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.

Aqueous photocatalytic oxidation of steroid estrogens

Concerns have increased regarding the detection of endocrine-disrupting compounds in the effluents of sewage treatment plants (STPs). These compounds are able to disrupt normal function of the endocrine system of living organisms even at trace concentrations. Natural and synthetic steroid estrogens (SEs) are believed to be responsible for the majority of the endocrine-disrupting effects. Municipal sewage, the main source of SEs in the environment, is a complex mixture of a wide range of pollutants at concentrations much higher than those of SEs. Low concentrations of SEs in the presence of copollutants thus make their removal problematic. The main objectives of the present work were to study the potential of photocatalytic oxidation (PCO) to effectively treat SE-containing aqueous solutions and to identify the optimum conditions for such treatment. The results showed that SEs can be effectively degraded photocatalytically. Due to the adsorption properties of SEs on the TiO2 photocatalyst surface alkaline medium was found to be beneficial for SE oxidation despite the presence of co-pollutants in concentrations characteristic for the sanitary fraction of municipal sewage. The potential of PCO to selectively oxidise SEs was examined in the presence of copollutants of the sanitary fraction of sewage - urea, saccharose and human urine. The impact of ethanol, often used as a solvent in the preparation of SE stock solutions, was also studied and the results indicated the need to use organic solvent-free solutions for the study of SE behaviour. Photocatalytic oxidation of SEs appeared to be indifferent towards the presence of urea in concentrations commonly found in domestic sewage. The effect of other co-pollutants under consideration was far weaker than could be expected from their concentrations, which are from one hundred to a few thousands times higher than those of the SEs. Although higher concentrations can dramatically slow down the PCO of SEs, realistic concentrations of co-pollutants characteristic for the sanitary fraction of domestic sewage allowed selective removal of SEs. This indicates the potential of PCO to be a selective oxidation method for SE removal from the separate sanitary fraction of municipal sewage.

Wet oxidation of recalcitrant lignin waters: Experimental and kinetic studies

The dissertation is based on four articles dealing with recalcitrant lignin water purification. Lignin, a complicated substance and recalcitrant to most treatment technologies, inhibits seriously pulp and paper industry waste management. Therefore, lignin is studied, using WO as a process method for its degradation. A special attention is paid to the improvement in biodegradability and the reduction of lignin content, since they have special importance for any following biological treatment. In most cases wet oxidation is not used as a complete ' mineralization method but as a pre treatment in order to eliminate toxic components and to reduce the high level of organics produced. The combination of wet oxidation with a biological treatment can be a good option due to its effectiveness and its relatively low technology cost. The literature part gives an overview of Advanced Oxidation Processes (AOPs). A hot oxidation process, wet oxidation (WO), is investigated in detail and is the AOP process used in the research. The background and main principles of wet oxidation, its industrial applications, the combination of wet oxidation with other water treatment technologies, principal reactions in WO, and key aspects of modelling and reaction kinetics are presented. There is also given a wood composition and lignin characterization (chemical composition, structure and origin), lignin containing waters, lignin degradation and reuse possibilities, and purification practices for lignin containing waters. The aim of the research was to investigate the effect of the operating conditions of WO, such as temperature, partial pressure of oxygen, pH and initial concentration of wastewater, on the efficiency, and to enhance the process and estimate optimal conditions for WO of recalcitrant lignin waters. Two different waters are studied (a lignin water model solution and debarking water from paper industry) to give as appropriate conditions as possible. Due to the great importance of re using and minimizing the residues of industries, further research is carried out using residual ash of an Estonian power plant as a catalyst in wet oxidation of lignin-containing water. Developing a kinetic model that includes in the prediction such parameters as TOC gives the opportunity to estimate the amount of emerging inorganic substances (degradation rate of waste) and not only the decrease of COD and BOD. The degradation target compound, lignin is included into the model through its COD value (CODligning). Such a kinetic model can be valuable in developing WO treatment processes for lignin containing waters, or other wastewaters containing one or more target compounds. In the first article, wet oxidation of "pure" lignin water was investigated as a model case with the aim of degrading lignin and enhancing water biodegradability. The experiments were performed at various temperatures (110 -190°C), partial oxygen pressures (0.5 -1.5 MPa) and pH (5, 9 and 12). The experiments showed that increasing the temperature notably improved the processes efficiency. 75% lignin reduction was detected at the lowest temperature tested and lignin removal improved to 100% at 190°C. The effect of temperature on the COD removal rate was lower, but clearly detectable. 53% of organics were oxidized at 190°C. The effect of pH occurred mostly on lignin removal. Increasing the pH enhanced the lignin removal efficiency from 60% to nearly 100%. A good biodegradability ratio (over 0.5) was generally achieved. The aim of the second article was to develop a mathematical model for "pure" lignin wet oxidation using lumped characteristics of water (COD, BOD, TOC) and lignin concentration. The model agreed well with the experimental data (R2 = 0.93 at pH 5 and 12) and concentration changes during wet oxidation followed adequately the experimental results. The model also showed correctly the trend of biodegradability (BOD/COD) changes. In the third article, the purpose of the research was to estimate optimal conditions for wet oxidation (WO) of debarking water from the paper industry. The WO experiments were' performed at various temperatures, partial oxygen pressures and pH. The experiments showed that lignin degradation and organics removal are affected remarkably by temperature and pH. 78-97% lignin reduction was detected at different WO conditions. Initial pH 12 caused faster removal of tannins/lignin content; but initial pH 5 was more effective for removal of total organics, represented by COD and TOC. Most of the decrease in organic substances concentrations occurred in the first 60 minutes. The aim of the fourth article was to compare the behaviour of two reaction kinetic models, based on experiments of wet oxidation of industrial debarking water under different conditions. The simpler model took into account only the changes in COD, BOD and TOC; the advanced model was similar to the model used in the second article. Comparing the results of the models, the second model was found to be more suitable for describing the kinetics of wet oxidation of debarking water. The significance of the reactions involved was compared on the basis of the model: for instance, lignin degraded first to other chemically oxidizable compounds rather than directly to biodegradable products. Catalytic wet oxidation of lignin containing waters is briefly presented at the end of the dissertation. Two completely different catalysts were used: a commercial Pt catalyst and waste power plant ash. CWO showed good performance using 1 g/L of residual ash gave lignin removal of 86% and COD removal of 39% at 150°C (a lower temperature and pressure than with WO). It was noted that the ash catalyst caused a remarkable removal rate for lignin degradation already during the pre heating for `zero' time, 58% of lignin was degraded. In general, wet oxidation is not recommended for use as a complete mineralization method, but as a pre treatment phase to eliminate toxic or difficultly biodegradable components and to reduce the high level of organics. Biological treatment is an appropriate post treatment method since easily biodegradable organic matter remains after the WO process. The combination of wet oxidation with subsequent biological treatment can be an effective option for the treatment of lignin containing waters.

Kloorifenoleja sisältävien jätevesien AOP-käsittely

Kirjallisuustyössä tutkittiin tehostetun hapetuksen menetelmiä (engl. Advanced Oxidation Processes, AOPs) kloorifenolien käsittelyssä. Tutkittava aine valittiin US EPA:n (United States Environmental Protection Agency) ympäristölle haitallisten aineiden listalta. Työssä tutkitut AOP-menetelmät olivat otsonointi kasvatetussa pH:ssa, O3/H2O2-prosessi, fotolyyttinen otsonointi (O3/UV), H2O2/UV-prosessi ja Fenton-prosessi (H2O2+Fe2+). AOP-käsittelyssä OH-radikaalien oletetaan pääosin aiheuttavan epäpuhtauksien hapettumisen. Kirjallisuustyössä tutkittiin OH-radikaaleihin vaikuttavien parametrien, kuten pH:n, lämpötilan sekä hapettimien ja hapetettavan aineen konsentraatioiden vaikutusta kloorifenolien hapetusprosessissa. Työn tarkoituksena oli selvittää tehokkain AOP-käsittely kloorifenoleja sisältävien jätevesien käsittelylle. AOP-käsittelyjen tehokkuutta verrattiin hajoamisnopeusvakioiden, puoliintumisaikojen sekä hapettimen kemikaalikulutuksen ja kustannuksen perusteella. Fenton-prosessin ja otsonoinnin pH:ssa 9 todettiin olevan tehokkaimpia menetelmiä kloorifenolien hapetuksessa. Fenton-prosessin hapetusnopeus oli tehokkaampaa 4-CP:n ja 2,4-DCP:n hapetuksessa, kun taas otsonointi pH:ssa 9 hapetti nopeammin 2,3,4,6-TeCP:n ja 2,4,6-TCP:n. Kustannustehokkuuden perusteella Fenton-prosessi oli otsonointia tehokkaampi. Parhaan menetelmän valinta kloorifenoleiden poistamiseksi oli vaikeaa, sillä useissa tutkimuksissa oli tutkittu vain yhtä menetelmää. Lisäksi eri tutkimuksissa käytetyt prosessiolosuhteet olivat erilaiset, joka hankaloitti tutkimusten vertailua. Lopullinen AOP-menetelmän valinta tulisikin suorittaa vasta laboratoriotutkimusten jälkeen.

Mäskin sisältämän ligniinin modifiointi PCD-hapetuksella

Teoriaosassa tutkittiin mäskin muodostumista oluentuotantoprosessissa, ligniiniä ja sen pilkkoutumista hapetuksella, eri kehittyneitä hapetusmenetelmiä ja hapetuksella saatavia potentiaalisia pääkomponentteja. Kehittyneissä hapetusmenetelmissä keskityttiin pääasiassa pulssitettuun koronapurkaukseen perustuvaan PCD-menetelmään (Pulsed Corona Discharge). Tutkittavana pääkomponenttina toimi glyoksyylihappo. Työn kokeellisessa osassa tutkittiin mäskistä erotetun ligniinin pilkkoutumista PCD-hapetuksella. Tässä menetelmässä hapetus perustuu sähköpurkauksen aikana syntyvien hydroksyyliradikaalien ja otsonin muodostumiseen, jotka voivat toimia hapettimina. Kokeissa käytettiin oluentuotannosta saatua mäskiä, josta ligniiniä liuotettiin natriumhydroksidi-vesi-liuoksen avulla uuttamalla.. Tämän jälkeen liuosta käsiteltiin PCD laitteistossa. PCD-käsiteltyä tuotetta analysoitiin mittaamalla ligniinin ja aldehydien pitoisuudet siitä spektrofotometrin avulla. Työn tarkoituksena on tutkia PCD hapetusmenetelmän soveltuvuutta mäskin sisältämän ligniinin muokkaamiseen siten, että siitä syntyvää tuotetta voitaisiin käyttää jossakin muussa sovelluksessa, kuten esimerkiksi lääkkeiden raaka-aineena lääketeollisuudessa. PCD hapetusmenetelmä on koronasähköpurkauksiin perustuva laite, jota käytetään pääasiassa vedenpuhdistuksessa hajoittamaan haitallisia orgaanisia yhdisteitä. Tämän työn perusteella ligniiniä hajosi, aldehydejä muodostui ja hapetusnäytteiden pH laski hapetusajan kasvaessa. Tämä viittasi vahvasti glyoksyylihapon muodostumiseen PCD-laitteistossa.

Formation of nitrates in water in presence of formate and oxalate treated with pulsed corona discharge (PCD)

Tavallisten hapetusmenetelmien sijasta kehittyneitä hapetusmenetelmiä (AOP) on kehitetty yhä enemmän, jotta hapetusprosessista tulisi kannattavampi, tehokkaampi, ympäristöystävällisempi ja sitä voitaisiin hyödyntää laajalti eri paikoissa. Uusi teknologia, joka käyttää otsonia ja hydroksyyliradikaalia sähköimpulssien kanssa, on yksi mahdollinen tehokkaampi vedenkäsittelymentelmä. Kyseistä menetelmää kutsutaa pulsed corona discharge (PCD) -menetelmäksi, joka käyttää prosessissa muodostuvia otsonia ja hydroksyyliradikaalia hapettavina tekijöinä. Tässä työssä tutkittiin nitraatin muodostumista vedessä, kun vettä käsiteltiin PCD-laitteessa ja, kun oksalaatti- ja formaatti-ioneja oli sekoittuneina veteen. Nitraatteja muodostuu PCD–laitteessa veteen, kun ilman typpi reagoi hapettimina toimivien otsonin ja hydroksyyliradikaalin kanssa. Aiemmissa tutkimuksissa nitraatin muodostumisen on todistettu parantuvan, kun karboksyylihapot muurahais- ja oksaalihappo ovat sekoittuneina veteen. Tässä tutkimuksessa tarkoituksena oli tutkia, miten formaatti- ja oksalaatti-ionien, joiden pitoisuudet olivat 0 ppm, 50 ppm ja 100 ppm, läsnäolo vedessä vaikuttaa nitraatin muodostumiseen. PCD-kokeista saadut näytteet analysoitiin ionikromatografilla. Kyseisessä tutkimuksessa nitraatin muodostuminen oli samansuuruista jokaisessa kokeessa hapetusajan kasvaessa samalla, kun otettujen näytteiden pH-arvot laskivat. Tuloksena voitiin pitää sitä, ettei formaatti- tai oksalaatti-ioneilla ollut vaikutusta nitraatti-ionien muodostumiseen.

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.

Oxidation of Aqueous Thiosulfate Solutions by Pulsed Corona Discharge

The aim of this Master’s thesis focused on the oxidation of sodium thiosulfate using non thermal plasma technology as an advance oxidation process (AOP). By using this technology we can degrade certain toxic chemical compounds present in mining wastewaters as pollutants. Different concentrations of thiosulfate and pulse frequencies were used in the PCD experiments and the results in terms of various delivered energies (kWh/m3) and degradation kinetics were compared. Pulsed corona discharge is an energy efficient process compared to other oxidation processes using for the treatment of waste water pollutants. Due to its simplicity and low energy costs make it attractive in the field of waste water treatment processes. This technology of wastewater treatment has been tested mainly on pilot scale level and in future the attempts are to be focus on PCD investigations on larger process scale. In this research work of oxidation of thiosulfate using pulsed corona discharge, the main aim of this research was to study degradation of a studied toxic and not environmental friendly chemical compound. The focus of this research was to study the waste waters coming from the gold mines containing leachate compound thiosulfate. Literature review contained also gold leaching process when cyanide is used as the leachate. Another objective of this work was to compare PCD process with other processes based on their energy efficiencies. In the experimental part two concentrations of sodium thiosulfate, 1000ppm and 400ppm, were used. Two pulse generator frequencies of 833 and 200 pulses per second (pps) were used. The chemical analyses of the samples taken during semi-batch PCD oxidation process were analyzed by ion chromatographic (IC). It is observed after the analyses that among different frequencies and concentrations, the most suitable ones for the process is 200pps and 1000ppm respectively because the pollutants present in the waste water has more time to react with the OH radicals which are the oxidants and the process is energy efficient compared to other frequencies.

Wet Oxidation of TMP Concentrated Paper Mill Process Water. Kinetics of the reaction

Työn tarkoituksena oli tutkia lämpötilan, paineen, pH:n ja katalyytin vaikutusta paperitehtaan TMP-konsentroidun prosessiveden märkähapetuksessa. Teoriaosio sisältää katsauksen sellu- ja paperiteollisuuteen, jätevesien käsittelyyn, nanosuodatuksen ja märkähapetusprosessin toimintaperiaatteet ja sovellukset hybriditeknologialle nanosuodatus-märkähapetuksessa. Empiirinen osa koostuu märkähapetuskokeista eri lämpötiloissa, paineissa, pH:ssa ja eri katalyyseillä. Työssä tutkittiin näiden vaikutusta kemialliseen hapenkulutukseen (COD), Biologiseen hapenkulutukseen (BOD), Välittömästi saatavana olevan biologisen hapenkulutukseen (IABOD), ligniiniin, täysin orgaanisen hiileen (TOC) ja rasvaliukoisten uuteaineiden (LWEs) pitoisuuteen. Tuloksina kokeellisesta työstä saatiin korkeimmat COD:n alenemat ja BOD/COD (biohajoavuus) suurimmilla lämpötilaolosuhteilla (COD:n alenema 70 % ja BOD/COD 97 % 200 °C:ssa ja hapen 10 bar osapaineella). Tutkimuksessa, jossa selvitettiin hapen osapaineen vaikutusta saatiin tuloksena, että hapen osapaineen kasvu parantaa orgaanisen kuormituksen poistoa: COD poisto oli olosuhteilla130°C, 5bar 5 %, olosuhteilla 130 °C, 15bar 15 %, olosuhteilla 170 °C, 5bar 20 % ja olosuhteilla 170 °C, 15bar 50 %. Lähes täydellinen LWEs –poisto saavutettiin 150 °C ja 10bar olosuhteilla, vaikka tässä lämpötilassa ei saavutettu korkeata orgaanisen kuormituksen poistoa. Emäksinen pH vaikutti suosivan hapettavia reaktioita, koska korkein COD:n poisto saavutettiin näissä olosuhteilla; kuitenkin alkalisen väliaineen tehokkuudelle löydettiin tärkeä lämpötilariippuvuus.

Catalytic Wet Oxidation of Paper Mill Debarking Water

The objective of the research was to study the influence of temperature, oxygen pressure, catalysts loading and initial COD concentration of debarking wastewater on the pollutants during the catalytic oxidation. More importantly, how the addition of catalyst affects the wet oxidation process. The whole work was divided into two main sections, theoretical and experimental parts. The theoretical part reviews the pulp and paper industry from wood processing to paper production as well as operations that generate wastes. Treatment methods applicable for industrial pulp and paper mill effluents were also discussed. Wet oxidation and catalytic wet oxidation processes including mechanism, reactions, kinetics and industrial applications were previewed. In the experimental part, catalytic wet oxidation process were studied at 120-180°C, 0-10 bar oxygen pressure, 0-1 g/L catalyst concentration and 1000-3000 mg/L initial COD concentration. Responses, such as Chemical oxygen demand (COD), Total organic carbon (TOC), colour, lignin/tannin, Biochemical oxygen demand (BOD) and pH were measured. In the experiment, the best conditions occurred at 180°C, 10 bar, l g/L catalyst concentration and 3000mg/L initial COD. At these conditions; 74% COD, 97% lignin/tannin, 54% TOC, 90% colour were removed from the wastewater. pH was greatly reduced from 7 to 4.6. Lignin/tannin was removed most. Lignin/tannin showed linear dependency with colour during oxidation. Temperature made the most impact in reducing contaminants in debarked wastewater.

0 AND 02 ADSORPTION ON Ag/Cu[100]

In this work the adsorption mechanisms of atomic and molecular oxygen on Cu(100) surface are studied using ab initio simulation methods. Through the atomistic scale under-standing of the elementary oxidation processes we can further understand the large-scale oxidation. Copper is a material widely used in industry which makes it an interesting subject, and also understanding the oxidation of copper helps us understand the oxidation mechanism of other metals. First we have a look on some theory on surface alloys in general and behaviour of Ag on Cu(100) surface. After that the physical background there is behind the methods of density functional calculations are discussed, and some methods, namely potential energy surfaces and molecular dynamics, are introduced. Then there is a brief look on the numerical details used in the calculations, and after that, the results of the simulations are exhibited.

Practical applications of a systematic approach to the chemical abatement of pollutants in water and air

The present dissertation is devoted to the systematic approach to the development of organic toxic and refractory pollutants abatement by chemical decomposition methods in aqueous and gaseous phases. The systematic approach outlines the basic scenario of chemical decomposition process applications with a step-by-step approximation to the most effective result with a predictable outcome for the full-scale application, confirmed by successful experience. The strategy includes the following steps: chemistry studies, reaction kinetic studies in interaction with the mass transfer processes under conditions of different control parameters, contact equipment design and studies, mathematical description of the process for its modelling and simulation, processes integration into treatment technology and its optimisation, and the treatment plant design. The main idea of the systematic approach for oxidation process introduction consists of a search for the most effective combination between the chemical reaction and the treatment device, in which the reaction is supposed to take place. Under this strategy,a knowledge of the reaction pathways, its products, stoichiometry and kinetics is fundamental and, unfortunately, often unavailable from the preliminary knowledge. Therefore, research made in chemistry on novel treatment methods, comprisesnowadays a substantial part of the efforts. Chemical decomposition methods in the aqueous phase include oxidation by ozonation, ozone-associated methods (O3/H2O2, O3/UV, O3/TiO2), Fenton reagent (H2O2/Fe2+/3+) and photocatalytic oxidation (PCO). In the gaseous phase, PCO and catalytic hydrolysis over zero valent ironsare developed. The experimental studies within the described methodology involve aqueous phase oxidation of natural organic matter (NOM) of potable water, phenolic and aromatic amino compounds, ethylene glycol and its derivatives as de-icing agents, and oxygenated motor fuel additives ¿ methyl tert-butyl ether (MTBE) ¿ in leachates and polluted groundwater. Gas-phase chemical decomposition includes PCO of volatile organic compounds and dechlorination of chlorinated methane derivatives. The results of the research summarised here are presented in fifteenattachments (publications and papers submitted for publication and under preparation).

Combination of pulsed corona discharge with TiO2 photocatalysis: verification of hypothesis

The oxidation potential of pulsed corona discharge concerning aqueous impurities is limited in respect to certain refractory compounds. This may be enhanced in combination of the discharge with catalysis/photocatalysis as developed in homogeneous gas-phase reactions. The objective of the work consists of testing the hypothesis of oxidation potential enhancement in combination of the discharge with TiO2 photocatalysis applied to aqueous solutions of refractory oxalate. Meglumine acridone acetate was included for meeting the practical needs. The experimental research was undertaken into oxidation of aqueous solutions under conditions of various target pollutant concentrations, pH and the pulse repetition rate with plain electrodes and the electrodes with TiO2 attached to their surface. The results showed no positive influence of the photocatalyst, the pollutants were oxidized with the rate identical within the accuracy of measurements. The possible explanation for the observed inefficiency may include low UV irradiance, screening effect of water and generally low oxidation rate in photocatalytic reactions. Further studies might include combination of electric discharge with ozone decomposition/radical formation catalysts.

Perfluorattuja yhdisteitä sisältävien jätevesien puhdistus- ja analyysimenetelmät

Perfluoratut alkyyliyhdisteet eli PFAS-yhdisteet ovat synteettisiä orgaanisia yhdisteitä, joissa on fluorattu hiiliketju. Hiilen ja fluorin väliset vahvat sidokset ovat muodostuneet ongelmaksi jätevedenpuhdistamoilla, sillä yhdisteet eivät hajoa puhdistamoilla käytössä olevilla vedenpuhdistusmenetelmillä. Yhdisteitä kertyy luontoon jätevesien mukana. Kandidaatintyössä on vertailtu yhdisteitä sisältävien vesien käsittelymenetelmiä parhaiten soveltuvan menetelmän löytämiseksi. Menetelmien kustannuksia tai soveltuvuutta vedenpuhdistamomittakaavan prosessiksi ei ole arvioitu. Lisäksi työssä on koottu yhdisteitä sisältävien jätevesien analysointiin sopivia analyysimenetelmiä. Soveltuvat puhdistus- ja analyysimenetelmät on esitelty uusien tieteellisten artikkelien pohjalta. Mahdollisia erotusmenetelmiä ovat membraanierotus ja sorptio. Membraaneista soveltuvimpia ovat nanosuodatus- ja käänteisosmoosimembraanit, joilla erottuvat jopa 0,0001 μm:n kokoiset partikkelit. PFAS-yhdisteet voidaan erottaa sorptiolla muun muassa aktiivihiileen. Yhdisteiden rakenne hajoaa nykyaikaisilla hapetusmenetelmillä ja polttamalla lietteen mukana. Hapettaminen permanganaatin avulla ei tuottanut hyvää tulosta, mutta fotokemiallisella hapetuksella ja alhaisen lämpötilan plasmatekniikalla (NTP) yhdisteiden rakenne hajosi lähes kokonaan. Fotokemiallinen hapetus onnistui erityisesti perfluorokarboksyylihapoilla, joiden rakenne hajosi jopa kolmessa tunnissa. Yleisimmin käytetty analyysimenetelmä on nestekromatografin ja massaspektrometrin yhdistelmä (LC-MS/MS) ja matriisivaikutus minimoidaan tyypillisesti kiinteäfaasiuutolla (SPE). Työssä esitellyistä käsittelymenetelmistä parhaiten soveltuva on NTP-menetelmä, koska sillä saatiin tutkimusten mukaan hajotettua yhdisteiden rakenne muita menetelmiä lyhyemmässä ajassa ja se soveltuu parhaiten kaikille PFAS-yhdisteille. NTP-menetelmässä ei tarvita katalyyttiä tai lisäkemikaaleja. Voimakkaana hapettimena toimivat epästabiilit hydroksyyliradikaalit, jotka syntyvät koronapurkauksen kautta. Koronapurkauksessa muodostuu myös otsonia ja lisäksi vapaa happi voi tehostaa hapettumista. Menetelmässä muodostuvien hajoamistuotteiden hallinta vaatii lisätutkimusta. Mahdollinen hallintakeino voisi olla esimerkiksi hapettumisessa vapautuvien fluoridi-ionien saostaminen. Muodostuvien hajoamistuotteiden toksisuutta voitaisiin tarkkailla biosensorilla.

Advanced analysis and design methods for preparative chromatographic separation processes

Preparative liquid chromatography is one of the most selective separation techniques in the fine chemical, pharmaceutical, and food industries. Several process concepts have been developed and applied for improving the performance of classical batch chromatography. The most powerful approaches include various single-column recycling schemes, counter-current and cross-current multi-column setups, and hybrid processes where chromatography is coupled with other unit operations such as crystallization, chemical reactor, and/or solvent removal unit. To fully utilize the potential of stand-alone and integrated chromatographic processes, efficient methods for selecting the best process alternative as well as optimal operating conditions are needed. In this thesis, a unified method is developed for analysis and design of the following singlecolumn fixed bed processes and corresponding cross-current schemes: (1) batch chromatography, (2) batch chromatography with an integrated solvent removal unit, (3) mixed-recycle steady state recycling chromatography (SSR), and (4) mixed-recycle steady state recycling chromatography with solvent removal from fresh feed, recycle fraction, or column feed (SSR–SR). The method is based on the equilibrium theory of chromatography with an assumption of negligible mass transfer resistance and axial dispersion. The design criteria are given in general, dimensionless form that is formally analogous to that applied widely in the so called triangle theory of counter-current multi-column chromatography. Analytical design equations are derived for binary systems that follow competitive Langmuir adsorption isotherm model. For this purpose, the existing analytic solution of the ideal model of chromatography for binary Langmuir mixtures is completed by deriving missing explicit equations for the height and location of the pure first component shock in the case of a small feed pulse. It is thus shown that the entire chromatographic cycle at the column outlet can be expressed in closed-form. The developed design method allows predicting the feasible range of operating parameters that lead to desired product purities. It can be applied for the calculation of first estimates of optimal operating conditions, the analysis of process robustness, and the early-stage evaluation of different process alternatives. The design method is utilized to analyse the possibility to enhance the performance of conventional SSR chromatography by integrating it with a solvent removal unit. It is shown that the amount of fresh feed processed during a chromatographic cycle and thus the productivity of SSR process can be improved by removing solvent. The maximum solvent removal capacity depends on the location of the solvent removal unit and the physical solvent removal constraints, such as solubility, viscosity, and/or osmotic pressure limits. Usually, the most flexible option is to remove solvent from the column feed. Applicability of the equilibrium design for real, non-ideal separation problems is evaluated by means of numerical simulations. Due to assumption of infinite column efficiency, the developed design method is most applicable for high performance systems where thermodynamic effects are predominant, while significant deviations are observed under highly non-ideal conditions. The findings based on the equilibrium theory are applied to develop a shortcut approach for the design of chromatographic separation processes under strongly non-ideal conditions with significant dispersive effects. The method is based on a simple procedure applied to a single conventional chromatogram. Applicability of the approach for the design of batch and counter-current simulated moving bed processes is evaluated with case studies. It is shown that the shortcut approach works the better the higher the column efficiency and the lower the purity constraints are.