EXPERIMENTAL INVESTIGATION ON FERRIC CHLORIDE AS COAGULANT

IN WATER TREATMENT PROCESS

By

Manit Pongchalermporn

A research study submitted as a partial fulfillment of the requirements for the degree of
Master of Engineering

Examination Committee Prof. C. Visvanathan (Chairperson)

Prof. Samorn Muttamara
Dr. Nguyen Thi Kim Oanh

Nationality Thai
Previous Degree Master of Science
Mahidol University
Bangkok, Thailand

Scholarship Donor Asian Institute of Technology-Partial Scholarship

Asian Institute of Technology

School of Environment, Resources and Development
Bangkok, Thailand
August 2002

i
 Acknowledgement

I would like to dedicate the success of this study to my parents, friends and
Mahasawat Waterworks Authority (MWA), Special thanks for Mr. Nilcharat Koohirun,
former deputy governer to Metropolitan Waterworks Authority, who already passed away,
he always encourage me to study at AIT.

I would like to express the sincere gratitude and highly appreciation to my advisors,
Prof. C. Visvanathan, Dr. Nguyen Thi Kim Oanh and especially Prof. Samorn Muttamara
for their great contributions to enable me to accomplish this study.

I also wish to express my thankful to Mr. Ittidej Boonyavit, the Department Director
of Mahasawat Water Treatment Plant for his advice, understanding and strongly supporting
my further study. Sincere thanks to Siam PVS Chemicals Co., Ltd. for providing Ferric
Chloride for this experiment.

Of course I have to thank to the staff of Mahasawat Water Treatment Plant for their
support and good cooperation during the experiment.

I feel indebt to all Professors at UEEM and everyone who involved for my success,
there is no word to express my feelings to them except “Thank you”. It will be always in my
mind and through out my life as well.

ii
 Abstract

Pilot scale experiments were done for water treatment processes at Mahasawat Water
Treatment Plant. Two phase of experiment were performed; 1) High turbidity raw water
from Tha Chin River and 2) Low turbidity raw water from Mae Klong River. Raw water
from each phase was treated by two coagulants, Aluminum Sulfate (Alum, which is the
traditional coagulant for Metropolitan Waterworks Authority) and Ferric Chloride.

Phase I: average raw water turbidity was around 30 NTU, by applying 55 and 25
mg/L of Aluminum Sulfate and Ferric Chloride as coagulants, the overall treatment after
filtration were 95.6 and 98.8%, respectively.

Phase II: average raw water turbidity was around 17 NTU, by applying 40 and 15
mg/L of Aluminum Sulfate and Ferric Chloride as coagulants, the overall treatment after
filtration were 97.4 and 98.1% respectively.

Average filter run period for Aluminum Sulfate and Ferric Chloride were 23 and 34
hours, respectively. By using Ferric Chloride, filter run period can prolong 32.4%.

Costs of drinking water production were 0.142 and 0.105 Baht/m3 when using
Aluminum Sulfate and Ferric Chloride, respectively. By using Ferric Chloride, chemical
cost can be saved 26.0%.

iii
 Table of Contents

Chapter Title Page

Title page i
Acknowledgement ii
Abstract iii
Table of contents iv
List of figures vi
List of tables vii
List of abbreviations viii

1 Introduction 1
1.1 General 1
1.2 Objective of the study 2
1.3 Scope 2

2 Literature Review 3
2.1 Coagulation 3
2.2 Mechanisms of coagulation 3
2.3 Influence of mixing on coagulation 5
2.4 Conventional coagulants 6
2.5 Hydrolysis specification of inorganic metal salts 7
2.6 Coagulation Diagrams 10
2.7 Natural aquatic humic substances 10

3 Methodology 17
3.1 Introduction 17
3.2 Data collection 17
3.3 Experimental Set Up 17
3.4 Experimental Procedure 20
3.5 Sample Collection 20
3.6 Results Interpretation and Conclusion 22

4 Results and Discussion 23

4.1 Phase I: Tha Chin River Raw Water 23

4.1.1 Aluminum Sulfate as Coagulant 23
4.1.2 Ferric Chloride as Coagulant 26
4.2 Phase II: Mae Klong River Raw Water 30
4.2.1 Aluminum Sulfate as Coagulant 30
4.2.2 Ferric Chloride as Coagulant 34
4.3 Turbidity Treatment Efficiency Comparison 38
4.3.1 Phase I: Tha Chin River Raw Water (High Turbidity) 38
4.3.2 Phase II: Mae Klong River Raw Water (Low Turbidity) 39
4.4 Ferrous, Manganese and Residual Aluminum in filtered water 41
4.5 Total Solids 41
4.6 Filter Run Period 41
4.7 Expected Savings for Mahasawat Water Treatment Plant (MWTP) 42

iv
Chapter Title Page

5 Conclusions and Recommendations 43

5.1 Conclusions 43
5.2 Recommendations 43

References 44
Appendices 46

v
 List of Abbreviations

Al Aluminum
Alum Aluminum Sulfate
AWWA American Water Works Association
cm. Centimeter
°C Degree Celcius
DOC Dissolved Organic Carbon
DOM Dissolved Organic Matter
Fe Ferrous
F:A Ferric Chloride : Aluminum Sulfate
L/hr Litre per hour
m. Meter
mg/L milligram per litre
mL MilliLitre
mol wt Molecular Weight
M Molar
Mn Manganese
MWA Metropolitan Waterworks Authority
NTU Nephelometric Turbidity Unit
pH Negative logarithm of the effective hydrogen-iron concentration
rpm Revolutions per minute
U Unit

vi
 List of Figures

Figure Title Page

2.1 Stoichiometry of coagulation of fulvic acid 5

2.2 Reaction schematics of coagulation 7
2.3 Coagulation behavior of Fe(lII) polymeric species 9
2.4 Comparison of different coagulants 11
2.5 Design and operation diagram for alum coagulation 12
2.6 Design and operation diagram for ferric iron coagulation 13

3.1 Schematic Diagram for water treatment process 18

3.2 Experimental setup for pilot scale water treatment plant 19
3.3 Experimental setup 19
3.4 Jar test equipment 21

4.1 Logarithm graph from jar test for Aluminum Sulfate as coagulant, Phase I 24
4.2 Turbidity of raw water, clarified water and filtered water for Aluminum 24
sulfate as coagulant, Phase I
4.3 Alkalinity of raw water and clarified water for Aluminum sulfate as 25
coagulant, Phase I
4.4 pH of raw water, clarified water and filtered water for Aluminum sulfate 25
as coagulant, Phase I
4.5 Turbidity removal efficiency of clarified and filtered water for Aluminum 26
sulfate as coagulant, Phase I
4.6 Pressure drop of sand filter for Aluminum sulfate as coagulant, Phase I 26
4.7 Logarithm graph from jar test for Ferric Chloride as coagulant, Phase I 27
4.8 Turbidity of raw water, clarified water and filtered water for Ferric Chloride 28
as coagulant, Phase I.
4.9 Alkalinity of raw water and clarified water for Ferric Chloride as coagulant, 28
Phase I
4.10 pH of raw water, clarified water and filtered water for Ferric Chloride 29
as coagulant, Phase I
4.11 Turbidity removal efficiency of clarified and filtered water for Ferric Chloride 29
as coagulant, Phase I
4.12 Pressure drop of sand filter for Ferric Chloride as coagulant, Phase I 30
4.13 Jar test results for Aluminum Sulfate as coagulant, Phase II 31
4.14 Turbidity in raw water, clarified water and filtered water for Aluminum 32
Sulfate as coagulant, Phase II
4.15 Alkalinity in raw water and clarified water for Aluminum Sulfate as coagulant, 32
Phase II
4.16 pH in raw water, clarified water and filtered water for Aluminum Sulfate as 33
coagulant, Phase II
4.17 Turbidity removal efficiency clarified water and filtered water for Aluminum 33
Sulfate as coagulant, Phase II
4.18 Pressure drop for Aluminum Sulfate as coagulant, Phase II 34
4.19 Jar test result for Ferric Chloride as coagulant, Phase II 35
4.20 Turbidity in raw water, clarified water and filtered water for Ferric Chloride 35
as coagulant, Phase II

vii
Figure Title Page

4.21 Alkalinity in raw water and clarified water for Ferric Chloride as coagulant, 36
Phase II
4.22 pH in raw water, clarified water and filtered water for Ferric Chloride as 36
coagulant, Phase II.
4.23 Turbidity removal efficiency in clarified water and filtered water for Ferric 37
Chloride as coagulant, Phase II
4.24 Pressure drop for Ferric Chloride as coagulant, Phase II 37
4.25 Average turbidity in different sampling points of experiment Phase I 38
4.26 Average turbidity treatment efficiency in clarified and filtered water of 39
experiment Phase I
4.27 Average turbidity in different sampling points of experiment Phase II 40
4.28 Average turbidity treatment efficiency in clarified and filtered water of 40
experiment Phase II.

viii
 List of Tables

Table Title Page

3.1 Parameters and their experimental procedures 21

4.1 Jar Test result for Aluminum Sulfate as coagulant, Phase I 23

4.2 Jar Test result for Ferric Chloride as coagulant, Phase I 27
4.3 Turbidity results(NTU) from Jar Test for Ferric Chloride as coagulant feeding 31
rate 25 mg/L
4.4 Jar test result for Ferric Chloride as Coagulant, Phase II 34
4.5 Residual chemicals concentration, comparing with the standard of filtered 41
water from the experiments.
4.6 Comparison conclusion of Ferric Chloride and Aluminum Sulfate 42

ix
 Chapter 1

Introduction

1.1 General

Aluminum Sulfate, commonly know as Alum, has been widely used as coagulant in
water treatment process in Thailand and around the world for over a century. Coagulation
is one of the most important step in drinking water treatment. Its purpose is to destabilize
the suspended colloidal and dissolved contaminants in water, so they may be removed by
subsequent processes. Coagulation typically involves the addition of metallic salts to the
water. The salts undergo complex hydrolysis reaction, and the reaction products cause the
destabilization of contaminants in the water. The destabilization contaminants are then
bought into contact with one another so that aggregation occurs. Metallic salts of
aluminum sulfate and Fe(III) are typically used as coagulants, the most common being
aluminum sulfate. Coagulation diagrams have been developed to assist the design
engineers and plant operators in identifying conditions for the mechanisms of effective
coagulation. The diagrams are based on the removal of turbidity and indicate the pH and
coagulant dosage, it which this removal is effective. To be more applicable to natural
surface water, the diagrams should also incorporate the removal of dissolved organic
constituents. Regions of removal for natural aquatic humic substances have not been
previously investigated using the coagulation diagram. Although numerous studies have
addressed the removal of natural aquatic humic substances by alum coagulation, few
studies have extensively investigated the effectiveness of Fe(III) coagulant.

Aluminum Sulfate has been used as a main chemical usage in Metropolitan

Waterworks Authority (MWA) for water treatment process for more than 3 decades. This
is because of its lowest price compare to other chemicals.

However, Ferric Chloride becomes more acceptable for its application on water
treatment process in many countries such as Australia, United States of America and
Canada. Because it shows an effective solution for destablilization of particles, removal of
dissolved organic matter, induction of flocculation and also improvement of filtration.

In order to promote Ferric Chloride to be a real application in water treatment

process, the comparison experimental study of Alum and Ferric Chloride was done in
Mahasawat Water Treatment Plant. Further application of Ferric Chloride might be
possible for all MWA’s water treatment plant if the study shows that using Ferric Chloride
is better than Aluminum Sulfate.

1
1.2 Objective of the Study

The objective of this study is to investigate the effectiveness of ferric chloride for
turbidity and dissolved organic removal in water treatment process, through pilot scale
experiment unit.

Specific objectives are as below:

ƒ To study the efficiency of Ferric Chloride, and
ƒ To investigate the cost-effectiveness of Ferric Chloride compare with
Aluminum Sulfate.

1.3 Scope of the Study

ƒ Conducting the standard jar test as batch experiment in order to investigate the
optimum operating condition, and
ƒ Setting up a pilot scale experimental unit for application of continuous flow
experiment and measuring parameters involved.

2
 Chapter 2

Literature Review

2.1 Coagulation

Conventional water treatment typically involves the following sequence of

physicochemical processes: rapid mixing; slow mixing, or flocculation; sedimentation; filtration;
and disinfection. Variations in this sequence include direct filtration, which eliminates
sedimentation, and in-line filtration, which eliminates both flocculation and sedimentation. In the
treatment of drinking water, coagulation is considered a pretreatment process. Its effectiveness
affects the efficiency of sedimentation and filtration.

Coagulation involves the addition of chemicals into water to produce chemical species
that act to destabilize contaminants and improve their removal. In water treatment, chemical
coagulants are used to destabilize particles, remove dissolved organic matter, induce flocculation,
and improve filtration (AWWA Coagulation Committee 1988). The processes of rapid mixing
and flocculation are collectively known as coagulation. The purposes of rapid mixing are to
provide quick and uniform dispersion of chemicals and to cause the destabilization of the
particles in the raw water (AmirtharaJah and Mills, 1982). Slow mixing provides an opportunity
for particles to aggregate and form a settleable or filterable mass.

Numerous reviews of the fundamental theory and mechanisms of coagulation have been
published (O'Melia, 1972; Dempsey, 1984; AWWA Coagulation Committee, 1988; Gray, 1988;
Gregory, 1989; Amirtharajah and O'Melia, 1990). The purpose of this section is to provide a
general overview of the mechanisms of coagulation, the influence of mixing on coagulation,
typical coagulants, and coagulation diagrams. This overview is followed by a detailed review of
the hydrolysis of inorganic metal salts, specifically ferric chloride, and the mechanisms by which
humic substances are removed during coagulation with metal salts.

2.2 Mechanisms of Coagulation

Different mechanisms of destabilizing contaminants using chemical coagulants have been

identified. These mechanisms include double layer compression, charge neutralization, sweep
coagulation, and interparticle bridging (O'Melia, 1972; and Dempsey, 1984). The type of
interaction between the chemical coagulant and the contaminants determines the mechanism of
coagulation.

Double Layer Compression

The theory of double layer compression has its foundation electrostatic repulsion between
similarly charged particles. When oppositely charged ions surround the particles, the electrostatic
repulsion is reduced. At a certain concentration of ions, the double layer will theoretically be
compressed to an extent that enables attractive forces to hold the particles together. This
mechanism is not considered to be significant for the treatment of most freshwaters (Dempsey,
1984).

3
Adsorption-Charge Neutralization

Charge neutralization involves the interaction of a chemical coagulant and a charged

contaminant (Stumm and O'Melia, 1968). Dempsey et al. (1984) reported that stoichiometry
exists between the coagulant and the contaminant under conditions of charge neutralization. They
demonstrated stoichiometry between aquatic fulvic acid and the coagulant polyaluminum
chloride, as presented in Figure 2.1. The stoichiometry between coagulant dosage and
concentration of a contaminant to be removed is indicative of adsorptive interactions (Tang and
Stumm, 1987). Evidence of adsorptive interaction is the occurrence of charge reversal. Excessive
coagulant concentrations may result in restabilization of particles by reversing the charge on the
contaminant (O'Melia, 1972; Dempsey, 1984). Conditions leading to restabilization can be
detected by monitoring the electrophoretic mobility or zeta potential of the particles.

Sweep Coagulation

The removal of contaminants through the formation of a solid precipitate is referred to as

sweep coagulation. This mechanism of coagulation is common when metal salts such as alum or
ferric chloride are used as coagulants. Voluminous hydroxide precipitates formed because the
water is supersaturated to several orders of magnitude above the solubility of the metal salt
(AWWA Coagulation Committee, 1988). When aluminum and ferric salts are used, the solid
precipitate species that typically formed are Al(OH)3 (aluminum hydroxide) and Fe(OH)3 (ferric
hydroxide), respectively. Dissolved contaminants adsorb to the solid precipitate and are removed
with it; particulate contaminants are removed by enmeshment or entrapment within a mass of the
solid precipitate.

Dempsey (1984) pointed out that particulate contaminants are typically negatively
charged and that the solid precipitates formed during conditions of sweep coagulation are
positively charged. He suggested that particulate contaminants are electrostatically attracted to
the solid precipitates.

Interparticle Bridging

Interparticle bridging is a mechanism of particle destabilization that involves the use of

high molecular weight (mol wt > 106) polymers as coagulants. Some of the functional groups on
the polymers bond to the surface of the contaminants, and others extend out and contact the
surface of other particles in the solution. The polymer serves as a "bridge" between two or more
particles (O'Melia, 1972).

4
 Aluminum Dosage (mg/L)

Note: C/Co = ratio of final to initial fulvic acid concentration; TOC = total organic carbon.
Source: Dempsey, Ganho, and O'Melia, 1984.

Figure 2.1 Stoichiometry of coagulation of fulvic acid.

2.3 Influence of Mixing on Coagulation

Charge neutralization requires rapid and uniform mixing of the chemicals added to the
water and contact between the charged contaminant particulates and the hydrolysis species of the
coagulant (Amirtharajah and Mills, 1982). This contact must occur before the hydrolysis
speciation reaches the state where solid hydroxide precipitate is formed (O'Melia, 1972). The
purpose of rapid mixing is to provide quick and uniform dispersion of the chemicals added to the
untreated water, creating the coagulant species that cause destabilization.

Slow mixing is an important step when the mechanism is sweep coagulation. A report
prepared by the AWWA Coagulation Committee (1988) reviewed the fundamentals of slow
mixing and flocculation. The process of slow mixing promotes contact between the solid

5
hydroxide precipitate and the particulate matter to be removed. Collisions between particles occur
by Brownian motion, fluid motion, and differential sedimentation. The frequency of collisions is
dependent on properties of the water and the particles as well as the type of mixing. Properties of
the water include temperature, viscosity, and density. Properties of the particles to be removed
include number concentration, density, and size. Mixing conditions may vary depending on
detention time, flow conditions, and mixing intensity.

2.4 Conventional Coagulants

Metal salts and high molecular weight organic polymers can induce coagulation under
appropriate conditions. The selection of a coagulant is based on the characteristics of the raw
water to be treated and the desired mechanism of coagulation. Raw water characteristics that
must be considered are turbidity, temperature, concentration of DOM, pH, buffer capacity, ionic
strength, and calcium concentration. Jar testing is a valuable technique for evaluating the
effectiveness of coagulants.

Inorganic Metal Salts

Because of their ionic charge, all simple salts present in natural waters can affect the
stability of colloidal particles. However, simple salts are not effective as coagulants because they
do not promote the formation of strong aggregates that are resistant to shear (Gregory, 1989).
Salts that release adsorbing counterions are more effective coagulants. When these salts are
added to water, counterions are released and adsorb to the particle surfaces. The charge on these
particles is reduced to nearly zero.

The mechanism of coagulation for metal salts of aluminum and iron involves either the
adsorption of coagulant species to the contaminant to be removed or the entrapment of the
contaminant within a hydroxide precipitate (O'Melia, 1972; Gregory, 1978). The reaction
schematics are shown in Figure 2.2.

Dempsey (1984) reported that alum is the most commonly used coagulant for water
treatment in the United States and that polyaluminum chloride is widely used in Japan. Fe(III)
salts are also used as coagulants in drinking water treatment but are more commonly used in
wastewater treatment The effective pH range for Fe(III) salts is reportedly broader than that for
aluminum salts (Gregory, 1989; Hall and Packham, 1965).

Polymeric Coagulants

Polyelectrolytes that have nonionic, anionic, or cationic character have been developed as
coagulants. These high molecular weight products interact with the surfaces of particles in the
water through hydrophobic and hydrogen bonding (Gregory, 1989). The primary mechanism of
coagulation with polyelectrolytes is interparticle bridging. These products tend to produce flocs
that are more resistant to high shear stresses than are flocs formed with inorganic coagulants.
High shear stresses during mixing or flow within pipes and channels may cause floc breakup.

6
Source: Amirtharajah and Mills, 1982.

Figure 2.2 Reaction schematics of coagulation.

2.5 Hydrolysis Speciation of Inorganic Metal Salts

When a metal salt is added to water, a series of complex hydrolysis reactions occur.
Gregory (1989) described the hydrolysis of a metal salt as the progressive replacement of water
molecules in the hydration shell with hydroxyl groups. The positive charge is reduced until the
formation of the solid hydroxide precipitate occurs. The hydrolysis speciation is continuously
changing and is influenced by many factors. Dempsey (1984) provided as many of these factors,
which include the pH and temperature of the water, the presence of particulate and dissolved
matter, the mixing conditions, and the time of reaction. Other factors sometimes considered are
the concentration and age of the coagulant solution.

Impact of Hydrolysis Speciation

When inorganic metal salts are used as coagulants, the mechanism of coagulation is
controlled by the hydrolysis speciation. The efficiency of charge neutralization as a mechanism
of coagulation depends upon the speciation of the coagulant. Amirtharajah and Mills (1982)
stressed that the intensity of rapid mixing is of utmost importance for charge neutralization
because the coagulant species must come in contact with the charged contaminants before the
solid hydroxide precipitate forms. The hydrolysis of the coagulant influences the efficiency of
contaminant removal and the settleability of fIoc (AWWA Coagulation Committee, 1988).

Hydrolysis of Fe(III) Salts

The mechanisms of coagulation for Fe(III) salts are a function of the hydrolysis speciation
of Fe (III) in water (Stumm and Morgan, 1962; Stumm and O'Melia, 1968; Black, 1967; Johnson
and Amirtbarajah, 1983; Matijevic and Janauer, 1966). The hydrolysis of a metal salt is primarily
7
dependent on the characteristics of the raw water and is affected by the intensity and duration of
rapid mixing. The process that hydrolyzes Al (III) is essentially identical to that for Fe(lII).Al(III)
speciation was reviewed in detail by Baes and Mesmer (1976), and many of the major species
formed during hydrolysis are shown in Figure 2.2.

The following possible hydrolysis reactions of Fe(III) in aqueous solution were reported
by Stumm and coworkers (Stumm and Morgan, 1962; Stumm and O'Melia, 1968; Tang and
Stumm, 1987):

Fe3+ + H2O <=> Fe(OH)2+ + H+

Fe3+ + 2H2O <=> Fe(OH)2 + + 2H+

2Fe3+ + 2H2O <=> Fe2(OH)24+ + 2H+

3Fe3+ + 4 H2O <=> Fe3(OH)45+ + 4H+

Fe3+ + 3 H2O <=> Fe(OH)3 + 3H+

Similar reactions were reported by Snoeyink and Jenkins (1980). All of these reactions
follow the general expression

xFe3+ + yH2O <=> Fex(OH)y (3x-y)+ + yH+

Fe3+ does not exist in natural waters as a simple ion but exists as an aquocomplex species,
such as Fe(H2O)63+ (O'Melia, 1972). However, to simplify the reaction expressions, the water
molecules are typically not shown.

Tang and Stumm (1987) evaluated the speciation of ferric chloride and presented several
reactions that can form complexes between Fe(III) and Cl-.

These were given as

Fe3+ + Cl- <=> FeCl2+

Fe3+ + 2Cl- <=> FeCl2+

Fe3+ + 3Cl-<=>FeCl3o

Fe3+ + 4Cl- <=>FeCl4

After an extensive evaluation of factors controlling the hydrolysis speciation of Fe (III),

Tang and Stumm (1987) proposed the hydrolysis-polymerization-precipitation scheme presented
in Figure 2.3. This scheme incorporates those previously proposed by Dousma and de Bruyn
(1976) and Knight and Sylva (1974) and shows the chemical species expected to be present
during various stages of hydrolysis. The extent of hydrolysis of a coagulant is dependent on the
age of the coagulant solution as well as its concentration. In addition, elevated temperature
promotes hydrolysis reactions (Tang and Stumm, 1987). In the Tang and Stumm scheme, type A

8
solutions contain monomers, oligomers, and complexes with chlorides that occur during the
initial stages of hydrolysis. At low OH-:Fe ratios, rapid precipitation is favored under conditions
characteristic for type B solutions.

Note: am = amorphous species of iron; B = [OH-a] I [FeT]; B* = [OH-b] [FeT]; [FeT] = total iron concentration.
Source: Adapted from Water Research, Vol 21, H.X.-Tang and W. Stumm, The Coagulating Behaviors of Fe(III)
Polymeric Species-/ and II, pages 115-128, Copyright 1987, with kind permission from Elsevier Science Ltd,
The Boulevard, Langford Lane, Kidlington OX5 1 GB, UK.

Figure 2.3 Coagulation behavior of Fe(III) polymeric species.

When OH- is more abundant, polymerization characteristic of type C solutions is more

likely to occur than is precipitation. The formation of high level polymers is characteristic of type
D solutions. A decrease in the charges of type D species occurs because of deprotonation and
leads to precipitation characteristic of type E solutions.

Tang and Stumm (1987) monitored changes in the color of the ferric chloride solutions
during hydrolysis. According to these researchers, the color of the solution indicates the extent of
hydrolysis. A yellow color indicates the presence of monomers oroligomers of Fe(III) hydrolysis;
a brown color indicates the polynuclear species present after extended hydrolysis. The addition of
base to an Fe(III) solution causes the hydrolysis reactions to proceed, as indicated by the change
in color of the solution from clear yellow to cloudy red-brown.

The effect of Fe(III) concentration on the coagulation of kaolinite suspensions with FeCl3
(ferric chloride) as the coagulant was also investigated by Tang and Stumm (1987). FeCl3
solutions of greater than 0.1 M concentration behaved as type A solutions, and concentrations
near 0.01 M behaved as type B solutions. Solutions below 0.005 M acted as type C, and those
below 0.0001 M acted as type D. The concentration of the coagulant and conditions of the
untreated water, such as pH, affected the chemical speciation of the coagulant. This speciation
9
determines the mechanism and efficiency of coagulation. Tang and Stumm (1987) suggested that
concentrated FeCl3 solutions (>=O.1 M, or type A) are more advantageous for coagulation than
more dilute concentrations. Type B solutions are typical of sweep coagulation conditions, which
require higher coagulant dosages.

Other investigations by Tang and Stumm (1987) identified differences in coagulation with
aluminum and iron salts. Positive charges were higher for hydrolysis species of aluminum salts
than iron salts, which indicate that lower dosages of aluminum salts are required for charge
neutralization. Based on residual turbidity, coagulation with aluminum salts was less efficient
after charge neutralization occurred. Iron salts were found to require slightly higher dosages for
charge neutralization. However, even though charge reversal occurred at the highest iron dosages,
optimum turbidity removal was still achieved. Therefore, Tang and Stumm (1987) suggested that
iron salts are more suitable for coagulation by charge neutralization than aluminum salts because
of their hydrolysis speciation. Under similar conditions, iron salts exhibited higher OH:metal ion
ratios than aluminum salts, which implies lower charge density and higher binding ability. A 0.3
MFeCl3 solution was found to be much more effective than AlCl3 (alum) and 0.01 M FeCl3 based
on turbidity removal. These results are presented in Figure 2.4.

2.6 Coagulation Diagrams

Coagulation diagrams for effective turbidity removal were developed by superimposing

treatment data on thermodynamic stability diagrams for the inorganic coagulant (Amirtharajah
and Mills 1982; Johnson and Amirtharajah 1983). The diagrams are based on the speciation of
aluminum and iron salts with respect to the solubility of solid precipitates-Al(OH)3 for aluminum
salts and Fe(OH)3 ferric salts. These diagrams also indicate the mechanism of coagulation
responsible for panicle removal depending on the pH and coagulant dosage. Coagulation
diagrams for Al(III) and Fe(III) salts are presented in Figures 2.5 and 2.6, respectively.
Additional information about coagulation diagrams can be found in Amirtharajah and O 'Melia
(1990).

2.7 Natural Aquatic Humic Substances

Humic substances are complex, organic polycondensate mixtures that exist in all soil and
aquatic environments. These substances have been studied extensively because of their
environmental significance. Because of extreme complexity of humic substances, many
researchers studying them have focused their efforts on functional group characterization, metal
complexation properties, and acidic properties.

10
Note: PACI = polyaluminum chloride; PFC = polyferric chloride; 0 = days.
Source: Adapted from Water Research, Vol 21, H.x. Tang and W. Stumm, The Coagulating Behaviors of Fe(lII)
Polymeric Species and II, pages 115-128, Copyright 1987 with kind permission from Elsevier Science Ltd. The
Boulevard, Langford Lane, Kidlington OX5 1 GB. UK.

Figure 2.4 Comparison of different coagulants.

.

This section comprehensively reviews the current understanding of the origin, classification,
molecular size, elemental composition, molecular structure, and characteristic properties of humic
substances. Methods for isolating DOM and the impact of humic substances on water treatment are also
discussed. Much of the material presented in this section focuses on humic substances from the Suwannee
River because humic substances from this source were used in the research project.

Overview

Humic substances are extremely complex mixtures of randomly condensed organic

compounds that originate from the decomposition of plant and animal residues (MacCarthy and
Suffet 1989). Aquatic humic substances are classified as fulvic acids, humic acids or humic
according to their aqueous solubility under varying pH conditions. Fulvic acids are soluble in
water at all pH conditions. Humic acids are not soluble in water below a pH of 2. Humic is not
soluble in water at any pH. The molecular weight of fulvic acids typically ranges between 500
and 2,000 Daltons (Thurman et al., 1982). Humic acids have molecular weights greater than
2,000 Daltons. The elemental composition of humic substances provides information about their
nature, and source. Through various analytical and chemical techniques, functional groups in the
structure of humic substances have been characterized. These functional groups determine the
geochemical behavior of humic substances. Humic substances have a significant impact on the
processes used in the treatment of drinking water.

11
Source: Amirtharajah and Mills, 1982.
.-.
Figure 2.5 Design and operation diagram for alum coagulation

Origin of Humic Substances

Hall and Packham (1965) stated that the color in surface waters is caused by complex
organic compounds of natural origin derived from water soluble peptizable components of soil
humus and peat. They suggested that humic substances in the soil result from the polymerization
of polyphenolic units from bacterial synthesis or the breakdown of lignin residues of higher
plants. More recently, MacCarthy and Suffet (1989) stated that humic substances are extremely
complex mixtures of organic materials resulting from the decomposition of plant and animal
tissues.

12
Source: Johnson and Amirtharajah 1983.

Figure 2.6 Design and operation diagram for ferric iron coagulation

Stevenson (1985) reviewed the polyphenol theory, which is currently widely accepted as
an explanation of the origin of humic substances in soils. This theory suggests that humic
substances are formed by a multistage process. According to this theory, plant materials
decompose into simple monomers. The metabolism of these monomers increases the biomass of
the soil. The biomass carbon is repeatedly recycled by the synthesis of new cells. Concurrently,
reactive monomers are polymerized into high molecular weight polymers. The various pathways
by which humic substances are formed vary with environmental conditions such as the moisture,
temperature of the soil, and type of surrounding vegetation.

The dissolved organic carbon (DOC) found in surface waters is predominantly

allochthonous (originating elsewhere), entering the water through runoff from the soil within a
watershed. This DOC is derived from the decay of Vegetation. Malcolm (1985) stated that humic
substances in mineral soils typically originate from the decay of higher plants, which contain
cellulose and lignin. Whereas allochthonous humic substances are prevalent in rivers, bogs, and
swamps, autochthonous humic substances are common in clear lakes (Steinberg and Muenster
1985). The autochthonous humic substances result from the decomposition of aquatic plants and
animals (Malcolm 1985). Diatoms and algae, which contain hemicellulose and proteins, and also
aquatic animals, which contain protein and chitinous substances, contribute to the composition of
aquatic humic substances.

Thurman and Malcolm (1983) suggested that the fulvic acid found in the Suwannee
River originated from recent degradation of terrestrial plant materials (within a 25-year period)
and not from older organic matter from the swamp peats.

13
 The composition of humic substances varies depending on their source and method of
extraction. In natural waters, dissolved humic substances are mixed with amino acids, sugars,
and aliphatic and aromatic acids (MacCarthy and Suffet, 1989). Humic substances are also
associated with various metal ions, clays, and amorphous oxides of aluminum and iron
(Thurman et al., 1982). Humic substances may be separated from these materials by passing the
mixture through a hydrophobic resin. Hydrophilic compounds such as amino acids and simple
sugars pass through the column, whereas hydrophobic humic substances sorb to the resin.
However, the isolation and separation processes may alter the natural state of the humic
substances and change their molecular size (Thurman et al., 1982).

Malcolm (1985) estimated that 50 percent of the DOC in uncolored surface waters in the
United States consists of humic substances. The average concentration of carbon in these surface
waters is 2.2 mg/L, which translates into 4.4 mg humic substance/L based on an average
elemental weight of 50 percent carbon. The DOC for colored surface waters may range from 5 to
more than 50 mg/L, and humic substances may contribute up to 80 percent of the DOC.

It is proposed to use Ferric Chloride instead of Aluminum Sulfate (Alum) during

pretreatment of Raw Water in Bangkok. It is anticipated that modifying water treatment plants to
use both Alum and Ferric Chloride will enable savings in the cost of chemicals at the treatment
plants. Raw water is treated by the following steps to produce Drinking Water (Austin, 1975):

1. Pretreatment - In a contact basin, potassium permanganate is added to the water. This

removes iron and manganese and improves the color. Carbon dioxide in combination with lime is
used to recarbonate the Raw Water. The Raw Water in its natural state is too soft for domestic
use.

2. Coagulation and flocculation any mineral and organic compounds present in the water
must be bound together to facilitate their removal by filtration. The particles are destabilized
(coagulation) in a flash mixer, by adding alum and then agglomerated into bulky floccules, called
"flocs". This occurs inside a coagulation tank (flocculation).

3. Filtration - Flocculated water is passed through a filter, to remove the impurities. A

nonionic polymer is added in a low energy mixer to act as a filtration aid. This slows penetration
of very fine flocs into the filter bed. The filters are composed of coal and sand over 0.1 m of
gravel. The filters are regulated to maintain equal flow to each one.

4. Post-treatment - Lime combined with carbon dioxide is added to control the pH and
prevent scaling in the distribution network. Chlorine is used to disinfect the water prior to
distribution. To protect treated water from contamination during distribution to consume,
ammonia is also added to form monochloramine.

5. Residuals - Waste by-products (residuals) are collected by washing the filters

(backwash). The washwater is sent to thickeners. Residuals are treated with a non-ionic polymer
in centrifuges, and then taken by truck to drying beds. Water from the thickeners (supernatant) is
recycled upstream of the plant.
This project will test the practicality of replacing alum in the coagulation and flocculation
step (Step 2) with ferric chloride. The ferric chloride will coagulate mineral and organic
compounds in the Raw Water to allow flocculation.
14
 The use of ferric chloride and other iron compounds for coagulation in water treatment
was first patented in 1884 (Carnduff, 1971). Issiah Smith Hyatt proposed using perchloride of
iron or ferric chloride in the treatment of New Orleans water.

In a similar study for the Metropolitan Toronto water supply (Carnduff, 1976), it was
found that dosages of ferric chloride necessary to produce high-quality water were smaller than
required for alum treatment. However, the cost savings were a function of fluctuating commodity
prices. The study recommended that plant design should allow the use of either compound when
commodity prices favoured it. The study also recommended the use of chemically resistant
plastics for ferric chloride tanks, pipes and pumps. These were considered significantly cheaper
than tantalum and titanium alternatives.

Treatment by using ferric chloride is also a way of avoiding the clogging of mains by
postprecipitation of aluminium complexes. This problem occurs when treating Raw Water with a
high pH with alum.

The Toronto study (Carnduff, 1976) used jar tests and plant scale testing to determine the
effectiveness of flocculation and the quality of filtered water produced. A similar methodology
was used for this study. The objectives of the study are to determine the effectiveness of
flocculation; the dosage range required for treatment; the quality of the filtered water produced
with respect to turbidity, taste and colour; and a cost comparison with a similar treatment using
alum.

The Woronora Water Filtration Plant, near Sydney Australia uses ferric chloride for
coagulation of mineral and organic impurities (General Water Australia, 2001). The Raw Water
quality and Treated Water quality (shown below) are comparable to Bangkok:

Table 2.1 Raw water quality parameters and their ranges

Raw Water Quality Parameters Range
Turbidity 0.5-10.7 NTU
Apparent Color 2-70 CU
Iron 0.02-1 mg/L
Manganese 0.003-0.07 mg/L
Aluminium 0.069-0.4 mg/L
Hardness 2.6-22.8 mg/L as CaCO3
Alkalinity 0.5-12.5 mg/L as CaCO3
pH 5.06-7.54
Temperature 10-26.6°C
Algae 0-5,000 U/mL

15
 Table 2.2 Treated water quality parameters and their ranges
Treated Water Quality Parameters Range
Turbidity <0.3 NTU
True Color <5 HU
Iron <0.2 mg/L
Manganese <0.03 mg/L
Aluminium <0.2 mg/L
Coliforms 0
Trihalomethanes <0.2 mg/L
pH 7.7-8.1
Calcium Carbonate -3.5 to -0.5

Table 2.3 Raw water quality parameters and their ranges

Precipitation Potential Range
Fluoride 1 mg/L
Chlorine Residual 0.5-1.7 mg/L

The Woronora plant supplies up to 160 million litres of drinking water per day (General
Water Australia).

16
 Chapter 3

Methodology

3.1 Introduction

Aluminum sulfate is a traditional coagulant for coagulation process in Thailand. Ferric

chloride is to be an alternative coagulant for this process. In order to compare these coagulants,
the experiment was established to investigate the efficiency and cost-effectiveness
comparisons.

The activities in this study are:

• Data collection
• Experimental set up
• Sample collection and
• Result interpretation and conclusion

3.2 Data Collection

The data about coagulation was collected from previous studies and researches
worldwide.

The main topics for data collection are:

• Coagulation and its mechanisms

• Coagulants
• Coagulation diagrams
• Natural aquatic humic substances

3.3 Experimental Set Up

The experimental module of simulated water treatment system was established as

shown in Figure 3.1.
Raw water from the Tha Chin River and also Mae Klong River were feed into the
mixing tank together with the coagulant solution. Circulating pump was employed for rapid
mixing. The mixed water-coagulant would then flows to flocculating tank which paddles were
employed for completely agitation. The third tank was settling tank, which flocs were settled
and the clarified water would overflow and flow to the sand filter. Settled flocs would be
drained through the drained valve. Sand filter with 120 cm. sand bed was used for filtration.
Totally 13 sets of tubes were used for head loss detection. Filtered water was drained at the
bottom of the sand bed.

17
 AGITATOR MOTOR
MIXING
VOLT 220 V OUTPUT 20/30
W
PMASR SINGLE AMPERE
0.24/0.26 A SAND
CYCLE 50/60 Hz RPM
FILTER
MIXING 2830/3300 2
FOCCULATING SETTLING TANK
TANK INPUT 45/55 W CAP 1UF
TANK
OVERCm.FLOW

Cm.
ROTAMETER
Cm. Manomet
Cm. er
1 Cm.
DRAIN VALVE Cm.
DIAPHRAGM
Cm.
DOSING PUMP
WATER

ROMINENT ELECTROMO Cm.

RAW

TYPE G 41 0216SS Cm.

GEGAN 2 BAR Cm.
10 L/h Chemical Cm.
CIRCULATING PUMP Solution
PIPE 17 MM. Tank WASH WATER
HEAD (MAX) 3.5/4.5
3 OUT LET
M. Legend:
CAPACITY ROTAME 1: Influent
2: Clarified Water
TER process
Figure 3.1 Schematic Diagram for water treatment 3: Effluent (Filtered Water)

18
Figure 3.2 Experimental setup for pilot scale water treatment plant

Figure 3.3 Experimental setup.

19
3.4 Experimental Procedure

3.4.1 Chemicals Preparation

ƒ Aluminum Sulfate Solution was prepared by diluting 189.7 mL

(50% w/w) to 20 L of tap water.
ƒ Ferric Chloride Solution was prepared by diluting 214.3 mL (40%
w/w) to 20 L of tap water.

3.4.2 Experimental Procedure

ƒ Adjust the flow rate of chemical feeding pump to the calculated

dosage,
ƒ Adjust the flow rate of raw water to 150 l/hr,
ƒ Start circulating pump,
ƒ Mixed water-chemical will flow to the flocculating tank, start
agitator motor, adjust to 20 rpm.,
ƒ After flocculation tank, water will overflow to settling tank for
sedimentation. If the sludge is filled up to the “HIGH” level, all
sludge will be drained,
ƒ Clarified water will overflow to the sand filter column, with 120 cm.
sand bed and fixed water level of 100 cm. above sand level, with
filtration rate of 90 l/hr. The left-over water will overflow out of the
sand filter,
ƒ There are 13 pores on the side of filter column, distance between
each pore is 10 cm., as shown in Figure 3.1,

3.4.3 Scenarios

Raw water from 1) Tha Chin River and 2) Mae Klong River, were used as influent
to the system. These 2 sources of raw water had different turbidity, which were had around
30 and 20 NTU for Tha Chin and Mae Klong River, respectively. Two scenarios were set
up to investigate the performance of coagulants:

Phase I: Tha Chin River raw water: High Turbidity, and

Phase II: Mae Klong River raw water: Low Turbidity.

3.5 Sample Collection

Jar test was performed prior to the experimental run to investigate the feeding rate
of coagulants, as shown in Figure 3.4.

20
 Figure 3.4 Jar test equipment.

Two coagulants were used for coagulation of raw water:

1) Aluminum Sulfate
2) Ferric Chloride

Sampling was performed in accordance with procedure described in Standard

Methods of Water and Wastewater Examination (AWWA, 1992). The water samples were
collected as a representative of 1) influent, 2) clarified water and 3) filtered water as
illustrated in Figure 3.1. All samples were analyzed at the Mahasawat Water Treatment
Plant Laboratory. The analytical parameters and their methods were presented in Table 3.1.

Table 3.1 Parameters and their experimental procedures.

Parameters Units Method Point of sampling Frequency
pH pH pH Meter 1, 2 and 3 Every 4 hours
Turbidity NTU Turbidimeter 1, 2 and 3 Every 2 hours
Alkalinity mg/L Test Kit 1 and 2 Every 4 hours
Total Solid (TS) mg/L Conductivity Drained sludge Once a day
Meter
Aluminum ion mg/L AWWA* 3 Once a day
Ferrous ion mg/L AWWA* 3 Once a day
Manganese ion mg/L AWWA* 3 Once a day
*Note: Standard as standard method (AWWA, 1992)

Total Solids (TS) were analyzed for sludge concentration, moreover residual
Aluminum Ferrous and Manganese were only analyzed for contamination of drinking
water fro the process.

21
 All system equipment and status, which were pumps, motors, inlet, outlet and
sludge quantity were checked every 2 hours.

3.6 Results Interpretation and Conclusion

The results from experiments were analyzed to compare the performance and
removal efficiency of two coagulants: 1) Aluminum Sulfate and 2) Ferric Chloride.
Moreover, the cost-effectiveness and filter run period of those two coagulants were also
calculated.

22
 CHAPTER 4

Results and Discussion

Aluminum Sulfate is the main coagulant for MWA water treatment. Ferric Chloride
would be the comparative coagulant. Jar test was performed by using the water from Tha
Chin and Mae Klong River. According to MWA standard of water treatment, water after
clarified should have turbidity lower than 5 NTU and water after sand bed filtration should
have turbidity lower than 2 NTU.

The total experimental period was separated into 2 phases according to the feeding
rate: Phase I: Raw water from Tha Chin River (high turbidity) and Phase II: Raw water
from Mae Kong River (low turbidity).

4.1 Phase I: Tha Chin River Raw Water

4.1.1 Aluminum Sulfate as Coagulant

The result of jar test in phase I showed that 55 mg/L of Alum feeding rate were
appropriate. Aluminum Sulfate feeding rate of 55 mg/L was applied to the experiment
totally 14 hours (excluding system preparation). As shown in Figure 4.2, turbidity in raw
water were high, 26 – 31 NTU and after clarification and filtration, turbidity were reduced
to 4.0 – 6.7 and 0.68 – 1.55 NTU, respectively, and the average treatment efficiency were
82.4 and 95.6%, respectively. (Figure 4.5)

Alkalinity in raw water were in a range of 100 – 108 mg/L, after clarification they
were reduced to 52 – 60 mg/L (Figure 4.3) or around 47.5% removal efficiency.

pH was reduced from 7.81 – 8.17 in raw water to 6.75 – 7.29 and 6.80 – 7.24 after
clarification and filtration, respectively, as shown in Figure 4.4.

Effluent water quality as well. Moreover, jar test was performed only a guideline
for practical application of coagulant to the raw water.

Figure 4.6 shows the pressure drop in sand bed filter for the lowest pipe,
extrapolated pressure drop up to 50 cm. were used for filter run expectation. Filter run
period for Aluminium Sulfate for Phase I was calculated to be 18 hours.

Table 4.1 Jar Test result for Aluminum Sulfate as coagulant, Phase I.
Alum Dose (mg/L) Turbidity(NTU) pH Alkalinity (mg/L)
0 29.0 8.12 104
35 15.5 7.30 92
40 13.2 7.21 92
45 9.7 7.11 88
50 6.8 7.04 86
55 4.5 6.95 86
60 3.1 6.87 82

23
 65

60

55
Alum Dose (mg/L)

50

45

40

35

30
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
Tubidity (NTU)

Figure 4.1 Logarithm graph from jar test for Aluminum Sulfate as coagulant, Phase I.

Tha C hin, Alum

35
30
T u rb id ity , N T U

25
Raw Water
20
C larified Water
15
Filtered Water
10
5
0
0 2 4 6 8 10 12 14
R un Time, Hour

Figure 4.2 Turbidity of raw water, clarified water and filtered water for Aluminum sulfate
as coagulant, Phase I.

24
 Tha C hin, A lum

110
100
A lkalin ity (mg /L )

90
Raw Water
80
C larified Water
70
60
50
0 2 4 6 8 10 12 14
R un Time, Hour

Figure 4.3 Alkalinity of raw water and clarified water for Aluminum sulfate as coagulant,
Phase I.

Tha C hin, A lum

9

8
Raw Water
pH

C larified Water
7 F iltered Water

6
0 2 4 6 8 10 12 14
R un Time, Hour

Figure 4.4 pH of raw water, clarified water and filtered water for Aluminum sulfate as
coagulant, Phase I.

25
 Tha C hin, A lum
100
95
% Tu rb id ity
R em o v al

90 C larified Water
85 F iltered Water

80
75
0 2 4 6 8 10 12 14
R un Time, Hour
Figure 4.5 Turbidity removal efficiency of clarified and filtered water for Aluminum
sulfate as coagulant, Phase I.

Tha Chin/ Alum

25

20
Run Time, Hour

15
y =0.3798x - 1.2617
10 2
R =0.9632
5

0
0 10 20 30 40 50 60
Total Pressure Drop, cm.

Figure 4.6 Pressure drop of sand filter for Aluminum sulfate as coagulant, Phase I.

4.1.2 Ferric Chloride as Coagulant

The result from jar test is illustrated in Table 4.2 and Figure 4.7, 25 mg/L of Ferric
Chloride feeding rate was selected.

During experiment, turbidity of raw water were 30 – 34 NTU, and reduced to 4.0 –
5.8 and 0.08 – 0.90 NTU after clarification and filtration respectively as shown in Figure
4.8, with the average treatment efficiency of 84.7 and 98.8%, respectively (Figure 4.11).

Alkalinity in raw water were in a range of 96 – 104 mg/L, after clarification they
were reduced to 76 – 90 mg/L (Figure 4.9) or around 16.4% removal efficiency.

26
 pH was reduced from 7.82 – 8.14 in raw water to 7.19 – 8.04 and 7.16 – 7.86 after
clarification and filtration, respectively. (Figure 4.10)

Figure 4.12 shows the pressure drop in sand bed filter for the lowest pipe, with the
same method of extrapolation, filter run period for Ferric Chloride for Phase I was
calculated to be 25 hours.

Table 4.2 Jar Test result for Ferric Chloride as coagulant, Phase I.

Ferric Chloride Dose (mg/L) Turbidity(NTU) pH Alkalinity (mg/L)

0 30.0 8.17 98
15 8.2 7.10 84
20 6.5 6.94 78
25 5.2 6.88 78
30 3.6 6.81 72
35 2.9 6.76 70
40 2.4 6.68 64

45

40

35
FeCl 3 Dose (mg/L)

30

25

20

15

10
0 1 2 3 4 5 6 7 8 9
Turbidity (NTU)

Figure 4.7 Logarithm graph from jar test for Ferric Chloride as coagulant, Phase I.

27
 Tha Chin,FeCl3
40
T u rb id ity , N T U

30
Raw Water
20
C larified Water
F iltered Water
10

0
0 2 4 6 8 10 12 14 16 18 20
Run T ime, Hour
Figure 4.8 Turbidity of raw water, clarified water and filtered water for Ferric Chloride as
coagulant, Phase I.

Tha Chin, FeCl3

110
A lk alin ity (m g /L )

100

Raw Water
90
C larified Water

80

70
010 5 15 20
Run Time, Hour
Figure 4.9 Alkalinity of raw water and clarified water for Ferric Chloride as coagulant,
Phase I.

28
 Tha Chin, FeCl3
8.2
8
7.8
Raw Water
pH

7.6
C larified Water
7.4 F iltered Water
7.2
7
0 2 4 6 8 10 12 14 16 18 20
Run T ime, Hour
Figure 4.10 pH of raw water, clarified water and filtered water for Ferric Chloride as
coagulant, Phase I.

Tha Chin, FeCl3

100
%T u rb id ity R em o v al

95

90 C larified Water
F iltered Water
85

80
0 2 4 6 8 10 12 14 16 18 20
R un Time, Hour

Figure 4.11 Turbidity removal efficiency of clarified and filtered water for Ferric Chloride
as coagulant, Phase I.

29
 Tha Chin/ FeCl3
30
25
Run Time, Hour

20
15 y =0.5683x - 2.762
2
10 R =0.9843

5
0
0 10 20 30 40 50 60
Total PressureDrop, cm.WC
Figure 4.12 Pressure drop of sand filter for Ferric Chloride as coagulant, Phase I.

4.2 Phase II: Mae Klong River Raw Water

4.2.1 Aluminum Sulfate as Coagulant

The same method was used. Jar test was performed with the water from Mae
Klong River. Results of jar test are as shown in Table 4.3 and Figure 4.13, and found that
the appropriate Aluminum Sulfate feeding rate was selected to be 40 mg/L in order to get a
better water quality.

Figure 4.14 shows the result of turbidity in raw water, clarified water and filtered
water. Turbidity of raw water ranged from 16 – 20 NTU, while turbidity of clarified and
filtered water were ranged from 2.2 – 5.6 and 0.24 – 0.53 NTU, respectively. The average
efficiency of turbidity treatment after clarified and filtered were 80.3 and 97.4%,
respectively. (Figure 4.17)

The Alkalinity of raw water and clarified water are shown in Figure 4.15, with the
value of 98 – 104 and 46 – 90 mg/L, respectively. The average efficiency of alkalinity
treatment after clarified was 30.1%

pH of raw water, clarified water and filtered water were shown in Figure 4.16, the
ranges were 6.83 – 7.97, 5.43 – 7.53 and 5.96 – 7.66, respectively.

Figure 4.18 shows the pressure drop in sand bed filter for the lowest pipe, with the
same method of extrapolation, filter run period for Aluminum Sulfate for Phase I was
calculated to be 23 hours.

30
Table 4.3 Turbidity results(NTU) from Jar Test for Ferric Chloride as coagulant feeding
rate 25 mg/L.
Aluminum Sulfate Dose (mg/L) Turbidity(NTU) pH Alkalinity (mg/L)
0 15.0 7.50 92
15 11.3 7.30 82
20 8.6 7.26 80
25 6.4 7.18 78
30 5.0 7.10 78
35 3.5 7.04 76
40 3.3 6.93 72

40

35

y = -18.887Ln(x) + 60.518
2
R = 0.982
Alum Dose (mg/L)

30

25

20

15

10

0.0 2.0 4.0 6.0 8.0 10.0 12.0

Turbidity (NTU)

Figure 4.13 Jar test results for Aluminum Sulfate as coagulant, Phase II.

31
 Mae K long, A lum
25
T u r b id ity , N T U

20
15 Raw W ater
Clarified W ater
10 Filtered W ater

5
0
0 2 4 6 8 10 12 14
R un Time, Hour
Figure 4.14 Turbidity in raw water, clarified water and filtered water for Aluminum
Sulfate as coagulant, Phase II.

Mae K long, A lu m
120
A lk a lin ity (m g /L )

100
Raw W ater
80 C larified W ater

60

40
0 2 4 6 8 10 12 14
R u n Time, Hour
Figure 4.15 Alkalinity in raw water and clarified water for Aluminum Sulfate as
coagulant, Phase II.

32
 Mae K long, Alum
9

Raw Water
pH

7 Clarified Water
Filtered Water

5
0 2 4 6 8 10 12 14
Run Time, Hour
Figure 4.16 pH in raw water, clarified water and filtered water for Aluminum Sulfate as
coagulant, Phase II.

M ae K long, Alum
100
% Turbidity R emoval

90

Clarified Water
80
Filtered Water

70

60
0 2 4 6 8 10 12 14
Run T ime, Ho ur
Figure 4.17 Turbidity removal efficiency clarified water and filtered water for Aluminum
Sulfate as coagulant, Phase II.

33
 Mae Klong/Alum
25

20
Run Time, Hour

15
y=0.5404x- 4.4565
10 2
R =0.9973
5

0
0 10 20 Total Pressu
30re Drop, cm. 40 50 60

Figure 4.18 Pressure drop for Aluminum Sulfate as coagulant, Phase II.

4.2.2 Ferric Chloride as Coagulant

According to jar test, as shown in Table 4.4 and Figure 4.19, 15 mg/L of Ferric
Chloride feeding rate was selected to obtain the same water quality as using Aluminum
Sulfate.

During phase II, the turbidity of raw water was dropped down to 15 – 19 NTU, and
the analyzed results from clarified and filtered water were 1.6 – 4.3 and 0.14 – 0.80 NTU,
respectively (Figure 4.20), with the average turbidity treatment efficiency of 85.0 and
98.1%, respectively (Figure 4.23).

The Alkalinity of raw water and clarified water are shown in Figure 4.21, with the
value of 100 – 110 and 62 – 86 mg/L, respectively. The average efficiency of alkalinity
treatment after clarified was 30.3%.

pH of raw water, clarified water and filtered water were shown in Figure 4.22, the
ranges were 7.54 – 8.24, 6.97 – 7.55 and 5.71 – 7.70, respectively.

Figure 4.24 shows the pressure drop in sand bed filter for the lowest pipe, with the
same method of extrapolation, filter run period for Ferric Chloride for Phase I was
calculated to be 34 hours.
Table 4.4 Jar test result for Ferric Chloride as Coagulant, Phase II.
Ferric Chloride Dose (mg/L) Turbidity(NTU) pH Alkalinity (mg/L)
0 15.0 7.39 92
5 7.0 7.22 84
10 3.5 7.14 82
15 2.7 7.08 78
20 2.1 7.07 70
25 1.3 6.91 68
30 1.0 6.48 62

34
 35

30

25
FeCl 3 Dose (mg/L)

20

15

10

0
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
Turbidity (NTU)

Figure 4.19 Jar test result for Ferric Chloride as coagulant, Phase II.

Mae Klong, FeCl 3

25
T u rb i d i ty , N T U

20
15 Raw W ater
Clarified W ater

10 Filtered W ater

5
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26
Run Time, Hour
Figure 4.20 Turbidity in raw water, clarified water and filtered water for Ferric Chloride as
coagulant, Phase II.

35
 Mae Klong, FeCl 3

110
Alkalin ity (m g/L)

90
Raw W ater
Clarified W ater

70

50
0 2 4 6 8 10 12 14 16 18 20 22 24 26
Run Time, Hour
Figure 4.21 Alkalinity in raw water and clarified water for Ferric Chloride as coagulant,
Phase II.

Mae Klong, FeCl 3

8
R aw Water

7 C larified Water
pH

Filtered Water

5
0 2 4 6 8 10 12 14 16 18 20 22 24 26
Run Time, Hour
Figure 4.22 pH in raw water, clarified water and filtered water for Ferric Chloride as
coagulant, Phase II.

36
 Mae Klong, FeCl3

100
% Tu r b id ity R em o v al

90
Clarified Water
Filtered Water

80

70
0 2 4 6 8 10 12 14 16 18 20 22 24 26
R un T ime, Hour
Figure 4.23 Turbidity removal efficiency in clarified water and filtered water for Ferric
Chloride as coagulant, Phase II.

Mae Klong/ FeCl3

40
35
30
Run Time, Hour

25
y=0.8096x- 6.5443
20 2
R =0.9764
15
10
5
0
0 10 20 30 40 50 60
Total PressureDrop, cm.
Figure 4.24 Pressure drop for Ferric Chloride as coagulant, Phase II.

37
4.3 Turbidity Treatment Efficiency Comparison

The results of experiment for water treatment process by using Aluminum Sulfate
and Ferric Chloride were discussed in section 4.1 and 4.2.

4.3.1 Phase I: Tha Chin River Raw Water (High Turbidity)

The obtained results show that during Phase I, the average raw water for both
cases were high, 32.3 and 28.0 NTU for Ferric Chloride and Aluminum Sulfate,
respectively, as shown in Figure 4.25. The final effluent or filtered water from Ferric
Chloride as coagulant had a better quality with an average turbidity of 0.4 NTU. Ferric
Chloride and Aluminum Sulfate were fed 25 and 55 mg/L, respectively, or can be
calculated to a ratio of F:A = 1:2.2.

Figure 4.26 illustrates the average treatment efficiency of turbidity in clarified

and filtered water of both experiments with Ferric Chloride and Aluminum Sulfate, with
the final effluent achieved 98.8 and 95.6%, respectively.
35
32.3
30
28.0
Turbidity 25
(NTU)
20

15

10

5 4.9 4.9

0 1.2
0.4
Raw
Water C larified
Water F iltered F erric C hloride
Water A luminum S ulfate

Figure 4.25 Average turbidity in different sampling points of experiment Phase I.

38
 100 98.8

95 95.6

90
84.7
Turbidity
Treatment 85 82.4
Efficiency
(%) 80

75

70

C larified Water F erric C hloride

F iltered Water A luminum S ulfate

Figure 4.26 Average turbidity treatment efficiency in clarified and filtered water of
experiment Phase I.

4.3.2 Phase II: Mae Klong River Raw Water (Low Turbidity)

Phase II had lower turbidity, 16.3 and 18.3 NTU for Ferric Chloride and Aluminum
Sulfate, respectively, as shown in Figure 4.27, with the turbidity in filtered water of 0.4 and
0.5 NTU, respectively. For this experiment, feeding rate of Ferric Chloride was reduced to
15 mg/L, while that of Aluminum Sulfate was increased up to 40 mg/L. The ratio of
feeding rate of F:A increased to 1:2.67 while Ferric Chloride achieved a better water
quality.

Figure 4.28 illustrates the average treatment efficiency of turbidity in clarified

and filtered water of both experiments with Ferric Chloride and Aluminum Sulfate, with
the final effluent achieved 98.1 and 97.4%, respectively.

39
 20 18.3
18 16.3
16
Turbidity14
(NTU)
12
10
8
6
4 3.5
2.8
2
0 0.4 0.5
Raw
Water C larified
F iltered F erric C hloride
Water
Water A luminum S ulfate

Figure 4.27 Average turbidity in different sampling points of experiment Phase II.

100 85.0 98.1 97.4

90 80.3
80
Turbidity 70
Treatment
60
Efficiency
(%) 50
40
30
20
10
0

C larified Water F erric C hloride

F iltered Water A luminum S ulfate

Figure 4.28 Average turbidity treatment efficiency in clarified and filtered water of
experiment Phase II.

4.4 Ferrous, Manganese and Residual Aluminum in filtered water

The standard of MWA indicated that Ferrous and Manganese in drinking water
should not more than 0.3 and 0.1 mg/L, respectively. Average Ferrous and Manganese in
drinking water after filtration when using Ferric Chloride as coagulant were 0.06 (max
0.27) and 0.01 (max 0.05) mg/L, respectively. The analyzed apparent colors were below
the standard.

40
 Average residual Aluminum in filtered water when using Aluminum Sulfate was
0.15 mg/L (max 0.39). The standard of MWA allows 0.5 mg/L for drinking water. All data
is concluded as shown in Table 4.5.

Table 4.5 Residual chemicals concentration, comparing with the standard of filtered water
from the experiments.
Coagulant Parameter Range Average Standard
Ferrous ion 0.00 – 0.27 0.06 0.30
Ferric Chloride Manganese ion 0.00 – 0.05 0.01 0.10
Apparent color < 5.0 < 5.0 < 15.0
Aluminum Sulfate Aluminum ion 0.00 – 0.39 0.15 0.20

4.5 Total Solids

Sludge generated from flocs, drained from the bottom of sedimentation tank was
analyzed for Total Solids in order to investigate the sludge concentration.

The results show that the average Total Solids (TS) of sludge from Ferric
Chloride and Aluminum Sulfate as coagulant were 39.9 and 28.7 mg/L, respectively.

Higher TS indicated that the sludge is denser in term of mass per volume. In
order to dispose the sludge, denser sludge can be handled easier such as by dewatering or
transportation. Moreover, it can be noted here that the sludge generated from using
Aluminum Sulfate as coagulant is bulky sludge, which can disturb the efficiency of the
system and also lead to the clogging or fouling of the system.

4.6 Filter Run Period

From the study, Ferric Chloride could prolong the filter run up to 34 hours. While
Aluminum Sulfate could utilize filter for 23 hours, which means 32.4% of backwashing
water can be saved.

4.7 Cost Comparison

The price of each coagulant (2002) is;

1) Aluminum Sulfate: 3,550 Baht/ton (Dry weight)

2) Ferric Chloride : 7,000 Baht/ton (Dry weight)

Calculation of unit price of treatment per cubic meter of raw water shows below
(according to the best ratio from pilot scale experiment; F:A = 1:2.67);

ƒ 40 mg/L of Aluminum Sulfate

= 1,000 (L/m3) * 40 (mg/L) * 3,550 (Baht/ton) / 109 (mg/ton)

= 0.142 Baht/m3

ƒ 15 mg/L of Ferric Sulfate

41
 = 1,000 (L/m3) * 15 (mg/L) * 7,000 (Baht/ton) / 109 (mg/ton)
= 0.105 Baht/m3

According to this study, 26.0% of money can be saved by using Ferric Chloride
instead of Aluminum Sulfate.

4.7 Expected Savings for Mahasawat Water Treatment Plant (MWTP)

Nowadays, MWTP utilized around 25 tons of Aluminum Sulfate and 8,000 m3 of

backwashing water daily (in 16 filter units). According to the results of this study, if Ferric
Chloride is to be used substitute to Aluminum Sulfate;

• 26.0% of chemical cost can be saved (Aluminum Sulfate = 3,550

Baht/ton)

= 25 tons/day * 3,550 Baht/ton * 0.260

= 23,075 Baht/day

• 32.4 % of backwashing water also can be saved (Backwashing water =

1.30 Baht/m3)

= 8,000 m3/day * 1.30 Baht/m3 * 0.395

= 3,370 Baht/day

Totally 26,445 Baht per day or around 10 million Baht per year can be saved, if
MWTP decides applying Ferric Chloride as coagulant in water treatment process.
However, for more practical values of saving money, real application of Ferric Chloride to
water treatment process at MWTP is highly suggested.

In the year 2022, MWTP will expand the size of this plant up to 64 filter units or
4 times of the size nowadays. The water production will expand from 600,000 m3/d to
3,200,000 m3/d. The saving amount can be calculated to be:
= (3,200,000/600,000)*23,075 + (64/16)*3,370
= 136,547 Baht/day

Totally around 50 million Baht per year can be saved beyond the year 2022 if
Ferric Chloride is applied in MWTP.

Table 4.6 concludes the comparisons of water treatment by using Ferric Chloride
and Aluminum Sulfate.

Table 4.6 Comparison conclusion of Ferric Chloride and Aluminum Sulfate

Ferric Aluminum % Advantages of Ferric Chloride
Chloride Sulfate over Aluminum Sulfate
TS of sludge (mg/L) 39.9 28.7 28.1
Filter Run Period (hrs) 34 23 32.4
Cost (Baht/m3 raw water) 0.105 0.142 26.0

42
 Chapter 5

Conclusions and Recommendations

5.1 Conclusions

ƒ Raw water from Tha Chin and Mae Klong Rivers were used as feeding influent for
the pilot scale experiment;

Phase I: Raw water from Tha Chin River, average turbidity of 30 NTU

o Clarification and Filtration efficiency in term of Turbidity with Aluminium

Sulfate as coagulant were 82.4 and 95.6%, respectively. Average turbidity
concentration in filtrated water was 1.2 NTU.
o Clarification and Filtration efficiency with Ferric Chloride in term of
Turbidity as coagulant were 84.7 and 98.8%, respectively. Average
turbidity concentration in filtrated water was 0.4 NTU.

Phase II: Raw water from Mae Klong River, average turbidity of 17 NTU

o Clarification and Filtration efficiency in term of Turbidity with Aluminium

Sulfate as coagulant were 80.3 and 97.4%, respectively. Average turbidity
concentration in filtrated water was 0.5 NTU.
o Clarification and Filtration efficiency with Ferric Chloride in term of
Turbidity as coagulant were 85.0 and 98.1%, respectively. Average
turbidity concentration in filtrated water was 0.4 NTU.

ƒ By using Aluminum Sulfate as coagulant, average residual Aluminum was 0.15,

less than the standard. Average residual Ferrous and Manganese ions from
coagulation of Ferric Chloride were 0.06 and 0.01, respectively, which lower than
the standard values (0.30 and 0.10 mg/L).

ƒ Average filter run period for Aluminum Sulfate and Ferric Chloride were 23 and 34
hours, respectively. By using Ferric Chloride, filter run period can prolong 32.4%.

ƒ Costs of drinking water production were 0.142 and 0.105 Baht/m3 when using
Aluminum Sulfate and Ferric Chloride, respectively. By using Ferric Chloride,
chemical cost can be saved 26.0%.

5.2 Recommendations

ƒ This study’s result can be used as a guideline for substitution of Ferric Chloride to
Aluminum Sulfate, longer period of pilot scale experiments shall be performed, in
order to gain more data for interpretation.
ƒ Dual media of sand filter may be applied for filtration to study the results.
ƒ For more practical results, real application of Ferric Chloride in water treatment
process shall be performed at MWTP.
ƒ Sludge generated from both coagulants have to be analyzed in more parameters to
investigate their characteristics.

43
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