Design and Evaluation of Micro-Channel

Photoreactor for Wastewater Treatment

Applications

1
CHAPTER ONE: GENERAL INTRODUCTION
1.1. Introduction to advanced oxidation processes
1.2. Classification of oxidation processes
1.3. Advantages of photocatalytic technology
1.4. Applications of photocatalytic technology
1.4.1. Chemistry applications
1.4.1.1. Synthesis of chemicals
1.4.1.2. Synthesis of polymers
1.4.2. Energy applications
1.4.2.1. Hydrogen production by water
cleavage/splitting
1.4.2.2. CO2 conversion to hydrocarbon fuels
1.4.3. Environmental applications
1.4.3.1. Air purification
1.4.3.2. Degradation of water contaminants
1.4.3.3. Decomposition of crude oils
1.4.3.4. Self-cleaning surfaces
1.5. Motivations
1.6. Problem statement
1.7. Research objectives

CHAPTER TWO: LITERATURE REVIEW

2.1 Background and history
2.2 Photocatalytic reactors
2.2.1 ???
2.2.2 ???
2.2.3 ???
2.2.4 ???

2
 2.2.5 Micro-channel photoreactors
2.3 Photocatalysts
2.3.1 Role of semiconductors
2.3.2 Modification of semiconductors
2.3.3 Role of photocatalyst carrier
2.4 Light sources
2.5 Mechanism of photocatalytic oxidation of organic
pollutants
2.6 Parameters affecting on photocatalytic oxidation
process
2.7 Modeling and theory
2.7.1 Kinetic modeling of photocatalytic oxidation
2.7.2 Activation energy
2.7.3 Thermodynamic parameters

CHAPTER THREE: METHODOLOGY

3.1 Development of photocatalyst
3.1.1 Chemicals and reagents
3.1.2 Synthesis of photocatalysis
3.1.3 Characterizations
3.2 Equipment and photocatalytic oxidation
3.2.1 Design of micro-channel photoreactor
3.2.2 Photocatalytic oxidation of organics

3
CHAPTER ONE:
GENERAL INTRODUCTION

1.1. Introduction to advanced oxidation processes [1]

In recent decades, problems affecting the environmental quality of
ecosystems have become increasingly critical and frequent. An
ecosystem consists of abiotic and biotic components (including human
influences) that present an interconnected and interdependent
network through soil, air and water. Changes to only one of these
segments can result in changes in the ecosystem as a whole. These
problems are due in large part to the impact of anthropic activities,
mainly due to population growth and increased industrial activity [1,
2].
One of the major environmental problems today refers to the impact
associated with the disposal of industrial wastewater and other
residues into superficial and underground water bodies. Solutions to
this issue require combined approaches, concerning generation,
treatment, and disposal into the environment not only of effluents but
passive residues produced by specific treatments: physical (resulting
primarily from the formation of low-solubility solids and auxiliary
reagent for flocculation and precipitation); chemical (promising, but
still undergoing up-scaling as emergent processes); microbiological
(the most commonly used on industrial scale in terms of versatility
and cost); or combined hybrid process.
Several techniques are available for wastewater treatment (as
mentioned before, chemical, physical and biological processes) as well
as the use of combinations of these techniques to an optimal result.
When organic compounds in wastewaters present recalcitrant
characteristics precluding treatments by conventional biological
methods, chemical oxidation can be used as pre- or post-treatment,
decreasing toxicity before applying a conventional biological process or

4
conditioning the effluent to required maximum concentrations (i.e.,
oxidize non-biodegradable residues). Chemical oxidation can also be
used as a post treatment to oxidize non-biodegradable residues
present in wastewater treated by biological processes. Each treatment
technique has positive aspects and constraints in relation to
applicability, efficiency and cost [3]. In this context, Advanced
Oxidative Degradation Processes (AOPs) comprise a set of techniques
that, under certain conditions, could transform the vast majority of
organic contaminants into carbon dioxide, water, and inorganic ions
as a result of oxidation reactions, which involve transitory oxidant
species. [1]

1.2. Classification of oxidation processes

The availability of the earth’s fresh water resources has drastically
depleted or contaminated due to improper water management, leading
to the vulnerable situation. On the other hand the demand for safe
potable water is increasing day-by-day due to the exponential growth
of population and inability of the traditional treatment1 .
There are many traditional and contemporary purification techniques
available or practiced for delivering safe water as per the local
standards and these spans from basic filtration, adsorption to most
advanced techniques; membrane separation and advanced oxidation
processes (AOPs).
Amongst the contemporary, the latter one is recognized as highly
effective in delivery of safe drinking water free of organics, inorganics,
and microbes2-3. Owing to strong reactive oxygen species generation
ability of AOPs it was considered for treating different types of water
and wastewaters containing the various classification of pollutants
including endocrine disrupting chemicals (EDCs), persistent organic
pollutants (POPs), total organic carbon (TOC) and micropollutants4-5.
This AOPs is a broad classification wherein consists of various
techniques for the generation of reactive oxygen species and is shown
in Figure 1. In general, the realistic aim of any water purification
5
techniques is to render water that is free of toxic matters (organic,
inorganic and biological).
In this regard, AOPs are characterized as best water
treatment/purification processes that involve generation of hydroxyl
radical (*OH) in sufficient quantity to affect water purification at
standard temperature and pressure6.
The significant advantage of AOPs over all existing chemical and
biological processes is that they are totally “environmental-friendly” as
they neither transfer pollutants from one phase to the other (as in
chemical precipitation and adsorption) nor produce massive amounts
of hazardous sludge7-10.
The first AOP based water purification/treatment in full scale was
proposed in early 1980s and followed by considerable achievements
have been reported11, 12. Thus, the present review will emphasize on
the various aspects of AOPs for efficient water management. [4]

Fig. 3. Classification of advanced oxidation processes. [3]

6
Classification of advanced oxidation processes. The nature
of the catalysts used in these AOPs has not been mentioned
for the sake of clarity. [2]

1.3. Advantages of photocatalytic technology

i. Higher resistance to toxic compounds. For semiconductor
photocatalysts, such as inorganic oxides of Ti02, ZnO and
Fe203, components which are toxic to many other methods
(especially to biological ones) are often very suitable substrates
to be oxidized on these photocatalyst surfaces.

ii. Wide area of application. The results of twenty years research

show that photocatalytic methods can be used to eliminate
many highly toxic contaminants from wastewater by chemical
oxidation or reduction, to simultaneously treat various organic

7
 compounds and inorganic compounds in wastewater, and to
treat polluted air.

iii. The treatment of low concentrations of pollutants. According to

research results obtained in recent years, photocatalytic
methods can be used to treat ppm- and even ppb levels of
organic and inorganic pollutants in ground- and surface water.

iv. Simple, light apparatus. A photocatalytic reactor consists only

of a cell with simple appendices. It can be easily built at low
costs and can even be installed in a truck for rapid emergency

treatment of waste in the field. [5]

v. Unlike reverse osmosis, nano and ultrafiltration, photocatalysis

is a cheap and a potential “stand alone” technology for water
treatment. As photocatalysis makes use of sunlight or UV
radiation, the technology is inexpensive, environmentally
friendly and can be applied worldwide. It requires minimal
equipment, is highly deployable and appropriate for developing
countries and remote sites with no access to electricity.

[]Nanotechnology-Based Water Treatment Strategies

http://www.greenmillennium.com/benefit/

8
 [6]
1.4. Applications of photocatalytic technology
Heterogeneous photocatalysis has been demonstrated as a low cost
and sustainable technology for the treatment of a host of pollutants in
air and water including organics and heavy metals, etc., with Japan,
USA, India and China as major users of this technology, Figure 9 [1].
Unlike reverse osmosis, nano and ultrafiltration, photocatalysis is a
cheap and a potential “stand alone” technology for water treatment.
As photocatalysis makes use of sunlight or UV radiation, the
technology is inexpensive, environmentally friendly and can be applied
worldwide. It requires minimal equipment, is highly deployable and
appropriate for developing countries and remote sites with no access
to electricity. Photocatalysis has also been used successfully in many
developing nations to destroy pathogens [5, 92] and algal blooms in
fresh water supplies. Photodisinfection sensitized by TiO2 has been
used to degrade the green algae, treat humic substances [100] which
act as substrates for bacterial growth, inhibit bacterial degradation of
impurities in natural water, and aid the transport of metals in the
environment and complex with Fe, Pb, Mn, making it harder to
remove them. Specific examples of applications are as follows. [7]

9
 [8]

1.4.1. Chemistry applications

1.4.1.1. Synthesis of chemicals

1.4.1.2. Synthesis of polymers

10
 1.4.2. Energy applications
In recent decades, the use of petroleum and coal resources has been
increasing, and the number of unrepairable resources on Earth is
getting fewer and fewer. Furthermore, combustion of fossil fuels has
caused many environmental problems that have significantly
influenced the development of science and technology of
photocatalytic processes in the energy field as below :

1.4.2.1. Hydrogen production by water

cleavage/splitting
Hydrogen is considered the most promising clean energy source of the
21st century. Hydrogen is characterized by being odorless, non-toxic,
environmentally friendly, and capable of producing a large amount of
energy. Hydrogen energy is a secondary energy source and needs to be
prepared from other hydrogen-containing substances such as water
and fossil fuels. There are a variety of ways of producing hydrogen,
and the most common way is to decompose fossil fuels to produce
hydrogen. However, this method relies on fossil fuels in the final
analysis. The photocatalytic degradation of water to produce hydrogen
to achieve the conversion of solar energy to hydrogen energy is an
effective method to solve energy and environmental problems. The
photocatalytic decomposition of water to generate hydrogen can
convert solar energy into hydrogen energy, which is an effective
method to solve energy and environmental problems. [9]

Photocatalytic water splitting into H2 and O2 using semiconducting

catalysts has received much attention due to the potential of this
technology, as well as the great economic and environmental interest
for the production of the clean fuel H2 from water using solar energy.

During the past 40 years, various photocatalyst materials have been

developed to split water into H2 and O2 under UV and visible light

11
illumination. The direct splitting of water using a particulate
photocatalyst would be a good way to produce clean and recyclable H2
on a large scale [6–9]. A number of photocatalysts have been proposed
and achieved high quantum efficiencies under UV illumination. At
present, there is a lack of suitable materials with sufficiently band gap
positions for overall water splitting, and the stability necessary for
practical applications.

Fig. 1. Schematic illustration of water splitting over semiconductor

photocatalysts . Source: Ref. [103].

Basic principles of photocatalytic hydrogen generation Fig. 1a shows a

schematic diagram of water splitting into H2 and O2 over
photocatalysts.

Photocatalysis on semiconductor particles involves three main steps:

(i) absorption of photons with energies exceeding the semiconductor
bandgap, leading to the generation of electron (e) and hole (hþ) pairs
in the semiconductor particles; (ii) charge separation followed by
migration of these photogenerated carriers in the semiconductor
particles; (iii) surface chemical reactions between these carriers with
various compounds (e.g., H2O); electrons and holes may also

12
recombine with each other without participating in any chemical
reactions [3,7].
When a photocatalyst is used for water splitting, the energetic position
of the bottom of the conduction band must be more negative than the
reduction potential of water to produce H2, and that of the top of the
valence band must be more positive than the oxidation potential of
water to produce O2, as shown in Fig. 1b.
Furthermore, the photocatalyst must be stable in aqueous solutions
under photoirradiation.

1.4.2.2. CO2 conversion to hydrocarbon fuels

Photocatalytic reduction of CO 2 is similar to the process of
photosynthesis for green plants. The photocatalysts play the role of
green plants to convert CO2 into fuel using ultraviolet (UV) or visible
light in the photocatalytic reduction of CO 2 and the principle is
illustrated in Fig.1. Typically, this reaction can be divided into four
steps: Firstly, the catalyst is activated by the UV or visible light from
sunlight or an illuminated light source. Subsequently, the electrons in
the valence band (VB) leap into the conduction band (CB),
simultaneously, the holes are left in the VB and form the negative-
electron (e−) and positive-hole (h+) pairs, which respectively act as the
reductants and oxidants for reducing and oxidizing the substances.
Thirdly, the generated electronhole pairs separate and transport to the
surface of catalysts. Finally, CO2 is reduced by the negative-electron
and generates the corresponding products such as CH 4, CH3OH, and
CO [42]. In general, the photocatalytic activity and product selectivity
of photocatalytic CO2 reduction are greatly related to the reaction
system and the photocatalysts [36]. As shown in Fig.2, photocatalytic
CO2 reduction can yield a wide variety of products. Among these
products, the most common are CH3OH and CH4, while HCOOH, CO,

13
HCHO, ethanol (CH3CH2OH), and elemental carbon also are detected
[43].
The photocatalytic CO2 reduction mainly is performed in gas or liquid
phase system. It has been reported that CO and CH4 are the main
products in the gas phase system. However, the main products in the
liquid phase system include CH3OH, CH3COOH, and HCOOH
[24,26,34]. In theory, CO formation is superior to CH 4 during the
reaction because more electrons are required to generate CH4 [46]. But
the formation of CO can be suppressed by the increasing electron
density due to the metal doping or other promoter. The surface
electron density can also be boosted by constructing a heterojunction.
[12]

14
 1.4.3. Environmental applications
Several environmental applications of photocatalysts are reported.
Here we are trying summarizing all these.[11]

1.4.3.1. Air purification

Traditional methods of reducing indoor air pollution include
controlling pollutant sources, increasing the air exchange and using
air purifiers. These methods have the following disadvantages. Source
control is difficult to achieve in many places. Increasing the air
exchange might even transport more pollutants from outdoor
environment [31]. Common air purifiers often use sorption materials
to adsorb gases or odors which only transfer the contaminants to
another phase rather than eliminating them and additional disposal
or handling steps are subsequently required. Heterogeneous
photocatalytic oxidation (PCO) has been studied for several decades
[32] and shown as an effective method for water or air purification.
Some metal oxide semiconductors like TiO2 and ZnO are commonly
used as the photocatalyst in PCO reaction. Among them, TiO2 is
widely used because of its many appropriate characteristics [30]: (a) It
is inexpensive, safe, very stable, and has high photocatalytic

15
efficiency; (b) it promotes ambient temperature oxidation of the major
indoor air pollutants; (c) no chemical additives are required.

However, TiO2 can only be activated by UV light which is only 0.001–

0.05 W/m2 in indoor illumination [33]. To extend TiO2 as
photocatalyst to visible light region, it is necessary to enlarge the
photo absorption of TiO2 into visible light region (400–700 nm).

In the presence of air or oxygen, UV-irradiated TiO2 is capable of

destructing many organic contaminants completely. The activation of
TiO2 by UV light can be written as:
TiO2 + hν → h+ + e−: (1)
idative and reductive reactions are expressed as
Oxidative reaction:
OH− + h+ → OH (2)
Reductive reaction:
O2ads + e− → O2−ads (3)
In the degradation of organic compounds, the hydroxyl radical (OH ∗),
which comes from the oxidation of adsorbed water or adsorbed OH−,
is the primary oxidant; and the presence of oxygen can prevent the re-
combination of hole-electron pairs. For a complete PCO reaction, the
final products of reactions are CO2 and H2O.
OH∗ + pollutant + O2 → products (CO2; H2O; etc:): (4)
[11]

1.4.3.2. Degradation of water contaminants

Increasing demand and shortage of clean water sources due to the
rapid development of industrialisation, population growth and long-
term droughts have become an issue worldwide. With this growing
demand, various practical strategies and solutions have been adopted
to yield more viable water resources. The storage of rainwater for daily

16
activities and increasing the catchments capacity for storm water are
just a few examples that could resolve the problems in short-term.
Water industries and governments in some arid areas with abundant
of sunlight, less rainfall and long-term drought have a challenge to
seek viable water resources. It is estimated that around 4 billion
people worldwide experience to have no or little access to clean and
sanitized water supply, and millions of people died of severe
waterborne diseases annually [52]). These statistical figures are
expected to grow in the short future, as increasing water
contamination due to overwhelming discharge of micropollutants and
contaminants into the natural water cycle [53-55]. In view to suppress
the worsening of clean water shortage, development of advanced with
low-cost and high efficiency water treatment technologies to treat the
wastewater is desirable.
One of a few attractive options is the possible reuse of onsite rural
wastewater or the treated municipal wastewater from treatment plants
for agricultural and industrial activities [56, 57]. Since these
wastewaters constitute one of the largest possible water resources, its
reuse is anticipated to offset more clean water resource. Recycling
wastewaters are usually associated with the presence of suspended
solids, health-threat coliforms and soluble refractory organic
compounds that are both tedious and expensive to treat [58].
Currently available water treatment technologies such as adsorption
or coagulation merely concentrate the pollutants present by
transferring them to other phases, but still remain and not being
completely “eliminated” or “destroyed” [59]. Other Conventional water
treatment methods such as sedimentation, filtration, chemical and
membrane technologies involve high operating costs and could
generate toxic secondary pollutants into the ecosystem [60]. These
concentrated toxic contaminants are highly redundant and have been
concerned worldwide due to the increasing environmental awareness
and legislations. Chlorination has been the most commonly and
widely used disinfection process. The disinfection by-products

17
generated from chlorination are mutagenic and carcinogenic to
human health [61-63]. These have lead to the rapid R&D in the field of
“Advanced Oxidation Processes (AOPs)” as the innovative water
treatment technologies. The rationales of these AOPs are based on the
in situ generation of highly reactive transitory species (i.e. H2O2, OH-,
O2 -, O3) for mineralization of refractory organic compounds, water
pathogens and disinfection by-products [64, 65]. Among these AOPs,
heterogeneous photocatalysis employing semiconductor catalysts
(TiO2, ZnO, Fe2O3, CdS, GaP and ZnS) has demonstrated its
efficiency in degrading a wide range of ambiguous refractory organics
into readily biodegradable compounds, and eventually mineralized
them to innocuous carbon dioxide and water. Among the
semiconductor catalysts, titanium dioxide (TiO2) has received the
greatest interest in R&D of photocatalysis technology. The TiO2 is the
most active photocatalyst under the photon energy of 300 nm < l <
390 nm and remains stable after the repeated catalytic cycles,
whereas Cds or GaP are degraded along to produce toxic products
[66]. Other than these, the multi-faceted functional properties of TiO2
catalyst, such as their chemical and thermal stability or resistance to
chemical breakdown and their strong mechanical properties have
promoted its wide application in photocatalytic water treatment. A
number of important features for the heterogeneous photocatalysis
have extended their feasible applications in water treatment, such as;
(1) ambient operating temperature and pressure, (2) complete
mineralization of parents and their intermediate compounds without
secondary pollution and (3) low operating costs. The fact that the
highly reactive oxygen species (ROS) generated as a result of the
photo-induced charge separation on TiO2 surfaces for microbial
inactivation and organic mineralization without creating any
secondary pollution is well-documented. So far, the application of
such TiO2 catalysts for water treatment is still experiencing a series of
technical challenges. The post-separation of the semiconductor TiO2
catalyst after water treatment remains as the major obstacle towards

18
the practicality as an industrial process. The fine particle size of the
TiO2, together with their large surface area-to-volume ratio and
surface energy creates a strong tendency for catalyst agglomeration
during the operation. Such particles agglomeration is highly
detrimental in views of particles size preservation, surface-area
reduction and its reusable lifespan. Other technical challenges include
in the catalysts development with broader photoactivity range and its
integration with feasible photocatalytic reactor system. In addition,
the understanding of the theory behind the common reactor
operational parameters and their interactions is also inadequate and
presents a difficult task for process optimization. A number of
commonly made mistakes in studying kinetic modelling on either the
photomineralization or photo-disinfection have also been seen over the
years. [11]

1.4.3.3. Decomposition of crude oils

1.4.3.4. Self-cleaning surfaces

In practice, surface cleaning of building materials like tiles, facades
and glass panes causes considerable trouble, high consumption of
energy and chemical detergents and, consequently, high costs. To
realize self-cleaning material surfaces there are two principal ways:
the development of so-called superhydrophobic or super-hydrophilic
surfaces. The wetting of a solid with water, where air is the
surrounding medium, is dependent on the relation between the
interfacial tensions (water/air, water/solid and solid/air). The ratio
between these tensions determines the contact angle θ between a
water droplet on a given surface. A contact angle of 0o means
19
complete wetting, and a contact angle of 180o corresponds to
complete non-wetting. Hydrophobic surfaces with low wettability and
contact angles of about 100o are known for a long time. The higher
this angle the lower is the value of the adhesion work. Decreasing of
the contact angle leads to enlarged values of the adhesion work
(hydrophilic surfaces). By transferring the microstructure of selected
plant surfaces to practical materials, superhydrophobic
surfaces could be developed. The water repellency of plant surfaces
has been known for many years. That water-repellent surface also
indicate self-cleaning properties has been completely overlooked.
Recently, Barthlott et al. [79] investigated and proved the correlation
between the microstructure, wettability and contaminants in detail
using lotus leaves. This was called the Lotus Effect because it can be
demonstrated beautifully with the great leaves of the lotus plant. The
microrough surfaces show contact angles higher than 130o. That
means, the adhesion of water, as well as particles is extremely
reduced. Water which contacts such surfaces will be immediately
contracted to droplets. The particles of contaminants adhere to the
droplet surfaces and are removed from the rough surface when the
droplets roll off. Cleaning procedures based on low contact angles are
known since the discovery of soap (3 rd millennium BC). Generally,
detergents reduce the surface tension of water and the contact angle
will lowered. Another very interesting possibility to cause low contact
angles without detergents is the use of active thin films on the
material surface. For the preparation of these thin layers mainly
photocatalytic active metal oxides or sulfides have been applied. In the
last years TiO2 coated materials are of increasing interest [12]. If TiO2
of the anatase type is exposed to UV light very low contact angles are
obtained (< 1o). These materials have the unique property of
“attracting” rather than repelling water (super-hydrophilicity). The
water lies flat on the surface in sheets instead of forming droplets. If
the illumination is stopped, the super-hydrophilic behaviour of the
TiO2 surface is retained for approximately two days. Furthermore, UV

20
illumination of titanium dioxide leads to the formation of powerful
agents with the ability to oxidize and decompose many types of
bacteria, organic and inorganic materials. Titanium oxide particles
decompose organic matters when irradiated with ultraviolet rays. This
fact has long been known as a choking phenomenon that occurs with
a paint containing a TiO2 pigment. During a self-cleaning process
with a photocatalyst, contaminants on a substrate are photo
decompose, wherein radicals and active oxygen generated by
ultraviolet irradiation on a photocatalyst decompose the organic
contaminants into carbon dioxide, thereby allowing the surface of the
substrate to remain clean. It has been reported that a positive
hydrophilic effect appears when a TiO2 photocatalyst is irradiated
with ultraviolet rays. This characteristic is widely applied to glasses,
mirrors and building materials. If a TiO2 photocatalytic coating
material is used in an outdoor location exposed to rainwater, organic
contaminants on the surface of coating are decomposed by light
irradiation and the residual inorganic particles are readily washed
away by the rainwater, hence the coated surface exhibits the expected
self-cleaning effect. Radicals and active oxygen generated by the
activity of a TiO2 photocatalyst are effective in decomposing and
preventing the propagation of bacteria and fungi. Because of their
small selectivity against bacteria species and their ability to
decompose the toxins produced by bacteria, TiO2 photocatalysts have
been increasingly used for interior finishing materials in hospitals and
medical equipment. On the other hand, the intensity of ultraviolet
rays available indoors is one digit lower compared with that available
outdoors, and it is difficult to offer sufficient photocatalytic effect with
ultraviolet rays in a room alone. In addition, there are many places
where the intensity of ultraviolet rays is lower than expected such as
in cars that are equipped with UV-cut glasses. To operate effectively in
these locations, novel photocatalysts responsive to visible light, and
capable of performing within the visible light spectrum in the region of
500-600 nm wavelength as well as the UV band have been developed

21
and commercialized. It should be understood from the spectra of
sunlight [80] that the energy efficiency of photocatalysts under
sunlight will be improved with expansion of the effective wavelength to
500-600 nm. Visible light-responsive photocatalysts can be produced,
for example, through change in the band structure with the addition
of new energy levels resulting from the presence of impurities by
doping a TiO2 photocatalyst with another element such as nitrogen or
sulfur [81, 82]. The photocatalyst thus obtained is yellowier compared
with conventional anatase-type photocatalysts, and capable of
absorbing a portion of the visible light. Usually, the crystal size of the
visible light responsive photocatalysts is designed to be somewhat
larger than that of conventional anatase-type photocatalysts. One
reason for this arrangement is to avoid a shift of the optical absorption
edge to a shorter wavelength side, resulting from the quantum size
effect occurring when the crystal size is less than 10 nm. In order to
investigate the photocatalytic activity of a visible light-responsive
photocatalyst, a dye (Methylene Blue) was allowed to be adsorbed onto
a layer of visible lightresponsive photocatalyst, and was then
decomposed with a white fluorescent lamp. The result is
shows that decolorization is minor on the irradiated area of the
anatase TiO2 layer and that the dye in the irradiated area of the
visible light-responsive photocatalyst (diameter: 11 nm) layer has been
virtually completely decomposed following irradiation with a
fluorescent lamp. Commercialized applications of antibacterial visible
light-responsive photocatalyst include window blinds and wallpapers.
To be able to form a photocatalyst layer on the surface of these resin-
coated products, a transparent primer coating agent, composed
principally of inorganic components, is applied to form an
intermediate layer to improve durability, and then a coating solution,
containing photocatalyst particles, is applied to form the top layer.
[11]

22
 1.5. Motivations
1. The importance of fresh water to life
2. Increasing of water pollution
3. Demands for drinking water with time
4. Available UV light sources
5. Ecofriendly
6. Low cost with high efficiency

1.6. Problem statement

It's required to design and evaluate Micro-Channel
photoreactor for wastewater treatment applications

1.7. Research objectives

i. To synthesize a novel photocatalysts.

ii. To design a microchannel photocatalytic reactor.
iii. To investigate the efficiency of the obtained
photocatalyst for wastewater application.
iv. To study the kinetics of photocatytic oxidation.
v. To analysis the thermodynamic properties.

23
 CHAPTER TWO: LITERATURE REVIEW
2.1 Background and history
The widespread occurrence of organic micropollutants such as
pesticides, pharmaceuticals and personal care products, flame
retardants, and endocrine disrupting compounds (EDCs) in receiving
bodies and drinking water influents has been a global issue of concern
for academia and environmental agencies for over two decades, and
more recently in the general public. In many cases, these pollutants
can be traced back to their incomplete removal and discharge from
wastewater treatment facilities. Although the direct effect of these
compounds on human health is not yet fully understood the
detrimental effect on organisms in these receiving bodies from EDCs
has already been demonstrated (Routledge & Sumpter, 2005), such as
the feminization of male fish due to the release of natural hormones
(Rodgers-Gray et al., 2000). Research on organic micropollutants in
relation to the point of wastewater discharge can be divided into two
major areas: upstream treatment and downstream monitoring.
Developing advanced technologies and improved operation of
wastewater treatment plants results in higher quality effluents. At the
same time, in the downstream analysis, improved techniques to detect
pollutants at lower concentrations and tools to evaluate the toxicity of
the contaminated stream, feed back to the upstream process in order
to optimize plant operation. With looming water scarcity in many parts
of the world, providing clean drinking water and sustainable

24
development will require the use of water recycling in the future and it
will be imperative that recycled water will not impact both
environmental and human health (Falconer et al., 2006).
Consequently, extensive research and development in both upstream
processing and downstream monitoring are needed.
For the treatment of drinking water and tertiary wastewater, a group
of chemical oxidative technologies classified as advanced oxidation
processes (AOPs) has garnered a significant level of interest
academically and industrially over the last three decades.

All AOPs are characterized by the production of highly reactive and

non-selective hydroxyl radicals, which are the strongest oxidants in an
aqueous medium (Staehelin & Hoigne, 1985). Hydroxyl radicals are
capable of oxidizing nearly all organic compounds to water, carbon
dioxide, and mineral salts through a process termed mineralization
(Chen et al. 2000b). The technologies that can be classified as AOPs
fall under two general categories. The first utilizes UV in conjunction
with other chemical additives, examples of this are: UV/H2O2,
UV/O3, UV/TiO2, and UV/Fenton. When no UV source is used the
technology can be termed as a dark oxidative process, such as:
ozonation (O3), Fenton’s reagent, ultrasound, and microwaves to
name a few. Of the many AOPs developed three have garnered the
most study and use industrially: ozonation, UV/H2O2, and
photocatalysis utilizing either ultraviolet (UV) or solar irradiation with
titanium dioxide (TiO2). There has been significant research done on
each of these AOPs with respect to reactor design, optimization, and
modeling. In depth reaction kinetics of many pollutants have also
been investigated, which are essential for large-scale application. [13]

25
 [14]

2.2 Photocatalytic reactors

2.2.1 ???
2.2.2 ???
2.2.3 ???
2.2.4 ???
2.2.5 Micro-channel photoreactors
2.3 Photocatalysts
2.3.1 Role of semiconductors
2.3.2 Modification of semiconductors
2.3.3 Role of photocatalyst carrier
2.4 Light sources
2.5 Mechanism of photocatalytic oxidation of organic
pollutants
2.6 Parameters affecting on photocatalytic oxidation
process
2.7 Modeling and theory

26
 2.7.1 Kinetic modeling of photocatalytic oxidation
2.7.2 Activation energy
2.7.3 Thermodynamic parameters

References

27
1. Advanced Oxidative Degradation Processes:
Fundamentals and Applications
2. General and Prospective Views on Oxidation Reactions
in Heterogeneous Catalysis
3. Nanocatalysts in Fenton Based Advanced Oxidation
Process for Water and Wastewater Treatment
4. A Review on Advanced Oxidation Processes for
Effective Water Treatment
5. ADVANCED OXIDATION TECHNOLOGIES
PHOTOCATALYTIC TREATMENT OF WASTEWATER
6. TiO2 photocatalyst for water treatment applications
7. Heterogeneous Photocatalysis: Recent Advances and
Applications
8. Photoenergy conversion with TiO2 photocatalysis: New
materials and recent applications
9. Recent Advances and Applications of Semiconductor
Photocatalytic Technology
10. Photochemical splitting of water for hydrogen
production by photocatalysisn : A review
11. Environmental application of photocatalysis
12. Photocatalytic conversion of carbon dioxide: From
products to design the catalysts

13. Water Treatment Using Advanced Oxidation

Processes: Application Perspectives

14. Advanced Oxidation Handbook

28
29