application of advanced oxidation processes to wastewater treatment

213 Pages·2009·11.71 MB·English

S APPLICATION OF ADVANCED OXIDATION PROCESSES
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XI Dissertation presented for the
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APPLICATION OF ADVANCED OXIDATION PROCESSES TO
WASTEWATER TREATMENT

Dissertation presented for the
Doctor of Philosophy degree in Chemistry at the
University of Trás-os-Montes and Alto Douro by

MARCO PAULO GOMES DE SOUSA LUCAS

Supervisor: Prof. Dr. José Alcides Silvestre Peres

CQVR - Chemistry Centre of Vila Real
Chemistry Department
School of Life Sciences and Environment
University of Trás-os-Montes and Alto Douro
October 2009
Acknowledgements

ACKNOWLEDGEMENTS

I will try to express my gratitude to people who made this thesis possible and
enriched my life.
I am profoundly grateful to my research Supervisor, Prof. José Alcides Silvestre
Peres for his proficient guidance, for interesting scientific discussions we had, for the
preparation of scientific papers, support and encouraging attitude during the course of this
research work. From deep inside, thank you Professor Peres for your unconditional and
invaluable support and your always opportune and heartfelt help and friendship.
I want to thank to the Chemistry Department Directors Prof. Luís Carvalho and
Prof. Verónica Bermudez and also to the CQVR Director Prof. Pedro Tavares for their
great facilities.
My acknowledgment also to Prof. Albino Dias, Dra. Carla Amaral, Prof. Ana
Sampaio, Prof. Rui Bezerra and Prof. António Pirra (University of Trás-os-Montes and
Alto Douro - UTAD) for their technical guidance and support during the work developed.
I want to thank to the technicians of the UTAD laboratories were I have worked:
Mrs. Irene Fraga, Mrs. Augusta Fraga, Mr. Luís Fernando and Mr. Carlos Matos for their
friendship and valuable help.
During my Ph.D. work I performed laboratory work at the Plataforma Solar de
Almería (PSA), Spain, under the supervision of Dr. Manuel Ignacio Maldonado and Dr.
Sixto Malato to whom I am very grateful for receiving me in their laboratories, for the
interesting scientific discussions and technical guidance during my stay and for the
preparation of scientific papers. I also would like to offer my sincere thanks and my special
recognition to all friends that I have made along my stay in Almería. They are: Elena
Guillen, Nikolaus Klamerth, Carla Sirtori, Theodora Velegraki, Ana Zapata, Elli, Agustin,
Rosa Mosteo and Gemma Raluy. Also a special thanks to Vitor Vilar for his friendship and
help during our stay in Almería… and for the delicious Paella… and also for the not so
delicious but necessary pasta with tuna!!!
In my stay in the United Kingdom, at the University of Nottingham, Department of
Chemical and Environmental Engineering, I was supervised by Prof. Gianluca Li Puma to
who I am very grateful for receiving me, for the scientific discussions and for the
preparation of scientific papers. I also would like to offer my thanks and my recognition to
Acknowledgements

all friends that I made in Nottingham: Yan, Steve Bouzalakos, Marco Kostadinov, Aimaro,
Ana Luisa, Bin Gao, Mark, Richelieu Barranco, Maria Mediero and special thanks to
Silvana Araújo who hosted me at her home in Nottingham.
I would like to thank to all the members of the Jury for accepting being examiners
of this work.
I want to thank to my family, first of all to my wife Carmen. I am immensely
grateful to who has always supported me and has believed in me. Her love, patience, help,
and understanding during the past few years have been determinant for the good
development of my work and for everything we have shared, my deepest gratitude.
Although my son has not born yet, I would like to thank to Dinis for giving quiet nights to
his mommy and to me… until now!
To my parents António Lucas and Cecília Gomes, and my brother Nuno, who have
supported me and have been willing to make considerable sacrifices for giving to me all
the possible advantages in my life. I thank them for their affection and love.
To my parents-in-law José Carneiro and Amélia Carneiro for there availability and
support along this period. Also to my brothers-in-law José Luís and Goretti for their
friendship and especially to my nephews Carolina and Francisco who are a source of
happiness and peace each time that I am with them.
My thanks to João Azevedo and his wife Isabel Guedes for their notable friendship
and valuable help whenever needed.
Also thanks to my special “Confratis” friends for their invaluable and resistant
friendship: Telmo, Francisco, Fernando and Pica which make our encounters an
opportunity to share the joys and blues of life as well as transforming our dinners in very
interesting, remarkable occasions and a place to “recharge the batteries”. Thanks to all of
them for the opportunities in celebrating life.
Finally, I would like to thank the financial support of “Fundação para a Ciência e a
Tecnologia” (FCT) and “Águas de Trás-os-Montes e Alto Douro” (with special emphasis
to Dr. Alexandre Chaves) for the grant SFRH/BDE/15576/2005, for making this thesis
possible through the financing of my scholarship.

My deepest gratitude to them all!
Preface

PREFACE

This Ph.D. thesis structure results from different papers published and/or submitted
for publication in international journals, during the work carried out mainly at CQVR
(Centro de Química de Vila Real) in the Chemistry Department, School of Life Sciences
and Environment, University of Trás-os-Montes and Alto Douro (UTAD), throughout the
period between May 2006 and September 2009.
The main goal of this dissertation was trying to understand the application of
several Advanced Oxidation Processes (AOPs) and determine the main operational factors
that control the decomposition of the organic content present in textile and winery
wastewaters. These types of wastewaters were selected as the study target objects for two
main reasons: first, because they are an important environmental problem in the North of
Portugal. The textile industry biggest factories can be found spreading throughout Porto
and Braga districts, especially in the Ave hydrographic basin. Second, since we would like
work with a synthetic wastewater (textile effluents) and a wastewater generated by an
agricultural process characterised by the presence of natural organic matter (winery
effluents). Therefore, in the experiments where there were simulated textile wastewater
was used a model compound, a synthetic azo dye named Reactive Black 5 (RB5). Winery
wastewater experiments were performed with authentic effluent provided by some local
cellars and at other times by the dilution of wine and grape juice.
To achieve this knowledge can be a remarkable contribution in increasing the
efficiency of AOPs treatment processes when applied to textile and winery wastewaters, as
well as to acquire a more detailed understanding of the main advantages and drawbacks of
each technology.
The dissertation is organized in 9 chapters. Chapter 1 considers a general
introduction and review of the state-of-the-art focused in the textile and winery
wastewaters, and also in the treatment technologies that will be tested in this thesis -
advanced oxidation processes (Fenton’s reagent, photo-Fenton, photo-ferrioxalate,
heterogeneous photocatalysis (TiO ), ozone, ozone/UV and ozone/UV/H O ) to the above
2 2 2
mentioned wastewaters.
In chapter 2 starts the study related to textile wastewaters. It is shown the treatment
of a model textile compound, the azo dye Reactive Black 5, with Fenton/UV-C and
Preface

ferrioxalate/H O /solar light processes. Here the main objective was analysing the
2 2
feasibility of decolourization and mineralization of RB5 by the cited AOPs. The influences
of different operational parameters (source and intensity of light, pH, hydrogen peroxide,
ferrous iron and RB5 concentration) and the reaction kinetics of each process is also
studied. An important issue to take into account within this study is to evaluate the
treatment capacity of the ferrioxalate/H O /solar light process once the utilization of solar
2 2
light as a UV source clearly reduces the environmental and economical impact of the
treatment process.
The combination of an AOP with an aerobic biological process is studied in
chapter 3. In this study the Fenton’s reagent capacity to treat high concentrated RB5
solutions by itself is first tested and then selected the optimal ferrous iron and hydrogen
peroxide dosages. Afterwards the treatment capacity of the Candida oleophila yeast with
the same RB5 concentrations studied in the Fenton’s reagent experiments is evaluated.
Finally, the experimental work regarding the textile wastewater is concluded through the
combination of Fenton’s reagent and Candida oleophila. As additional information it is
important highlight that the application of the Candida oleophila yeast to wastewaters with
high phenolic content is protected by a Portuguese national patent (Lucas M.S., Peres J.A.,
Amaral C., Sampaio A., Dias A.A. Processo biológico aeróbio de tratamento de efluentes
agro-industriais com elevado teor em compostos aromáticos baseado na aplicação de
microrganismos da espécie Candida oleophila. Portuguese Patent nº 103 738 assigned at
13th August 2009.
In chapter 4, starts the application of advanced oxidation processes to the treatment
of winery wastewaters. In this chapter the performance of several AOPs is evaluated,
specifically the Fenton’s reagent, ferrioxalate and heterogeneous photocatalysis (TiO )
2
processes combined with different UV radiation sources, in the degradation of one of the
most representative phenolic compounds present in the winery wastewaters: the gallic acid.
From this AOPs screening we tried to select the optimal process to further application to
winery wastewaters. A toxicological assessment will be carried out with the marine
bacteria Vibrio fischeri to evaluate the influence of each AOP studied in the gallic acid
detoxification.
Chapter 5 presents the work done during a research stay performed in the
Plataforma Solar de Almería (Spain) during the Ph.D. scholarship. Despite in chapter 4 the
AOP selected as best treatment option was photo-Fenton with the UV TNN 15/32 lamp, an
Preface

attempt was made to test the application of the photo-Fenton process but using solar light
as UV radiation source in a Compound Parabolic Collector (CPC) pilot-solar plant to
winery wastewaters treatment. This study was done trying to meet the optimal conditions
in the use of solar light in the wastewater treatment once it is applied in a CPC reactor.
This work makes possible to evaluate the performance of solar photochemical AOPs, such
as heterogeneous photocatalysis (with TiO , TiO /H O and TiO /S O 2-) and
2 2 2 2 2 2 8
homogeneous photocatalysis like photo-Fenton.
Chapters 6 and 7 are addressed to the use of ozone and ozone-related processes to
the treatment of winery wastewaters. This work was carried during a research stay at the
Department of Chemical and Environmental Engineering, University of Nottingham,
United Kingdom. In chapter 6 the kinetics of ozonation of winery wastewater is studied in
detail in a pilot-scale, semi-batch bubble column reactor. The performance of both
processes was compared, as well as the effect of the most relevant operating conditions.
The study investigates the relationship between pH, ORP, COD, UV absorbance (254 nm),
total polyphenol content and ozone consumption as a function of time and the prevalent
kinetic conditions (fast, intermediate and slow kinetic regime) for the reaction of ozone
with the dissolved organic species. Furthermore, a kinetic ozonation model is presented
and used to estimate the kinetic coefficients of the ozonation of winery wastewater under
the prevailing experimental conditions. In chapter 7 the effectiveness of different ozone-
based AOP (O , O /UV and O /UV/H O ) on the treatment of winery wastewater, in a
3 3 3 2 2
pilot-plant scale reactor is researched. The effect of initial pH, organic load of winery
wastewater and hydrogen peroxide concentration is investigated in the same pilot scale
reactor.
Chapter 8 presents a combined treatment: long term aerated storage and Fenton’s
reagent, to winery wastewaters. The main goal is to evaluate the capacity of treating
winery wastewater in a long term biologic aerated storage, with different aeration schemes,
combined with Fenton’s reagent. This chemical oxidation process, that uses low-priced
reactants, was used as a secondary chemical treatment step for the oxidation of the
recalcitrant organic compounds or metabolites that could not be oxidized biologically.
Finally, in chapter 9, the main conclusions are summarized and future research
developments are proposed.
CONTENTS

Abstract xv
Resumo xix
Nomenclature xxiii
Figure Caption xxvii
Table Captions xxxv

1. INTRODUCTION 1

1.1. The water resource 1
1.2. Textile industry 2
1.2.1. Dyes 4
1.2.2. Dyes and the environment 6
1.2.3. Textile wastewater treatment processes 7
1.3. Winery wastewater 10
1.3.1. Production process and sources of wastes 11
1.3.2. Winery wastewater treatment processes 14
1.4. Advanced oxidation processes 17
1.4.1. Fenton’s reagent 19
1.4.2. Photo-Fenton system 20
1.4.3. Photo-ferrioxalate 22
1.4.4. Heterogeneous photocatalysis 23
1.4.5. Ozonation 25
1.4.6. Ozone/UV 27
1.4.7. Ozone/UV/H O 28
2 2
REFERENCES 29

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2. DEGRADATION OF REACTIVE BLACK 5 BY FENTON/UV-C AND
FERRIOXALATE/H2O2/SOLAR LIGHT PROCESSES 39

ABSTRACT 39
2.1. Introduction 40
2.2. Experimental 42
2.2.1. Material 42
2.2.2. Photoreactor 42
2.2.3. Analysis 43
2.3. Results and Discussion 44
2.3.1. Photochemical decolorization of Reactive Black 5 44
2.3.2. Kinetic analysis of ferrioxalate processes 47
2.3.3. Effect of pH 48
2.3.4. Effect of H O dosage 49
2 2
2.3.5. Effect of iron dosage 51
2.3.6. Effect of dye concentration 53
2.3.7. Effect of solar light intensity 55
2.3.8. Mineralization study 55
2.4. Conclusions 57
REFERENCES 57

3. DEGRADATION OF A TEXTILE REACTIVE AZO DYE BY A COMBINED
CHEMICAL-BIOLOGICAL PROCESS: FENTON’S REAGENT-YEAST 61

ABSTRACT 61
3.1. Introduction 62
3.2. Experimental 63
3.2.1. Reagents and microbiological media 63
3.2.2. Fenton’s reagent experiments 64
3.2.3. Yeast (Candida oleophila) experiments 64
x
3.2.4. Other analytical procedures 65
3.3. Results and discussion 65
3.3.1. Reactive Black 5 decolorization with Fenton’s reagent 65
3.3.2. Reactive Black 5 decolorization with Candida oleophila 66
3.3.3. Kinetic analysis 67
3.3.4. Fenton’s reagent process 67
3.3.5. Candida oleophila process 68
3.3.6. Optimization of Reactive Black 5 decolorization by Fenton’s reagent 69
3.3.7. Combining Fenton’s reagent and Candida oleophila on RB5
decolorization 70
3.4. Conclusions 72
REFERENCES 72

4. GALLIC ACID PHOTOCHEMICAL OXIDATION AS A MODEL COMPOUND OF WINERY
WASTEWATER 75

ABSTRACT 75
4.1. Introduction 78
4.2. Materials and methods 78
4.2.1. Chemicals 78
4.2.2. Experiments and analysis 78
4.2.3. TiO characterization 80
2
4.3. Results and discussion 80
4.3.1. Gallic acid photoxidation 80
4.3.2. Influence of H O on gallic acid photoxidation 82
2 2
4.3.3. Influence of Fenton’s processes on gallic acid photoxidation 85
4.3.4. Influence of TiO on gallic acid photoxidation 87
2
4.3.5. Toxicity assessment 89
4.4. Conclusions 91
REFERENCES 91
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