Table Of ContentPhotocatalytic Oxidation in Drinking Water Treatment
Using Hypochlorite and Titanium Dioxide
Photocatalytic Oxidation in Drinking Water Treatment
Using Hypochlorite and Titanium Dioxide
PROEFSCHRIFT
terverkrijgingvandegraadvandoctor
aandeTechnischeUniverstiteitDelft,
opgezagvandeRectorMagnificusprof.ir.K.C.A.M.Luyben,
voorzittervanhetCollegevoorPromoties,
inhetopenbaarteverdedigenopwoensdag25september2013om10:00
door
AmerEL-KALLINY
MasterofScienceinChemistry
AinShamsUniversity,Egypt
geborenteGiza,Egypt
Ditproefschriftisgoedgekeurddoordepromotor:
Prof.dr.ir.L.C.Rietveld
Samenstellingpromotiecommissie:
RectorMagnificus Voorzitter
Prof.dr.Ir.L.C.Rietveld TechnischeUniversiteitDelft,promotor
Dr.H.W.Nugteren TechnischeUniversiteitDelft
Prof.dr.ir.P.W.Appel TechnischeUniversiteitDelft
Prof.dr.R.AbdelWahaab NationalResearchCenter(NRC),Cairo,Egypt
Prof.dr.M.Kennedy UNESCO-IHE/TechnischeUniversiteitDelft
Prof.dr.D.Wolbert ÉcoleNationaleSupérieuredeChimiedeRennes
Prof.dr.T.C.Schmidt UniversityDuisburg-Essen,Germany
Prof.J.P.vanderHoek TechnischeUniversiteitDelft,reservelid
This research was conducted within the framework of INNOWATOR project and
financially supported by Agentschap NL and the Organization for Prohibition of
ChemicalWeapons(OPCW).
Proefschrift,TechnischeUniversiteitDelft
MetsamenvattinginhetNederlands/WithsummaryinDutch
ISBN978-94-6186-214-3
©2013AmerS.El-Kalliny
Allrightsreserved
Printedby:CPIKoninklijkeWöhrmann,theNetherlands
INTHEMEMORYOFMYFATHER
TOMYFAMILY (MOTHER, WIFE & DAUGHTER)
Contents
Summary xiii
Samenvatting xix
1 Introduction 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Advancedoxidationprocesses . . . . . . . . . . . . . . . . . . . . . 2
1.3 Homogeneousphoto-oxidationwithhypochlorite . . . . . . . . . . . 3
1.4 Heterogeneousphoto-oxidation . . . . . . . . . . . . . . . . . . . . . 4
1.4.1 Mechanismofheterogeneousphotocatalysis(UV/TiO ) . . . 5
2
1.4.2 Immobilizationofthephotocatalyst . . . . . . . . . . . . . . 7
1.4.3 Solarreactors . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.5 Thesisaimsandoutline . . . . . . . . . . . . . . . . . . . . . . . . . 9
2 LPUV/NaOClprocessbasedonfluence 17
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2 Basicconcepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.3 Materialsandmethods . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.3.1 Experimentalapproach . . . . . . . . . . . . . . . . . . . . . 21
2.3.2 Photolysisandphoto-oxidation . . . . . . . . . . . . . . . . 22
2.3.3 Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
vii
viii Contents
2.3.4 Fluencecalculation . . . . . . . . . . . . . . . . . . . . . . . 23
2.4 Resultsanddiscussion . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.4.1 (cid:129)OHformationinNaOCl/UVandH O /UVprocesses . . . . 24
2 2
2.4.2 Theroleofthesodiumbicarbonatescavenger . . . . . . . . . 25
2.4.3 HAdegradationbyLPUV/NaOClwith&withoutbicarbonate 27
2.4.4 Chloroformdegradation . . . . . . . . . . . . . . . . . . . . 29
2.4.5 ChloroformandAOXlevelsformedbyUV/chlorineprocess . 31
2.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3 MPUV/NaOClversusLPUV/NaOCl 39
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3.2 Basicconcepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.3 Experimentalmethods . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.3.1 Experimentalapproach . . . . . . . . . . . . . . . . . . . . . 44
3.3.2 Photolysisandfree-radicalreactions . . . . . . . . . . . . . . 44
3.3.3 Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.3.4 Thefree-radicaldosecalculations . . . . . . . . . . . . . . . 45
3.3.5 Theabsorbedphotonicfluxcalculations . . . . . . . . . . . . 46
3.4 Resultsanddiscussion . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.4.1 HAdegradationbyUV/NaOClwith&withoutbicarbonate . . 47
3.4.2 Chloroformdegradation . . . . . . . . . . . . . . . . . . . . 49
3.4.3 ChloroformandAOXlevelsformedbyUV/NaOClprocess . . 51
3.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4 Wovenmeshphotocatalyst 59
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.2 Experimentalmethods . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.2.1 Experimentalapproach . . . . . . . . . . . . . . . . . . . . . 61
4.2.2 PreparationoftheimmobilizedTiO catalyst . . . . . . . . . 62
2
Contents ix
4.2.3 Treatmentofthecoatedfilms . . . . . . . . . . . . . . . . . . 63
4.2.4 CharacterizationoftheTiO coatings . . . . . . . . . . . . . 64
2
4.2.5 Measurementsoftransmittedlightthroughthemeshstructure 64
4.2.6 Theoryandmodelequations . . . . . . . . . . . . . . . . . . 65
4.2.7 Evaluationofphotocatalyticactivity . . . . . . . . . . . . . . 67
4.2.8 Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4.3 Resultsanddiscussion . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.3.1 Performanceandcharacterizationofcoatedmeshes . . . . . . 68
4.3.2 Lightdistributioninastructureofpackedmeshes . . . . . . . 73
4.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5 Fixed-bedsolarphotocatalyticreactor 85
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5.2 Experimentalmethods . . . . . . . . . . . . . . . . . . . . . . . . . 87
5.2.1 Experimentalapproach . . . . . . . . . . . . . . . . . . . . . 87
5.2.2 PreparationoftheimmobilizedTiO catalyst . . . . . . . . . 88
2
5.2.3 Fixedbedreactorandphotocatalyticactivityevaluation . . . . 88
5.2.4 AdsorptionexperimentsofHAinthedark . . . . . . . . . . . 89
5.2.5 Analyticalmethods . . . . . . . . . . . . . . . . . . . . . . . 90
5.2.6 Solarradiationevaluation . . . . . . . . . . . . . . . . . . . 90
5.3 Resultsanddiscussion . . . . . . . . . . . . . . . . . . . . . . . . . 92
5.3.1 AdsorptionbehaviorofHAoncoatedmeshes . . . . . . . . . 92
5.3.2 SolarphotocatalyticdegradationofHA . . . . . . . . . . . . 94
5.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
6 Degradationofatrazine 103
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
6.2 Materialsandmethods . . . . . . . . . . . . . . . . . . . . . . . . . 104
6.2.1 PreparationoftheimmobilizedTiO catalyst . . . . . . . . . 104
2
x Contents
6.2.2 Adsorptionexperimentsinthedark . . . . . . . . . . . . . . 105
6.2.3 Evaluationofphotocatalyticactivity . . . . . . . . . . . . . . 105
6.2.4 Analyticalmethods . . . . . . . . . . . . . . . . . . . . . . . 106
6.2.5 Photocatalystregenerationexperiments . . . . . . . . . . . . 107
6.3 Resultsanddiscussions . . . . . . . . . . . . . . . . . . . . . . . . . 107
6.3.1 AdsorptionofatrazineonTiO coatedontomeshes . . . . . 107
2
6.3.2 Directphotolysisofatrazine . . . . . . . . . . . . . . . . . . 108
6.3.3 Solarphotocatalyticdegradationofatrazine . . . . . . . . . . 109
6.3.4 Photocatalystregeneration . . . . . . . . . . . . . . . . . . . 111
6.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
7 Conclusionsandrecommendations 117
7.1 Homogeneousphoto-oxidation(UV/NaOCl) . . . . . . . . . . . . . . 118
7.2 Heterogeneousphoto-oxidation(solarlight/TiO ) . . . . . . . . . . . 119
2
7.3 Overallconclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
7.4 Recommendations. . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
7.4.1 Practicalrecommendations . . . . . . . . . . . . . . . . . . . 122
7.4.2 Experimentalrecommendations . . . . . . . . . . . . . . . . 123
Listofpublications 125
Acknowledgments 127
Abouttheauthor 131
Description:1.4.1 Mechanism of heterogeneous photocatalysis (UV/TiO2) . 5 .. cursor (H2O2, O3 of een semiconductor). In dit proefschrift den dat de vorming van adsorbeerbare organische halogeenverbindingen (AOX) hoger was bij de .. which turns disinfection and photolysis processes into an AOP.
