Final Black Book

USE OF CAVITATIONAL REACTOR FOR WASTE WATER TREATMENT
CHAPTER- 1
INTRODUCTION
1
1. Introduction
It is clear that water is one of the essential substances for living system and it is
necessary for human survival on the earth. All humans daily consume water to sustain life and
maintain a good health, therefore water conservation is important and its quality must meet
specific standards. The quality of water is determined by many factors such as physical,
chemical or biological parameters. The main sources of drinking water are lakes, reservoirs,
canal, ground water, sea water, rain water, atmospheric water generation and fog collection
that depending on the source of pollutant, their pollution could be different.
All water on earth is not good for drinking purpose and there must be use of some
treatment process to achieve the standard quality therefore we are facing a challenge to produce
suitable drinking water. General treatment of drinking water is consisting of several stages to
remove or reduction of suspended, dissolved solid and microbial pollutants. Main process of
water treatment includes flocculation, sedimentation and media filtration to remove colloidal
and suspended solids, ion exchange, carbon adsorption and membrane processes to remove
dissolved solids; and at last stage a disinfection for microbial inactivation that often performed
by chlorination, ozonation and ultraviolet radiation(UV). Any process of drinking water has
some purification limitation and application problems such as high cost, ineffective for removal
some pollutant. For example, common problem in membrane filtration is fouling and in
disinfection with chlorine product DBPs (disinfection by products) is a serious problem. Many
investigations have been performing to eliminate this limitation by application of innovates
technique such as semiconductor catalysts, forward osmoses, advance oxidation process and
magnetic purification. One of the innovate technologies that was used for improvement of
water treatment process is application of ultrasound (US) waves having a frequency of 20,000
Hz or above that is called Sonication or Cavitation.
2
1.1 Ultrasound
Ultrasound is longitudinal wave with a frequency above 20 kHz. This frequency is above the
sonic range (20 Hz to 20 kHz) at which humans can hear and below the mega-sonic region
(>600 kHz). In US waves, energy is transmitted by the vibration of the molecules in the
environment where the wave is being spread. US could generate by two techniques, firstly
magnetostrictive electrical energy is converted to mechanical energy (or vibration) with a
magnetic coil attached to vibrating piece like nickel and Terphenyl-D. Secondly for
piezoelectric technique, the electrical energy is converted to high frequency electric energy
with piezoelectric crystals attached to the vibrating piece (sonotrode, probe or horn).
1.2 Cavitation
Cavitation is the phenomena of the formation, growth and collapse of microbubbles or

cavities occurring in extremely small interval of time (milliseconds) in a liquid. Cavitation can
generate in two ways, if cavitation occurs by passage of ultrasonic waves, it is acoustic
cavitation or ultra-sonication and if it occurs due to pressure variation in liquid, it is
hydrodynamic cavitation. By collapse of cavities, a large amount of energy will be released
and according to the hot spot theory, when bubbles collapses, pressure can reach to 500-
10,000 atm and temperature reach to 3000- 5000K. Consequently, in these extreme condition,
hydroxyl (OH) and hydrogen (H) radicals would be formed by thermal dissociation of water
and oxygen. These radicals penetrate into water and oxidize dissolved organic compounds.
Hydrogen peroxide (H2O2) is formed as a consequence of OH and HO2 radical
recombination.
US increases transport of small molecules in a liquid solution by increasing the
convection in an otherwise stagnant or relatively slow moving fluid. It also can increase
convection in liquid by two mechanisms. The fist mechanism is micro-streaming, cavitation
sets up eddy currents in the fluid surrounding the vibrating bubbles and the eddy currents in
turn exert a twisting and rotational motion on nearby cells. In the vicinity of vibrating gas
bubbles intracellular organelles are also subjected to rotational forces and stresses. This
microscopic fluid movement is called micro-streaming. In the micro-streaming, the cycles of
3
low and high acoustic pressure because the gas bubbles to expand and shrink which in turn
creates shear flow around the oscillating bubbles. The second mechanism of enhancing
convection is acoustic streaming that momentum from directed propagating sound waves is
transferred to the liquid, causing the liquid to flow in the direction of the sound propagation.
By US irradiation application, a number of mechanical, acoustical, chemical and biological
changes occur in a liquid due to acoustic cavitation. In this study, the feasibility and efficiency
of different applications of US technique as a free-chemical and environmental friendly process
for water treatment were evaluated.
1.3 Types of Cavitation
1.3.1 Acoustic Cavitation

Intense sound fields in liquids generate cavities or bubbles that start to oscillate and
move around in the liquid, a phenomenon called acoustic cavitation. The basic element to start
an investigation with is the single, spherical bubble in an infinite liquid subject to a sinusoidal
sound field. The best experimental approximation so far is realized in the acoustic bubble trap
as mainly used for sonoluminescence studies, and in bubbles generated by focused laser light.
Both cases have been combined to investigate transient single bubble dynamics and its
sonoluminescence in an acoustic field. Theoretical bubble models have been conceived with
different states of sophistication to include different influences and phenomena as, for instance,
liquid compressibility, heat and mass transfer across the bubble wall or stability of the surface.
Noteworthy is the strong collapse of a bubble at high sound pressure amplitudes leading to
shock wave and light emission and high speed liquid jet formation under appropriate
conditions. The interior of a bubble is usually treated as homogeneous with respect to
temperature and pressure. However, this may not be true in the last phase of 610 W a strong
collapse. This problem is not only tackled by continuum mechanics via partial differential
equations but also in a molecular dynamics approach. The next step in bubble dynamics
investigations is given by bubble interaction. It leads to complicated forms of attraction and
repulsion already in the case. of two spherical, interacting bubbles. A survey of bubble
structures as they appear in acoustic cavitation is given in. A particle model has been
formulated to address the problem of multi bubble systems in an ultrasonic field as a way to
cope with acoustic cavitation bubble ensembles.
4
Advantages of Acoustic Cavitation.
It increases the rate of reaction up to a million times.

It can also shift the reactions equilibrium, therefore increasing the yield of the reaction.
It can even change the entire process of the reaction by changing the reaction pathway.
It can be used in fat removal and many other medical uses.
Disadvantages of Acoustic Cavitation.

It causes great damage to the nearby materials or surface.
The process is not feasible on large scale.
High energy is required.
Overall cost increases.
1.3.2 Hydrodynamic Cavitation.

Hydrodynamic cavitation describes the process of vaporization, bubble generation and bubble
implosion which occurs in a flowing liquid as a result of a decrease and subsequent increase in
local pressure.
Hydrodynamic cavitation is normally caused by moving fans, impellers or disturbances created
by venturimeter or orifice meter.
5
Advantages of Hydrodynamic Cavitation.
A greener technology that does not necessarily need additional chemicals.
Can be coupled with other AOPs, if required.
Bulk temperature is ambient, bulk pressure is in range of 3-atm.
Enhances performance of existing effluent treatment facility (improves efficiency of aerobic

reactor, increases biodegradability of effluent (BOD: COD ratio), reduces COD of effluent
etc.).
1.3.3 Optic Cavitation.

It is produced by photons of high intensity light (laser) rupturing the liquid continuum.
Here high intensity laser lights are used for producing the effect.
1.3.4 Particle Cavitation.

Cavitation here is produced by the beam of elementary particles, e.g. a neutron beam rupturing
a liquid, as in the case of a bubble chamber.
6
CHAPTER-2
LITERATURE REVIEW
7
2. Literature Review
Industrial Wastewater Treatment Using Hydrodynamic Cavitation and
Heterogeneous Advanced Fenton Processing

Anand G. Chakinala1, Parag R. Gogate, Arthur E. Burgess, David H. Bremner
A combination of hydrodynamic cavitation and heterogeneous Advanced Fenton

Process (AFP) based on the use of zero valent iron as the pseudo-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 as additional oxidant on
the extent of mineralization as measured by total organic carbon (TOC) content have been
studied with the aim of maximizing the extent of degradation. It has been observed that elevated
pressures, higher operating temperature and the absence of copper windings are more favorable
for a rapid TOC mineralization. A new approach of latent remediation has also been
investigated where hydrodynamic cavitation is only used as a pretreatment with an aim of
reducing the total cost of remediation. It has been observed that this novel approach of latent
remediation works very well with about 50% to 60% removal of TOC using only an initial 15
min treatment by hydrodynamic cavitation.
Acoustic Cavitation
Olivier Louis nard and Jos Gonzlez-Garcia
The benefit of acoustic cavitation owes to its ability to concentrate acoustic energy in
small volumes. This results in temperatures of thousands of kelvins, pressures of GPa, local
accelerations 12 orders of magnitude higher than gravity, shockwaves, and photon emission.
In a few words, it converts acoustics into extreme physics. The counterpart is that it constitutes
a complex multidisciplinary problem, involving a wide range of temporal and spatial scales,
and is therefore difficult to measure. Furthermore, it is a diphasic problem in essence, with the
peculiarity that the cavitation bubbles rise up from nowhere and self-arrange in a fascinating
variety of structures. For all these reasons, it is difficult to control, to predict, and to scale up.
8
Several features of cavitation fields remain unexplained, although the progress in optic
recording systems recently shed light on previously unreachable characteristics. From a
theoretical point of view, the physics of the single-bubble model has progressed considerably,
thanks to single-bubble sonoluminescence experiments. From an engineering point of view,
the main unknown remains the bubble size distribution and spatial repartition, which in general
constitute the main barrier to extrapolate the more or less known action of one bubble on a
specific process, to macroscopically observed effects. We first present general results for
bubbles in a quiet liquid (Section 2). Then, in Section 3, the purely radial forced oscillations of
a single bubble in an infinite liquid will be addressed, focusing on thermal effects, solvent
evaporation in inertial bubbles, and their relevance to sonochemistry. Bubbles loss of
sphericity and the resulting effects will be presented in Section 4. The last section addresses
cavitation bubble fields and their interaction with the sound field, from both experimental and
theoretical points of view.
Acoustic cavitation and its chemical consequences

By Kenneth S. Suslick, Yuri Didenko, Ming M. Fang, Taeghwan Hyeon, Kenneth J. Kolbeck,
William B. McNamara III, Millan M. Mdleleni and Mike Wong
Acoustic cavitation is responsible for both sonochemistry and sonoluminescence.
Bubble collapse in liquids results in an enormous concentration of energy from the conversion
of the kinetic energy of liquid motion into heating of the contents of the bubble. The high local
temperatures and pressures, combined with extraordinarily rapid cooling, provide a unique
means for driving chemical reactions under extreme conditions. A diverse set of applications
of ultrasound to enhance chemical reactivity has been explored, with important applications in
mixed-phase synthesis, materials chemistry, and biomedical uses. For example, the
sonochemical decomposition of volatile organometallic precursors in lowvolatility solvents
produces nanostructured materials in various forms with high catalytic activities.
Nanostructured metals, alloys, carbides and sulphides, nanometre colloids, and nanostructured
supported catalysts can all be prepared by this general route. Another important application of
sonochemistry to materials chemistry has been the preparation of biomaterials, most notably
protein microspheres. Such microspheres have a wide range of biomedical applications,
including their use as echo contrast agents for sonography, magnetic resonance imaging
contrast enhancement, and oxygen or drug delivery.
9
Physical and Chemical Effects of Acoustic Cavitation in Selected Ultrasonic
Cleaning Applications
Nor Saadah Mohd. Yusof, Bandar Babgi, Mecit Aksu
Acoustic cavitation in a liquid medium generates several physical and chemical effects.
The oscillation and collapse of cavitation bubbles, driven at low ultrasonic frequencies (e.g.,
20 kHz), can generate strong shear forces, microjets, microstreaming and shockwaves. Such
strong physical forces have been used in cleaning and flux improvement of ultrafiltration
processes. These physical effects have also been shown to deactivate pathogens. The efficiency
of deactivation of pathogens is not only dependent on ultrasonic experimental parameters, but
also on the properties of the pathogens themselves. Bacteria with thick shell wall is found to
be resistant to ultrasonic deactivation process. Some evidence does suggest that the chemical
effects (radicals) of acoustic cavitation are also effective in deactivating pathogens. Another
aspect of cleaning, namely, purification of water contaminated with organic and inorganic
pollutants, has also been discussed in detail. Strong oxidizing agents produced within acoustic
cavitation bubbles could be used to degrade organic pollutants and convert toxic inorganic
pollutants to less harmful substances. The effect of ultrasonic frequency and surface activity of
solutes on the sonochemical degradation efficiency has also been discussed in this overview.
10
CHAPTER- 3
ADVANCED OXIDATION PROCESS
11
3. Advanced Oxidation Processes
(H202 as an Additive)
Oxidation is defined as the transfer of one or more electrons from an electron donor
(reductant) to an electron acceptor (oxidant), which has a higher affinity for electrons. These
electron transfers result in the chemical transformation of both the oxidant and the reductant,
in some cases producing chemical species with an odd number of valence electrons. These
species, known as radicals, tend to be highly unstable and, therefore, highly reactive because
one of their electrons is unpaired. Oxidation reactions that produce radicals tend to be followed
by additional oxidation reactions between the radical oxidants and other reactants (both organic
and inorganic) until thermodynamically stable oxidation products are formed. The ability of an
oxidant to initiate chemical reactions is measured in terms of its oxidation potential. The most
powerful oxidants are fluorine, hydroxyl radicals (OH), ozone, and chlorine with oxidation
potentials of 2.85, 2.70, 2.07 and 1.49 electron volts, respectively. The end products of
complete oxidation (i.e., mineralization) of organic compounds such as MTBE or benzene are
carbon dioxide (CO2) and water (H2O).
Fig 3.1: -AOPs for waste water treatment
12
AOPs involve the two stages of oxidation discussed above: 1) the formation of strong
oxidants (e.g., hydroxyl radicals) and 2) the reaction of these oxidants with organic
contaminants in water. However, the term advanced oxidation processes refer specifically to
processes in which oxidation of organic contaminants occurs primarily through reactions with
hydroxyl radicals (Glaze et al., 1987). In water treatment applications, AOPs usually refer to a
specific subset of processes that involve O3, H2O2, and/or UV light. However, in this analysis,
AOPs will be used to refer to a more general group of processes that also involve TiO2
catalysis, cavitation, E-beam irradiation, and Fentons reaction. All of these processes can
produce hydroxyl radicals, which can react with and destroy a wide range of organic
contaminants, including Methyl tert-butyl ether MTBE. Although a number of the processes
noted above may have other mechanisms for destroying organic contaminants, in general, the
effectiveness of an AOP is proportional to its ability to generate hydroxyl radical.
Advantages and Disadvantages.
The combined H2O2 process has been demonstrated to be more effective at removing MTBE
and other natural and synthetic organics than O3 or H2O2 alone. In addition, using a
combination of O3 and H2O2 to produce hydroxyl radicals, rather than just O3, allows a lower
dosage of O3 to be used. This is desirable for reducing costs and bromate formation potential.
The theoretical yield of hydroxyl radicals via H2O2/O3 technology is less than that of the H2O2
technology; however, the yield is less affected by water quality (i.e., turbidity, iron, and nitrates
lower the yield for UV processes but not H2O2/O3 processes). Once the hydroxyl radicals are
formed, however, the chemical destruction and interferences are the same for both
technologies.
The use of O3 can result in the potential formation of bromate; however, bromate formation
can be mitigated by lowering the pH to <6.5, increasing the H2O2 to O3 ratio, or adding another
radical scavenger that will react with hydroxyl radicals prior to the bromide (e.g., ammonia).
13
The H2O2/O3 process typically requires an air permit for ozone emissions in addition to an off-
gas treatment system for ozone destruction. The hydrogen peroxide reacts rapidly with most of
the applied ozone and, thus, the air exiting the contactor has been observed to typically contain
ozone concentrations less than 1 mg/L. This concentration is significantly higher than the 1-
hour Clean Air Act standard of 0.12 ppm. Current methods for removal of ozone in the off-gas
include thermal destruction, catalytic reduction, or a combination of the two.
3.1 Ozonation.
Ozone is a powerful oxidizing agent and has many uses in water treatment, including
oxidation of organic chemicals. Ozone can be used as a primary disinfectant. Ozone gas (O3)
is formed by passing dry air or oxygen through a high-voltage electric field. The resultant
ozone-enriched air is dosed directly into the water by means of porous diffusers at the base of
baffled contactor tanks. The contactor tanks, typically about 5 m deep, provide 1020 minutes
of contact time. Dissolution of at least 80% of the applied ozone should be possible, with the
remainder contained in the off-gas, which is passed through an ozone destructor and vented to
the atmosphere.
The performance of ozonation relies on achieving the desired concentration after a

given contact period. For oxidation of organic chemicals, such as some oxidizable pesticides,
a residual of about 0.5 mg/l after a contact time of up to 20 minutes is typically used. The doses
required to achieve this vary with the type of water but are typically in the range 25 mg/l.
Higher doses are needed for untreated waters, because of the ozone demand of the natural
background organics. Ozone reacts with natural organics to increase their biodegradability,
measured as assimilable organic carbon. To avoid undesirable bacterial growth in distribution,
ozonation is normally used with subsequent treatment, such as biological filtration or granular
activated carbon (GAC), to remove biodegradable organics, followed by a chlorine residual, as
ozone does not provide a disinfectant residual. Ozone is effective for the degradation of a wide
range of pesticides and other organic chemicals.
14
3.2 Fentons Reagent
Fentons reagent is a solution of hydrogen peroxide with ferrous ions as a catalyst that
is used to oxidize containments of waste water. Fentons reagent can be used to destroy organic
compounds such as trichloroethylene (TCE) and tetrachloroethylene, perchloroethylene (PCE).
It was developed in the 1890s by Henry John Horstman Fenton as an analytical reagent.
Iron(II) is oxidized by hydrogen peroxide to iron(III), forming a hydroxyl radical and

a hydroxide ion in the process. Iron(III) is then reduced back to iron(II) by another molecule
of hydrogen peroxide, forming a hydroperoxyl radical and a proton. The net effect is
a disproportionation of hydrogen peroxide to create two different oxygen-radical species, with
water (H+ + OH) as a by-product.
Fe2+ + H2O2 Fe3+ + HO + OH
Fe3+ + H2O2 Fe2+ + HOO + H
The free radicals generated by this process then engage in secondary reactions. For
example, the hydroxyl is a powerful, non-selective oxidant. Oxidation of an organic compound
by Fenton's reagent is rapid and exothermic and results in the oxidation of contaminants to
primarily carbon dioxide and water.
Reaction was suggested by Haber and Weiss in the 1930s as part of what would become
the HaberWeiss reaction. Iron(II) sulphate is typically used as the iron catalyst. The exact
mechanisms of the redox cycle are uncertain, and non-OH oxidizing mechanisms of organic
compounds have also been suggested. Therefore, it may be appropriate to broadly
discuss Fenton chemistry rather than a specific Fenton reaction. In the electro-Fenton process,
hydrogen peroxide is produced in situ from the electrochemical reduction of oxygen. Fenton's
reagent is also used in organic synthesis for the hydroxylation of arenes in a radical
substitution reaction such as the classical conversion of benzene into phenol.
15
3.3 Process of H2O2 Oxidation:
When H2O2 is added to water, it participates in a complex chain of reactions that result
in the formation of radicals such as the hydroxyl radical (OH) and the superoxide radical (O2)
(Hoigne, 1998). Like O3, these radical products (OH and O2) are oxidants capable of MTBE
destruction. Of the radical intermediates formed in ozonated water, OH is the most powerful
MTBE oxidant, even more powerful than O3 itself. Direct oxidation of ethers by O3 is known
to occur very slowly; this reactions second-order kinetic rate constant is less than 1 M-1s-1
(Buxton et al., 1988). By contrast, oxidation of ethers by radical oxidants is extremely rapid.
Hydroxyl radicals react with MTBE according to a rate constant of 1.6 x 109 M-1s-1 (Buxton
et al., 1988).H2O2 can be combined with ozone to enhance the transformation of O3 to OH in
solution. H2O2 is a weak acid, which partially dissociates into the hydroperoxide ion (H2O2) in
water. H2O2 reacts slowly with O3, whereas the H2O2- ion can rapidly react with O3 to form
OH.
H2O2 + H2O HO2- + H3O+
16
CHAPTER-4
MATERIALS, METHODS AND PROCEDURE
17
4. Materials, Method and Procedure
4.1 Characteristics of Industrial wastewater:
The experimental studies were performed to evaluate the efficacy of the process for
degradation of industrial wastewater effluent obtained from Excel industries, Lote. The current
investigation is very important in the context of application to wastewater treatment as the
majority of the reported literature deals with simulated effluents and the results may or may
not be reproduced for real industrial applications due to the presence of trace components. The
effluent stream used in the present work consisted of a complex mixture containing
phosphonate compounds with a pH of 3.2, an initial COD of 3328 mg/L. COD indicates the
concentration of all organic compounds which can be fully oxidized using strong oxidizing
agents. The effluent consists of some chlorides of about 1138 ppm and amount of phosphate is
around 3436 ppm.
4.2 Experimental setup:

Acoustic cavitation was generated by using a sonicator. Sonicator having following
specifications: -
Power Rating: 120 watts
Frequency: 20 kHz
Programmable Timer: 10 hours
Adjustable Pulse On/Off: 1 second to 1 minute
Dimensions (W x L x H): 8 x 5.25 x 8.5 in. (203 x 387 x 216 mm).
Also, COD digester was used with following specifications: -

Temp. Range: Above and to 180C or higher Resolution: 1C.
Display: Digital 12 mm Red LED
Control: Digital Electronic Temp Controller.
Heater Rating: 750 Watts.
Sensor: PT-100
Timer: Selectable 15, 30, 45, 60, 90
or 120 min with alarm
18
Hole Size: 40 mm dia. x 80 mm depth

Glass Tube: 38 mm. dia, 15 nos (5 x 3 rows)
Sample Volume: 20 ml. each
Dimension: 500 W x 270 D x 210 mm H
4.3 Experimental Methodology
Method 1: - In this method only cavitation has been used.
Here 100 ml of effluent was taken in a 250-ml beaker and then ultrasonic sound waves were
passed through the effluent using a sonicator.
The batches were taken after every 38 minutes after each 38-min. time interval a 5-ml sample
was taken from the beaker.
The irradiation time was 30 min. Similarly, 4 samples were taken i.e. total time required was 2
hr. and 32 min. the sample was under sonicator. After 4 samples were collected they were sent
for COD testing.
Fig 4.1: - Sonicator
19
4.3.1 Chemical Oxygen Demand (COD)
REAGENTS:
Standard Potassium dichromate (K2Cr2O7) digestion solution, 0.25M: -Dissolve about 12.259
grams of K2Cr2O7 in 100 ml distilled water and fill it in 1000 ml volumetric flask and dilute it
to 1000 ml by using distilled water.
Standard ferrous ammonium sulfate titrant (FAS), approximately 0.10M: -Dissolve 39.2 g Fe
(NH4)2(SO4)2.6H2O in distilled water. Add 20 mL conc.H2SO4, cool, and dilute to 1000 ml.
PROCEDURE:
Place sample (2 to 5 ml) in digester tube and Add K2Cr2O7 digestion solution (10 ml).
Carefully add sulphuric acid (20 ml) to the solution very carefully as the solution may tend to
bump
Place tubes in block digester preheated to 150C and reflux for 2 h behind a protective shield.
Cool to room temperature and place vessels in test tube rack. Some mercuric sulfate may
precipitate out but this will not affect the analysis.
Add 1 to 2 drops of Ferroin indicator and stir rapidly on magnetic stirrer while titrating with
standardized 0.10 M FAS.
The end point is a sharp color change from blue-green to reddish brown, although the blue
green may reappear within minutes.
In the same manner reflux and titrate a blank containing the reagents and a volume of distilled
water equal to that of the sample
Formulae to calculate COD
20
Fig 4.2: - COD Digester.
4.3.1.1 COD Digester:
COD Digester is the most accepted Thermo-reactor for Determination of Chemical

Oxygen Demand in Various Substances. Chemical Oxygen Demand (COD) is a Measure of
the Capacity of Water to Consume Oxygen during the Decomposition of Organic Matter and
the Oxidation of Inorganic Chemicals such as Ammonia and Nitrite. COD Measurements are
commonly made on Samples of Waste Waters or of Natural Waters Contaminated by Domestic
or Industrial Wastes. Chemical Oxygen Demand is measured as a Standardized Laboratory
assay in which a closed Water Sample is incubated with a Strong Chemical Oxidant under
Specific Conditions of Temperature and for a Particular Period of Time. COD Digester is
specially designed as per IS & ASTM standard suitable for 15 tubes or 24 tubes. COD digester
is used for chemical oxygen demand method for monitoring waste water influent and industrial
process water.
21
4.3.2 Ozonation Using a Ozonator.
Take 100 ml of waste water sample.

Set the time on ozonator to 10 min.
Dip the upper knob in the water sample.
After 10 minutes take 3 ml sample and repeat same for 1 hr.
Repeat same for 30 minutes.
Fig 4.3: - Ozonator.
4.3.3 Fentons reagent.
Take 100 ml waste water sample.

Put 1 g of FeSO4 and 2 g of H2O2 (0.5 ratio)
Now stir the sample for 30 minutes and take 3 ml of treated sample out.
Take the next samples after each 30 minute until 4 samples are collected.
Sent it to COD test.
Repeat the procedure for different ratios of FeSO4/H2O2.
22
4.3.4 Combination of Cavitation and Ozonation.
Take 100 ml of waste water sample.

Set the time on ozonator to 30 min.
Dip the upper knob in the water sample.
Now place the beaker under the sonicator for cavitating and ozonating at the same time.
After 30 minutes take 3 ml sample and repeat same for 1 hr.
Repeat same for 10 minutes.
4.3.5 Combination of Cavitation and Fentons reagent.
Take 100 ml waste water sample.

Put 1 g of FeSO4 and 2 g of H2O2 (0.5 ratio)
Now stir the sample for 30 minutes and take 3 ml of treated sample out.
At the same time put the beaker under the sonicator.
Take the next samples after each 30 minute until 4 samples are collected.
Sent it to COD test.
Repeat the procedure for different ratios of FeSO4/H2O2.
23
CHAPTER- 5
RESULTS AND DISCUSSION
24
5. Results and Discussion
5.1 Analysis based on cavitation alone

For 90 Watts
Temperature range: - 480c 540c
Time Vol Power Burette reading COD

Sr. No (min) (ml) (watts) (ml) (ppm) % Degradation
1 30 3 90 24.3 1880 30.88

2 60 3 90 24.4 1840 32.35
3 90 3 90 24.6 1760 35.29
4 120 3 90 24.8 1680 38.23
Table 5.1- Degradation at Power 90 watt by Sonolisis alone
90 watts
45
38.23
40
35.29
35 32.35
30.88
30
% Degradation
25
20
15
10
5
0
30 60 90 120
Time (min)
Fig 5.1- %Degradation for 90 watts
25
For 100 Watts

Time Volume Power Burette reading COD

1 30 3 100 23.2 2320 14.7

2 60 3 100 23.3 2280 16.17
3 90 3 100 23.5 2200 19.11
4 120 3 100 23.9 2040 25
100 watts
30
25
25
19.11
% Degradation
20
16.17
14.7
15
10
0
30 60 90 120
Time (min)
Fig 5.2- % Degradation for 100 watts
26
For 110 Watts

Time Vol Power Burette reading COD

1 30 3 120 23.5 2200 19.11

2 60 3 120 23.7 2120 22.05
3 90 3 120 23.9 2040 25
4 120 3 120 24.2 1920 29.41
110 watts
35
29.41
30
25
25 22.05
% Degradation
19.11
20
15
10
0
30 60 90 120
Time (min)
Fig 5.3- %Degradation for 110 watts
27
Comparison: -
Time vs % Degradation
45
38.23
40 35.29
35 30.88 32.35
29.41
30
% Degradation
25
25 22.05
19.11 25
20
15 19.11
16.17
10 14.7
5
0
30 60 90 120
Time (min)
90 watts 100 watts 110 watts
Fig 5.4- % Degradation at different powers
DISCUSSION
The graph shows a comparative study between cavitation at different powers.
The graph also shows that maximum % degradation is obtained at 90 watts.
With variable time and constant power, degradation goes on increasing but, rate of
degradation goes on decreasing.
28
5.2 Analysis based on ozonation alone

For 1 hour
Time interval: 10 minutes.
Flow rate: 400 mg/hr.
Time B. R COD
Sr. NO % Degradation
(ml) (ml) (ppm)
1 10 22.9 1626.66 40.13
2 20 23.2 1546.66 43.13
3 30 23.5 1466.66 46.07
4 40 23.8 1386.66 49.01
5 50 23.9 1360 50
6 60 24.1 1306 51.98
Table 5.4: - % Degradation by ozonation for 1 hour.
1 hour
60
50 51.98
49.01
50 46.07
43.13
40.13
% Degradation
40
30
20
10
0
10 20 30 40 50 60
Time (min)
Series 1
Fig 5.5: - % Degradation by ozonation for 1 hour.
29
For 2 hour
Time interval 30 minutes
Time B. R COD
(min) (ml) (ppm)
1 30 22.7 1680 38.23
2 60 23.4 1493.3 45.09
3 90 23.9 1360 50
4 120 24.6 1173.3 56.86
2 hour
60 56.86
50
50 45.09
38.23
% Degradation
40
30
20
10
0
30 60 90 120
Time (min)
Series 2
30
Ozonation for 3 Hour

Time interval: 30 min
Time B. R COD
(min) (ml) (ppm)
1 30 23.3 1520 44.11
2 60 23.8 1386.7 49.01
3 90 24.1 1306.7 51.96
4 120 24.5 1200 55.88
5 150 24.9 1093.3 59.8
6 180 25.4 960 64.7
3 Hour
70 64.7
59.88
60 55.88
51.96
49.01
50 44.11
% Degradation
40
30
20
10
0
30 60 90 120 150 180
Time (min)
31
5.3 Analysis based on Cavitation with Ozonation

Power: 90 watts
Time interval: 30 min
Time B. R COD
(min) (ml) (ppm)
1 15 22.3 1786.7 34.11
2 30 23.3 1520 44.11
3 60 24 1333.3 50.98
4 90 25.2 1013.3 62.7
5 120 25.9 826.66 69.7
Table 5.7: - % Degradation by cavitation with ozonation.
Combination of cavitation and ozonation
80
69.7
70 62.7
60
50.98
% Degradation
50 44.11
40 34.11
30
20
10
0
15 30 60 90 120
Time (min)
Fig 5.8: - % Degradation by cavitation with ozonation.
32
5.4 Analysis based on Fentons reagent alone
For Fe2+/H2O2 ratio to be 0.33
FeSO4: - 1 gram
H2O2: - 3 grams
Time Vol Burette reading COD

Sr. No (min) (ml) Fe2+/H2O2 (ml) (ppm) % Degradation
1 30 3 0.33 20.8 2186 19.6

2 60 3 0.33 21.9 1893.33 30.39
3 90 3 0.33 23.5 1466.66 46.07
4 120 3 0.33 23.8 1386.667 49.01
Table 5.8: - % Degradation by Fenton at 0.33 ratio.
Fe2+/H2O2 ratio to be 0.33

60
50.98
50 46.07
% Degradation
40
30.39
30
19.6
20
10
0
30 60 Time (min) 90 120
Fig 5.9: - % Degradation by Fenton at 0.33 ratio.
33

Power: 90 watts
FeSO4: 1 gram
H2O2: 2 grams

1 30 3 0.5 21.9 1893.33 43

2 60 3 0.5 23.1 1573.33 46
3 90 3 0.5 23.7 1413.33 47
4 120 3 0.5 24.2 1280 50.98

60
50.98
50 46 47
43
40
% Degradation
30
20
10
0
30 60 90 120
Time (min)
34
FeSO4: - 1 gram
H2O2: - 10 grams
Time Vol Burette

2+
Sr. No (min) (ml) Fe /H2O2 reading (ml) COD (ppm) % Degradation
1 30 3 0.1 21.9 1876.8 31

2 60 3 0.1 22.1 1822.4 33
3 90 3 0.1 22.8 1653.216 39.22
4 120 3 0.1 23.1 1550.4 43

50
43
45
39.22
40
33
35 31
% Degradation
30
25
20
15
10
5
0
30 60 90 120
Time (min)
35
5.5 Analysis based on Cavitation with Fentons reagent

Power: 90 watts
FeSO4: 1 gram
H2O2: 2 grams

1 30 3 0.5 21.9 1893.33 30.39

2 60 3 0.5 23.1 1573.33 42.15
3 90 3 0.5 23.7 1413.33 48.03
4 120 3 0.5 24.2 1280 52.94
Table 5.11: - % Degradation by Cavitation with Fentons reagent.
Combination of Cavitation and Fenton's Reagent

60
52.94
48.03
50
42.15
40
% Degradation
30.39
30
20
10
0
30 60 90 120
Time (min)
Fig 5.12: - % Degradation by Cavitation with Fentons reagent.
36
5.6 Combined results for all systems:
80
69.7
70 62.7
60 56.86
50.98 50
% Degradation
50 44.11 52.94 90 watts

45.09
48.03
40 38.23 Ozonation
42.15
30.88 38.23
30 35.29 Fentons
30.39 32.35 Reagent
cavitation with
20
ozonation
cavitation with
10 fenton
0
30 60 90 120
Time (min)
Fig 5.13: - % Comparison of all methods.
DISCUSSION
From above graph, it is clear that Cavitation with Ozonation is the best method for
waste water treatment.
Also, Ozonation gives the best results when used alone.
37
CHAPTER- 6
CONCLUSIONS AND FUTURE WORKS
38
6.1 Conclusions: -
Firstly, it was observed that with the increase in time, degradation increases.
Then it was found that the rate of degradation is much faster in first 30 min and gradually
decreases with the increase in time.
Increase in power also causes increase in average degradation in cavitation.
Combination of AOPs like Ozonation and Fentons Reagent with cavitation increases the
extent of degradation up to 69%.
Combination of ozonation and cavitation is the most feasible way to treat the water.
6.2 Future Works
Combination of Cavitation and Fentons reagent and also with ozonation for water treatment.
Study on different other parameters like BOD, TDS, TOC etc.
Effect of different frequencies of sound.
39
REFERENCES
1. Kumar et al., J Chem Eng Process Technol 2014, 5:3

http://dx.doi.org/10.4172/21577048.1000193
2. Environmental Protection Agency (EPA). Hydrodynamic Cavitation Oxidation Destroys

Organics. Development in innovative ground water treatment. 1994 (USA).
3. S.K. Khanal, D. Grewell, S. Sung, J. Van Leeuwen, Ultrasound applications in wastewater

sludge pretreatment: a review, Crit. Rev. Environ. Sci. Technol. 37(2007) 277313.
4. Moholkar, V.S. & Pandit, A.B., Bubble behaviour in hydrodynamic cavitation: Effect of
turbulence. AIChE Journal. 43 (6), pp. 1641-1648, 1997
5. Weissler, A., Ultrasonic in chemistry. J Chem Educ, pp. 28-30, 1948.
6. Hammitt, Frederick G., Cavitation and multiphase flow phenomena.McGraw-Hill, USA,

1980.
7. TECHCOMMENTARY: Advanced Oxidation Processes for Treatment of Industrial

Wastewater. An EPRI Community Environmental Center Publ. No. 1, 1996.
8. Parag R.Gogate*, Aniruddha B.Pandit, Advances in Environmental Research 8 (2004) 501

551, 4 April 2003.
9. Shutilov, V.A. Fundamental Physics of Ultrasound; Gordon & Breach Science Publishers:
New Cork, 1988.
10. Gottschalk, C., Libra, J. A. & Saupe, A. Ozonation of Water and Waste Water.
WileyVCH,2000.
11. Gogate, R. Parag, Aniruddha, B., Pandit, A.B., Cavitation Reactors: Efficiency analysis using
a model reaction. AIChE Journal. 47, pp. 2526-2537, 2001.
40
12. Moholkar, V.S. & Pandit, A.B., Bubble behaviour in hydrodynamic cavitation: Effect of
turbulence. AIChE Journal. 43 (6), pp. 1641-1648,1997.
13. Karpel Vel Leitner, N., Delanoe, F., Acedo, B., Papillault, F. & Legube, B. Catalytic
ozonation of succinic acid in aqueous solution: A kinetic approach. In Proc. Int. Reg. Conf.
Ozonation and AOPs in Water Treatm., September 2325, 1998, Poitiers, France.
14. N. Sarkar, S.K. Ghosh, S. Bannerjee, K. Aikat, Bioethanol production from

agricultural wastes: an overview, Renewable Energy 37 (2012) 1927.
15. D. Gottlieb, E. Vigoda-gadot, A. Haim, M. Kissinger, The ecological footprint as

an educational tool for sustainability: a case study analysis in an Israeli public
high school, Int. J. Educ. Dev. 32 (2012) 193200.
41

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USE OF CAVITATIONAL REACTOR FOR WASTE WATER TREATMENT

Cavitation is the phenomena of the formation, growth and collapse of microbubbles or

1.3 Types of Cavitation

1.3.1 Acoustic Cavitation

Advantages of Acoustic Cavitation.

It increases the rate of reaction up to a million times.

Disadvantages of Acoustic Cavitation.

1.3.2 Hydrodynamic Cavitation.

Advantages of Hydrodynamic Cavitation.

A greener technology that does not necessarily need additional chemicals.

Can be coupled with other AOPs, if required.

Bulk temperature is ambient, bulk pressure is in range of 3-atm.

Enhances performance of existing effluent treatment facility (improves efficiency of aerobic

1.3.3 Optic Cavitation.

1.3.4 Particle Cavitation.

Industrial Wastewater Treatment Using Hydrodynamic Cavitation and

Heterogeneous Advanced Fenton Processing

A combination of hydrodynamic cavitation and heterogeneous Advanced Fenton

Acoustic cavitation and its chemical consequences

Physical and Chemical Effects of Acoustic Cavitation in Selected Ultrasonic

ADVANCED OXIDATION PROCESS

3. Advanced Oxidation Processes

Fig 3.1: -AOPs for waste water treatment

Advantages and Disadvantages.

The performance of ozonation relies on achieving the desired concentration after a

3.2 Fentons Reagent

Iron(II) is oxidized by hydrogen peroxide to iron(III), forming a hydroxyl radical and

Fe2+ + H2O2 Fe3+ + HO + OH

Fe3+ + H2O2 Fe2+ + HOO + H

3.3 Process of H2O2 Oxidation:

H2O2 + H2O HO2- + H3O+

MATERIALS, METHODS AND PROCEDURE

4. Materials, Method and Procedure

4.1 Characteristics of Industrial wastewater:

4.2 Experimental setup:

Programmable Timer: 10 hours

Adjustable Pulse On/Off: 1 second to 1 minute

Dimensions (W x L x H): 8 x 5.25 x 8.5 in. (203 x 387 x 216 mm).

Also, COD digester was used with following specifications: -

Hole Size: 40 mm dia. x 80 mm depth

4.3 Experimental Methodology

Method 1: - In this method only cavitation has been used.

Fig 4.1: - Sonicator

4.3.1 Chemical Oxygen Demand (COD)

Formulae to calculate COD

Fig 4.2: - COD Digester.

4.3.1.1 COD Digester:

COD Digester is the most accepted Thermo-reactor for Determination of Chemical

4.3.2 Ozonation Using a Ozonator.

Take 100 ml of waste water sample.

Fig 4.3: - Ozonator.

4.3.3 Fentons reagent.

Take 100 ml waste water sample.

4.3.4 Combination of Cavitation and Ozonation.

Take 100 ml of waste water sample.

4.3.5 Combination of Cavitation and Fentons reagent.

Take 100 ml waste water sample.

RESULTS AND DISCUSSION

5. Results and Discussion

5.1 Analysis based on cavitation alone

Time Vol Power Burette reading COD

1 30 3 90 24.3 1880 30.88

Table 5.1- Degradation at Power 90 watt by Sonolisis alone

Fig 5.1- %Degradation for 90 watts