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Solar
Detoxification
by Julian Blanco Galvez, Head of Solar Chemistry and
Sixto Malato Rodriguez, Researcher in the Solar Chemistry Area,
Plataforma Solar de Almeria, Spain
1. Introduction
Aims
Objectives
Notation and units
1.1 Solar Chemistry
1.2 Water contaminants
1.3 Photodegradation principles
1.3.1 Definitions
1.3.2 Heterogeneous photocatalysis
1.3.3 Homogeneous photodegradation
1.4 Application to water treatment
1.5 Gas-phase detoxification
2. Solar irradiation
Aims
Objectives
Notation and units
2.1 The power of light
2.1.1 Ultraviolet light
2.1.2 Visible light
2.1.3 Infrared light
2.2 The solar spectrum
2.3 Solar ultraviolet irradiation
2.4 Atmospheric attenuation of solar radiation
2.4.1 Annual available ultraviolet radiation
2.5 Solar radiation measurement
2.5.1 Detectors
2.5.2 Filters
2.5.3 Input Optics
3. Experimental systems
Aims
Objectives
Notation and units
3.1 Laboratory systems
3.2 Solar detoxification pilot plants
3.3 Operation of pilot plant
3.3.1 Once-through operation
3.3.2 Batch operation
3.3.3 Modelling once-through and batch operation
3.4 Evaluation of solar UV radiation inside
photoreactors
3.4.1 Radiometers calibration
3.4.2 Correlation between radiometric and
spectroradiometric data
3.4.3 Collector efficiency
3.4.4 Actinometric experiments
3.5 Simplified method for the evaluation of solar UV
radiation inside photoreactors
8. Economic Assessment
Aims
Objectives
Notation and units
8.1 Photochemical and biological reactors coupling
8.2 Cost calculations
8.2.1 Example A: TiO2-based detoxification plant
8.2.2 Example B: Photo-Fenton based detoxification
plant
8.3 Solar or electric photons?
8.4 Solar resources assessment
8.5 Comparison with other technologies
8.5.1 Thermal oxidation
8.5.2 Catalytic oxidation
8.5.3 Air stripping
8.5.4 Adsorption
8.5.5 Membrane technology
8.5.6 Wet oxidation
8.5.7 Ozone oxidation
8.5.8 Advanced oxidation processes
9. Project engineering
Aims
Objectives
Notation and units
9.1 Feasibility study
9.1.1 Identification of target recalcitrant hazardous
compounds
9.1.2 Identification of possible pre-treatments
9.1.3 Identification of most adequate photocatalytic
process
9.1.4 Determination of optimum process parameters
9.1.5 Post-treatment process identification
9.1.6 Determination of treatment factors
9.2 Feasibility study example
9.2.1 Background
9.2.2 Experimentation. TiO2-Persulphate tests
9.2.3 Photo-Fenton tests
9.2.4 Conclusions and Treatment Factors
9.3 Preliminary design
9.4 Preliminary design example
9.5 Final design and project implementation
9.6 Example of final design and project
implementation
1. INTRODUCTION
AIMS
This unit describes an alternative source of energy that combines sunlight and chemistry to
produce chemical reactions. It outlines the basic chemical and physical phenomena that are
related with solar chemistry. This chapter will review approaches that have been taken,
progress that has been made and give some projections for the near and longer term prospects
for commercialisation of solar photochemistry. It also introduces the focus of this book: Solar
Detoxification.
OBJECTIVES
By the end of this unit, you will understand the main factors causing the 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 sustaining advanced oxidation processes.
5. Describe the most important features of heterogeneous photocatalysis making it applicable
to the treatment of contaminated aqueous effluents.
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Heat Photons
Increase of Modification of
Temperature chemical bonds
From the outset, it was recognized that direct conversion of light to chemical energy held
promise for the production of fuels, chemical feedstock, and the storage of solar energy.
Production of chemicals by reactions that are thermodynamically ‘uphill’ can transform solar
energy and store it in forms that can be used in a variety of ways. Wide ranges of such
chemical transformations have been proposed. A few representative examples are given in
Table 1.1 to illustrate the concept.
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∆H (kJ/mol)
Table 1.1 Representative chemical reactions that can store solar energy (Thermochemical
processes)
These processes generally start with substances in low-energy, highly-oxidized forms. The
essential feature is that these reactions increase the energy content of the chemicals using
solar energy. For such processes to be viable, they must fulfil the following requirements, as
outlined by NREL (1995) and slightly modified by the authors:
• The thermochemical reaction must be endothermic.
• The process must be cyclic and with no side reactions that could degrade the
photochemical reactants.
• The reaction should use as much of the solar spectrum as possible.
• The back reaction should be very slow to allow storage of the products, but rapid when
triggered to recover the energy content.
• The products of the photochemical reaction should be easy to store and transport.
The other pathway for the use of sunlight in photochemistry 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 photochemical reactions with useful
products. Photochemical reactions can be used to carry out a wide range of chemical
syntheses ranging from the simple to the complex. Processes of this type may start with more
complex compounds than fuel-producing or energy-storage reactions and convert them to
substances to which the photochemical step provides additional value or destroy harmful
products. The principles of photochemistry are well understood and examples of a wide range
of types of synthetic transformations are known (Figure 1.2). Therefore, the problem becomes
one of identifying applications in which the use of solar photons is possible and economically
feasible. The processes of interest here are photochemical, hence, some component of the
reacting system must be capable of absorbing photons in the solar spectrum. Because photons
can be treated like any other chemical reagent in the process, their number is a critical element
in solar photochemistry (see Chapter 2).
hυ<700nm
CHO CHO
O Methylene blue/O2 O
O O
hυ<390nm
C6Cl5OH+9/2O2+ 2H2O 6CO2 + 5HCl
TiO2
Figure 1.2 Furfural photo-oxidation and pentachlorophenol mineralization (Photochemical
processes).
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SOLAR DETOXIFICATION
Because they are very technologically and environmentally attractive, solar chemical
processes have seen spectacular development in recent years. In the beginning, research in
solar chemistry was centered only on converting the solar energy into chemical energy, which
could then be stored and transferred over long distances. Together with this important
application, other environmental uses have been developed, so that today the entire range of
solar chemical applications has a promising future. In principle, any reaction or process
requiring an energy source can be supplied by solar energy.
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SOLAR DETOXIFICATION
In any case, a consensus exists that the environmental impact of a given contaminant depends
on the degree of exposure (its dispersion and the resulting concentration in the environment)
and on its toxicological properties. The assessment of exposure involves comprehension of
the dispersion of a chemical in the environment and estimation of the predicted concentration
to which organisms will be exposed. For example, the pesticide fenaminphos oxidizes very
quickly (half-life 10 days) into sulphoxide and sulphone, while its pesticidal properties remain
unaffected. A half-life of 70 days has been found for degradation of fenaminphos and its two
metabolites. Furthermore, the two metabolites are more mobile (soluble) than fenaminphos
(Hayo and Werf, 1996). Assessment of the contaminant’s effect involves summarizing data
on the effects of the chemical on selected representative organisms and using these data to
predict a no-effect concentration on a specific niche. Organisms may consume chemicals
through ingestion of food and water, respiration and through contact with skin. When a
chemical crosses the various barriers of the body, it reaches the metabolic tissue or a storage
depot. Toxicity of a chemical is usually expressed as the effective concentration or dose of the
material that would produce a specific effect in 50% of a large population of test species
(EC50 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 toxicological response in the study. For example, the pesticide
methamidophos, which has been classified as a Restricted-Use Pesticide (RUP) by the U.S.
EPA, is highly toxic for mammals (acute oral LD50 = 16 mg/kg in rats and 30-50 mg/kg in
guinea pigs), birds (bobwhite quail 8-11 mg/kg) and bees. The 96-hour LC50 is 25-51 mg/L in
rainbow trout, but concentrations as low as 0.22 ng/L are lethal to larval crustaceans in 96-
hour toxicity tests. A 56-day rat feeding study resulted in a NOEL of 0.03mg/kg/day (Tomin,
1994).
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SOLAR DETOXIFICATION
hydroxide (•OH) and superoxide (O2•-) radicals (see Table 1.3). These can then be used to
chemically decompose a pollutant into harmless end-products. Alternatively, light can be used
directly to break up pollutant molecule bonds photolytically. These processes are called
Advanced Oxidation Processes (abbreviated as AOPs). Many oxidation processes, such as
TiO2/UV, H2O2/UV, Photo-Fenton and ozone processes (O3, O3/UV, O3/H2O2) are currently
employed for this purpose.
Fluorine 3.06
Ozone 2.07
Oxygen 1.23
Hypochlorite 0.94
Iodine 0.54
Table 1.3. Oxidation potentials of common substances and agents for pollution abatement.
The more positive the potential, the better the species is an oxidizing agent
When a given wavelength λ of light enters a medium, its spectral irradiance Eλ (W m-2 nm-1)
is attenuated according to the Lambert-Beer law, which is expressed in two ways, one for gas
phase and the other for liquid phase:
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SOLAR DETOXIFICATION
The term photocatalysis implies the combination of photochemistry with catalysis. Both light
and catalyst are necessary to achieve or to accelerate a chemical reaction. Photocatalysis may
be defined as the “acceleration of a photoreaction by the presence of a catalyst”.
Heterogeneous processes employ semiconductor slurries for catalysis, whereas homogeneous
photochemistry is used in a single-phase system. Any mechanistic description of a
photoreaction begins with the absorption of a photon, being sunlight the source of photons in
solar photocatalysis. In the case of homogeneous photocatalytic processes, the interaction of a
photon-absorbing species (transition metal complexes, organic dyes or metalloporphyrines), a
substrate (e.g. the contaminant) and light can lead to a chemical modification of the substrate.
The photon-absorbing species (C) is activated and accelerates the process by interacting
through a state of excitation (C*). In the case of heterogeneous photocatalysis, the interaction
of a photon produces the appearance of electron/hole (e- and h+) pairs, the catalyst being a
semiconductor (e.g. TiO2, ZnO, etc). In this case, the excited electrons are transferred to the
reducible specimen (Ox1) at the same time that the catalyst accepts electrons from the
oxidizable specimen (Red2) which occupies the holes. In both directions, the net flow of
electrons is null and the catalyst remains unaltered.
hν (1.4)
C → C*
C* + R → R* + C* (1.5)
R* → P (1.6)
hν
C → C(e − + h + ) (1.7)
h + + Red 2 → Ox 2 (1.8)
e − + Ox1 → Red1 (1.9)
means that the two charge carriers should react at the semiconductor/electrolyte interface with
the species in solution. Under steady state conditions the amount of charge transferred to the
electrolyte must be equal and opposite for the two types of carriers. The semiconductor-
mediated redox processes involve electron transfer across the interface. When electron/hole
pairs are generated in a semiconductor particle, the electron moves away from the surface to
the bulk of the semiconductor as the hole migrates towards the surface (see Figure 1.3). If
these charge carriers are separated fast enough they can be used for chemical reactions at the
surface of the photocatalyst, i.e., for the oxidation or reduction of pollutants.
hν
recombination
Red1 Oxid2
Oxid1 Red2
recombination
Figure 1.3. Fate of electrons and holes within a particle of illuminated semiconductor in
contact with an electrolyte.
Metal oxides and sulphides represent a large class of semiconductor materials suitable for
photocatalytic purposes. Table 1.4 lists some selected semiconductor materials, which have
been used for photocatalytic reactions, together with band gap energy required to activate the
catalyst. The final column in the table indicates the wavelength of radiation required to
activate the catalysts. According to Plank’s equation, the radiation able to produce this gap
must be of a wavelength (λ) equal or lower than that calculated by Eq. 1.10.
hc
λ= (1.10)
EG
where EG is the semiconductor band-gap energy, h is Planck’s constant and c is the speed of
light.
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SOLAR DETOXIFICATION
Photooxidation involves the use of UV light plus an oxidant to generate radicals. The
hydroxyl radicals then attack the organic pollutants to initiate oxidation. Three major oxidants
are used: hydrogen peroxide (H2O2), ozone and Photo-Fenton reaction. H2O2 absorbs fairly
weakly in the UV region with increasing absorption as the wavelength decreases. At 254 nm,
ελ is 18 M-1 cm-1, whereas at 200 nm is 190 M-1 cm-1. The primary process for absorption of
light below 365 nm is dissociation to yield two hydroxyl radicals:
hν
H 2 O2 → 2 • OH (1.11)
The use of hydrogen peroxide is now very common for the treatment of contaminated water
due to several practical advantages: (i) the H2O2 is available as an easily handled solution that
can be diluted in water to give a wide range of concentrations; (ii) there are no air emissions;
(iii) a high-quantum yield of hydroxyl radicals is generated (0.5). The major drawback is the
low molar extinction coefficient, which means that in water with high UV absorption the
fraction of light absorbed by H2O2 may be low unless very large concentrations are used.
Furthermore, especially as concerns the focus of this text, H2O2 absorption is very low in the
Solar UV range (up 300 nm).
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SOLAR DETOXIFICATION
The essential step of the Fenton reaction is the same as for all AOPs. Highly reactive radicals
(like HO• and HO2•) oxidize nearly all organic substances to yield CO2, water and inorganic
salts. In the case of Photo-Fenton, Fe2+ ions are oxidized by H2O2 while one •OH is produced
(1.18), and the Fe3+ or complexes obtained then act as the light absorbing species that produce
another radical while the initial Fe2+ is recovered (1.19 and 1.20).
Fe 2+ + H 2 O2 → Fe 3+ + OH − + OH • (1.18)
Fe 3+ + H 2 O + hν → Fe 2 + + H + + OH • (1.19)
Some pollutants are able to dissociate only in the presence of UV light. For this to happen, the
pollutant must absorb light emitted by a lamp (or the sun) and have a reasonable quantum
yield of photodissociation. Organic pollutants absorb light over a wide range of wavelengths,
but generally absorb more strongly at lower wavelengths, especially below 250 nm (Figure
1.4). In addition, the quantum yield of photodissociation tends to increase at lower
wavelengths, since the photon energy is increasing (eq. 1.1). The net chemical result of
photodissociation is usually oxidation, since the free radicals generated can react with
dissolved oxygen in the water. In practice, the range of waste waters that can be successfully
treated by UV alone is very limited. This defect is more relevant when solar energy is used
(see Figure 1.4) because only photons up 300 nm are available.
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SOLAR DETOXIFICATION
Figure 1.4. UV spectra between 200 and 400 nm of Acrinathrin and sunlight.
O2 e-
TiO2 Particle
h+ H2O
WATER
•
OH + H+
Figure 1.5. Effect of UV radiation on a TiO2 particle dispersed in water
For all of the above reasons, from now on only this method is dealt with in this text.
Whenever different semiconductor materials have been tested under comparable conditions
for the degradation of the same compounds, TiO2 has generally been demonstrated to be the
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SOLAR DETOXIFICATION
most active. Only ZnO is as active as TiO2. TiO2’s strong resistance to chemical and
photocorrosion, its safety and low cost, limits the choice of convenient alternatives (Pelizzetti,
1995). Furthermore, TiO2 is of special interest since it can use natural (solar) UV. 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
semiconductor particles, e.g., 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 waste water using
irradiated TiO2 suspensions is the most promising process and R&D in this field has grown
very quickly during the last years.
hν
TiO2 → e − + h + + TiO2 (1.21)
e − + h + + TiO2
→ TiO2 + heat and / or hν ' (1.22)
(TiO IV −O 2 − −Ti IV ) −OH 2 + hBV
+
→ (TiO IV −O 2 − −Ti IV ) −OH • + H +
(1.23)
−
O2( ads ) + eBC → O2−(•ads )
(1.24)
To date, evidence supports the idea that the hydroxyl radical (•OH) is the main oxidizing
specimen responsible for photooxidation of the majority of the organic compounds studied.
The first effect, after absorption of near ultraviolet radiation, 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 dissolvent is
oxidoreductively active (water) it also acts as a donor and acceptor of electrons. Thus, on a
hydrated and hydroxylated TiO2 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 preadsorbed molecular oxygen, forming a superoxide radical (Eq.
1.24).
Whatever the formation pathway, it is well known that O2 and water are essential for
photooxidation 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
and successive steps in oxidation/addition lead to ring opening. The resulting aldehydes and
carboxylic acids are decarboxylated and finally produce CO2. However, the important issue
governing the efficiency of photocatalytic oxidative degradation is minimizing electron-hole
recombination by maximizing the rate of interfacial electron transfer to capture the
photogenerated electron and/or hole. This issue is discussed in more detail later.
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Three exhaustive reviews by Blake (1994, 1995, 1997) describe almost 1800 studies carried
out before 1996.
Despite encouraging laboratory-scale data and some industrial-scale tests, chemical oxidation
detoxification is still restricted to a few experimental plants. The broader application of those
technologies requires: i) reactor optimization and modeling and ii) 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.
On the other hand, there are indications that mineralization may not be complete with some
organic substrates in the gas-phase. The TiO2 photocatalyst loses its activity after prolonged
use and must be reactivated with moist air that 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 like 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 USA (Rajeshwar, 1996).
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Ketones Acetone
Terpenes α-Pinene
Table 1.5. VOCs amenable to treatment via Photocatalytic Oxidation (Jakobi et al., 1996).
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SELF-ASSESSMENT QUESTIONS
1. The solar energy is useful only to substitute fossil fuels converting it into thermal energy
thus provoking chemical reactions.
2. Toxicity of a chemical is the same for all the species.
3. Biological treatment techniques are the cheapest wastewater treatment methods.
4. The energy of a photon depends of the ambient temperature.
5. Heterogeneous photocatalysis employs liquid catalysts.
6. Light driven oxidative processes are initiated by excited electrons of the catalyst surface.
7. Ozone can be produced from air.
8. The most important characteristics of a photocatalysts are: stability to chemical and
photocorrosion, safety, cost and band-gap.
9. The electron/hole recombination can be avoided increasing reaction temperature.
10. Heterogeneous photocatalysis can be applied only to monoaromatics.
PART B.
1. Which is the most important difference between thermochemical and photochemical solar
processes?
2. Which are the usual ways to express the toxicity of a chemical in the environment?
3. Why biodegradation, which is a major mechanism in wastewater treatment, is quite
inefficient to treat 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? And if the extinction coefficient is 0.3?
5. What is the wavelength able to excite a semiconductor which band-gap is 4.0 eV?
6. Name three important characteristics of heterogeneous photocatalysis to be used as water
treatment process.
7. Why TiO2 is the most suitable photocatalyst for wastewater treatment?
8. Which is the more important electron acceptor in water?
9. Which is the most important product of photocatalytic degradation with organic
contaminants?
10. Why hydroxyl radicals react with organic substances?
Answers
Part A
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1. False; 2. False; 3. True; 4. False; 5. False; 6. False; 7. True; 8. True; 9. False; 10. False.
Part B
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2. SOLAR IRRADIATION
AIMS
This unit 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. This chapter
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. Moreover, 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.
OBJECTIVES
At the end of this unit, 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 the consequences
for 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.
Comprehend the basic principles on which solar radiation measurement is based.
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TBDUV Typical “best day”. Completely clear sky during all the hours of
sunlight
Uλ 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
Φ Quantum yield No units
λ. Wavelength nm, µm
a)
X-rays M icrowaves
40
Vis0-
UV ibl 77 Infrared
100-400 nm e 0 770-10 6 nm
nm
100 1000 10000
W avelength λ , nanometers
b) λ
Figure 2.1
The optical portion of the electromagnetic spectrum (a)
and light wave front modelled as a straight-line (b).
Like all electromagnetic waves, light waves can interfere with each other, become
directionally polarised, and bend slightly when passing through an edge. These properties
allow light to be filtered by wavelength or amplified coherently 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.
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SOLAR DETOXIFICATION
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 (100-280 nm) is almost
completely absorbed in air within a few hundred meters. 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.
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SOLAR DETOXIFICATION
object blocks it; diffuse radiation does not. In general, the direct component of global
radiation on cloudy days is minimum and the diffuse component is maximum, and the
opposite on clear days.
2000 2000
-1
1500 1500
Irradiance, W m µm
Extraterrestrial
-2
500 500
0 0
0.6 1.2 1.8 2.4 3.0 3.6 4.2
Wavelength, µ m
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 vapor, liquid water
droplets and clouds. The spectral irradiance data are for the sun at a solar zenith angle of
48.19º. 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 48.19º 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
atmosphere, 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).
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SOLAR DETOXIFICATION
Z enith
60º º
2
48.
A
M
AM 1.
5 A tm osphere
2 .0
D irect
radiation
Sunrise D iffuse
radiation
Sunset
G lobal radiation EARTH
Figure 2.4
Air mass and solar components
The AM 1.5 global irradiance is shown for a flat surface facing the sun and tilted 37º from the
horizontal. The 37º tilt angle is used because it is the latitude of the Plataforma Solar de
Almería, where most of the research presented here was done. The scarce 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.
Solar ultraviolet radiation is, as explained above, only a very small part of the solar spectrum,
between 3.5% and 8% of the total of the solar spectrum, as demonstrated by measurement,
although this ratio may be different for a given location on cloudy and clear days. The
percentage of global UV radiation (direct + diffuse) generally increases with regard to total
global when atmospheric transmissivity decreases mainly because of clouds, but also because
of aerosols and dust. In fact, the average percentage ratio between UV and total radiation on
cloudy days is up to two percentage points more than values on clear days.
The efficiency of a chemical reaction is calculated from the ratio between the products and the
departing reactants. In photochemistry, it is very common to use the quantum yield concept,
which is calculated from a known amount of photons absorbed in the reaction. Quantum yield
(Φ) is defined as the ratio between the number of reacting molecules (∆n) and the quantity of
photons absorbed by the system (Na):
∆n
Φ = (2.1)
Na
Experimentally, the 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, Φ = 1. If it is less than 1, it means that deactivation processes or other
reactions competing with the one studied exist. Over 1 indicates a series of reactions the
promoter of which has been excited by a photon. In the case of photocatalysis by UV
radiation, the number of photons that reach the reacting mixture and are thereby susceptible to
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SOLAR DETOXIFICATION
being absorbed, will be in relation to the UV solar spectrum. For reactors using solar
radiation, knowledge of the solar UV spectrum is important for the following reasons:
• The radiation (sunlight) that reaches them is not constant. This prevents correct
comparison between experiments carried out at different times of the day or seasons of the
year or under different atmospheric conditions.
• The extensive bibliography on photocatalytic decomposition of organic compounds
indicates that the majority of the experiments in which the 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 those 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 optimum conditions for decomposition of the contaminant. 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, etc.) and any possible modification, in each case, to improve photodegradation
conditions.
• Any economic comparison between solar radiation and electric lamps as the UV photon
source requires knowledge 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 of them (direct UV) reaches 22 W
m-2 between 300 and 400 nm, the longer (global UV) reaches 46 W m-2.
The number of photons, Nλ, supplied by a monochromatic 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):
Qλ λ
Nλ = = Qλ (2.2)
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:
λ 1 λ2
N = ∫λ 2 N (λ )dλ = ∫ Q( λ )λdλ (2.3)
1
hc λ1
20 20
Photon flux, 10-20 photons m-2 s-1 µm-1
15 15
UVG
10 10
8.4 x 1019 photons m-2 s-1
5 5
UVD
3.6 x 1019 photons m-2 s-1
0 0
0.30 0.32 0.34 0.36 0.38 0.40
Wavelength, µm
Figure 2.5
Ultraviolet spectra on the earth surface (standard ASTM)
Equation 2.3 gives the ratio between photonic and radiometric quantities, defining from here
22
SOLAR DETOXIFICATION
the photon flux density I [Einstein s-1 m-2] as the number of incident photons per unit of
surface and time:
d2 N
I = (2.4)
N 0 dt dA
where N0 is Avogadro’s number (6.023 x 1023). 1 Einstein = 1 mol of photons = 6.02 x 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 (ID = 3.6 x 1019 photons m-2 s-1 = 6 x 10-5 Einstein m-2 s-1,
IG = 8.4 x 1019 photons m-2 s-1 = 14 x 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, at different hours
of the day and in different seasons, making it necessary to know these data for the particular
location and in real time. This data will be very useful in those cases where this is not
possible.
23
SOLAR DETOXIFICATION
0.7
1.2
0.6
1.0
0.5
Clear sky Clear sky
0.8
0.4
-1
-1
W m nm
W m nm
0.6
-2
-2
0.3
0.4
0.2
0.2 0.1
Clouds
Clouds
0.0 0.0
400 600 800 1000 1200 300 325 350 375 400
Wavelength, nm Wavelength, nm
Figure 2.6
Solar spectra on the earth surface (Plataforma Solar de Almería) between 300 and 1100 nm.
Clouds modify the total UV energy reaching the earth’s surface, but the wavelength
distribution is not affected. This cannot be guaranteed, however, if the data for all 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 interval by the following operation. Summations have been used to
treat the discrete values nm to nm:
λ = 400 nm
UVλ
fλ = λ = 400 nm
, therefore ∑f λ =1 (2.6)
∑ UV
λ = 300 nm
λ
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 all the spectra recorded may be observed. If the spectrum of
UV radiation is assumed to have a fixed form, then 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 the radiometers,
see the following section in this chapter).
0.06
λ = 400nm
0.05 UV
fλ = λ = 400nm
λ
, therefore ∑ fλ = 1
0.04
λ
∑ UVλ
= 300nm
λ = 300nm
-1
fλ, nm
0.03
0.02
24
SOLAR DETOXIFICATION
June
April
40
30 October
UV, W m-2
20
January
10
0
6 8 10 12 14 16 18 20
SOLAR HOUR
Figure 2.8
TBDUV of different periods of the year at Plataforma Solar de Almería (37º N)
incident light over a dynamic 10-decade range. A wide dynamic range is a prerequisite for
most applications. The radiometer should be able to cover the entire dynamic range of any
detector that will be plugged into it. This usually means that the instrument should be able to
cover at least 7 decades of dynamic range with minimal 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 control the instrument remotely may also be
desired. Lastly, portability and battery life may be an issue for measurements 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 photon 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
measurement units are spectral, spatial or temporal distributions of optical energy. The
biggest hurdle in light measurement is the very 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, the irradiance decreases with distance. The 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 units systems are based. Spectral
responsivity 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
wavelength. Since a detector measures only absorbed light, it cannot differentiate between 1
photon (200 nm) and 10 photons (2000 nm). The light must be filtered by wavelength before
it reaches the detector.
Sensitivity to the band of interest is a primary consideration when choosing a detector. You
can control the peak responsivity 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 signal.
Another consideration is blindness to out-of-band radiation. If you are measuring solar
ultraviolet in the presence of massive amounts of visible and infrared light, for example, you
would select a detector that is insensitive to the long wavelength light that you intend to filter
out. Lastly, 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, generating a current that is
proportional 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 NIST (National Institute of Standards
and Technology, USA).
26
SOLAR DETOXIFICATION
The phototube is a light sensor that is based on the photoemissive effect. The phototube is a
bipolar tube which consists of a photoemissive cathode surface that emits electrons in
proportion to incident light, and an anode which collects the electrons emitted. The anode
must be biased at high voltage (50 to 90 V) in order to attract electrons 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 provide sensitivity only to ultraviolet light, providing as
much as a million to one long wavelength rejections. 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 other band. Because of this, an infrared photon
often lacks the energy required to pass the detection threshold of a quantum detector. Infrared
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 responsibility, 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 thermopile consists of a number of thermocouple junctions in series, which
convert energy into a voltage using the Peltier effect. Thermopiles are convenient sensors for
measuring the infrared, 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 labs.
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 4200 nm, but for long wavelength sensitivity out to 40 microns,
Potassium Bromide windows are used. Another strategy employed by thermal detectors is to
modulate incident light with a chopper. This allows the detector to measure differentially
between the dark (zero) and light states. Quantum-type detectors are often used in the near
infrared, especially below 1100 nm. Specialized detectors such as InGaAs offer excellent
responsivity from 850 to 1700 nm. Typical silicon photodiodes are not sensitive above 1100
nm. These types of detectors are typically employed to measure a known artificial near-IR
source without including long wavelength background ambient. Most radiometric IR
measurements are made without lenses, filters, or diffusers, relying on just the bare detector to
measure incident irradiance.
27
SOLAR DETOXIFICATION
100
90
de
80 e Silicon photodiode
cuum photodio
opil
70 erm
Th 1.0
60
0.8 Detector
50 Filter
%
Solar-blind va
0.6
40
0.4
30
0.2
20
Combined responsivity
0.0
10 220 240 260 280 300 320
Wavelength, nm
0
200 400 600 800 1000 1200
Wavelength, nm
Figure 2.9
Responsivities of three detectors.
In the inset is shown a schematic of the effect of a filter on detector responsivity.
2.5.2 Filters
A detector’s overall spectral sensitivity is equal to the product 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 solve a transmission curve for the ideal filter. Filter
bandwidth decreases with thickness according to Lambert-Beer’s law (see Eqs. 1.2 and 1.3),
so by varying filter thickness, you can selectively 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. Colored glass filters are doped with materials that selectively 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 filters 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 photochemical process.
28
SOLAR DETOXIFICATION
60º 60º
50%
Figure 2.10
Relative spatial response of an ideal cosine diffuser (up)
and a radiance lens barrel (down).
Cosine Diffusers. A bare silicon cell has a near perfect cosine response, as do all diffuse
planar surfaces. As soon as you place a filter in front of the detector, however, you change the
spatial responsivity of the cell by restricting off-angle light. Fused silica or optical quartz with
a ground (rough) internal hemisphere makes an excellent diffuser with adequate transmission
in the ultraviolet. Teflon is an excellent alternative for UV and visible applications, but is not
an effective diffuser for infrared light.
Figure 2.11
Solar Global UV detector (tilted 37º and facing south) with a cosine diffuser
Radiance Lens Barrels. Radiance and luminance optics frequently employ a dual lens system
that provides an effective viewing angle of less than 4º. The trade-off of a restricted viewing
angle is a reduction in signal. Radiance optics merely limit the viewing angle to less than the
extent of a uniform area source. This input optic is used to measured direct sunlight, but
29
SOLAR DETOXIFICATION
mounted on a mobile sun-tracking platform (one loop per day) to follow the sun from sunrise
to sunset.
Figure 2.12
Solar Direct UV detector installed on a solar tracking system
Fibre Optics. Fibre optics allow measurements in tight places or where irradiance levels and
heat are very high. Fibre optics consist of a core fibre and a jacket with an index of refraction
chosen to maximise total internal reflection. Glass fibres are suitable for use in the visible, but
quartz or fused silica is required for transmission in the ultraviolet. Fibres are often used to
continuously monitor UV curing ovens, due to the attenuation and heat protection they
provide. Typical fibre optics restrict the field of view to about ±20º in the visible and ±10º 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% 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 uniform radiance and as input optics for measuring
total power. Often, a lamp is place 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 50 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
±8º, so cannot be used in full immersion applications where a cosine response is required.
30
SOLAR DETOXIFICATION
Hulstrom, R.; Bird, R.; Riordan, C. Spectral Solar Irradiance Data Sets for Selected
Terrestial Conditions. Solar Cells, 15, 365-391, 1985.
Iqbal, M. An Introduction to Solar Radiation. Academic Press, Canada. 1983.
Riordan, C.J.; Hulstrom, R.L.; Myers, D.R.. Influences of Atmosferic Conditions and Air
Mass on the Ratio of Ultraviolet to Total Solar Radiation. Solar Energy Research
Institute (SERI)/TP-215-3895. 1990.
SELF-ASSESSMENT QUESTIONS
PART B.
1. Which is the most important difference between ultraviolet, visible and infrared light?
2. Which are the usual units to express the solar spectrum power?
3. Why the Air mass at Sun zenith is called AM 1?
4. Cite at least two reasons to justify the importance of knowing the solar spectrum in
photochemistry?
5. Which is the typical unit in photochemistry? Why?
6. Why clouds do not absorb UV light?
7. Which is the usefulness of Equation 2.6?
8. Convert the following fraction of power associated with each wavelength (corresponding
to a standardised spectrum between 300 and 400 nm) in solar spectrum power knowing
that the total measured power is 40 W/m2.
λ, nm fλ
300 0.0002
302 0.0004
304 0.0007
306 0.0011
308 0.0017
310 0.0023
312 0.0032
9. Why is it very difficult the measurement of infrared light measured with quantum
radiometer?
31
SOLAR DETOXIFICATION
10. How is it possible to vary the spectral responsivity of a sensor without changing its type of
filter?
Answers
Part A
1. False; 2. False; 3. True; 4. True; 5. False; 6. False; 7. True; 8. True; 9. False; 10. False.
Part B
1. Wavelength, ultraviolet light between 100 and 400 nm, visible light between 400 and 770
nm and infrared light between 770 and 106 nm.
2. W m-2 nm-1 or W m-2 µm-1
3. Because this is the direct beam solar irradiance minimum path length through the
atmosphere.
4. (a) The radiation that reaches the solar reactors is not constant. (b) In order to compare
laboratory results with solar results or to use the information obtained with lamps. (c) The
determination of the efficiency of the components of the solar reactor and the possible
modifications to improve the conditions of photodegradation. (d) To perform economic
comparisons between solar radiation and electric lamps.
5. Einstein. Because it is 1 mol of photons and therefore, the quantum yield of a
photochemical reaction (rate 1 M/min) that absorbs 1 Einstein L-1 min-1 is 1.
6. Because pure water does not absorb UV light.
7. To represent spectra in a standardised manner. This will permit the comparison between
spectra recorder at different sites, hour of the day and/or different seasons.
8.
λ, nm UVλ, W m-2 nm-1
300 0.0080
302 0.0160
304 0.0280
306 0.0440
308 0.0680
310 0.0920
312 0.1280
9. Infrared light contains the least amount of energy per photon of any other band. Because
of this, an infrared photon often lacks the energy required to pass the detection threshold
of a quantum detector.
10. Varying filter thickness.
32
SOLAR DETOXIFICATION
3. EXPERIMENTAL SYSTEMS
AIMS
This unit describes the experimental systems necessary for performing pilot-plant-scale solar
photocatalytic experiments. Various laboratory set-ups are also shown in order to emphasise
the big differences between these small photoreactors and pre-industrial-scale pilot plants. It
outlines the basic components of these pilot plants and the different possibilities for operating
them. This chapter will review modelling of the experiments from a chemical engineering
point of view. Finally, an extensive overview of relationships between radiometer
measurements and the photons that actually reach the photoreactor is presented.
OBJECTIVES
By the end of this unit, you will know 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
necessities of the research to be performed in 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 a relationship between solar radiometer measurements and the photons that actually
reach the reaction.
6. Employ chemical actinometers to validate all the calculations performed to obtain the
photon flux inside photoreactors.
33
SOLAR DETOXIFICATION
Figure 3.1
Laboratory typical stirred tank reactor.
Figure 3.1 shows a basic scheme of a microphotoreactor used in laboratory experiments. The
photoreactor consists of a flask made of Pyrex with a flat bottom window constituted by an
optical filter generally made of quartz (fused silica) to let enter all the UV-visible radiation
with λ ≥ 220 nm. For an isothermal reaction, or when one wants to change the temperature of
the medium for determining the activation energy of the reaction (see section 4.7), the system
is equipped with a jacketed envelope through with flows a temperature-constant fluid (e.g.
water) delivered by a thermostat. There are several upper apertures to introduce the reacting
mixture, the catalyst, a controlled gas atmosphere and also to withdraws 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, that it is at the right level. The determination of gaseous CO2 is made in
oxygen confined atmosphere by sampling amounts of supernatant gas phase through the
ground top and the valve, linked to a GC by a stainless steel tubing.
34
SOLAR DETOXIFICATION
Figure 3.2
Laboratory typical recirculating system.
Figure 3.2 shows a schematic and a photo of the recirculating system. Water, contaminants
and titanium dioxide are continuously recirculated through a 250 mL Pyrex reactor. During
photocatalytic degradation experiments some parameters as pH, CO2 and O2 can be monitored
in situ by specific electrodes (probes). Air is introduced inside the reactor flask through a flow
cell and distributed via a sintered-glass tip to maintain a constant oxygen concentration in the
system. Irradiation is carried out by a solar simulator equipped with a high-pressure xenon arc
lamp and a parabolic reflector. Since solar simulators contain a significant thermal
component, it is necessary to decrease the temperature using a small heat exchanger. The
entire reactor is fabricated with chemically resistant materials (Pyrex, Teflon and Viton).
35
SOLAR DETOXIFICATION
The design procedure for a pilot solar detoxification system requires the selection of a reactor,
catalyst operating mode (slurry or fixed matrix), reactor-field configuration (series or
parallel), treatment-system mode (once-through or batch), flow rate, pressure drop, pre-
treatment, catalyst and oxidant loading method, pH control, etc., so 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. This is the crucial difference between pilot and
process plants. A pilot plant must fulfil all the present and future requirements of the research
to be performed in it.
In Figure 3.3 a detailed drawing of a plant is given. Usually, a detoxification pilot plant is
constructed with several solar collectors. All the modules are connected in series, but with
valves that permit to bypass any number of them. Sampling valves are in the outlet of each of
the modules. All the tubes and valves are black HDPE, material chosen because it is strongly
resistant to chemicals, weather-proof and opaque, in order to avoid any photochemical effect
outside of the collectors. There are storage-feeder tanks available, also made of HDPE and
having different capacities, where the test mixtures are prepared. Four different operating
modes are possible: recirculation, once-through, partial recirculation, and system cleaning.
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
Figure 3.3
Photocatalytic Detoxification Pilot Plant (the batch mode is shown).
36
SOLAR DETOXIFICATION
When concentrating solar collectors are used, the temperature of the water which flows
through them rises considerably. Obviously, the slower the flow rate used in once-through
experiments and the longer recirculation experiments, the greater the increase of temperature
is. Therefore, to avoid evaporation and damage to plastics, cooling 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 system is used) has to be installed to move the treatment water
through the reactor. The flow rate (in batch mode) has to be such that it guarantees only a
small amount of reactant is converted each time 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 has to be
installed to regulate the flow to the rate desired. The most important sensors required for the
system are temperature, pressure and dissolved oxygen (at least in the reactor outlet). Other
sensors, such as pH, selective electrodes, etc., could be useful depending on the type of
experiments to be carried out. As constant pure oxygen is required for the oxidation of
organics, 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 predefined cycle, or continuously.
Atmospheric oxygen can be also stirred into the reaction medium in the reservoir tank. In this
case, the dissolved O2 is kept at a concentration of around 6-8 mg/L. An UV-radiation sensor
must be placed in a position where the solar UV light reaching the photoreactor can be
measured, permitting the evaluation of the incident radiation as a function of hour of the day,
clouds, and atmospheric 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 demineralised water (conductivity less than 10 µS, organic carbon content <
0.5 mg/L) is recommended for cleaning as well as in the tests themselves.
37
SOLAR DETOXIFICATION
The modules are kept illuminated a little longer (experimental time) than necessary to allow
the water in the holding tank to go through the reactor and approach the discharging tank.
This time (texp) is:
V + nVmod
t exp = tube (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 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 corresponding to each sample
collected at the end of the experiment is calculated with the following equation:
nV
t R ,i = i illu (3.2)
Q
where i is the number of modules through which the samples 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.
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 up in the holding tank (now called the batch tank). The automatic control sets the
maximum 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 experiment. Recirculation is continued and the
test lasts however long required, even up to several days. Samples may now be taken at any of
the sampling ports, since as the system is in recirculation mode, tR is the same for samples
taken at any point in the system. The (t R,i, Concentration) pairs are thus obtained (Eq. 3.3).
V
t R ,i = illu t exp,i (3.3)
VTOT
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).
38
SOLAR DETOXIFICATION
Recirculation line
Batch
Tank C1(t)
SOLAR REACTOR
C2(t)
Figure 3.4
Schematic of two pilot plant operation concepts: A once-through operation (top) and a batch
operation (bottom).
In a large field system, the amount of conversion each time the mixture passes through the
reactor is noticeable. 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. Because the rate usually decreases with concentration, 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, 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 allow more than 1 %
conversion per pass (C1(t) ≈ C2(t)) to be avoided. This 1% has been selected because is very
far from the error associated to 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, and VTOT is 250 L, the flow rate must be 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
39
SOLAR DETOXIFICATION
inlet concentration (which does not change with time) and the reaction kinetics. However,
because the system is a transient process, the normal 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 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 a numerical routine is required to fit
the data from the batch test. This routine also takes into account the volume of the 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*
∫C2 r = −∫0 dτ (3.6)
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 Eq. 3.6, the time spent in
the reactor is equal to tR, and the starting concentration is C0, thus:
C1 dC tR
∫C0 r ∫0 dτ= − (3.7)
• Regime 3: tR≥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 concentration at time t,
it must be known what went into the reactor at time tR-τ. This defines the lowest limit on
the rate integral:
C1 ( t R ) dC τ
∫C2 (tR −τ ) r ∫0 dτ
= − (3.8)
Having defined these three regimes, the balance of material in the well-mixed tank may now
be written:
dC 2 (t R )
− Vbatch = Q[C1 (t R ) − C 2 (t R )] (3.9)
dt
where Vbatch is the volume in the batch tank. Now, only linking Eq. 3.9 with the different
forms of Eq. 3.6 remains to be done. 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 Eq 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 Eq 3.9 and the value for C2(t) predicted. This
prediction is then compared to the experimental values for the concentration in the batch tank,
with iteration until the k value which provides 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, in any case, this method is only really necessary when the recirculation
flow is not high enough (See Eq. 3.5).
40
SOLAR DETOXIFICATION
Use of the experimental time as the calculation unit could give rise to misinterpretation of
results, because the reactor consists of illuminated and non-illuminated elements. Large
experimental reactors require much instrumentation and the reactor must also be as versatile
as possible, substantially 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, the differences in the
incident radiation in the reactor during an experiment are not taken into account. Furthermore,
the more different the environmental conditions of the experiments 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 the radiant power density measured by radiometers. This
permits extrapolation of known data from one scale to another, as well as avoiding the
problem arising from a variable source of radiation (sunlight).
Recalling Eq. 2.4, the photon flux density I [Einstein s-1 m-2] is the number of incident
photons per unit of surface and time:
2
d N
I= (3.10)
N 0 dt dA
where N0 is Avogadro’s number (6.023 x 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 day and from season to season, so that it is necessary 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.
41
SOLAR DETOXIFICATION
SPECTROPHOTOMETRIC MEASUREMENT OF UV
IT IS IMPOSSIBLE TO
EVALUATE THE PHOTON RADIOMETERS CALIBRATION
FLUX WITHOUT ON-LINE
SPECTRUM NO
MEASUREMENTS IS IT THE UV SPECTRUM CONSTANT?
YES
IT IS POSSIBLE TO OBTAIN AN EQUATION WHICH CORRELATE THE
RADIOMETRIC AND SPECTROPHOTOMETRIC DATA
ACTINOMETRIC EXPERIMENTS
EFFICIENCIES NO
EXPERIMENTAL ACTINOMETRIC QUANTUM YIELD =
CALCULATION
CALCULATED (BY PREVIOUS EQUATION) QUANTUM YIELD?
NOT CORRECT
YES
END
Figure 3.5
Calculating procedure to find out the photon flux inside a solar reactor.
where UVΣ (W m-2) is the summation of the radiation measurements (above 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 day are
compared considering n = 400 nm, which is the ultraviolet-visible threshold, after which the
radiometers should not measure.
Table 3.1
Radiometric and spectroradiometric UV measurements at different times of day compared
considering n = 400 nm
42
SOLAR DETOXIFICATION
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 of the previous example are given in Table 3.2, together with the %
of error at each interval.
UVΣ(1), W m-2
Table 3.2
Radiometric and spectroradiometric UV measurements at different times of day compared
considering n > 400 nm.
It seems that, taking as the upper limit a wavelength of 403-404 nm, the radiation measured
by both instruments is in agreement. The radiometer measurement interval is fundamental for
the calculation of the photon flux that reaches the interior of the reactor. The alternative might
be on-line measurement of the solar spectrum with a solar spectroradiometer, but this is very
often not possible because of the price and/or the manpower required for a spectroradiometer.
If the UV radiation spectrum is assumed to have a fixed shape similar to that in Figure 2.6, a
standardised spectrum is available in the wavelengths measured by the radiometer. Therefore,
using the standardised spectrum and the irradiance data (W m-2) measured by the radiometer,
the spectral distribution can be calculated for all of these data:
UVλ* = f λ UV (3.13)
*
where UV λ are the spectral data calculated with the standard spectrum (fλ) and the radiometer
data. Therefore, the number of photons is only a function of the intensity (measurable in real
time with the radiometers). Once the spectral distribution of the radiometer measurements is
known, the number of photons incident per unit of time and surface (N) corresponding to
those measurements can be found. Recalling Eq. 2.3, which relates the number of photons
from a given polychromatic source of light to the energy corresponding to each wavelength,
this can be transformed for this case into the following (using summations of discrete values):
1 λ = 404 nm *
N 300− 404 nm = ∑UVλ λ
hc λ =300 nm
(3.14)
43
SOLAR DETOXIFICATION
where N300-404nm are incident photons. But, as the spectral distribution is assumed to be
constant, Eqs. 3.13 and 3.14 yield:
UV λ = 404 nm
N 300− 404 nm = ∑ fλ λ
hc λ =300 nm
(3.15)
∑f
λ =300 nm
λ λ = 368.79 nm
To calculate the values corresponding to other intervals, the same procedure is followed.
Returning to Eq. 3.15, the number of photons corresponding to the average radiation at any
given instant for the radiometer is:
N 300 −404 nm = 1.856 × 10 18 UV (3.16)
2
where N300-404nm is the incident photons, between 300 and 404 nm, per m and second, when
UV is measured in W m-2 and λ in nm, with speed of light c = 2.988 × 1017 nm s-1 and the
Planck’s constant h = 6.626 × 10-34 J s. If Einstein (moles of photons) is used as the unit, the
result is:
N
I 300 − 404 nm = 300 − 404 nm = 3.083 × 10 −6 UV (3.17)
N0
1
η R,λ 1'
1+1’ I
2 Reflected I
3+4 I inside photoreactor, IE
η Efficiency factors
2 ηT ,λ
3 4
ABSORBER
MIRROR
Figure 3.6
Drawing of the various loss factors (η) affecting the photon flux (I) inside a photoreactor.
The solar radiation that reaches ground level without being absorbed or scattered is called
direct radiation, the radiation that has been dispersed but reaches the ground is called diffuse
radiation and the sum of both is called global radiation (see Chapter 2). Global radiation is
collected directly by the transparent absorber tube without intervention of the collector. In
44
SOLAR DETOXIFICATION
Figure 3.6 the path followed by I until it arrives inside the absorber tube is shown. It must
arrive at the surface and be reflected (part is lost due to ηR,i) in the right direction by the real
mirror surface (ηC), before penetrating (ηT,λ) in the tube. Furthermore, the parabolic
concentration factor must also be considered (ratio of surface area of the parabola capturing
the radiation and surface area of the tube, Sp/ST) if it is a concentrating solar collector (see
Chapter 6). Therefore, the effective photon flux corresponding to the UV inside the absorber
(IE) is:
S
I E = f I , P ,η C ,η R ,i ,ηT ,λ (3.18)
ST
Only the transmissivity of the glass, ηT,λ, affects the radiation reaching the absorber without
being reflected by the mirror (1’). In this case Eq. 3.18 is simplified:
I E = f ( I ,η T , λ ) (3.19)
Since ηT,λ depends on the wavelength, in order to evaluate IE, Eq. 3.15 must be recalculated as
follows:
S UV λ = 404 nm
I E = P × η C × η R ,i ∑ f λ ηT , λ λ (3.20)
ST hc λ =300 nm
where, if UV is W m-2, the units of IE are Einstein m-2 s-1 incident in the inside of the tube.
Sp/ST, as accurate as possible, is used to determine IE in each case. For this it is necessary to
make the corresponding trigonometric calculations based on the collector characteristics.
Once this is known, the same ratio can be calculated for the reactor volume. Therefore, Sp/ST
in Eq. 3.20 is substituted by this ratio (collector area/collector volume). In this way, photon
flux is obtained in units congruent with the reaction rate (M s-1) so that an estimated quantum
yield (ΦE) similar to that in Eq. 2.1 can be obtained, but using moles of incident photons
instead of moles of photons absorbed by the catalyst.
reaction rate
ΦE = (3.21)
I E∗
where I*E are Einstein L-1s-1 of UV irradiance incident inside the tube. To calculate the values
corresponding to other wavelength intervals, the same procedure is followed.
45
SOLAR DETOXIFICATION
• The analytic methods should be simple and the reagents should be easily synthesised and,
even better, commercially available. This is, if possible, much more important in the case
of pilot plants, because of the large volumes of actinometer that have to be prepared.
• The system should be sufficiently sensitive for low radiation intensities and the evaluation
of photons absorbed should be simple.
For this case, a common uranyl-oxalate system is explained as an example. Very complete
information on actinometric systems has been summarised by Kuhn et al. (1989):
( )
hv ∗
UO22 + → UO22 +
(3.22)
( UO2 )
2+ * 2+
+ H 2 C2 O4 → UO2 + CO + CO2 + H 2 O
Absorptivity of this solution may be estimated from:
Absorbed Photons
= 1 − exp(− µλ 2b) (3.23)
Incident Photons
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
Eq. 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 is 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, 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
point 3.4.3. The oxalic acid degradation rate calculated by the experiments or by Eq. 3.21 has
to 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 due to changes in
weather, and the impossibility of using an actinometer inside the reactor while the
photocatalytic experiments are being performed, make it impossible.
The above procedure is usually the most appropriate but, several parameters are very often not
available: on-site solar spectrum, collector reflectivity, absorber transmissivity, etc. In these
cases, a shorter procedure can be used. Although not the best solution, it is frequently very
useful. Nevertheless, an UV radiometer mounted at the same angle as the solar collector is
always necessary for data evaluation. This radiometer sends a signal to a computer in which
the data (UV) are stored. As radiation data are collected continuously, it is very easy to
calculate the average incident radiation on the collector surface ( UV n ), for each period of t,
and apply Eq. 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:
S
EUV,n = EUV,n-1 + ∆ t n UV n P
VTOT (3.24)
∆ t n = t n - t n −1
46
SOLAR DETOXIFICATION
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 is linear with the intensity of
radiation (see Chapter 4). For this purpose, several different experiments must be carried out
in the photoreactor to determine this effect at very different solar radiation conditions
(morning, noon, with and without clouds, summer, winter, etc) without changing the kinetic
order of the reaction.
-r, µM min-1
UV, W m-2
Figure 3.7
Typical photocatalytic degradation (-rDCA) in a solar pilot plant under different UV solar light
intensities.
The results of a typical test are shown in Figure 3.7. The reaction rate is calculated at the
beginning of the experiment (zero order) and UV corresponds to exactly the same 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 Eq. 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 experiment. Obviously, UV power
changes during the day and clouds, on the first day, make this variation still more noticeable,
but with Eq. 3.24, the data for both days can still be combined and compared with other
photocatalytic experiments. Consequently, with EUV, the reaction rate (-r) is expressed in
terms of mass of reactant degraded per kJoule of UV incident on the collector surface. If r is
expressed in these units, collector efficiency is already included in it through the use of
incident surface radiation, since different r with the same substance and different solar
collectors, means collector efficiency is different.
47
SOLAR DETOXIFICATION
C, mg L-1
UV, W m-2
t, min
C, mg L-1
2nd day
1st day
EUV, kJ L-1
Figure 3.8
Photocatalytic degradation in a solar pilot plant. Plots of concentration (z) as a function of
experiment time (up) and accumulated energy (down). Solar UV power throughout the
experiment is also shown.
48
SOLAR DETOXIFICATION
SELF-ASSESSMENT QUESTIONS
PART B.
1. Why is it necessary filtering IR in laboratory photoreactors?
2. Why a pilot plant has to be as versatile as possible?
3. Which are the main characteristics of the material to be used for connecting the pilot plant
photoreactors?
4. Which are the most important sensors to be installed throughout and at a photocatalytic
pilot plant?
5. Why is it very important the flow rate in batch experiments?
6. Why residence time is not the best variable for obtaining kinetic constants in solar
photocatalysis?
7. Which are the essential data, necessary for obtaining an equation similar to the following,
for correlating radiometric measurements and photonic flux inside a photocatalytic solar
photoreactor?
N
I λ1− λ 2 = λ1− λ 2 = f (UV )
N0
8. Which is the wavelength considered equivalent to the following normalised spectrum?
λ, nm fλ
300 0.0002
310 0.0023
320 0.0063
49
SOLAR DETOXIFICATION
330 0.0109
340 0.0118
350 0.0124
360 0.0127
370 0.0159
380 0.0156
390 0.0160
9. If Einstein (moles of photons) is used as the unit, which is the number of photons
corresponding to the average radiation at any given instant in the previous example?
10. Which are the essential data for radiation evaluation in a solar photocatalytic reactor?
Answers
Part A
1.False; 2. False; 3. False; 4. True; 5. False; 6. True; 7. False; 8. True; 9. False; 10. True.
Part B
1. Because IR beams could heat the slurry suspensions very quick.
2. Because the necessity of accomplishing all the experiments with enough confidence and
fulfilling all the actual and future necessities of the research to be performed in it.
3. All the tubes and valves must be strongly resistant to chemicals, weather-proof and
opaque, in order to avoid any photochemical effect outside of the photoreactors.
4. Temperature, pressure, dissolved oxygen and solar irradiation.
5. Because it is directly related with the conversion per pass and, therefore, with the
modelling of the photoreactor.
6. Because when time is the independent variable, the differences in the incident radiation in
the reactor during an experiment are not taken into account.
7. Solar spectra.
λ = 390 nm λ = 390 nm
8. ∑ fλ = 1 ;
λ = 300 nm
∑f
λ = 300 nm
λ λ = 373.6 nm
50
SOLAR DETOXIFICATION
OBJECTIVES
By the end of this unit, you will know the main aspects of experimental photocatalysis
variables and you will be able to do 7 things:
1. Understand why blank experiments are always necessary in photocatalysis.
2. Design experiments that avoid the effects of oxygen and pH and, thereby, reduce the
number of variables affecting the tests.
3. Comprehend the influence of catalyst concentration and how to find the optimum catalyst
mass in an experimental reactor.
4. How a Langmuir Hinshelwood (L-H) model, which, although it does not explain the
photocatalytic mechanisms, may be used in heterogeneous photocatalysis to obtain the
kinetic constants for reactor optimisation.
5. Arrange experiments to obtain L-H parameters.
6. Describe the interdependence of the photocatalytic reaction rate and illumination intensity
and when this relationship is directly proportional.
7. Determine useful parameters for describing photocatalysis efficiency without knowing the
amount of photons absorbed by the system and, why quantum yield is almost impossible
to be calculated in heterogeneous photocatalysis experimental systems.
51
SOLAR DETOXIFICATION
In any case, the focus here is on fundamental photocatalytic parameters and therefore the
photolytic effect will be discussed from this point of view. These tests have to be performed in
order to find out the decomposition rates without the semiconductor. As TiO2 readily sticks to
the glass in the photoreactors, it is necessary to carry out these tests at the beginning, before
the catalyst comes into contact with the photoreactors. In pilot-plant-scale experiments,
removal of the thin coating of catalyst on the tubes after TiO2 suspensions have circulated
through them is a very hard, 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 the absence or evaluating the importance of the following effects:
• 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.
organic pollutant + O2
→ CO
semiconductor
2 + H 2 O + mineral acids (4.1)
ultra − bandgap energy
The concentration of oxygen also affects the reaction rate, which is faster when the partial
pressure of oxygen (pO2) in the atmosphere in contact with the water increases. In any case, it
seems that the difference between using air (pO2 = 0.21 atm) or pure oxygen (pO2 = 1 atm) is
not drastic (See Figure 4.1). In an industrial plant it would be purely a matter of economy of
design. In Figure 4.1 it is clear that when all the oxygen contained in the water has been
consumed, photodecomposition of TOC comes to a halt. At the moment injected oxygen
reaches the reactor, photodecomposition continues. Therefore, injection of pure O2 becomes
necessary in once-through experiments (See Figure 3.3 and Figure 3.4) at low flow rates. At
52
SOLAR DETOXIFICATION
high flow rates or with recirculation, the addition of oxygen is not always necessary since the
illumination time per pass is short. The water again recovers the oxygen consumed when it
reaches the tank (open to the atmosphere and stirred).
3.0
2.0
air
1.5
C/C0
1.0
0 20 40 60 80 100
pO2
0.5
TOC
0.0
0 10 20 30 40
Illumination time, min
Figure 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.
4.3 pH INFLUENCE
The pH of the aqueous solution significantly affects TiO2, including the charge of the particle
and the size of the aggregates it forms. The pH at which the surface of an oxide is uncharged
is defined as the Zero Point Charge (pHzpc), which for TiO2 is around 7. Above and below this
value, the catalyst is negatively or positively charged according to:
− TiOH 2+ ↔ TiOH + H + (4.2)
− +
− TiOH ↔ −TiO + H (4.3)
The equilibrium constants of these reactions (Kormann et al. 1991) are pKTiOH2+ = 2.4 and
pKTiOH = 8.0, the abundance of all the species as a function of pH: -TiOH ≥ 80% when
3<pH<10; -TiO- ≥ 20% if pH>10; -TiOH2+ ≥ 20% when pH<3. Under these conditions, the
photocatalytic degradation of the ionisable organic compounds is affected by the pH. At first
sight, and for pollutants for which pKa is outside the range of 1-13, a very acidic solution
appears to be detrimental and a very basic solution to be favourable, since the variations are
modest or non-existent around 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 possesses an advantage over other processes. In many cases, a very important
feature of photocatalysis is not taken into account when it is to be used for decontamination of
water, is that during the reaction, a multitude of intermediate products are produced that may
behave differently depending on the pH of the solution. To use only the rate of decomposition
of the original substrate could yield an erroneous pH as the best for contaminant degradation.
53
SOLAR DETOXIFICATION
Therefore, a detailed analysis of the best pH conditions should include not only the initial
substrate, but also the rest of the compounds produced during the process.
Mean particle-size measurements (presented in Figure 4.2) have been found to be constant at
pH far from pH ≈ 7. 300 nm sizes increase to 2-4 µm when dispersion reaches pHzpc. The zero
surface charge yields zero electrostatic surface potential that cannot produce the interactive
rejection necessary to separate the particles within the liquid. This induces a phenomenon of
aggregation and 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 for transmitting and/or absorbing light. Furthermore, larger clusters sediment 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 for
separating the catalyst from water (by sedimentation and/or filtration) at completion of
photocatalytic treatments.
3000
pHZPC= 6.9
2500
Mean size, nm
2000
1500
1000
500
0
2 4 6 8 10 12
pH
Figure 4.2
Mean particle size of TiO2 (P-25) suspended in water versus pH. [TiO2]=0.2 g/L.
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 sulphuric acid have generally been chosen to produce basic or acid pH,
respectively. Organic buffers must be avoided because they are potential consumers of •OH,
and toxic inorganic acids or bases the same, for evident reasons.
54
SOLAR DETOXIFICATION
UV LAMP
UV path length
LAMP
PROTECTION
CHAMBER
Cooling
water
REACTION CHAMBER
UV UV LAMP
UV 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.
There are a number of studies in the literature on the influence of catalyst concentration on
process efficiency. The results are very different, 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 of the reactor and coaxial with it (see Figure 4.3a), [TiO2]OPT is very
high (on the order of several grams per litre) if the path length is short (several mm). On
the other hand, [TiO2]OPT is low (hundreds of mg per litre) if several centimetres are
crossed (see Figure 4.4 solid circles).
• If the lamp is outside (see Figure 4.3c), but the path length is short (1-2 cm max.), the
maximum rate is obtained with 1-2 g L-1 of TiO2 (see Figure 4.4 solid squares).
• If the lamp is outside, but the path length is several centimetres 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 corresponds to a photoreactor with a large diameter and
solid triangles to one with a smaller diameter, but both several centimetres. In this case, it
is very clear than the optimum rate is attained at lower catalyst concentrations when the
photoreactor diameter is wider.
In all the cases described above, a “screening” effect is produced when the TiO2 concentration
is very high. The reaction rate diminishes due to the excessive opacity of the solution, which
prevents the catalyst farthest in from being illuminated. Besides, the larger the size (see Figure
4.2), the less the opacity of the suspension. When the radiation comes from a parabolic trough
collector, something similar to what is shown in Figure 4.3b occurs. In any case, these are
only approximations based on the results obtained by different authors and, because of all of
the above, it is always necessary to find out, experimentally, the optimum catalyst
concentration for the plant studied. That is, the minimum concentration at which the
maximum reaction rate is obtained. But it does not seem to be necessary to test a very wide
range of concentrations. This effect is shown in Figure 4.4. Usually, the reaction rate increases
very quickly with TiO2 concentration, but only at low catalyst concentrations (usually below
100 mg/L). After that, the reaction rate stabilises and at very high catalyst concentrations the
55
SOLAR DETOXIFICATION
reaction rate decreases. When this point is found, it is not really necessary to continue
checking any higher because no more useful information is going to be obtained.
1.2
1.0
0.6 TOC
1.0
relative rate
0.4
0.5
0.2
0.0
0.0 0.2 0.4 0.6 0.8
-1
TiO2, g L
0.0
0.0 0.4 0.8 1.2 1.6 2.0
-1
TiO2, g L
Figure 4.4
Influence of catalyst concentration on the rate of photocatalysis (normalised rates have been
used to make it more easily understood) in different reactors (see text). The continuous line is
only to clarify the tendency. In the inset, relative reaction rates of degradation (two different
photoreactors) and mineralization (TOC) of the same contaminant are shown. See text for
comments.
As shown in Figure 4.4, initial substrate behaviour is not always the same as that of TOC.
This is due to the influence of intermediate products generated during the photocatalytic
reaction. That is, the screening effect influences the decomposition of the original product in a
different way than the other organic species present in the reaction and, in the example
presented, to mineralise the contaminant it is unnecessary to use more than 0.2 g L-1 of TiO2.
As oxidation proceeds, less and less of the surface of the TiO2 particles is covered as the
contaminant is decomposed. Evidently, at total decomposition, the rate of degradation is zero
and a decreased photocatalytic rate is to be expected with increasing illumination time (or the
accumulated energy, see Eq. 3.24). Most authors agree that, with minor variations, the
expression for the rate of photomineralization of organic substrates with irradiated TiO2
follows the Langmuir Hinshelwood (L-H) law for the same saturation-type kinetic behaviour
in any of four possible situations: (i) the reaction takes place between two adsorbed
substances; (ii) the reaction occurs between a radical in the solution and the adsorbed
substrate; (iii) the reaction takes place between the radical linked to the surface and the
substrate in the solution; and (iv) the reaction occurs with both species in solution. In all
cases, the expression of the equation rate is similar to the L-H model. From kinetic studies
only, it is therefore not possible to find out whether the process takes place on surface or in
solution. Although the L-H isotherm has been rather useful in modelling the process, it is
generally agreed that both rate constants and orders are only "apparent". They serve to
describe the rate of degradation, and may be used for reactor optimization, but they have no
physical meaning, and may not be used to identify surface processes. Thus, while not a useful
56
SOLAR DETOXIFICATION
tool for describing the active species involved in oxidation, engineers and solar designers
seem to have a common understanding on the usefulness of the unmodified L-H model.
1.0
(C0 - C) = krt
Normalised Concentration
2.5
0.8
2.0 ln (C0/C) = k’t
0.6 1.5
ln (C0/C)
1.0
0.4 0.5
0.0
0 5 10 15
0.2
EUV, kJ/L or time, min
0.0
0 5 10 15 20 25
EUV, kJ/L or time, min
Figure 4.5
Typical photocatalytic degradation. The insert shows data adjusted to Eq. 4.6.
Due to the above, for L-H standard data treatment, it is assumed that the reaction occurs on
the surface, which is also the assumption most widely accepted as possible. Under these
conditions, two extreme situations are defined to illustrate the adsorption on the catalyst
surface: (I) substrate and water compete for the active catalyst sites and (II) the reactant and
the solvent are adsorbed on the surface without competing for the same active catalyst sites.
According to the L-H model, the reaction rate (r) is proportional to the fraction of surface
covered by the substrate (θx). In each case the following expression can be obtained:
dC k r KC
r=- = krθ x = (4.4a)
dt 1 + KC + K s C s
dC k KC
r=- = krθ x = r (4.4b)
dt 1 + KC
where kr is the reaction rate constant, K is the reactant adsorption constant, C is he
concentration at any time, KS is the solvent adsorption constant and CS is its concentration (in
water CS ≈ 55.5 M). As CS >>C and, CS remains practically constant, the part of the catalyst
covered by water is unalterable over the whole range of C and the previous equations can be
integrated:
C K K
ln 0 + ( C 0 - C) = k r t (4.5a)
C 1+ K s Cs 1+ K s C s
C
ln 0 + K( C 0 - C) = k r Kt (4.5b)
C
When C0 is very small, both equations can be reduced to an order one-reaction rate equation:
C
ln 0 = k ′t (4.6)
C
So, if ln (C0/C) is represented versus t (or the accumulated energy, see Eq. 3.24), a line, the
slope of which is the apparent reaction rate constant k’, should be obtained (see Figure 4.5).
Likewise, at higher concentrations, both equations can be simplified by adjusting them to zero
order, (C0 - C) = krt, as might be the case at the beginning of the experiment represented in
Figure 4.5.
57
SOLAR DETOXIFICATION
Using an L-H model, graphics similar to those depicted in Figure 4.6 may be obtained from
the experimental data and from the linearisation of the previous equations. The effect of the
initial concentration on the degradation rate is shown in Figure 4.6a, where, due to the
saturation produced on the semiconductor surface as the concentration of the reactant
increases, it reaches a point at which the rate becomes steady. Figure 4.6b shows a
linearisation of Eqs. 4.4, where the slope of that straight line is (1+KSCS)/krK, but could also
be 1/krK. Finally, Eqs. 4.7 are obtained from Eqs. 4.5 when the concentration is half of the
initial (C/C0 = 0.5):
0.693(1 + K S C S ) 0.5 C 0
t 1/2 = + (4.7a)
kr K kr
0.693 0.5 C 0
t 1/2 = + (4.7b)
kr K kr
t1/2
-1
r0
r0
-1
C0 C0 C0
a) b) c)
Figure 4.6
Graphics related to the adjustment of data to a L-H type kinetic model
It should be emphasised that photodecomposition gives rise to intermediates, which could also
be adsorbed competitively on the surface of the catalyst. The concentration of these
intermediates varies throughout the reaction up to their mineralization and thus, Eq. 4.4 may
also take the following form:
k r KC
r= n
(4.8)
1 + KC + ∑ K i C i (i = 1, n )
i =1
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 important for the design and optimisation 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 are held constant. Due to this, a series of tests at
different initial substrate concentrations has to be performed to demonstrate whether the
experimental results could be adjusted with this model. The concentration range has to be
wide enough to allow correct fit of the L-H linearisation. This means, from the lowest
concentration at which the initial rate could be determined until the limit where the
relationship 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 experiments to
be carried out for this purpose. From the slope of the line corresponding to the starting points
of each of the experiments, the initial degradation rate can been calculated. Figure 4.7 shows
58
SOLAR DETOXIFICATION
the initial rate calculated. From 0.2-0.4 mM of substrate the initial rate is steady. At this
concentration, catalyst saturation occurs and the reaction rate becomes constant.
2.0 2.0
1.5 3 1.5
-1
r0, mM h
2
1.0 1.0
1/r0
1
(krK)-1 = 0.0381
0.5 0.5
(kr)-1 = 0.638
0
0 25 50 75
1/C0
0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0
C0, mM
Figure 4.7
Initial degradation rate as function of the initial substrate concentration. The insert shows the
linear transformation of Eq. 4.4 from which the rate constant and the adsorption coefficient
can be estimated from the intercept and the slope, respectively.
The constants can be calculated from the graphic inserted in Figure 4.7 using the L-H model.
k r KC 0 1 1 1 1
r0 = → = + (4.9)
1 + KC 0 r0 k r k r K C0
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 Eq. 4.5. With this, definition of reactor volume
and surface (see Eq. 3.2 or 3.3) is possible. If accumulated energy is used instead of time,
them Eq. 3.24 should be used for obtaining the kinetic constants and, afterwards, for reactor
design.
Since 1990, the kind of solar technology, which should be involved in detoxification, has been
clarified. Initial experiments 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 systems
for water treatment is firmly based on two factors, first the 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 demonstrated by experiment that above a certain UV photon flux,
reaction rate dependency on intensity goes down from one to a half order (Ollis, 1991;
Herrmann, 1995). This does not seem to occur at a particular radiation intensity, as different
researchers obtain different results, but presumably is significantly affected by experimental
conditions. Some authors impute the transition of r = f (I1.0) to r = f (I0.5), to the excess of
59
SOLAR DETOXIFICATION
photogenerated species (e-, h+ and •OH). This can be demonstrated as follows. According to
section 1.4, the five basic simplified equations are:
TiO2 + hν → e − + h + (4.10a)
− +
e + h → N + energy (4.10b)
− −
A+e → A (4.10c)
+ +
D+h → D (4.10d)
− +
A + D → Intermediates → Products (4.10e)
and the rate-limiting step is the reaction in the adsorbed phase (Eq. 4.10e). Therefore:
[ ][ ]
r = re = k e A − D + (4.11)
In an n-type semiconductor such as titania, the photo-induced holes are much less numerous
than electrons (photo-induced electrons plus n-electrons): [p+]<<[e-]. Therefore holes are the
limiting active species. Thence:
r = re = rd = k d [D ] p + [ ] (4.12)
At any instant, one has:
[ ]
d p+
[ ][ ]
= ra − rb − rd = 0 = k a − k b e − p + − k d [D ] p + [ ](4.13)
dt
Thence:
p+ = [ ] ka I
[ ]
k b e + k d [D ]
−
(4.14)
and:
k a k d [D ]I
r= (4.15)
[ ]
k b e − + k d [D ]
From the above equation, it can be seen that the reaction rate is directly proportional to light
flux. In the case of high fluxes, the instantaneous concentrations [e-] and [p+] become much
larger than kd[D] and [e-] ≈ [p+]. Therefore Eq 4.14 becomes:
[ ] k I
p + ≈ a − ; Therefore p + ≈ a
kb e [ ]
2
[ ]
k I
kb
(4.16)
r=k
r = k I½
r=kI
FOTONIC FLUX
Figure 4.8
60
SOLAR DETOXIFICATION
Relation between the photocatalytic reaction rate and the intensity of the radiation received.
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 sunUV = 22 WUV m-2), quantum yield diminishes.
This effect should be measured experimentally in each device, but this limit (several suns) is
usually accepted as a general rule.
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 (20ºC-80°C ). However,
at very low temperatures (-40°C-0°C), activity decreases and activation energy Ea becomes
positive. By contrast, at "high" temperatures (>70-80°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 Eqs. 4.4 θ tends toward 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 temperature
increases above 80°C, nearing the boiling point of water, the exothermic adsorption of
reactants is disfavoured and this tends to become the rate-limiting step.
In photochemistry, a concept called quantum yield is used to evaluate the results obtained and
compare different experimental conditions. Recalling Eq. 2.1 (Φ = ∆n Na-1), the quantum
yield of a photochemical reaction is defined with regard to the number of reacting molecules
and the number of photons absorbed.
61
SOLAR DETOXIFICATION
In this book, a heterogeneous system made up of a suspended solid (TiO2), a gas (O2) in
bubbles and/or dissolved 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: a) evaluate the light
absorption of a very complex reactive mixture, which, moreover, changes its composition
throughout the reaction, b) from this basis, determine the photon flux that arrives at each
particle of the catalyst to photoactivate it, and c) 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 heterogeneous 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 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 radiation of a certain wavelength (Eq.
3.21) incident on the inside of the reactor for calculation of Na. The value obtained from this
is called the estimated quantum yield: ΦE. No distinction is made between the photons
corresponding to each wavelength, assuming that all of them have the same effect on the
surface of the catalyst. In all cases, this simplification is accepted as valid by a multitude of
authors and widely used in the bibliography. Consequently, the reported “quantum yields”
have sometimes been reported as lower limits not allowing for scattered light. A simple means
of assessing process efficiencies for equal absorption of photons is therefore desirable in
heterogeneous photocatalysis (Eq. 4.18). The initial photoconversion 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 scientist (belonging to different research groups)
considered among the most important 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 organic pollutants and, like many of theses, is essentially degraded by oxidation rather
than reduction.
rate of disappearance of substrate
ζr = (4.18)
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 conditions 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 laboratories or
pilot plants possible because ζr is basically independent of the fundamental photocatalysis
parameters (light intensity, reactor geometry and TiO2 concentration for a given catalyst).
However, it depends on the initial concentration 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.
62
SOLAR DETOXIFICATION
1.0 1.0
C/C0
0.8 Average 0.8
Normalized Concentration
TOC/TOC0
Average
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
0 5 10 15 20 25
EUV, kJ/L
Figure 4.9
Plots of the normalised concentration as a function of the accumulated energy for the
photodegradation and mineralization of phenol. C0 = 20 mg/L , TiO2 = 200 mg/L, pH0 = 5.
The mineralization rate (measured by TOC analysis) is also included because efficiencies
based on the disappearance of organic carbon (ζr ,TOC, Eq. 4.19) provide more practical
information.
rate of disappearance of substrate TOC
ζ r ,TOC = (4.19)
rate of disappearance of TOC from phenol
Phenol and pesticide experiments have been performed under the exact same conditions. With
sunlight, it is not possible to work under constant illumination conditions. Therefore, Eq. 3.24
is used to avoid this uncertainty and reaction rates used to determine ζr and ζr ,TOC are
calculated using EUV instead of time. Relative photonic efficiencies of the two pesticides
tested are reported in Table 4.1. All the efficiencies are lower than unity, indicating that the
initial photocatalytic oxidative degradations of the test substances, at the selected initial
concentration, are less efficient than for phenol.
Photolysis tests have to be performed always before photocatalysis tests in order to find out
decomposition rates without the semiconductor. The water to be treated must contain enough
dissolved oxygen. To unambiguously exclude the effect of pH, the reagents used to modify 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, therefore, must be
63
SOLAR DETOXIFICATION
always tested first. The direct application of the Langmuir-Hinshelwood model produces an
empirical equation, which fits the degradation experimental data accordingly. This equation is
useful in a wide range of initial concentrations and is necessary for engineering plant design.
Experimentation at pilot plant level is essential to obtain these equations. Above a certain flux
of UV photons, reaction rate changes depending on intensity. It may only be intuited that at
intensities of several suns, quantum yield diminishes. This effect should be measured
experimentally in each device, but this limit is generally accepted. The optimum temperature
is generally between 20 and 80°C. The use of relative photonic efficiencies renders
comparison of process effectiveness between studies carried out in different reactors possible.
SELF-ASSESSMENT QUESTIONS
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?
64
SOLAR DETOXIFICATION
3. What is the main difference between bubbling oxygen and air inside a photoreactor?
4. To unambiguously exclude the pH effect, what are the reagents most often used to change
the pH?
5. Why are L-H constants called “apparent” in photocatalysis?
6. Calculate the L-H constant corresponding to the following experimental data:
Table 4.2 belongs here.
Experimental data from a series of photocatalytic experiments at different initial
concentration.
7. What is the most accepted reason for photocatalytic reaction rate dependence on change of
order of intensity?
8. What is the usual UV power of light intensity where the change of order is produced?
9. What is the optimum temperature range for heterogeneous photocatalytic reactions?
10. Why is use of a secondary actinometer necessary?
Answers
Part A
1.True; 2. False; 3. False; 4. False; 5. False; 6. True; 7. True; 8. False; 9. False; 10. True.
Part B
1. As TiO2 readily sticks to the materials of the photoreactors.
2. This type of experiment evaluates the importance of the treatment without catalyst, the
increase in temperature in the reactor and the adsorption of pollutant or its metabolites in
the materials of the pilot plant.
3. The concentration of O2 inside the reactor. By bubbling oxygen, the [O2] is almost five
times greater than by bubbling air.
4. Sodium hydroxide and hydrogen chloride or sulphuric acid.
5. Because with kinetic studies only, it is impossible to find out whether the process is on the
surface or in solution and therefore, the constants obtained have no physical meaning, and
may not be used to identify surface processes.
6. kr = 2.19 mg L-1 min-1; K = 0.0192 (mg/L)-1
7. The transition of r = f(I1.0) to r = f (I 0.5) is usually attributed to the excess of
photogenerated species (e-, h+ and •OH).
8. Above 50-75 WUV per square meter of photoreactor surface, the quantum yield
diminishes.
9. Between ambient temperature and 60-70 ºC.
10. Because ζr is basically independent of photocatalysis fundamental parameters (light
intensity, reactor geometry and TiO2 concentration for a given catalyst).
65
SOLAR DETOXIFICATION
OBJECTIVES
By the end of this unit, you will know why photocatalysis for the treatment of contaminated
water is important and 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.
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. Find out 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.
66
SOLAR DETOXIFICATION
In general, the types of compounds that have been degraded include alkanes, haloalkanes,
aliphatic alcohols, carboxylic acids, alkenes, aromatics, haloaromatics, polymers, surfactants,
herbicides, pesticides and dyes. A partial tabulation of organic compounds successfully
degraded by photocatalysis is provided in Table 5.1. Eq. 5.1 generally holds true for an
organic compound of general formula CnHmOp.
(m − 2 p) m
C n H mOp + + n O2 → nCO2 + H 2 O (5.1)
4 2
In the case of organic compounds containing halogens, Eq. 5.2 shows how the corresponding
halide is formed.
(m − 2 p) m−q
C n H mO p X q + + n O2 → nCO2 + H 2 O + qHX (5.2)
4 2
Under photocatalytic oxidative conditions, sulphur is recovered as sulphate in sulphur
containing compounds according to Eq. 5.3
C n H m O p S r + xO2 → nCO2 + yH 2 O + zH 2 SO4 (5.3)
OH O O O O
Cl Cl Cl Cl . Cl Cl Cl Cl . Cl . Cl
. OH OH OH
-H2O -HCl OH
Cl Cl Cl . Cl Cl Cl Cl Cl
Cl Cl
Cl Cl HO Cl O O
Figure 5.1
SOLAR DETOXIFICATION
The effectiveness of degradation is not demonstrated only because the entire initial compound
is decomposed. As observed in the HPLC chromatograms (Figure 5.2), oxamyl
(chromatogram A, retention time 4.45 min) disappears nearly completely (chromatogram B).
However, many new organic compounds appear.
Furthermore, the stoichiometry proposed for the general reactions (Eqs. 5.1-5.3) has to be
demonstrated in each case by a correct mass balance. Reactives and products might be lost
and this will originate not confident results. Mineralization rate is determined by monitoring
inorganic compounds, such as CO2, Cl-, SO42-, NO3-, PO43-, etc. 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 concentration of hydrogen ions (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 which take place in
the medium: the effect of the TiO2 suspension, the formation of CO2 and intermediates, etc.
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 Eq. 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, since these intermediates contain
differing amounts of chlorides
hυ
C 6 Cl 5 OH + O2 + 2 H 2 O TiO
→6CO2 + 5HCl
9
(5.4)
2 2
In Figure 5.3, a complete pentachlorophenol degradation test is shown. The products obtained
are practically stoichiometrically correct. The slight difference may be attributed to the facts
that all the TOC is not 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 dearomatization 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 mineralised into NH4+ and mostly NO3-.
Ammonium ions are relatively stable and the proportion depends mainly on the initial
oxidation degree of nitrogen and on the irradiation time. The pollutants containing sulphur
atoms are mineralised into sulphate ions. Organophosphorous pesticides produce phosphate
69
70
OXAMYL
A
min.
Figure 5.2
0.12 0.6
0.10 0.5
[PCP], TOC], mM
Cl-
0.08 0.4
PCP
0.04 0.2
0.02 0.1
0.00 0.0
0 5 10 15 20 25 30 35
tR, min
Figure 5.3
71
SOLAR DETOXIFICATION
ions. However, phosphate ions in the pH range used remained adsorbed on TiO2. This strong
adsorption partially inhibits the reaction rate that, however, remains acceptable. Until now, the
analyses of aliphatic fragments resulting from the degradation of the aromatic ring have only
revealed formate and acetate ions. Other aliphatics (presumably acids, diacids, and
hydroxylated compounds) are very difficult to separate from water and to analyse. Formate
and acetate ions are rather stable, which in part explains why total mineralization takes much
longer than dearomatization.
72
HIDROXY DERIVATIVES PYRIMIDIL DERIVATIVES ALIPHATIC
OH DERIVATIVES
N NH2 N CH3
N CH3
O O
N C NH C
N CH3 NH2
CH3 CH3
NH2
O C
N CH3
NH 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
Figure 5.4 CH3
OH
73
SOLAR DETOXIFICATION
However, it is very difficult to identify all the intermediary compounds en-route to complete
mineralization. Toxicity testing of 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 intermediary 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 mixtures 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 photocatalytically treated
waters before total mineralization is determining the biodegradability (BOD) in sludge from
biological activated sludge plants. 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 biological activated sludge used for the BOD tests is used for disposing the treated
water. This test produces non-universal results, but could be very useful if the biological
treatment plant that will 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.
74
SOLAR DETOXIFICATION
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-
thiosulphate 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
selectively recover noble heavy metals. For instance, silver has been separated from copper in
solutions simulating industrial 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 Pb2+ 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 water
containing Ag becomes stricter.
One strategy for inhibiting e-/h+ recombination is to add other (irreversible) electron acceptors
to the reaction. Outstanding enhancement of the rate of degradation of various organic
contaminants through the use of inorganic peroxides has been demonstrated (Pelizzetti et al.
1991, Malato et al. 1998). The addition of other oxidising species could have several different
effects:
• Increase the number of trapped e- in the e-/h+ pairs and, consequently, avoid
recombination.
• Generate more •OH and other oxidising species.
• Increase the oxidation rate of intermediate compounds.
• Avoid problems caused by a low O2 concentration.
It must be mentioned here that in highly toxic wastewater where degradation of organic
pollutants is the major concern, the addition of an inorganic anion to enhance the organic
degradation rate may often be justified. For better results, these additives should fulfil the
following criteria: dissociate into harmless by-products and lead to the formation of •OH or
other oxidising agents. There is another advantage related to the use of this type of oxidant
when solar energy is the photon source. Although scientific research on photocatalytic
detoxification has been conducted for at least the last three decades, industrial/commercial
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 commercialisation. The increase of the photocatalytic reaction rate
with these additives would decrease photoreactor dimensions proportionally and dramatically
decrease overall costs.
75
SOLAR DETOXIFICATION
5.2.2. Persulphate
In homogeneous reactions, the persulphate ion accepts an electron and dissociates (Eq. 5.14).
The sulphate radical anion is also generated adequate thermal and photolytic (wavelength <
270 nm) conditions. This radical goes through the reactions explained below (Eq 5.16 and
5.17). Persulphate can therefore be a beneficial oxidising agent in photocatalytical
detoxification because SO4•- is formed from the oxidant compound by reaction with the
photogenerated semiconductor electrons (e-CB, Eq. 5.15). In addition, it can trap the
photogenerated electrons and/or generate hydroxyl radicals. The sulphate radical anion (SO4•-)
76
SOLAR DETOXIFICATION
is a very strong oxidant (Eo = 2.6 V) and engages in at least three reaction modes with organic
compounds: by abstracting a hydrogen atom from saturated carbon, by adding to unsaturated
or aromatic carbon and by removing one electron from carboxylate anions and from certain
neutral molecules.
S 2 O82− +eaq
−
→SO4−• + SO42−
(5.14)
S 2 O82− +eCB
−
→SO4−• + SO42−
(5.15)
−• − 2−
SO +e
→SO
4 CB 4 (5.16)
SO4−• + H 2O
→ • OH + SO42− + H + (5.17)
The TiO2 band-gap represents only 5% of the solar spectrum (see Chapter 2). From the
standpoint of solar collecting technology, it is therefore a rather inefficient process even for a
high added-value application. In contrast to other Advanced Oxidation Technologies,
photocatalysis has the advantage of being solarizable and of being an environmentally friendly
technology. TiO2 is a cheap photostable catalyst, and the process may be run at ambient
temperature and pressure conditions. Furthermore, the oxidant, molecular oxygen (O2), is the
mildest one. Therefore, basically, TiO2 is a mild catalyst that works at mild conditions with
mild oxidants. However, as concentration and number of contaminants increase, the process
becomes more complicated and challenging problems, such as catalyst deactivation, slow
kinetics, low photoefficiencies and unpredictable mechanisms need to be solved. It is clear
that naked TiO2 needs extra help to undertake practical applications of industrial and
environmental interest and this could lead to the loss of some of the charm of its mild
operation. Moreover, even reactor set-ups using artificial light, and the cost of running the
lamps involved in them, will be much cheaper if visible radiant flux can be employed.
77
SOLAR DETOXIFICATION
The redox process is based on the migration of electrons and holes to the semiconductor
surface and two further oxidation and reduction steps (see Figure 5.1). Two basic lines of
R&D attempt to balance both half-reaction rates, one by adding electron acceptors (additional
oxidants, already commented on above) and the other by modifying catalyst structure and
composition. Both try to promote competition for electrons and avoid recombination of e-/h+
pairs. A third approach has focused not only on increasing quantum yield but finding new
catalysts with band-gaps that match the solar spectrum better. Unfortunately, the choice of
convenient alternatives for substituting titanium dioxide in photocatalytic detoxification
systems is limited. The appropriate semiconducting material should be:
• Non toxic.
• Stable in aqueous solutions containing highly reactive and/or toxic chemicals.
• Not photo-corrodible under band-gap illumination.
• Economical, that is, an increase in photocatalytic reaction rates must be always be
accompanied by a non-proportional increase in overall process costs.
Generally, metal oxides 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 (e. g. CdS) are usually unstable and photodegrade in 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.
e-
ν
hν
Metal
h+
Figure 5.5
79
80
Figure 5.6
SOLAR DETOXIFICATION
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.
81
82
ν
hν
e-
CdS e-
h+
TiO2
Figure 5.7
e-
Dye* CB CB CB
A A A-
ν
hν
Dye VB VB VB
Figure 5.8
83
SOLAR DETOXIFICATION
• It is a reliable, simple and rapid way to close the mass balance at any moment to get an
idea of the remaining amount of intermediates and check the extraction methods and
analysis of intermediates.
The basic techniques for the determination of TOC in water have remained relatively
unchanged for 20 years. Organic compounds are converted to CO2 using a combination that
may include chemical oxidizing agents, ultraviolet radiation or high-temperature combustion
(Wangersky, 1993). The CO2 is then measured using non-dispersive infrared absorption,
micro-coulometry or conductimetric techniques. Since many water samples contain inorganic
forms of carbon (HCO3- and CO32-), it is usually necessary to remove theses species, typically
using a gas stripping technique prior to measurement of TOC. Some part 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 able to manage non-filtered samples.
When TiO2 is filtered from the sample, there is an important loss of organic compounds
because they are adsorbed onto the solid retained in the filter.
Important advantages of the GC/MS-based methods are: a) the large amount of structural
information they yield and the spectra libraries available either from data bases or from
research papers which make DP identification feasible; b) the durability and reliability of the
GC-MS interface; and c) the highly efficient sensitivity and separation that avoids overlapping
compounds with similar structures. However, GC-MS based methods have important
drawbacks because of their low capacity to analyse very polar, low volatile and 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
disadvantage 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
ionisation (CI). From the molecular weight and interpretation of fragmentation patterns, it is
possible to hypothesise a molecular structure. However, even an EI mass spectrum does not
provide enough information about the location of the functional groups (e.g., position of a
hydroxyl group on a benzyl ring). A comparison with a standard, when commercially
available, is required for unequivocal confirmation. When by-product standards are not
commercially 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 procedure), has become a typical procedure for
identifying the less volatile and polar compounds. Nevertheless, derivation is not easy and it is
also time-consuming. Because of this, LC-MS techniques are gaining in importance. LC
techniques present several advantages over GC: (i) little or no cleaning of the sample is
required, (ii) high polar, low volatile and thermally labile compounds are more easily
84
SOLAR DETOXIFICATION
analysed, (iii) direct analysis of the samples is possible, avoiding polar DPs to escape from
extraction procedures. The major role of LC-MS in the degradation processes studied is (i) to
check DP molecular weight and (ii) to detect DPs which are not directly amenable with GC-
MS techniques.
85
86
CH2 CH3
N CH2 CH3 N
CH3 N N CH2 CH3
CH2 CH3 CH3
CH2CH2OH CHOHCH3
H3CO
N N R1 N
CH2CH3 +R 1 N
CH2CH3
P O H3CO
H3CO P O = R1
O H3CO
S
CH2COH
R1 N
Pyrimiphos Methyl CH2CH3
CH2 CH3
O N O
CH3 N CH2 CH3
OCH3 P OCH3 + N
+ SCH3 P OCH3
OCH3 = R2 OCH3 CH2COOH
R1 N
OH CH2CH3
CH2CHO
R2 N
CH2CH3
CH2COOH
R2 N
CH2CHO CH3
R1 N
CH2CH3
CH2COOH
CH3 R2 N
R2 N CH2CH3
CH2CHO
H
R1 N
CH2CH3
CH3 CH3
R2 N R2 N
CH3 CH2CH3
H
H R1 N
R2 N CH2CH3
CHO CHO
R2 N
CH2CH3
HOH2C N NH2 N
HOC O
N H N
OH R2 N O OCH3
OH CH2CH3 O P
OCH3
S
Figure 5.9
SOLAR DETOXIFICATION
type adsorbent. Polymeric adsorbents can be used over pH2-13 without decomposition of the
adsorbent material.
Many of the above tests require specialised 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 increased interest in bacterial screening to assess toxicity.
Studies of effects on microbial function or activity constitute a more direct, rapid and sensitive
approach to measure chemical stress. These can be classified by the type of measurement
used:
• Monitoring transformation of carbon, sulphur or nitrogen.
• Determination of the activity of microbial enzymes such as dehydrogenases, adenosine
triphosphatases and other enzymes.
• Measurement of growth, mortality and photosynthesis.
• Determination of glucose uptake activity using radioisotopes.
• Measurement of oxygen consumption using a dissolved oxygen electrode or respirometer.
• Measurement of luminescence using a photometer.
The development and applications of biological toxicity testing are rapidly increasing.
Numerous bioassay procedures are now available, however, it is difficult to state the
sensitivity of these tests, and therefore, a universal-monitoring device for toxicity testing is
unlikely to be available. In any case, most of the recent studies have dealt with the use of the
bacterial luminescence assay for toxicity screening. The use of toxicity tests for evaluation of
photocatalytic treatments is not very common for the moment, but several papers have already
been published (Jardim et al., 1997; Herrmann et al. 1999).
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SOLAR DETOXIFICATION
The degradation of the original contaminants is monitored preferably by HPLC, and the final
mineralization by TOC and Ionic Chromatography, but identification of intermediate products
has to be by MS techniques (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 significant number of DPs. As the detection of all DPs is almost
impossible, the use of different organism for determining toxicity is very important in order to
guarantee that the treatment is correct.
Agüera, A., Fernández-Alba, A. R., GC-MS and LC-MS Evaluation of Pesticide Degradation
Products Generated from Advanced Oxidation Processes in Waters: An overview.
Analusis, 26, 123-130, 1998.
Chiron, S., Fernandez-Alba, A.R. and Rodriguez, A., Pesticide Chemical Oxidation
Processes: An Analytical Approach. Trends Anal. Chem., 16, 518-526, 1997.
Herrmann, J.M., Guillard, Ch., Argüello, M., Agüera, A., Tejedor, A., Piedra, L. and
Fernández-Alba, A. Photocatalytic Degradation of Pesticide Pyrimiphos-Methyl.
Determination of the Reaction Pathway and Identification of Intermediate Products by
Various Analytical Methods. Catalysis Today, 1999, in press.
Herrmann, J.M. Heterogeneous Photocatalysis: an Emerging Discipling Involving Multiphase
System. Catalysis Today, 24, 157-164, 1995.
Jardim, W.F., Moraes, S.G. and Takiyama, M.M.K. Photocatalytic Degradation of Aromatic
Chlorinated Compouns using TiO2: Toxicity of Intermediates. Wat. Res., 31, 1728-
1732, 1997.
Malato, S., Blanco, J., Richter, C, Braun, B. and M. I. Maldonado. Enhancement of the Rate of
Solar Photocatalytic Mineralization of Organic Pollutants by Inorganic Oxidising
Species. Appl. Catal. B: Environ., 17, 347-360, 1998.
Pelizzetti, E., Carlin, V., Minero C. and M. Grätzel. Enhancement of the Rate of
Photocatalytic Degradation on TiO2 of 2-Chlorophenol, 2,7-Dichlorodibenzodioxin
and Atrazine by Inorganic Oxidizing Species. New J. Chem., 15, 351-359, 1991.
Tapp, J.F., Wharfe, J.R and Hunt, S.M. Toxic Impacts of Wastes on the Aquatic Environment,
Royal Soc. Chem., 1996.
Tothill, I.E. and Turner, A.P.F. Developments in Bioassay Methods for Toxicity Testing in
Water Treatment. Trends in Anal. Chem., 15, 178-187, 1996.
Wangersky, P.J. Dissolved Organic Carbon Methods: a Critical Review. Marine Chem., 41,
61-74, 1993.
88
SOLAR DETOXIFICATION
PART B.
Answers
Part A
1.False; 2. True; 3. False; 4. True ; 5. False; 6. False; 7. True; 8. False; 9. True; 10. False.
Part B
TiO / hυ
1. C 2 H 8 NO 2 PS + 7O 2 2
→ 2CO 2 + H 3 PO 4 + H 2 SO 4 + HNO 3 + H 2 O
2. Because reactives and products could be lost causing results not to be reliable.
3. Because the products of incomplete degradation and their concentrations may be
sufficiently innocuous for discharge directly into the environment or for further biological
treatment.
89
SOLAR DETOXIFICATION
90
SOLAR DETOXIFICATION
FIGURE CAPTIONS
Figure 5.1. Major general processes for the photo-oxidative or photo-reduction degradation of
organic compounds in aqueous solution sensitised by semiconductor particles. Examples of
photo-oxidation (PCP) and photo-reduction (CCl4) are shown.
Figure 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
considering 1 mMol TOC = 6 mMol of C = 72 mg of C.
Figure 5.4. Chemical structures of pyrimethanil and its degradation products obtained during a
photocatalytic treatment with TiO2.
Figure 5.6. Concentrating solar reactor with platinum/titanium dioxide catalyst on ceramic
saddles. Tested on air contaminated by spray paint at Fort Carson Army Base in Colorado
(USA). Courtesy of National Renewable Energy Laboratory (USA).
Figure 5.8. Steps of excitation with a sensitizer in the presence of an adsorbed organic
electron acceptor (A).
Figure 5.9. Degradation pathway proposed for pirimiphos-methyl dissolved in water when
illuminated in the presence of TiO2.
91
SOLAR DETOXIFICATION
AIMS
This unit discusses the basic factors related to solar photocatalytic process technology and
applications. Main 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.
OBJECTIVES
When you have completed this unit, 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. Main characteristics of different types of collectors for solar water detoxification
applications.
4. Advantages and disadvantages of using non-concentrated sunlight.
5. Factors concerned with main technological components: reactor, reflectors and catalyst.
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 (either 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:
• Non concentrating or low-temperature, up to 150º C
• Medium concentrating or medium temperature, from 150º C to 400º C
• High concentrating or high temperature, over 400º C.
This traditional classification considers only the thermal efficiency of the solar collectors.
However, in photocatalytic applications, the thermal factor is 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.
Figure 6.1 Non-concentrating solar collectors for domestic heat water application
Figure 6.2 Medium concentrating solar collector. Recirculating parabolic trough reactor for water purification
using titanium dioxide slurry at NREL. Courtesy of National Renewable Energy Laboratory (USA)
High concentrating collectors have a focal point instead of a linear focus and are based on a
93
SOLAR DETOXIFICATION
paraboloid with solar tracking. Typical concentration ratios are in the range of 100 to 10000
and precision optical elements are required. They include parabolic dishes and solar furnaces.
Figure 6.3 High concentration solar collector. Fix Focus solar reactor (PSA, Spain)
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 analysis of medium concentrating and non
concentrating solar collector efficiency with regard to direct incident radiation. Direct
radiation is the radiation which has no interference from the atmosphere and, consequently, a
known direction, and can therefore be concentrated. Global radiation is composed of direct
and diffuse radiation. The data represented in Figure 6.4, correspond to direct radiation in an
ideal cloudless 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 orientations: elevation tracking, azimuth
tracking and azimuth tracking slightly tilted 8º with regard to 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 to know the amount of direct radiation available at any given time for
each collector configuration. 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%
better than elevation tracking (north-south movement 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 Hemispheres) whereas it is almost constant around the
year in the second case. A slight 8º tilt to the south in the northern hemisphere and the
opposite in the south increases yearly efficiency about 5% 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 than one-axis PTCs, attaining maximum efficiency with an inclination (to the south in
the Northern Hemisphere and to the north in the Southern Hemisphere) from the horizontal
equal to the local latitude. This configuration, that is, angle of tilt set at the angle of latitude of
the site, maximizes the annual energy collection in a flat-plate collector. Although the
calculations made here are for a specific location and latitude, the comparisons of solar
radiation collection and conclusions obtained are qualitatively valid for any other location.
94
SOLAR DETOXIFICATION
The first engineering-scale outdoor reactor for solar detoxification was developed by Sandia
National Laboratories (USA) at the end of the eighties (see Figure 6.6) where a parabolic-
trough solar thermal collector was modified simply by replacing the absorber/glazing-tube
combination with a Pyrex tube through which contaminated water could flow. Since then,
many different concepts with a wide variety of designs have been proposed and developed all
over the world, in a continuous effort to improve performance and reduce the cost of solar
detoxification systems. Among these different concepts, several of the most important with
regard to the definition of the overall system are those related to whether or not radiation must
be concentrated, the type of reflective surface to be used, the way the water circulates through
the reactor (tube, falling film or stirred vessel) and the way in which the catalyst is employed.
Figure 6.6 First engineering scale outdoor solar detoxification reactor using one-axis parabolic trough
collector. Part of the 465 m2 parabolic trough system at Sandia National Laboratory. Courtesy
of National Renewable Energy Laboratory (USA)
One of the most important reactor design issues is the decision between concentrating or non-
concentrating collector system. Concentrating systems have the advantage of a much smaller
reactor-tube area, which could mean a shorter circuit in which to confine, control and handle
the contaminated water to be treated. The alternative of using high-quality ultraviolet-light-
transmitting reactors and supported-catalyst devices also seems more logical, both
economically and from an engineering point of view, if concentrating collector systems are to
be used.
95
SOLAR DETOXIFICATION
absorbed by water vapour, as much as 50 percent of this, or more in very humid locations or
during cloudy or partly cloudy periods, can be diffuse. As non-concentrating solar collectors
can make use of both direct and diffuse UV radiation, their efficiency can be noticeably
higher. The second disadvantage of concentrating collectors is their complexity, cost and
maintenance requirements. The consequence of these disadvantages is that present state-of-
the-art favours the use of non-concentrating reactors for solar photocatalytic applications. An
additional disadvantage of concentrating reactors is that the quantum efficiency is low, due to
a square root rather than linear dependence of rate on light flux, as already explained in
chapter 4.
For many of the solar detoxification system components, the equipment is identical to that
used for other types of water treatment and construction materials are commercially available.
Most piping may be made of polyvinylidene fluoride (PVDF), chlorinated polyvinyl chloride
(CPVC), or simply polyethylene. In any case, piping, as well as the rest of the materials, must
be resistant to corrosion by the original contaminants and their possible by-products in the
destruction process. Neither must materials be reactive, interfering with the photocatalytic
process. All materials used must be inert to degradation by UV solar light in order to be
compatible with the minimum required lifetime of the system (10 years).
Optical material requirements are similar to other closed solar systems, but photocatalytic
reactors must transmit UV light efficiently because of the process requirements. In some
cases, when a steam pressure of contaminants in water is sufficiently low, a closed system
could not be required and then 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 bar for nominal system pressure drop and a
maximum of 5 to 7 bar. 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 due to 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
solar photocatalytic systems is the requirement of a catalyst; in the case of TiO2 it can be
deployed in several ways, such as a slurry or as a fixed catalyst (like a fiberglass matrix
inserted in the reactor tube).
As explained previously, the first engineering-scale facility was developed from one-axis
PTCs (Sandia National Labs, USA, 1989) and the second from two-axis PTCs (Plataforma
Solar de Almería, Spain, 1990, Figure 6.7). Both facilities are considerably large pilot plants
96
SOLAR DETOXIFICATION
(hundreds of square meters of collecting surface) and can be considered the first steps in
industrialisation of the photocatalytic process.
Figure 6.7 CIEMAT 384 m2 solar detoxification facility using two-axis parabolic trough
collectors at Plataforma Solar de Almería (PSA, Spain)
Although one-axis tracking has been demonstrated to be the most economically suitable for
solar thermal applications, certain particularities of photocatalytic research make two-axis-
tracking PTCs efficient for finding out exactly how much radiation reaches the photoreactor
at any given time and also, therefore, permitting accurate evaluation of all 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.
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
C= (6.2)
ðd
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 under
point 6.4.1, as it can be considered independently of the solar collector used.
The collector structure supports the reflecting concentrator 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 collectors 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 containing the
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SOLAR DETOXIFICATION
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. Typical overall optical efficiencies in a PTC are in the range of 50
to 75 percent, with the following breakdown:
− Tracking system: 90%-95%
− Reflector/Concentrator (reflectivity): 80%-90%
− Absorber/Reactor (transmittance): 80%-90%
− Mechanical collector errors: 90%-95%
Parabolic-trough collectors make efficient use of direct solar radiation and, as an additional
advantage, the thermal energy collected from the concentrated radiation could 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.
Based on extensive effort in the designing of small non-tracking collectors, a wide number of
non-concentrating solar reactors have been developed for solar photocatalytic applications,
which can be classified as follows:
- Trickle-down flat plate, based on a tilted plate facing the sun over which the water to be
treated falls slowly; the catalyst is fixed on plate surface.
- Free-falling film, similar to the trickle-down flat plate, but with a higher flow rate and
normally with a catalyst attached to the surface on which the liquid to be treated
circulates. It is usually open to the atmosphere, so it can be used only when volatile
compounds are not present.
- Pressurized flat plate, consisting of two plates 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 circulate faster than a flat plate, but functioning basically the same.
- Shallow solar ponds. This is a very interesting variety, as pond reactors are easily built on-
site, especially for industrial wastewater treatment. Since manufacturing industries already
use ponds for microbiological treatment of wastewater, shallow solar ponds can be used
for the front or back end of a combined solar/microbiological treatment scheme (see also
chapter 8.1).
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SOLAR DETOXIFICATION
Figure 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. Courtesy of Institut für Solarenergieforschung GmbH (Hannover,
Germany)
Any falling film or flat reactor must be covered to avoid direct contact with the atmosphere.
The use of an uncovered reactor is not recommended due to many factors: loss of volatile
contaminants, dust and dirt inside the reaction mixture, etc.
Although one-sun designs possess important advantages, the design of a robust one-sun
photoreactor is not trivial, due to the need for a large area of weather-resistant, and chemically
inert ultraviolet-transmitting reactors. The amount of materials required makes it necessary
for them to be relatively inexpensive. Those that best meet these requirements are certain
types of plastics, e.g., fluoropolymer films, but these, although highly versatile, possess lower
tensile strength than the rigid glass pipe and reduces the pressure capacity of the photoreactor
system. This combination of low pressure capacity and large volume, coupled with the need
to either keep a catalyst slurry suspended or ensure good mass transfer to a supported catalyst,
requires carefully designed fluid control..
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 suspension, which means that turbulent flow
must be assured throughout the hydraulic circuit. Containment of volatile organic
contaminants to prevent their escape into the atmosphere is also of concern in a large reactor.
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SOLAR DETOXIFICATION
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 as a result most of the reactor tube circumference is illuminated, but
due to the ratio of CPC aperture to tube diameter, no one 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 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 l/3 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.
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SOLAR DETOXIFICATION
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 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 2θ a , which is the angular range over which all or almost all rays are
accepted (i.e., reflected into the reactor tube) without moving the collector.
The solution is given in two separate portions, an ordinary involute for A to B and an outer
portion from B to C:
θ + θ a + π 2 − cos (θ − θ a ) π 3π
ρ=r for θ a + ≤θ ≤ −θ a part BC of the curve (6.6)
1 + sin(θ − θ a ) 2 2
1
C= (6.7)
sinθ a
In the special case of θ a =90º, CR=1 and every CPC curve is an ordinary involute (points B
and C are coincident). So, optimum CPC acceptance half-angles ( θ a ) for photocatalytic
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 forgive the reflector-tube
alignment errors, which is an important virtue for a low-cost photoreactor array.
101
y
Fig. 6.12
θa
R C
r
O θa
x
θ
S
A B
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SOLAR DETOXIFICATION
Figures 6.13(a) and 6.13(b) View of CPC shape (a) and CPC photoreactor array (b). PSA
(Spain)
CPC reflectors are usually made of polished aluminium and the structure can be a simple
photoreactor support frame with connecting tubing. Since this type of reflector is considerably
less expensive than tubing, their use is very cost-effective compared to deploying non-
concentrating tubular photoreactors without use of any reflectors, but preserving the
advantages of using tubing for the active photoreactor area.
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
TiO2 uses 300 to 385 nm 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
minimising thermal heating of the photoreactor.
103
104
Focus
Focus
Fig. 6.14
SOLAR DETOXIFICATION
Concentrating collectors focus only the direct sunlight and cannot collect the 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 northern European locations with small solar detoxification pilot plants
(Figure 6.15).
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SOLAR DETOXIFICATION
Finally, one-sun photoreactors have additional advantages, 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 smaller reactor-tube area requirement (smaller
circuit, better control and handling of contaminated water to be treated). Nevertheless, state-
of-the-art technology 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, USA) 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.
Due to all the above, and, furthermore, although it was first thought that PTCs were the ideal
technological alternative, their high cost and the fact that they can only be operated with
direct solar radiation (implying location only in highly insolated areas), have decided the
question in favour of the static non-concentrating collector alternative. Their intrinsic
simplicity, low maintenance and operating cost and potential for reducing the manufacturing
cost, make one-sun systems the natural selection 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 moreover,
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 acceptance angle,
the radiation coming from the hemisphere and place it on the absorber perimeter.
In addition to the solar collector type, the most important technical issues related with solar
detoxification hardware are the reflective surface and the reactor tube, which are addressed
here in more detail.
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, absorption, 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 specularly reflects a
portion of incoming light. Diffuse reflection is typical of particulate substances like powders.
If you shine a light on baking flour, for example, you will not see a directionally shiny
component. The powder will appear uniformly bright from every direction. Many reflections
are a combination of both diffuse and specular components. One manifestation of this is a
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 strictest requirements are those of PTCs,
for example, UV-mirror materials need to have a specular reflectance between 300-400 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 performance parameters as:
σ
C ε = C ρ s sum (6.8)
σ
Where:
C = concentration in the absence of surface and tracking errors, as defined in eq. 6.2
ρ s = specular reflectance
σ sum = half angular extent of sun (Gaussian distribution) = 2.73 mrad
σ = total optical error, which is function of the slope, specularity and tracking errors
The greater the errors are, and particularly the reflective surface errors, the lower the effective
concentration ratio is. So, 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, since these lower quality requirements (lower specular reflectance) are directly
translated into lower manufacturing cost, since 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 400 nm of traditional silver-coated mirrors is very
low (reflected radiation/incident radiation) and aluminium-coated mirrors is the best option in
this case (Figure 6.18).
108
Specular Diffuse Spread
Fig. 6.17
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SOLAR DETOXIFICATION
Aluminium is the only metal surface that is highly reflective throughout the ultraviolet
spectrum. Reflectivities range from 92.3 percent at 280 nm. to 92.5 percent at 385 nm.
Comparable values for silver are 25.2 percent and 92.8 percent, respectively. A new 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 elements, 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, mainly with regard to outdoor
durability. The ideal reflective surface for solar photocatalytic applications must be:
- highly reflective in the UV range,
- acceptable durability under outdoor conditions for extended service lifetimes and
- reasonable price to permit the technology to be competitive against alternative
technologies
The surfaces currently available that best fit these requirements are:
− electropolished anodized aluminium (electrolytically formed aluminium oxide outer layer)
− organic plastic films with an aluminium coating (three-part “sandwich”-type plastic-
aluminium-plastic composition)
Anodized coatings with tin oxide can provide good protection against some chemicals and
good resistance to abrasion. Typically, thin (2-3 µm) oxide layers are used to provide some
measure of resistance to abrasion but little protection against moisture or pollutants is
provided. 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.
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SOLAR DETOXIFICATION
Normally, due to their lack of rigidity, these films must be bonded over a stiff substrate and
about two percent specular reflectivity is lost in this process. Also, the reflectivity of each
film at the end of its lifetime (from 5 to 10 years) would be only 88 percent of the new bonded
value.
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 heater systems in large part because of its simple
design. Nevertheless, for water treatment, the reactor must be hard 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 residence times inside the reactor, resulting in
decreased performance compared to an ideal-flow situation. If the catalyst is used in
suspension (slurry in the case of TiO2), the Reynold number (Re) must always be over 4000
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.
The choice of materials that are both transmissive to UV light and resistant to its destructive
effects is limited. Also, temperatures inside a one-sun solar photocatalytic 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 temperatures of around 60 to 70°C in order
to insure that there will be no damage which could reduce the flow. Finally, low pH resistance
is needed since the production of inorganic acids as reaction by-products is quite normal (i.e.
the destruction 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 and temperature and chemical
resistance, but the slight advantage in transmission in the terrestrial solar spectrum over other
materials does not justify its high cost, which makes it completely unfeasible for
photocatalytic applications.
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SOLAR DETOXIFICATION
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 photoreactors due to their good UV
transmittance, excellent ultraviolet stability and chemical inertness. Several different types,
such as ETFE (ethylenetetrafluoroethylene), PTFE (polytetrafluoroethylene), ECTFE
(ethylenechloridetetrafluroethylene), PVDF (polyvinylidene fluoride), FEP (fluorinated
ethylenepropylene), PFA and TFE (tetrafluoroethylene), can be extruded into tubing and used
as a photoreactor. Tubular fluoropolymers are very strong, possess excellent tear resistance,
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 fluoropolymer tube may
have to be increased, which in turn will lower its UV transmittance. In addition, due to 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 (since less material is
used) and higher UV transmittance and therefore higher photoreactor performance. The
problem is that ETFE tubing is not as readily available as FEP tubing. 50-mm-outer-diameter,
0.6-mm-wall FEP tubing has a UV hemispherical transmittance (300 to 400 nm), of 61.6%.
This light is transmitted as diffuse, as fluoropolymer materials are poor IR-diffusers, but make
an 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 tube form,
but none possess the necessary UV and chemical stability for detoxification of water that may
be contaminated with a variety of solvents or other pollutants. Also, low cost polymeric
materials are significantly more susceptible to attack by the 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 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 properties 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 adequate.
Figure 6.21 Glass tubes manufacturing. Different compositions mean that the glass can be
used for a wide variety of applications. Courtesy of Schott-Rohrglas GmbH
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SOLAR DETOXIFICATION
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 due to the damaging impact of solar radiation in the same
wavelength region (UV-solarisation). 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 having a wavelength below 400 nm, is especially
harmful. Furthermore, the oxidised Fe3+ ion absorbs in the UV. As a result, enhancement of
transmittance in the 300-400 nm region could only be accomplished by strong reduction in
iron content down to 50 ppm (Figure 6.22), but penalised by 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 performance, 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, large collector area means also a considerable number of reactors and, as
consequence, high system pressure rating. Thus, fluoropolymer tubes are not the best choice
of material since high-pressure is linearly related to thickness and could result in higher cost.
A detailed analysis is recommended for any specific design.
One of the most important parameters in a tubular photoreactor design is the diameter, as in
both homogeneous 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 particle. The intensity of illumination affects the relationship between reaction rate
and catalyst concentration. The dispersion and absorption of light causes photon density to
diminish almost exponentially over the length of the optical path within a catalyst suspension.
At higher light intensity, the catalyst concentration can be higher.
In the case of TiO2 heterogeneous photocatalysis, when catalyst concentration is very high, a
“screening” effect produces excessive opacity of the solution, preventing the catalyst particles
farthest in from being illuminated and reducing system efficiency. The lower the catalyst
concentration, the less opaque the suspension. 1 g L-1 of TiO2 catalyst reduces transmittance
to zero in a 10-mm-inner-diameter cylinder with concentrated light in a parabolic trough
collector (Figure 6.23). Therefore, in a wider diameter tube, only an outer layer is illuminated.
This means that larger inner reactor diameter permits use of lower optimum catalyst
concentrations. Practical inner diameters for tubular photoreactor would be in the range of 25
to 50 mm. Diameters that are very small do not make sense because of the associated high
pressure-drop and very large diameters imply a considerable dark volume, thus reducing
overall system efficiency.
113
114
Fig. 6.22
0,9
0,8
A
0,7
T ransm itance
0,6
B
0,5
C
A: 0ppm F e , 91% ( 300- 400 nm )
0,4 D
B: 50ppm F e , 88%
E C : 100ppm F e , 84.5%
0,3
F D : 150ppm F e , 83.5%
0,2 E : 200ppm F e , 81%
F : 250ppm F e , 80%
0,1
0
250 275 300 325 350 375 400
W avelength [nm ]
Fig. 6.23
1 cm R = 29 mm
ID = 58 mm
Illuminated area
[TiO2] = 1 g L-1
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SOLAR DETOXIFICATION
photocatalysis, where Degussa P-25 titanium dioxide is often the standard 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.
Supported catalyst configurations eliminate the need for catalyst filtration, but with the main
objection of an important 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), have a low pressure-drop,
long lifetime, and reasonable cost but, in the case of water treatments, to present this has not
been possible.
Fixed-catalyst designs must solve several problems. As the catalyst must be exposed to
sunlight and in contact with the pollutant, the support must be configured to efficiently route
the pollutant 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 pressure, which means
more power for pumping, and thereby higher operating costs. Also, the same criteria
discussed 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,
aluminium, many types of plastic (Figure 6.24) and ceramics such as alumina, silicon carbide
and silica, in the most diverse shapes. TiO2 coatings on tiny hollow glass beads called
microballoons for catalyst removal, by screening rather than filtering, have also been tested.
Figure 6.24(a) and 6.24(b) (a) Experimental concentrating solar reactor using titanium
dioxide immobilised on glass wool for treating contaminated air streams. (b) Parabolic trough
reactor for water purification with immobilised titanium dioxide. Courtesy of National
Renewable Energy Laboratory (USA)
Support of TiO2 on a stiff surface by adherence can be done using several different
techniques, such as dip-coating with solvents, deposits from precursors, vapour deposition,
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SOLAR DETOXIFICATION
and sol-gel formation. Several important performance requirements are directly related to the
process used for catalyst fixation, such as the durability of the coating, catalyst activity,
lifetime, etc. Surface area of the catalyst coating must also be considered because 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 (USA)
using silica beads as the catalyst support, have approached the efficiency of the slurry, but the
high pressure-drop across the bed made the system impractical. In aqueous systems,
compared to an unsupported catalyst, immobilisation of TiO2 results in a reduction in
performance around 60 to 70 percent. An important direct consequence of this fact is the
necessity of multiply by a factor of about 3 the size of necessary solar collector field if similar
efficiencies want to be obtained, making the overall system clearly less cost efficient and
competitive than slurry systems. In addition to the above, a key question is how long a
supported catalysts will last in a real stream of water; a short period of activity would mean
frequent replacement and, consequently, an important rise in the overall system cost.
To the contrary of fixed catalyst configurations, slurry configurations have the advantage of
higher throughputs (in the range of 200 to 400 percent) a low pressure-drop through the
reactor and excellent fluid-to-catalyst mass transfer.
However, best performance can be obtained when microfiltration is combined with previous
titanium dioxide sedimentation. About 90% 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 TiO2 aggregation
conditions. The suspension can easily be destabilized by adding an electrolyte (such as NaCl)
and/or adjusting the pH to point 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 is 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 about 10-6
molar.
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SOLAR DETOXIFICATION
Therefore, more than 200 hours are needed for 75% of titanium dioxide to settle at pH 4.5, but
at pH 7, only 5 hours of storage are needed to recover 90 to 95%. This can be directly
recovered in a conic-bottom tank and 5 to 10% of the remaining catalyst can be recovered by
microfiltration (see also chapter 9).
Catalyst recovered, usually in highly concentrated slurry, can be reused but not indefinitely.
Slurry lifetime has been tested with satisfactory results under laboratory conditions (i.e.,
deionized water and only one contaminant), but with real water treatments catalyst lifetime
would be diminished due to poisoning by contaminants. However, in specific applications,
tests have demonstrated that the catalyst can be reused up to 10 times, or even more, without
any problem.
If part of the catalyst is lost in the drainage water, the percentage of catalyst that remains
useful after each run is a relevant parameter. In field tests conducted by NREL in Florida, it
was reported that approximately 10% of the catalyst was washed away in the discharge water.
In tests performed at the Plataforma Solar de Almería, 2.5% of catalyst was lost. From this
point of view, about a 5 to 10% addition of catalyst could be an interesting option to
compensate possible loss and periodic replacement in case of catalyst poisoning.
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SOLAR DETOXIFICATION
the best option. In TiO2 heterogeneous photocatalysis, suspended catalyst systems gives
efficiencies higher than supported catalysts. After their use, TiO2 can be agglomerated and
sedimented. Best recovery performances are obtained with a two step process: sedimentation
and microfiltration.
SELF-ASSESSMENT QUESTIONS
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SOLAR DETOXIFICATION
PART B.
1. Why are concentrating solar systems more efficient than non-concentrating ones, when
thermal applications are considered?
2. Why are non-concentrating solar systems more efficient than concentrating ones, when
UV photocatalytic applications are considered?
3. Which must be the diameter of a PTC reactor tube if the aperture width is 2.5 m and a
geometric concentration ratio of 10 is desired to be achieved?
4. What is the geometric concentration ration of a CPC if their semi-aceptance angle is 70º?
5. A PTC with a geometric concentration ratio of 6 has an effective concentration ratio of 4.
What is the total optical error of the reflective surface if their specular reflectance is 85%?
6. What is the main factor that limits the UV transmittance of standard glass?
7. Why reactor tubes of 200 mm inner diameter are not practical at TiO2 slurry systems?
8. Cite at least three of the main problems of supported catalyst systems.
9. How can titanium dioxide slurry particles be aggregated and sedimented?
10. Why the Reynold number must be higher than 4000, at TiO2 slurry systems?
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 looking at the
sun.
2. Because, besides non-concentrating systems have not solar tracking device, they can
collect the UV solar light, which is an important contribution to the yearly efficiency.
3. Using equation (6.2); d = 2500 / (10 x 3.1416) = 79.6 mm.
4. Using equation (6.7); C = 1 / sin (70) = 1.06.
5. Using equation (6.8); σ = 6 x 0.85 x 2.73 / 4 = 3.48 mrad.
6. The presence of Fe ions, specially Fe+3, which absorbs the UV light.
7. Because of 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 necessity of 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 get the point of zero charge and the
isoelectric point of the colloidal solution.
10. Because turbulent flow regime must be assured to guaranty adequate fluid mixture and to
avoid possible catalyst settlement.
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SOLAR DETOXIFICATION
AIMS
This unit describes main proven and potential applications of solar detoxification processes
with demonstrated technical feasibility. Advantages and limitations of these applications are
also discussed.
OBJECTIVES
When you have completed this unit, you will have an appreciation of the following subjects:
1. Limiting factors and necessary conditions to feasible solar detoxification applications.
2. Main applications related with contaminated water.
3. Technical considerations about gas phase treatment processes.
7.1 INTRODUCTION
Detoxification is today the most successful photochemical application of solar photons, with
several relevant installations and projects already in operation. This is due not only to the fact
that solar detoxification is an outstanding demonstration of how well suited solar energy is to
environmental conservation, but also because, contrary to most photochemical processes, it is
non-selective and can be employed with complex mixtures of contaminants. During the last
decade, the number of references and related patents on heterogeneous photocatalytic removal
of toxic and hazardous compounds from water and air can be counted by thousands and the
number of applications and target compounds are numerous.
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SOLAR DETOXIFICATION
Photocatalytic oxidation processes (PCO) currently under development are included in the
same group of Advanced Oxidation Technologies (AOT) with other radical-promoting
processes like plasma, electron-beam, etc. The main advantage of PCO over other AOTs is its
potential for incorporating solar energy in the form of solar photons, whereby the degradation
process acquires significant additional environmental value. If solar photons can be collected
and used efficiently at low cost, the number of opportunities for PCO may increase
dramatically. Although solar driven PCO was at first considered a universal method of
degrading organic pollutants, a profusion of contradictory results during recent years (positive
results in almost real problems together with other experimental results pointing out
uncertainties and negative performance) has lead to confused public perception. Solar PCO
technology is currently viewed as very sensitive to many things and scientific opinion is
evolving toward 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 of solar detoxification. The only really 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 TiO2 photocatalysis, but in others, the Fe cycle is affected by the
contaminants and Photo-Fenton does not work at all. As consequence, preliminary research is
always required for assessing potential pollutant treatment and optimising the best option for
any specific problem, nearly on a case-by-case basis.
To find out if a specific water-contamination problem can be treated with solar detoxification
technology is not always easy, since low efficiencies produce hydroxyl radicals and slow
kinetics may limit economic feasibility. As mentioned above, preliminary tests are normally
needed for assessment of process viability. In attempt to provide some guidelines for the
reader, the following general affirmations may be made:
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SOLAR DETOXIFICATION
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.
Applications that fulfil both groups of requirements may be considered serious candidates for
solar detoxification and a detailed feasibility test study would be worth to be considered.
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SOLAR DETOXIFICATION
At the moment, and from the experience accumulated by many scientists and researchers in
the last 10 years, solar detoxification seems to be a good solution for destroying, among
others, the following contaminants found in industrial waste-water:
− Phenols
− Agrochemical waste
− Halogenated hydrocarbons
− Antibiotics, antineoplastics and other chemical biocide compounds from the
pharmaceutical industry
− Wood preservative waste (PCP, fungicides)
− Hazardous metal ions
7.2.1 Phenols
These substances include phenol, cresol and other phenol substitutes. All the phenols are very
toxic. Their maximum concentration in a biological wastewater treatment plant inlet (BWTP)
is 1-2 mg/L. Even very low concentrations of phenols (1-10 mg/L) in fresh water produce
unpleasant odour/taste during the chlorinating process, so any discharge of phenols must be
avoided. The solar detoxification technology would therefore be useful for treatment of water
containing this type of contaminants.
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 BWTP. Figure 7.1 shows two degradation tests
carried out on chemical industry waste water containing a large number of compounds,
mainly phenols, and including formol, phthalic acid, fumaric acid, maleic acid, glycol
compounds, xylene, toluene, methanol, butanol and phenylethylene, among others.
As observed in Figure 7.1, complete degradation of all initial substances and their
intermediates is possible at reasonable degradation rates. Table 7.1 shows examples of
industrial processes that generate wastewater-containing phenols that could be good targets
for solar photocatalytic processes.
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SOLAR DETOXIFICATION
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 phenols are the
raw materials. Phenolic resins are obtained from the reaction of phenol or a phenol substitute
with formaldehyde. The reaction may be portrayed as indicated in Figure 7.2.
The ingredients are boiled in a reflux condenser (Figure 7.3) and condensation water is
usually removed by vacuum distillation. This condensation water contains several mg/L of
reagents, being of which are very toxic.
Phenol-formaldehyde resins are usually prepared with 40% formaldehyde by volume, then,
approximately 750 L of water is removed for each ton of final product. When solid
formaldehyde is used, only 160 L of condensation water are removed from the final mixture.
These phenolic residues contain between 600–2000 mg/L of phenol and between 500-
1300 mg/L of formaldehyde.
Pesticides are one of the best fields of application of solar detoxification technology for which
solar detoxification appears to be an ‘omnivorous’ technique. This is because they are
employed in very diluted solutions or suspensions of mullet-component formulas, in small
volumes and in batches. Very good results have been obtained with organohalogenated and
organophosphorous pesticides, carbamats, thiocarbamats, 2,4-D (2,4 dichlorophenoxyacetic
acid), triazines, etc. Besides the large amount of pesticide waste generated in agriculture,
there is also a huge amount of industrial waste from factories producing the active ingredients
125
126
Fig. 7.2
SOLAR DETOXIFICATION
and, especially, in factories where the active components and other additives are stored,
weighed according to the product formula, mixed and packed.
Example: estimation of the required field. A feasibility study has determined that a 6 m2
photoreactor can completely mineralize 250 L of wastewater containing 100 mg/L of
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SOLAR DETOXIFICATION
chloroform in 8 hours of sunlight and 25000 L are to be treated. As all the parameters are
linear, assuming unchanged weather and waste-water conditions, the direct result is 600 m2 of
collector field in 8 hours, or 300 m2 in 16 hours to treat the 25000 L, while for a 100-m2 field
48 sunny hours would be necessary to complete the treatment.
Table 7.3 Examples of processes potentially producer of antibiotic and antineoplastic waste
The chemical industry also produces a great variety of biocides used as preservatives,
especially in paint. Common examples of these compounds are: phenyl mercuric acetate,
dithiocarbamates and other sulfuric compounds, halogenated phenols, halogenated phenol-
formaldehyde condensates, quaternary ammonium salts, etc. A medium sized chemical
company could typically produce 500 t/yr of this type of product. As equipment must be
cleaned between each batch, approximately 500–1000 m3 of rinse water could be generated
per year, with a normal concentration of 200–500 mg/L of the biocide, for which solar
treatment is feasible.
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SOLAR DETOXIFICATION
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. In one Spanish province
alone there are about 100 wood-preserving firms and the wood (timber and sawed pieces) are
treated in concentrated pesticide baths. When the baths become weakened, their content is
replaced with fresh product. A conservative assumption is that 5% of the chemicals in the
bath are discharged as waste.
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 concentration of
metals is insufficient. The ability to remove metals depends on the standard reduction
potential for the reduction reaction. For example, Ag2+, Cr6+, Hg2+, and Pt2+ can be treated by
photocatalytic reduction, but Cd2+, Cu+2, and Ni+2 cannot.
Figure 7.6 Cr+6 to Cr+3 solar photocatalytic reduction at PSA Solar Detoxification Facility
(CPC’s collectors loop). See also Figure 7.7
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SOLAR DETOXIFICATION
Because they are highly toxic, photocatalytic degradation of cyanides is another potential
industrial application having the advantage that it neither produces highly toxic substances
such as cyanogen chloride nor sludges and avoiding the use of additional chemical reactants
such as chlorine.
+
CN − + 2 OH − + 2 hVB → OCN − + H 2 O (7.1)
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:
+ −2
OCN − + 2 H 2 O + 3 hVB → CO 3 + 1
2 N2 + 4 H + (7.2)
In all the applications mentioned in this chapter, the presence of inorganic ions (such as
chloride, phosphate, nitrate, sulphate, etc) 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
significantly the feasibility of the overall treatment process.
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SOLAR DETOXIFICATION
Seaport tank terminals must carry out cleaning operations 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 distributed this way, many
chemicals, e.g., phenol, metham sodium, perchloroethylene, trichloroetylene, methylen
chloride, sodium dichromate, etc., and other compounds, such as styrene, toluene, nonil
phenol, benzene chloride, etc., may be successfully 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
crystals remaining in the top and valves. 7400 L of condensed water containing 6.4% phenol
is then discharged into a storage waste tank for later recovery of the phenol by distillation 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
16000 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 application: treatment of wastewater from
cleaning a tank that had contained metham sodium. Metham sodium or Vapam is a
dithiocarbamate used as soil fumigant to control weeds, nematodes, fungi and insects (soil
steriliser). This compound is a direct competitor of methyl bromide, another soil disinfectant
and one of the ozone-depleting chemicals.
In a medium-sized seaport tank terminal (typically about 70 tanks with 28000 m3 average
storage capacity) at least 15 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 scrubber these plants may use for VOC
emission-control equipment. All these residues can easily be managed by solar detoxification
because they can be stored individually in small tanks or containers until the treatment
process can be run.
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SOLAR DETOXIFICATION
Solar detoxification can be considered a good solution for ‘in-situ’ treatment and
decontamination of groundwater containing substances where conventional biological
treatment is difficult 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
contaminated water). Tests have shown that the majority of pollutants found in contaminated
groundwater are easily destroyed by photocatalysis. Groundwater remediation also has the
advantage of a processing time-scale of months or years.
The difficulty is that standard discharge must normally be drinking-water quality, which is
difficult and costly (for any treatment technology to be used). Groundwater 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, airforce bases, harbours, railway stations, power plants and substations. The
contaminated groundwater must be pumped out from a series of extraction wells located
downstream of the contamination plume. After treatment, the effluent is injected again into
the water table through upstream injection wells.
The first known treatment of contaminated groundwater by solar photocatalysis was carried
out on 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 World War II, a part of the grounds now occupied by LLNL was a Naval Air Station
training and maintenance 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 local ground water,
where they are now slowly migrating off site. Today, TCE is present in the groundwater at
concentrations ranging up to 500 ppb, which means 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 technology
and demonstrated the technical feasibility of this application.
The system consisted of two solar troughs, each 36.5 m long, with effective concentration
ratio of approximately 20 and total solar collector area of 158 m2 using a TiO2 slurry and
yielded outlet concentrations below 5 ppb, which meets the limits for drinking-water process
feasibility demonstration. One of the main problems reported was the required acid
pretreatment which had an important negative effect on the effectiveness of the process.
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SOLAR DETOXIFICATION
Figure 7.10 Part of the 156 m2 parabolic trough water treatment system tested on
contaminated ground water at a site at LLNL (USA) in 1992. Courtesy of National
Renewable Energy Laboratory (USA)
Another application 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 (USA). Contaminants of interest that were present in the groundwater
included benzene, toluene, ethyl benzene, and xylenes (BTEX). 30 one-sun collector modules
(1.22 m x 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 length (Figure 7.11).
Treatment of initial concentrations of 1 to 2 mg/L of BTEX was performed in a batch system
obtaining typical destruction levels of 50% to 75% in 3 hours. The total volume treated during
each run was 530 L.
Figure 7.11 One-sun reactor built by American Energy Technology, Inc. for treating
contaminated groundwater in Florida (USA) in 1992. Courtesy of National Renewable Energy
Laboratory (USA)
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SOLAR DETOXIFICATION
Many sites are contaminated by lindane, some of them very well known in Europe. Figure
7.13 shows the photocatalytic degradation of Lindane (technical grade) suspension in water,
simulating the final step of contaminated landfill treatment and demonstrating the technical
feasibility of the solar treatment process (maximum solubility of lindane: 10 mg/L).
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SOLAR DETOXIFICATION
important. Among them, ultraviolet irradiation with lamps is widely used to destroy biological
contaminants, primarily at a 254-nanometer wavelength. Solar ultraviolet, 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 essentially 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 resulting in the disintegration of the cell.
Disinfection of viruses, such as Phage MS2 and poliovirus 1, can also be found in the
literature.
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SOLAR DETOXIFICATION
Figure 7.15 shows the possible trichloroethylene (TCE) PCO degradation pathways. Some
intermediates detected are formed in the presence of chloride, so it has been proposed that °Cl
could be the driving force instead of °OH. Other authors have proposed that both mechanistic
approaches via °Cl and °OH are essentially correct and the eventual pathway depends on the
characteristics of the catalyst (e.g., internal surface or porosity). TCE is one of the most
studied compounds because it is a major gas-phase air pollutant. Their photocatalytic
oxidation with titanium dioxide has received good reports in the literature.
Figure 7.16 shows a lab experiment performed on TCE using a monolithic TiO2-based
catalyst at different temperatures. Photoeffect was clearly differentiated by using appropriate
filters. As it can be observed, temperature played a negative role due to adsorption-desorption
phenomena. Nevertheless, apart from high photonic efficiencies (up to 95%) reported with
TCE, it is not easy to find applications for pure photocatalytic gas-phase treatment processes,
as not many compounds have been found to be significantly affected by photocatalysis, being
necessary in most cases a combination of photocatalytic degradation and destructive
thermocatalysis.
In addition to that, 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 due to the natural uncontrollability of the sun as the energy source. As
a result, it is not trivial 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.
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SOLAR DETOXIFICATION
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 phenols normally present in air streams at concentrations of less than
5000 ppm. Some applications for air purification or degradation of emissions in the
semiconductor industry are also under development.
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SOLAR DETOXIFICATION
Figure 7.17 shows a recent one-sun reactor with PTFE window material and titanium dioxide
immobilized on polypropylene supports for gas-phase solar detoxification successfully tested
by NREL (USA). For additional information on gas-phase experimental treatment systems,
see also Figure 6.24 and Figure 5.6.
Contrary to water phase, in which catalyst may be used in the more efficient slurry
configurations, in gas phase this is not possible and all experimental systems developed to
date use an immobilised catalyst. This is apparent in the figures above. As discussed in
Section 6.5, the catalyst must be anchored onto some type of inert support inside the gas-
phase stream treatment reactor. Characteristics of such a system must be being very active
(high degradation efficiency), have a low pressure-drop, long lifetime, and reasonable cost.
Very diverse types of catalysts have been used in gas-phase systems, from MgSiO4/TiO2/Pt
monoliths to TiO2 immobilised on glass fibers, ceramic substrates, inert plastic materials, etc.
As in water phase, residence times must be as long as possible to increase degradation
efficiency.
One interesting potential application of gas-phase solar detoxification technology is the gas
treatment from contaminated landfill recovering (see chapter 7.5). Chlorinated volatile
organic compounds (CVOC) are among the most pervasive subsurface ground contaminants
and the remediation technologies most used for CVOC ultimately produce a gas-phase stream
containing CVOC, either from soil venting from the unsaturated zone or ground water
recovery from the saturated zone and subsequent air stripping. In the past, direct discharge of
gaseous CVOC to the atmosphere was normal, but early in the 90s, many regulations began to
require the abatement of these emissions using the best available technologies.
Other possible applications are the small air pollution sources. These applications are not
uncommon and some examples are dry cleaners, auto repair shops, bakeries, or coffee
roasters, etc. 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 perform 24-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
TiO2 particles as sensitizers 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 combination with
UV fluorescent lamps. The use of thin TiO2 films as a method of keeping surfaces free of
biological material would be of particular value where sterile surfaces are essential, such as
operating rooms in hospitals. Although very few demonstrations have been reported to date, it
is expected that more will take place in the future.
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SOLAR DETOXIFICATION
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 are 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).
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SOLAR DETOXIFICATION
AFB: Field Test Results.” Solar 1993. Proceedings of the American Solar Energy Society
Annual Conference; pp. 235-239. ASES, 1993.
4. Malato, S. “Solar photocatalytic decomposition of pentachlorophenol dissolved in water”.
Doctoral thesis. Editorial Ciemat. 1999.
5. Mehos, M.S.; Turchi, C.S. “Field Testing Solar Photocatalytic Detoxification on TCE-
Contaminated Groundwater”. Environmental Prog. 12(3); pp. 194-199. 1993.
6. Nimlos, R; Wolfrum, E.J.; Gratson, D.A.; Watt, A.S.; Jacoby, W.A.; Turchi, C. “Review
of Research Results for the Photocatalytic Oxidation of Hazardous Wastes in Air”.
NREL/TP-433-7043, 1995.
7. Prairie, M. ; Evans, L.R.; Martinez, S.L. “Destruction of Organics and Removal of Heavy
Metals in Water Via TiO2 Photocatalysis”. Chemical Oxidation: Technology for the
Nineties, Second International Symposium. Lancaster, PA: Technonomic Publishing
Company, 1994.
8. Vincent, M. “Solar Detox Market”. Training and Mobility of Researchers Summer
School: Industrial Applications of Solar Chemistry. September 1998. Editorial Ciemat.
9. Watts, R.J.; Kong, S.; Orr, M.P.; Miller, G.C; Henry, B.E. “Photocatalytic inactivation of
coliform bacteria and viruses in secondary wastewater effluent”. Wat. Res. Vol. 29, No. 1
pp. 95-100, 1995.
10. Yves, P.; Blake, D.; Magrini-Bair, K.; Lyons, C.; Turchi, C.; Watt, A.; Wolfrum, E.;
Prairie. M. “Solar Photocatalytic Processes for the Purification of Water: State of
Development and Barriers to Commercialization.” Solar Energy 56, No. 5, pp. 429-437,
1996.
SELF-ASSESSMENT QUESTIONS
PART B.
1. Why is the environmental market still reluctant to accept solar detoxification processes?
2. Indicate the three existing solar photocatalytic processes.
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SOLAR DETOXIFICATION
3. What is the main advantage of Photocatalytic Oxidation Processes over the rest of the
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 photocalysis is an oxidation-reduction process, what is the normal reductant
agent when only organic compounds are present?; and 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 4 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 water treatment process based on TiO2 photocatalysis?
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 initially successful experimental results presumed a wide range of practical
applications, but later confusing and discouraging results led to 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 can not 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.
100000
500
8. R = 4 = 64 hours of sunlight.
50
4
9. Via °Cl, °OH or °Cl + °OH radicals attack, depending the eventual pathway on the
catalyst characteristics.
10. The presence of high concentration of organic contaminants and inorganic ions
simultaneously.
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SOLAR DETOXIFICATION
8 ECONOMIC ASSESSMENT
AIMS
This unit discusses the main factors entering into the cost of solar detoxification systems and
describes how to go about the economic assessment of specific solar photocatalytic
applications. They are also qualitatively compared with other treatment technologies.
OBJECTIVES
After completing this unit, you will be able to:
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SOLAR DETOXIFICATION
NΦ (E>3.2 eV) Number of photons with energy higher than 3.2 eV per unit of photons m-2 h-1
time and surface
PCP Pentachlorophenol
RDX Hexahydro-1,3,5-trinitro-1,3,5-triazine
S Surface of solar collector field m2
TCE Trichloroethylene
TNT Trinitrotoluene
TOC Total Organic Carbon mg L-1 or
moles of C L-1
Tf Treatment Factor
Tfm Mass Treatment Factor g h-1 m-2
Tfv Volumetric Treatment Factor L h-1 m-2
UV-A Ultraviolet Radiation A
z Elevation over sea level m
α Solar altitude degrees
δs Solar declination degrees
φPH Nominal average photonic flux electric lamp photons s-1
ΨAOS Average Oxidation State dimensionless
∆ m (TOC ) g
T fm = 2
(8.1)
tS h m
The Volumetric Treatment Factor (Tfv) of a specific solar detoxification system can be defined
as the volume of contaminated water the system is able to treat per unit of time and solar
collector surface:
∆V L
T fv = 2
(8.2)
tS hm
Tfm and Tfv obviously depend on the specific solar system and the waste water to be treated.
The same system yields different treatment factors with different contaminants and it is also
different depending on the solar irradiation, higher on sunny days than cloudy days. The most
practical units are those indicated in Equations 8.1 and 8.2: the grams of TOC degraded per
hour and square meter of solar collector field, in the case of Tfm, and the litres of water treated
per hour and square meter of solar collector field in the case of Tfv.
50 mg L−1 x 5000 L −3 g g
T fm = 2
x 10 = 0.55 (8.3)
300 m x 1.5 h mg h m2
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SOLAR DETOXIFICATION
5000 L L
T fv = 2
= 11.11 (8.4)
300 m x 1.5 h h m2
Treatment Factors are a powerful tool for comparison of different detoxification systems and
checking treatment feasibility for different waste-water problems. The efficiency of solar
detoxification systems is usually around 0.05 to 1 g of organic compounds degraded per hour
and square meter. This is a function of several parameters, such as system geometry and
materials, the contaminants and their concentration, UV-A irradiation, catalyst concentration,
etc. Nevertheless, this parameter does not necessarily imply better or worse performance of a
specific system, because this depends on the discharge objectives. Contaminant treatment, in
its strictest meaning, is the complete mineralization (TOC = 0) of the contaminants, but, as
indicated in Chapter 7, normally photocatalytic processes only make sense for hazardous non-
biodegradable pollutants (toxic organic pollutants not treatable in conventional biological
treatment plants). When feasible, biological treatment of biodegradable residual waters are the
cheapest treatment technologies and also the most compatible with the environment.
Therefore, biologically recalcitrant compounds could be treated with photocatalytic
technologies until biodegradability is achieved, later transferring the water to a conventional
biological plant. Such a combination of photocatalytic and biological treatments, reduces
treatment time and optimises the overall economics, since the solar detoxification system can
be significantly smaller. Due to the kinetic mechanism explained in chapter 4, the first part of
the photocatalytic process is the quickest, producing the main part of TOC degradation, and
the last phase is the longest, with a minimum contribution to complete degradation.
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SOLAR DETOXIFICATION
In the above example (equation 8.2), “treat” could mean totally degrade organic contaminants
or only to biodegradability. 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.
TOC − COD
Average Oxidation State = Ψ AOS = 4 x (8.5)
TOC
Where TOC (Total Organic Carbon) and COD (Chemical Oxygen 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 oxidised state of carbon, and -4 for CH4, the most reduced state of carbon.
The latter is given by the reaction:
CH 4 + 2 O 2 → CO 2 + 2 H 2 O (8.6)
Where, TOC = 1 (moles of C L-1) and COD = 2 (moles O2 L-1) so, according to equation 8.5,
ΨAOS = –4. With CO2, as oxidation is impossible, COD = 0 and ΨAOS = +4. An example is
oxidation of formic acid:
H − COOH + O 2 → CO 2 + 2 H 2 O (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 when to switch from the Advanced
Oxidation Process to Biological Treatment.
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SOLAR DETOXIFICATION
Oxidised substances are typical of biological processes. Usually treatment performance is best
for low-molecular-weight organic compounds. Photodegradation treatment performance is
also better at the beginning, 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, afterward,
biological treatment. Figure 8.3 shows the typical evolution of ΨAOS when recalcitrant toxic
compounds 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 Curve A (Figures 8.3 and 8.4), because it means that the overall chemical
status of the degradation process does not progress, ΨAOS remains constant, and toxicity is
decreasing, thereby increasing biodegradability. Nevertheless, even at low concentrations,
toxic substances could be formed during the degradation process (Curve B, Situation B)
increasing overall toxicity. This does not necessarily impede connection to biological
treatment, but it does force the point of connection 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 TiO2 photocatalytic process followed by aerobic biotreatment has
also been successfully employed by NREL (USA) for the treatment of waste water from
munitions manufacturing plants (pinkwater) containing low concentrations of high explosives,
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 initially increases the toxicity of the wastewater. The reason is the proliferation at the
beginning of the process of many reaction by-products as well as with the initial contaminants
themselves. 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 treatment process.
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SOLAR DETOXIFICATION
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, electricity power, etc, are available on site and that 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:
concrete foundations, civil engineering, 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 connection assembly, etc.
− Project Contingency. Since the general conceptual design cannot include all the details of
the specific final design, at that point, total field costs are still necessarily incomplete, and
to properly account for any unidentified costs, a contingency item must be added to the
cost. This could be from 10% to 20% of the Facility Cost, depending on the degree to
which the 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, specifications, procurement of system components, scheduling,
project management, system assembly, training of operators and engineering support.
Engineering costs are estimated to be 50% of the Total Facility Cost.
− Spare Parts. 0.5% of the total facility cost is normally 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 notice 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 considering a CPC solar field. These costs are based on real bids and plants which have
been built.
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SOLAR DETOXIFICATION
The sum of personnel, maintenance materials, electricity and chemical supplies, is the Total
Operating Cost of the solar detoxification system. To obtain the Annual Treatment Cost, per
m3 of treated wastewater, total installed costs are converted to an annual levelized cost
considering a fixed-charge rate (FCR), which is obtained by calculating all the fixed costs
148
SOLAR DETOXIFICATION
(excluding operation) for the life of the plant. The annual levelized cost and treatment cost
can be calculated as:
Annual Levelized Cost = Total Installed Cost x FCR + Operating Cost (8.8)
Annual Cost
Treatment Cost ( Euros / m 3 ) = (8.9)
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, etc. For solar detoxification treatment
plants, a plant life of 12 years with a depreciation period of 10 years may normally be
assumed. With this data, and considering, for example, that the plant is financed by a debt
with a 5% interest rate and that the total annual expenses due to taxes, insurance, etc, are 2%
of the total installed cost, an FCR of 17% is obtained.
− +
TiO 2 + hν → eCB + hVB (λ < 390 nm) (8.10)
+ •
hVB + H 2O → OH + H + (8.11)
S 2 O82 − + eCB
−
→ •
SO4− + SO42− (8.12)
•
SO4− + H 2 O → •
OH + SO42 − + H + (8.13)
It is estimated that the plant would operate about 3,000 hours per year. An estimation of the
yearly treatment cost, in 1999 Euros, can be performed as follows:
149
A Facility Cost Data from table 8.1 (300 m2 of solar collector system 140,875 Euros
aperture area)
B Project Contingency 15% of the Facility Cost is estimated 21,131 Euros
C Engineering and Setup 50% of A+B (Total Facility Cost) 81,003 Euros
D Spare Parts 0.5% of A+B (Total Facility Cost) 8,100 Euros
E Total Installed Cost A+B+C+D 251,109 Euros
F Personnel cost 0.25 man-year is considered. A 20,000 Euros/man-year of 5,000 Euros
cost is considered
G Maintenance material cost 2% of A+B (Total Facility Cost) is estimated 3,240 Euros
H Electricity 5 kW of average electricity consumption so the 3,000 1,500 Euros
yearly operation hours would consume 15,000 kWh of
electricity. A cost of 0.1 Euro/kWh is considered
I Chemical supplies TiO2 catalyst used at 200 mg L-1 of concentration
and reusing up to 10 times. This means 120 kg 1,080 Euros
per year.
S2O8Na2 (MW = 238) used at concentrations from 53,550 Euros
5 to 10 mM with an overall consumption per
batch cycle of 15 mM. This means 21,420 kg per
year.
1,344 Euros
Sodium hydroxide (NaOH; 50% solution) for pH
adjustment and neutralization of the treated water. 4,800 kg
of yearly estimated consumption
J Total Operating Cost F+G+H+I 65,714 Euros
150
Table 8.2
SOLAR DETOXIFICATION
To obtain the treatment cost, an FCR of 17%, with 10-year plant depreciation, is estimated.
Fe 2 + + H 2 O 2 → Fe 3+ + OH − + • OH (8.14)
3+ 2+ + •
Fe + H 2 O + hν → Fe + H + OH (λ < 580 nm) (8.15)
As in the previous case, 3000 operating hours per year are estimated. The yearly treatment
cost would then be:
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SOLAR DETOXIFICATION
A Facility Cost Data from table 8.1 (200 m2 of solar collector system 104,337 Euros
aperture area)
B Project Contingency 12% of the Facility Cost is estimated 12,520 Euros
C Engineering and Setup 50% of A+B (Total Facility Cost) 58,429 Euros
D Spare Parts 0.5% of A+B (Total Facility Cost) 5,843 Euros
E Total Installed Cost A+B+C+D 181,129 Euros
F Personnel cost 0.20 man-year is considered. A 20,000 Euros/man-year of 4,000 Euros
cost is considered
G Maintenance material cost 2% of A+B (Total Facility Cost) is estimated 2,337 Euros
H Electricity 4 kW of average electricity consumption so the 3000 yearly 1,200 Euros
operation hours would consume 12,000 kWh of electricity.
A cost of 0.1 Euro/kWh is considered
I Chemical supplies FeSO4±7 H2O (MW = 278) catalyst at 1mM concentration,
which means 1,668 kg per year. 549 Euros
Hydrogen peroxide (H2O2; 30% solution) with an overall
consumption per treatment cycle of 33.75 mM. As MW =
34, the total yearly needed amount is 22,950 kg. 17,442 Euros
Sulphuric acid (SO4H2; 98%) at 1 mM concentration for
iron sedimentation by pH adjustment. As MW = 98, the
yearly consumption is 580 kg. 180 Euros
Sodium hydroxide (NaOH; 50% solution) for batch mode
neutralization of the treated water. MW = 40; 3,036 kg of
yearly estimated consumption. 849 Euros
J Total Operating Cost F+G+H+I 26,557 Euros
Table 8.4 Estimated operating cost of a Photo-Fenton Solar Detoxification plant
in 1999 Euros
Also as in the previous example, an FCR of 17% with a 10-year plant depreciation period is
estimated.
Two additional examples of solar photocatalytic treatment cost found in the literature are the
following:
− Groundwater remediation at Livermore, California, by NREL (USA). Average treatment
capacity of 4.4 L/s of water, with a peak flow of 30 L/s, inlet concentration of 400 ppb
TCE and maximum outlet concentration of 5 ppb. Total treatment cost was reported as
$4.07/m3.
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SOLAR DETOXIFICATION
− Study for a site at the Rocky Flats Plant near Boulder, Colorado (Bechtel Corp., 1991) to
treat an annual volume of 2246 m3 with a peak water flow of 6.3 L/s. The levelized cost of
treated water was estimated at $10.57/m3. This cost was heavily dominated by the
expensive system required to treat inorganic components of the water at Rocky Flats.
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, photopolymerisation processes, attracting insect, etc. They can also be used for
photocatalytic degradation processes.
The most suitable of the different types of electric lamps available for UV-photon production
are the low-pressure mercury fluorescent lamps (the same common fluorescent light normally
used for illumination), which are based on the generation of an electric arc through a sealed
chamber containing mercury vapour. The result is 245-nm radiation which is absorbed by a
phosphorous wall coating, producing a fluorescent radiation which, depending on the coating,
can be adjusted to any spectrum. As for any arc lamp, ballast is required to provide the
appropriate current and voltage to start. Several studies have demonstrated that these lamps
are the easiest, simplest and cheapest way to produce UV photons and, in fact, are already being
used in commercially available TiO2 photocatalytic lamp systems.
Another type is the germicidal lamp, which is basically the same, but the 254-nm light passes
directly through transparent glass. As their peak light emission is centred at the mentioned
wavelength, they produce fewer valid photons and are less efficient for photocatalytic
applications. Medium and high-pressure mercury lamps are also similar to the low-pressure
lamps, but the higher pressure generates higher intensity radiation and also tends to shift the
spectrum towards the visible light. Finally, metal halide lamps, high-pressure sodium lamps
and incandescent lamps cannot be used for UV light production.
Figure 8.5 shows two typical low-pressure 40-W mercury fluorescent lamps with dominant
emission spectrum centred at 313 and 340 nm. According to manufacturer data, the initial
standard efficiency of these lamps is between 25% and 30% of UV-photon production and an
average efficiency (lifetime) of about 20%. Average lamp life is around 20,000 hours.
With the above data, it is easy to obtain the equivalence between UV-lamp and solar systems. As
an example, we can calculate how many standard 40-W UV-fluorescent lamps are equivalent to
a 500-m2 TiO2-based solar plant with an average yearly global UV irradiation of 20 W m-2. The
parameter used to compare them is the number of useful UV photons generated or collected. In
153
154
Fig. 8.5
SOLAR DETOXIFICATION
the case of the solar plant, this can be obtained directly from the standard ASTM solar spectrum
(assuming constant spectral distribution) using the following equation (see also Section 8.4):
photons
N Φ ( E > 3.2 eV ) = 5.8 10 21 I UVg 2
(8.16)
m h
Where:
NΦ (E>3.2 eV) = Number of photons with energy over 3.2 eV (wavelength up to 387 nm) per unit of
time and surface.
I UVg = Yearly average global UV irradiation (W m-2).
The total amount of UV photons collected yearly by the solar plant would be:
Where:
NUV = Total UV photons (with energy over 3.2 eV) collected yearly.
HS = Total yearly hours of operation of a solar detoxification system. This value depends on the
geographic location, but it may be estimated at 3500 (near the equator to parallel 20) to 2500
(40th to 50th parallels). In the example, 3000 is used.
S = Surface area of solar collector field (500 m2 in the example).
I UVg = Yearly average global UV irradiation during the 3000 estimated hours of operation. 20 W
m-2 in this example (see also Chapter 8.4).
Where:
φPH = Nominal average photonic flux of the lamp. Manufacturer’s information usually places this
value between 1.3 to 1.4 x 1019 photons per second (standard 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 detoxification system = the full year (8760
hours).
NL = Number of lamps of the system.
So, according to equation 8.18, in the example considered, the equivalent number of lamps
would be 394.
From this particular example, the following general equation for estimating the equivalent
number of any type of electric lamps can be obtained:
I UVg HS
N L = 5.8 x 10 21 S (8.19)
Φ H
PH L
155
SOLAR DETOXIFICATION
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)
28
- 5 x 10 (5.E+28)
- 1029 (1.E+29)
29
- 5 x 10 (5.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 estimated 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% 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.
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 1999 Euros.
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 1999 Euros.
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SOLAR DETOXIFICATION
Table 8.8 Estimated Yearly Cost of collecting 1.E+29 solar UV photons at different yearly
average UV global irradiation. Costs are indicated in 1999 Euros.
Table 8.9 Estimated Yearly Cost of collecting 5.E+29 solar UV photons at different yearly
average UV global irradiation. Costs are indicated in 1999 Euros.
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SOLAR DETOXIFICATION
expensive in the case of lamps, depending on the total installed power. Using equation 8.18
the equivalent 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 ⇒ 1132 lamps (40 W low pressure mercury fluorescent tubes)
- 1.E+30 photons ⇒ 2265 lamps (40 W low pressure mercury 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 their total availability (24 hours a day),
which is an average of 3 times higher than solar systems. Total yearly cost is obtained using
equation 8.8 with an FCR of 17% as calculated above for the solar system. The operating cost
includes only electricity, replacement of lamp and the cost of labour involved in replacement. To
obtain these values, a 20,000-hour lifetime has been considered for the lamps. The cost of the
lamp system may be considered linearly dependent on the number of lamps.
Table 8.11 Estimated Yearly Cost of UV photon generation with electric lamps considering
two different reactor costs: 100 and 200 Euros/lamp. Electricity cost = 0.15 Euros/kWh. FCR
= 17%. Costs are indicated in 1999 Euros.
158
SOLAR DETOXIFICATION
The main uncertainty in Table 8.11 is the cost of the reactor 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 compactly 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
per-lamp reactor cost is estimated low (100 Euros) and another in which it is estimated high
(200 Euros).
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.
- 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 summarised in Figure 8.6, which shows the
comparative cost of solar and electric technologies for UV-photon collection and generation,
respectively. Three different amounts of photons are plotted (1.E+29, 5.E+29, 1.E+30) against
the average global solar UV-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 which determines the advantage of
solar over lamp-based technology, as the yearly UV-photon requirement of the majority of
possible applications will be in the range of 1.E+29 to 1.E+30 This threshold is normally
between 10 and 12 WUV/m2, which corresponds to 0.015 Euros/kWh for electricity. If a different
cost is considered, Table 8.11 must be updated. This is the case of Figure 8.7, which corresponds
to a cost of 0.05 Euros/kWh. In this case, the threshold solar advantage over lamp-based systems
is logically higher than before.
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SOLAR DETOXIFICATION
nm) comprises roughly 2-3% of the direct beam energy and 4-6% of the combined direct
beam and diffuse irradiation (global). Non-concentrating systems have an advantage with
regard to resource assessment as there are extensive data on the total energy (direct and
diffuse) available from sunlight and the 4-6% conversion factor makes resource assessment a
straightforward process for non-concentrating systems.
The cost of a specific solar detoxification treatment plant may be easily estimated from the
indications in Sections 8.1, 8.2 and 8.3, once the degradation process has been assessed and
treatment factors have been and identified. Nevertheless, the yearly average UV irradiation at
the specific location of potential solar detoxification plants must be known. In the so-called
“solar belt”, this is usually between 15 and 30 W m-2. It would be best if the location had a
database of historical global UV irradiation available, such as the case in Figure 8.8.
According to Section 2.4, for reliable estimation of the annual average UV radiation, the so-
called “cloud factor” (f) must be found. This is the average percentage of global UV radiation
that is expected to be lost due to clouds throughout the year. The cloud factor is also intended
to be a measurement of atmospheric transparency and is affected by all the atmospheric
components, which can absorb or scatter solar radiation. Figure 8.9 shows the results obtained
at PSA, following the procedure indicated in Section 2.4.
Another interesting alternative for estimating the annual UV radiation availability is through
the Lambert-Beer Law (also called the Bourguer Law), which indicates that light attenuation
through a continuous medium is proportional to the flux radiation and the distance covered:
I b, λ = I o , λ e − cλ m (8.20)
where:
Ib,λ = Intensity of solar irradiation on the earth’s surface at a specific wavelength, λ.
Io,λ = Intensity of extraterrestrial solar irradiation at the same wavelength, λ.
cλ = Atmosphere attenuation coefficient at 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 arrive at the same terrestrial
location. If the elevation of the sun is 90º then m = 1.
The air mass ratio can be obtained for any moment by the following equations:
m = m o e −0.0001184 Z (8.21)
m o = 1229 + (614 sin α ) − 614 sin α
2
(8.22)
where:
mo = Air mass ratio at sea level
z = elevation over sea level in meters
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SOLAR DETOXIFICATION
α = Solar altitude, defined as the angle formed by the solar vector to the horizontal surface of
the earth.
Equations 8.21 to 8.24 allow solar irradiation at any specific location on earth to be detailed;
Ib,λ must be measured at the specific location and Io,λ can easily be calculated. Due to the
earth’s slightly eccentric elliptical orbit, solar extraterrestrial radiation varies ±3.4% along the
year depending on the Day number:
2πN
I o, λ = I o ,λ (N ) = I SC ,λ 1 + 0.034 cos (8.25)
365
λ2
I SC ,λ = ∫ E (λ ) dλ (8.26)
λ1
Where:
Isc,λ = Solar Constant associated with the spectral interval (λ1,λ2) to which is intended to
obtain the atmospheric attenuation coefficient (cλ). This interval must also be coherent with
the measure of Ib,λ (i.e., if we are using a solar radiometer which measures within the interval
295 to 400 nm, Isc,λ must be calculated to the same interval).
E(λ) = Extraterrestrial irradiation, which can be found in Table 8.12.
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SOLAR DETOXIFICATION
λ Eλ λ Eλ λ Eλ
-2 -1 -2 -1 -2 -1
(µm) (W m µm ) (µm) (W m µm ) (µm) (W m µm )
0,115 0,007 0,43 1639 0,90 891
0,14 0,03 0,44 1810 1,00 748
0,16 0,23 0,45 2006 1,2 485
0,18 1,25 0,46 2066 1,4 337
0,20 10,7 0,47 2033 1,6 245
0,22 57,5 0,48 2074 1,8 159
0,23 66,7 0,49 1950 2,0 103
0,24 63,0 0,50 1942 2,2 79
0,25 70,9 0,51 1882 2,4 62
0,26 130 0,52 1833 2,6 48
0,27 232 0,53 1842 2,8 39
0,28 222 0,54 1783 3,0 31
0,29 482 0,55 1725 3,2 22,6
0,30 514 0,56 1695 3,4 16,6
0,31 689 0,57 1712 3,6 13,5
0,32 830 0,58 1715 3,8 11,1
0,33 1059 0,59 1700 4,0 9,5
0,34 1074 0,60 1666 4,3 5,9
0,35 1093 0,62 1602 5,0 3,8
0,36 1068 0,64 1544 6,0 1,8
0,37 1181 0,66 1486 7,0 1,0
0,38 1120 0,68 1427 8,0 0,59
0,39 1098 0,70 1369 10,0 0,24
0,40 1429 0,72 1314 15,0 0,0048
0,41 1751 0,75 1235 20,0 0,0015
0,42 1747 0,80 1109 50,0 0,0004
Table 8.12 Extraterrestrial solar irradiation
The Solar Constant for the whole solar spectrum (total solar radiation) is 1353 W m-2. In the
case of the UV spectrum (295 to 400 nm), using Table 8.12, it is:
400
This value of 104.4 W m-2 represents 7.72% of total extraterrestrial irradiation. As the
percentage on the earth’s surface is lower (normally from 4 to 6 percent), this means that the
atmosphere filters UV radiation relatively more than the overall spectrum.
With this background, by measuring Ib,λ, the atmospheric attenuation coefficient (cλ) can be
calculated. This parameter include all the factors relevant to solar irradiation, such as Raleigh
dispersion, ozone absorption, atmospheric turbidity and spray, absorption by water molecules,
clouds, etc. The knowledge of cλ at a specific location makes it possible to forecast solar
irradiation during the year. Variations in cλ over the year also enable conclusions to be made
about changes in atmosphere performance (with regard to solar light) at the specific location.
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SOLAR DETOXIFICATION
The following technologies 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, biological treatment technologies are not discussed.
Incineration is a source of debate with opposition to the construction of new incinerators from
the local populations. This is because of the increasing perception of incineration as a cause of
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 1000 Euros/ton depending on the nature of the
contaminants and the facility utilisation 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%. Furthermore, the resulting ash is generally more stable and less likely to leach
into groundwater than the parent compounds. On the other hand, poor combustion during
incineration 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 moisture in air. Benzene, chloroform, and TCE have frequently been found in stack
emissions. Finally, generation of organic compounds and dioxins due to incomplete
destruction has always been a concern.
163
164
2 000
WAO & Incineration Recovery
1000 Incineration
Wet Advanced Oxidation (WAO)
Fenton
-1
100 Biological
O3
Biological
H2O2
10
Biological
1
0 10 20 30 40 50 60 70 80
3 -1
Flow Rate (m h )
Fig. 8.10
SOLAR DETOXIFICATION
Catalyst materials, such as platinum, palladium, and metal oxides such as chrome-alumina,
cobalt oxide, etc, are introduced into the combustion unit in either a monolithic or beaded
configuration. The average catalyst lifetime is normally 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 comparison to 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 which 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 temperatures between
250ºC and 500ºC, since excessive heat can deactivate most catalysts.
- Catalyst poisoning from metals or halogens and / or binding from particulate matter over
time can decrease destruction efficiency. Periodic catalyst replacement or reactivation
would then be required.
Catalytic incinerators have a higher initial cost compared with thermal incinerators, but its
lower fuel costs and thereby lower operating cost offset this.
pA = H cA (8.28)
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 and, 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, etc). The technology has been applied
to a wide range of organic compounds with varying degrees of effectiveness at contaminant
165
SOLAR DETOXIFICATION
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 this technology
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 emissions from air strippers are limiting their applicability and
increasing their cost, as secondary air-phase treatment systems (i.e., real treatment processes)
are required afterward.
8.5.4 Adsorption
Adsorption of organic compounds on a solid adsorbent is widely used for treating hazardous
organic compounds in water. Contaminated water is forced through tanks containing 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 pesticides, 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 carbon canister that must be
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 maximise surface area with adsorption directly on the fibre’s surface.
Carbon regeneration and 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 fueled by electricity, natural gas, or oil is the most commonly used. The adsorbed
materials are pyrolyzed, forced off, and finally oxidized at over 900ºC.
As with air stripping, the main objection of adsorption by GACs is that they only displace
contamination to a large sorbent phase, which remains a regeneration or disposal problem, the
contaminants not really having been treated. The use of active carbon adsorption is also
feasible only as long as current legislation continues to allow 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 is destroyed by burning. Furthermore, each time it is
regenerated, only about 50% 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 new. Finally, increasing transportation and carbon regeneration costs are
reducing its cost-effectiveness. Consequently, GAC processes are expensive to operate and
generate undesirable secondary waste gases and changing environmental regulations indicate
that open burning of these materials may be prohibited within a few years.
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The initial investment is small and operating costs are medium. GAC is a mature technology
and 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 slower, because as
concentration increases, contaminant loads of carbon also increase. Therefore, GAC
processing costs are lower in large plants due to the economies of scale.
The main membrane processes are reverse osmosis, ultrafiltration and microfiltration, all of
which are pressurised. 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 drinking water. Polluted water is forced through semipermeable membranes (about 150
micrometers thick) under pressures as high as 100 bar, 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, hollow fiber,
etc.
Many types of organic compounds can be separated by membranes, including salts and
chlorinated and organophosphoric pesticides. Reverse osmosis requires periodic cleaning and
rejuvenation of filters. Residues, which contain 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 drawbacks 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.
When treatment conditions are below the critical point of water, 374ºC and 225 bar, reactions
take place in the water and the process is denominated subcritical wet oxidation or low
pressure wet oxidation; otherwise, it is called supercritical wet oxidation. Low-pressure wet
oxidation achieves 99% efficiency in the destruction of contaminants with residence times of
around one hour; supercritical wet oxidation can achieve 100% efficiency with a residence
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SOLAR DETOXIFICATION
time of 5 minutes, but higher temperatures and pressures are required. The main disadvantage
of wet oxidation systems is their very high installation and operating costs.
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, permanganate, etc. Ozone is used to oxidise low
concentrations of organic contaminants and also inorganic compounds and water-soluble
metals converting them to their insoluble form to permit separation of e.g. Fe++ and Mn++.
Another important application of ozone is disinfection. Investment costs of ozone technology
are medium as are its operating cost of from 5 to 15 Euros/m3.
Ozone treatment is reported to be more effective for hazardous organic contaminants when
used in combination with UV oxidation, similar to the synergistic effect that can be observed
between UV radiation and an oxidiser such as hydrogen peroxide in wastewater treatment.
This treatment process can be used selectively and reportedly acts on chlorinated
hydrocarbons faster than on other organic compounds. Halogenated organic compounds are
oxidised to simpler organic forms and, in some cases, are oxidised to carbon dioxide, 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 usually used to remove
metals. The concentration of inorganic chemicals in wastewater must be low so as not to
absorb or shield the UV rays.
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 (TiO2) or homogeneous (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.
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SOLAR DETOXIFICATION
From the economic perspective, to date, Solar Detoxification cost estimates have been based
on limited field experience. However, this experience and projections of capital and operating
costs show that solar photocatalytic oxidation of water costs from a few Euros up to 20-30
Euros/m3. This cost is higher than for the air stripping, adsorption or membrane technologies,
but with the important advantage that while solar detoxification is a real treatment process,
the others are only contaminant separation technologies. There is also a possibility of
optimising the cost of a specific treatment process by combining two (or more) different
technologies; Figure 8.11 shows the combination of solar detoxification and GAC for removal
of pentachlorophenol (PCP).
The investment and operating costs of solar detoxification are lower than for technologies
such as incineration or wet oxidation while other AOP technologies have similar investment
and operating costs.
It is unclear at present how much of the hazardous-waste treatment market could be captured
by Solar Detoxification technology, but potentially it is very large. Environmental
remediation field studies have demonstrated that technology selection is clearly not based on
cost alone. Factors such as complete on-site treatment (which limits owner liability),
community acceptance and absence of undesirable by-products are commonly considered
carefully in addition to cost. It is expected that, because of it is so attractive in these areas, the
Solar Detoxification system should be able to build a significant market share in the near
future.
169
Photocatalysis
Costs
GAC
Photocatalysis + GAC
% Eliminated PCP
Fig. 8.11
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SOLAR DETOXIFICATION
SELF-ASSESSMENT QUESTIONS
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 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%.
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.
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SOLAR DETOXIFICATION
1. Operating 2800 hours per year, a 300-m2 solar detoxification plant treats 5,000 m3 of
water containing 250 mg L-1 of hazardous contaminants yearly. If, once 50% 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 m2. 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 (40W tube) would be equivalent to a 350-m2 solar
collector field working 3500 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 air-stripping, absorption and membrane
treatment technologies of hazardous wastewater?
10. When is an oxidation process defined as supercritical?
ANSWERS
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SOLAR DETOXIFICATION
Part A
1. False; 2. True; 3. False; 4. True; 5. True; 6. True; 7. False; 8. True; 9. False; 10. False
Part B
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. Personnel, maintenance materials, electricity and chemicals cost.
4. FCR is the factor 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.
5. 20%.
6. As solar irradiation is proportional to the amount of useful photons and this is linearly
dependent on the reaction rate:
25
V = 3500 = 4375 m 3
20
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, but they can not be considered real
hazardous-wastewater treatment technologies.
10. When it takes place at temperatures and pressures higher than the critical point of water
(225 bars and 374ºC). If a fluid other than water is used, these conditions are defined by
the specific critical point of the working fluid.
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SOLAR DETOXIFICATION
9 PROJECT ENGINEERING
AIMS
This unit 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.
OBJECTIVES
After completing this unit, you will have a basic knowledge of the following subjects:
1. Feasibility study for Solar Detoxification applications.
2. Initial pre-design of an engineering system.
3. Implementation and management of Solar Detoxification projects.
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SOLAR DETOXIFICATION
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 engineering data required before the final
design may 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 wastewater of a similar original. This
means that the design of a specific solar detoxification system is a complex procedure
requiring a prior feasibility study following the method defined below:
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 feasibility
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 experimental
solar systems.
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SOLAR DETOXIFICATION
These possible impurities, mainly inorganic ions, could even lead to the no viability of the
degradation process and the only way to avoid it 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 noticed that such treatment increases both capital and system operating costs and
may also affect the control strategy of the treatment plant.
In the end, the specific impurities for each case must be identified and, depending on their
effect on the overall photocatalytic process, design or not a particular pre-treatment.
Other pre-treatments are independent of the presence of impurities. This is the case of oxygen,
hydrogen peroxide, persulfate or any other oxidant injected into the process stream before the
start of the photocatalytic process to act as whole receptors on the titanium dioxide catalyst. In
many cases reduction of initial pH to between 5 and 6 is also recommended to enhance the
initial degradation rate.
A good example is shown in Figure 9.2, where the Photo-Fenton photocatalytic process is
seen to be highly efficient in degrading about 6000 mg L-1 of initial TOC, compared to the
relative inefficiency of TiO2 heterogeneous photocatalysis. The reason for this is the waste
water, taken from a cataphoretic painting process at an automobile assembly plant, which
came from an ultrafiltration process, leaving no inorganic impurities at all present, and the
homogeneous process works quite well. By contrast, heterogeneous degradation does not
work due to the high presence of organic matter.
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SOLAR DETOXIFICATION
In other cases, the Photo-Fenton Fe cycle may be affected by the presence of impurities that
produce just the opposite result. In the case of Photo-Fenton, pH must also be around 2.5 to
avoid the formation of non-soluble iron hydroxides. It is thus clear that this first research step
is absolutely necessary in order to decide on the most appropriate process for further in depth
study.
Figure 9.3 Catalyst mixing system for the LLNL water treatment system. Courtesy of
National Renewable Energy Laboratory (USA)
It might also be very advisable to individually test the photocatalytic degradation of the key
recalcitrant contaminants identified in order to check whether there are significant differences
from those obtained with the real wastewater problem. 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 again to try and identify possible additional
pre-treatments, which 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.
Depending on the nature of the waste water treated and its later use, and whether solar
detoxification is used for water purification, such as in ground water decontamination, the
post-treatment system could then require additional processes, such as:
- carbon dioxide removal,
- elimination of possible residual hydrogen peroxide (if used in the photocatalytic process),
- cation-exchange bed to remove specific existing inorganic compounds,
- GAC filters to remove trace quantities of organic materials.
And any other possible treatment process necessary to meet the specific local regulatory
requirements before discharging water.
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, volatilising compounds with low boiling
points, or for the system, because, e.g., a cation exchanger at the inlet of a post-treatment
system limits the inlet temperature. If so, a water-to-
air heat exchanger must be installed at the inlet of the post-treatment system, or inserted in the
water circuit in the solar collector field.
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.
9.2.1 Background
In the Mediterranean, intensive agriculture in greenhouses has become a very important part
of the economy, especially during recent years. In southeastern Spain, the province of
Almería alone has more than 40,000 hectares of such greenhouses, and this is now the most
important economic activity in the area. However, important environmental problems
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SOLAR DETOXIFICATION
associated with this activity have also arisen, such as the extensive and intensive use of
pesticides (requirements are about 200 times greater than for conventional agricultural
methods).
One particular problem is caused by the enormous number of empty pesticide bottles disposed
of each year. According to 1995 data, 5,200 tons of pesticides were consumed in the region,
producing around 1.5 million empty bottles and containers, 99% of that are plastic, and having
an average volume of 1.9 litres. A small amount of pesticide residue always remains in the used
bottles and, therefore, they are 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 reuse, and most of them are thrown away with the rest of the regular agriculture 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 total organic carbon content of persistent toxic
compounds. As the water must be reused, those contaminants have to be treated and eliminated.
Solar Photocatalytic 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 started with research (Fig. 9.4) on the pesticide market in Almería that
provided the qualitative and quantitative distribution of pesticides consumed in the region. From
these, 10 pesticides, with all the main chemical families present, were selected as representative
from among those most used by the greenhouses, to carry out a complete, previously defined,
solar degradation test program. Table 9.1 shows the list of pesticides used.
Table 9.1 Selected pesticides for the feasibility study assessment. CIEMAT (Spain), 1996
179
180
Nematocides (2314)
Molluskicides (23)
Fig. 9.4
SOLAR DETOXIFICATION
- although pesticides, which are sprayed in concentrations between 200 ppm and 3000 ppm
depending on the product, are diluted in water before their application, pesticides in water
from the washing process are always more diluted than in normal use.
- the 10 pesticides selected are considered representative of the entire market (more than 300).
- the same number of empty plastic containers are generated by each of the 10 selected
products.
- the same amount of residue remains in all the containers.
Under these hypotheses, a mixture of the ten selected pesticides, each at the same concentration,
with a total TOC of 100 mg L-1, was considered representative of the water to be found after
washing, very similar what may be expected and was used in solar degradation experiments in
both Helioman (Fig. 7.5) and CPC (Fig. 7.6) systems, were performed.
Figure 9.5 (a) shows mineralization of total organic carbon from the insecticide abamectin in
the parabolic trough system. The TOC is observed to practically disappear after one hour of
exposition to sunlight (good weather conditions). Photocatalytic degradation tests performed
in a CPC system show a very similar pattern. Figure 9.5 (b) shows degradation of TOC from
the insecticides, acrinathrin, methamidophos and lufenuron (three different experiments on
sunny days). Each one (listed in Table 9.1) was individually tested and similar degradation
was observed: degradation of about 100 ppm of TOC in a residence time between 1 and 2
hours, with good solar irradiation. Residence times (tR) were calculated as:
VR
tR = tT (9.1)
VT
where tT is the total time elapsed since the beginning of the experiment, VR the (illuminated)
reactor volume and VT the total volume of the hydraulic loop.
However, the experiments of most practical interest are those in which the mixture of all 10 of
the selected compounds was used. These were performed in the CPC system as well as in
parabolic troughs assuming the four hypotheses considered. For these experiments 10 ppm of
each pesticide were added to 250 L of distilled water, and homogenised for 30 minutes.
Samples were taken periodically and the total organic carbon (TOC) in the suspension was
analysed and pesticide concentration monitored by liquid chromatography. Figure 9.6 shows
some of the results obtained, which included toxicity measurements throughout the
experiment. As the complete mineralization of all organics present in the water was not
intended, it should be observed that no highly toxic compound is generated. Microtox
(widely accepted toxicity measurement system), is usually expressed in terms of the EC50,
which is the effective concentration causing a 50% reduction in light from a luminescent
marine bacterium (photobacterium phosporeum), indicating that 50% of the bacteria present
have been killed.
181
Fig. 9.5 (a)
182
Fig. 9.5 (b)
183
SOLAR DETOXIFICATION
In the case displayed in the figure 9.6, a TOC reduction of 90% is followed by an important
toxicity reduction (to obtain the EC50, a 40% of concentration is just needed from initial
sample, while for the final one the needed concentration is 135%).
All titanium dioxide tests were conducted in 200-mg L-1 slurry concentrations, with 5 to 10
mM persulfate, which has been found to be the optimum concentration in PSA experiments.
Na2S2O8 was added at the beginning of the tests and at regular intervals to assure continuous
presence throughout tests by measuring the S2O82- consumed. This addition of persulfate does
not imply any environmental problem since it only produces small concentrations of sulphates
which increase the salinity of the water treated (maximum sulphates permissible in drinking
water is 250 mg/L; there is no limit for waste water). In the experiments indicated in Figure 9.7,
80% of the TOC was removed in from 2 to 4 hours and 90% in 2,5 to 5 hours.
An increase in the concentration of iron did not improve the degradation rate as much as had
been expected from previous laboratory experiments. The poor performance of the 0.5-mM
iron test may have been caused by the high initial TOC and a slight deviation in pH
adjustment. Nevertheless, 80% of the initial TOC was removed in less than 3 hours. With an
excess of H2O2, degradation can be improved up to 90%.
One of the difficulties in both the Photo-Fenton and TiO2-Persulfate experiments giving rise
to possible error, was measurement of the initial amount of pesticide, since the highly viscous
liquids strongly adhered to the glass-measuring cylinder. Furthermore, the amount of distilled
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 up to 60 minutes reaction time.
184
Fig. 9.6
185
SOLAR DETOXIFICATION
TiO2-Persulfate Photo-Fenton
(90% degradation) (80% degradation)
Tfm Tfv Tfm 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
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
Treatment factors are observed to be significantly higher with Photo-Fenton, and the last 10%
of degradation cannot be achieved with this process. This fact is an important issue in plant
design philosophy at the preliminary design stage.
The final figures for volume of water to be treated, hazardous contaminant and its
concentration, necessary collector surface, pre and post-treatment processes, etc, must be
assessed at this point. A typical list of the data to required for the preliminary design might be
the following:
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SOLAR DETOXIFICATION
− 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 from 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 waste water and there are valid figures for a feasibility study estimation, but
this cannot be used as the reference parameter for calculating the collector field area because
the solar radiation, which obviously is an essential parameter, is not included in the
calculation of the treatment factors, as Table 9.2 (obtained from Figures 9.7 and 9.8 in the
previous example) shows.
Treatment factors, Tfm and Tfv, are based on the use of residence time, tR , or the time the water
has been exposed to radiation, as the unit of calculation for analysis, and this could lead to
erroneous conclusions when there are important differences in the radiation incident in the
reactor due to 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 an 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:
S CPC
EUV,n = EUV,n-1 + t n UV G,n ; t n = t n - t n −1 (9.2)
VTOT
Where:
UV G,n is the average UV radiation incident on the collector surface for each ∆t interval;
tn is the experimental time for each sample taken to monitor the degradation process;
SCPC is the solar collector surface (CPC or any other type of collector);
VTOT is the total plant 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 direct comparison
between different experiments performed on different days with different weather conditions
possible, as well as calculation of the size of the solar field specific to the solar conditions at
the site. It must be remembered 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.
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SOLAR DETOXIFICATION
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 of solar detoxification system operation. 20 to 25
percent larger collector area (than the theoretical figure) is always recommended.
EUV VTOT
S= (9.3)
H S UVG
The feasibility study and preliminary design are basic components of the final design, as they
must supply all the data essential for the engineers and scientists to proceed confidently with
the final design. In addition, these steps must demonstrate that the final solar detoxification
plant will accomplish the treatment objectives before significant expenditures are made in
detailed design or implementation.
With equation 9.2 (ACPC = 9 m2; VTOT = 250 L), Figure 9.7 can be transformed into Figure
9.9, where TOC degradation 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 direct comparison of the Photo-Fenton and TiO2 processes possible, the amount of UV
light collected in Figure 9.10 was calculated the same way as for TiO2 (using data from the
same radiation sensor having a measuring range of 300-400 nm), even though iron
compounds absorb light up to wavelengths of 580 nm. From PSA measurements (Licor-1800
Spectroradiometer), an average of 7.11 times more solar energy up to 580 nm is available
than from the solar spectrum up to 390 nm.
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SOLAR DETOXIFICATION
From the different various tests carried out, the best conditions found for the titanium dioxide
process are a TiO2 catalyst concentration of 200 mg L-1 with 10 mM of persulfate addition. In the
case of the Photo-Fenton process, iron concentration is 1 mM. When Figures 9.9 and 9.10 are
compared, it seems clear that the Photo-Fenton process, although unable to achieve full
mineralization of the contaminants in the water, in this case, is more energy-efficient. The TiO2-
persulfate process requires 27 kJUV L-1 for 80 percent of TOC degradation or 30 kJ L-1 for the 90
percent mineralization. The Photo-Fenton process needs only the equivalent of 11.5 kJUV L-1 for
80 percent disappearance of TOC.
The most appropriate conceptual design is, therefore, the one shown in Figure 9.11, where the
water contaminated with the pesticide is treated in a batch process until 80 percent mineralization
of TOC is achieved. At this point, water is transferred to the post-treatment process (iron
precipitation, sedimentation and recuperation), and either reused for bottle washing or discharged
through an activated carbon filter to guaranty discharge quality. The water to be reused is
pumped back to wash the shredded plastic until contamination reaches a TOC of 100 ppm. In
this closed cycle, water may be reused about 5 to 10 times before final discharge. With this
design, about 95 percent of the contaminants are mineralized by solar photocatalysis and the
remaining 5 percent would be removed with a GAC filter.
The size of the solar field can be calculated with the following design parameters:
− Photo-Fenton is the photochemical degradation process selected.
− The initial TOC of water entering the solar detoxification facility will be 100 mg/L, which
includes not only the active ingredient, but also the rest of the components in the
commercial formulation.
− A TOC of 100 ppm is considered equivalent to about 200 mg L-1 of contaminant
concentration (from the ratio of average carbon weight against the average molecular
weight of the selected pesticides).
− The final TOC signifying water removal from the solar plant is 20 mg/L.
− The plant is designed to treat 375 kg of pesticides from the plastic-bottle washing process
yearly.
− The total volume of water to be treated yearly is 1,875 m3 (375,000 mg / 200 mg L-1).
− 3,000 hours of operation yearly.
− The average local global UV irradiation is 18.6 W m-2.
− The average solar energy necessary to degrade the contaminants is 12 kJUV L-1 (from
Figure 9.10).
So, using equation 9.3, the collector field area will be:
189
Catalyst Chemical Oxygen
oxidant (Air)
Mixer
Sun
Pre-treatment
(pH adjustment,
filtering, etc)
Pump
Tank Solar UV
Industrial TOC >
Pump light
Discharge bottles 100 ppm
(irrigation washing
water) process
Filter
Contaminated
water
YES
Chemical reactor
NO (CPC solar
TOC < collector field)
GAC filter Reutilization ?
20 ppm
Tank
TOC > UV light
Pump
100 ppm
Industrial Filter
Contaminated
bottles OR water
washing
process Chemical reactor
(solar collectors field)
TOC <
10 ppm
J L− 1 L
EUV VTOT 11.5 x 10 3 x 1875 x10 3 = 112 m 2
S= = (9.4)
H S UVG 3000 x 3600 x 18.6 s W m 2 −
And the proposed size of the solar collector field (CPC) would be 140 m2 (including a 25
percent margin). With this and the data above, the cost of the treatment facility may be
estimated following the procedure indicated in chapter 8. Figure 9.12 shows a proposed
layout for the complete facility.
Two important items in the layout in Figure 9.12 with regard to the pre and post-treatment
processes are sludge removal before treatment of the contaminated water in the solar field and
one-step iron sedimentation by neutralisation (in batch-mode), after the photocatalytic
treatment.
After the feasibility study and the preliminary design phase, the final design process might be
affected by different factors, such as:
− Uncertainty of key assumptions.
− Availability of design data.
− Availability of competent contractors.
− Project cost or size.
− Possible restrictions imposed by local regulations.
− Owner’s acceptance of risk, due to the implementation of a new technology based on
energy from the sun, input which obviously cannot be controlled.
The last factor, project risk, must not be dismissed, as it could be one of the key factors in
implementing the 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 24-hour-a-day operation. To avoid this risk, an
adequate buffer system must be designed and, 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 treatment 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
192
Inspection
area
Lighterage quay Shredding
(empty bottles) area
Washing
area
Total plant required area: Hot air dried &
2000 to 3000 square meters bag packed area
Store
Office Area
Micro- 15 m3
filtration
unit Loading berth
(final product)
Fig. 6.12
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SOLAR DETOXIFICATION
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 of solar detoxification installations at specific
locations.
Another possible problem could be the uncertainty of important assumptions used during the
feasibility study or the preliminary design phase. This could be the case of 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 impossible to carry out a
feasibility study with all these contaminants (it was performed with 10), a real uncertainty
exists with regard to the final design of the plant.
A possible solution for 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 necessary
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 normally accepted sources such as bids from other recently built
detoxification plants, quotes from vendors and equipment suppliers, construction industry cost
estimation guides, etc.
All these possible alternatives, when appropriate, in detail, must be reflected 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, etc., 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 construction contract. Issues such as responsibility sharing among the parties,
payment procedures, settlement of disputes, insurance, guaranty, etc 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 performance 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.
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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 be
vary considerably, depending 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: 2 to 5 months.
− Preliminary design: 1 to 2 months.
− Licensing: variable, depending on local regulations.
− Final design and contracts: 2 to 3 months.
− Vendor selection. Equipment and solar collector procurement: 4 to 6 months.
− Facility erection and installation: about 2 months.
− Start up, checkout and training: 1 to 2 months.
Finally, the documentation necessary for proper operation and maintenance of the facility
must be supplied.
For this project, a specific TiO2 catalyst was developed in the ENEL laboratories (Italy) by
synthesising titania powders with an innovative process in which a suitable reactant vapour
induced by a CO2 laser beam is pyrolysed. In the preliminary laboratory experiments, an
impressive 10 percent photon efficiency was obtained with this catalyst, when selected
chlorinated solvents at concentrations close to solubility were treated (Calza, Minero and
Pelizzetti, 1997). Real contaminated water generally contains chlorinated solvents at similar
concentrations. Figure 9.13 shows the manufacturing process for this catalyst.
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SOLAR DETOXIFICATION
Figure 9.13 Laser device for TiO2 catalyst powders manufacturing. Courtesy of ENEL SpA
(Italy), 1999
The design solar-collector was a 100-m2 CPC, having a flexible modular structure adjustable
to different angles of inclination (Figure 9.14) for easy on-site assembly and installation. The
collectors were erected based on the following design data:
− Acceptance angle: 90º
− Truncation angle: 90º
− Internal absorber radius: 14.6 mm
− External absorber radius: 16.0 mm
− Optical gap: 1.4 mm
− Sunlight concentration ratio: 1.0
The CPC collectors were fabricated from a galvanised sheet frame containing 16 parallel
highly reflective anodised-aluminium CPC reflectors with 1.5-m-long reactor tubes. Each
tube had a connector at the ends to join it to the previous and following adjacent collector
tube forming a complete module of collectors connected in a row. Figure 9.15 shows the
CPC-trough manufacturing process. The reflector on which the glass reactor tube is
assembled is later mounted in a box frame. The overall unit is installed on the supporting
structure on-site (see also Figure 9.19).
196
197
Fig. 9.14
SOLAR DETOXIFICATION
Figures 9.15 (a), (b) and (c) Manufacturing of CPC shape reflector.
Courtesy of AO SOL ENERGIAS RENOVÁVEIS Lda. (Portugal), 1999
The detoxification plant was installed at the facilities of a waste management and treatment
company in Madrid (Spain). Design batch-system treatment efficiency was 2 m3 of water
contaminated with non-biodegradable chlorinated solvents, in approximately two to three
hours (depending on the solar irradiation). One of the first problems was the location within
the factory for aesthetic reasons, because the solar facility had to be oriented to the south and
because of the orientation of existing buildings. This is a common problem in any solar
installation in existing buildings since they are normally built without considering their
orientation. One possible solution to this problem is the installation of the solar facility on the
roof, however, in this case, it was 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 during the
year.
The main plant components designed were the civil engineering, i.e., foundations and pits,
pumps, piping and fittings, hydraulic system, tanks, automation and control, electrical and
mechanical installation and TiO2 recovery system. The main plant parameters are:
− 2 Modules (21 collectors each) in parallel rows,
−
total collector aperture area: 100 m2,
− total circuit volume: 800 L,
− total plant volume: 2000 L,
− catalyst configuration: slurry,
− completely airtight with air injection (oxygen supply).
The plant consisted of two parallel rows of 21 collectors and 31 m length each. East-West
orientation was chosen with a small structural tilt (1%) in the same orientation as a way to
dry-out and to avoid the accumulation of rain water on the CPC troughs (Figure 9.17).
Civil engineering must consider the possibility of an accident (e.g., broken glass reactor) and
spillage of hazardous water during treatment. For this possibility, a small sidewall and a sump
for containment and collection of possible leaks, were designed and constructed (Figure 9.18).
198
Fig. 9.16
199
200
Fig. 9.17
SOLAR DETOXIFICATION
Figures 9.18 (a) and (b) Solar Detoxification plant construction. Lateral wall and pit for
possible leaks containment and collection. Courtesy of HIDROCEN S.L. (Spain), 1999
Once the frame support has been prepared, the next step is the installation of the solar
collector (Figure 19). Collector inclination is equal to local latitude (40 degrees North) and
the distance between rows was calculated to minimize shadowing of collectors. To this end,
the angle of sunlight at noon on December 21st (lowest maximum sun elevation) was used as a
design parameter to define row separation.
Figures 9.19 (a) and (b) Supporting structure and CPC units installation. Courtesy of AO SOL
ENERGIAS RENOVÁVEIS Lda. (Portugal), 1999
The final system design was modular with glass collector 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 be carefully calculated to guarantee similar flow rates in
all the reactor tubes. Nominal flow was turbulent (Re between 10000 and 20000) to avoid
catalyst settlement. Water input and output manifolds at the ends of the modules connect the
photoreactor array to the main feed pipe (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.
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Figure 9.20 Photoreactor array input water manifold system. Source: CIEMAT (Spain), 1999
The Solar Detoxification facility was designed to be operated in batch mode. The water to be
treated is initially stored in the 2-m3 storage tank, from which it flows into the buffer tank and
solar collector loop, completely filling them by force of gravity, and then recirculates
continuously through the reactors until desired contaminant destruction is achieved. The TiO2
catalyst and chemical additives are prepared separately in small tanks and are fed into the
treatment loop in the equivalent of two recirculation cycles to guarantee complete
homogenisation. The total treatment-loop volume is about 800 L, 600 L being continuously
exposed to the solar radiation in the reactors. Once the desired destruction is obtained, the
water is transferred to the catalyst separation tank, the treatment circuit is filled again with
new wastewater to be treated (Figures 9.21) and the process is restarted.
Figures 9.21 (a), (b) and (c) (a) Installation of main tanks of Solar Detoxification facility:
buffer tank (smaller in right place), storage tank (left) and catalyst separation tank (conic tank
on the back). (b) Installation of tank level sensors. (c) Installation of catalyst separation
system. Source: CIEMAT (Spain), 1999
The plant was designed with full automatic control systems and minimum operation and
maintenance requirements. Achieved level of water treatment is indirectly measured by
measuring sunlight availability. In this way, a solar UV-A sensor is incorporated within the
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SOLAR DETOXIFICATION
electronic control devices, with the function of solar UV integration from the beginning of the
treatment process (Figure 9.22). This sensor is connected to a Programmable Logic Controller
(PLC) and, once the level of energy to fulfil the treatment has been achieved (previously
determined from preliminary test for plant design, according to each specific contaminated
wastewater to be treated), the PLC stops the main pump, transfer the water to the catalyst
separation tank and advise the operator that the treatment has been completed.
Figures 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
The PLC also receives other data signals (flow-rate, tank levels, temperatures, etc) for system
pump and valve control. 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.
Figures 9.23 (a) and (b) Two views of the completed Solar Detoxification treatment plant.
Source: CIEMAT (Spain), 1999
CHAPTER SUMMARY
Implementation of any Solar Detoxification project must follow a three-step sequence:
Feasibility Study, Preliminary Design and Final Engineering Design. The objective of the
Feasibility Study is the assessment of the practicability of the solar photocatalytic technology
for the treatment of the wastewater problem by preliminary testing. In addition, the feasibility
study must identify the recalcitrant hazardous compounds, possible pre- and post-treatment
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processes, the most appropriate photocatalytic process, the optimum process parameters and
the treatment factors. The objective of the preliminary design is to develop specific
parameters for the positioning, layout, and size of the solar detoxification facility from the
feasibility study previously performed. This phase should include sufficient engineering
details to proceed 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, presence of hazardous
contaminants and their concentration, necessary collector surface, pre and post-treatment
processes, etc, must also be defined at this preliminary design level. The objective of the final
engineering design is to develop the necessary documentation to proceed with the
construction of the facility through selected contractors and vendors. This phase is usually
carried out for construction of the treatment plant by contract between the owner or
responsible party and the engineering firm responsible of the project.
SELF-ASSESSMENT QUESTIONS
1. The reason for 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 sulphates in the discharge water.
4. Once the preliminary design is completed, no additional data should initially be required
to proceed with the detailed engineering development (final 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 (photons up to 580 nm
compared to 390 nm of the solar spectrum, respectively), it is always the best option.
7. Final project design is usually associated with the construction of the treatment plant, but
not necessarily.
8. A technology confidentiality agreement among the parties should be included, if
appropriate, in the general conditions of the contract.
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9. Any specific documentation to be provided with the treatment facility, in addition to the
operation and maintenance manuals, should be defined in the Technical Specifications of
the contract.
10. When wastewater is treated by batch processing, the flow rate must be as low as possible
to save pump energy.
PART B.
Using these data, estimate the size of a solar detoxification plant necessary to treat 10,000
m3 of the same wastewater yearly operating 3000 h per year at a location with 24.5
WUV/m2 average solar irradiation.
8. Why is it always advisable to check the feasibility and preliminary design data before
beginning the final project design?
9. How can the risk of long cloudy periods (which could reduce the possibilities of
installation of a solar detoxification plant) be mitigated?
10. What are the main issues to be considered when designing the hydraulic loop for a solar
detoxification facility?
ANSWERS
Part A
1. True; 2. False; 3. False; 4. True; 5. True; 6. False; 7. True; 8. True; 9. False; 10. False.
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Part B
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 equation 9.1, the factor is 0.746:
280
tR = tT = 0.746 tT
375
S T UVG
EUV = (9.4)
VTOT
The second system may be considered more efficient than the first one, as it needs less
specific energy to achieve the same degradation.
7. From the five tests performed, the average treatment factor is 11 L h-1 m-2, and the average
solar irradiation, 30.76 W/m2. As there is a linear relationship with solar irradiation, if the
yearly average is 24.5, the equivalent treatment factor is:
24.5
11 x = 8.76 L h -1 m −2
30.76
10000 10 3 L
-1 −2
= 380 m 2
8.76 L h m 3000 h
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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.
10. To guarantee the same flow rate in all the reactor tubes, to minimise the “dark volume”
(volume not exposed to solar radiation) and to avoid catalyst settlement when a
heterogeneous photocatalytic process is implemented.
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10 INTERNATIONAL COLLABORATION
AIMS
This unit 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.
OBJECTIVES
At the end of this unit, you will appreciate the scale, nature and content of these programmes,
and some of the national and regional initiatives in progress around the world. You will
acquire basic information concerning the mechanisms and possibilities for proposing and
establishing international collaboration in the field of solar detoxification and you will also
know how to receive updated information on those possibilities.
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SolarPACES is one of the international co-operative programs 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 program 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, United Kingdom
and the United States. All the countries, with the exception of the UK, 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 development efforts.
In 1991, Germany, Spain, Switzerland and the USA decided to go on to a 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 (1998 SolarPACES Annual Report).
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 program’s
“Implementing Agreement”, which defined the SolarPACES charter and conditions of
membership. The current Implementing Agreement, valid from 1996 until
December 31, 2001, is an amendment of the original one signed on September 23, 1977. The
Implementing Agreement may be extended by agreement of two or more participants, then
being applied only to those participants.
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 on-going
tasks:
− Task I; Concentrating Solar Energy Power Systems.
− Task II; Solar Chemistry Research, where solar detoxification is included.
− Task III; Solar Technology and Applications.
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An Operating Agent, nominated by the ExCo, is responsible for overseeing the work of each
Task and each member country nominates a National Co-ordinator within each of the three
Tasks. Each task maintains a detailed program of work that defines all task activities,
including their objectives, participants, plans and budgets. In addition to technical reports of
the activities and their participants, accomplishments and progress are summarised in the
SolarPACES annual report. Many SolarPACES activities involve close co-operation among
members 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 with
the development of technologies and systems in the field of solar-driven thermochemical,
photochemical and electrochemical processes for the production of energy carriers, chemical
commodities and for 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.
The core of the work of SolarPACES is development of new and advanced concentrating
solar technologies and solving the wide range of technical problems associated with their
commercialisation. This means that, from advanced solar concentrating technologies in
general to solar detoxification applications in particular, industrial participation plays a
critical role. Many of the Task’s international activities and teams involve industrial co-
operation. In fact, in some countries (e.g., the UK 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 member countries. The small annual fee paid by
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member countries is used to support a limited range of co-operative activities approved by the
ExCo, such as publication and distribution of documents, scholarships and activities
promoting international awareness.
The Task II Operating Agent is the Paul Scherrer Institute (PSI) of Switzerland, which co-
ordinates the activities in close co-operation with the National Co-ordinators. Operating
Agent and National Co-ordinators normally meet once a year to review the progress of Task
activities, discuss technical issues and prepare future Task development.
http://www.demon.co.uk/tfc/SolarPACES.html
The Fifth Framework Programme, adopted in December 1998, defines the Community
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 combining 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 with solar detoxification of water.
The Fifth Framework Programme consists of seven Specific Programmes, of which four are
Thematic Programmes and three are Horizontal Programmes. The Thematic Programmes are:
− Quality of life and management of living resources
− User-friendly information society
− Competitive and sustainable growth
− Energy, environment and sustainable development
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The specific topic of water treatment is in the “Energy, environment and sustainable
development” programme. The strategic goal of this programme is to promote environmental
science and technology to improve quality of life and boost growth, competitiveness and
employment, while meeting the need for sustainable management of resources and protection
of the environment. Within this programme, research and technology development (RTD)
will concentrate on six key actions (two for the “energy” area, four to the “environment and
sustainable development” area). The first of the four key actions in the “environment” section
is “Sustainable management and quality of water”, specifically addressed to water treatment
and purification technologies, with the objectives, among others, of:
− developing improved waste-water treatment techniques and technologies,
− developing technologies for rational water reuse,
− developing technologies for water purification,
− enhancing waste-water treatments,
− minimising environmental impacts from waste water treatment.
Priority attention will be given to research initiatives addressed to waste water treatment and
re-use, water pollution abatement from contaminated land, landfills and sediments and ground
and surface waters diffuse pollution (persistent organic chemicals) abatement. The existing
budget for RTD initiatives related to the key action “Sustainable management and quality of
water”, for the period 1998-2002, is about 450 million Euro.
It may be observed that all these objectives and research initiatives are perfectly coherent with
the processes and technologies indicated in this book, providing an adequate framework for
international co-operation on solar detoxification applications and further research initiatives.
The “key action” concept is an important characteristic of 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 the Fifth
Framework Programme’s basic support of European research, is international co-operation.
Entities of 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 participation of third countries in FP5 may differ from
one Programme to another depending on the status of the country, with regard to the
participation in EC research activities. Specific rules apply for the Programme “Confirming
the international role of Community research”.
In addition to EU member countries, institutions and entities from other states have a special
status when participating 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) have Association Agreements either in force or expected to enter into
force during 1999. Switzerland has also concluded the Association Agreement negotiations.
Other countries, such as Argentina, Australia, Canada, China, Russia, South Africa and USA
have signed Co-operation Agreements with the EU for participation and collaboration in
research activities. In addition, some specific regions also have special relationship with the
EU, such as other European countries (Albania, Bosnia-Herzegovina, Former Yugoslav
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Republic of Macedonia Malta, Turkey and European Microstates and Territories), the so-
called Mediterranean Partnership (Algeria, Republic of Cyprus, Egypt, Jordan, Lebanon,
Malta, Morocco, Palestine Authority, Syria, Tunisia and Turkey) or 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 (MC), so it is always recommended that
up-to-date information and conditions for participation be obtained for the specific call to
which it is intended to submit a proposal.
The EC partially finances RTD activities carried out under the Specific Programmes
implemented within its Framework Programmes. The types of activities normally aided are:
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together with it. The bursary applicant must not be more than 40 years of age, must be a
national of one of the eligible countries and intending to return there at the end of the training
period. Applications from female researchers are encouraged.
As previously indicated, when planning an RTD proposal for submission to one of the
programmes or to key actions, researchers should be aware of the conditions of participation
by entities from non-EU countries and international organisations.
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Networks, Pre-competitive Research Projects and Innovative Projects must be within the
scope of the 16 sub-programs to be eligible. There are presently about 8600 Latin-American
scientist participating in CYTED Program activities, with more than 1000 universities, R&D
institutions and companies involved. Solar detoxification activities can be promoted within at
least the following two sub-programs:
- MATERIALS TECHNOLOGY. International co-ordinator: Miguel José Yacamán.
Consejo Nacional de Ciencia y Tecnología (CONACYT). Mexico.
- CATALYSIS AND ADSORBENTS. International co-ordinator: Paulino Andreu.
Petróleos de Venezuela, S.A. Venezuela.
Some solar detoxification initiatives are already in progress under the CYTED umbrella.
Among them are the “Latin-American Network of Semiconductor Oxides and Materials
Related to Optical Environmental Applications”, co-ordinated by Dr. Miguel Angel Blesa
(Comisión Nacional de Energía Atómica, Argentina), with partner institutions from
Argentina, Brazil, Mexico, Cuba and Spain.
The program 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 some tasks for project co-ordination.
Complete updated information about the CYTED Program can be found at the following web
address:
http://www.cicyt.es/ivpm/cyted.htm
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programs with relevant industrial collaboration: The United Stated and Spain. Their research
programs are briefly described below.
Work in these areas at the Solar Energy Research Institute (SERI), which became the
National Renewable Energy Laboratory (NREL), and at Sandia National Laboratories (SNL)
had begun gradually in the mid-1980s. At the same time, there was a strong push, driven by
regulatory pressure, to develop new technologies for correcting past environmental
contamination of soil and of ground and surface water. The regulatory pressure created a
business environment encouraging development of new, environmentally friendly processes.
Many large and small companies studied 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 program elements were pursued:
− Technology Research, to develop process chemistry
− System Engineering, to develop reactors and solar concentrators 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 R&D for the project.
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 commercialisation,
and universities were expected to provide more basic 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 development of processes that would use
concentrating solar hardware so the existing knowledge base in solar companies could be
tapped. 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 U. S.
Army, 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 conducted research and development work
in all R&D areas: basic, applied, demonstration, and transfer to commercialization. Basic
216
SOLAR DETOXIFICATION
research included core Photocatalytic Oxidation (PCO) R&D and catalysts development
work, as well as conducting research into new areas of photochemistry such as photo-induced
adsorption and high-temperature solar PCO. Applied research projects consisted of
remediation of chloroethylenes in the gas and water phase, gas and water phase solar
photoreactor development, and application research including 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 programs, including the Strategic
Environmental Research Defense Program, SEMATECH, and the U.S. Army.
In 1992, a co-operative research and development agreement was entered into with United
Technologies to develop PCO for air treating applications. In 1993, another agreement was
entered into with International Technology Corporation (IT) for the purpose of conducting
research and development to commercialise PCO remediation technologies coupled to air
stripping systems. In 1994, a third co-operative research and development agreement was
signed with SEMATECH to apply PCO to semiconductor manufacturing. Work with
SEMATECH resulted in a field demonstration at a semiconductor manufacturing plant-
treating emissions from a semiconductor manufacturing operation in 1996. In 1995 and 1996,
PCO applications were investigated for the Department of Defence for remediation of
trichloroethylene in water and air streams and for treating paint booth emissions. In 1997, two
field test demonstrations were completed for PCO/thermal treatment at a military paint booth
installation and 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 Program. The Department of Defence 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 organisations.
10.4.2 Spain
The CIEMAT’s Department of Renewable Energies, a public research institution devoted to
energy and the environment belonging to the Spanish Ministry of Industry and Energy, has
been working on solar chemistry processes since 1987. Research on Solar Detoxification
applications also started at that time, mainly at the PSA, the CIEMAT’s solar research facility,
which is located in southeastern Spain. In 1990, through the EU-DGXII “Access to Large
217
SOLAR DETOXIFICATION
Installation Program”, 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.
Due to reasonable initial expectations for the technical 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 detoxification processes and applications. This research
activity was later transformed, in 1998, into a formal CIEMAT Research Project with the
more specific scientific and technological objectives of developing and transferring a feasible
solar detoxification technology to industry. The main project objective is the development of
a technology that would make the use of solar photons in environmental chemical
applications in general, and solar detoxification processes in particular, technically and
economically viable. This is 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. Specific project objectives are the following:
− Development and optimisation of solar water detoxification technology for the treatment
of hazardous non-biodegradable contaminants in industrial wastewater.
− Development and optimisation of gas-phase solar detoxification technology (including
engineering, photoreactor and catalyst) to the photocatalytic detoxification of VOCs from
industrial gaseous emissions.
− Assessment of technical and economic viability of other Solar Chemistry processes with
potential application in Spain and other countries with similar characteristics, such as high
temperature solar detoxification of hazardous wastes, solar reforming, solar gasification of
biomass wastes, solar synthesis of fine chemicals, etc).
An important part of the contents of this book is the result of CIEMAT activities in solar
detoxification of hazardous water contaminants during recent years.
During the entire period, a major source of scientific background has come from the EC
“Access to Large-Scale Scientific Installations” (1990-1993), “Human Capital and Mobility”
(1994-1995) and “Training and Mobility of Researchers” (1996-1998). These programs have
facilitated PSA Solar Detoxification Facility access for many relevant European universities
and other research groups and have made possible a continuous exchange of ideas leading to
photochemical 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 programs, have provided CIEMAT 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 waste water and identify the most suitable targets. Moreover, these
tests have been used to verify the continuous modification and improvement of the solar
technology. Industrial collaboration with the CIEMAT Solar Detoxification project has
increased significantly since 1997, with the development of several important projects and
demonstration initiatives. Sections 9.2, 9.4 and 9.6 of this book are examples of this
collaboration.
218
SOLAR DETOXIFICATION
It may be affirmed that the result of this combined photochemical research from university
and industrial collaboration in hardware development and testing has lead to the current state
of the art of the solar detoxification technology, which this book has tried to reflect.
Twenty guidelines indicating the requirements for water projects may be found in the
document Lessons Learned in Water, Sanitation and Health (reference 6). As these guidelines
are basically addressed to water and sanitation projects funded by international aid, some
important conclusions may be arrived at concerning solar detoxification water treatment
projects. These and other guidelines were obtained as the result of many years of experience
and underline the necessity of promoting co-operation with local authorities and institutions,
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 are to guarantee the long-term sustainability of any facility installed.
From such guidelines as these, lessons learned and general recommendations 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 institutions 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 technologies that require adequate previous training. Also, the collaboration of
local institutions is very important in itself since any water treatment project is usually closely
related to sanitary and health issues.
A typical mistake is to focus the project on construction, forgetting the necessary previsions
and provisions to ensure the technical and financial sustainability of the renewable 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 designed in such a way that their
operation and maintenance costs as well as part of the initial construction cost can be borne by
the user or users.
Another relevant recommendation is that projects should not promote dependency on foreign
aid or foreign technical assistance. One possible way to avoid this when innovative
technologies, such as solar detoxification, are implemented is to promote the development of
the private sector on the area. Local companies, acting as interface between the users and the
foreign engineering company, could provide the necessary technical assistance and also
promote new projects and initiatives at local level.
219
SOLAR DETOXIFICATION
Among the denominated Advanced Oxidation Processes (AOPs), based on catalytic and
photochemical techniques, Solar Detoxification has become especially attractive to the
treatment of water contaminants. This has been due to the synergistic combination of solving
difficult environmental problems by using solar energy with the possibilities of creating new
jobs and activities. Solar Detoxification could be considered, then, as a good example of the
concept of sustainable development which, as sooner the better, mankind must achieve.
SELF-ASSESSMENT QUESTIONS
220
SOLAR DETOXIFICATION
PART B.
1. How would you define an Implementing Agreement of the International Energy Agency?
2. What is SolarPACES?
3. Indicate the initial members of the present stage of the SolarPACES project, initiated in
1991.
4. How many countries have signed the SolarPACES Implementing Agreement in 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
with environmental research.
8. Indicate the name of the Horizontal Programme, within the EU-FP5, specifically
addressed to promote 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.
221
SOLAR DETOXIFICATION
Part B
222
SOLAR DETOXIFICATION
10 INTERNATIONAL COLLABORATION
AIMS
This unit 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.
OBJECTIVES
At the end of this unit, you will appreciate the scale, nature and content of these programmes,
and some of the national and regional initiatives in progress around the world. You will
acquire basic information concerning the mechanisms and possibilities for proposing and
establishing international collaboration in the field of solar detoxification and you will also
know how to receive updated information on those possibilities.
223
SOLAR DETOXIFICATION
SolarPACES is one of the international co-operative programs 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 program 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, United Kingdom
and the United States. All the countries, with the exception of the UK, 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 development efforts.
In 1991, Germany, Spain, Switzerland and the USA decided to go on to a 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 (1998 SolarPACES Annual Report).
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 program’s
“Implementing Agreement”, which defined the SolarPACES charter and conditions of
membership. The current Implementing Agreement, valid from 1996 until
December 31, 2001, is an amendment of the original one signed on September 23, 1977. The
Implementing Agreement may be extended by agreement of two or more participants, then
being applied only to those participants.
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 on-going
tasks:
− Task I; Concentrating Solar Energy Power Systems.
− Task II; Solar Chemistry Research, where solar detoxification is included.
− Task III; Solar Technology and Applications.
224
SOLAR DETOXIFICATION
An Operating Agent, nominated by the ExCo, is responsible for overseeing the work of each
Task and each member country nominates a National Co-ordinator within each of the three
Tasks. Each task maintains a detailed program of work that defines all task activities,
including their objectives, participants, plans and budgets. In addition to technical reports of
the activities and their participants, accomplishments and progress are summarised in the
SolarPACES annual report. Many SolarPACES activities involve close co-operation among
members 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 with
the development of technologies and systems in the field of solar-driven thermochemical,
photochemical and electrochemical processes for the production of energy carriers, chemical
commodities and for 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.
The core of the work of SolarPACES is development of new and advanced concentrating
solar technologies and solving the wide range of technical problems associated with their
commercialisation. This means that, from advanced solar concentrating technologies in
general to solar detoxification applications in particular, industrial participation plays a
critical role. Many of the Task’s international activities and teams involve industrial co-
operation. In fact, in some countries (e.g., the UK 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 member countries. The small annual fee paid by
225
SOLAR DETOXIFICATION
member countries is used to support a limited range of co-operative activities approved by the
ExCo, such as publication and distribution of documents, scholarships and activities
promoting international awareness.
The Task II Operating Agent is the Paul Scherrer Institute (PSI) of Switzerland, which co-
ordinates the activities in close co-operation with the National Co-ordinators. Operating
Agent and National Co-ordinators normally meet once a year to review the progress of Task
activities, discuss technical issues and prepare future Task development.
http://www.demon.co.uk/tfc/SolarPACES.html
The Fifth Framework Programme, adopted in December 1998, defines the Community
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 combining 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 with solar detoxification of water.
The Fifth Framework Programme consists of seven Specific Programmes, of which four are
Thematic Programmes and three are Horizontal Programmes. The Thematic Programmes are:
− Quality of life and management of living resources
− User-friendly information society
− Competitive and sustainable growth
− Energy, environment and sustainable development
226
SOLAR DETOXIFICATION
The specific topic of water treatment is in the “Energy, environment and sustainable
development” programme. The strategic goal of this programme is to promote environmental
science and technology to improve quality of life and boost growth, competitiveness and
employment, while meeting the need for sustainable management of resources and protection
of the environment. Within this programme, research and technology development (RTD)
will concentrate on six key actions (two for the “energy” area, four to the “environment and
sustainable development” area). The first of the four key actions in the “environment” section
is “Sustainable management and quality of water”, specifically addressed to water treatment
and purification technologies, with the objectives, among others, of:
− developing improved waste-water treatment techniques and technologies,
− developing technologies for rational water reuse,
− developing technologies for water purification,
− enhancing waste-water treatments,
− minimising environmental impacts from waste water treatment.
Priority attention will be given to research initiatives addressed to waste water treatment and
re-use, water pollution abatement from contaminated land, landfills and sediments and ground
and surface waters diffuse pollution (persistent organic chemicals) abatement. The existing
budget for RTD initiatives related to the key action “Sustainable management and quality of
water”, for the period 1998-2002, is about 450 million Euro.
It may be observed that all these objectives and research initiatives are perfectly coherent with
the processes and technologies indicated in this book, providing an adequate framework for
international co-operation on solar detoxification applications and further research initiatives.
The “key action” concept is an important characteristic of 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 the Fifth
Framework Programme’s basic support of European research, is international co-operation.
Entities of 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 participation of third countries in FP5 may differ from
one Programme to another depending on the status of the country, with regard to the
participation in EC research activities. Specific rules apply for the Programme “Confirming
the international role of Community research”.
In addition to EU member countries, institutions and entities from other states have a special
status when participating 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) have Association Agreements either in force or expected to enter into
force during 1999. Switzerland has also concluded the Association Agreement negotiations.
Other countries, such as Argentina, Australia, Canada, China, Russia, South Africa and USA
have signed Co-operation Agreements with the EU for participation and collaboration in
research activities. In addition, some specific regions also have special relationship with the
EU, such as other European countries (Albania, Bosnia-Herzegovina, Former Yugoslav
227
SOLAR DETOXIFICATION
Republic of Macedonia Malta, Turkey and European Microstates and Territories), the so-
called Mediterranean Partnership (Algeria, Republic of Cyprus, Egypt, Jordan, Lebanon,
Malta, Morocco, Palestine Authority, Syria, Tunisia and Turkey) or 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 (MC), so it is always recommended that
up-to-date information and conditions for participation be obtained for the specific call to
which it is intended to submit a proposal.
The EC partially finances RTD activities carried out under the Specific Programmes
implemented within its Framework Programmes. The types of activities normally aided are:
228
SOLAR DETOXIFICATION
together with it. The bursary applicant must not be more than 40 years of age, must be a
national of one of the eligible countries and intending to return there at the end of the training
period. Applications from female researchers are encouraged.
As previously indicated, when planning an RTD proposal for submission to one of the
programmes or to key actions, researchers should be aware of the conditions of participation
by entities from non-EU countries and international organisations.
229
SOLAR DETOXIFICATION
Networks, Pre-competitive Research Projects and Innovative Projects must be within the
scope of the 16 sub-programs to be eligible. There are presently about 8600 Latin-American
scientist participating in CYTED Program activities, with more than 1000 universities, R&D
institutions and companies involved. Solar detoxification activities can be promoted within at
least the following two sub-programs:
- MATERIALS TECHNOLOGY. International co-ordinator: Miguel José Yacamán.
Consejo Nacional de Ciencia y Tecnología (CONACYT). Mexico.
- CATALYSIS AND ADSORBENTS. International co-ordinator: Paulino Andreu.
Petróleos de Venezuela, S.A. Venezuela.
Some solar detoxification initiatives are already in progress under the CYTED umbrella.
Among them are the “Latin-American Network of Semiconductor Oxides and Materials
Related to Optical Environmental Applications”, co-ordinated by Dr. Miguel Angel Blesa
(Comisión Nacional de Energía Atómica, Argentina), with partner institutions from
Argentina, Brazil, Mexico, Cuba and Spain.
The program 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 some tasks for project co-ordination.
Complete updated information about the CYTED Program can be found at the following web
address:
http://www.cicyt.es/ivpm/cyted.htm
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SOLAR DETOXIFICATION
programs with relevant industrial collaboration: The United Stated and Spain. Their research
programs are briefly described below.
Work in these areas at the Solar Energy Research Institute (SERI), which became the
National Renewable Energy Laboratory (NREL), and at Sandia National Laboratories (SNL)
had begun gradually in the mid-1980s. At the same time, there was a strong push, driven by
regulatory pressure, to develop new technologies for correcting past environmental
contamination of soil and of ground and surface water. The regulatory pressure created a
business environment encouraging development of new, environmentally friendly processes.
Many large and small companies studied 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 program elements were pursued:
− Technology Research, to develop process chemistry
− System Engineering, to develop reactors and solar concentrators 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 R&D for the project.
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 commercialisation,
and universities were expected to provide more basic 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 development of processes that would use
concentrating solar hardware so the existing knowledge base in solar companies could be
tapped. 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 U. S.
Army, 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 conducted research and development work
in all R&D areas: basic, applied, demonstration, and transfer to commercialization. Basic
231
SOLAR DETOXIFICATION
research included core Photocatalytic Oxidation (PCO) R&D and catalysts development
work, as well as conducting research into new areas of photochemistry such as photo-induced
adsorption and high-temperature solar PCO. Applied research projects consisted of
remediation of chloroethylenes in the gas and water phase, gas and water phase solar
photoreactor development, and application research including 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 programs, including the Strategic
Environmental Research Defense Program, SEMATECH, and the U.S. Army.
In 1992, a co-operative research and development agreement was entered into with United
Technologies to develop PCO for air treating applications. In 1993, another agreement was
entered into with International Technology Corporation (IT) for the purpose of conducting
research and development to commercialise PCO remediation technologies coupled to air
stripping systems. In 1994, a third co-operative research and development agreement was
signed with SEMATECH to apply PCO to semiconductor manufacturing. Work with
SEMATECH resulted in a field demonstration at a semiconductor manufacturing plant-
treating emissions from a semiconductor manufacturing operation in 1996. In 1995 and 1996,
PCO applications were investigated for the Department of Defence for remediation of
trichloroethylene in water and air streams and for treating paint booth emissions. In 1997, two
field test demonstrations were completed for PCO/thermal treatment at a military paint booth
installation and 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 Program. The Department of Defence 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 organisations.
10.4.2 Spain
The CIEMAT’s Department of Renewable Energies, a public research institution devoted to
energy and the environment belonging to the Spanish Ministry of Industry and Energy, has
been working on solar chemistry processes since 1987. Research on Solar Detoxification
applications also started at that time, mainly at the PSA, the CIEMAT’s solar research facility,
which is located in southeastern Spain. In 1990, through the EU-DGXII “Access to Large
232
SOLAR DETOXIFICATION
Installation Program”, 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.
Due to reasonable initial expectations for the technical 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 detoxification processes and applications. This research
activity was later transformed, in 1998, into a formal CIEMAT Research Project with the
more specific scientific and technological objectives of developing and transferring a feasible
solar detoxification technology to industry. The main project objective is the development of
a technology that would make the use of solar photons in environmental chemical
applications in general, and solar detoxification processes in particular, technically and
economically viable. This is 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. Specific project objectives are the following:
− Development and optimisation of solar water detoxification technology for the treatment
of hazardous non-biodegradable contaminants in industrial wastewater.
− Development and optimisation of gas-phase solar detoxification technology (including
engineering, photoreactor and catalyst) to the photocatalytic detoxification of VOCs from
industrial gaseous emissions.
− Assessment of technical and economic viability of other Solar Chemistry processes with
potential application in Spain and other countries with similar characteristics, such as high
temperature solar detoxification of hazardous wastes, solar reforming, solar gasification of
biomass wastes, solar synthesis of fine chemicals, etc).
An important part of the contents of this book is the result of CIEMAT activities in solar
detoxification of hazardous water contaminants during recent years.
During the entire period, a major source of scientific background has come from the EC
“Access to Large-Scale Scientific Installations” (1990-1993), “Human Capital and Mobility”
(1994-1995) and “Training and Mobility of Researchers” (1996-1998). These programs have
facilitated PSA Solar Detoxification Facility access for many relevant European universities
and other research groups and have made possible a continuous exchange of ideas leading to
photochemical 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 programs, have provided CIEMAT 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 waste water and identify the most suitable targets. Moreover, these
tests have been used to verify the continuous modification and improvement of the solar
technology. Industrial collaboration with the CIEMAT Solar Detoxification project has
increased significantly since 1997, with the development of several important projects and
demonstration initiatives. Sections 9.2, 9.4 and 9.6 of this book are examples of this
collaboration.
233
SOLAR DETOXIFICATION
It may be affirmed that the result of this combined photochemical research from university
and industrial collaboration in hardware development and testing has lead to the current state
of the art of the solar detoxification technology, which this book has tried to reflect.
Twenty guidelines indicating the requirements for water projects may be found in the
document Lessons Learned in Water, Sanitation and Health (reference 6). As these guidelines
are basically addressed to water and sanitation projects funded by international aid, some
important conclusions may be arrived at concerning solar detoxification water treatment
projects. These and other guidelines were obtained as the result of many years of experience
and underline the necessity of promoting co-operation with local authorities and institutions,
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 are to guarantee the long-term sustainability of any facility installed.
From such guidelines as these, lessons learned and general recommendations 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 institutions 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 technologies that require adequate previous training. Also, the collaboration of
local institutions is very important in itself since any water treatment project is usually closely
related to sanitary and health issues.
A typical mistake is to focus the project on construction, forgetting the necessary previsions
and provisions to ensure the technical and financial sustainability of the renewable 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 designed in such a way that their
operation and maintenance costs as well as part of the initial construction cost can be borne by
the user or users.
Another relevant recommendation is that projects should not promote dependency on foreign
aid or foreign technical assistance. One possible way to avoid this when innovative
technologies, such as solar detoxification, are implemented is to promote the development of
the private sector on the area. Local companies, acting as interface between the users and the
foreign engineering company, could provide the necessary technical assistance and also
promote new projects and initiatives at local level.
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SOLAR DETOXIFICATION
Among the denominated Advanced Oxidation Processes (AOPs), based on catalytic and
photochemical techniques, Solar Detoxification has become especially attractive to the
treatment of water contaminants. This has been due to the synergistic combination of solving
difficult environmental problems by using solar energy with the possibilities of creating new
jobs and activities. Solar Detoxification could be considered, then, as a good example of the
concept of sustainable development which, as sooner the better, mankind must achieve.
SELF-ASSESSMENT QUESTIONS
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SOLAR DETOXIFICATION
PART B.
1. How would you define an Implementing Agreement of the International Energy Agency?
2. What is SolarPACES?
3. Indicate the initial members of the present stage of the SolarPACES project, initiated in
1991.
4. How many countries have signed the SolarPACES Implementing Agreement in 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
with environmental research.
8. Indicate the name of the Horizontal Programme, within the EU-FP5, specifically
addressed to promote 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.
236
SOLAR DETOXIFICATION
Part B
237
Solar Detoxification
by
Julian Blanco Galvez, Head of Solar Chemistry
and
Sixto Malato Rodriguez, Researcher in the Solar Chemistry Area,
Plataforma Solar de Almeria
Spain
SYNOPSIS
AIMS
The book is divided into two parts, with five chapters each. First
one addresses the theory and fundamentals of the water
decontamination by means of solar energy. The objective of this
part is to provide enough background to the reader for the second
part of the book, addresses the practical applications and systems
engineering of the process.