitosinvestoinnissa huomioitiin erilaiset tuhkien käsittelymäärät ja niiden vaikutukset kustannuksiin ja investoinnin kannattavuuteen. SWOT-analyysin avulla selvitettiin hyödyntämisen vahvuudet, heikkoudet, mahdollisuudet ja uhkatekijät. Polttoainesuhteella ei ollut poissulkevaa vaikutusta tuhkien hyötykäyttövalintaan. Lentotuhkat soveltuivat parhaiten lannoitehyötykäyttöön ja pohjatuhkat maarakennushyötykäyttöön. Rakeistuslaitosinvestointi olisi kannattava etenkin suuremmilla tuhkamäärillä.

Arinakattilalaitoksen polttoainekäytön tarkastelu

Tässä diplomityössä on tutustuttu Lahti Energia Oy:n Heinolan voimalaitoksen energiantuotantoon. Heinolan voimalaitos on vanha, mutta sen pääkattilana toimiva arinakattila on uusittu 2004. Voimalaitoksen toimintaa halutaan kehittää nykyaikaisemmaksi ja energiatehokkaammaksi. Voimalaitoksella on nykyään kolme asiakasta, joista uusin on liittynyt höyryverkkoon vuonna 2011. Työssä on tutkittu miten voimalaitoksen polttoaineiden käyttö muuttuu uuden asiakkaan myötä. Diplomityön teoriaosassa on keskitytty antamaan tietoa erilaisista polttoaineista sekä arinapolttamisesta polttotekniikkana. Työssä on laskettu voimalaitoksen asiakkaiden käyttämä energiavuositasolla, voimalaitoksen kattilahyötysuhde, prosessihyötysuhde ja niiden avulla laitoksen tarvitsema polttoaine-energia vuodessa. Laskelmat antavat hyvän yleisen kuvan voimalaitoksen käytöstä tällä hetkellä. Käyttöennusteen avulla voidaan arvioida myös laitoksen taloudellista tilaa polttoaineseoksen näkökulmasta.

Current status of the waste-to-energy chain in the County of North Savo, Finland

The aim of this report is to describe the current status of the waste-to-energy chain in the province of Northern Savonia in Finland. This work is part of the Baltic Sea Region Programme project Remowe-Regional Mobilizing of Sustainable Waste-to-Energy Production (2009-2012). Partnering regions across Baltic Sea countries have parallelly investigated the current status, bottle-necks and needs for development in their regions. Information about the current status is crucial for the further work within the Remowe project, e.g. in investigating the possible future status in target regions. Ultimate result from the Northern Savonia point of view will be a regional model which utilizes all available information and facilitates decision-making concerning energy utilization of waste. The report contains information on among others: - waste management system (sources, amounts, infrastructure) - energy system (use, supply, infrastructure) - administrative structure and legislation - actors and stakeholders in the waste-to-energy field, including interest and development ideas The current status of the regions will be compared in a separate Remowe report, with the focus on finding best practices that could be transferred among the regions. In this report, the current status has been defined as 2006-2009. In 2009, the municipal waste amount per capita was 479 kg/inhabitant in Finland. Industrial waste amounted 3550 kg/inhabitant, respectively. The potential bioenergy from biodegradable waste amounts 1 MWh/inhabitant in Northern Savonia. This figure includes animal manure, crops that would be suitable for energy use, sludge from municipal sewage treatment plants and separately collected biowaste. A key strategy influencing also to Remowe work is the waste plan for Eastern Finland. Currently there operate two digestion plants in Northern Savonia: Lehtoniemi municipal sewage treatment sludge digestion plant of Kuopion Vesi and the farm-scale research biogas plant of Agrifood Research Finland in Maaninka. Moreover, landfill gas is collected to energy use from Heinälamminrinne waste management centre and Silmäsuo closed landfill site, both belonging to Jätekukko Oy. Currently there is no thermal utilization of waste in Northern Savonia region. However, Jätekukko Oy is pretreating mixed waste and delivering refuse derived fuel (RDF) to Southern Finland to combustion. There is a strong willingness among seven regional waste management companies in Eastern Finland to build a waste incineration plant to Riikinneva waste management centre near city of Varkaus. The plant would use circulating fluidized bed (CFB) boiler. This would been a clear boost in waste-to-energy utilization in Northern Savonia and in many surrounding regions.

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.

Oxidation rates of carbon and nitrogen in char residues from solid fuels

Computational fluid dynamics (CFD) modeling is an important tool in designing new combustion systems. By using CFD modeling, entire combustion systems can be modeled and the emissions and the performance can be predicted. CFD modeling can also be used to develop new and better combustion systems from an economical and environmental point of view. In CFD modeling of solid fuel combustion, the combustible fuel is generally treated as single fuel particles. One of the limitations with the CFD modeling concerns the sub-models describing the combustion of single fuel particles. Available models in the scientific literature are in many cases not suitable as submodels for CFD modeling since they depend on a large number of input parameters and are computationally heavy. In this thesis CFD-applicable models are developed for the combustion of single fuel particles. The single particle models can be used to improve the combustion performance in various combustion devices or develop completely new technologies. The investigated fields are oxidation of carbon (C) and nitrogen (N) in char residues from solid fuels. Modeled char-C oxidation rates are compared to experimental oxidation rates for a large number of pulverized solid fuel chars under relevant combustion conditions. The experiments have been performed in an isothermal plug flow reactor operating at 1123-1673 K and 3-15 vol.% O2. In the single particle model, the char oxidation is based on apparent kinetics and depends on three fuel specific parameters: apparent pre-exponential factor, apparent activation energy, and apparent reaction order. The single particle model can be incorporated as a sub-model into a CFD code. The results show that the modeled char oxidation rates are in good agreement with experimental char oxidation rates up to around 70% of burnout. Moreover, the results show that the activation energy and the reaction order can be assumed to be constant for a large number of bituminous coal chars under conditions limited by the combined effects of chemical kinetics and pore diffusion. Based on this, a new model based on only one fuel specific parameter is developed (Paper III). The results also show that reaction orders of bituminous coal chars and anthracite chars differ under similar conditions (Paper I and Paper II); reaction orders of bituminous coal chars were found to be one, while reaction orders of anthracite chars were determined to be zero. This difference in reaction orders has not previously been observed in the literature and should be considered in future char oxidation models. One of the most frequently used comprehensive char oxidation models could not explain the difference in the reaction orders. In the thesis (Paper II), a modification to the model is suggested in order to explain the difference in reaction orders between anthracite chars and bituminous coal chars. Two single particle models are also developed for the NO formation and reduction during the oxidation of single biomass char particles. In the models the char-N is assumed to be oxidized to NO and the NO is partly reduced inside the particle. The first model (Paper IV) is based on the concentration gradients of NO inside and outside the particle and the second model is simplified to such an extent that it is based on apparent kinetics and can be incorporated as a sub-model into a CFD code (Paper V). Modeled NO release rates from both models were in good agreement with experimental measurements from a single particle reactor of quartz glass operating at 1173-1323 K and 3-19 vol.% O2. In the future, the models can be used to reduce NO emissions in new combustion systems.

Konversiosähköauton mitoitussuunnitelma

Sähköautojen tulemista on odotettu jo pitkään ja ne ovat potentiaalisia fossiilisilla polttoaineilla toimivien polttomoottoreiden korvaajia. Hybridiautoja on tullut markkinoille entistä enemmän ja ne osaltaan auttavat vähentämään fossiilisten polttoaineiden käyttöä. Sähköautot ovat toistaiseksi jääneet taka-alalle. Tässä työssä on tehty konversiosähköauton mitoitussuunnitelma museoikäiseen autoon. Työssä on mitoitettu kolme sähköisen voimansiirron pääkomponenttia sähkömoottori, taajuudenmuuttaja ja akusto. Mitoitussuunnitelma toimii hyvänä pohjana, jonka avulla konversiota voidaan alkaa rakentamaan.

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.

Fluid dynamic modelling and simulation of circulating fluidized bed reactors: importance of the interface turbulence transfer

The main objective of this work is to analyze the importance of the gas-solid interface transfer of the kinetic energy of the turbulent motion on the accuracy of prediction of the fluid dynamic of Circulating Fluidized Bed (CFB) reactors. CFB reactors are used in a variety of industrial applications related to combustion, incineration and catalytic cracking. In this work a two-dimensional fluid dynamic model for gas-particle flow has been used to compute the porosity, the pressure, and the velocity fields of both phases in 2-D axisymmetrical cylindrical co-ordinates. The fluid dynamic model is based on the two fluid model approach in which both phases are considered to be continuous and fully interpenetrating. CFB processes are essentially turbulent. The model of effective stress on each phase is that of a Newtonian fluid, where the effective gas viscosity was calculated from the standard k-epsilon turbulence model and the transport coefficients of the particulate phase were calculated from the kinetic theory of granular flow (KTGF). This work shows that the turbulence transfer between the phases is very important for a better representation of the fluid dynamics of CFB reactors, especially for systems with internal recirculation and high gradients of particle concentration. Two systems with different characteristics were analyzed. The results were compared with experimental data available in the literature. The results were obtained by using a computer code developed by the authors. The finite volume method with collocated grid, the hybrid interpolation scheme, the false time step strategy and SIMPLEC (Semi-Implicit Method for Pressure Linked Equations - Consistent) algorithm were used to obtain the numerical solution.

Drop Size Measurements in a Laboratory Scale Venturi Scrubber

Venturi scrubbers are high efficiency gas cleaners in which suspended particles are removed from gas streams by droplets formed by liquid atomisation, usually in the venturi throat. The size of the droplets formed is of fundamental importance to the performance of the equipment, both in terms of pressure drop and collection efficiency. In this study, drop sizes in a cylindrical laboratory scale venturi scrubber were measured using a laser diffraction technique. Gas velocity and liquid to gas ratios varied from 50 to 90 m/s and 0.5 to 2.0 l/m3, respectively. Water was inserted as perpendicular jets at the beginning of the throat. Measurements were performed at three positions: two located along the throat, and the last one at the end of the diffuser. The data presented here are a typical example of pneumatic atomisation and can be relevant to other industrial applications such as combustion and engine technology. Finally, results are compared to available correlations and the validity of these equations is discussed.