REDUCTION OF COD FROM SECONDARY EFFLUENT OF

CETP BY CHLORINATION

By

FORAM MANOJKUMAR PAREKH

Enrollment No. 160280718012

Guided By:

Prof. Gaurang H Ban

Head of Department of Environmental Engineering
L.D. College of Engineering, Ahmedabad

A Thesis Submitted to
Gujarat Technological University
In Partial Fulfillment of the Requirements for the Master of Engineering Degree
in Environmental Management

May, 2018

L. D. College of Engineering, Ahmedabad- 380015

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 Acknowledgements
Research is essentially a collective work, where every step is taken with all caution and care. I
am proud to be a part of L.D. College of Engineering, the institute which gave me an
opportunity to embark on this project work. The completion of this work is not a result of an
individual’s efforts but of co-operation, support and guidance of number of individuals
directly or indirectly related to the work.

I wish to express my profound gratitude to my respected guide Prof. Gaurang H Ban for
practical suggestions, constant and valuable guidance, invaluable time and expert advice in
completing this dissertation work within the stipulated timeframe.

I am also grateful to Prof. Minarva Pandya, Prof. Dimpi Shah and Prof. Yogesh Gajera for
their constant inputs support throughout the dissertation.

I am highly thankful to Shrey, Jay, Isha, Aparna, Niyati, and Jatin, my colleagues to help me
during each phase till the completion of this work.

I would like to thank my mother Kirti Parekh, my father Manoj Parekh and my sister Dharmi
Parekh for their helping hand and for standing as support pillars throughout the dissertation
work.

Lastly, I would like to thank all those who have helped me directly or indirectly in making this
attempt a successful one.

-Foram Parekh

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 Table of Contents
CERTIFICATE ........................................................................................................................... ii

COMPLIANCE CERTIFICATE ............................................................................................... iii

PAPER PUBLICATION CERTIFICATE..................................................................................iv

THESIS APPROVAL CERTIFICATE.......................................................................................v

DECLARATION OF ORIGINALITY ...................................................................................... vi

Acknowledgements .................................................................................................................. vii

Table of Contents..................................................................................................................... viii

List of Figures ............................................................................................................................ xi

List of Tables ............................................................................................................................ xii

Abstract .................................................................................................................................... xiii

CHAPTER 1 ..............................................................................................................................14

1.1 Background ..................................................................................................................... 14

1.1.1 Water Pollution ........................................................................................................ 14
1.1.2 Concept of CETP ..................................................................................................... 16
1.1.3 Existing CETP at Vatva ........................................................................................... 16
1.1.4 Nonbiodegradable Pollutants ................................................................................... 19
1.1.5 Treatment of Nonbiodegradable Pollutant ............................................................... 20
1.1.6 Chlorination ............................................................................................................. 20
1.2 Need of the Study ........................................................................................................... 20
1.3 Aim of the Study ............................................................................................................. 21
1.4 Objectives of the Study ................................................................................................... 21
1.5 Methodology ................................................................................................................... 21
1.6 Scopes of the Study......................................................................................................... 24

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CHAPTER 2 ..............................................................................................................................25

2.1 Literature Based on Characteristics of Wastewater ........................................................ 25

2.1.1 Statistical analysis to identify the main Parameters to the wastewater quality index
of CETP: a case study at Vapi, Gujarat, India .................................................................. 25
2.2 Literature Based on Chlorination Treatment .................................................................. 26
2.2.1 Application of chlorine dioxide for secondary effluent polishing ........................... 26
2.2.2 The Removal of COD and Color from Textile Industry by Chlorine Hypochlorite 27
2.2.3 Oxidation of Various reactive dyes with in situ electro generated active chlorine for
.............................................................................. textile dyeing industry wastewater treatment 28
2.2.4 Reduction of COD and BOD reduction by Oxidation : A CETP case study........... 28
2.2.5 COD reduction of pharmaceutical industry wastewater by electro oxidation process
by generation of in situ hypochlorus acid. ........................................................................ 29
2.2.6 Treatment of Textile wastewater With Chlorine: An Effective Method ................. 30
CHAPTER 3 ..............................................................................................................................32

3.1 Concept of Chlorination.................................................................................................. 32

3.2 Chemistry of Chlorine with Organics ............................................................................. 32
3.3 Chemicals Used For Chlorination .................................................................................. 34
3.3.1 Chlorine ................................................................................................................... 34
3.3.2 Chlorine dioxide ...................................................................................................... 35
CHAPTER 4 ..............................................................................................................................37

4.1 Sample Collection ........................................................................................................... 37

4.2 Characterization of Wastewater ...................................................................................... 38
4.3 Selection of Chemicals and Reactor ............................................................................... 39
4.4 Selection of Contact Time .............................................................................................. 39
4.5 conducting trials at lab scale ........................................................................................... 39
4.6 Evaluation of Efficiency of Chemicals With Respect To Different Dosage And Contact
Time. ..................................................................................................................................... 39
4.7 Procedure followed for treatment ................................................................................... 40
CHAPTER 5 ..............................................................................................................................42

5.1 Results and Data Presentation......................................................................................... 42

CHAPTER 6 ..............................................................................................................................50

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 6.1 Conclusions..................................................................................................................... 50
REFERENCES ..........................................................................................................................51

PAPERS ................................................................................................................................ 51
BOOKS: ................................................................................................................................ 52
WEBSITES: .......................................................................................................................... 52
Appendix A Student Review Card ..........................................................................................53

Appendix B Student Compliance Report ..................................................................................58

Appendix C Turnitin Originality Report ...................................................................................59

Appendix D Paper Publication Certificates ...............................................................................62

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 List of Figures
Figure 1.1 Flow Diagram of Treatment Process at CETP ........................................................ 18
Figure 1.2 Mechanism of removal of organics from wastewater ............................................. 19
Figure 2.1 Diagram of Chlorination treatment ......................................................................... 27
Figure 2.2 Chlorination treatment for textile wastewater ......................................................... 30
Figure 3.1 Relation of chlorination species with pH ................................................................ 33
Figure 3.2 Degradation of organic matter by chlorination ....................................................... 33
Figure 3.3 Oxidation potential of chlrination chemicals .......................................................... 36
Figure 4.1 Application of chlorination after secondary treatment ............................................ 38
Figure 4.2 Wastewater after chlrination treatment ................................................................... 40
Figure 4.3 Initial wastewater and after the treatment ............................................................... 41
Figure 5.1 Graph of COD concentration with contact time for calcium hypochlorite ............. 44
Figure 5.2 Graph of COD removal efficiency with contact time for calcium hypochlorite ..... 44
Figure 5.3 Graph of TSS concentration with contact time for calcium hypochlorite ............... 45
Figure 5.4 Color removal efficiency of calcium hypochlorite with contact time ..................... 45
Figure 5.5 COD concentration with contact time for sodium chlorite .................................... 47
Figure 5.6 COD removal efficiency with contact time for sodium chlorite ............................. 48
Figure 5.7 TSS concentration with contact time for sodium chlorite ....................................... 48
Figure 5.8 Color removal efficiency with contact time ............................................................ 49

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 List of Tables
Table 1.1 Profile of industries at CETP .................................................................................... 16
Table 4.1 Characteristics of wastewater of CETP .................................................................... 38
Table 4.2 Trial runs taken for the experiment .......................................................................... 39
Table 5.1 Results for calcium hypochlorite for 300 mg/L ........................................................ 42
Table 5.2 Results for calcium hypochlorite for 600 mg/L ........................................................ 42
Table 5.3 Results for calcium hypochlorite for 900 mg/L ........................................................ 43
Table 5.4 Results for calcium hypochlorite for 1200 mg/L ...................................................... 43
Table 5.5 COD removal efficiency of calcium hypochlorite.................................................... 43
Table 5.6 Results for Sodium Chlorite for 300 mg/L ............................................................... 46
Table 5.7 Results for Sodium Chlorite for 600 mg/L .............................................................. 46
Table 5.8 Results for Sodium Chlorite for 900 mg/L .............................................................. 46
Table 5.9 Results for Sodium Chlorite for 1200 mg/L ............................................................ 46
Table 5.10 Removal efficiency of COD by Sodium Hypochlorite........................................... 47

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 Abstract
Common Effluent Treatment Plant is established for treatment of wastewater generated by
small and medium scale industries for abatement of pollution. In CETP, many industrial
wastewater contains nonbiodegradable organics. Mainly CETPs treat wastewater by
conventional secondary treatment. conventional processes are able to treat soluble
biodegradable organics. But nonbiodegradable organics cannot be treated by conventional
biological treatment processes. This wastewater has low BOD/COD ratio (<0.2) which
indicate the presence of nonbiodegradable organics. Ultimately it contributes COD in effluent
of secondary clarifier. Therefore, it requires further advanced oxidation process for removal of
nonbiodegradable organics. Chlorination is one of advanced chemical process to oxidize
nonbiodegradable organics. Different chemicals and chlorine gas are used for the chlorination.
In this study, Secondary effluent of CETP is treated with chlorination using chemical calcium
hypochlorite and Sodium Chlorite. Calcium Hypochlorite is added by pulse input and Sodium
chlorite is added with acid by pulse input method. Study is carried out at different contact time
between 10-90 min and different concentration of chemicals between 300-1800 mg/L.
Removal efficiency of COD increases as the contact time and concentration increases. Sludge
generation increases as concentration and contact time increases. Sludge generation for
Calcium Hypochlorite is higher than the sludge generation for Sodium Chlorite Optimum
condition selected for Calcium Hypochlorite is for 900 mg/L for 70 min contact time which
gives 63 % COD removal efficiency and less sludge generation. Optimum condition selected
for Sodium Chlorite is for 1200 mg/L for 90 min contact time which gives 63% COD removal
efficiency and less sludge generation. Color can also be removed by the chlorination
treatment. COD removal efficiency ranges for calcium hypochlorite is between 18% to 71%
and for Sodium Chlorite is between 7 to 63%.

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 Reduction of COD from secondary effluent of CETP by chlorination

CHAPTER 1

Introduction

1.1 Background

1.1.1 Water Pollution

According to the Water (Prevention and Control of Pollution) Act, 1974 definition of water
pollution is,

Pollution means “ such contamination of water or such alteration of the physical , chemical or
biological properties of water or such discharge of any sewage or trade effluent or of any other
liquid, gaseous, or solid substance into water (whether directly or indirectly ) as may, or is
likely to create a nuisance or render such water harmful or injurious to public health or safety
or to domestic, commercial, industrial, agricultural or other legitimate uses, or to the life and
health of animals or plants or of aquatic organisers.”

There are generally two types of sources of water pollution which are point sources and non
point sources. A pipe or drain type identifiable source of pollution are called point sources.
Non-point sources of pollution are often termed ‘diffuse’ pollution and they are refer to the
wide area source generally not a single source. The various type of point source pollutant
found in water pollution as varied as the types of business, industry, agricultural and urban
sources that produce them.
In point sources, industries are huge source of water pollution. It produces pollutants which
are extremely harmful to people and environment. Various types of industries like chemical
industry, food related industry, textile industry, pulp paper industry, etc. produce different
types of pollutants including toxic waste.

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The effects of water pollution can be broadly classified into three categories:

1. Physico- chemical effects :

 Aesthetically unacceptable due to color, odor and taste present in wastewater

 Addition of organic matter results in depletion of dissolved oxygen of water

bodies.

2. Biological effects :

 Some lives are sensitive to pollution results into breaking down of food chain.

 Presence of pathogens cause water borne diseases.

3. Toxic effects:

 In some cases animals may be killed by poison.

 Toxic waste like pesticides may cause bioaccumulation food web.

Pollutants which are present in the wastewater are,

• Organic compounds (soluble and insoluble)

• Inorganic compounds (soluble and insoluble)

• Nutrients

• Suspended solids

• Pathogens

Pollutants can be classified in two types based on the degradability of the pollutant, which are

1. Biodegradable pollutant: those pollutants which can be broken down into simpler,
harmless, substances in nature in due course of time by action of micro-organisms like
bacteria called biodegradable pollutants. E.g. domestic wastes, urine, faecal matter,
agriculture residues, paper, wood, cloth, vegetable or plant stuff, etc.

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Non-biodegradable pollutant: Those pollutants which cannot be broken down into simpler,
harmless substances in nature are called non-biodegradable pollutants. E.g. DDT, plastics,
insecticides, pesticides, metals, etc.

1.1.2 Concept of CETP

In India there are so many small and medium scale industries which are very important for the
economic growth of the country. These industries are producing large amount of wastewater.
But due to lack of finance and area availability they are unable to treat wastewater
individually. So for that government of India introduced the concept of Common Effluent
Treatment Plant where wastewater from individual units are collected at one place and treated.
By CETP pollution caused by industrial units are reduced.

1.1.3 Existing CETP at Vatva

The Green Environment Services co-op. Society Ltd. In Vatva CETP established for the
treatment of industrial wastewater and their safe disposal. Capacity of CETP is 16 MLD for
treating wastewater. It has 673 member units of different small and medium scale industries
situated in Vatva. Industrial profile of CETP is as shown in Table 1.1.

Table 1.1 Profile of industries at CETP

Type of Industry Micro Small Medium Large Total

Dyes, Intermediates & Chemicals 47% 36% 4% <0.5% 88%

Pharmaceuticals and Food 1% 3% 4%
industries
Textile Processing 2% 1% <0.2% 3%
Engineering and Plastic 1% 2% <0.2% <0.2% 3%
Processing
Ice Factories 2% 2%
Total 53% 42% 4% 1% 100%

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Treatment Plant:

Wastewater from industrial units are collected in sump and then treated in treatment plant.
Primary and secondary treatment is provided to wastewater and then disposed into Mega
pipeline. Flow diagram of treatment plant is shown in Error! Reference source not found..

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Figure 1.1 Flow Diagram of Treatment Process at CETP

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1.1.4 Nonbiodegradable Pollutants

Organic matter in wastewater has been estimated as an equivalent quantity, such as chemical
oxygen demand (COD) or biological oxygen demand (BOD). However, the adoption of
tertiary treatment processes to remove nutrients and refractory organic matter requires a
classification of the subordinate fractions of wastewater organic matter. The total COD of
wastewater organic matter can be classified into four types which are readily biodegradable
COD (rbCOD), slowly biodegradable COD (sbCOD), non-biodegradable soluble COD
(nbdsCOD) and non-biodegradable particulate COD (nbdPCOD). rbCOD, such as volatile
fatty acids, is readily degraded by microbial metabolism. sbCOD, composed of particulate
organic matter, is degraded slowly by a series of microbial actions, such as adsorption,
hydrolysis, and metabolism. nbdsCOD, which is refractory in biodegradation, is contained in
industrial discharges. Aromatic compounds are used in various industries and are typical
examples of nbdsCOD. nbdpCOD is also non-biodegradable, but is removed easily by
sedimentation in a conventional WWTP. For biodegradable organic matter, such as for
biological oxygen demand (BOD). Thus, some industrial discharges are likely to contain a
large amount of refractory non-biodegradable organic matter.

A conventional WWTP having generally activated sludge system are not capable to treat
nonbiodegradable organic matter so they are disposed into the water bodies.

Figure 1.2 Mechanism of removal of organics from wastewater

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1.1.5 Treatment of Nonbiodegradable Pollutant

Organics present in the wastewater in terms of COD and BOD are generally treated by
conventional treatment like activated sludge process. This conventional treatment processes
removes only biodegradable organics present in the wastewater. When nonbiodegradable or
refractory organics are present in the wastewater , it requires tertiary treatment. It is important
to remove these matters from wastewater because it is harmful to aquatic life when discharged
into water bodies. And also to meet the discharge standard it is necessary to provide tertiary
treatment for removal of refractory organics.

Many advanced oxidation processes are there for removal of nonbiodegradable organics from
wastewater, which are:
 Chlorination
 Fenton process
 Adsorption
 Ozonation
 Hydrodynamic cavitation

1.1.6 Chlorination

Wastewater containing refractory organics cannot be oxidized by biological processes, so due

the complexity of these organic chemicals are used for the oxidation of these matters.
Chlorination is one of oxidation process which is used to convert the complex organic
compounds into simpler form and then convert into carbon dioxide and water. Different
chemicals like chlorine, chlorine dioxide are used for the chlorination as they act as oxidizing
agent. Chlorination is generally used as tertiary treatment.

1.2 Need of the Study

Most of the CETPs are providing biological treatment to the wastewater. In the effluent of
CETP ratio of BOD/COD is very low which indicates nonbiodegradable substances in water.
Conventional biological treatment removes only biodegradable dissolved organic matter from
the wastewater. When the wastewater contains complex organics, it cannot be removed by

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 Reduction of COD from secondary effluent of CETP by chlorination

biological treatment. It requires some oxidation processes which can oxidize complex organics
into simple organics. It is required to treat the wastewater for environmental prevention
because if it is discharged in water bodies, it harm aquatic life and environment. For
legislative purpose also it is required that COD should be reduced to prescribed limit
described by Authority.

Chlorination is one of the oxidation process used for the treatment of refractory or
nonbiodegradable organics. Chlorine has strong oxidizing power that can reduce the COD of
wastewater. Chlorination can be apply after the biological treatment for removal of
nonbiodegradable COD. Advantage of chlorination treatment over other oxidation process is
that it requires less time and cost of treatment is low.

1.3 Aim of the Study

Aim of the study is “To reduce the COD of secondary effluent of CETP by Chlorination”.

1.4 Objectives of the Study

 To carry out literature survey on chlorination treatment.

 To reduce COD of secondary effluent by chlorination.

 To remove the colour from the wastewater by chlorination.

 To find efficiency of chlorination at different contact time.

 To find optimum dosage of sodium chlorite and calcium hypochlorite.

 To find the amount of sludge generation.

 Compare both chemicals in terms of removal efficiency and sludge generation

1.5 Methodology

Methodology adopted for the present study is as following:

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Conceptual study of chlorination treatment

Find need of study

Literature review related to work

To decide scope, aim and objective

Assessment of characteristics of secondary efluent of

CETP

To treat secondary effluent by chlorination using

sodium chlorite and calcium hypochlorite.

To check efficiency of COD removal by both

chemicals

To check removal efficiency of color removal by both

chemicals.

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 Reduction of COD from secondary effluent of CETP by chlorination

Find efficiency of COD removal at different contact

time.

Find optimum dosage of chemicals for efficient

removal of COD

To check sludge generation after treatment.

To estimate cost of treatment

Results and coclusion.

Final report drafting.

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 Reduction of COD from secondary effluent of CETP by chlorination

1.6 Scopes of the Study

 Study mainly focuses on reduction of COD by chlorination treatment.

 Overflow of secondary clarifier is taken for the chlorination treatment.
 Chemicals for chlorination : Sodium chlorite and Calcium hypochlorite.
 Parameters measured before and after the treatment are COD, Color and TSS.
 Varying parameters are contact time and chemical concentration.
 All analysis are done by standard method APHA.

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 Reduction of COD from secondary effluent of CETP by chlorination

CHAPTER 2

Literature Survey

Various research works have been conducted which gives the basic understanding of the
Chlorination treatment and different methods used for treatment of wastewater by
chlorination. The present chapter deals with the review of such literature works which are
taken as the basis for the present study.

2.1 Literature Based on Characteristics of Wastewater

2.1.1 Statistical analysis to identify the main Parameters to the wastewater quality index
of CETP: a case study at Vapi, Gujarat, India

Author name:

Shah Abhishek, khambete A.KJ

Publication:

Journal of Environmental Research and Development Vol.7 No. 3, January-March 2013

Findings:

 The Wastewater Quality Index (WWQI) for wastewater of Common Effluent Treatment
Plant (CETP) was found considering all the parameters described by Central Pollution
Control Board (CPCB).
 Chemical oxygen demand is measured after the secondary treatment.

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 BOD/COD ratio is less than 0.2 in treated effluent of CETP

 Average COD of treated effluent is 507 mg/L.

2.2 Literature Based on Chlorination Treatment

2.2.1 Application of chlorine dioxide for secondary effluent polishing

Author:

F.Vaezi, K. Naddafi, F. Karimi and M. Alimohammadi

Publication:

International journal of Environmental Science and Technology Vol 1, No 2, 97-101, summer

2004.

Findings :

 In this study, the efficiency of chlorine dioxide in the process of preparing the
effluent of Sahebgharanieh Plant of Tehran for COD removal has been determined.
 In this study secondary effluent from polishing industry is treated with chlorine
dioxide to reuse the wastewater.
 Chlorine dioxide is generated by direct acid system using sulphuric acid. Experiment is
carried out by taking 60 min contact time and various ClO2 concentrations.
 Contact time for ClO2 should longer than 20 min.
 Total COD reduction at one hour contact time for concentrations 1/1, 1/2, 1/4 are about
42%, 49%, 59% respectively.

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2.2.2 The Removal of COD and Color from Textile Industry by Chlorine Hypochlorite

Author:

Mohamadreza Massoudinejad, Mansour Ghderpoori and Mansour Rezazadeh Azari

Publication:

International Journal of Advanced Science and Technology Vol.76, pp 35-42, 2015

Findings:

Figure 2.1 Diagram of Chlorination treatment

 In this study textile industry effluent is treated with calcium hypochlorite solution. In
this study two stabilization tank is used. Flow is taken 8m3/d.
 Textile wastewater contains residual nonbiodegradable organics.
 1 mg/L of calcium hypochlorite with retention time 10 min COD reduced by 65%.
 The removal efficiency of COD removal is 96 to 98%.
 Residual chlorine can be removed by sodium thiosulfate.

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2.2.3 Oxidation of Various reactive dyes with in situ electro generated active chlorine for
textile dyeing industry wastewater treatment

Author:

D. Rajkumar, Jong Guk Kim

Publication:

Journal of Hazardous Materials B136, 203-212, 2006

Findings:

 In this study dyeing wastewater is treated by chlorination by electro generated method.

Titanium anode Statistical analysis to identify the main Parameters to the wastewater
quality index of CETP: A case study at Vapi, Gujarat, India and stainless steel cathode
is used for the electrochemical oxidation. Volume of rector used was 1 L.
 All reactive dyes can be degraded by chlorine mediated electrochemical oxidation.
 Degradation rate is affected by temperature and initial dye concentration.
 Limitation of this treatment is formation of chlorinated organic compounds.

2.2.4 Reduction of COD and BOD reduction by Oxidation : A CETP case study

Author:

Prashant K Lalwani, Malu D. Devadasan

Publication:

International Journal of Engineering Research and Applications (IJERA)

Findings:

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 In this study CETP wastewater is segregated according to the BOD/COD ratio.

Comparative study is done by using Fenton’s reagent and sodium hypochlorite.
 COD and BOD reduction is carried out at different doses and contact time.
 Sodium hypochlorite solution is used in concentration of 2, 4 , 6, 8, 10 ml.
 Maximum COD removal by chlorination is 45.14%.

2.2.5 COD reduction of pharmaceutical industry wastewater by electro oxidation process

by generation of in situ hypochlorus acid.

Author:

Jugal M. Patel, Dr. Dipak S. Vyas, Mrs Sejal M. Patel

Publication:

IJARIIE-ISSN(0)-2395-4396 Vol-2 Isuue-3 2016

Findings:

 In this present work, to reduction of Chemical Oxygen Demand (COD) is measured by

electrochemical oxidation treatment of pharmaceutical waste water which was
collected after primary treatment.
 Electrodes used for electrochemical oxidation graphite, iron and copper.
 Contact time taken were 30,60,90 min.
 production of hypochlorous acid was achieved by the use of sodium chloride solution
for chlorine production
 The hypochlorous acid was utilized for the oxidation of organic matter present in the
wastewater.
 Maximum COD removal efficiency is 68.26 % at pH 7 for contact time of 90 min.

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2.2.6 Treatment of Textile wastewater With Chlorine: An Effective Method

Author:

A. K. M. A. Quader

Publication:

Chemical Engineering Research Bulletin 14 (2010) 59-63

Findings:

Figure 2.2 Chlorination treatment for textile wastewater

 In this study, treatment of textile wastewater is treated with chlorine gas for removal of
COD, BOD, TDS.
 As shown in fig, chlorination treatment is applied before the secondary treatment and
dechlorination is applied after the aeration tank.
 residual chlorine is measured in overflow of the aeration tank.
 Sodium thiosulfate is used for dechlorination.
 removal of parameter COD, BOD by chlorination is given in the following table.

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Plant A Plant B
Parameters
BT AT BT AT

pH 10.62 7.46 8.5 6.5

COD 256 128 480 160

BOD 86 40 230 36

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 Reduction of COD from secondary effluent of CETP by chlorination

CHAPTER 3

Chlorination

3.1 Concept of Chlorination

Chlorination is used for many other purposes other than disinfection. chlorine compounds are
strong oxidizing agents. so chlorination can be used in wastewater treatment for oxidation of
different pollutant mainly complex organics which cannot be removed by microbial treatment.
Chlorine oxidize complex organics or refractory organics in simple form and then convert into
carbon dioxide and water. It is not one step process, it is multiple step process which is
indicated by multiple arrows in the following equation.

3.2 Chemistry of Chlorine with Organics

Chlorine solutions are made from Chlorine gas, Sodium Hypochlorite and other
Hypochlorites, or Chlorine gas. Which comprise of three species- molecular chlorine,
undissociated acid and hypochlorite ions which depends upon the pH of solution. As shown in
Figure 3 below for 0.1 M solution, pH less than 4 Cl2 is present, pH between 4 and 5 only
HOCl is present and when pH is greater than 5 it forms hypochlorite ions, At pH 7.5 solution
contains both HOCl and OCl- in similar amount. commercial sodium hypochlorite solutions,
chlorine is present exclusively as OCl- by pH 11.

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Figure 3.1 Relation of chlorination species with pH

Figure 3.2 Degradation of organic matter by chlorination

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3.3 Chemicals Used For Chlorination

Chemicals used for chlorination are majorly of two types, chlorine and chlorine dioxide.

3.3.1 Chlorine
Chlorine is in gas form under normal pressure and temperature. Chlorine gas can be
compressed to a liquid and stored in containers. Chlorine is available as Calcium Hypochlorite
(Ca(OCl)2) in granular form and as Sodium Hypochlorite (NaOCl) in liquid form. In all forms
chlorine act as oxidizing agent.

Chlorine gas completely hydrolyses in water and form,

Hypochlorous acid (HOCl):

Cl2 + H2O HOCl + H+ + Cl-

The Hypochlorous acid dissociates into hydrogen ions (H+) and hypochlorite ions in the
reversible reaction:

HOCl H+ + OCl-

Hypochlorous acid is a weak acid with a pKa of approximately 7.5 at 25 °C. Hypochlorous
acid, the prime disinfecting agent, is therefore dominant at a pH below 7.5 and is a more
effective disinfectant than hypochlorite ion, which dominates above pH 7.5.

Many of the safety concerns related to transport , storage and feeding of liquid gaseous
chlorine are eliminated by use of calcium hypochlorite and sodium hypochlorite. chlorine is
available in form of calcium hypochlorite and sodium hypochlorite. properties of both
chemicals are discussed below.
Sodium Hypochlorite:

Sodium hypochlorite (NaOCl) is only available in liquid form and usually contains 12.5 to 17
percent of chlorine.

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 Reduction of COD from secondary effluent of CETP by chlorination

reactions in water:

NaOCl + H2O HOCl + NaOH

Calcium Hypochlorite:

Calcium hypochlorite is available commercially in either dry or a wet form. high test calcium
hypochlorite contains at least 70% chlorine. in a dry form it is available as an off-white colour
powder or as granules. Because of its oxidizing potential, it should be stored in cool, dry
location away from the chemicals in corrosion resistant container.

reactions in water:

Ca(OCl)2 + 2H2O HOCl + Ca(OH)2

3.3.2 Chlorine dioxide

Chlorine dioxide is available as monomeric free radicals. chlorine dioxide vapours are very
explosive so cannot be stored alone or compressed with other gases. so it is required to
manufacture chlorine dioxide at the point of use.

Oxidation state of chlorine dioxide is +4 which is between Chlorite (+3) and Chlorate (+5).
No ion or Acid have the same degree of oxidation. Chlorine dioxide is strong oxidizing agent
which can decompose to chlorite. In the presence of alkali, it dissolves into water to form
chlorite and chlorate:

when chlorine dioxide dissolves in water it forms greenish-yellow colour. It is unstable and
decomposes fastly, it is generated at point of application before its use. chlorine dioxide can be
generated by solution of sodium chlorite (NaClO2) mixing and reacting with chlorine solution
in water as per the following reaction.

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Advantage of Chlorine dioxide over chlorine is that is produces less harmful byproducts than
chlorine and hypochlorite.

Oxidation potential of different chlorine compounds are given in the table.

Chemical E0 (V)

HOCl/Cl- +1.49

ClO2/ClO2- +0.95

ClO2/Cl- +0.76

ClO3/Cl- +0.62

Figure 3.3 Oxidation potential of chlrination chemicals

E0= standard electrode potential (redox potential) in water at 25◦C. the oxidation reduction state of an
aqueous environment can be stated in terms of its redox potential. in chemistry it is generally expressed
in volts, E.

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CHAPTER 4

Experimental Set Up and Study: Laboratory Scale

Treatment of wastewater

The experimental study is to be carried out on laboratory scale in order to determine the
removal efficiency of COD by Sodium Chlorite and Calcium Hypochlorite.

The present study can be broken down to different stages which are:
 Application of chlorination treatment
 Characterization of wastewater
 Selection of dosage of chemicals
 Selection of contact time
 Evaluation of efficiency of chemicals for removal of COD with respect to different
dosage and contact time.

4.1 Sample Collection

Chlorination is applied after the biological treatment. Sample is taken from the outlet of
secondary clarifier.

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Figure 4.1 Application of chlorination after secondary treatment

4.2 Characterization of Wastewater

Wastewater sample is collected from secondary clarifier. Parameter pH, COD and BOD of
wastewater sample is measured in the laboratory. Methods used for the assessment of pH,
COD and BOD are of Standard Method.

Table 4.1 Characteristics of wastewater of CETP

Parameter Value

pH 7.44

BOD 42 mg/L

COD 742 mg/L

BOD/COD ratio 0.056

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4.3 Selection of Chemicals and Reactor

Two chemicals are used for treatment of wastewater which are “Sodium chlorite” and
“Calcium Hypochlorite”. Dosages of both chemicals taken are 1800 mg/L, 900 mg/L, 450
mg/L and 300 mg/L.

Reactor taken for the experiment is 200 mL.

4.4 Selection of Contact Time

Experiment is carried out at different contact time. As per the literature review removal time
for both the chemicals is in the range of minute (0 – 90 min).

4.5 conducting trials at lab scale

Trials for treatment of secondary effluent for different concentration and at different time are
conducted as shown in table

Table 4.2 Trial runs taken for the experiment

No. of Trials Chemicals for Contact time Chemical

chlorination (min) concentration
(mg/L)

Trial 1 Calcium 10,30,50,70,90 1800,900,450,300

Hypochlorite

Trial 3 Sodium Chlorite 10,30,50,70,90 1800,900,450,300

4.6 Evaluation of Efficiency of Chemicals With Respect To Different Dosage And

Contact Time.

Efficiency will be evaluated by following formula.

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% Removal efficiency = [(Initial COD – final COD) / Initial COD] * 100

4.7 Procedure followed for treatment

The steps followed for treatment of wastewater by chemicals are as follows:

 Secondary effluent of volume 200 mL is taken for treatment.

 Then chemical is added of selected concentration by pulse input method.
 For Sodium Chlorite Chlorine dioxide is generated by adding sulphuric acid which
decrease the pH between 2- 4 so the removal can be achieved.
 And it is mixed on magnetic stirrer for 5 mins.
 wastewater samples are taken at different, contact time which are 10, 30, 50, 70 and
90 mins.
 Parameters COD, TSS and Colour are measured before and after the treatment. All
the parameters are measured by standard methods.

Figure 4.2 Wastewater after chlrination treatment

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Figure 4.3 Initial wastewater and after the treatment

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 Reduction of COD from secondary effluent of CETP by chlorination

CHAPTER 5

Results and Discussions

5.1 Results and Data Presentation

Two different chemicals Calcium Hypochlorite and Sodium Chlorite is used for the COD
removal from the wastewater. Results obtained for both chemicals are shown in following
table.

1. Results for Calcium Hypochlorite

Table 5.1 Results for calcium hypochlorite for 300 mg/L

Contact time (min), Concentration of calcium hypochlorite is

Parameter
300 mg/L
Initial 10 30 50 70 90
COD(mg/L) 792 648 522 468 396 378
TSS(mg/L) 184 472 756 916 1220 1416
Colour(Co-
11364 1320 995 937 893 858
unit)

Table 5.2 Results for calcium hypochlorite for 600 mg/L

Contact time (min), Concentration of calcium hypochlorite is

Parameter
600 mg/L
Initial 10 30 50 70 90
COD(mg/L) 774 594 486 378 342 324
TSS(mg/L) 168 644 908 1136 1403 1542
Colour(Co-
11364 1184 965 883 857 824
unit)

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Table 5.3 Results for calcium hypochlorite for 900 mg/L

Contact time (min), Concentration of calcium hypochlorite is

Parameter
900 mg/L
Initial 10 30 50 70 90
COD(mg/L) 738 504 432 288 270 234
TSS(mg/L) 136 748 1012 1460 1760 2156
Colour(Co-
11364 1100 936 856 820 786
unit)

Table 5.4 Results for calcium hypochlorite for 1200 mg/L

Parameter Contact time (min), Concentration of calcium hypochlorite is

1200 mg/L
Initial 10 30 50 70 90
COD(mg/L) 756 468 378 270 252 216
TSS(mg/L) 168 944 1340 1884 2200 2608
Colour(Co- 11364 947 834 793 762 746
unit)

Results obtained for different concentration of calcium Hypochlorite is shown in Table 5.1 to
5.4. Parameters measured were COD, TSS and Color at contact time 10-90 min. For the
highest concentration 900 mg/L and maximum contact time 90 min COD obtained was 216
mg/L with TSS concentration of 2608 mg/L. Concentration of COD decreases as the
concentration increases and contact time increases. Maximum color removal obtained was 746
Co-unit. Concentration of TSS ranges from 472 to 2608 mg/L concentration.

Table 5.5 COD removal efficiency of calcium hypochlorite

Concentration Contact Time (min)

10 30 50 70 90
300 18.18 34.09 40.90 50 52.27
600 23.25 37.20 51.16 55.81 58.14
900 31.70 41.46 60.97 63.41 68.29
1200 38.09 50 64.28 66.66 71.42

As shown in Table 5.5 COD removal efficiency increases with the increase in concentration.
COD removal efficiency ranges from 18.18 % to 71.42% for different concentrations.

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Figure 5.1 Graph of COD concentration with contact time for calcium hypochlorite

Figure 5.2 Graph of COD removal efficiency with contact time for calcium hypochlorite

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Figure 5.3 Graph of TSS concentration with contact time for calcium hypochlorite

Figure 5.4 Color removal efficiency of calcium hypochlorite with contact time

As shown in Figure 5.1 COD removal efficiency increases with increase in contact time. TSS
concentration and color removal efficiency increases with time and concentration.

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2. Results for Sodium Chlorite

Table 5.6 Results for Sodium Chlorite for 300 mg/L

Contact time (min), Concentration of Sodium Chlorite is 300

Parameter
mg/L
Initial 10 30 50 70 90
COD(mg/L) 738 684 594 504 450 414
TSS(mg/L) 176 204 312 544 636 776
Colour(Co-
10932 1647 1389 1195 1024 963
unit)

Table 5.7 Results for Sodium Chlorite for 600 mg/L

Contact time (min), Concentration of Sodium Chlorite is 600

Parameter
mg/L
Initial 10 30 50 70 90
COD(mg/L) 684 630 540 450 360 342
TSS(mg/L) 180 244 476 580 704 816
Colour(Co-
10932 1463 1190 1062 994 886
unit)

Table 5.8 Results for Sodium Chlorite for 900 mg/L

Contact time (min), Concentration of Sodium Chlorite is 900

Parameter
mg/L
Initial 10 30 50 70 90
COD(mg/L) 702 612 522 432 306 297
TSS(mg/L) 156 308 688 796 896 992
Colour(Co-
10932 1420 1108 988 904 876
unit)

Table 5.9 Results for Sodium Chlorite for 1200 mg/L

Contact time (min), Concentration of Sodium Chlorite is 1200

Parameter
mg/L
Initial 10 30 50 70 90
COD(mg/L) 738 630 486 378 288 270
TSS(mg/L) 116 536 740 832 1036 1124
Colour(Co-
10932 1395 1103 976 894 883
unit)

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Results obtained for COD removal with Sodium chlorite is shown in Table 5.6 to 5.9.
Maximum sludge generation for sodium chlorite is 1124 mg/L which is less than calcium
hypochlorite. It can be said that sludge generation is less than the calcium hypochlorite. Color
removal is less for sodium Hypochlorite than calcium hypochlorite. Minimum COD obtained
was 270 mg/L for 1200 mg/L concentration at 90 min.

Table 5.10 Removal efficiency of COD by Sodium Hypochlorite

Concentration Contact Time (min)

10 30 50 70 90
300 7.31 19.51 31.70 39.02 43.90
600 7.89 21.05 34.21 47.36 50
900 12.82 25.64 38.46 56.41 57.69
1200 14.63 34.14 48.78 60.97 63.41

COD removal efficiency by Sodium Hypochlorite is shown in Table 5.10. COD removal
efficiency of Sodium Chlorite ranges between 7.31 %- 63.41 %. Maximum removal efficiency
obtained was 63.41%.

Figure 5.5 COD concentration with contact time for sodium chlorite

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Figure 5.6 COD removal efficiency with contact time for sodium chlorite

Figure 5.7 TSS concentration with contact time for sodium chlorite

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Figure 5.8 Color removal efficiency with contact time

As shown in above figures COD concentration decreases as concentration of Sodium chlorite

increases. Color removal efficiency increases as increase in contact time and concentration.
Color removal is less as compared to calcium hypochlorite.

3. Cost Estimation

Chemicals Cost/Kg Chemical Cost/L (in Rs.) Cost/MLD (in

(in Rs.) required to treat Rs.)
1 L wastewater
Calcium Hypochlorite 640 Rs. 0.0315 g (for 35% 0.020. 20000
pure chemical and
900 mg/L conc.)
Sodium Chlorite 712 Rs. 0.0058 g ( for 65% 0.004 4000
pure chemical and
900 mg/L conc.)

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CHAPTER 6

Conclusion

6.1 Conclusions

 As shown in results as the concentration of chemical increases removal efficiency for

COD increases for both chemicals Calcium Hypochlorite and Sodium Chlorite.
 As concentration increases TSS concentration increases for the chemicals.
 For Calcium Hypochlorite COD Removal Efficiency ranges between 18 % to 71% for
different concentration and different contact time.
 For Sodium Chlorite COD removal efficiency ranges between 7% to 63% for different
concentration and different contact time.
 Sludge generation for Calcium Hypochlorite is higher than the sludge generation for
Sodium Chlorite.
 Optimum condition selected for Calcium Hypochlorite is for 900 mg/L for 70 min
contact time which gives 63 % COD removal efficiency and less sludge generation.
 Optimum condition selected for Sodium Chlorite is for 1200 mg/L for 90 min contact
time which gives 63% COD removal efficiency and less sludge generation.
 Cost of Calcium Hypochlorite to treat 1 Litre wastewater is 2 paisa and of Sodium
Chlorite is 0.4 paisa.
 Chlorination treatment can be used as tertiary treatment after the secondary treatment
as it gives COD 216 mg/L (<250 mg/L) which is in the limit of discharge standard of
COD into the mega pipeline.

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REFERENCES

PAPERS

[1] F., Vaezi, Naddafi K, Karimi F., and Alimohammadi M. “Application of chlorine
dioxide for secondary effluent polishing.” International Journal of Environmental
Science and Technology, Vol 1, 2004: 97-101.

[2] Marie Debordea, Ursvon Gunten. “Reaction of chlorine with inorganic and organic
compounds during treatment - kinetics and mechanism: A critical review.” WATER
RESEARCH, 2008: 13-51.

[3] Metcalf, and Eddy. Wastewater Engineering Treatment and Reuse 4th Edition.
McGraw Hill Publication, 2010.

[4] Mohamadreza Massoudinejad, Mansour Ghaderpoori and Mansour Rezazadeh Azari.

“The Removal of COD and color from Textile Industry by Chlorine Hypochlorite.”
Journal of Advanced Science and Technology Vol 76, 2008: 35-42.

[5] Patel, Jugal M., Dipak S. Vyas, and Sejal M. Patel. “COD Reduction of
Pharmaceutical industry waste water by electro oxidation process by generation of in
situ hypochlorus acid.” IJARIIE, 2016: 2395-4396.

[6] Quader, A. K. M. A. “TREATMENT OF TEXTILEWASTEWATER WITH

CHLORINE: AN EFFECTIVE METHOD.” Chemical Engineering Research Bulletin
14, 2010: 59-63.

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[7] Rajkumar D, and Guk Kim Jong. “oxidation of various reactive dyes with in situ
electro generated active chlorine for textile dyeing industry wastewater treatment .”
Journal of Hazardous Materials B136 , 2006: 203-212.

[8] Shah, Abhishek, and A.K.J Khambete. “Statistical Analysis to identify the main
parameter to the wsatewater quality index of CETP: A case study at Vapi, Gujarat,
India.” Journal of Environmental Research And Development Vol 7, 2013.

[9] Yun-Young Choi, Seung-Ryong Baek, Jae-In Kim, Jeong-Woo Choi, Jin Hur, Tae-U
Lee, Cheol-Joon Park, and Byung Joon Lee. “Characteristics and Biodegradability of
Wastewater Organic Matter in Municipal Wastewater Treatment Plants Collecting
Domestic Wastewater and Industrial Discharge .” Water, 2017: 409-420.

BOOKS:

[10] Metcalf, and Eddy. Wastewater Engineering Treatment and Reuse 4th Edition.
McGraw Hill Publication, 2010.

WEBSITES:

[11] www.who.int/ipcs/publications/ehc/216_disinfectants_part_2.pdf
[12] www.industrialgreenchem.com/pdf-docs/presentations/
[13] www.eurochlor.org/media/14969/sd15-environmentalsafety-final.pdf

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Appendix A Student Review Card

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 Reduction of COD from secondary effluent of CETP by chlorination

Appendix B Student Compliance Report

Compliance report based on the review comments given in Dissertation

Phase-I:

Comments
1. Objective should include more objective.

2. More parameters should be measured.

3. The formation of report should be done properly.

Close out:
1. Done

2. color is added as parameter.

3. Done.

Compliance report based on the review comments given in Mid Semester

Thesis Progress Review:

Comments
1. Graphical representation should be proper

2. concentration of chemical should be taken with common difference.

Close out:
1. Done

2. Done

Date: 2-5-2018

Place: Ahmedabad

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Appendix C Turnitin Originality Report

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Appendix D Paper Publication Certificates

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63