Formation and Control of Trace Metal Emissions in Co-Firing of Biomass, Peat, and Wastes in Fluidised Bed Combustors

Environmentally harmful consequences of fossil fuel utilisation andthe landfilling of wastes have increased the interest among the energy producers to consider the use of alternative fuels like wood fuels and Refuse-Derived Fuels, RDFs. The fluidised bed technology that allows the flexible use of a variety of different fuels is commonly used at small- and medium-sized power plants ofmunicipalities and industry in Finland. Since there is only one mass-burn plantcurrently in operation in the country and no intention to build new ones, the co-firing of pre-processed wastes in fluidised bed boilers has become the most generally applied waste-to-energy concept in Finland. The recently validated EU Directive on Incineration of Wastes aims to mitigate environmentally harmful pollutants of waste incineration and co-incineration of wastes with conventional fuels. Apart from gaseous flue gas pollutants and dust, the emissions of toxic tracemetals are limited. The implementation of the Directive's restrictions in the Finnish legislation is assumed to limit the co-firing of waste fuels, due to the insufficient reduction of the regulated air pollutants in the existing flue gas cleaning devices. Trace metals emission formation and reduction in the ESP, the condensing wet scrubber, the fabric filter, and the humidification reactor were studied, experimentally, in full- and pilot-scale combustors utilising the bubbling fluidised bed technology, and, theoretically, by means of reactor model calculations. The core of the model is a thermodynamic equilibrium analysis. The experiments were carried out with wood chips, sawdust, and peat, and their refuse-derived fuel, RDF, blends. In all, ten different fuels or fuel blends were tested. Relatively high concentrations of trace metals in RDFs compared to the concentrations of these metals in wood fuels increased the trace metal concentrations in the flue gas after the boiler ten- to hundred-folds, when RDF was co-fired with sawdust in a full-scale BFB boiler. In the case of peat, lesser increase in trace metal concentrations was observed, due to the higher initial trace metal concentrations of peat compared to sawdust. Despite the high removal rate of most of the trace metals in the ESP, the Directive emission limits for trace metals were exceeded in each of the RDF co-firing tests. The dominat trace metals in fluegas after the ESP were Cu, Pb and Mn. In the condensing wet scrubber, the flue gas trace metal emissions were reduced below the Directive emission limits, whenRDF pellet was used as a co-firing fuel together with sawdust and peat. High chlorine content of the RDFs enhanced the mercuric chloride formation and hence the mercury removal in the ESP and scrubber. Mercury emissions were lower than theDirective emission limit for total Hg, 0.05 mg/Nm3, in all full-scale co-firingtests already in the flue gas after the ESP. The pilot-scale experiments with aBFB combustor equipped with a fabric filter revealed that the fabric filter alone is able to reduce the trace metal concentrations, including mercury, in the flue gas during the RDF co-firing approximately to the same level as they are during the wood chip firing. Lower trace metal emissions than the Directive limits were easily reached even with a 40% thermal share of RDF co-firing with sawdust.Enrichment of trace metals in the submicron fly ash particle fraction because of RDF co-firing was not observed in the test runs where sawdust was used as the main fuel. The combustion of RDF pellets with peat caused an enrichment of As, Cd, Co, Pb, Sb, and V in the submicron particle mode. Accumulation and release oftrace metals in the bed material was examined by means of a bed material analysis, mass balance calculations and a reactor model. Lead, zinc and copper were found to have a tendency to be accumulated in the bed material but also to have a tendency to be released from the bed material into the combustion gases, if the combustion conditions were changed. The concentration of the trace metal in the combustion gases of the bubbling fluidised bed boiler was found to be a summary of trace metal fluxes from three main sources. They were (1) the trace metal flux from the burning fuel particle (2) the trace metal flux from the ash in the bed, and (3) the trace metal flux from the active alkali metal layer on the sand (and ash) particles in the bed. The amount of chlorine in the system, the combustion temperature, the fuel ash composition and the saturation state of the bed material in regard to trace metals were discovered to be key factors affecting therelease process. During the co-firing of waste fuels with variable amounts of e.g. ash and chlorine, it is extremely important to consider the possible ongoingaccumulation and/or release of the trace metals in the bed, when determining the flue gas trace metal emissions. If the state of the combustion process in regard to trace metals accumulation and/or release in the bed material is not known,it may happen that emissions from the bed material rather than the combustion of the fuel in question are measured and reported.

Sellu- ja paperiteollisuuden haitallisimmat ilmapäästöt

Diplomityössä luotiin katsaus sellu- ja paperiteollisuuden haitallisimpiin ilmapäästöihin ja ilmapäästömäärien kehitykseen Suomessa 1990-luvun alusta nykypäivään. Työssä tutustuttiin sellu- ja paperiteollisuuden ilmapäästöjä rajoittavan lainsäädännön ajankohtaisiin asioihin Suomessa ja Euroopan Unionissa, sekä tarkasteltiin nykyisen lainsäädännön perustana olleita ilmastosopimuksia eli kansainvälisen ilmastopolitiikan syntyä ja kehittymistä. Työssä on myös selvitetty ilman osuutta paperinvalmistuksessa, tutustuttu ilmapäästöjen rajoittamismenetelmiin ja eri mittausmenetelmiin ilmapäästöjen toteamiseksi. Työn puitteissa suoritettiin mittalaitetestejä eri paperitehtailla. Haitallisimpia ja määrällisesti suurimpia ilmapäästöjä sellu- ja paperiteollisuudessa ovat typen ja rikin oksidit, pelkistyneet rikkiyhdisteet, hiukkaset, haihtuvat orgaaniset yhdisteet (VOC) ja hiilidioksidi. Ilmapäästömäärät Suomessa ovat typenoksideja lukuun ottamatta olleet laskussa 1990-luvun alusta nykypäivään. Tärkein kasvihuonekaasu on hiilidioksidi, jonka määrää rajoitetaan Kioton sopimuksessa. Vuoden 2002 aikana selvinneekin, mikä on Kioton sopimuksen vaikutus Suomen metsäteollisuuteen. Päästömittauksia tarvitaan lainsäädännön raja-arvojen toteamiseksi, mittauksia suorittavat sertifioidut päästömittauslaboratoriot. Suoritetuissa mittalaitetesteissä havaittiin mittalaitteiden soveltuvuudessa kosteiden paperiprosessin poistokaasujen määrittämiseen suuria eroja.

Levyteollisuuden energia-, kustannus- ja ympäristövaikutukset

Kuluvien vuosien aikana ei ole tehty kattavia tutkimuksia levyteollisuuden sähkönkulutuksista, joten on aika selvittää suurimpien sähkökäyttöjen kulutukset sekä muodostaa tutkittaville tehtaille energiataseet. Tutkittavia tehtaita ovat OSB- ja lastulevytehtaat. Yksittäisten sähkömoottoreiden kulutukset saadaan selville käyttämällä hyväksi teoreettisia lähteitä, kenttä-ja laboratoriotutkimusta. Ympäristölainsäädäntö ja siihen kiinteästi liittyvä lupakäytäntö muodostavat levyteollisuudelle yhden viimeaikojen suurimmista haasteista. Tulevaisuudessa lainsäädäntö tulee vielä entisestäänkin kiristymään. Euroopan ympäristölainsäädäntö perustuu pitkälti yhtenäislupadirektiiviin eli IPPC-direktiiviin. Direktiivin keskeinen osa on ympäristöluvan hankkiminen, koska teollista toimintaa ei voi harjoittaa ilman hyväksyttyä viranomaisen lupaa. Lupa myös velvoittaa toiminnanharjoittajan käyttämään parasta käyttökelpoista tekniikkaa päästöjen kontrolloinnissa. Yhdysvalloissa parhaan käyttökelpoisen tekniikan (BAT) vaatimus on sisälletty ympäristövirasto EPA:n MACT-standardeihin. Levyteollisuuden tehtaista syntyvät päästöt ovat hyvin samankaltaisia. Tehtaista on helposti erotettavissa kaksi suurta päästölähdettä, joita ovat kuivaus ja kuumapuristus. Merkittävimpiä päästöjä ovat haihtuvat orgaaniset yhdisteet, hiukkaset, typen oksidit, hiilimonoksidi ja rikkidioksidit. Työn loppuosa on varattu tuotantojen kustannusvaikutusten ja tunnuslukujen tarkasteluille. Saatavilla tiedoilla on keskeinen rooli tehtaiden jokapäiväisessä toiminnassa. Analysoinnin tarpeeseen vaikuttaa osaltaan nykyisen toimintaympäristön muutosherkkyys ja levymarkkinoiden kireä kilpailutilanne.

Gas-phase photocatalytic oxidation of volatile organic compounds

Substances emitted into the atmosphere by human activities in urban and industrial areas cause environmental problems such as air quality degradation, respiratory diseases, climate change, global warming, and stratospheric ozone depletion. Volatile organic compounds (VOCs) are major air pollutants, emitted largely by industry, transportation and households. Many VOCs are toxic, and some are considered to be carcinogenic, mutagenic, or teratogenic. A wide spectrum of VOCs is readily oxidized photocatalytically. Photocatalytic oxidation (PCO) over titanium dioxide may present a potential alternative to air treatment strategies currently in use, such as adsorption and thermal treatment, due to its advantageous activity under ambient conditions, although higher but still mild temperatures may also be applied. The objective of the present research was to disclose routes of chemical reactions, estimate the kinetics and the sensitivity of gas-phase PCO to reaction conditions in respect of air pollutants containing heteroatoms in their molecules. Deactivation of the photocatalyst and restoration of its activity was also taken under consideration to assess the practical possibility of the application of PCO to the treatment of air polluted with VOCs. UV-irradiated titanium dioxide was selected as a photocatalyst for its chemical inertness, non-toxic character and low cost. In the present work Degussa P25 TiO2 photocatalyst was mostly used. In transient studies platinized TiO2 was also studied. The experimental research into PCO of following VOCs was undertaken: - methyl tert-butyl ether (MTBE) as the basic oxygenated motor fuel additive and, thus, a major non-biodegradable pollutant of groundwater; - tert-butyl alcohol (TBA) as the primary product of MTBE hydrolysis and PCO; - ethyl mercaptan (ethanethiol) as one of the reduced sulphur pungent air pollutants in the pulp-and-paper industry; - methylamine (MA) and dimethylamine (DMA) as the amino compounds often emitted by various industries. The PCO of VOCs was studied using a continuous-flow mode. The PCO of MTBE and TBA was also studied by transient mode, in which carbon dioxide, water, and acetone were identified as the main gas-phase products. The volatile products of thermal catalytic oxidation (TCO) of MTBE included 2-methyl-1-propene (2-MP), carbon monoxide, carbon dioxide and water; TBA decomposed to 2-MP and water. Continuous PCO of 4 TBA proceeded faster in humid air than dry air. MTBE oxidation, however, was less sensitive to humidity. The TiO2 catalyst was stable during continuous PCO of MTBE and TBA above 373 K, but gradually lost activity below 373 K; the catalyst could be regenerated by UV irradiation in the absence of gas-phase VOCs. Sulphur dioxide, carbon monoxide, carbon dioxide and water were identified as ultimate products of PCO of ethanethiol. Acetic acid was identified as a photocatalytic oxidation by-product. The limits of ethanethiol concentration and temperature, at which the reactor performance was stable for indefinite time, were established. The apparent reaction kinetics appeared to be independent of the reaction temperature within the studied limits, 373 to 453 K. The catalyst was completely and irreversibly deactivated with ethanethiol TCO. Volatile PCO products of MA included ammonia, nitrogen dioxide, nitrous oxide, carbon dioxide and water. Formamide was observed among DMA PCO products together with others similar to the ones of MA. TCO for both substances resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide and water. No deactivation of the photocatalyst during the multiple long-run experiments was observed at the concentrations and temperatures used in the study. PCO of MA was also studied in the aqueous phase. Maximum efficiency was achieved in an alkaline media, where MA exhibited high fugitivity. Two mechanisms of aqueous PCO – decomposition to formate and ammonia, and oxidation of organic nitrogen directly to nitrite - lead ultimately to carbon dioxide, water, ammonia and nitrate: formate and nitrite were observed as intermediates. A part of the ammonia formed in the reaction was oxidized to nitrite and nitrate. This finding helped in better understanding of the gasphase PCO pathways. The PCO kinetic data for VOCs fitted well to the monomolecular Langmuir- Hinshelwood (L-H) model, whereas TCO kinetic behaviour matched the first order process for volatile amines and the L-H model for others. It should be noted that both LH and the first order equations were only the data fit, not the real description of the reaction kinetics. The dependence of the kinetic constants on temperature was established in the form of an Arrhenius equation.

Assessment of Coals from Russia and Countries of Former Soviet Union for Utility Fluidized Bed Boilers

With the occurrence of fossil fuels such as oil, gas and coal we found new sources of energy that have played a critical role in the progress of our modern society. Coal is very ample compared to the other two fossil fuels. Global coal reserves at the end of 2005 were estimated at 847,5 billion tones. Along with the major energy sources, coal is the most fast growing fuel on a global basis, it provides 26% of primary energy needs and remains essential to the economies of many developed and developing countries. Coal-fired power generation accounts for 41% of the world‘s total electricity production and in some countries, such as South Africa, Poland, China, Australia, Kazakhstan and India is on very high level. Still, coal utilization represents challenges related to high emissions of air pollutants such as sulphur and nitrogen dioxides, particulate matter, mercury and carbon dioxide. In relation to these a number of technologies have been developed and are in marketable use, with further potential developments towards ―Near Zero Emission‖ coal plants. In present work, coals mined in Russia and countries of Former Soviet Union were reviewed. Distribution of coal reserves on the territory of Russia and the potential for power generation from coal-fired plants across Russia was shown. Physical and chemical properties of coals produced were listed and examined, as main factor influencing on design of the combustion facility and incineration process performance. The ash-related problems in coal-fired boilers were described. The analysis of coal ash of Russia and countries of Former Soviet Union were prepared. Feasible combustion technologies also were reviewed.

Tekniset vaatimukset huonekohtaisen ilmanpuhdistimen valitsemiseksi sisäilmaongelmaisessa kohteessa

Tässä työssä tarkastellaan rakennusten sisäilman laatua heikentäviä epäpuhtauksia sekä niiden suodattamiseen huonekohtaisissa ilmanpuhdistimissa käytettäviä suodatustekniikoita. Tavoitteena oli selvittää ilmanpuhdistimien soveltuvuus sisäilmaongelmista kärsiviin kohteisiin. Ilmanpuhdistimia testattiin laboratoriossa ja testitulosten perusteella arvioitiin niiden teknisiä ominaisuuksia. Lisäksi laadittiin valintakriteerit huonekohtaisen ilmanpuhdistimen valitsemiseksi sisäilmaongelmaisessa kohteessa. Diplomityö tehtiin Helsingin kaupungin kiinteistöviraston Tilakeskuksessa vastaamaan tarpeeseen selvittää ilmanpuhdistimien teknisiä ominaisuuksia. Laboratoriotesteissä laitteista löydettiin eroavaisuuksia, ja tulosten perusteella laitteet asetettiin paremmuusjärjestykseen. Työssä suoritetun tutkimuksen perusteella voidaan todeta, että nykyisin markkinoilla olevat huonekohtaiset ilmanpuhdistimet soveltuvat pääosin melko heikosti sisäilmaongelmien ratkaisemiseen. Tähän syynä on erityisesti laitteiden aiheuttama suuri melupäästö.

The role of nuclear power in the future energy system

Currently widely accepted consensus is that greenhouse gas emissions produced by the mankind have to be reduced in order to avoid further global warming. The European Union has set a variety of CO2 reduction and renewable generation targets for its member states. The current energy system in the Nordic countries is one of the most carbon free in the world, but the aim is to achieve a fully carbon neutral energy system. The objective of this thesis is to consider the role of nuclear power in the future energy system. Nuclear power is a low carbon energy technology because it produces virtually no air pollutants during operation. In this respect, nuclear power is suitable for a carbon free energy system. In this master's thesis, the basic characteristics of nuclear power are presented and compared to fossil fuelled and renewable generation. Nordic energy systems and different scenarios in 2050 are modelled. Using models and information about the basic characteristics of nuclear power, an opinion is formed about its role in the future energy system in Nordic countries. The model shows that it is possible to form a carbon free Nordic energy system. Nordic countries benefit from large hydropower capacity which helps to offset fluctuating nature of wind power. Biomass fuelled generation and nuclear power provide stable and predictable electricity throughout the year. Nuclear power offers better energy security and security of supply than fossil fuelled generation and it is competitive with other low carbon technologies.

Practical applications of a systematic approach to the chemical abatement of pollutants in water and air

The present dissertation is devoted to the systematic approach to the development of organic toxic and refractory pollutants abatement by chemical decomposition methods in aqueous and gaseous phases. The systematic approach outlines the basic scenario of chemical decomposition process applications with a step-by-step approximation to the most effective result with a predictable outcome for the full-scale application, confirmed by successful experience. The strategy includes the following steps: chemistry studies, reaction kinetic studies in interaction with the mass transfer processes under conditions of different control parameters, contact equipment design and studies, mathematical description of the process for its modelling and simulation, processes integration into treatment technology and its optimisation, and the treatment plant design. The main idea of the systematic approach for oxidation process introduction consists of a search for the most effective combination between the chemical reaction and the treatment device, in which the reaction is supposed to take place. Under this strategy,a knowledge of the reaction pathways, its products, stoichiometry and kinetics is fundamental and, unfortunately, often unavailable from the preliminary knowledge. Therefore, research made in chemistry on novel treatment methods, comprisesnowadays a substantial part of the efforts. Chemical decomposition methods in the aqueous phase include oxidation by ozonation, ozone-associated methods (O3/H2O2, O3/UV, O3/TiO2), Fenton reagent (H2O2/Fe2+/3+) and photocatalytic oxidation (PCO). In the gaseous phase, PCO and catalytic hydrolysis over zero valent ironsare developed. The experimental studies within the described methodology involve aqueous phase oxidation of natural organic matter (NOM) of potable water, phenolic and aromatic amino compounds, ethylene glycol and its derivatives as de-icing agents, and oxygenated motor fuel additives ¿ methyl tert-butyl ether (MTBE) ¿ in leachates and polluted groundwater. Gas-phase chemical decomposition includes PCO of volatile organic compounds and dechlorination of chlorinated methane derivatives. The results of the research summarised here are presented in fifteenattachments (publications and papers submitted for publication and under preparation).

Germinability of Norway spruce and scots pine pollen exposed to open air

Summary

Effect of soil wetness on air composition and nitrous oxide emission in a loam soil

Selostus: Maan märkyyden vaikutus ilman koostumukseen ja dityppioksidiemissioon hiuemaassa