Combination of photo-oxidation processes with biological treatment Doctoral Thesis

371 Pages·2002·4.4 MB·English

UNIVERSITAT DE BARCELONA
FACULTAT DE QUÍMICA
DEPARTAMENT D’ ENGINYERIA QUÍMICA I METAL·LÚRGIA
Combination of photo-oxidation processes with
biological treatment
DDooccttoorraall TThheessiiss
Fares Al-Momani
Directed by Dr. Santiago Esplugas
Barcelona, June, 2003
PROGRAMA BIENAL DE INGENIERIA QUIMICA
AMBIENTAL

Bienio 1999-2001

Memoria presentada por Fares Al-Momani, Ingeniero Químico, para
optar por el grado de Doctor en Ingeniería Química.

Fares Al-Momani

La presente tesis ha sido realizada en el Departamento de Ingenieria
Química y Metalurgia de la Universidad de Barcelona, bajo la dirección
del Dr. Santiago Esplugas Vidal, quien autoriza su presentación:

Dr. Santiago Esplugas Vidal

Barcelona Abril del 2003
En el primer lugar quiero expresar mi mas profunda gratitud al Dr. Santiago Esplugas por la
dirección, soporte y colaboración prestada, sin los que hubiera sido imposible la pronta y satisfactoria
realización de este trabajo.

También deseo hacer constar mi agradecimiento al Dra. Carmen Sans por su apoyo
durante todas las fases de esta investigación, especialmente en los temas biológicos y
por la ayuda que me ha ofrecido cuando la he necesitado, muchísima gracias de
verdad Carmen.

A Claudita, le doy las gracias de todo corazón por haberme animado y apoyado en
todos los momentos. Un agradecimiento especial a mi familia por todo su cariño y
aliento. Aunque están a gran distancia los tengo siempre en mi corazón.

A Nadia, Sandra, Oscar y Anastasius por todos los momentos que hemos pasado
juntos en el laboratorio durante estos años, donde hemos compartido muchísimas
cosas, muchas gracias por todo.

Así mismo quiero agradecer todos mis amigos dentro y fuera de la Universidad. los
me han acompañado durante estos cuatro años. Durante este tiempo han sido como
mi segunda familia, gracias Miguel, Monia , Zaid, Mohammed, Verónica, Cristina,
Neus, Eva, y a todos los otros

Mi sincero agradecimiento a la Agencia Española de Cooperación Internacional
(AECI) y la Universidad de Barcelona por la beca concedida en mi favor durante el
tiempo de mis estudios de doctorado.

Mi agradecimiento para Dra. Evelyne Touraud y Dr. Jean Roussy, asi como a todos
los que mi hicieron posible mi estancia en Ales-France, gracias Fouad, Tiaa y todos
los nuevos amigos.

A al secretaria del Departamento de Ingeniería Química y Metalurgia por toda su
colaboración en los aspectos administrativos.

Also I would Like to express my deep and special grateful to friends who help me a
lot during the last 8 years and their were always beside me supporting and helping to
let me do my best effort, thank you Thaker, Reema my sisters Alaa y Sara you are
always in my mind and my heart.
The ability to think straight, some knowledge of the past, some
vision of the future, some skill to do useful service, some urge to
fit that service into the well-being of the community- these are
the most vital things education must try to produce.
Virginia Gildersleeve
INDEX

1. Introduction…………………………………………………......….....…...
1
1.1. Point and non-point sources ………………………...….….....…... 3
1.2. Causes of pollution ………………………..……………..…....….... 3
1.3. Additional forms of water pollution ………………………....….... 4
1.4. Classifying water pollution ……………………….……...…....….. 4
1.5. Legislation ………………………......................................…....…… 5

2. Constituents found in wastewater………………………...……....…...
7
2.1. Contaminants of concern in wastewater treatment……..…..…... 8
2.2. Physical characteristics ……………………….................…....….. 8
2.3. Chemical characteristics ………………………...............…....…... 9
2.4. Biological characteristics ………………………...……...….....….. 12

3. Wastewater treatment processing……………………...…...…...…..…
14
3.1. Physical unit operations ………………………...……….…...…... 14
3.2. Chemical unit processes ……………………...……….……...….. 14
3.3. Advanced treatment processes ……………………...……….….. 14
3.3.1. Supercritical water oxidation (SWO) .………………...…… 14
3.3.2. Electrochemical oxidation ……………………...……….…… 15
3.3.3. Wet oxidation ………………………………………………… 16
3.3.4. Adsorption of organic compounds onto activated carbon …... 17
i
3.3.5. Chemical oxidation……………….………...……….…...…… 17
Advanced Oxidation Processes (AOP’s) ……………………...……… 18
3.3.5.1. Processes based in the ultraviolet light radiation …….. 20
3.3.5.1.1. Photochemical process ………….………...……….. 20
3.3.5.1.2. UV/H2 O2 process ………………………………...… 21
3.3.5.1.3. Photocatalysis ………………………………...……. 23
3.3.5.1.4. UV/Fe(III) ………………………………...………… 23
3.3.5.1.5. Vacuum ultraviolet process (VUV)............................... 23
3.3.5.1.6. Fenton and Photo-Fenton ........................................... 24
3.3.5.2. Ozonation (O3) .................................................................... 28
3.3.5.2.1. UV/ O3 process ........................................................... 29
3.3.5.2.2. H2O2 / O3 process ..................................................... 30
3.3.5.2.3. UV/H3O2 / O3 process ............................................... 31
3.3.5.2.4. O3 /UV/Fe process....................................................... 32
3.4. Biological treatment.......................................................................... 33
3.4.1. Objective of biological treatment .............................................. 33
3.4.2. Role of microorganisms ...........................................………….. 33
3.4.3. Introduction to microbial metabolism ..................................…. 34
3.4.4. Bacterial growth .................................................................…… 34
3.4.5. Basic types of Bioreactors ............................................……… 38
Sequencing batch reactors ............................................………… 39
3.5. Combined AOP’s with Biological treatment…………………….. 41

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4. Studied compounds ....................................................................………..
45
4.1. Phenol (POH) .......................................................................………. 47
4.1.1. Source and utilization ..........................................................…. 47
4.1.2. Properties and Features ........................................................…. 48
4.1.3. Effects of phenol ..........................................................………... 49
4.2. Chlorophenols ..........................................................…................…. 49
4.2.1. Source and utilization ..........................................................….. 49
4.2.2. Toxicity ..........................................................…....................…. 50
4.2.3. Environmental considerations of chlorophenols ................…. 51
4.2.4. Chemical properties ..........................................................……. 51
4.3. 2,4-Dichlorophenol (DCP) ..........................................................… 52
4.3.1. Source and utilization ..........................................................….. 52
4.3.2. Physical properties ..........................................................……... 52
4.3.3.Uses ..........................................................…........................….... 52
4.4. Dyes ..........................................................…....................………….. 53
4.4.1. Utilization ..........................................................…….....…….. 53
4.4.2. Environmental considerations of dye pollution ...........……... 53

5. Objectives ............................................................….......…………….……
55

6. Equipment and reactant ..............................................................….……
61
6.1. Equipments .............................................................................…...… 62
6.2. Reactant .........................................................................................… 73
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6.3. Analytical Methods ................................................................….…. 75
6.3.1. Actinometry …………………………………………………… 77
6.3.2. pH …………………………………………………………...… 77
6.3.3. High Performance Liquid Chromatography (HPLC)………... 77
6.3.4. Determination the chemical oxygen demand (COD)………... 78
6.3.5. Determination the total organic carbon (TOC) ……….……... 79
6.3.6. Determination of the biological oxygen demand ………...…... 80
6.3.7. Determination of total suspended solids ………...………….… 82
6.3.8. Determination of total volatile suspended solids ………...…… 83
6.3.9. Inhibition test of activated sludge ……...…………...……… 84

Result and discussion

7. Treatment of DCP and POH by AOP´s based on UV-light …….…
87
7.1. Treatment of DCP and POH by direct UV- light ……….……..… 87
7.1.1. Photo-degradation ………...…………...…………...……….… 87
7.1.2. Influence in biodegradability ………...…………...…………... 89
7.1.3. Change on oxidation state ………...…………...……………… 90
7.2. Treatment of DCP and POH by UV/ H2 O2 ………...…………... 91
7.2.1. Photo- degradation ..………...…………...…………...……….. 91
7.2.2. Influence biodegradability ………...…………...………….…. 94
7.2.3 Change on oxidation state ………...…………...………….…… 95
7.3. Treatment of DCP and POH by UV/Fe(III) …...………….…... 96
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7.3.1. Photo-degradation ………...…………...…………...………… 96
7.3.2. Influence in biodegradability ………...…………...………….. 98
7.3.3 Change on oxidation state ………...…………...…………...…
99
7.4. Treatment of DCP and POH by Fenton’s and Fenton like
reagents………………………………………….…………………. 100
7.4.1. Degradation ………...…………...…………....…………...…... 100
7.4.2. Dechlorination ………...…………...……….…...………….…. 103
7.4.3. Influence in Biodegradability ………...…….……...…………. 104
7.4.4. Change on oxidation state ………...…………...…………...… 108
7.5. Treatment of DCP and POH by photo-Fenton ………...………. 110
7.5.1. Photo-degradation ………...…………...…………...………… 110
7.5.2. Dechlorination ………...…………...…………...………….…. 122
7.5.3 Influence in Biodegradability ………...…………...…………. 122
7.5.4. Change on oxidation sate ………...…………...…………...…. 129
7.5.5. Optimum conditions ………...…………...…………...……….. 132
7.5.6. High concentrated POH solutions ………...…………...…….. 133
7.6. Aerobic biological oxidation ………...…………...…………...…. 136
7.6.1. Aerobic biological oxidation of DCP ………...…………...…. 136
7.6.2. Aerobic biological oxidation of POH ………...…………...… 140
7.7. Mineralization ………...…………...…………...…………...…….. 146
7.8. Intermediates identification ………...…………...…………...….. 148
7.9. Comparison of the different studied processes ……….…………. 154

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8. Treatment of DCP by AOP´s based on UVA-light ……...………...
161
8.1. Treatment of DCP by UVA /H2 O2 and direct UVA-light……… 161
8.1.1. Photo-degradation ………...…………...…………...…………. 161
8.1.2. Quantum yield ……...…………...…………...…………...…… 163
8.1.3. Influence in biodegradability ………...…………...…………... 165
8.1.4. Change on oxidation state .………...…………...…………...… 166
8.2. Treatment of DCP by UVA/Fe(III) process ………...………….... 168
8.2.1. Photo-degradation ………...…………...…………...…………. 168
8.2.2.. Influence in biodegradability………...…………...…………... 170
8.2.3. Change on oxidation state ………...…………...…………...…. 171
8.3. Treatment of DCP by Photo-Fenton ………...…………...………. 173
8.3.1 Photo-degradation ………...…………...…………...………….. 173
8.3.2 Dechlorination ………...…………...………………………….. 181
8.3.3. Influence in biodegradability ………...…………...…………... 182
8.3.4. Change on oxidation state ………...…………...……………… 188
8.4. Mineralization ………...…………...…………...…………...……... 192
8.5. Intermediates identification………...…………...…………...….… 193
8.6. Comparison of the different studied processes ………...………... 195

9. Combined photo-Fenton with biological sequencing batch
reactors ……………...…………...…………...…………...……………….
201
9.1. Aerobic sequencing batch reactor ………...…………...………… 201
9.2. Anaerobic sequencing batch reactor………...…………...………. 210
9.3. Kinetic study ………...…………...…………………...………….... 216
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