Ultrasound-assisted electrochemical treatment of wastewaters containing organic pollutants by using novel Ti/Ta2O5-SnO2 electrodes

Advanced oxidation processes (AOPs) are modern methods using reactive hydroxyl radicals for the mineralization of organic pollutants into simple inorganic compounds, such as CO2 and H2O. Among AOPs electrochemical oxidation (EO) is a method suitable for coloured and turbid wastewaters. The degradation of pollutants occurs on electrocatalytic electrodes. The majority of electrodes contain in their structure either expensive materials (diamond and Pt-group metals) or are toxic for the environment compounds (Sb or Pb). One of the main disadvantages of electrochemical method is the polarization and contamination of electrodes due to the deposition of reaction products on their surface, which results in diminishing of the process efficiency. Ultrasound combined with the electrochemical degradation process eliminates electrode contamination because of the continuous mechanical cleaning effect produced by the formation and collapse of acoustic cavitation bubbles near to the electrode surface. Moreover, high frequency ultrasound generates hydroxyl radicals at water sonolysis. Ultrasound-assisted EO is a non-selective method for oxidation of different organic compounds with high degradation efficiencies. The aim of this research was to develop novel sustainable and cost-effective electrodes working as electrocatalysts and test their activity in electrocatalytic oxidation of organic compounds such as dyes and organic acids. Moreover, the goal of the research was to enhance the efficiency of electrocatalytic degradation processes by assisting it with ultrasound in order to eliminate the main drawbacks of a single electrochemical oxidation such as electrodes polarization and passivation. Novel Ti/Ta2O5-SnO2 electrodes were developed and found to be electrocatalytically active towards water (with 5% Ta content, 10 oxide film layers) and organic compounds oxidation (with 7.5% Ta content, 8 oxide film layers) and therefore these electrodes can be applicable in both environmental and energy fields. The synergetic effect of combined electrolysis and sonication was shown while conducting sonoelectrochemical (EO/US) degradation of methylene blue (MB) and formic acid (FA). Complete degradation of MB and FA was achieved after 45 and 120 min of EO/US process respectively in neutral media. Mineralization efficiency of FA over 95% was obtained after 2 h of degradation using high frequency ultrasound (381, 863, 1176 kHz) combined with 9.1 mA/cm2 current density. EO/US degradation of MB provided over 75% mineralization in 8 h. High degradation kinetic rates and mineralization efficiencies of model pollutants obtained in EO/US experiments provide the preconditions for further extrapolation of this treatment method to pilot scale studies with industrial wastewaters.

Pulsed corona discharge as an advanced oxidation process for degradation of organic

Advanced oxidation processes (AOPs) have been studied and developed to suffice the effective removal of refractory and toxic compounds in polluted water. The quality and cost of wastewater treatment need improvements, and electric discharge technology has a potential to make a significant difference compared to other established AOPs based on energy efficiency. The generation of active oxidant species such as ozone and hydroxyl radicals by high voltage discharge is a relatively new technology for water treatment. Gas-phase pulsed corona discharge (PCD), where a treated aqueous solution is dispersed between corona-producing electrodes free of the dielectric barriers, was developed as an alternative approach to the problem. The short living radicals and ozone formed in the gas phase and at the gas-liquid interface react with dissolved impurities. PCD equipment has a relatively simple configuration, and with the reactor in an enclosed compartment, it is insensitive towards gas humidity and does not need the gas transport. In this thesis, PCD was used to study and evaluate the energy efficiency for degrading various organic compounds, as well as the chemistry of the oxidation products formed. The experiments investigate the aqueous oxidation of phenol, humic substances, pharmaceutical compounds (paracetamol, ibuprofen, indomethacin, salicylic acids, -estradiol), as well as lignin degradation and transformation to aldehydes. The study aims to establish the influence of initial concentration of the target pollutant, the pulsed discharge parameters, gas phase composition and the pH on the oxidation kinetics and the efficiency. Analytical methods to measure the concentrations of the target compounds and their by-products include HPLC, spectrophotometry, TOC and capillary electrophoresis. The results of the research included in this summary are presented in the attached publications and manuscripts accepted for publication. Pulsed corona discharge proved to be highly effective in oxidizing each of the target compounds, surpassing the closest competitor, conventional ozonation. The increase in oxidation efficiencies for some compounds in oxygen media and at lower pulse repetition frequencies shows a significant role of ozone. The role of the ·OH radicals was established in the surface reactions. The main oxidation products, formation of nitrates, and the lignin transformation were quantified. A compound specific approach is suggested for optimization of the PCD parameters that have the most significant impact on the oxidation energy efficiency because of the different characteristics and responses of the target compound to the oxidants, as well as different admixtures that are present in the wastewater. Further studies in the method’s safety (nitration and nitrosation of organic compounds, nitrite and nitrate formation enhancement) are needed for promoting the method.

Bacterial community structure and petroleum hydrocarbon degradation in the Baltic Sea

The Baltic Sea is unique by its biological, geochemical and physical features. The number of species of larger organisms is small and the species composition is distinctive. On the contrary microbial communities are diverse. Because of the low salinity levels, bacterial communities differ from the ones in the oceans. Knowing the structure of these communities better and how they response to different environmental conditions helps us to estimate how different factors affect the balance and function of the Baltic Sea ecosystem. Bacteria are the key players when it comes to natural biogeochemical processes and human-induced phenomena like eutrophication, oil spills or disposal of other harmful substances to the sea ecosystem. In this thesis, bacterial community structure in the sea surface microlayer and subsurface water of the Archipelago Sea were compared. In addition, the effect of diatom derived polyunsaturated aldehydes on bacterial community structure was studied by a mesocosm experiment. Diesel, crude oil and polycyclic aromatic hydrocarbon degradation capacity of the Baltic Sea bacteria was studied in smaller scale microcosm experiments. In diesel oil experiments bacteria from water phase of the Archipelago Sea was studied. Sediment and iron manganese concretions collected from the Gulf of Finland were used in the crude oil and polycyclic aromatic hydrocarbon experiments. The amount of polycyclic aromatic hydrocarbon degradation genes was measured in all of the oil degradation experiments. The results show how differences in bacterial community structure can be seen in the sea surface when compared to the subsurface waters. The mesocosm experiment demonstrated how diatom-bacteria interactions depend on other factors than diatom derived polyunsaturated aldehydes, which do not seem to have an effect on the bacterial community structure as has been suggested in earlier studies. The dominant bacterial groups in the diesel microcosms differed in samples taken from a pristine site when compared to a site with previous oil exposure in the Archipelago Sea area. Results of the study with sediment and iron-manganese concretions indicate that there are diverse bacterial communities, typical to each bottom type, inhabiting the bottoms of the Gulf of Finland capable to degrade oil and polycyclic aromatic hydrocarbon compounds.  

Developing Processes and Learning in a Project-based Firm

Tämän diplomityön tavoitteena on kuvata tiedonkulkua projektiliiketoimintaa harjoittavassa yrityksessä sekä analysoida kuvausta määrittäen mahdolliset kehityskohdat. Työssätuotetut kuvaukset ja kehityskohtien määrittäminen toimivat pohjana yrityksen kehittäessä projektien hallintaansa tulevaisuudessa. Työssä valitaan tietojohtamisen näkökulma sopivaksi lähestymistavaksi yrityksen toiminnananalysointiin. Haastatteluin kerätyn tutkimusmateriaalin perusteella luodaan prosessikuvaukset jotka mallintavat tietovirtoja yrityksen projektien aikana tapahtuvien prosessien välillä. Kuvausta peilataan tietämyksen luomisen sekä projektien tietojohtamisen teoriaan ja määritetään kehityskohteita. Kehityskohteiden määrittämisen lisäksi ehdotetaan mahdollisia toimenpiteitä tiedon ja tietämyksen hallinnan kehittämiseksi. Kokemusten ja opittujen asioiden sekäpalautteen kerääminen projektien aikana sekä niiden jälkeen havaittiin tärkeimmäksi kehityskohdaksi. Näiden keräämisen voidaan todeta vaativan järjestelmällisyyttä jotta projektien onnistumiset sekä niissä saavutetut parannukset voidaan toistaa jatkossa ja virheet sekä epäonnistumiset sitä vastoin välttää.

Innovation Benchmark Study: Analysis of Innovation Processes in Finnish Companies

Liikevaihdon orgaaninen kasvu on ensisijainen tekijä ja haaste yritysjohdolle yrityksen omistaja-arvon kasvattamiseksi. Tutkimus tarkastelee suosivatko suomalaisyritykset pääasiallisesti olemassa olevaa liiketoimintaa palvelevia innovaatioita vai tukevatko nykyhetken toimintatavat myös uusia kasvua kiihdyttäviä radikaaleja innovaatioita. Lisäksi työ kartoitti suomalaisyritysten innovaatioprosessien kehitysalueita käyttäen itsearviointitutkimusta.Tulokset johtivat kolmeen johtopäätökseen. Tutkimus osoitti, että vastaajayritykset ovat keskittyneet innovaatiotoiminnassaan vahvasti ydinliiketoimintaansa, jättäen potentiaaliset kasvumahdollisuudet huomioimatta. Yritykset tavoittelevat maksimaalisia tuottoja keskittymällä tuotteidensa korkeaan suorituskykyyn. Lyhyen aikavälin epärealistiset tuotto-odotukset sekä projekteille suunnatut arviointikriteerit rajoittavat liiketoimintaa mullistavien radikaalien innovaatioiden kehittymistä organisaatiossa. Toiseksi, tutkimus osoitti, että suuri osa yrityksistä käyttää perinteisen projektien arviointi- ja kehitysprosessin lisäksi vaihtoehtoisia ja huonosti kontrolloitavissa olevia kehitysprosesseja, mikäli projektille annetaan kielteinen rahoituspäätös standardin prosessin sisällä. Kolmanneksi, suomalaisyritysten innovaatioprosesseissa paljastui merkittäviä puutteita mitattavien elementtien suhteen.

Managing Business Processes in Corporate Expansion

Yrityksen laajentuessa kansainvälisesti, olemassa olevat rutiinit jäävät vanhoiksi ja liiketoimintaprosessien johtaminen muuttuu. Kyseisten prosessien täytyy olla läpinäkyviä ja tietovirtojen hyvin suunniteltuja. Prosessien harmonisointi aiheuttaa haasteita yrityksessä ja konsernin etu tulee ottaa huomioon. Ahlstrom konserni laajentuu merkittävästi kaikilla liiketoiminta-alueillaan ja kansainvälinen laajentuminen vie Ahlstrom Glassfibre Oy:n täysin uuteen tilanteeseen. Liiketoimintaprosessien johtamiseen vaikuttavat konsernin ohjaus, mahdollisuudet muutosten implementoimiseksi, toimintaympäristön tekijät ja järjestelmien muodostama arkkitehtuuri. Tässä tutkimuksessa keskitytään ydinprosessien tietovirtoihin ja työ on tehty Karhulan tehtaalla Suomessa. Johtamismallin luomiseksi vaaditaan yrityksessä ongelmia määrittelevää työskentelyä. Tämä ongelmanmääritys oli työn tärkein tavoite. Ongelma-alueiden tutkimuksen pohjalta muodostettiin ratkaisu, jossa käsiteltiin systemaattisen liiketoimintaprosessien johtamisen mahdollisuuksia ja vaatimuksia. Lopputuloksena voidaan todeta, että suurin painopiste löytyy informaatioteknologian ja liiketoiminnan rajapinnoista. Tähän työhön liittyvät myös prossien harmonisointi ja integrointi.

Aligning Technology Innovation Processes for Possible Collaboration

Diplomityön tavoitteena on innovaatioprosessien selventäminen ja yhteensovittaminen radikaalien teknologia innovaatioiden osalta. Prosessien yhteensovittamisen edellytyksenä on teknologia innovaation radikaalisuuden ymmärtäminen. Kohteena on alkuvaiheen innovaatioprosessi jonka aikana virallinen yhteistyö ei vielä ole mandollista. Kehitetyn mallinavulla voidaan arvioida yrityksen kokemaa radikaalisuutta innovaatioprosessin alkuvaiheessa. On tärkeää ymmärtää miten vuorovaikutuksessa olevat yritykset kokevat innovaation radikaalisuuden prosessin alkuvaiheessa. Prosessien eroavaisuudet voidaan sanoa riippuvan yritysten näkökulmasta, koska niiden toiminnot määrittyvät koetun radikaalisuuden mukaan.Yhtäläisenä koettu radikaalisuus luo pohjan avoimelle vuorovaikutukselle ja antaa viitteitä syvemmästä yhteistyöstä tulevaisuudessa. Vertikaalisti sijoittuneiden yritysten prosessien esitetty yhteensovitus perustuu molemminpuoliseen radikaalisuuteen ja sisäisen hyväksynnän vastaavuuteen. Tällöin osapuolet ovat mukana samalla sitoumuksella prosessin jatkumisen ollessa epävarma.

Wet Oxidation of Concentrated Wastewaters: Process Combination and Reaction Kinetic Modeling

The accumulation of aqueous pollutants is becoming a global problem. The search for suitable methods and/or combinations of water treatment processes is a task that can slow down and stop the process of water pollution. In this work, the method of wet oxidation was considered as an appropriate technique for the elimination of the impurities present in paper mill process waters. It has been shown that, when combined with traditional wastewater treatment processes, wet oxidation offers many advantages. The combination of coagulation and wet oxidation offers a new opportunity for the improvement of the quality of wastewater designated for discharge or recycling. First of all, the utilization of coagulated sludge via wet oxidation provides a conditioning process for the sludge, i.e. dewatering, which is rather difficult to carry out with untreated waste. Secondly, Fe2(SO4)3, which is employed earlier as a coagulant, transforms the conventional wet oxidation process into a catalytic one. The use of coagulation as the post-treatment for wet oxidation can offer the possibility of the brown hue that usually accompanies the partial oxidation to be reduced. As a result, the supernatant is less colored and also contains a rather low amount of Fe ions to beconsidered for recycling inside mills. The thickened part that consists of metal ions is then recycled back to the wet oxidation system. It was also observed that wet oxidation is favorable for the degradation of pitch substances (LWEs) and lignin that are present in the process waters of paper mills. Rather low operating temperatures are needed for wet oxidation in order to destruct LWEs. The oxidation in the alkaline media provides not only the faster elimination of pitch and lignin but also significantly improves the biodegradable characteristics of wastewater that contains lignin and pitch substances. During the course of the kinetic studies, a model, which can predict the enhancements of the biodegradability of wastewater, was elaborated. The model includes lumped concentrations suchas the chemical oxygen demand and biochemical oxygen demand and reflects a generalized reaction network of oxidative transformations. Later developments incorporated a new lump, the immediately available biochemical oxygen demand, which increased the fidelity of the predictions made by the model. Since changes in biodegradability occur simultaneously with the destruction of LWEs, an attempt was made to combine these two facts for modeling purposes.

Technology selection and group decision support systems: Case studies on supporting strategic technology selection processes

The objective of the dissertation is to increase understanding and knowledge in the field where group decision support system (GDSS) and technology selection research overlap in the strategic sense. The purpose is to develop pragmatic, unique and competent management practices and processes for strategic technology assessment and selection from the whole company's point of view. The combination of the GDSS and technology selection is approached from the points of view of the core competence concept, the lead user -method, and different technology types. In this research the aim is to find out how the GDSS contributes to the technology selection process, what aspects should be considered when selecting technologies to be developed or acquired, and what advantages and restrictions the GDSS has in the selection processes. These research objectives are discussed on the basis of experiences and findings in real life selection meetings. The research has been mainly carried outwith constructive, case study research methods. The study contributes novel ideas to the present knowledge and prior literature on the GDSS and technology selection arena. Academic and pragmatic research has been conducted in four areas: 1) the potential benefits of the group support system with the lead user -method,where the need assessment process is positioned as information gathering for the selection of wireless technology development projects; 2) integrated technology selection and core competencies management processes both in theory and in practice; 3) potential benefits of the group decision support system in the technology selection processes of different technology types; and 4) linkages between technology selection and R&D project selection in innovative product development networks. New type of knowledge and understanding has been created on the practical utilization of the GDSS in technology selection decisions. The study demonstrates that technology selection requires close cooperation between differentdepartments, functions, and strategic business units in order to gather the best knowledge for the decision making. The GDSS is proved to be an effective way to promote communication and co-operation between the selectors. The constructs developed in this study have been tested in many industry fields, for example in information and communication, forest, telecommunication, metal, software, and miscellaneous industries, as well as in non-profit organizations. The pragmatic results in these organizations are some of the most relevant proofs that confirm the scientific contribution of the study, according to the principles of the constructive research approach.