Renewable Energies series

Solar detoxification

Edited by
Julián Blanco Gálvez
Sixto Malato Rodríguez
In the SAME series:

Geothermal energy
Solar photovoltaic project development
Solar photovoltaic systems: technical training manual

The designations employed and the presentation of material throughout

this publication do not imply the expression of any opinion whatsoever
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Organization.

Published in 2003 by the United Nations Educational,

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Typeset by S R Nova Pvt. Ltd., Bangalore,
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ISBN 92-3-103916-4
© UNESCO 2003
All rights reserved
Printed in FRANCE

Everyone is aware of the strong capacity of sunlight to
degrade all kinds of objects. It is also well known that, to
prevent degradation and deterioration, objects should be
sheltered from sunlight or light irradiation in general.
This characteris- tic of sunlight is based on the property
of solar photons to directly degrade and break down
organic molecules, an effect that it is known as
‘photolysis’.
In the 1970s, it was discovered that this effect could be
sub- stantially enhanced with the help of a catalyst,
opening up the field of solar photocatalysis. But it was not
until the mid-1980s (coinciding with a growing
environmental consciousness across the world) that this
process was given environmental application, and its use
in the treatment and degradation of hazardous substances
in water, air and soil began to be appre- ciated as a very
attractive proposition. Of these three potential applications
(water, air and soil), the treatment of water con- taminants
using sunlight is considered of special relevance because
of the magnitude of water-contamination problems and
its potential for worldwide application.
Solar photocatalytic degradation of water
contaminants (a process also known as ‘solar detoxification’)
is an outstand- ing example of how well solar applications
and environmen- tal problems fit together. This remarkable
application is currently the focus of many research
institutions, and since 1990 it has also been the main
research and development object of the Solar Chemistry
group at Plataforma Solar de Almería (PSA, the largest
European facility for solar energy applications) and the
solar centre of CIEMAT, a public insti- tution in Spain
devoted to research and technological devel- opment in the
areas of energy and the environment.
The Solar Chemistry group at PSA have been
participating in the chemical application of water solar
detoxification since
Preface
1990, in particular in projects researching photocatalytic
decontamination of used water at both national and
interna- tional levels. The experience they acquired with
solar detoxifi- cation systems at the engineering level led
to the development and the installation at PSA of
Europe’s largest solar detoxi- fication facility at pilot-
plant scale, and this has been suc- cessfully used by
many European research institutions. The authors hope
that this book will illustrate the cross-linked synergistic
relationships that have been developed among different
European research groups involved in the PSA
photocatalysis research program over the last twelve years.
This book summarizes most of the scientific and
techno- logical research performed at PSA in this area
since 1990, through close collaboration with many
scientific colleagues from a large number of universities,
research institutions and private companies and through
many collaborative efforts, networking activities and
joint projects.
The book is divided into two parts of five chapters
each. Part A addresses the theory and fundamentals
of water decontamination by means of solar energy. The
objective of this part is to provide the reader with a
background in readi- ness for Part B, which addresses
the practical applications and systems engineering of
the process. Our main motiva- tion in writing this book
was to collect, in a comprehensive and extensive way,
all the work performed at PSA and make it accessible not
only to people interested in solar and photo- catalytic
applications, but also to all those who are interested in
learning how environmental technology could help
to solve environmental problems in general.
Julián Blanco Gálvez
Sixto Malato Rodríguez

Our deep gratitude is owed to our colleagues Dr Manuel
Romero, Dr Benigno Sánchez, Dr Ana Isabel Cardona
and Alfonso Vidal from our mother institution CIEMAT,
and to Dr Christoph Richter (DLR-PSA), who has been
deeply involved in most of our projects. This gratitude
is also extended to all CIEMAT-PSA staff for their great
helpfulness and high skill, which made possible the
design, construction and operation of the photocatalysis
pilot plants that have been the bases of the success of all
the projects we have been involved with. The
management and execution of these projects is directly
related to the knowledge we have gathered from them,
most of it included in this book. We would also like to
give special recognition to Juan Antonio Camacho, Ginés
García, Jose Manuel Molina, Jaime Aranda, Bernabé
Calatrava and Angel Soler, together with the Operation
and Maintenance team of the PSA.
We are grateful to the directors of the Plataforma
Solar de Almería and Centro de Investigaciones
Energéticas, Medioambientales y Tecnológicas
(CIEMAT) for the support they gave us in producing this
book.
In addition, this book would not have been possible
with- out the help, contributions and assistance of
many people around the world who either provided
text and graphic material, reviewed the manuscript
or simply provided valuable suggestions.
For these reasons, we want to acknowledge the
contribu- tions of Professor Jaime Giménez and Dr
David Curcó (University of Barcelona), Professor
Xavier Domènech and Dr José Peral (University
Autónoma de Barcelona), Dr Daniel Blake and Alan
Lewandoswky (NREL, United States),
Acknowledgements
Mike Prairie and Jim Pacheco (Sandia National Labs,
United States), Dr Detleft Bahneman and Dr Roland
Goslich (ISFH, Germany), Professor Ezzio Pelizzetti and
Professor Claudio Minero (University of Torino, Italy),
Professor Jean-Marie Herrmann (CNRS, France), Dr
César Pulgarín (Ecole Politechnique Federale de
Lausanne, Switzerland), Dr Manuel Collares-Pereira and
Joao Farinha Mendes (INETI, Portugal), Dr Karl-Heinz
Funken and Dr Christian Sattler (DLR, Germany),
Professor Marc Anderson (University of Wisconsin–
Madison, United States), Dr Yogi Goswami (Solar
Energy and Energy Conversion Laboratory, University of
Florida, United States), Professor Leonardo Palmisano
(University of Palermo, Italy), Dr Charles Giannotti
(CNRS, France), Dr Mirella Musci and Maria Cristina
Casalle (CESI, Italy), Professor Rupert Bauer (Technical
University of Vienna, Austria) and Professor Octav Enea
(University of Poitiers, France).
Our acknowledgement and gratitude are also due to
Martin Vincent (Ecosystem S.A., Spain), Joao Oliveira
(Ao Sol, Portugal), Alex Ryer (International Light,
Inc.), Dr Dieter Doënitz (Schott-Rohrglas GmbH,
Germany) and Dr V.H. Kuester (ALANOD Aluminium –
Veredlung GmbH and Co, Germany).
For reasons of space we cannot mention all the
people who have made a contribution to the content of
this book but, finally, we cannot forget the crucial help
of Carmen Montesinos and Deborah Fuldauer, who
devoted many long hours to the revision and
correction of the various manuscripts.
To our families, for their patience and moral support.
 Contents

List of Figures xii The solar spectrum 19

1
List of Tables xvii Solar ultraviolet irradiation 21
Notes on the Editors xix Atmospheric attenuation of solar radiation 22
ANNUAL AVAILABLE ULTRAVIOLET RADIATION 24
1. Introduction Solar radiation measurement 24
Detectors 25
Aims and objectives 1 Filters 26
Input optics 26
Solar chemistry 2
Water contaminants 3 Summary 28
Photodegradation principles 6 Bibliography 28
Definitions 6 Self-assessment questions 29

3
Heterogeneous PHOTOCATALYSIS 6
Homogeneous PHOTODEGRADATION 7
Application to water treatment 9 Experimental Systems
Gas-phase detoxification 10

Summary 13 Aims and objectives 31

2
Bibliography 14
Self-assessment questions 15 Laboratory systems 32
Solar detoxification pilot plants 34
Operation of pilot plants 36
2. Solar Irradiation Once-through OPERATION 36
BATCH OPERATION 37
Aims and objectives 17 Modelling once-through AND BATCH OPERATION 37
Evaluation of solar UV radiation inside
photoreactors 39
The power of light 18
CALIBRATION of RADIOMETERS 39
ULTRAVIOLET light 18 CORRELATION between RADIOMETRIC AND SPECTRORADIOMETRIC
Visible light 19 DATA 40
INFRARED light 19
3.
x Contents

Collector efficiency 41 Composite semiconductors 73

Actinometric experiments 42 SURFACE SENSITIZATION 73
Simplified method for the evaluation of solar UV Recommended analytical methods 73
radiation inside photoreactors 43 ORIGINAL CONTAMINANTS 73
MINERALIZATION MEASUREMENTS (TOC) 73
Summary 44 ANALYSIS of INTERMEDIATES 74
Bibliography 44 EXTRACTION methods 76

4
Self-assessment questions 46 Toxicity ANALYSIS 76

6
Summary 77
4. Fundamental Parameters Bibliography 77
in Photocatalysis Self-assessment questions 78

Aims and objectives 49

6. Solar Detoxification
Direct photolysis 50 Technology
Influence of oxygen 51
pH influence 51
Aims and objectives 81
Influence of catalyst concentration 52
Initial contaminant concentration influence 54 Solar collector technology generalities 82
Radiant flux influence 56 Collectors for solar water detoxification: features 85
Temperature effect 57 Specific FEATURES of SOLAR UV light UTILIZATION 85
Quantum yield 57 PARABOLIC trough collectors 86
One-sun (NON-CONCENTRATING) collectors 87
Summary 59 Compound PARABOLIC CONCENTRATOR (CPC) 89

5
Bibliography 59 HOLOGRAPHIC collectors 91
Self-assessment questions 60 Concentrated versus non-concentrated sunlight 91
Technical issues 93
Reflective SURFACES 93
PHOTOCATALYTIC REACTOR 95
5. Water Decontamination
Catalyst issues 98
by Solar Detoxification
Slurry versus supported CATALYST 98
CATALYST RECUPERATION AND reuse 99
Aims and objectives 63
Summary 100

7
Detoxification of pollutants 64 Bibliography 101
TOTAL MINERALIZATION 65 Self-assessment questions 102
DEGRADATION PATHWAYS 67
Toxicity reduction 68
DETOXIFICATION of INORGANIC POLLUTANTS 69
Quantum yield improvement through 7. Solar Detoxification
additional Applications
oxidants 69
Hydrogen peroxide 70 Aim and objectives 105
PERSULFATE 71
Other OXIDANTS 71 Introduction 106
Catalyst modification 71 Industrial wastewater treatment 108
METAL semiconductor MODIFICATION 72
 9
Contents xi

Phenols 108 9. Project Engineering

AGROCHEMICAL compounds 109
HALOGENATED HYDROCARBONS 110 Aims and objectives 151
Antibiotics, ANTINEOPLASTICS AND other
PHARMACEUTICAL biocide compounds 111 Feasibility study 152
Wood PRESERVATIVE WASTE 111 IDENTIFICATION of TARGET RECALCITRANT
REMOVAL of HAZARDOUS METAL ions from WATER 112 HAZARDOUS compounds 153
Other APPLICATIONS 112 IDENTIFICATION of possible PRE-TREATMENTS 153
Seaport tank terminals IDENTIFICATION of most SUITABLE PHOTOCATALYTIC process 154
113 DETERMINATION of the optimum process PARAMETERS 154
Groundwater decontamination POST-TREATMENT process IDENTIFICATION 155
114 Contaminated landfill DETERMINATION of TREATMENT FACTORS 155
cleaning 115 Water disinfection Feasibility study example 156
116 BACKGROUND 156
Gas-phase treatments 117 EXPERIMENTATION: TiO2-PERSULFATE tests 157
Photo-Fenton tests 158

8
Summary 121 Conclusions AND TREATMENT FACTORS 159
Bibliography 121 Preliminary design 160
Self-assessment questions 123 Preliminary design example 161
Final design and project implementation 163
Example of final design and project
implementation 165
8. Economic Assessment

10
Summary 171
Aims and objectives 125 Bibliography 171
Self-assessment questions 172
Photochemical and biological

reactors 10. International

Collaboration
coupling 127
Cost calculations 129
EXAMPLE A: TiO2-BASED SOLAR DETOXIFICATION Aims and objectives 175
PLANT 131
EXAMPLE B: Photo-Fenton BASED SOLAR DETOXIFICATION International Energy
PLANT 131
Solar or electric photons? 133 Agency:
Solar resources assessment the SolarPACES programme 176
139 The European Union 178
Comparison with other technologies 142 The CYTED programme 180
THERMAL OXIDATION 142 Main research activities 181
CATALYTIC OXIDATION 142 United STATES 181
Air stripping 143 SPAIN 182
Recommendations for successful water
Adsorption 143 treatment projects in developing countries
MEMBRANE technology 144 183
Wet OXIDATION 145
Ozone OXIDATION 145 Summary 184
ADVANCED OXIDATION processes 145 Bibliography 184
Self-assessment questions 186
Summary 146
Bibliography 146
Self-assessment questions 148
List of Figures

1.1 Schematic view of solar chemical applications 3 2.7 Normalized solar UV spectra shown
1.2 Furfural photo-oxidation and in Figure 2.6 24
pentachlorophenol mineralization 2.8 TBDUV at different periods of the year at
(photochemical processes) 3 Plataforma Solar de Almería (37 °N) 24
1.3 Behaviour of electrons and holes within a 2.9 Responsivities of three detectors. In the inset
particle of illuminated semiconductor in is shown a schematic of the effect of a filter
contact with an electrolyte 7 on detector responsivity 26
1.4 UV spectra of acrinathrin and of sunlight 2.10 Relative spatial response of an ideal cosine
between 200 and 400 nm 9 diffuser (up) and a radiance lens barrel (down)
1.5 Effect of UV radiation on a TiO2 particle 27
dispersed in water 9 2.11 A solar global UV detector (tilted 37° and facing
1.6 Diagram of an experimental system with south) with a cosine diffuser 27
a cross-section view of a gas-phase 2.12 A solar direct UV detector installed on a
monolithic photoreactor 11 solar tracking system 27
1.7 Schematics and photo of a tubular gas-
phase photoreactor 12 3.1 Typical stirred-tank laboratory reactor 33
1.8 Diagram of the experimental system
3.2 Typical recirculating laboratory system 34
and photo of a tubular gas-phase
photoreactor (dismounted) 13 3.3 a) Photocatalytic detoxification pilot-plant scheme.
b) CPCs at Plataforma Solar de Almería.
2.1 The optical portion of the electromagnetic c) Double-skin sheet collector at Plataforma Solar
spectrum a), and a light wave front modelled de Almería. d) Two types of non-concentrating
as a straight line b) 19 solar collectors at the solar detoxification test
2.2 Visible-light colour distribution 19 stand at the University of Florida 35
2.3 a 3.4 Schematic of two pilot plant operation concepts:
World solar irradiance, MWh m–2 year–1 20 a once-through operation and a batch operation 37
2.3b Spectral solar radiation plotted from 0.2 3.5 Procedure used to calculate the photon flux
to 4.5 µm 20 inside a solar reactor 40
2.4 Air mass and solar components 21 3.6 A diagram of the various loss factors affecting
2.5 Ultraviolet spectra at the Earth’s the photon flux inside a photoreactor
surface (standard ASTM) 22 42
2.6 Solar spectra at the Earth’s surface 3.7 Typical photocatalytic degradation (rDCA)
between 300 and 1,100 nm 23 in a solar pilot plant under different UV
solar light intensities 44

3.8 Photocatalytic degradation in a solar pilot plant.
Concentration is plotted as a function of
experiment time (top) and accumulated energy
(bottom).
Solar UV power throughout the experiment is
also shown 44
4.1 Effect of the concentration of dissolved oxygen
on photocatalytic mineralization. [O2]0 = 8.5 mg
L–1. In the inset, the usual effect of partial
pressure of oxygen on the photocatalytic reaction
rate is
shown 51
4.2 Mean particle size of TiO 2 (P-25) suspended in
water versus pH [TiO2] = 0.2 g/L 52
4.3 Different laboratory photoreactor designs and
zones of radiation penetration when illuminated
in different ways 53
4.4 Influence of catalyst concentration on the
rate of photocatalysis (normalized rates
have been
used to make it more easily understood) in
different reactors. In the inset, relative reaction
rates of degradation (two different photoreactors)
and mineralization (TOC) of the same
contaminant
are shown 53
4.5 Typical photocatalytic degradation. The insert
shows data adjusted to Equation 4.6 55
4.6 Graphics related to the adjustment of data
to an L–H type kinetic model 55
4.7 Initial degradation rate as function of the initial
substrate concentration. The insert shows the
linear transformation of Equation 4.4, from
which the rate constant and the adsorption
coefficient can be estimated from the intercept
and the slope, respectively 56
4.8 The relation between the photocatalytic
reaction rate and the intensity of the
radiation received 57
4.9 Plots of normalized concentration as a function
of accumulated energy for the
photodegradation and mineralization of
phenol. C0 = 20 mg/L,
TiO2 = 200 mg/L, pH0 = 5 59
5.1 General processes for the photo-oxidative or
photo-reduction degradation of organic
compounds in aqueous solution sensitized by
semiconductor particles. Examples of photo-
oxidation (PCP) and photoreduction (CCl4) are
shown 65
List of Figures xiii
5.2 HPLC-UV chromatograms of
photodegradation of oxamyl before
photocatalytic treatment a) and when the
oxamyl has completely disappeared b) 66
5.3 Evolution of H+ and Cl– during pentachlorophenol
degradation. To more clearly demonstrate that
reaction 5.4 is completed, the concentration of
TOC in mM is calculated assuming 1 mMol TOC
=
6 mMol of C = 72 mg of C 67
5.4 Chemical structures of pyrimethanil and
its degradation products obtained during
a photocatalytic treatment with TiO2
68
5.5 Electron capture by a metal in contact
with a semiconductor surface 72
5.6 Concentrating solar reactor with a
platinum/titanium dioxide catalyst on ceramic
saddles. Tested on air contaminated by spray
paint at Fort Carson Army Base in Colorado,
USA 72
5.7 The excitation process in a
semiconductor- semiconductor
photocatalyst 73
5.8 Steps of excitation with a sensitizer in
the presence of an adsorbed organic
electron acceptor 73
5.9 Degradation pathway proposed for
pirimiphos-methyl dissolved in water
when illuminated in the presence of TiO2
75
6.1 Non-concentrating solar collectors for
domestic water-heating applications 83
6.2 Medium concentrating solar collector:
recirculating parabolic trough reactor for water
purification using titanium dioxide slurry at
NREL 83
6.3 A high-concentration solar collector: a fixed-
focus solar reactor 83
6.4 Yearly efficiency of solar collectors in an
ideal cloudless year: a PTC-one axis with
different orientations 84
6.5 Yearly efficiency of solar collectors in ideal
cloudless year: flat plate with different
inclinations 84
6.6 The first engineering-scale outdoor solar
detoxification reactor using a one-axis parabolic
trough collector. Part of the 465 m 2 parabolic
trough system at Sandia National Laboratory 85
6.7 A CIEMAT 384 m2 solar detoxification facility
using two-axis parabolic trough collectors, at
Plataforma Solar de Almería 86
xiv List of Figures
6.8 Solar ray reflection on a one-axis parabolic
trough collector 87
6.9 Experimental set-up of a thin-film fixed-bed
reactor tested by ISFH at PSA installations. The
housing is made of Plexiglas and the catalyst is
fixed on a flat glass plate 88
6.10 One-sun water treatment reactors with PTFE
tubes at NREL: early reactor a) and reactor
with titanium dioxide immobilized on
fibreglass bundles b) 88
6.11 Solar reflection on a CPC collector 89
6.12 Obtention of CPC involute 90
6.13 View of CPC shape a) and CPC
photoreactor array b) 90
6.14 Holographic concentration of solar light 91
6.15 Solar detoxification pilot plant in Cologne 92
6.16 Flux distribution on an absorber in the course of
the solar day (6:00 to 18:00). Simulation of CPC
behaviour with the following data: collector
orientation east–west; semi-acceptance angle 60°;
truncation angle 80°; absorber radius 13.6 mm;
optical gap 2 mm; concentration ratio 1.17 92
6.17 Specular, diffuse and spread reflection
from a surface 93
6.18 Reflectivity of fresh metal coatings for mirrors 94
6.19 Reflectivity of different aluminium and plastic
film surfaces 95
6.20 Transmittance of different materials suitable for
the manufacture of photoreactor tubes 96
6.21 Glass-tube manufacture. Different compositions
mean that the glass can be used for a wide variety
of applications 97
6.22 Influence of iron on borosilicate glass light
transmission (oxidative conditions).
Samples: flat glass 3-mm in thickness
97
6.23 Zone of tubular reactor where light penetrates if
the catalyst concentration is 1 g L–1 (TiO2
heterogeneous photocatalysis) 98
6.24 a) Experimental concentrating solar
reactor using titanium dioxide
immobilized on glass wool for treating
contaminated air streams.
b) Parabolic trough reactor for water
purification with immobilized
titanium dioxide 99
6.25 Sedimentation experiments at different pH.
[TiO2] = 0,2 g /L; [NaCl] = 0 M. The Y axis
shows
the absorbance of the solution at 800 nm;
no absorbance means absence of TiO2 100
7.1 Complete mineralization of a complex mixture
of organic contaminants containing phenols
using TiO2 (200 mg/L) and persulfate as an
electron scavenger 108
7.2 Formation of phenolic resins 109
7.3 Reactor condensation wastewater from
the manufacture of phenolic resins
109
7.4 Photocatalytic degradation of
dichloromethane, chloroform,
trichloroethylene and tetrachloroethylene
using a titania catalyst manufactured by
ENEL (Italy) 110
7.5 Degradation of PCP at a PSA solar
detoxification facility (Helioman’s collectors’
loop) 112
7.6 Cr+6 to Cr+3 solar photocatalytic reduction at a
PSA solar detoxification facility (CPC’s collectors’
loop). See also Figure 7.7 112
7.7 Simultaneous oxidation of phenol and
reduction of Cr+6 to Cr+3 using solar
detoxification technology 113
7.8 Degradation of metham sodium wastewater
from a tank-cleaning process. Catalyst
deactivation is observed after partial
degradation of the initial TOC content 114
7.9 Generic concept of contaminated
groundwater treatment 114
7.10 Partial view of the 156 m 2 parabolic-trough
water treatment system tested on
contaminated groundwater at a site at LLNL
(United States) in 1992 115
7.11 One-sun reactor built by American Energy
Technology, Inc. for treating contaminated
groundwater in Florida (United States) in 1992 115
7.12 Non-concentrating solar detoxification
system for BTEX-contaminated
groundwater at a commercial site in
Gainesville, Florida (United States), 1996
116
7.13 Simulation of contaminated landfill treatment
using solar detoxification: mineralization of
lindane 117
7.14 Common ultraviolet band designations based
on biological effects 117
7.15 Scheme of TCE gas-phase mineralization
with PCO and a monolithic catalyst based
on sepiolite/TiO2/Pt 118

7.16 Destruction efficiencies of 400 ppm of TCE 9.1
using a MgSiO4/TiO2/Pt monolithic catalyst:
thermocatalytic and photocatalytic processes at 9.2
different temperatures 118
7.17 Flat-plate reactor for treating contaminated air
exiting from air-stripping units at McClelland 9.3
Air Force Base, California, 1997 120
7.18 Self-cleaning windows. Evolution of 9.4
photocatalytic treatment processes on glasses
coated with titanium dioxide 121 9.5
8.1 Conceptual scheme of photocatalytic +
biological technologies coupling 127
8.2 Elimination of tensioactive compounds
from agrochemical industrial wastewater
after a few minutes of photocatalytic
treatment 128
8.3 Photodegradation process: usual relationship
between the average oxidation state and time.
Points A and B are also related to Figure 8.4 129
8.4 Photodegradation process: normal relationships 9.6
between toxicity and time. Points A and B are
also related with Figure 8.3 129
8.5 Ultraviolet spectra: solar (standard and PSA
measured spectrum) and two low-pressure 40
W mercury lamps (QUV fluorescent lamps:
UVB-313 and UVA-340) 134
8.6 Comparative cost of UV photon 9.7
collection/generation with solar technology
(CPCs) and electric lamps (electricity cost =
€0.15/kWh), respectively. Data from tables 8.6 to 9.8
8.11. (Costs are indicated in
euros, 1999) 139
8.7 Comparative cost of UV photon
collection/generation with solar technology 9.9
(CPCs) and electric lamps (electricity cost =
€0.05/kWh), respectively. Data from tables 8.6 to
8.11. (Costs are indicated in
euros, 1999) 139 9.10
8.8 Average direct and global UV irradiance (sunrise
to sunset) at PSA (Almería, Spain).
Meteorological data records from 1991 to 1995
139
8.9 Average ‘cloud factor’ for global UV irradiance
(sunrise to sunset) at PSA (Almería, Spain). 9.11
Meteorological data records from 1991 to 1995 140
8.10 Technology fit map: range of application of
different water treatment technologies 142 9.12
8.11 Optimization of solar detoxification and
GAC technologies to PCP degradation 9.13
146
9.14
List of Figures xv
Experimental mobile pilot plant for solar
water detoxification 153
Treating wastewater from the painting section at a
car assembly factory (ultrafiltration from
cataphoresis process) 154
Catalyst mixing system for the LLNL water
treatment system 155
Tonnes of pesticides used in the Almeria
region (1995 data) 156
a) Solar mineralization of TOC from the
insecticide abamectin; test performed in a
parabolic trough system; average direct UV light:
38.1 watts m–2.
b) Samples of photocatalytic degradation in
CPC system; average global UV solar
radiation was:
26.2 watts m–2 (acrinatrin test); 33.6 watts m–2
(methamidophos) and 33.7 watts m–2
(lufenuron test). TiO2 (Degussa P25): 200 mg
L–1 157
TOC mineralization of a mixture of ten
selected pesticides (parabolic troughs); direct
UV sunlight:
36.3 watts/m2; TiO2 (Degussa P25) concentration:
200 mg L–1; persulfate addition: 0.01 molar; treated
volume: 250 l. EC50 toxicity measured by
Microtox® 158
TOC mineralization of a mixture of ten
selected pesticides (CPCs). TiO 2 (Degussa
P25) concentration: 200 mg L–1, slurry 158
Pesticide degradation by Photo-Fenton
process: comparison of different iron
concentrations for 100 ppm of pesticides in
wastewater 159
TOC degradation of a mixture of ten selected
pesticides by TiO2 (Degussa P25) – persulfate
process. Degradation in function of UV
collected energy (300 to 400 nm) 161
TOC degradation of a mixture of ten
selected pesticides by Photo-Fenton
process and with different iron
concentrations. Degradation in function of
UV collected energy
(300 to 400 nm) 161
Conceptual design of a solar
detoxification plant for treatment and
recycling of pesticide bottles 162
Layout design of solar detoxification plant for
treatment and recycling of pesticide bottles 163
Laser device for manufacturing TiO2
catalyst powder 165
Modular CPC solar collector 165
xvi List of Figures
9.15 Manufacturing CPC reflectors 166
9.16 Solar detoxification plant layout 167
9.17 Solar detoxification plant design,
isometric drawing 167
9.18 Solar detoxification plant construction,
showing lateral wall and pit to collect and
contain any potential leaks 168
9.19 Installation of supporting structure
and CPC units 168
9.20 Photoreactor array input water manifold system 168
9.21 a) Installation of the main tanks in a solar
detoxification facility. From left to right:
storage tank, catalyst separation tank, buffer
tank.
b) Installation of tank fluid-level sensors.
c) Installation of catalyst separation system 169
9.22 a) Installation and testing of the UV-A sensor
device (front left). b) Testing the PLC and
electronic equipment 170
9.23 a) and b) Two views of the completed
solar detoxification treatment plant
170
List of Tables

1.1 Representative chemical reactions that can store 7.3 Examples of processes that are potentially
solar energy (thermochemical processes) 3 producers of antibiotic and antineoplastic
1.2 Some of the organic compounds included in wastewater 111
various lists of hazardous substances 7.4 Qualitative degradation rates of different
identified by the US EPA 4 compounds screened for photocatalytic activity:
1.3 Oxidation potentials of common substances slow (s), medium
and agents for pollution abatement. The more (m) and fast (f ) 119
positive the potential, the better the species is
as an oxidizing agent 5 8.1 Estimated cost of typical sizes of solar
1.4 Photocatalytic properties of detoxification facility (euros, 1999) 130
selected semiconductors 7 8.2 Estimated operating cost of a TiO 2-
1.5 VOCs amenable to treatment via persulfate solar detoxification plant (euros,
photocatalytic oxidation 12 1999) 132
3.1 Radiometric and spectroradiometric UV 8.3 Estimated annual treatment cost of a TiO2-
measurements at different times of the persulfate solar detoxification plant (euros,
1999) 132
day (n = 400 nm) 40
8.4 Estimated operating cost of a Photo-Fenton
3.2 Radiometric and spectroradiometric UV
solar detoxification plant (euros, 1999) 133
measurements at different times of the
8.5 Estimated annual treatment cost of a Photo-
day (n > 400 nm) 40
Fenton solar detoxification plant (euros, 1999)
4.1 Relative photonic efficiencies for the two 133
pesticides treated, with phenol as the standard 8.6 Estimated yearly cost of collecting 1.E+28
reference solar UV-photons at different yearly average
(C0 = 20 mg/L) 59 UV global
irradiation (Costs are indicated in euros, 1999.)135
5.1 Some examples of TiO2-sensitized 8.7 Estimated yearly cost of collecting 5.E+28
photodegradation of organic substrates 65 solar UV photons at different yearly average
7.1 Example of processes producing phenol residues UV global
in wastewater 109 irradiation (Costs are indicated in euros, 1999.)136
7.2 Examples of processes that are potentially 8.8 Estimated yearly cost of collecting 1.E+29
producers of wastewater containing solar UV photons at different yearly average
agrochemical residues 110 UV global irradiation (euros, 1999) 136
8.9 Estimated yearly cost collecting 5.E+29 solar
UV photons at different yearly average UV
global irradiation (euros, 1999) 136
8.10 Estimated yearly cost of collecting 1.E+30
solar UV photons at different yearly average
UV global irradiation (euros, 1999) 137
xviii List of Tables
8.11 Estimated yearly cost of UV photon generation 9.1
with electric lamps. Electricity cost = 0.15
Euros/kWh; FCR = 17 per cent. In Table 8.11A
the cost per lamp is €100; in Table 8.11B the cost 9.2
per lamp is €200. (euros, 1999) 138
8.12 Extraterrestrial solar irradiation 141
Selected pesticides for the feasibility
study assessment, CIEMAT (Spain),
1996 156
Degradation of pesticide mixture: mass
treatment factor (Tfm) and volumetric treatment
factor (Tfv) obtained for TiO2-persulfate and
Photo-Fenton processes, CIEMAT (Spain),
1998 159

Julián Blanco Gálvez
Julián Blanco Gálvez obtained a Diploma in Industrial
Engineering from Seville University and a Masters in
Environmental Sciences from the International Open
University. He has sixteen years of experience
working in different industrial sectors and during 1989
also worked as a consultant for the Spanish
Normalization Institution AENOR.
Since 1990 he has worked at the Plataforma Solar de
Almería (PSA) on R&D projects linked to solar and
environ- mental technology. From 1990 to 1993, he was
the project leader for the design and construction of the
first European pilot plant for experimentation in solar
detoxification of industrial wastewaters. In 1993 he
became the head of PSA’s Solar Chemistry department,
which is devoted to the development of technology
required for the utilization of solar radiation in
photochemical processes. Since 1995 he has also headed
the CIEMAT Solar Chemistry department of PSA,
directing staff and scientific installations in Almería and
Madrid on many national and international projects. In
the same year, he was appointed Spanish National
Representative for the Task II group of International
Energy Agency – SolarPACES (Solar Power and
Chemical Energy Systems), with the objective of
worldwide coordination and knowledge sharing of
international solar research activities.
He has given multiple lectures in courses, conferences
and seminars, including EURESCO conferences and is
the co-author of 4 books, more than 30 international
publica- tions and about 70 contributions to International
Congress and Symposiums.
Notes on the Editors
Sixto Malato Rodríguez
Sixto Malato Rodríguez obtained a Diploma in
Chemical Engineering from the Facultad de Ciencias of
University of Granada, a Masters in Environmental
Sciences from the Instituto de Investigaciones
Ecológicas, and a PhD in Chemical Engineering from the
University of Almería.
His professional career began in 1987 as Junior
Researcher in the Chemical Engineering Department of
the University of Almería. In 1988, he joined the
Production Department in an oil refinery (REPSOL S.A.)
in Puertollano. Since 1990 he has worked at the
Plataforma Solar de Almería. He participated in the
development of all solar photochemistry activities and
all projects linked to the solar detoxification of water
that took place in the early 1990s at the Plataforma
Solar de Almería. At present, he has a permanent
position as Senior Researcher of the Spanish Ministry of
Science and Technology.
He has taken part in nine European Union Framework
Programmes, nine National R&D Projects, and five
R&D Contracts related to the development of solar
technologies for wastewater treatment. He has been
involved in the design and construction of all the
European pilot plants for experi- mentation in solar
detoxification of industrial wastewaters.
He is the author and co-author of several books as well
as contributing chapters and articles to more than 50
publica- tions. He has co-authored 14 articles in
technical journals and 85 contributions to different
International Congresses and Symposiums. He has
assisted in 21 Workshops and Conferences relating
to water treatment and has taught courses related to
advanced wastewater treatment.

Aims
This chapter describes an alternative
source of energy that combines sunlight
and chemistry to produce chemical
reactions.
It outlines the basic chemical and
physical phenomena involved in solar
chemistry.
It reviews approaches that have been taken
and progress that has been made, and gives
some projections for the short- and long-
term prospects for the commercialization
of solar photochemistry. It also introduces
the focus of this book: solar detoxification.
Introduction 1 CHAPTER 1
Objectives
By the end of this chapter you will
understand the main factors that cause
photochemical reactions and you will be
able to do five things:
1. Distinguish perfectly between
thermochemical and
photochemical processes.
2. Understand the impact of pollutants
on the environment.
3. Calculate the energy flux of a light
source and its relationship with
semiconductor excitation.
4. Understand the basic principles
of advanced oxidation processes.
5. Describe the most important
features of heterogeneous
photocatalysis and their
application in the treatment of
contaminated aqueous effluents.
2 Solar Detoxification

NOTATION AND UNITS

Symbol Description Units
Aλ Absorbance at wavelength λ
AOPs Advanced Oxidation Processes
c Speed of light nm/s, m/s
ci Concentration of component i mol
EG Semiconductor band-gap energy eV, J
Eλ Spectral irradiance W m–2 nm–1
Eλo Spectral irradiances incident into the medium W m–2 nm–1
Eλ l Spectral irradiances at a distance l W m–2 nm–1
EC50 Concentration that produce an effect in 50% of a population mg/L,
mg/kg
GAC Granulated activated carbon
h Planck’s constant Js
LC50 Concentration that produces death in 50% of a population mg/L,
mg/kg
NOEL No observed effect level mg/kg/day
pi Partial pressure of component i atm
U Energy of a photon eV, J
αλ Absorption coefficient cm–1 atm–1
ελ Extinction coefficient mol–1 cm–1
8 Quantum yield
λ Wavelength nm, µm

1.1. Solar chemistry from the thermal energy obtained from the Sun for the
general purpose of substituting for fossil fuels.
• PHOTOCHEMICAL processes: solar photons are directly
The dramatic increases in the cost of oil beginning in 1974 absorbed by reactants and/or a catalyst, causing a
focused attention on the need to develop alternative sources reaction. Photo- chemical processes produce a chemical
of energy. It has long been recognized that the sunlight reaction from the energy of the Sun’s photons for the
falling on the Earth’s surface is more than adequate to general purpose of carrying out new processes.
supply all the energy that human activity requires. The
challenge is to collect this dilute and intermittent energy It should be emphasized, as a general principle, that the first
and to convert it to forms that are convenient and case is associated with processes that are feasible with con-
economical, and to use solar photons in place of those from ventional sources of energy. The second is related only to
lamps. It must be kept in mind that today there is clear completely new processes or reactions that are presently
worldwide consensus regarding the need to find a long- car- ried out with electric arc lamps, fluorescent lamps or
term replacement for fossil fuels (which were produced lasers.
millions of years ago and today are merely consumed) by From the outset, it was recognized that direct
identifying other inexhaustible or renewable energy conversion of light into chemical energy held promise for
sources. Under these circumstances, the growth and the production of fuels and chemical feedstock and the
development of solar chemical applications can be of storage of solar energy. Production of chemicals by
special relevance. These technologies can be divided in two reactions that are thermodynamically ‘uphill’ can
main groups (Figure 1.1): transform solar energy and store it in forms that can be
used in a variety of ways. Wide ranges of such chemical
• THERMOCHEMICAL processes: solar radiation is transformations have been pro- posed. A few
converted into thermal energy, which causes a chemical representative examples are given in Table 1.1 to
reaction. Thermochemical processes produce a chemical illustrate the concept.
reaction
 Introduction 3

h < 700 nm
CHO CHO
O O
Methylene blue/O2
O O

h < 390 nm
Heat Photons C6Cl5OH + 9/2O2 + H2 6CO2 + 5HCl
O TiO2

Increase of Modification of FIGURE 1.2. Furfural photo-oxidation and pentachloro- phenol

temperature chemical bonds mineralization (photochemical processes).
Thermochemical process Photochemical process
Steam reforming of methane Excitation of a semiconductor that give useful products. Photochemical reactions can be
CH4 + H2O  CO+ 3H2 – 206 kJ/mol h + SC  e– + p+ used to carry out a wide variety of chemical syntheses,
600º–850 ºC h  EG of SC
rang- ing from the simple to the complex. Processes of this
FIGURE 1.1. Schematic view of solar chemical applications. type may start with more complex compounds than fuel-
producing or energy-storage reactions and convert them
TABLE 1.1. Representative chemical reactions that can
to substances for which the photochemical step provides
store solar energy (thermochemical processes).
additional value or destroys harmful by-products. The
AH (kJ/mol) principles of photo- chemistry are well understood and
there is a wide range of known types of synthetic
CO2(g) → CO(g) + 1/2O2 286 transformations (Figure 1.2). Given this, the problem
CO2(g) + 2H2O(g) → CH3OH(l) + 3/2O2 727 becomes one of identifying applications in which the use
2 2 2 of solar photons is possible and economically feasible.
H O(l) → H (g) + 1/2O 286 The processes of interest here are photochemical;
CO2(g) + 2H2O(l) → 1/6C6H12O6(s) + O2 467 processes in which some component of the reacting
These processes generally start with substances in system is capable of absorbing photons in the solar
low- energy, highly-oxidized forms. The essential feature spectrum. As pho- tons should be treated like any
is that these reactions increase the energy content of the other chemical reagent in the process, their number is
chemicals using solar energy. For such processes to be a critical element in solar photochemistry (see Chapter
viable, they must fulfil the following requirements, as 2).
outlined by the National Renewable Energy Laboratory Because they are very attractive technologically and
(NREL) (1995) and slightly modified by the authors: envi- ronmentally, solar chemical processes have seen
• The thermochemical reaction must be endothermic. spectacular development in recent years. In the
beginning, research in solar chemistry was centred only
• The process must be cyclic and have no side reactions
on converting the solar energy into chemical energy,
that could degrade the photochemical reactants.
which could then be stored and transferred over long
• The reaction should use as much of the solar spectrum distances. But together with this impor- tant application,
as possible. other environmental uses have since been developed, so
• The back reaction should be very slow, to allow storage that today the entire range of known solar chemical
of the products, but rapid when triggered to recover applications has a promising future. In principle, any
the energy content. reaction or process requiring an energy source can utilize
• The products of the photochemical reaction should be solar energy.
easy to store and transport.
The other way that sunlight is used in photochemistry 1.2. Water contaminants
is to use solar photons as replacements for those from
artificial sources. The goal in this case is to provide a cost-
effective and energy-saving source of light to drive Environmental pollution is a pervasive problem with wide-
photochemical reactions spread ecological consequences. Recent decades have
witnessed increased contamination of the Earth’s drinking-
water reserves. The inventory of priority pollutants
compiled
4 Solar Detoxification

by the United States Environmental Protection Agency In any case, a consensus exists that the environmental
(US EPA) provides a convenient frame of reference for impact of a given contaminant depends on the degree of
under- standing the importance of removing such exposure (its dispersion and the resulting concentration
contamination from the Earth (Table 1.2). in the environment) and on its toxicological properties.

TABLE 1.2. Some of the organic compounds included in various lists of hazardous substances identified by the US EPA.
Acetaldehyde o-,m-,p- Maneb Poly-chlorinated
Cresols Mechlorethamine biphenyls (PCBs)
Acetamide
Acetone Cumene Melamine Pyrene
Acetonitrile Cyclohexane Methanol Quinone
2,4-Diaminoanisole Methoxychlor Quintozene
Acetophenon
4,4’-Diaminodiphenyl ether Methyl acrylate Safrole
e Acrolein
Diazomethane Methyl Set-Butyl alcohol
Acrylamide
Dibenzofuran isocyanate Sevin (carbaryl)
Acrylic acid
1,2-Dibromoethane Methyl tert-butyl Styrene
Acrylonitrile
1,2- ether Methylene Terephthalic acid
Aldrin
Dichlorobenzene bromide 4,4’- Tert-Butyl
4-
1,1-Dichloroethane Methylenedianiline alcohol
Aminoazobenzene
2,4-Dichlorophenol Methylhydrazine Tetrachlorvinpho
Aniline
1,2- 4- s
o-Anisidine hydrochloride
Dichloropropane Methylphenol 1,1,2,2-Tetrachloroethane
Anthracene
Dichlorvos Mirex Tetrahydrofuran
Atrazine
Dicofol Mustard gas Thioacetamide
Benzamide
Diepoxybutane Nitrilotriacetic Thioure
Benzene
Diethanolamine acid o- a
Benzidine
Dimethyl Nitroaniline Toluene
Benzo(a)pyrene
phthalate 2,4- Nitrobenzene 2,4-Toluene
Benzyl chloride
Dinitrophenol Nitrofen diamine Toluene
Benzenehexachlori
1,2- Nitrogen mustard diisocyanate
de Beta-Propoxur
Dinitrotoluene Nitroglycerin o-Toluidine
Biphenyl hydrochloride Total
Bis(2- 2,4- 5-Nitro-o-anisidine
Dinitrotoluene Nitrophenol xylenes
Chloroethoxy)methane Toxaphene
Bromoethane 1,4-Dioxane 2-
1,2-Diphenylhydrazine Nitropropane Triaziquon
Captan e
Carbary Disulfoton n-Butyl
Endosulfan alcohol Trichlorfon
l 2,4,6-Trichlorophenol
Carbon disulfide Epichlorohydrin n-Dioctyl phthalate
Ethylbenzene N- Trifluralin
Carbon 1,2,4-Trimethylbenzene
tetrachloride Ethylene glycol Nitrosodiethylamine
Ethylene thiourea N-Nitrosopiperidine 2,2,4-Trimethylpentane
Catechol 2,4,6-Trinitrotoluene
Chlordane Fluometuron N-Nitroso-N-
Formaldehyde ethylurea Urethane (ethyl
Chloroacetic acid carbamate) Vinyl
Chlorobenzene Hexachlorobenzen Octachloronaphthalen
e e Octane bromide
Chlorodibenzodioxin Vinyl chloride
s, Hexachloroethane Oxirane
Hexane Parathion Vinylidene chloride
various Xylene (mixed
Chlorodibenzofurans Hydroquinone (DNTP)
Isophorone Pentachlorobenzene isomers) Zineb
2-Chloroethyl vinyl
ether 2-Chlorophenol Isopropyl alcohol Pentachlorophenol
p-Chloro-m-cresol Lindane Phenanthrene
Malathion Phosgene
Phthalic anhydride
Polybrominatedbipheny
ls

The assessment of exposure involves an understanding of
the dispersion of a chemical in the environment and estima-
tion of the predicted concentration to which organisms
will be exposed. For example, the pesticide fenaminphos
oxidizes very quickly (a ten-day half-life) into sulfoxide and
sulfone, while its pesticidal properties remain unaffected. A
half-life of seventy days has been found for degradation of
fenaminphos and its two metabolites. Furthermore, the two
metabolites are more mobile (soluble) than fenaminphos
(Hayo and Van Der Werf, 1996). Assessment of the
contam- inant’s effect involves summarizing data on the
effects the chemical has on selected representative
organisms and using these data to predict a no-effect
concentration in a specific niche.
Organisms may consume chemicals through ingestion
of food and water, respiration or skin contact. When a
chemical crosses the various barriers of the body, it
reaches the meta- bolic tissue or a storage depot. The
toxicity of a chemical is usually expressed as the
effective concentration or dose of the material that would
produce a specific effect in 50 per cent of a large
population of test species (EC 50 or ED50). If the effect
recorded is lethal, the term ‘LC50’ (or LD50) is used. The ‘no
observed effect level’ (NOEL or NOEC) is the dose
immediately below the lowest level eliciting any type of
tox- icological response in the study. For example, the
pesticide methamidophos, which has been classified as a
‘Restricted- Use Pesticide’ (RUP) by US EPA, is highly
toxic for mammals (acute oral LC50 = 16 mg/kg in rats
and 30 to 50 mg/kg in guinea pigs), birds (bobwhite
quail, CD50 = 8 to 11 mg/kg) and bees. The ninety-six-
hour LC50 is 25 to 51 mg/L in rainbow trout, but
concentrations as low as 0.22 ng/L are lethal to larval
crustaceans in ninety-six-hour toxicity tests. A fifty-six-
day rat-feeding study resulted in a NOEL of
0.03 mg/kg/day (Tomlin, 1997).
Decontamination of drinking water is mainly by
pro- cedures that combine flocculation, filtration,
sterilization and conservation, to which a limited number
of chemicals are added. Normal human sewage water can
be efficiently treated in conventional biological
processing plants. But very often these methods are
unable to reduce the power of the contaminant. In these
cases, some form of advanced biolog- ical processing is
usually preferred in the treatment of effluents
containing organic substances. Biological treatment
techniques are well established and relatively cheap.
However, these methods are susceptible to toxic com-
pounds that inactivate the waste-degrading
microorganisms.
Introduction 5
To solve this problem, apart from reducing emissions,
two main water-treatment strategies are followed: first,
chemical treatment of drinking water and contaminated
surface and groundwater, and second, chemical treatment
of waste- waters containing non-biodegradable
compounds.
Chemical treatment of polluted surface and
groundwater or wastewater is part of a long-term strategy
to improve the quality of water by eliminating toxic
compounds of human origin before returning the water to
its natural cycles. This type of treatment is suitable when
a biological processing plant cannot be adapted to certain
types of pollutants that did not exist when it was
designed. In such cases, a poten- tially useful approach is
to partially pre-treat the toxic waste using oxidation
technologies to produce intermediates that are more
readily biodegradable. Light can be used, under certain
conditions, to encourage chemicals to break down the
pollutants into harmless by-products. Light can have a
dramatic effect on a molecule or solid because when it
absorbs light its ability to lose or gain electrons is often
altered. This electronically excited state is both a better
oxidizing and a better reducing agent than its counterpart
in the ground. Electron transfer processes involving
excited- state electrons and the contact medium (for
example water) can therefore generate highly reactive
species like hydroxide ( •OH) and superoxide (O •–)
radicals (see Table 1.3). These can then be used to
decompose a pollutant chemically into harmless end-
products. Alternatively, light can be used directly to
2
break up pollutant molecule bonds photolytically.
TABLE 1.3. Oxidation potentials of common substances and
agents for pollution abatement. The more positive the
potential, the better the species is as an oxidizing agent.
Oxidizing reagent Oxidation potential, V
Fluorine 3.06
•
Hydroxide radical ( OH) 2.80
Ozone 2.07
Hydrogen peroxide 1.77
Chlorine dioxide 1.57
Chlorine gas 1.36
Oxygen 1.23
Hypochlorite 2 0.94
Iodine 0.54
Superoxide radical (O•–) –0.33
6 Solar Detoxification

These processes are called ‘Advanced Oxidation Processes’ processes employ semiconductor slurries for catalysis,
(AOPs). Many oxidation processes, such as TiO 2/UV, whereas homogeneous photochemistry is used in a
H2O2/UV, Photo-Fenton and ozone processes (O 3, single- phase system. Any mechanistic description of a
O3/UV, O3/H2O2) are currently employed for this photo- reaction begins with the absorption of a photon,
purpose. sunlight being the source of photons in solar
photocatalysis. In the case of homogeneous
1.3. Photodegradation principles photocatalytic processes, the interac-
tion of a photon-absorbing species (transition metal com-
1.3.1. Definitions plexes, organic dyes or metalloporphyrines), a substrate
(e.g.
the contaminant) and light can lead to chemical modification
of the substrate. The photon-absorbing species (C) is acti-
For the benefit of those who may have a limited vated and accelerates the process by interacting through a
background state of excitation (C*). In the case of heterogeneous
in photochemistry, a brief outline of some basic concepts photo- catalysis, the interaction of a photon produces the
of photochemistry is presented here. In order for photo- appear- ance of electron/hole (e– and h+) pairs, the
chemistry to take place, photons of light must be catalyst being a semiconductor (e.g. TiO 2 or ZnO). In
absorbed. The energy of a photon is given by this case, the excited electrons are transferred to the
reducible specimen (Ox 1) while concurrently the catalyst
hc
U (1.1) accepts electrons from the oxidizable specimen (Red 2)
λ that occupies the holes. In both directions, the net flow of
electrons is null and the catalyst remains unaltered.
where h is Planck’s constant (6.626 × 10–34 J.s), c is the
speed of light and λ is the wavelength. For a molecule’s
bond to be broken, U must be greater than the energy
of
that bond. Chν C* (1.4)
When a given wavelength λ of light enters a medium, C*  R  R*  (1.5)
its spectral irradiance Eλ (W m nm ) is attenuated
–2 –1
C* R*  P (1.6)
according to the Lambert-Beer law, which is expressed
in two ways, one for the gas phase and the other for the
liquid phase: Chν C(e   h  ) (1.7)
ln(Eλo / Eλl )  αλ pil gas phase (1.2) h  Red  Ox (1.8)
2 2
log(Eλo / Eλl )  ελ cil liquid phase e Ox1  (1.9)
(1.3
Red1
)
Eo and El are the incident spectral irradiance and at a
λ λ
distance l into the medium, αλ is the absorption 1.3.2. Heterogeneous photocatalysis
coefficient (cm–1 atm–1), pi is the partial pressure (atm)
of component i, ελ is the extinction coefficient (M–1 cm– The concept of heterogeneous photocatalytic degradation
1), and c is the concentration (M) of component i. The
i is simple: a stable solid semiconductor is irradiated to
absorbance Aλ at wavelength λ is the product ελcil. The stimulate a reaction at the solid/solution interface. By
photochemical quantum yield (φ) is defined as the definition, the solid can be recovered unchanged after
number of molecules of the target compound that react many turnovers of the redox system. When a
divided by the number of photons of light absorbed by semiconductor is in contact with a liq- uid electrolyte
the compound in a fixed period of time. Normally, this solution containing a redox couple a charge transfer
unit is the maximum quantum yield attainable. occurs across the interface to balance the potentials of the
The term ‘photocatalysis’ implies the combination of two phases. An electric field is formed at the surface of the
photochemistry and catalysis. Both light and catalyst are semiconductor. The bands bend as the field forms from
necessary to achieve or to accelerate a chemical reaction. the mass of the semiconductor towards the interface.
Photocatalysis may be defined as the ‘acceleration of a pho- During pho- toexcitation (a photon with appropriate
toreaction by the presence of a catalyst’. Heterogeneous energy is absorbed), band bending provides the
conditions for carrier separation. In the case of
semiconductor particles, there is no ohmic
 Introduction 7

h TABLE 1.4. Photocatalytic properties of selected semi-

conductors.

recombination
Band gap energy Corresponding
Material required to wavelength
activate required (nm)
catalyst (eV)
2
BaTiO3 3.3 375
Red1 Oxid
CdO 2.1 590
CdS 2.5 497
Oxid1 Red2
CdSe 1.7 730
Fe2O3 2.2 565
recombination
GaAs 1.4 887
GaP 2.3 540
FIGURE 1.3. Behaviour of electrons and holes within a SnO2 3.9 318
particle of illuminated semiconductor in contact with an
electrolyte. SrTiO3 3.4 365
TiO2 3.0 390
contact to extract the majority carriers and to transfer them WO3 2.8 443
by an external conductor to a second electrode. This ZnO 3.2 390
means that the two charge carriers should react at the
ZnS 3.7 336
semiconductor/ electrolyte interface with the species in
solution. Under steady-state conditions, the amount of Summarizing, a semiconductor particle is an ideal
charge transferred to the electrolyte must be equal and photo- catalyst for a specific reaction if:
opposite for the two types of carriers. The • The products formed are highly specific.
semiconductor-mediated redox processes involve
electron transfer across the interface. When electron/ hole • The catalyst remains unaltered during the process.
pairs are generated in a semiconductor particle, the elec- • The formation of electron/hole pairs is required
tron moves away from the surface to the mass of the (gener- ated by the absorption of photons with energy
semi- conductor as the hole migrates towards the surface greater than that necessary to move an electron from
(see Figure 1.3). If these charge carriers are separated the valence band to the conduction band).
quickly enough they can be used for chemical reactions at • Photon energy is not stored in the final products,
the surface of the photo- catalyst: that is, for the oxidation being an exothermic reaction that is only retarded
or reduction of pollutants. kinetically.
Metal oxides and sulfides represent a large class of
semi- conductor materials suitable for photocatalytic 1.3.3. Homogeneous photodegradation
purposes.
Table 1.4 lists a selection of semiconductor materials that
have been used for photocatalytic reactions, together
with the band-gap energy required to activate the The use of homogeneous photodegradation (a single-
catalyst. The final column in the table indicates the phase system) to treat contaminated water dates back
wavelength of radia- tion required to activate the to the early 1970s. The first applications concerned
catalysts. According to Planck’s the use of UV/ozone and UV/H O . The use of UV
equation, the radiation required to produce this gap must be light for the 2 2

of a wavelength (λ) equal to or less than that calculated photodegradation of pollutants can be classified into two
by equation 1.10. principal areas:
hc • PHOTO-OXIDATION: light-driven oxidative processes
λ (1.10) princi- pally initiated by hydroxyl radicals.
EG • Direct PHOTODEGRADATION: light-driven processes in
where EG is the semiconductor band-gap energy, h is which degradation proceeds following direct excitation
Planck’s constant and c is the speed of light. of the pollutant by UV light.
8 Solar Detoxification

Photo-oxidation involves the use of UV light plus an Since the net result of ozone photolysis is the
oxidant to generate radicals. The hydroxyl radicals conversion of ozone into hydrogen peroxide, UV-ozone
then attack the organic pollutants to initiate oxidation. would appear to be only a rather expensive method of
Three major oxidants are used: hydrogen peroxide making hydrogen per- oxide. However, there are other
(H2O2), ozone and Photo-Fenton reaction. H2 O2 oxidation-related processes that occur in solution, such
absorbs photons fairly weakly in the UV region, with as the direct reaction of ozone with a pollutant (see Table
absorption increasing as the wavelength decreases. At 1.3). Ozone may have advantages in water, with high
254 nm, ελ is 18 M–1 cm–1, whereas at 200 nm it is 190 inherent UV absorbance, but it faces the same problem as
M–1 cm–1. The primary process for the absorption of light hydrogen peroxide as far as its use in solar- energy
below 365 nm is dissociation, to yield two hydroxyl processes is concerned.
radicals: The essential process of the Fenton reaction
(Safarzadeh- Amiri et al., 1996) is the same as for all
AOPs. Highly
2 2
H 2O hν (1.11) reactive radicals (such as HO • and HO2•) oxidize nearly all

OH organic substances to yield CO 2, water and inorganic salts.
The use of hydrogen peroxide is now very common In the case of Photo-Fenton, Fe2+ ions are oxidized by
for H2O2 producing one •OH ion (1.18), and the Fe 3+ or
the treatment of contaminated water due to several complexes obtained then act as the light-absorbing
practical advantages: species producing
• H2O2 is available as an easily handled solution that another radical while the initial Fe 2+ is recovered (1.19 and
can be diluted in water to give a wide range of 1.20) 
concentrations. . Fe2  H2O2  Fe3  OH  (1.18)
• There are no air emissions. OH
• A high-quantum yield of hydroxyl radicals is (1.19)
generated (0.5). Fe3  H2O hν  Fe2  H  OH
(1.20)
[Fe(OOCR)]2  hν  Fe2  CO2  R
The major drawback is the low molar-extinction Note that in Equation 1.20, the ligand R-COO– can
coefficient, which means that in water, when UV be replaced by other organic groups (e.g. ROH or
absorption is high, the fraction of light absorbed by H 2O2 RNH2). Compared with other homogeneous photo-
may be low unless very large concentrations are used. oxidation processes, the advantage of Photo-Fenton is
Furthermore, especially as concerns the focus of this the improved light sensitivity (up to a wavelength of
text, H2O2 photon absorption is very low in the Solar UV 600 nm, correspon- ding to 35 per cent of the solar
range (up to 300 nm). radiation). On the other hand, disadvantages, such as
Ozone is generated as a gas in air or oxygen in the low pH values required (usually below pH 4) and
concen- trations generally ranging from 1 to 8 per cent the necessity of removing iron after the reaction, remain.
(v/v). It has a strong absorption band centred at 260 Some pollutants are able to dissociate only in the
nm with ελ = 3,000 M–1 cm–1. Absorption of light at pres- ence of UV light. For this to happen, the
this wavelength leads to the formation of H2O2: pollutant must
absorb light emitted by a lamp (or the Sun) and have a
O3 
hν O( 1 D) 
2
(1.12) reasonable quantum yield of photodissociation.
Organic pollutants absorb light over a wide range of
O O(1 D)  H2O  H2O2 (1.13) wavelengths, but generally absorb light more strongly at
lower wavelengths,
Hydroxyl radicals are then formed by the reaction of especially below 250 nm (Figure 1.4). In addition, the
ozone quantum yield of photodissociation tends to increase
at
with the hydrogen peroxide conjugate base: lower wavelengths, since the photon energy is increasing
H2O2  H2O  HO2  (1.14 (Eq. 1.1). The net chemical result of photodissociation is
H3O  ) usually oxidation, since the free radicals generated can
react with dissolved oxygen in the water. In practice, the
HO2  O3 O3  HO2 (1.15
range of wastewaters that can be successfully treated by
)
O  H O  HO  UV alone is very limited. This defect is more relevant
3 2 3 (1.16 when solar energy
OH )
HO3  OH  O2 (1.17
)
 Introduction 9

h  3.0 eV
O2
Arbritary units

O2 e–

TiO2 Particle
UV solar spectrum
h+ H2O
UV acrinathrin spectrum
WATER

200 220 240 260 280 300 320 340 360 380 400
Wavelength, nm OH+H +

FIGURE 1.4. UV spectra of acrinathrin and of sunlight Figure 1.5. Effect of UV radiation on a TiO 2
between 200 and 400 nm. particle dispersed in water.

is used (see Figure 1.4) because only photons up to 300
nm are available.
1.4. Application to water
treatment
As mentioned above, UV light can be used in several
ways. However, direct photolysis can occur only when
the contam- inant to be destroyed absorbs incident light
efficiently. In the case of UV/ozone and UV/hydrogen
peroxide this does not happen. Absorption by some
sensitizer must initiate the reaction, and limited
absorption by the solute or the additive restricts
efficiency. Furthermore, these mixtures often still require
large quantities of added oxidant. By contrast, in het-
erogeneous photocatalysis dispersed solid particles
absorb larger fractions of the UV spectrum efficiently
and generate chemical oxidants in situ from dissolved
oxygen or water (see Figure 1.5). These advantages make
heterogeneous photo- catalysis a particularly attractive
method for environmental detoxification. The most
important features of this process that make it applicable
to the treatment of contaminated
aqueous effluents are:
• The process takes place at ambient temperature.
• Oxidation of the substances into CO 2 is
complete.
• The oxygen necessary for the reaction is obtained
from
Whenever different semiconductor materials have been
tested under comparable conditions for degradation of the
same compounds, TiO2 has generally been demonstrated to
be the most active, equalled only by ZnO. TiO 2’s
strong resistance to chemical and photocorrosion, as well
as its safety and low cost, limits the choice of convenient
alterna- tives (Herrmann, 1999). Furthermore, TiO 2 is of
special interest as it can use natural (solar) UV light. This is
because it has an appropriate energetic separation between
its valence and conduction bands, which can be surpassed
by the energy content of a solar photon (see Table 1.4).
Other semi- conductor particles, for example, CdS or GaP,
absorb larger fractions of the solar spectrum and can form
chemically activated surface-bond intermediates, but
unfortunately these photocatalysts are degraded during
the repeated catalytic cycles involved in heterogeneous
photocatalysis. Therefore, degradation of the organic
pollutants present in wastewater using irradiated TiO 2
suspensions is the most promising process, and R&D in this
field has grown very quickly during the last few years.
TiO2 hν e   h   TiO
2 (1.21)
e  h  TiO2  TiO2  heat and/or
 
(1.22)
hν’
(TiOIV  O2  TiIV )  OH2  h+
BV
 (TiOIV  O2  TiI )  OH  H
(1.23)
V

the atmosphere.  

O2(ads)   (1.24)
• The catalyst is cheap, innocuous and 2(ads)
 eB O
reusable. C
• The catalyst can be attached to different types of inert
To date, evidence supports the idea that the hydroxyl
matrices.
radical (•OH) is the main oxidizing specimen responsible
For all these reasons, from now on only this method will for photo- oxidation of the majority of the organic
be dealt with in this text. compounds studied. The first effect, after absorption of
near ultraviolet radiation,
10 Solar Detoxification
λ < 390 nm, is the generation of electron/hole pairs,
which are separated between the conduction and valence
bands (Eq. 1.21). In order to avoid recombination of the
pairs generated (Eq. 1.22), if the solvent is
oxidoreductively active (i.e. water) it also acts as a
donor and acceptor of electrons. Thus, on a hydrated
and hydroxylated TiO 2 surface, the holes trap •OH
radicals linked to the surface (Eq. 1.23). In any case, it
should be emphasized that even trapped electrons and
holes can rapidly recombine on the surface of a particle
(Eq. 1.22). This can be partially avoided through the
capture of the electron by pre-adsorbed molecu- lar
oxygen, forming a superoxide radical (Eq. 1.24).
Whatever process the photo-oxidation takes, O2 and
water are essential for photo-oxidation with TiO2. There
is no degradation in the absence of either. Furthermore,
the oxidative species formed (in particular the hydroxyl
radicals) react with the majority of organic substances.
For example, in aromatic compounds, the aromatic part
is hydroxylated, then successive steps in
oxidation/addition lead to breaking of the rings. The
resulting aldehydes and carboxylic acids are
decarboxylated and finally produce CO2. However, the
important issue governing the efficiency of
photocatalytic oxidative degradation is to minimize
electron-hole recombi- nation by maximizing the rate of
interfacial electron transfer to capture the
photogenerated electron and/or hole. This issue is
discussed in more detail later.
Photocatalytic degradation has been
commonly investigated with monoaromatics, and
most
consequently these pollutants appear as model
compounds in dozens of scien- tific papers. Some
monoaromatics investigated include: benzene,
dimethoxybenzenes, halobenzenes, nitrobenzene,
chlorophenols, nitrophenols, benzamide and aniline,
most of which are recognized as priority pollutants (see
Table 1.2). In addition to these, several other types of
molecules have also been investigated as substrates for
photocatalytic degradation:
• HALOALIPHATICS (e.g. trichloroethylene or TETRACHLOROMETHANE):
important because so many of these compounds have
been released into the environment and contaminate
waters. Some also originate during water treatment by
chlorination.
• WATER-MISCIBLE solvents (e.g. ETHANOL or ALKOXYETHANOL):
these compounds are very difficult to detoxify, as they
are resistant to treatment and are poorly adsorbed
on granulated activated carbon (GAC).
• Pesticides: contaminate waters with a high level of
agricul- tural runoff. Among the recently investigated
compounds are triazines, organophosphorous,
carbamates, phenoxy- acids and organochlorines.
• SURFACTANTS: surface active agents are entering
domestic and industrial wastewater in increasing
amounts. Because their biodegradability may be one of
the more important constraints to their use,
photocatalytic degradation has received increasing
attention.
• Dyes: strongly coloured compounds can be
removed by adsorption but it is always better to
destroy them by oxidation.
Four exhaustive reviews by Blake (1994, 1995, 1997,
1999) describe almost 3,000 studies in this field carried
out before 1999.
Despite encouraging laboratory-scale data and some
industrial-scale tests, chemical oxidation detoxification is
still restricted to a few experimental plants (Dillert et al.,
1999). The broader application of those technologies
requires:
• reactor optimization and modelling, and
• assessment of the efficiency of oxidation technology
to reduce the toxicity of effluents.
The following chapters of this book will attempt to
highlight these matters.
1.5. Gas-phase detoxification
Airborne pollutants (such as volatile compounds) can be
treated during the gas phase with the UV/TiO 2 process.
Gas- phase treatment offers several advantages. In
general, substrate mass-transport is an order of
magnitude faster in the gas phase than in the liquid
phase. This in turn leads to much faster reaction rates.
Oxidant starvation may be less of a problem in the gas-
phase. There is also no interference on the photocatalytic
surface from other species that are invari- ably present in
aqueous treatment media (for example, anions). In
addition, photocatalysis separation after use is not a
problem, unlike aqueous slurry suspensions. As solar
energy is used to drive the process, no fuel is required,
gaseous affluent volume is reduced, no NO x is generated,
no products of incomplete combustion are produced,
CO2 emanating from fuel burning is avoided, and
substantial fuel saving may be achieved. Since no
burning takes place,
 Introduction 11

Co2
ANALYSER
PC MFC

MFC
DRY
AIR GC/MS
SAMPLING TOL.OR XYL.
VALVE
VENT RELIEF T
VALVE FILTER
VENT

FC
Xe
T REACTOR LAMP
H2 AIR
FC
DAS

VENT FID
VENT TCD
HEAT
GC TRACE
REACTOR

HEAT
EXCHANGER
He

OUTLET (REAR-FED)
INLET (REAR-FED) INLET (FRONT-FED)
OUTLET (FRONT-FED)

FRONT
THERMOCOUPLE
REAR
THERMOCOUPLES

MONOLITHIC
CATALYST

QUARTZ
WINDOW

FIGURE 1.6. Diagram of an experimental system with a cross-section view of a gas-phase monolithic photoreactor.
oxygen is only necessary at a stoichiometric ratio. Solar
con- centrators enable small-size solar furnaces and even
mobile solar parabolic dishes to be sufficient for on-site
destruction of low productions of highly toxic
compounds.
On the other hand, there are indications that
mineraliza- tion may not be complete with some
organic substrates in the gas-phase. The TiO2
photocatalyst becomes less effective after prolonged use
and must be reactivated with moist air, which
presumably restores the original degree of
hydroxylation on the oxide surface. There are also
indications that product (or intermediate) adsorption on
the TiO2 surface may be problematic during the course of
the reaction.
Pollutant substrates such as trichloroethylene,
acetone, formaldehyde, m-xylene and NOx have been
treated with TiO2/UV in the gas-phase in bench-scale
tests. Field tests have also been conducted to treat effluent
air emissions using this technique at different
manufacturing plants in the United States (Rajeshwar,
1996).
12 Solar Detoxification

In figures 1.6, 1.7 and 1.8, different gas-phase photo- from the front part of the reactor. A 4,000 W Xenon
catalytic reactors are shown. Figure 1.6 presents a reactor lamp, which supplies the photonic flux, has been
designed for use with monolithic catalysts (Avila et adapted for this reactor. A Pyrex window is used to filter
al., 1998). The reactor (40 mm inner diameter, 200 mm wavelengths below 300 nm (see Figure 1.4), a filter is
length) permits a change in the direction of gas flow used to remove IR radia- tion, and an electric heating
from the rear to the front and vice versa. The monolythic jacket used to control tempera- ture. A series of
catalysts are placed inside the reactor so that light thermocouples are installed to monitor the temperature
illuminates the internal sur- faces of the channels from of the reactor inlet and outlet and, at various points
the front. Gases are usually fed inside different channels of the monolith, to obtain
axial and radial temperature profiles. A reactant gas
consist- ing of air with a flow of several litres per
TABLE 1.5. VOCs amenable to treatment via photocatalytic minute is mixed with the VOC (hundreds of ppm)
oxidation ( Jacoby et al., 1996). before entering the reac- tor. Contaminants are
pumped through the monolith and outlet gases, heat
Class of compound Chemicals tested traced to avoid condensation, are sub- sequently
analysed by direct sampling (on-line) using a gas
Aromatics Benzene, toluene
chromatograph (GC) with a flame ionization detector
Nitrogen-containing ring Pyridine, picoline, nicotine (FID). Manual (off-line) samples that can be removed
Aldehydes Acetaldehyde, through a sampling valve are Tenax adsorbent to trap
formaldehyde volatile compounds from the air. In addition, CO2
Ketones Acetone concentration is measured with an infrared gas
Alcohols Methanol, ethanol, propanol analyser, to calculate the carbon-mass balance.
Ethylene, propene, tetramethyl In figures 1.7 and 1.8 a different type of gas-
Alkane ethylene phase photoreactor is shown. The tubular photoreactor
sTerpenes α-pinene consists of a Pyrex tube (Figure 1.7) containing a
Sulfur-containing organics Methyl thiophene tubular matrix of TiO2-based catalyst surrounding a
Dichloroethylene, UV lamp. The stream
trichloroethylene,
Chlorinated tetrachloroetylene of gas flows between the inner wall of the catalyst and the
ethylenes Dichloroacetyl chloride, surface of the UV lamp. The UV lamp irradiance is
tetrachloroacetyl similar to the solar spectrum. A heat-trace box
Acetyl chlorides chloride (Figure 1.8) that controls process temperature
encloses the photoreactor.

Catalytic monolith

Outlet gases Inlet gases

Thermocouple Fluorescent lamp

FIGURE 1.7 Schematics and photo of a tubular gas-phase photoreactor.

 Introduction 13

Secondary pollutant
H2 O
Check
valve
MFC O2

MFC
P GENERATOR
AIR
VOCs
P
Peak H2 Air He

DAS Vent FID

Vent TCD
PHOTOREACTOR
GC (HP6890)
C
He
Filter
C Analizador
HEAT
de CO2 C TRACE
REACTOR

Relief valve Tenax

Vent Venteo

FIGURE 1.8 Diagram of the experimental system and photo of a tubular gas-phase photoreactor (dismounted).

Two thermocouples, located at the inlet and the outlet,

give the reaction temperature of gases in contact with the Summary
catalyst surface. In this case a stream of dry CO 2-free air
is delivered from an air generator at flow rates of several A description is given of how solar chemistry could
litres per minute. The VOC is bubbled into the airstream become a significant segment of the chemical
and through the catalyst in the reactor. Outlet gases are industry and how it can be used, under certain
analysed by on-line GC and manual samples are Tenax conditions, to provoke the chemical breakdown of
adsorbent. pollutants into harmless by- products. The behaviour of
contaminants in environmental
14 Solar Detoxification
water is summarized. The basic concepts of
photochemistry relating to photolysis of chemical bonds,
homogeneous photodegradation and heterogeneous
photocatalysis are reviewed. The use of semiconductors
for wastewater treat- ment, with particular reference to
TiO2, is discussed. Examples of the waste materials that
have been treated suc- cessfully using TiO2 are
presented. Gas-phase photocatalysis is also introduced.
Bibliography
AVILA, P.; BAHAMONDE, A.; BLANCO, J.; SÁNCHEZ,
B.; CARDONA, A.I. AND ROMERO, M. 1998. Gas-
phase
photo-assisted mineralization of volatile compounds by
monolithic titania catalysts. In: Applied CATALYSIS B:
ENVIRONMENTAL, No. 17, pp. 75–88.
BLAKE, D.M. 1994. BIBLIOGRAPHY of Work on the
PHOTOCATALYTIC REMOVAL of HAZARDOUS Compounds from
WATER AND Air, May. Springfield, Va., 22161,
National Technical Information Service, US Depart. of
Commerce. UPDATE Number 1: To June 1995, October 1995.
UPDATE Number 2: To October 1996, January 1997. UPDATE
Number 3: To JANUARY 1999, May 1999.
DILLERT, R.; CASSANO, A.E.; GOSLICH, R. AND BAHNEMANN, D.
1999. Large (1) scale studies in solar catalytic wastewater
treatment. CATALYSIS TODAY, No. 54, pp. 267–82.
HAYO, M.G. AND VAN DER WERF, H. 1996. Assessing the
impact of pesticides on the environment. AGRICULTURAL
Ecosystems AND Environment, No. 60, pp. 81–96.
HERRMANN, J.M. 1999. Heterogeneous photocatalysis:
fundamentals and applications to the removal of
various types of aqueous pollutants. CATALYSIS TODAY,
No. 53, pp. 115–29.
JACOBY, W.A.; BLAKE, D.M.; FENNELL, J.A.; BOULTER,
J.E.; VARGO, L.M.L.; GEORGE, M.C. AND DOLBERG,
S.K. 1996.
Heterogeneous photocatalysis for control of volatile
organic compounds in indoor air. JOURNAL of the Air WASTE
MANAGEMENT ASSOCIATION, Vol. 46, No. 9, pp. 891–8.
NATIONAL RENEWABLE ENERGY LABORATORY. 1995. SOLAR
Photochemistry – Twenty YEARS of Progress: WHAT’S Been
Accomplished, AND Where Does It LEAD? Golden, Colo.,
NREL Report NREL/TP-433-7209.
RAJESHWAR, K. 1996. Photochemical strategies for abating
environmental pollution. Chemistry AND Industry, No.
17, pp. 454–8.
SAFARZADEH-AMIRI, A.; BOLTON, J.R. AND CATER, S.R. 1996.
The use of iron in advanced oxidation processes. JOURNAL of
ADVANCED OXIDATION Technology, Vol. 1, No. 1, pp. 18–26.
TOMLIN, C.D.S. 1997. The Pesticide MANUAL. 11th ed.
Farnham, Surrey, United Kingdom, British Crop
Protection Council.

Self-assessment questions
Part A: True or false?
1. Solar energy is useful only to substitute for fossil
fuels; it is converted into thermal energy, thus provoking
chemical reactions.
2. The toxicity of a chemical is the same for
all species.
3. Biological treatment techniques are the
cheapest wastewater treatment methods.
4. The energy of a photon depends on the
ambient temperature.
5. Heterogeneous photocatalysis employs
liquid catalysts.
6. Light-driven oxidative processes are initiated by
excited electrons on the catalyst surface.
7. Ozone can be produced from air.
8. The most important characteristics of photocatalysts
are: resiliance against chemical and photocorrosion,
safety, cost and band-gap.
9. The electron/hole recombination can be avoided
by increasing reaction temperature.
10. Heterogeneous photocatalysis can only be applied
to monoaromatics.
Introduction 15
Part B
1. What is the most important difference
between thermochemical and photochemical
solar processes?
2. What is the usual way of expressing the toxicity
of a chemical in the environment?
3. Why is biodegradation (a major mechanism in
wastewater treatment) quite inefficient in treating
certain types of wastewater?
4. What is the percentage of absorbed photons in a
solution with the following characteristics:
extinction coefficient = 1327 cm–1 M–1,
concentration of substrate
0.01 M, illuminated pathlength = 5.6 cm, with an extinction
coefficient of 0.3?
5. What wavelength is required to excite a
semiconductor with a band-gap of 4.0 eV?
6. Name three important characteristics of
heterogeneous photocatalysis when used in a water-
treatment process.
7. Why is TiO2 the most suitable photocatalyst
for wastewater treatment?
8. What is the most important electron acceptor in water?
9. What is the most important product of
photocatalytic degradation of organic contaminants?
10. Why do hydroxyl radicals react with
organic substances?
16 Solar Detoxification
Answers
Part A
1) False. 2) False. 3) True. 4) False. 5) False. 6)
False.
7) True. 8) True. 9) False. 10) False.
Part B
1. In thermochemical processes, solar radiation is
converted into thermal energy; in photochemical
processes the solar photons are absorbed directly by the
reactants, giving rise to the reaction.
2. The toxicity of a chemical is usually expressed as the
effective concentration or dose of the material that
would produce a specific effect in 50 per cent of a large
population of test species (EC 50 or ED50).
3. Because in the case of very toxic compounds,
microorganisms need an extended period of
adaptation, during which they are not completely
non-viable.
4. 100 per cent and 3.8 per cent.
5. λ Š 310 nm.
6. The process takes place at ambient temperature, the
oxygen necessary for the reaction is obtained from the
atmosphere, and the catalyst is cheap, innocuous and
can be reused.
7. It has exhibited the highest activity. It is highly
stable to chemical and photocorrosion. It can use natural
UV.
8. Dissolved oxygen.
9. Carbon dioxide.
10. Because of its very high oxidation potential.

Aims
This chapter describes the power of light
as a source of energy. It outlines the
basic
principles that are related to the light
spectrum and specifically to the solar
spectrum.
It discusses solar UV radiation and its
photon flux in more detail, because this part
of the solar spectrum is the most important
for driving chemical processes. The major
atmospheric variables determining the
amount of UV solar radiation on the Earth’s
surface are discussed. A method for
calculating UV attenuation at a given site is
presented. Finally, solar radiation
measurement systems are described.
2
Introduction 17
CHAPTER 2
Solar Irradiation
Objectives
At the end of this chapter you will
understand the main factors affecting
solar radiation behaviour and you will
be
able to do six things:
1. Discriminate between the
different components of solar
radiation and their principal
characteristics.
2. Recognize typical solar spectra and
understand the effect of Sun position on the
solar power reaching the Earth’s surface.
3. Find the photon flux of a
polychromatic source of energy with
simple calculations.
4. Describe the most important
components of the Earth’s atmosphere and
their effect on power and spectral
distribution of the solar radiation.
5. Understand the procedures that
permit solar power to be calculated from
available radiation at any given site.
6. Comprehend the basic principles on
which solar radiation measurement is
based.
18 Solar Detoxification

NOTATION AND UNITS

Symbol Description Units

AM Air mass ratio

fn Cloud factor
fλ Fraction of power associated with a wavelength nm–1
–
H Radiance exposure monthly average kJ m–2
HTBD TBDUV radiance exposure kJ m–2
I Photon flux density Einstein s–1 m–2
NA Quantity of photons absorbed by the system Photons s–1
N0 Avogadro’s number, 6.023 × 10 23
Photons mol–1
Nλ Number of photons supplied by a source of light of wavelength λ Photons s–1
Qλ Energy of a monochromatic source of light of wavelength λ W m–2 µm–1
T Transmittance
Tλ Transmittance of direct-bean solar radiation under cloudless skies at a specific wavelength
TA,λ Transmittance related to absorption and dispersion by aerosols
Tg,λ Transmittance resulting from absorption of atmospheric gases
To,λ Transmittance related to the effect of the ozone layer
TR,λ Transmittance related to the molecules of air
Tv,λ Transmittance resulting from absorption by steam
TBDUV Typical ‘best day’. Completely clear sky during all the hours of sunlight
U Energy of one photon eV, J
UVD Direct ultraviolet light W m–2
UVG Global ultraviolet light W m–2
UVλ Ultraviolet irradiance associated with a wavelength W m–2 nm–1
8 Quantum yield
λ Wavelength nm, µm

2.1. The power of light
Light is just one of various electromagnetic waves
present in space. The electromagnetic spectrum covers an
extremely broad range, from radio wavelengths of a
metre or more, down to x-rays with wavelengths of less
than one billionth of a metre. Optical radiation lies
between radio waves and x-rays on that spectrum and
has a unique combination of ray, wave and quantum
properties. At x-ray and shorter wavelengths,
electromagnetic radiation tends to be quite particle-like
in its behaviour, whereas toward the long wave- length
end of the spectrum behaviour is mostly wavelike. The
UV-visible portion occupies an intermediate position,
having both wave and particle properties in varying
degrees (See Figure 2.1a).
Like all electromagnetic waves, light waves can interfere
with each other, become directionally polarized, and bend
slightly when passing through an edge. These properties
allow light to be filtered by wavelength or amplified coher-
ently as in a laser. In radiometry, light’s propagating wave
front is modelled as a ray travelling in a straight line (See
Figure 2.1b). Lenses and mirrors redirect these rays along
predictable paths. Wave effects are insignificant in a large-
scale optical system, because the light waves are randomly
distributed and there are plenty of photons.
2.1.1. Ultraviolet light
Short wavelength UV-light exhibits more quantum
proper- ties than its visible or infrared counterparts.
Ultraviolet light

FIGURE 2.1. The optical portion of the electromagnetic
spec- trum a), and a light wave front modelled as a straight
line b).
is arbitrarily broken down into three bands, according to
its effects. UV-A (315 to 400 nm), which is the least
harmful type of UV light, because it has the least
energy (recall Eq. 1.1), is often called ‘black light’, and
is used for its relative harmlessness and its ability to
cause fluorescent materials to emit visible light – thus
appearing to glow in the dark. UV-B (280 to 315 nm) is
typically the most destructive form of UV light, because
it has enough energy to damage biological tissues, yet
not quite enough to be completely absorbed by the
atmosphere. UV-B is known to cause skin cancer. Since
the atmosphere blocks most of the extraterrestrial UV-B
light, a small change in the ozone layer could
dramatically increase the danger of skin cancer. UV-C
(100 to 280 nm) is almost completely absorbed in air
within a few hundred metres. When UV-C photons
collide with oxygen atoms, the energy exchange causes
the formation of ozone. UV-C is never observed in
nature, however, since it is absorbed so quickly.
Germicidal UV-C lamps are often used to purify water
because of their capability to kill bacteria.
2.1.2. Visible light
Visible light is concerned with the radiation perceived by
the human eye. The lumen (lm) is the photometric
equivalent of the watt, weighted to match the eye response
of the ‘standard observer’. Yellowish-green light receives
the greatest weight because it stimulates the eye more
than blue or red light of equal radiometric power (1 W at
555 nm = 683.0 lumens). To put this into perspective: the
human eye can detect a flux of
Solar Irradiation 19
Blue Green Yellow Red
400 500 600 700 nm
FIGURE 2.2. Visible-light colour distribution.
about 10 photons per second at 555 nm; this corresponds to
a radiant power of 3.58 × 10–18 W (or J s–1). Similarly, the
eye can detect a minimum flux of 214 and 126 photons per
second at 450 nm and 650 nm, respectively.
2.1.3. Infrared light
Infrared light contains the least amount of energy per
photon of any band and is unique in that it has primarily
wave prop- erties. This can make it much more difficult
to manipulate than ultraviolet and visible light. Infrared
is more difficult to focus or refract with lenses, diffracts
more, and is difficult to diffuse. Since infrared light is a
form of heat, infrared detec- tors are sensitive to
environmental changes such as a person moving in the
field of view. Night vision equipment takes advantage of
this effect, amplifying infrared to distinguish people and
machinery that are concealed in the darkness.
2.2. The solar spectrum
The total energy coming from that huge reactor, the Sun,
from which the Earth receives 1.7 × 1014 kW, amounts to
1.5 × 1018 kWh per year, or approximately 28,000 times
world consumption (Figure 2.3a). Radiation beyond the
atmosphere has a wavelength of between 0.2 µm and 50
µm, which is reduced to between 0.3 µm and 3.0 µm when
reaching the Earth’s surface, because of the absorption of
part of it by different atmospheric components (ozone, oxy-
gen, carbon dioxide, aerosols, steam and clouds). The solar
radiation that reaches the ground without being absorbed or
scattered is called ‘direct radiation’; radiation that reaches the
ground but has been dispersed is called ‘diffuse radiation’; and
20 Solar Detoxification

FIGURE 2.3a. World solar irradiance, MWh m–2 year–1.

2,000 2,000
Irradiance, Wm2 µm1

1,500 Extraterrestrial 1,500

Direct air mass 1.5
Global 37° air mass 1.5
1,000 1,000

500 500

0 0
0.6 1.2 1.8 2.4 3.0 3.6 4.2
Wavelength, µm

FIGURE 2.3b. Spectral solar radiation plotted from 0.2 to 4.5 µm.

the sum of both is called ‘global radiation’. In other words, it
is the direct radiation that produces shadow when an opaque
object blocks it; diffuse radiation does not. In general, the
direct component of global radiation on cloudy days is min-
imum and the diffuse component is maximum, and the
opposite is true on clear days.
Figure 2.3b shows the standard solar radiation spectra
(Hulstrom et al., 1985) at ground level on a clear day.
The dotted line corresponds to the extraterrestrial
radiation in the same wavelength interval. When this
radiation enters the atmosphere, it is absorbed and
scattered by atmospheric components such as air
molecules, aerosols, water vapour,

FIGURE 2.4. Air mass and solar components.
liquid water droplets and clouds. The spectral irradiance
data are for the Sun at a solar zenith angle of 48.19°.
This zenith angle corresponds to an air mass of 1.5,
which is the ratio of the direct-beam solar-irradiance path
length through the atmosphere at a solar zenith angle of
48.19° to the path length when the Sun is in a vertical
position. AM = 1 when the Sun is directly overhead
(zenith). As air mass increases, the direct beam traverses
longer path lengths in the atmos- phere, which results in
more scattering and absorption of the direct beam and a
lower percentage of direct-to-total radiation (for the
same atmospheric conditions).
The AM 1.5 global irradiance is shown for a flat
surface facing the Sun and tilted 37° from the horizontal.
The 37° tilt angle is used because it is the latitude of the
Plataforma Solar de Almería in Spain, where most of the
research pre- sented here was done. The limited part of
the solar spectrum that can be used in photocatalysis with
TiO2 may be clearly seen (see Table 1.4), but as the
energy source is so cheap and abundant, even under
these limitations its use is of interest.
2.3. Solar ultraviolet irradiation
Solar ultraviolet radiation is, as explained above, only a
very small part of the solar spectrum, amounting to
between 3.5 per cent and 8 per cent of the total solar
spectrum, as demon- strated by measurement (this figure
may vary for a given location on cloudy and clear days).
The percentage of global
Solar Irradiation 21
UV radiation (direct + diffuse) generally increases with
regard to total global solar radiation when atmospheric
transmissivity decreases, mainly because of clouds, but
also because of aerosols and dust. In fact, the average
ratio of UV to total radiation on cloudy days is up to two
percentage points more than on clear days.
The efficiency of a chemical reaction is calculated
from the ratio of the products to the departing reactants.
In photo- chemistry, it is very common to use the
quantum yield con- cept, which is calculated from a
known amount of photons absorbed in the reaction.
Quantum yield (8) is defined as the ratio of the
number of reacting molecules (An) to the quantity of
photons absorbed by the system (NA):
n
 (2.1)
NA
Experimentally, quantum yield is expressed as the number
of moles of reactant in an interval of time t, divided into
the number of moles of photons absorbed during the
same period. Knowledge of the quantum yield is rather
important for an understanding of the mechanism of a
photochemical reaction. If every absorbed photon
produces a molecular transformation, 8 = 1. If it is less
than 1, it means that deactivation processes have
occurred or other reactions have competed with the one
studied. 8 > 1 indicates a series of reactions has taken
place, the promoter of which has been excited by a
photon. In the case of photocatalysis by UV radi- ation,
the number of photons that reach the reacting mixture
and are thereby susceptible to being absorbed will be in
rela- tion to the UV solar spectrum. For reactors using
solar radi- ation, knowledge of the solar UV spectrum is
important for the following reasons:
• The radiation (sunlight) that reaches them is not con-
stant. This prevents direct comparison between
experi- ments carried out at different times of the day
or seasons of the year or under different atmospheric
conditions.
• The extensive literature on photocatalytic
decomposition of organic compounds indicates that
the majority of the experiments in which photon flux
is known are carried out in laboratory reactors
illuminated by lamps. In order to compare these
results with solar radiation or to use the information
contained in these reports, it is necessary to know the
photon flux inside the solar reactor.
• The quantum yield of the reaction tested under a
given experimental condition provides information
on the
22 Solar Detoxification

optimum conditions for decomposition of the
contami- nant. Knowledge of the photon flux in
this situation is basic to the determination of the
efficiency of the solar reactor components
(reflective surface, absorber tube, control system,
concentration factor and so on) and to development
of any possible modifications to these
components to improve photodegradation
conditions.
• Any economic comparison between solar radiation
and electric lamps as the UV photon source requires
knowl- edge of the photon flux incident on the solar
reactor.
The two spectra shown in Figure 2.5 correspond to the
same spectra shown in Figure 2.3 for the solar UV
spectrum range at ground level. The shorter spectrum
(direct UV) reaches 22 W m–2 between 300 and 400
nm, the longer spectrum (global UV) reaches 46 W m–
2.
The number of photons, Nλ, supplied by a monochro-
matic source of light with wavelength λ and energy Qλ
is related to the energy of one photon, Uλ, by Planck’s
equation (Eq. 1.1):
Q λ
N λQ (2.2)
λ λ
Wλ hc
When a source of light is polychromatic, as is solar
radiation, the number of photons is given by an integral
covering the whole range of wavelengths of that source:
λ2
N   N(λ )dλ 
1

λ2
Q(λ (2.3)
)dλ
λ1 hc λ1
Equation 2.3 gives the ratio between photonic and radio-
metric quantities, defining the photon flux density I
[Einstein s–1 m–2] as the number of incident photons per
unit of surface and time:
d2N
I 
N0dtdA (2.4)
where N0 is Avogadro’s number (6.023 × 1023). 1 Einstein =
1 mol of photons 6.02 × 1023 photons.
Using the spectrum data and the above equations
in congruent units [S.I.], it is possible to determine the
photon flux density I (I D = 3.6 × 1019 photons m–2 s–1
= 6 × 10–5 Einstein m–2 s–1, IG = 8.4 × 1019 photons m–2
s–1 = 14 × 10–5 Einstein m–2 s–1). These two values give
an idea of the energy coming from the Sun and
available for photocatalytic reactions with TiO2, which
only uses the part of the UV spectrum up to 390 nm,
as explained below. In any case, the UV radiation
values described vary from one location to another and,
obviously, vary at differ-
ent hours of the day and in different seasons, making it
necessary to know these data for the particular location
and in real time. These equations will be very useful in
those cases where this is not possible.
2.4. Atmospheric attenuation
of solar radiation

A general expression for transmittance (T) of direct-

beam solar radiation under cloudless skies at a specific
wavelength (λ) is (Iqbal, 1983):

Tλ  TR,λTA,λTo,λTg,λTv,λ (2.5)

TR,λ is the spectral transmittance resulting from the

 disper- sion produced by molecules of air (dimensions
of many of which are =1 Å, Raleigh dispersion). TA,λ is the
spectral trans- mittance related to absorption and
dispersion by aerosols (solid or liquid particles
suspended in the air). To,λ corre- sponds to the effect of
 the ozone layer. Tg,λ is the transmit- tance resulting from
absorption of atmospheric gases (such as carbon dioxide
FIGURE 2.5. Ultraviolet spectra at the Earth’s surface and oxygen). Tν,λ corresponds to absorp- tion by water
vapour. The effect of each of these parameters
(standard ASTM). within the range in question (300 nm–400 nm) would be
 Solar Irradiation 23

the following (Riordan et al., 1990):
• TR,λ = exp(–0.008735 λ–4.08 M'), where M' is air
mass corrected according to its density, which
depends on pressure and, therefore, altitude.
Accordingly, this factor would be practically constant
for a given site.
• TA,λ = exp(–λ–α β M) where M is air mass, β is the
turbid- ity coefficient, which usually varies between 0
and 0.5 and is a reflection of the amount of aerosols in
the air, and α is an index of the size of the aerosol
molecules. β will vary depending on the atmospheric
contamination at the
site. Where there is no contamination it varies only
slightly. The same reasoning is valid for α.
• T
o,λ is constant for a specific site since the ozone layer
has
a practically constant thickness (for now).
• Tg,λ only influences wavelengths over UV.
• Tv,λ does not affect the UV spectrum.
Keeping in mind, then, the different transmittances, it
may be assumed that the solar UV spectrum does not
vary sub- stantially at a specific site throughout the year,
unless atmos- pheric conditions (other than clouds) do
so. The dominating attenuator of solar radiation is cloud.
Under overcast skies there is no direct-beam radiation,
and under partly cloudy skies there is intermittent direct-
beam radiation when clouds are not obscuring the Sun’s
disk. Clouds are often assumed to have a wavelength-
independent attenuation function in
the UV range, but in the near-infrared region (see Figure
2.6) they cause increased absorption, due to the water
vapour and liquid water they contain (Tv,λ).
Clouds modify the total UV energy reaching the Earth’s
surface, but wavelength distribution is not affected. This
can- not be guaranteed, however, if the data for the spectra
shown in Figure 2.6 are not represented in a standardized
manner as in Figure 2.7. This can be done for any
wavelength inter- val by the following operation.
Summations have been used to treat the discrete values nm
to nm:
λ400
fλ 
UVλ nm
(2.6)
, therefor fλ

λ400 nm
e λ300
nm
=1
 UVλ
λ300 nm
where fλ, is the fraction of power associated with
wavelength λ and UVλ is the irradiance, W m–2 nm–1
corresponding to each wavelength and measured with a
spectroradiometer. In Figure 2.7, the homogeneity of the
spectra recorded may be observed. If the spectrum of
UV radiation is assumed to have a fixed form, then a
standardized spectrum can be considered as standard for
each site. Therefore, the number of photons
corresponding to this range of wavelengths is only a
function of the intensity (measurable in real time with
radiometers, see the following section in this chapter).

0.7
1.2
0.6

1.0
0.5
Clear sky Clear sky
0.8
0.4
Wm-2nm-1
Wm-2nm-1

0.6
0.3

0.4
0.2

0.2 0.1
Clouds
Clouds
0.0 0.0
400 600 800 1,000 1,200 300 325 350 375 400
Wavelength, nm Wavelength, nm

FIGURE 2.6. Solar spectra at the Earth’s surface (Plataforma Solar de Almería) between 300 and 1,100 nm.
 Solar Irradiation 25

0.03

λ400 nm
U λ
fλ  λ400Vnm , therefor  fλ
0.02
 U λ
e λ300 nm =1

λ300 nmV
f, nm-1

0.01

Area below each curve = 1

0.00
300 325 350 375 400
Wavelength, nm
FIGURE 2.7. Normalized solar UV spectra shown in Figure 2.6.

2.4.1. Annual available ultraviolet

radiation
A general index of atmospheric transmittance
incorporating all the processes described above is the so-
called ‘cloud fac- tor’ (fn). For the calculation of fn, the
annual average ultra- violet radiation level must be found.
Knowledge of this factor enables the amount of energy that
reaches the Earth’s surface to be predicted for a given
place at any time of the year. It
should be noted that the cloud factor for global radiation
is
always lower than for direct radiation, as the diffuse
compo-
nent of solar radiation is maximum when direct radiation
is absent (global = direct + diffuse). This factor is
calculated (Eq. 2.7) from the ratio of average radiation
(affected by all atmospheric phenomena) to the highest
attainable radiation at all times of the year. This is
usually calculated for each month separately. To find out
the highest UV radiation avail- able each month, a typical
‘best day’ (completely clear sky during all daylight hours)
is selected for each month (TBDUV) from among all the
days for which average radiation is calcu- lated. The
parameters taken into account in selecting the TBDUV
are absence of clouds and proximity to the fifteenth day
of each month (See Figure 2.8). Several days per month
(corresponding to each year for the period to be
analysed) must be chosen and compared to find the day
with the maximum HTBD.
 H 
fn  1    tions. The radiometer should be able to cover the entire
 HTBD 
(2.7)
where HTBD (kJ m–2) is the TBDUV radiance exposure
(direct or global). This is obtained by the sum of the UV
irradiance
FIGURE 2.8. TBDUV at different periods of the year at
Plataforma Solar de Almería (37 °N).
throughout the day. In this case, being discrete values, it
has been calculated by summing hourly irradiance valves
from
– –2
sunrise to H (kJ ) is the average of the month.
sunset. m
This is calculated by multiplying the monthly average irradi-
ance by the monthly average of hours of sunlight. The
cloud factor for UV radiation is calculated from data
collected with radiometers that are UV-specific. The UV-
radiation database must be large enough to be considered
statistically correct (at least four to five years).
2.5. Solar radiation measurement
Detectors translate light energy into an electrical
current (Ryer, 1997). Light striking a silicon photodiode
causes a charge to build up between internal ‘P’ and ‘N’
layers. When an external circuit is connected to the cell,
an electrical current is produced. This current is
linear with regard to the incident light over a
dynamic ten-decade range. A wide dynamic range is a
prerequisite for most applica-
dynamic range of any detector that will be plugged into it.
This usually means that the instrument should be able
to cover at least seven decades of dynamic range with
minimal
 24 Solar Detoxification
linearity errors. The current or voltage measurement
device should be the least significant source of error in
the system. The second thing to consider when choosing
a radiometer is the type of features offered. Ambient
zeroing, integration ability and a ‘hold’ button should be
standard. The ability to multiplex several detectors to a
single radiometer or to con- trol the instrument
remotely may also be desired. Last, portability and
battery life may be an issue for measure- ments made
in the field.
Light is all around us every day, yet it remains the most
elusive form of energy to measure accurately. A single pho-
ton of light travels in a straight line in one direction at a
given wavelength. A light bundle consists of a jumbled
mixture of billions and billions of photons at different
wavelengths, going in different directions, at different
moments in time. The watt (W), the fundamental unit of
optical power, is defined as a rate of energy of one joule (
J) per second. Optical power is a function of both the
number of photons and the wavelength. Each photon
carries an energy that is described by Planck’s equation
(Eq. 1.1). All light measure- ment units are spectral, spatial
or temporal distributions of optical energy. The biggest
hurdle in light measurement is the spatial nature of light.
Irradiance is a measure of the energy density received
from a light source. Since light expands outward from a
point source, irradiance decreases with distance. Irradiance
also decreases with incident angle. Carefully designed input
optics cannot prevent measurement errors caused by lax
attention to the measurement geometry upon which the
unit’s systems are based. Spectral responsiv- ity and
detectivity present a very different problem. Many
properties of light are dependent on wavelength, and the
energy of one photon is inversely proportional to its wave-
length. Since a detector measures only absorbed light, it
cannot differentiate between one photon (200 nm) and ten
photons (2,000 nm). The light must be filtered by
wavelength before it reaches the detector.
Sensitivity to the band of interest is a primary
considera- tion when choosing a detector. You can
control peak respon- sivity and bandwidth through the
use of filters, but you must have an adequate signal to
start with. Filters can suppress out-of-band light but
cannot boost the signal. Another con- sideration is
blindness to out-of-band radiation. If you were
measuring solar ultraviolet in the presence of
massive amounts of visible and infrared light, for
example, you would select a detector that was
insensitive to the long wave- length light that you
intended to filter out. Last, linearity,
stability and durability are considerations. Some detector
types must be cooled or modulated to remain stable.
High voltages are required for other types. In addition,
some can be burned out by excessive light, or have their
windows permanently ruined by a fingerprint.
2.5.1. Detectors
Planar-diffusion-type silicon photodiodes are perhaps the
most versatile and reliable sensors available. The P-
layer material at the light-sensitive surface and the N
material at the substrate from a P–N junction, which
operates as a photoelectric converter, generate a current
that is propor- tional to the incident light. Silicon cells
operate linearly over a ten-decade dynamic range, and
remain true to their original calibration longer than any
other type of sensor. For this reason, they are used as
transfer standards at the United States National
Institute of Standards and Technology (NIST).
The phototube is a light sensor that is based on the
photo- emissive effect. It is a bipolar tube consisting of a
photoemis- sive cathode surface that emits electrons in
proportion to incident light, and an anode that collects
the electrons emit- ted. The anode must be biased at high
voltage (50 to 90 V) in order to attract electrons strongly
enough to cause them to jump through the vacuum of the
tube. Some phototubes use a forward bias of less than 15
volts, however. The cathode material determines the
spectral sensitivity of the tube. Solar- blind vacuum
photodiodes use Cs-Ta cathodes to ensure sensitivity
only to ultraviolet light, providing as much as a million
rejecting long wavelengths for every UV wavelength
accepted. A UV glass window is required for sensitivity in
the UV down to 185 nm, with fused silica windows
offering transmission down to 160 nm.
The thermopile is a heat-sensitive device that
measures radiated heat. Infrared light contains the least
amount of energy per photon of any band. Because of
this, an infrared photon often lacks the energy required to
pass the detection threshold of a quantum detector.
Infrared light is usually measured using a thermal
detector such as a thermopile, which measures
temperature change due to absorbed energy. While these
thermal detectors have a very flat spectral respon- sibility,
they suffer from temperature sensitivity, and usually
must be artificially cooled. The sensor is usually sealed
in a vacuum to prevent heat transfer except by radiation.
A ther- mopile consists of a number of thermocouple
junctions in
26 Solar Detoxification
, ,
FIGURE 2.9. Responsivities of three detectors. In the inset
is shown a schematic of the effect of a filter on detector
respon- sivity.
series, which convert energy into a voltage via the Peltier
effect. Thermopiles are convenient sensors for measuring
infrared light, because they offer adequate sensitivity and
a flat spectral response in a small package. More
sophisticated bolometers and pyroelectric detectors need
to be chopped and are generally used only in calibration
laboratories.
The best method of operating a thermal detector is
by chopping incident radiation, so that drift is zeroed out
by the modulated reading. The quartz window in most
thermopiles is adequate for transmitting from 200 to
4,200 nm, but for long wavelength sensitivity, up to
40 microns, Potassium bromide windows are used.
Another strategy employed by thermal detectors is to
modulate incident light with a chop- per. This allows
the detector to measure differentially between the
dark (zero) and light states. Quantum-type detectors
are often used in the near infrared range, especially
below 1,100 nm. Specialized detectors such as InGaAs
offer excellent responsivity from 850 to 1,700 nm.
Typical silicon photodiodes are not sensitive above
1,100 nm. These types of detectors are typically
employed to measure a known arti- ficial near-IR
source without including long wavelength
background ambient radiation. Most radiometric IR
meas- urements are made without lenses, filters or
diffusers, relying on just the bare detector to measure
incident irradiance.
2.5.2. Filters
A detector’s overall spectral sensitivity is equal to the
prod- uct of the responsivity of the sensor and the
transmission of
the filter. Given a desired overall sensitivity and a known
detector responsivity, you can then draw a transmission
curve for the ideal filter. Filter bandwidth decreases with
thickness according to Lambert-Beer’s law (see
Equations.
1.2 and 1.3), so by varying filter thickness you can selec-
tively modify the spectral responsivity of a sensor to
match a particular function. Multiple filters cemented in
layers give a net transmission equal to the product of the
individual transmissions. Filters operate by absorption or
interference. Coloured glass filters are doped with
materials that selec- tively absorb light by wavelength,
and obey Lambert-Beer’s law. The peak transmission is
inherent to the additives, while bandwidth is dependent
on thickness. Sharp-cut fil- ters act as long-pass filters,
and are often used to subtract out long-wavelength
radiation in a secondary measurement. Interference
filters rely on thin layers of dielectric to cause
interference between wave fronts, providing very
narrow bandwidths. Any of these filter types can be
combined to form a composite filter that matches a
particular photo- chemical process.
2.5.3. Input optics
When selecting input optics for a measurement
application, consider both the size of the source and the
viewing angle of the intended real-world receiver.
Suppose, for example, that you were measuring the
erythemal (sunburn) effect of the Sun on human skin.
While the Sun may be considered very much a point
source, skylight, refracted and reflected by the
atmosphere, contributes significantly to the overall
amount of light reaching the Earth’s surface. Sunlight is a
combina- tion of a point source and a 2π steradian area
source. The skin, since it is relatively flat and diffuse, is an
effective cosine receiver. It absorbs radiation in
proportion to the incident angle of the light. An
appropriate measurement system should also have a
cosine response. If you aimed the detector directly at the
Sun and tracked the Sun’s path, you would be measuring
the maximum irradiance. If, however, you wanted to
measure the effect on a person lying on the beach, you
might want the detector to face straight up, regardless of
the Sun’s position. This example can be extended to solar
collectors (see Chapter 6).
Different measurement geometries necessitate
specialized input optics. Radiance and luminance
measurements require a narrow viewing angle (< 4°) in
order to satisfy the conditions underlying the
measurement units. Power measurements,
 Solar Irradiation 27

FIGURE 2.11. A solar global UV detector (tilted 37° and

fac- ing south) with a cosine diffuser.

FIGURE 2.10. Relative spatial response of an ideal cosine

diffuser (up) and a radiance lens barrel (down).

on the other hand, require a uniform response to

radiation, regardless of input angle, to capture all light.
There may also be occasions when the need for additional
signal or the desire to exclude off-angle light affects the
choice of input optics. A high-gain lens, for example, is
often used to amplify a distant point source. A detector can
be calibrated to use any input optics as long as they
reflect the overall goal of the measurement.
FIGURE 2.12. A solar direct UV detector installed on a solar
Cosine diffusers tracking system.
A bare silicon cell has a near-perfect cosine response, as
do all diffuse planar surfaces. As soon as you place a signal. Radiance optics merely limits the viewing angle to
filter in front of the detector, however, you change the less than the extent of a uniform area source. This input
optic is used to measured direct sunlight, and is
spatial re- sponsivity of the cell by restricting off-angle
light. Fused silica or optical quartz with a ground mounted on a mobile sun-tracking platform (one loop
(rough) internal hemisphere makes an excellent per day) to follow the Sun from sunrise to sunset.
diffuser, with adequate transmission in the ultraviolet.
Teflon is an excellent alterna- tive for UV and visible Fibre optics
applications, but is not an effective diffuser for infrared Fibre optics allows measurements in tight places or
light. where irradiance levels and heat are very high. Fibre optics
consists of a core fibre and a jacket with an refraction
Radiance lens barrels index chosen to maximize total internal reflection. Glass
Radiance and luminance optics frequently employ a dual fibres are suitable for use in the visible, but quartz or fused
lens system that provides an effective viewing angle of less silica is required for trans- mission in the ultraviolet. Fibres
than 4°. The trade-off of a restricted viewing angle is a are often used to continuously
reduction in
28 Solar Detoxification
monitor UV curing ovens, due to the attenuation and heat
pro- tection they provide. Typical fibre optics restricts the
field of view to about ±20° in the visible and ±10° in the
ultraviolet.
Integrating spheres
An integrating sphere is a hollow sphere coated inside
with barium sulfate, a diffuse white reflectance coating
that offers greater than 97 per cent reflectance between
450 and 900 nm. The sphere is baffled internally to
block direct and first- bounce light. Integrating spheres
are used as sources of uni- form radiance and as input
optics for measuring total power. Often, a lamp is placed
inside the sphere to capture light that is emitted in any
direction.
High-gain lenses
In situations with low irradiance from a point source,
high- gain input optics can be used to amplify the light by
as much as fifty times while ignoring off-angle ambient
light. Flash sources such as tower beacons often employ
Fresnel lenses, making near field measurements difficult.
With a high-gain lens you can measure a flash source
from a distance without compromising signal strength.
High-gain lenses restrict the field of view to ±8°, and so
cannot be used in full immersion applications where a
cosine response is required.
Summary
The three principal components of light (ultraviolet,
visible and infrared) and their wavelength distribution
have been described. Typical solar spectra and air mass
effects (Sun position) have been shown. The calculation
of photonic
fluxes (Einstein) from radiometric measurements (W)
and spectral data (nm–1) has been introduced. The
attenuating components of the atmosphere and their
effect on UV radia- tion have been discussed to achieve a
final conclusion: the UV spectrum is constant at a
definite emplacement under defined circumstances. This
characteristic permits standard- ization of the solar-UV
spectrum, which is very helpful for finding a standard
photon flux. The cloud factor index has been described
and its calculation from a UV-radiation data- base has
been explained. Finally, solar radiation measure- ment
systems have been described, with special emphasis on
their main components. Their correct combination will
per- mit accurate analysis of solar radiation and correct
evaluation of the quantum yield of photochemical
reactions.
Bibliography
HULSTROM, R.; BIRD, R. AND RIORDAN, C. 1985. Spectral
solar irradiance data sets for selected terrestrial conditions.
SOLAR Cells, No. 15, pp. 365–91.
IQBAL, M. 1983. An Introduction to SOLAR RADIATION. Canada,
Academic Press.
RIORDAN, C.J.; HULSTROM, R.L. AND MYERS, D.R. 1990.
Influences of Atmospheric Conditions AND Air MASS on the
RATIO of ULTRAVIOLET to TOTAL SOLAR RADIATION. Golden,
Colo., Solar Energy Research Institute (SERI)/TP-215-3895.
RYER, A. 1997. Light MEASUREMENT HANDBOOK. Newburyport,
Mass., International Light Inc.
 Solar Irradiation 29

Self-assessment questions Part B

Part A: True or false? 1. What is the most important difference

between ultraviolet, visible and infrared light?
1. The visible portion of light is more powerful than 2. What are the usual units used to express solar
the UV portion. spectrum power?
2. Most solar UV light at the Earth’s surface is between 3. Why is the air mass at Sun zenith called AM 1?
100 and 280 nm.
4. Cite at least two reasons to justify the importance
3. The solar radiation that reaches ground level without of understanding the solar spectrum in
being absorbed or scattered is called ‘direct radiation’. photochemistry.
4. Any economic comparison between using solar 5. What is the basic measurement unit in
radiation and electric lamps as the UV photon source, photochemistry, and why?
requires knowledge of the photon flux incident on the
solar reactor.
6. Why do clouds not absorb UV light?
5. The UV photon flux density at the Earth’s surface is
7. What is the usefulness of equation 2.6?
in the range of thousands of photons per square metre.
8. Convert the following fraction of power associated
6. Clouds absorb UV light. with each wavelength (corresponding to a standardized
spectrum from 300 to 400 nm) into solar spectrum power
7. Clouds scatter UV light. given that the total measured power is 40 W/m2.
8. The cloud factor for UV light is determined TABLE 2.1
using specific UV radiometers.
λ, nm fλ
9. The best detector to measure infrared light
is a phototube. 300 0.0002
302 0.0004
10. A detector’s overall spectral sensitivity is equal to 304 0.0007
the product of the transmission of the sensor and the
responsivity of the filter. 306 0.0011
308 0.0017
310 0.0023
312 0.0032

9. Why is the measurement of infrared light

with a quantum radiometer very difficult?

10. How is it possible to vary the spectral responsivity

of a sensor without changing its type of filter?
30 Solar Detoxification

Answers 5. Einstein. Because it is 1 mol of photons and

therefore, the quantum yield of a photochemical
reaction (rate
Part A 1 M/min) that absorbs 1 Einstein L –1 min–1 is 1.

1) False. 2) False. 3) True. 4) True. 5) False. 6) False.
7) True. 8) True. 9) False. 10) False.
Part B
6. Because pure water does not absorb UV light.
7. To represent spectra in a standardized manner. This
will permit comparison between spectra recorded at
different sites, hours of the day and/or different seasons.

1. Wavelength: ultraviolet light is from 100 to 400 8. TABLE 2.2

nm, visible light is from 400 to 770 nm, and infrared
light is from 770 to 106 nm. λ, nm UVλ, W m–2 nm–1

2. W m–2 nm–1 or W m–2 µm–1. 300 0.0080

302 0.0160
3. Because zenith corresponds to the minimum path 304 0.0280
length through the atmosphere of direct-beam solar
irradiance. 306 0.0440
308 0.0680
4. a) The radiation that reaches the solar reactors is 310 0.0920
not constant. 312 0.1280
b) In order to compare laboratory results with
solar results or to use the information obtained
with lamps. 9. Infrared light contains the least amount of energy
c) To determine the efficiency of the per photon of any band. Because of this, an infrared
components of the solar reactor and the possible photon often lacks the energy required to pass the
modifications to improve the conditions of detection threshold of a quantum detector.
photodegradation.
d) To perform economic comparisons between 10. By varying filter thickness.
solar radiation and electric lamps.

Experimental Systems
Aims
This chapter describes the experimental
systems necessary for performing
pilot-plant-scale solar photocatalytic
experiments. Various laboratory set-ups
are also shown in order to emphasize
the
differences between these small
photoreactors and pre-industrial-scale pilot
plants.
The chapter outlines the basic components
of these pilot plants and the different
possibilities for operating them. Modelling
of the experiments is reviewed from a
chemical engineering point of view.
Finally, an extensive overview of the
relationships between radiometer
measurements and the photons that
actually reach the photoreactor is
presented.
3
Solar Irradiation 31
CHAPTER 3
Objectives
By the end of this chapter, you will
understand the most important features
of large-scale outdoor photocatalytic
experiments and you will be able to do
six things:
1. Design a simple, versatile solar
detoxification pilot system to fit the
present and future needs of the research
to be performed with it.
2. Understand pilot-plant operation
and decide among different options.
3. Calculate the kinetic constant using
the appropriate method depending on
pilot-plant characteristics and operation.
4. Perform on-site calibration of solar-
UV radiometers.
5. Find the relationship between solar
radiometer measurements and the
photons that actually reach the
reaction.
6. Employ chemical actinometers to
validate all the calculations performed to
measure the photon flux inside
photoreactors.
32 Solar Detoxification

NOTATION AND UNITS

Symbol Description Units
C or Ci Reactant concentration M or mg L–1
EUV Accumulated energy (per unit of volume) incident on the reactor kJ L–1
I Photon flux density Einstein s–1 m–2
IE Effective photon flux corresponding to the UV inside the absorber of a photoreactor Einstein s–1 m–2
I*E Volumetric effective photon flux corresponding to the UV inside the absorber
of a photoreactor Einstein L–1s–1
fλ Fraction of power associated with a wavelength nm–1
k First order kinetic constant min–1, h–1
N Photon flux density Photons s–1 m–2
Q Flow rate L min–1, m3 h–1
r Reaction rate M min–1, mg L–1 min–1
Sp Surface area of the reflector of a photoreactor capturing the radiation m2
ST Surface area of the tube of a photoreactor m2
texp Experimental time min, s, h
tR Residence time min, s, h
UV Measurements provided by a radiometer W m –2
UVλ Ultraviolet irradiance associated with a wavelength W m–2 nm–1
–2 –1
UV*λ Spectral data calculated with the standard spectrum and radiometric data W m nm
UVΣ Summation of the measurements provided by a spectroradiometer W m –2
V Volume L, m3
VTOT Volume of the entire pilot plant L, m3
x Conversion
E
8 Estimated quantum yield using moles of incident photons instead of moles of
photons absorbed by the catalyst
η Loss factors affecting the photon flux
λ Wavelength µm, nm
µλ Coefficient of absorptivity cm–1
τ One residence time min, s, h

3.1. Laboratory systems
The treatment of contaminated water necessarily includes
the design of an efficient photoreactor. Basic laboratory
research on the process has mostly been performed with
experimental devices in which efficiency is not as
important as obtaining appropriate conditions that will
permit reproducibility of the results and provide exhaustive
data on the effects of all impor- tant parameters (Cassano,
2000). This is correct when the goal is fundamental
knowledge of the process, but is not always sufficient to
attempt a change of scale. Two different types of
laboratory photoreactors are presented here. One is a
continuous stirred tank reactor (Figure 3.1) and the other
a recirculating system (Figure 3.2).
Figure 3.1 shows the basic set up of a
microphotoreactor used in laboratory experiments. The
photoreactor consists of a flask made of Pyrex with a flat
bottom, generally made of quartz, which constitutes an
optical filter permitting UV- visible radiation with λ Š
220 nm to enter. For an isothermal reaction, or when one
wants to change the temperature of the medium to
determine the activation energy of the reac- tion (see
Section 4.7), the system is equipped with a jacketed
envelope, through which flows a temperature-constant
fluid (for example, water) delivered by a thermostat.
There are
 Experimental Systems 33

GC/FID
or Valve
GC/MS

Septum

Photoreactor
Pollutant Magnetic
stirrer
+ TiO2

H2O

Water
cell
Optical H2O
disk

UV lamp

FIGURE 3.1. Typical stirred-tank laboratory reactor (courtesy of Laboratoire de Photocatalyse, Catalyse et
Environnement, (E.R. au CNRS), Ecole Centrale de Lyon).

several upper apertures to introduce the reacting mixture,
the catalyst, or a controlled gas atmosphere, and also to
with- draw samples, either from the slurry or from the
gas phase through the ground top and the valve for
analysis by GC (gas chromatography) or GC/MS (gas
chromatography-mass spectrometry, see Chapter 5). A
good stirring is obtained with a magnetic stirrer,
curiously working perpendicularly to the rotating magnet
stirrer to ensure it is at the right level. The determination
of gaseous CO2 is made in an oxygen- confined
atmosphere by sampling amounts of supernatant gas
phase through the ground top and the valve, linked to a
GC by stainless-steel tube.
The UV light is provided by a lamp introduced in a
water- cooled envelope that is closed by a silica optical
disk – used to prevent the formation of ozone in the
laboratory atmos- phere. All the IR beams, which could
heat the slurry sus- pensions, are removed by a water
cell, which contains an optical disk transparent to the
wavelength domain desired.
The radiant flux (in W/m 2) is measured for each
experiment by a radiometer positioned in the place of the
photoreactor. The photograph represents a simple
photoreactor, without a cooled jacket and open to the air,
used for a routine experi- ment of water detoxification
using an illuminated slurry of titania. Mixing is sufficient
to supply gaseous oxygen to the medium (see Section
4.2).
Figure 3.2 shows the set up and a photograph of the
recirculating system. Water, contaminants and titanium
dioxide are continuously recirculated through a 250 mL
Pyrex reactor. During photocatalytic degradation
experi- ments, parameters such as pH, CO 2 and O2 can
be moni- tored in situ via specific electrodes (probes). Air
is introduced into the reactor flask through a flow cell
and distributed via a sintered-glass tip to maintain a
constant oxygen concentra- tion in the system. A solar
simulator equipped with a high- pressure xenon arc lamp
and a parabolic reflector carries out irradiation. As solar
simulators contain a significant thermal
34 Solar Detoxification

Probes above, a simple modification of the parabolic-trough

solar thermal collector has been successfully developed
and is used for experiments in which the catalyst is
Magnetic deployed in suspension. Parabolic concentrating-type
mixer reactors have been used for applications such as
groundwater remediation and removal of metals from
Photoreactor Xenon lamp water. A disadvantage of concentrat- ing reactors is that
they cannot concentrate diffuse solar radiation. This is
not a major problem for solar thermal applications,
Pump Neutral filter because diffuse radiation forms a small fraction of total
solar radiation. However, solar photocatalytic detox-
Cooling
Sampling ification with TiO2 as a catalyst uses only the ultraviolet
Probes
valve por- tion of solar radiation, and as much as 50 per cent or
more of this may be in diffuse form, especially at humid
locations and during cloudy or partly cloudy periods.
Therefore, concen- trating reactors would be more useful
Neutral
filter
at dry, high, direct- insolation locations. Another
disadvantage of concentrating reactors is that quantum
Photoreactor

Cooling
system
Pump
FIGURE 3.2. Typical recirculating laboratory system.
component, it is necessary to decrease the temperature
by using a small heat exchanger. The entire reactor is
con- structed with chemically resistant materials (Pyrex,
Teflon and Viton).
3.2. Solar detoxification
pilot plants
The first outdoor engineering-scale photoreactor
developed was a transformed solar thermal parabolic-
trough collector in which the absorber/glazing-tube
combination had been replaced by a simple Pyrex glass
tube through which contaminated water could flow
(Goswami, 1995). Since that time, research all over the
world has advanced a number of reactor concepts and
designs, including concentrating and non-concentrating
reactors (Malato et al., 2002). The catalyst can be
deployed in several ways, including using a fixed cat-
alyst, a slurry or large neutral-density particles. As
mentioned
efficiency is low, because their rate has an inverse
square, rather than a linear, dependence on light flux (see
Chapter 4). These disadvantages tend to favour the use of
non-concentrating reactors. In any case, these are aspects
which will be discussed in detail in Chapter 6.
Whatever the type of collector, solar detoxification
pilot plants have several components and design
characteristics in common, which can be discussed here.
The design procedure for a pilot solar detoxification
system requires the selection of reactor, catalyst
operating mode (suspension or fixed matrix), reactor-
field configura- tion (series or parallel), treatment-
system mode (once- through or batch), flow rate,
pressure drop, pre-treatment, catalyst and oxidant
loading method, and pH control method. A pilot plant has
to be as versatile as possible to allow for these variables
and, at the same time, provide sufficient confidence in
the experiments carried out in it. A pilot plant must fulfil
all the present and future requirements of the research to
be performed in it. In Figure 3.3a, a detailed drawing of
a plant is given. Usually, a detoxification pilot plant is
constructed with several solar collectors (Figures 3.3b,
c and d show different solar collector designs). All the
modules are connected in series, but with valves that
permit bypassing any number of them. Sampling valves
are in the outlet of each of the modules. All the tubes and
valves are made of black HDPE (chosen because it is
strongly resistant to chemicals and is weatherproof and
opaque) in order to avoid any photochemical effect
outside the collectors. The test mix- tures are prepared in
storage-feeder tanks, also made of HDPE, of various
capacities. Four different operating modes
 Experimental Systems 35

a)
Solar collector
T n Closed valve
modules
in series
Opened valve
Sensors
T
Pump
Discharge
Refrigeration system (optional)
tank

Pr O2

PIC
Contaminant
GAC + TiO2 Holding
Flow control
filter tank
FIC FCV
O2
Disposal
Pr Batch tank
FI
Clean water

b) c)

d)

FIGURE 3.3. a) Photocatalytic detoxification pilot-plant scheme (batch mode is shown). b) CPCs at Plataforma Solar de
Almería (Spain). c) Double-skin sheet collector (ISFH-Hannover design) at Plataforma Solar de Almería (Spain). d) Two
types of non-concentrating solar collectors at the solar detoxification test stand at the University of Florida. (Courtesy
of the Solar Energy and Energy Conversion laboratory, University of Florida.)
36 Solar Detoxification
are possible: recirculation, once-through, partial
recirculation and system cleaning.
When concentrating solar collectors are used, the
temperature of the water flowing through them rises con-
siderably. Obviously, the slower the flow rate used in
once- through experiments, and the longer the
recirculation experiment, the greater the increase of
temperature is. Therefore, to avoid evaporation and
damage to plastics, cool- ing is necessary, and a closed-
circuit water-cooling system has to be installed.
A centrifugal pump with an electric motor
(calculated to provide sufficient flow when the
maximum length of the sys- tem is used) has to be
installed to pump the water to be treated through the
reactor. The flow rate (in batch mode) has to be such
that only a small amount of reactant is con- verted
each time it passes through the reactor, and the
concentration throughout the system remains
relatively constant (this reasoning will become clear
below). Either a flow-rate control loop made up of a
flow meter connected to a controller (which in turn
governs an automatic electric valve) or an electric
pump with a speed controller must be installed to
regulate the flow to the rate desired. The most
important sensors required for the system are
temperature, pressure and dissolved oxygen sensors (at
least in the reactor outlet). Other sensors, such as pH
and selective electrode sensors, could be useful
depending on the type of experi- ments to be carried
out. As constant pure oxygen is required for the
oxidation of organic substances, an injection system at
the reactor inlet allows oxygen to be added to the reactor –
either at planned intervals by opening and closing in a
pre- defined cycle, or continuously. Atmospheric oxygen
can also be stirred into the reaction medium in the
reservoir tank. In
this case, the dissolved O2 is kept at a concentration of
around 6 to 8 mg/L. A UV-radiation sensor must be
placed in a position where the solar UV light reaching the
photoreactor can be measured, permitting evaluation of
incident radiation as a function of the hour of the day,
cloud cover, and atmos- pheric or other environmental
variations. All these data have to be sent by an
appropriate transmitter from the sensors to a computer,
which stores the results for later evaluation. To clean the
system, a drainage tube, with an active carbon filter to
retain any organic compound not decomposed during the
experiments, must be hooked up to the sewage pipelines.
Use of demineralized water (conductivity less than 10
µS,
organic carbon content less than 0.5 mg/L) is
recommended for cleaning as well as in the tests
themselves.
3.3. Operation of pilot plants
3.3.1. Once-through operation
The experimental procedure begins when the pump is
turned on and the system is filled with clean water. The
required modules are selected and the corresponding
valves are set to bypass the rest. Then the water is
pumped through the circuit and the modules are covered.
Obviously, the max- imum pump flow rate is necessary
for this procedure. The amounts required to obtain the
initial concentrations of catalyst, contaminant and any
other ingredient in the exper- iment are added to the
holding tank. When the time needed for the mixture to
combine has expired, this is verified by taking samples at
two different points in the reactor at the same time for
analysis. A few minutes later two more samples are taken
and, if the four are the same, the concentration of the
reactives may be considered to be the same throughout the
reactor. Simultaneously, the automatic control sets the
flow rate (Q), which will then be kept constant during
the experiment, oxygen injection is activated, and valves
are adjusted so that the fluid flows to the discharge tank.
After that the modules to be used are put into operation.
This marks the beginning of the experiment.
The modules are kept illuminated a little longer than
nec- essary to allow the water in the holding tank to go
through the reactor and approach the discharging tank.
This experi- mental time (texp) is:
Vtube  nVmod
texp  (3.1)
Q
where Q is the flow rate, Vtube is the volume in the pipes
between the modules and the tank and Vmod is the volume in
each module, with n the number of modules in the series.
At this time, samples are taken at all the valves in the
outlets of each of the modules in the experiment. This
provides ‘n’ number of samples with different residence or
illumination times (tR,i) to enable determination of kinetics.
Under these conditions, the reactor behaves according to the
ideal plug- flow model, as explained later. The residence
time corre- sponding to each sample collected at the end
of the experiment is calculated with the following equation:
niVillu
tR,i  (3.2)
Q

where i is the number of modules through which the
sam- ples have passed before being collected and Villu
is the volume in the illuminated section of each module.
When the test is over, n samples have been obtained
with a reactor residence time that is a function of the
flow rate. Thus, if the procedure is repeated at a
different flow rate, that group of samples has a
different tR and the number of points (tR,i,
concentration) necessary to evaluate any experiment
can be obtained.
3.3.2. Batch operation
Solar detoxification pilot plants are frequently operated
in a recirculating batch mode, as depicted in Figure 3.3.
In this scheme, the fluid is continuously pumped between
a reactor zone and a tank in which no reaction occurs,
until the desired degradation is achieved. The systems
are operated in a discontinuous manner by recirculating
the slurry solution using an intermediate reservoir tank
and a centrifugal pump. This type of operation differs
little from the previous one.
When concentration of the reactives is the same
throughout the reactor, oxygen injection (if necessary) is
activated and the position of the valves is maintained so
that the fluid begins and ends in the holding tank (now
called the ‘batch tank’). The automatic control sets the max-
imum flow rate, which has to be such that it guarantees that
only a small amount of reactant is converted each time it
goes through the reactor. Then the modules that are going
to be used are put into operation. This begins the experi-
ment. Recirculation is continued and the test lasts as long as
required, even up to several days. Samples may now be
taken at any of the sampling ports – as the system is in recir-
culation mode, tR is the same for samples taken at any point
in the system. The (tR,i, concentration) pairs are thus
obtained (Eq. 3.3).
Villu
tR,i  t exp, (3.3)
VTOT i time the mixture passes through the reactor is noticeable.
where VTOT is the volume of the entire pilot plant. Villu
and VTOT are defined at the beginning of the experiment
by the number of modules used and the level of water in
the batch tank. The experimental time (texp) is the
difference in time between the initial sample (initial
concentration of the pollutant, t = 0) and samples
collected during the experiment (t > 0).
Experimental Systems 37
FIGURE 3.4. Schematic of two pilot plant operation
concepts: a once-through operation (top) and a batch
operation (bottom).
3.3.3. Modelling once-through
and batch operations
In general, once-through operations can be modelled as
plug-flow. The variation in concentration (dC) over time
(dt) for once-through experiments and for first-order
reactions (typical in photocatalysis) would be:
Ci
ln  ktR,i (3.4)
C0
where tR,i is calculated by Equation 3.2. For most
laboratory- scale batch systems, the amount of
conversion that occurs each time the mixture passes
through the reactor is small, and the concentration
throughout the system is relatively constant. The entire
system can easily be modelled as a sim- ple batch system
in which only a fraction (i.e., the part in the reactor) of
the total mixture is undergoing reaction. In this case,
Equation 3.4 above can also be applied, using Equation
3.3 to calculate tR,i.
In a large field system, the amount of conversion each
As the relatively clean water in the reactor is mixed with
the ‘dirty’ water in the batch tank, the water sent from it to
the reactor has a lower and lower concentration of
reactant. Because the conversion rate usually decreases
with concen- tration, the overall rate in the reactor
responds likewise. Thus, unless properly accounted for,
the presence of the tank will alter the perceived
performance of the photoreactor. Two solutions are
available to solve this problem. The first,
38 Solar Detoxification
and also the easier of the two, is to use a very high flow
rate to achieve low conversion each time through. This
high flow rate (Eq. 3.5) must ensure a rate of less than 1
per cent con- version per pass (C1(t) = C2(t)). This 1
per cent has been selected because is very far from the
error associated with any chemical method applied for Ci
analysis.
V r
Q  TOT (3.5)
C0 x
where r is the reaction rate, C0 the initial concentration of
the reactant and x the conversion (0.01). For example, if the
initial reactant concentration is 50 mg L–1, the reaction rate
is
0.1 mg L–1 min–1, VTO is 250 L, the flow rate must
and T be
– 1
over 50 L min . When this is not possible because the
reaction rate is very high, initial concentration very low
and/or the pump is not strong enough, the mathematical
formulation is the following:
In steady state, the concentration in the reactor
outlet at time t, C1(t) is determined from the inlet
concentration (which does not change with time) and
the reaction kinetics. However, because the system is a
transient process, the nor-
mal steady-state plug flow reactor equation cannot be
used to model the photoreactor. Because the inlet
concentration changes with time, C2(t) is defined by
the concentration of
what went into the reactor one residence time prior to t,
C2(t–τ), and the kinetics. The batch tank is still modelled
as a well-mixed tank. Solving these equations is more
difficult than the low-conversion-per-pass case, and the
numerical routine is required to fit the data from the
batch test. This routine also takes into account the volume
of piping between the reactor outlet and the batch tank.
The defining equations for the system components
shown in Figure 3.4 are given by basic chemical
engineering principles. For the plug flow reactor:
C1 dC τ*
C    dτ (3.6)
2 r 0
In the batch process, both concentrations vary with time,
that is, C1 = C1(tR) and C2 = C2(tR). A solution for C1(tR)
and C2(tR) for all tR can be obtained if three different time
regimes are defined as follows:
• Regime 1: tR = 0 (Reactor exposed to sunlight at t = 0).
By definition we have C1 = C2 = C0
• Regime 2: 0 < tR < τ. Under these conditions, the fluid
exiting the reactor has been illuminated for less than one
complete reactor residence time. In Equation 3.6, the
time spent in the reactor is equal to tR, and the starting
concentration is C0, thus:
C1 tR
dC
    dτ (3.7)
C0 r 0
• Regime 3: tR Š τ. Now the fluid exiting the reactor has
been illuminated for one complete residence time and
τ* = τ. However, to solve for the reactor outlet concen-
tration at time t, what went into the reactor at time t – τ
R
must be known. This defines the lowest limit on the rate
integral
: τ
dC
C1 (tR )
   dτ
 (3.8)
C2 (tR τ) r 0
Having defined these three regimes, the balance of
material in the well-mixed tank may now be written as:
dC2 (tR )
 Vbatch  Q[C1(tR )  C2 (tR (3.9)
dt
)]
where Vbatch is the volume in the batch tank. Now, it only
remains to link Equation 3.9 with the different forms of
Equation 3.6. To do this, we must define an expression
for the rate. A simple first-order rate expression (typical
in photocatalysis) can be used as an example (see Eq.
3.4). The algorithm that solves Equation 3.6 for C1(t) as
a function of C2, at the different time regimes using first-
order kinetics is the solution:
• Regime 1: C1 = C2 = C0
• Regime 2: C1(t) = C0 exp(–kt)
• Regime 3: C1(t) = C2(t – τ) exp(–kτ)
This expression for C1(t) is substituted into Equation 3.9
and the value for C2(t) predicted. This prediction is
then com- pared to the experimental values for the
concentration in the batch tank, with iteration until the k
value providing the best fit to the data is obtained. This
methodology can be used to solve numerically for the
concentration profile in any batch process. Although it
is only really necessary when the recir- culation flow is
not high enough (See Eq. 3.5).

3.4. Evaluation of solar
UV radiation inside photoreactors
Solar ultraviolet radiation is an essential parameter for the
cor- rect evaluation of data obtained during photocatalytic
experi- ments in a solar water-decontamination pilot
plant. The kinetic constants of photocatalytic processes
can be obtained by plotting substrate concentration as a
function of three dif- ferent variables: time, incident
radiation power inside the reac- tor, and photonic flux
absorbed by the catalyst. Depending on the procedure, the
complexity of obtaining these constants, as well as their
applicability, varies. When the photonic flux absorbed by
the catalyst is used as an independent variable,
extrapolation of the results is better. However, many
parame- ters (incident photons passing through the
reactor without interacting with the catalyst, the directions
in which light scat- ters, distribution of the sizes of TiO2
particle suspended in the liquid and so on) must be known
for this, making it impracti- cal in a reactor used for pilot-
plant experiments.
Use of the experimental time as the calculation unit
could give rise to misinterpretation of the results,
because the reac- tor consists of illuminated and non-
illuminated elements. Large experimental reactors
require much instrumentation and the reactor must also
be as versatile as possible, substan- tially increasing the
non-illuminated volume. With use of residence time –
that is, the time the water has been exposed to the
radiation – the conclusions would also be erroneous.
This is because, when time is the independent variable,
dif-
ferences in the incident radiation in the reactor
during
an experiment are not taken into account. Furthermore,
the more different the environmental conditions of the
experi-
ments to be compared (different days, different periods
of the year or atmospheric variations), the more critical
this becomes. The only way to avoid this problem is to
use a relationship between experimental time, plant
volume, collector surface and radiant power density,
measured by radiometers. This permits extrapolation of
known data from one scale to another (using the same
type of solar collector), as well as avoiding the problem
arising from a variable source of radiation (sunlight).
Recalling Equation 2.4, the photon flux density I
[Einstein s–1 m–2] is the number of incident photons per
unit of surface and time:
d2N
I= (3.10)
N0dt dA
Experimental Systems 39
where N0 is Avogadro’s number (6.023 × 1023). Using
solar spectrum data (See Figures 2.6 and 2.7) and the
former equations in congruent units [S.I.], it is possible to
determine the photon flux density. In any case, the UV
radiation values vary from one location to another and,
obviously, during the course of a day and from season to
season, so that it is neces- sary to know these data for a
given location and in real time. The calculation of the
photon flux in any photochemical reactor could be
undertaken following the flow diagram shown in Figure
3.5.
3.4.1. Calibration of radiometers
Solar UV radiometers (See Chapter 2.5) provide data in
terms of the incident W m –2 reaching their surface, which
gives an idea of the energy reaching any surface in the
same position as they are with regard to the Sun.
According to their manufacturers, UV instruments are
sensitive to ultravi- olet radiation (see Figure 2.9). But in
their technical descrip- tions, the interval of wavelengths
covered in their calibration is not usually reported.
Therefore, that specification, so important in the
calculation of photonic flux, is not certifi- able. In order
to resolve this uncertainty, on-site calibration is
necessary. This is performed by comparing the data pro-
vided by the UV radiometers with those from a
spectrora- diometer (which gives data in terms of W m –2
nm–1) in the same position as each of the radiometers.
This gives:
λn
UV   UVλ (3.11)
λ300
nm
where UVΣ (W m–2) is the summation of the radiation
meas- urements (from 300 nm up to n, in 1 nm intervals)
provided by the spectroradiometer. An example (with
only a few measured data) is shown in Table 3.1. The
two ways of measuring UV at different times of the day
are compared, with n = 400 nm, which is the ultraviolet-
visible threshold, above which the radiometers should
not measure.
In view of these results, the conclusion is that the UV
radiometer measures beyond 400 nm. In order to find the
real interval, the same procedure is carried out for n
values over 400 nm, at 1 nm intervals. The results are
given in Table 3.2, together with the percentage of error
at each interval.
It seems that, taking as the upper limit a wavelength of
403–404 nm, the radiation measured by both instruments is
40 Solar Detoxification

Spectrophotometric measurement of UV
It is impossible to
evaluate the photon Radiometer calibration
flux without on-line
spectrum NO
measurements Is the uv spectrum constant?
YES
It is possible to obtain an equation that correlates the
radiometric and spectrophotometric data

Determination of spectral collector

efficiencies (reflectivity, trasmissivity, etc.)

Equation to obtain photon flux inside the photoreactor

as function of on-line uv measurements

Actinometric experiments

Efficiencies NO
Experimental actinometric quantum yield =
calculation calculated (by previous equation) quantum yield?
not correct
YES

END
FIGURE 3.5. Procedure used to calculate the photon flux inside a solar reactor.

TABLE 3.1. Radiometric and spectroradiometric UV measurements at different times of the day (n = 400 nm).
UV, W m–2 Local time UVΣ, W m–2 UV–UVΣ, W m–2 100(UV–UVΣ)/UVΣ,%
13.69 10:31 11.68 2.01 +17.2
17.43 11:00 16.01 1.42 +8.9
26.96 12:59 25.42 1.54 +6.1
17.68 15:34 16.00 1.68 +10.5

TABLE 3.2. Radiometric and spectroradiometric UV measurements at different times of the day (n > 400 nm).
UV (1)
, W m–
UV, W m–2 2
Σ
n = 401 n = 402 n = 403 n = 404 n = 405
13.69 11.99(+14.2) 12.33(+11.0) 13.30(+2.9) 13.53(+1.2) 13.10(+4.5)
17.43 16.42(+6.2) 16.87(+3.3) 17.33(0.0) 17.79(–2.1) 18.25(–4.7)
26.96 26.01(+3.6) 25.4(+6.1) 27.32(–1.3) 27.0(0.0) 28.65(–6.3)
17.68 16.39(+7.6) 16.81(+5.2) 17.24(+2.5) 17.67(0.0) 18.51(–4.4)
1. Under each n in the table is shown the UV obtained with the data from the spectoradiometer when Equation 3.11 is applied. To the right of
each value (in parentheses), the percentage of error between these measurements and the UV that appears in the column to t he left is
indicated:100(UV – UVΣ)/UVΣ.

in agreement. The radiometer measurement interval is 3.4.2. Correlation between radiometric

funda- mental for calculation of the photon flux that
reaches the interior of the reactor. The alternative might
be on-line meas- urement of the solar spectrum with a
solar spectroradiometer, but this is very often not possible
because of the price and/or the labour force required to
operate a spectroradiometer.
and spectroradiometric data
Now, recalling Equation 2.6, it is possible to standardize
the UV spectrum up to the radiometer cut-off wavelength.
In this case, 404 nm is used. It is also used as an
example in the
 Experimental Systems 41

above calculations to clarify the explanation, but similar the number of photons corresponding to the average
reasoning could be applied to any wavelength interval. radia- tion at any given instant for the radiometer is:

UV
λ404  N300404  1.856  1018 (3.16)
fλ  λ404 nmλ , therefor nm
fλ (3.12)
e  =1
nm
UV

 UV λ300
nm
where N is the nmber of incident photons,
λ300 λ 300–404
nm nm
between 300 and 404 nm, per m2 per second, with UV
If the UV radiation spectrum is assumed to have a measured in W m–2 and λ in nm, speed of light c = 2.988 ×
fixed shape similar to that shown in Figure 2.6, a 1017 nm s–1 and Planck’s constant h = 6.626 × 10–34 J s.
standardized spectrum is available in the wavelengths If Einstein (moles of photons) is used as the unit, the
result is:
measured by the radiometer. Therefore, using the
standardized spectrum and the irradiance data (W m–2)
measured by the radiometer, the
N300404 nm
spectral distribution can be calculated for all of these I300404   3.083  106 (3.17)
data:
nm UV
N
0
UV*λ  fλ UV (3.13)

where UV*λ are the spectral data calculated with the 3.4.3. Collector efficiency
standard
spectrum (fλ) and the radiometer data. Therefore, the number
of photons is only a function of intensity (measurable in real
time with the radiometers). Once the spectral distribution All the factors that contribute to collector efficiency are
of the radiometer measurements is known, the number of shown in Figure 3.6. Using the combination of these
inci- dent photons per unit of time on surface (N) factors as defined below and Equation 3.17, photon flux
corresponding to those measurements can be found. may be calculated.
Recalling Equation 2.3, which relates the number of
photons from a given polychro- matic source of light to • ηC includes all the errors produced while the collector
the energy corresponding to each wavelength, this can be was built up.
transformed for this case into the fol- lowing (using • ηR,λ is the reflectivity of the parabolic mirror surface
summations of discrete values): (usually aluminium, see Chapter 6). Since the reflection
spectrum does not vary over a wide range, and variation
1 λ404 nm
N300404 nm   UV*λ λ
hc λ300
(3.14 is uniformly distributed over the whole interval
) (300–400 nm), an average spectral distribution may
nm
be considered. However, as the surface is
outdoors and
where N300–404 nm are incident photons. But, as the spectral could become dirty or damaged, it has to be measured
distribution is assumed to be constant, Equations. 3.13 periodically, in which case the value is ηR,i. With
and frequent cleaning (before every experiment), it may
3.14 yield: be considered constant and is then ηR.
UV λ404 nm
N300404 nm 
hc
 fλ λ (3.15 • ηT,λ is the spectral transmissivity of the absorber tube.
λ300 )
nm The solar radiation that reaches ground level without being
Therefore, the wavelength considered equivalent to the absorbed or scattered is called ‘direct radiation’, the radia-
summation would be: tion that has been dispersed but reaches the ground is
λ404 nm ‘global‘diffuse
called radiation’,
radiation’ and 2).
(see Chapter theGlobal
sum ofradiation
both is called
is col-
 fλ λ  368.79 lected directly by the transparent absorber tube without
λ300 nm intervention of the collector. In Figure 3.6 the path
nm
 42 Solar Detoxification

To calculate the values corresponding to other intervals, followed by I until it arrives inside the absorber tube is
the same procedure is followed. Returning to Equation shown. It must arrive at the surface and be reflected (part
3.15, is
 Experimental Systems 43

calculated for the reactor volume. Therefore, Sp/ST

in Equation 3.20 is substituted by this ratio (collector
area/col- lector volume). In this way, photon flux is
obtained in units congruent with the reaction rate (M s–1)
so that an estimated quantum yield (8 ) similar to that
in Equation 2.1 Ecan be obtained, but using moles of
incident photons inside the tube instead of moles of
photons absorbed by the catalyst.

reaction rate
E  
(3.21)
I E

FIGURE 3.6. A diagram of the various loss factors (η) E

where I* is photon flux in Einstein L –1 s–1 of UV
affecting the photon flux (I) inside a photoreactor.
irradiance incident inside the tube. To calculate the
values correspon- ding to other wavelength intervals, the
lost due to ηR,i) in the right direction by the real mirror same procedure is followed.
surface (ηC), before penetrating (ηT,λ) in the tube.
Furthermore, the parabolic concentration factor must 3.4.4. Actinometric experiments
also
be considered (the ratio of the surface area of the parabola
capturing the radiation to the surface area of the tube,
Sp/ST) if it is a concentrating solar collector (see Chapter In a chemical actinometer, the photochemical conversion
6). Therefore, the effective photon flux of the UV inside is directly related to the amount of photons absorbed.
the absorber (IE) is: This method has been used since the 1930s, but because
of recent progress in radiation sensors and semiconductor
and elec- tronic equipment development, physical
measuring devices
 SP  have become more popular for photochemistry. In the
I  f I, , η , η ,η (3.18)
E   S C R,i T,λ   case of reactors with simple geometries, they are
T
preferable because they are very quick, simple and
precise. In the case
in hand, the chemical actinometer is needed for
On cloudy days, only the transmissivity of the glass, ηT,λ,
validation (see Figure 3.5) of all the calculations
affects the radiation reaching the absorber without being
performed to obtain the equations detailed above. A good
reflected by the mirror (1' ). In this case Equation 3.18 is chemical actinometer meets the following specifications:
simplified:
• The photochemical system should be simple and the
IE  f (I,ηT,λ ) (3.19) reaction should be reproducible, under well-defined and
easily controlled conditions. The quantum yields should
Since ηT,λ depends on the wavelength, in order to evaluate be well known for a wide range of wavelengths if
IE, Equation 3.15 must be recalculated as follows: poly- chromatic wavelength radiation has to be
measured.
S  UV λ404 nm • The quantum yield should be independent of the
intensity of radiation, actinometer concentration and
IE   P  ηC  ηR,i   fλ ηT,λ λ (3.20 temperature (large pilot plants cannot be thermo-
)
 ST  hc λ300
nm
statized).
• The reagents and products should be reasonably stable,
where, if UV is W m–2 and the units of I Eare Einstein so errors do not arise between the time the sample is
m–2 s–1. S /S , as accurately as possible, is used to taken and the time it is analysed.
determinep T
IE in each case. For this it is necessary to make the corre- • The analytic methods should be simple and the
sponding trigonometric calculations based on the reagents should be easily synthesized and, even
collector characteristics. Once this is known, the same better, commer- cially available. This is especially
ratio can be important in the case of
 44 Solar Detoxification
pilot plants, because of the large volumes of
actinometer that have to be prepared.
• The system should be sufficiently sensitive for low
radia-
tion intensities, and the evaluation of photons absorbed
should be simple.
For this case, a common uranyl-oxalate system provides
an example. Very complete information on actinometric
sys- tems has been summarized by Kuhn et al. (1989):
hν
UO2  (UO2 )*
2 2 (3.22
(UO22 )*  H2 C2 O4 UO22  CO  CO 2 H O2 ) for data evaluation. This radiometer sends a signal to a
Absorptivity of this solution may be estimated
from:
Absorbed Photons
1 λ
2b (3.23
Incident Photons
exp(µ ) )
where b is the inside reactor radius, 2b is the light
path length and µλ is the coefficient of absorptivity.
General characteristics of the actinometer and
experimental details may be found in Curcó et al. (1996)
and references therein.
Photon flux inside the reactor during the actinometric
experiments may be calculated from Equation 3.20.
However, in this case the range of wavelengths is
widened to 536 nm (actinometer activity cut-off) and
solar spectra up to 536 nm are used. If the photon flux
inside the reactor and the characteristics of the
actinometer are known, the oxalic acid degradation rate
can be calculated from IE(300–536),
µλ, the oxalic acid quantum yield in the mixture and the
area/volume ratios in each case. The comparison
between this calculated acid decomposition rate and
the rate measured in the actinometric experiments
gives an idea of the validity of the equations in Section
3.4.3. The oxalic acid degradation rate calculated
through the experiments or by Equation 3.21 (combined
with Eq. 3.23) should be quite close. Therefore, all the
equations developed are assumed to be valid.
However, actinometry would not be useful for finding
the photon flux at any given time inside a photoreactor
illuminated by solar radiation. The variations in solar
intensity as a result of changes in weather, and the
impossibility of using an actinometer inside the reactor
while the photocatalytic experiments are being
performed, make it impossible.
3.5. Simplified method for the
evaluation of solar UV radiation
inside photoreactors
The above procedure is usually the most appropriate, but
several parameters are very often not available: such as
meas- urement of the on-site solar spectrum, collector
reflectivity, and absorber transmissivity. In these cases, a
shorter proce- dure can be used. Although not the best
solution, it is fre-
quently very useful. Nevertheless, a UV radiometer mounted
at the same angle as the solar collector is always necessary
computer in which the data are stored. As radiation data
are collected continuously, it is very easy to calculate the
average incident radiation on the collector surface (UV),
for each period of t,
and apply Equation 3.24 to that average. Consequently, the
amount of energy collected by the reactor (per unit of
volume) from the start of the experiment until each sample
is
collected may be found by:
SP
EUV ,n = EUV,n1 + tn
VTOT (3.24)
UVn
tn = tn  tn1
where tn is the experimental time at which each sample
was taken, SP is the collector surface, VTOT is the total
plant volume and EUV,n is the accumulated energy (per
unit of volume, kJ L–1) incident on the reactor for each
sample taken during the experiment. This procedure is
correct only if the rate of the photoprocesses under
examination has a linear relationship to the intensity of
radiation (see Chapter 4). For this purpose, several
different experiments must be carried out in the
photoreactor, to determine this effect under very
different solar-radiation conditions (morning, noon,
with and without clouds, summer, winter and so on)
without changing the kinetic order of the reaction.
The results of a typical test are shown in Figure 3.7.
The reaction rate is calculated at the beginning of the
experiment (where reaction rate is constant)
corresponding exactly to the period used for the
calculation of r. Therefore, the rate is linear with regard
to the radiation intensity under the same experimental
conditions and in the same reactor where Equation 3.24
is going to be applied. Figure 3.8 shows the
improvement obtained using this equation to calculate
the reaction rate in a two-day photocatalytic
degradation
 Experimental Systems 45

same substance using different solar collectors would

indi- cate that their collector efficiency is different.

Summary
A pilot plant has to be as versatile as possible in order for
any photocatalytic experiment to be performed with
suffi- cient confidence. The pilot plant must fulfil all the
actual and future necessities of the research to be
performed in it. Plants may be operated in once-through
or recirculation mode. The calculation of residence time
in the reactor is dif- ferent in each case, affecting the
conversion rate. In any case, the use of residence time
to calculate reaction rates (very common in chemical
FIGURE 3.7. Typical photocatalytic degradation (rDCA) in engineering) is not always advis- able because solar
a solar pilot plant under different UV solar light power is not constant. Knowledge of the wavelength
intensities. interval at which the UV radiometers used are active is
basic to data treatment. On-line measurement of
90
40 1st day 2nd day
UV power is essential and reactor efficiency must
–2

30 60
UV,Wm

always be calculated considering, at least, the amount

–1
C, mg L

20 of energy
10 30 incident on it.
0 Therefore, it is necessary to find a relationship between
0 250 500 750 0 radiometer measurements and the photons that actually
t, min reach the reaction. The estimation of quantum yields
using
90
Equation 3.21 enables results obtained in the photoreactor
to be compared with others, and thereby makes use of
60
–1
C, mg L

exist- ing literature on the compounds that are going to

2nd day
be tested.
1st day 30 This is very important when working with a large
reactor, where any test means a considerable outlay of
time and
0 expense. So, A priori, the more information available, the
0 10 20 –1 30 40
fewer experiments are necessary and the faster useful
EUV, kJ L
conclu- sions may be arrived at. Actinometric
experiments have been
FIGURE 3.8. Photocatalytic degradation in a solar pilot shown to be useful to contrast the validity of equations
plant. Concentration (•) is plotted as a function of related to photon flux calculation.
experiment time (top) and accumulated energy (bottom).
Solar UV power throughout the experiment is also
shown. Bibliography
experiment. UV power varies during the day and clouds,
on the first day, make this variation still more noticeable, CASSANO, A.E. 2000. Reaction engineering of
but with Equation 3.24, the data for both days can still be suspended solids in heterogeneous photocatalytic
com- bined and compared with other photocatalytic reactors.
experiments. Consequently, with EUV, the reaction rate CATALYSIS TODAY, No. 58, pp. 167–97.
(r) is expressed in terms of mass of reactant degraded per
kJoule of UV incident on the collector surface. If r is CURCÓ, D.; MALATO, S.; BLANCO, J. AND GIMÉMEZ, J. 1996.
expressed in these units, col- lector efficiency is already Photocatalysis and radiation absorption in a solar plant.
included in it through the use of incident surface SOLAR Energy MATERIALS AND SOLAR Cells, No. 44,
radiation. Different values for r with the pp. 199–217.
 46 Solar Detoxification

GOSWAMI, D.Y. 1995. Engineering of solar photocatalytic MALATO, S.; BLANCO, J.; VIDAL, A. AND RICHTER, C. 2002.
detoxification and disinfection processes. In: K.W. Photocatalysis with solar energy at a pilot-plant scale: an
Böer (ed.), ADVANCES in SOLAR Energy. Boulder, Colo., overview. Applied CATALYSIS B: ENVIRONMENTAL, Vol. 37,
American Solar Energy Society. pp. 1–15.
KUNH, H.J.; BRASLAVSKY, S.E. AND SCHMIDT, R. 1989.
Chemical actinometry. Pure & Applied Chemistry., Vol.
61, No. 2, pp. 187–210.
 Experimental Systems 47

Self-assessment questions 2. Why does a pilot plant have to be as versatile as possible?

3. What are the main characteristics of the material to

Part A: True or false? be used for connecting the pilot plant photoreactors?

1. The photocatalytic laboratory microreactors 4. Which are the most important sensors to install
must be open to the atmosphere. in a photocatalytic pilot plant?
2. The power of the pilot plant pump should be low 5. Why is the flow rate very important in
to avoid high cost. batch experiments?
3. The residence time corresponding to each
sample collected at the end of once-through 6. Why is residence time not the best variable to use
experiments is calculated with the following for obtaining kinetic constants in solar
equation: photocatalysis?
nV
tR,i  i illu
VTOT 7. What are the essential data (necessary for obtaining
4. Generally, a once-through operation system can an equation similar to the following) for correlating
be modelled as a plug-flow reactor. radiometric measurements and photonic flux inside a
photocatalytic solar photoreactor?
5. The kinetic constants of photocatalytic processes
can only be obtained by plotting substrate Nλ1λ2
concentration as a
function of time. Iλ1λ2   f (UV)
N0
6. The interval of wavelengths covered in their
calibration
is not usually reported in UV instruments’ technical 8. What wavelength is considered equivalent to
descriptions. the following normalized spectrum?
7. The spectral transmissivity of the photoreactor
absorber tube does not affect the photocatalytic reaction TABLE 3.3
rate.
λ, nm fλ
8. Quantum yield estimated by using moles of
incident photons is always lower than quantum yield 300 0.0002
calculated by using moles of photons absorbed by the 310 0.0023
catalyst. 320 0.0063
9. The quantum yield of a chemical actinometer 330 0.0109
should increase when the intensity of radiation does. 340 0.0118
10. The amount of energy collected by the 350 0.0124
reactor (per unit of volume) from the 360 0.0127
commencement of the
370 0.0159
experiment until each sample is collected as calculated
by the following equation is only a simplified 380 0.0156
procedure. 390 0.0160

S
EUV,n = + tn UVn P
EUV,n1 VTOT
tn = tn  tn1 9. If Einsteins (moles of photons) are used as the unit,
what is the number of photons corresponding to the
Part B average radiation at any given instant in the previous
example?

1. Why is it necessary to filter IR in 10. What data are essential for radiation evaluation in a
laboratory photoreactors? solar photocatalytic reactor?
 48 Solar Detoxification

Answers 4. Temperature, pressure, dissolved oxygen and

solar irradiation sensors.
Part A 5. Because it is directly related to the conversion rate
per pass and, therefore, to the modelling of the
1) False. 2) False. 3) False. 4) True. 5) False. 6) True. photoreactor.
7) False. 8) True. 9) False. 10) True.
6. Because when time is the independent variable,
differences in the incident radiation in the reactor
Part B during an experiment are not taken into account.

1. Because IR beams could heat the slurry suspensions 7. Solar spectra.

very quickly.
λ390 λ390
2. Because of the need to accomplish all the
nm
fλ  1; nm
fλ λ  373.6 nm
experiments with confidence and fulfil all the actual 8.  
λ300 λ300
and future nm nm
requirements of the research to be performed in 9. 3.135 × 10–6 UV (Einstein s–1 m–2).
it.
10. Radiation data from a radiometer mounted at the
3. All the tubes and valves must be strongly resistant to same angle as the solar collector.
chemicals, weatherproof and opaque, in order to avoid
any photochemical effect outside the photoreactors.
 Fundamental Parameters
in Photocatalysis
4CHAPTER 4

Aims 3. Comprehend the influence of

catalyst concentration and know how
to find the optimum catalyst mass in an
This chapter describes the fundamental experimental reactor.
parameters related to heterogeneous
photocatalysis reactions. Examples are
4. Understand how a Langmuir–
shown to provide a better understanding of
Hinshelwood (L–H) model, although it
oxygen, pH, catalyst concentration, initial
does not explain the photocatalytic
substrate concentration, radiation intensity
mechanisms, may be used in
and the effect of temperature. The chapter
heterogeneous photocatalysis to obtain the
outlines the basic tests used to understand
kinetic constants for reactor optimization.
experimental system behaviour when these
parameters change, and why these changes
affect the photocatalytic reaction rate. 5. Arrange experiments to obtain L–
Finally, an overview of the different ways H parameters.
of evaluating quantum yields is presented.
6. Describe the interdependence of the
photocatalytic reaction rate and
Objectives illumination intensity and know when
this relationship is directly proportional.
By the end of this chapter, you will
understand the main aspects of 7. Determine useful parameters for
experimental photocatalysis variables and describing photocatalysis efficiency
you will be able to do seven things: without knowing the amount of photons
absorbed by the system, and understand
1. Understand why blank experiments why quantum yield is almost impossible to
are always necessary in photocatalysis. calculate in heterogeneous photocatalysis
experimental systems.
2. Design experiments that avoid the
effects of oxygen and pH and thereby
reduce the number of variables affecting
the tests.
50 Solar Detoxification

NOTATION AND UNITS

Symbol Description Units

C or Ci Reactant concentration M or mg L–1
C0 Initial reactant concentration M or mg L–1
CS Solvent concentration M or mg L–1
E Activation energy kJ mol–1
I Photon flux corresponding to the UV inside a photoreactor Einstein L–1 s–1
k' Apparent reaction rate constant min–1
Kr Reaction rate constant M min–1
K Reactant adsorption constant M–1
KS Solvent adsorption constant M–1
L–H Langmuir–Hinshelwood model
NA Number of photons absorbed Photons s–1
pKa –log (acid ionization constant)
pO2 Oxygen partial pressure atm
r Reaction rate M min–1
An Number of reacting molecules Molecules s–1
8 Quantum yield
θx Fraction of surface covered by the substrate
ζr Relative photonic efficiency

4.1. Direct photolysis
As mentioned in Chapter 1, some pollutants can only be
dissociated in the presence of UV light. For this, the
pollutant must absorb the light of the lamp (or the Sun)
with a reason- able photodissociation quantum yield.
Although organic pol- lutants absorb light over a wide
range of wavelengths, absorption is generally stronger at
the lower wavelengths. However, such natural
photodegradation is usually very slow. For example, at
least ten days under perfectly sunny condi- tions is
necessary to reduce 50 mg /L acrinathrin to half this
quantity. One-half of 100 mg/L pentachlorophenol at pH
7.3 decomposes in forty-eight hours. So the photolytic
reaction rate is usually different from one substance to
another, even in the same experimental device. The
photolytic half-lives of hun- dreds of substances have been
summarized by Tomlin (1997). In any case, the focus here
is on fundamental photo- catalytic parameters and
therefore the photolytic effect will be discussed from this
point of view. Tests have to be performed in order to find
out the decomposition rates without the influ- ence of the
semiconductor. As TiO2 readily sticks to the glass
in the photoreactors, it is necessary to carry out these tests
at the beginning of the experiment, before the catalyst
comes into contact with the photoreactors. In pilot-plant-
scale experi- ments, removal of the thin coating of catalyst
on the tubes after TiO2 suspensions have circulated through
them is a very diffi- cult, complex and expensive task. In
laboratory tests, TiO2 can only be removed with an
ultrasonic cleaner or by abrasion. This type of experiment
will focus on demonstrating whether the following are true
or evaluating their importance:
• The treatment is not feasible without a catalyst.
• Increase in temperature (due to illumination) in
the reactor does not cause product loss.
• There is no adsorption of pollutant or its metabolites
in the materials of the pilot plant.
After these tests have been performed, the photocatalytic
experiment results may be considered accurate and the
kinetic parameters can be determined properly. Any side-
effect of the photocatalytic reaction rate can be
quantified and subtracted from the global rate, resulting
in the real photocatalytic reaction rate.
 Fundamental Parameters 51

4.2. Influence of oxygen consumed, photodecomposition of TOC comes to a

halt. At the moment injected oxygen reaches the reactor,
photo- decomposition continues. Therefore, injection of
In semiconductor photocatalysis for water purification, pure O2 becomes necessary in once-through experiments
the pollutants are usually organic and, therefore, the (see Figures
overall process can be summarized by Equation 4.1. 3.3 and 3.4) at low flow rates. At high flow rates or with
Given the reaction stoichiometry of this equation, there recirculation, the addition of oxygen is not always
is no photo- mineralization unless O 2 is present. The necessary since the illumination time per pass is short.
literature provides a consensus regarding the influence of The water again recovers the oxygen consumed when it
oxygen. It is necessary for complete mineralization and reaches the tank (open to the atmosphere and stirred).
does not seem to be in com- petition with other reactives
during the adsorption on TiO 2 since the places where
oxidation takes place are different 4.3. pH influence
from those of reduction+
(see Figure 1.5). The O 2 avoids the
recombination of e–/h (Eq. 1.24) and photoactivated
oxygen (O2•–) also reacts directly (Table The pH of the aqueous solution significantly affects TiO2,
1.3). including the charge of the particle and the size of the
aggregates it forms. The pH at which the surface of an
organic pollutant     
semiconductor
ultra-bandgap (4.1 oxide is uncharged is defined as the ‘zero point charge’
O2 energy )
CO2  H2O  mineral acids (pHzpc), which for TiO2 is around 7. Above and below
this value, the catalyst is negatively or positively
The concentration of oxygen also affects the reaction charged according to:
rate, which is faster when the partial pressure of oxygen
O
TiOH  TiOH  H
(p ) in 2
the atmosphere in contact with the water increases. In 2 (4.2)
any TiOH  TiO  H
case, it seems that the difference between using air (pO2 (4.3)
=
0.21 atm) or pure oxygen (pO2 = 1 atm) is not drastic
(see
Figure 4.1). In an industrial plant this would be The equilibrium constants of these reactions
purely a (Hoffmann et al., 1995) are pKTiOH+ = 2.4 and pKTiOH =
matter of economy of design. In Figure 4.1 it is clear that 8.0, the abun- dance of2 all the species as a function of pH
when all the oxygen contained in the water has is given by –TiOH
–
been Š 80 per cent when 3 < pH < 10; –TiO Š 20 per cent if pH
+
> 10; –TiOH2 Š 20 per cent when pH < 3. Under these con-
3.0 ditions, the photocatalytic degradation of the ionizable
organic compounds is affected by the pH. At first sight,
2.5 O2 and for pollutants for which pKa is outside the range of 1
to 13, a very acidic solution appears to be detrimental
Reaction rate

2.0 and a very basic solution to be favourable, since the

Air
variations are mod- est or non-existent around
C/C0

1.5
neutrality. Because even at extreme pHs the change in
the photocatalytic rate is generally less than one order of
magnitude, the TiO2 water treatment definitively
1.0
0 20 40 60 80 100
possesses an advantage over other processes. In many
pO
2
cases, a very important feature of photocatalysis is not
0.5 taken into account when it is to be used for
TOC decontamination of water: namely, that during the
0.0 reaction a multitude of intermediate products are
0 10 20 30 40
produced that may behave differ- ently depending on the
Illumination time, min pH of the solution. To use only the
FIGURE 4.1. Effect of the concentration of dissolved oxygen
on photocatalytic mineralization. = 8.5 mg L–1. In rate of decomposition of the original substrate could yield an
[O2]0 the
inset, the usual effect of partial pressure of oxygen on the photocatalytic reaction rate is shown.
 52 Solar Detoxification

erroneous pH as the best for contaminant degradation.

Therefore, a detailed analysis of the best pH conditions

3,000
2,500
pHZPC = 6.9
Mean size, nm
2,000
1,500
1,000
500
0 is calculated for a definite amount of TiO2 in which all
2 4 6 8 10
pH
FIGURE 4.2. Mean particle size of TiO2 (P-25) suspended in
water versus pH [TiO2] = 0.2 g/L.
should include not only the initial substrate but also the
rest of the compounds produced during the process.
The mean TiO2 particle size (presented in Figure
4.2) has been found to be constant at pH far from pH =
7. Sizes increase to 2 to 4 µm when dispersion reaches
pHzpc. The zero surface charge yields zero electrostatic
surface potential, which cannot produce the interactive
rejection necessary to separate the particles within the
liquid. This induces a phenomenon of aggregation and
the TiO2 clusters become larger. The large mean size in
suspension at pH = 7 becomes much smaller at pH far
from 7. This effect is clearly related to the capability of
the suspension of transmitting and/or absorbing light.
Furthermore, larger clusters sedi- ment more quickly
than small particles; thus the agitation necessary to
maintain perfect homogeneity must be more vigorous. In
contrast, these variations in particle size could be an
advantage when separating the catalyst from water (by
sedimentation and/or filtration) at the completion of the
photocatalytic treatments.
To unambiguously exclude the pH effect, the reagents
used to change the pH must contain counterions that
have no effect on the rate of water treatment. Sodium
hydroxide and hydrogen chloride or sulfuric acid have
generally been chosen to produce a basic or acidic pH,
respectively. Organic buffers must be avoided because
they are potential con- sumers of •OH. For evident
reasons this is the same for toxic inorganic acids or bases.
Fundamental Parameters 53
4.4. Influence of catalyst
concentration
Whether in static, slurry or dynamic flow photoreactors,
the initial reaction rates were found to be directly
proportional to catalyst mass. This indicates a truly
heterogeneous catalytic regime. However, above a
certain value, the reaction rate levels off and becomes
independent of catalyst mass. This limit depends on the
geometry and working conditions of the photoreactor and
12
the particles – that is, all the surface exposed – are
totally illuminated. When catalyst concentra- tion is very
high, after travelling a certain distance on an opti-
cal path, turbidity impedes further penetration of light in
the reactor. In any given application, this optimum
catalyst mass ([TiO2]OPT) has to be found in order to
avoid excess catalyst and ensure total absorption of
efficient photons.
There are a number of studies in the literature on the
influence of catalyst concentration on process efficiency.
The results vary widely, but from all of them it may be
deduced that radiation incident on the reactor and path
length inside the reactor are fundamental in determining
the optimum catalyst concentration:
• If the lamp is inside the reactor and coaxial with it
(see Figure 4.3a), [TiO2]OPT is very high (to the order
of several grams per litre) if the path length is short
(several mm). On the other hand, [TiO 2]OPT is low
(hundreds of mg per litre) if several centimetres are
crossed (see Figure
4.4 solid circles).
• If the lamp is outside the reactor (see Figure 4.3c), but
the path length is short (1 to 2 cm max.), the maximum
rate is obtained with 1 to 2 g L –1 of TiO (see Figure
4.4 solid squares). 2
• If the lamp is outside, but the path length is several
cen- timetres long, similar to a reactor illuminated by
solar radiation (see Figure 4.3b and 3.6), the
appropriate catalyst concentration is several hundreds
of milligrams per litre. An example of this is shown in
Figure 4.4, where open circles correspond to a
photoreactor with a large diameter and solid triangles
to one with a smaller diame- ter, but both of several
centimetres. In this case, it is very clear that the
optimum rate is attained at lower catalyst
concentrations when the photoreactor diameter is
wider.
In all of the cases described above, a ‘screening’ effect is
produced when the TiO2 concentration is very high.
The
 54 Solar Detoxification

UV Lamp
UV path length

Lamp
protection
chamber

Cooling
Reaction chamber water

UV
UV UV Lamp
UV

UV UV UV

UV
UV
UV UV

a) b) c)
FIGURE 4.3. Different laboratory photoreactor designs and zones of radiation penetration when illuminated in different ways.

reaction rate diminishes because of the excessive 1.2

opacity of the solution, which prevents the catalyst
further in from being illuminated. Besides, the larger 1.0
the size (see Figure 4.2), the less the opacity of the
suspension. When the radiation comes from a parabolic
Relative rate

0.8
trough collector, some- thing similar to what is shown
in Figure 4.3b occurs. In any case, these are only 0.6 TOC
approximations based on the results obtained by 1.0
Relative rate

different authors and, because of all of the above, it

0.4
is always necessary to find out experimentally the 0.5
optimum catalyst concentration for the plant studied.
0.2
That is, the minimum concentration at which the 0.0
maximum reaction rate is obtained. But it does not seem 0.0 0.2 0.4 –1 0.6
TiO2, g L
0.8

to be necessary to test a very wide range of 0.0

0.0 0.4 0.8 1.2 1.6 2.0
concentrations. This effect is shown in Figure 4.4. –1
TiO2, g L
Usually, the reaction rate increases very quickly with
TiO2 concentration, but only at low catalyst FIGURE 4.4. Influence of catalyst concentration on the rate
concentrations (usually below 100 mg/L). After that, of photocatalysis (normalized rates have been used to
the reaction rate stabilizes, and at very high catalyst make it more easily understood) in different reactors (see
concentra- tions the reaction rate decreases. When this text). The continuous line is only to clarify the tendency.
point is found, it is not really necessary to continue In the inset, relative reaction rates of degradation (two
checking any higher because no more useful different photore- actors) and mineralization (TOC) of
information is going to be obtained. As shown in Figure the same contaminant are shown. See text for comments.
4.4, initial substrate behaviour is not always the same as
that of total organic carbon (TOC). This is because of the during the photocatalytic reaction. That is, the screening
influence of intermediate products generated effect influences the decomposition of the original
product in
 Fundamental Parameters 55

a different way than the other organic species present in According to the L–H model, the reaction rate (r) is
the reaction and, in the example presented, to mineralize proportional to the fraction of surface covered by the
the con- taminant it is unnecessary to use more than 0.2 g substrate (θx). In each case the following expression
L–1 of TiO . 2
can be obtained:
4.5. Initial contaminant dC k r KC
r  kr θx 
concentration influence dt 1  KC  K (4.4a)
s Cs

dC k KC
As oxidation proceeds, less and less of the surface of the r= = kr θ x = r (4.4b)
TiO2 particles is covered, as the contaminant is dt 1  KC
decomposed.
Evidently, at total decomposition, the rate of degradation is where kr is the reaction rate constant, K is the reactant
zero. A decreased photocatalytic rate is to be expected with adsorption constant, C is the concentration at any time, KS
increasing illumination time (or accumulated energy, see is the solvent adsorption constant and CS is its
Eq. 3.24). Most authors agree that, with minor variations, concentration (in water CS = 55.5 M). As CS >> C and CS
expres- sion of the rate of photomineralization of organic remains practically constant, the part of the catalyst covered
substrates with irradiated TiO2 follows the Langmuir–
by water is unalter- able over the whole range of C and the
Hinshelwood (L–H) law for the same saturation-type
previous equations can be integrated:
kinetic behaviour in any of four possible situations:
C0 K k K
1. The reaction takes place between two adsorbed ln + (C  C)  r (4.5a)
C 1  Ks Cs 1
substances. KsCs
0
2. The reaction occurs between a radical in the solution
and
the adsorbed substrate. C0
ln  0 C)  kr Kt (4.5b)
3. The reaction takes place between the radical linked to K(C C
the
surface and the substrate in the solution.
4. The reaction occurs with both species in solution. When C0 is very small, both equations can be reduced to an
order-one reaction rate equation:
In all cases, the expression of the equation rate is similar
to
the L–H model. From kinetic studies only, it is therefore not C0
ln = kt (4.6)
possible to find out whether the process takes place on the C
surface or in solution. Although the L–H isotherm has So, if ln(C0/C) is plotted against t (or the accumulated
been rather useful in modelling the process, it is energy, see Eq. 3.24), a line, the slope of which is the
generally agreed that both rate constants and orders are apparent reaction rate constant k', should be obtained
only ‘apparent’. They serve to describe the rate of (see Figure 4.5). Likewise, at higher concentrations, both
degradation, and may be used for reactor optimization, equations can be simplified by adjusting them to zero
but they have no physical meaning, and may not be used
order, (C0 – C) = krt, as might be the case at the
to identify surface processes. Thus, while not a useful
beginning of the experiment represented in Figure 4.5.
tool for describing the active species involved in
Using an L–H model, graphics similar to those
oxidation, engineers and solar designers seem to have a
depicted in Figure 4.6 may be obtained from the
common understanding of the usefulness of the
experimental data and from the linearization of the
unmodified L–H model.
previous equations. The effect of the initial concentration
As a consequence of the above, for L–H standard data on the degradation rate is shown in Figure 4.6a, where,
treatment, it is assumed that the reaction occurs on the due to the saturation produced on the semiconductor
sur- face, which is also the assumption most widely
surface as the concentration of the reactant increases, a
accepted as possible. Under these conditions, two point is reached at which the degrada- tion rate becomes
extreme situations are defined to illustrate the adsorption
steady. Figure 4.6b shows a linearization of Equations
on the catalyst surface: 4.4, where the slope of that straight line is (1 +
• Substrate and water compete for the active catalyst KSCS)/krK, but could also be 1/krK. Finally, Equations 4.7
are obtained from Equations 4.5 when the concentration
sites.
is half
• The reactant and the solvent are adsorbed on the
surface without competing for the same active
catalyst sites.
 56 Solar Detoxification

of the initial concentration (C/C0 = 0.5):
0.693(1  KSC S )
t 0
0.5C
1/2
0.693 0.5C0
t1 / 2 
kr K
It should be emphasized that photodecomposition
gives
rise to intermediates, which could also be adsorbed
compet- itively on the surface of the catalyst. The
concentration of these intermediates varies throughout
the reaction up to their mineralization, and thus
Equation 4.4 may also take the following form:
r
1  KC   K i C i (i 
1,n)
where i is the number of intermediates formed during
degradation (the solvent is also included in the
summation). An understanding of the reaction rates and
how the
reaction rate is influenced by different parameters is
impor- tant for the design and optimization of an
industrial system. The L–H reaction rate constants are
useful for comparing the reaction rate under different
experimental conditions. Once the reaction constants kr
and K have been evaluated, the disappearance of
reactant can be estimated if all other factors
1.0
(C0 - C)=k t r
Normalized concentration
are held constant. Because of this, a series of tests at
different initial substrate concentrations has to be
(4.7a performed to demonstrate whether the experimental
 )
results could be
kr K kr adjusted in line with this model. The concentration range
has to be wide enough to allow correct fit of the L–H
 (4.7b lineariza- tion. This means, from the lowest
kr ) concentration at which the initial rate could be
determined until the limit where the rela-
tionship between initial reaction and initial concentration
remains constant (see Figure 4.6). The results shown in
Figure 4.5 correspond to an example of each of the
experi- ments to be carried out for this purpose. From the
slope of the line corresponding to the starting points of
each of the exper- iments, the initial degradation rate can
be calculated. Figure
4.7 shows the initial rate calculated in this way. From 0.2 to
0.4 mM of substrate the initial rate is steady. At this concen-
k r KC tration, catalyst saturation occurs and the reaction rate
n
(4.8)
becomes constant.
The constants can be calculated from the graphic
inserted in Figure 4.7 using the L–H model.
i1
krKC0 1 1
r0 = 1 + KC  1 = 1 +k K C
r k (4.9)
0 0 r r 0
kr= 1.57 mM h–1
K = 16.75 mM–1
With known kr and K, the time required to degrade a
definite substrate concentration (C0) down to a certain
level (C) may be found from Equation 4.5. With this,
reactor volume and surface area (see Eq. 3.2 or 3.3) can
be defined. If accumu- lated energy is used instead of
time, then Equation 3.24 should be used for obtaining
the kinetic constants and, afterwards, for reactor design.

2.5
0.8
Ln(C0 /C) = k’t
2.0
ln (C0/C)

0.6 1.5

1.0
0.4 0.5

0.0
0.2 0 5 10 15
t1/2
r0–1
r0

EUV, kJ/L or time, min

0.0
–1
0 5 10 15 20 25 C0 C0 C0

EUV, kJ/L or time, min a) b) c)

FIGURE 4.5. Typical photocatalytic degradation. The FIGURE 4.6. Graphics related to the adjustment of data to an
insert shows data adjusted to Equation 4.6. L–H type kinetic model.
 Fundamental Parameters 57

2.0 2.0 A  e   A (4.10c)

D h  D (4.10d)
1.5 3 1.5 A  D  Intermediates  (4.10e)
 Products

–1
r0, mMh

2
1.0 
and the rate-limiting step is the reaction in the adsorbed
l/r0

1.0
 phase (Eq. 4.10e). Therefore:
–1
1 (kr K) = 0.0381

0.5 –1
(kr ) = 0.638
0.5
r  r  k A  D  (4.11)
0 e e   
0 25 50 75
 1/C0
0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 In an n-type semiconductor such as titania, the photo-
C0, mM induced holes are much less numerous than electrons
(photo-induced electrons plus n-electrons): [p+]<<[e–].
FIGURE 4.7. Initial degradation rate as function of the Therefore holes are the limiting active species.
initial substrate concentration. The insert shows the Thence:
linear trans- formation of Equation 4.4, from which the
rate constant and the adsorption coefficient can be r  re  rd  kd[D]p 
estimated from the inter-
cept and the slope,   (4.12)
respectively. 
At any instant, one has:

   
d  p   r  r  r  0
4.6. Radiant flux influence A b d 
dt p  
(4.13)
 kA  kb e    p    kd [D]
     
Since 1990, the kind of solar technology that should be
involved in detoxification has been clarified. Initial   
thence
experi- ments with parabolic troughs for water and :   
dishes or furnaces for gas-phase treatments have evolved   
to lower flux systems. The reason for using one-sun p   kA I (4.14)
systems for water
treatment is firmly based on two factors: first the   kb e    kd [D]
high percentage of UV photons in the diffuse
component of solar radiation and, second, the low-order
dependence of rates on light intensity. It has been and:
demonstrated by experiment that above a certain UV
photon flux, reaction rate dependency on
k k [D]I
intensity goes down from one to a half order (Mills et r  kb eA d  kd[D] (4.15)
al.,
1993;
any Herrmann, 1995). This does not seem to occur at
 
particular radiation intensity, as different researchers obtain
different results, but presumably is significantly affected
by experimental conditions. Some authors impute the From the above equation, it can be seen that the reaction
rate is directly proportional to light flux. In the case of
transition of r = f(I1.0) to r = f(I0.5) to the excess of
high fluxes, the instantaneous concentrations [e–] and [p+]
photogenerated species (e –, h+ and •OH). This can be
d than k [D] and [e ] = [p+].
become much larger –
demonstrated as follows. According to Section 1.4, the
five basic simplified equations are: Therefore Equation 4.14 becomes:
TiO2  hν  e h  2  k I
(4.10a kI
  h  N 
eenergy  p  k Ae ; therefor  p   A (4.16)
)  b  kb
(4.10b)  
e 
 58 Solar Detoxification


The reaction rate becomes:
 k I 1 / 2
r  re  rd  kd [D] A 
 kb 
which means that r is proportional to I0.5 and that the rate
of electron-hole formation is greater than the rate of
photocatalysis, which favours electron-hole
recombination. Therefore optimum use of light power
corresponds to the region where r is proportional to I.
At higher radiation intensities, another transition,
from r = f(I0.5) to r = f(I0), is produced. At this moment,
the photo- catalytic reaction is no longer dependent on
the radiation received, depending only on mass transfer
within the reac- tion. Thus, the rate is constant although
the radiation increases. This effect may be due to
different causes, such as a lack of electron scavengers
(that is, O2) or organic mole- cules in the proximity of the
TiO2 surface and/or an excess of products occupying
active centres of the catalyst. Actually, these phenomena
appear more frequently when working with a supported
catalyst and/or at slow agitation speeds, which implies
less catalyst surface is in contact with the liq- uid and
there is less turbulence. It does not favour reactant
contact with the catalyst or dispersion of products from
the proximity of the catalyst to the liquid.
Many articles on this aspect of photocatalysis
provide information on the light intensity at which the
change of order is produced. The values found are very
dissimilar. It may only be intuited that at an intensity of
several Suns (1 Sun = 22 W m–2), quantum yield
diminishes.
UV ThisUV
r=k I½½
r=k
r=k
Reaction rate
r=kI
r=kI
Fotonic flux
FIGURE 4.8. The relation between the photocatalytic
reaction rate and the intensity of the radiation received.
effect should be measured experimentally in each device,
but this limit (several Suns) is usually accepted as a
general rule.
(4.17)
4.7. Temperature effect
Because of photonic activation, photocatalytic
systems do not require heating and operate at room
temperature. The true activation energy Et is nil,
whereas the apparent activation energy EA is often very
low (a few kJ/mol) in the medium temperature range
(20 ºC to 80 °C). However, at very low temperatures
(–40 °C to 0 °C), activity decreases and activation
energy EA becomes positive. By contrast, at ‘high’
temperatures (>70 °C to 80 °C), for various types of
photocatalytic reactions, the activity decreases and
the apparent activation energy becomes negative. This
behaviour can be easily explained within the frame of
the Langmuir- Hinshelwood mechanism described
above. The decrease in temperature favours
adsorption, which is a spontaneous exothermic
phenomenon. In Equation 4.4, θ tends towards unity,
whereas KC becomes >>1. In addition, the lowering
temperature also favours adsorption of the final
reaction products, desorption of which tends to be the
rate-limiting step. To the contrary, when the temperature
increases above 80 °C, nearing the boiling point of
water, the exothermic adsorption of reactants is
disfavoured – this tends to become the rate-limiting step.
In addition to these mechanical effects, other conse-
quences of plant engineering must be considered. If
temper- ature is high, the materials (see Section 3.2)
used for the plant should be temperature resistant (more
expensive), and oxygen concentration in water decreases.
Consequently, the optimum temperature is generally
between 20 °C and 80 °C. This absence of need for
heating is attractive for photo- catalytic reactions carried
out in aqueous media, and in par- ticular for
environmental purposes (photocatalytic water
purification). There is no need to waste energy heating
water that already possesses a high thermal capacity.
4.8. Quantum yield
In photochemistry, a concept called ‘quantum yield’ is used to
evaluate the results obtained and to compare different
exper- imental conditions. Recalling Equation 2.1 (Φ = An
N –1), A

the quantum yield of a photochemical reaction is defined
with regard to the number of reacting molecules and the
number of photons absorbed.
In this book, a heterogeneous system made up of a
sus-
pended solid (TiO ), a gas (O ) in bubbles and/or
dissolved
2 2
in an aqueous solution of a multitude of compounds
(initial
substrate, intermediates, H +, anions) is described.
Finding out the amount of photons absorbed by the
catalyst from the behaviour of the radiation incident on a
suspension such as this is very difficult. In order to
calculate this, if so desired, one would have to:
• evaluate the light absorption of a very complex
reactive mixture, which, moreover, changes its
composition throughout the reaction;
• from this basis, determine the photon flux that arrives
at each particle of the catalyst to photoactivate it; and
• estimate the photons absorbed and dispersed.
Furthermore, it seems that this, for the moment, is a
difficult undertaking (Serpone et al., 1996). Remember
that, in het- erogeneous catalysis, the reaction rate is
usually expressed as a function of the grams of catalyst.
In photocatalysis, it should include the number of active
centres, as well as the surface area of the catalyst. But as a
consequence of the above comments, the number of
active centres is unknown and the surface of catalyst
exposed to light is undetermined.
This is therefore simplified by considering only the
radia- tion of a certain wavelength (Eq. 3.21) incident on
the inside of the reactor in calculating NA. The value
obtained from this is called the ‘estimated quantum yield’:
ΦE. No distinction is made between the photons
corresponding to each wave- length, assuming that all
of them have the same effect on the
surface of the catalyst. This simplification has been
accepted as valid by a multitude of authors and is widely
used in the bibliography. Consequently, quantum yields
have some-
times been reported as lower limits, not allowing for
scat- tered light. A simple means of assessing process
efficiencies for equal absorption of photons is therefore
desirable in het- erogeneous photocatalysis (Eq. 4.18).
The initial photocon- version of phenol has been chosen
as the standard process, and Degussa P-25 titania as the
standard photocatalyst. This compromise has been
adopted by a group of scientists (belonging to different
research groups) considered among the most important in
this field in the world (Serpone et al., 1996). The choice
of phenol was dictated by the recognition that the
molecular structure of phenol is present in many
Fundamental Parameters 59
organic pollutants and, like many of these, it is
essentially degraded by oxidation rather than reduction.
rate of disappearance of
ζ (4.18)
substrate
r
rate of disappearance of
phenol
where ζr is called ‘relative photonic efficiency’. When the
reaction rate for the test substances and phenol
(secondary actinometer) are obtained under identical
experimental con- ditions, there is no need to measure
the photon flux. The use of relative photonic efficiency
renders comparison of process efficiencies between
studies carried out in different laborato- ries or pilot
plants possible, because ζr is basically independ- ent of
the fundamental photocatalysis parameters (light
intensity, reactor geometry and TiO2 concentration for
a given catalyst). However, it depends on the initial
concentra- tion of substrate and on temperature. In any
case, based on initial rates of degradation, ζr illustrates
only one aspect of photodegradation and is also useful to
compare different photocatalyst materials for water-
treatment purposes.
An example of an application of ζr to degradation
of pesticides (lufenuron and propamocarb) under
sunlight is shown in the following paragraphs. Phenol
(20 mg/L) has been used to calculate ζr following the
method proposed above. In Figure 4.9 the experiments
carried out with phenol are shown.
The mineralization rate (measured by TOC analysis)
is also included because efficiencies based on the
disappear- ance of organic carbon (ζr,TOC, Eq. 4.19)
provide more practical information.
ζr,TOC
rate of disappearance of substrate TOC (4.19)

rate of disappearance of TOC from
phenol
Phenol and pesticide experiments have been performed
under exactly the same conditions. With sunlight, it is
not possible to work under constant illumination
conditions. Therefore, Equation 3.24 is used to avoid
this uncertainty and reaction rates used to determine ζr
and ζr,TOC are calcu- lated using EUV instead of time.
Relative photonic efficiencies of the two pesticides tested
are reported in Table 4.1. All the photonic efficiencies
are lower than one, indicating that the initial
photocatalytic oxidative degradations of the test sub-
stances, at the selected initial concentration, are less
efficient than for phenol.
 60 Solar Detoxification

1.0 1.0 equation that fits the degradation experimental data

accord- ingly. This equation is useful in a wide range of
C/C0
initial con- centrations and is necessary for engineering
Normalized concentration

0.8 Average
Average 0.8
TOC/TOC0
0
plant design. Experimentation at pilot-plant level is
Average
Average essential to obtain these equations. Above a certain flux of
0.6 0.6
UV photons, the reac- tion rate changes depending on
intensity. It may only be intu- ited that at intensities of
0.4 0.4 several Suns, quantum yield diminishes. This effect
should be measured experimentally in each device, but
0.2 0.2 this limit is generally accepted. The optimum temperature
is generally between 20 °C and 80 °C. The use of relative
0.0 0.0 photonic efficiencies renders comparison of process
0 5 10 15 20 25 effectiveness between studies carried out in different
EUV, kJ/L reactors
FIGURE 4.9. Plots of normalized concentration as a possible.
function of accumulated energy for the
photodegradation and mineralization of phenol. C0 = 20
mg/L, TiO2 = 200 mg/L, pH0 = 5. Bibliography
TABLE 4.1. Relative photonic efficiencies for the two pesti-
HERRMANN, J.M. 1995. Heterogeneous photocatalysis: an
cides treated, with phenol as the standard reference (C0
emerging discipline involving multiphase system.
= 20 mg/L).
CATALYSIS TODAY, No. 24, pp. 157–64.
Substrate Rate µmol/kJ ξr ξr,TOC
HOFFMANN, M.R.; MARTIN, S.T.; CHOI, W. AND BAHNEMANN,
D.
Propamocarb 5.8 0.21 0.48 1995. Environmental applications of semiconductor
Lufenuron 8.8 0.32 0.73 photocatalysis. Chemistry Review, No. 95, pp. 69–96.

MILLS, A.; DAVIES, R.H. AND WORSLEY, D. 1993.

Summary
Photolysis tests always have to be performed before photo-
catalysis tests in order to find out decomposition rates with-
out the presence of the semiconductor. The water to be
treated must contain enough dissolved oxygen. To unam-
biguously exclude the effect of pH, the reagents used to
mod- ify the pH must contain counterions that have no
effect on the rate of water treatment. The optimum catalyst
concentration always depends on the experimental device
used and, there- fore, must be always tested first. Direct
application of the Langmuir–Hinshelwood model produces
an empirical
Water purification by semiconductor photocatalysis.
CHEMICAL Society Review, No. 22, pp. 417–25.
SERPONE, N.; SAUVÉ, G.; KOCH, R.; TAHIRI, S.; PICHAT,
P.; PICCINNI, P.; PELIZZETTI, E. AND HIDAKA, H. 1996.
Standardization protocol of process efficiencies and
activation parameters in heterogeneous photocatalysis:
relative photonic efficiencies ζr. JOURNAL of Photochemistry
AND Photobiology A: Chemistry, No. 95, pp. 191–203.
TOMLIN, C.D.S. 1997. The Pesticide MANUAL, 11th ed.
Farnham, Surrey, British Crop Protection Council.
 Fundamental Parameters 61

Self-assessment questions 3. What is the main difference between bubbling

oxygen or air inside a photoreactor?
Part A: True or false? 4. To unambiguously exclude the pH effect, what are
the reagents most often used to change the pH?
– +
1. Oxygen avoids recombination of e /h and promotes 5. Why are L–H constants called ‘apparent’ in
• OH formation. photocatalysis?

2. The reagents used to change the pH must 6. Calculate the L–H constant corresponding to
contain organic buffers. the following experimental data taken from a
series of photocatalytic experiments at different
3. The optimum concentration of the catalyst is initial concentrations:
always around 1 g /L.
TABLE 4.2.
4. Initial substrate behaviour is the only
t, min C, mg L–1 C, mg L–1 C, mg L–1 C, mg L–1 C, mg L–1 C, mg L–1
fundamental parameter for choosing [TiO2]OPT.
0 2.5 5 12 23 50 100
5. By applying the Langmuir–Hinshelwood (L–H) 5 2 4 10 20 45 90
rate law, it is possible to find out whether the
photocatalytic process occurs on the surface or in 10 1.5 3 8 17 40 80
solution. 15 1 2 6 14 35 70
20 0.5 1.5 5 11 30 60
6. When C0 is very small, L–H isotherm equations can
be reduced to an order-one reaction rate equation. 25 0.3 1 4 9 25 50
30 0.1 0.5 3 7 22 45
7. It has been demonstrated that above a certain 35 2 5 19 40
UV-photon flux, reaction rate dependence on intensity
40 1.5 4 16 35
changes from one to a half order.
45 1 3 13 30
8. Temperature does not affect the 50 2 11 25
photocatalytic reaction rate.
55 9 22
9. The amount of photons absorbed by the catalyst 60 7 19
must be known to compare photocatalytic reactors. 65 5 16

10. Simplifications must be employed to 70 4 13

calculate photocatalytic efficiencies.

Part B
1. Why is it necessary to carry out a blank test
before putting TiO2 in a photoreactor?
2. What are blank photocatalysis experiments mainly
for?
7. What is the most accepted reason why
photocatalytic reaction rate dependence on intensity
changes order?
8. What is the usual UV power of light intensity at
which the change of order is produced?
9. What is the optimum temperature range
for heterogeneous photocatalytic reactions?
10. Why is a secondary actinometer necessary?
 62 Solar Detoxification

Answers 5. Because with kinetic studies only, it is impossible

to determine whether the process is on the surface or in
solution, and therefore the constants obtained have no
Part A physical meaning, and may not be used to identify
surface processes.
1) True. 2) False. 3) False. 4) False. 5) False. 6) True.
6. kr = 2.19 mg L–1 min–1; K = 0.0192 (mg/L)–1
7) True. 8) False. 9) False. 10) True.
7. The transition of r = f(I1.0) to r = f(I0.5) is usually
Part B
1. Because readily sticks to the materials of attributed to the excess of photogenerated species (e–,
TiO2 the h+ and •OH).
photoreactors.

2. This type of experiment evaluates the effect of the 8. Above 50 to 75 WUV per square meter of
treatment without catalyst, the increase in temperature photoreactor surface, the quantum yield diminishes.
in the reactor and the adsorption of the pollutant or its
metabolites in the materials of the pilot plant. 9. Between ambient temperature and 60 to 70 ºC.

3. The concentration of O2 inside the reactor. By 10. Because ζr is basically independent of fundamental
bubbling oxygen, the O 2 concentration is almost five photocatalysis parameters (light intensity, reactor
times greater than by bubbling air. geometry and TiO2 concentration for a given catalyst).

4. Sodium hydroxide and hydrogen chloride or

sulfuric acid.

Water Decontamination
by Solar Detoxification
Aims
This chapter describes the most important
applications of photocatalysis for water
decontamination. It outlines the
decomposition of organic and inorganic
contaminants and the usefulness of biological
testing in addition
to chemical analyses. Examples are also
given to help understand the degradation
pathways involved in the decomposition
of the initial compounds. The use of
modified catalysts and additional oxidants
to increase process efficiency by trapping
the photogenerated electrons and/or by
producing extra oxidizing species is
discussed. Finally, an overview of the most
common sophisticated analytical techniques
is presented.
Objectives
By the end of this chapter you will know
why photocatalysis for the treatment of
contaminated water is important and will
understand the best analytical techniques
for determining the degree of
decontamination during treatment. You
will:
1. Be able to describe the
stoichiometric parameters of the
reactions involved in the photocatalytic
process.
5
Fundamental Parameters 63
CHAPTER 5
2. Understand how it is possible to
combine photocatalytic and biological
processes.
3. See how photocatalysis can treat not
only organic but also inorganic
contaminants.
4. Discover different ways to improve
process efficiency by modifying the
catalyst and/or adding other extra-electron
acceptors.
5. Review the most common analytical
tools used to determine the degradation
rate of the original contaminants.
6. Learn the most sophisticated
analytical techniques used to describe the
complicated mechanisms involved in the
photocatalytic degradation of organic
substances.
7. Understand how to determine the
toxicity of water and why this is so
important for water treatment.
64 Solar Detoxification

NOTATION AND UNITS

Symbol Description Units
API Atmospheric pressure ionisation
BOD Biological oxygen demand mg O2/L
CI Chemical ionisation
DPs Degradation products
Eo Oxidation potential V
ECD Electron capture detector
EI Electron impact
FID Flame ionisation detector
GC Gas chromatography
HPLC High pressure liquid chromatography
LC50 Concentration of a chemical that is lethal to 50% of the exposed population mg/L
LLE Liquid-liquid extraction
Poct Water/octanol partition coefficient
MS Mass spectrometry
NMR Nuclear magnetic resonance
NPD Nitrogen phosphorus detector
SPE Solid phase extraction
TOC Total organic carbon mg/L

5.1. Detoxification of pollutants of oxidative degradation reactions that may lead to

Chemists play a significant role in devising new
methods to solve environmental problems. Existing
methods deal with concentrated contaminants; what is
still needed is an effective method for handling toxic
materials that are widely dispersed in the
environment. Irradiated TiO 2 efficiently degrades
nearly every significant functional group, including
the most environmentally recalcitrant materials. The
primary processes associated with semi- conductor-
sensitized photodegradation of organic sub- stances
are illustrated in Figure 5.1. As shown by Equations
1.21 to 1.24, the hydroxyl radical (•OH) is the major
intermediate reactive responsible for organic sub-
2
strate oxidation. The free radical HO • and its
conjugate O •– are also involved in degradation
2
processes, but these
radicals are much less reactive than free hydroxyl
radi-
cals, which react strongly with most organic
substances by hydrogen abstraction or electrophilic
addition to dou-
ble bonds. Free radicals further react with molecular
oxygen to give a peroxy radical, initiating a sequence
com- plete mineralization of the contaminant. In
addition, hydroxyl radicals may attack aromatic rings
at positions occupied by a halogen, generating a
phenol homologue. The electrons of the conduction
band can also degrade organic compounds by
reductive pathways, as is shown in Figure 5.1 in the
case of tetrachloromethane.
In general, the types of compounds that have been
degraded include: alkanes, haloalkanes, aliphatic
alcohols, carboxylic acids, alkenes, aromatics,
haloaromatics, poly- mers, surfactants, herbicides,
pesticides and dyes. A partial tabulation of organic
compounds successfully degraded by photocatalysis is
provided in Table 5.1. Equation 5.1 generally holds true
for an organic compound of general formula C nHmOp
 (m  2p)  m
C n Hm O p    n O2  nCO2  H2O (5.1)
 4  2
In the case of organic compounds containing halogens,
Equation 5.2 shows how the corresponding halide is
formed.
 Water Decontamination 65

CO2 h  TiIVOH A-
-
Inorganic acids
Water
TiIIIOH A
Oxidized TiIVOH
intermediate
+
Organic
pollutant TiIIIOH+
IfA = O 2

O2 O2-  HO •, HO
2
- ,H O , OH
2 22 H2O
CCl4 +e -cbCCl •••3+Cl-
CCl •+ e -:CCl + Cl- Organic Oxidized
3 cb 2 pollutant intermediate

OH O O O O
Cl Cl Cl Cl . Cl Cl Cl Cl Cl . Cl
. OH OH . OH
-H O -HCl OH
Cl Cl
2
Cl . Cl Cl Cl Cl Cl
Cl Cl
Cl Cl HO Cl O O

FIGURE 5.1. General processes for the photo-oxidative or photo-reduction degradation of organic compounds in
aqueous solution sensitized by semiconductor particles. Examples of photo-oxidation (PCP) and photoreduction
(CCl4) are shown.

TABLE 5.1. Some examples of TiO 2-sensitized photodegradation of organic substrates.

Class Example
Alkanes Methane, hexane, cyclohexane, dodecane, octane
Haloalkanes Trichloroethylene, carbon tetrachloride, dibromomethane,
chloroform Aliphatic alcohols Methanol, isobutanol, decanol, ethanol, butyl alcohol
Carboxylic acids Formic, acetic, malic, oxalic, lactic, salicylic, decanoic, chloroacetic
acids Alkenes Cyclohexene, isobutene, butadiene, propene
Aromatics Toluene, nitrobenzene, nitrotoluene, hydroxybenzoic acid, diphenylmethane,
xylene Haloaromatics chlorobenzoic acid, chlorobenzene, chlorophenols, bromophenols, PCBs
Polymers Polyethylene, polyvinylalcohol, PVC
Surfactants Dodecylbenzene sulfonate, dodecylsulfate, trimethylphosphate
Herbicides Atrazine, bentazon, simazine, propetryne, prometron, 2-4 D,
monuron
Pesticides Lindane, methamidophos, imidacloprid, DDT, oxamyl, endosulfan,
phenitrothion Dyes Methylene blue, methyl orange, red dye 79, cresol violet, congo red

CHOX  (m  2p)  5.1.1. Total mineralization

 n
O  
m  q 4
n m p q 2

 nCO  HO (5.2) In photodegradation, transformation of the parent organic

qHX
2 2
2 compound is desirable in order to eliminate its toxicity and
persistence, but the principal objective is to mineralize
Under photocatalytic oxidative conditions, sulfur is all pollutants. The effectiveness of degradation is not
recov- ered as sulfate in sulfur-containing compounds demon- strated purely by the entire initial compound
according to Equation 5.3 being decomposed. As observed in the HPLC
chromatograms
C n HmOpSr  xO2  nCO2  yH2O  (5.3 (Fig. 5.2), oxamyl (chromatogram A, retention time 4.45 min)
zH2SO4 )
66 Solar Detoxification
Oxamyl
A
min.
FIGURE 5.2. HPLC-UV chromatograms of photodegradation of oxamyl before photocatalytic treatment a) and
when the oxamyl has completely disappeared b).
disappears nearly completely (chromatogram B).
However, many new organic compounds appear.
Furthermore, the stoichiometry proposed for the
general reactions (Eqs. 5.1 to 5.3) has to be demonstrated
in each case by a correct mass balance. Reactives and
products might be lost, which will lead to results about
which we cannot be confident. The mineralization rate is
determined by monitor- ing inorganic compounds, such
as CO2, Cl–, SO 2–, NO – and 4 3
PO43–. When organics decompose, a stoichiometric
increase in the concentration of inorganic anions is
produced in the
water treated and, likewise, very often an increase in the
con-
centration of hydrogen ions occurs (decrease in pH). For
this
reason, the analysis of these two products of the reaction is
of interest for the final mass balance. However, the
decrease in pH is not a very reliable parameter of this
balance, save
in some cases, because it is influenced by other processes
that take place in the medium: the effect of the TiO 2
suspen- sion, the formation of CO 2 and intermediates and
so on.
In order to demonstrate that there are no product
losses, the molar ratio must be in accordance with the
organic substrate structure. For example, the
pentachlorophenol decomposition reaction to which
mass balances should be adjusted is shown in
Equation 5.4. Therefore, [Cl –] = 5 [PCP]0, but this
only occurs at the end of the experiment, when the
TOC is almost 0. During the degradation, the
formation of intermediates impedes this, as these inter-
mediates contain differing amounts of chlorides.
hν
9
C Cl OH  O  2H O  
  5HCl
6CO
6 5
2 2 2 TiO 2
2
(5.4)
In Figure 5.3, a complete pentachlorophenol degradation
test is shown. The products obtained are practically
stoichio- metrically correct. The slight difference may be
attributed to

0.12
0.10
[PCP], TOC], mM
–
Cl
0.08
0.06 TOC H 0.3
PCP
0.04
0.02
0.00
0 5 10 15 20
tR, min
FIGURE 5.3 Evolution of H and Cl– during pentachloro-
+ ical oxidation parameters. Cost-effective treatment to
phenol degradation. To more clearly demonstrate that reac-
tion 5.4 is completed, the concentration of TOC in mM is
calculated assuming 1 mMol TOC = 6 mMol of C = 72 mg
of C.
the fact that not all the TOC is completely decomposed
and that results obtained with four different analytical
techniques were compared.
The oxidation of carbon atoms into CO2 is relatively
easy. It is, however, in general, markedly slower than the
dearoma- tization of the molecule. Until now, the
absence of total mineralization has been observed only
in the case of s-triazine herbicides, for which the final
product obtained was essentially 1,2,5-triazine-2,4,6,
trihydroxy (cyanuric acid), which is fortunately not
toxic. This is due to the strong stability of the triazine
nucleus, which resists most methods of oxidation. For
chlorinated molecules, Cl – ions are easily released into
the solution. Nitrogen-containing molecules are
mineralized into NH + and NO–. Ammonium ions are
rela-
4 3
tively stable and the proportion depends mainly on the
ini-
tial oxidation degree of nitrogen and on the irradiation
time. The pollutants containing sulfur atoms are
mineralized into sulfate ions. Organophosphorous
pesticides produce phosphate ions. However,
phosphate ions in the pH range used remained
adsorbed on TiO2. This strong adsorption partially
inhibits the reaction rate, which, however, remains
acceptable. Until now, the analyses of aliphatic
fragments resulting from the degradation of the
aromatic ring have mainly revealed formate and
acetate ions. Other aliphatics (presumably acids,
diacids, and hydroxylated compounds) have been also
found. Formate and acetate ions are fairly
Water Decontamination 67
0.6 stable, which in part explains why total mineralization
takes much longer than dearomatization.
0.5
0.4 5.1.2. Degradation pathways
+
As pointed out above, a variety of degradation products
(DPs) are formed in photocatalytic processes.
0.2 Nevertheless, in most cases no attention is paid to the
possible formation of these DPs, although they allow the
0.1 degradation processes to be better understood and
evaluated and thereby enable comparison among the
0.0 degradation pathways of different types of compounds,
25 30 35
functional groups, and chem-
com- plete compound mineralization is usually not
feasible, and the generation of by-products appears to
be unavoidable with photocatalytic degradation.
Identification of those by- products is key to
maximizing overall process efficiency. Since hydroxyl
radicals react non-selectively, numerous by-products
are formed at low concentrations. On the other hand,
some of the degradation products obtained are of
interest, because they may be more toxic and persistent
than the parent compound. In some cases of
photocatalytic TiO2 treatments, only traces of these
metabolites are detectable because they are degraded
faster than the parent compounds and mineralization is
almost total in a short time. But in other cases, such as
s-triazine herbicides (mentioned above), overall
conversion to the final degradation products takes longer.
For example, primary intermediates of the photocat-
alytic degradation of various aromatic pollutants detected
and identified correspond to hydroxylation of the
benzene ring (see Figure 5.1). Maximum transient
concentrations are much lower for these intermediates
than for the initial pollu-
tants, since CO , acetate and formate are formed in the initial
2
stages of degradation. The orientation of the hydroxylation of
the aromatic ring depends on the nature of the
substituents. For instance, for chlorophenols and
dimethoxybenzenes, the para and ortho positions (with
respect to OH for the chlorophenols) are favoured, as is
expected. In contrast, for benzamide and nitrobenzene,
the hydroxylation occurs at all free sites, whereas a meta-
orientation is expected for elec- tron-withdrawing
substituents. A list of compounds pro- duced during
photodegradation of a pesticide (pyrimethanil) with TiO 2
is shown in Figure 5.4. It will give an idea of the
complexity of the chemical reactions involved in
photocat- alytic methods.
68 Solar Detoxification

Hidroxy derivatives Aliphatic

Pyrimidil derivatives
OH derivatives
N N CH3 NH2 N CH3
O O
C NH C
N N CH3 NH2
CH3 CH3
NH2
O C
CH3
NH N CH3

NH N CH3 O CH NH2
N
OH
CH3 N
OH N CH3 CH3
NH

N Pyrimethanil
CH3

Phenyl derivatives
OH
N O NH2 N
N N CH3 C NH C C NH2
CH3
O O
N OH
CH3 O OH O OH O
C CH3 C CH3 CH
NH NH NH
OH N CH3
NH OH
OH
N
OH
OH
CH3

FIGURE 5.4. Chemical structures of pyrimethanil and its degradation products obtained during a photocatalytic
treatment with TiO2.

5.1.3. Toxicity reduction en-route to complete mineralization. Toxicity testing of

The success of photocatalytic degradation in wastewater
treatment depends on how much the cost of illumination
(that is, energy) can be kept down. This can be achieved
by improving the efficiency of photocatalytic
degradation, for example, by modifying the catalyst and
the photoreactor design or by using additional oxidants.
It is also possible to envisage incomplete photocatalytic
degradation to detoxify the wastewater. The products of
incomplete degradation and their concentrations may be
sufficiently innocuous to be dis- charged directly into the
environment or to undergo further biological treatment.
Biological treatment of biodegradable residual waters is
currently most compatible with the envi- ronment and is
the least expensive option. However, it is very difficult to
identify all the intermediary compounds
the photocatalytically treated wastewater is therefore
necessary, particularly when incomplete degradation is
planned. Any number of whole-organism bioassays
could be used for the assessment of water quality before
disposal. Since it is not feasible to determine the specific
toxicity of every toxic inter- mediary compound, whole-
effluent toxicity testing using aquatic organisms is a
direct, cost-effective and relevant means of determining
effluent toxicity. Therefore, bioassays can provide a
more direct and appropriate measure of mix- tures of
toxins than chemical analyses alone, which are not
sufficient to assess potential effects on aquatic biota
(Tapp et al., 1996). A review of these tests is shown at
the end of this chapter.
Another useful technique for evaluating the feasibility
of disposing of photocatalytically treated waters before
total

mineralization is to determine the biodegradability
(BOD) in sludge from biologically activated sludge
plants (Pulgarín et al., 1999). This sludge is inoculated
with the treated water and BOD tests are carried out. In
this case, the results are obtained in terms of ‘relative
biodegradability’. This means that once biodegradability
is achieved, it can only be assured if the same
biologically activated sludge used for the BOD
tests is used for disposing of the treated water. This test
produces non-universal results, but could be very useful
if
the biological treatment plant that is to receive the
effluent from the photocatalytic treatment is known prior
to design of the photocatalytic plant. This permits
disposal of the
pre-treated water into a biological (low cost) treatment.
5.1.4. Detoxification of inorganic
pollutants
Photocatalytic processes may also transform inorganic
substances from the environment. Specifically, H2S and
CN– can be converted into less-toxic materials, and
various strate- gic and/or toxic metals can be removed
from waste effluents. The toxicity of H2S is comparable to
that of HCN. In the pres- ence of light and a
semiconductor catalyst, the products of oxidation are
molecular hydrogen and sulfur. Free cyanides are
generated in large quantities in heat-treating operations
and in metal-finishing industries. The greatest amounts
of cyanide-containing wastes are produced by precious-
metals milling operations and coal gasification processes.
CNO– is the first product of the photocatalytic oxidation
of cyanides in the presence of polycrystalline TiO2 in an
aqueous medium. The proposed mechanism implies the
oxidation of cyanide by the photogenerated holes and the
reduction of oxygen by electrons according to Equation
5.5. The reacting mixture must be at pH10 to avoid the
formation of volatile HCN.
CN  2h  2OH  CNO  (5.5
H2O ) water
Cyanate ions are photo-oxidized to nitrates and a
satisfactory nitrogen balance is achieved according to the
overall reaction shown in Equation 5.6. At strong oxidant
conditions, volatile nitrogen-containing species are not
produced or are quickly
2 photo-oxidized
3 to NO– and NO–.
CNO  4O2  2OH 3H2O  3CO2  3NO  electron/hole recombination (reverse of Eq. 1.21), which,
4H2O2
(5.6)
Water Decontamination 69
It has been discovered that ozonation (production of
drink- ing water) generates low levels of bromate ions,
recognized as a suspected agent of cancer. Drinking
water treated with ozone will typically have in the range
of tens of µg/L of bromate, and TiO 2 is able to sensitize
the photodecom- position of bromate (Eq. 5.7).
2BrO h 
ν /TiO
2
 2Br   3O (5.7)
3 2
Heavy metals are generally toxic and can be removed
from industrial waste effluents as small crystallites
deposited on the photocatalyst, as demonstrated by
Equation 5.8:
n n
M n  H O h 
ν /TiO
2
 M 0  nH   O (5.8)
2 2 42
Under identical conditions, the following reactivity
pattern has been found: Ag > Pd > Au > Pt >> Rh >> Ir
>> Cu = Ni
= Fe = 0 for AgNO3, PdCl2, AuCl3, H2PtCl6 or Na2PtCl6,
RhCl3, H2IrCl6, Cu(NO3)2, Ni(NO3)2 and Fe(NO3)3. As
the
photodeposition conversion increases, the metal
particles form agglomerates, reaching several hundreds
of nm. Silver photodeposition has been applied in the
recovery of Ag from used photographic baths in which
the silver-thiosulfate complex is decomposed, Ag +
being reduced to Ag°. Because of their favourable redox
potentials, only noble metals can be photodeposited. This
property has been used to selec- tively recover noble
heavy metals. For instance, silver has been separated
from copper in solutions simulating indus- trial
electrolytic baths. Other toxic, heavy non-noble metals
could be removed from water. Mercury, because of its
favourable redox potential, was photoreduced as a
zero- valent metal. The cations Pb 2+ and Tl3+ have been
deposited on UV-irradiated TiO2 powder as PbO2 and
Tl2O3. Similarly, uranium has been photodeposited on
TiO2 as U3O8 from uranyl solutions. From an
application point of view, the
recovery of silver from photographic baths seems the
most promising issue, provided legislation on discharge
containing Ag becomes stricter.
5.2. Quantum yield improvement
through additional oxidants
One practical problem in using TiO 2 as a photocatalyst is
in the absence of proper electron acceptors, is extremely
70 Solar Detoxification

inefficient and thus represents a major energy-wasting peroxide reacts with conduction-band electrons (Eq. 5.9)
step, as well as limiting the achievement of a high to generate hydroxyl radicals, which are required for the
quantum yield. Oxygen has been chosen in most of the photomineralization of organic pollutants.
applications for this
purpose, although its role is not related only to electron
scavenging (see Chapter 4). But with only dissolved H2O2  e  OH  OH (5.9)
oxygen as an oxidant, low mineralization photo-
efficiencies (produc-
tion of CO2) are obtained (in the range of 1 to 5 per The following reactions (Eq. 5.10 and 5.11) can also produce
•
OH (reaction 5.11, which requires Z < 300 nm, does not
cent).
One strategy for inhibiting e –/h+ recombination is to take place with solar radiation).
add other (irreversible) electron acceptors to the
reaction.
Outstanding enhancement of the rate of degradation of
various organic contaminants through the use of H2O2  O
2
 OH  OH  (5.10)
inorganic peroxides has been demonstrated (Pelizzetti et
al., 1991; Malato et al., 2000). The addition of other O2 H2O2  h  2OH (5.11)
oxidizing species
could have several different effects, including:
The effect of this electron acceptor deserves some further
• increasing the number of trapped e – in the e–/h+ pairs comment. In some cases, the addition has been found to
and, consequently, avoiding recombination; be beneficial, increasing the degradation rate. The
effect
• generating more •OH and other oxidizing depends on the concentration, generally showing an
species; H2 O2
• increasing the oxidation rate of intermediate optimum range of concentration. At higher
compounds; concentrations the improvement starts to lessen. Whereas
• avoiding problems caused by a low O 2 concentration. this beneficial effect can easily be explained in terms of
prevention of elec- tron/hole recombination and
It must be mentioned here that in highly toxic additional •OH production through reactions 5.9 to 5.11,
wastewater where degradation of organic pollutants is inhibition could be explained in terms of TiO 2 surface
the major concern, the addition of an inorganic anion to modification by H2O2 adsorption, scavenging of
photoproduced holes (Eq. 5.12), and reaction with
enhance the organic degradation rate may often be hydroxyl radicals (Eq. 5.13).
justified. For better results, these additives should fulfil
the following criteria: they should dissociate into
harmless by-products and lead to the forma- tion of •OH
or other oxidizing agents. There is another advan-
tage related to the use of this type of oxidant when solar H2O2  2h  O2  2H (5.12)
energy is the photon source. Although scientific research 
H O  OH  H O  HO (5.13)
on
photocatalytic detoxification has been conducted for at used chemical and therefore very cheap. Being an electron
least the last three decades, industrial/commercial acceptor, hydrogen
applications, engineering systems and engineering design
methodologies have only been developed recently. In this
type of installation, the photoreactor is by far the most
expensive component and a barrier to commercialization.
Increase the photocatalytic reaction rate with these
additives would decrease photoreac- tor dimensions
proportionally and dramatically decrease overall costs.

5.2.1. Hydrogen peroxide

Hydrogen peroxide is the obvious candidate. It can

increase the efficiency of the process at high irradiance
(see Section 4.6) and it has been tested with a large
number of com- pounds. Also, it is a very commonly
 Water Decontamination 71

2 2 2 2

The inhibition of adsorption not only depends on

the characteristics of the pollutant but also on the
hydrogen peroxide/organic concentration ratio. This
may be explained in terms of Langmuir–Hinshelwood
kinetics, rC = krKC/ (1 + KC) and competitive
adsorption (see Chapter 4). If pol- lutant concentration
(C) is too low and H2O2 concentration too high,
organic adsorption decreases because of adsorption of
hydrogen peroxide and, therefore, the additional
hydroxyl radicals generated by H2O2 do not react
efficiently. When C is higher, the radicals react more
easily and rC increases. When C is still higher, the
reaction rate is not as affected by adsorption (1 + KC =
KC; rC = kr). In the latter situation the reaction rate is
only dependent on •OH concentration related to
favourable (Eqs. 5.9 to 5.11) and unfavourable
reactions (Eqs. 5.12 and 5.13). There is an optimum
ratio of H2O2/C under these circumstances, whereby
organic material is
 72 Solar Detoxification


sufficient to consume generated hydroxyls and to avoid HSO5  e   OH  SO42 or

detrimental reactions, if the peroxide level is not too high. HSO  e   OH  SO (5.21)
At high molar ratios an inhibition effect would be
5 4
expected, because the unfavourable reactions become
more and more
pronounced. All this may be summarized as: first, if Chlorate has been proven insufficient to improve effective-
pollu- tant concentration is low, the hydrogen ness. However, both 4IO – and bromate increase the
peroxide easily inhibits the degradation rate and, mineral- ization rate in all cases tested. Nevertheless,
second, if the molar ratio between H2O2 and pollutant is these additives are very expensive compared to
too high, the same is true. hydrogen peroxide and peroxydisulfate, and their
application would dramatically increase treatment cost.
5.2.2. Persulfate Even more importantly, they do not dissociate into
harmless products (Br – and I–), because hundreds of
mg/L of these anions are undesirable in water. Potassium
In homogeneous reactions, the persulfate ion accepts an peroxymonosulfate (commercially called ‘oxone’) was also
elec- tron and dissociates (Eq. 5.14). The sulfate radical examined as an irreversible electron acceptor. The
anion is also generated under adequate thermal and formula of this salt is 2KHSO5.KHSO4.K2SO4, written
photolytic (wavelength <270 nm) conditions. This in aqueous solution as HSO –. Upon accepting an electron
radical goes through the reactions explained below from the conduction band, HSO– would dissociate into
(Eqs. 5.16 and 5.17). Persulfate can therefore be a 5
two different pathways (Eq. 5.21). The disadvantage is
beneficial oxidizing agent in photocatalytical its high molecular weight. 5 Many grams of oxone are
detoxification because SO •– is formed from the oxidant necessary to achieve 1 active mol (HSO–).
compound by reaction with the 4 photogenerated
semiconductor electrons (e– , Eq. 5.15). In addition, it
5
can trap the photogenerated electrons and/or generate
5.3. Catalyst modification
C
B
hydroxyl radicals. The sulfate radical anion (SO•–) is a
very strong oxi- dant (E = 2.6 V) and engages in at least
o
4
three reaction modes with organic compounds: by The TiO2 band-gap represents only 5 per cent of the solar
abstracting a hydrogen atom from saturated carbon, by
spectrum (see Chapter 2). From the standpoint of solar-
adding to unsaturated or aromatic carbon, and by
removing one electron from carboxylate anions and collecting technology, it is therefore a rather inefficient
from certain neutral molecules. process even for a high added-value application. In
contrast
S O2  e  SO  SO2 (5.14) to other advanced oxidation technologies, photocatalysis has
2 8 aq 4 4
S2O2
8
 eCB
 SO4 SO24 (5.15) the advantage of being solarizable and of being an environ-
mentally friendly technology. TiO2 is a cheap photostable
SO4  eCB SO24 (5.16
SO  H O   OH  SO2  H ) catalyst, and the process may be run at ambient temperature
and pressure conditions. Furthermore, the oxidant, molecu-
(5.17
)
4 2 4
lar oxygen (O2), is the mildest one. TiO 2 is a mild
catalyst that works at mild conditions with mild oxidants.
5.2.3. Other oxidants However, as concentration and number of contaminants
increase, the process becomes more complicated and
challenging prob- lems such as catalyst deactivation,
Other compounds could also potentially increase the slow kinetics, low photo- efficiencies and unpredictable
reac- tion rate because they are also electron scavengers. mechanisms need to be solved. It is clear that naked TiO 2
The most frequently tested so far in heterogeneous needs extra help to under- take practical applications of
photocatalysis are described in Equations 5.18 to 5.21. industrial and environmental interest, and this could lead
IO   8H 
+ to the
of loss of
its mild some of Moreover,
operation. the charm even reactor set-ups using

4 8e 

4H 2 O I (5.18)
+
artificial light, which must bear the cost of running the lamps
ClO3  6e H 3H2O 
6
(5.19
involved in them, will be much cheaper if visible radiant flux
Cl )

6H
+

BrO3  6e 3H2O  (5.20 can be employed.

Br )
 Water Decontamination 73

The redox process is based on the migration of Figure 5.6). Loading of Pt is optimum to achieve the
electrons and holes to the semiconductor surface, and on maxi- mum photocatalytic rate, affecting the distribution
two further oxidation and reduction steps (see Figure of elec- trons in the system. Above the optimum metal
5.1). Two basic lines of R&D have attempted to balance content, efficiency decreases, because once negatively
both half-reaction rates, one by adding electron acceptors charged, Pt particles become attractive for holes, which
(additional oxidants, already commented on above) and recombine with
the other by modifying catalyst structure and
composition. Both try to promote com- petition for
electrons and to avoid recombination of e –/h+ pairs. A
Metal
third approach has focused not only on increasing Metal
quantum yield but also on finding new catalysts with h
band- gaps that match the solar spectrum better. e-
Unfortunately, the choice of convenient alternatives for
substituting titanium dioxide in photocatalytic

detoxification systems is limited. An appropriate
semiconducting material should be:

• non toxic, 
Metal
• stable in aqueous solutions containing highly
reactive and/or toxic chemicals,
 h+
• not photo-corrodible under band-gap illumination,
• economical – that is – an increase in photocatalytic

FIGURE 5.5. Electron capture by a metal in contact with a
reaction rates must always be accompanied by a non- semiconductor surface.
proportional increase in overall process costs.
Metal oxides generally fulfil these criteria, but most
metal oxides are wide band-gap semiconductors or
insulators. Although iron (III) oxide is one of the few
exceptions (see Table 1.4), it has demonstrated
satisfactory activity in a limited number of cases. Other
non-oxide semiconductors (for example, CdS) are
usually unstable and photodegrade over time. A few
examples will be given in the following sections to
illustrate the large body of work conducted in the area of
photocatalyst modification.

5.3.1. Metal semiconductor modification

The addition of noble metals to a semiconductor could

modify the photocatalytic process by changing the
semicon- ductor surface properties. Figure 5.5 is an
illustration of the capacity of a metal in contact with a
semiconductor surface to capture electrons. After
excitation, the electron migrates to the metal, where it
becomes trapped and e–/h+ recombina- tion is avoided.
The hole is then free to migrate to the surface, where
oxidation of the organics can occur (see Figure 5.1).
The Pt/TiO 2 system (Pt deposited on titania by the FIGURE 5.6. Concentrating solar reactor with a platinum/
impregnation and reduction method) is the metal- titanium dioxide catalyst on ceramic saddles. Tested on
semiconductor system most commonly studied (see air contaminated by spray paint at Fort Carson Army
Base in Colorado, USA. (Courtesy of the US National
Renewable Energy Laboratory.)
 74 Solar Detoxification
h
e-
CdS e-
EG= 3.2 eV EG= 2.5 eV
h+
TiO2
FIGURE 5.7. The excitation process in a semiconductor-
semiconductor photocatalyst.
electrons into inefficient thermal energy. Care must
therefore be taken in studies conducted with modified
metal semi- conductors to use the optimum quantity of
metal.
5.3.2. Composite semiconductors
Coupled semiconductors provide a way to increase the
separation between charges and reduce the energy
(increas- ing wavelength) necessary to excite the system.
Figure 5.7 shows CdS-TiO 2 as an example. The energy
from light (λ < 497 nm) is large enough to cause an
electron to leave the CdS valence band and to go over to
the conduction band. The hole remains in the CdS, while
the electron is transferred to the TiO2 conduction band.
The separate charges are then free to undergo electron
transfer with the species adsorbed on the surface.
5.3.3. Surface sensitization
Surface sensitization of a wide band-gap semiconductor
via chemisorbed or physisorbed dyes can increase the
efficiency of the excitation process. The wavelength
range can be expanded by charge transfer from the
sensitizer to the semi- conductor. Figure 5.8 illustrates
the excitation, charge trans- fer and regeneration steps. If
the oxidative energy level of the excited state of the dye
is more negative than the semi- conductor conduction
band, then the dye can transfer the electron to the
conduction band of the semiconductor. The electron in
turn can be transferred to reduce an organic acceptor
adsorbed on the surface. Without the presence of a redox
couple, the dye-semiconductor system can also be used in
oxidative degradation of the dye itself. This is important
e-
Dye*
CB CB CB
A A A-
h
VB VB VB
Dye
FIGURE 5.8. Steps of excitation with a sensitizer in the
presence of an adsorbed organic electron acceptor (A).
because of the large number of dye substances found in
industrial textile wastewater.
5.4. Recommended analytical
methods
5.4.1. Original contaminants
The analyses performed on samples collected during
photo- catalytic treatment have to be as complete as
possible in order to adjust the mass balance for the
photocatalytic decomposition of the contaminants and
assure that the ana- lytical data are reliable and the
organic compounds have not disappeared in some other
way (for example, through evap- oration, adsorption in
the reactor, or adsorption in the cata- lyst) besides
photocatalysis. Liquid chromatography (HPLC) with UV
detection is the method of choice for analysis of
samples from photocatalytic treatment, as it allows
direct injection of the aqueous sample into the
analytical column, avoiding the necessity of prior
extraction. Samples only require filtering to remove
TiO2 or any other particles that could damage the
chromatographic column before they are injected into
the equipment. A device made up of a syringe and 0.22
µm membrane filters is used for this purpose. Gas
chromatography is only suggested if HPLC is not viable,
or when a pre-concentration is necessary as a result
of very low concentration of the parent compounds.
5.4.2. Mineralization measurements (TOC)
Total organic carbon (TOC) analyses of samples taken
during photocatalysis degradation experiments are vital
for the following reasons:
• As identification of all the intermediates generated
during photodecompositon is not possible,
pinpointing the moment at which only CO2
remains and the water is considered completely
decontaminated is crucial.

• Determination of the CO 2 produced might be
reasonable, since this must be stoichiometric with the
organic carbon present at the beginning in the
organic molecule. However, since the reactors are
usually large and not airtight, loss of the carbon
dioxide produced into the atmosphere prevents this.
For the same reasons, the samples might become
contaminated by atmospheric CO2 and falsify results.
• The analyses provide a reliable, simple and rapid way
to establish the mass balance at any moment, to get an
idea of the remaining amount of intermediates and to
check the extraction methods and analysis of
intermediates.
The basic techniques for the determination of TOC in
water have remained relatively unchanged for twenty
years. Organic compounds are converted to CO 2 via a
combination of actions that may include chemical
oxidizing agents, ultra- violet radiation or high-
temperature combustion (Wangersky, 1993). The CO2 is
then measured using non-dispersive infrared
absorption, micro-coulometry or conductimetric
techniques. As many water samples contain inorganic
forms of carbon (HCO – and CO 2–), it is usually
necessary to 3 3
remove these, typically using a gas stripping technique
prior
to measurement of TOC. Some of the organic carbon
(VOCs) may also, very often, be removed by this
procedure. In the case of heterogeneous photocatalysis, it
is necessary to use a TOC analyser that can manage non-
filtered samples. When TiO 2 is filtered from the sample,
there is a notable loss of organic compounds, because
they are adsorbed onto the solid retained in the filter.
5.4.3. Analysis of intermediates
In order to analyse a reaction mixture containing
pesticides and their degradation products (DPs), it is
necessary to have analytical screening methods available
that permit separation and identification of compounds
with very different hydrophilic–hydrophobic
characteristics and spanning very different
concentration ranges. The use of gas chromato-
graphy with classical detectors, like ECD, NPD or
FID, is obviously insufficient. But gas or liquid
chromatographic systems coupled with mass
spectrometry (GC/MS and LC/MS) represent a good
fast alternative for achieving very useful structural
information about the compounds gener- ated in such
processes (Agüera and Fernández-Alba, 1998).
Water Decontamination 75
Advantages of the GC-MS-based methods are:
• the large amount of structural information they yield
and the spectra libraries available either from
databases or from research papers that make DP
identification feasible;
• the durability and reliability of the GC-MS interface; and
• their highly efficient sensitivity and separation,
which avoids overlapping compounds with similar
structures.
However, GC-MS-based methods have important
draw- backs because of their low capacity to analyse
very polar, less volatile and less thermally unstable
compounds. Identification of DPs is usually based on
their EI (Electron Impact) mass spectra, mainly by
comparing the unknown compound spectrum with
published spectra. A disadvan- tage of EI is that it does
not usually provide molecular weight information.
Additional and very useful structural information on DPs
can be obtained by chemical ionization (CI). From the
molecular weight and interpretation of frag- mentation
patterns, it is possible to hypothesize a molecu- lar
structure. However, even an EI mass spectrum does
not provide enough information about the location of the
functional groups (for instance, the position of a
hydroxyl
group on a benzyl ring). Comparison with a standard
(when commercially available) is required for
unequivocal confirmation. When by-product standards
are not com- mercially available, the laboratory
synthesis of DPs could be a solution.
Because GC methods require compounds with high
vapour pressures, derivation of at least the acid fraction
(BF3/MeOH or diazomethane) has become a typical
procedure for identifying less volatile and more polar
compounds. How- ever, derivation is not easy and it is
also time-consuming. Because of this, LC-MS
techniques are gaining in impor- tance. LC techniques
present several advantages over GC:
• Little or no cleaning of the sample is required.
• High polar, low volatile and thermally stable
compounds are more easily analysed.
• Direct analysis of the samples is possible, avoiding
polar DPs escaping from extraction procedures.
The major role of LC-MS in the degradation processes
stud- ied is, first, to check DP molecular weight and,
second to detect DPs that are not directly amenable with
GC-MS techniques.
The ready availability of atmospheric pressure
ionization (API), electrospray (ESP)/ionspray (ISP) and
atmospheric
 76 Solar Detoxification

CH2 CH3
N CH2 CH3 N
CH3 N N CH2 CH3
CH2 CH3 CH3
CH2CH2 CHOHCH3
N N R N
OH
1 CH CH
2

+R 1 N CH CH
H3CO H3 CO
2 3 2 3
P O
H3CO
3

P = R1
O H3CO
O
S CH2COH
R1 N
Pyrimiphos methyl CH2CH3
O CH2 CH3
CH3 N N CH CH O
2 3

OCH3 P OCH3 + N + SCH3 P OCH3

OCH3 = R2 OCH3
R1 N
CH2COOH
OH CH2CH3
CH2CHO
R2 N
CH2CH3
CH2COOH
R2 N CH3
CH2CHO
R1 N
CH2CH3
CH2COOH
CH3 R2 N CH CH
R2 N 2 3
CH2CHO
H
R1 N
CH3 CH CH2CH3
3
R2 N R2 N
3

CH3 CH2CH3

H
H R1 N
R2 N CH2CH3
CHO
CHO
R2 N
CH2CH3

HOH2C N NH2 HOC N O

N N
H
H

OH R2 N CH CH O O OCH3
OH
2 3 P
OCH3
S

FIGURE 5.9. Degradation pathway proposed for pirimiphos-methyl dissolved in water when illuminated in the
presence of TiO2.

pressure chemical ionization (APCI) LC-MS interfaces
that provide general structural information and
sensitivity has expanded the applicability of LC-MS,
allowing identi- fication of a large range of polar-
transformation products. LC-MS presents important
weaknesses, since the informa- tion they provide usually
lacks detailed structural data and is less sensitive and
discriminating than that provided by GC- MS. These
disadvantages can frequently prevent DP identifi- cation
as a consequence of the low detection threshold or
overlapping peaks. As the DPs obtained are very
complex (see Figure 5.9), mass spectrometry-based
techniques do not
provide enough structural information for the
unequivocal structural elucidation of the DPs in many
cases, and this must be done by more complex, time-
consuming techniques such as LC/MS/MS or NMR. But
the combination of both GC/MS and LC/MS is very
useful and, in many cases, enough structural information
to evaluate the degradation process may be found
quickly. Other analytical measures, such as total organic
carbon (TOC) or ion chromatography (IC), can be of
great help in assessing the success of the degradation
process by evaluating the mineralization rate achieved or
by establishing the mass balance of the whole process.

5.4.4. Extraction methods
Common handling procedures for the analysis of samples
of chemically treated water involve the use of extraction
methods, because identification of degradation products
has to be carried out at sub-mg/L level. Trace organic
com- pounds in wastewater are still typically enriched by
liquid– liquid extraction (LLE) using an appropriate
solvent. However, solid-phase extraction (SPE) is gaining
in acceptance (Chiron et al., 2000), mainly because SPE
generates less matrix inter- ference, and a wide range of
new adsorbents (able to trap DPs with a wide range of
polarities) are commercially avail- able, including:
alkylsilanes (modified silica, such as C-18 and end-
capped C-18); porous polymers, such as poly (styrene-
divinylbenzene) PRP-1 or PLRP-S; and carbon mod- ified
materials, such as porous graphitic carbon (PGC). SPE
materials are expected to show different behaviours
with respect to capacity and breakthrough volumes of
both ana- lyte and matrix interferences. Because the
retention of a com- pound is higher in its neutral form
than in its ionic form, phenol and benzoic acid
extractions are better under acidic conditions while
amines are best recovered at alkaline condi- tions.
Problems may arise with multifunctional compounds.
The retention of hydrophilic compounds (Log Poct <0)
such as aminophenols or cyanuric acid is poor, but can
be high with porous graphitic carbon. On the other
hand, short- chain aliphatics such as oxalic or formic
acids (usually the final organic photo-oxidation
degradation products) may not be recovered at all. In
order to identify as many chemicals as possible, a
sequential extraction scheme involving different SPE
adsorbents could be proposed. A C-18 phase is used
initially to select all neutral hydrophobic compounds at
pH7. The C-18 filtrates are then passed through a
polymeric adsorbent, also at pH7, where medium-polar
compounds are retained. Subsequently, filtrates are
acidified to pH4.5 and pH2.5, respectively, to extract
the majority of acidic compounds with a polymeric or
carbon-type adsorbent. Polymeric adsorbents can be
used over pH2-13 without decomposition of the
adsorbent material.
5.4.5. Toxicity analysis
The test organisms in these assays include
representatives from four groups: microorganisms,
plants, invertebrates and fish. The Organisation for
Economic Cooperation and Development (OECD) has
proposed a minimum data set to assess the effects of
chemicals on the environment.
Water Decontamination 77
The OECD lists mortality in fish, impaired reproduction
in crustaceans and inhibition of growth in algae as
examples of ecotoxicity tests needed to predict the
impact of released chemicals upon ecosystems. The
two main invertebrate toxicity tests routinely used are
the twenty-one-day Dapinia and the seven-day
Ceriodaphinia survival and reproduction tests. Tests are
conducted by exposing the organisms to the toxins
under control conditions. After the required incuba- tion
period, live organisms are counted. Fish bioassays have
been conducted for decades. The distinct
physiological and behavioural responses of fish to low
levels of pollutants has been employed in the
development of fish monitors that act as indicators of
water quality (Tothill and Turner, 1996). The tests are
usually based on larval growth and survival, where
newly hatched fish are exposed to a range of effluents for
up to seven days. The acute lethality test with fish
measures the concentration of a chemical that is lethal to
50 per cent of the exposed population after 96 h
(LC 50). Species such as rainbow trout (Oncorhynchus
mykiss) and fat- head minnow (PIMEPHALES PROMELAS) are
commonly used. During recent years, research has been
carried out to reduce or replace acute fish tests with in
vitro assays, using cultured fish cell lines. The use of algae
in bioassays has proved useful in detecting metals,
herbicides, pesticides and crude oil com- pounds.
However, the culturing and preparation of the algae
suspension is a lengthy process and, further, it is difficult
to maintain an identical culture of algae each time the
bioassay is conducted.
Many of the above tests require specialized equipment
and operator skills and are time consuming. The use of
higher organisms such as fish may also be ethically
undesirable. In the last few years there has been an
increased interest in bacterial screening to assess toxicity.
Studies of effects on microbial function or activity
constitute a more direct, rapid and sensi- tive approach to
measuring chemical stress. These can be classified by
the type of measurement used:
• measurements monitoring the transformation of
carbon, sulfur or nitrogen,
• measurements that determine the activity of
microbial enzymes such as dehydrogenases,
adenosine triphos- phatases and other enzymes,
• measurements of growth, mortality and photosynthesis,
• measurements that determine glucose uptake
activity using radioisotopes,
• measurements of oxygen consumption using a
dissolved oxygen electrode or respirometer,
• measurement of luminescence using a photometer.
 78 Solar Detoxification
The development and applications of biological toxicity
testing are rapidly increasing. Numerous bioassay proce-
dures are now available, but it is difficult to assess the
sensi- tivity of these tests, and therefore a universal
monitoring device for toxicity testing is unlikely to
become available in the near future. In any case, most
recent studies have dealt with the use of the bacterial
luminescence assay for toxicity screening. The use of
toxicity tests for evaluation of photo- catalytic treatments
is not very common for the moment, but several relevant
papers have already been published (Herrmann et al.,
1999; Fernández-Alba et al., 2002).
Summary
Photocatalytic degradation of organic and inorganic
compounds follows a definite stoichiometry that has to
be determined by appropriate analytical techniques
during photocatalytic experiments in order to close the
mass balance between reactives and products.
Furthermore, degradation pathways and the by-products
formed are so complex that analysis of water toxicity
during the treatment is recommended to assure that it
decreases. The photocat- alytic degradation of
contaminants by photocatalysis can be enhanced by the
use of additional oxidants such as hydrogen peroxide and
persulfate and/or modification of the catalyst using
deposited metals, composite semiconductors or dye
sensitizers.
Preferably, the degradation of the original
contaminants should be monitored by HPLC, and the
final mineralization by TOC and Ionic Chromatography,
but identification of intermediate products has to be
achieved through MS tech- niques (GC-MS and HPLC-
MS). A combination of several MS techniques with
several extraction methods is better in order to assure the
identification and quantification of a sig- nificant number
of DPs. As the detection of all DPs is almost impossible,
the use of different organisms for determining toxicity is
very important in order to guarantee that the treatment
is correct.
Bibliography
AGÜERA, A. AND FERNÁNDEZ-ALBA, A.R. 1998. GC-MS and
LC-MS evaluation of pesticide degradation products
generated from advanced oxidation processes in
waters: an overview. ANALUSIS, No. 26, pp.123–30.
CHIRON, S.; FERNÁNDEZ-ALBA, A.; RODRÍGUEZ, A. AND
GARCÍA-CALVO, E. 2000. Pesticide chemical oxidation:
state of the art. WAT. Res., Vol. 34, No. 2, pp. 366–
77.
FERNÁNDEZ-ALBA, A.R.; HERNANDO, L.; DIAZ, G. AND
CHISTI, Y. 2001. Toxicity of pesticides in wastewater:
a comparative assessment of rapid bioassays. ACTA
CHIMICA ACTA, No. 426, pp. 289–301.
HERRMANN, J.M.; GUILLARD, CH.; ARGÜELLO, M.; AGÜERA,
A.; TEJEDOR, A.; PIEDRA, L. AND FERNÁNDEZ-ALBA, A. 1999.
Photocatalytic degradation of pesticide pyrimiphos-methyl:
determination of the reaction pathway and identification of
intermediate products by various analytical methods.
CATALYSIS TODAY, No. 54, pp. 353–368.
MALATO, S.; BLANCO, J.; MALDONADO, M.I.;
FERNÁNDEZ-IBÁÑEZ, P. AND CAMPOS, A. 2000. Optimizing solar
photocatalytic mineralization of pesticides by adding
inorganic oxidizing species: application to the
recycling of pesticide containers. Applied CATALYSIS B:
ENVIRONMENTAL, No. 28, pp. 163–74.
PELIZZETTI, E.; CARLIN, V.; MINERO, C. AND GRÄTZEL, M. 1991.
Enhancement of the rate of photocatalytic degradation
on TiO2 of 2-chlorophenol, 2,7-dichlorodibenzodioxin
and atrazine by inorganic oxidizing species. New
JOURNAL of Chemistry, No. 15, pp. 351–9.
PULGARIN, C.; INVERNIZZI, M.; PARRA, S.; SARRIA, V.; POLANIA, R.
AND PÉRINGER, P. 1991. Strategy for the coupling of
photochemical and biological flow reactors useful in
mineralization of biorecalcitrant industrial pollutants.
CATALYSIS TODAY, No. 54, pp. 341–54.
TAPP, J.F.; WHARFE, J.R. AND HUNT, S.M. 1996. Toxic IMPACTS
of WASTES on the AQUATIC Environment. London, Royal Society
of Chemistry.
TOTHILL, I.E. AND TURNER, A.P.F. 1996. Developments
in bioassay methods for toxicity testing in water
treatment. Trends in ANALYTICAL Chemistry, No. 15,
pp. 178–87.
WANGERSKY, P.J. 1993. Dissolved organic carbon
methods: a critical review. MARINE Chemistry, No.
41, pp. 61–74.

Self-assessment questions
Part A: True or false?
1. Electrons in the conduction band cannot
degrade organic compounds.
2. When organics decompose, an increase in the
concentration of hydrogen ions is produced in the
water.
3. The final objective of photocatalytic treatment is
always the total mineralization of the organic
contaminants.
4. Inorganic compounds are degraded through
oxidative and/or reductive photocatalytic pathways.
5. The addition of other oxidants to the
photocatalytic process only produces additional
oxidant species.
6. Hydrogen peroxide always enhances the
decomposition of organics.
7. Liquid chromatography (HPLC) with UV
detection is the method of choice for analysing
samples from photocatalytic treatment because it is
the easiest.
8. TOC analysis is a method for measuring
CO2 production during experiments.
9. GC/MS and LC/MS are complementary methods.
10. There is a universal monitoring device for
toxicity testing.
Water Decontamination 79
Part B
1. What is the general stoichiometry for the
total mineralization of methamidophos
(C2H8NO2PS)?
2. Why is the analysis of the initial compound not
enough to determine the efficiency of contaminant
degradation?
3. Why is toxicity determination during a
photocatalytic experiment very important?
4. What are the final products in the
photocatalytic treatment of CN–?
5. What are the main advantages of an additional oxidant?
6. What are the most common oxidants used
for photocatalytic degradation of contaminated
water?
7. What metals are used for doping TiO 2, and how do
they increase photoefficiency?
8. What is the most common analytical technique
for determining the disappearance of the initial
compound during photocatalysis in water, and why?
9. What is the principal advantage of applying MS-
based analytical methods to the photocatalytic
degradation of organic compounds?
10. What are the most common toxicity tests in
use today?
 80 Solar Detoxification

Answers 5. Increasing the number of trapped e – of the e–/h+

pairs, generating more •OH as well as other
oxidizing species; increasing the oxidation rate of
Part A intermediate compounds; and avoiding problems
caused by a
1) False. 2) True. 3) False. 4) True. 5) False. 6) False. low concentration of O 2.
7) True. 8) False. 9) True. 10) False.
6. Hydrogen peroxide and persulfate.
Part B
7. Noble metals. After excitation, the electron migrates
to the metal where it becomes trapped and e –/h+
1. C2H 8NO2PS  7O2   2CO2  H 3PO 4
T iO2 / h
recombination is avoided.
H2SO4  HNO3 
H2O 8. Liquid chromatography (HPLC). This method
permits direct injection of the aqueous sample into
2. Because reactives and products could be lost, the analytical column, avoiding the necessity of
causing the results to be unreliable. extraction procedures.

3. Because the products of incomplete degradation 9. The identification of unknown compounds

and their concentrations may be sufficiently produced during photocatalytic treatment of
innocuous for discharge directly into the contaminated water.
environment or for further biological treatment.
10. Bacterial screening tests.
4. NO– and CO .
3 2
 Solar Detoxification
Aims
This chapter discusses the basic factors
related to solar photocatalytic process
technology and applications. The key
issues related to the use of solar ultraviolet
radiation and their implications for
appropriate materials, and reactors for
efficient light collection and use are
discussed here.
Technology
6 CHAPTER 6
Objectives
When you have completed this chapter,
you will have a basic knowledge and
understanding of the following areas:
1. The key issues in collector
technology related to solar water
detoxification.
2. The specific peculiarities of the use
of solar ultraviolet light.
3. The main characteristics of different
types of collectors for solar water
detoxification applications.
4. Advantages and disadvantages of
using non-concentrated sunlight.
5. Factors concerned the with the
main technological components: the
reactor, reflectors and catalysts.
82 Solar Detoxification

NOTATION AND UNITS

Symbol Description Units
CPC Compound parabolic concentrator
CPVC Chlorinated polyvinyl chloride
CR Concentration Ratio (solar collector)
C Geometric concentration ratio
Cε Effective concentration ratio
d Reactor tube diameter mm
D Aperture width (parabolic collector) mm
f Focal length (parabolic trough collector) mm
ECTFE Ethylenechloride tetrafluroethylene
ETFE Ethylenetetrafluoroethylene
FEP Fluorinated ethylenepropylene
IEP Isoelectric point
IFSH Institut für Solarenergieforschung GmbH (Hanover, Germany)
IR Infrared light (solar radiation)
NREL National Renewable Energy Laboratories
PSA Plataforma Solar de Almería
PTFE Polytetrafluoroethylene
PTC Parabolic trough collector
PVDF Polyvinylidene fluoride
PZC Point of zero charge
Re Reynolds number
UV Ultraviolet light (solar radiation)
TFE Tetrafluoroethylene
θA Semi-acceptance angle (parabolic collectors) degrees
ρs Specular reflectance
Optical error (reflective surfaces) mrad
σ

6.1. Solar collector technology • non-concentrating or low-temperature, up to 150 °C,

generalities
Traditionally, different solar collector systems have
been classified depending on the level of concentration
attained by them. The concentration ratio (CR) can be
defined as the ratio of the collector aperture area to the
absorber or reactor area. The aperture area is the area
intercepting radiation and the absorber area is the area
of the component (whether fully illuminated or not)
receiving concentrated solar radiation. This CR is
directly related to the working system temperature and,
according to this criterion, there are three types of
collectors:
• medium-concentrating or medium temperature,
from 150 °C to 400 °C ,
• high-concentrating or high temperature, over 400 °C .
This traditional classification considers only the
thermal efficiency of the solar collectors. However, in
photocatalytic applications, the thermal factor is
usually irrelevant (as already explained in Chapter 4),
whereas the amount of useful radiation collected (in the
case of the TiO2 catalyst, with a wavelength shorter then
385 nm) is very important.
Non-concentrating solar collectors (Figure 6.1) are
static and non-solar-tracking. Usually, they are flat
plates, often aimed at the Sun at a specific tilt,
depending on the

geographic location. Their main advantage is their
simplicity and low cost. An example is domestic hot-
water technology. Medium-concentrating solar
collectors concentrate sunlight between five and fifty
times, so continuous tracking of the Sun is required.
Parabolic trough collectors (PTC) and holographic
collectors (Fresnel lenses) are in this group. The first
have a parabolic reflecting surface (Figure 6.2) which
concentrates the radiation on a tubular receiver located in
the focus of the parabola. They may be one-axis tracking,
either azimuth (east–west movement around a north–
south-oriented axis) or elevation (north–south
movement around an east–west-oriented axis), or two-
axis tracking (azimuth + elevation). Fresnel lens
collectors consist of
FIGURE 6.1. Non-concentrating solar collectors for
domestic water-heating applications.
FIGURE 6.2. Medium concentrating solar collector:
recircu- lating parabolic trough reactor for water
purification using titanium dioxide slurry at NREL
(Courtesy of the US National Renewable Energy
Laboratory).
Solar Detoxification Technology 83
refracting surfaces (similar to convex lenses) that deviate
the radiation at the same time that they concentrate it
onto a focus.
High-concentrating collectors have a focal point
instead of a linear focus and are based on a paraboloid
with solar tracking. Typical concentration ratios are in
the range of 100 to 10,000 and precision optical elements
are required. They include parabolic dishes and solar
furnaces.
Up to now, the solar collectors used for
photocatalysis have been in the two first categories. In
order to illustrate the variation in performance
between different orientations, Figures 6.4 and 6.5
show, respectively, a comparative analy- sis of
medium-concentrating and non-concentrating solar
collector efficiency with regard to direct incident
radiation. Direct radiation is the radiation that has no
interference from the atmosphere and, consequently,
has a known direction, and can therefore be
concentrated. Global radiation is com- posed of direct
and diffuse radiation. The data represented in Figure 6.4
correspond to direct radiation in an ideal cloud- less
year (based on average meteorological data on sunny
days at the Plataforma Solar de Almería), and show
the energy available from direct radiation on the
aperture plane of a one-axis parabolic-trough collector
with different orien- tations: elevation tracking,
azimuth tracking and azimuth tracking slightly tilted 8°
from the horizontal.
The calculations performed are geometric and based
on the cosine of the incident angle, this angle being the
one formed by the solar ray with the line normal to the
aperture plane of the collector. They allow the amount of
direct radi- ation available at any given time for each
collector
FIGURE 6.3. A high-concentration solar collector: a fixed-
focus solar reactor (PSA, Spain).
84 Solar Detoxification

FIGURE 6.4. Yearly efficiency of solar collectors in an ideal cloudless year: a PTC-one axis with different orientations.

FIGURE 6.5. Yearly efficiency of solar collectors in an ideal cloudless year: flat plate with different inclinations.
 Solar Detoxification Technology 85

configuration to be known. In Figure 6.4, it may be

observed that the annual efficiency of azimuth tracking
(east–west movement around a north–south-oriented
axis) is about 10 per cent better than elevation tracking
(north–south move- ment around an east–west-oriented
axis). In the first case, this efficiency increases notably in
the summer and decreases in the winter (identical in the
Northern and Southern hemi- spheres), whereas it is
almost constant year-round in the second case. A slight 8°
tilt to the south in the Northern hemi- sphere and the
opposite in the south increases yearly efficiency about 5 per
cent in the azimuth-tracking configuration, due to the
reduction of the cosine factor over the year.
In the case of non-concentrating flat-plate
collectors, it may be observed that efficiencies are lower
FIGURE 6.6. The first engineering-scale outdoor solar
than with one- axis PTCs, attaining maximum efficiency
detoxi- fication reactor using a one-axis parabolic trough
with an inclination (to the south in the Northern
collector. Part of the 465 m 2 parabolic trough system at
Hemisphere and to the north in the Southern
Sandia National Laboratory. (Courtesy of the US
Hemisphere) from the horizontal equal to the local
National Renewable Energy Laboratory.)
latitude. This configuration – that is – the angle of tilt set
at the angle of latitude of the site, maximizes the annual
energy collected in a flat-plate collector. Although the tion with a Pyrex tube through which contaminated water
calcu- lations made here are for a specific location and could flow. Since then, many different concepts with a
latitude, the comparisons of solar radiation collection wide variety of designs have been proposed and
and the conclu- sions obtained are qualitatively valid developed world- wide, in a continuous effort to improve
for any other location. performance and reduce the cost of solar detoxification
systems. Among these different concepts, the most
important with regard to the definition of the overall
6.2. Collectors for solar water system are those related to whether or not radiation must
detoxification: features be concentrated, to the type of
reflective surface to be used, to the way the water circulates
through the reactor (tube, falling film or stirred vessel),
6.2.1. Specific features of and to the way in which the catalyst is employed.
solar UV light utilization One of the most important reactor design issues is
decid- ing between concentrating or non-concentrating
The specific hardware needed for solar photocatalytic collector systems. Concentrating systems have the
appli- cations has much in common with that used advantage of a much smaller reactor-tube area, which
for thermal applications. As a result, reactors and could mean a shorter circuit in which to confine, control
photocatalytic systems have both followed and handle the contami- nated water to be treated. The
conventional solar thermal collector designs, such as use of high-quality ultraviolet- light-transmitting reactors
parabolic troughs and non-concentrating collectors. At and supported-catalyst devices also seems more logical,
this point, their designs begin to diverge, as: from both an economic and an engi- neering point of
view, if concentrating collector systems are to be used.
• The fluid must be exposed to ultraviolet solar
Nevertheless, concentrating reactors have two
radiation, therefore the absorber must be UV-
important disadvantages compared to non-concentrating
transparent.
ones. The first is that they cannot concentrate (that is,
• Temperature does not play a significant role in the
use) diffuse solar radiation, which is unimportant for
photocatalytic process, so no insulation is required.
solar thermal applica- tions because diffuse radiation is a
The first engineering-scale outdoor reactor for solar small fraction of the total solar radiation. However, solar
detoxifi- cation was developed by Sandia National photocatalytic detoxification with TiO2 as a catalyst uses
Laboratories (United States) at the end of the 1980s (see only the UV fraction of the solar
Figure 6.6) in which a parabolic-trough solar thermal
collector was modi- fied simply by replacing the
absorber/glazing-tube combina-
86 Solar Detoxification

spectrum, and since this radiation is not absorbed by solar photocatalytic systems is the need for a catalyst; in
water vapour, as much as 50 per cent of it, or even more the case of TiO2 it can be deployed in several ways, such as
in very humid locations or during cloudy or partly cloudy slurry or as a fixed catalyst (such as a fibreglass matrix
periods, can be diffuse. As non-concentrating solar inserted in the reactor tube).
collectors can make use of both direct and diffuse UV
radiation, their effi- ciency can be noticeably higher. The
second disadvantage of concentrating collectors is their 6.2.2. Parabolic trough collectors
complexity, cost and mainte- nance requirements. The
consequence of these disadvan- tages is that present Solar photoreactors for water detoxification were
state-of-the-art favours the use of non-concentrating originally designed for use in line-focus parabolic-trough
reactors for solar photocatalytic applica- tions. An concentra- tors. This was in part because of the historical
additional disadvantage of concentrating reactors is that emphasis on trough units for solar thermal applications.
their quantum efficiency is low, due to a square root Furthermore, PTC technology is relatively mature and
rather than linear dependence of rate on light flux, as existing hardware could be easily modified for solar
already explained in Chapter 4. photocatalytic processes. PTCs, considered medium
For many of the solar detoxification system concentrating collectors, are of two types:
components, the equipment is identical to that used for
other types of water treatment, and construction • one-axis parabolic trough, or
materials are commer- cially available. Most piping may • two-axis parabolic trough.
be made of polyvinylidene fluoride (PVDF), chlorinated
polyvinyl chloride (CPVC), or simply polyethylene. As explained previously, the first engineering-scale
Piping, as well as the rest of the materi- als, must be facility was developed from one-axis PTCs (Sandia
resistant to corrosion by the original contami- nants and National Labs, United States, 1989) and the second from
their possible by-products in the destruction process. two-axis PTCs (Plataforma Solar de Almería, Spain,
Neither must materials be reactive, interfering with the 1990, Figure 6.7). Both facilities are quite large pilot
photocatalytic process. All materials used must be inert plants (hundreds of square meters of collecting surface)
to degradation by UV solar light in order to be compat- and can be considered the first steps in industrialization
ible with the minimum required lifetime of the system of the photocatalytic process.
(ten years). Although one-axis tracking has been demonstrated
Optical material requirements are similar to other to be the most economically suitable for solar thermal
closed solar systems, but photocatalytic reactors must app- lications, certain peculiarities of photocatalytic
transmit UV light efficiently because of the process research make two-axis-tracking PTCs efficient for
requirements. In some cases, when the steam pressure of finding out exactly
contaminants in water is sufficiently low, a closed
system might not be required, in which case a
transmissive UV containment material could be avoided.
All pipes, reactor and connection devices must be
strong enough to withstand the necessary water-flow
pressure. Typical parameters are 2 to 4 bars for nominal
system pressure drop and a maximum of 5 to 7 bars.
Concentrating system materials must also be able to
withstand possible high temperatures that could result
from absorption of concentrated visible and infrared light
in the reactor.
With regard to the reflecting/concentrating
materials, aluminium is the best option because of its
low cost and high reflectivity in the solar terrestrial UV
spectrum. Commercially available film products
incorporate a thin aluminium foil with an acrylic coating.
The last peculiarity of FIGURE 6.7. A CIEMAT 384 m2 solar detoxification
facility using two-axis parabolic trough collectors, at
Plataforma Solar de Almería (PSA, Spain).

how much radiation reaches the photoreactor at any
given time and also, therefore, permit accurate evaluation
of the other parameters related to the photocatalytic
process. This accuracy allows comparison of
experiments carried out in such large photoreactors with
lab-scale photoreactors, where the calculation of incident
radiation is much easier. This also makes it possible to
reduce the number of variables during testing, using the
knowledge acquired by other authors.
The equation of the parabola is:
x2
y (6.1)
4f
where f is the focal length. If D is the aperture width and
d, the reactor tube diameter, the geometric concentration
of the collector C is:
D breakdown:
C
πd (6.2)
The basic components of a parabolic-trough collector
for photocatalytic applications are: the reflecting
concentrator, the absorber tube (photoreactor), the
drive-tracking system and the overall structure. Of these,
the last two do not differ in photocatalysis from the
applications for which they were originally designed,
and are identical to those existing for thermal
applications. Reflective surfaces and photoreactor
technology are specifically discussed in Section 6.4.1, as
they can be considered independently of the solar
collector used. The collector structure supports the
reflecting concentra- tor system, which reflects direct
insolation onto the receiver tubes. Two-axis PTCs
consist of a turret on which there is a platform
supporting several parallel parabolic trough collec- tors,
with the absorber in the focus. The platform has two
motors controlled by a two-axis (azimuth and
elevation) tracking system. Thus the collector aperture
plane is always perpendicular to the solar rays, which
are reflected by the parabola onto the reactor tube at
the focus through which the contaminated water to be
detoxified circulates. One-axis PTCs have only one
motor and a one-axis solar-tracking system; the reactor
tube (linear focus of the parabola) is then positioned in
the same plane as the normal vector of the collector
aperture plane and the solar vector (see Figure 6.8).
The angle formed by these two vectors is called the
incident angle of solar radiation.
After all optical losses have been considered, the
effective concentrating ratio of PTCs is usually between
5 and 20.
Solar Detoxification Technology 87
FIGURE 6.8. Solar ray reflection on a one-axis parabolic
trough collector.
Typical overall optical efficiencies in a PTC are in the
range of 50 to 75 per cent, with the following
• tracking system: 90 to 95 per cent
• reflector/concentrator (reflectivity): 80 to 90 per cent
• absorber/reactor (transmittance): 80 to 90 per cent
• mechanical collector errors: 90 to 95 per cent.
Parabolic-trough collectors make efficient use of direct
solar radiation. As an additional advantage, the thermal
energy collected from the concentrated radiation can be
used in parallel for other applications. The size and
length of the reactor is smaller, receiving a large amount
of energy per unit of volume, so handling and control of
the liquid to be treated is simpler and cheaper, and the
risk of leaks, which in many cases can be dangerous, is
lower. In general, this can also be translated into a
reactor able to withstand higher pressures and able to
employ potentially costly supported-catalyst
configurations.
6.2.3. One-sun (non-concentrating)
collectors
One-sun non-concentrating collectors (CR = 1) are, in
prin- ciple, cheaper than PTCs, as they have no moving
parts or solar tracking devices. They do not concentrate
radiation, so their efficiency is not reduced by factors
associated with reflection, concentration and solar
tracking. Manufacturing costs are cheaper because their
components are simpler, which also means easy and
low-cost maintenance. Also, the non-concentrating
collector support structures are easier and cheaper to
install and the surface required for their
88 Solar Detoxification

installation is smaller, because as they are static they do front or back end of a combined solar/microbiological
not project shadows on the others. treatment scheme (see also Section 8.1).
Based on extensive effort in the designing of small Any falling film or flat reactor must be covered to
non- tracking collectors, a large number of non- avoid direct contact with the atmosphere. The use of an
concentrating solar reactors have been developed for uncovered reactor is not recommended because of many
solar photocatalytic applications, which can be classified factors, includ- ing loss of volatile contaminants and dust
as follows: and dirt inside the reaction mixture.
• Trickle-down FLAT PLATE: based on a tilted plate Although one-sun designs possess notable
facing the Sun, over which the water to be treated falls advantages, the design of a robust one-sun photoreactor
slowly; the catalyst is fixed on the plate surface. is complex, as a result of the need for a large area of
weather-resistant and chemically inert ultraviolet-
• FREE-FALLING film: similar to the trickle-down flat plate,
transmitting reactors. The amount of materials
but with a higher flow rate and normally with a
required makes it necessary for them to be relatively
catalyst attached to the surface on which the liquid to
inexpensive. Those that best meet these requirements are
be treated circulates. It is usually open to the
certain types of plastics, for instance,
atmosphere, so it can be used only when volatile
compounds are not present.
• Pressurized FLAT PLATE: consisting of two plates
a)
between which water circulates, using a separating wall
(which can be filled in with fibre) to which the catalyst
is attached.
• TUBULAR: this kind of collector usually consists of
many small tubes connected in parallel to make the flow
circu- late faster than a flat plate, but functioning
basically the same way.
• SHALLOW SOLAR ponds: this is a very interesting variety,
as pond reactors are easily built on-site, especially for
indus- trial wastewater treatment. Since
manufacturing indus- tries already use ponds for
microbiological treatment of wastewater, shallow
solar ponds can be used for the b)

FIGURE 6.9. Experimental set-up of a thin-film fixed-bed

reactor tested by ISFH at PSA installations. The housing is FIGURE 6.10. One-sun water treatment reactors with PTFE
made of Plexiglas and the catalyst is fixed on a flat glass tubes at NREL: early reactor a) and reactor with titanium
plate. (Courtesy of the Institut für Solarenergieforschung dioxide immobilized on fibreglass bundles b). (Courtesy of
GmbH, Hanover, Germany.) US National Renewable Energy Laboratory.)

fluoropolymer films, but these, although highly
versatile, possess lower tensile strength than the rigid
glass pipe and reduce the pressure capacity of the
photoreactor system. This combination of low pressure
capacity and large volume, cou- pled with the need to
either keep a catalyst slurry suspended or to ensure good
mass transfer to a supported catalyst, requires carefully
designed fluid control.
Non-concentrating systems require significantly more
pho- toreactor area than concentrating photoreactors and,
as a result, full-scale detoxification systems (hundred of
square meters of collectors) must be designed to withstand
the oper- ating pressures anticipated for fluid circulation
through a large field. As a consequence, the use of tubular
photoreactors has a decided advantage because of the
inherent structural efficiency of tubing; tubing is also
available in a large variety of materials and sizes and is a
natural choice for a pressurized fluid system. Finally, its
construction must be economical and should be efficient
with low-pressure drop.
If a supported catalyst is used, the photoreactor has to
be much larger than in a concentrating system. If the
catalyst is circulated in a slurry, the design would have to
avoid low- flow regions where the catalyst could settle
out of suspen- sion, which means that turbulent flow
must be assured throughout the hydraulic circuit.
Containment of volatile organic contaminants to prevent
their escape into the atmos- phere is also of concern in a
large reactor.
6.2.4. Compound parabolic
concentrator (CPC)
CPC collectors are a very interesting cross between
trough
concentrators and one-sun systems and are one of the
best options for solar photocatalytic applications. CPCs
have been found to provide the best optics for low
concentration systems, and these non-imaging
concentrators are exten- sively employed for evacuated
tubes. CPCs are static collec- tors with a reflective
surface following an involute around a cylindrical
reactor tube. This can be designed with CR = 1
(or near 1), giving it the advantages of both PTCs and
one- sun collectors.
Thanks to the reflector design, almost all the UV
radiation arriving at the CPC aperture area (not only
direct, but also diffuse) can be collected and is available
for the process in
the reactor. The UV light reflected by the CPC is more or
less distributed around the back of the tubular
photoreactor and
Solar Detoxification Technology 89
FIGURE 6.11. Solar reflection on a CPC collector.
as a result most of the reactor tube circumference is
illumi- nated; but because of the ratio of CPC aperture to
tube diam- eter, no single point on the tube receives
much more than one Sun of UV light. As a result, the UV
light incident on the reactor is very similar to that of a
one-sun photoreactor and, as in the case of flat-plate
collectors, maximum yearly efficiency is normally
obtained at the same collector angle inclination as the
local latitude.
Performance is very close to that of the simple tubular
photoreactor, but only about one-third of the reactor
tube material is required. As in a parabolic trough, the
water is more easily piped and distributed than in
many one-sun designs. All these factors contribute to
excellent CPC collector performance in solar
photocatalytic applications.
The explicit equation for a CPC reflector with a tubular
reactor can be obtained from Figure 6.11; a generic reflector
point S can be described in terms of two parameters, angle
θ, subtended by lines originating at O (centre of the
reactor tube) to A and R, and distance ρ, given by segment
RS:
θ  OA a OR (6.3)
ρ  RS (6.4)
RS being tangent to the reactor tube at R. One important
parameter for CPC definition is the angle of acceptance
2θA, which is the angular range over which all or almost
all rays are accepted (that is, reflected into the reactor
tube) without moving the collector.
The solution is given in two separate portions, an
ordi- nary involute from A to B and an outer portion from
B to C:
ρ  rθ for θ  θA  π 2 part AB of the
(6.5)
curve
θ  θ A  π 2  cos(θ  θ A )
ρr
1  sin(θ  θ A )
π 3π
for θA   θ   θ part BC of the curve (6.6)
A
2 2
90 Solar Detoxification

a)

b)

FIGURE 6.12. Obtention of CPC involute.

The CPC concentration ratio (CR) is given

by:
1 (6.7)
C
sinθ A

In the special case of θA = 90°, CR = 1 and every CPC

curve is an ordinary involute (points B and C are
coincident). So, optimum CPC acceptance half-angles
(θA) for photocat- alytic applications are obtained from
60 to 90 degrees either side of the normal. This wide
acceptance angle allows the reflector to direct both
direct-normal and diffuse sunlight onto the reactor, as
UV light collection is not highly sensitive to these
acceptance angles. An additional advantage is that these
wide acceptance reflectors skip reflector-tube alignment
errors, which is an important virtue for a low-cost
photo- reactor array.
CPC reflectors are usually made of polished
aluminium. The structure can be a simple photoreactor
support frame with connecting tubing. Since such FIGURE 6.13. View of CPC shape a) and CPC
reflectors are significantly less expensive than tubing, photoreactor array b). (PSA, Spain).
their use is very cost-effective compared to deploying
non-concentrating tubular photoreac- tors without using
any reflectors, and preserves the advan- tages of using
tubing for the active photoreactor area.

6.2.5. Holographic collectors
Another innovative idea is the holographic concentrator.
This concept has been extensively explored with regard
to solar thermal applications as well as in the area of
concentrators for photovoltaic systems. Holographic
surfaces are highly wave- length-selective and their
development for solar thermal applications, which
require the full solar spectrum, has proved to be a very
difficult task. However, holographic tech- nologies could
be very appropriate for narrow-wavelength- band
processes such as photovoltaics and photochemistry.
Holography is basically a diffractive technology. It
records the interference pattern between a reference
beam of highly coherent monochromatic light and an
object beam using the same light source. In the case of
solar holographic concentrators, the object beam is the
one in the focal region (point-focus or line-focus
concentrator) and the reference beam is the virtual image
of the Sun as a source. Once cre- ated, sunlight incident
on the holographic optic element will focus back to the
focal region by either transmission or reflection,
depending on whether the reference beam used to create
the hologram strikes the diffractive material from the
same or the opposite direction as the object beam. As a
holo- gram is a passive optical device, it is not possible to
track the Sun without moving the device.
Normally, holographic elements are made with
highly coherent monochromatic laser light, in order to
obtain the most efficient hologram at that wavelength.
Efforts carried out with the Sun as the source of light
have resulted in a maximum usable bandwidth of about
100 nm, obviously insufficient for thermal applications.
However, as the photocatalytic process with TiO 2 uses
300 to 385 nm
Focus
A Holographic optic element Holographic optic element
B Holographic optic element
Focus
FIGURE 6.14. Holographic concentration of solar light.
Solar Detoxification Technology 91
photons, the holographic concentrator could very well be
a good way not only to supply these photons while
filtering out those that are unnecessary, but also to
minimize thermal heating of the photoreactor.
Solar holographic concentrators can theoretically
avoid the technological complexities associated with the
curved support of conventional reflecting concentrators.
However, many significant issues remain unresolved.
One of the most important is whether the devices
developed in research programs can be feasibly
translated to realistic cost-effective scale for the
collection of solar energy. Also, there are not many
holographic materials in the UV wavelength region, and
their ability to survive in an outdoor environment is
unknown.
6.3. Concentrated versus
non-concentrated sunlight
The use of concentrating or non-concentrating collectors is
based on laboratory and engineering-scale experiments
carried out by many different research groups. As already
mentioned, during these experiments it was found that non-
concentrating collectors have the advantage of collecting
diffuse light. UV light is more susceptible to Rayleigh
scatter- ing by atmospheric gases, mainly water vapour,
than visible light. The same mechanism scatters blue light
more than red light, which is what causes the sky to appear
blue. Because of this scattering, as much as half of the UV
radiation arrives at the Earth’s surface as diffuse light, even
on a clear day. Near- UV wavelengths (from 285 to 385 nm)
comprise only 2 to 3 per cent of the energy in direct
sunlight, but they make up 4 to 6 per cent of combined
diffuse and direct sunlight.
Concentrating collectors focus only direct sunlight
and cannot collect diffuse light. Thin clouds, dust, and
haze reduce the direct-beam component of sunlight more
than the diffuse component. As a result, non-
concentrating collectors can use a resource that is not
only larger but also less variable than that available to
concentrating collectors, permitting, in many locations,
continual operation of the non-concentrating
detoxification system. Under cloudy conditions, non-
concentrating devices can continue operating
(although at lower rates), while a trough unit would
have to shut down. This fact has been successfully
demonstrated even in north- ern European locations
with small solar detoxification pilot plants (Figure
6.15).
92 Solar Detoxification
FIGURE 6.15. Solar detoxification pilot plant in Cologne
(Courtesy of Deutsche Forschungsanstalt für Luft- und
Raumfahrt – DLR).
An additional benefit of a non-concentrating
design is that the efficiency of the photocatalytic process
frequently decreases as light intensity increases (as
explained in Chapter 4). This behaviour means that
catalysts are unable to process all of the UV energy
available to the desired pollutant destruction reactions
when subjected to high UV fluxes. Lower light intensities
also slow down the rate of recombination, thus yielding
higher efficiency (see Figure 4.8). Nevertheless,
different researchers have obtained different results when
testing with low radiation intensities; so presumably, they
are significantly affected by experimental conditions.
Some authors attribute the transition of
r  f (I 0.5 ), to the excess of photogeneratedr species
 f (I1.0 )(e ,
+ •
h and OH). At higher radiation intensities, another

transition from r  f (I0.5 )  r  f (I0 ) is produced. At
this moment, the photocatalytic reaction departs from
its dependence on radiation received, depending only
on mass transfer within the reaction, so the rate remains
constant although radiation increases. This effect may be
due to several causes, such as the lack of electron
scavengers (that is, O2), or organic molecules in the
proximity of TiO2 surface and/or excess of products
occupying active catalyst centres and so on. Actually,
this phenomenon appears to be more frequent with
supported catalysts and/or at slow mixing speeds. This
implies a small catalyst surface is in contact with the
liquid and there is less turbulence, which does not favour
contact of reactants with the catalyst and dispersion of
products.
Finally, one-sun photoreactors have additional advan-
tages, such as decreasing optical losses from reduced or
non-existing reflective surface. On the other hand,
among possible advantages of concentrating systems is a
much
Radiation distribution on absorber (o) of CPC type concentrator
Solar hour : 06:00 to 18:00 DER–ITE/INETI
Inc.angles : 90 to –90 degrees
FIGURE 6.16. Flux distribution on an absorber in the
course of the solar day (6:00 to 18:00). Simulation of
CPC behav- iour with the following data: collector
orientation east–west; semi-acceptance angle 60°;
truncation angle 80°; absorber radius 13.6 mm; optical
gap 2 mm; concentration ratio 1.17. (Courtesy of the
Renewable Energy Dept. INETI, Portugal.)
smaller reactor-tube area requirement (the smaller circuit
provides better control and handling of the contaminated
water to be treated). Nevertheless, state-of-the-art
technol- ogy cannot match the higher efficiency of non-
concentrating systems. This has been demonstrated by
many comparative efficiency studies, such as the one
performed by NREL (National Renewable Energy
Laboratories, United States) with seven different small
–
collectors (from 18 to 157 litres total capacity and from
0.4 m2 to 53 m2 reflecting surface). Results showed that
one-sun collectors were significantly more efficient than
concentrating collectors.
As a consequence of the above, although it was
first thought that PTCs were the ideal technological
alternative, given their high cost and the fact that they
can only be oper- ated with direct solar radiation
(implying location only in highly insolated areas), the
question has been decided in favour of the static non-
concentrating collector alterna- tive. Their intrinsic
simplicity, low maintenance and operat- ing costs and
potential for reducing manufacturing costs, make one-
sun systems the natural choice for solar water
detoxification.
Among the different technologies previously
described, CPCs seem to be one of the best-developed
options for system design and implementation. In this
specific case, and since the absorber is illuminated
differently during the morning and the afternoon, if the
radiation distribution is integrated over the solar day an
almost regular distribution of light is

obtained along the reactor perimeter (Figure 6.16). This
agrees with the optical characteristic of low-
concentrating CPC-type collectors, which can collect
within their accept- ance angle the radiation coming from
the hemisphere and place it on the absorber perimeter.
6.4. Technical issues
strictest requirements are those of PTCs; for example, UV-
mirror materials need to have a specular reflectance of
In addition to the solar collector type, the most
important
technical issues related to solar detoxification hardware
are the reflective surface and the reactor tube, which
are addressed here in more detail.
6.4.1. Reflective surfaces
The optical quality requirements of reflective surfaces for
solar applications are usually related to the concentration
required by the particular application under
consideration. The higher the concentration desired, the
stricter the requirements for quality of parameters. Light
reflected off a polished or mirrored surface obeys the
law of reflection: the angle between the incident ray and
the normal to the surface is equal to the angle between
the reflected ray and the normal. When light reflects off a
rear surface mirror, the light first passes through the
glass substrate, resulting in reflection losses, secondary
reflections, refraction, absorp- tion and scattering of light
passing through the transparent substrate (second-surface
mirrors). Precision optical systems use first-surface
mirrors that are aluminized on the outer surface to avoid
these phenomena.
When light obeys the law of reflection, it is termed a
‘specular reflection.’ Most hard polished (shiny) surfaces are
primarily specular in nature. Even transparent glass
specu- larly reflects a portion of incoming light. Diffuse
reflection is typical of particulate substances like
powders. If you shine
Specular Diffuse
FIGURE 6.17. Specular, diffuse and spread reflection from a surface.
Solar Detoxification Technology 93
a light on baking flour, for example, you will not see a
direc- tionally shiny component. The powder will
appear uni- formly bright from every direction. Many
reflections are a combination of both diffuse and
specular components. One manifestation of this is
spread reflection, which has a dominant directional
component that is partially diffused by surface
irregularities (Figure 6.17).
In the case of solar detoxification applications, the
between 300 to 400 nm in order to achieve concentration
ratios of from 1 to 20. For this configuration, the
effective concentration ratio (Cε) can be related to the
optical per- formance parameters by:
 σ  
C  C ρ sum  (6.8)
ε  s 
 σ 
Where: C = concentration in the absence of surface
and tracking errors, as defined in Equation 6.2; ρ s =
specular reflectance; σsum = half angular extent of the
Sun (Gaussian distribution) = 2.73 MRAD; and σ = total
optical error, which is a function of the slope, specularity
and tracking errors.
The greater the errors, and particularly the reflective
sur- face errors, the lower the effective concentration
ratio. The reverse is also true: the lower the effective
concentration ratio is, the higher the optical errors may
be and therefore, the lower the quality of reflective
surface required. This is an important additional factor
in favour of low or non- concentrating systems, as these
lower-quality requirements (lower specular reflectance)
translate directly into lower manufacturing cost, as the
reflector element can represent a considerable fraction of
collector cost.
Another important factor is the reflective base
material. For solar photocatalytic applications, the
reflective surface must clearly be made of a highly
reflective material for ultraviolet radiation. The
reflectivity between 300 and
Spread
94 Solar Detoxification
FIGURE 6.18. Reflectivity of fresh metal coatings for
mirrors.
400 nm of traditional silver-coated mirrors is very
low (reflected radiation/incident radiation) and
aluminium- coated mirrors are the best option in this
case (Figure 6.18). Aluminium is the only metal surface
that is highly reflec- tive throughout the ultraviolet
spectrum. Reflectivities range from 92.3 per cent at 280
nm to 92.5 per cent at 385 nm. Comparable values for
silver are 25.2 per cent and 92.8 per cent, respectively.
A fresh deposited aluminium surface is fragile and
needs to be protected from weathering and abrasion,
but the conventional glass cover used for silver-
backed mirrors has the drawback of significantly filtering
UV light (an effect that is duplicated due to the light
path through the glass). The thin oxide layer that forms
naturally on aluminium is not sufficient to protect it
in outdoor environments. Under such exposure
conditions, the oxide layer continues to grow and
UV reflectance drops off
dramatically.
Various optical technologies require UV-reflective
ele- ments, such as UV mirrors for medical imaging,
astronomical telescopes, microscopy, UV curing, indoor
lighting, microlithography, industrial micro-machining
and UV laser reflection. Nevertheless, the specific
requirements of these applications are very different from
those of solar ones, mainly with regard to outdoor
durability. The ideal reflective surface for solar
photocatalytic applications must be:
• highly reflective in the UV range,
• acceptably durable under outdoor conditions for
extended service lifetimes,
• reasonably priced, to permit the technology to be
com- petitive against alternative technologies.
The surfaces currently available that best fit these
require- ments are:
• electropolished anodized aluminium
(electrolytically formed aluminium oxide outer layer)
and
• organic plastic films with an aluminium coating (multi-
layer ‘sandwich’-type plastic–aluminium–plastic
composition).
Anodized coatings with thin oxide can provide good pro-
tection against some chemicals and good resistance to
abra- sion. Typically, thin (2–3 µm) oxide layers are
used to provide some measure of resistance to abrasion,
but they give little protection against moisture or
pollutants. Thicker oxide layers (up to 50 µm) are usually
specified when anodized aluminium is intended for
engineering/marine applications
but, unfortunately, such a coating results in considerably
lower reflectance in the UV range.
An interesting alternative approach is to cover the
aluminium with a protective acrylic lacquer. Acrylic
lacquer- ing provides impressive outdoor resistance
(more than 1,000 hours in a salt-spray fog chamber
without significant degra- dation), but also reduces UV
reflectance. A compromise between outdoor resistance
and UV reflectance could be an optimum solution.
Another possible solution is aluminium-coated plastic
film. Several commercial coated plastic film products
have been used successfully in parabolic-trough
applications.
• ECP-244 (3M film, no longer manufactured)
consisting of a 10-µm-thick aluminium surface
covered by a 76-µm- thick acrylic surface. Average
reflectivity of new film between 280 and 385 nm
thick is about 63 per cent.
• SA-85P (manufactured also by 3M); this film has a
50-µm-thick polyester backing, a 10-µm-thick alu-
minium surface, and a very thin 2.5-µm-thick
acrylic covering. Average reflectivity in the same
range is 87 per cent for new films. The superior
reflectivity is due to the much thinner protective
acrylic coating.
• ECP-305 (3M); a silver reflective film similar in
composi- tion to SA-85.
• Other companies and even some research
institutions have developed similar coated films,
usually a combina- tion of over-100-µm-thick
polyester backing on 10-µm aluminium foil with a
thin outer film of acrylic or a copolymer that is
highly resistant to outdoor exposure and has good UV
transmittance.

100
90
C
80
Spectral total reflectance
70
60
50
40
30
20
10
0 0
280
FIGURE 6.19. Reflectivity of different aluminium and plastic film surfaces. (Curve (d) courtesy of Alanold Aluminium-
Veredlung GmbH & Co., Germany).
Normally, because of their lack of rigidity, these films must
be bonded over a stiff substrate and about 2 per cent
specular reflectivity could be lost in this process. Also,
the reflectivity of each film at the end of its lifetime
(from five to ten years) would be only 88 per cent of the
original bonded value.
6.4.2. Photocatalytic reactor
The requirements for the photocatalytic reactor are
similar to other advanced water or air oxidation
processes, with the additional necessity of an
illuminated photocatalyst. The photocatalytic reactor
must contain the catalyst and be transparent to UV
radiation, providing good mass transfer of the
contaminant from the fluid stream to an illuminated
photocatalyst surface, with minimal pressure drop across
the system.
As mentioned before, the square-root dependence on
light intensity provides better photo-efficiencies for
one-sun designs, which leads to a flat-plate geometry. This
geometry is widely used for solar-powered domestic hot
water systems, in large part because of its simple design.
Nevertheless, for water treatment, the reactor must be
robust enough to work under usable water pressure, and
tube configurations clearly seem the most appropriate for
fluid containment and pumping. Adequate flow
distribution inside the reactor must be assured, as non-
uniform distribution leads to non-uniform
Solar Detoxification Technology 95
D 100
90
80
B
70
60
50
A
40
A 3M ECP-244 aluminized film 30
B 3M SA-85 aluminized film
20
C Hostaflon ET aluminized polymer
D ALANOLD UV-MIRO aluminium 10
290 300 310 320 330 340 350 360 370 380
Wavelength (nm)
residence times inside the reactor, resulting in decreased
per- formance compared to an ideal-flow situation. If the
catalyst is used in suspension (a slurry in the case of
TiO2), the Reynold number (Re) must always be over
4,000 in order to guarantee turbulent flow. This is
critical in avoiding catalyst settlement. Another
important design issue is that internal reactor materials
must not react with either the catalyst or the pollutants to
be treated or their by-products.
There is only a limited choice of materials that are
both transmissive to UV light and resistant to its
destructive effects. Also, temperatures inside a one-
sun solar photocat- alytic reactor can easily exceed 40
°C, due to the absorption of the visible portion of the
solar spectrum. Therefore, a one-sun reactor must be
able to withstand summer temper- atures of around 60
to 70 °C to guarantee that no damage will occur that
could reduce the flow. Finally, low pH resistance is
needed, since the production of inorganic acids as
reaction by-products is quite normal (that is, the
destruc- tion of chlorinated hydrocarbons leads to the
production of HCl).
Common materials that meet these requirements are
fluoropolymers, acrylic polymers and several types of
glass. Quartz has excellent UV transmission as well as
good temperature and chemical resistance, but its slight
advantage in terms of transmission in the terrestrial solar
spectrum does not justify its high cost, which makes it
completely unfeasi- ble for photocatalytic applications.
96 Solar Detoxification
FIGURE 6.20. Transmittance of different materials suitable for the manufacture of photoreactor tubes.
Plastics work well as long as they fulfil
transmittance, pressure and thermal resistance
specifications as well as maintaining their properties
during outdoor operation. Fluoropolymers are a good
choice of plastic for photoreac- tors due to their good UV
transmittance, excellent ultraviolet stability and chemical
inertness. Several different types, such as ETFE
(ethylene-tetrafluoroethylene), PTFE (polytetrafluo-
roethylene), ECTFE (ethylenechloride-
tetrafluroethylene), PVDF (polyvinylidene fluoride),
FEP (fluorinated ethylene- propylene), PFA and TFE
(tetrafluoroethylene), can be extruded into tubing and
used as a photoreactor. Tubular fluoropolymers are very
strong, possess excellent tear resist- ance and are
flexible and lighter than glass. One of their greatest
disadvantages is that in order to achieve a desired
minimum pressure rating, the wall thickness of a
fluoropoly- mer tube may have to be increased, which in
turn will lower its UV transmittance. In addition, as a
result of the lack of rigidity, tube connections can
withstand much lower pressures than glass tubes. ETFE
and FEP are among the best candidates; ETFP has higher
tensile strength (extrude-like) than FEP; this could mean
thinner-walled tubes, resulting in cost savings (as less
material is used) and higher UV trans- mittance – and
therefore higher photoreactor performance. The problem
is that ETFE tubing is not as readily available as FEP
tubing. FEP tubing with a 50 mm outer diameter and
0.6 mm wall has a UV hemispherical transmittance (300
to 400 nm), of 61.6 per cent. This light is transmitted as
diffuse,
as fluoropolymer materials are poor IR-diffusers, but
make excellent visible/UV diffusers (diffusion usually
varies with wavelength).
Acrylics could also potentially be used to enclose
the photoreactor. However, acrylics are very brittle and
would have to be employed in sheets, which increases
their cost. On the positive side, acrylic polymer sheets
can be shaped with channels and flow patterns that could
themselves be used as solar reactors. Other lower-cost
polymers are available in tubular form, but none possess
the necessary UV and chem- ical stability for
detoxification of water that may be contami- nated with a
variety of solvents or other pollutants. Also, low-cost
polymeric materials are significantly more suscepti- ble to
attack by pollutant molecules, and the dissolution of
organic contaminants in polymer materials could be a
way of avoiding the degradation process.
Glass is another alternative for photoreactors.
Standard glass, used as a protective surface, is not
satisfactory because it absorbs part of the UV radiation
that reaches it, due to its iron content. Borosilicate glass
has good transmissive prop- erties in the solar range,
with a cut-off of about 285 nm. Therefore, such a low-
iron-content glass would seem to be the most suitable.
Two undesirable effects reduce the performance of a
glass reactor for solar detoxification: increased
absorption in the solar UV range between 300 and 400
nm, and a further decrease of UV transmittance during
operation because of

the damaging impact of solar radiation in the same
wave- length region (UV solarization). Both effects are
caused to a large extent by polyvalent ions that change
charge. The effect of the Fe ions in the glass, which
change charge from Fe2+ to Fe3+ due to photo-oxidation
by photons with a wavelength below 400 nm, is
especially harmful. Furthermore, the oxidized Fe3+ ion
absorbs UV light. As a result, enhancement of
transmittance in the 300 to 400 nm region could only be
accomplished by a strong reduction in iron content,
down to
FIGURE 6.21. Glass-tube manufacture. Different composi-
tions mean that the glass can be used for a wide variety
of applications. (Courtesy of Schott-Rohrglas GmbH.)
FIGURE 6.22. Influence of iron on borosilicate glass light transmission (oxidative conditions). Samples: flat glass 3 -
mm in thickness. (Courtesy of Schott-Rohrglas GmbH.)
Solar Detoxification Technology 97
50 ppm (Figure 6.22), but this incurs a corresponding
increase in cost.
Therefore, as both fluoropolymers and glass are
valid photoreactor materials, cost becomes an important
issue. In large volumes, glass piping could be more
expensive than fluoropolymer tubing, but from the
perspective of perform- ance, the choice is the material
that has the best combination of tensile strength and UV
transmittance. On this basis, if a large field is being
designed, the large collector area means also a
considerable number of reactors and, as consequence, a
high system pressure rating. Fluoropolymer tubes are not
the best choice of material as high pressure is linearly
related to thickness and could result in higher cost. A
detailed analy- sis is recommended for any specific
design.
One of the most important parameters in a tubular pho-
toreactor design is the tube’s diameter, as in both homoge-
neous or heterogeneous photocatalysis it must be
guaranteed that all arriving useful photons are kept inside
the reactor and do not go through it without intercepting a
catalyst par- ticle. The intensity of illumination affects the
relationship between reaction rate and catalyst
concentration. The disper- sion and absorption of light
causes photon density to dimin- ish almost exponentially
over the length of the optical path within a catalyst
suspension. At higher light intensity, catalyst
concentration can be higher.
98 Solar Detoxification
1 cm
ID = 58 mm
Illuminated ar–1ea
[TiO2] = 1 g L
FIGURE 6.23. Zone of tubular reactor where light
penetrates if the catalyst concentration is 1 g L–1 (TiO2
heterogeneous photocatalysis).
In the case of TiO2 heterogeneous photocatalysis,
when catalyst concentration is very high, a ‘screening’
effect pro- duces excessive opacity of the solution,
preventing the cata- lyst particles farthest in from being
illuminated and reducing system efficiency. The lower
the catalyst concentration, the less opaque the
suspension. One g L–1 of TiO2 catalyst reduces
transmittance to zero in a 10-mm-inner-diameter
cylinder with concentrated light in a parabolic-trough
collec- tor (Figure 6.23). In a wider diameter tube,
only an outer layer is illuminated. This means that a
larger inner reactor diameter permits use of lower
optimum catalyst concentra- tions. Practical inner
diameters for a tubular photoreactor would be in the
range of 25 to 50 mm. Diameters that are very small do
not make sense because of the high associated pressure-
drop, and very large diameters imply a considerable dark
volume, thus reducing overall system efficiency.
6.5. Catalyst issues
The catalyst plays a major role, not only because of its
impor- tance to the process, but also from a technological
point of view. This is especially relevant in heterogeneous
photocatal- ysis, where Degussa P-25 titanium dioxide is
often the stan- dard particulate material against which
other catalysts have been, and continue to be, measured.
TiO2 in aqueous-phase applications can be used in
suspensions (slurry) or supported. In the first case, the
catalyst must be recovered. The technological
implications of this are discussed below.
6.5.1. Slurry versus supported catalyst
One of the major solar photoreactor system design issues
is whether to use a suspended or a supported catalyst.
The majority of experiments to date have used small
TiO2
particles suspended in the contaminated water, which
makes it necessary to recover them after treatment. This
process is addressed in the next section.
Supported catalyst configurations eliminate the need
for catalyst filtration (but with a significant reduction in
system efficiency). The idea is to attach the catalyst to a
support inside the reactor, as is done for gas-phase
stream treatment, which requires the catalyst to be
anchored onto some type of inert support. Desirable
characteristics of such a system would include being
very active (comparable to slurries) and having a low
pressure-drop, a long lifetime, and a reasonable cost;
however, in the case of water treatments, this has not yet
been achieved.
Fixed-catalyst designs must address several problems.
As the catalyst must be exposed to sunlight and be in
contact with the pollutant, the support must be configured
to route the pollutant efficiently to the illuminated zone
and, at the same time, maintain a high flow rate in the water
– to ensure good mixing without significantly increasing
system pres- sure, which usually means more power for
pumping, and thereby higher operating costs. Also, the
same criteria dis- cussed for photoreactor materials must be
kept in mind and applied when choosing a support.
Supports tested so far have included fibreglass beads,
metal fibres, steel mesh, alu- minium, many types of plastic
(Figure 6.24) and ceramics such as alumina, silicon
carbide and silica, in the most diverse shapes. TiO 2
coatings on tiny hollow glass beads called
‘microballoons’ for catalyst removal by screening rather
than filtering have also been tested.
Support of TiO2 on a stiff surface by adherence can be
achieved via several different techniques, such as dip
coating with solvents, deposits from precursors, vapour
deposition and sol-gel formation. Several important
performance requirements are directly related to the
process used for cata- lyst fixation, such as the durability
of the coating and catalyst activity and lifetime. The
surface area of the catalyst coating must also be
considered, because a good contact of photons and target
molecules with the catalyst is required for efficient
performance.
Studies performed to date have not yet identified a
fixed- catalyst system that performs as efficiently as
slurry systems. Several exceptions, such as a test
performed by NREL (United States) using silica beads
as the catalyst support, have approached the efficiency of
the slurry – the high pres- sure-drop across the bed made
the silica-bead system imprac- tical. In aqueous systems,
compared to an unsupported

a)
b)
FIGURE 6.24. a) Experimental concentrating solar
reactor using titanium dioxide immobilized on glass
wool for treat- ing contaminated air streams. b) Parabolic
trough reactor for water purification with immobilized
titanium dioxide. (Courtesy of the US National
Renewable Energy Laboratory.)
catalyst, immobilization of TiO2 results in a reduction in
per- formance around 60 to 70 per cent. An important
direct con- sequence of this fact is the necessity of
multiplying by a factor of about three the size of the
necessary solar collector field if similar efficiencies are
desired, making the overall sys- tem clearly less cost
efficient and less competitive than slurry systems. In
addition to the above, a key question is how long
supported catalysts will last in a real stream of water? A
short period of activity would mean frequent
replacement and, consequently, a marked rise in the
overall system cost.
In contrast to fixed catalyst configurations, slurry
configurations have the advantage of higher
throughputs (in the range of 200 to 400 per cent) a
low pressure-drop
Solar Detoxification Technology 99
through the reactor and excellent fluid-to-catalyst mass
transfer.
6.5.2. Catalyst recuperation and reuse
The need to remove the catalyst from the clean water
after treatment was initially considered a major
disadvantage of a slurry system; because ultrafiltration,
which was believed to be difficult and costly, would be
required for efficient sepa- ration of the submicron-sized
TiO2 particles from the slurry. Although it is true that
titanium dioxide powder particles are only about 0.03 µm
(30 nm) in diameter, or even smaller in some cases
(specially manufactured TiO2 can be up to
0.01 µm), once in water, the particles always
agglomerate into larger ones (from 0.3 to 0.6 µm),
simplifying the prob- lem considerably, since
microfiltration, which is much less expensive than
ultrafiltration, can be used. Carbon-graphite membranes
of 0.2-µm can effectively concentrate titanium dioxide
slurry from less than 1 g L–1 to up to 100 g L–1 with 2 to 3
bar trans-membrane pressure and permeate flow rates of
about 2,500 L h –1 per square meter of membrane.
Recovery rates of over 99 per cent have been obtained
with
0.5 µm membranes and no titanium dioxide has been
detected in water filtered with 0.2 µm membranes.
However, best performance can be obtained when
microfiltration is combined with previous titanium
dioxide sedimentation. About 90 per cent of the catalyst
can easily be recovered by sedimentation and the rest by
microfiltration. This means a significant reduction in
time and electricity in the typical recovery process for
TiO2 concentrations of about 200 mg L–1. The lifetime
of membranes and the time between cleanings is also
increased considerably. This could be particularly
important with high volumes of water.
Titanium dioxide sedimentation is closely related to
colloidal stability and TiO 2 aggregation conditions. The
suspension can easily be destabilized by adding an
electrolyte (such as NaCl) and/or adjusting the pH to point
of zero charge (PZC) and the isoelectric point (IEP) on
the surface of the catalyst particles, as both factors
modify the surface charge. Progressive particle
agglomeration (sizes from 1 to 10 µm) and settlement
are then obtained. In the case of TiO2 (Degussa P-25),
at concentrations of 200 mg L–1, the PZC is obtained at
about pH 7 (6.8 ± 0.2, in experiments at the Plataforma
Solar de Almería) when NaCl concentration is to the
order of 10–6 molar.
100 Solar Detoxification

FIGURE 6.25. Sedimentation experiments at different pH. [TiO 2] = 0,2 g/L; [NaCl] = 0 M. The Y axis shows the
absorbance of the solution at 800 nm; no absorbance means absence of TiO 2 (see also Figure 4.2).

Therefore, more than 200 hours is needed for 75 per

cent of titanium dioxide to settle at pH 4.5, but at pH 7
Summary
only five hours of storage is needed to recover 90 to 95
Solar collectors are traditionally divided into three
per cent. This can be directly recovered in a conic-bottom
cate- gories: non-concentrating (or low temperature,
tank, and 5 to 10 per cent of the remaining catalyst can be
up to 150 °C), medium-concentrating (or medium
recovered by micro- filtration (see also Chapter 9).
temperature, from 150 °C to 400 °C ) and high-
Catalyst recovered, usually in highly concentrating (or high temperature, over 400 °C ).
concentrated slurry, can be reused – but not Concentrating solar systems make use of direct
indefinitely. Slurry lifetime has been tested with
radiation and need solar tracking mecha- nisms. Non-
satisfactory results under laboratory conditions (that
concentrating systems are much simpler as they do not
is, deionized water and only one contami- nant), but
need solar tracking and can collect direct and diffuse
with real water treatments catalyst lifetime would be
solar radiation with slightly lower annual efficiencies.
diminished because of contaminants. However, in
The specific hardware needed for solar
specific applications, tests have demonstrated that the
photocatalytic applications is very similar to that used
catalyst can be reused up to ten times, or even more,
for conventional thermal applications, with the
with- out any problem.
following major differences: the fluid must be exposed to
If part of the catalyst is lost in the drainage water, the the ultraviolet solar radiation (so the absorber must be
per- centage of catalyst that remains useful after each run
transparent to this radiation) and no thermal insulation is
is a rel- evant parameter. In field tests conducted by required, as the temperature does not play a significant
NREL in Florida, it was reported that approximately 10
role in the photocatalytic process. Besides, solar
per cent of the catalyst was washed away in the discharge
photoreactors for water detoxification were originally
water. In tests per- formed at the Plataforma Solar de designed to use line-focus parabolic-trough con-
Almería, 2.5 per cent of catalyst was lost. From this
centrators; non-concentrating collectors are used for solar
point of view, addition of 5 to 10 per cent more catalyst photocatalytic applications. They are more efficient
could be an interesting option to compensate possible
than concentrator-based systems because of the use of
loss and periodic replacement in case of catalyst
both direct and diffuse UV light, the square-root
poisoning. dependence between reaction rate and light intensity, and
their intrinsic simplicity.

CPCs (static collectors with a reflection surface
following an involute around a cylindrical reactor tube)
are a very interesting cross between trough concentrators
and one-sun systems, and have been found to provide the
best optics for low-concentration systems. CPCs designed
with a concentra- tion ratio of one, or near one, are
among the best options for solar photocatalytic
applications. Aluminium is the only metal surface that
offers high reflectivity values in the UV spectrum.
Electropolished anodized aluminium and organic plastic
films with an aluminium coating film are the most
appropriate reflective surfaces to use for solar
detoxification applications. Photocatalytic reactors must
be both transmis- sive and resistant to UV light.
Common materials that meet these requirements are
fluoropolymers, acrylic polymers and borosilicate glass,
and tubular photoreactors designs are the best option. In
TiO2 heterogeneous photocatalysis, sus- pended
catalyst systems give efficiencies higher than sup- ported
catalysts. After use, TiO2 can be agglomerated and
sedimented. Best recovery performances are obtained
with a two-step process: sedimentation and
microfiltration.
Bibliography
BLAKE, D.M.; LINK, H.F. AND EBER, K. 1992. Solar
photocatalytic detoxification of water. In: K.W. Boer
(ed.), ADVANCES in SOLAR Energy, pp. 167–210. Boulder,
Colo., American Solar Energy Society, Inc.
BLAKE, D.M.; MAGRINI, K.; WOLFRUM, E. AND MAY, E.K.
1997.
Material issues in solar detoxification of air and water.
In: C.M. Lampert, C.G. Granqvist, M. Gratzel and S.K.
Deb (eds), OPTICAL MATERIALS Technology for Energy Efficiency
AND SOLAR Energy Conversion XV, pp. 154–62. Bellingham,
Wash., SPIE – The International Society for Optical
Engineering.
Solar Detoxification Technology 10
1
BLANCO, J.; MALATO, S.; GARCÍA, G.; ARANDA, J.; SÁNCHEZ, M.;
SICILIA, F. AND ROMÁN, M.I. 1991. FINAL CONFIGURATION of
PSA SOLAR DETOXIFICATION Loop. Plataforma Solar de
Almería. (Technical Report: TR 06/91.)
FERNÁNDEZ, P.; DE LAS NIEVES, F.J. AND MALATO, S. 1999.
TiO2 SEDIMENTATION Procedure. (Proceedings of the Second
Users European Workshop Training and Mobility of
Researchers Programme at Plataforma Solar de Almería,
Serie Ponencias), Madrid, CIEMAT.
JORGENSEN, G. AND RANGAPRASAD, G. 1991. ULTRAVIOLET
Reflector MATERIALS for SOLAR DETOXIFICATION of HAZARDOUS
WASTE, SERI/TP-257-4418. Golden, Colo.
KREIDER, J.F. 1979. Medium AND High TEMPERATURE SOLAR
Processes. New York, Academic Press.
MAY, E.K.; GEE, R.; WICKHAM, D.T.; LAFLOON, L.A. AND
WRIGHT, J.D. 1991. Design AND FABRICATION of Prototype SOLAR
RECEIVER/REACTORS for the SOLAR DETOXIFICATION of CONTAMINATED
WATER. Golden, Colo., Industrial Solar Technology
Corporation. (Final report for an NREL subcontract.)
PACHECO, K.; WATT, A.S. AND TURCHI, C.S. 1993. Solar
detoxification of water: outdoor testing of prototype
photoreactors. In: A. Kirkpatrick and W. Worek (eds),
ASME/ASES Joint SOLAR Energy Conference, pp. 43–9.
New York, American Society of Mechanical
Engineers.
RABL, A. 1985. Active SOLAR Collectors AND Their APPLICATIONS.
Oxford, Oxford University Press.
WENDELIN, T. 1992. A survey of potential low-cost
concentrator concepts for use in low-temperature water
detoxification. In: W.B. Stine, J. Kreider and K.
Watanabe (eds), ASME INTERNATIONAL SOLAR Energy
Conference,
pp. 15–20. New York, American Society of
Mechanical Engineers.
102 Solar Detoxification

Self-assessment questions Part B

Part A: True or false? 1. Why are concentrating solar systems more efficient
than non-concentrating ones when thermal applications
are considered?
1. The best yearly efficiency of a static non-
concentrating solar collector is obtained when the
2. Why are non-concentrating solar systems more
inclination from the horizontal is equal to the local
efficient than concentrating ones when UV
latitude.
photocatalytic applications are considered?
2. Higher inclination than the local latitude gives
3. What must the diameter of a PTC reactor tube be if
higher efficiencies in winter than in summer (non-
the aperture width is 2.5 m and a geometric
concentrating solar collector).
concentration ratio of 10 is needed to be achieved?
3. Temperature plays an important role in
4. What is the geometric concentration ratio of a
solar photocatalytic degradation of water
CPC if the semi-acceptance angle is 70°?
contaminants.
5. A PTC with a geometric concentration ratio of 6 has
4. Diffuse UV solar light is a small portion of total
an effective concentration ratio of 4. What is the total
UV radiation, especially on a cloudy day.
optical error of the reflective surface if specular
reflectance is 85 per cent?
5. Non-concentrating solar collectors can use both
direct and diffuse solar light.
6. What is the main factor that limits the UV
transmittance of standard glass?
6. Concentrating solar collectors obtain better
efficiencies than non-concentrating ones in solar water
7. Why are reactor tubes of 200 mm inner diameter
detoxification applications.
not practical in TiO2 slurry systems?
7. Silver is not used in UV solar reflectors because of
8. Cite at least three of the main problems
its price.
of supported-catalyst systems.
8. Quartz is the best material for photocatalytic
9. How can titanium dioxide slurry particles be
reactors. aggregated and sedimented?
9. Supported catalyst systems have similar
10. Why must the Reynold number be higher than
efficiencies to slurry systems.
4,000 in TiO2 slurry systems?
10. Although the particles of titanium dioxide are very
small, once in water they agglomerate into ones that are
ten to twenty times larger.

Answers
Part A
1) True. 2) True. 3) False. 4) False. 5) True. 6) False.
7) False. 8) True. 9) False. 10) True.
Part B
1. Because they need a solar tracking system and
the collectors are always directed towards the Sun.
2. Besides not having a solar tracking device,
non-concentrating systems can collect UV solar light,
which is an important contribution to their yearly
efficiency.
3. Using Equation 6.2); d = 2500/(10 × 3.1416)
= 79.6 mm.
Solar Detoxification Technology 10
3
4. Using Equation 6.7); C = 1/sin (70) = 1.06.
5. Using Equation 6.8); σ = 60.85 × 2.73/4 = 3.48 mrad.
6. The presence of Fe ions, especially Fe +3, which
absorbs the UV light.
7. Because most of the inner volume of the reactor
would be dark due to the opacity of the catalyst
suspension.
8. Less efficiency, much higher pressure-drop and the
need for periodic replacement.
9. TiO2 slurry suspensions can be destabilized by
adding a small quantity of electrolyte, such as NaCl,
and/or adjusting the pH to 7 in order to reach the point
of zero charge and the isoelectric point of the colloidal
solution.
10. Because a turbulent flow regime must be assured
to guarantee adequate fluid mixture and to avoid
possible catalyst settlement.
 Solar Detoxification
Aim
This chapter describes the main proven
and potential applications of solar
detoxification processes with
demonstrated technical feasibility. The
advantages and limitations of these
applications are also discussed.
Applications
7 CHAPTER 7
Objectives
When you have completed this chapter
you will have an appreciation of the
following subjects:
1. The limiting factors and necessary
conditions of feasible solar
detoxification applications.
2. The main applications related
to contaminated water.
3. The technical considerations
for gas-phase treatment
processes.
106 Solar Detoxification

NOTATION on transferring laboratory research carried out by photo-

chemical groups to solar-engineered testing using
Symbol Description existing technology. These first results aroused
AOT Advanced oxidation technologies enthusiasm in the photochemical research community.
BTEX Benzene, toluene, ethyl benzene, and Their extrapolation to practical situations assumed an
xilenes BWTP Biological wastewater treatment plant ability to degrade almost any organic contaminant as
well as some metals. Later, more appropriate collectors
CVOC Chlorinated volatile organic compounds
and reactors were developed, but the need to understand
EDTA Ethylene diamine tetraacetic acid
the fundamentals of certain aspects of the reaction led to
EPA Environmental Protection Agency (USA) an increasing number of studies on kinet- ics,
HMX 1,3,5,7-tetranitro-1,3,5,7-tetrazacycloctane mechanisms, performance of mixtures and operating
IR Infrared light parameters, with varying results. It was a period of both
LLNL Lawrence Livermore National Laboratory promising and discouraging results. At present, a third
(USA) NREL National Renewable Energy Laboratory sce- nario seems to be underway, in which the boundary
(USA) PAH Polynuclear aromatic hydrocarbons condi- tions of applications have been determined and
the technology is focusing on a few specific initial
PCP Pentachlorophenol
applications, with the peculiarity that early
PCO Photocatalytic oxidation processes development and still- unsolved questions coexist with
PSA Plataforma Solar de Almería (Spain) near-commercial and indus- trial applications of the
PTFE Polytetrafluoroethylene technology. As a result, the environmental market,
PVC Polyvinyl chloride although very receptive to clean energy sources, is still
RDX Hexahydro-1,3,5-trinitro-1,3,5-triazine reluctant to adopt ‘high-risk’ initiatives with regard to solar
SNL Sandia National Laboratories (USA) detoxification processes.
TCE Trichloroethylene From the point of view of practical applications,
TNT Trinitrotoluene hetero- geneous photocatalysis with a semiconductor
VOC Volatile organic compounds (TiO2) is the process for which solar technologies are
most extensively employed today, although in some
specific applications; a well-known homogeneous phase
reaction, photo-Fenton, shows higher water-phase
7.1. Introduction degradation rates. In other solar detoxification options,
such as sensitized-photochemical oxidation by singlet
Detoxification is today the most successful oxygen, there is still very limited experi- ence to date.
photochemical application of solar photons, with a Photocatalytic oxidation processes (PCO) currently
number of installations and projects already in operation. under development are included in the same group of
This is due not only to the fact that solar detoxification is advanced oxidation technologies (AOT) as other
an outstanding demonstra- tion of how well suited solar radical- promoting processes. The main advantage of
energy is to environmental preservation, but also PCO over other AOTs is its potential for incorporating
because, unlike most photochemical processes, it is non- solar energy in the form of solar photons, whereby the
selective and can be employed with complex mixtures degradation process acquires significant additional
of contaminants. During the last decade, the number of environmental value. If solar photons can be collected
references and related patents on heteroge- neous and used efficiently at low cost, the number of
photocatalytic removal of toxic and hazardous com- opportunities for PCO may increase dramatically.
pounds from water and air can be counted in thousands, Although solar-driven PCO was at first considered a
and the number of applications and target compounds are univer- sal method of degrading organic pollutants, a
numerous. profusion of contradictory results in recent years
An analysis of the historical evolution of solar (positive results in almost real-life conditions together
photocatal- ysis clearly identifies three different stages of with other experimental results pointing out uncertainties
development. Initially, the efforts of solar-conscious and negative performance) has led to confused public
researchers focused perception. Solar PCO technology is currently viewed as
a very sensitive issue and scientific

opinion is evolving towards a more conservative period
of specific applications.
Within this context, treatment of industrial
wastewater, though difficult to develop, seems one of the
most promising fields of application for solar
detoxification. The only general rule is that there is no
general rule at all, each real case being completely
different from any other. In some cases, the Photo-
Fenton process has demonstrated higher degradation
efficiencies than heterogeneous TiO 2 photocatalysis, but
in others, the Fe cycle is affected by the contaminants
and Photo-Fenton does not work properly. As a
consequence, preliminary research is always required to
assess potential pollutant treatment and to optimize the
best option for any specific problem, practically on a
case-by-case basis.
It is not always easy to decide whether a specific
water- contamination problem can be treated with solar
detoxifica- tion technology, since low efficiencies
produce hydroxyl radicals and slow kinetics may limit
economic feasibility. As mentioned above, preliminary
tests are normally needed to assess process viability. In
an attempt to provide some guide- lines for the reader, the
following general affirmations may be
made:
• –1
MAXIMUM ORGANIC CONCENTRATION of SEVERAL hundred mg L :
photodegradation processes work well in low or
medium concentrations up to a few hundred ppm of
organics. The upper limit depends on the nature of
the contaminants, but concentrations over 1 gr L–1 are
normally not suitable for solar photocatalytic
processes unless previously diluted.
• NON-BIODEGRADABLE CONTAMINANTS : when possible,
bio- logical treatments are always the most cost-
effective processes. Only when the contaminants are
persistent (non-biodegradable) do photocatalytic
processes make sense.
• HAZARDOUS CONTAMINANTS present within complex mixtures of
ORGANICS: one of the main advantages of solar
photocataly- sis is that it is non-selective, so non-
biodegradable con- taminants can be treated within a
complex mixture of other organic compounds. Solar
detoxification also works very well with individual
contaminants, but a mixture of contaminants increases
its utility. Hazardous contami-
nants also usually appear in concentrations
susceptible to photocatalytic treatment.
• CONTAMINANTS with no EASY CONVENTIONAL TREATMENT:
an additional situation in which solar photocatalysis
will be
Solar Detoxification 107
Applications
useful is when contaminants are present in
concentra- tions that make conventional treatment
difficult.
The above recommendations provide an indication of the
type of industrial wastewater for which solar
detoxification can potentially be employed. Nevertheless,
several additional conditions are needed before a
complete solar detoxification feasibility study can be
undertaken.
• Throughputs should be REASONABLE: spatial velocities or
sur- face throughputs in the solar collector and solar-
photon consumption related to the total volume to be
treated should be acceptable. The treatment capacity
must be high enough to make photocatalytic
degradation practi- cal. Many aqueous organic
oxidation processes are too slow to be economically
viable.
• SOLAR photons must be used efficiently: the technology
to be applied must optimize the collection of solar
photons to be used. The overall energy needed per
molecule destroyed must also be low enough to make
the process feasible. The use of external oxidants, such
as electron
scavengers, like S2O=8, H 2O ,2 O ,3or other substances,
could increase the quantum yield.
• The PHOTOCATALYTIC process should be RELIABLE (no CATALYST
DEACTIVATION): the degradation process must work
contin- uously without problems such as catalyst
deactivation. Collector components, catalysts and
the overall system must also be durable, guaranteeing
long periods of oper- ation without incident.
• OPERATION AND MAINTENANCE processes must be simple: the
implementation of any real solar detoxification technol-
ogy application must require minimum operation and
system supervision. As treatment processes are non-
productive, personnel costs associated must be reduced
to a minimum. These considerations also apply to
maintenance.
• BATCH system TREATMENT: it is clear that water
treatment with solar detoxification should be run in
recirculation mode with batch loads of contaminants
to guarantee complete destruction. This means that
the treatment must be independent of the process
generating the wastewater and that on-line treatments
normally are not feasible.
Applications that fulfil both groups of requirements may
be considered serious candidates for solar detoxification,
and a detailed feasibility test study would be worth
consideration.
108 Solar Detoxification

7.2. Industrial wastewater

treatment
As previously indicated, solar detoxification technology
may be considered feasible for industrial effluents
containing highly toxic compounds for which
biological waste treat- ment plants are not feasible at
medium or low pollutant concentrations. This
technology is linearly dependent on the energy flux. It is
therefore also linearly dependent on the collector
surface, and investment in turn depends on the collector
surface. Land limitations must also be considered.
Normally, several hundred up to 2,000 m 2 is not a t
problem for a medium-sized factory. As a conclusion, a
FIGURE 7.1. Complete mineralization of a complex
reasonable order of magnitude of inflows for a solar
mixture of organic contaminants containing phenols
detoxification plant, using current technology, would be
using TiO2 (200 mg/L) and persulfate as an electron
in the range of several dozens up to a few hundred m 3
scavenger.
per day.
At the moment, and from the experience accumulated
by many scientists and researchers in the last ten years,
solar detoxification seems to be a good solution for BWTP. Figure 7.1 shows two degradation tests carried
destroying, among others, the following contaminants out on chemical industry wastewater containing a large
found in indus- trial wastewater: number of compounds, mainly phenols, and including
formol, phthalic acid, fumaric acid, maleic acid, glycol
• phenols compounds, xylene, toluene, methanol, butanol and
• agrochemical waste phenylethylene, among others.
• halogenated hydrocarbons As observed in Figure 7.1, complete degradation of
• antibiotics, antineoplastics and other chemical all initial substances and their intermediates is possible at
reasonable degradation rates. Table 7.1 shows examples
biocide compounds from the pharmaceutical
of industrial processes that generate wastewater
industry
containing phenols that could be good targets for solar
• wood preservative waste (PCP, fungicides) photocatalytic processes.
• hazardous metal ions. One such application is the treatment of condensation
water from the manufacture of phenol-formaldehyde, one
of the oldest synthetic resins used in industry, for which
7.2.1. Phenols phenols are the raw materials. Phenolic resins are
obtained from the reaction of phenol or a phenol
substitute with formaldehyde. The reaction may be
These substances include phenol, cresol and other phenol portrayed as indicated in Figure 7.2.
substitutes. All the phenols are very toxic. Their The ingredients are boiled in a reflux condenser
maximum concentration in a biological wastewater (Figure 7.3) and condensation water is usually removed
treatment plant inlet (BWTP) is 1 to 2 mg/L. Even very by vacuum distillation. This condensation water contains
low concentrations of phenols (1 to 10 mg/L) in sev- eral mg/L of reagents that are very toxic.
freshwater produce unpleasant odours/tastes during the
Phenol-formaldehyde resins are usually prepared with
chlorinating process, so any dis- charge of phenols must
formaldehyde (40 per cent) – approximately 750 L of water
be avoided. The solar detoxification technology would
is removed for each ton of final product. When solid
therefore be useful in the treatment of water containing
formaldehyde is used, about 160 L of condensation water
this type of contaminant.
is
Phenols can easily be degraded by solar
photocatalysis. A few hundred square meters of solar
CPC collectors could crack or completely destroy the
phenols contained in small volumes of industrial
effluents prior to discharging to a
 Solar Detoxification 109
Applications

TABLE 7.1. Example of processes producing phenol residues in wastewater.

Chemicals Process Waste description Quantity
Condensation water containing
1. Phenols & Phenol-formaldehyde
formaldehyde resins less than 2,000 mg/L of phenols and 500 L/ton of phenolic resin
formaldehyde
2. Phenols Storage tanks, ships, Rinsing water containing less than 0.1% of the total production diluted
in lorries, piping 15,000 mg/L 60 volumes of water
0.1% of the total production diluted
3. Phenols Phenol production Spills, cleaning water
in 60 volumes of water

FIGURE 7.2. Formation of phenolic resins. (Courtesy of Ecosystem S.A., Spain).

removed from the final mixture. These phenolic residues

contain between 600 to 2,000 mg/L of phenol and
between 500 to 1,300 mg/L of formaldehyde.

7.2.2. Agrochemical compounds

This family includes a broad range of chemicals that
Reflux
are extensively used in agriculture. Some of these
compounds are soluble in water, others are used as
suspensions; some are oil-based pesticides and some are
used as dusts. However, the majority of them are
dissolved, suspended or emulsified in water prior to
Phenolic spraying; the amount of wastewater gener- ated can vary
wastewater
greatly depending on handling. Water-borne
contamination originates in many different processes,
such as cleaning and rinsing of spraying equipment,
dumping of leftover spray solutions, and plastic bottle
recycling.
Pesticides are among the best candidates for the
applica- tion of solar detoxification technology. This is
because they are employed in very diluted solutions
or suspensions of multi-component formulas, in
small volumes and in batches. Very good results have
been obtained with organo- halogenated and
organophosphorus pesticides, carbamats, thiocarbamats,
2,4-D (2,4 DICHLOROPHENOXYACETIC ACID) and tri- azines. As
well as the large amount of pesticide waste gener- ated in
agriculture, there is also a huge amount of industrial
Final products
waste from factories producing the active ingredients,
FIGURE 7.3. Reactor condensation wastewater from the manu- partic- ularly in factories where the active components
facture of phenolic resins. (Courtesy of Ecosystem S.A., and other
Spain).
110 Solar Detoxification

TABLE 7.2. Examples of processes that are potentially producers of wastewater containing agrochemical residues.
Chemicals Process Waste description Quantity
Wet scrubbing alkaline solution
Pesticides (NaOH) containing dissolved, 500 m3/year for a medium-sized
suspended and partially degraded company
Packagin pesticides
g (at high/medium concentration) 2,000 m3/year for a medium-sized
Floor-cleaning water, mixer- and reactor- company, with 0.05% of the active
Pesticides Manufacturing / cleaning and rinsing water components dissolved or suspended
Packaging in
100 parts of water
Water used to clean and rinse application
Pesticides Land application equipment. Formed by diluted —
spray solution (<100 mg/L)
Pesticides Land application Spraying solution prepared in excess —
An estimated 0.2 to 0.5 g of
Water used to clean and rinse plastic
pesticide Pesticides Plastic container recycling bottles prior to crushing and
per empty plastic bottle of 2 L average
pelletisation
volume, dissolved in 500 volumes of
(<100 mg/L)
wate
r

additives are stored, weighed according to the product

for- mula, mixed and packed.
A complete description of an example of
photocatalytic degradation technology used for these
compounds can be found in Chapter 9. Another potential
example is the treat- ment of rinse water from cleaning
sprayers in agrochemical applications. This rinse water
contains pesticides and must be properly managed to
avoid contamination of the soil, ground- water and
surface water, which can occur if it is improperly
discharged. In many areas, farmers prepare the spraying
solu- tion at spring used by the whole town. Such places
are suit- able for the installation of a small or medium-
sized solar treatment plant. The technology could also be
of interest to large farm owners or pesticide application
companies.
FIGURE 7.4. Photocatalytic degradation of
7.2.3. Halogenated hydrocarbons dichloromethane, chloroform, trichloroethylene and
tetrachloroethylene using a titania catalyst manufactured
by ENEL (Italy). (Courtesy of University of Turin, Italy).
Solar detoxification has also been shown to be efficient
in the degradation of halogenated solvents. Halogenated halogenated wastes are factories of halocompounds
com- pounds are found in much pharmaceutical industry manu- facturing. The waste can be estimated as a low
waste, and increasing concerns about volatile organic percentage of the total production, dissolved at 100 to
compound (VOC) emissions and environmental 200 mg/L.
regulations and direc- tives are pushing industrial
managers to control VOC emissions. One of the VOC- Example: estimation of the required field
emission-control methods is wet scrubbing, and solar A feasibility study has determined that a 6 m2
detoxification can treat the contaminated water from the photoreactor can completely mineralize 250 L of
scrubbers. Other sources of wastewater containing 100 mg/L of chloroform in eight
hours of sunlight. Say
 Solar Detoxification 111
Applications

25,000 L are to be treated. As all the parameters are
linear, assuming unchanged weather and wastewater
conditions, 600 m2 of collector field over eight hours, or
300 m2 over sixteen hours is needed to treat the 25,000
L, while for a 100-m2 field, forty-eight sunny hours
would be necessary to complete the treatment.
Another potential halo compound application of
solar detoxification is treatment of the effluents from the
manufac- turing of PVC (polyvinyl chloride), which is
produced in huge quantities worldwide. The mass of
these effluents is
2.5 times greater than the final production of PVC (1 ton
of PVC produces approximately 2.5 m 3 of effluent) and
may be contaminated with short-chain polymers or vinyl
chloride, the PVC monomer.
The chemical industry also produces a great variety of
biocides used as preservatives, especially in paint.
Common examples of these compounds include: phenyl
mercuric acetate, dithiocarbamates and other sulfuric
compounds, halogenated phenols, halogenated phenol-
formaldehyde condensates and quaternary ammonium
salts. A medium- sized chemical company could
typically produce 50 t/yr of this type of product. As
equipment must be cleaned between each batch,
approximately 500 to 1,000 m 3 of rinse water could be
generated per year, with a normal concentration of 200 to
50 mg/L of the biocide, for which solar treatment could
be feasible.

7.2.4. Antibiotics, antineoplastics and 7.2.5. Wood preservative waste

other pharmaceutical biocide compounds
There are two main types of pharmaceutical industries:
factories producing fine chemicals (that is, high-value
chemical products) and those that produce and mix raw
materials and components to obtain a final product (a
chemical commodity). Since antibiotics are intrinsically
bio- cides, they cannot be treated in biological treatment
plants. Antineoplastics are citotoxic (some of them
inhibit cellular division) and are commonly used in
chemotherapy of leukemia and tumours. Both of them
are ecotoxic and should be degraded before dumping into
streams or sewage systems. Manufacturing equipment
(hoppers, conveyors/belt feeders, weighing and mixing
equipment, pill-forming or container-filling machines) is
normally cleaned thoroughly with a huge amount of
water. This can be stored and treated in batches,
presenting ideal conditions for solar detoxifica- tion
treatment.
The most toxic and persistent of the wood preservatives
is pentachlorophenol (PCP). This insecticide is very
well- known to solar detoxification researchers because
it was one of the first compounds studied exhaustively in
photocatalytic degradation. Although it is now banned,
PCP is still pro- duced and used in wood-protecting
varnishes, because of its effectiveness against
woodworms and termites.
Other compounds in this group are creosote and
organic insecticides and fungicides. Although precise
information on the amount and chemical composition of
these residues is scant, the general impression is that they
produce a huge amount of waste. Wood-preserving
companies usually treat the wood (timber and sawed
pieces) in concentrated pesti- cide baths. When the baths
become less effective, their content is replaced with fresh
product. A conservative assumption is that 5 per cent of
the chemicals in the bath is discharged as waste.

TABLE 7.3. Examples of processes that are potentially producers of antibiotic and antineoplastic wastewater.
Chemicals Process
Pill forming and raw
1. Antibiotics material mixing process at
manufacturing of
pharmaceutical specialities
2. Antibiotics Antibiotic production
3. Antineoplastics
4. Antineoplastics
Waste description Quantity
Cleaning water coming from pill and
container-filling equipment, 3–5,000 L /d at a medium sized factory
containing
less than 1,000 mg/L of organic
compounds
0.05% of total production dissolved
Fermentators and liophilisators cleaning
in
500 volumes of water
Same as 1
Same as 2
112 Solar Detoxification
FIGURE 7.5. Degradation of PCP at a PSA solar
detoxification facility (Helioman’s collectors’ loop). See
also Figure 5.3 showing the solar photocatalytic
mineralization of PCP at the Helioman collectors.
7.2.6. Removal of hazardous
metal ions from water
One additional advantage of the heterogeneous photo-
catalytic process is the presence of a reductive chemistry
pathway that can be exploited to remove reducible
species, such as hazardous heavy metal ions. It is
important to remember that both oxidation and reduction
must occur simultaneously to maintain process activity,
so it is possible to use the presence of organics as
reductants for the reduc- tion of metals and, at the same
time, the metals as oxidants for the oxidation of organics.
In general, the higher the con- centrations of organics,
the faster the metal reduction rates. Similarly, an increase
in the concentration of metals increases the organics’
oxidation rate.
Oxygen is usually the oxidant when there are no
other oxidants or metals present, and water acts as the
reductant element. Dissolved oxygen can compete
with dissolved metals for conduction-band electrons
and therefore can inhibit the rate of metal removal.
However, dissolved oxygen can be helpful for the
degradation of the organics if the con- centration of
metals is insufficient. The ability to remove metals
depends on the standard reduction potential for the
reduction reaction. For example, it has been assessed
that Ag2+, Cr6+, Hg2+, and Pt2+ can be treated by
photocatalytic reduction, but Cd2+, Cu+2, and Ni+2
cannot.
Specific applications described in the literature are
the elimination of specific organometallic compounds
(organic agents forming complexes with metal ions)
such
FIGURE 7.6. Cr+6 to Cr+3 solar photocatalytic reduction at
a PSA solar detoxification facility (CPC’s collectors’ loop).
See also Figure 7.7.
as phenylmercury, or the removal of silver from black
and white photoprocessing waste. The presence of
organometal- lic compounds usually complicates
wastewater treatment, as the metal becomes more inert
and the effectiveness of tradi- tional processes for
aqueous metal removal, such as alkaline precipitation
and ion exchange, is reduced. Although the rate of metal
removal is generally slow, it remains attractive to solar
detoxification technology, as these applications are
normally widely distributed and can be processed in
batches. When there are only metals, inexpensive and
non-hazardous sacrificial reductants (such as EDTA or
citric acid) can be added to enable photocatalytic
treatment.
Another application of interest is the reduction of Cr +6
to Cr+3. Photocatalytic reduction of Cr(VI) is very
sensitive to pH, and is more efficient below pH 2. It
leaves the reduc- tion product, Cr(III), in solution in this
range of pH. Around pH 5, Cr(III) forms a stable
precipitate. The Cr(VI) reduction rate is very sensitive to
the nature of the organic matter that is simultaneously
being destroyed. Generally, the more easily oxidized the
organic compounds, the higher the photocat- alytic
reduction rate; this means that different waste streams
may exhibit dramatically different treatment rates
depending on their specific chemical composition.
7.2.7. Other applications
Many other potential applications of solar photocatalysis
may be found in the literature. Among them are the
destruction of organics in recyclable water from the
microelectronics

, ,
, ,
, ,
, ,
, ,
, ,
FIGURE 7.7. Simultaneous oxidation of phenol and
reduction of Cr+6 to Cr+3 using solar detoxification
technology (PSA, Spain).
industry, the removal of explosives (such as TNT, RDX
and HMX) from aqueous munitions waste, and the
oxidative degradation of cyanides.
Because they are highly toxic, photocatalytic
degradation of cyanides is another potential industrial
application, with the advantage that it produces neither
highly toxic sub- stances such as cyanogen chloride nor
sludges and avoids the use of additional chemical
reactants such as chlorine.
CN  2OH  2h+V  OCN  (7.1
B H2O )
Furthermore, photocatalytic oxidation can transform CN –
into less toxic substances, such as OCN –, and by
carefully selecting reaction conditions, complete
oxidation to CO2 and N2 can be obtained:
OCN  2H2O  V  CO2  12  4H (7.2
3h B N2 3 ) Vapam) is
In all the applications mentioned in this chapter, the
presence of inorganic ions (such as chloride, phosphate,
nitrate and sulfate) in water can have a negative effect on
the destruction rates of the target compounds. High
concentrations of inorganic ions have been found to
reduce the performance of the titania catalyst and, as a
consequence, reduce signifi- cantly the feasibility of the
overall treatment process.
7.3. Seaport tank terminals
A large percentage of the international chemical
trade is shipped by sea. There are many tank terminals in
harbours
Solar Detoxification 113
Applications
all over the world used for receiving, storing and
distributing raw chemicals and fuels to industry. Final
distribution of the stored product is in bulk by tank
trucks (except for a small amount in drums in the same
terminal enclosure).
Seaport tank terminals must carry out cleaning opera-
tions and also have to control emissions from the stored
products. These cleaning operations usually produce
huge amounts of water contaminated with low
concentrations of the chemical from tanks, pipelines,
jetty pipelines and hoses. Among the compounds
normally transported and distrib- uted this way, many
chemicals (such as phenol, metham sodium,
perchloroethylene, trichloroetylene, methylen chlo- ride,
sodium dichromate, and compounds such as styrene,
toluene, nonil phenol and benzene chloride), may be suc-
cessfully treated by solar detoxification.
Example: Cleaning of phenol tanks
At the end of a contract for the rental of a 600-m3 tank
that had contained phenol, terminal personnel proceed to
clean it for refill with styrene. This is done in a two-step
operation. First, saturated steam is injected to dissolve
any phenol crys- tals remaining in the top and valves.
7,400 L of condensed water containing 6.4 per cent
phenol is then discharged into a waste storage tank for
later recovery of the phenol by dis- tillation or its
destruction by thermal treatment. Then the
inside of the tank is rinsed out using a hose with a special
spray nozzle. This rinse water contains 450 mg/L of
phenol
in a total volume of 16,000 L. The conditions (volume,
concentration, transparency) of the waste generated in
this second step are ideally suited to solar detoxification.
Figure 7.8 shows an example of another potential appli-
cation: treatment of wastewater from cleaning a tank that
had contained metham sodium. Metham sodium (or
a dithiocarbamate used as soil fumigant to control weeds,
nematodes, fungi and insects (soil sterilizer). This
compound is a direct competitor of methyl bromide,
another soil disin- fectant and one of the ozone-depleting
chemicals.
In a medium-sized seaport tank terminal (typically about
seventy tanks with 28,000 m3 average storage capacity), at
least fifteen cleaning operations are completed each year,
with huge amounts of residues generated annually in the
pipeline connection pit (‘snake pit’), hoses and cleaning of
ships. There is also a potential application in any wet scrub-
ber these plants may use for VOC emission-control equip-
ment. All these residues can easily be managed by solar
detoxification because they can be stored individually in
114 Solar Detoxification
260
240
Total organic carbon (ppm)
220
200
180
160
140
120
100
0 10 20 30
Residence time (min)
FIGURE 7.8. Degradation of metham sodium wastewater
from a tank-cleaning process. Catalyst deactivation is
observed after partial degradation of the initial TOC
content. (PSA, Spain).
small tanks or containers until the treatment process
can be run.
7.4. Groundwater decontamination
Remediation of contaminated groundwater is a challenge
in many parts of the world and especially in developed
coun- tries. Typical substances found in contaminated
groundwater are chlorinated hydrocarbons (including
PCBs), aromatics from a variety of sources including
fuels (for instance, ben- zene and toluene), and a wide
variety of other chemicals that includes pesticides,
solvents, phenols (PCP, creosote), TNT and DNT, dyes,
polynuclear aromatic hydrocarbons (PAHs) and even
dioxins.
Solar detoxification can be considered a good solution
for in situ treatment and decontamination of
groundwater con- taining substances where conventional
biological treatment is not feasible due to dilution of
pollutants. Also, groundwater is clear and transparent
and there is always good storage capacity (the aquifer is
in itself a holding ‘tank’ for contami- nated water). Tests
have shown that the majority of pollutants found in
contaminated groundwater are easily destroyed by
photocatalysis. Groundwater remediation also has the
advan- tage of a processing timescale of months or
years.
The difficulty is that standard discharge must
normally achieve drinking-water quality, which is
difficult and costly (for any treatment technology that is
used). Groundwater
Solardetox
Scrubber
Date: 21 October 1993
Metham sodium
TiO2+ persulfate Contamination
Water table Vadose zone
Saturated
zone Contamination plume
Recharging
well Well
40 50 60 70
FIGURE 7.9. Generic concept of contaminated groundwater
treatment. (Courtesy of ECOSYSTEM S.A., Spain).
also tends to have a high mineral and salt content,
resulting in the need for pre- and post-treatment systems.
Typically, contaminated sites are old chemical plants,
oil recycling plants (engine lubricant oil), refineries,
chemical weapon and explosive factories, pesticide plants,
coke and gas factories, air force bases, harbours, railway
stations, power plants and substations. The contaminated
groundwater must be pumped out from a series of
extraction wells located down- stream of the contamination
plume. After treatment, it is re- injected into the water table
through upstream injection wells.
The first known treatment of contaminated
groundwater by solar photocatalysis was carried out
experimentally in the 1990s in the grounds of the
Lawrence Livermore National Laboratory (LLNL) in
Livermore, California. This was also the first on-site
application of solar photocatalysis technology. During
the Second World War, a part of the grounds now
occupied by LLNL was a Naval Air Station training and
main- tenance facility. Trichloroethylene (TCE) and
other toxic chemicals were used extensively in normal
operations to clean engine parts and other machinery. Over
the years, unconfined TCE and other volatile organic
compounds entered the local groundwater, where they are
now slowly migrating off site. Today, TCE is present in
the groundwater at concentrations ranging up to 500 ppb,
which is 100 times the acceptable EPA limit for drinking
water. The field experiment, developed by three US
government laboratories (NREL, SNL and LLNL), was
conducted at LLNL in 1991 using available trough tech-
nology, and demonstrated the technical feasibility of this
application.
The system consisted of two solar troughs, each 36.5
m long, with an effective concentration ratio of
approximately

FIGURE 7.10. Partial view of the 156 m2 parabolic-trough
water treatment system tested on contaminated
groundwater at a site at LLNL (United States) in 1992.
(Courtesy of the US National Renewable Energy
Laboratory).
20 and a total solar collector area of 158 m 2 using a
TiO2 slurry. It yielded outlet concentrations below 5
ppb, which meets the limits for a drinking-water
process feasibility demonstration. One of the main
problems reported was the required acid pre-treatment,
which had a marked negative impact on the
effectiveness of the process.
Another application that can be found in the literature
is the one-sun solar detoxification facility installed in
1993 on a groundwater site contaminated by a former
jet-fuel handling area at Tyndall Air Force Base in
Florida (United States). Contaminants of interest that
were present in the groundwater included benzene,
toluene, ethyl benzene, and xylenes (BTEX). Thirty one-
sun collector modules (1.22 m ×
2.4 m) connected in series were used, each collector
module made up of 66 UV transparent parallel tubes with
a 0.64 cm inner diameter and 2.4 m in length (Figure
7.11). Treatment of initial concentrations of 1 to 2 mg/L
of BTEX was per- formed in a batch system, obtaining
typical destruction lev- els of 50 per cent to 75 per cent
in three hours. The total volume treated during each run
was 530 L.
One last example is the photocatalytic cleaning of
groundwater contaminated by gasoline from
underground storage tanks (Figures 7.12a and b). In this
case the ground- water was contaminated with BTEX
(benzene, toluene, ethyl benzene and xylenes) at a
concentration of about 1 ppm. The test site was a gasoline
station and the system consisted of six non-concentrating
solar reactors of 3 m2, each using TiO2 slurry and a
1,900 L storage tank.
Solar Detoxification 115
Applications
FIGURE 7.11. One-sun reactor built by American Energy
Technology, Inc. for treating contaminated groundwater in
Florida (United States) in 1992. (Courtesy of the US
National Renewable Energy Laboratory).
7.5. Contaminated landfill cleaning
Soil decontamination is another potential application of
solar detoxification. There are contaminated landfill sites
all over the world for which, depending on the nature of
the con- taminants, water- or gas-phase photocatalytic
treatments could be used. If the contaminants are
soluble in water, water (or steam) can be used to extract
them, and solar detoxification can then treat this water
later. If the contami- nants are volatile organic
compounds, they can be desorbed from the solid as a
gaseous product using either vacuum extraction or heat
and pumped into a gas-phase solar detox- ification
system (see also Section 7.7).
One example of this application is the
mineralization of lindane suspended in landfill
leachate. The reaction between benzene and chlorine
under UV light produces six stable isomers of
hexachlorocyclohexane that are carcinogens. Only one
of them, Lindane, which makes up 14 per cent of the
final mixture, is actually an insecticide. The other
isomers, hazardous compounds and also very stable in
the environment, have been spread throughout the
environment for decades or dumped in badly managed
landfills (many sites are contaminated by lindane, some
of them very well known in Europe). Lindane is one of
the oldest chlorinated insecticides and, because of its
stability in the environment, is banned for agrochemical
and veteri- nary use in most countries. However, it is
still used as ectoparasiticide to eliminate lice in
children and for other
116 Solar Detoxification

a)

b)

FIGURE 7.12. Non-concentrating solar detoxification system for BTEX-contaminated groundwater at a commercial
site in Gainesville, Florida (United States), 1996. (Courtesy of the Solar Energy and Energy Conversion Laboratory,
University of Florida).

pharmaceutical and medicinal uses, with the approval of

health authorities.
Figure 7.13 shows the photocatalytic degradation of
Lindane (technical grade) suspension in water,
simulating the final step of contaminated landfill
treatment and demon- strating the technical feasibility of
the solar treatment process (maximum solubility of
lindane: 10 mg/L).
7.6. Water disinfection
Chlorine is the most commonly used chemical for water
dis- infection because of its ability to inactivate bacteria
and viruses. Nevertheless, the presence of organic
impurities in the water can generate unwanted by-
products of disinfec- tion, such as trihalomethanes and
other carcinogens. As a
 Solar Detoxification 117
Applications

UV-C UV-B UV-A

(100-280nm)
(100-280 nm) (280-315) (315-400
(280-315) (315-400nm)
nm)

UV-C* UV-B* UV-A*

UV-C* UV-B* UV-A*
* Definitions
* Definitions
based on
based on
biological
biological
effect
effect Ozone- Germicidal
Ozone- Germicidal
producing Erythemal
producing Eryt hemal

Far UV Near UV
(“black
Near light”)
UV
Far UV
(“black light”)

100 150 200 250 300 350 400

FIGURE 7.13. Simulation of contaminated landfill FIGURE 7.14. Common ultraviolet band designations
treatment using solar detoxification: mineralization of based on biological effects. (Courtesy of International
lindane (PSA Solar Detox Facility, Spain). Light, Inc., USA).

result, other water-disinfection technologies are
becoming increasingly important. Among them,
ultraviolet irradiation with lamps is widely used to
destroy biological contami- nants, mainly using 254-
nanometer wavelength. Solar ultra- violet, which is
primarily at 290 to 400 nm wavelengths, is much less
active as a germicide (see Figure 7.14).
Despite the broad spectrum of research, the potential
use of solar detoxification technology for water
disinfection is still largely unexplored. However, the
antibacterial effect of TiO2 has been demonstrated on
several microorganisms, including Escherichia Coli,
Lactobacillus, Streptococcus, and others. In all cases, the
photocatalytic oxidation effect of TiO2 particles was
able to effectively sensitize bacteria to photo-killing by
solar exposure. This photo-killing action is associated
with the disruption of the cell wall and membrane
through photocatalytically induced surface oxidation
result- ing in the disintegration of the cell. Disinfection
of viruses such as Phage MS2 and poliovirus 1 can also
be found in the literature.
Homogeneous methylene-blue-sensitized
photochemical disinfection has also been found to be
highly effective with
E. Faecalis bacillus spores through singlet oxygen
photo- oxigenation. Singlet oxygen is generated by
absorption of a photon by a photosensitizer (dye) that is
excited and trans- fers its energy to a dissolved oxygen
molecule. Photo-killing occurs when this singlet oxygen
penetrates into the microor- ganism resulting in
oxidation and inactivation of cellular
components. Successful pilot plant experiments using
this technique have been carried out in Israel and
Germany.
Two major disadvantages of sensitized
photodisinfection in comparison with conventional
techniques are the gener- ally slow kinetics and the lack
of residual disinfection capac- ity (after exposure to
light). On the positive side, the presence of biological
and organic contamination in surface waters is usually
highest in summer, when the greatest amount of solar
radiation is available for the process. One possible
realistic approach might be preliminary solar detox-
ification to partially disinfect water and reduce the level
of organic contaminants, followed by limited
chlorination to maintain disinfection in distribution
pipelines and inhibit formation of undesired by-products.
7.7. Gas-phase treatments
Gas-phase photocatalytic oxidation is one of the
advanced oxidation technologies (AOTs) with promising
applications for end-of-pipe treatment of gaseous
emissions and air purification. The first pilot
experiments were also carried out in the 1990s. In the
United States, the ambitious DOE Solar Industrial
Program motivated development of the photocatalytic
oxidation technology. Some examples of applications
are cleaning of exhaust streams from the
microelectronics industry and treatment of off-gases
after
118 Solar Detoxification

.
OH
Mineralization
.
A4 . Cl
Cl C Cl CHCl2 CHCl
1 3

H Cl H Cl H Cl O2 H Cl O
O2
Cl
C C Path A C C. C C
Cl
C C 6 7
A2 . A3
Cl Cl Cl Cl O O
(1) (2) Cl
Cl Cl Cl Cl O. A5
A1 2a 3 4 H .
C C Cl Cl
. . Cl Cl O
Cl H Cl
Cl
C C
Cl Cl
Cl Cl 5
8
H Cl
.C C
Path B Cl
Cl Cl
2b

FIGURE 7.15. Scheme of TCE gas-phase mineralization with PCO and a monolithic catalyst based on sepiolite/TiO 2/Pt.

The fundamental background of radical attack on

organic contaminants photocatalyzed with the assistance
of smog has been addressed by several tropospheric
chemistry specialists but, unfortunately, some crucial
questions related to the basic fundamentals of gas-phase
PCO still persist. A critical screening of the related
literature reveals conflicting results among the authors
regarding the influence of different process parameters.
The reaction mechanism in gas-phase, based on hydroxyl
radicals, has also recently been revised by other possible
options, resulting in a presently confusing stage for gas-
phase photocatalytic treatment processes.
Figure 7.15 shows the possible trichloroethylene
(TCE) PCO degradation pathways. Some intermediates
have been shown to form in the presence of chloride, and
it has been proposed that Cl could be the driving force
FIGURE 7.16. Destruction efficiencies of 400 ppm of TCE instead of OH. Other authors have proposed that both
using a MgSiO4/TiO2/Pt monolithic catalyst: mechanistic approaches via Cl and OH are essentially
thermocatalytic and photocatalytic processes at different correct and that the eventual pathway depends on the
temperatures (CIEMAT, Spain). characteristics of the cata- lyst (for example, internal
surface or porosity). TCE is one of the most studied
compounds because it is a major gas-phase air pollutant.
Its photocatalytic oxidation with titanium diox- ide has
extraction of contaminated soil vapour. Indoor air quality received good reports in the literature.
in houses, vehicles and spacecraft has also been a matter Figure 7.16 shows a lab experiment performed on
of study in the United States and Japan. In Europe TCE using a monolithic TiO 2-based catalyst at different
several ini- tiatives also address the development of gas- tempera- tures. Photoeffect was clearly differentiated by
phase solar PCO as an end-of-pipe technology for the using appro- priate filters. As it can be observed,
treatment of VOC emissions but, unlike water temperature played a negative role as a result of
detoxification, all the above- mentioned experiments adsorption–desorption phenom- ena. Nevertheless, apart
have been basically conducted with lamps. Very few from high photonic efficiencies (up to 95 per cent)
solar installations can be found in the liter- ature and reported with TCE, it is not easy to find appli- cations for
there continues to be a serious lack of solar-driven gas- pure photocatalytic gas-phase treatment processes,
phase PCO.
 Solar Detoxification 119
Applications

as not many compounds have been found to be
significantly affected by photocatalysis, in most cases a
combination of photocatalytic degradation and
destructive thermocatalysis is necessary.
In addition, a major problem for solar gas-phase PCO
is the difficulty, or even impossibility, of working in
batch systems, implying an important additional
difficulty for solar-driven processes because of the
natural uncontrol- lability of the Sun as the energy
source. As a result, it is not easy to find a niche for
solar-driven PCO applied to gas- phase and air
purification. Hybrid solar–electric or pure electric
devices using lamps are therefore envisaged for initial
practical applications.
Table 7.4 summarizes NREL experience with gas-
phase photocatalytic degradation of different
contaminants. Aromatic compounds like BTEX have
slow or medium reac- tion rates and TCE is the fastest.
BTEX tests demonstrate deactivation of the TiO2 catalyst
and the need to add ozone to enhance the process and
make PCO degradation possible. This and other possible
technology combinations could be
another way of promoting gas-phase applications.
Possible targets are the majority of hazardous air
pollutants requiring abatement technologies:
halogenated, aliphatic and aromatic hydrocarbons,
alcohols, glycols, ethers, epoxides and phe- nols,
normally present in air streams at concentrations of less
than 5,000 ppm. Some applications for air purification or
degradation of emissions in the semiconductor industry
are also under development.
Figure 7.17 shows a one-sun reactor with PTFE
window material and titanium dioxide immobilized on
polypropy- lene supports for gas-phase solar
detoxification successfully tested by NREL (United
States). For additional information on gas-phase
experimental treatment systems, see also Figure 6.24 and
Figure 5.6.
Unlike water phase, in which a catalyst may be used
in efficient slurry configurations, in gas phase this is not
possi- ble and all experimental systems developed to date
use an immobilized catalyst. As previously discussed in
Section 6.5, the catalyst must be anchored onto some
type of inert support inside the gas-phase stream
treatment reactor.

TABLE 7.4. Qualitative degradation rates of different compounds screened for photocatalytic activity: slow (s),
medium (m) and fast (f ). (Courtesy of US National Renewable Energy Laboratory).
Compound Rate Compound Rate
Acetaldehyde m Methanol m
Acetonitrile s Methylene chloride s
Acetone s Methylethyl ketone m
Benzene s Methylisobutyl ketone m
Benzaldehyde m Perchloroethylene f
Butyl acetate m Propyl amine m
Butyl amine m Propylnitrile s
Decane m Tetraethylethylene m
Dichloroacetyl chloride m Toluene s
Dichlorobenzene s Trichloroethylene f
Diethyl amine m Xylenes m
Diisopropyl amine m Sec-butyl amine m
Ethane s t-butyl amine s
Ethanol m 1-butanol m
Ethyl acetate m 1-propanol m
Ethylbenzene m 1,1-dichloroethylene f
Ethylene m 2-propanol m
Fuel oil m 1,2-dichloroethylene f

a)
b)
FIGURE 7.17. Flat-plate reactor for treating contaminated
air exiting from air-stripping units at McClelland Air
Force Base, California, 1997. (Courtesy of the US
National Renewable Energy Laboratory).
Such a system must be being very active (a high
degradation efficiency), with low pressure-drop, a
long lifetime, and a reasonable cost. Very diverse
types of catalysts have been used in gas-phase systems,
from MgSiO4/TiO2/Pt monoliths to TiO2 immobilized
on glass fibres, ceramic substrates and inert plastic
materials. As in water-phase, residence times must be
as long as possible to increase degradation effi-
ciency.
Solar Detoxification 121
Applications
One interesting potential application of gas-phase
solar detoxification technology is the gas treatment from
contami- nated landfill recovery (see Section 7.5).
Chlorinated volatile organic compounds (CVOC) are
among the most pervasive subsurface ground
contaminants, and the remediation tech- nologies most
used for CVOC ultimately produce a gas- phase stream
containing CVOC, either from soil venting from the
unsaturated zone or groundwater recovery from the
saturated zone and subsequent air stripping. In the past,
direct discharge of gaseous CVOC to the atmosphere
was normal, but since the early 1990s many regulations
have required the abatement of these emissions using
the best available technologies.
Other possible applications are small air pollution
sources. These applications are not uncommon: examples
are dry cleaners, auto repair shops, bakeries and coffee
roast- ers. Additional potential solar applications include
remote sites, storage-tank vents or potentially explosive
waste streams. Finally, the regeneration of a carbon bed
or other adsorbent materials could be another promising
application for a solar system. In this application, the
adsorbent can per- form twenty-four-hour VOC removal,
and the solar system can be used to purge and destroy the
contaminants during daylight hours.
With regard to air disinfection, most of the work
carried out has been focused on the use of TiO 2 particles
as sensi- tizers for the destruction of bacteria and viruses
in air. In this field, a very interesting application is the
fabrication of self-disinfecting surfaces. Several studies
have reported the antibacterial effect of titanium dioxide
on indoor air in com- bination with UV fluorescent
lamps. The use of thin TiO 2 films as a method of
keeping surfaces free of biological material would be of
particular value where sterile surfaces are essential, such
as in operating theatres in hospitals. Although very few
demonstrations have been reported to date, it is expected
that more will take place in the future.
Finally, solar photocatalysis is the process that
makes self-cleaning glasses work efficiently. Fouling of
glasses is mainly due to dust and/or atmospheric particles
stuck on the surface on greasy stains, mainly of fatty
acids. Self-cleaning glasses could be coated with an
invisible thin layer of titania, which, under the
simultaneous presence of oxygen (air), atmospheric
water vapour and solar UV-light, is able to decompose
fatty acids by successive photodecarboxylation (photo-
kolbe) reactions and allow coated glasses to recover their
initial clearness (Figure 7.18).
 120 Solar Detoxification
FIGURE 7.18. Self-cleaning windows. Evolution of
photo- catalytic treatment processes on glasses coated
with titanium dioxide. (Courtesy of Laboratoire de
Photocatalyse, Catalyse et Environnement (E.R. au
CNRS), Ecole Central de Lyon, France).
Summary
Solar detoxification technologies could provide the
environ- mental waste management industry with a new
tool to destroy waste using clean energy from the Sun.
Nevertheless, in spite of the large number of patents and
publications, industry is still reluctant to adopt the
process because of discouraging and contradictory
results, which has led research to focus on specific
potential applications. Solar detoxification is a useful
technology for addressing non- biodegradable
hazardous contaminants where no easy treatment by
conventional technologies is available,
concentrations up to several hundred mg L–1. Phenols,
agro- chemical wastes, halogenated hydrocarbons,
biocide com- pounds from the pharmaceutical industry,
wood-preserving waste, hazardous metal ions, cyanides
and aqueous muni- tions waste are among the industrial
wastewater applica- tions. Other interesting
applications are the treatment of groundwater
contamination and seaport tank terminals, the cleaning of
contaminated landfills and water disinfection. Gas-phase
applications are in an even more confusing situation as
some crucial questions related to the basic fun-
damentals still persist. In solar gas-phase PCO, the
catalyst must be used immobilized, and diverse types of
supporting substrates, such as glass fibres, ceramic
substrates, inert plastic materials, and monoliths can be
used. Some potential gas-phase applications are gas
treatment from contaminated landfill recovery,
degradation of emissions in the semicon- ductor industry,
air purification, air disinfection and self- cleaning
windows.
Bibliography
ACHER, A.; FISCHER, E.; ZELLINGHER, R. AND MANOR, Y. 1990.
Photochemical disinfection of effluents: pilot plant studies.
WATER RESEARCH, Vol. 24, No. 7, pp. 837–43.
GOSWAMI, D.; YOGI, J.; KLAUSNER, G.D.; MATHUR,
A.; MARTIN, K.; SCHANZE, P.; WYNESS, C.T.; TURCHI,
C. AND
MARCHAND, E. 1993. Solar photocatalytic treatment of
groundwater at Tyndall AFB: field test results. In: SOLAR
1993: proceedings of the AMERICAN SOLAR Energy Society
ANNUAL Conference, pp. 235–9.
MALATO, S. 1999. SOLAR PHOTOCATALYTIC Decomposition of
PENTACHLOROPHENOL Dissolved in WATER. Doctoral thesis.
Editorial CIEMAT.
MEHOS, M.S. AND TURCHI, C. 1993. Field testing solar
photocatalytic detoxification on TCE-
contaminated groundwater. ENVIRONMENTAL Progress,
Vol. 12, No. 3, pp. 194–9.
NIMLOS, R.; WOLFRUM, E.J.; GRATSON, D.A.; WATT, A.S.;
JACOBY, W.A. AND TURCHI, C. 1995. Review of RESEARCH Results
for the PHOTOCATALYTIC OXIDATION of HAZARDOUS WASTES in Air.
at NREL /TP-433-7043.
NREL. 1995. Development of A Homogeneous Aqueous PHASE
PHOTOCATALYST for the SOLAR DETOXIFICATION of WATER.
Final Report to NREL. Markham, Ontario, Solarchem
Environmental Systems.
PRAIRIE, M.; EVANS, L.R. AND MARTINEZ, S.L. 1994.
Destruction of organics and removal of heavy metals in
water via TiO2 photocatalysis. In: CHEMICAL OXIDATION:
Technology for the Nineties, Second INTERNATIONAL Symposium.
Lancaster, Pa., Technonomic Publishing Company.
(Symposium proceedings.)
VINCENT, M. 2000. Solar detox market. In: TRAINING AND
Mobility of RESEARCHERS Summer School: INDUSTRIAL APPLICATIONS
of SOLAR Chemistry, September 1998, Chapter 8.
Madrid, Editorial Ciemat, pp. 261–280
122 Solar Detoxification
WATTS, R.J.; KONG, S.; ORR, M.P.; MILLER, G.C.
AND HENRY, B.E. 1995. Photocatalytic
inactivation of coliform bacteria and viruses in
secondary wastewater effluent. WAT. Res., Vol.
29, No. 1, pp. 95–100.
YVES, P.; BLAKE, D.; MAGRINI-BAIR, K.; LYONS, C.;
TURCHI, C.; WATT, A.; WOLFRUM, E. AND PRAIRIE. M.
1996. Solar
photocatalytic processes for the purification of water:
state of development and barriers to
commercialization. SOLAR Energy, Vol. 56, No. 5, pp.
429–37.

Self-assessment questions
Part A: True or false?
1. Preliminary research is required to assess
potential treatment of pollutants in any specific
problem on a case-by-case basis.
2. Solar photocatalytic processes work well with
organic concentrations of over 1 gr/L.
3. Non-biodegradable organic contaminants are the
most logical target for solar photocatalytic processes.
4. There is no sense in addressing complex mixtures
of hazardous contaminants with solar photocatalysis.
5. An indication that solar photocatalytic technology
may have a possible application could be the lack of an
easy conventional treatment.
6. External oxidants must always be used as electron
scavengers, when feasible, to increase the quantum yield
of degradation processes.
7. There is usually no difference between the treatment
of contaminated water in a batch or on-line process.
8. Typical solar detoxification plants process from
several dozen up to a few hundred m 3 per day.
9. The presence of high concentrations of inorganic
ions negatively affects the destruction rate and the
overall feasibility of solar detoxification processes.
10. It is difficult to find applications for pure
photocatalytic gas-phase treatment processes as not
many compounds have been found to be affected by a
significant photocatalytic effect.
Solar Detoxification 123
Applications
Part B
1. Why is the environmental market still reluctant
to accept solar detoxification processes?
2. Indicate the three existing solar
photocatalytic processes.
3. What is the main advantage of photocatalytic
oxidation processes over other advanced oxidation
technologies?
4. In addition to the use of solar energy, indicate one
main advantage of solar photocatalysis.
5. Indicate at least three conditions indicative of a
viable solar photocatalytic process.
6. Indicate why water treatment with solar
photocatalysis must normally be in a batch system.
7. As solar photocatalysis is an oxidation-reduction
process, what is the normal reductant agent a) when
only organic compounds are present, and b) when
metals are present?
8. From testing it has been found that a 4-m2
collector system can treat a 50-L sample of
wastewater containing 200 mg/L of TOC from
organic compounds in four
hours of sunlight. How long would it take to treat 100
m3 of the same wastewater with a 500-m2 treatment
system?
9. What are the proposed mechanisms for gas-
phase photocatalytic degradation of chlorinated
organic compounds?
10. What is the worst situation for a water
treatment process based on TiO 2 photocatalysis?
 124 Solar Detoxification
Answers
Part A
1) True. 2) False. 3) True. 4) False. 5) True. 6) True.
7) False. 8) True. 9) True. 10) True.
Part B
1. Because early successful experimental results
presumed a wide range of practical applications, but
confusing and discouraging results later led to the
current concentration on applications with specific
required boundary conditions.
2. Heterogeneous TiO2 photocatalysis, homogeneous
Photo-Fenton and homogeneous sensitized-
photochemical oxidation by singlet oxygen.

3. Their potential solarization, introducing an important
additional environmental value in the pollutant
degradation process.
4. The fact that it is a non-selective process,
making possible the treatment of complex
mixtures of
non-biodegradable organic contaminants.
5. Reasonable throughputs, efficient use of solar
photons and reliable photocatalytic process with no
catalyst deactivation.
6. Because the degradation process is driven by solar
photons, a source which cannot be controlled, making
it necessary to separate the treatment from the
wastewater generating process.
7. When only organic compounds are present, oxygen is
the normal oxidant and water acts as the reductant
element. When metals are present, oxygen is also the
oxidant and the metals themselves are the reductant
elements.
 100,000 
8. R  4  500  64 hours of sunlight.
 50 
4
9. Depending on the catalyst characteristics and the
boundary conditions, the main degradation
mechanism can be based on the attack of ºCl or ºOH
or ºCl + ºOH radicals.
10. The presence of high concentration of
organic contaminants and inorganic ions
simultaneously.
 8
Solar Detoxification 123
Applications

CHAPTER 8

Economic Assessment

Aims
This chapter discusses the main factors
that affect the cost of solar detoxification
systems and analyses the economic cost of
specific solar photocatalytic applications.
They are also qualitatively compared with
other treatment technologies.
Objectives
After completing this unit, you will be able to:
1. Determine the feasibility of a two-step
photocatalytic–biological treatment process.
2. Estimate the cost of solar
photocatalytic treatment.

3. Estimate the feasibility of solar

detoxification as a function of local
solar resources.

4. Compare possible alternative or

complementary treatment
technologies.
126 Solar Detoxification

NOTATION AND UNITS

Symbol Description Units

AOPs Advanced oxidation processes
AST American Standards for Testing and
M Materials Atmosphere attenuation dimensionless
cλ coefficient at λ Chemical oxygen demand moles of O2 L–
1
COD Cosine of the incident angle of solar radiation to collector surface
cos p Compound parabolic concentrator
CPC Extraterrestrial irradiation
École Polytechnique Fédérale de Lausanne (Switzerland) W m–2 µm–1
E(λ)
EPF Cloud factor
L Fixed charge rate %
f Granular-activated %
FCR carbon Solar time angle
GA Henry’s Law constant degrees
C Total yearly hours of operation of a lamp-based system dimensionles
hs Total yearly hours of operation of a solar detoxification system s hours
hours
H Intensity of solar irradiation over terrestrial surface at specific wavelength, W m–
HL λ 2
W
HS Intensity of extraterrestrial solar irradiation at the wavelength, λ m–2 W
Ib,λ Solar constant associated with a spectral interval (λ1, λ2) m–2 W
Io,λ Yearly average global UV irradiation m–2
I Local latitude degrees
– sc,λ dimensionless
I UVg Air mass ratio
Air mass ratio at sea dimensionless
L Moles L–1
level Molar
m Mili molar 10–3 moles L–
mo Molecular weight
1
gr mol–1
M Daynumber dimensionless
mM National Renewable Energy Laboratory
MW (USA) Number of electric lamps
N Total yearly collected UV photons (energy higher than 3.2 eV) photons
NRE Number of photons with energy higher than 3.2 eV per unit of time and photons m–2 h–
1
L NL surface Pentachlorophenol
NUV Hexahydro-1,3,5-trinitro-1,3,5-triazine
NΦ (E>3.2 Surface of solar collector field
Trichloroethylene m2
eV)
PCP Trinitrotoluene
RD Total organic
XS carbon Treatment mg L–1 or moles of C L–
TCE factor
TNT Mass treatment factor 1
Volumetric treatment g h–1 m–2
TO L h–1 m–2
C factor Ultraviolet
radiation A Elevation over
Tf m
sea level Solar altitude
Tfm degrees
Solar declination
Tfv Nominal average photonic flux electric
degrees
photons s–1
UV-A lamp Average oxidation state
dimensionles
z s
α
δs
φPH
ΨAOS
 Economic Assessment 127

8.1. Photochemical and biological geometry and materials, the contaminants and their
reactors coupling concentration, UV-A irradiation level and catalyst
concen- tration. Nevertheless, this parameter does not
necessarily imply better or worse performance of a
The mass treatment factor (Tfm) of a specific solar specific system, because this depends on the discharge
detoxifica- tion system can be defined as the amount of objectives. Contaminant treatment, in its strictest
organic sub- stances the system is able to treat per unit of meaning, is the com- plete mineralization (TOC = 0) of
time and solar collector surface: the contaminants but, as previously indicated (Chapter
7), normally photocatalytic
m(TOC)  g  processes only make sense for hazardous non-biodegrad-
T   (8.1) able pollutants (toxic organic pollutants not treatable in
fm
tS  2 conventional biological treatment plants). When feasible,
hm

The volumetric treatment factor (Tfv) of a specific solar biological treatment of biodegradable residual waters is
detoxification system can be defined as the volume of the cheapest treatment technology and also the most
con- taminated water the system is able to treat per unit compati- ble with the environment. Therefore,
of time and solar collector surface: biologically recalci- trant compounds could be first
treated with photocatalytic
technologies until biodegradability is achieved, later trans-
V  L  ferring the water to a conventional biological plant. Such a
Tfv
tS  hm2
(8.2)
combination of photocatalytic and biological treatments

could reduce treatment time and optimize the overall
Tfm and obviously depend on the specific solar system economics, since the solar detoxification system could be
Tfv and
the wastewater to be treated. The same system yields significantly smaller. As a consequence of the kinetic
differ- mech- anism (explained in Chapter 4), the first part of
ent treatment factors with different contaminants and the photo- catalytic process is the quickest, with higher
also varies depending on the solar irradiation, higher reaction rates producing the main part of TOC
on sunny days than on cloudy days. The most practical degradation, and the last phase is the longest, with lower
units are those indicated in Equations 8.1 and 8.2: the reaction rates and contri- bution to complete degradation.
grams of TOC degraded per hour and square metre of An example might be agrochemical compounds,
solar collector field, in the case of Tfm, and the litres of which are normally effectively cracked by photocatalytic
water treated per hour and square metres of solar degrada- tion processes. The active component of the
collector field in the case of Tfv. pesticide disappears after several minutes of irradiation,
but TOC
Example of calculation of treatment factors
If a specific solar detoxification plant having 300 m 2 of
col- lectors can treat 5 m3 of wastewater containing 50
mg L–1 of organic compounds in ninety minutes, the
treatment factors will be:
50 mg L1  5,000 3 g g
L
Tfm  
300 m2  1.5 10  0.55 (8.3)
mg
hm2
h

5,000 L L (8.4)
Tfv   11.11
300 m  1.5
2 hm2
h
such as system
Treatment factors are a powerful tool for comparing
differ- ent detoxification systems and checking treatment
feasibil- ity for different wastewater problems. The
efficiency of solar detoxification systems is usually from
0.05 to 1 g of organic compounds degraded per hour and
square metre. This is a function of several parameters,
 128 Solar Detoxification

FIGURE 8.1. Conceptual scheme of photocatalytic +

biologi- cal technologies coupling. (Courtesy of EPFL,
Switzerland).

usually becomes negligible only after two or three
hours of irradiation. Design of a solar detoxification
system to reduce the TOC (that is, disappearance of a
specific com- pound or compounds) only until toxicity
is low enough to be sent on to a biological treatment
plant might therefore
be of interest.
In the previous example (Eqs. 8.3 and 8.4), ‘treatment’
could mean the total degradation of organic contaminants
or the degradation only until the achievement of
biodegrad- ability. Therefore, the treatment factor may
also depend on the system objective, and a very low
treatment factor for complete mineralization could be
transformed into a feasible one for integration with
biodegradation.
The feasibility of combining photocatalytic and
biological
treatments to achieve highly efficient abatement of
pollutants
that cannot be treated by either biological or
photocatalytic
a)
b)
FIGURE 8.2. Elimination of tensioactive compounds from
agrochemical industrial wastewater after a few minutes
of photocatalytic treatment (PSA, Spain).
Economic Assessment 129
methods alone has already been demonstrated at EFPL.
This strategy is based on the average oxidation state
(ΨAOS), which can be defined from the following
formula:
Average Oxidation State
 TOC 
    4 
COD (8.5)
AOS
 
TOC
where TOC (total organic carbon) and COD (chemical
oxy- gen demand) are expressed in moles of C L–1 and
moles of O2 L–1, respectively. Average oxidation state
can be between
+4 for CO2, the most oxidized state of carbon, and –4 for
CH4, the most reduced state of carbon. The latter is given
by the reaction:
CH4  2O2  CO2  (8.6)
2H2O
where, TOC = 1 (moles of C L–1) and COD = 2 (moles
O2 L–1) so, according to Equation 8.5, TAOS = –4. With
CO2, as oxidation is impossible, COD = 0 and TAOS =
+4. An example is oxidation of formic acid:
HCOOH  O2  CO2  2H2O (8.7)
In this case, TOC = 1 (moles of C L–1) and COD = 1
(moles O2 L–1), so ΨAOS = 0. When photodegradation is
applied, the average oxidation state of intermediates is a
function of photo-treatment time and could be a
good indication of when to switch from the advanced
oxidation process to biological treatment.
Oxidized substances are typical of biological
processes. Usually treatment performance is best for
organic com- pounds of low molecular weight.
Photodegradation treat- ment performance is also better
at the beginning of the process, when organic molecules
are broken up into simpler ones. As a consequence, it
makes sense to always check the feasibility of a two-step
process in which the photocatalytic treatment is
employed first to increase biodegradability and
biological treatment is applied afterwards. Figure 8.3
shows the typical evolution of ΨAOS when recalcitrant
toxic com- pounds are treated. Normally, a plateau is
observed after a time, suggesting that the chemical nature
of intermediates formed will no longer vary significantly.
As Figure 8.4 shows, there are two possible extreme
situations (A and B) with regard to the evolution of
toxicity.
Sometimes, there is a direct correlation between ΨAOS
and toxicity. This is the best situation (as reflected in
point A of Figures 8.3 and 8.4), because it means that
the overall
 130 Solar Detoxification
FIGURE 8.3. Photodegradation process: usual relationship
between the average oxidation state and time. Points A and
B are also related to Figure 8.4. (Courtesy of EPFL,
Switzerland.)
FIGURE 8.4. Photodegradation process: normal
relationships between toxicity and time. Points A and B
are also related with Figure 8.3. (Courtesy of EPFL,
Switzerland.)
chemical status of the degradation process does not
progress (AOS remains constant, and toxicity
decreases, thereby increasing biodegradability).
Nevertheless, even at low concentrations, toxic
substances could be formed during the degradation
process (point B of Figures 8.3 and 8.4), increasing
overall toxicity. This does not neces- sarily impede
initiation to biological treatment, but it does force the
point of commencement to be moved to the right (point
B).
As previously indicated, the feasibility of combining
Photo-Fenton (see Section 1.3.3) and a biological process
to
treat certain non-biodegradable toxic compounds has
been demonstrated at EPFL (Switzerland). A TiO 2
photocatalytic process followed by aerobic biotreatment
has also been suc- cessfully employed by NREL (United
States) for the treat- ment of wastewater from munitions
manufacturing plants (pinkwater) containing low
concentrations of high explo- sives, such as RDX
(hexahydro-1,3,5-trinitro-1,3,5-triazine), TNT
(trinitrotoluene), HMX and PETN.
It must be pointed out that photocatalytic degradation
of recalcitrant organic compounds quite often increases
the toxicity of the wastewater during its initial phase.
The rea- son is the proliferation at the beginning of the
process of many reaction by-products. Therefore, it is
important that the photocatalytic treatment be long
enough to eliminate this increased toxicity. Also, with
regard to the parameters of toxicity, it is very important
that no intermediates formed be more toxic than the
initial compounds, because this could disable the overall
feasibility of the treatment process.
The feasibility of such a photocatalytic–biological
process combination must always be assessed because it
could pro- vide an important cost reduction in the
treatment of haz- ardous compounds in wastewater, by
reducing the size of the necessary solar collector field. It
must be taken into account that, as with most solar
systems, the economics of water detoxification systems
are dominated by their capital cost. Thus, by reducing the
capital cost of the system, the process- ing cost is
decreased.
8.2. Cost calculations
Cost is always a key topic when innovative technologies
are considered, and standard commercial procedures
indicate that any new technology should provide
significant reduc- tions in processing costs over
competing technologies or significant new technical
contributions for its successful marketing. In the case of
solar detoxification, its main contri- bution is the
environmental added value of using solar energy to
solve water contamination problems.
This section addresses the main factors influencing
‘final installed cost’, ‘operating cost’ and ‘treatment cost’ of a
solar detoxification system. The installed cost includes all
costs associated with the design, construction, and start-
up of the facility, but it is assumed that normal services
and facilities such as water and electricity are available
on-site and that
130 Solar Detoxification

land is also available at no cost. The four main
components of installed cost are:
• FACILITY cost: the total field cost includes the direct cost
of equipment and system components, plus the
direct cost of installation labour. The major
components are: civil engineering, concrete
foundations, connection to power and water supply,
solar collectors, tanks, manifolds, piping, pumps
and valves, structures and supports, electrical
equipment, control system, instrumentation,
catalyst separation unit, collector, and piping and
con- nection assembly.
• Project contingency: since the general conceptual
design cannot include all the details of the specific final
design, at this point, total field costs are still
necessarily incom- plete, and to properly account for any
unidentified costs, a contingency item must be added
to the cost. This could be from 10 to 20 per cent of the
facility cost, depending on the degree of design
definition. The sum of facility cost and contingencies is
the ‘total facility cost’.
• System engineering AND ASSEMBLY : this includes
system design and integration into existing
installations, specifi- cations, procurement of system
components, scheduling, project management, system
assembly, training of opera- tors and engineering
support. Engineering costs are esti- mated to be 50
per cent of the total facility cost.
• SPARE PARTS: 0.5 per cent of the total facility cost is
nor- mally included as a spare parts allowance.
The sum of the facility cost, contingencies, engineering and
spare parts is the ‘total installed cost’. It is important to note
that the cost of a previous feasibility study is not considered
here because the extension and depth of this study depends
on many factors, specific to each situation, which are
difficult to estimate. Table 8.1 shows the cost for different
typical facility sizes for a CPC solar field. These costs are
based on real plant built recently (shown in Section 9.6).
In addition to the total installed cost, the second deter-
mining factor in the cost of water treatment is the
‘operating cost’. The operating cost must include all
personnel and material costs required to operate and
maintain the facility (supervision, procurement,
maintenance and so on), chemi- cal supplies and
electricity costs. Usually, it comprises:
• Personnel: these costs are linearly dependent on
facility size. Considering a solar detoxification facility
normally operating seven days per week and fifty-two
weeks per year, personnel requirements for a 500-m2
solar plant are estimated to be only 0.1 person/year,
since the plant is completely automated. Also, because
of the simplicity of one-sun collectors, the total annual
maintenance require- ment is also estimated to be 0.25
person/year, mainly for periodic cleaning.
• Cost of MAINTENANCE MATERIALS: the annual cost of
mainte- nance materials is mainly due to mechanical,
electrical and instrumentation equipment, which could
amount to about 2 per cent of the total facility cost.

TABLE 8.1. Estimated cost of typical sizes of solar detoxification facility (euros, 1999).

Collector area (m2) 100 200 300 500 1 000 10 000

Control, pumps and
instrumentation 23 228 25 190 27 900 32 048 50 793
20 221

Piping, valves,
structures and
Manifolds, tanks 22 201 28 315 38 471 58 311 232 139
14 647
supports
and
Catalyst separation 3 507 4 473 6 078 9 212 36 673
recovery 2 314
Collectors and 21 220
reactor 42 440 63 660 106 100 168 556 1 338 891

tubes
Civil engineering 6 025 12 050 18 075 30 125 60 250 602 500
Equipment transport 601 911 1 162 1 579 2 393 9 525

TOTAL INVESTMENT 65 028 104 337 140 875 210 251 330 770 2 270 522
Cost/m2 650 522 470 420 331 227

• Electricity: the facility consumes electricity for
pumps, control system, instrumentation and lighting:
the vast majority (around 90 per cent) by the main
system pump(s). The average annual consumption of
this auxil- iary power consumption, per m3 of treated
water, is diffi- cult to estimate as the ratio between total
treated volume and plant size is directly dependent on
the nature of the contaminants. It could more easily be
estimated as a func- tion of the solar field size, as this
determines total pres- sure-drop and, consequently,
pump specifications. In view of this, yearly power
consumption can be estimated as between 40 and 80
kWh per m2 of installed solar field.
• CHEMICAL supplies: although one of the main factors in
the yearly operating cost is the consumable chemicals,
an estimate cannot be given here because it depends
heavily on each specific treatment process. The
chemicals used
by Photo-Fenton processes are completely different
from TiO2 processes; they also depend on the nature
and com- position of the wastewater, for which
some pre or post- treatment might be needed, with
specific chemicals in each case. A case-by-case
cost study must therefore be performed. Two
examples can be found in Sections 8.2.1 and 8.2.2.
The sum of costs for personnel, maintenance materials,
elec- tricity and chemical supplies is the ‘total operating
cost’ of the solar detoxification system. To obtain the
‘annual treat- ment cost’, per m3 of treated wastewater, total
installed costs are converted to an annual levellized cost
considering a fixed charge rate (FCR), which is obtained by
calculating all the fixed costs (excluding operation) for the
life of the plant. The annual levellized cost and treatment
cost can be calcu- lated as:
Annual Levelized Cost
 Total Installed Cost  FCR  Operating (8.8)
Cost
Treatment Cost (Euros/m3 )
(8.9
Annual Cost ) 8.2.2. Example B: Photo-Fenton based

Annual Treatment
Capacity
The ‘fixed charge rate’ represents the equivalent revenue that
must be generated annually to meet all the charges on each
euro of facility investment. FCR is normally equal to the
sum of the return on debt, taxes, depreciation, insurance and
so on. For solar detoxification treatment plants, a plant
life of
Economic Assessment 131
twelve years with a depreciation period of ten years
may normally be assumed. With this data and
considering, as an example, that the plant is financed by a
debt with a 5 per cent interest rate and that the total
annual expenses due to taxes, insurance and so on are 2
per cent of the total installed cost, an FCR of 17 per cent
is obtained (0.1 from the ten year depreciation + 0.05 +
0.02 = 0.17).
8.2.1. Example A: TiO2-based solar
detoxification plant
A 300-m2 solar detoxification plant has been designed
(see also Chapter 9) for the yearly treatment of 6,000
m3 of wastewater contaminated by pesticide, using a
TiO2-persulfate (see Section 5.2) photocatalytic system:
TiO2  hν  e  h (λ  390 (8.10)
CBnm)
V (8.11)
B
h+V  H2O  OH  H+

B (8.12)
S2O82  eCB
  SO  SO2
4 4
(8.13)

SO  H O  OH  SO2  H
4 2 4
It is estimated that the plant would operate about 3,000
hours per year. An estimate of the yearly treatment cost,
in 1999 euros, can be performed as in Table 8.2.
To obtain the treatment cost, an FCR of 17 per cent,
with ten-year plant depreciation, is estimated (Table 8.3).
It should be noted that a 4 per cent reduction in the
FCR (from 0.17 to 0.13) has a greater effect on the
annual treat- ment cost than a 50 per cent reduction in the
solar collector field. Also, about 50 per cent of the
annual operating cost is the cost of the persulfate itself, so
any reduction in this affects
the treatment cost very significantly. In this way, it must
be taken into account that addition of consumable
reagents (such as persulfate) may not necessarily be
required by spe- cific TiO2 photocatalytic applications.
solar detoxification plant
A 200-m2 solar detoxification plant has been designed for
the yearly treatment of 6,000 m 3 of wastewater
contaminated by pesticides, using Fenton’s reagent (H2O2
and Fe2+) irradiated
132 Solar Detoxification

TABLE 8.2. Estimated operating cost of a TiO 2-persulfate solar detoxification plant (euros, 1999).

A Facility cost Data from table 8.1 (300 m 2 of solar collector system
aperture area) 140 875
B Project contingency 15% of the facility cost is estimated 21 131
C Engineering and setup 50% of A+B (total facility cost) 81 003
D Spare parts 0.5% of A+B (total facility cost) 8 100

E TOTAL INSTALLED COST A+B+C+D 251 109

F Personnel cost 0.25 person/year @ € 20 000/person/year. 5 000

G Maintenance material cost
H Electricity
I Chemical supplies
T
J ABLE 8.3. Estimated annual
TOTAL OPERATING COSTtreatment cost of a TiO 2-persulfate solar detoxification plant (euros, 1999).
2% of A+B (total facility cost) is estimated 3 240
5 kW/hour average consumption, 3 000 operation
hours/year = 15 000 kWh @ 0.1 €/kWh. 1 500
– TiO2 catalyst at 200 mg–1 concentration, re-used up to
10 times = 120 kg per year. 1 080
– S2O8Na2 (MW 238), at concentrations of 5–10 mM, overall
consumption per batch cycle of 15mM = 21 420 kg per year. 53 550
– Sodium hydroxide, NaOH (MW 40), 50% solution, for
pH adjustment and neutralization of the treated
water = approximately 4 800 kg per year. 1 344
F+G+H+I 65 714

K Annual levelized cost E × FCR + J (formula 8.8) 108 402

L Annual treament cost K is divided by 6 000 (yearly treated volume) 18.0/m3

in the UV-V range (Photo-Fenton method):
Fe2  H2O2  Fe3  OH  OH (8.14
) water. Reduction is likely to be difficult due to the
Fe3  H2O  hν  Fe2  H  OH (λ  580 nm)
(8.15
) the volume of
As in the previous case, 3,000 operating hours per year
are estimated. The yearly treatment cost would then be
that shown in Table 8.4.
Also as in the previous example, an FCR of 17 per cent
with a ten-year plant depreciation period is estimated
(Table 8.5).
Two additional conclusions from this example may be
added:
• For a depreciation period of twenty years (longer
facility lifetime), the FCR would be 12 per cent
(0.05 + 0.05 +
0.02 = 0.12) and this would mean a very significant
reduction in treatment cost.
• Operation is a significant portion of the cost of treated
low capacity factor of the facilities and the costs of
consum- able supplies, which are proportional to
treated water.
Two additional examples of solar photocatalytic
treatment cost found in the literature are the following:
• Groundwater remediation at Livermore, California,
by NREL (United States). Average treatment
capacity of
4.4 L/s of water, with a peak flow of 30 L/s, inlet
con- centration of 400 ppb TCE and maximum outlet
concen- tration of 5 ppb. Total treatment cost was
reported as US$4.07/m3.
 Economic Assessment 133

TABLE 8.4. Estimated operating cost of a Photo-Fenton solar detoxification plant (euros, 1999).

A Facility cost Data from table 8.1 (300 m 2 of solar 104 337
collector system aperture area)
B Project contingency 12% of the facility cost is estimated 12 520
C Engineering and setup 50% of A+B (total facility cost) 58 429

D Spare parts 0.5% of A+B (total facility cost) 5 843

E TOTAL INSTALLED COST A+B+C+D 181 129

F Personnel cost 0.20 person/year @ € 20 000/person/year. 2 337

G Maintenance material cost
H Electricity
I Chemical supplies
2% of A+B (total facility cost) is estimated 3 240
4 kW/hour average consumption, 3 000 operation hours/year
= 12 000 kWh @ 0.1 €/kWh. 1 200
– FeSO4 7H2O (MW 278) catalyst at 1mM concentration,
= 1 668 kg per year. 1 080
– Hydrogen peroxide, H2O2 (MW 34), 30% solution, overall
consumption per treatment cycle of 33.75 mM, = 22 950 kg per year. 17 442
– Sodium hydroxide, NaOH (MW 40), 50% solution, for batch mode
neutralization of the treated water = approximately 3 036 kg per year. 849

J TOTAL OPERATING COST F+G+H+I 65 714

TABLE 8.5. Estimated annual treatment cost of a Photo-Fenton solar detoxification plant (euros, 1999).

K Annual levelized cost E × FCR + J (formula 8.8) 57 349

L Annual treatment cost K is divided by 6 000 (yearly treated volume) 9.5/m3

• Study for a site at the Rocky Flats plant near Boulder,
Colorado (Bechtel Corp., 1991) to treat an annual
volume of 2,246 m3 with a peak water flow of 6.3 L/s.
The levellized cost of treated water was estimated at
US$10.57/m3. This cost was dominated by the
expensive system required to treat inorganic
components of the water at Rocky Flats.
8.3. Solar or electric photons?
Another important aspect to bear in mind in an economic
assessment is the threshold at which the collection of
solar photons required to drive the photochemical
reactions
becomes cheaper than photons generated by electricity.
Obviously, when only a small amount of solar irradiation
is available, solar-driven processes make no sense, so
the measurement of the solar resource available at a
specific loca- tion might permit a reasonable initial
estimation of the advis- ability of a more in-depth study
on solar photocatalytic processes.
Electric ultraviolet lamps are currently available on
the market for a variety of applications, such as lighting,
food processing, medical treatment, tanning, lacquer
drying, photochemical synthesis, photo-polymerization
processes and attracting insects. They can also be used
for photo- catalytic degradation processes.
134 Solar Detoxification

The most suitable of the different types of electric and 30 per cent of UV-photon production and an average
lamps available for UV-photon production are the low- efficiency (lifetime) of about 20 per cent. Average lamp
pressure mercury fluorescent lamps (the same common life is around 20,000 hours.
fluorescent light normally used for illumination), which With the above data, it is easy to obtain the
are based on the generation of an electric arc through a equivalence between UV-lamp and solar systems. As an
sealed chamber con- taining mercury vapour. The result example, we can calculate how many standard 40-W
is 245-nm radiation that is absorbed by a phosphorous UV-fluorescent lamps are equivalent to a 500-m2 TiO2-
wall coating producing a fluo- rescent radiation which, based solar plant with an average yearly global UV
depending on the coating, can be adjusted to any irradiation of 20 W m–2. The parameter used to compare
spectrum. As for any arc lamp, ballast is required to them is the number of useful UV photons generated or
provide the appropriate current and voltage to start. collected. In the case of the solar plant, this can be
Several studies have demonstrated that these lamps are obtained directly from the standard ASTM solar
the easiest, simplest and cheapest way to produce UV spectrum (assuming constant spectral distribution) using
pho- tons and, in fact, they are already being used in the following equation (see also Section 8.4):
commercially available TiO 2 photocatalytic lamp
systems.
Another type is the germicidal lamp, which is N  5.8  1021 I  (8.16)
basically photons
the same except that the 254-nm light passes directly Φ(E  3.2
eV)  m2h 
UVg  

through transparent glass. As their peak light emission is

centred at the mentioned wavelength, they produce fewer Where
:
valid photons and are less efficient for photocatalytic N8 (E>3.2 eV) = number of photons with energy over 3.2 eV
appli- cations. Medium and high-pressure mercury lamps (wavelength up to 387 nm) per unit of time
are also similar to the low-pressure lamps, but the higher and surface.
pressure generates higher intensity radiation and also –
IUVg = yearly average global UV irradiation (W m–2).
tends to shift the spectrum towards the visible light.
Finally, metal halide lamps, high-pressure sodium lamps The total amount of UV photons collected yearly by the
and incandescent lamps cannot be used for UV light solar plant would be:
production.
NUV  NΦ (E > 3.2 eV) HSS  5.8  1021
Figure 8.5 shows two typical low-pressure 40-W
mercury
fluorescent lamps with dominant emission spectrum (8.17)
centred at 313 and 340 nm. According to manufacturer  20  3,000  500  1.74 
data, the ini- tial standard efficiency of these lamps is 1029
Where
between 25 per cent :
NUV = total UV photons (with energy over 3.2 eV) collected
1.0 1.0 yearly.
0.9
2
PSA spectrum (25 WUV/m ) 0.9
HS = total yearly hours of operation of a solar
0.8
ASTM spectrum detoxification system. This value depends on the
0.8
geographic loca- tion, but it may be estimated at
Irradiance (W m nm )
–1

0.7 UVA–340
0.7 3,500 (near the equa- tor to parallel 20) to 2,500
(40th to 50th parallels). In the example, 3,000 is
–2

0.6 UVB–313
0.6
0.5 used.
0.5
0.4
S = Surface area of solar collector field (500 m 2 in the
0.4

0.3 example).
0.3
–
0.2 0.2 IUVg = yearly average global UV irradiation during the 3,000
0.1 0.1
estimated hours of operation. 20 W m –2 in this
exam- ple (see also Chapter 8.4).
0.0 0.0
270 290 310 330 350 370 390 410
So if the lamps must supply the same amount of UV energy:
Wavelength (nm)
FIGURE 8.5. Ultraviolet spectra: solar (standard and PSA
measured spectrum) and two low-pressure 40 W mercury NUV  1.74  1029  ΦPH HL NL
lamps (QUV fluorescent lamps: UVB-313 and UVA-340).  5.04  1022  8,760  NL (8.18)
 Economic Assessment 135

Where: 5 × 1029 (5.E+29)

φPH = Nominal average photonic flux of the lamp.
Manufacturer’s information usually places this
value between 1.3 to 1.4 × 1019 photons per second
(stan- dard mercury UV lamps with emission
spectrum centred at 360 nm). In the example, this
has been translated to photons per hour.
HL = Total yearly hours of operation of a lamp-based
detox- ification system, which in this case is the
full year (8,760 hours).
NL = Number of lamps of the system.
So, according to Eq. 8.18, in the example considered, the
equivalent number of lamps would be 394.
From this particular example, the following general
equa- tion for estimating the equivalent number of any
type of electric lamps can be obtained:
 I UVg   HS 
N  5.8  1021 S collec- tion is only affected by the reactor system, since

 ΦPH HL 
L
(8.19
) a lamp system. In the case of a lamp-based system, however,
Based on these equations, the cost of collecting UV
photons with solar technology may be compared to the
generation of the same amount of UV photons using
electric lamps. This is done considering the following
amounts of photons to drive the photochemical process:
1028 (1.E+28)
5 × 1028 (5.E+28)
1029 (1.E+29)
1030 (1.E+30)
Using Equations 8.16 and 8.17, the solar field necessary
(with different possible yearly average UV global
irradiation) can be calculated to collect the targeted
amounts of photons. Once the solar fields have been
calculated, their cost can be esti- mated from the data in
Table 8.1 (using a polynomial fitting). Finally, with the
estimated cost of the solar field, the annual cost can be
calculated using Equation 8.8, considering an FCR of 17
per cent, as in the previous examples. No operating costs
are considered. It should be noticed that the only cost
included here is the cost of the solar collector, including
the reactor tubes, as it is the only hardware related to UV-
photon collection. The results are shown in Tables 8.6 to
8.10.
The comparison of electric and solar UV photon
the rest of the system components are quite similar in
design and cost. In the case of a solar system it is
necessary to include the cost
of the solar collector field, which does not exist in the case of
in addition to the electrical installation itself, one must
include the cost of the lamps and their periodic
replacement, the cost of electricity and the higher cost of
the reactor, which has to be more complex than a simple
tube so as to either allocate the lamp inside the reactor or
situate it exter- nally. On the other hand, reactors based
on lamps can be more compact than solar collectors, thus
needing much less space. All these factors make the cost
comparison of both systems a difficult task. Using
Equation 8.18 the equivalent

TABLE 8.6. Estimated yearly cost of collecting 1.E+28 solar UV-photons at different yearly average UV global
irradiation (Costs are indicated in euros, 1999).
–
I UVg Hs S Yearly cost Photon cost
(WUV/m2) (hours) (m2) Investment cost (FRC = 17%) (€/1.E+25 photons)
40 3 500 12 13 345 2 269 2.27
35 3 500 14 13 638 2 319 2.32
30 3 500 16 14 029 2 385 2.39
25 3 000 23 15 124 2 571 2.57
20 3 000 29 16 082 2 734 2.73
15 2 500 46 18 953 3 222 3.22
10 2 500 69 22 779 3 872 3.87
5 1 500 230 49 457 8 408 8.41
136 Solar Detoxification

TABLE 8.7. Estimated yearly cost of collecting 5.E+28 solar UV photons at different yearly average UV global
irradiation (Costs are indicated in euros, 1999).
–I
(WUV/m2 ) Hs
(hours) S(m ) Yearly
(FRC = 17%) Photon
(€/1.E+25 photons)
2 Investment
UVg cost cost
40 3 500 62 cost
21 550 3 663 0.73
35 3 500 70 23 013 3 912 0.78
30 3 500 82 24 963 4 244 0.85
25 3 000 115 30 419 5 171 1.03
20 3 000 144 35 187 5 982 1.20
15 2 500 230 49 457 8 408 1.68
10 2 500 345 68 404 11 629 2.33
5 1 500 1 149 198 524 33 749 6.75

TABLE 8.8. Estimated yearly cost of collecting 1.E+29 solar UV photons at different yearly average UV global
irradiation (euros, 1999).
–I
(WUV/m2 ) Hs
(hours) S(m ) Yearly
(FRC = 17%) Photon
(€/1.E+25 photons)
2 Investment
UVg cost cost
40 3 500 123 cost
31 782 5 403 0.54
35 3 500 141 34 701 5 899 0.59
30 3 500 164 38 589 6 560 0.66
25 3 000 230 49 457 8 408 0.84
20 3 000 287 58 942 10 020 1.00
15 2 500 460 87 262 14 835 1.48
10 2 500 690 124 709 21 201 2.12
5 1 500 2 299 376 772 64 051 6.41

TABLE 8.9. Estimated yearly cost collecting 5.E+29 solar UV photons at different yearly average UV global
irradiation (euros, 1999).
–I
(WUV/m2 ) Hs
(hours) S(m ) Yearly
(FRC = 17%) Photon
(€/1.E+25 photons)
2 Investment
UVg cost cost
40 3 500 616 cost
112 712 19 161 0.38
35 3 500 704 126 990 21 588 0.43
30 3 500 821 145 945 24 811 0.50
25 3 000 1 149 198 524 33 749 0.67
20 3 000 1 437 243 928 41 468 0.83
15 2 500 2 299 376 772 64 051 1.28
10 2 500 3 448 546 036 92 826 1.86
5 1 500 11 494 1 479 332 251 486 5.03
 Economic Assessment 137

TABLE 8.10. Estimated yearly cost of collecting 1.E+30 solar UV photons at different yearly average UV global
irradiation (euros, 1999).
–I
(WUV/m2 ) Hs
(hours) S(m ) Yearly
(FRC = 17%) Photon
(€/1.E+25 photons)
2 Investment
UVg cost cost
40 3 500 1 232 cost
211 554 35 964 0.36
35 3 500 1 407 239 321 40 684 0.41
30 3 500 1 642 276 016 46 923 0.47
25 3 000 2 299 376 772 64 051 0.64
20 3 000 2 874 462 527 78 630 0.79
15 2 500 4 598 706 316 120 074 1.20
10 2 500 6 897 999 924 169 987 1.70
5 1 500 22 989 2 048 971 348 325 3.48

number of lamps (NL) to generate the same amount of
UV photons can be obtained directly:
1.E+28 photons → 23 lamps (40 W low pressure
mercury fluorescent tubes)
5.E+28 photons → 113 lamps (40 W low pressure
mercury fluorescent tubes)
1.E+29 photons → 226 lamps (40 W low pressure
mercury fluorescent tubes)
5.E+29 photons → 1,132 lamps (40 W low pressure mer-
cury fluorescent tubes)
1.E+30 photons → 2,265 lamps (40 W low pressure mer-
cury fluorescent tubes).
With these data, Table 8.11 shows the estimated cost of
UV photon generation with electric lamps. The main
advantage of an electric system is its total availability
(twenty-four hours a day), which is on average three
times higher than solar systems. The total yearly cost is
obtained by using Equation 8.8 with an FCR of 17 per
cent as calculated above for the solar-based system. The
operating cost includes only electricity, replacement of
lamps and the cost of labour involved in replacement.
To obtain these values, a 20,000- hour lifetime has been
assumed for the lamps. The cost of the lamp system may
be considered as linearly dependent on the number of
lamps.
The main uncertainty in Table 8.11 is the cost of the
reac- tor in the lamp-based photocatalytic system. It is
clear that this item would necessarily be an expensive
component of the electric system as it must include
piping, external UV- reflectors to avoid loss of UV
photons, supports, wiring, and
even – depending on how compact the system assembly
is – a cooling system. As this cannot be estimated with
any precision, Table 8.7 attempts to cover a complete
range of possible costs by presenting two conservative
estimates, one in which the estimate of per-lamp reactor
cost is low (€100) and another in which it is high (€200).
The main conclusions arrived at from a comparison of
Table 8.11 and Tables 8.6 to 8.10 are the following:
• The available solar UV-irradiation for a specific
location is the main factor in determining the cost of a
solar-based system.
• The cost of collecting photons with solar technology
decreases proportionally as the yearly total increases
because of the reduction in collector production cost
for larger numbers. This is not the estimated case of
lamp- based systems as they are much more compact.
• When fewer photons are needed (1.E+28), lamp-
based systems are cheaper than solar.
• Solar-based systems with collector apertures of over
100 m2 are clearly cheaper than lamp-based systems
when the average yearly global UV irradiation is
over 15 W/m2 (this must be considered a qualitative
approach rather than quantitative).
• The threshold UV radiation (below which lamp-
based systems are cheaper than solar) decreases as the
yearly amount of photons increases.
All data included in Tables 8.6 to 8.11 are
summarized in Figure 8.6, which shows the
comparative cost of solar and electric technologies for
UV-photon collection and
138 Solar Detoxification

TABLE 8.11. Estimated yearly cost of UV photon generation with electric lamps. Electricity cost = 0.15 Euros/kWh;
FCR = 17 per cent. In Table 8.11A the cost per lamp is €100; in Table 8.11B the cost per lamp is €200 (euros,
1999).

TABLE 8.11A

Number of 1.00E+2 5.00E+2 1.00E+2 5.00E+2 1.00E+3

photons Number Unit
8 8 9 9 0
of lamps
Lamp, ballast and 23 113 226 1 132 2 265
6.80 154 770 1 540 7 701 15 402
accessories
Reactor cost 100.00 2 265 11 325 22 650 113 249 226 499
A) Investment cost 106.80 2 419 12 095 24 190 120 950 241 900
Electricity cost
52.56 1 190 5 952 11 905 59 524 119 048
(0.15 €/kWh)
Lamp replacement 2.98 67 337 675 3 373 6 746
Labour cost of
3.15 71 357 714 3 571 7 143
replacement
B) OPERATION cost 58.69 1 329 6 647 13 294 66 468 132 937
TOTAL COST: 76.85 1 741 8 703 17 406 87 030 174 060
A × FCR + B
Cost per 1E+25 UV photons 1.74 1.74 1.74 1.74 1.74

TABLE 8.11B

Number of 1.00E+2 5.00E+2 1.00E+2 5.00E+2 1.00E+3

photons Number Unit
8 8 9 9 0
of lamps
Lamp, ballast and 23 113 226 1 132 2 265
6.80 154 770 1 540 7 701 15 402
accessories
Reactor cost 200.00 4 530 22 650 45 300 226 499 452 997
A) Investment cost 206.80 4 684 23 420 46 840 234 199 468 399
Electricity cost 52.56 1 190 5 952 11 905 59 524 119 048
(0.15 €/kWh)
Lamp replacement 2.98 67 337 675 3 373 6 746
Labour cost of
3.15 71 357 714 3 571 7 143
replacement
B) OPERATION cost 58.69 1 329 6 647 13 294 66 468 132 937
TOTAL COST: 93.85 2 126 10 628 21 256 106 282 212 564
A × FCR + B
Cost per 1E+25 UV photons 2.13 2.13 2.13 2.13 2.13

generation, respectively. Three different amounts of
photons are plotted (1.E+29, 5.E+29, 1.E+30) against the
average global solar irradiation by adjusting the data in
Tables 8.8,
8.9 and 8.10 (yearly cost).
Figure 8.6 enables easy calculation of the solar
threshold that determines the advantage of solar over
lamp-based tech- nology, as the yearly UV-photon
requirement of the majority of possible applications will
be in the range of 1.E+29 to
 Economic Assessment 139

(electrical lamps)
e
c

FIGURE 8.6. Comparative cost of UV photon
collection/gener- ation with solar technology (CPCs) and
electric lamps (elec- tricity cost = €0.15/kWh),
respectively. Data from tables 8.6 to 8.11 (Costs are
indicated in 1999 euros).
FIGURE 8.7. Comparative cost of UV photon
collection/gener- ation with solar technology (CPCs) and
electric lamps (elec- tricity cost = €0.05/kWh),
respectively. Data from tables 8.6 to 8.11 (Costs are
indicated in 1999 euros).

1.E+30. If a figure of €0.15/kWh is assumed for

electricity cost, a threshold between 10 and 12 WUV/m 2
is obtained (see Figure 8.6). If a different cost is
assumed, Table 8.11 must be updated. This is the case of
Figure 8.7, which corre- sponds to a cost of €0.05/kWh.
In this case, the threshold for solar advantage over
lamp-based systems is logically higher than before.

8.4. Solar resources assessment

Because the dimensioning of a solar photocatalytic

system is directly related to the amount of UV light
available, accurate assessment of the solar resource is
important. Solar UV-light (300 to 400 nm) comprises
roughly 2 to 3 per cent of the direct beam energy and
4 to 6 per cent of the combined direct beam and diffuse FIGURE 8.8. Average direct and global UV irradiance
irradiation (global). Non-concentrat- ing systems have (sunrise to sunset) at PSA (Almería, Spain).
an advantage with regard to resource assessment, as Meteorological data records from 1991 to 1995.
there are extensive data on the total energy (direct and
diffuse) available from sunlight and the 4 to 6 per cent
30 W m–2. However, the best situation is when a
conversion factor makes resource assessment a straight-
database of historical global UV irradiation is available,
forward process for non-concentrating systems.
such as the case in Figure 8.8.
The cost of a specific solar detoxification treatment
As noted in Section 2.4, to reliably estimate the annual
plant may be easily estimated from the indications in
average UV radiation, the so-called ‘cloud factor’ (f ) must be
Sections 8.1,
found. This is the average percentage of global UV
8.2 and 8.3, once the degradation process has been assessed
radiation that is expected to be lost due to clouds throughout
and treatment factors have been identified. Nevertheless,
the year. The cloud factor is also intended to be a
the yearly average UV irradiation at the specific location
measurement of atmospheric transparency and is affected
of potential solar detoxification plants must be known. In
by all the atmos- pheric components that can absorb or
the so-called ‘solar belt’ (between the Earth parallels 40
scatter solar radiation. Figure 8.9 shows the results obtained
North and 40 South), this irradiation is usually between
at PSA, following the procedure indicated in Section 2.4.
15 and
 Economic Assessment 141

α = Solar altitude, defined as the angle formed by the solar

vector to the horizontal surface of the Earth
Solar altitude can be obtained as follows:

sin α  sin(L) sin(δS )  cos(L) cos(δS ) (8.23)

cos(hS )
(8.24)
 2π(10,5  N) 
δ  sin(23, 45) cos 
s  
 36,525 

 Where:
 L = Local latitude.
 δs = Solar declination.
 hs = Solar time angle, which is zero at noon, positive
FIGURE 8.9. Average ‘cloud factor’ for global UV irradiance before and negative after noon. It can be calculated
(sunrise to sunset) at PSA (Almería, Spain). Meteorological at any time by adding 15º of each hour of difference
data records from 1991 to 1995. with respect to the noon (Example: at 15.00 hours
of solar time, hs = –45º).
Another interesting alternative for estimating the N = Day number; 1 at 1 January and 365 (or 366) at 31
annual UV radiation availability is through the Lambert- December. 23.45 is the angle formed by the Earth’s
Beer Law (also called the ‘Bourguer Law’), which axis and the plane formed by the Sun and the elliptical
indicates that light attenuation through a continuous tra- jectory of the Earth.
medium is proportional to the flux radiation and the
distance covered: Equations 8.21 to 8.24 allow solar irradiation at any specific
Ib,λ  Io,λ e c m
λ
(8.20) location on Earth to be detailed; must be measured at the
Ib,λ
specific location and Io,λ can easily be calculated. Due to the
where: Earth’s slightly eccentric elliptical orbit, solar
Ib,λ = Intensity of solar irradiation on the Earth’s surface at extraterrestrial radiation varies ±3.4 per cent throughout the
a specific wavelength, λ. year depending on the day number:
Io,λ = Intensity of extraterrestrial solar irradiation at the
 2πN  
same wavelength, λ. Io,λ  Io,λ (N)  Isc,λ 1  0.034 cos  
cZ = Atmosphere attenuation coefficient at 365  (8.25)
λ.
m = Air mass ratio (see Chapter 2), defined as the  

oblique optical path described by a photon in the
atmosphere relative to the minimum vertical path to λ2 
arrive at the same terrestrial location. If the Isc,λ   E(λ) dλ (8.26)
elevation of the Sun is 90°, then m = 1. λ1

The air mass ratio can be obtained for any moment by Where:
the
following equations: Isc,λ = Solar constant associated with the spectral
0.0001184 Z
interval (λ1,λ2) to which is intended to obtain the
m  mo e (8.21 atmospheric attenuation coefficient (cλ). This
) interval must also be coherent with the measure of
mo  1,229  (614 sin  614 sin Ib,λ (i.e., if we are using a solar radiometer which
α measures within the interval 295 to 400 nm, Isc,λ
α)2 (8.22
must be calculated to the same interval).
where: )
mo = Air mass ratio at sea level E(λ) = Extraterrestrial irradiation, which can be found in
z = Elevation above sea-level in Table 8.12.
metres
 140 Solar Detoxification

TABLE 8.12. Extraterrestrial solar irradiation.

λ Eλ λ Eλ λ Eλ
(µm) (W m–2 µm–1) (µm) (W m–2 µm–1) (µm) (W m–2 µm–1)
0.115 0.007 0.43 1 639 0.90 891
0.14 0.03 0.44 1 810 1.00 748
0.16 0.23 0.45 2 006 1.2 485
0.18 1.25 0.46 2 066 1.4 337
0.20 10.7 0.47 2 033 1.6 245
0.22 57.5 0.48 2 074 1.8 159
0.23 66.7 0.49 1 950 2.0 103
0.24 63.0 0.50 1 942 2.2 79
0.25 70.9 0.51 1 882 2.4 62
0.26 130 0.52 1 883 2.6 48
0.27 232 0.53 1 842 2.8 39
0.28 222 0.54 1 783 3.0 31
0.29 482 0.55 1 725 3.2 22.6
0.30 514 0.56 1 695 3.4 16.6
0.31 689 0.57 1 712 3.6 13.5
0.32 830 0.58 1 715 3.8 11.1
0.33 1 059 0.59 1 700 4.0 9.5
0.34 1 074 0.60 1 666 4.3 5.9
0.35 1 093 0.62 1 602 5.0 3.8
0.36 1 068 0.64 1 544 6.0 1.8
0.37 1 181 0.66 1 486 7.0 1.0
0.38 1 120 0.68 1 427 8.0 0.59
0.39 1 098 0.70 1 369 10.0 0.24
0.40 1 429 0.72 1 314 15.0 0.0048
0.41 1 751 0.75 1 235 20.0 0.0015
0.42 1 747 0.80 1 109 50.0 0.0004

The solar constant for the whole solar spectrum (total that the atmosphere filters UV radiation relatively more
solar radiation) is 1,367 W m –2 (value adopted by the than the overall spectrum.
World Radiation Center, with an uncertainty of 1 per With this background, by measuring Ib,λ, the
cent). In the case of the UV spectrum (295 to 400 nm), atmospheric attenuation coefficient (cλ) can be calculated.
using Table 8.12, it is: This parameter includes all the factors relevant to solar
irradiation, such as Raleigh dispersion, ozone absorption,
atmospheric turbidity
400 2 and spray, absorption by water molecules, clouds and so on.
Isc,UV
 E(λ) dλ  118.1  13.6  104.4 W (8.27
) The knowledge of at a specific location makes it possible to
 cλ
m
295
forecast solar irradiation during the year. Variations in cλ
This value of 104.4 W m–2 represents 7.72 per cent of total over the year also enable conclusions to be made about
extraterrestrial irradiation. As the percentage on the Earth’s changes in atmosphere performance (with regard to solar
surface is lower (normally from 4 to 6 per cent), this means light) at the specific location.
142 Solar Detoxification

8.5. Comparison with other
technologies
A general qualitative approach to the range of
application of different treatment technologies
(concentration of contaminant versus flow rate to be
treated) is provided in Figure 8.10.
The technologies discussed below may be considered
the main competitors of aqueous-phase solar
detoxification for the treatment of hazardous water
contaminants. As only non-biodegradable contaminants
are considered here, bio- logical treatment technologies
are not discussed.
8.5.1. Thermal oxidation
Most of the thermal oxidation technologies (also known as
‘thermal incineration’) are used to destroy hazardous wastes
at high temperatures (normally higher than 650 °C). At such
temperatures, chemical bonds are effectively broken and
transformed into other more benign substances. There are
different technologies (rotary kilns, infrared furnaces, con-
ventional incinerators and so on), but almost all of them are
variations of the same process. Incineration is typically a
two-step process in which a primary combustion chamber
burns the waste material at temperatures of about 1,000 °C
and the exhaust gases containing desorbed oxidized or par-
tially oxidized organic contaminants are transferred to the
secondary combustion chamber (afterburner) where these
gases are burned to produce carbon dioxide, carbon monox-
ide, inorganic acids and water. Afterburners generally oper-
ate at about 1,200 °C and residence times in both
chambers
depend on the contaminants to be destroyed. Natural gas
or propane is the usual energy source. Electricity can also
be used in the primary chamber, as in infrared furnaces.
Incineration is the most frequently used treatment for
highly concentrated wastes or contaminated soil. The
standard per- formance requirement is 99.9999 per cent
(required by law in many countries).
Incineration is a source of debate, with opposition to
the construction of new incinerators coming from the
local pop- ulations because of the increasing perception
that they cause health and safety problems. Incineration
is also an energy- intensive process subject to stream size
and concentration constraints, with significant capital
equipment and operating costs. As a consequence, it is
expensive compared to other treatment processes.
Typical operating costs are also high, in the range of
€200 to €1,000 per ton, depending on the nature of the
contaminants and the facility utilization factor. Fuel is
the primary factor affecting operating cost.
The advantages of incineration are that the volume of
waste is greatly reduced, often by as much as 90 per cent.
Furthermore, the resulting ash is generally more stable
and less likely to leach into groundwater than the parent
com- pounds. On the other hand, poor combustion during
incin- eration often produces by-products that are at least
as toxic as the parent material. Metals such as lead,
mercury, and chromium could be released into the air.
The burning of some plastics can produce hydrogen
chloride, which becomes hydrochloric acid rain if
combined with the mois- ture in air. Benzene,
chloroform, and TCE have frequently been found in stack
emissions. Finally, generation of organic compounds and
dioxins as a consequence of incomplete destruction has
always been a concern.

2,000
8.5.2. Catalytic oxidation
WAO & incineration recovery
1,000 Incineration
Wet advanced oxidation (WAO)
Chemical oxidation Catalytic oxidation (also known as ‘catalytic incineration’) is
WAO & biological
Advanced oxidation processes very similar to thermal oxidation. Contaminants are pre-
TOC (mg L)
-1

Biological
100 heated, mixed, and combusted at high temperatures to
form carbon dioxide and water. The main difference is the
presence of a catalyst inside the combustion unit that
10 Ozone reduces the acti- vating energy necessary for combustion.
Solar detoxification
H2 O2
Therefore, combus- tion occurs at a lower temperature
Biological than for thermal oxidation and, as a result, fuel costs for
1 catalytic oxidation are usually lower than for an
0 10 20 30 40 50 60 70 80
3 –1 equivalent thermal oxidation system.
Flow rate (m h )
Catalytic materials, such as platinum or palladium,
FIGURE 8.10. Technology fit map: range of application of and metal oxides such as chrome-alumina or cobalt oxide
different water treatment technologies. are

introduced into the combustion unit in either a
monolithic or beaded configuration. The average catalyst
lifetime is nor- mally from two to five years, after which
deactivation by inhibitors, blinding by external particles
and thermal ageing, render it ineffective.
The most relevant characteristics of catalytic in
compari- son with thermal oxidation systems are the
following:
• Not every organic contaminant may be treated by
catalytic oxidation systems, which are not effective
for streams containing lead, arsenic, phosphorus,
bismuth, antimony, mercury, iron oxide, tin, zinc or
other catalyst deactivators.
• Catalytic oxidation systems are usually applied to
low concentration streams, since high concentrations
may be associated with high heat content that can
generate enough heat from combustion to deactivate
the catalyst.
• Associated with the above-mentioned characteristics,
air is usually not required for the combustion process.
• Temperature and pressure through the catalyst bed
should be monitored to preserve catalyst activity.
Catalytic oxidation systems normally operate at
tempera- tures between 250 °C and 500 °C, since
excessive heat can deactivate most catalysts.
• Catalyst poisoning from metals or halogens and/or
bind- ing from particulate matter over time can
decrease destruction efficiency. Periodic catalyst
replacement or reactivation is then required.
Catalytic incinerators have a higher initial cost than
thermal incinerators, but their lower fuel costs and
thereby lower operating cost offset this.
8.5.3. Air stripping
Air stripping is a liquid-to-gas transfer process whereby
pol- luted water is sprayed into the air, allowing volatile
organics to escape. It is also widely used for
contaminated soil con- taining VOCs. The basic principle
of air-stripping technology is the process of mass transfer
of diffusion and volatilization. The natural tendency of
any organic compound to volatilize from the aqueous to
gaseous phase is given by Henry’s Law, which gives the
partial pressure pA produced by a com- pound of
concentration cA dissolved in a liquid solvent.
pA  HcA (8.28)
Economic Assessment 143
The Henry’s Law Constant H can then be expressed as
a dimensionless ratio of a compound’s concentration in
air to its concentration in water. The application of Henry’s
Law Constant makes it possible to assess the maximum
efficiency of an air-stripping system theoretically
possible under ideal conditions. A compound with high
H values is more likely to be removed from water and
soil by air-stripping. Normally, compounds with an H
over 0.001 can be removed effectively.
H is over 0.01 for many organic compounds, which is
the reason the air-stripping process is so widely used.
Conventional air-stripping treatments of hazardous
organic compounds in water are based on packed or tray
columns in which water and air usually flow downward
and upward respectively, with a very high contact area
between the two phases (spray chambers, venturi
scrubbers, plate or tray towers, packed towers and so
on). The technology has been applied to a wide range of
organic compounds with varying degrees of
effectiveness at contaminant concentrations between
250 and 10,000 mg L –1. The initial investment in air
stripping may be considered medium and operating costs
are low.
The main environmental objection to air stripping is
the undeniable fact that it does not really destroy
hazardous compounds, but simply transfers them to
another medium, as the organic compounds stripped
from water are released directly into the atmosphere.
Tighter restrictions on emis- sions from air strippers are
limiting their applicability and increasing their cost, as
secondary air-phase treatment systems (that is, real
treatment processes) are required afterward.
8.5.4. Adsorption
Adsorption of organic compounds on a solid adsorbent is
a widely used technique for treating hazardous organic
com- pounds in water. The water is forced through tanks
contain- ing activated carbon and contaminants are
retained by weak intermolecular forces. Many organic
and some inorganic compounds are efficiently removed,
including chlorinated hydrocarbons, organic phosphorus,
carbonate-based pesti- cides, polychlorinated biphenyls
(PCB) and trace metals. Carbon, derived from wood,
coal, or other carbonaceous raw materials, is the most
commonly used adsorbent. Other adsorbents include
silica gel, alumina and zeolite. For carbon
adsorption, the organic compounds are transferred to a
144 Solar Detoxification
carbon canister that must be later transported for disposal
or regeneration.
Three types of carbon adsorbents are common: activated
granules, activated powders and fibres. Granular activated
carbon (GAC) is currently the most common type of carbon
adsorbent because of the significant surface area provided
by the granules. Powdered activated adsorbents are
generally cheaper. They are of lower quality than granular
activated carbon and they cannot be regenerated. They are
used in packed columns with high-pressure drops. Powder
coatings are used exclusively in batch operations. Carbon
fibres are used in a honeycomb structure to maximize
surface area with adsorption directly on the fibre’s surface.
Carbon regeneration and the recovery and disposal
of contaminants are the primary factors in the operating
cost. Periodical regeneration in which the carbon is
cleaned and reactivated, restoring its capacity for
adsorption and further use, is necessary. A thermal
regeneration process fuelled by electricity, natural gas or
oil is the most commonly used. The adsorbed materials
are pyrolyzed, forced off, and finally oxidized at over
90 °C.
As with air stripping, the main objection to adsorption
by GACs is that they only displace contamination to a
large sor- bent phase, and a regeneration or disposal
problem remains as the contaminants are not really
treated. The use of active carbon adsorption is also
feasible only as long as current leg- islation allows
storage of this type of waste. In the European Union,
regulations on waste generation are becoming stricter.
The common practice of using carbon only once is
expensive and polluting because the used carbon is
usually destroyed by open burning. Carbon regeneration
by indirect firing is feasible only for about four cycles,
after which the carbon must be destroyed. Furthermore,
each time it is regenerated, only about 50 per cent of the
carbon is reused. The remainder is too fine and restricts
the flow in filtration units. Often, the regenerated carbon
also loses some of its activity and is not as efficient as
when new. Finally, increas- ing transportation and
carbon regeneration costs are reduc- ing its cost
effectiveness. Consequently, GAC processes are
expensive to operate and generate undesirable
secondary waste gases, and changing environmental
regulations indi- cate that open burning of these
materials may be prohibited in the near future.
GAC is a mature technology with small initial
investment and moderate operating costs, so significant
cost reduction is not anticipated. Sensitivity studies have
shown how costs are
likely to be affected by different contaminants,
concentration and plant size. These studies indicate that
cost does not increase linearly with concentration, but
much more slowly, because as concentration increases
contaminant loads of car- bon also increases. Therefore,
GAC processing costs are lower in large plants as a
result of the economies of scale.
8.5.5. Membrane technology
Membrane technology refers to the use of a semi-
permeable membrane to separate contaminants from a
wastewater stream; this separation technique is often
used to purify materials or to pre-concentrate waste
streams prior to treat- ment, so it is not a real treatment
technology. A waste stream (typically aqueous) is passed
across a porous membrane, where diffusion of specific
species takes place, separating and concentrating species
of interest. The membrane is a composite of a polyamide
barrier on a polysulfone support, which normally rejects
organic molecules with a high molec- ular weight.
The main membrane processes are reverse osmosis,
ultra- filtration and microfiltration, all of which are
pressurized. Ionic exchange by resins can also be
considered a membrane process. Nevertheless, the most
common process is reverse osmosis, which has been used
for years to treat and purify drinking water. Polluted
water is forced through semi- permeable membranes
(about 150 micrometers thick) under pressures as high as
100 bars, separating contaminants from the clean water.
Membranes (normally ceramic or polymeric) are
manufactured in different configurations such as plate-and-
frame, spiral-wound, tubular, capillary tube and hollow
fibre.
Many types of organic compounds can be
separated by membranes, including salts and
chlorinated and organophosphoric pesticides. Reverse
osmosis requires peri- odic cleaning and rejuvenation of
filters. Residues that con- tain high concentrations of
salts, heavy metals and toxins must be disposed of
either in landfills or by incineration. Additionally,
reverse osmosis is an especially intensive energy
consumer, because of the high hydraulic pressures
needed to offset osmotic pressure, which require
substantial pumping power. Depending on membrane
porosity and the nature of water contaminants, 2.5 to 5
kWh are needed per cubic meter of water treated. As a
result, the major draw- backs of the membrane
technology are its relatively high cost for large-scale
applications and the fact, again, that it is not a real
treatment process but only a separation technology.

8.5.6. Wet oxidation
Wet oxidation, by which organic and inorganic
compounds present in water (or any other liquid) are
oxidized with oxy- gen or air in the presence of water,
has been commercially available since the 1970s
(Zimpro Passavant Environmental Systems, Inc.). This
process is normally used with water con- taining 1 per
cent to 30 per cent hazardous organic matter (that is, 10
to 300 g L–1) and treatment conditions vary from 180 °C
at 20 bars to 400 °C at 280 bars. During the process,
water favours the dissolution of oxygen and heat transfer
to the compounds to be treated.
When treatment conditions are below the critical
point of water, 374 °C and 225 bars, reactions take place
in the water and the process is denominated ‘subcritical wet
oxidation’ or ‘low pressure wet oxidation’; otherwise, it is
called ‘supercrit- ical wet oxidation’. Low-pressure wet
oxidation achieves 99 per cent efficiency in the
destruction of contaminants with residence times of
around one hour; supercritical wet oxida- tion can
achieve 100 per cent efficiency with a residence time of
five minutes, but higher temperatures and pressures are
required. The main disadvantage of wet oxidation
systems is their very high installation and operating costs.
8.5.7. Ozone oxidation
Ozone (O3), used as an oxidizing agent since the
beginning of the twentieth century, is considered an
effective treatment process. Despite some controversial
reports, ozone is not known to produce toxic or
mutagenic substances. It can be generated by a high
voltage discharge in the presence of oxygen. After
generation it must immediately be diluted in the water to
be treated, as it is a very unstable gas. This means that
ozone must be generated at the point of treatment.
Ozone treatment has become very common in recent
years thanks to improvement in ozone generators, and
the technology is quickly replacing many traditional
oxidation processes based on chlorine, hydrogen
peroxide, perman- ganate and so on. Ozone is used to
oxidize low concentrations of organic contaminants as
well as inorganic compounds and water-soluble metals,
converting them to their insoluble form to permit
separation of metallic ions (for instance, Fe++ and
Mn++). Another important application of ozone is
disinfection.
Ozone treatment is reported to be more effective for
haz- ardous organic contaminants when used in
combination
Economic Assessment 145
with UV oxidation, similar to the synergistic effect that
can be observed between UV radiation and an oxidizer
such as hydrogen peroxide in wastewater treatment. This
treatment process can be used selectively and reportedly
acts on chlo- rinated hydrocarbons faster than on other
organic com- pounds. Halogenated organic compounds
are oxidized to simpler organic forms and, in some cases,
to carbon diox- ide, water and innocuous salts. The
combined UV-ozone system has also been observed to
precipitate heavy metals, such as oxides or metals,
although UV oxidation is not usu- ally used to remove
metals. The concentration of inorganic chemicals in
wastewater must be low so as not to absorb or shield the
UV rays. Investment costs of ozone technology are
medium, its operating cost being in the range of €5 to
€15/m3.
8.5.8. Advanced oxidation processes
In addition to all the conventional technologies indicated
above, a new type of treatment, commonly referred as
‘advanced oxidation processes’ (AOPs), is emerging. AOPs
are increasingly being considered as alternatives to
more conventional technologies because they destroy
hazardous organic compounds rather than transferring
them to other media. They also have a potentially lower
cost and greater effectiveness. AOPs are generally
characterized by their abil- ity to generate hydroxyl
radicals, some examples being UV/hydrogen peroxide,
UV/ozone, UV photocatalytic oxida- tion and solar
detoxification.
Solar detoxification has some unique advantages over
other AOPs, such as:
• The use of sunlight as the photon source, which
means it is a ‘green’ technology.
• The process can be either heterogeneous (TiO 2) or
homo- geneous (Photo-Fenton), with the possibility of
providing chemical pathways and surface interactions
not available in other treatment systems.
• A reductive chemical pathway is used to remove
reducible species, such as heavy metal ions and some
organic compounds.
• It can be operated in the liquid or gas phase, in
contrast to processes using ozone or hydrogen
peroxide, which are generally applied only in the
liquid phase.
Solar detoxification is a modular technology offering the
advantage of system flexibility, which is important when
146 Solar Detoxification

treating low to moderate flow rates. However, this community acceptance and absence of undesirable by-
same attribute decreases the possibilities for the products are commonly considered carefully in addition
economies of scale that other pollution control to cost. It is expected that, because it is so attractive in
technologies benefit from. Thus, while the cost of solar these areas, the solar detoxification system should be
detoxification remains relatively con- stant as flow rate able to build a significant market share in the near future.
increases, the normalized costs for other technologies
usually drop.
From the economic perspective, to date, solar Summary
detoxifica- tion cost estimates have been based on very
limited field expe-
rience. However, this experience and projections of capital
and operating costs show that solar photocatalytic
treatment of water could cost from a few euros up to €20 As photocatalytic processes only make sense for hazardous
or €30 per m3. This cost is higher than air stripping, non-biodegradable pollutants and, when feasible, biological
adsorption or membrane technologies, but with the treatment of residual water is always the cheapest, it makes
important advantage that solar detoxification is a real economic sense to combine the two processes. Biologically
treatment process, while the others are only contaminant recalcitrant compounds can be treated with photocatalytic
separation technologies. There is also a pos- sibility of technologies until biodegradability is achieved, transferring
optimizing the cost of a specific treatment process by the water to a conventional biological plant later. Such a
combining two (or more) different technologies; Figure combination, based on the average oxidation state parame-
8.11 shows the combination of solar detoxification and ter, could reduce treatment time and optimize the overall
GAC for removal of pentachlorophenol (PCP). economics. Operation and investment costs of solar
In addition, the investment and operating costs of detoxifi- cation plants are estimated to be lower than
solar detoxification are lower than for technologies such alternative tech- nologies such as incineration or wet
as incin- eration or wet oxidation, while other AOP oxidation, in the same range as ozone, and higher than air
technologies have similar investment and operating stripping, adsorption or membrane separation technologies.
costs. The latter, however, are not real treatment technologies.
It is unclear at present how much of the hazardous- Solar collecting of UV pho- tons is clearly feasible at
waste treatment market could be captured by solar locations where yearly average solar UV irradiation is
–2, which means almost the entire ‘Sun
detoxification technology, but potentially it is very large. higher than 15 W m
Environmental remediation field studies have belt’.
demonstrated that technology selection is clearly not
based on cost alone. Factors such as complete on-site
treatment (which limits owner liability), Bibliography
BECHTEL CORPORATION. 1991. CONCEPTUAL Design of A
PHOTOCATALYTIC WASTEWATER TREATMENT PLANT. Sandia
Photocatalysis National Laboratory Report. SAND91-7005,
Albuquerque, N.M.

BLANCO, J. AND MALATO, S. 1994. Photocatalitic treatment of

Costs

hazardous wastewater; cost comparison between solar

GAC and electrical technologies. In: A. Roy and W. Grasse
(eds), INTERNATIONAL Conference on COMPARATIVE Assessments
of SOLAR Power Technologies. Jerusalem, Israel, pp. 217–30.

Photocatalysis + GAC BLANCO, J. AND MALATO, S. 1996. TECNOLOGÍA de FOTOCATÁLISIS

% Eliminated PCP
FIGURE 8.11. Optimization of solar detoxification and
GAC technologies to PCP degradation.
SOLAR. Almeria, Instituto de Estudios Almerienses and
CIEMAT (eds), SolarPACES (International Energy
Agency).

KENNETH, M.E.; GEE, R.; WICKHAM, D.T.; LAFLOON, L.A.
AND WRIGHT, J.D. 1991. Design AND FABRICATION of Prototype
SOLAR RECEIVER/REACTORS for the SOLAR DETOXIFICATION of
CONTAMINATED WATER. Industrial Solar Technology
Corporation. NREL report, Golden, Colo.
MALATO, S.; BLANCO, J.; RICHTER, C.; BRAUN, B. AND
MALDONADO, M.I. 1998. Enhancement of the rate of solar
photocatalytic mineralization of organic pollutant by
inorganic oxidizing species. Applied CATALYSIS B:
ENVIRONMENTAL, Vol. 17, pp. 347–56.
MEHOS, M.; WILLIAMS, T. AND TURCHI, C.S. 1994.
Overview
of SOLAR DETOXIFICATION Activities in the United STATES,
NREL/TP-471-7262. Golden, Colo., National
Renewable Energy Laboratory.
NEPCCO ENVIRONMENTAL SYSTEMS. 1997. GAS PHASE
PHOTOCATALYTIC OXIDATION REMEDIATION AND Process Pollution
MARKET Study. Final Report for NREL., Golden, Colo.
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O’BRIEN & GERE ENGINEERS, INC. 1995. INNOVATIVE Engineering
Technologies for HAZARDOUS WASTE REMEDIATION. New York,
International Thomson Publishing.
PULGARIN, C.; INVERNIZZI, M.; PARRA, S.; SARRIA, V.;
POLANIA, R. AND PÉRINGER, P. 1999. Strategy for the
coupling of photochemical and biological flow
reactors useful in mineralization of biorecalcitrant
industrial pollutants. CATALYSIS TODAY, No. 54, pp.
341–52.
RUPPERT, G. AND BAUER, R. 1994. UV-O3, UV-H2O2, UV-TiO2
and the Photo-Fenton reaction-comparison of advanced
oxidation processes for wastewater treatment.
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148 Solar Detoxification
Self-assessment questions
Part A: True or false?
1. The average oxidation state of any organic
compound is a number between 0 and +4.
2. When contaminated water is treated by oxidation,
its average oxidation state increases.
3. If toxicity increases with oxidation, biodegradability
will not be achieved.
4. If toxicity decreases during photocatalytic
treatment, biodegradability increases.
5. The solar UV irradiation available for a specific
location is the main factor in determining the cost of a
solar system.
6. The threshold below which electrical systems are
cheaper than solar ones decreases when the total
yearly amount of photons needed increases.
7. The air mass ratio is equal to 1 at solar noon at
any latitude.
8. Standard required performance for thermal
oxidation technologies is 99.9999 per cent.
9. Catalytic oxidation processes usually require
higher temperatures than non-catalytic oxidation
processes.
10. Ozone oxidation can normally be applied to
high concentrations of organic contaminants.
Part B
1. Operating 2,800 hours per year, a 300-m2 solar
detoxification plant treats 5,000 m 3 of water
containing 250 mg L–1 of hazardous contaminants
yearly. If, once 50 per cent of TOC degradation has
been attained, the wastewater is biodegradable and it
is transferred to a biological treatment plant, what
would be the mass and
volumetric treatment factors of the photocatalytic facility?
2. Why may toxicity of wastewater increase at
the beginning of photocatalytic treatment?
3. What are the main factors in the operating cost of a
solar detoxification treatment plant?
4. What is the fixed charge rate? How can it be calculated?
5. What is the standard average efficiency of UV
photon production of mercury fluorescent lamps?
6. A solar TiO2 detoxification facility can treat 3,500
m3 of contaminated water yearly with an average
global solar irradiation of 20 W m 2. How much water
could be treated at a different location with an average
solar irradiation of 25 W m2?
7. How many mercury fluorescent lamps (40 W
tube) would be equivalent to a 350-m2 solar
collector field working 3,500 hours per year where
average solar UV irradiation is 26 W m2?
8. What are the main differences between catalytic
and non-catalytic thermal oxidation?
9. What is the main environmental objection to
using air-stripping, absorption and membrane
technologies to treat hazardous wastewater?
10. When is an oxidation process defined as supercritical?
 Economic Assessment 149

Answers 5. 20 per cent.

6. As solar irradiation is proportional to the

Part A amount of useful photons and this is linearly
dependent on the reaction rate:
1) False. 2) True. 3) False. 4) True. 5) True. 6)
25
True. V  3,500  4,375
7) False. 8) True. 9) False. 10) False. m3
20
Part B
7. Using Eq. 8.19:
1. Using Eqs 8.1 and 8.2:
 IUVg 
∆m(TOC) (250  5,000) 2 g N  5.8  1021   HS 


  

 

Tfm    0.74 L
PH   HL 
tS 2,800  hm2
 
300
26
 S  5.8  10 21 3,500
350
∆V 5,000,000 L 1.35  1019  8,760
3,600
Tfv    5.9  434 lamps
tS 2,800  300 hm2

The total mass of organic substances is divided in
two, as only 50 per cent is really degraded, but not the
total volume, which may be considered to be completely
treated.
2. Due to the presence of not only the initial
toxic compounds but also the many by-
products of the degradation reaction at the
beginning of the process.
3. Costs of personnel, maintenance materials,
electricity and chemicals.
8. Catalytic oxidation a) does not treat every organic
contaminant; b) is typically applied to low
concentrations;
c) does not usually require air for combustion; d) requires
monitoring of temperature and pressure to preserve
catalyst activity; e) requires periodic replacement or
reactivation of the catalyst.
9. The air-stripping, absorption and membrane
technologies only transfer the contaminants to a different,
more easily managed, medium. They cannot be considered
real hazardous-wastewater treatment technologies.

4. FCR is the factor that converts total installed cost (or
total plant investment) into annual treatment cost,
considering the volume of wastewater to be treated. FCR
is obtained by calculating all the fixed costs (except
operation) for the life of the plant.
10. When it takes place at temperatures and pressures
higher than the critical point of water (225 bars and 374
°C). If a fluid other than water is used, these
conditions are defined by the specific critical point of
the working fluid.

150 Solar Detoxification
Project Engineering
Aims
This chapter describes the systematic
process of feasibility study, preliminary
design, final design and construction of a
solar detoxification plant, using the
knowledge explained in the previous
chapters. Some important aspects of
project management are also indicated.
9
CHAPTER 9
Objectives
After completing this chapter, you will
have a basic knowledge of the following
subjects:
1. Feasibility studies for solar
detoxification applications.
2. Initial pre-design of an
engineering system.
3. Implementation and management of
solar detoxification projects.
152 Solar Detoxification

NOTATION AND UNITS

Symbol Description Units
CIEMAT Centro de investigaciones energéticas, medioambientales y tecnológicas (Spain)
COD Chemical oxygen demand mg L–1
CPC Compound parabolic collector
DG-XII Directorate General XII of European commission
EC European Commission
EUV,n Accumulated UV energy incident on the reactor, since the start of the degradation
process up to tn , per unit of volume k J L–1
GAC Granulated active carbon
Hs Total yearly hours of operation of a solar detoxification system h
LLNL Lawrence Livermore National Laboratory (USA)
mM Mili molar 10–3 moles L–1
PLC Programmable logic controller
ppm Parts per million (equivalent to mg l–1)
PSA Plataforma Solar de Almería
Re Reynolds number dimensionless
S Solar collector field area m2
T Experimentation time min
Tfm Mass treatment factor g h–1 m–2
Tfv Volumetric treatment factor L h–1 m–2
TOC Total organic carbon mg L–1
tR Residence time min/h
tT Total elapsed time (since beginning of photocatalytic process) min
UVG Global ultraviolet solar irradiation WUV m–2
UVG, Average incident radiation on the collector surface for each At interval (At = t – t ) W m–2
n n n–1 UV
n
VR Illuminated reactor volume L
VT Total volume of hydraulic circuit L
VTOT Total solar detoxification plant volume L

9.1. Feasibility study
Solar detoxification projects, just as any other
engineering project, must follow the logical sequence of
pre-design, pre- liminary design and final design with the
final objective of designing and building facilities of
feasible construction and satisfactory operation, for
which contractors can confidently make bids. Without
competent design, implementation and operation, no
engineering project can succeed.
The pre-design phase must define the scientific and
engi- neering data required before the final design can
proceed. In solar detoxification projects the pre-design
phase might be
more properly called a ‘feasibility study’, as any new potential
application of solar detoxification must be tested before
going ahead with the design and implementation of the
treatment plant. When complex mixtures of hazardous
contaminants are present, degradation pathways and
reaction kinetics could be very different even from those of
other wastewaters of a simi- lar origin. This means that the
design of a specific solar detox- ification system is a
complex procedure requiring a prior feasibility study
following the method defined below:
• identify targeted recalcitrant hazardous compounds
• identify any pre-treatment that could enhance photo-
catalytic efficiency

FIGURE 9.1. Experimental mobile pilot plant for solar
water detoxification (CIEMAT, Spain, 1996).
• identify the best photocatalytic process (e.g. TiO2/TiO2
+
persulfate/TiO2 + other oxidant/Photo-Fenton)
• determine optimum process parameters (e.g.
catalyst concentration, additional oxygen)
• assess toxicity and biodegradability to determine the
best moment to stop the photocatalytic process
• identify possible post-treatment processes
• determine treatment factors.
All this can be done in the laboratory using indoor
reactors with simulated solar radiation, as described in
Section 3.1. Nevertheless, it is always much better to
carry out the feasi- bility study using experimental solar
devices, as the results obtained will necessarily be more
reliable when extrapolated to the engineering level.
Section 3.2 describes several exper- imental solar
systems.
9.1.1. Identification of target recalcitrant
hazardous compounds
The first step must be a complete analysis of the
wastewater to be treated in order to identify the target
chemicals and their initial and desired final
concentrations. This is very important to avoid
inadequate data in the following phases of the project.
Also, depending on the specific application, the nature of
the contaminants and/or their concentration may change
before the system is actually constructed, as the time
between the study and its implementation could take
months or even years. As some differences normally
arise when laboratory experiments are compared with
Project Engineering 153
engineering-scale pilot plant tests, at a later stage of the
project, it is important to know whether the differences
are a consequence of the reactor and system
configurations or of variations in the wastewater.
9.1.2. Identification of possible
pre-treatments
The objective of pre-treatment, if necessary, is to
condition contaminated waters for organic
destruction. This can be achieved by addressing any
constituents of the contaminated water that interfere
with the process. The presence of initial impurities in
the wastewater to be treated could produce a
significant reduction in process efficiency because of:
• unexpected chemical reactions due to the presence
of specific compounds
• incomplete destruction of one or several components
• presence of substances that inactivate the catalyst
• presence of substances that reduce the oxidation kinetics
• presence of substances that block UV solar radiation.
These possible impurities, mainly inorganic ions, could
even lead to the non-viability of the degradation process.
The only way to avoid this is by designing some form of
pre-treatment to adjust the chemistry of the water to
conditions suitable for the detoxification process. It
should be noted that such pre-treatment increases capital
and system operating costs and may also affect the control
strategy of the treatment plant.
Examples of pre-treatment are the following:
• Filtering, in the case of turbidity or cloudy water that
could block incoming solar UV-irradiation.
• Acidification, to eliminate substances such as bi-
carbonate.
• Adjustment of pH to reduce the concentration of total
dissolved solids by precipitation.
• Addition of hydrogen peroxide to precipitate
substances such as dissolved iron ions that react to
form a ferric oxide precipitate, which may then be
removed by filtering.
• Cation bed exchange, in the case of impurities such as
calcium ions that would adversely affect the process.
In the end, the specific impurities for each case must be
iden- tified and, depending on their effect on the
overall photo- catalytic process, a particular pre-
treatment should be designed if necessary. Other pre-
treatments are independent
154 Solar Detoxification

of the presence of impurities. This is the case for oxygen, which came from an ultrafiltration process, leaving no inor-
hydrogen peroxide, persulfate or any other oxidant ganic impurities present; thus the homogeneous process
injected into the process stream before the start of the works quite well. By contrast, heterogeneous degradation
photocatalytic process to act as hole receptors on the does not work because of the high presence of organic matter.
titanium dioxide cata- lyst. In many cases reduction of In other cases, the Photo-Fenton Fe cycle may be
initial pH to between 5 and 6 is also recommended to affected by the presence of impurities that produce the
enhance the initial degradation rate. opposite result. In the case of Photo-Fenton, pH must
also be around
9.1.3. Identification of most suitable 2.5 to avoid the formation of non-soluble iron
photocatalytic process hydroxides. It is clear that this first research step is
absolutely necessary in order to decide on the most
appropriate process for further in-depth study.
With regard to solar photocatalysis, when complex
mixtures of organic contaminants are present, no general
indication can be given at all and each case is completely 9.1.4. Determination of the optimum
different from process parameters
every other. It is therefore recommended that different pho-
tocatalytic processes be tested in the beginning to identify
the one that is the most adequate. Until both This phase seeks the definition of the essential scientific and
heterogeneous TiO2 photocatalysis and homogeneous engineering data required before proceeding with system
Photo-Fenton processes have been extensively analysed, design. This can be done by defining, implementing and
no advantage can be ascribed to any particular conducting an experimental plant to determine the
application. following parameters:
A good example is shown in Figure 9.2, where the • catalyst load
Photo- Fenton photocatalytic process is seen to be highly
efficient in degrading about 6,000 mg L–1 of initial TOC, • pH required
compared to the relative inefficiency of TiO2 • oxygen
heterogeneous photocatalysis. The reason for this is the • additional oxidant load, if any
wastewater, taken from a cat- aphoretic painting process • contaminant concentration, if this can be varied.
at an automobile assembly plant,

Pure wastewater
20,000 100

COD
16,000 80
–1
H2O2 consumption (mg L )
COD and TOC (mg L )
–1

TOC Photo-Fenton
12,000 COD Photo-Fenton 60
TOC Titanium dioxide
COD Titanium dioxide
H2O2 consumption (Photo-Fenton)
8,000 40
TOC

4,000 20

0 0
0 100 200 300 400 500 600 700 800
Residence time (min)

FIGURE 9.2. Treating wastewater from the painting section at a car assembly factory (ultrafiltration from cataphoresis
process). (CIEMAT, Spain, 1999).

FIGURE 9.3. Catalyst mixing system for the LLNL water
treatment system. (Courtesy of the US National Renewable
Energy Laboratory).
It will also assess the photocatalytic degradation process
over time:
• total organic carbon of the wastewater
• individual concentration of key hazardous compounds
identified during the first step (Section 9.1.1)
• toxicity
• average oxidation state.
It might also be strongly advisable to individually test the
pho- tocatalytic degradation of the key recalcitrant
contaminants identified in order to check whether there
are significant dif- ferences from those obtained with the
real wastewater prob- lem. Reaction rates are normally
higher when individual compounds are tested, but if
there are significant differences, it might be worthwhile
repeating the pre-treatment process to try and identify
possible additional pre-treatments that could speed up the
detoxification process. Obviously, potential gains in
overall reaction rate must always be weighed against
the cost of adding additional processes and reagents.
The disappearance of hazardous contaminants must
nor- mally be parallel to the reduction of toxicity and the
increase in biodegradability. These and the evolution of
the average oxidation state would determine the optimum
point at which to stop the oxidative process and transfer
the wastewater to a conventional biological treatment
plant (see Section 8.1).
Project Engineering 155
9.1.5. Post-treatment process
identification
Post-treatment processes adjust the water chemistry to
conditions suitable for discharge. In the case of industrial
wastewater that is to undergo further, biological
treatment, post-treatment may be reduced to:
• pH adjustment
• catalyst separation/precipitation and recovery.
Depending on the nature of the wastewater treated and
its later use, and whether solar detoxification is used for
water purification (as in groundwater
decontamination), the post- treatment system could
then require additional processes to meet the specific
local regulatory requirements before discharging
water. As an example, possible treatment processes
are:
• carbon dioxide removal
• elimination of possible residual hydrogen
peroxide (if used in the photocatalytic process)
• using a cation-exchange bed to remove specific
existing inorganic compounds
• using GAC filters to remove trace quantities of
organic materials.
Another possible factor that could require post-
treatment is the water temperature. Temperature has a
negligible influence on the photocatalytic process and
the use of non- concentrating solar technology
considerably reduces the increase in water temperature
during the treatment process. However, the usual
recirculation or batch system design may cause the water
to become too hot for the process in summer, volatilizing
compounds with low boiling points, or too hot for the
system, as in the case of a cation exchanger at the inlet of a
post-treatment system; as this limits the inlet tempera-
ture, a water-to-air heat exchanger must be installed
before the post-treatment system, or inserted in the water
circuit in the solar collector field.
9.1.6. Determination of treatment factors
After all the above factors have been analysed and the
steps indicated have been systematically followed, a
feasibility study to calculate the treatment factors for the
best system configuration proposed may be carried out.
These treatment factors – mass treatment factor (Tfm) and
volumetric
156 Solar Detoxification

treatment factor (Tfv) – have already been defined in Section
8.1 (Eqs. 8.1 and 8.2) and must be associated with the
average solar UV irradiation recorded during the tests
performed. These values will permit the necessary solar
field size to be established.
All the information assembled during the feasibility
study must be documented in a report, which may also
include any additional relevant data collected and
recommendations for future activities.
9.2. Feasibility study example
One example of a feasibility study could be the treatment
of pesticide-contaminated water from the recycling of
agro- chemical plastic containers.
9.2.1. Background
In Mediterranean countries, intensive agriculture in
green- houses has become a very important part of the
economy, especially in recent years. In southeastern
Spain, the province of Almería alone has about 25,000
hectares of such greenhouses, and intensive agriculture is
currently the most important economic activity in the
area. However, important environmental problems
associated with it have also arisen,
such as the extensive and intensive use of pesticides
(require- ments are about 200 times greater than for
conventional agri- cultural methods).
One particular problem is caused by the enormous
were consumed in the region, producing around 1.5
million empty bottles and containers with an average
volume of
1.9 L, 99 per cent of which are plastic. A small amount
of pesticide residue always remains in the used bottles
and they are therefore hazardous waste, which cannot
be handled in the same way as conventional garbage. To
date, there has been no way to dispose of these bottles
and recover them for re-use; most of them are thrown
away with the rest of the regular agricultural waste or
just dumped anywhere. In order to solve this
environmental problem, a process was designed to
recycle the high-quality plastic in these bottles into a
valuable raw material. The recycling process shreds the
plastic, which is then washed, leaving a relatively small
amount of water contaminated by a few hundred mg L–1
of total organic carbon content of persistent toxic
compounds. As the water must be re-used, those con-
taminants have to be treated and eliminated. Solar photo-
catalytic detoxification was proposed to treat the
wastewater and a feasibility study was carried out.
The experimental research was performed at the
PSA Solar Detoxification facility. Definition of the work
necessary
Nematocides (2,314)
Molluskicides (23)
Insecticides (827) Herbicides (134)
Phytoregulators (698)
Acaricides (52)
Others (55)
Fungicides (1,115)

num-
ber of empty pesticide bottles disposed of each year. FIGURE 9.4. Tonnes of pesticides used in the Almeria region
According to 1995 data, about 5,200 tonnes of pesticides (1995 data) (Source: AEPLA, Spain).
TABLE 9.1. Selected pesticides for the feasibility study assessment, CIEMAT (Spain), 1996.
Commercial name Producer Active ingredient Formula
Rufast Rhône-Poulenc Acrinatrin C26H21F6NO5
Vertimec Merck Abamectin C48H72O14
Thiodan AgrEvo Endosulfan α-β C9H6Cl6O3S
Dicorzol AgrEvo Formetanate C11H16ClN3O2
Confidor Bayer Imidacloprid C9H10ClN5O2
Match Ciba-Geigy Lufenuron C17H8Cl2F8N2O3
Tamaron 50 Bayer Methamidofos C2H8NO2PS
Vydate DuPont Oxamyl C7H13N3O3S
Scala AgrEvo Pyrimethanil C12H13N3
Previcur AgrEvo Propamocarb C9H20N2O2
 Project Engineering 157

started with research on the pesticide market in Almería good solar irradiation. Residence times (tR) were calculated
(Figure 9.4), which provided the qualitative and as:
quantitative V
R
distribution of pesticides consumed in the region. tR  tT (9.1)
From these, ten pesticides (with all the main chemical V T
families
present) were selected as representative of those most
Where tT is the total time elapsed since the beginning of
used by the greenhouses in order to carry out a complete
solar degradation test program. Table 9.1 shows the list the experiment, VR the illuminated reactor volume and
of pesti- cides used. VT the total volume of the hydraulic loop.

9.2.2. Experimentation: a) 80
Two–axis parabolic trough system
TiO2-persulfate tests –2
TiO2+ S 2O8= (10 M) TEST

TOC concentration (mg L )

–1
The test programme included individual and combined 60 Active compound: Abamectin
tests of selected compounds under different conditions.
In order to simplify the study, and the number of tests to
be carried out, the following was assumed:
40 4
• Although pesticides, which are usually sprayed in TOC evolution
con- centrations between 200 ppm and 3,000 ppm pH evolution
depending on the product, are diluted in water before

pH
20 2
their applica- tion, pesticides in wastewater from the
washing process are always more diluted than they
are in normal use.
• The ten pesticides selected are considered 0 0
representative of the entire local market (several 0.0 0.5 1.0 1.5 2.0
hundreds of such com- pounds are used in the area). Residence time (h)
• The same numbers of empty plastic containers are
gener- ated by each of the ten selected products. b) 125 125
CPC system. TOC evolution
• The same amount of residue remains in all the =
TiO2+ S 2O8 (10
–2
M) TESTS
TOC concentration (mg L )
–1

containers. 100 100

Under these hypotheses, a mixture of the ten selected

pesticides, with a total TOC content of 100 mg L–1, 75 75
was considered representative of the wastewater to be Acrinathrin
Methamidophos
found after washing. Wastewater was artificially Lufenuron
generated by mixing identical concentrations of the 50 50
selected pesti- cides and tested in solar degradation
experiments in both Helioman (Figure 7.5) and CPC
(Figure 7.6) systems. 25 25
Figure 9.5 a) shows mineralization of total organic
carbon from the insecticide abamectin in the parabolic
0 0
trough system. The TOC is found to practically 0 1 2 3
disappear after one Residence time (h)
hour of exposure to sunlight (with good weather FIGURE 9.5. a) Solar mineralization of TOC from the
conditions). Photocatalytic degradation tests performed insecticide abamectin; test performed in a parabolic
in a CPC system show a very similar pattern. Figure 9.5 trough system; average direct UV light: 38.1 watts m–2. b)
b) shows degradation of TOC from the insecticides Samples of photocatalytic degradation in CPC system;
acrinathrin, methamidophos and lufenuron (three average global UV solar radiation was: 26.2 watts m–2
different experiments on sunny days). Each one was (acrinathrin test); 33.6 watts m–2 (methamidophos) and
individually tested and similar degradation was 33.7 watts m–2 (lufenuron test). TiO2 (Degussa P25): 200
observed (see Table 9.1): degradation of about 100 ppm mg L–1. (CIEMAT, Spain, 1996).
of TOC in a residence time of from one to two hours,
with
158 Solar Detoxification

120 1.5
Mixture of ten Persulfate conc.: 10 mM (constant)
selected pesticides
TOC Persulfate conc.: 8.5 mM (constant)
100

EC50 (%) P. phosphoreum

Total organic carbon (mg L )

TOC concentration (mg L )

–1
Persulfate conc.: 5 mM (constant)
–1

EC50
Persulfate conc.: 20 mM (initial)
80 1.0

60

40 0.5
EC50

20

0 0.0
0.0 0.5 1.0 1.5 2.0
Residence time (min)
Residence time (h)
FIGURE 9.7. TOC mineralization of a mixture of ten selected
FIGURE 9.6. TOC mineralization of a mixture of ten selected
pesticides (CPCs). TiO2 (Degussa P25) concentration: 200
pesticides (parabolic troughs); direct UV sunlight: 36.3
mg L–1, slurry. (CIEMAT, Spain, 1998).
watts/m2; TiO2 (Degussa P25) concentration: 200 mg L–1;
persulfate addition: 0.01 molar; treated volume: 250 l.
EC50 toxicity measured by Microtox®. (CIEMAT,
Spain, 1996). All titanium dioxide tests were conducted in 200-mg
slurry concentrations with 5 to 10 mM persulfate, L–1
which has been found to be the optimum concentration in
However, the experiments of most practical interest PSA experiments. Na S O was added at the start of the
2 2 8
are those in which the mixture of all ten of the selected
com- pounds was used. These were performed in the tests and at regular intervals to assure continuous
CPC system presence through- out tests by measuring the S O2–
as well as in parabolic troughs, assuming the four hypotheses consumed. This addition 2 8
previously considered. For these experiments, 10 ppm of persulfate does not imply any environmental problem
of each pesticide was added to 250 L of distilled since it only produces small concentrations of sulfates
water and homogenized for thirty minutes. Samples were that increase the salinity of the water treated (maximum –1
taken period- ically and the total organic carbon in the sulfate permissible in drinking water is 250 mg L ; there
suspension was analysed; pesticide concentration was is no limit for wastewater). In the experiments indicated
monitored by liquid chromatography. Figure 9.6 in Figure 9.7, 80 per cent of the TOC was removed in a
shows some of the results obtained, which included period of two to four hours and 90 per cent in a period of
toxicity measurements throughout the experiment. As the two and a half to five hours.
complete mineralization of all organ- ics present in the
water was not intended, it should be observed that 9.2.3. Photo-Fenton tests
no highly toxic compound was generated. Microtox®
(a widely accepted toxicity measurement system) is
usually expressed in terms of the EC50, which is the Photo-Fenton experiments were also conducted to
effec- tive concentration causing a 50 per cent deter- mine the effect of the initial TOC and iron
reduction in light from a luminescent marine concentration on the degradation rate. Initial
bacterium (PHOTOBACTERIUM phosporeum), indicating that concentrations were 100 to 500 ppm of TOC and 0.25
50 per cent of the bacteria pres- ent have been killed. mM to 2 mM of iron (Fe) concen- tration. After initial
homogenization for thirty minutes, the pH was adjusted
In the case displayed in Figure 9.6, a TOC reduction
to 2.5 or 2.8 by addition of sulfuric acid. Ferrous sulfate
of 90 per cent is followed by a marked toxicity reduction
was added immediately afterwards and H 2O2 was added
(to obtain the EC50, a 40 per cent concentration of the
in portions of 10 to 20 per cent of the stoichiometry
initial sample is required, while the final concentration
(from previous COD measurements) until the experiment
required is 135 per cent).
was completed. Additional iron concentration
 Project Engineering 159

increases the degradation until a maximum rate is
reached. This occurred when iron compounds absorbed
all the irradiated photons. Figure 9.8 shows the
degradation curves for different experiments with
approximately 100 ppm of pesticides.
The field experiences showed that an increase in the
concentration of iron did not improve the degradation rate
as much as had been expected from previous laboratory
experi- ments. The poor performance of the 0.5-mM iron
test may have been caused by the high initial TOC and a
slight devia- tion in pH adjustment. Nevertheless, 80 per
cent of the initial TOC was removed in less than three
hours. With an excess of H2O2, degradation can be
improved up to 90 per cent.
One of the difficulties in both the Photo-Fenton and
TiO2-persulfate experiments that gave rise to possible
error was the measurement of the initial amount of
pesticide, because the highly viscous liquids adhered
strongly to the glass-measuring cylinder. Furthermore,
the amount of dis- tilled water to be added could not be
calculated accurately. Both of these factors caused
fluctuation in the concentration of total TOC. Since not
all the pesticide could be dissolved at once in the distilled
water, TOC increased during the first sixty minutes of
the reaction.
9.2.4. Conclusions and treatment factors

The total volume treated was the same for all the
experiments (250 L), and the CPC collector field (2 ×
60° semi-aperture angle, 1 Sun concentration and total
irradiated volume of 110 L) was formed by three
Total organic carbon (mg L )
–1

stationary modules with an overall aperture area of 9

Residence time (min)
FIGURE 9.8. Pesticide degradation by Photo-Fenton
process: comparison of different iron concentrations for
100 ppm of pesticides in wastewater (CIEMAT, Spain,
1998).
m2. Collectors were orientated to the south and tilted 37°,
which is similar to the local latitude, to obtain the
maximum yearly efficiency. With these data and the
results shown in figures 9.7 and 9.8, the mass treat- ment
factor, Tfm (Eq. 8.1), and volumetric treatment factor, Tfv
(Eq. 8.2) for both the TiO2-persulfate and Photo-
Fenton processes can be obtained. Table 9.2 shows
the results.
Treatment factors are observed to be significantly
higher with Photo-Fenton, and the last 10 per cent of
degradation cannot be achieved with this process. This
fact is an important issue in plant design at the
preliminary design stage.

TABLE 9.2. Degradation of pesticide mixture: mass treatment factor (Tfm) and volumetric treatment factor (Tfv)
obtained for TiO2-persulfate and Photo-Fenton processes, CIEMAT (Spain), 1998.

TiO2-persulfate (90% Photo-Fenton (80%

Tfm
degradation) Tfv T
degradation)
fm Tfv
Test 1 0.81 6.44 2.28 18.52
Test 2 0.59 4.69 3.88 31.45
Test 3 0.86 7.41 3.11 26.88
Test 4 0.89 7.65 2.43 22.83
Test 5 0.60 6.06 3.07 28.74
Test 6 1.18 13.89 — —
Test 7 0.93 11.26 — —
AVERAGE 0.84 8.20 2.95 25.68
160 Solar Detoxification
9.3. Preliminary design
The goal of preliminary design is to develop specific
param- eters for the siting, layout, and dimensions of the
solar detoxification facility, on the basis of the feasibility
study. The preliminary design is complete when it
provides all of the necessary basic elements for the final
design and con- struction, often considered as equivalent
to 30 to 40 per cent of the complete final design. No
additional data should have to be developed after the
completion of the preliminary design because this should
include sufficient engineering details to proceed rapidly
to the final design. This step typically formulates a
schematic process diagram and a site layout plan.
The final figures for volume of water to be treated,
hazardous contaminant and its concentration,
necessary collector surface and pre- and post-treatment
processes, must be assessed at this point. A typical list of
the data required for
the preliminary design might be the
following:
• amounts and characteristics of
wastewater
• photocatalytic process
• collector field surface and residence
time
• throughput capacity
• flow rates (maximum, minimum and mean)
• loading rates
• cleanup targets
• discharge rates
• chemicals and dosages
• horsepower
• utility requirements
• site security measures
• spill-containment and leak-detection provisions
• construction materials
• instrumentation and control
• monitoring and alarms
• operating requirements
• process diagram
• plant layout.
These data are basically no different than those required
for any other hazardous-waste remediation engineering
process. The main difference here is the need to calculate
the size of the collector field. Determination of treatment
factors gives a good idea of how the photocatalytic
process works with a specific wastewater and there are
valid figures for a feasibility study estimation. This
cannot be used as the reference
parameter for calculating the collector field area,
however, because the solar radiation, which obviously is
an essential parameter, is not included in the calculation
of the treatment factors, as Table 9.2 above (obtained
from Figures 9.7 and
9.8 in the previous example) shows.
Treatment factors, Tfm and Tfv, are based on the use of
res- idence time, tR, or the time the water has been
exposed to radiation, as the unit of calculation for
analysis. This could lead to erroneous conclusions when
there are important differences in the radiation incident
in the reactor because of clouds or time of day. One way
to avoid this problem is to use a relationship between
experimental time, plant volume, collector surface and
the radiant power density, UVG, as measured by a UV
solar radiometer. The amount of energy collected by the
reactor (per unit of volume) from the start of the
experiment until each sample is collected may then be
found by Equation 9.2:
SCPC
EUV,n = UV,n +
UVG,n
tn VTOT ;
E (9.2)
1
tn = tn  tn1
Where:
UVG,n is the average UV radiation incident on the collector
surface for each At interval;
tn is the experimental time for each sample taken to
monitor the degradation process;
SCPC is the effective solar collector surface (CPC or any
other type of collector used);
VTOT is the total plant hydraulic volume;
EUV,n is the accumulated energy (per unit of volume, kJ L–
1) incident on the reactor for each sample taken during the
degradation process.
Equation 9.2 permits any specific photocatalytic
degradation experiment to refer to the useful energy
available to the process instead of the residence time,
making a direct com- parison between different
experiments (performed on differ- ent days with different
weather conditions) possible, as well as enabling the
calculation of the size of the solar field spe- cific to the
solar conditions at the site. It must be remem- bered that
only solar irradiation up to 390 nm is useful for the TiO2
process, but for Photo-Fenton it is useful up to 580 nm.
Equation 9.3, for calculation of the total solar
collector field area, can be obtained from Equation 9.2.
HS is the yearly total of hours solar detoxification system
operation.
 Project Engineering 161

A collector area 20 to 25 per cent larger than the
theoretical figure is always recommended.
EUV VTO
S (9.3)
HS T
UVG
The feasibility study and preliminary design are basic
com-
ponents of the final design, as they must supply all the
data essential for the engineers and scientists to proceed
confi- dently with the final design. In addition, these
steps must demonstrate that the final solar
detoxification plant will accomplish the treatment
paths are plotted against the useful UV energy collected,
instead of the residence time (see Section 9.3).
With the same procedure and the data from Figure 9.8,
Figure 9.10 is obtained. In order to make possible the
direct comparison of the Photo-Fenton and TiO2
processes, the amount of UV light collected in Figure
9.10 was calculated
the same way as for TiO 2 (using data from the same
radiation sensor having a measuring range of 300 to 400
nm), even
Persulfate conc.: 10 mM
Persulfate conc.: 8.5 mM

Total organic carbon (mg L )

–1
Persulfate conc.: 5 mM
objectives before significant expenditures are made in
detailed design or implementation.

9.4. Preliminary design example

As with the example of treatment of water contaminated
by pesticides from the recycling of agrochemical plastic
contain- ers (Section 9.2), the main item in the
preliminary design is the calculation of the necessary
collector field surface, for which the following data
–1
have either been previously collected or assumed: Collected UV solar energy (kJ L )

• The annual number of empty pesticide bottles FIGURE 9.9. TOC degradation of a mixture of ten selected
generated throughout the province of Almería is 1.5 pesticides by TiO2 (Degussa P25) – persulfate process.
million. Degradation in function of UV collected energy (300 to
• The plant is to be designed to treat an initial 50 per 400 nm) (CIEMAT, Spain, 1998).
cent of this annual total of bottles (which is realistic,
taking into account their geographical distribution):
750,000 plastic bottles.
• The CPC collector technology has been selected for
the plant.
The following hypotheses have also previously been
Total organic carbon (mg L )
–1

formulated:
• Average residual TOC in an empty pesticide bottle
(from prior analysis) is about 0.7 g; if the bottle has
previously been rinsed, the quantity is 0.1 g.
• 0.5 g average residue content per bottle is used as a
con- servative estimate. This would mean a total
amount of 375 kg of pesticides (750,000 × 0.5 mg)
to be treated yearly by the solar detoxification facility. Collected UV solar energy (kJ L1)
• Average volume of the plastic bottles is 1.9 L.
• Annual total of operating hours in Almería for a FIGURE 9.10. TOC degradation of a mixture of ten
solar detoxification facility is about 3,000. selected pesticides by Photo-Fenton process and with
different iron concentrations. Degradation in function of
With Equation 9.2 (ACPC = 9 m2; VTOT = 250 L), Figure UV collected energy (300 to 400 nm). (CIEMAT, Spain,
9.7 can be transformed into Figure 9.9, where TOC 1998.)
degradation
162 Solar Detoxification

though iron compounds absorb light up to wavelengths washing or discharged through an activated carbon filter
of 580 nm. From PSA measurements (Licor-1800 to guarantee discharge quality. The water to be re-used
spectral radiometer), an average of 7.11 times more is pumped back to wash the shredded plastic until
solar energy up to 580 nm is available than from the contamina- tion reaches a TOC of 100 ppm. In this
solar spectrum up to 390 nm. closed cycle, water may be re-used about five to ten times
From the different tests carried out, the best before final discharge. With this design, about 95 per
conditions found for the titanium dioxide process are a cent of the contaminants are mineralized by solar
TiO2 catalyst concentration of 200 mg L–1 with 10 mM photocatalysis and the remaining 5 per cent would be
of persulfate addi- tion. In the case of the Photo-Fenton removed with a GAC filter.
process, iron concen- tration is 1 mM. When Figures 9.9 The size of the solar field can be calculated with the
and 9.10 are compared, it seems clear that the Photo- following design parameters:
Fenton process, although unable to achieve full
mineralization of the contaminants in the water, is more • Photo-Fenton is the photochemical degradation
energy-efficient in this case. The TiO 2- persulfate process selected.
process requires 27 kJ L–1 for 80 per cent of TOC • The initial TOC of water entering the solar
degradation or 30 kJ L–1 for the 90
U per cent mineral- detoxification facility will be 100 mg L –1, which
V includes not only the
U
ization. The Photo-Fenton process needs only the equivalent
V active ingredient, but also the rest of the components in
of 11.5 L–1 for 80 per cent disappearance of the commercial formulation.
kJUV TOC.
The most appropriate conceptual design is, therefore, • A TOC of 100 ppm is considered equivalent to about
the one shown in Figure 9.11, where the water 200 mg L–1 of contaminant concentration (from the
contaminated with the pesticide is treated in a batch ratio of average carbon weight against the average
process until 80 per cent mineralization of TOC is molecular weight of the selected pesticides).
achieved. At this point, water is transferred to the post- • The final TOC signifying water is to be removed from
treatment process (iron precipita- tion, sedimentation and the solar plant is 20 mg/L–1.
recuperation), and either re-used for
Catalyst Chemical Oxygen
oxidant (Air)
Mixer
Sun
Pre-treatment
(pH adjustment,
Pump filtering, etc)

Tank Solar UV
Industrial
Industrial TOC >
Pump light
Discharge bottle
bottles 100 ppm
(irrigation washing
washing
water) process
process
Filter
Contaminated
water
YES
Chemical reactor
NO (CPC solar
TOC < collector field)
GAC
GAC filter
filter Reutilization ??
Reutilization 20 ppm

Post-treatment Batch process

(catalyst recovering,
pH adjustment, etc.)

Washing cycle Detoxification cycle

FIGURE 9.11. Conceptual design of a solar detoxification plant for treatment and recycling of pesticide bottles (CIEMAT,
Spain).
 Project Engineering 163

Inspection
area
Lighterage quay
(empty bottles) Shredding
area
Washing
Total plant area required: area
2,000 to 3,000 square meters Hot air dried &
Bag packed area

Office Washing
Solar CPC field area
(about 140 m2 of collectors)

Lab

3
15 m

3
Micro- 15 m
filtration unit Loading berth
(final product)

South

FIGURE 9.12. Layout design of a solar detoxification plant for treatment and recycling of pesticide bottles (CIEMAT, Spain).

• The plant is designed to treat 375 kg of pesticides 9.5. Final design and project
from the plastic-bottle washing process yearly. implementation
• The total volume of water to be treated yearly is 1,875 m3
(375,000 mg/200 mg L–1). The fundamentals of the final engineering design process
• 3,000 hours of operation annually. are no different from any other treatment facility
• The average local global UV irradiation is 18.6 W project. The objective is to develop the
documentation necessary for selected contractors and
m–2. So, using equation 9.3, the collector field area vendors to proceed with construc- tion of the facility.
This phase of the project is usually associ- ated with the
will be: construction of the treatment plant through a contract
between the owner or responsible party and the
EUV VTOT engineering firm responsible for the project. Final design
S=
HS UVG and
11.5  10  1,875 
3 1
(J L )L 2 construction are normally on a turnkey basis.
103  112 m (9.4 After the feasibility study and the preliminary design
= s(Wm2 ) ) phase, the final design process might be affected by
3,000  3,600  18.6 different
factors, such as:
and the proposed size of the solar collector field (CPC)
would be 140 m2 (allowing a 25 per cent margin). With • uncertainty of key assumptions
this and the data above, the cost of the treatment facility • availability of design data
may be estimated, following the procedure indicated in • availability of competent contractors
Chapter 8. Figure 9.12 shows a proposed layout for the • project cost or size
complete facility.
Two important items in the layout in Figure 9.12, • possible restrictions imposed by local regulations
with regard to the pre- and post-treatment processes, are • owner’s acceptance of risk, due to the implementation
sludge removal before treatment of the contaminated of a new technology based on energy from the Sun,
water in the solar field and one-step iron sedimentation input which obviously cannot be controlled.
by neutralization (in batch mode), after the The last factor, project risk, must not be dismissed, as it
photocatalytic treatment. could be one of the key factors in implementing solar
detoxification
164 Solar Detoxification
technology. The possibility of clouds blocking sunlight
for a period of several days (or even weeks) could force a
similar period of plant inactivity, which could well be
incompatible with a continuous operation. To avoid this
risk, an adequate buffer system must be designed. Even
so, there is always a certain risk for the owner.
One way to mitigate this problem, should it arise,
might be to design a hybrid system combining a solar
collector and electric UV-lamp systems. Such a concept
would benefit from continuous operation, even during
prolonged periods of bad weather, because the lamp
system can be turned on when sunlight is insufficient. It
can also increase the treat- ment rate to handle occasional
peak demand. However, it requires the additional
installation of the UV-lamp system and the energy to
operate the lamps when sunlight is unavailable.
Depending on the local solar resources (see Section 8.3
for a comparison between solar and electric photon
costs), solar–electric hybrid systems may be more
expensive than solar-only systems, but they could reduce
the above-mentioned risk for solar detoxification
installations at specific locations.
Another possible problem relates to the uncertainty
of important assumptions used during the feasibility
study or the preliminary design phase. This could be
the case in the example of pesticide treatment shown
in Sections 9.2 and 9.4, where the real wastewater to
be treated may contain more than 300 possible
different compounds. As it is impos- sible to carry out a
feasibility study for all these contaminants (it was
performed with ten), a real uncertainty exists with
regard to the final design of the plant.
A possible solution to this problem is to approach the
final design and construction of the facility in a two-step
process, designing and installing a pilot plant first, with a
reduced number of solar collectors, to check and validate
the figures obtained in the feasibility and preliminary
phases. After some tests have been performed in this pilot
plant, the estimated area of solar collectors is confirmed
or modified and the plant is enlarged to its final
dimensions. Pilot-plant construction must be based on the
confidence that all installed systems are valid, with or
without slight modifications to the plans.
When the final design is complete, a detailed project
cost estimation must be prepared. This is usually based on
nor- mally accepted sources such as bids from other
recently built detoxification plants, quotes from vendors
and equipment suppliers, and construction industry cost-
estimation guides. All these possible alternatives, when
appropriate, must be reflected in detail in the contract
between the engineering
firm and the owner or responsible party. Typically, the
main contract documents are the following:
• bidding documents
• general and supplementary terms and conditions
• technical specifications
• contract drawings.
The bidding documents describe the different items of
the plant and are the basis for payment. These
documents should include additional information such as
the proposed schedule and milestones, possible
alternatives to the price, and an agreement among the
parties on the total price of the plant.
The general and supplementary terms and
conditions must contain the standard and specific clauses
of the con- struction contract. Issues such as sharing of
responsibility among the parties, payment procedures,
settlement of disputes, insurance and guarantees must
also be included. It is important to specify such issues as
training of personnel, documentation to be provided,
technology confidentiality, initial plant performance
check period and any other services required by the
contractor or engineering firm.
The technical specifications must contain the
perform- ance requirements and the criteria for facility
acceptance. Specific details of the equipment and
materials to be used in the treatment plant (depending on
the characteristics of the wastewater to be treated) should
also be included. The contract drawings should
identify the conditions of the plant location and the
possible requirements and/or restrictions for
construction. As appropriate, they may include plans,
sections and general details relevant to plant location.
The complete design and construction schedule for a
solar detoxification facility could vary considerably,
depend- ing mainly on the requirements of the feasibility
study and any possible delays in obtaining the necessary
permits. A sample schedule might be the following:
• FEASIBILITY study: two to five months.
• PRELIMINARY design: one to two months.
• Licensing: variable, depending on local regulations.
• FINAL design AND CONTRACTS: two to three months.
• Vendor selection, equipment AND SOLAR collector procurement:
four to six months.
• FACILITY erection AND INSTALLATION: about two months.
• START up, checkout AND TRAINING: one to two months.
Finally, the necessary documentation for proper
operation and maintenance of the facility must also be
supplied.
 Project Engineering 165

9.6. Example of final design

and project implementation
This section describes the design and construction of the
solar detoxification plant used in the project entitled ‘Solar
detoxification technology in the treatment of persistent non-
biodegradable chlorinated water contaminants’. The project,
partially financed by the DG-XII of European Commission,
was aimed at the treatment of wastewater containing C1 and
C2 chlorinated hydrocarbons such as methylene chloride,
trichloroethylene, tetrachloroethylene, chloroform and
methyl chloroform.
FIGURE 9.13. Laser device for manufacturing TiO2 catalyst
For this project, a specific TiO2 catalyst was developed powder. (Courtesy of ENEL SpA, Italy, 1999).
in the ENEL laboratories (Italy) by synthesizing titania
powders through an innovative process in which a
suitable reactant vapour induced by a CO 2 laser beam is
pyrolyzed. In the preliminary laboratory experiments, an
impressive 10 per cent photon efficiency was obtained
with this catalyst, when selected chlorinated solvents at
concentrations close to solu- bility were treated (Calza et
al., 1997). Real contaminated water generally contains
chlorinated solvents at similar con- centrations. Figure
9.13 shows the manufacturing process for this catalyst.
This 10 per cent photon efficiency repre- sents a
significant improvement in catalyst efficiency over
Degussa P-25 titania, attributable to both the higher
specific surface area of the laser powders and to better
crystallization
because of the thermal treatment. FIGURE 9.14. Modular CPC solar collector (Courtesy of AO
The designed solar-collector was a CPC with a SOL ENERGIAS RENOVÁVEIS Lda., Portugal, 1999).
flexible modular structure adjustable to different angles
of inclina- tion (Figure 9.14) for easy on-site assembly
the glass reactor tube was assembled was later mounted
and installation. Total dimension of solar collector CPC
in a box frame. The overall unit was installed on the
field was 100 m2. The collectors were erected based on
supporting structure on-site (see also Figure 9.19).
the following design data:
The detoxification plant was installed at the facilities of
• ACCEPTANCE ANGLE: 90° a waste management and treatment company in Madrid
• TRUNCATION ANGLE: 90° (Spain); it was designed to operate in batch mode, treating
about 2 m3 of wastewater (contaminated with non-
• INTERNAL ABSORBER RADIUS: 14.6 mm biodegradable chlorinated solvents) in approximately two to
• EXTERNAL ABSORBER RADIUS: 16.0 mm three hours, depending on the existing solar irradiation. One
• OPTICAL GAP: 1.4 mm of the first problems was the plant’s location within the fac-
• Sunlight CONCENTRATION RATIO: 1.0 tory. Aesthetic aspects related to the distribution of existing
buildings had to be taken into consideration, along with the
The CPC collectors were constructed from a galvanized need to orientate the solar facility towards the south. This is
sheet frame containing sixteen parallel, highly reflective a common problem in any solar installation in existing
anodized- aluminium reflectors with 1.5 m-long reactor build- ings since they are normally built without considering
tubes. Each tube had connectors at both ends to join it to their orientation. One possible solution to this problem is to
the previous and following the collector tubes, forming a install the solar facility on the roof. However, in this case,
complete mod- ule of collectors connected in a row. this was
Figure 9.15 shows the CPC-trough manufacturing
process. The reflector on which
166 Solar Detoxification

a)
The essential plant components designed were the
foun- dations and pits, the pumps, piping and fittings,
hydraulic system, tanks, automation and control,
electrical and mechanical installation and TiO 2 recovery
system. The basic plant parameters were:

• two parallel rows with twenty-one collectors each

b)
c)
FIGURE 9.15. a) b) and c) Manufacturing CPC reflectors.
(Courtesy of AO SOL ENERGIAS RENOVÁVEIS Lda.,
Portugal, 1999).
not possible and the plant was installed on the ground
as shown in the layout in Figure 9.16. Obviously, an
important factor that must always be avoided is
shadowing of the solar collector field by other buildings
or constructions.
• total collector (tilted 40°) aperture area: 100 m2
• total loop volume: 800 L
• total plant volume: 2,000 L
–1
• catalyst configuration: slurry (TiO 2 200 mg L )
• completely airtight environment to avoid escape of
volatile compounds into the atmosphere
• 1.5 × 1.5-m collectors with sixteen 29.2-mm-ID tubes.
The plant consisted of two parallel rows of twenty-one
col- lectors, each 31 m in length. An east–west
orientation was chosen with a small structural tilt (1 per
cent) in the same orientation to avoid the accumulation
of rainwater on the CPC troughs.
The possibility of an accident (for instance, a broken
glass reactor) or spillage of hazardous water during
treatment must always be considered. Because of this
possibility, a sump and a small sidewall to collect and
contain possible leaks were designed and constructed
(Figure 9.18).
Once the frame support has been prepared, the next step
is the installation of the solar collector (Figure. 9.19).
Collector inclination should be equal to local latitude (40
degrees North). The distance between rows was calculated
to minimize shad- owing of collectors. To this end, the
angle of sunlight at noon on 21 December (lowest
maximum Sun elevation) was used as a design parameter
to define row separation (this is recom- mended when
there is no problem of available land space).
The final system design was modular, with glass
collec- tor reactor tubes connected in series by HDPE
quick- connections. Water flows simultaneously
through all the parallel tubes and there is no limit to
the number of collector components in the modules.
Pipes are made of PVC-C and tanks are made of
polyester-resin-reinforced glass. The hydraulic circuit
was carefully designed to obtain the highest volumetric
efficiency with minimum ‘dark zones’. The different
sections of the pipes must always be carefully calculated
to guarantee similar flow rates in all the reactor tubes.
Nominal flow was turbulent (Re between 10,000 and
20,000) to avoid catalyst settlement. Water input and
output manifolds at opposite ends of the modules
connect the photoreactor array to the main feed pipe
 Project Engineering 167
20.0
1.35
5.4

0.49

4
+0.0
.4
0.49 arqueta

2
268 m +0.0
de solera

11.5
6.8 62°
17.3 (aprox)
28°
0.1
6.0

28

1.35
3.2
33.4

FIGURE 9.16. Solar detoxification plant layout. (Courtesy of ECOSYSTEM S.A., Spain, 1999).

Detoxified water + TiO2 (200 mg/L) pH adjustment

Sedimentation
tank

2 m3 2 m3 TiO2 < 5 mg/L Clean

0.1 m 3 Membrane water
0.2m
TiO2 slurry
Waste
water 0.2 m3 0.3 m3

Air In
microfiltration
TiO2 In system

21 modules per row

100 m2
800 L

FIGURE 9.17. Solar detoxification plant design, isometric drawing. (Courtesy of ECOSYSTEM S.A., Spain, 1999).
168 Solar Detoxification

a) b)

FIGURE 9.18. a) and b) Solar detoxification plant construction, showing lateral wall and pit to collect and contain any
poten- tial leaks. (Courtesy of HIDROCEN S.L., Spain, 1999).

a) b)

FIGURE 9.19. Installation of supporting structure and CPC units. (Courtesy of AO SOL ENERGIAS RENOVÁVEIS
Lda., Portugal, 1999).
(Figure 9.20). All materials in contact with the water to
be treated must be carefully selected according to the
nature of the contaminants and the required pH.
The solar detoxification facility was designed for
opera- tion in batch mode. Wastewater enters the system
from a 2-m3 wastewater storage tank as detoxified water
from the previous run leaves to the catalyst
sedimentation tank. When the system is completely filled
(0.8 m3), a pump recirculates the water through the
collectors and a small tank (0.1 m 3). The concentrated
TiO2 slurry and the air necessary for the reaction are
injected in the circuit. Once the water is detoxi- fied, the
entire volume goes to the sedimentation tank and the
system is filled with more wastewater for another batch.
Meanwhile, the detoxified water and the TiO 2 in the FIGURE 9.20. Photoreactor array input water manifold system
sedimentation tank undergo pH adjustment to provoke (Source: CIEMAT, Spain, 1999).
fast
 Project Engineering 169

a) b)

c)

FIGURE 9.21. a) Installation of the main tanks in a solar detoxification facility. From left to right: storage tank, catalyst
separa- tion tank, buffer tank. b) Installation of tank fluid-level sensors. c) Installation of catalyst separation system.
(Source: CIEMAT, Spain, 1999.)
 a)
170 Solar Detoxification
b)
FIGURE 9.22. a) and b) a) Installation and testing of the
UV- A sensor device (front left). b) Testing the PLC and
electronic equipment. (Courtesy of ECOSYSTEM S.A.,
Spain, 1999).
sedimentation of the catalyst. The concentrated catalyst
slurry is transferred from the bottom of the tank to
another smaller tank from which the catalyst enters the
photoreactor (see Figure 9.17). The supernatant is
removed through an outlet in the side almost at the
bottom of the sedimentation tank, and enters another tank
(0.3 m3), where the small frac- tion of the initial catalyst
contained in the supernatant
a)
b)
FIGURE 9.23. a) and b) Two views of the completed
solar detoxification treatment plant.
(<7 mg L–1) is removed by microfiltration with a suitable
membrane before disposal of the water. The membrane
has two outlets, one for clean water and one for the
concentrated slurry. The concentrated slurry is
recirculated through the membrane until there are several
grams of catalyst per litre. Then this is added to the TiO 2
injection tank and also re- used.
The plant was designed with full automatic
control systems and minimum operation and
maintenance require- ments. The level of water
treatment achieved is indirectly measured by
measuring sunlight availability. A solar UV-A sensor is
connected to a programmable logic controller
(PLC). Once the level of energy required for the
treatment has been achieved (pre-determined
through preliminary plant-design tests, according to
each specific contaminated wastewater to be treated),
the PLC stops the main pump, transfers the water to
the catalyst separation tank and advises the operator
that the treatment has been completed.

The PLC also receives other data signals (e.g. flow-
rate, tank levels and temperatures) needed to control the
system pumps and valves. Specifically developed
software controls all normal operating procedures and
sequences, so very little direct human intervention is
needed. Orders are introduced through a keyboard and a
printer indicates alarms and main system events.
Summary
Implementation of any solar detoxification project must
follow a three-stage sequence: feasibility study,
preliminary design and final engineering design. The
objective of the feasibility study is to assess the
practicability of the solar photocatalytic technology for
the treatment of the waste- water problem by preliminary
testing. In addition, the study must identify the
recalcitrant hazardous compounds, possible pre and post-
treatment processes, the most appro- priate
photocatalytic process and optimum process param- eters
and treatment factors. The function of the preliminary
design is to develop specific parameters for the
positioning, layout and dimensions of the solar
detoxification facility on the basis of the feasibility study
previously performed. This phase should include
sufficient engineering details to pro- ceed rapidly to the
final design, including a schematic process diagram and
a site layout. The final figures for the volume of water to
be treated, the presence of hazardous contaminants and
their concentrations, the collector sur- face required and
pre- and post-treatment processes must also be defined at
this preliminary design level. The objec- tive of the final
engineering design is to develop the neces- sary
documentation to proceed with the construction of the
facility through selected contractors and vendors. This
phase is usually carried out through a contract between
the plant owner or manager and the engineering firm
responsi- ble for the project.
Project Engineering 171
Bibliography
BECHTEL CORPORATION. 1991. CONCEPTUAL Design of A
PHOTOCATALYTIC WASTEWATER TREATMENT PLANT. Sandia
National Laboratory Report. SAND91-7005,
Albuquerque, N.M.
BLANCO, J.; MALATO, S. AND RICHTER, C. 1997. Solar
detoxification plant for a hazardous plastic bottle
recycling plant in El Ejido: feasibility study. In: Becker,
M. and Böhmer, M. (eds), Proceedings of 8th Symposium on
SOLAR THERMAL CONCENTRATING Technologies, Vol. 3. Heidelberg,
Germany, C. F. Müller Verlag, pp. 1451–1740.
BLANCO, J.; MALATO, S.; FERNÁNDEZ, P.; VIDAL, A.;
MORALES, A.; TRINCADO, P.; OLIVEIRA, J.C.; MINERO, C.;
MUSCI, M.; CASALLE, C.; BRUNOTTE, M.; TRATZKY, S.;
DISCHINGER, N.; FUNKEN, K.-H.; SATTLER, C.; VINCENT,
M.;
COLLARES-PEREIRA, M.; MENDES, J.F. AND RANGEL, C.M. 2000.
Compound parabolic concentrator technology
development to commercial solar detoxification
applications.
SOLAR Energy, Vol. 67, Nos. 4–6, pp. 317–30.
CALZA, P.; MINERO, C. AND PELIZZETTI, E. 1997. Photocatalytic
transformations of chlorinated methanes in the presence
of electron and hole scavengers. JOURNAL of the CHEMICAL
Society (FARADAY TRANSACTIONS), Vol. 93, pp. 3765–71.
GOSWAMI, D. 1995. Engineering of solar photocatalytic
detoxification and disinfection processes. ADVANCES in
SOLAR Energy, Vol. 10, pp. 165–209.
O’BRIEN & GERE ENGINEERS, INC. 1995. INNOVATIVE Engineering
Technologies for HAZARDOUS WASTE REMEDIATION. New York,
International Thomson Publishing.
RADIAN CORPORATION. 1991. CONCEPTUAL Design Report for
the Mobile SOLAR DETOXIFICATION Unit: DRAFT Report. Denver,
Colo., Solar Energy Research Institute.
172 Solar Detoxification

Self-assessment questions Part B

Part A: True or false? 1. Is the implementation of a specific pre-treatment

1. The purpose of identifying possible pre-
treatment processes is to make possible or enhance
photocatalytic wastewater degradation.
2. It may be possible to avoid pre- and post-
treatment processes, depending on the specific
conditions of the photocatalytic wastewater
degradation process.
3. When TiO2-persulfate degradation is employed,
specific post-treatment is required to remove the excess
sulfates in the discharge water.
4. Once the preliminary design is completed, no
additional data should initially be required to proceed
with the detailed final engineering design.
5. The technical and economic feasibility of the solar
detoxification process must be demonstrated by the
feasibility study and the preliminary design,
respectively.
6. As Photo-Fenton uses more photons than the
TiO2 process (using solar photons up to 580 nm
compared to only 390 nm), it is always the best
option.
7. Final project design is usually included within
the construction of the treatment plant, but not
necessarily.
process always recommended to increase the efficiency
of the photocatalytic treatment? Why, or why not?
2. In which cases could water temperature
play a significant role in the solar detoxification
process?
3. Why should treatment factors not be used to
calculate the solar collector area for a specific case of
wastewater treatment?
4. An experimental solar detoxification system is 375 L
in total volume, with a 250-L reactor volume?
5. Why is an increase in TOC concentration observed
in many photocatalytic degradation experiments?
6. An experimental system, made up of 25 m 2 of solar
collectors, can degrade 75 per cent of the TOC in 150 L
of a specific wastewater in 150 minutes, with an average
solar UV irradiation of 33 W/m 2. Another system with
15 m2 of solar collectors can also degrade 75 per cent of
the TOC in 100 L of the same wastewater in 120 minutes
with an average solar UV irradiation of 38 W/m2. Which
of the two systems is more energy efficient?
7. The following results were obtained for a
specific wastewater in several photocatalytic tests
with
TiO2-persulfate:
TABLE 9.3

8. A technology confidentiality agreement among Tes

Treatment Average
the parties should be included, if appropriate, in the t factor UV irradiation (W m–2)
solar
–1 –2
general conditions of the contract. 1 (L
11h m ) 28.5
2 13 33.4
9. Any specific documentation to be provided for
3 10 31.8
the treatment facility, in addition to the operation
and maintenance manuals, should be defined in the 4 9 26.9
technical specifications of the contract. 5 12 33.2

10. When wastewater is treated by batch Using these data, estimate the size required for a
processing, the flow rate must be as low as solar detoxification plant treating 10,000 m 3.
possible, to save pump energy.
 Project Engineering 173

8. Why is it always advisable to check the feasibility 10. What are the main issues to be considered
and preliminary design data before beginning the final when designing the hydraulic loop for a solar
project design? detoxification facility?

9. How can the risk of long cloudy periods

(which could reduce the feasibility of installing a
solar detoxification plant)?
174 Solar Detoxification

Answers EUV2 
15(120  60)38  41.04 kJ L1
103
Part A 100
The second system may be considered more efficient
1) True. 2) False. 3) False. 4) True. 5) True. 6) False. than the first one, as it needs less specific energy to
7) True. 8) True. 9) False. 10) False. achieve the same degradation.

Part B 7. From the five tests performed, the average

1. Not always, because potential gains in overall
reaction rate must always be weighed against
additional associated costs.
2. Because when hazardous compounds with low
boiling points, such as volatile organic compounds
(VOCs), are to be treated, possible transfer of the
contaminants from liquid to gas phase must be taken into
account.
3. Because the solar radiation is not considered.
Treatment
factors are a good tool for comparing degradation
performance in experimental systems, but as local
available solar irradiation is an essential design factor,
they cannot be used to calculate the required solar field.
4. Using Eq. 9.1, the factor is 0.746:
280
t t  0.746 t
R
375 T T
5. The initial presence of non-dissolved compounds in
the wastewater.
6. The problem can be solved by using equation
9.3, modified as follows:
treatment factor is 11 L h–1 m–2 and the average solar
irradiation is
30.76 W m–2. As there is a linear relationship between these
factors, if the yearly average is:
24.5
11  8.76 L h1 m2
30.76
And the estimated solar field would be:
10,000 10 3 L
 380 m2
8.76 L h1 m2 3,000 h
The final estimate, with a 25 per cent increase, would be
475 m2.
8. Because final design and project implementation do
not normally follow immediately after the feasibility
study
and preliminary design phases, but often happen some
time later. Furthermore, sometimes specific assumptions
and design data must be validated in a pilot plant before
the final plant design can be completed.
9. A first approach is the design of an adequate buffer
system. A second and more radical approach is the
design of hybrid systems, combining solar collectors
and electric UV lamps.

EUV  ST UVG (9.4) 10. To guarantee the same flow rate in all reactor tubes, to
VTOT minimize the ‘dark volume’ (volume not exposed to solar
radiation) and to avoid catalyst settlement when a
25(150  60)33
EUV1   49.5 k J L1 heterogeneous photocatalytic process is implemented.
103
150
 International Collaboration
Aims
This chapter describes some of the
programmes and initiatives promoting
national or international collaboration in
research, development and
implementation of innovative sustainable
technologies that include solar
detoxification projects within their scope.
10 CHAPTER10
Objectives
At the end of this chapter, you will
appreciate the scale, nature and content of
these programmes, and some of the
national and regional initiatives in progress
worldwide.
You will have acquired basic information
concerning the mechanisms and
possibilities of proposing and establishing
international collaboration in the field of
solar detoxification and you will also
know how to receive updated information
regarding those possibilities.
176 Solar Detoxification

NOTATION

Symbol Description
CIEMAT Centro de Investigaciones Energéticas, Medioambientales y Tecnológicas (Spain)
DG-XII Directorate General XII (of European Commission): Science, Research and
Development DG-XVII Directorate General XVII (of European Commission): Energy
DOE Department of Energy (USA)
DOD Department of Defense (USA)
EC European Commission
EPA Environmental Protection Agency (USA)
EU European Union
ExCo Executive Committee (SolarPACES)
FP5 Fifth Framework Programme (EU)
IEA International Energy Agency
NREL National Renewable Energy Laboratory (USA)
OECD Organization for Economic Co-operation and
Development PCO Photocatalytic oxidation
PSA Plataforma Solar de Almería
PSI Paul Scherrer Institute (Switzerland)
SANDIA Sandia National Laboratories (USA)
SolarPACES Solar Power And Chemical Energy
Systems RTD Research and technological
developments
SERI Solar Energy Research Institute (USA)
SMEs Small and medium-sized enterprises
SNL Sandia National Laboratories (USA)
SSPS Small solar power systems
WHO World Health Organization

10.1. International Energy Agency: SolarPACES is one of the international co-operative

the SolarPACES programme
The International Energy Agency (IEA), founded in
1974, is the energy forum for industrialized countries.
Based in Paris, the IEA is an autonomous agency within
the frame- work of the Organisation for Economic Co-
operation and Development (OECD). An important
function of the IEA is the promotion of enhanced
international collaboration on energy research and the
development and application of new and efficient energy
technologies. To date, the IEA has set up more than sixty
‘implementing agreements’ linking member countries in
R&D, technology demonstration and informa- tion
initiatives. One of these implementing agreements is
called SolarPACES (Solar Power And Chemical
Energy Systems).
programmes managed under the umbrella of the IEA to
help find solutions to worldwide energy and
environmental problems, bringing together teams of
national experts from around the world to focus on the
development and marketing of systems based on solar
technologies.
The SolarPACES programme was initiated in 1977
under its former name of SSPS (Small Solar Power
Systems). Two dissimilar solar facilities were designed
in the project’s Stage 1 by ten contracting parties from
Austria, Belgium, Germany, Greece, Italy, Spain,
Sweden, Switzerland, the United Kingdom and the
United States. All these countries, with the exception
of the United Kingdom, continued the project through
Stage 2 (building, testing and evaluation), which was
completed in Almería, in southern Spain, at the end
of 1984. In the course of

the subsequent Stage 3, eight countries (all but Greece)
proceeded with solar-related research and development
in various forms, especially in advanced solar
thermal and solar chemical applications. The two
SSPS facilities were transformed into what has since
become the world’s most versatile solar test centre, the
Plataforma Solar de Almería (PSA), which continues
to serve as the site of multiple co-operative
international testing and develop- ment efforts.
In 1991, Germany, Spain, Switzerland and the United
States decided to move on to Stage 4 and sought
increased participation from both member and non-
member countries. As of 1999, there are fourteen
members of SolarPACES: Australia, Brazil, Egypt, the
European Commission (DG XII and DG XVII), France,
Germany, Israel, Mexico, Russia, South Africa, Spain,
Switzerland, the United Kingdom and the United States.
In 1998 alone, contacts were maintained with
representatives of Azerbaijan, Chile, Ghana, India,
Italy, Japan, Jordan, South Africa, Turkey, Uzbekistan
and Zimbabwe. Membership is open to all countries,
subject to executive committee approval, and involves a
government (or its nominated contracting party)
becoming a signatory to the programme’s ‘implementing
agreement’, which defined the SolarPACES charter and
conditions of membership. The current implementing
agreement is an amendment of the original one signed
on 23 September 1977. The imple- menting agreement
may be extended by agreement of two or more
participants, the extension being applied only to those
participants.
An executive committee (ExCo) composed of
individuals nominated from each member country
oversees all SolarPACES activities. The ExCo meets
twice a year to formulate strategic objectives, direct the
programme of work, review results and
accomplishments, and report to the IEA. An elected
chairperson presides over the ExCo meetings, and
throughout the year, an executive secretary deals with
day-to-day programme management.
The ongoing work and activities are co-ordinated
through specific ‘tasks’ or areas of work, defined within the
implementing agreement. SolarPACES currently has
three such ongoing tasks:
• TASK I: Concentrating Solar Energy Power Systems.
 TASK II: Solar Chemistry Research, including solar
detoxification.
• TASK III: Solar Technology and Applications.
International Collaboration 177
An operating agent, nominated by the executive
committee, is responsible for overseeing the work in
each task area, and each member country nominates a
national coordinator for each of the three tasks. For
each task area a detailed and specific programme of
work that defines all task activities is maintained. In
addition to technical reports of the activities and their
participants, accomplishments and progress are
summarized in the SOLARPACES A NNUAL Report.
Many SolarPACES activities involve close co-
operation among member countries (either through
sharing of task activities or, occasionally, cost-sharing),
although some co-operation is limited to sharing of
information and results with other participants.
The activities formally identified within Task II
(Solar Chemistry Research) are related to the
development of technologies and systems in the field of
solar-driven thermo- chemical, photochemical and
electrochemical processes for the production of energy
carriers, chemical commodities and the detoxification
and recycling of waste materials. As indicated in the
current implementing agreement, Task II activities are
divided into three sectors, Sector II.3 being completely
devoted to solar detoxification activities and research.
• Sector II.1: Solar Production of Energy
Carriers. The objectives of this sector are to:
Explore new ideas and concepts for the
thermochemical, photochemical and electrochemical
production of chemi- cal fuels and chemical heat
pipes for storage and trans- portation of solar energy;
Develop and test the required solar process
technology; Assess their technical and economic
feasibility and implementation;
Set priorities of research and development needs.
 Sector II.2: Solar Production of Chemical
Commodities. The objectives of this sector are to:
Identify chemical processes for the solar production
of fine and bulk chemical commodities;
Develop and test the required solar process
technologies; Assess their technical and economic
feasibility and implementation.
• Sector II.3: Solar Detoxification and
Recycling. The objectives of this sector are
to:
Test and evaluate solar detoxification processes;
Further develop and demonstrate solar detoxification
systems up to commercial level.
178 Solar Detoxification
The core of the work of SolarPACES is the development
of new and advanced concentrating technologies and the
solu- tion of the wide range of technical problems
associated with their commercialization. This means
that, from advanced solar concentrating technologies in
general to solar detoxifi- cation applications in
particular, industrial participation must play a critical
role. Many of the task’s international activities and
teams involve industrial co-operation. In fact, in some
countries (for example, the United Kingdom and
Australia), the SolarPACES contracting party is an
industrial company.
SolarPACES attempts to give added value to
national work already funded by its member
governments. It is, therefore, not in itself a ‘big-budget’
operation and normally does not provide funding for
work to be carried out in mem- ber countries. The small
annual fee paid by member coun- tries is used to support
a limited range of co-operative activities approved by
the ExCo, such as scholarships, publication and
distribution of documents, and activities promoting
international awareness.
The Task II operating agent is currently the Paul
Scherrer Institute (PSI) of Switzerland, which co-
ordinates activities in close collaboration with the
national co-ordinators. The operating agent and national
coordinators normally meet once a year to review the
progress of task activities, discuss technical issues and
prepare future task development.
Full additional information on activities,
conferences, reports, newsletters and contact addresses
can be found at the SolarPACES website:
http://www.solarpaces.org
10.2. The European Union
In recent years, the European Commission (EC) has
become one of the most active institutions in the
financing and promoting of both solar detoxification
research and inter- national collaboration. A significantly
high number of proj- ects related to photocatalytic
research was approved and financed during the 1990s
(Third and Fourth Framework Programmes). A large
part of the information contained in this book was
obtained from projects, networks and activities
promoted and partly financed by the European
Commission through these framework programmes.
The Fifth Framework Programme, adopted in
December 1998, defines the EC activities in the field of
research, technological development and demonstration
for 1998– 2002. Its differs notably from its predecessors
in that it
focuses on a limited number of objectives and areas
combin- ing technological, industrial, economic, social
and cultural aspects. Environmental protection is one of
these priority areas, water treatment being one of its
specific objectives, thereby providing a good scenario for
co-operative research, development and demonstration
initiatives related to solar detoxification of water.
The Fifth Framework Programme consists of
seven specific programmes, of which four are thematic
and three are horizontal. Future EC framework
programmes are expected to follow the same
philosophy of complementary thematic and horizontal
action. Exhaustive documentation related to all these
programmes is provided by the EC at the
following websites: http://europa.eu.int and
http://www.cordis.lu (CORDIS is a European
Community research and development database).
The specific topic of water treatment falls within the
‘Energy Environment and Sustainable Development’ pro-
gramme. The strategic goal of this programme is to promote
environmental science and technology to improve the
quality of life and boost growth, competitiveness and
employment, while meeting the need for sustainable
management of resources and protection of the environ-
ment. Within this programme, research and technology
development (RTD) will concentrate on six key actions
(two for the ‘energy’ area, four for ‘environment and sustain-
able development’). The first of the four key actions in the
‘environment’ section is ‘Sustainable Management and
Quality of Water’, specifically addressed at water treatment
and purification technologies, with the objectives (among
others) of:
• developing improved wastewater treatment
techniques and technologies
• developing technologies for rational water re-use
• developing technologies for water purification
• enhancing wastewater treatments
• minimizing environmental impacts from wastewater
treatment.
Priority will be given to research initiatives addressed
at wastewater treatment and re-use, abatement of water
pollu- tion from contaminated land, landfills and
sediments, and diffuse ground- and surface-water
pollution (persistent organic chemicals) abatement. It
may be observed that all these objectives and research
initiatives are perfectly consistent with the processes
and technologies indicated

in this book, providing an adequate framework for
interna- tional co-operation on solar detoxification
applications and further research initiatives.
The ‘key action’ concept is an important characteristic
developed in the Fifth Framework Programme. Its
objective is to address the many and varied aspects of the
economic and social issues to be targeted, by integrating
the entire spectrum of activities and disciplines needed
to achieve the specified objectives, using a problem-
solving approach.
An important aspect of the overall European
research strategy, in addition to its basic support of
European research, is international cooperation. Entities
from non-EU countries and international organisations
may participate in all programmes, as well as in the
horizontal programme: ‘Confirming the International Role
of Community Research’. Conditions for the participation
of non-EU countries may differ from one programme to
another, depending on the status of the country, with
regard to participation in EC research activities.
In addition to EU member countries, institutions and
entities from other states have a special status when
partici- pating in EC research activities. Countries that
have signed association agreements may participate
under the same conditions as EU member countries.
Iceland, Liechtenstein, Norway, Israel and candidates for
EU membership (currently Bulgaria, Republic of
Cyprus, Czech Republic, Estonia, Hungary, Latvia,
Lithuania, Poland, Romania, Slovakia and Slovenia) had
association agreements either in force or expected to
enter into force during 1999. Switzerland has also
concluded association agreement negotiations. Other
countries, such as Argentina, Australia, Canada, China,
Russia, South Africa and the United States have signed
co- operation agreements with the EU for participation
and collaboration in research activities. In addition, some
specific regions also have special relationships with the
EU, includ- ing other European countries (Albania,
Bosnia-Herzegovina, former Yugoslav Republic of
Macedonia, Malta, Turkey and European microstates
and territories), the ‘Mediterranean partnership’
(Algeria, Republic of Cyprus, Egypt, Jordan, Lebanon,
Malta, Morocco, Palestine Authority, Syria, Tunisia and
Turkey) and the European NIS (Armenia, Azerbaijan,
Belarus, Georgia, Moldova, Russia and Ukraine).
In some work programmes, the developing countries
are grouped into the following geographic areas: African,
Caribbean, Pacific (ACP) countries; Asian and Latin
American (ALA) countries; and the Mediterranean
countries
International Collaboration 179
(MC). It is therefore always advisable to obtain up-to-
date information and conditions for participation for the
specific area to which one intends to submit a proposal.
European framework programmes, such as FP5, are
implemented through specific work programmes
describing the activities and the research areas in detail.
These work programmes are regularly revised to ensure
their continued relevance in the light of evolving needs
and developments. Work programmes provide a means
of focusing attention on areas or sub-areas, thereby
optimizing opportunities for launching collaborative
projects and establishing theme networks. The types of
RTD activities normally financed by the EC are:
• Shared-cost activities.
Research and technological development (R&D)
projects: projects obtaining new knowledge for
product process or service development or
improvement, and/or to meet the needs of Community
policies.
Demonstration projects: projects designed to prove
the viability of new technologies offering potential
economic advantages, but which cannot be
immediately commercialized.
Combined R&D and demonstration projects: projects
combining the above elements.
Support for access to research infrastructures: actions
enhancing access to research infrastructures for Com-
munity researchers.
‘SME co-operative’ research projects: projects enabling at
least three mutually independent SMEs from at least two
member states or one member state and one associated
state jointly to commission research carried out by a
third party.
‘SME exploratory’ awards: support a project exploratory
phase of up to twelve months (for example, feasibility
studies, validation and partner search).
• Training fellowships.
These may be either fellowships, whereby individual
researchers apply directly to the Commission, or host
fellowships, where institutions apply to host a number
of researchers. There is also a bursary for young
researchers from developing countries. When
preparing a joint research proposal or concerted
action proposal for sub- mission to any of the
programmes, a consortium may include an application
for an international training bursary. These bursaries
are intended to allow young
180 Solar Detoxification
researchers from developing countries, including
emerg- ing economies and Mediterranean countries,
to work for up to six months in a European research
institute participating in an EC financed project.
These bursary applications must be submitted with
the proposal application and will be evaluated
together with it. The bursary applicant must not be
more than forty years of age, must be a national of
one of the eligible countries and intend to return
there at the end of the training period. Applications
from female researchers are encouraged.
• Research training networks and thematic networks.
Training networks for promoting training-through-
research, especially of researchers at pre- and post-
doctoral level, and thematic networks for bringing
together, for example, manufacturers, users,
universities and research centres around a given
objective.
• Concerted actions.
Actions co-ordinating RTD projects already in receipt
of funding, for example to exchange experiences, to
reach a critical mass and to disseminate results. These
include co-ordination networks between Community-
funded projects.
• Accompanying measures.
Actions contributing to the implementation of a
specific programme or the preparation of future
activities of the programme. They will also seek to
prepare for or to support other indirect RTD actions.
As previously indicated, when planning an RTD proposal
for submission to one of the programmes or to key
actions, researchers should always be aware of the
conditions for participation by entities from non-EU
countries and international organizations.
10.3. The CYTED programme
The CYTED programme (Programa Iberoamericano de
Ciencia y Tecnología para el Desarrollo) offers another
opportunity for international collaboration. CYTED is
the Latin-American science and technology for
development programme. It was created in 1984 by
institutional agree- ment between Argentina, Bolivia,
Brazil, Chile, Colombia, Costa Rica, Cuba, Ecuador, El
Salvador, Spain, Guatemala, Honduras, Mexico,
Nicaragua, Panama, Paraguay, Peru, Portugal,
Dominican Republic, Uruguay and Venezuela.
The CYTED programme’s objective is to promote co-
operation in development through applied research and
technology for transferable results to the production
systems of the participant countries. The programme is
aimed at helping universities, research centres,
institutions and pri- vate companies to use scarce
resources to better advantage, to modernize production
systems, improve the quality of life and enhance co-
operative activities among Latin- American and
European countries.
To date, the programme is divided into nineteen
different sub-programmes, each directly managed by an
international co-ordinator appointed by the General
International Secretariat, which is made up of the
representatives of gov- ernmental research institutions in
the participating countries and manages the overall
program. Each sub-programme also has national
representatives. There are three different ways to
participate:
• Field of study networks: to promote interaction,
co- operation and transfer of knowledge and
technology among groups working on similar subjects.
 Pre-competitive RESEARCH projects: research projects
per- formed through the creation of an international
comple- mentary team. Immediate market application
potential is not required.
• INNOVATIVE projects: to promote technological
development through co-operation between business and
research cen- tres from different countries for industrial
productivity and competitiveness improvement.
Innovation projects must be addressed to developing
new technologies, prod- ucts, processes and services in
line with existing or potential market.
Networks, pre-competitive research projects and
innovative projects must be within the scope of the
nineteen sub- programmes to be eligible. There are
presently about 8,600 Latin-American scientists
participating in CYTED pro- gramme activities, with
more than 1,000 universities, R&D institutions and
companies involved. Solar detoxification activities can
be promoted within at least the following two sub-
programmes: ‘materials technology’ and ‘catalysis and
adsorbents’. Some solar detoxification initiatives are
already in progress under the CYTED umbrella.
The programme philosophy is to share existing
national research resources to create a synergistic effect,
reinforcing and consolidating national research. There is
an agreement to this end among all the participating
countries by which

companies and research institutions participating in
approved (‘certified’) projects are financed nationally. The
type of support and the financial mechanisms are
those normally used within each country to promote
development of scientific research and technology.
Limited central financial support is only provided for
project co-ordination of some tasks.
The normal procedure for a CYTED-supported
activity is the following:
1. A project is initiated by a Latin-American company
or research institution.
2. The national co-ordinator of the appropriate CYTED
sub- programme is contacted.
3. A preliminary project proposal is defined.
4. An appropriate project partnership is sought. A
collabo- ration agreement is reached.
5. A project proposal is prepared by the project co-
ordinator following a specific format.
6. Project eligibility is confirmed by the CYTED
national co-ordinators involved.
7. The project is certified and approved by the CYTED
General Secretariat.
8. National financing is requested through the national
co-ordinators.
9. The project is carried out with follow-up, conclusion
and reporting.
Complete and updated information about the CYTED
programme can be found at their website: http://
www. ciyt.com.
10.4. Main research activities
Although many scientists in different countries are very
well known for their continuous effort in the
development of photocatalytic techniques and
technologies (the acknowl- edgement at the beginning of
this book is just a small sample), only two countries
have had government-financed solar detoxification
technology research and development programmes with
relevant industrial collaboration: the United States and
Spain. Their research programmes are briefly
described below.
International Collaboration 181
10.4.1. United States
The US Department of Energy sponsored a ten-year
effort to apply photochemical technology to the
destruction of environmental contaminants. The solar
detoxification project was begun in the late 1980s,
initially funded by the Department of Energy (DOE) as
part of its solar thermal programme. In 1991 it was
incorporated in a new solar industrial programme. The
goal of the project was to develop marketable solar
detoxification technology with the follow- ing objectives:
• To advance the state of development of photocatalytic
water treatment chemistry so that it could be adopted
by industry.
• To bring the solar treatment of gas streams containing
hazardous organic compounds to a point where it
could be transferred to industry.
• To develop remedial solar treatment technology for
con- taminated soil.
Work in these areas had begun slowly in the mid-
1980s at the Solar Energy Research Institute (SERI),
which later became the National Renewable Energy
Laboratory (NREL), and at Sandia National Laboratories
(SNL). At the same time, there was a strong push, driven
by regulatory pressure, to develop new technologies for
ameliorating past environ- mental contamination of
ground and surface water. The regulatory pressure
created a business environment that encouraged the
development of new, environmentally friendly
processes. Many large and small companies investi-
gated a wide range of technologies; solar technologies
were especially attractive because of the potential
reduction in the cost of energy.
In order to reach the DOE goals, the following
programme elements were pursued:
• Technology RESEARCH: to develop process chemistry.
 System engineering: to develop reactors and solar
concen- trators and to create a solid understanding of
available solar resources applicable to the processes.
• System AND MARKET ASSESSMENT: to evaluate process cost
and application information that could guide the
research and development process.
Subcontractors from industry and academia were
heavily involved in all of these areas. Involving industry
at an early phase was expected to smooth the path to
commercialization,
182 Solar Detoxification
and universities were expected to provide more
comprehen- sive understanding as a foundation for the
technology. Initial research areas included aqueous phase
applications, catalyst development and concentrating
solar reactor development.
The project was initially directed toward the
develop- ment of processes that would use concentrating
solar hard- ware so that existing knowledge could be
used. This led to a field test at Lawrence Livermore
National Laboratory using parabolic-trough reactors to
treat contaminated ground water, as well as
participation in the DOE, EPA, DOD Tri-Agency
project to treat contaminated soil. The latter project
involved the US Army, the environmental Protection
Agency, and DOE. The NREL/SNL participation was to
assist with bench-scale solar testing of the high-flux
process. Science Applications International Corporation
(SAIC) was the prime contractor for the Army. That
project culminated in a test of a reactor on a solar dish by
SAIC.
The photochemistry research team at NREL/SNL
con- ducted very important research and development
work in all areas: basic, applied, demonstration, and
transfer to com- mercialization. Basic research
included core photocatalytic oxidation (PCO) R&D
and catalyst development work, as well as research
into new areas of photochemistry such as photo-
induced adsorption and high-temperature solar PCO.
Applied research projects consisted of remediation of
chloroethylene in the gas and water phase, solar
photoreactor development, and application research
includ- ing indoor air quality, hybrid biological/PCO
processes, and processes for treatment of munitions-
production wastewater. Many of the projects were co-
funded by other agencies and programmes, including
the Strategic Environmental Research Defense
Program, SEMATECH, and the US Army.
A pilot-scale test conducted in 1991 at Lawrence
Livermore National Laboratory treated contaminated
groundwater containing 200 parts per billion (ppb) of
TCE. PCO reduced TCE levels to below 5ppb, within the
drinking water standard set by the Environmental
Protection Agency (EPA). But the results of this field test
suggested that the ben- efits of concentrated sunlight
were insufficient to overcome the added costs of
building concentrators. Efforts to find a supported
catalyst with activity close to that of slurried cata- lysts
were also carried out. A second field test was conducted
at Tyndall Air Force Base using a non-concentrating
pho- toreactor system. The results of the Tyndall field
test moved PCO research from the aqueous phase
into gas-phase research, because the data gathered
from this test suggested
that air stripping the volatile organic pollutant
compounds (VOCs), followed by PCO treatment, could
be more cost- effective and more efficient when the
water to be treated contained a high background level of
substances, which resulted in a reduction of catalyst
activity.
In 1992, a co-operative research and development agree-
ment was entered into by NREL with United Technologies
to develop PCO for air-treating applications. In 1993,
another agreement was entered into with the International
Technology Corporation (IT) for the purpose of conducting
research and development to commercialize PCO remedia-
tion technologies coupled to air-stripping systems. In 1994,
a third co-operative research and development agreement
was signed with SEMATECH to apply PCO to semiconduc-
tor manufacturing. In 1996, work with SEMATECH
resulted in a field demonstration at a semiconductor
manufacturing plant treating emissions. In 1995 and 1996,
PCO applica- tions were investigated by the Department
of Defense for remediation of trichloroethylene in water
and airstreams and for treating paint-booth emissions. In
1997, two field test demonstrations were also completed for
PCO/thermal treat- ment at a military paint-booth
installation, and for PCO remediation of TCE
contaminated groundwater. Other industrial collaboration
partners have been the International Fabricare Institute and
the American Bakers’ Association.
In 1996, the DOE Office of Industrial Technology
terminated dedicated funding to the solar detoxification
programme. The Department of Defense project was
successfully completed in 1997 after four demonstrations
had been completed. PCO work at NREL continues in
applied areas of gas-phase PCO for DOE Industries of
the Future applications, indoor air quality and tandem
processes such as PCO/biofiltration. This work is funded
by a number of government and private sector
organizations.
10.4.2. Spain
The CIEMAT Department of Renewable Energies, a public
research institution belonging to the Spanish Ministry of
Science and Technology and devoted to energy and the
environment issues, has been working on solar chemistry
processes since 1987. Research into solar detoxification
applications also started at that time, mainly at the PSA, the
CIEMAT’s solar research facility in southeastern Spain. In
1990, through the EU-DGXII ‘Access to Large Installations
programme’, the PSA designed and erected a large solar

detoxification facility in co-operation with some relevant
European photochemical research groups, and the first
solar tests were successfully carried out.
Because of the quite high initial expectations for the
tech- nical feasibility of solar detoxification, in 1994
CIEMAT defined solar chemistry research as one of its
areas of activity, focusing mainly on water- and gas-
phase solar emissions processes and applications, with
the main objective of developing and transferring a
feasible solar detoxification technology to industry. This
was to be done by assessing the scientific and
technological bases that make possible an engineering
approach to photochemical processes using solar
radiation at pre-industrial scale. An important part of the
content of this book is the result of CIEMAT activities in
solar detoxification of hazardous water contaminants
in recent years.
Since the early 1990s, a major source of scientific
background has also come from the EC programmes
‘Access to Large-Scale Scientific Installations’ (1990–3),
‘Human Capital and Mobility’ (1994–5) and ‘Training and
Mobility of Researchers’ (1996–8). These programmes have
facilitated PSA solar detoxification facility access for many
European universities and other research groups and have
made possible a continuous exchange of ideas leading to
photo- chemical process improvement. In addition to this
scientific database, a large number of national and
international initiatives in solar detoxification, supported
by Spanish and European research programmes, have
provided CIEMAT with an important complementary
technological background. Some important initiatives are
still underway.
Industrial participation is also a fundamental pillar of
the overall CIEMAT activity in solar detoxification.
Since 1993, it has collaborated with many Spanish
companies in a large number of small projects that have
made it possible to test the feasibility of photocatalytic
degradation of industrial wastewater and to identify the
most suitable targets. Moreover, these tests have been
used to verify the continu- ous modification and
improvement of the solar technology. Industrial
collaboration with the CIEMAT solar detoxi- fication
project has increased significantly since 1997, with the
development of several important projects and demon-
stration initiatives. Sections 9.2, 9.4 and 9.6 of this book
are examples of this collaboration.
It may be affirmed that the result of this combined
photochemical research from university and industrial
collaboration in hardware development and testing has
led
International Collaboration 183
to the current state-of-the-art of the solar detoxification
technology, and this book has tried to reflect that.
10.5. Recommendations for
successful water treatment
projects in developing countries
Finally, because of the high rate of failure of water system
projects in developing countries, most of which are espe-
cially suitable for such applications since they are in the
‘Sun belt’, some guidelines for water treatment projects to
be carried out in those countries are included here as a
complement to the previous sections.
Twenty guidelines indicating the requirements for
water projects may be found in the document Lessons
LEARNED in WATER, SANITATION AND HEALTH (WASH, 1993). As
these guide- lines are basically addressed to water and
sanitation projects funded by international aid, some
important conclusions could be of relevance to solar
detoxification water treatment projects. These and other
guidelines were obtained as the result of many years of
experience and underline the neces- sity of promoting
co-operation with local authorities and institutions,
and supporting local plans and requirements, rather
than promoting the most convenient project dictated by
the developed country. Adequate information, training
and local skill must also be built up to guarantee
the long-term sustainability of any facility installed.
In addition to the lessons learned and general
recommen- dations for addressing water-related projects
in developing countries, it may be affirmed that special
emphasis must be placed on training local people and
involving local institu- tions for collaborative projects
on solar detoxification. If local technical or managerial
skills are inadequate, the success of any renewable
energy project would be difficult, and this is more so in
the case of solar detoxification tech- nologies, which
require adequate previous training. Also, the
collaboration of local institutions is very important in itself
as any water-treatment project is usually closely related
to san- itary and health issues.
A typical mistake is to focus the project on
construction, forgetting the necessary previsions and
provisions to en- sure the technical and financial
sustainability of the renew- able technology installation.
This issue must be foreseen from the beginning of the
project. Therefore, it is highly recommended that
projects financed by foreign aid be
184 Solar Detoxification

designed in such a way that their operation and ission and the Latin-American CYTED network. All
maintenance costs, as well as part of the initial three mechanisms are currently promoting and/or
construction cost, can be borne by the user or users. supporting activities and projects on solar
Another relevant recommendation is that projects detoxification topics with important international
should not promote dependency on foreign aid or foreign collaboration. During the 1990s, the United States and
technical assistance. One possible way to avoid this Spain were the most active countries in solar
when innovative technologies such as solar detoxification technology development, resulting in the
detoxification are implemented is to promote the present state-of-the-art of the technology. A brief review
development of the private sector in the area. Local of the governmental activities of both countries has
companies, acting as the interface between the users and also been provided. International collaboration with
the foreign engineering company, could provide the developing countries must be addressed with special care
necessary technical assistance and also promote new because of the high rate of failure of water-related
projects and initiatives at local level. projects. We have noted several general
As contaminated drinking water is a typical recommendations and lessons learned from the wide
problem, water purification and disinfection is a very experience of many international organizations in the
interesting appli- cation of the solar detoxification case of solar detoxification initiatives, when considering
technology in developing countries. The World Health their implementation in developing countries.
Organisation (WHO) has divided water contaminants,
the main cause of diseases in Bibliography
developing countries, into five categories: biological, inor-
ganic, organic, aesthetic and radioactive contaminants. With
regard to organic constituents of health significance, the BLAKE, D.M.; CARLSON-BOYD, L.E.; LEE RECCA, L. AND
main WHO recommendation is to encourage efforts to KISSELL, G. 1997. PHOTOCHEMICAL Pollution Control: The FINAL
pro- tect water sources from organic contamination, as Report of the SOLAR INDUSTRIAL PROGRAM. SOLAR DETOXIFICATION
treatment of the latter tends to be complicated. Whenever Project. Golden, Colo., National Renewable Energy
possible, these industrial and agricultural contaminants Laboratory, 1998. (CD-ROM), Golden, Colo.
must be treated at their source. Solar detoxification is
always an alternative to be considered for this. IEA. 1996. Implementing Agreement for the ESTABLISHMENT
Among the denominated advanced oxidation of A Project on SOLAR Power AND CHEMICAL Energy Systems
processes (AOPs), based on catalytic and photochemical (SOLARPACES). International Energy Agency. (Update
techniques, solar detoxification has become especially of 1977 document.)
attractive for the treatment of water contaminants. This
has been because of the synergistic combination of GRASSE, W.; BECKER, M.; STEINFELD, A. AND TYNER, C. 1999.
solving difficult environ- mental problems by using solar
energy with the possibilities of creating new jobs and (eds). SOLAR Power AND CHEMICAL Energy Systems (SOLARPACES)
economic activity. Solar detoxifica- tion could be Almeria, International Energy Agency.
considered, then, as a good example of the concept of
sustainable development that humankind must achieve, NIEWOEHNER, J.; LARSON, R.; AZRAG, E.; HAILU, T.; HORNER, J.
and the sooner the better. AND VAN ARSDALE, P. 1997. Opportunities for RENEWABLE
Energy Technologies in WATER Supply in Developing Country
Summary VILLAGES. Golden, Colo., National Renewable Energy
Laboratory. (NREL/SR-430-22359.)
This chapter has reviewed different existing mechanisms SolarPACES. 1994. SOLAR THERMAL Power AND SOLAR CHEMICAL
to promote international collaboration in the area of solar Energy Systems, SOLARPACES PROGRAM of the INTERNATIONAL
de- toxification: the International Energy Agency Energy Agency, September. Birmingham, United Kingdom,
SolarPACES project, the research programmes of the update 1998. (Brochure.)
European Comm-
 International Collaboration 185

SolarPACES. 1996. TOWARDS the Twenty-First WASH. 1993. Lessons LEARNED in WATER, SANITATION AND HEALTH;
Century: IEA/SOLARPACES STRATEGIC PLAN, March. Thirteen YEARS of Experience in Developing Countries.
Birmingham, United Kingdom. (Brochure.) Alexandria, Va., Water and Sanitation for Health
Project (WASH). (Updated edition.)
186 Solar Detoxification
Self-assessment questions
Part A: True or false?
1. IEA headquarters are located in London.
2. SolarPACES is one of the more than sixty
implementing agreements of the International Energy
Agency.
3. The PSA was built during the initial stages of the
SolarPACES project to test and evaluate the different
solar technologies in electricity production existing at
that time.
4. Attendance at the SolarPACES periodic meetings is
restricted to the Executive Committee members,
operating agents and national co-ordinators from the
different country members.
5. The Fifth Framework Programme of the European
Union (1998–2002) consists of seven specific
programmes, of which four are thematic and three are
horizontal.
6. ‘Sustainable Management and Quality of Water’ is
one of the four key actions of the environment section of
the EU-FP5 ‘Energy, Environment and Sustainable
Development’ work programme.
7. Participation of institutions, organizations and
companies from non-EU countries is possible in all EU-
FP5 programmes.
8. An application for an international co-operation
training bursary (EU-FP5 programmes) can be made to
any of the programmes, independently of the submission
of a joint research proposal or concerted action initiative.
9. CYTED is a Latin-American network of
governmental research organizations to promote,
support and reinforce national research initiatives.
10. When addressing international collaborative
projects to be implemented in developing countries, it
is highly advisable to get information from the
experience of similar or related initiatives previously
implemented in the same area.
Part B
1. How would you define an implementing agreement
of the International Energy Agency?
2. What is SolarPACES?
3. List the initial members of the present stage of
the SolarPACES project, initiated in 1991.
4. How many countries had signed the
SolarPACES implementing agreement by 1999?
5. Indicate the different work areas defined at
the SolarPACES Implementing Agreement.
6. Which specific sector of SolarPACES
implementing agreement includes the research
activities on solar detoxification?
7. Indicate the name of the thematic programme,
within the EU-FP5, more directly related to
environmental research.
8. Indicate the name of the horizontal programme,
within the EU-FP5, specifically addressed to promoting
international collaboration.
9. Indicate the type of actions normally supported by
the different EU-FP5 programmes.
10. Indicate the different shared-cost actions
allowed within the different EU-FP5 programmes.

Answers
Part A
1) False. 2) True. 3) True. 4) False. 5) True. 6) True.
7) True. 8) False. 9) True. 10) True.
Part B
1. An ‘implementing agreement’ is a specific contract
between several IEA members to collaborate in the
research, development and application of a defined
energy related issue.
2. SolarPACES (Solar Power And Chemical
Energy Systems) is one of the IEA implementing
agreements focused on the development and
marketing of systems based on solar technologies.
3. Germany, Spain, Switzerland and the United States.
4. Twelve countries (Australia, Brazil, Egypt,
France, Germany, Israel, Mexico, Russia, Spain,
Switzerland, United Kingdom and United States)
plus the European Commission (DG XII and DG
XVII).
International Collaboration 187
5. Three ongoing tasks or thematic areas of work are
defined within the SolarPACES Implementing
Agreement:
• TASK I: Concentrating Solar Energy Power Systems
• TASK II: Solar Chemistry Research
• TASK III: Solar Technology and Applications
6. Sector II.3
7. Energy, Environment and Sustainable Development.
8. Confirming the international role of
Community research.
9. Shared-cost actions, training fellowships, research
training networks and thematic networks, concerted
actions and accompanying measures.
10. The different shared-cost actions allowed within
the EU-FP5 Programmes are:
• research and technological development
(R&D) projects
• demonstration projects
• combined R&D and demonstration projects
• support for access to research infrastructures
• ‘SME co-operative’ research projects
• ‘SME exploratory’ awards.