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.

A mathematical model of coal-fired fluidised bed boilers

A mathematical model of a large coal-fired fluidized bed boiler for power generation is synthesised. The effect of variations in the main parameters of the model on variables such as the background carbon concentrations in the bed, and the transient response of heat evolution are studied. The mechanisms of solids mixing within the bed, combustion and the flow of heat to the boiler tubes are shown to result in a characteristic dynamic response, knowledge of which is essential for the proper control and regulation of a practical system.

The kinetics of NO and N2O reduction over coal chars in fluidised-bed combustion

This paper presents a comprehensive and critical review of the mechanisms and kinetics of NO and N2O reduction reaction with coal chars under fluidised-bed combustion conditions (FBC). The heterogeneous reactions of NO and N2O with char/carbon surface have been well recognised as the most important processes in reducing both NOx and N2O in situ FBC. Compared to NO-carbon reactions in FBC, the reactions of N2O with chars have been relatively less understood and studied. Beginning with the overall reaction schemes for both NO and N2O reduction, the paper extensively discusses the reaction mechanisms including the effects of active surface sites. Generally, NO- and N2O-carbon reactions follow a series of step reactions. However, questions remain concerning the role of adsorbed phases of NO and N2O, and the behaviour of different surface sites. Important kinetics factors such as the rate expressions, kinetics parameters as well as the effects of surface area and pore structure are discussed in detail. The main factors influencing the reduction of NO and N2O in FBC conditions are the chemical and physical properties of chars, and the operating parameters of FBC such as temperature, presence of CO, O-2 and pressure. It is shown that under similar conditions, N2O is more readily reduced on the char surface than NO. Temperature was found to be a very important parameter in both NO and N2O reduction. It is generally agreed that both NO- and N2O-carbon reactions follow first-order reaction kinetics with respect to the NO and N2O concentrations. The kinetic parameters for NO and N2O reduction largely depend on the pore structure of chars. The correlation between the char surface area and the reactivities of NO/N2O-char reactions is considered to be of great importance to the determination of the reaction kinetics. The rate of NO reduction by chars is strongly enhanced by the presence of CO and O-2, but these species may not have significant effects on the rate of N2O reduction. However, the presence of these gases in FBC presents difficulties in the study of kinetics since CO cannot be easily eliminated from the carbon surface. In N2O reduction reactions, ash in chars is found to have significant catalytic effects, which must be accounted for in the kinetic models and data evaluation. (C) 1997 Elsevier Science Ltd.

Model-based measurement and control of fluidised bed spray granulation processes

Magdeburg, Univ., Fak. für Verfahrens- und Systemtechnik, Diss., 2012

Advanced control methods for reducing nitrogen oxides in a fluidized bed boiler

Tämän työn tarkoituksena oli löytää keinoja erään leijukerroskattilan typenoksidipäästöjen vähentämiseksi. Koska päästöt olivat jo alunperin alhaiset leijukerrostekniikan ja hybridin SNCR/SCR –typenpoistolaitteiston ansiosta, päätettiin päästöjä lähteä vähentämään parantamalla ammoniakkiruiskutuksen säätöä. Alkuperäinen ammoniakkiruiskutuksen säätö oli liian hidas, jotta satunnaisten häiriöiden aiheuttamat typenoksidipiikit olisi pystytty poistamaan. Ammoniakkiruiskutusta parannettiin lisäämällä jokaiseen ammoniakkilinjaan mäntäpumput, joiden avulla ammoniakkia voidaan syöttää sinne, missä sitä eniten tarvitaan. Ammoniakkiruiskutuksen säätöön kehitettiin uusi sumeaan logiikkaan perustuva säätäjä. Myös muita kehittyneitä säätömenetelmiä kuten neuroverkkoa hyödynnettiin säätäjän kehityksessä. Ammoniakkiruiskutuksen säätäjää testattiin menestyksekkäästi Ruotsissa Brista Kraftin Märstassa sijaitsevalla voimalaitoksella

Development of Furnace Model for Bubbling Fluidized Bed Boiler

The aim of this thesis was to develop a model, which can predict heat transfer, heat release distribution and vertical temperature profile of gas phase in the furnace of a bubbling fluidized bed (BFB) boiler. The model is based on three separate model components that take care of heat transfer, heat release distribution and mass and energy balance calculations taking into account the boiler design and operating conditions. The model was successfully validated by solving the model parameters on the basis of commercial size BFB boiler test run information and by performing parametric studies with the model. Implementation of the developed model for the Foster Wheeler BFB design procedures will require model validation with existing BFB database and possibly more detailed measurements at the commercial size BFB boilers.

Characterization Method for Comminution Behavior of Limestone and Fuel Ash in a Circulating Fluidized Bed Boiler

Työn tavoite oli kehittää karakterisointimenetelmät kalkkikiven ja polttoaineen tuhkan jauhautumisen ennustamiselle kiertoleijukattilan tulipesässä. Kiintoainekäyttäytymisen karakterisoinnilla ja mallintamisella voidaan tarkentaa tulipesän lämmönsiirron ja tuhkajaon ennustamista. Osittain kokeelliset karakterisointimenetelmät perustuvat kalkkikiven jauhautumiseen laboratoriokokoluokan leijutetussa kvartsiputkireaktorissa ja tuhkan jauhatumiseen rotaatiomyllyssä. Karakterisointimenetelmät ottavat huomioon eri-laiset toimintaolosuhteet kaupallisen kokoluokan kiertoleijukattiloissa. Menetelmät kelpoistettiin kaupallisen kokoluokan kiertoleijukattiloista mitattujen ja fraktioittaisella kiintoainemallilla mallinnettujen taseiden avulla. Kelpoistamistaseiden vähäisyydestä huolimatta karakterisointimenetelmät arvioitiin virhetarkastelujen perusteella järkeviksi. Karakterisointimenetelmien kehittämistä ja tarkentamista tullaan jatkamaan.

Heat transfer in superheaters of the bubbling fluidized bed boiler conversions

It is often reasonable to convert old boiler to bubbling fluidized bed boiler instead of building a new one. Converted boiler consists of old and new heat surfaces which must be fitted to operate together. Prediction of heat transfer in not so ideal conditions sets challenges for designers. Two converted boilers situated in Poland were studied on the grounds of acceptance tests and further studies. Calculation of boiler process was performed with boiler design program. Main interest was heat transfer in superheaters and factors affecting it. Theory for heat transfer is presented according to information found from literature. Results obtained from experimental studies and calculations have been compared. With correct definitions calculated parameters corresponded well to measured data at boiler maximum design load. However overload situations revealed to be difficult to model at least without considering changes in the combustion process which requires readjustments to the design program input values.

Modeling of water/steam circulation in Circulating Fluidized Bed boiler

A distinctive design feature of steam boiler with natural circulation is the presence of the steam drum which plays a role of the separator of vapor from the flow of water-and-steam mixture coming into steam drum from the furnace tubes. Steam drum with unheated downcomer tubes, deducing from it, and riser (screen/furnace tubes) inside the furnace is a closed circulation loop in which movement of water (downcomer tubes) and water-and-steam mixture (riser tubes) is organized. The movement of the working fluid is appears due to occurrence of the natural pressure, determined by the difference in hydrostatic pressure and the mass of water and water-and-steam mixtures in downcomer and riser tubes and called the driving pressure of the natural circulation:

Modeling of water/steam circulation in Circulating Fluidized Bed boiler

A distinctive design feature of steam boiler with natural circulation is the presence of the steam drum which plays a role of the separator of vapor from the flow of water-and-steam mixture coming into steam drum from the furnace tubes. Steam drum with unheated downcomer tubes, deducing from it, and riser (screen/furnace tubes) inside the furnace is a closed circulation loop in which movement of water (downcomer tubes) and water-and-steam mixture (riser tubes) is organized. The movement of the working fluid is appears due to occurrence of the natural pressure, determined by the difference in hydrostatic pressure and the mass of water and water-and-steam mixtures in downcomer and riser tubes and called the driving pressure of the natural circulation: S drive = H steam (ρ down + ρ mix) g where: ρ down - density of water in downcomer tubes; ρ mix - density of water in riser tubes; H steam - height of steam content section; g - acceleration of gravity. In steam boilers with natural circulation the circulation rate is usually between 10 and 30. Thus, consumption of water in the circulation circuit “circulation rate times” more than steam output of the boiler. There are two aspects of the design of natural water circulation loops. One is to ensure a sufficient mass flux of circulating water to avoid burnout of evaporator tubes. The other is to avoid tube wall temperature fluctuation and tube vibration due to oscillation of circulation velocity. The design criteria are therefore reduced, in principle, to those of critical heat flux, critical flow rate for burnout, and flow instability. In practical design, however, the circulation velocity and the void fraction at the evaporator tube outlet are used as the design criteria (Seikan I., et. al., 1999). This study has been made with assumption that the heat flux in the furnace of the boiler even all the time. The target of the study was to define the circulation rate of the boiler, thus average heat flux do not change it. I would like to acknowledge professionals from “Foster Wheeler” company for good and comfortable cooperation.

Model development for circulating fluidized bed boiler operation

Comprehensive understanding of the heat transfer processes that take place during circulating fluidized bed (CFB) combustion is one of the most important issues in CFB technology development. This leads to possibility of predicting, evaluation and proper design of combustion and heat transfer mechanisms. The aim of this thesis is to develop a model for circulating fluidized bed boiler operation. Empirical correlations are used for determining heat transfer coefficients in each part of the furnace. The proposed model is used both in design and offdesign conditions. During off-design simulations fuel moisture content and boiler load effects on boiler operation have been investigated. In theoretical part of the thesis, fuel properties of most typical classes of biomass are widely reviewed. Various schemes of biomass utilization are presented and, especially, concerning circulating fluidized bed boilers. In addition, possible negative effects of biomass usage in boilers are briefly discussed.

Carbonation of Mg(OH)2 in a pressurised fluidised bed for CO2 sequestration

I takt med den ekonomiska tillväxten har CO2-utsläppen till atmosfären ständigt ökat, och utan kraftiga åtgärder kommer de att fortsätta att öka i allt snabbare takt. Konsekvenserna av en påtagligt förhöjd atmosfärisk CO2-halt är fortfarande osäkra (men eventuellt katastrofala) och fenomenet går under namnet global uppvärmning eller klimatförändring. CCS från engelskans ”carbon dioxide capture and storage” framstår som ett alternativ för att bekämpa de ständigt ökande CO2-utsläppen. Ett av de mer intressanta, och för Finlands del ända CCS-alternativet, baserar sig på naturens egna sätt att begränsa atmosfärisk CO2, nämligen vittring. Naturlig vittring, som förenklat innefattar nedbrytningen av sten/berg (även känd som erosion) och de därpå följande reaktionerna med CO2-mättat regnvatten. Slutresultatet är en utfällning av fasta mineraler som nu bundit CO2 i form av kalcium- och magnesiumkarbonat. Kalciumkarbonat är även bättre känt som kalksten, d.v.s. CO2 blir bundet i sten. Det gäller dock att snabba upp denna process, som i naturen är ytterst långsam, på ett ekonomiskt och miljömässigt hållbart sätt. Hittills har ett antal metoder för att påskynda naturlig vittring, eller med andra ord öka CO2-upptagningsförmågan av olika mineraler föreslagits. De mera etablerade uttrycken (lånade från engelskan) talar om mineralkarbonatisering och CO2-mineralisering. Till skillnad från många andra CO2-mineraliseringsalternativ är det alternativ som behandlas i denna avhandling i hög grad baserat på möjligheten att utnyttja den värme som frigörs vid karbonatisering. I teorin är det möjligt att föreställa sig en mineraliseringsprocess som inte kräver extern energi, men tillsvidare har man dock inte lyckats uppnå detta mål. Den process som presenteras i denna avhandling går ut på att man utvinner magnesium ur i naturen vanligt förekommande magnesiumrika mineraler, konverterar det till magnesiumhydroxid och därefter karbonatiserar det till magnesiumkarbonat. I rätta förhållanden kan magnesiumhydroxid reagera med CO2 mycket snabbt och i nuläget har processen potential att minska CO2-utsläppen från industri där spillvärme finns till förfogande (t.ex. cement- och stålindustrin). Fortsatt forskning är dock ett måste för att kunna påverka CO2-utsläppen i en globalt signifikant skala.

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.

Modeling of temperature regimes in a furnace of bubbling fluidized bed boiler

The work is mainly focused on the technology of bubbling fluidized bed combustion. Heat transfer and hydrodynamics of the process were examined in the work in detail. Special emphasis was placed on the process of heat exchange in a freeboard zone of bubbling fluidized bed boiler. Operating mode of bubbling fluidized bed boiler depends on many parameters. To assess the influence of some parameters on a temperature regime inside the furnace a simplified method of zonal modeling was used in the work. Thus, effects of bed material fineness, excess air ratio and changes in boiler load were studied. Besides the technology of combustion in bubbling fluidized bed, other common technologies of solid fuels combustion were reviewed. In addition, brief survey of most widely used types of solid fuel was performed in the work.

Particle model for simulating limestone reactions in novel fluidised bed energy applications

The development of carbon capture and storage (CCS) has raised interest towards novel fluidised bed (FB) energy applications. In these applications, limestone can be utilized for S02 and/or CO2 capture. The conditions in the new applications differ from the traditional atmospheric and pressurised circulating fluidised bed (CFB) combustion conditions in which the limestone is successfully used for SO2 capture. In this work, a detailed physical single particle model with a description of the mass and energy transfer inside the particle for limestone was developed. The novelty of this model was to take into account the simultaneous reactions, changing conditions, and the effect of advection. Especially, the capability to study the cyclic behaviour of limestone on both sides of the calcination-carbonation equilibrium curve is important in the novel conditions. The significances of including advection or assuming diffusion control were studied in calcination. Especially, the effect of advection in calcination reaction in the novel combustion atmosphere was shown. The model was tested against experimental data; sulphur capture was studied in a laboratory reactor in different fluidised bed conditions. Different Conversion levels and sulphation patterns were examined in different atmospheres for one limestone type. The Conversion curves were well predicted with the model, and the mechanisms leading to the Conversion patterns were explained with the model simulations. In this work, it was also evaluated whether the transient environment has an effect on the limestone behaviour compared to the averaged conditions and in which conditions the effect is the largest. The difference between the averaged and transient conditions was notable only in the conditions which were close to the calcination-carbonation equilibrium curve. The results of this study suggest that the development of a simplified particle model requires a proper understanding of physical and chemical processes taking place in the particle during the reactions. The results of the study will be required when analysing complex limestone reaction phenomena or when developing the description of limestone behaviour in comprehensive 3D process models. In order to transfer the experimental observations to furnace conditions, the relevant mechanisms that take place need to be understood before the important ones can be selected for 3D process model. This study revealed the sulphur capture behaviour under transient oxy-fuel conditions, which is important when the oxy-fuel CFB process and process model are developed.