Treatment of match box industry

TREATMENT OF MATCH BOX INDUSTRY
WASTEWATER BY SOLAR PHOTO- FENTON
PROCESS
A PROJECT REPORT
Submitted by
MAHESHKUMAR.K
RAVIKUMAR.R
SARAVANAKUMAR.P
SUNDARAMOORTHY.G
In partial fulfilment for the award of the degree
of
BACHELOR OF ENGINEERING
IN
CIVIL ENGINEERING
S.VEERASAMY CHETTIAR
COLLEGE OF ENGINEERING AND TECHNOLOGY
PULIYANGUDI
ANNA UNIVERSITY: CHENNAI 600 025
APRIL-2017

ANNA UNIVERSITY: CHENNAI 600 025
BONAFIDE CERTIFICATE
Certified that this project report “TREATMENT OF MATCH BOX
INDUSTRY WASTEWATER BY SOLAR PHOTO- FENTON PROCESS”
is the bonafide work of MAHESHKUMAR.K (952613103017) who carried out
the project work under my supervision. Certified further, that to the best of my
knowledge the work reported here in does form part of any other report or
dissertation on the basis of which a degree or award was conferred on an earlier
occasion on this or any other candidate.
SIGNATURE SIGNATURE
Prof.M.ESAKIMUTHU.ME. (PhD) Mr.A.SHANMUGASUNDARAM.ME,
HEAD OF THE DEPARTMENT PROJECT GUIDE
Civil Engineering Department Civil Engineering Department
S.Veerasamy Chettiar College S.Veerasamy Chettiar College
of Engineering and Technology of Engineering and Technology
Puliyangudi. Puliyangudi.
This is certifying that is bonafide record of work done by the above student
in CE6811- PROJECT WORK, during the academic year 2016-2017.
Submitted for the University Examination held on 10.04.2017.
INTERNAL EXAMINER EXTERNAL EXAMINER

ACKNOWLEDGEMENT
Our special and sincere thanks to our honourable Chairman
Dr.V.MURUGAIAH.D.Litt., who give us full support.
We express our deep sense of gratitude and sincere thanks to our respected
Principal Prof.Dr.V.SRINIVASARAGAVAN.ME. PhD. forgive us permission
to do this project work.
We highly thank to Prof. M.ESAKIMUTHU.M.E. (PhD), Head of the
Department of Civil Engineering For his guidance, Encouragement and providing
the needs for a successful completion of our project work.
Our special thanks to Mr.A.SHANMUGASUNDARAM.M.E, Our
project guide for his guidance throughout the project work.
At least, we wish our gratitude to all other teaching and non-teaching staff
members of Civil Engineering and to our friends who are all helped us to
complete this project work successfully.

ABSTRACT
The rapid increase in population and the increased demand for
industrial establishments to meet human requirements have created problems
such as overexploitation of available resources, leading to pollution of land, air
and water requirements. The wood and wood production of the match stick
products generate a considerable amount of pollutants characterized by
biochemical oxygen demand (BOD), chemical oxygen demand (COD),
suspended solids (SS), toxicity and colour when untreated or poorly treated waste
water are discharged to receiving waters. This match box industry wastewater and
performance of available treatment processes. Comparisons of all treatment
processes are presented. Colour can be removed effectively by coagulation,
chemical oxidation and ozonation. The suspended solids are removed by primary
treatment such as sedimentation. By comparing all the treatment processes, solar
photo-Fenton process is more efficient and economical among advanced
oxidation processes. In this study, the efficiency of solar photo-Fenton process
for the treatment of match box industry wastewater was evaluated and the
removal of colour and COD were investigated. The experiment is conducted in a
lab scale solar photo-Fenton reactor of capacity seven litters which are exposed
to the sunlight with the irradiation time of one hour. . The maximum removal
efficiencies of COD and colour removal was 94% and 100% respectively under
optimal conditions (Fe2+
= 1g/L, H2O2= 35ml/L and pH=5). The rate of
degradation of solar/Fe2+
/ H2O2 was three times faster than solar/Fe2+
. The solar
photo-Fenton process is the biological Treatment is an effective treatment method
there by reducing the cost of the treatment.

TABLE OF CONTENTS
CHAPTER TITLE PAGE
ACKNOWLEDGEMENT iii
ABSTRACT iv
LIST OF TABLES vii
LIST OF FIGURES xi
LIST OF SYMBOLS AND ABBREVIATIONS xv
1. INTRODUCTION 1
1.1 GENERAL 1
1.2 PROCESS DESCRIPTION 2
1.3 SOURCES OF POLLUTION 6
1.4 WASTE WATER CHARACTERISTICS 7
1.5 EFFECTS OF THE MATCH BOX INDUSTRY
WASTEWATER ON THE ENVIRONMENT 8
1.6 NEED FOR THE STUDY 9
2. REVIEW OF THE LITERATURE 11
2.1 GENERAL 11
2.2 LITERATURE SURVEY FOR TREATMENT
OF WASTE WATER 11
3. MATERIALS AND METHODS 33
3.1 GENERAL 33
3.2 COLLECTIONAND CHARACTERIZATION OF
WASTEWATER 33
3.3 MATERIALS 36
3.4 EXPERIMENTAL METHODS 36
3.5 EFFECT OF OPERATING PARAMETERS 37
3.5.1 Effect of pH 37

3.5.2 Effect of Fe2+
concentration 38
3.5.3 Effect of H2O2 concentration 38
3.5.4 Effect of liquid depth 39
3.5.5 Effect of biodegradability 39
4. RESULTS AND DISCUSSION 40
4.1 GENERAL 40
4.2 CHARACTERIZATION OF MATCH BOX
INDUSTRY WASTEWATER 40
4.3 EFFECT OF OPERATING PARAMETERS 41
4.3.1 Effect of pH 41
4.3.1.1 Effect of pH on turbidity 41
4.3.2 Effect of pH on COD removal 46
4.3.3 Effect of time 51
4.3.3.1 Effect of time on turbidity 51
4.3.3.2 Effect of time on COD removal 56
4.3.4 Effect of Dosage of concentration on
Turbidity and COD removal 60
4.3.4.1 Effect of Fe2+
concentration 60
4.3.4.2 Effect of H2O2 concentration 66
4.3.5 Effect of liquid depth 73
5. SUMMARY AND CONCLUSION 75
5.1 GENERAL 75
5.2 SUMMARY 75
5.3 CONCLUSION 76
REFERENCES 77

LIST OF TABLES
TABLE TITLE PAGE
1.1 The wastewater general characteristics 8
3.1 Analysis methods for the treatment of match box
Wastewater 34
4.1 Initial characteristics of match box industry
Wastewater 40
4.2 Effect of pH on turbidity day-1 41
4.9 Effect of pH on COD removal day-1 46

4.16 Effect of time on turbidity day-1 51
4.23 Effect of time COD removal day-1 56
4.30 Effect of Dosage of concentrationFe2+
on
Turbidity and COD removal day-1 61
on
on

on
on
Turbidity ad COD removal day-5 64
on
on
4.37 Effect of Dosage of concentration H2O2on

4.44 Effect of liquid depth on COD removal 73

LIST OF FIGURES
FIGURE TITLE PAGE
3.1 Schematic methodology of solar photo-Fenton
Process 35
3.2 solar photo-Fenton reactors 37

4.29 Effect of Dosage of concentration Fe2+
on
on
on

on
on
on
on
4.36 Effect of Dosage of concentration H2O2
Turbidity and COD Removal day-1 67

4.43 Effect of liquid depth on COD removal 74

LIST OF SYMBOLS AND ABBREVIATIONS
AC - Anaerobic Contact
AF - Anaerobic Filter
AOX - Absorbable Organic Halides
ASB - Aerated Stabilization Basin
BAT - Best Available Technology
BKM - Bleached Kraft Mill
BOD - Biochemical Oxygen
COD - Chemical Oxygen Demand
CTMP - Chemi-Thermo Mechanical Pulping
CWO - Catalytic Wet Oxidation
DSFF - Down flow Stationary Fixed Film
EGS - Expanded Granular Sludge Blanket
FB - Fluidized Bed
FSB - Facultative Stabilization Basin
HRT - Hydraulic Retention Time
N - Nitrogen
NF - Nano Filtration
P - Phosphorus
PAC - Poly Aluminium Chloride
PACT - Powdered Activated Carbon
PEO - Poly Ethylene Oxide
SCWO - Super Critical Wet Oxidation
SRT - Solids Retention Time
SS - Suspended solids

TS - Total Solids
UASB - Up flow Anaerobic Sludge Blanket
UF - Ultra filtration
VLR - Volumetric Loading Rate
WAO - Wet Air Oxidation

CHAPTER 1
INTRODUTION
1.1 GENERAL
Nowadays, one of the major problems facing industrialized nations
is contamination of the environment by hazardous chemicals. Among the
industries involved are petroleum refining, organic chemicals and synthetic
industries, milling and coal conversion, pulp and paper manufacturing and textile
processing industries. Even the use of fuel for heating and transportation, the use
of agricultural and domestic pesticides, insecticides, detergents and aerosol
sprays have contributed to this ever-growing problem. The large number of
publications reporting its effects and damages to human health, animals and the
environment.
Match box industry demands a large amount of process Water and
generates large Quantities of wastewater. Characteristics of the effluent consist
of large amounts of suspended solids, nitrogen in several chemical forms and oils,
phosphorus, chlorides. Contamination of soil, ground water, surface water and air
with hazardous and toxic chemicals is one of the major problems faced by the
industrialised world today. There is still a need for advanced techniques to
remove these pollutants. The need to remediate contaminated areas has led to the
development of new technologies that emphasise the destruction of pollutants
rather than the conventional approach to disposal. Advances in technology have
resulted in greater water demands for industry. The volume of wastewater from
the industries has increased, and needs treatment. This wastewater contains a
variety of suspended solids, oils, metals, and organics. The successful cleaning
of these new wastewaters prior to discharge, using existing treatments, has yet to
be improved comparatively. The Solar Photo-Fenton process has proved to be
rather effective in the degradation and mineralization of single organic toxicants
and the mixtures of various organic wastes. Many studies have shown that the

effectiveness of the Solar Photo-Fenton process in waste treatment depends on
the initial concentrations of H2O2 and Fe (III), their ratios, the initial pH, and
reaction temperature. The COD removal rate is higher with the solar photo-
Fenton process.
Three processes are investigated in this study:
Photo-Fenton process (H2O2/Fe+2
/UV): This process involves the
hydroxyl radical (OH) formation in the reaction mixture through photolysis of
hydrogen peroxide (H2O2/UV) and Fenton reaction (H2O2/Fe+2
).
1.2 PROCESS DESCRIBTION
There are two main types of matches:
Safety matches:
Which can only produce fire when struck against the specially
prepared surface on the match box.
Strike-anywhere matches:
Which can produce fire when struck against any frictional surface.
Being the commoner type and the cheaper to produce, the first type will be
discussed here.
Now, let’s look at the steps involved in starting a match stick
production company.

MATCH BOX PRODUCTION
The manufacturing process was developed soon after the invention
of the match.
The process:
Safety matches manufactured in the country are of the standard type
with wooden veneer or cardboard boxes and wooden splints. Most of the raw
materials are the same regardless of the level of production, but the process is
slightly different in the mechanized and hand-made sector.
Raw materials:
The major raw materials used in the production of safety matches are
soft wood used to make the match sticks (also known as “splints”) and boxes and
chemicals for the match head and friction surface of the boxes. With the exception
of sulphur, all the basic raw materials are produced within India. A number of
Indian trees found suitable for use in the match industry like;
1. Semul (bombax ceiba, known as Indian cotton wood) is good for boxes as
well as splints
2. White mutty (ailanthus malabarica) suitable for high quality splints
3. Indian aspen (evodia roxburghina) from plantations in Kerala is now being
used
The manufacturing process:
Matches are manufactured in several stages. In the case of wooden-
stick matches, the matchsticks are first cut, prepared, and move to a storage area.

When the matchsticks are needed, they are inserted into hole in a long perforated
belt. The belt carries them through the rest of process, where they are dipped into
several chemical tanks, dried, and packaged in boxes. Cardboard-stick matches
used in match books are processed similar manner.
Here is a typical sequence of operation for manufacturing wooden-sticks
matches:
Cutting the matchsticks:
1. Logs of white pine or aspen are clamped in a debarking machine and slowly
rotated while spinning blades cut away the outer bark of the tree.
2. The stripped logs are then cut into short length about 1.6 ft (0.5m) long.
Each length is placed in a peeler a long, thin sheet of wood from the outer
surface of the log. This sheet is about 0.1 in (2.5mm) thick and is a called
veneer. The peeling blade move inward toward the core of the rotating log
until only a small, round post is left. This post is discarded and may be used
for fuel or reduced to wood chips for use in making paper and chip board.
3. The sheets of veneer are stacked and fed into a chopper. The chopper has
many sharp blades that cut down through the stack to produce as many as
1000 matchstick in a single stroke.
Treating the matchstick:
1. The matchsticks are dumped into a large vat filled with a dilute solution of
ammonium phosphate.
2. After they have soaked for several minutes, the matchstick are removed
from the vat and placed in a large, rotating drum, like a clothes dryer. The

dumpling action inside the drum dries the sticks and act to polish and clean
them of any splinters or crystallized chemical.
3. The dried sticks are then dumped in to a hopper and blown through a metal
duct to the storage area. In some operations the sticks are blown directly
into the matchmaking facility rather than going to storage.
Forming the match heads:
1. The sticks are blown from the storage area to a conveyer belt that transfers
them to be inserted into hole on a long, continuous, perforated steel belt.
The sticks are dumped into several V-shape feed hoppers that line them up
with the hole in the perforated belt. Plungers push the matchsticks into the
holes across the width of the slowly moving belt. A typical belt may have
5.-100 holes spaced across its width. Any sticks that do not seat firmly into
the holes fall to a catch area beneath the belt and are transferred back to the
feed hoppers.
2. The perforated belt holds the matchsticks upside down and immerses the
lower portion of the sticks in a bath of hot paraffin wax. After they emerge
from the wax, the sticks allowed to dry.
3. Further down the line, the matchsticks are positioned over a tray filled with
a liquid solution of the matchstick head chemicals. The tray is then
momentarily raised to immerse the ends of the stick in the solution. Several
thousand stick are coated at the same time. This cycle repeats itself when
the next batch of sticks is in position. If the matches are the strike –
anywhere kind, the stick move on to another tray filled with a solution of
the tip chemical, and the match ends are immersed in that tray, only this
time not quite as deeply. This gives strike-anywhere matches their
characteristics two-toned appearance.

4. After the match heads are coated, the matches must be dried very slowly
or they will not light properly. The belt loops up and down several times
as the matches dry for 50-60 minutes.
Quality control:
The chemicals for each portion of the match head are weighted and
measured exactly to avoid any variation in the match composition that might
affect performance. Operators constantly monitor the operation and visually
inspect the product at all stages of manufacture. In addition to visual inspection
and other normal quality control procedure, match production requires strict
attention to safety. Considering that there may be more than one million matches
attached to the perforated belt at any time means that the working environment
must be kept free of all sources of accidental ignition.
1.3 SOURCES OF POLLUTION
The match box industry is one of the largest and most polluting
industries in the world. In fire sticks processing and subsequent red phosphorus
is done using large quantity of water and they are discharged as effluent. The
most significant sources of pollution are chemical preparation, Wooden sticks,
match boxes and match books are made from cardboard, ammonium phosphate,
phosphorus sesquisuifide and potassium chlorate, non-toxic chemicals, powdered
glass, animal glue, zinc oxide, paraffin wax, antimony trisulphide, inert fillers,
water soluble, red phosphorus, white phosphorus, gum Arabic or urea
formaldehyde, chemical cream mixing, cream mix washing, washing, mixing
machine and coating operations. Among the processes, Match Company
generates high strength Wastewater especially by chemical mix. Industrial
effluent from Match Company contains several toxic and non-biodegradable

organic materials, which include sulfur compounds, chemicals, chloride and red
phosphorus. Match Company is normal water users. Their consumption of fresh
water can seriously harm habitat near mills, reduce water levels necessary for
fish, and alter water temperature, affect the ground water recharge, bad smell
produced on air, affect the soil and human body health, a critical environmental
factor for fish. They also increase the amount of phosphorus substances in the
water, causing death to the zoo plankton and fish, as well as profoundly affecting
the terrestrial ecosystem.
1.4 WASTEWATER CHARACTERISTICS
The characteristics of the waste water generated from various processes of
the match box industry depend upon the type of the process, type of the chemical
materials, process technology applied, management practices, internal circulation
of the effluent for recovery, and the amount of water to be used in the particular
process. Considering the legislation of wastewater purification, total suspended
solids (TSS), organic matter, total nitrogen and phosphorus must be removed
from the match box industry. The wastewater contained high amounts of oil &
grease. Therefore, the oil & grease were pre-treated by the lamella separator
before the biological treatment. Composition of the wastewater used in this study
was analyzed before the experimental studies. Samples are characterized before
the experiments to obtain their chemical and physical properties. This wastewater
is characterized with a low organic load and a low biodegradability index
(BOD5/COD) which means that this wastewater is difficult to be degraded by the
traditional treatment such as the biological treatment. On the other hand, the
wastewater contained a large amount of suspended solids which can be easily
removed by filtration. Previous work showed that changes in pH and temperature
did not increase the amount of solids removed by filtration. The general

characteristics of wastewater produced are given below. Table 1.1 shows the
wastewater general characteristics.
Parameter Values
pH 3
COD (mg/L) 70400 mg/L
Turbidity 101NTU
Colour Brown
Total solids (mg/L) 10000 mg/L
Total suspended solids ( mg/L) 7500 mg/L
Total dissolved solids (mg/L) 2500 mg/L
Total fixed solids(mg/L) 5000 mg/L
Total volatile solids(mg/L) 5000 mg/L
Table 1.1 shows the wastewater general characteristics.
The untreated wastewater cannot be discharged to the environment
with the above characteristics. Therefore the wastewater has to be treated to bring
down the value to the permissible limits according to MINAS disposal limits.
1.5 EFFECTS OF THE MATCH BOX INDUSTRY WASTEWATER ON
THE ENVIRONMENT
The pollutants discharged from the match box industry affect all
aspects of the environment such as water, air and land. Various authors reported

the appearance of toxic effects on various species due to exposure of match box
industry effluents. The toxic effects on various fish species are respiratory stress,
mixed function oxygenise activity, toxicity and
Mutagen city, liver damage, or geotaxis effects, and lethal effects. Discharging
untreated wastewater causes slime growth, thermal impacts, scum formation,
colour problems and loss of aesthetic beauty in the environment. They also
increase the toxic substances in the water. The untreated wastewater affects health
and causes diarrheal, vomiting, headaches, nausea, and eye irritation on children
and workers. The studies found marked increases in inorganic and organic forms
of nitrogen and red phosphorus in the soil, soil bulk density had decreased, and
the soil had higher rates of respiration and more earthworms. Therefore nitrogen
and red phosphorus either accumulated in the soil or was lost to groundwater. The
concentration of dissolved inorganic phosphorus in soil water increased. It was
noted that the microbial biomass (i.e. worms) had increased in comparison to the
non-irrigated soils and that this has been seen previously to increase both
infiltration and fine pores. However, adverse changes to soil structural properties
(such as porosity) and infiltration rate, downstream contamination of streams and
groundwater. Treated wastewater, on the other hand, contains fewer nutrients
resulting in a lower risk of ground and surface water contamination, but still has
a risk associated with the relatively high content of sodium, even after treatment
of wastewater.
1.6 NEED FOR THE STUDY
Generation of wastewaters in industrial processes is sometimes
unavoidable and in most cases a process to reduce the organic load and other
contaminants must be employed before water discharge. The effluent is collected
from the collection tank. Then it is fed into the primary clarifier where alum, lime
to precipitate the sulphur compounds as CaSO4.Then it enters the equalization

tank and before it enters into the biological treatment, it is supplied with the
nutrients. In the activated sludge process, the bacteria employed are Pseudomonas
Aerobatic and Bacillus. Then it enters the secondary clarifier and the treated
effluent is taken out and the sludge is passed into drying beds. To remove part of
the organic load, biological processes are usually used, because they are more
economical than chemical processes. In some cases, due to high organic load,
toxicity or presence of bio recalcitrant compounds, biological processes cannot
be used, since chemical oxygen demand (COD) removal cannot be achieved by
biological process. Biological processes do not effectively decolorize the
wastewater. Most of the compounds are refractory compounds-toxic to organisms
used for treatment. Detention time is more and supply of nutrient is necessary.
Biodegradation is less. To increase the efficiency of the process, there is a need
for the advanced treatment. The solar Photo-Fenton process is one of the
techniques which are called “Advanced Oxidation Processes (AOP’s)”.These
processes can completely degrade the organic pollutants into harmless inorganic
substances such as CO2 and H2O under moderate conditions. The AOPs are
characterized by the production of ˙OH radicals which are an extraordinary
reactive species and capable of mineralizing organic pollutants. The solar Photo-
Fenton process has proved to be rather effective in degradation and mineralization
of organic pollutants. Previously to increase both infiltration and fine pores.
However, adverse changes to soil structural properties (such as porosity) and
infiltration rate, downstream contamination of streams and groundwater. Treated
wastewater, on the other hand, contains fewer nutrients resulting in a lower risk
of ground and surface water contamination, but still has a risk associated with the
relatively high content of sodium, even after treatment of wastewater.

CHAPTER 2
REVIEW OF LITERATURE
2.1 GENERAL
The increasing industrialization and its effluent discharges have
accentuated the environmental problems to a large extent. Besides many other
industries, the match box industries are also responsible for creating major water
pollution. Various treatment processes are used for treating the waste water from
match box industry.
2.2 LITERATURE SURVEY FOR TREATMENT OF WASTE WATER
Pollution from the match box industry can be minimized by various
internal process changes and management measures such as the Best Available
Technology (BAT).Plant process modifications and cleaner technologies have
the potential to reduce the pollution load in effluents. However, this approach
cannot eliminate waste generation. Assessment of the water quality of the
receiving ecosystems and periodic ecological risk assessments are required to
validate the effectiveness of various treatment methods. Process technologies that
are currently applied can be broadly classified as the physico-chemical and
Biological treatment methods. These technologies are discussed in the following
sections.
Dennis P. Kumar, Abdul Rahman Mohamed Subhash Bhatia
(2002). Reported a Photo catalytic processes have been suggested as an

alternative treatment for water pollutants. Although presently many treatment
methods are being used, most of them do not completely destroy the pollutants
but only offer phase transfer or partial degradation of the pollutants. In photo
catalytic processes, a semiconductor photocatalyst is activated with ultraviolet
(UV) irradiation. The activated photocatalyst promotes the formation of hydroxyl
radicals, which in tum completely degrades the pollutants. In the present study,
an ultraviolet irradiated photo reactor system was used to degrade methylene blue
dye in aqueous solutions. The photocatalyst used was titanium dioxide (1iO/
Experiments were performed with varying catalyst loading, initial concentration
of dye, circulation flow rate and air flow rate. Initial reaction rates of dye
degradation were used to compare the effect of varying the above variables. The
effect of increasing the catalyst loading from 0 to 0.4 wt% showed that an increase
in the initial reaction rate, reaching an optimum at catalyst loading of 0.2 wt%.
Effect of initial concentration has proven that lower initial concentration resulted
in more efficient degradation of the dye. The increase in the initial reaction rate
degradation with increasing circulation flow rate confirmed the significant role
played by external mass transfer. Introduction of air to the system did not
significantly increase in the initial reaction rate when the air flow rate was
increased from 0 to 4.0 litter min-l. Photo catalysis has proven to be a promising
technology in the treatment of wastewater contaminated with organic pollutants.
The photo catalytic process involves the excitation of a semiconductor particle
using UV irradiation, which generates an electron-hole pair. The photogene rated
hole through a series of reactions produces a hydroxyl radical, which due to its
high oxidation potential, degrades organic pollutants in wastewaters. In the
present study the optimum catalyst weight loading for the degradation of
methylene blue dye was 0.2 wt %. Any further increase in catalyst weight loading
did not enhance the photo catalytic degradation of the dye. The circulation flow
rate was found to affect the initial rate of reaction for the photo catalytic
degradation of methylene blue dye. The increase in circulation flow rate from 0.8

to 3.2 litters Minot increased the initial reaction rate showing the presence of
external mass transfer. The initial concentration of the methylene blue dye was
found to affect the degradation of the dye. Higher initial concentration resulted in
lower degradation efficiencies. Introduction of air to the system did not show any
significant enhancement to the degradation of the dye.
Nora San Sebastián Martinez, Joseph F´ıguls Fernandez, Xavier
Font Segura, Antonio Sánchez Ferrier (2003). Reported A The pre-oxidation of
an extremely polluted pharmaceutical wastewater (chemical oxygen demand
(COD) value of 362,000 mg/l) using the Fenton’s reagent has been systematically
studied using an experimental design technique. The parameters influencing the
COD removal of the wastewater, namely temperature, ferrous ion and hydrogen
peroxide concentrations have been optimized to achieve a COD global reduction
of 56.4%. The total range of the proposed experimental design, however, could
not be tested because under some conditions (hydrogen peroxide concentration
over 5 M) the Fenton’s reaction became violent and could not be controlled,
probably due to the high exothermic effect associated with COD oxidation. For
the tested conditions, the optimal values of hydrogen peroxide and ferrous ion
concentration were 3 and 0.3 M, respectively, whereas temperature only showed
a mild positive effect on COD removal. In addition, during the first 10 min of
Fenton’s reaction, more than 90% of the total COD removal can be achieved.
Fenton’s reaction has proved to be a feasible technique for the pre-oxidation of
the wastewater under study, and can be considered a suitable pre-treatment for
this type of wastewaters. From the data here presented, we can conclude that: (1)
Operational parameters influencing the Fenton’s reaction in the pre-oxidation of
an extremely polluted wastewater have been studied by means of an experimental
design, in which the factors considered were temperature, ferrous ion and
hydrogen peroxide concentration. (2) The optimal values of hydrogen peroxide
and ferrous ion concentrations were 3 and 0.3 M, respectively; a COD reduction

of 56.4% resulted. (3) Temperature only showed a mild positive effect on COD
removal. Consequently, temperature should not be considered in the optimization
of the Fenton’s reaction for this wastewater. (4) In the first 10 min of the Fenton’s
reaction, more than 90% of COD removal can be achieved. This finding is of
special interest in the industrial application of Fenton’s reagent, because it
permits a significant COD reduction in a very short period of time. (5) The results
here presented can be considered as an effective pre-treatment of this type of
wastewaters, when direct biological treatments are not possible.
Chantanapha Sahunin, Jittima Kaewboran and Mali Hunsom (2006).
Reported a Treatment of textile wastewater was carried out at room temperature
in a batch reactor by using the Photo-Fenton oxidation process. The effects of
initial pH of the solution (pH = 1-7), ferrous ion concentration (0-100 mg×l-1)
and UV power (0-120 W) on chemical oxygen demand (COD) and colour
removal were examined. The results showed that this process was enhanced at
the acidic pH range. The optimum condition was found to be at pH = 3, 80 mg
Fe2+
×l-1, 5-10 minutes operating time, 60 W UV power and 200 mg H2O2 ×l-1.
At this condition, approximately 52% and 90% of COD and colour were
removed, respectively. During the treatment process, a small amount of sludge
(5.8×10-5 kg×kg COD-1) was generated. The presence of heterogeneous
Photocatalyst such as TiO2 in the system accelerated the removal percentage of
COD and colour. The author attempted to remove the .COD and Colour from
textile wastewater by employing the Photo- Fenton oxidation process in a batch
reactor. The results indicated that the COD and colour was fast removed during
the first 5-10 minutes and they can reborn at very long operating time due to photo
reduction of Ferric ion in the system. To remove the COD and colour
simultaneously, the optimum condition in this study was found to be at 80 mg
Fe2+
×l-1, UV power = 60 W, initial pH = 3, 200 mg H2O2 ×l-1 and 5-10 minutes
operating time. At this condition, approximately 52% and 90% of the COD and

colour were respectively removed. Using a heterogeneous catalyst such as TiO2
can expedite the removal of COD and colour in textile wastewater, and it can be
reused in the system by using a simple filtration. By employing the Photo-Fenton
oxidation process, it was found that this process was more suitable for colour
removal than COD removal.
Bhaskaran Varatharajan and S. Kanmani (2007). Reported a in the
present study, the treatability of wastewater from a pharmaceutical industry by
combined solar photo Fenton oxidation and activated sludge process was
investigated. The wastewater was considered non-biodegradable as it contained
significant amount of organic compounds whose degradation was not possible by
conventional biological treatment system. The characteristics of the wastewater
have shown to contain high COD (25600 mg/L) and BOD3 (4890 mg/L) and the
biodegradability of wastewater measured, as BOD3/COD ratio was 0.19. In order
to enhance the biodegradability of the pharmaceutical wastewater, photo assisted
oxidation process, H2O2/ Fe2+
/ Solar was applied to the wastewater as a pre-
treatment step to biological degradation. The influence of the reaction parameters
such as pH, dosage of HaC^ and Fe (II) and BOD3/ COD as a function of the
time of photochemical pre-treatment were studied. A COD removal of 88% was
observed in one hour photochemical treatment time at pH 3 and at the dosage of
H2O2 (65 ml) and Fe2+
(1.34 g). The biodegradability of wastewater has
enhanced from 0.19 to 0.4 (measured as BOD3/ COD ratio) after 40 min
photochemical treatment time. The combined solar photo Fenton oxidation and
biodegradation of wastewater has resulted in BOD removal of 93 % and COD
removal of 95 %.In the present work, treatability of wastewater from a
pharmaceutical industry was evaluated by combining solar photo Fenton
oxidation and activated sludge process. Raw Pharmaceutical wastewater had low
biodegradability (0.19) as determined from BOD3/COD ratio. In order to enhance
the biodegradability of pharmaceutical wastewater, solar photo Fenton oxidation

process was applied retreatment of photo Fenton oxidation process led to an
increase in biodegradability of the wastewater from 0.19 to 0.4 in 40 min
photochemical treatment time. The combined solar photo Fenton oxidation and
biodegradation of the wastewater has resulted in 93% BOD removal and 95%
COD removal. In conclusion, the combined solar photo Fenton oxidation and
activated sludge process could be used as an alternative technique for the
degradation of wastewater from pharmaceutical industries located in tropical
areas. For the treatment of large quantities of pharmaceutical wastewater, a pilot
plant study for scaling up of the solar photo Fenton process need to be conducted
to evaluate its applicability in the field.
Neval BAYCAN PARILTI (2010). Reported a as an advanced
oxidation treatment, the Fe (III)/ H2O2/Solar-UV process was applied to a
petrochemical refinery wastewater in Izmir, Turkey. A solar photo catalytic
reactor was used for the advanced oxidation. The Box-Wilson experimental
design method was employed to optimize the wastewater flow rate, oxidant and
catalyst concentrations as significant factors for maximum organic matter
removal. Organic matter removal was monitored throughout the operation period.
The maximum reduction in the TOC concentration was 49% with the addition of
2677 mg/L H2O2 and 0.5mm Fe (III) at a 10 L/h flow rate after 8 hours of
exposure to solar irradiation. The Photo catalytic degradation of petrochemical
industry wastewater by the Fe (III)/ H2O2/Solar-UV process was investigated
using the Box-Wilson experimental design. The most important factors affecting
the performance of the Fe (III)/ H2O2/Solar-UV process are the hydrogen
peroxide and Fe (III) concentrations. The Box-Wilson statistical experimental
design was used to optimize the oxidant dosage and flow rate in the solar
oxidation process for maximum colour and TOC removal. The experimental
results indicate that, Fe (III) and H2O2 concentrations are important parameters
for TOC removal. The Fe (III) requirement for an over 49% TOC removal was

0.5 mm which can be considered as a low Fe requirement compared to other
advanced oxidation processes. The solar irradiation accelerates the formation of
OH radicals as Fe (III) does. So exposing to sunlight can be considered as the
main reason for the low Fe (III) requirement in the treatment of the petrochemical
industry wastewater. However, decreasing the removal efficiency at high Fe
concentrations (>0.5 mm) is mainly because of the turbidity caused by the excess
Fe concentration, which, decreased the effectiveness of the solar radiation on
oxidation. The maximum TOC removal was achieved at the highest concentration
of H2O2 studied (2677 mg/L). The effect of flow rate on the removal of these
pollutants was negligible compared to the other selected factors. The removal of
the pollutants was the maximum (49% for TOC) for the flow rate of 10 L/h.
feeding the system with higher flow rates resulted in a slight decrease in removal
efficiencies. The removal efficiency was 44% for TOC at the maximum flow rate
of 50 L/h. The reason for obtaining a slight difference in the removal efficiency
for the lowest and the highest feeding rates could be the same exposure time to
the solar irradiation. The effect of flow rate may be more obvious if the system is
operated at higher flow rates. The optimal conditions for the organic matter
degradation of the petrochemical industry wastewater are about 49%. TOC
removal was determined as a 10 L/h flow rate, 2677 mg/L H2O2 concentration,
and, a 0.5 mm Fe (III) addition.
Mark Watkins and David Nash (2010). Reported a Dairy factory
wastewaters are increasingly being considered a valuable resource. However,
these waters may also contain contaminants, natural or artificial, that may
adversely affect the land to which they are applied. This review investigates dairy
wastewaters, factors affecting their composition, some probable effects on land
and compounds that may be used to trace the migration of pollutants. Dairy
factory wastewaters differ depending on the types of products made by the factory
and the treatment afforded wastewaters. In addition to milk and milk by-products,

dairy factory wastewaters contain cleaning chemicals that contribute to the salt
load, and synthetic compounds. From the limited studies where the effects on
dairy processing wastewaters on land have been measured, the consensus of the
literature results acknowledges the utility to agriculture can be highly variable
and depends on the land to which it was applied and wastewater characteristics
including concentrations of phosphorus, nitrogen, carbon and sodium. Excessive
applications of nutrients such as nitrogen and phosphorus have resulted in runoff
to nearby watercourses. Even fewer studies have investigated the use of organic
marker compounds in the dairy industry. Lipids, terpenes and sterols found in the
plants consumed by livestock would be useful for identifying pollutants from the
dairy industry. However, a library of biological marker compounds and their
likely sources is needed before such a technology could be applied more widely.
Potable water is a precious resource. The composition of dairy factory
wastewaters depend on the products being manufactured, cleaning processes and
the recycling protocols deployed in the plant, as well as the wastewater treatment
methods and the diet of the cows. These all affect the concentrations of nutrients,
inorganic salts, organics, and BOD in the various wastewater streams. Increased
recycling of these wastewaters is in everybody’s interests. In addition to in-plant
recycling, dairy factory wastewaters can be used to irrigate pasture or public
grounds, thereby conserving potable water and reusing the nutrients they contain.
However, there are potential risks. Irrigation needs to be carefully managed to
prevent Stalinisation or nutrient export in leach ate and surface runoff so that the
production of the land remains viable, even after cessation of irrigation.
Biological marker compounds are one possible technology that can assist in that
regard.
MIRA PETROVIC JELENA RADJENOVIC, DAMIA BARCELO
(2011). Reported A Due to their insufficient removal in conventional wastewater
treatments, advanced drinking and wastewater treatment options should be

considered for the removal of pharmaceutically active compounds (PhACs) from
urban, hospital and industrial wastewaters. This paper summarizes the current
state-of-the-art in two often applied advanced oxidation processes (AOPs),
namely TiO2 assisted photo catalysis and photo-Fenton process. Their
possibilities in removing PhACs are discussed, giving examples for several most
studied compounds. Photo catalytic degradation by photo-Fenton and TiO2
catalysis has been established as effective treatments for water containing
pesticides, endocrine disrupting compounds (EDCs), pharmaceuticals and other
trace organic contaminants. However, radical-induced reactions occurring in
photo catalytic treatments evolve through complex parallel consecutive pathways
of intermediate products. Since hydroxyl-radicals are not selective, various by-
products are formed at low concentration levels. The identification of these
intermediates and determination of kinetics of their degradation is crucial due to
their potential presence in the effluent of the treatment, and apprehension of their
degradation pathways is necessary in order to determine the key steps of
photodecomposition.
G.GINNI (2011). Reported A The rapid increase in population and
the increased demand for industrial establishments to meet human requirements
have created problems such as overexploitation of available resources, leading to
pollution of land, air and Water requirements. The wood pulping and wood
production of the paper products generate a considerable amount of pollutants
characterized by biochemical oxygen demand (BOD), chemical oxygen demand
(COD), suspended solids (SS), toxicity and colour when untreated or poorly
treated waste water are discharged to receiving waters. Pulp and paper mills
generate varieties of pollutants depending upon the type of the pulping process
.This paper is the state of art review of treatability of the pulp and paper mill
wastewater and performance of available treatment processes. Comparisons of all
treatment processes are presented. Combinations of anaerobic and aerobic

treatment processes are found to be efficient in the removal of soluble
biodegradable organic pollutants. Colour can be removed effectively by
coagulation, chemical oxidation and ozonation. The suspended solids are
removed by primary treatment such as sedimentation. BOD and COD present in
the wastewater are removed by biological treatment such as activated sludge
process, aerated lagoons. In the secondary treatment processes, activated sludge
process is the most commonly used. Aerated lagoons are efficient in removing
BOD over 95% in most of the reported results. The tertiary treatment used to
remove the recalcitrant compounds present in the wastewater. By comparing all
the treatment processes, solar photo-Fenton process is more efficient and
economical among advanced oxidation processes. In this study, the efficiency of
solar photo-Fenton process for the treatment of pulp and paper mill wastewater
was evaluated and the removal of colour and COD were investigated. The
experiment is conducted in a lab scale solar photo-Fenton reactor of capacity
seven litters which are exposed to the sunlight with the Irradiation time of one
hour. . The maximum removal efficiencies of COD and colour removal was 94%
and 100% respectively under optimal conditions (Fe2+
= 1g/L, H2O2= 5 g/L and
pH=4).The degradation kinetics was evaluated with the optimized value and it
was observed that it follows the first order reaction. The rate of degradation of
solar/Fe2+
/H2O2 was three times faster than solar/Fe2+
.The biodegradability of
wastewater was also increased during treatment from 0.028 to 0.83 Thus coupling
of solar photo-Fenton process with the biological treatment is an effective
treatment method thereby reducing the cost of the treatment. In this study, it has
been found that photo-Fenton oxidation is an appropriate process for the pre-
treatment of pulp and paper mill wastewater. The optimum pH for the process is
4.With the ferrous ion dosage of 1 g/L, concentration of H2O2 as 5 g/L, about
94% of COD was removed within one hour of reaction time and nearly 100
percent colour removal was achieved in a reaction time of 10 minutes. The effect
of liquid depth influences the degradation of organic compound. With the

increase in liquid depth, the degradation rate decreases. The degradation rate of
solar/Fe2+
/H2O2 process is three times faster than solar/Fe2+
process. For
untreated samples, the BOD/COD ratio was 0.028, while solar photo-Fenton
process enhanced the biodegradability value to 0.8. Thus coupling of solar photo-
Fenton process with the biological treatment is an effective treatment method
thereby reducing the cost of the treatment.
Shumaila Kiran1, Shaukat Ali, Muhammad Asgher and Shahzad Ali
Shahid (2012). Reported a Dye house effluents of textile industries leads to severe
environmental problems when disposed to aquatic bodies without proper
treatment. This work was carried out to optimize the Photo-Fenton process for
decolourization and mineralization of a commercial textile dye, Reactive Blue
222. The effect of different process parameters on decolourization efficiency of
Photo-Fenton process was investigated. The optimal conditions for process were
observed as; pH level 3.5, H2O2 concentration 1× 10-2M, FeSO4 concentration
3.5 × 10-5 mole L-1, temperature 50˚C and process time 50 min. The maximum
95% dye decolourization was achieved along with a significant (P< 0.05)
reduction of chemical oxygen demand and total organic. The degradation
products were characterized by UV–visible and FTIR spectral techniques. The
results provide evidence that Photo-Fenton process was able to oxidize and
mineralize the selected ago dye into non-toxic metabolites. Photo- Fenton process
was found to be more efficient for the photo catalytic degradation of Reactive dye
222. Based on the results, it can be concluded that the decolourization of dye is
strongly dependent on various Reaction parameters e.g. pH, concentration of
H2O2, concentration of Fe2SO4 and reaction temperature. Water quality
parameters (COD, TOC, TSS and Phenolics) analyzed after the Photo-Fenton
treatment of textile effluent which showed a major reduction in pollution load.
FTIR spectral analysis of decolorized products confirmed the degradation of dye
under study into simpler compounds indicating the efficiency of Photo-Fenton

process for effective treatment of hazardous chemicals like textile wastewater
having ago dyes.
Youssef Samet, Emna Hmani and Ridha Abdelhédi (2012). Reported
A The degradation of chlorpyrifos in water by Fenton (H2O2/Fe2+
) and solar
photo-Fenton (H2O2/Fe2+
/solar light) processes was investigated. A laboratory-
scale reactor was designed to evaluate and select the optimal oxidation condition.
The degradation rate is strongly dependent on pH, temperature, H2O2 dosing rate,
and initial concentrations of the insecticide andFe2+
. The kinetics of organic
matter decay was evaluated by means of chemical oxygen demand (COD)
measurement. Overall kinetics can be described by a pseudo-second-order rate
equation with respect to COD. The optimum conditions were obtained at pH 3,
H2O2 dosing rate 120 mg∙min–1, [Fe2+
] 0 5.0 mm, initial COD 1 330 mg∙ℓ–1
and 35°C for the Fenton process. However, in the solar photo-Fenton process, the
degradation rate increased significantly. To achieve 90% of COD removal, the
solar photo-Fenton process needs 50% less time than that used in the Fenton
process which translates to a 50% gain of H2O2. The results of this study indicate
that dark Fenton and solar photo-Fenton processes are powerful methods for the
degradation of the insecticide chlorpyrifos, but the solar-photo-Fenton process is
50% more efficient than the Fenton process. The degradation rate by the 2
processes can be expressed as a pseudo-second-order reaction with respect to
COD. COD removal was influenced by the dosing rate of the hydrogen peroxide
(H2O2 continuously introduced in the solution), the initial concentration of
chlorpyrifos, the amount of iron salt, the pH of solution and the temperature. The
optimum conditions were observed at pH 3, with an initial Fe2+
concentration of
5.0 mm and H2O2 dosing rate of 120 mg∙min–1. The experiments carried out
within the temperature range 20–45°C showed an optimum COD removal at
35°C, which allowed for computation of the apparent global activation energy
(14.44 kJ∙mol–1). The results obtained with this preliminary study suggest that

solar photo-Fenton is a promising pre-treatment process for pesticide-containing
wastewater.
Anne Heponiemi and Ulla Lassi (2012). Reported A the
characteristics and treatment of food industry wastewaters by different advanced
oxidation processes was considered. Typically, the amount and composition of
the effluent varies considerably. The high organic matter content is a basic
problem in food industry wastewaters but the organic compounds are usually
easily biodegradable and the effluents can be treated by conventional anaerobic
or aerobic biological methods. However, as a consequence of diverse
consumption, the forming effluents may contain compounds which are poisonous
to micro-organisms in the biological treatment plant. The pre-treatment of the
effluent by chemical oxidation, especially with AOPs, can oxidise bio refractory
pollutants to a more easily biodegradable form. Thus, the combination of AOP
and biological treatment may be a possible solution for the treatment of variable
food industry wastewaters.
Ebrahiem E. Ebrahiem, Mohammednoor N. Al-Maghrabi, Ahmed
R. Mobarki (2013). Reported A The general strategy of this study was based on
evaluation of the possibility of applying advanced photo-oxidation technique
(Fenton oxidation process) for removal of the residuals organic pollutants present
in cosmetic wastewater. The different parameters that affect the chemical
oxidation process for dyes in their aqueous solutions were studied by using
Fenton’s reaction. These parameters are pH, hydrogen peroxide (H2O2) dose,
ferrous sulphate (Fe2SO4/7H2O) dose, Initial dye concentration, and time. The
optimum conditions were found to be: pH 3, the dose of 1 ml/l H2O2 and 0.75 g/l
for Fe (II) and Fe (III) and reaction time 40 min. Finally, chemical oxygen
demands (COD), before and after oxidation process was measured to ensure the
entire destruction of organic dyes during their removal from wastewater. The

experimental results show that Fenton’s oxidation process successfully achieved
very good removal efficiency over 95%. The following conclusions might be
drawn as a result of application of a photo-Fenton reaction which indicates that
the optimum irradiation time was 40 min. at pH 3, the dose of 1 ml/l H2O2 and
0.75 g/l for Fe (II) and Fe (III). Under these conditions, 95.5% COD removal
was obtained. Finally, it is highly recommended to apply the used technique
(Fenton’s oxidation process) as treatment of wastewater containing organic
compound.
Ranjana Das (2014). Reported an Occurrence of persistent organic
compounds in industrial effluents and their efficient removal technique has
emerged as a crucial problem to waste water treatment plants. This review aims
to focus on the plight associated with the effluents from textile industry,
agricultural and pharmaceutical effluents. The occurrence of dyes, pesticides and
endocrine disrupting chemicals in aquatic ecosystems may cause chronic
diseases, affect the human endocrine system and have appeared as crucial factor
to consider for drinking and non-potable end uses of water. Extensive researches
have been attempted to screen effective and safe method of contaminants removal
by modifying conventional treatments as well as advanced processes by
renowned authors. This paper aims to review different possible routes of effluent
treatment emphasizing on complete mineralization of the targeted contaminants.
With this purpose, a comprehensive review has been presented to deliver
Essential information about dealing with photo catalytic mineralization of
pollutants. This review aims to focus on the recent application and advances for
the heterogeneous photo catalytic system to reveal its efficacy of wastewater
treatment specifically dye/textile effluent, pesticide contaminated water and
pharmaceutical effluents. In most of the reviewed literature, TiO2 has been
suggested to be an efficient and profitable photocatalyst for mineralization of
organic pollutants such as dyes, pesticides and EDCs in wastewater in The

presence of UV, visible or solar light but some researchers have also aimed to
explore novel low cost catalysts composition. Majority of studies are related to
optimization of degradation process parameters, studies on kinetics and
mechanistic path way of degradation which are crucial for efficient design and
the application of the photo catalytic degradation process to ensure sustainable
operation. In spite of extensive process investigations, understanding of photo
reactor design and its modelling as well as the scale up policy seems inadequate
which limits the industrial exploitation of the photo catalytic degradation
technique. The application of this technique for real waste waters requires further
investigation to achieve eco-friendly discharge. This review is not comprehensive
but covers the recent application and developments of photo catalysis in treatment
of industrial waste water and is hoped to be informative to relate researchers for
betterment of the existing processes.
Abdel-Ail, Fergal, Abdel-Wahid, El-Shatha, M.F. (2015). Reported
a Nowadays, water pollution and its scarcity are the main problems that
humankind is facing. In this regards, great attention is being given to the removal
of organic pollutants from wastewater by advanced oxidation processes (AOPs)
that are based on generation of highly reactive species, especially hydroxyl
radicals. Among them, Fenton and photo-Fenton’s oxidation processes. In this
work, a comparison between Fenton process and photo-Fenton oxidation process
as advanced oxidation processes for treatment of tannery wastewater was made.
Firstly, the physicochemical characteristics of the filtered effluent were
determined, The chemical oxygen demand (COD) is 554 ppm, total organic
carbon (TOC) is 170.8 ppm, total dissolved solids is 50gl-1 and the pH is 3.5. The
maximum COD removal is (82.7%) for Fenton’s oxidation process and for photo-
Fenton process giving maximum COD removal (90.1%) at pH 3, Fe2+
0.5gl-1,
H2O2 and 30gl-1 and time 2h. All experiments were performed at ambient
temperature followed by precipitation of chromium with NaOH at pH 8.5, stirring

0.5h, and settling 2h. The low cost iron sulphate and high COD removal make
photo-Fenton process superior method for degradation of organic pollutants from
tannery wastewater. This study was made with the help of UV-Vis/NIR
spectrophotometer and FT-IR analyses. The target from this study is the
comparison between different advanced oxidation processes of tannery
wastewater treatment. In this experimental work, The COD removal percentage
by Fenton (Fe2+
/H2O2) and photo-Fenton followed by coagulation with NaOH
was investigated. The optimum COD removal under these AOPs indicated that
the efficiency for degradation of organic pollutants present in tannery wastewater
was in the case of photo-Fenton (90.1%) H2O2/UV oxidation (85%) Fenton
(82.7%). The use of high concentration of hydrogen peroxide for tannery
wastewater treatment by AOPs results in mineralization of the recalcitrant
organic pollutants. Reduction of COD percentage by hybrid technology of AOPs
and chemical precipitation of chromium is a cost-effective method for tannery
wastewater treatment.
Dorota Krzemińska, Ewa Neczaj, Gabriel Borowski (2015). Reported
high organic matter content is a basic problem in food industry wastewaters.
Typically, the amount and composition of the effluent varies considerably. In the
article four groups of advanced processes and their combination of food industry
wastewater treatment have been reviewed: electrochemical oxidation (EC),
Fenton’s process, ozonation of water and photo catalytic processes. All advanced
oxidation processes (AOP`s) are characterized by a common chemical feature:
the capability of exploiting high reactivity of HO• radicals in driving oxidation
processes which are suitable for achieving decolonization and odour reduction,
and the complete mineralization or increase of bioavailability of recalcitrant
organic pollutants. Food industry uses large amounts of water for many different
purposes including cooling and cleaning, as a raw material, as sanitary water for
food processing, for transportation, cooking and dissolving, as auxiliary water

etc. In principle, the water used in the food industry may be used as process and
cooling water or boiler feed water. As a consequence of diverse consumption, the
amount and composition of food industry wastewaters varies considerably.
Characteristics of the effluent consist of large amounts of suspended solids,
nitrogen in several chemical forms, fats and oils, phosphorus, chlorides and
organic matter. AOP’s constitute a promising technology for the treatment of
food industry wastewaters containing difficult to biodegradable organic
contaminants. It involves the generation of free hydroxyl radical (HO•), a
powerful, non-selective chemical oxidant to change organic compounds to a more
biodegradable form or of carbon dioxide and water. These processes can reduce
a broad spectrum of chemical and biological contaminants which are otherwise
difficult to remove with conventional treatment processes of food industry
wastewater.
Dheeaa al deen Atallah Aljuboury, Puganeshwary Palaniandy, Hamidi
Bin Abdul Aziz, Shaik Feroz (2015). Reported A The aim of this study is to
investigate the performance of employing the solar photo-catalyst of TiO2 to treat
petroleum wastewater from Sohar oil Refinery (SOR), evaluate the performance
of employing this process by a central composite design (CCD) with response
surface methodology (RSM) and evaluate the relationships among operating
variables such as TiO2 dosage, pH, C0 of COD, and reaction time to identify the
optimum operating conditions. Quadratic models prove to be significant with
very low probabilities (<0.0001) for the following two responses: total organic
carbon (TOC) and chemical oxygen demand (COD). TiO2 Dosage and pH are the
two main factors that improved the TOC and COD removal while C0 of COD
and reaction time are the actual factors. The optimum conditions are a TiO2
dosage (0.6 g/L), C0 of COD (1600 ppm), pH (8), reaction time (139 min) in this
method. TOC and COD removal rates are 15.5% and 48.5%, respectively. The
predictions correspond well with experimental results (TOC and COD removal

rates of 16.5%, and 45%, respectively). Using renewable solar energy and treating
with minimum TiO2 input make this method to be a unique treatment process for
petroleum wastewater. In the present study, the performance of employing of
solar photo-catalyst of TiO2 in the AOP on degradation of TOC and COD from
petroleum wastewater at Sohar Oil Refinery in Oman is investigated. A central
composite design (CCD) with response surface methodology (RSM) is applied to
evaluate the relationships among operating variables, such as TiO2 dosage, C0 of
COD, pH, and reaction time, to identify the optimum Operating conditions.
Quadratic models for the following two responses prove to be significant with
very low probabilities (<0.0001): chemical oxygen demand (COD) and Total
Organic Carbon (TOC). The obtained optimum conditions include a TiO2 dosage
(0.6 g/L), C0 of COD (1600 ppm), pH (8), reaction time (139 min). TOC and
COD removal rates are 15.5% and 48.5%, respectively. The predictions
correspond well with experimental results (TOC and COD removal rates of
16.5%, and 45%, respectively). The solar photo-catalyst of TiO2 of high COD
wastewater is a unique treatment process utilizing renewable solar energy and
treating the wastewater with minimum chemical input.
Umadevi.V (2015). Reported a Advanced oxidation Process such as
Fenton, Photo Fenton and Photo Oxidation like processes constitute a promising
technology for the treatment of waste water containing non bio degradable
organic compounds. In Fenton’s process iron and hydrogen peroxide are the two
chemicals used as reagents. Oxidation using Fenton’s reagent causes the
dissociation of the oxidant and the formation of reactive hydroxyl radicals that
destroy organic pollutants to harmless compounds. The Fenton reaction has a
short reaction time among all advanced oxidation processes. The reagents are
cheap and nontoxic as well as there is no energy involved as catalyst and the
process is easy to run and control. In this work efforts are made to investigate the
potential application of Fenton’s reaction as a pre-treatment technique for

hospital waste water. The prime objective of this study is to evaluate the
improvement in biodegradability of pollutants in hospital wastewater using the
Fenton process. The physical and chemical characteristics of the waste water have
been analysed. Experiments were conducted with varying doses for optimization
of process variables for the process. The effect of operating conditions on the
efficiency of the process has been investigated. The appropriate conditions for
the Fenton process for application to hospital wastewater are reported for the
design of the treatment process. Fenton Treatment is used for removing COD and
enhancement of biodegradability of waste water. Both oxidation and coagulation
contributed to COD removal through Fenton treatment of waste water. Relative
contributions depend primarily on pH, molar ratio of reagents. From the results
of the experiments for treating the non-biodegradable waste water by Fenton’s
oxidation, the following conclusions can be drawn: 1. The COD removal
efficiency by oxidation was effected by the pH value .The most effective reaction
was observed at pH=3.0 2. The reaction time of Fenton process was 90 minutes
to complete the reaction between ferrous sulphate and hydrogen peroxide. 3. The
optimum H2O2/Fe2+
were 1.2:1 according to the results of ferrous Sulphate and
hydrogen peroxide. 4. The removal efficiency of COD 89.87% and 5. Improved
the biodegradability of waste water from 0.205 of influent to 0.54 of effluent
waste water.
Vasilica-Ancuta Simion, Igor Cretescu, Doina Lutic, Constantin
Luca, Ioannis Poulios (2015). Reported a Nowadays, an efficient wastewater
management involves the use of advanced treatment technologies able to
decompose hardly biodegradable compounds with reasonable costs at the lowest
possible environmental impact. In our work we used one of the most efficient
advanced wastewater treatment, the Fenton reaction and its photo-assisted
version. The hydrogen peroxide was the oxidizer; despite its relatively high cost,
its high activity in oxidizing of a large variety of organic persistent pollutants in

the presence of Fe3+
ions as catalyst, makes it an alternative which is worth to be
considered even in practical medium scale systems. The Fenton and photo-Fenton
oxidation were performed using a model dye, the xanthenes-type Rhoda mine 6G,
widely used in a series of biotechnology applications, but having major
drawbacks when released in natural water flows, mainly mutagen and carcinogen
effects. Therefore, a parametric case study was performed in order to define the
optimal operating parameters (the pH value, the hydrogen peroxide concentration
and the iron catalyst concentration). The oxidative degradation of Rhoda mine
6G by Fenton reaction was more effective when combined with UV irradiation.
Each parameter of the oxidative treatment is essential for the colour and TOC
removal. The optimal values found for the total colour degradation and
mineralization of the dye was as follows: 16 ppmFe3+
, 100 ppm H2O2 and pH of
4.5. This research studied the performance of the Fenton system during UV
irradiation on the degradation of Rhoda in 6G dye. The essential role of all
components in the reaction medium was highlighted first: the oxidizer, the
catalyst and the UV irradiation. A parametric study allowed defining the optimal
set of working conditions judged from the point of view of dye decolorizing and
its total mineralizing. The role of the oxidizer was rather to be an efficient initiator
of the dye degradation, since its use at a low concentration of 27 ppm leads to the
total decolorizing in several tens of minutes, while the high degrees of
mineralizing required higher concentrations of oxidizer (around 100 ppm). The
Fe3+
ions concentrations necessary for a high yield of the reaction were around
16 ppm and the pH value ranging between 3.5 and 4.7. The possibility to enhance
the performance of Fenton oxidation process of Rhoda in 6G dye in water solution
in the presence of UV irradiation was proved and quantified.
Aola Hussein Flamarz Tahir1, Nagham Obeid Kareim1 & Shatha
Abduljabbar Ibrahim (2016). Reported a Different Advanced Oxidation
Processes (Photo Fenton process, Fenton process and H2O2/UV) were studied in

order to reduce COD from oily compounds aqueous solution using batch system.
To get the optimum condition, different variables were studied for each of these
processes; such as pH, time, concentration of H2O2, concentration
Of oil, concentration of Fe2SO4·7H2O and temperature as parameters. It was
found that the optimal pH value for the three processes was 3 and the optimal
temperature was 30°
C for Photo-Fenton and UV/H2O2 system and 20°
C for
Fenton process. Photo-Fenton process gave a maximum COD reduction of 80.59
% (COD from 2684 to 521 mg/l), Fenton gave 53.22 % (COD from 2587-1130)
and the combination of UV/H2O2 gave a COD reduction of 22.69 % (COD from
2450 to 1894). The percentage of removal found was after the total reaction time
(180 min.). The optimum chemical reagents for Photo-Fenton, Fenton and
UV/H2O2 were as the following H2O2 = 800 mg/l, 1500 mg/l and 2000 mg/l,
Fe2SO4·7H2O = 60 mg/l, 100 mg/l. The COD removal from synthetic vegetable
oil wastewater was investigated by the Photo-Fenton, Fenton and UV/H2O2
processes. The COD removal efficiency was strongly affected by many factors
such as the concentration of H2O2, Fe2SO4.7H2O, pH, temperature and the oily
content amount. It was found that the Photo-Fenton, Fenton and combination of
UV and H2O2 processes have the potential to partially reduce the COD of oily
wastewater in different removal percentage. The overall results of this study
indicate that the application of Photo-Fenton process is a feasible method to treat
vegetable oily content wastewaters achieving a significant decrease of COD.
Optimum initial pH was found 3 for all three processes studied; temperature of
30°
C was found optimum for Photo-Fenton and UV/H2O2 system and 20°
C for
Fenton system. Optimum chemical reagents dosage for Photo-Fenton at H2O2 =
800 mg/l and Fe2SO4.7H2O = 60 mg/l, leads to a COD reduction of 80.59 %.
Fenton’s reagent at H2O2 = 1000 mg/l and Fe2SO4.7H2O = 1500 mg/l, leads to a
COD reduction of 53.22 %. UV/H2O2 combination process a low COD removal
efficiency 22.69 % was found.

CHAPTER 3
MATERIALS AND METHODS
3.1 GENERAL
The match box industry is one of the most important in the world, but
it discharges a variety of gaseous, liquid and solid wastes into the environment.

The pulp and paper mill wastewater was treated by solar photo- Fenton process.
The parameters such as pH, reagent concentration and time were optimized to
achieve high COD, colour and toxicity reduction.
3.2 COLLECTION AND CHARACTERIZATION OF WASTEWATER
The wastewater samples were collected from the match box industry
located at kovilpatti, thoothukudi and the initial characteristics of wastewater was
done by the standard methods. The table 3.1 shows the analysis methods for the
characterization of experimental parameters. The figure 3.1 shows the schematic
methodology of solar photo Fenton process.
3.3 MATERIALS
Tray reactor, waste water, Phosphate buffer solution, magnesium
sulphate, calcium chloride, ferric chloride, manganese sulphate, alkali iodide
azide, concentrated sulphuric acid, sodium thiosulfate, starch indicator,
potassium dichromate, mercuric sulphate, ferrous ammonium sulphate, ferroin
indicator, analytical grade iron sulphate and hydrogen peroxide were used.
Table 3.1 Analysis methods for the treatment of match box industry
Wastewater
Parameter Values
pH 3

Turbidity 101NTU
Colour Brown
3.4 EXPERIMENTAL METHOD
The figure 3.2 shows the solar photo Fenton tray reactor made of
metal. The photo-Fenton reactions were carried out in a three litter tray reactor
with the working volume of 2L. The whole system was exposed under strong
solar irradiation, form 11.00 AM to 03.00 PM from February to march. When the
system was exposed to the sunlight; it was recorded as the beginning of the
experiment. The sample was taken from the reactor for every 20 minutes to
analyzed COD and the colour was monitored in the absorbance range of 475nm.
Treatment of match box industry wastewater by solar Photo-Fenton process
Collection and characterization of wastewater (pH, COD, Turbidity, colour, TS,
TDS, TSS..,)

Figure 3.1 Schematic methodology of solar photo-Fenton proces
Fabrication of lab solar photo- Fenton reactor
 Metal tray reactor
 Volume – 2 L
 Size - 21.5 cm x 21.5 cm x 15 cm
Operating parameters
 pH - 3 to 5
 Fe2+
- 1 to 7 g/L
 H2O2 - 5 to 35 ml/L
 Solar irradiation time –1 hr COD
and
 Liquid depth, biodegradability
COD
&
COLOUR
Treat match box industry wastewater by solar Photo-Fenton process

Figure 3.2 solar photo-Fenton reactors
3.5 EFFECT OF OPERATING PARAMETERS
The effect of operating parameters such as pH, ferrous ion, hydrogen
peroxide, irradiation time, liquid depth and biodegradability were analyzed.
3.5.1 Effect of pH
The degradation of the waste material under the sunlight and the
COD removal in different reactions was found to be dependent on pH of the
solution. Therefore pH is an important parameter and it affects the efficiency of
the Fenton’s treatment process. In order to study the effect of pH, it was varied in
the range of 3 to 5 and the reaction was carried out for 1 hour with the dosage of
Fe2+
- 1g/L and H2O2 - 15g/L. The sample was taken for every five minutes and
it was quenched by adding sodium sulphite. The treated wastewater sample was
WASTE WATER + Fe2+
+ H2 O2

then filtered to separate the catalyst. The supernatant was taken to analyze the
colour and COD.
3.5.2 Effect of 𝐅𝐞 𝟐+
concentration
The degradation of organic compounds and the removal of colour
were investigated by varying the dosage of Fe2+
from 1 to 7 g/L. From the figure
4.3 and figure 4.4, it was observed that as the concentration of Fe2+
increased
from 1 to 7, 99% of colour was removed within 10 minutes. Also degradation of
COD increases as Fe2+
increases. Maximum COD reduction occurs when the
Fe2+
dosage was 1.0 g/L and it was taken as the optimum dosage. This is because
the catalyst ferrous sulphate accelerates the decomposition of H2O2. The results
are shown in table 4.30 to table 4.37. Further addition of iron becomes inefficient.
The increase in decolourization and COD removal was due to the production of
hydroxyl radicals. The optimum dosage of FeSO4 as 280 mg/L. Conducted a
study on the solar driven photo- Fenton process for treating water containing
phenol as a contaminant evaluated by means of pilot-scale experiments with a
parabolic trough solar reactor (PTR). About 90% of COD was removed within 3
hours of irradiation or less under the optimum Fe (II).
3.5.3 Effect of H2O2 concentration
The degradation of COD and decolourization were studied by
varying the dosage of H2O2 in the range of 0 to 25 g/L with the optimum value
of pH and the concentration of Fe2+
. The wastewater sample of volume 2 L was
taken and with this, ferrous sulphate and hydrogen peroxide were added and
stirred well. The photo-Fenton reactions were carried out for one hour under
strong solar radiation from 12.00 pm to 1.00 pm. The sample was taken for every
five minutes and the removal of colour and COD were analyzed by standard
methods.

3.5.4 Effect of liquid depth
To study the effect of liquid depth, different volumes of wastewater
samples were taken in the reactors. The depth was varied as 1.15 cm, 1.13 cm,
1.16 cm, 1.12 cm, 1.11 cm and 0.9 cm. The depth plays an important role in the
degradation of COD. The volume of wastewater samples taken were 1 L, 2 L, 3
L, 4 L, 5 L and 6 L. These samples were taken in the reactors and ferrous sulphate
and hydrogen peroxide were added and stirred well. The system was exposed to
sunlight for one hour from 12.00 pm to 1.00 pm. The samples were taken for
every five minutes and the COD and decolourization were analyzed by standard
methods.
3.5.5 Effect of biodegradability
The match box industry wastewater is non - biodegradable in nature
and they contain recalcitrant compounds. Significant enhancement of
biodegradability was studied using solar/Fe2+
/H2O2.The experiment was carried
out in the batch reactor of volume 7 L with the working volume of 2 L for 1 hour.
The samples were taken for every 10 minutes and it was analyzed for BOD and
COD. The biodegradability of the wastewater was evaluated by BOD/COD ratio.
CHAPTER 4
RESULTS AND DISCUSSION
4.1 GENERAL

The wastewater from match box industry wastewater was
investigated in the following study. Lab scale solar photo-Fenton reactors were
used for the Reactions to be carried out. COD and BOD were analysed using
standard Methods and the colour was monitored using visible spectrophotometer.
4.2 CHARACTERIZATION OF MATCH BOX INDUSTRY
WASTEWATER
The initial characteristics of sample wastewater were analysed by
Standard methods given in table 4.1
Table 4.1 Initial characteristics of match box industry wastewater
Parameter Values
pH 3
Turbidity 101NTU
Colour Brown
4.3 EFFECT OF OPERATING PARAMETERS
4.3.1 Effect of pH

The effect of pH was studied by varying the pH from 5 to 3 with the dosage
of Fe2+
=1g/L and H2O2 = 5ml/L. It is clear that at 100% colour was removed
within 10 minutes of irradiation time. The Decolourization decreases as the pH
increases from 5 to 3. The percentage removal of COD is given in table 4.2 to 4.8
and table 4.9 to 4.15 respectively.
4.3.1.1 Effect of pH on turbidity
COD reduction increases rapidly as the pH increases from 3 to 5. At
a reaction higher than pH, it has been found that the Turbidity decreases. This is
because the ferrous catalyst was inactivated with the formation of ferric hydro
complexes and also due to the decomposition of H2O2. Hence the maximum
removal of colour and COD removal was obtained at pH. This is due to the
formation of dominating .This form of iron species could be generated at pH 5-3
and its activity is higher than the non-complex form of Fe2+
in Fenton’s
oxidation.
Table 4.2 Effect of pH on turbidity day-1
pH Turbidity
(NTU)
5 28
5 24
4.8 20
4.7 27
4.5 32

Figure 4.1 Effect of pH on turbidity day-1
pH Turbidity
(NTU)
4.5 31
4.3 20
4.2 21
4.2 22
4.1 24
0
5
10
15
20
25
30
35
4.4 4.5 4.6 4.7 4.8 4.9 5 5.1
TUBIDITY
pH
Turbidity

pH Turbidity
(NTU)
4.1 22
3.9 25
3.8 30
0
5
10
15
20
25
30
35
4 4.1 4.2 4.3 4.4 4.5 4.6
TUBIDITY
pH
Turbidity
0
5
10
15
20
25
30
35
3.75 3.8 3.85 3.9 3.95 4 4.05 4.1 4.15
TUBIDITY
pH
Turbidity

pH Turbidity
(NTU)
3.8 23
3.8 29
3.7 30
pH Turbidity
(NTU)
3.7 21
0
5
10
15
20
25
30
35
3.68 3.7 3.72 3.74 3.76 3.78 3.8 3.82
TUBIDITY
pH
Turbidity

3.2 19
pH Turbidity
(NTU)
3.2 20
3 18
18.5
19
19.5
20
20.5
21
21.5
3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8
TUBIDITY
pH
Turbidity

pH Turbidity
(NTU)
3 18
3 17
4.3.2 Effect of pH on COD removal
17.5
18
18.5
19
19.5
20
20.5
2.95 3 3.05 3.1 3.15 3.2 3.25
TUBIDITY
pH
Turbidity
16.8
17
17.2
17.4
17.6
17.8
18
18.2
0 0.5 1 1.5 2 2.5 3 3.5
TUBIDITY
pH
Turbidity

COD reduction increases rapidly as the pH increases from 3 to 5. At
a reaction higher than pH, it has been found that the COD removal decreases.
This is because the ferrous catalyst was inactivated with the formation of ferric
hydro complexes and also due to the decomposition of H2O2. Hence the
maximum removal of colour and COD removal was obtained at pH. This is due
to the formation of dominating species. This form of iron species could be
generated at and its activity is higher than the non-complex form of Fe2+
in
Fenton’s oxidation.
Table 4.9 Effect of pH on COD removal day-1
pH COD
(mg/L)
% COD
removal
5 22400 68.1
5 22400 68.1
4.8 19200 72.7
4.7 16000 77.2
4.5 12800 81.8

Figure 4.8 Effect of pH on COD removal day-1
pH COD
(mg/L)
% COD
removal
4.5 22400 68.1
4.3 19200 72.7
4.2 12800 81.8
4.2 16000 77.2
4.1 19200 72.7
0
20
40
60
80
100
4.4 4.5 4.6 4.7 4.8 4.9 5 5.1
%COD
pH
% COD

pH COD
(mg/L)
% COD
removal
4.1 16000 77.2
3.9 19200 72.7
3.8 16000 77.2
0
10
20
30
40
50
60
70
80
90
4 4.1 4.2 4.3 4.4 4.5 4.6
%COD
pH
% COD
72
73
74
75
76
77
78
3.75 3.8 3.85 3.9 3.95 4 4.05 4.1 4.15
%COD
pH
% COD

pH COD
(mg/L)
% COD
removal
3.8 19200 72.7
3.8 16000 77.2
3.7 22400 68.1
pH COD
(mg/L)
% COD
removal
3.7 16000 77.2
3.2 12800 81.8
66
68
70
72
74
76
78
3.68 3.7 3.72 3.74 3.76 3.78 3.8 3.82
%COD
pH
% COD

pH COD
(mg/L)
% COD
removal
3.2 9600 86.3
3 8800 87.5
76
77
78
79
80
81
82
83
3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8
%COD
pH
% COD
86.2
86.4
86.6
86.8
87
87.2
87.4
87.6
2.95 3 3.05 3.1 3.15 3.2 3.25
%COD
pH
% COD

pH COD
(mg/L)
% COD
removal
3 5600 90
3 1600 92
4.3.3 Effect of time
4.3.3.1 Effect of time on turbidity
Table 4.16 Effect of time on turbidity day-1
Time
(min)
Turbidity
(NTU)
89.5
90
90.5
91
91.5
92
92.5
0 0.5 1 1.5 2 2.5 3 3.5
%COD
pH
% COD

20 28
40 24
80 20
160 27
320 32
Figure 4.15 Effect of time on turbidity day-1
Time
(min)
Turbidity
(NTU)
60 31
120 20
180 21
240 22
300 24
0
10
20
30
40
0 50 100 150 200 250 300 350
Turbidity
Time (min)
Turbidity

Time
(min)
Turbidity
(NTU)
90 22
120 25
270 30
0
10
20
30
40
0 50 100 150 200 250 300 350
Turbidity
7
Turbidity
0
5
10
15
20
25
30
35
0 50 100 150 200 250 300
Turbidity
Time (min)
Turbidity

Time
(min)
Turbidity
(NTU)
120 23
240 29
360 30
Time
(min)
Turbidity
(NTU)
150 21
300 19
0
5
10
15
20
25
30
35
0 50 100 150 200 250 300 350 400
Turbidity
Time (min)
Turbidity

Time
(min)
Turbidity
(NTU)
180 20
360 18
18.5
19
19.5
20
20.5
21
21.5
0 50 100 150 200 250 300 350
Turbidity
Time (min)
Turbidity
17.5
18
18.5
19
19.5
20
20.5
0 50 100 150 200 250 300 350 400
Turbidity
Time (min)
Turbidity

Time
(min)
Turbidity
(NTU)
190 18
380 17
4.3.3.2 Effect of time on COD removal
Table 4.23 Effect of time COD removal day-1
Time
(min)
COD
(mg/L)
% COD
removal
20 22400 68.1
16.8
17
17.2
17.4
17.6
17.8
18
18.2
0 50 100 150 200 250 300 350 400
Turbidity
Time (min)
Turbidity

40 22400 68.1
80 19200 72.7
160 16000 77.2
320 12800 81.8
Figure 4.22 Effect of time COD removal day-1
Time
(min)
COD
(mg/L)
% COD
removal
60 22400 68.1
120 19200 72.7
180 12800 81.8
240 16000 77.2
300 19200 72.7
0
5000
10000
15000
20000
25000
20 40 80 160 320
CODremoval
Time (min)
% COD
COD

Time
(min)
COD
(mg/L)
% COD
removal
90 16000 77.2
180 19200 72.7
270 16000 77.2
0
5000
10000
15000
20000
25000
60 120 180 240 300
CODremoval
Time (min)
% COD
COD
0
5000
10000
15000
20000
25000
90 180 270
CODremoval
Time (min)
% COD
COD

Time
(min)
COD
(mg/L)
% COD
removal
120 19200 72.7
240 16000 77.2
360 22400 68.1
Time
(min)
COD
(mg/L)
% COD
removal
0
5000
10000
15000
20000
25000
120 240 360
CODremoval
Time (min)
% COD
COD

150 16000 77.2
300 12800 81.8
Time
(min)
COD
(mg/L)
% COD
removal
180 9600 86.3
360 8800 87.5
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
150 300
CODremoval
Time (min)
% COD
COD

Time
(min)
COD
(mg/L)
% COD
removal
190 5600 90
380 1600 92
8200
8400
8600
8800
9000
9200
9400
9600
9800
180 360
CODremoval
Time (min)
% COD
COD
0
1000
2000
3000
4000
5000
6000
190 380
CODremoval
Time (min)
% COD
COD

4.3.4 Effect of Dosage of concentration on turbidity and COD removal
4.3.4.1 Effect of 𝐅𝐞 𝟐+
concentration
The degradation of organic compounds and the removal of colour
were investigated by varying the dosage of Fe2+
from 1 to 7 g/L. From the figure
4.3 and figure 4.4, it was observed that as the concentration of Fe2+
increased
from 1 to 7, 99% of colour was removed within 10 minutes. Also degradation of
COD increases as Fe2+
increases. Maximum COD reduction occurs when the
Fe2+
dosage was 1.0 g/L and it was taken as the optimum dosage. This is because
the catalyst ferrous sulphate accelerates the decomposition of H2O2. The results
are shown in table 4.30 to table 4.37. Further addition of iron becomes inefficient.
The increase in decolourization and COD removal was due to the production of
hydroxyl radicals. The optimum dosage of FeSO4 as 280 mg/L. Conducted a
study on the solar driven photo- Fenton process for treating water containing
phenol as a contaminant evaluated by means of pilot-scale experiments with a
parabolic trough solar reactor (PTR). About 90% of COD was removed within 3
hours of irradiation or less under the optimum Fe (II).
Table 4.30 Effect of Dosage of concentration𝐅𝐞 𝟐+
on turbidity and COD
removal day-1
Concentration
Fe2+
(g/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
1 22400 68.1 28
1 22400 68.1 24
1 19200 72.7 20

1 16000 77.2 27
1 12800 81.8 32
Figure 4.29 Effect of Dosage of concentration 𝐅𝐞 𝟐+
removal day-1
Table 4.31 Effect of Dosage of concentration 𝐅𝐞 𝟐+
removal day-2
Concentration
Fe2+
(g/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
2 22400 68.1 31
2 19200 72.7 20
2 12800 81.8 21
0
10
20
30
40
50
60
70
80
90
1 1 1 1 1
%COD&Turbidity
Fe2+ concentration
% COD Turbidity

2 16000 77.2 22
2 19200 72.7 24
removal day-2
removal day-3
Concentration
Fe2+
(g/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
3 16000 77.2 22
0
10
20
30
40
50
60
70
80
90
2 2 2 2 2
%COD&Turbidity
Fe2+ concentration
% COD Turbidity

3 19200 72.7 25
3 16000 77.2 30
removal day-3
removal day-4
Concentration
Fe2+
(g/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
4 19200 72.7 23
4 16000 77.2 29
4 22400 68.1 30
0
20
40
60
80
100
3 3 3
%COD&Turbidity
Fe2+ concentration
% COD Turbidity

removal day-4
removal day-5
Concentration
Fe2+
(g/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
5 16000 77.2 21
5 12800 81.8 19
0
50
100
4 4 4
%COD&Turbidity
Fe2+ concentration
% COD Turbidity
0
20
40
60
80
100
5 5
%COD&Turbidity
Fe2+ concentration
% COD Turbidity

removal day-5
removal day-6
Concentration
Fe2+
(g/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
6 9600 86.3 20
6 8800 87.5 18
removal day-6
removal day-7
0
20
40
60
80
100
6 6
%COD&Turbidity
Fe2+ concentration
% COD Turbidity

Concentration
Fe2+
(g/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
7 5600 90 18
7 1600 92 17
removal day-7
4.3.4.2 Effect of 𝐇 𝟐 𝐎 𝟐 concentration
The effect of H2O2 was investigated with the optimized value of
Fe2+
= 1 g/L and pH= 4 and by varying the dosage of H2O2 from 5 to 35 ml/L.
The degradation of COD and decolourization increases as the concentration of
H2O2 increases until the critical concentration is achieved. Above this critical
concentration, the degradation of COD and decolourization decrease as a result
of scavenging effect explained by the following equations.
H2O2+ OH HO2+ H2O .....(4.1)
0
20
40
60
80
100
7 7
%COD&Turbidity
Fe2+ concentration
% COD Turbidity

HO2+ OH H2O + O2 .....(4.2)
OH + OH H2O2 .....(4.3)
Table 4.37 Effect of Dosage of concentration 𝐇 𝟐 𝐎 𝟐on turbidity and COD
removal day-1
Concentration
H2O2
(ml/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
5 22400 68.1 28
5 22400 68.1 24
5 19200 72.7 20
5 16000 77.2 27
5 12800 81.8 32

Figure 4.36 Effect of Dosage of concentration 𝐇 𝟐 𝐎 𝟐turbidity and COD
removal day-1
Table 4.38 Effect of Dosage of concentration𝐇 𝟐 𝐎 𝟐 on turbidity and COD
removal day-2
Concentration
H2O2
(ml/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
10 22400 68.1 31
10 19200 72.7 20
10 12800 81.8 21
10 16000 77.2 22
0
10
20
30
40
50
60
70
80
90
5 5 5 5 5
%COD&Turbidity
H2O2 concentration
% COD Turbidity

10 19200 72.7 24
removal day-2
removal day-3
Concentration
H2O2
(ml/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
15 16000 77.2 22
15 19200 72.7 25
0
10
20
30
40
50
60
70
80
90
10 10 10 10 10
%COD&Turbidity
H2O2 concentration
% COD Turbidity

15 16000 77.2 30
removal day-3
removal day-4
Concentration
H2O2
(ml/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
20 19200 72.7 23
20 16000 77.2 29
20 22400 68.1 30
0
20
40
60
80
100
15 15 15
%COD&Turbidity
H2O2 concentration
% COD Turbidity

removal day-4
removal day-5
Concentration
H2O2
(ml/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
25 16000 77.2 21
25 12800 81.8 19
0
20
40
60
80
100
20 20 20
%COD&Turbidity
H2O2 concentration
% COD Turbidity
0
20
40
60
80
100
25 25
%COD&Turbidity
H2O2 concentration
% COD Turbidity

removal day-5
Table 4.42 Effect of Dosage of concentration 𝐇 𝟐 𝐎 𝟐on turbidity and COD
removal day-6
Concentration
H2O2
(ml/L)
COD
(mg/L)
% COD
removal
Turbidity
(NTU)
30 9600 86.3 20
30 8800 87.5 18
removal day-6
removal day-7
Concentration COD % COD Turbidity
0
20
40
60
80
100
30 30
%COD&Turbidity
H2O2 concentration
% COD Turbidity

H2O2
(ml/L)
(mg/L) removal (NTU)
35 5600 90 18
35 1600 92 17
removal day-7
The results are shown in table 4.37 to 4.43. It is clear the increasing amount of
H2O2 leads to greater COD and colour removal. There was a small difference
between the COD removal with 5 g/L, 10 g/L and 15 g/L of H2O2 dosage.
Therefore, it was not worth taking large amount of H2O2 dosage for increasing
degradation. Hence lower dose of 5 g/L of H2O2 was taken as the optimum
dosage. Further increase in H2O2 concentration lowered the degradation rate.
This is because of the excess H2O2 reacts with the hydroxyl radicals earlier
formed and hence acts as an inhibiting agent of degradation by consuming the
hydroxyl radicals responsible for Degrading the pollutant molecule. The rate of
0
20
40
60
80
100
35 35
%COD&Turbidity
H2O2 concentration
% COD Turbidity

degradation decreases as H2O2 increases after optimum condition; this is
because that more H2O2 Molecules are available for Fe2+
ions to react, which
increases the number of OH. Therefore, the rate of reaction also increases the
rates of the reaction become fast and OH. Radicals are consumed rapidly due to
more availability of H2O2 molecules.
4.3.5 Effect of liquid depth
In order to study the effect of liquid depth, different volumes of
wastewater samples were taken in the reactors and the chemicals such as ferrous
sulphate (Fe2+
= 1g/L) and hydrogen peroxide (H2O2 = 5 g/L) were added and
stirred well. The photo-Fenton reactions were carried out under strong solar
radiation from 12.00 pm to 1.00 pm. The samples were taken for every five
minutes to analyse COD and colour. The percent removal of COD is given in
table 4.44. It was observed that the colour removal was nearly the same in all the
heights with the slight differences. Maximum colour removal was achieved
within 10 minutes of irradiation time. But in the case of COD removal, the depth
plays an important role. As the depth increases, Degradation of COD decreases.
This is because, for smaller depths, light can penetrate well. As the depth
increases, the light cannot penetrate deep into the reactor for photolysis shallow
solar pond having depth of 1mm gives the best results.
Table 4.44 Effect of liquid depth on COD removal
Days Liquid depth
(mm)
COD
(mg/L)
% COD
removal
0 20 70400 0

1 18 12800 81.8
2 15 19200 72.7
3 11 16000 77.2
4 9 22400 68.1
5 6 12800 81.8
6 3 8800 87.5
7 1 1600 92
Figure 4.43 Effect of liquid depth on COD removal
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25
%COD
DEPTH(mm)
Effect of liquid depth on COD removal

CHAPTER 5
SUMMARY AND CONCLUSION
5.1 GENERAL
The literature review showed that an internal process change is one
of the options to be adopted by the match box industry to reduce the pollution at
the source.
5.2 SUMMARY
The development of pollution treatment strategies, technologies, and
their implementation in match box industries requires a detailed understanding of
the manufacturing processes as well as the physical, chemical and biological
properties of the multitude of pollutants generated. Thus choosing the right
combination and sequence of treatment methods is the successful handling of
pollution problems in the match box industries. Based on the above literature
review, the following conclusions are made. Among the various treatment

processes currently used for match box industry effluent treatment, only a few are
commonly adopted by match box industry especially for tertiary treatment.
Sedimentation is the most commonly adopted process by the match box industry
to remove suspended solids. Coagulants are the preferred option for removing
turbidity and colour from the wastewater. Adsorption processes are used to
remove colour, COD. They are rather expensive. Activated coke alone can
remove 90% of the COD, and colour.
5.3 CONCLUSION
In this study, it has been found that solar photo-Fenton oxidation is
an appropriate process for the pre-treatment of match box industry wastewater.
The optimum pH for the process is 5.With the ferrous ion dosage of 1 g/L,
concentration of H2O2 as 5 ml/L, about 92% of COD was removed within one
hour of reaction time and nearly 100 percent colour removal was achieved in a
reaction time of 10 minutes. The effect of liquid depth influences the degradation
of organic compound. With the increase in liquid depth, the degradation rate
decreases. The degradation rate of solar/Fe2+
/H2O2 process is three times faster
than solar/Fe2+
process. Thus coupling of solar photo-Fenton process with the
biological treatment is an effective treatment method thereby reducing the cost of
the treatment.

REFERENCES
1. Huaili Zheng, Yunxia Pan, Xinyi Xiang (2006), ‘Oxidation of acidic dye
Eosin Y by the solar photo-Fenton processes’, College of Chemistry and
Chemical Engineering, Chongqing University, Chongqing’,
doi:10.1016/j.jhazmat.2006.12.018.
2. Nogueira K.R.B., Teixeira A.C.S.C., Nascimento C.A.O and Guardani
(2008),’Use of solar energy in the treatment of water contaminated with
Phenol by photochemical processes’, Brazilian Journal of Chemical
Engineering, Vol 25, No. 04, pp. 671 – 682, October – December, 2008.
3. Modh Azam Sheikh, Anil Kumar, Mukesh Paliwal, Rameshwar Ameta and
Khandelwal R.C. (2008), ‘Degradation of organic effluents containg
Wastewater by photo-Fenton oxidation processes, Indian Journal of
Chemistry, Vol. 47 A, pp. 1681-1684.

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