Thesis On Photocatalytic Degradation of Methylene Blue

1.
INTRODUCTION
Pollution is the process of making land, water, air or other parts of the environment dirty and
unsafe or unsuitable to use. This can be done through the introduction of pollutants into a natural
environment. Toxic pollution affects more than 200 million people worldwide, according to Pure
Earth, a non-profit environmental organization. In some of the world‟s worst polluted places,
babies are born with birth defects, children have lost 30 to 40 IQ points, and life expectancy may
be as low as 45 years because of cancers and other diseases. Water pollution happens when
chemicals or dangerous foreign substances are introduced to water, including chemicals, sewage,
pesticides and fertilizers from agricultural runoff, or metals like lead or mercury . The need to
maintain a cleaner environment for the survival of both aquatic and terrestrial lives including
human beings is very crucial and is a subject of increasing concern to the environmentalist.
Pollution caused by agents such as heavy metals and dyes are amongst the list which rendered the
environment unwholesome and posed serious health concern to the populace. Industrial effluents
are one of the major causes of environmental pollution because effluents discharged from dyeing
industries are highly colored with a large amount of suspended organic solid. Untreated disposal
of this colored water into the receiving water body either causes damage to aquatic life or to
human beings by mutagenic and carcinogenic effect. As a matter of fact, the discharge of such
effluents is worrying for both toxicological and environmental reasons. Conventional wastewater
treatment methods for removing dyes including physicochemical, chemical and biological
methods, such as coagulation and flocculation, adsorption, ozonation, electrochemical techniques,
and fungal decolorization, Photocatalysis etc.
The textile dyeing and finishing industry has created a huge pollution problem as it is one of the
most chemically intensive industries on earth, and the No. 1 polluter of clean water (after
agriculture). More than 3600 individual textile dyes are being manufactured by the Industry
today. The industry is using more than 8000 chemicals in various processes of textile manufacture
including dyeing and printing. A fraction of these are listed. Many of these chemicals are
poisonous and damaging to human health directly or indirectly. Large quantities of water are
required for textile processing, dyeing and printing. The daily water consumption of an average
sized textile mill having a production of about 8000 kg of fabric per day is about 1.6 million
liters. 16% of this is consumed in dyeing and 8% in printing. Specific water consumption for
dyeing varies from 30 - 50 liters per kg of cloth depending on the type of dye used. The overall
DEPARTMENT OF CHEMICAL ENGINEERING
INDIAN SCHOOL OF MINES, DHANBAD Page 1
water consumption of yarn dyeing is about 60 liters per kg of yarn. Dyeing section contributes to
15% - 20% of the total waste water flow. Water is also required for washing the dyed and printed
fabric and yarn to achieve washing fastness and bright backgrounds. Washing agents like caustic
soda based soaps; enzymes etc. are used for the purpose. This removes the surplus color and paste
from the substrate. Water is also needed for cleaning the printing machines to remove loose color
paste from printing blankets, printing screens and dyeing vessels. It takes about 500 gallons of
water to produce enough fabric to cover one sofa. The World Bank estimates that 17 to 20 percent
of industrial water pollution comes from textile dyeing and finishing treatment given to fabric.
Some 72 toxic chemicals have been identified in water solely from textile dyeing, 30 of which
cannot be removed5. This represents an appalling environmental problem for the clothing and
textile manufacturers.
Mills discharge millions of gallons of this effluent as hazardous toxic waste, full of color and
organic chemicals from dyeing and finishing salts. Presence of sulphur, naphthol, vat dyes,
nitrates, acetic acid, soaps, chromium compounds and heavy metals like copper, arsenic, lead,
cadmium, mercury, nickel, and cobalt and certain auxiliary chemicals all collectively make the
effluent highly toxic. Other harmful chemicals present in the water may be formaldehyde based
dye fixing agents, hydro carbon based softeners and non bio degradable dyeing chemicals. The
mill effluent is also often of a high temperature and pH, both of which are extremely damaging.
The colloidal matter present along with colors and oily scum increases the turbidity and gives the
water a bad appearance and foul smell. It prevents the penetration of sunlight necessary for the
process of photosynthesis. This interferes with the Oxygen transfer mechanism at air water
interface. Depletion of dissolved Oxygen in water is the most serious effect of textile waste as
dissolved oxygen is very essential for marine life. This also hinders with self purification process
of water. In addition when this effluent is allowed to flow in the fields it clogs the pores of the soil
resulting in loss of soil productivity. The texture of soil gets hardened and penetration of roots is
prevented. The waste water that flows in the drains corrodes and incrustates the sewerage pipes. If
allowed to flow in drains and rivers it effects the quality of drinking water in hand pumps making
it unfit for human consumption. It also leads to leakage in drains increasing their maintenance
cost. Such polluted water can be a breeding ground for bacteria and viruses. Impurities in water
affect the textile processing in many ways. In scouring and bleaching they impart a yellow tinge
to white fabric.

Effluent treatment methods can be classified into physical, chemical and biological methods;
(Exclusive treatment by one of these three methods has proved to be insufficient in removing
color and other effluent from textile industry wastewater. While some dyes are difficult to
biodegrade few, particularly the hydrolyzed reactive and certain acidic dyes are not readily
absorbed by active sludge; hence they escape treatment. Combination of various effluent
treatment methods can remove more than 85% of unwanted matter . The resulting effluent is
usually high in color. A complimentary treatment process is needed to remove color and if
possible residual impurities. The textile industry has been condemned to be the world‟s worst
environment polluters. It requires large amounts of Chemicals and Water at every step of the
textile manufacturing and finishing process. Water is needed to convey the chemicals into the
fabric and to wash it at the beginning and end of every step. It becomes full of chemical additives
and is then expelled as wastewater; which in turn pollutes the environment. Water: a finite
resource is thus becoming scarce. Water pollution is indeed a serious problem in most countries.
The textile industry continues to search for an economical solution to decolorize the nearly 200
billion liters of colored effluent produced annually. Nations, states, industries are spending
billions in cash on research to reduce pollution and on construction of effluent treatment plants.
The public concern for industrial air and water pollution is leading to considerable restrictions on
all industrial activities polluting the environment. Governments have proposed laws limiting the
amount and kind of waste that can be dumped as such. Considering the adverse effect on
environment and health of people due to the effluent being thrown out of the Textile Dye Industry
we need to wake up to the serious problem and make every effort to reduce pollution and
construct effluent treatment plants at the sites churning out billions of liters of waste water.
Many dyes are widely used in different industries, such as textile, paper, rubber, plastics, leather,
food and pharmaceutical. These industries release colored wastewater which may present an
ecotoxic hazard and introduce the potential danger of bioaccumulation, which affect the human
food chain. Wastewater containing small amounts of dyes can affect the aquatic life because of its
toxicity and resistance to breakdown with time. Most of the dyes are toxic and carcinogenic,
causing allergy, skin irritation. Chemical, physical and biological methods were used for
removing dyes from wastewater. Adsorption is an effective and low-cost physical and chemical
method for removing dyes from wastewater.

Therefore realizing the importance of keeping our planet clean, it is needed to work for
eco-friendly alternative technologies for all areas of daily life. Sustainable energy production and
pollutant destruction are two of the areas in which intense research is being carried out.
Semiconductor-mediated photocatalysis is a well-established technique for pollutant degradation
and hydrogen (clean fuel) production by water splitting.
1.1 Photocatalysis and Photocatalyst

Photocatalysis is the acceleration of a photoreaction in the presence of a catalyst and the catalyst
so used is called Photocatalyst. Generally the photocatalyst used are semiconductor materials.The
appropriate positioning of valence (VB) and conduction (CB) bands in semiconductors
(Figure1a) makes them suitable materials for the absorption of light irradiation which results into
formation of electron(e)-hole(h) pair at conduction and valance band respectively. The electron
and hole pair facilitates the active sites for generation of reactive Hydroxyl radicals (•OH) which
in secondary reactions mineralizes the organic pollutants into CO2 and this technique is termed as
Advanced oxidation processes (AOPs), are methods by which oxidizing molecules are generated
for the mineralization of organic chemicals. The most common oxidizing agents used are ozone
and hydroxyl radicals; hydroxyl radicals, with an oxidation potential of Eº = +3.6 V, are by far
the stronger oxidizer (Eºozone = 2.07 V) (Halmann,1996). A variety of semiconductors have been
examined for their photocatalytic capacity (e.g., TiO2, ZnO, SnO2, and CdS); TiO2 and ZnO have
been shown to be the most active amongst those tested.
1.2 Titanium Dioxide

TiO2 (titanium Dioxide) is the most widely used Photocatalyst because it is relatively nontoxic,
inexpensive, and stable. Because naturally occurring titanium dioxide is usually complexed with
other minerals and metals, when pure grades are needed, it is synthetically manufactured instead
of mined.
Manoj et al. (2012) reported that The most commonly used synthetic TiO2 is Degussa‟s P25 is
comprised of two nono crystalline structures of photocatalyst. TiO2, anatase (70%) and rutile
(30%). Degussa‟s P25 TiO2 is in 20nano meter size range which provides maximum surface to
volume ratio. P-25 TiO2 is a multifunctional semiconductor photocatalyst that can be an energy
catalyst (in water splitting to produce hydrogen fuel), an environmental catalyst (in water and air
purification), or an electron transport medium in dye-sensitized solar cells .Compared to other
available semiconductor photocatalysts, Nano crystalline titanium dioxide is unique in its

chemical and biological inertness, photostability (i.e., not prone to photoanodic corrosion),
Photocatalytic water and air purification using Nano crystalline titanium dioxide is a predominant
advanced oxidation process (AOP) because of its efficiency and eco-friendliness. Titanium oxide
Photocatalysis may not require any additional reagents beyond the Nano crystalline titanium
dioxide catalyst.
Figure 1. (a)VB and CB positions in metals, semiconductors, and insulators; (b) Tree diagram
showing applications of TiO2.
The photocatalytic degradation of real pollutant systems, such as cosmetics and

pharmaceutical wastewaters, paper mill wastewater ,grey water ,Textile waste water and
municipal wastewater. Cheaper sources of TiO2, such as bulk-synthesized TiO2 pigment and iron-
containing industrial TiO2 by-products , have been explored for the photocatalytic degradation of
phenol and humic acids. Interestingly, their activities were found to be comparable with those of
the commercially available Degussa P25 TiO2 photocatalyst, the benchmark TiO2 photocatalyst
for all applications.
1.2.1 Properties of TiO2
Titanium is widely distributed over the surface of the earth and is the ninth most abundant
element in the earth‟s crust comprising an estimated 0.62% of the earth crust. The naturally
occurring titanium ores are Ilmenite, mineral Rutile and Brookite. Ilmenite is a black sand or rock
and has the formula FeTiO3. The iron is partially oxidized to the trivalent state and ore also
contains some impurities of silicon compounds. The TiO2 concentration in the ore varies from
45% to 60% depending upon the origin. Rutile is naturally occurring TiO2 and its color vary from
brown to reddish black, and its major impurities are iron compounds. The TiO2content in this ore
normally varies from 90 to 95%. TiO2exists in three different phases: anatase, Rutile and
Brookite. TiO2 is chemically inert and thermally stable, non flammable and non toxic. Ibhadon et
al 2013 Electronic properties such as band gap play an important role for a semiconductor
photocatalyst. Anatase phase TiO2 has higher band gap (3.2 eV) compared with other two phases
of Rutile (3.0 eV) and Brookite. Anatase TiO2 is more popular as photocatalyst although Rutile
has been found to be effective under certain specific circumstances
1.2.2 Reaction mechanism on TiO2 surface
TiO2 as a photocatalyst is use to mineralize organic pollutant by the formation of reactive

hydroxyl radicals (OH•), and also produce Hydrogen (H2) and Oxygen molecules (O2) by slitting
of water molecule.
.
(a) (b)
Figure-2 a) photocatalytic water -splitting from hydrogen production and b) formation of
reacting species (hydroxyl radicals and superoxide ions) when illuminated under UV and solar
light.
Shon et al .(2007) reported Photocatalytic mechanism of water-splitting to produce hydrogen and
oxygen and the formation of the precursor species of hydroxyl radical and superoxide ions when
illuminated under UV light The energy level between Valence Band (VB) and Conduction Band
(CB) is called band gap. At normal state, electrons and the protons remain in the VB but when

TiO2 is excited by photon with energy greater than its band gap energy level, electrons in the VB
jump to the CB, creating e-/h+ pair. Because of its high band gap of 3.2 eV (anatase), only UV
light source has been found to be effective in the excitation of the electrons in TiO2.
To produce hydrogen, water should be efficiently broken into hydrogen and oxygen by
hydrolysis. When TiO2 is irradiated by Solar/UV light, e-/h+ pair is formed and when it comes
into contact with absorbed water, it gets oxidized by positive holes which in the process forms
hydroxyl radicals (OH•), having strong oxidative decomposing power and therefore reacts with
organic matter. In the presence of oxygen, the intermediate radicals in the organic compounds and
oxygen molecules undergo radical chain reactions and consume oxygen to finally form carbon
dioxide and water as shown below:
Under certain conditions, organic compounds directly react with the positive holes (h+) resulting
in oxidative decomposition. In the presence of air, oxygen reduction takes place instead of
hydrogen generation and forms superoxide anions .which attach to the intermediate products in
the oxidative reaction, forming peroxide or changing to hydrogen peroxide and then later to water.
1) TiO2 + hν → e− + h+
2) O2 + e− → O2−
3) O2−+ H2O → OH −
4) OH −+h+ → OH −
5) OH −+ pollutant → CO2 + H2O
1.3 LECA Granules
Lightweight extended clay aggregate (LECA) or expanded clay (exclay) is a light

weight aggregate made by heating clay to around 1,200 °C (2,190 °F) in a rotary kiln. The
yielding gases expand the clay by thousands of small bubbles forming during heating producing a
honeycomb structure. LECA has an approximately round or potato shape due to circular
movement in the kiln, and is available in different sizes and densities. LECA is used to make
lightweight concrete products and other uses.
The chemical composition of the LECA shows that the ratio of SiO2/Al2O3 (64.83/15.05) is 4.31
which indicating that the LECA is silicate component. For this reason, TiO2 particles actually

agglomerate on the LECA surface. Also, using LECA as a catalyst support will help increasing
the photodegradation rate by progressively allowing an increased quantity of substrate to come in
contact with the TiO2 through the means of adsorption. This is important because the oxidizing
species that generated by the photocatalyst does not migrate very far from the active centers of the
TiO2 and therefore, degradation takes place virtually on the catalyst surface.
Figure 3 LECA particles
Some characteristics of LECA are: lightness, thermal insulation by low conductivity coefficient
soundproofing by high acoustic resistance, moisture impermeable, incompressible under
permanent pressure and gravity loads, non–decomposition against severe condition, fire resistant,
Ph of nearly 7, freezing and melting resistance, easy movement and transportation, lightweight
backfill and finishing, reduction of construction dead load and earthquake lateral load, perfect
sweet soil for plants, material for drainage and filtration.
1.4 Methylene blue
It is a heterocyclic aromatic chemical compound with the chemical formula C16H18N3SCl and
mass number is equal to 319.85 g/mol. At room temperature it appears as a solid, odorless, dark
green powder, that yields a blue solution when dissolved in water. The hydrated form has 3
molecules of water per unit of methylene blue. It has vast industrial and pharmaceutical
applications.

The discharge from textile industries contains Methylene blue as one of the major pollutant. MB
Dye due to its dark blue color absorbs light energy which results darkness beneath water medium
and water bodies never receive light. Hence it is threat to aquatic life. As it is a heavy and
complex carbon compound, the COD value is also high.
1.8 Ultrasound
Ultrasound represents mechanical waves, i.e. a variation of pressure or density with frequencies
above the human hearing threshold (ca. 18 kHz). As it is not perceived, high sound intensities are
feasible, where non-linear phenomena like acoustic cavitation occur. The ultrasonic energy has
the capacity to produce crack propagation from within the particle to its outer surface, producing
an efficient fracture. Due to high sound intensities, the tensile stress of the liquid exceeds. Little
gas bubbles are formed during the expansion cycle of the sound wave and grow over one or
several cycles. After having reached a critical size, they collapse. During the collapse, a lot of
energy is released inducing extreme thermodynamic conditions of several thousand Kelvin and a
few hundred bars in the vicinity of the imploding bubble. These extreme thermodynamic
conditions induce different mechanical effects. Cavitational collapse of bubbles on solid surfaces
leads to micro jet and shock-wave impacts on the surface of the solids, together with interparticle
collisions which can result in particle size reduction. Capitation and all the results of this
phenomenon (release of temperature and pressure, intense shear forces, shock waves, microjets)
have important beneficial effects on chemical reactions: Acceleration of the reaction (also radical
reactions), promotion of the mass transfer, higher efficiency of the catalyst, generation of useful
reactive species, possible switching of the reaction pathway, reduction of the reaction steps
Ultrasound-assisted reactions are performed under less forceful conditions, and crude or technical
reagents can also be used. Old synthetic processes which have fallen into disuse due to low
efficiency or expense can be revitalized by ultrasound.

Chapter 2
Literature survey

2 Literature survey
The literature survey to the topic elucidated the various approach used for the degradation to
organic pollutant in slurry as well as in immobilized reactor systems. It gave clear understanding
for the photocatalysis/ photocatalyst used.
Using Degussa P25 TiO2 as a photocatalyst , the photocatalytic reaction were conducted at
various pH, and it was found that best degradation was achieved within the pH range of 9-10.The
light source used in the reactor system had a remarkable role on its kinetics. The percentage
degradation of pollutant achieved under solar light and UV light could be compared. It was UV
light under which degradation dominates over degradation by sun light.
2.1 Immobilization of TiO2
Immobilization of TiO2 on various substrates is an important research area with its photocatalytic
water treatment applications .The primary aim of doing so is to avoid the post separation
difficulties associated with the powder form of the TiO2 catalyst. However, there are several other
advantages including higher surface area, superior adsorption properties. and increased surface
hydroxyl groups or reduced charge recombination are achievable in immobilized systems.
Immobilization of TiO2 can be done on powder/pellet substrates ,soft/thin materials or on
rigid/thick substrates. Some of the recent examples of powder/pellet substrates include activated
carbon, vermiculite (magnesium-aluminium silicates), and volcanic ash . Sedimentation of these
TiO2 immobilized systems could be easier than the TiO2 catalyst alone systems, since they are
heavier particles. TiO2 immobilized on soft/thin substrates, normally referred as TiO2 membrane
or films, are applicable in ultra filtration and bacterial inactivation. Since they are immobilized
with TiO2, they can act as self cleaning surfaces.
Many substrate as glass, Activated Carbon, Zeolites etc. are used to immobilize nano crystalline
TiO2 on substrate surface . Lightweight extended clay aggregate (LECA) particles are also used
to immobilized TiO2 . LECA/ TiO2 particles floats on liquid surface hence provides adequate
light irradiation on photocatalyst surface.
Kumar et al. (2013) reported various other methods of immobilization of TiO2 on different
supports are available. Various methods are listed in the table 1 as below.

Table 1 : Different methods and support of immobilization
S.no Support Method
1 Glass Chemical vapor deposition (APCVD
Dried for 60 h at ambient

temperature
2 Activated carbon Chemical vapor deposition
3 Zeolites Sol–gel method and photo reductive

deposition
4 Glass sheets Sol–gel and hydrothermal
5 PET bottle Thermal treatment
6 Pumice stone Impregnating TiO2 milk, drying and

heat treatment
7 Quartz sand Dry/wet physical deposition
8 Porous nickel sheet Thermal treatment
9 Polythene films Thermal treatment method-ironing
2.2 Adsorption:
The phenomenon of attracting and retaining the molecules of a substance on the surface of a solid
resulting into higher concentration of the molecule on the surface is called Adsorption. The
substance on the surface of which adsorption takes place is called Adsorbent and the substance
adsorbed is known as adsorbate.
Solids, particularly when finely divided, have large surface area and therefore show this property
of adsorption to a much larger extent. Charcoal, Silica gel, alumina gel, clay etc. are good
adsorbents because they have highly porous structure and hence large surface area.
2.3 pH:
2.3.1 Effect of pH on adsorption
The adsorption of pollutants by any adsorbent depends significantly on Coulombic interactions,
or those electrostatic communications between the adsorbent surface and the adsorbate. These
interactions are influenced largely by the pH of the system, given that it directly affects the
surface charge of the adsorbate. Briefly, the Electrical Double Layer theory (EDL) describes the
electrical potential of a surface according, in part, to the properties of the surrounding
environment. One of the points described by the EDL is the Zeta Potential, or the electrical
potential of the particle at a distance from the bulk solid (i.e., at the shear plane). This value is
affected by the pH of the environment; as the concentration of H+ or OH- ions in solution varies,
the point to which the internal charge of the surface extends, changes, thereby altering the
potential at the shear plane (the zeta potential). The pH at which the zeta potential equals zero is
known as the point of zero charge (pHPZC); at a higher pH, the surface charge is negative,
whereas at a lower pH, the surface charge is positive. As one might expect, as the surface charge
of the adsorbent changes with the pH, the interaction with various cationic and anionic species is
affected.. Dai (1994) focused on the effect of zeta potential on the adsorption of cationic dyes
by an activated carbon with a pHPZC of 6.2. As expected, the dyes absorbed better to the carbon
in a basic environment than in an acidic system. At the high pH, adsorption was enhanced
because of the electrostatic attraction between the negatively charged carbon and the positively
charged dyes. At a low pH, where the surface had a positive charge, the adsorption was inhibited
because of repulsive forces. Dai continued his study in a later report (1998) to include three
anionic dyes; again, predictably, adsorption was enhanced at the lower pH ranges where the AC
carried a positive charge, and retarded at the higher pH values where the surface had a negative
charge.

The pH of the system can also influence the complexes on the surface of the carbon. Venkata
Mohan et al. (2002) reported that the maximum dye removal for their system occurred in the
neutral pH ranges. This is attributed to the idea that at neutral pHs, the oxygen functional groups
can be oxidized, thus imparting a positive charge to the surface, and aiding in dye adsorption. At
the more extreme pH ranges, it is hypothesized that adsorption is reduced due to the formation of
water complexes on the carbon surface.
2.3.2 Effect of pH on photocatalysis
The effect of pH on the degradation of dyes is threefold: 1) on the generation of OH▪, 2) on the
chemistry of the dye itself, and 3) on the adsorption of the dyes onto the TiO2 particles via the
zeta potential of the particles. In the degradation of reactive blue 4 (Neppolian et al., 2002, A), an
ideal pH range between 4 and 10 was determined, with the percent of dye degraded falling rapidly
in the highly acidic or basic systems. This is explained by the fact that higher proton
concentrations in the acidic environments retard hydroxyl radical efficiency. In the basic
environments, aside from the hydroxyl radical scavenging (Neppolian et al, 2002, B), the actual
chemistry of the dye changes, making it more stable and thus reducing destruction. Sauer et al.
(2002) focused on the idea that as the pH changes, the surface charge of the TiO2 particles also
changes (pHPZC of TiO2 = 6.8). One would expect that at a pH below 6, the anionic dye would
preferentially adsorb to the surface of the positively charged titania particles. Conversely, at a pH
above 6, the dye would face electrostatic hindrance, thus decreasing adsorption and access to
hydroxyl radicals. This hypothesis is supported by the experimental data, which showed a
significant decrease in degradation of the dye at higher pH values. The effect of the charge of the
dye on its degradation with respect to pH is most clearly demonstrated by (Lachheb et al. 2002)
who compared four cationic dyes to one anionic dye. In this study, the trends of decolorization
with respect to pH correlated directly with the charge of the dye; as pH increased, the degradation
rate of the cationic dyes increased, whereas that of the anionic dye decreased. Nevertheless, one
must not be quick to use pH and surface charge as the sole determining factor to predicting dye
degradation. For example, (Sökmen et al. 2002) showed that for the cationic dye, atrazone
orange, as the pH decreased, the decolorization rate increased. This counters the idea that at lower
pHs a reduced destruction would occur solely because the titania surface has a positive charge,
and would therefore repel the dye

2.4 Effect of catalyst dosages:
Catalyst dosing may be defined as the amount of catalyst added to per liter of solution.
The amount of catalyst is one of the main parameters in photocatalytic degradation studies. In
order to avoid the use of excess catalyst it is necessary to find out the optimum catalyst loading
for efficient wastewater treatment. The amount of catalyst has both positive and negative impact
on the photodecomposition rate. For Degussa P-25 nano sized TiO2 powder ,The increased
amount of catalyst increases the quantity of photons absorbed and consequently the degradation
rate(Sakthivel et al). Further increase in catalyst above certain amount, the TiO2 nano powder
get dispersed inside the wastewater and the turbidity of wastewater increases. For this reason, the
light penetration into the wastewater is decreases which attributes a decreased photocatalysis.we
can define the term Catalyst Loading, is the amount of catalyst immobilized on the support.
2.5 Objective and Scope
2.5.1 Objective:
From the various methods of immobilization of TiO2 nano powder over different supports that
has been practiced so far,
1. We can exploited these techniques to immobilize TiO2 nano powder over LECA suface,
hence TiO2/LECA can be formed.
2. Photocatalytic test for all TiO2/LECA sample is to be run in a batch reactor system .
3. Based on parameter viz Catalyst activity, mechanical strength, ratio of TiO2 Loading/
peeling off the LECA surface etc., the best technique should be chosen.
4. Optimum pH value for Photo degradation is to be found with the best TiO2 /LECA
combination.
5. Dependency of rate of Photocatalysis on TiO2 loading is to be analyzes at optimum pH
value of the reaction medium.
6. Dependency of reaction kinetics on concentration is to be analyzed based on certain
amount of catalyst loading and pH value.

2.5.2 Scope:
To solve environmental problems, AOP is an efficient eco-friendly approach to treat wastewater,

TiO2 Nanopowder serves as most efficient photocatalyst but the pitfall of using TiO2
Nanopowder is its expensive separation from reaction slurry system. The step of post separation
of TiO2 Nanopowder is eliminated by the approach of immobilization of TiO2 Nanopowder on
LECA support. With all optimal conditions for photocatalysis TiO2 / LECA .We can design
1. a floating bed reactor for scale up operations.

2. Inverse fluidized bed reactor.

Chapter 3
Materials and Synthesis

3 Materials and Synthesis
Materials
The raw wastewater used in the experiments was prepared solution of methyl blue of specified
concentration in ppm, TiO2 ( Degussa P-25 ) photocatalyst was purchased from Degussa Co.
Ltd., Germany, TiO2 ( lab Titanium(IV) oxide, MERCK) and LECA Granules. Other required
chemicals were Double Distilled water, NaOH (0.1 N), Ethanol absolute 99.9% pure, Nitric acid (
HNO3 ) 0.1 N , TiCl4 (99.7% pure) was used. For Light irradiation , Solar lamp (OSRAM ultra-
vitalux 300W made in SK) and for pH measurement pH meter was used.
3.1Experimental
3.1.1 Selection of LECA granules for coating
For each batch of reaction system catalyst are needed to immobilized on LECA granule surfaces.
The reaction is heterogeneous catalytic reaction which occurs on catalyst surface.The surface area
of the catalyst is the parameter which plays a vital role in the rate of reaction.
To compare the catalytic activity of different TiO2 /LECA samples we were need to fix
the surface area of each TiO2 /LECA samples and this was possible by fixing the weight of LECA
granules. For given mass of LECA , number and size of LECA granules were fixed which
facilitated almost same surface area available for photocatalytic reaction.
Basis for each TiO2 /LECA sample
Number of LECA granules were taken= 20
Weight of LECA granules =11.75 to11.96 grams
𝑥𝑖𝐷𝑖
Size of each LECA granules = =1.1 cm
𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒
xi = Fraction of number of total particle
Di = Diameter of ith particle

3.1.2 Experimental setup :
The experimental setup for the photocatalytic reaction consist of a beaker, magmatic stirrer, Light
source.
Volume of beaker = 250 ml
Diameter of the beaker =6.6 cm
Area of beaker = 34.195 cm2
Type of light source =solar light 300W
Height of light source from liquid interface = 15.8 cm
3.2.1 Preparation of TiO2 by sol gel process using TiCl4 as precursor.
All of the chemicals were analytical grade. 7.5 ml TiCl4 was added dropwise into 75 ml ethanol at
room temperature. A large amount of HCl gas was exhausted during the mixing process. A light
yellow solution was obtained and gelatinized for several days to form solgel as shown in figure
4.a. Then, the sol-gel solution was vaporized at 80 ±C until a dry-gel was obtained as in figure
4b. The dry-gel precursor was calcined at different temperatures for definite time in air to form
TiO2 powders figure 4c. In order to promote the decomposition of organic components in the
precursor, the initial heating rate was maintained at 5 ± C/min. Zhu et al.(2000)
Figure 4.a 4.b 4.c

Figure 4.a Shows the gelatinized form of product obtained from TiCl4/ethanol mixture. 4.b
Shows the sticky gel formed by prolong drying 4.c Shows the TiO2 powder and coating on
LECA.
3.2.Methods to immobilize/Coat TiO2 on LECA particle surfaces
Table 2
S.NO Particle Material of coating

I LECA TiO2+H20 (heat treatment method)
II LECA TiO2 + ETHANOL +NITRIC ACID
(1:27:1) (ethanol method)
III LECA Sol gel process using TiCl4+ETHANOL
IV LECA TiO2 + ETHANOL+NITRIC ACID

(1:6:2)
V MODIFIED LECA TiO2+ ETHANOL+NITRIC ACID
(1:6:2)
3.2.2 Immobilization of Degussa P25 (TiO2) Using Heat Treatment method
The catalyst (TiO2) was immobilized on 11.56 grams (number of granules=20) LECA
using heat treatment method. Certain amount of LECA was washed with acidic water maintained
at pH= 3. After washing LECA were dried in oven at 110 oC . Suspension Titanium dioxide was
prepared by adding 5 % (w/v) Degussa P25 TiO2 in doubled distilled water which were
maintained at pH=9. To prepare specified suspension ,1.25g of TiO2 were introduced to 24 ml of
Double distilled water maintained at pH=9. The resulting suspension was stirred continuously for
120 minutes followed by 30 minutes of sonication to form a milky solution that is stable for
several hours. The suspension was then applied on the surfaces of LECA. The coated surface was
then dried in an oven for 1 h at 110 °C. After drying, the surface was visually examined to check
the uniformity of coating. It was observed that 4 to 5 coats provide uniform deposition of titanium
dioxide. The dried surface was then calcined at 500 °C for 3–4 h. After calcinations at high
temperature, the coated sample was cooled to room temperature. The heating and cooling
processes were performed gradually to avoid cracking of film/coating of immobilized titanium

dioxide on the surface. The prepared titanium dioxide film was then flushed with water to remove
the loosely bound catalyst particles. The immobilized film of TiO2, thus prepared, on the LECA
particle surface by heat treatment technique. The TiO2 film was examined every time after
coating, if it was unsatisfactory the particle were coated again to get satisfactory film thickness.
The amount of TiO2 loaded with respect to number of coating is tabulated and also shown in the
graph.
Weight of photocatalyst TiO2=Weight of LECA + Weight of TiO2
The terms „Weight of catalyst‟ remains constant while the term „Weight of TiO2‟ keeps
varying with number of TiO2 coatings. For given mass of LECA 11.89g (20 number) maximum
attainable TiO2 loading was 0.43g.If we use same catalyst in a liter of solution, the normalized
basis of catalyst loading will be equal to 2.15 grams of TiO2/liter of MB solution. Similarly
different catalyst loading on fixed Weight and number of LECA were normalized on per liter MB
solution basis.
Table No – 3 Dependency of amount of TiO2 loaded on number of coatings
Number of
0 1 2 3 4 5 6 7 8 9
coating
TiO2 /liter 0 0.55 0.7 0.8 1 1.35 1.72 1.95 2.14 2.15
2.5
2
TiO2 /liter
1.5
1
TiO2 /liter
0.5
0
0 2 4 6 8 10 12
Number of coating

Figure 5: Dependency of amount of TiO2 loaded on number of coatings.
Figure: 6 TiO2 film coating by heat treatment method.
.3.2.3 Degussa P-25 TiO2/LECA photocatalyst preparation
Simple and efficient method has been used to prepare photocatalyst (Fig. 1). 1.02 grams
titanium dioxide powder (P-25) was added to 27 ml ethanol as the base medium of the slurry in
which the titania powder can be properly dispersed. 1 ml of dilute nitric acid with a pH = 3.5 was
added to make easier dispersion of the titania powder in ethanol and produce uniform slurry. The
slurry was sonicated in 30 min to separate the agitated TiO2 powders and obtain more uniform
slurry. After the slurry was prepared, 11.66 g of LECA granules (which were previously washed
in deionized water assisted by air bubbling for few minutes to remove dust)was added to the
slurry. In the final stage of process, the LECA granules had been adsorbed enough to titania
slurry, and filtered from the slurry and dried at 120 oC, in 12 h, then calcinated at 500o C in 30
min. To estimate how much TiO2 was loading over LECA granules, the weight of TiO2 is
measured before and after the coating and the difference of both the reading gave the amount of
TiO2 loading on the LECA surface.
The TiO2 film was examined every time after coating, if it was unsatisfactory the particle
were coated again to get satisfactory film thickness. In our case we coated LECA for 3 times.
catalyst loading was found to be 0.202g of TiO2 for 11.66g of LECA. Coating were also tried
using different approach as the methods mentioned in the above table numbered from III to V. A
brief note is given as below

TiO2 film was also coated on LECA using the gel formed in sol gel process TiCl4 as precursor.
The coated gel was then calcined at 500oC with rate of 7oC/min for 1 hour and cooled down
slowly. And In IV and V method the ratio of TiO2 to ethanol was maintained at 1:6 while keeping
otherwise conditions except for V method where LECA granules was modified to make its
surface more rough.
This modification was done which attributes more loading of TiO2 on to the rough surface. the
amount of TiO2 loaded on surface were 0.34 grams and 0.71 grams for 12.24 g and 13.36 of
LECA for methods IV and V respectively.
(a) (b) (c)

Figure: 7(a) coating by ethanol method (b) coating of TiO2 /ethanol (1:6) on LECA
(c) coating of TiO2 /ethanol (1:6) on modified LECA.
3.3 Concentration Calibration chart

To measure the concentration of the MB dye in UV-vis spectroscopy, one needs the calibration
chart to analyze the concentration of given sample, which basically is an Absorbance vs.
concentration plot fitted into a linear fit.
Standard solution MB dye of different concentrations (1 ppm to 10 ppm) was prepared. For the all
different concentration samples corresponding light absorbance of 664 nm was analyzed in UV-
vis spectroscopy and data was tabulated. The data so collected was used to plot graph of
Absorbance vs. concentration profile fitted into a linear fit as in graph 2. The regression
coefficient value was found to be equal to 0.976.
Table-4

Conc
0 1 2 3 4 5 6 7 8 9 10
(ppm)
Absorbance 0 0.408 0.448 0.713 0.88 1.137 1.407 1.667 1.7 1.877 2.02
Absorbance vs. Conc

2.5
y = 0.216x
R² = 0.976
2
1.5
Absorbance
0.5
0
0 2 4 6 8 10 12
Conc (ppm)
Figure 8: Absorbance vs. Concentration calibration plot.
3.4 Adsorption studies
Adsorption of reactant / Methylene Blue (MB) dye on Photocatalyst and LECA particle was
studied during the course of degradation reaction. The adsorption of dye on TiO2 nano particle or
on the substrate LECA causes a decrease in concentration with respect to initial concentration.
Initially a 200 ml of 20ppm solution of MB was prepared for each six 200 ml beakers. The
beakers were numbered from 1 to 6, to each of beaker certain amount of TiO2 /LECA were
added as detailed in the table below. The system was set free for 60 minutes thereafter
concentration was measured and compared with the initial concentration.

Table-5
Sample 1 2 3 4 5 6
number
Type of P-25 TiO2/TiCl4 TiO2/TiCl4 TiO2/LECA Modified Pure LECA
material TiO2 /LECA LECA/
TiO2
Figure-9 shows the effect of adsorption on LECA with TiO2/H2O, TiO2/Ethanol ,and the reactor
setup.
3.5 Kinetic studies of Photocatalytic reaction
The reaction kinetics was studied on 200 ml of 20 ppm MB solution. 200 ml of 20 ppm sample
was taken in 200 ml beaker and the pH=9 was maintain. To this solution different photocatalyst
as P-25 TiO2 , TiO2/LECA was added with stirring rate maintained at 200 rpm. The System was
agitated on such rate that every LECA granule could rotate properly and mixed thoroughly with

the liquid phase. The reaction setup (figure 9) was kept under dark condition for half an hour so
that adsorption on photocatalyst may occur had reached to equilibrium. Post adsorption period 2
ml of sample of MB was taken out from the reactor in sample bottle to measure its
concentration. A solar lamp was kept ready for irradiation over reactor system. Now the timer was
started at time t=0 When the solar lamp is switched on, the samples were collected at time
interval of 15 minutes till 60 minutes. MB Samples were collected through out the course of
reaction. As the ime passed the pH was varying which was maintained addition appropriate
acidic or basic solution.
Table: 5
Sample number C1 C2 C3 C4 C5 C6 C7
TiO2/ TiO2/ TiO2 TiO2/Ethanol/

P-25 LECA/H2O Ethanol /Ethanol/ LECA Pure
Photocatalyst TiO2 TiO2/TiCl4 /LECA modified LECA
LECA 1:6
1:27 1:6
Weight of
TiO2 0.20 0.20 0.204 0.190 0.71 0.24 0.00
immobilized
(in grams)
Keeping otherwise parameters same every time but The Different prepared TiO2 immobilized
photocatalysts (TiO2 with different substrate) were introduced to MB solution, and the same
reaction procedure was practiced to evaluate rate kinetics. The Different prepared TiO2
immobilized photocatalysts samples was numbered as C1,C2…C7 as tabulated in table 5 , the
table also summarize the weight if catalyst loaded on corresponding supports. Test for
photocatalysis was done for all catalysts numbering from C1 to C7.Post reaction the
Photocatalysts were filtered off, dried and reused for another trial to check their activity. The
percentage dye removal due to all photocatalysts were analyzed . Percentage dye removal
obtained from the 2nd trail is compared to the percentage dye removal obtained from
corresponding 1st trial. The variation of concentration with respect to time for different catalyst
C1 to C7 [ref table No 5] is tabulate as below in table 6a to 6g which was obtained freshly
prepared photocatalyst. The Reaction kinetics, mechanical strength of coating, Loading of TiO2
TiO2 peeling off from the surface are the various parameter which are helpful to select a good

method of immobilization of TiO2 . From these test we had find a suitable method to carry on
further experiments.
Table 6a: Variation of concentration with respect to time for catalyst sample C1
sample
C1
s.no time C Co ln(C/Co)
1 -30 20
3 0 19.5344 19.5344 0
4 30 13.80755 19.5344 -0.34696
5 60 8.018624 19.5344 -0.89041
6 90 5.199172 19.5344 -1.32368
7 120 3.445422 19.5344 -1.73513
8 180 0.623383 19.5344 -3.44477
Table 6b: Variation of concentration with respect to time for catalyst sample C2
sample
C2
1 -30 20
2 0 19.2094 19.2094 0
3 15 17.50621 19.2094 -0.09284
4 30 17.21708 19.2094 -0.1095
5 45 16.53942 19.2094 -0.14965
6 60 15.541 19.2094 -0.21192

7 120 12.37181 19.2094 -0.43998
8 180 9.137113 19.2094 -0.74306
Table 6c: Variation of concentration with respect to time for catalyst sample C3
sample
C3
1 -30 20
2 0 17.67094 17.67094 0
3 30 13.86274 17.67094 -0.24272
4 60 11.38907 17.67094 -0.43927
5 90 9.717113 17.67094 -0.59803
6 120 7.771153 17.67094 -0.8215
7 180 5.792211 17.67094 -1.11541
Table 6d: Variation of concentration with respect to time for catalyst sample C4
Sample
C4
1 -30 20
2 0 18.49098 18.49098 0
3 30 15.39743 18.49098 -0.18308
4 60 12.91062 18.49098 -0.35923
5 90 10.942 18.49098 -0.52467

6 120 7.259944 18.49098 -0.93491
7 180 5.864202 18.49098 -1.14842
Table 6e: Variation of concentration with respect to time for catalyst sample C5
Sample
C5
1 -30 20
2 0 16.32653 16.32653 0
3 15 15.75985 16.32653 -0.03533
4 30 15.12076 16.32653 -0.07672
5 45 13.33084 16.32653 -0.20271
6 60 11.79804 16.32653 -0.32486
7 120 8.937153 16.32653 -0.60257
8 150 6.568058 16.32653 -0.91057
9 180 5.866567 16.32653 -1.02352
Table 6f: Variation of concentration with respect to time for catalyst sample C7
Sample
C7
1 -30 20
2 0 15.32235 15.32235 0
3 180 14.40706 13.024 0.100924

Table 6g: Variation of concentration with respect to time for catalyst sample C6
Sample
C6
1 -30 20
2 0 15.87317 15.87317 0
3 15 15.00976 15.87317 -0.05593
4 30 14.30976 15.87317 -0.10369
5 45 10.5561 15.87317 -0.40793
6 60 10.00488 15.87317 -0.46156
7 120 7.04878 15.87317 -0.81178
8 150 5.27561 15.87317 -1.10154
9 180 3.536585 15.87317 -1.50147
3.6 Kinetic studies of Photocatalytic reaction at different pH of medium.
Out of available different techniques, sample catalyst synthesized from heat treatment method
was tested for photocatalysis at different pH of the medium. A batch of 200 ml 20 ppm solution
of methylene blue dye was prepared. The pH of the reactor medium was maintained at 1,3,5,6,7,9
for different batches of reactors. To the batches of MB solution at different pH, photocatalyst
TiO2/LECA were added with basis of 1 gram TiO2/liter . The system was set under agitated
condition at 200 rpm in dark for an hour and post this session was illuminated by solar bulb.

Table 7 a
pH = 1
S.No Time (min) concentration(ppm)
1 Dark adsorption 0 20
2 Photocatalysis 60 18.98
Table 7b
pH = 3
S.No Time (min) Concentration(ppm)
Table 7c
pH = 6
Table 7d
pH = 7
Table 7e
pH = 9

3.7 Kinetic studies of Photocatalytic reaction at different catalyst dosing.
A batch of 200 ml 20 ppm solution of methylene blue dye was prepared. The batch reactor system
was fed with different photocatalyst loading. The ratio of photocatalyst loading to per liter of MB
solution was maintained as 0.5g/liter,1 g/liter, 1.5 g/liter, 1.75 g/liter, 2.0 g/liter for different batch
reactors. The system was set under agitated condition at 200 rpm in dark for an hour and post this
session it was illuminated by solar bulb. The whole reactions were carried out at optimal pH value
of the medium.
Table -8 a
Photocatalyst loading=0.75g/l
S.No Time (min) concentration (ppm)
Table -8b
Photocatalyst loading=1 g/l

Table -8c
Table -8d

Table -8e
Photocatalyst loading=2g/l
Table -8f
3.8 Kinetic studies of Photocatalytic reaction at different initial Concentrations.
At optimum pH and catalyst loading of the medium Photocatalysis was run at different value of
initial concentrations. All the procedure was set same as previous photocatalytic tests.
3.9 Effect of agitation on rate of reaction and TiO2 coating.
The pH and catalyst loading of the solution medium was set constant for A batch of 200 ml 20
ppm solution of methylene blue dye. The PC reaction was carried out at different rotational speed
of the agitator. The variation of concentration of with respect to time was studied.
Table.9a : Photocatalysis at different agitations
rpm=200

Table 9b
rpm=300
Table 9c
rpm=400

Chapter 4
RESULTS AND DISCUSSION

4 RESULT AND DISCUSSION
It has been agreed that the kinetics of photocatalytic degradation using irradiated TiO2 follows the
Langmuir–Hinshelwood (L-H) law of heterogeneous photocatalytic reactions. According to the L-
H model, when initial concentration Co is very small, the following pseudo-first-order rate
equation is followed.
𝐶
ln = −𝑘𝑡
𝐶𝑜
Where, k is pseudo-first-order rate constant and C is the concentration at time t. A plot of
ln(C/Co) versus time represents a straight line, the slope of which upon linear regression equals
the pseudo-first-order rate constant (k).
4.1 Photocatalytic activity of prepared coatings
Before evaluating the photocatalytic activity, all the prepared films were kept in a magnetically
stirred vessel containing water for 3 h to check the film adherence to the supports. The films were
physically examined to see any kind of deterioration. All the films showed a good adherence
strength as a little peeling of films from the support was observed, while for sample C5 and C6
peeling of film was more due to formation of thick coat. The photocatalytic degradation of MB
was then performed with sample coatingsC1, C2, C3, C4, C5, C6 and C7 (as in table-5)
separately for a period of 3 h in each case. The decrease in concentration of dye was recorded
with respect to time and shown in Fig.9a. It was observed for decrease in the concentration of dye
after 3 h under solar light illumination for all seven case in terms of percentage
removal/degradation by each kind of coating can be shown as in the chart.figure-10 .The chart
also indicates the percentage removal of dye caused by adsorption on the surfaces. A decrease of
96.88% to 31.65 % of dye concentration was monitored for wide range of substrates for same
period under solar illumination onC1 to C7, respectively. From the recorded data of concentration
and time a plot of ln(C/ Co) v/s time (min) was plotted to get a straight line, best fitted by straight
line equations with regression coefficient as high as 0.95, 0.98, 0.983, 0.97, 0.96, 0.97 and 1 for
C1,C2,C3 ……up to C7 respectively. The values of Reaction half-life for the degradation of
methylene blue (MB) for C1 to C7 substrates were calculated, and tabulated in

Table 10: The percentage removal of MB dye due to adsorption and photocatalytic
reactions using different photocatalyst samples.
TiO2 TiO2 TiO2 TiO2
S.no P25 TiO2 TiO2/H2O LECA
/TiCl4 /ETH /EH/ML /ET 1:6
Total %removal 96.88 48.12 71.033 71.54 77 76.58 27

% removal by
adsorption 1.74 4 11.64 10.2 20.21 21.89 27
100
90
80
70
Total %removal
60
50 % removal by
adsorption
40
30
20
10
Figure-10 : The chart shows the percentage removal of MB dye due to adsorption and photocatalytic
reactions using different photocatalyst samples.
The concentration values were measures and plotted with respect to time for all the prepared
immobilized photocatalysts as shown in Fig 11. time “t=-30 min” refers to the time for
Adsorption in dark i.e. Dark adsorption and time t=0 to t= 180 minutes was dedicated for
photocatalysis.The concentration vs. time was fitted into different reaction kinetics. The fitting of
data in first order kinetics was most adaptable as it fitted well. ln(C/Co) vs. time was plotted
which gave a straight line passing through origin.The regression coefficient for straight lines

obtained from all sample catalyst were quit high to confirm first order kinetics. The reactions
followed pseudo-first-order kinetics according to the L-H law. The pseudo-first-order reaction
rate constants were determined from the slopes of the plot of ln(C/C0) verses time for all the
prepared coatings . Table 6 shows the values of pseudo-first-order reaction rate constant for C1
,C2,…..C7 [ref. table 4] coated films. The reaction rate constant half life also the half life time of
photocatalytic reaction is tabulated and compared.
Table -11: rate constant and t1/2
Type of coating Rate constant k /min Half life t1/2

p-25 tiO2 0.017 40.77058824
TiO2/TiCl4 0.003 231.0333333
TiO2/H2O 0.006 115.5166667
TiO2/ET 0.006 115.5166667
TiO2/ET 1:6 0.005 138.62
TiO2/ET/ML 1:6 0.007 99.01428571
25
20
15 C2
C3
Conc (ppm)
C4
10
C5
C6
5 C1
0
-50 0 50 100 150 200
Time (min)
Figure :11 Variation of concentration of MB with respect to time for different catalysts prepared

250
200
Reaction half life

150
(min)
100
50
Figure 12: Reaction half life for different catalysts prepared.
The lowest half-life time and highest reaction constant were obtained for C1 film which is an
indication of highest photocatalytic activity. While the lowest rate constant was obtained for
uncoated LECA or pure LECA it is quite obvious and also that in absence of any photocatalyst
the photoactivity will be least. Where as sample coating C3 and C4 were found to be optimized
with respect to TiO2 loading on the surface and photoactivity. Also the loss of TiO2 from the
surface is very less which was all quest to use. But again immobilization by heat treatment
method was found very convenient hence was selected for all future PC studies for our work.
4.2 Effect of pH on photocatalysis:
The effect of pH on the degradation of dyes is threefold: 1) on the generation of OH▪, 2) on the
chemistry of the dye itself, and 3) on the adsorption of the dyes onto the TiO2 particles via the
zeta potential of the particles. The cationic dye results a good Degradation/adsorption in high pH
valued medium and Anionic dyes gives a good degradation/adsorption in low valued pH medium.
It all occurs due to columbic interaction between the opposite charges. Degradation of MB dye
was conducted at various pH values of the medium, and it was found that the maximum color
removal is at pH=6. At very basic of medium (pH=12), high concentration of OH- effected the
chemistry of dye. Hence MB changed its color to violet from blue at pH =12 but below this
value of pH ,MB retains its blue color. For pH range below 12 we can compare the dye removal

by photocatalysis. The dependency of dye removal/degradation on pH is shown in the figure 13.
For the sake of comparison of dye removed attributed by Adsorption and Photocatalysis at
different pH, we had defined a relation as below
𝐶𝑕𝑎𝑛𝑔𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 (∆𝐶)

% 𝑅𝑒𝑚𝑜𝑣𝑎𝑙 =
𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 (𝐶𝑜)
The dependency of dye degradation on pH is shown in the table and the graph also.The
percentage dye removal was the difference between the initial concentration and the
concentration after adsorption in ratio with initial dye concentration, while the percentage
photocatalysis is difference between the concentration after adsorption and final dye
concentration after photocatalysis in ratio with initial dye concentration.
Table No. 12 Effect of pH on percentage MB dye removal for given amount of catalyst.
% total %
pH % adsorption
Photocatalysis Removal
1 5 26.94 32.02
3 8.3 29.76 38.05
5 14 34 48
6 22 47.8 69.8
7 20 37.1 57.1
9 3.5 16.5 20
100
90
80
70
% dye removal
60
50 % adsorption
40
% Photocatalysis
30
total % Removal
20
10
0
0 2 4 6 8 10
pH

Figure 13: shows % dye removal due to adsorption ,Photocatalysis and total percentage dye removal at
different pH values.
Figure 14 : spent catalyst TiO2/LECA at different pH of reaction medium
4.3 Effect of Catalyst dosing on Photocatalysis

As the catalyst loading on LECA surface were increased the rate of Photocatalysis also
increased. Heterogeneous catalytic reaction occurs on the catalyst surface and in the pores of the
catalyst .The higher catalyst loading provides greater surface area for reaction which favors
comparatively higher conversion in a given time. At lower amount of TiO2 loading on LECA
granule surfaces, only small fraction of total surface area of LECA was coated with TiO2 and so
only that much fraction of area was available for the participating in the photocatalysis. Hence at
lower TiO2 loading conversion will be less. As the TiO2 Loading was increase the fractional area
available for photocatalysis also increased which attributed to higher dye removal. The
dependency of dye removal with respect to TiO2 loading is shown as following Graph 5.

100
90
80
%Dye removal
70
60
50
40
30
20
10
0
0 0.5 1 1.5 2 2.5 3
TiO2 dosing (gram/liter)
Graph 15: dependency of dye removal on TiO2 loading.
4.4 Effect of agitation on rate of reaction and TiO2 coating:
Rate of Photocatalysis in a floating bed reactor was highly influenced by the flow pattern of the
liquid medium. When the percentage dye removal was compared among the reactors at different
rate of agitation, it was found that the reactor having higher agitation rate had highest percentage
of dye removal. Higher agitation encountered intimate contact between liquid and solid phases.
Hence resistance to mass transfer from bulk to the film was lesser or in other words higher
agitation attributed a higher value of mass transfer coefficient.
At higher agitation , the floating TiO2/LECA tended to revolve over the liquid interface and has
enough kinetic energy to roam from liquid interface to deep liquid bed and again from deep
liquid bed to the liquid interface also the TiO2/LECA were able to rotate along its spherical axis
As a result of that the whole surface area of each TiO2/LECA granule got introduced to light
illumination introduced from the top. Due to revolution of TiO2/LECA, it faced the light
illumination with freshly adsorbed MB dye on its surface. The local concentration available for
photocatalysis increases at higher agitation.
4.4.1 Effect of Agitation on TiO2coating on LECA At higher agitation the attrition

among the TiO2/LECA granules were high which resulted into loss of TiO2 from the LECA
surface. In the following table we analyzed the TiO2 loss at different rpm

Table No.13 Dependency of percentage Dye removal on agitation.
% dye TiO2 loss/gram

rpm Removal TiO2 loaded
1 100 56 0
2 200 66 0.0049
3 300 71.15 .0497=0.05
4 400 74.1 0.333
4.5 Effect of initial Concentrations of MB on rate of reaction
The rate of photocatalysis increased with increase in initial concentration. According to already
verified LH model of heterogeneous photocatalysis, the photocatalysis of MB dye followed first
order rate kinetics. The reaction rate depends only on the concentration of one reactant and rate
will of first order with respect to reactant. At low concentration of MB dye, the rate of
photocatalysis had solely depended on the reactant adsorbed on the photocatalyst surface. The
increase in concentration of MB dye had increased the adsorption and hence the photocatalysis.
After certain concentration of MB dye ,it was observed that further increase in concentration of
MB didn‟t push the rate of reaction up. The rate of reaction was decreased when the
concentration of MB dye was maintained very high. At higher concentration of MB dye the
whole surface of photocatalyst was saturated of the adsorbate dye molecules. Hence the rate of
reaction was independent of concentration of MB and was zero order with respect to MB
concentration.
4.7 Catalyst Regeneration
After the degradation reaction was accomplished ,the photocatalyst (TiO2+ LECA) was removed
from the liquid and dried at 90 oC temperature. It was found that good amount MB dye was
adsorbed on the photocatalyst surfaces. Due to heavy adsorption MB Dye on the TiO2 +LECA,
photocatalyst (TiO2 +LECA ) turned blue in color. The spent Photocatalyst was still retaining its
photoactivity after single use But the Dyes that were already adsorbed on TiO2 +LECA surface
after single use had already blocked the active sites for adsorption. In such situation the
consequent use of TiO2 +LECA makes no contribution in dye removal due to adsorption but
only due to photocatalysis. Hence the repeated use of TiO2 +LECA without regeneration hampers
the effectiveness of photocatalysis.
To improve the activity of photocatalyst TiO2 +LECA It is urged to regenerate it therefore TiO2
+LECA was kept in sun for several hours which helps it to regain its original white color by the
degradation of adsorbed MB dye. The other approach to regenerate it was to keep in furnace at
550oC for two hours. The later technique was more effective as it consumed less time and gave
very satisfactory result. The activity of photocatalyst remained same after regeneration provided
there was no TiO2 loss from LECA surface.

Chapter 5
CONCLUSIONS

5 CONCLUSIONS
Immobilization of Degussa P-25 TiO2 on LECA support was carried out by many different
methods. Based on the parameters as loading of TiO2, Photoactivity of loaded TiO2 , loss of TiO2
from the LECA surface and cost of coating, The best immobilization technique was searched.
Immobilization by Heat treatment technique was found to be the best upon consideration of
various parameters. The photocatalyst TiO2+LECA was selected to use for all consequent uses.
The effect of pH on adsorption and photocatalysis was studied at different pH of the medium. The
MB dye solution was maintained in acidic, basic, neutral medium at different pH values
(pH=1,3,5,6,7,9). The Adsorption and photocatalysis was studied at different pH renges.it was
observed that maximum adsorption and Photocatalysis was achieved in a MB solution medium
maintained at pH=6.
At fixed pH = 6 and for a given TiO2 the photocatalysis was conducted at different agitation,300
rpm was found to be the adequate rotation speed for stirring in context of percentage dye removal
and TiO2 loss due to attrition. The Dye removal due to photocatalysis is also dependent on the
exposure time to light illumination and bulk to film liquid mass transfer coefficient. At high
agitation The exposure time to light increases due to frequent movement of TiO 2 /LECA within
the liquid and along the axis of LECA at the liquid interface. But at high agitation the granules
posses high kinetic energy. the attrition of such granules results in loss of coated catalyst on the
surface of LECA granules.
At fixed pH and agitation , the percentage removal of dye was studied with respect to different
TiO2 loading. It was found that catalyst dosing of 1 gram TiO2 / liter (0.201g TiO2 loading on
11.89g LECA) was found to be most appreciable as it gave moderate percentage removal of dye
without any remarkable TiO2 loss. This much loading was able to facilitate many repeated use
without any makeup TiO2.
The heterogeneous photocatalytic reaction had found good agreement with Langmuir-
Hinshelwood law of heterogeneous photocatalysis, according to which it follows first order
reaction kinetics for low concentration of reactant. As the concentration was increased the rate of
reaction also increased but after certain value of concentration, the reaction rate was decreasing
instead of expected increase. The reason for this phenomena was analyzed and was found that at
concentration beyond 70ppm, the MB solution became dark blue in color and the light was unable
to penetrate it. Hence light were unable to excite the TiO2 surface beneath MB solution.
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DEPARTMENT OF CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

1.1 Photocatalysis and Photocatalyst

1.2 Titanium Dioxide

DEPARTMENT OF CHEMICAL ENGINEERING

The photocatalytic degradation of real pollutant systems, such as cosmetics and

1.2.1 Properties of TiO2

1.2.2 Reaction mechanism on TiO2 surface

TiO2 as a photocatalyst is use to mineralize organic pollutant by the formation of reactive

DEPARTMENT OF CHEMICAL ENGINEERING

1.3 LECA Granules

Lightweight extended clay aggregate (LECA) or expanded clay (exclay) is a light

DEPARTMENT OF CHEMICAL ENGINEERING

Figure 3 LECA particles

1.4 Methylene blue

DEPARTMENT OF CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

2.1 Immobilization of TiO2

DEPARTMENT OF CHEMICAL ENGINEERING

S.no Support Method

1 Glass Chemical vapor deposition (APCVD

Dried for 60 h at ambient

2 Activated carbon Chemical vapor deposition

3 Zeolites Sol–gel method and photo reductive

4 Glass sheets Sol–gel and hydrothermal

5 PET bottle Thermal treatment

6 Pumice stone Impregnating TiO2 milk, drying and

7 Quartz sand Dry/wet physical deposition

8 Porous nickel sheet Thermal treatment

9 Polythene films Thermal treatment method-ironing

DEPARTMENT OF CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

2.5 Objective and Scope

DEPARTMENT OF CHEMICAL ENGINEERING

To solve environmental problems, AOP is an efficient eco-friendly approach to treat wastewater,

1. a floating bed reactor for scale up operations.

DEPARTMENT OF CHEMICAL ENGINEERING

Materials and Synthesis

DEPARTMENT OF CHEMICAL ENGINEERING

3.1.1 Selection of LECA granules for coating

Basis for each TiO2 /LECA sample

Number of LECA granules were taken= 20

Weight of LECA granules =11.75 to11.96 grams

xi = Fraction of number of total particle

Di = Diameter of ith particle

DEPARTMENT OF CHEMICAL ENGINEERING

Volume of beaker = 250 ml

Diameter of the beaker =6.6 cm

Area of beaker = 34.195 cm2

Type of light source =solar light 300W

Height of light source from liquid interface = 15.8 cm

3.2.1 Preparation of TiO2 by sol gel process using TiCl4 as precursor.

Figure 4.a 4.b 4.c

S.NO Particle Material of coating

IV LECA TiO2 + ETHANOL+NITRIC ACID

3.2.2 Immobilization of Degussa P25 (TiO2) Using Heat Treatment method

DEPARTMENT OF CHEMICAL ENGINEERING

Weight of photocatalyst TiO2=Weight of LECA + Weight of TiO2

Table No – 3 Dependency of amount of TiO2 loaded on number of coatings

DEPARTMENT OF CHEMICAL ENGINEERING

Figure: 6 TiO2 film coating by heat treatment method.