Plasmapolttoprosessin kehittäminen ja optimointi

Ydinvoimaloidenprimaarivesikierron puhdistukseen käytetään ioninvaihtohartsia. Käytönjälkeen ioninvaihtohartsi luokitellaan matalaja keskiaktiivisiin jätteisiin. Plasmakäsittelyllä käytetyn ioninvaihtohartsin tilavuutta voidaan pienentää sekä sen orgaaninen luonne poistaa. Plasmakäsittelyn tarkoituksena on hapettaa orgaaninen aines oksideiksi, jotka poistuvat prosessista savukaasuina. Epäorgaaninen aines, joka sisältää radioaktiivisen aineksen, on tarkoitus hapettaa oksideiksi ja sulfideiksi, jotka voidaan kerätä talteen tuhkana. Tässä diplomityössä käsitellään käytetyn ioninvaihtohartsin käsittelyyn suunnitellun plasmapolttoprosessin kehittämistä ja optimointia. Ioninvaihtohartsin plasmakäsittelyssä syntyvien reaktiotuotteiden selvittäminen suoritettiin tarkastelemalla ainetaseita sekä aihetta käsitteleviä tutkimuksia. Näiden perusteella parannettiin jäähdytystä, suunniteltiin jatkuvatoiminen syöttömenetelmä sekä laadittiin toimintaalueen reunaehdot laitteistolle. Koelaitteistossa 6,5 kW:n rfteho syötetään sovitinpiirin ja kuparisen induktiokelan kautta plasmaan. Plasmakaasuna on käytetty hapenja argonin seoskaasua. Plasmapolttoa on seurattu massaspektrometrilla, optisella emissiospektrometrilla, lämpösekä painemittareilla. Laskennan ja kokeiden pohjalta selvitettiin optimaalinen seossuhde plasmakaasulle, paineen ja tehon noston vaikutus hartsin polttonopeuteen sekä jatkuvatoimisen syöttömenetelmän edut panostoimiseen syöttöön. Rfgeneraattorin teho rajoitti jatkuvatoimisen polttonopeuden 130 g/h ja hetkellisen polttonopeuden 175 g/h. Radioaktiivisten aineiden pidätys oli 93,5 % cesiumin osalta. Tulosten perusteella 4 kg/h ioninvaihtohartsia polttavan laitteiston tehon lähteeksi tarvitaan 65 kW rfgeneraattori. Palamattoman hartsin ja tuhkan kulkeutuminen partikkelisuodattimille sekä reaktiotuotteena syntyvien rikinoksidien käsittely vaatii vielä jatkotutkimusta.

New families of highly efficient, halogen-free flame retardants for polypropylene (PP)

The driving forces for current research of flame retardants are increased fire safety in combination with flame retardant formulations that fulfill the criteria of sustainable production and products. In recent years, important questions about the environmental safety of antimony, and in particular, brominated flame retardants have been raised. As a consequence of this, the current doctoral thesis work describes efforts to develop new halogen-free flame retardants that are based on various radical generators and phosphorous compounds. The investigation was first focused on compounds that are capable of generating alkyl radicals in order to study their role on flame retardancy of polypropylene. The family of azoalkanes was selected as the cleanest and most convenient source of free alkyl radicals. Therefore, a number of symmetrical and unsymmetrical azoalkanes of the general formula R-N=N-R’ were prepared. The experimental results show that in the series of different sized azocycloalkanes the flame retardant efficacy decreased in the following order: R = R´= cyclohexyl > cyclopentyl > cyclobutyl > cyclooctanyl > cyclododecanyl. However, in the series of aliphatic azoalkanes compounds, the efficacy decreased as followed: R = R´= n-alkyl > tert-butyl > tert-octyl. The most striking difference in flame retardant efficacy was observed in thick polypropylene plaques of 1 mm, e.g. azocyclohexane (AZO) had a much better flame retardant performance than did the commercial reference FR (Flamestab® NOR116) in thick PP sections. In addition, some of the prepared azoalkane flame retardants e.g. 4’4- bis(cyclohexylazocyclohexyl) methane (BISAZO) exhibited non-burning dripping behavior. Extrusion coating experiments of flame retarded low density polyethylene (LDPE) onto a standard machine finished Kraft paper were carried out in order to investigate the potential of azoalkanes in multilayer facings. The results show that azocyclohexane (AZO) and 4’4-bis (cyclohexylazocyclohexyl) methane (BISAZO) can significantly improve the flame retardant properties of low density polyethylene coated paper already at 0.5 wt.% loadings, provided that the maximum extrusion temperature of 260 oC is not exceeded and coating weight is kept low at 13 g/m2. In addition, various triazene-based flame retardants (RN1=N2-N3R’R’’) were prepared. For example, polypropylene samples containing a very low concentration of only 0.5 wt.% of bis- 4’4’-(3’3’-dimethyltriazene) diphenyl ether and other triazenes passed the DIN 4102-1 test with B2 classification. It is noteworthy that no burning dripping could be detected and the average burning times were very short with exceptionally low weight losses. Therefore, triazene compounds constitute a new and interesting family of radical generators for flame retarding of polymeric materials. The high flame retardant potential of triazenes can be attributed to their ability to generate various types of radicals during their thermal decomposition. According to thermogravimetric analysis/Fourier transform infrared spectroscopy/MS analysis, triazene units are homolytically cleaved into various aminyl, resonance-stabilized aryl radicals, and different CH fragments with simultaneous evolution of elemental nitrogen. Furthermore, the potential of thirteen aliphatic, aromatic, thiuram and heterocyclic substituted organic disulfide derivatives of the general formula R-S-S-R’ as a new group of halogen-free flame retardants for polypropylene films have been investigated. According to the DIN 4102- 1 standard ignitibility test, for the first time it has been demonstrated that many of the disulfides alone can effectively provide flame retardancy and self-extinguishing properties to polypropylene films at already very low concentrations of 0.5 wt.%. For the disulfide family, the highest FR activity was recorded for 5’5’-dithiobis (2-nitrobenzoic acid). Very low values for burning length (53 mm) and burning time (10 s) reflect significantly increased fire retardant performance of this disulfide compared to other compounds in this series as well as to Flamestab® NOR116. Finally, two new, phosphorus-based flame retardants were synthesized: P’P-diphenyl phosphinic hydrazide (PAH) and melamine phenyl phosphonate (MPhP). The DIN 4102-1 test and the more stringent UL94 vertical burning test (UL94 V) were used to assess the formulations ability to extinguish a flame once ignited. A very strong synergistic effect with azoalkanes was found, i.e. in combination with these radical generators even UL94 V0 rate could be obtained.

Analytics for the modified kraft pulps

Tämän diplomityön tavoitteena on kehittää sopiva analyyttinen menetelmä muokatun kraft-sellukuidun substituutioasteen (DS) kvantitatiivista määrittämistä varten. Muokkauksella tarkoitetaan tässä yhteydessä joko kovalenttisesti tai adsorption avulla tapahtuvaa molekyylin kiinnittymistä sellukuidun pinnalle. Työn kirjallisuusosuudessa käsitellään lyhyesti eri muokkaustapoja ja yhdisteitä joiden avulla voidaan saavuttaa haluttuja ominaisuuksia sellusta valmistetuille lopputuotteille. Lisäksi kirjallisuusosuudessa käydään läpi käyttötarkoitukseen soveltuvimpia suoria ja epäsuoria analyysimenetelmiä. Analyysimenetelmistä kaikkein lupaavimpia testattiin työn kokeellisessa osassa. Diplomityön kokeellisessa osassa keskityttiin kehittämään muokatulle sellulle kvantitatiivista menetelmää DS:n määrittämiseksi Fourier-muunnos infrapuna-vaimennettu kokonaisheijastus (FTIR-ATR) spektrometrillä. Kirjallisuuskatsauksessa ei löytynyt yhtään dokumentoitua tutkimusta, jossa FTIR-ATR menetelmää olisi käytetty muokatun sellukuidun kvantitatiiviseen tutkimukseen. Muiden analyysimenetelmien, kuten alkuaineanalyysin, termogravimetrisen analyysin (TGA) ja valomikroskopian avulla pyrittiin tuottamaan lisätietoa muokkauksesta. Kvantitatiivisen FTIR-ATR menetelmän kehitykseen käytetyt muokatut sellukuidut olivat selluloosa-asetaattia ja selluloosa betainaattia. Saatujen tulosten perusteella muokattujen sulfiitti- ja kraft sellukuitujen DS:n kvantitatiivinen määrittäminen on mahdollista FTIR-ATR menetelmällä. Vähäinen kalibrointipisteiden määrä vaikeutti tarkan analyysimenetelmän tekemistä. Kehitetyn menetelmän suurimpina ongelmina olivat kiinteiden näytteiden heterogeenisyys sekä mahdollisten epäpuhtauksien tunnistaminen. Jatkotutkimusten avulla kehitettyä menetelmää on kuitenkin mahdollista käyttää muokattujen sellukuitujen jatkuvaan analysointiin selluteollisuudessa.

Titanium dioxide based nanomaterials for photocatalytic water treatment

Water treatment using photocatalysis has gained extensive attention in recent years. Photocatalysis is promising technology from green chemistry point of view. The most widely studied and used photocatalyst for decomposition of pollutants in water under ultraviolet irradiation is TiO2 because it is not toxic, relatively cheap and highly active in various reactions. Within this thesis unmodified and modified TiO2 materials (powders and thin films) were prepared. Physico-chemical properties of photocatalytic materials were characterized with UV-visible spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectrometry (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), ellipsometry, time-of-flight secondary ion mass spectrometry (ToF-SIMS), Raman spectroscopy, goniometry, diffuse reflectance measurements, thermogravimetric analysis (TGA) and nitrogen adsorption/desorption. Photocatalytic activity of prepared samples in aqueous environment was tested using model compounds such as phenol, formic acid and metazachlor. Also purification of real pulp and paper wastewater effluent was studied. Concentration of chosen pollutants was measured with high pressure liquid chromatography (HPLC). Mineralization and oxidation of organic contaminants were monitored with total organic carbon (TOC) and chemical oxygen demand (COD) analysis. Titanium dioxide powders prepared via sol-gel method and doped with dysprosium and praseodymium were photocatalytically active for decomposition of metazachlor. The highest degradation rate of metazachlor was observed when Pr-TiO2 treated at 450ºC (8h) was used. The photocatalytic LED-based treatment of wastewater effluent from plywood mill using commercially available TiO2 was demonstrated to be promising post-treatment method (72% of COD and 60% of TOC was decreased after 60 min of irradiation). The TiO2 coatings prepared by atomic layer deposition technique on aluminium foam were photocatalytically active for degradation of formic and phenol, however suppression of activity was observed. Photocatalytic activity of TiO2/SiO2 films doped with gold bipyramid-like nanoparticles was about two times higher than reference, which was not the case when gold nanospheres were used.

Market Opportunity Analysis of the Finnish Mineral Wool Market

Tutkimuksen tarkoituksena on tutkia markkinamahdollisuuksia Suomeneristevillamarkkinoilla. Tutkimuksessa on sekä teoreettinen, että käytännön osuus. Teoreettisessa osiossa luodaan pohja empiiriselle tutkimukselle tutkimalla markkinamahdollisuusanalyysin eri komponenttien sisältöä. Empiirisessä osiossa haastatellaan markkinoiden suurimpia asiakkaita, jotka vastaavat valtaosasta markkinoiden ostovolyymista. Näiden haastattelujen pohjalta pyritään löytämään ne mahdollisuudet mitä eristevillamarkkinoilla on. Tutkimus osoittaa, että markkinamahdollisuusanalyysin eri komponentit ovat tiiviissä keskinäisessä suhteessa. Kattavalla tutkimuksella kyetään osoittamaan eri mahdollisuuksia markkinoilla. Empiirisessä osiossa kyetään osoittamaan, että Suomen eristevillamarkkinoilla on mahdollisuuksia uudelle toimittajalle. Tutkimuksessa esitetään myös joitakin toimenpide-ehdotuksia näiden havaittujen mahdollisuuksien hyödyntämiseksi.

Analysis of patterns in mining time series using Qlucore

Raw measurement data does not always immediately convey useful information, but applying mathematical statistical analysis tools into measurement data can improve the situation. Data analysis can offer benefits like acquiring meaningful insight from the dataset, basing critical decisions on the findings, and ruling out human bias through proper statistical treatment. In this thesis we analyze data from an industrial mineral processing plant with the aim of studying the possibility of forecasting the quality of the final product, given by one variable, with a model based on the other variables. For the study mathematical tools like Qlucore Omics Explorer (QOE) and Sparse Bayesian regression (SB) are used. Later on, linear regression is used to build a model based on a subset of variables that seem to have most significant weights in the SB model. The results obtained from QOE show that the variable representing the desired final product does not correlate with other variables. For SB and linear regression, the results show that both SB and linear regression models built on 1-day averaged data seriously underestimate the variance of true data, whereas the two models built on 1-month averaged data are reliable and able to explain a larger proportion of variability in the available data, making them suitable for prediction purposes. However, it is concluded that no single model can fit well the whole available dataset and therefore, it is proposed for future work to make piecewise non linear regression models if the same available dataset is used, or the plant to provide another dataset that should be collected in a more systematic fashion than the present data for further analysis.

Global Spare Parts Supply Chain Analysis

In today’s global industrial service business, markets are dynamic and finding new ways of value creation towards customers has become more and more challenging. Customer orientation is needed because of the demanding after-sales business which is both quickly changing and stochastic in nature. In after-sales business customers require fast and reliable service for their spare part needs. This thesis objective is to clarify this challenging after-sales business environment and find ways to increase customer satisfaction via balanced measurement system which will help to find possible targets to reduce order cycle times in a large metal and mineral company Outotec (Filters)’ Spare Part Supply business line. In case study, internal documents and data and numerical calculations together with qualitative interviews with different persons in key roles of Spare Part Supply organizations are used to analyze the performance of different processes from the spare parts delivery function. The chosen performance measurement tool is Balanced Scorecard which is slightly modified to suit the lead time study from customer’s perspective better. Findings show that many different processes in spare parts supply are facing different kind of challenges in achieving the lead time levels wanted and that these processes’ problems seem to accumulate. Findings also show that putting effort in supply side challenges and information flows visibility should give the best results.

Production of magnesium carbonates from serpentinites for CO2 mineral sequestration : optimisation towards industrial application

Global warming is one of the most alarming problems of this century. Initial scepticism concerning its validity is currently dwarfed by the intensification of extreme weather events whilst the gradual arising level of anthropogenic CO2 is pointed out as its main driver. Most of the greenhouse gas (GHG) emissions come from large point sources (heat and power production and industrial processes) and the continued use of fossil fuels requires quick and effective measures to meet the world’s energy demand whilst (at least) stabilizing CO2 atmospheric levels. The framework known as Carbon Capture and Storage (CCS) – or Carbon Capture Utilization and Storage (CCUS) – comprises a portfolio of technologies applicable to large‐scale GHG sources for preventing CO2 from entering the atmosphere. Amongst them, CO2 capture and mineralisation (CCM) presents the highest potential for CO2 sequestration as the predicted carbon storage capacity (as mineral carbonates) far exceeds the estimated levels of the worldwide identified fossil fuel reserves. The work presented in this thesis aims at taking a step forward to the deployment of an energy/cost effective process for simultaneous capture and storage of CO2 in the form of thermodynamically stable and environmentally friendly solid carbonates. R&D work on the process considered here began in 2007 at Åbo Akademi University in Finland. It involves the processing of magnesium silicate minerals with recyclable ammonium salts for extraction of magnesium at ambient pressure and 400‐440⁰C, followed by aqueous precipitation of magnesium in the form of hydroxide, Mg(OH)2, and finally Mg(OH)2 carbonation in a pressurised fluidized bed reactor at ~510⁰C and ~20 bar PCO2 to produce high purity MgCO3. Rock material taken from the Hitura nickel mine, Finland, and serpentinite collected from Bragança, Portugal, were tested for magnesium extraction with both ammonium sulphate and bisulphate (AS and ABS) for determination of optimal operation parameters, primarily: reaction time, reactor type and presence of moisture. Typical efficiencies range from 50 to 80% of magnesium extraction at 350‐450⁰C. In general ABS performs better than AS showing comparable efficiencies at lower temperature and reaction times. The best experimental results so far obtained include 80% magnesium extraction with ABS at 450⁰C in a laboratory scale rotary kiln and 70% Mg(OH)2 carbonation in the PFB at 500⁰C, 20 bar CO2 pressure for 15 minutes. The extraction reaction with ammonium salts is not at all selective towards magnesium. Other elements like iron, nickel, chromium, copper, etc., are also co‐extracted. Their separation, recovery and valorisation are addressed as well and found to be of great importance. The assessment of the exergetic performance of the process was carried out using Aspen Plus® software and pinch analysis technology. The choice of fluxing agent and its recovery method have a decisive sway in the performance of the process: AS is recovered by crystallisation and in general the whole process requires more exergy (2.48–5.09 GJ/tCO2sequestered) than ABS (2.48–4.47 GJ/tCO2sequestered) when ABS is recovered by thermal decomposition. However, the corrosive nature of molten ABS and operational problems inherent to thermal regeneration of ABS prohibit this route. Regeneration of ABS through addition of H2SO4 to AS (followed by crystallisation) results in an overall negative exergy balance (mainly at the expense of low grade heat) but will flood the system with sulphates. Although the ÅA route is still energy intensive, its performance is comparable to conventional CO2 capture methods using alkanolamine solvents. An energy‐neutral process is dependent on the availability and quality of nearby waste heat and economic viability might be achieved with: magnesium extraction and carbonation levels ≥ 90%, the processing of CO2‐containing flue gases (eliminating the expensive capture step) and production of marketable products.