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.

The role of metal ions in selective and sustainable processes

Sustainability and recycling are core values in today’s industrial operations. New materials, products and processes need to be designed in such a way as to consume fewer of the diminishing resources we have available and to put as little strain on the environment as possible. An integral part of this is cleaning and recycling. New processes are to be designed to improve the efficiency in this aspect. Wastewater, including municipal wastewaters, is treated in several steps including chemical and mechanical cleaning of waters. Well-cleaned water can be recycled and reused. Clean water for everyone is one of the greatest challenges we are facing today. Ferric sulphate, made by oxidation from ferrous sulphate, is used in water purification. The oxidation of ferrous sulphate, FeSO4, to ferric sulphate in acidic aqueous solutions of H2SO4 over finely dispersed active carbon particles was studied in a vigorously stirred batch reactor. Molecular oxygen was used as the oxidation agent and several catalysts were screened: active carbon, active carbon impregnated with Pt, Rh, Pd and Ru. Both active carbon and noble metal-active carbon catalysts enhanced the oxidation rate considerably. The order of the noble metals according to the effect was: Pt >> Rh > Pd, Ru. By the use of catalysts, the production capacities of existing oxidation units can be considerably increased. Good coagulants have a high charge on a long polymer chain effectively capturing dirty particles of the opposite charge. Analysis of the reaction product indicated that it is possible to obtain polymeric iron-based products with good coagulation properties. Systematic kinetic experiments were carried out at the temperature and pressure ranges of 60B100°C and 4B10 bar, respectively. The results revealed that both non-catalytic and catalytic oxidation of Fe2+ to Fe3+ take place simultaneously. The experimental data were fitted to rate equations, which were based on a plausible reaction mechanism: adsorption of dissolved oxygen on active carbon, electron transfer from Fe2+ ions to adsorbed oxygen and formation of surface hydroxyls. A comparison of the Fe2+ concentrations predicted by the kinetic model with the experimentally observed concentrations indicated that the mechanistic rate equations were able to describe the intrinsic oxidation kinetics of Fe2+ over active carbon and active carbon-noble metal catalysts. Engineering aspects were closely considered and effort was directed to utilizing existing equipment in the production of the new coagulant. Ferrous sulphate can be catalytically oxidized to produce a novel long-chained polymeric iron-based flocculent in an easy and affordable way in existing facilities. The results can be used for modelling the reactors and for scale-up. Ferric iron (Fe3+) was successfully applied for the dissolution of sphalerite. Sphalerite contains indium, gallium and germanium, among others, and the application can promote their recovery. The understanding of the reduction process of ferric to ferrous iron can be used to develop further the understanding of the dissolution mechanisms and oxidation of ferrous sulphate. Indium, gallium and germanium face an ever-increasing demand in the electronics industry, among others. The supply is, however, very limited. The fact that most part of the material is obtained through secondary production means that real production quota depends on the primary material production. This also sets the pricing. The primary production material is in most cases zinc and aluminium. Recycling of scrap material and the utilization of industrial waste, containing indium, gallium and geranium, is a necessity without real options. As a part of this study plausible methods for the recovery of indium, gallium and germanium have been studied. The results were encouraging and provided information about the precipitation of these valuables from highly acidic solutions. Indium and gallium were separated from acidic sulphuric acid solutions by precipitation with basic sulphates such as alunite or they were precipitated as basic sulphates of their own as galliunite and indiunite. Germanium may precipitate as a basic sulphate of a mixed composition. The precipitation is rapid and the selectivity is good. When the solutions contain both indium and gallium then the results show that gallium should be separated before indium to achieve a better selectivity. Germanium was separated from highly acidic sulphuric acid solutions containing other metals as well by precipitating with tannic acid. This is a highly selective method. According to the study other commonly found metals in the solution do not affect germanium precipitation. The reduction of ferric iron to ferrous, the precipitation of indium, gallium and germanium, and the dissolution of the raw materials are strongly depending on temperature and pH. The temperature and pH effect were studied and which contributed to the understanding and design of the different process steps. Increased temperature and reduced pH improve the reduction rate. Finally, the gained understanding in the studied areas can be employed to develop better industrial processes not only on a large scale but also increasingly on a smaller scale. The small amounts of indium, gallium and germanium may favour smaller and more locally bound recovery.

Arsenic and heavy metal concentrations in agricultural soils in South Savo province

Selostus: Etelä-Savon viljelysmaan arseeni- ja raskasmetallipitoisuudet

Heavy-metal pollution and remediation of forest soil around the Harjavalta Cu-Ni smelter, in SW Finland

Abstract

Comparison of human and computer-based selective cleaning

Abstract

A decision support system for selective cleaning

[Abstract]

Combustibility of Paper Mill Rejects

Tämän työn tarkoituksena oli selvittää mekaanisen massan valmistuksen käsittävän paperitehtaan rejektija jätevirtojen poltettavuutta, jos paperitehtaan vesikiertojen sulkemisastetta lisätään. Jotta prosessin tilannetta sulkemisen jälkeen saatiin arvioitua, Anjalan paperitehtaan nykypäivän PK3:n prosessia tutkittiin kuorimolta jätevesilaitokselle. Kirjallisuusosassa käsiteltiin rejekti- ja jätevirtojen alkuperää mekaanista massaa käyttävässä paperitehtaassa. Myös tämän päivän jätevedenkäsittelyprosessit sekä sulkemisessa mahdolliset prosessiveden puhdistustekniikat esiteltiin lyhyesti. Lisäksikäytiin läpi nykypäivänä metsäteollisuudessa käytössä olevat polttotekniikat sekä polttoaineiden karakterisointi kattilan käytettävyyden ja päästöjen kannalta. Anjalan PK3:lla käytetään sekä peroksidi- että ditioniittivalkaistua tai pelkästään ditioniittivalkaistua hioketta riippuen tuotannossa olevasta lajista. PK3-prosessissa syntyneet jätevesi-, liete- ja muut jätevirrat selvitettiin molemmissa valkaisuolosuhteissa. Prosessin eniten liuennutta orgaanista ainesta sisältävät jätevesijakeet, 3-hiomon kuumankierron ja kirkassuodoksen ulosajot sekä kuoripuristimen suodos, valittiin puhdistettaviksi virroiksi prosessin sulkemista arvioitaessa. Kun peroksidivalkaisua käytettiin 3-hiomolla, TOC-kuorma jokeen oli 30 % suurempi kuin pelkällä ditioniittivalkaisulla. Jos prosessin sulkemisastetta lisättäisiin, TOC-kuorma olisi 30 %pienempi kuin tänäpäivänä peroksidivalkaisua käytettäessä (80 % puhdistustehokkuudella). Prosessin sulkemisastetta lisättäessä biolietettä muodostuisi n. 30 % vähemmän verrattuna nykytilanteeseen, sillä mikrobien ravintona käyttämää orgaanista ainesta päätyisi vähemmän jäteveteen. 3-hiomon peroksidivalkaisun vaikutus kattilan käytettävyyteen ja päästöihin oli pieni, sillä biolietteen osuus polttoaineen syötöstä oli vain 4 %. Vain osa biolietteestä muodostui 3-hiomolta peräisin olevaa orgaanista ainesta poistettaessa. Jos nykyisen pääpolttoaineen, PDF:n,osuuden jättää huomioimatta, SO2- ja NOx-päästöt sekä leijupedin sintrautuvuus ovat hiukan suuremmat käytettäessä peroksidivalkaisua 3-hiomolla kuin pelkästään ditioniittivalkaisulla. Jos kuoripuristimen ja hiomon suodosten puhdistuksen konsentraatit johdetaan poltettaviksi BFB-tyyppiseen kattilaan, leijupedin sintrautuminen tulisi olemaan suurin ongelma. Myös raskasmetalli-, SO2- ja NOx-päästöt lisääntyisivät merkittävästi verrattuna nykyiseen tilanteeseen. Sen sijaan kattilan korroosioriski tuskin lisääntyisi. Lisäksi konsentraattien kosteuspitoisuus olisi korkea, mikä tekisi poltosta kannattamatonta veden haihdutuksen vaatiessa paljon energiaa. Yksityiskohtaisempaa tutkimusta tarvitaan vielä prosessin sulkemisen vaikutuksista päästöihin ja kattilan käytettävyyteen. Myös muita konsentraattien hävittämismahdollisuuksia tulisi tutkia lisää.

Logistics Management in China's Development Zones - Finnish Metal Industry Perspective

Alikehittynyt infrastruktuuri, tiukat säädökset ja säädösten tulkitseminen, sekä monimutkaiset verotuskäytännöt ovat aiheuttaneet ongelmia suomalaisille Alikehittynyt infrastruktuuri, tiukat säädökset ja säädösten tulkitseminen, sekä monimutkaiset verotuskäytännöt ovat aiheuttaneet ongelmia suomalaisille yrityksille Kiinassa. Tutkimuksen perusteella yritykset eivät pysty vaikuttamaan infrastruktuurin kehittymiseen tai säädösten implementointiin, mutta ylläpitämällä suhteita ja valitsemalla oikeat partnerit yritykset pystyvät hallitsemaan ongelma-alueitaan. Etenkin ulkomaalaisille yrityksille oikean logistiikkaoperaattorin valinta on tärkeätä ja huomioon ottaen palvelutason, kulttuuritaustan sekä kansainväliset operaatiot on ulkomaalaisten yritysten tehokkaampaa käyttää kansainvälisiä operaattoreita kuin paikallisia toimijoita, jotkaovat usein halvempia, mutta eivät pysty toimimaan kansainvälisellä tasolla. Vientiin keskittyneiden yritysten tulisi sijoittua vapaakauppa-alueille tai vientiin painottuneille teollisuusalueille. Kyseisillä alueilla liiketoiminta mannermaahan on rajoitettu, eivätkä alueet täten sovellu yrityksille, jotka ovat keskittyneet Kiinan markkinoille. Paikallisesti operoivien yritysten tulisi sijoittua normaaleihin teollisuuspuistoihin ja käyttää tullin valvomia varastoja tukemaan kansainvälisiä toimintojaan.Tulisi myös muistaa etteivät kiinalaiset teollisuuspuistot täytä kansainvälisiä kriteerejä, joten säädöksiin on tärkeätä tutustua huolella jamielipiteitä kerätä toisilta yrityksiltä. Kiinassa merkittävimmät logistiikkaongelmat ilmenevät tuonnin ja viennin yhteydessä, jolloin säädökset ja toimintamallit ovat kontrolloidumpia. Etenkin tullaus- ja arvonlisävero ongelmat liittyvät kiinteästi tuonti- ja vientiprosessiin. Tutkimuksen tulokset osoittivat, että tullausprosessi tehostuu yhteistyön ja koulutuksen kautta, mutta arvonlisäverosta aiheutuvien kustannusten minimointi vaatii logistiikkapuistojen käyttöä. Mikäli asiakas haluaa tehdä tullauksen kotiprovinssissaan tai yritys tekee kauppaa ALV -vapautettujen yritysten kanssa, tulisi logistiikkapuistojen käyttöä lisätä. Käytettäessä logistiikkapuistoja yritykset välttävät tuotteiden kuljetukset Hongkongiin jatakaisin säästäen huomattavasti kustannuksissa ja toimitusajoissa. Logistiikkapuistoja on myös mahdollista käyttää ratkaisuna kasvaviin ja viivästyviin ALV palautuksiin. Tutkimuksen tulosten mukaan toimintaympäristö ja vientipainotteinen valmistus ohjaavat 3PL yritysten valintaa ja vaihtoehtoisten logistiikkapalvelujen implementointia. Etabloiduttaessavapaakauppa-alueille vientiin ja tuontiin liittyvät ongelmatekijät vahvistuvat sekä rajoitukset kiinan liiketoimintaan kasvavat, mikä tekee yhteistyönkansainvälisten logistiikkaoperaattoreiden kanssa välttämättömäksi ja kannustaa hyödyntämään logistiikkapuistoja.

A support system for evaluating a suitable joining method in the production of sheet metal goods

This report illustrates a comparative study of various joining methods involved in sheet metal production. In this report it shows the selection of joining methods, which includes comparing the advantages and disadvantages of a method over the other ones and choosing the best method for joining. On the basis of various joining process from references, a table is generated containing set of criterion that helps in evaluation of various sheet metal joining processes and in selecting the most suitable process for a particular product. Three products are selected and a comprehensive study of the joining methods is analyzed with the help of various parameters. The table thus is the main part of the analysis process of this study and can be advanced with the beneficial results. It helps in a better and easy understanding and comparing the various methods, which provides the foundation of this study and analysis. The suitability of the joining method for various types of cases of different sheet metal products can be tested with the help of this table. The sections of the created table display the requirements of manufacturing. The important factor has been considered and given focus in the table, as how the usage of these parameters is important in percentages according to particular or individual case. The analysis of the methods can be extended or altered by changing the parameters according to the constraint. The use of this table is demonstrated by pertaining the cases from sheet metal production.

Value added logistical support service Part 2. Outsourcing process of spare part logistics in metal industry

The aim of this research study was to find out guidelines for outsourcing of logistics processes. The study was outlined to spare parts and `business-to-business' (B2B) markets in metal industry. This study can be applied as a manual for outsourcing especially warehousing and transportation activities. The study also touches other important areas of spare part logistics like manufacturing, customer service, procurement, quality control, reverse and recycling logistics, logistics technologies and valueadded services. The method of study consisted of three areas. Firstly exchanging views with logistics experts in participating companies, and secondly compiling material based on author's practical experience in logistics business with several international and domestic logistics service providers and vendors. Thirdlythe study includes also references to literature material. Due to the fact thatthe outsourcing of logistics functions can be handled widely and from differentpoint of views, in this study it is concentrated mainly on giving general levelguidelines for defining logistics strategy, hints both for tendering process and implementation project, and not forgetting the aftercare of business partnership.

Freezing Point Depressions of Dilute Solutions of Alkali Metal Chlorides and Bromides

Freezing point depressions (¿Tf) of dilute solutions of several alkali metal chlorides and bromides were calculated by means of the best activity coefficient equations. In the calculations, Hückel, Hamer and Pitzer equationswere used for activity coefficients. The experimental ¿Tf values available in the literature for dilute LiCl, NaCl and KBr solutions can be predicted within experimental error by the Hückel equations used. The experimental ¿Tf values for dilute LiCl and KBr solutions can also be accurately calculated by corresponding Pitzer equations and those for dilute NaCl solutions by the Hamer equation for this salt. Neither Hamer nor Pitzer equations predict accurately the freezing points reported in the literature for LiBr and NaBr solutions. The ¿Tf values available for dilute solutions of RbCl, CsCl or CsBr are not known at the moment accurately because the existing data for these solutions are not precise. The freezing point depressions are tabulated in the present study for LiCl, NaCl and KBr solutions at several rounded molalities. The ¿Tf values in this table can be highly recommended. The activity coefficient equations used in the calculation of these values have been tested with almost allhigh-precision electrochemical data measured at 298.15 K.

Metal surface and subsurface inspection using nondestructive optical methods

This thesis considers nondestructive optical methods for metal surface and subsurface inspection. The main purpose of this thesis was to study some optical methods in order to find out their applicability to industrial measurements. In laboratory testing the simplest light scattering approach, measurement of specular reflectance, was used for surface roughness evaluation. Surface roughness, curvature and finishing process of metal sheets were determined by specular reflectance measurements. Using a fixed angleof incidence, the specular reflectance method might be automated for industrialinspection. For defect detection holographic interferometry and thermography were compared. Using either holographic interferometry or thermography, relativelysmall-size defects in metal plates could be revealed. Holographic techniques have some limitations for industrial measurements. On the contrary, thermography has excellent prospects for on-line inspection, especially with scanning techniques.

Origins of production errors and significance of employee empowerment in reducing production error amount in sheet metal fabricating industry

The market place of the twenty-first century will demand that manufacturing assumes a crucial role in a new competitive field. Two potential resources in the area of manufacturing are advanced manufacturing technology (AMT) and empowered employees. Surveys in Finland have shown the need to invest in the new AMT in the Finnish sheet metal industry in the 1990's. In this run the focus has been on hard technology and less attention is paid to the utilization of human resources. In manymanufacturing companies an appreciable portion of the profit within reach is wasted due to poor quality of planning and workmanship. The production flow production error distribution of the sheet metal part based constructions is inspectedin this thesis. The objective of the thesis is to analyze the origins of production errors in the production flow of sheet metal based constructions. Also the employee empowerment is investigated in theory and the meaning of the employee empowerment in reducing the overall production error amount is discussed in this thesis. This study is most relevant to the sheet metal part fabricating industrywhich produces sheet metal part based constructions for electronics and telecommunication industry. This study concentrates on the manufacturing function of a company and is based on a field study carried out in five Finnish case factories. In each studied case factory the most delicate work phases for production errors were detected. It can be assumed that most of the production errors are caused in manually operated work phases and in mass production work phases. However, no common theme in collected production error data for production error distribution in the production flow can be found. Most important finding was still that most of the production errors in each case factory studied belong to the 'human activity based errors-category'. This result indicates that most of the problemsin the production flow are related to employees or work organization. Development activities must therefore be focused to the development of employee skills orto the development of work organization. Employee empowerment gives the right tools and methods to achieve this.