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Ozone Treatment Targeting Pharmaceutical Residues

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Ozone Treatment Targeting Pharmaceutical Residues Linköping University | Department of Physics, Chemistry and Biology (IFM) Master thesis, 30 ECTS | Industrial biotechnology and production Autumn term 2018 | LITH-IFM-A-EX--18/3589--SE Ozone Treatment Targeting Pharmaceutical Residues Validation and Process Control in a Wastewater Treatment Plant Erik Fornander Duration: Aug 2018 – Jan 2019 Location: Nykvarnsverket, Linköping Examiner: Carl-Fredrik Mandenius Supervisors Tekniska verken AB: Robert Sehlén Linköping University: Gunnar Hörnsten Linköpings universitet SE-581 83 Linköping 013-28 10 00, www.liu.se Avdelning, institution Datum Division, Department Date 2019-01-15 Department of Physics, Chemistry and Biology Linköping University Språk Rapporttyp ISBN Language Report category Svenska/Swedish Licentiatavhandling ISRN: LITH-IFM-A-EX--18/3589--SE Engelska/English Examensarbete _________________________________________________________________ C-uppsats Serietitel och serienummer ISSN D-uppsats Title of series, numbering ______________________________ Övrig rapport ________________ _____________ URL för elektronisk version Titel Title Ozone treatment targeting pharmaceutical residues Validation and process control in a wastewater treatment plant Författare Author Erik Fornander Sammanfattning Abstract Major studies conducted in Europe and North America has concluded that the current processes in wastewater treatment plants insufficiently degrade micropollutants e.g. pharmaceutical residues. Several sorption and oxidation methods has therefore been investigated with the purpose of removing or degrading micropollutants in wastewater. The main purpose of this project was, firstly, to validate the results from a pilot study conducted by Tekniska verken i Linköping AB (2014) which investigated the use of ozone to degrade pharmaceutical residues. Secondly, to investigate and design a suitable process control strategy for the ozonation process. Four different tests were conducted during the project, a dose-response test, step-response tests, a trace test, and a performance test. A poorer average reduction of pharmaceutical residues was observed in this project compared to the pilot study. An average reduction of approximately 80% was observed at the highest tested dose, 0.67 mg O3/mg DOC, N corr. Whilst an average reduction of 90% was observed at approximately 0.46 mg O3/mg DOC, N corr, in the pilot study. However, the quality of the wastewater was worse during this project compared to the pilot study. ΔUVA254 and off- gas concentration of ozone were found to be suitable control parameters for process control. A control strategy based on a combination of these parameters was designed, where ΔUVA254 was used as the main control parameter and the off-gas concentration of ozone was used as a limiting controller to ensure a sufficient mass transfer in the system. In conclusion, a suitable flow proportional base ozone dose valid for current water conditions has been identified, 10 mg/L. Differences in wastewater quality which heavily influence the ozonation process have been identified. Lastly, a control strategy for process control of the ozonation have been identified, designed and is ready for implementation. Nyckelord Keyword Ozone, Ozone treatment, Wastewater, Process control, Pharmaceutical residues, Wastewater treatment plant, Validation, Modelling Upphovsrätt Detta dokument hålls tillgängligt på Internet – eller dess framtida ersättare – under 25 år från publiceringsdatum under förutsättning att inga extraordinära omständigheter uppstår. Tillgång till dokumentet innebär tillstånd för var och en att läsa, ladda ner, skriva ut enstaka kopior för enskilt bruk och att använda det oförändrat för ickekommersiell forskning och för undervisning. Överföring av upphovsrätten vid en senare tidpunkt kan inte upphäva detta tillstånd. All annan användning av dokumentet kräver upphovsmannens medgivande. För att garantera äktheten, säkerheten och tillgängligheten finns lösningar av teknisk och administrativ art. Upphovsmannens ideella rätt innefattar rätt att bli nämnd som upphovsman i den omfattning som god sed kräver vid användning av dokumentet på ovan beskrivna sätt samt skydd mot att dokumentet ändras eller presenteras i sådan form eller i sådant sammanhang som är kränkande för upphovsmannens litterära eller konstnärliga anseende eller egenart. För ytterligare information om Linköping University Electronic Press se förlagets hemsida http://www.ep.liu.se/. Copyright The publishers will keep this document online on the Internet – or its possible replacement – for a period of 25 years starting from the date of publication barring exceptional circumstances. The online availability of the document implies permanent permission for anyone to read, to download, or to print out single copies for his/hers own use and to use it unchanged for non-commercial research and educational purpose. Subsequent transfers of copyright cannot revoke this permission. All other uses of the document are conditional upon the consent of the copyright owner. The publisher has taken technical and administrative measures to assure authenticity, security and accessibility. According to intellectual property law the author has the right to be mentioned when his/her work is accessed as described above and to be protected against infringement. For additional information about the Linköping University Electronic Press and its procedures for publication and for assurance of document integrity, please refer to its www home page: http://www.ep.liu.se/. © Erik Fornander Abstract Major studies conducted in Europe and North America has concluded that the current processes in wastewater treatment plants insufficiently degrade micropollutants e.g. pharmaceutical residues. Several sorption and oxidation methods has therefore been investigated with the purpose of removing or degrading micropollutants in wastewater. The main purpose of this project was, firstly, to validate the results from a pilot study conducted by Tekniska verken i Linköping AB (2014) which investigated the use of ozone to degrade pharmaceutical residues. Secondly, to investigate and design a suitable process control strategy for the ozonation process. Four different tests were conducted during the project, a dose-response test, step-response tests, a trace test, and a performance test. A poorer average reduction of pharmaceutical residues was observed in this project compared to the pilot study. An average reduction of approximately 80% was observed at the highest tested dose, 0.67 mg O3/mg DOC, N corr. Whilst an average reduction of 90% was observed at approximately 0.46 mg O3/mg DOC, N corr, in the pilot study. However, the quality of the wastewater was worse during this project compared to the pilot study. ΔUVA254 and off-gas concentration of ozone were found to be suitable control parameters for process control. A control strategy based on a combination of these parameters was designed, where ΔUVA254 was used as the main control parameter and the off-gas concentration of ozone was used as a limiting controller to ensure a sufficient mass transfer in the system. In conclusion, a suitable flow proportional base ozone dose valid for current water conditions has been identified, 10 mg/L. Differences in wastewater quality which heavily influence the ozonation process have been identified. Lastly, a control strategy for process control of the ozonation have been identified, designed and is ready for implementation. Abbreviations WWTP – Wastewater Treatment Plant PPCP – Pharmaceuticals and Personal Care Products UVA254 – Ultra Violet Absorption at wavelength 254 nm TVAB – Tekniska Verken i Linköping AB RCR – Risk Characterisation Ratio CWPharma – Clear Waters from Pharmaceuticals SIE – Specific Input Energy LOX – Liquid Oxygen HGT – Horizontal Gene Transfer OBP – Oxidation By-Product NDMA – N-nitrodimethylamine DOC – Dissolved Organic Carbon N corr – Nitrite corrected dose COD – Chemical Oxygen Demand TOC – Total Organic Carbon NTU - Nephelometric Turbidity Units FAU - Formazin Attenuation Units MBBR – Moving Bed Biofilm Reactor MF – FOMBR – Micro Filtration Forward Osmosis Membrane Bioreactor UF – MBR – Ultra Filtration Membrane Bioreactor PID – Proportional, Integral, Derivative PERT – Program Evaluation Review Technique MEC – Measured Environmental Concentration PNEC – Predicted No Effect Concentration EU-TGD – European Union Technical Guidance Document EDA – Ethylenediamine MS Excel – Microsoft Excel NOEC – No Effect Concentration LOD – Limit of Detection MTE – Mass Transfer Efficiency List of content 1. Introduction ................................................................................................................ 1 1.1 Purpose of the study ........................................................................................... 1 1.2 Expected impact of the study.............................................................................. 2 1.3 Objectives of the work ........................................................................................ 2 2 Theory and methodology ........................................................................................ 4 2.1 Scientific background .......................................................................................... 4 2.1.1 Ozone .......................................................................................................... 4 2.1.2 Degradation of pharmaceuticals with ozone .............................................. 7 2.1.3 Environmental effects ................................................................................
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