A

Project Report

On

Treatment of Municipal Wastewater by Chemical Coagulation

Followed by Ion Exchange Method
Submitted

to

NATIONAL INSTITUTE OF TECHNOLOGY,

RAIPUR (C.G.), INDIA
for

Award of Degree

of

Bachelor of Technology
in

Chemical Engineering
Guided by: Submitted by:
Dr. P.K.Chaudhari Aarikatla Venkata Ramanaiah (14113001)
Associate Professor Anjana Bhagat (14113007)
Department of Chemical Engineering Wadekar Sagar Pramod (14113059)

Dr. Kavita Tapadia

Assistant Professor
Department of Chemistry

DEPARTMENT OF CHEMICAL ENGINEERING

NATIONAL INSTITUTE OF TECHNOLOGY RAIPUR

1
 DEPARTMENT OF CHEMICAL ENGINEERING
NATIONAL INSTITUTE OF TECHNOLOGY RAIPUR

DECLARATION

We hereby declare that the project work report entitled “Municipal Wastewater Treatment
by Chemical Coagulation followed by Ion Exchange Method” which is being submitted to
National Institute of Technology, Raipur for the award of the degree of Bachelor of
Technology in CHEMICAL ENGINEERING is a bonafide report of the work carried out by us
under the guidance of Dr. P.K. Chaudhari, Associate Professor, Department of Chemical
Engineering, National Institute of Technology Raipur.

The matter presented in this project work report has not been submitted to any University or
Institution for the award of any degree.

Place: Raipur Aarikatla Venkata Ramanaiah (14113001)

Date: Anjana Bhagat (14113007)

Wadekar Sagar Pramod (14113059)

2
 DEPARTMENT OF CHEMICAL ENGINEERING
NATIONAL INSTITUTE OF TECHNOLOGY RAIPUR

CERTIFICATE

This is to certify that the Project Report entitled “Municipal Wastewater Treatment by
Chemical Coagulation followed by Ion Exchange Method” Submitted by:

(1) 14113001 Aarikatla Venkata Ramanaiah

(2) 14113007 Anjana Bhagat

(3) 14113059 Wadekar Sagar Pramod

in the partial fulfilment of the requirements for the award of the degree of Bachelor of
Technology in CHEMICAL ENGINEERING is a bonafide record of the work carried out under
my guidance and supervision at National Institute of Technology Raipur.

Dr. P. K. Chaudhari Dr. Kavita Tapadia

Associate Professor Assistant Professor
Department of Chemical Engineering Department of Chemistry
National Institute of Technology Raipur National Institute of Technology Raipur

Date:

Place: Raipur

3
 ACKNOWLEDGEMENT

In pursuing this research work, we have been abundantly fortunate. The cooperation,
inspiration, care and motivation provided to us during this period has made
acknowledging it an impossible task. We first of all take this opportunity to express our
heartfelt gratitude to our guides, Dr. P. K. Chaudhari and Dr. Kavita Tapadia who guided
us through this pursuit. Their guidance and support has been inspirational to us during
this tenure.

We are also thankful to the faculties and support staff at Department of Chemical
Engineering, National Institute of Technology Raipur, for constant help and
Departmental facilities that were instrumental in completion of this project.

Date: Aarikatla Venkata Ramanaiah (14113001)

Place: Raipur Anjana Bhagat (14113007)

Wadekar Sagar Pramod (14113059)

4
 CONTENTS
Cover Page………………………………………………………………………………..1

Declaration………………………………………………………………………………..2

Certificate…………………………………………………………………………………3

Acknowledgement………………………………………………………………………..4

Contents…………………………………………………………………………………...5

List of Figures……………………………………………………………………………..7

List of Tables………………………………………………………………………………8

Nomenclature………………………………………………………………………………9

Abstract…………………………………………………………………………………....10

Chapter 1 INTRODUCTION

1.1. Waste Water Treatment ………………………………………………………………12

1.2. Demineralization ……………………………………………………………………...12

1.3. Ion Exchange Method ………………………………………………………………...13

1.4. Ion Exchange Resin …………………………………………………………………...13

1.4.1. Types of Ion Exchange Resin ……………………………………………………….15

1.5. Resin Regeneration ……………………………………………………………………15

1.6. Total Dissolved Solids (TDS) …………………………………………………………16

1.6.1. Effects of TDS ………………………………………………………………………16

1.6.2. Sources of TDS ………………………………………………………………………16

1.7. Hardness of Water ……………………………………………………………………..16

1.7.1. Effects of Hardness ………………………………………………………………….17

1.8. Chemical Oxygen Demand (COD)……………………………………………………..17

1.8.1. Effects of COD……………………………………………………………………….17

5
Chapter 2 LITERATURE REVIEW

2.1. Study and Development ………………………………………………………………...18

Chapter 3 EXPERIMENTS

3.1. Characteristics of Municipal wastewater………………………………………………...21

3.2. Chemical Coagulation Studies…………………………………………………………...21

3.3. Ion Exchange Studies……………………………………………………………………22

3.4. Materials and Chemicals ………………………………………………………………...23

3.5. Ion Exchange Process …………………………………………………………………...23

3.5.1. Experimental Procedure ……………………………………………………………….24

3.5.2. Demineralization process ……………………………………………………………...24

3.5.3. Measurement of Total Hardness ………………………………………………………24

3.6. TDS level measurement …………………………………………………………………25

3.7. Conductivity measurement ……………………………………………………………...25

3.8. COD measurement……………………………………………………………………….26

Chapter 4 RESULTS AND DISCUSSIONS

4.1. Chemical Coagulation process……………………………………………………………27

4.2. Ion Exchange process…………………………………………………………………….28

4.2.1. Effect or resin ratio and pH…………………………………………………………….28

4.3. Effect of Flow Rate on Pollutants Removal……………………………………………...29

4.3.1. Effect of flow rate on TDS removal…………………………………………………....29

4.3.2. Effect of flow rate on Hardness removal……………………………………………….30

4.3.3. Effect of flow rate on COD removal……………………………………………………31

Chapter 5 REFERENCES…………………………………………………………………33

6
 LIST OF FIGURES

1.1. Schematic diagram of Ion Exchange method……………………………………..14

1.2. Mechanism of ion exchange process in aqueous solution…………………………15

3.1. Lab scale Ion exchange system……………………………………………………22

4.1. Jar Test Apparatus…………………………………………………………………27

4.2. Effect of flow rate on TDS removal………………………………………………30

4.3. Effect of flow rate on hardness removal………………………………………….31

4.4. Effect of flow rate on COD removal……………………………………………..32

7
 LIST OF TABLES

3.1. Characteristics of municipal wastewater…………………………………….21

3.2. Materials, Instruments and Chemicals……………………………………….23

4.1. Total hardness, COD and TDS values……………………………………….28

4.2. TDS of ion exchanged MWW at different flow rates……………………….29

4.3. Hardness of ion exchanged MWW at different flow rates………………….31

4.4. COD of ion exchanged MWW at different flow rates……………………...32

8
 NOMENCLATURE

TDS Total Dissolved solids

TSS Total Suspended Solids

COD Chemical Oxygen Demand

WBA Weak Base Anionic

SAC Strong Acid Cationic

WAC Weak Acid Cationic

SBA Strong Base Anionic

PPM Parts Per Million

EBT Eriochrome Black T

EDTA Ethylene Diamine Tetra Acetcic acid

OID Organized Industrial District

SAC Spectral Absorption Coefficient

MWW Municipal Waste Water

9
 ABSTRACT
Municipal wastewater samples were taken from a canal, this water was discharged as wastewater
from residential and restaurant bathrooms, kitchen and dishwashers etc. Chemical coagulation
and ion exchange methods were applied to treat the samples in the lab conditions. Optimum
removal efficiencies were determined based on the applications of different chemical species and
pH. FeCl3 at pH 7.5 has provided the maximum removal efficiencies in chemical coagulation
experiments. In the experiments, removal efficiencies for COD, TDS were 33% and 57%,
respectively. After chemical coagulation, ion exchange experiments were conducted to improve
the quality of wastewater. Our objective is to remove the total dissolved solids and hardness in
wastewater by ion exchange method and to measure the levels of COD, conductivity and TDS
levels before and after applying this method. Experiments were conducted by varying the
parameters like flow rate, pH and height of resin bed etc. Optimum resin ratios (dosages) were
determined. The experiments revealed that 1:2 resin ratio (H+ type/cation resin: OH- type/anion
resin) gave the best removal rates for parameters considered in this study. Study results indicated
that quality of wastewater was suitable for inland surface discharge.

10
Chapter 1 INTRODUCTION
Many techniques have been used for the treatment of wastewater, such as oxidation, biological
treatment, electrochemical or chemical coagulation, reverse osmosis etc, of such coagulation is
the most commonly used techniques. Inorganic coagulants such as salts of iron, magnesium and
aluminum can be used for the purification. Here, each of the coagulants produces different
efficiency levels depending upon the type of the wastewater samples. However, due to dwindling
water supplies, a better alternative is to attempt to further elevate the water quality of wastewater
effluent from the above process to a higher standard either for reuse or for safe inland surface
discharge. The amount of discharged effluents into the environment can be reduced by reusing
the wastewater once it has been treated. Reuse process can produce savings in water
consumption, chemicals and energy. In the similar way, the quality of treated wastewater can be
further improved if conventional treatment processes are combined with advanced processes
(such as ion exchange, membrane techniques).

Chemical coagulation is a common chemical treatment method which has been used widely
because of its advantages of having simple technology, low operating cost, high treatment
efficiency and application convenience. However, a high amount of sludge formation is the main
disadvantage of this process. Sludge removal process has to be done very carefully and slowly.

Ion exchanger systems currently have widespread use for obtaining high quality water. This
process involves the exchange of charged mobile ions from the aqueous phase for a fixed ion in
the solid phase. Wastewater mainly contains organic matter, total dissolved solids, metal ions
etc. Treatment of wastewater by ion exchange method mainly removes total dissolved solids and
hardness, therefore, this treated water can be used for other purposes. Some problems are
encountered during the use of ion exchanger systems such as loading, backwashing and
regeneration. Fouling is considered as the important problems of ion exchange resins. Organic
fouling is an irreversible fixation of organic materials to the resin. Different treatment processes
are proposed to protect the resins against organic fouling. Generally ion exchange process is
applied after different treatments such as chemical coagulation, lime flocculation and membrane
processes which helps in removing organic materials [1].

11
The main objective of this study was to treat the municipal wastewater samples and elevate the
water quality levels such that they are suitable for inland surface discharge or for feeding
livestock. The purpose is to remove total dissolved solids and hardness in wastewater by these
methods.

1.1. Waste Water Treatment

Wastewater treatment is the process of converting wastewater – water that is no longer needed or
is no longer suitable for use – into water that can be discharged back into the environment. It’s
formed by a number of activities including bathing, washing, using the toilet, and rainwater
runoff. Wastewater has full of contaminants including bacteria, chemicals and other toxins. Its
treatment aims at reducing the contaminants to acceptable levels to make the water safe for
discharge back into the environment.

There are two types of wastewater treatment namely chemical or physical treatment and
biological wastewater treatment. Biological waste treatment use biological matter and bacteria to
break down waste matter. Physical waste treatment use chemical reactions as well as physical
processes to treat wastewater. Biological treatment systems are ideal for treating wastewater
from households and business premises. Physical wastewater treatment plants are mostly used to
treat wastewater from industries, factories and manufacturing firms. This is because most of the
wastewater from these industries contains chemicals and other toxins that can largely harm the
environment [2]. There are different methods available for wastewater treatment such as
mechanical separation, coagulation, chemical purification, biological process, aeration and
boiling etc [3].

1.2. Demineralization

Demineralization or Deionization is the process of removal of ions from water using ion
exchange resin by ion exchange method. Ions are electrically charged molecules found in water
that has either a positive charge or negative charge. Positively charged ions are called cations
(Ca+2, Mg+2 etc.) and negatively charged ions (Cl -, SO4-2 etc.) are called anions. There are
major two types of Ion exchange resins called cation and anion used for demineralization

12
process of water. As the name implies cation resin removes cations and anion resin removes
anions from the water.

Cation exchange resin is divided into two subcategories called Weak Acid Cation (WAC) and
Strong Acid Cation (SAC).Anion resin divided into two subcategories called Weak Base Anion
(WBA) and Strong Base Anion (SBA) from which SBA resin further split into two categories
Type-1 and Type-2. Ion exchange resin structure is either gel or macro porous. Gel resins are
translucent while macro-porous are opaque. Typically gel based resin is the best choice for
conventional water treatment plant because of their higher capacity and better regeneration
efficiency.

1.3. Ion Exchange Method

Ion exchange is an exchange of ions between two electrolytes or between an

electrolyte solution and a complex. Typical ion exchangers are ion-exchange
resins (functionalized porous or gel polymer), zeolites, montmorillonite, clay. Ion exchangers
are either cation exchangers, which exchange positively charged ions (cations), or anion
exchangers, which exchange negatively charged ions (anions). There are
also amphoteric exchangers that are able to exchange both cations and anions simultaneously.

However, the simultaneous exchange of cations and anions can be more efficiently performed
in mixed beds, which contain a mixture of anion- and cation-exchange resins, or passing the
treated solution through several different ion-exchange materials. Ion exchanges can be
unselective or have binding preferences for certain ions or classes of ions, depending on
their chemical structure. This can be dependent on the size of the ions, their charge, or their
structure [4].

1.4. Ion Exchange Resin

An ion-exchange resin or ion-exchange polymer is a resin or polymer that acts as a medium

for ion exchange. It is an insoluble matrix (or support structure) normally in the form of small
(0.25–0.5 mm radius) micro-beads, usually white or yellowish, fabricated from an organic
polymer substrate. The beads are typically porous, providing a large surface area on and inside

13
Fig.1.1: Schematic diagram of Ion Exchange method

them. The trapping of ions occurs along with the accompanying release of other ions, and thus
the process is called ion exchange. There are multiple types of ion-exchange resin. Most
commercial resins are made of polystyrene sulfonate. Most typical ion-exchange resins are based
on cross-linked polystyrene. The actual ion-exchanging sites are introduced after polymerization.
Additionally, in the case of polystyrene, cross-linking is introduced by co-polymerization of
styrene and a few percent of divinyl-benzene. Cross-linking decreases ion-exchange capacity of
the resin and prolongs the time needed to accomplish the ion-exchange processes but improves
the robustness of the resin. Particle size also influences the resin parameters; smaller particles
have larger outer surface, but cause larger head loss in the column processes.

Ion-exchange resins are widely used in different separation, purification and decontamination
processes. The most common examples are water softening and water purification. In many
cases ion-exchange resins were introduced in such processes as more flexible alternatives to the
use of artificial or natural zeolites. And also, ion-exchange resins are highly effective in the
biodiesel filtration process [5].

14
Fig 1.2. Cation exchange resin: (a) Resin initially immersed in an aqueous solution containing B+
and X- ions. (b) Resin in equilibrium with aqueous solution.

1.4.1. Types of Ion Exchange Resin

(a) Strong Acid Cation Resin (SAC)

(b) Weak Acid Cation Resin (WAC)

(c) Strong Base Anion Resin (SBA)

(d) Weak Base Anion Resin (WBA)

1.5. Resin Regeneration

Most ion-exchange systems contain containers of ion-exchange resin that are operated on a
cyclic basis. During the filtration process, water flows through the resin container until the resin
is considered exhausted. That happened only when water leaving the exchanger contains more
than the desired maximal concentration of the ions being removed. Resin is then regenerated by
sequentially backwashing the resin bed to remove accumulated solids, flushing removed ions
from the resin with a concentrated solution of replacement ions, and rinsing the flushing solution
from the resin. Production of backwash, flushing, and rinsing wastewater during regeneration of
ion-exchange media limits the usefulness of ion exchange for wastewater treatment.

15
Water softeners are usually regenerated with brine containing 10% sodium chloride. Aside from
the soluble chloride salts of divalent cations removed from the softened water, softener
regeneration wastewater contains the unused 50 – 70% of the sodium chloride regeneration
flushing brine required to reverse ion-exchange resin equilibria. Deionizing resin regeneration
with sulfuric acid and NaOH is approximately 20–40% efficient [6].

1.6. Total Dissolved Solids (TDS)

Comprise inorganic salts and small amounts of organic matter that are dissolved in water. The
principal chemical constituents are usually the cations such as calcium, magnesium, sodium and
potassium and the anions such as carbonate, bicarbonate, chloride, sulfate. Maximum
contaminant level for TDS is 500 ppm. The two principal methods of measuring total dissolved
solids are gravimetric analysis and conductivity method. Gravimetric methods are the most
accurate and involve evaporating the liquid solvent and measuring the mass of residues left. This
method is generally the best, although it is time-consuming.

1.6.1. Effects of TDS

However, the presence of high levels of TDS in water may be objectionable to consumers owing
to the resulting taste and to excessive scaling in water pipes, heaters, boilers, and household
appliances. Water with extremely low concentrations of TDS may also be unacceptable to
consumers because of its flat, insipid taste, it is also often corrosive to water supply systems.

1.6.2. Sources of TDS

Some dissolved solids come from organic sources such as leaves, silt, plankton, and industrial
waste and sewage. Other sources come from runoff, urban areas, road salts used on street during
the winter, fertilizers and pesticides used on lawns and farms [7].

1.7. Hardness of Water

Hardness of water is mainly because of the dissolved salts of calcium and magnesium such as
carbonates, bicarbonates, sulfates and chlorides. According to their concentration water hardness
can be divided into following groups.

16
 Soft - 0- 60 mg/L
Medium - 60-120 mg/L
Hard - 120-180 mg/L
Very hard >180mg/L
Two types of hardness as temporary hardness and permanent hardness are known.

(i) Temporary hardness: can be removed simply by boiling.

(ii) Permanent hardness: can be removed using a water softener or ion exchange column.

1.7.1. Effects of Hardness

(i) Calcium and magnesium carbonates tend to be deposited as off-white solids on the inside
surfaces of pipes and heat exchangers.

(ii) With hard water, soap solutions form a white precipitates instead of forming lather.

(iii) Build-up of scale restricts the flow of water in pipes.

(iv) In boilers, the deposits impair the flow of heat into water, reducing the heating efficiency
and allowing the metal boiler components to overheat.

1.8. Chemical Oxygen Demand (COD)

Chemical Oxygen Demand or COD is a measurement of the oxygen required to oxidize soluble
and particulate organic matter in water. Chemical Oxygen Demand is an important water quality
parameter because, similar to BOD, it provides an index to assess the effect discharged
wastewater will have on the receiving environment.

1.8.1. Effects of COD

Higher COD levels mean a greater amount of oxidizable organic material in the sample, which
will reduce dissolved oxygen (DO) levels. A reduction in DO can lead to anaerobic conditions,
which is harmful to higher aquatic life forms. Generally, COD values are higher than the BOD
values.

17
 Chapter 2 LITERATURE REVIEW
Ion exchange resin exchanges the fixed ion in resin phase for a charged mobile ion from the
aqueous solution. Cationic exchange resin removes positively charged ions such as Na, Mg, Ca,
Pb, Al, Cu etc. Anionic exchange resin removes negatively charged ions such as nitrates,
sulfates, chlorides and other anions. Ion exchange resins are generally used to remove total
dissolved salts, hardness and metal ions etc. By comparison, strong-acid resin regeneration
requires a large excess of regenerant solution to provide the driving force for exchange to take
place. Therefore, WAC resins are normally utilized for softening high TDS produced water.

2.1. Study and Development

Journal Scientist /
Name, University Development
Year

They studied the ion exchange process for the removal of TDS and also for
Environmenta Li J,
l Science and Koner S, the water softening. They developed an efficient, easy to operate hardness
Technology German M,
removal process with reduced Na in both the treated water and in the spent
50(21): SenGupta
(2016) 11943- AK. regenerant. They used a cation exchange resin in Al3+-form
11950.
for hardness removal, that is, exchange of divalent Ca2+ or Mg2+ with
Lehigh
Aluminum-
Cycle Ion University, trivalent Al3+, is counterintuitive, and this is particularly so, because the
US
Exchange aluminum ion to be exchanged has higher affinity than calcium. Ion
and
Process
Jalpaiguri exchange accompanied by precipitation of aluminum hydroxide allows
for Hardness
Govt.
Removal. progress of the cation exchange reaction leading to hardness removal. Their
Engineering
College, experimental results demonstrated that calcium can be consistently removed
India.
for multiple cycles using a stoichiometric amount of AlCl3 as the
regenerant. The process essentially operates at the maximum possible
thermodynamic efficiency: removal of one equivalent of Ca2+ corresponds
to use of one equivalent of Al3+ as a regenerant. During the Al-cycle process
there is no increase in Na+ concentration and partial reduction in the total
dissolved solids (TDS) of the treated water [8].

18
Chemical Department of They proposed a generic design procedure for the continuous ion exchange
Engineering Chemical
process. The process was based on the optimized arrangement of parallel
Science Engineering
66 (2011) and batch columns. The continuity of the process was achieved by proper
6209-6219. Processing,
shifting of the inlet conditions. They also presented the method for the
Design of Rzszow optimization of the process variables. In their studies, the concept was
continuous University of
demonstrated on the example of ammonia removal from wastewaters. Two
ion exchange Technology,
process for Poland. different flow sheet schemes were considered utilizing fresh or recycled
the
regenerating agent. The superiority of the optimized process over the
wastewater
treatment. periodic operation was demonstrated. The procedure of the process design
suggested in this study was developed for an ideal ion-exchange system for
which gradual changes of bed properties were neglected. However, after
proper adjustments, it can potentially be used for real systems [9].

Journal of Yansheng Li, They studied the ion exchange process for the removal of metal ions from
Environmenta Yongbin Li,
the wastewater. A novel electrochemical ion exchange system with porous
l Sciences 23 Zhigang Liu,
(2011) S14- TaoWu, cylinder electrodes was proposed for treatment of wastewater. This system
S17. Ying Tian.
can be used for desalination without the costly ion-exchange membrane and
College of extra chemical reagents. Since the electrodes are completely uniform and
A novel
Environmenta
electrochemic no ion-exchange membrane was used in this system, it can be operated by
l and
al ion-
Chemical switching anodes and cathodes flexibly for eliminating the scaling on the
exchange
Engineering,
system and its surface of electrodes. The strong base ion-exchange resin grains placed
China.
application in
water among the anode and cathode have played as supporting electrolyte, which
treatment. was capable for the treatment of wastewater with low conductivity. The
concentrated and neutralized anolyte containing chlorine was effective for
disinfection and contaminants removal. Under the experimental conditions,
the removal percentage of total dissolved salts was 83% and
the removal percentage of chemical oxygen demand was 92% without
consumption of extra chemical reagents [10].

19
 They investigated the chemical precipitation and ion exchange processes
Desalination Faculty of
217 (2007) Engineering for the treatment of the effluents originating from an organized industrial
301-312. and
district (OID) wastewater treatment plant. The OID wastewater samples
Architecture,
Treatability Department of were taken, chemical precipitation and ion exchange methods were applied
studies with Environmental
to the samples in lab conditions. Optimum removal efficiencies were
chemical Engineering.
precipitation determined. According to their studies, Ca(OH)2 at pH 11 has provided the
and ion Uludug
maximum removal efficiency in chemical precipitation experiments.
exchange for University,
an organized Bursa, Turkey. Removal efficiencies for TSS, COD, Fe, SAC436 (spectral absorption
industrial
coefficient), SAC525, SAC620 were 96%, 27%, 94%, 75%, 88% and 90%,
district (OID)
effluent in respectively. Ion experiments were conducted to further improve the
Bursa,
wastewater quality. The experiments were conducted with resin ratios of
Turkey.
1:2 (10 g of H-type: 20 g of OH-type), 1:1 and 2:1 separately, with two
different resin types (i.e. resin I and resin II). Optimum dosage and resin
type were determined. The experiments revealed that 1:1 resin ratio gives
best removal efficiencies and resin I gave the best removal rates for the
parameters considered [11].

20
Chapter 3 EXPERIMENTS

The present experimental investigation consisted of two major parts: chemical coagulation and
ion exchange method. The two treatment units can be operated independently or in combined
sequence. The wastewater was first chemically treated using appropriate amounts of ferric
chloride (FeCl3). After sedimentation, the supernatant was finally treated by ion exchange.

3.1. Characteristics of Municipal Wastewater

Municipal wastewater was collected from canal, located near to Mahadev Ghat, Raipur. This
water generally consists of wastewater coming from residential, slabs and restaurant bathrooms,
kitchens etc. The characteristics of municipal wastewater used in this study are listed in Table
3.1.

Table 3.1: Characteristics of municipal wastewater used in this study

Parameters Levels
pH 7.15 + 0.4
COD, mg/L 213 + 20
TSS, mg/L 196 + 15
Salinity, g/kg 1.8
Conductivity, μS/cm 3460 + 150
Hardness, mg/L 1050 + 90
TDS, mg/L 1296 + 100

3.2. Chemical Coagulation Studies

Chemical coagulation experiments were performed in a jar test apparatus. FeCl3 and alum were
used as coagulants for the process. All experiments were performed at room temperature (27o –
29oC) with 600 ml samples. The pH of the samples was adjusted between 3 to 9 (i.e. 3, 4.5, 6, 7.5
and 9) with the addition of H2S04 and NaOH. After coagulation experiments samples were left
for sedimentation for 6 h. Then components analyses were performed to find COD, TDS and
hardness. The results revealed that the FeCl3 treated sample with pH 7.5 provided best removal

21
efficiencies. The supernatant was removed carefully and sent to ion exchange column for further
purification.

3.3. Ion Exchange Studies

After chemical coagulation step, the supernatant was transferred into a beaker for being used in
the ion exchange experiments. The chemically treated wastewater was pumped through the ion
exchange columns at different flow rates such as 1.3 l/h, 0.8 l/h and 1.5 l/h. Each resin column
had a diameter and height of 2.5 cm and 65 cm, respectively. The lab scale ion exchange system
is shown in Fig. 3.1.

Figure 3.1. Lab scale Ion exchange system

The resins were primarily employed for removing the inorganic and metal ions. They were
washed several times with deionized water. Before passing the coagulant treated water to ion
exchange column some experiments were conducted to determine the optimum resin ratio
(dosage). The resins were taken in the ratio of 1:2 (i.e. 1.5 g H-type: 3 g OH-type), 1:1 (1.5 g H-
type: 1.5 g OH-type), 2:1 (i.e. 3 g H-type: 1.5 g OH-type) in 60 ml samples of coagulant treated
water separately, each resin ratio at five different pH i.e. 3, 4.5, 6, 7.5 and 9. These total 15
samples each of 60 ml volume were placed in orbital shaker for 1 h. Then analytical analyses
were performed to these samples. Optimum resin dosages were found to be 1:2 with best
removal efficiencies. Then ion exchange column was filled with the resin ratio of 1:2, i.e. resin is

22
filled up to a height of 10 cm in cationic exchange column and to a height of 20 cm in anionic
exchange column (volume ratio) and the process was carried out by passing the chemically
(coagulant) treated water at different flow rates as mentioned.

3.4. Materials and Chemicals

The material and chemical used are listed in Table 3.2.

Table 3.2. Materials, Instruments and chemicals used for ion exchange and coagulation
experiments

Description Quantity
Coagulated water sample 5l
Column 2
Acid Cationic (SAC) resin 1 Kg
Base Anionic (SBA) resin 1 Kg
Burette 1
Peristaltic pump 1
NAOH 250 ml (0.01 M)
HCl or H2S04 0.01 N (100 ml)
EBT 120 ml
Ammonia buffer 100 ml
Digital pH meter 1
EDTA 250 ml (0.01 M)
UV Spectrophotometer 1
FeCl3 .6 H2O 100 gm
Filter Alum ( Al2 (SO4)3.18 H2O ) 100 gm
Orbital shaker 1

3.5. Ion Exchange Process

Ion exchange process is used for water softening and demineralization or deionization. In water
softening a cation resin in sodium form is used to remove hard metal ions from the water along

23
with some troublesome traces of iron and manganese, which is also present. These ions are
replaced by equivalent quantity sodium, so that the total dissolved solids content of the water
remains unchanged as does the PH and anionic content.

3.5.1. Experimental Procedure

1. Install an ion exchange column.

2. Cationic resins are filled in the column from the top of it. Firstly we dose it to the level of 10
cm from the sieve for the column.

3. The treated water is collected at the outlet of the cationic column.

4. Then the water is sent into the anionic column where resin is filled to level of 20cm from the
sieve of the column.

5. The treated water is collected at the outlet of the anionic column.

3.5.2. Demineralization Process

1. Two column containing cationic and anionic resins were used in series.

2. The water was run through a cation resin in H+ form and then through a anionic resin in OH-
form, by this, the cation resin removed the positively charged impurities.

3. The Ca2+, Mg2+ and Na+ attach themselves to the ion exchange resin, which then elutes off H+
from the previous acid regeneration. The solution leaving the cation exchanger is mostly acidic.

4. To remove the anionic impurities, the solution is run through the anion exchanger.

5. The treated water was collected at the outlet of the anionic resin.

6. Continue on until the hardness increases.

7. Shut off the pump.

3.5.3. Measurement of Total Hardness of Water

TITRATION

24
1. Pipette out 10 ml of the treated water sample into a conical flask.

2. Add 1ml of Ammonia buffer.

3. Add 2 drops of EBT indicator.

4. Fill the burette with EDTA.

5. Titrate the contents against standard EDTA (0.01M) solution.

6. Continue the titration till the color changes to blue from red wine color. Obtain concordant
reading for titration.

7. Note down the volume of EDTA used.

8. Calculate the Total hardness.

3.6. TDS Level Measurement

TDS level in treated water is measured by TDS meter. A TDS meter indicates the total dissolved
solids of a solution i.e. the concentration of dissolved solid particles. Dissolved ionized solids
particle such as salts and minerals, increases the electrical conductivity of the solution. Because
it is volume measure of ionized solids, it can be used to estimate TDS. The best way to measure
TDS of water in a laboratory is to evaporate the water leaving behind dissolved solutes as residue
and then weighing the residue. TDS is typically measured in parts per million (ppm).

Electrical conductivity of water is directly related to the concentration of dissolved ionized solids
in the water. Ions from the dissolved solids in water create the ability for that water to conduct
an electric current, which can be measured using a conventional conductivity meter or TDS
meter.

3.7. Conductivity Measurement

Conductivity can be measured as per the instruction manual supplied with the instrument
(conductivity meter) and the results may be expressed as mS/m. Note the temperature at which
measurement is made. Conductivity meter needs very little maintenance and gives accurate
results [12].

25
3.8. COD Measurement

COD can be measured in two ways, by titration method and by using UV-Spectrophotometer. In
this method, the COD was measured using a spectrophotometer instead of titrating with FAS.
The measuring wavelength was selected to be 620 nm. This wavelength was selected because it
has highest sensitivity for ions in present in the wastewater. The following steps were involved in
this method:

1. Take a COD vial, add 3 ml of wastewater sample, 2.3 ml of COD A solution to the sample and
then add 0.3ml of COD B solution.

2. Place the vial for digestion in the digester for 2 hours at 1500C. Then remove the vial from the
digester and keep it outside to reach room temperature.

3. Turn on the spectrometer and let warm up for 10-15 minutes.

4. Set the wavelength to 620 nm and calibrate with the blank sample. Be sure to clean the
cuvettes tubes on the outside before using in the spectrophotometer.

5. Note down the absorbance values displayed on the screen.

The formulae used for finding COD are:

(i) COD (mg/l) = 2248 x (D.F.) x (absorbance)

(ii) D.F. = (Total volume)/(Volume of sample)

26
Chapter 4 RESULTS AND DISCUSSIONS

In the present study, municipal wastewater is treated by chemical coagulation followed by ion
exchange method.

4.1. Chemical Coagulation Process

Coagulation experiments were performed in a jar test apparatus. The apparatus is as shown in the
figure given below. Different chemicals such as alum and ferric chloride were used as
coagulants. Different concentrations of chemicals per liter of wastewater sample was considered,
optimum dosage of coagulant and the best suitable type of coagulant were determined based on
the removal efficiencies of pollutants such as COD and the sludge forming capacity.

Figure 4.1. Jar Test Apparatus / Flocculator

The experiments revealed that the FeCl3 at pH 7.5 with a concentration of 15 mM (i.e., 4.0545
gm in 1 liter of wastewater sample) has provided the best removal rates. The COD and total
hardness of the effluent from this method was found out to be 185 mg/l and 450 mg/l,
respectively. The removal efficiency for COD and hardness in this method was 33% and 57%,
respectively. This coagulated MWW is considered for further studies.

27
4.2. Ion Exchange Process

4.2.1. Effect of resin ratio and pH

To optimize resin ratio and pH, the experiments were performed as per procedure mentioned in
3.3. The results obtained are given in Table 4.1. This table demonstrates the values of considered
parameters.

Table 4.1. TDS, Total hardness and COD values

Resin Ratio pH Total COD TDS

(Cation resin/ maintained Hardness(mg/l) mg/L (mg/l)
Anion resin)
1:1 3 170 94.4 1416
4.5 90 112.4 1356
6 120 121.3 1240
7.5 150 125.8 1200
9 120 98.9 1300

1:2 3 160 71.9 1308

4.5 150 94.4 1260
6 90 76.4 1168
7.5 140 98.9 1204
9 100 71.6 1188

2:1 3 230 134.8 1384

4.5 200 98.9 1472
6 190 187.4 1420
7.5 220 103.4 1520
9 130 181.3 1424

From Table 4.1, it can be seen that resin ratio of 1:2 and pH 6 gave best results as at this pH,
COD= 76.4 mg/l, Total hardness= 90 mg/l, TDS= 1168 mg/l were obtained. This ratio was used
for the further studies.

28
4.3. Effect of Flow Rate on Pollutants Removal

Important parameters in the ion exchange process are the resin amount and the flow rate of liquid
through the columns. Ion exchange column was filled with the resin ratio of 1:2, i.e. resin is
filled up to a height of 10 cm in cationic exchange column and to a height of 20 cm in anionic
exchange column (volume ratio) and the process was carried out by passing the chemically
treated water at different flow rates such as 1.3 l/h, 0.8 l/h and 1.5 l/h. The effect of flow rates on
the system was analyzed and the details are discussed below.

4.3.1. Effect of flow rate on TDS removal

The effect of flow rate on removal of TDS from chemically coagulated MWW was investigated
and the results are illustrated in Table 4.2. and Figure 4.2. It was observed that as the flow rate of
MWW was increased, then the amount of TDS in the treated water was also increases. We can
see from the figure that TDS curve for flow rate of 1.5 l/h lies above the TDS curves for the flow
rates of 1.3 l/h and 0.8 l/h.

Table 4.2. TDS of ion exchanged MWW at different flow rates, Resin ratio 1:2.

volume of wastewater TDS values in (mg/l) at different flow rates

treated(ml)
0.8 lit/hr 1.3 lit/hr 1.5 lit/hr
250 867 946 1082
500 864 940 1080
750 860 938 1068
1000 856 942 1054
1250 846 930 1012
1500 842 912 1010
1750 890 1022 1100

The figure 4.2 also reveals that the TDS values of the effluent reached essentially a constant
level at any particular flow rate before the resin becomes saturated. After treating 1500 ml of
chemically treated wastewater a sharp rise was observed in the TDS levels of the treated water at

29
all the three flow rates. Ion exchange experiments indicated that 1500 ml wastewater could be
treated with resin before saturation.

Figure 4.2. Effect of flow rate coagulation treated MWW on TDS removal

4.3.2. Effect of flow rate on hardness removal

The effect of flow rate on removal of hardness from chemically coagulated MWW with respect
to the volume of wastewater treated (in ml) through ion exchange column is illustrated in Table
4.3. and Figure 4.3. It was observed that as the flow rate of MWW was increased, then the
amount of hardness in the treated water also increases and if the flow rate was decreased then the
hardness also decreases. The figure 4.3 reveals that for any particular flow rate, the hardness
values of the effluent decreases slowly up to 1000 ml and slowly increases till 1500 ml and then
rises sharply after that. This indicates that the resin was saturated after treating 1500 ml of
coagulated MWW.

30
Table 4.3. Hardness of ion exchanged MWW at different flow rates, Resin ratio 1:2.

Volume of Wastewater
Treated (ml) 0.8 lit/hr 1.3 lit/hr 1.5 lit/hr
250 30 50 60
500 25 45 55
750 20 40 45
1000 20 35 45
1250 25 35 50
1500 30 45 55
1750 60 65 70

Figure 4.3. Effect of flow rate of coagulated MWW on hardness removal

4.3.3. Effect of Flow Rate on COD removal

The effect of flow rate on removal of COD from chemically coagulated MWW with respect to
the volume of wastewater treated (in ml) through ion exchange column is illustrated in Table 4.4
and Figure 4.4. It was observed that as the flow rate of MWW is increased, then the amount of

31
COD in the treated water also increases (i.e., COD removal decreases) and if the flow rate
decreases then the COD removal increases. The minimum COD value of 31 mg/l was obtained
for coagulated MWW at a flow rate of 0.8 l/h.

Volume of
Water Treated 0.8 l/h 1.3 l/h 1.5l/h
(mg/l)
250 46 112 120
500 36 96.66 110
750 34 83.18 98
1000 32 76.43 86
1250 31 74.43 84
1500 32 74 85
1750 39 88.91 100

Figure 4.3. Effect of flow rate of coagulated MWW on COD removal

32
Chapter 5 REFERENCES

[1] Seval Kutlu Akal Somalz, Gokhan Ekrem Ustun, Askin Birgul, Yucel Tasdemir, “Treatability
studies with chemical precipitation and ion exchange for an organized industrial district (OID)
effluent in Bursa, Turkey”, Desalination 217 (2007) 301-312.

[2] A.N. Angelakis, S.A. Snyder, “Waste Water Treatment and Reuse: Past, present and Future”,
Water 7 (2015) 4887-4895.

[3] John C. Crittenden, R. Rhodes, David W. Hand, Kerry J. Howe, George Tchobanoglous,
“MWH’s Water Treatment Principles and Design”, 3rd Edition (2012) 10-15.

[4] Gary B. and Pamela S. Williams, “Ion Exchange Experiments – Water Softening and
Deionization”, Honors Research Projects (2016) 345.

[5] D. Muraviev, V. Gorshkov, A. Warshawsky, M. Dekker, “Ion Exchange Resin”, New York
2000.

[6] Mischissin, Stephen G, "University of Rochester - Investigation of Steam Turbine Extraction

Line Failures" Arlington (2012) pp. 25–26.
[7] Howard, C.S., “Determination of total dissolved solids in water analysis”, (1933) Volume 5
Issue 1 pp. 4-6.
[8] Li J, Koner S, German M, SenGupta AK, “Aluminum-Cycle Ion Exchange Process
for Hardness Removal”, Environmental Science and Technology 50(21): (2016) 11943-11950.

[9] Department of Chemical Engineering and Processing, “Design of continuous ion exchange
process for the wastewater treatment”, Chemical Engineering Science 66 (2011) 6209-6219.

[10] Yansheng Li, Yongbin Li, Zhigang Liu, TaoWu, Ying Tian. “A novel electrochemical ion-
exchange system and its application in water treatment.”, (2011) S14-17.

[11] Faculty of Engineering and Architecture, Department of Environmental Engineering,

“Treatability studies with chemical precipitation and ion exchange for an organized industrial
district (OID) effluent in Bursa, Turkey”, Desalination 217 (2007) 301-312.

33
[12] Jones, G. and B. C. Bradshaw, “The measurement of the conductance of electrolytes: A
redetermination of the conductance of the standard potassium chloride solutions in absolute
units”, J. Amer, Chem. Soc. 55:1780.

34