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.

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.

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.

Lämpötilan vaikutus oksaalihapon hapetukseen pulssitetulla koronapurkauksella

Tutkimuksen tarkoituksena oli kartoittaa lämpötilan vaikutusta veden orgaanisten haitta-aineiden hapetuksessa PCD-menetelmällä. Kokeita tehtiin näytteiden eri alkulämpötiloilla. Malliyhdisteenä kokeissa käytettiin oksaalihappoa. Teoriaosuudessa käsiteltiin pulssittaista koronapurkausta ilmiönä. Lisäksi tarkasteltiin, kuinka PCD-menetelmällä muodostuu hapettimia neste-kaasufaasissa. Syntyvistä hapettimista keskityttiin otsoniin ja hydroksyyliradikaaliin. Kokeellisessa osuudessa esiteltiin käytetty PCD-laitteisto. Esittelyn jälkeen siirryttiin hapetuskokeiden kuvaamiseen ja analyysin suorittamiseen titrauksella. Lopuksi koottiin tulokset. Tutkimuksissa prosessin hapetustehon havaittiin heikentyvän lämpötilan noustessa tutkitulla lämpötila-alueella, mikä voi selittyä kaasufaasissa muodostuvan otsonin heikentyvällä liukoisuudella. Tuloksia voidaan pitää viitteellisinä, ja selkeän mallin muodostamiseksi tarvitaan jatkotutkimuksia laajemmalla lämpötila-alueella tarkasti toistettavilla koejärjestelyillä.

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.

How Lean Six Sigma and Agile principles optimize ITIL-based processes

Imagine the potential implications of an organization whose business and IT processes are well aligned and are capable of reactively and proactively responding to the external and internal changes. The Philips IT Infrastructure and Operations department (I&O) is undergoing a series of transformation activities to help Philips business keeping up with the changes. I&O would serve a critical function in any business sectors; given that the I&O’s strategy switched from “design, build and run” to “specify, acquire and performance manage”, that function is amplified. In 2013, I&O’s biggest transforming programme I&O Futures engaged multiple interdisciplinary departments and programs on decommissioning legacy processes and restructuring new processes with respect to the Information Technology Internet Library (ITIL), helping I&O to achieve a common infrastructure and operating platform (CI&OP). The author joined I&O Futures in the early 2014 and contributed to the CI&OP release 1, during which a designed model Bing Box and its evaluations were conducted through the lens of six sigma’s structured define-measure-analyze-improve-control (DMAIC) improvement approach. This Bing Box model was intended to firstly combine business and IT principles, namely Lean IT, Agile, ITIL best practices, and Aspect-oriented programming (AOP) into a framework. Secondly, the author implemented the modularized optimization cycles according to the defined framework into Philips’ ITIL-based processes and, subsequently, to enhance business process performance as well as to increase efficiency of the optimization cycles. The unique of this thesis is that the Bing Box model not only provided comprehensive optimization approaches and principles for business process performance, but also integrated and standardized optimization modules for the optimization process itself. The research followed a design research guideline that seek to extend the boundaries of human and organizational capabilities by creating new and innovative artifacts. The Chapter 2 firstly reviewed the current research on Lean Six Sigma, Agile, AOP and ITIL, aiming at identifying the broad conceptual bases for this study. In Chapter 3, we included the process of constructing the Bing Box model. The Chapter 4 described the adoption of Bing Box model: two-implementation case validated by stakeholders through observations and interviews. Chapter 5 contained the concluding remarks, the limitation of this research work and the future research areas. Chapter 6 provided the references used in this thesis.

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.