Chapter 1

INTRODUCTION

1.1 Water a valuable resource:

Water covers about 71% of the Earth's surface, and is essential for all known kind
of life. On Earth, 97 % of the planet's water is found in oceans, 1.7% in
groundwater, 1.7% in glaciers and the ice caps of Antarctica and Greenland, a
small fraction in other large water bodies. Only 2.5% of the Earth's water is fresh
water, and 98.8% of that water is in ice and groundwater. Less than 0.3% of all
freshwater is in rivers, lakes, and the atmosphere.
Safe drinking water is essential to humans and other living life. Water is the key to
life: a crucial resource for humanity and the rest of the living world. Everyone
needs it and not just for drinking. Society uses water to generate and sustained
economic growth and prosperity, through activities such as farming, commercial
fishing, energy production, manufacturing, transport and tourism. Water scarcity
has emerged as a prominent issue for communities across the country. Nearly
every region of the country has experienced water shortages in the last five years.
Water supplies have decreased due to the drying up of streams, the decline of
groundwater levels because of over pumping, contamination of water resources,
and an increase in drought conditions caused by climate change. The increase in
human population, urbanization and ever-increasing industrialization causes
depletion and contamination of our precious water resources. The society is less
concerned about the conservation and protection of our water body from being
polluted. Each year more than five million people die from water-related disease
and around one billion people do not have accesses to safe drinking water and still
we are deteriorating this precious natural resource. Only 1% of the total fresh water
on the earth is available for drinking purpose through the different water bodies
such as river, lakes, pond etc. Despite this fact that the world’s population is
growing by roughly 80 million people each year and demand for freshwater is
increasing by 64 billion cubic meters a year we are polluting this only available
(1%) form of water by contaminating this with waste.
1.2 Available Water and its use in India:
India accounts for 2.45% of land area and 4% of water resources of the world but
represents 16% of the world population. Total utilizable water resource in the
country has been estimated to be about 1123 billion cubic meter (BCM) (690 BCM
from surface and 433 BCM from ground), which is just 28% of the water derived
from precipitation. About 85% (688 BCM) of water usage is being diverted for
irrigation, which may increase to 1072 BCM by 2050. Major source for irrigation
is groundwater. Annual groundwater recharge is about 433 BCM of which 212.5
BCM is used for irrigation and 18.1 BCM for domestic and industrial use (CGWB,
2011). By 2025, demand for domestic and industrial water usage may increase to
96 BCM from current demand of 68 BCM. With the present population growth-
rate (1.9% per year), the population is expected to cross the 1.5 billion mark by
2050. Due to increasing population and all round development in the country, the
per capita average annual freshwater availability has been reducing since 1951
from 5177 m3 to 1869 m3, in 2001 and 1588 m3, in 2010. It is expected to further
reduce to 1341 m3 in 2025 and1140 m3 in 2050. Hence, there is an urgent need for
efficient water resource management through enhanced water use efficiency and
waste water recycling.
1.3 Water pollution:
Water pollution has many sources. The most polluting of them are the city sewage
and industrial waste discharged into the rivers. The effects of water pollution are
not only devastating to people but also to animals, fish, and birds. Polluted water is
unsuitable for drinking, recreation, agriculture, and industry. It diminishes the
aesthetic quality of lakes and rivers. More seriously, contaminated water destroys
aquatic life and reduces its reproductive ability. Eventually, it is a hazard to human
health. Nobody can escape the effects of water pollution.
1.4 Generation of Wastewater in India:
It is estimated that about 38,254 million liters per day (mld) of wastewater is
generated in urban centers comprising Class I cities and Class II towns having
population of more than 50,000 (accounting for more than 70 per cent of the total
urban population). The municipal wastewater treatment capacity developed so far
is about 11,787 mld, which is about 31 per cent of the wastewater generation in
these two classes of urban centers (CPCB, 2009). Apart from domestic sewage,
about 13468 MLD of wastewater is generated by industries of which only 60% is
treated. In case of small scale industries that may not afford cost of waste water
treatment plant, Common Effluent Treatment Plants (CETP) has been set-up for
cluster of small scale industries (CPCB, 2005a). The status of wastewater
generation and treatment capacity developed over the decades in urban centers
(Class I and Class II) is presented in Table 1.1.
Table1.1: Wastewater generation and treatment capacity in urban India
1.5 Wastewater Treatment Technologies:
At the present time, the treatment known as preliminary, primary, advanced
primary, secondary (without or with nutrient removal) and advanced (or tertiary)
treatment (see Table 1.2). In preliminary treatment, gross solids such as large
objective, rags and grit are removed that may damage equipment. In primary
treatment, a physical operation, usually sedimentation is used to remove the
floating and settleable materials found in wastewater. For advanced primary
treatment, chemicals are added to enhance the removal of suspended solids and to
a lesser extent dissolved solids. In secondary treatment, biological and chemical
processes are used to remove most of the organic matter. In advanced treatment,
additional combination of unit operations and processes are used to remove
residual suspended solids and other constituents that are not reduced significantly
by conventional secondary treatment (Metcalf & Eddy, 4thed.).
1.5.1 Preliminary and primary Treatment:
The purpose of preliminary treatment is the elimination of coarse solids and other
large materials often found in raw wastewater. Removal of these materials is
necessary to enhance the operation and maintenance (O&M) of subsequent
treatment units. Preliminary treatment operations typically include coarse
screening, grit removal, and in some cases, communication of large objects.
The unit operations most commonly used in the preliminary and primary stages of
wastewater treatment include screening, coarse solids reduction(comminution,
maceration, and screenings grinding), flow equalization, mixing and flocculation,
grit removal, sedimentation, high-rate clarification, accelerated gravity separation
(vortex separators), flotation, oxygen transfer, aeration, and volatilization and
stripping of volatile organic compound (VOCs) (Metcalf & Eddy, 4th ed.).

1.5.2 Secondary Treatment:

The objective of secondary treatment is the further treatment of the effluent from
primary treatment to remove the residual organics and suspended solids. In most
cases, secondary treatment follows primary treatment and involves the removal of
biodegradable dissolved and colloidal organic matter using biological treatment
processes. Depending on the metabolic function of microorganisms, biological
processes can be classified as aerobic processes, anaerobic processes, anoxic
processes, facultative processes, and combined processes. Further biological
treatment processes can be classified based on their treatment processes such as
suspended growth processes, attached growth processes, and combination thereof.
1.5.3 Tertiary Treatment:
Tertiary wastewater treatment also termed as advanced treatment processes is
employed when specific wastewater constituents which cannot be removed by
secondary treatment must be removed.
Some of the advanced treatment processes used to remove some of the specific
dissolved organics includes (1) carbon adsorption, (2) Ion Exchange (3) membrane
filtration, (4) reverse osmosis (5) chemical precipitation, (6) chemical oxidation,
(7) advanced chemical oxidation, (8) electrodialysis, and (9) distillation.
Adsorption
Adsorption is the process of accumulating substances that are in solution on a
suitable interface. Adsorption is a mass transfer operation in that a constituent in
the liquid phase is transferred to the solid phase. The adsorption process has not
been used extensively in wastewater treatment, but demands for a better quality of
treated wastewater effluent, including toxicity reduction, have led to an intensive
examination and use of the process of adsorption on activated carbon. Activated
carbon treatment of wastewater is usually thought of as a polishing process for
water that has already received normal biological treatment. The carbon in this
case is used to remove a portion of the remaining dissolved organic matter. The
adsorption process, takes place in four more or less definable steps: (l) bulk
solution transport, (2) film diffusion transport, (3) pore transport, and (4)
adsorption (or sorption). The principal types of adsorbents include activated
carbon, synthetic polymeric, and silica based adsorbents, although synthetic
polymeric and silica based adsorbents are seldom used for wastewater treatment
because of their high cost,activated carbon is most widely used adsorbent for the
wastewater and water purification unit. Activated carbon based wastewater
treatment can be effectively used for the removal of various organic pollutants
including, aromatic solvents (benzene, toluene, nitrobenzene), chlorinated
aromatics (PCBs, chlorophenol), polynuclear aromatics (acenaphthene,
benzopyrenes), pesticides and herbicides (DDT, aldrin, chlordane, atrazine),
chlorinated nonaromatics (carbon tetrachloride, trichloroethane, chloroform), high
molecular weight hydrocarbons (dyes, gasoline, amines) which are hard to degrade
by conventional biological processes. The major problem with the activated carbon
based treatment process is the regeneration and reactivation of the carbon after its
adsorptive capacity has been reached, which makes this process costly. More
effective methods for the regeneration and reactivation of carbon need to be
developed for the economical application of this process.
Ion exchange
Ion exchange is a unit process in which ions of a given species are displaced from
an insoluble exchange material by ions of a different species in solution. The most
widespread use of this process is in domestic water softening, where sodium ions
from a cationic exchange resin replace the calcium and magnesium ions in the
treated water, thus reducing the hardness. Ion exchange has been used in
wastewater applications for the removal of nitrogen, heavy metals and total
dissolved solids. Ion exchange processes can be operated in a batch or continuous
mode. In a batch process, the resin is stirred with the water to be treated in a
reactor until the reaction is complete. The spent resin is removed by settling and
subsequently is regenerated and reused. In a continuous process, the exchange
material is placed in a bed or a packed column, and the water to be treated is
passed through it. Continuous ion exchangers are usually of the down flow, packed
bed column type. Wastewater enters the top of the column under pressure, passes
downward through the resin bed, and is removed at the bottom. When the resin
capacity is exhausted, the column is backwashed to remove trapped solids and is
then regenerated. Naturally occurring ion-exchange materials, known as zeolites,
are used for water softening and ammonium ion removal. Zeolites used for water
softening are complex aluminosilicates with sodium as the mobile ion. Ammonium
exchange is accomplished using a naturally occurring zeolite clinoptilolite.
Synthetic aluminosilicates are manufactured but most synthetic ion exchange
materials are resins or phenolic polymers. Five types of synthetic ion-exchange
resins are in use: (1) strong-acid cation, (2) Weak-acid cation, (3) strong-base
anion, (4) weak- base anion, and (5) heavy-metal selective chelating resins. Most
synthetic ion-exchange resins are manufactured by a process in which styrene and
divinylbenzene are copolymerized. The styrene serves as the basic matrix of the
resin, and divinylbenzene is used to crosslink the polymers to produce an insoluble
tough resin. Important properties of ion-exchange resins include exchange
capacity, particle size, and stability. The exchange capacity of a resin is defined as
the quantity of an exchangeable ion that can be taken up.

1.6 Need for the development of advanced treatment processes:

Though, all of the above mentioned advanced treatment methods are effective in
reducing the pollutant concentration to a desired level (reusable water for some
application), but these methods are not much cost effective owing to their high
fabrication and maintenance cost. Most of these advanced treatment processes are
separative processes, which separate pollutant molecule from the wastewater
stream and these processes do not degrade (mineralize) pollutant molecule into the
end products (CO2, H2O, etc.).
Therefore in these processes, further separation and disposal of pollutant molecule
is required which is again a rigorous processes and also regeneration and
reactivation of separation media is required such as regeneration and reactivation
of activated carbon and ion exchange resins are required for their reuse. These
processes are mainly used after the secondary treatment for getting the desired
reduction in pollutant level and do not serve as a pretreatment option for the
conventional biological treatment processes for their efficiency improvement. Such
limitation makes these processes very costly and therefore there is a need for the
development of new techniques which can overcome these limitations. In the last
two decades lot of research work has been carried out for the development of new
technologies especially in the area of advanced oxidation technologies for the
degradation of complex biorefractory pollutants.

1.7Advanced oxidation processes (AOPs):

Advanced oxidation processes (AOPs) arc used to oxidize complex organic
constituents found in wastewaters that are difficult to degrade biologically into
simpler end products. When chemical oxidation is used, it may not be necessary to
oxidize completely a given compound or group of compounds. In many cases,
partial oxidation is sufficient to render specific compounds more amenable to
subsequent biological treatment or to reduce their toxicity. The oxidation of
specific compounds may be characterized by the extent of degradation of the final
oxidation products as follows:
1. Primary degradation: A structural change in the parent compound.
2. Acceptable degradation (defusing): A structural change in the parent
compound to the extent that toxicity is reduced.
3. Ultimate degradation (mineralization): Conversion of organic carbon to
inorganic CO2.
4. Unacceptable degradation (fusing): A structural change in the parent
compound resulting in increased toxicity.

Theory of Advanced Oxidation:

Advanced oxidation processes typically involve the generation and use of the
hydroxyl free radical (OH•) as a strong oxidant to destroy compounds that cannot
be oxidized by conventional oxidants such as oxygen, ozone, and chlorine. The
hydroxyl radical reacts with the dissolved constituents, initiating a series of
oxidation reactions until the constituents are completely mineralized. Nonselective
in their mode of attack and able to operate at normal temperature and pressures,
hydroxyl radicals are capable of oxidizing almost all reduced materials present
without restriction to specific classes or groups of compounds as compared to other
oxidants.
Advanced oxidation processes differ from the other treatment processes discussed
(Such as ion exchange, membrane filtration) because wastewater compounds are
degraded rather than concentrated or transferred into a different phase. Because
secondary waste materials are not generated, there is no need to dispose of or
regenerate materials.
In the last two decades different AOPs are developed and tested for the degradation
of different water pollutants (inorganic and organic compounds), these processes
includes cavitation (generated either by means of ultrasonic irradiation or using
constrictions such as valves, orifice, venturi, etc. in the hydraulic devices)
(Adewuyi, 2001; Weavers et al., 1998; Hua and Hoffmann, 1997; Gogate and
Pandit, 2000; Senthilkumar et al., 2000; Sivakumar and Pandit, 2002; Vichare et
al., 2000; Pang et al., 2011; Braeutigm et al., 2012), photocatalytic oxidation (using
ultraviolet radiation/near UV light/ Sun light in the presence of semiconductor
catalyst) (Choi et al., 2000; Adewuyi, 2005; Konstantinou and Albanis, 2004; Cao
et al., 2006; Zabar et al., 2012; Yang et al., 2009; Lin et al., 2012) and Fenton
chemistry (using reaction between Fe ions and hydrogen peroxide, i.e. Fenton’s
reagent) (Kusic et al., 2006; Bigda, 1996; Pera-Titus et al., 2004; Ma et al., 2005;
Xue et al., 2009; Santos et al., 2011; Karci et al., 2012). These AOPs are also used
in combinations named as hybrid methods such as sonochemical,
sonophotocatalytic, photolytic, Photo-Fenton, photochemical, etc. to get the
enhanced oxidation efficiency (Cheng et al., 2012; Wang et al., 2011; Pera-Titus et
al., 2004).
1.7.1 Cavitation:
Cavitation is defined as the phenomena of the formation, growth and subsequent
collapse of micro bubbles or cavities occurring in extremely small interval of time
(milliseconds) and at multiple lactations in the reactor, releasing large magnitudes
of energy. The effects of cavity collapse are, creation of hot spots, releasing highly
reactive free radicals, cleaning of solid surfaces, and enhancement in mass transfer
rates. The collapse of bubbles generates localized ‘‘hot spots’’ with transient
temperature of about 10,000 K, pressures of about 2000 atm (Didenko et al., 1999).
The consequences of these extreme conditions are the cleavage of water molecules
(into H• atoms and OH• radicals) and dissolved oxygen molecules. From the
reactions of these entities (O•, H•, OH•) with each other and with H2O and O2
during the rapid cooling phase, HO• 2 radicals and H2O2 are formed. These
radicals (OH•, O• and HOO•) then diffuse into the bulk liquid medium where they
react with organic pollutants and oxidize them. The following are the possible
reactions occurring as the result of cavity collapse.
Cavitation is classified into four types based on the mode of generation viz.
Acoustic, Hydrodynamic, Optic and Particle, but only acoustic and hydrodynamic
cavitation have been found to be efficient in bringing about the desired chemical
changes whereas optic and particle cavitation are typically used for single bubble
cavitation, which fails to induce chemical change in the bulk solution.

Acoustic cavitation:
In the case of acoustic cavitation, cavitation is produced using the high frequency
sound waves, usually ultrasound, with frequencies in the range of 16 kHz–100
MHz. Alternate compression and rarefaction cycles of the sound waves results in
various phases of cavitation such as generation of the bubble/cavity, growth phase
and finally collapse. Acoustic cavitations (tiny micro bubbles) are created when it
reaches rarefaction cycle where a negative acoustic pressure is sufficiently large to
pull the water molecules from each other (the critical molecular distance, R for
water molecules is 10-8 cm) (Lorimer and Mason, 1987). As a result, ‘voids’ are
created in the liquid. On the other hand, the acoustic pressure is positive during
compression cycle of ultrasonic wave to push molecules together. Cavitation
bubbles will grow over a few cycles by entrapping most of the vapor from the
medium to reach a critical size before the implosion of the bubbles occurs during
compression cycle producing high local temperature (up to 10000K) and pressure
(up to 2000atm).
Different types of acoustic cavitational reactors are being used including ultrasonic
horn, ultrasonic bath and multiple frequency cells. Since 1990, there has been an
increasing interest in the use of ultrasound to destroy organic contaminants present
in wastewater (Weavers et al., 1998; Nagata et al., 2000; Fındık and Gündüz, 2007;
Hamdaoui and Naffrechoux, 2008; Wang et al., 2007; Francony and Petrier, 1996;
Wang et al., 2006; Golash and Gogate, 2012; Bagal and Gogate, 2012). Many
researchers have reported that ultrasonic irradiation process was capable of
degrading various recalcitrant organic compounds such as phenol compounds,
chloroaromatic compounds, aqueous carbon tetrachloride, pesticides, herbicides,
benzene compounds, polycyclic aromatic hydrocarbons and organic dyes. The
frequency of ultrasound, irradiating surface, intensity of sound wave, calorimetric
efficiency of ultrasonic equipment (power dissipated into the system per unit
power supplied), physicochemical properties of the liquid medium and the
presence of air and solid particles are the important parameters which affects the
cavitational efficiency of acoustic cavitational reactor.

Hydrodynamic cavitation:
One of the alternative techniques for the generation of cavitation is the use of
hydraulic devices where cavitation is generated by the passage of the liquid
through a constriction such as valve, orifice plate, venturi etc. (Gogate and Pandit,
2000; SenthilKumar and Pandit, 1999; Moholkar et al., 1999; Gogate and Pandit,
2005; Moholkar and Pandit, 2001). There are not many reports depicting the use of
these equipments for wastewater treatment, but these offer higher energy
efficiencies, more flexibility and higher potential for scale-up as compared to their
acoustic counterparts (Sivakumar and Pandit, 2002; SenthilKumar et al., 2000;
Kalumuck and Chahine, 2000; Franke et al., 2011; Wang and Zhang, 2009; Wang
et al., 2011; Braeutigm et al., 2012). In the case of hydrodynamic cavitation (HC)
the intensity of the cavity collapses (final collapse pressure) and hence the
cavitational yield is very much dependent on the surrounding pressure field
(turbulent pressure field). The intensity of turbulence depends on the magnitude of
the pressure drop and the rate of pressure recovery, which, in turn, depends on the
geometry of the constriction and the flow conditions of the liquid, i.e., the scale of
turbulence. The intensity of turbulence has a profound effect on cavitation
intensity. Thus, by controlling the geometric and operating conditions of the
reactor, the required intensity of the cavitation for the desired physical or chemical
change can be generated with maximum energy efficiency.

1.8 Need for the development of cost effective technology:

Most of these AOPs have been tested for the wastewater treatment on the
laboratory scale and mainly for model organic component. There are lots of issues
arising before their successful implementation on the industrial scale. The
economic considerations and effectiveness of these processes in treating a real
industrial effluent on the larger scale are the major challenges to be overcome for
the successful implementation of these technologies. As most of these AOPs are
tested for the mineralization of water solution contacting only single organic
pollutants, raises the question against the capability of these processes in treating
the real industrial effluent having multiple pollutants. The real wastewater
obtained from different chemical processing industries contains a lot of
compounds, both organic and inorganic. Thus, it is important to check the
interference between two or more reactants, which may also result in the
formation of variety of intermediates. The high cost of fabrication and
maintenance is another drawback of these technologies. As, in the case of acoustic
cavitation the material and fabrication cost for the ultrasonic horn and transducers
is very high, making it an uneconomical operation to be tried on industrial scale.
In the case of photo catalytic processes the engineering design and fabrication
consideration for providing uniform distribution of UV radiation throughout the
reactor adds cost to the process and further the maintenance cost for catalyst
regeneration and UV lamp life makes this process even more costly. Similarly, for
the Fenton process the cost of chemical reagent (ferric chloride and H2O2) are
very high and further the separation of alum formed due to the addition of ferric
chloride and the presence of unreacted H2O2 in the discharged stream rendering it
unsuitable for subsequent biological treatment, makes it uneconomical process for
large scale operation.
There is a strong need for the development of new cost effective advanced
oxidation technologies for the treatment of biorefractory pollutants, which can be
used as an individual process or can be used in combination with the other
conventional treatment processes for the effective degradation of refractory
pollutants. These can be used as a pretreatment option for the conventional
(especially biological processes) treatment processes so that the efficiency of
conventional treatment processes can be improved, thereby reducing the operating
cost of such treatment operations. Among the above explained AOPs,
hydrodynamic cavitation has an advantage over other processes in terms of its
application on industrial scale, easy scale up and cost effective process.
The major advantages of hydrodynamic cavitation are:

 It is one of the cheapest and most energy efficient method of generating

cavitation.

 The equipment used for generating cavitation is simple.

 Maintenance of such reactors is very low.

 The scale-up of the above process is relatively easy.

 Independent of the wastewater composition, wastewater having high COD

can be treated more effectively.

 can be used at multiple location i.e. before and after the biological treatment

process and can serve multiple applications such as complete oxidation of

refractory pollutant, breakdown of complex molecule into smaller molecule
which can be further degraded by conventional processes, hence increase the
efficiency of conventional processes, and can also used for the disinfection,
thus reducing the chemical usages for disinfection.

 Very less or no use of additional oxidizing agent.

1.9 Hydrodynamic cavitation:

Hydrodynamic cavitation (HC) can simply be generated by the passage of the
liquid through a constriction such as an orifice plate. When the liquid passes
through the orifice, the kinetic energy/velocity of the liquid increases at the
expense of the pressure. If the throttling is sufficient to cause the pressure
around the point of vena contracta to fall below the threshold pressure for
cavitation (usually vapor pressure of the medium at the operating temperature),
millions of cavities are generated. Subsequently as the liquid jet expands, the
pressure recovers and this results in the collapse of the cavities. During the
passage of the liquid through the constriction, boundary layer separation occurs
and a substantial amount of energy is lost in the form of a permanent pressure
drop. Very high intensity turbulence occurs on the downstream side of the
constriction; its intensity depends on the magnitude of the pressure drop, which,
in turn, depends on the geometry of the constriction and the flow conditions of
the liquid. The intensity of turbulence has a profound effect on the cavitation
intensity (Moholkar and Pandit, 1997). Thus, by controlling the geometric and
operating conditions of the reactor, one can produce the required intensity of the
cavitation so as to bring about the desired change with maximum efficiency.
Also the collapse temperatures and pressures generated during the cavitation
phenomena are a strong function of the operating and geometric parameters
(Gogate and Pandit, 2000).
Figure 1.2 shows a typical setup to generate cavities hydrodynamically.
The pressure-velocity relationship of the flowing fluid as explained by
Bernoulli’s equation can be exploited to achieve this effect. The flowing liquid,
when it passes through a mechanical constriction, say an orifice or a partially
throttled valve, venture or an orifice (part a in Figure 1.2), its velocity increases
accompanied by increase in kinetic energy and corresponding decrease in the
local pressure (part b in Figure 1.2). If the throttling is sufficient to reduce the
absolute local pressure below the vapor pressure (at the operating temperature),
spontaneous vaporization of the medium in the form of micro-bubbles
(nucleation) occurs. With continued lowering of the pressure, the cavity
continues to grow by further vaporization or desorption of gases (if some gas is
dissolved in the medium) reaching its maximum size at the lowest pressure.
Subsequent increasing (pressure recovery) of the pressure compresses this from
fully grown cavity and is made to collapse in adiabatic phase, thus generating
the kind of extreme condition of pressure and temperature.

Figure 1.2: Fluid flow & Pressure variation in hydrodynamic

cavitation set-up
A dimensionless number known as cavitation number is used to relate the
flow conditions with the cavitation intensity. Cavitation number is given by the
following equation:
Where, P2 is the fully recovered downstream pressure, P v is the vapor pressure of
the liquid, Vo is the velocity at the throat of the cavitating constriction.
The cavitation number at which the inception of cavitation occurs is known as the
cavitation inception number Cvi. Ideally speaking, the cavitation inception occurs at
Cvi equal to 1 and there are significant cavitational effects at C v values of less than
1. In the earlier work by Gogate and Pandit (2000), it has been shown that the
cavities oscillate under the influence of fluctuating pressure field and the
magnitudes of pressure pulses generated are much less, insignificant to bring about
a desired chemical change for the case where Cv values are greater than 1.
However, cavitation has been found to occur at a higher cavitation number also,
possibly due to the presence of dissolved gases or some impurities in the liquid
medium (Harrison and Pandit, 1992). Yan and Thorpe (1990) have studied the
effect of geometry of cavitating device (orifice plates) on the inception of
cavitation. They observed that for a given size orifice, the cavitation inception
number remains constant within an experimental error for a specified liquid. The
cavitation inception number does not change with the liquid velocity and is a
constant for a given orifice size and is found to be increasing with an increasing
size and dimension of the orifice. Moholkar and Pandit (1997) have discussed
these observations in terms of increased turbulent fluctuating velocity magnitude
and its variation with the orifice dimensions.
In the hydrodynamic cavitation, the cavitational yield (for e.g. amount of pollutant
reduced per unit energy dissipated) depends on the intensity of cavity collapse
which in turn depends on the several parameters such as number of cavitational
events present, the maximum size of the cavity reached before its collapse and the
surrounding pressure field. In hydrodynamic cavitation all these parameters
depends on the geometry of cavitational device and the operating pressure. The
important parameters which decide the efficiency and the overall cavitational yield
are:

 Inlet pressure and the cavitation number

 Physicochemical properties of liquid and initial radius of the nuclei;
 Size and shape of the throat and divergent section (in the case of venturi)
 Percentage free area offered for the flow

The effect of the various design and operating parameters mentioned above has
been studied extensively in terms of the collapse pressures on the basis of the
numerical simulations using bubble dynamics equations (Senthilkumar and Pandit,
1999; Moholkar and Pandit, 1997; Gogate and Pandit, 2000; Moholkar et al., 1999;
Moholkar and Pandit, 2001; Bashir et al., 2011) and also on the basis of
experiments done in different reactors (Suslick et al., 1997; Senthilkumar et al.,
2000; Vichare et al., 2000; Sivakumar and Pandit, 2002; Pradhan and Gogate,
2010).
Vichare et al. (2000) have carried out optimization of hydrodynamic cavitation
using decomposition of potassium iodide as a model reaction. They have studied
the effect of various parameters (inlet pressure, flow geometry of orifice plates) on
the iodine liberation rate. They have concluded that in hydrodynamic cavitation,
altering flow geometry or increasing turbulence frequency (ƒT) and the fraction of
the flow area occupied by the shear layer can enhance the cavitational yield. The
optimum frequency of turbulence can be achieved by manipulating the flow
conditions and geometry of the cavitation device. for the plates having the same
flow area, it is advisable to use a plate with a smaller hole size opening, thereby
increasing the number of holes in order to achieve a larger area of the shear layer.
Because, for smaller hole sizes, the value of ƒT increases, leading to a more
efficient collapse. On the contrary, for larger hole sizes the frequency of turbulence
(ƒT) is likely to be much lower than the natural oscillation frequency of the
generated cavity, resulting in a lower collapse intensity. Also, if there is a choice
on the magnitude of the flow area, lower percentage area should be chosen, as with
a decrease in flow area, the intensity of cavitation increases. They have also stated
that the rate of iodine liberation increases with an increase in the inlet pressure.
Similar observations have also been made by the Sivakumar and Pandit (2002) in
which they carried out degradation of rhodamine-B using multiple hole orifice
plates. The results of the numerical simulation in hydrodynamic cavitation carried
out by Senthilkumar and Pandit (1999) were also consistent with the experimental
observations made by Vichare et al. (2000).
Bashir et al. (2011) have carried out optimization of the important
geometrical parameters of a cavitating venturi. They have found that the ratio of
the perimeter of the venturi to the cross sectional area of its constriction quantifies
the possible location of the inception of the cavity. The ratio of the throat length to
its height (in the case of a slit venturi) controls the maximum size of the cavity and
the angle of the divergence section controls the rate of collapse of a cavity. Based
on the numerical study, it was concluded that a slit venturi (α = 2.7) with the slit
length equal to its height (1:1) and a half angle of divergence section of 5.5 degrees
is an optimum geometry for best cavitational activity.
Senthilkumar et al. (2000) have studied the effect of different operating
parameters (inlet pressure and cavitation number) on the cavitation yield using KI
degradation. They have found out that the rate of iodine liberation increases with
an increase in inlet pressure, reaches a maximum and then decreases, similarly the
rate increases with a decrease in cavitation number, reaches a maximum and then
drops. Gogate and Pandit (2000) have also found the similar observation using the
bubble dynamic simulation for the hydrodynamic cavitation devices.
All of the above studies depicted that, in hydrodynamic cavitation, the cavitational
yield (efficiency of hydrodynamic cavitation in bringing about the desired changes
physical and chemical changes) depends on the geometrical parameters as well as
on operating parameters (operating pressure and cavitation number). Till date most
of the studies were carried out using the single and multiple hole orifice plate
having circular hole only, and hence there is a huge scope in the field of the design
of different hydrodynamically cavitating devices including different types of
venture having different size and shape such as circular and noncircular shape
(rectangular, square, elliptical, etc.), and orifice plates having throat of different
shapes.

1.9.1 Applications of hydrodynamic cavitation:

Ability of cavitation to deliver energy, in concentrated and desired form and on
length and time scales similar to that of transformation, makes it an attractive tool
to be utilized to bring about the transformations in an energy efficient manner. As a
result of this, cavitation is applied for several applications which utilize the
primary and secondary effects to bring about the transformations. Primary effects
are the ones which are direct result of volumetric oscillations or the collapse of
cavity, while secondary effects are those which occur as the result of primary
effects. Primary effects include extremely high pressure temperature (~ 10000 K),
high pressure (~ 2000 atm) and high velocity liquid micro jets (~ 100 – 300 m/s)
(Suslick et al., 1997). It is because of these primary effects that cavitation is
capable to bring about intensification of processes. Some secondary effects which
are the key benefits of cavitation include free radical generation, enhancement of
mass transfer rates, and increase in interfacial area. A few applications of
cavitation are listed below.

 Waste water treatment

 Water disinfection
  Biological cell disruptions

 Hydrolysis of fatty oils

 Pulp and paper digestion

 Preparation of nano particle

 Mixing and uniform dispersion

 Chemical synthesis

1.9.2 Applications of hydrodynamic cavitation to wastewater treatment

As explained earlier, the collapse of cavities releases large magnitude of energy
with transient temperature of 10000 K and pressure of about 2000 atm. Under
these extreme conditions (high temperature and pressure) water and other
dissolved gases can dissociate into free radicals (for e.g. water molecules dissociate
into H• and OH• radicals). These hydroxyl radicals thus generated reacts with the
pollutant molecules trapped inside the cavities and also these OH• radicals diffuses
into the bulk liquid medium where they react with the pollutant molecules and
oxidize them. The other mechanism which causes destruction of organic pollutant
is the thermal pyrolysis of pollutant molecules trapped inside the cavities or
present near the cavity surface during cavity collapse.
There are not many reports indicating the applications of the hydrodynamic
cavitation reactors in wastewater treatment schemes until now. Kalumuck and
Chahine (1998) have studied the destruction of p-nitro phenol in recirculation flow
loops using a variety of cavitating jet configurations and operating conditions and
have shown that, hydrodynamic cavitation can effectively degrade p-nitro phenol.
Submerged cavitating liquid jets were found to generate a two orders of magnitude
increase in energy efficiency compared to the ultrasonic method. The ultrasonic
destruction was studied in an ultrasonic horn.

Sivakumar and Pandit (2002) have reported that hydrodynamic cavitation

having orifice plate with multiple holes can be used for the destruction of the
rhodamine B complex in an efficient way as compared to acoustic cavitation.
Acoustic cavitation was studied using an ultrasonic horn (Operating frequency:
22.7 kHz; power input: 240 W; and capacity: 50 ml) an ultrasonic bath (Operating
frequency: 22 kHz; power input: 120 W; and capacity: 0.75 l) as well as a dual
frequency flow cell. They have found that the cavitational yield (grams of
rhodamine B degraded per unit energy supplied) for the hydrodynamic cavitation
set-up was approximately two times higher as compared to the best in the
sonochemical reactors (dual frequency flow cell, operating frequency: combination
of 25 and 40 kHz; power input: 240 W; and capacity: 1.5 l) Moreover, the
hydrodynamic cavitation set-up is able to degrade approximately 50 l of effluent
under a single operation as compared to a few milliliters in the case of the
ultrasonic horn and bath and 1.5 l for the ultrasonic flow cell.
Vichare et al. (2000) have studied the degradation of potassium iodide using
hydrodynamic cavitation. They have concluded that the intensity and number of
cavitation events can be effectively controlled by using different plates differing in
number and diameter of holes. They have found that the flow geometry of the
orifice plates considerably affects the rate of the iodine liberation. They have
recommended that for the plates having the same flow area, it is advisable to use a
plate with a smaller hole size, thereby increasing the number of holes (higher α, the
ratio of total perimeter of holes to the total area of the opening) to get the
maximum cavitational effects.
 Bremner et al. (2008) have carried out mineralization of 2, 4-
dichlorophenoxyacetic acid by acoustic and hydrodynamic cavitation in
conjunction with the advanced Fenton process. They have compared the efficacies
of acoustic and hydrodynamic cavitation in enhancing the degradation process. It
was observed that in 20 min of treatment time(beyond this time, the increase in
the TOC removal is only marginal), the combination of acoustic cavitation and the
advanced Fenton process gives around 60% TOC removal, whereas 70% TOC
removal is observed with hydrodynamic cavitation combined with the advanced
Fenton process. They have concluded that the use of zero-valent iron and
hydrogen peroxide in conjunction with acoustic or hydrodynamic cavitation is a
very effective means of destroying high concentrations of 2,4-
dichlorophenoxyacetic acid. A combination of advanced Fenton process and
cavitation has been observed to intensify the degradation process by way of
turbulence and generation of additional free radicals. The results achieved using
the hydrodynamic cavitation are particularly good in that this unit operates in a
continuous mode and hence large volumes of contaminated water might be treated
very cost-effectively particularly with low levels of polluted water, at equivalent
energy dissipation levels.
Chakinala et al. (2009) have studied a combination of hydrodynamic cavitation and
heterogeneous advanced Fenton process (AFP) based on the use of zero valent iron
as the catalyst has been investigated for the treatment of real industrial wastewater.
The effect of various operating parameters such as inlet pressure, temperature, and
the presence of copper windings on the extent of mineralization as measured by
total organic carbon (TOC) content have been studied. They have observed that
increased pressures, higher operating temperature and the absence of copper
windings are more favorable for a rapid TOC mineralization. They have concluded
that higher inlet pressures result in greater cavitational activity contributing to the
enhanced hydroxyl radical generation and hence increased TOC mineralization of
the effluent. Around 60% mineralization can be achieved at 1500 psi inlet pressure
as compared to 50% at 500 psi inlet pressure. They have observed that the addition
of copper has a negative impact on the mineralization of organic pollutants present
in wastewater. About 60% of TOC was removed in the presence of iron pieces
alone and only 40% of TOC was removed with copper windings on iron pieces
after 150 min of treatment. This was explained on the basis of relative rates of
hydroxyl radical generation due to the presence of iron and copper. It is well
accepted that the rate of hydroxyl radical generation and hence the extent of TOC
mineralization is much higher in the presence of iron as compared to copper metal.
Wang and Zhang (2009) have studied the degradation of alachlor aqueous
solution by using hydrodynamic cavitation. They have found that alachlor in
aqueous solution can be effectively decomposed with swirling jet-induced
cavitation. The effects of operating parameters such as fluid pressure, solution
temperature, and initial concentration of alachlor and medium pH on the
degradation rates of alachlor were also discussed. The results showed that the
degradation rates of alachlor increased with increasing pressure and decreased with
increasing initial concentration. An optimum temperature of 40ºC existed for the
degradation rate of alachlor and the degradation rate was also found to be slightly
depending on medium pH.
Wang et al. (2011) have studied the degradation of reactive brilliant red K-
2BP (K-2BP) in aqueous solution using swirling jet-induced cavitation combined
with H2O2. They have observed a synergetic effect between hydrodynamic
cavitation and H2O2. The degradation of K-2BP by hydrodynamic cavitation
combined with H2O2 follows pseudo first-order kinetics. A variety of experimental
conditions were investigated for the degradation of K-2BP by swirling jet-induced
cavitation combined with H2O2. It was found that lower pH and higher temperature
of medium, higher pressure of fluid, more addition of H 2O2 and lower dye initial
concentration are favorable for the degradation of K-2BP using hydrodynamic
cavitation.
Recently, Joshi and Goagate (2012) have investigated degradation of an
aqueous solution of dichlorvos using hydrodynamic cavitation reactor. They have
studied the effect of various additives such as hydrogen peroxide, carbon
tetrachloride, and Fenton’s reagent on the degradation rate with an aim of
intensifying the degradation rate of dichlorvos using HC. They have observed that
use of hydrogen peroxide and carbon tetrachloride resulted in the enhancement of
the extent of degradation at optimized conditions but significant enhancement was
obtained with the combined use of hydrodynamic cavitation and Fenton’s
chemistry. The maximum extent of degradation as obtained by using a
combination of hydrodynamic cavitation and Fenton’s chemistry was 91.5% in 1 h
of treatment time.
The above works depict that hydrodynamic cavitation has great scope in the
area of wastewater treatment because of its effectiveness in reducing the organic
pollutant and real industrial wastewater to a desirable level, cost effective method
as compared to other advanced oxidation technique and easy to scale up on an
industrial scale. Though hydrodynamic cavitation offers immense potential and
also higher energy efficiency and cavitational yields, use of these reactors is
perhaps lacking on larger scales. More work is indeed required both on theoretical
front as well as on the experimental front for better understanding of the
phenomena and subsequent design methodology.

1.10. Hybrid treatment strategy:

It has been observed that none of the methods can be used individually in
wastewater treatment applications with favorable economics and high degree of
treatment efficiency. The combination of adsorption may be used to overcome the
disadvantages associated with the individual technique. The similarity between the
mechanism of destruction in the case of different advanced oxidation techniques
and some of the common optimum operating conditions also point towards the
possible synergism between these methods.
The presence of gases and solid particles mainly provide additional nuclei
for the cavitation phenomena and hence the number of cavitation events occurring
in the reactor are enhanced resulting in a subsequent enhancement in the
cavitational activity and hence the net chemical/physical effects. This can be one of
the approaches for enhancing the applicability of cavitational reactors to
wastewater treatment.
Intensification can be achieved using the approach of combination of
cavitation and advanced oxidation process such as use of hydrogen peroxide,
ozone and photocatalytic oxidation, only for applications where free radical attack
is the governing mechanism (Gogate, 2008). For reactions governed by pyrolysis
type mechanism, use of process intensifying parameters such as solid particles,
sparging of gases etc., which results in overall increase in the cavitational intensity
is recommended.
Cavitation coupled with adsorption utilizes the advantages of two methods
to generate more •OH radicals and can effectively improve the degradation rate of
organic pollutants. Also cavitation gives additional mechanism in terms of
pyrolysis in the system, which can help in removing some of the chemicals which
are refractory to hydroxyl radicals.
1.11. Aims and Objectives of the research work:
The aim of the current research work is to investigate the degradation of organic pollutants using
cavitation reactors and its combination with adsorption techniques. The work involve an
integrated approach to give effective processing rates using an optimum utilization of the energy
and hence to achieve process intensification. The main objective is to achieve complete
degradation of the selected target pollutants using the optimum suitable approach based on
cavitation reactors and its combination with adsorption processes. Specially, the research is
intended for the following objectives.
1. Characterization of wastewater.

2. Design and fabrication of system.

3. Evaluation of performance of individual system such as hydrodynamic cavitation

and adsorption using Zeolite, fly ash and hydrogel in batch and continuous system
for treatment of effluent containing dye/organic matter.
4. Comparative study of cavitation effect and adsorption individually onto pollutants
using batch and continuous system.
5. Studies on operating parameters with individual treatment process parameters
such as
a. Effect of concentration.
b. Effect of pH.
c. Effect contact time.
6. Development of hybrid system consisting of hydrodynamic cavitation reactor and
adsorption bed using Zeolite for treatment of targeted pollutants for dye industry.
ORGANIZATION OF THE THESIS

The objective of this thesis was to study and development of the hybrid
process for the treatment of dye industry wastewater. Each chapter contains work
that provides insight into the process while maintaining a focus on its application
in a practical situation. This means that the work has been designed to resemble the
actual situation, i.e. treatment of a dye, as closely as possible while still allowing
for the accumulation of knowledge applicable to various conditions.
The thesis is sub-divided into the following main sections.

Chapter 2 Presents the data related to past work carried out by various
investigators for the removal of dye using various treatment
technologies i.e. Literature Review.

Chapter 3 Describes the design of hybrid process for the treatment of dye
industry wastewater. The methodology for selection of different
adsorbents and analytical techniques for preparation of dye solution
and the investigations of the various parameters are presented. This
chapter also discusses the regeneration of adsorbents beds loaded with
dye using NaOH and HCL as regenerant. Three different types of
adsorbents were used. Various characteristics were studied such as the
dye sorbed by the bed, the bed height, concentrations, pH, and contact
time.

Chapter 4 Deals with the observations of laboratory studies of preliminary batch

and continuous studies under the heading Observations and
calculations.

Chapter 5 Summarizes the results of batch and continuous study in graphical in

the form of Results and Discussion.
Chapter 6 Summarizes the conclusion of the thesis.

Chapter 7 Describes the summary of thesis.

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