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.

On sliding mode control ofhydraulic servo systems and a manipulator

The aim of the study is to developa novel robust controller based on sliding mode control technique for the hydraulic servo system with flexible load and for a flexible manipulator with the lift and jib hydraulic actuators. For the purpose of general control design, a dynamic model is derived describing the principle physical behavior for both the hydraulic servo system and the flexible hydraulic manipulator. The mechanism of hydraulic servo systems is described by basic mathematical equations of fluid powersystems and the dynamics of flexible manipulator is modeled by the assumed modemethod. The controller is constructed so as to track desired trajectories in the presence of model imprecision. Experimental and simulation results demonstratethat sliding mode control has benefits which can be used to guarantee stabilityin uncertain systems and improve the system performance and load tolerance.

Sliding Mode Control for Switched Mode Power Supplies

Control applications of switched mode power supplies have been widely investigated. The main objective ofresearch and development (R&D) in this field is always to find the most suitable control method to be implemented in various DC/DC converter topologies. Inother words, the goal is to select a control method capable of improving the efficiency of the converter, reducing the effect of disturbances (line and load variation), lessening the effect of EMI (electro magnetic interference), and beingless effected by component variation. The main objective of this research work is to study different control methods implemented in switched mode power supplies namely (PID control, hysteresis control, adaptive control, current programmed control, variable structure control (VSC), and sliding mode control (SMC). The advantages and drawbacks of each control method are given. Two control methods, the PID and the SMC are selected and their effects on DC/DC (Buck, Boost, and Buck-Boost) converters are examined. Matlab/SimulinkTM is used to implement PID control method in DC/DC Buck converter and SMC in DC/DC (Buck, and Buck Boost) converters. For the prototype, operational amplifiers (op-amps) are used to implement PID control in DC/DC Buck converter. For SMC op-amps are implemented in DC/DC Buck converter and dSPACETM is used to control the DC/DC Buck-Boost converter. The SMC can be applied to the DC/DC (Buck, Boost, and Buck-Boost) converters. A comparison of the effects of the PID control and the SMC on the DC/DC Buck converter response in steady state, under line variations, load variations, and different component variations is performed. Also the Conducted RF-Emissions between the PID and SMC DC/DC Buck Converter are compared. The thesis shows that, in comparison with the PID control, the SMC provides better steady-state response, better dynamic response, less EMI, inherent order reduction, robustness against system uncertainty disturbances, and an implicit stability proof. Giving a better steady-state and dynamic response, the SMC is implemented in a DC/DC resonant converter. The half-wave zero current switching (HWZCS) DC/DC Buck converter is selected as a converter topology. A general guideline to select the tank component values, needed for the designing of a HWZCS DC/DC Buck, is obtained. The implementation of the SMC to a HWZCS DC/DC Buck converter is analysed. The converter response is investigated in the steady-state region and in the dynamic region.

Propagation of the Ignition Front against Airflow in Packed Beds of Wood Particles

Combustion of wood is increasing because of the needs of decreasing the emissions of carbon dioxide and the amount of waste going to landfills. Wood based fuels are often scattered on a large area. The transport distances should be short enough to prevent too high costs, and so the size of heating and power plants using wood fuels is often rather small. Combustion technologies of small-size units have to be developed to reach efficient and environmentally friendly energy production. Furnaces that use different packed bed combustion or gasification techniques areoften most economic in small-scale energy production. Ignition front propagation rate affects the stability, heat release rate and emissions of packed bed combustion. Ignition front propagation against airflow in packed beds of wood fuels has been studied. The research has been carried out mainly experimentally. Theoretical aspects have been considered to draw conclusions about the experimental results. The effects of airflow rate, moisture content of the fuel, size, shape and density of particles, and porosity of the bed on the propagation rate of the ignition front have been studied. The experiments were carried out in a pot furnace. The fuels used in the experiments were mainly real wood fuels that are often burned in the production of energy. The fuel types were thin wood chips, saw dust, shavings, wood chips, and pellets with different sizes. Also a few mixturesof the above were tested. Increase in the moisture content of the fuel decreases the propagation rates of the ignition front and makes the range of possible airflow rates narrower because of the energy needed for the evaporation of water and the dilution of volatile gases due to evaporated steam. Increase in the airflow rate increases the ignition rate until a maximum rate of propagation is reached after which it decreases. The maximum flame propagation rate is not always reached in stoichiometric combustion conditions. Increase in particle size and density transfers the optimum airflow rate towards fuel lean conditions. Mixing of small and large particles is often advantageous, because small particles make itpossible to reach the maximum ignition rate in fuel rich conditions, and large particles widen the range of possible airflow rates. A correlation was found forthe maximum rate of ignition front propagation in different wood fuels. According to the correlation, the maximum ignition mass flux is increased when the sphericity of the particles and the porosity of the bed are increased and the moisture content of the fuel is decreased. Another fit was found between sphericity and porosity. Increase in sphericity decreases the porosity of the bed. The reasons of the observed results are discussed.

Extraordinary mode of singing by Finlanders

London : Joseph Mawman 1802

Mode of forcing a passage through the ice

Englantilaisen tutkimusmatkaajan E. D. Clarken Ahvenanmeren ylitys joulukuussa 1799. - Digitoitu valokuvasta, joka julkaistu kirjassa: R. Knapas & P. Koistinen, Historiallisia kuvia, 1993.

Micronization of Pharmaceuticals and Food Ingredients using Supercritical Fluid Techniques

Micronization techniques based on supercritical fluids (SCFs) are promising for the production of particles with controlled size and distribution. The interest of the pharmaceutical field in the development of SCF techniques is increasing due to the need for clean processes, reduced consumption of energy, and to their several possible applications. The food field is still far from the application of SCF micronization techniques, but there is increasing interest mainly for the processing of products with high added value. The aim of this study is to use SCF micronization techniques for the production of particles of pharmaceuticals and food ingredients with controlled particle size and morphology, and to look at their production on semi-industrial scale. The results obtained are also used to understand the processes from the perspective of broader application within the pharmaceutical and food industries. Certain pharmaceuticals, a biopolymer and a food ingredient have been tested using supercritical antisolvent micronization (SAS) or supercritical assisted atomization (SAA) techniques. The reproducibility of the SAS technique has been studied using physically different apparatuses and on both laboratory and semi-industrial scale. Moreover, a comparison between semi-continuous and batch mode has been performed. The behaviour of the system during the SAS process has been observed using a windowed precipitation vessel. The micronized powders have been characterized by particle size and distribution, morphology and crystallinity. Several analyses have been performed to verify if the SCF process modified the structure of the compound or caused degradation or contamination of the product. The different powder morphologies obtained have been linked to the position of the process operating point with respect to the vapour-liquid equilibrium (VLE) of the systems studied, that is, mainly to the position of the mixture critical point (MCP) of the mixture. Spherical micro, submicro- and nanoparticles, expanded microparticles (balloons) and crystals were obtained by SAS. The obtained particles were amorphous or with different degrees of crystallinity and, in some cases, had different pseudo-polymorphic or polymorphic forms. A compound that could not be processed using SAS was micronized by SAA, and amorphous particles were obtained, stable in vials at room temperature. The SCF micronization techniques studied proved to be effective and versatile for the production of particles for several uses. Furthermore, the findings of this study and the acquired knowledge of the proposed processes can allow a more conscious application of SCF techniques to obtain products with the desired characteristics and enable the use of their principles for broader applications.

Entry Strategy Issues in the Ophthalmic Industry: Entry Mode, Pricing and Distribution

Maahantulostrategia asettaa yrityksen kansainvälisiä liiketoimintoja ohjaavat tavoitteet, päämäärät, resurssit ja toiminnan suuntaviivat. Tämä diplomityö käsittelee yrityksen maahantulostrategian elementeistä operaatiomuodon valintaa, hinnoittelua ja jakelua. Työssä rakennetaan teoriakehys elementteihin liittyvien päätösten tutkimiseksi lääketeollisuuden ominaispiirteet huomioiden. Lääketeollisuudella on muihin teollisuudenaloihin verrattuna useita erityispiirteitä, joihin työ perehdyttää. Lisäksi työn olennainen osa on selvittää lääketeollisuuden maakohtaisia säädöksiä ja toimintamalleja. Diplomityö on tehty silmäläkkeitä valmistavalle, kehittävälle ja markkinoivalle Santen Oy:lle, joka suunnittelee toimintansa laajentamista Keski- ja Etelä-Euroopan markkinoille. Tässä laajentumisprosessissa ensimmäisenä kohdemaana on Saksa, jonka markkinoille suuntautuvia toimenpiteitä työ tutkii. Teoriakehyksen, markkinoiden ominaispiirteiden sekä useiden erilaisten analyysien pohjalta työn tavoitteena on antaa operaatiomuotoa, tuotteiden hinnoittelua ja jakelua koskevia suosituksia.

Particle Size Analysis of Pharmaceutical Powders by Laser Diffraction

Raaka-aineen hiukkaskoko on lääkekehityksessä keskeinen materiaaliparametri. Lääkeaineen partikkelikoko vaikuttaa moneen lääketuotteen tärkeään ominaisuuteen, esimerkiksi lääkkeen biologiseen hyväksikäytettävyyteen. Tässä diplomityössä keskityttiin jauhemaisten lääkeaineiden hiukkaskoon määrittämiseen laserdiffraktiomenetelmällä. Menetelmä perustuu siihen, että partikkeleista sironneen valon intensiteetin sirontakulmajakauma on riippuvainen partikkelien kokojakaumasta. Työn kirjallisuusosassa esiteltiin laserdiffraktiomenetelmän teoriaa. PIDS (Polarization Intensity Differential Scattering) tekniikka, jota voidaan käyttää laserdiffraktion yhteydessä, on myös kuvattu kirjallisuusosassa. Muihin menetelmiin perustuvista analyysimenetelmistä tutustuttiin mikroskopiaan sekä aerodynaamisen lentoajan määrittämiseen perustuvaan menetelmään. Kirjallisuusosassa esiteltiin myös partikkelikoon yleisimpiä esitystapoja. Työn kokeellisen osan tarkoituksena oli kehittää ja validoida laserdiffraktioon perustuva partikkelikoon määritysmenetelmä tietylle lääkeaineelle. Menetelmäkehitys tehtiin käyttäen Beckman Coulter LS 13 320 laserdiffraktoria. Laite mahdollistaa PIDS-tekniikan käytön laserdiffraktiotekniikan ohella. Menetelmäkehitys aloitettiin arvioimalla, että kyseinen lääkeaine soveltuu parhaiten määritettäväksi nesteeseen dispergoituna. Liukoisuuden perusteella väliaineeksi valittiin tällä lääkeaineella kyllästetty vesiliuos. Dispergointiaineen sekä ultraäänihauteen käyttö havaittiin tarpeelliseksi dispergoidessa kyseistä lääkeainetta kylläiseen vesiliuokseen. Lopuksi sekoitusnopeus näytteensyöttöyksikössä säädettiin sopivaksi. Validointivaiheessa kehitetyn menetelmän todettiin soveltuvan hyvin kyseiselle lääkeaineelle ja tulosten todettiin olevan oikeellisia sekä toistettavia. Menetelmä ei myöskään ollut herkkä pienille häiriöille.

Entry Mode Choice in a Hard Service Company

Pro gradun tavoitteena oli löytää tärkeimmät seikat, jotka vaikuttavat kansainvälisen operaatiomuodon valintaan. Tutkimuskohteena olivat suomalaiset pienet tai keskisuuret tuotteistetut ohjelmistopalveluyritykset. Tutkimusmenetelmänä käytettiin kvalitatiivista tutkimusta sekä case-tutkimusta. Tutkimus koostui kahdesta osasta: teoreettinen osa sekä empiirinen kahden case yrityksen analyysi. Operaatiomuodon valintaan vaikuttavat tekijät jaettiin sisäisiin (yritys, tuote ja päätöksentekijä), ulkoisiin (ala ja maa) ja operaatiomuodon (kontrolli, riski, resurssit, joustavuus, tuotot ja kulut) tekijöihin. Teoreettisesti operaatiomuodon valinta on erittäin monimutkainen päätös ja sitä on tutkittu monelta kannalta. Tämä empiirinen tutkimus osoittaa, että yrityksen resurssit olivat tärkein vaikuttava tekijä molemmissa yrityksissä.

Drug loading of mesoporous silicon particles

Porous silicon (PSi) is a promising material to be utilized in drug delivery formulations. The release rate of the drug compound can be controlled by changing the pore properties and surface chemistry of PSi. The loading of a poorly soluble drug into mesoporous silicon particles enhances its dissolution in the body. The drug loading is based on adsorption. The attainable maximum loaded amount depends on the properties of the drug compound and the PSi material, and on the process conditions. The loading solvent also essentially affects the adsorption process. The loading of indomethacin into PSi particles with varying surface modification was studied. Solvent mixtures were applied in the loading, and the loaded samples were analyzed with thermal analysis methods. The best degree of loading was obtained using a mixture of dichloromethane and methanol. The drug loads varied from 7.7 w-% to 26.8 w-%. A disturbing factor in the loading experiments was the tendency of indomethacin to form solvates with the solvents applied. In addition, the physical form and stability of indomethacin loaded in PSi and silica particles were studied using Raman spectroscopy. In the case of silica, the presence of crystalline drug as well as the polymorph form can be detected, but the method proved to be not applicable for PSi particles.