CHAPTER 1

INTRODUCTION

1.1 Background of Study

Textile industry is one of the main contributors to many Asian economies
including Malaysia. In textile processing, water usable for consumption and various
types of chemical additives have been used in large volumes. The used or unused
chemicals are discharged as effluents into the water streams as wastewater. The major
producer of wastewater comes from the stages of dyeing and finishing. The component
is the strong color due to the presence of extreme pH, large amount of suspended
solids(SS), presence of residual dyes and high chemical oxygen demand (COD). The
dyes can be highly visible if released at high concentrations. This effluent is
dangerously harmful, can cause cancer and of course is unsafe for the environment.
Thus, textile wastewater must be treated effectively so that they can be safely released
into the environment or municipal wastewater treatment plant (Verma et al., 2012).
Generally, textile effluents contain different composition of dyes and chemicals
that cause problem to our environment such as the reducing environmental quality. The
typical composition of textile effluents is shown in Table 1.1. Moreover, the textile
wastewater can be categorized into three types which are low, medium and high strength
wastewater based on their COD content as shown in Table 1.2.

Table 1.1: Characteristics of composite textile effluent (Al-Kdasi et al., 2005)

Parameters
Total Dissolved Solid (mg/L)
Total Suspended Solids (mg/L)
Chemical Oxygen Demand (mg/L)
Biological Oxygen Demand (mg/L)
Chloride (mg/L)
Color
pH
Chloride (mg/L)

Values
2900 3100
15-8000
150 12000
80 6000
1000 1600
Varies depending on the dye components
7-9
1000 1600

Table 1.2: Conductivity and Chemical Oxygen demand of textile effluent (Alves and
Pereira, 2012)
Wastewater type
COD(mg/L)
Conductivity (m/cm)
Low strength
460
2100
Medium strength
970
2500
High strength
1500
2900

The dye components in wastewater from the textile processes contain colors
which are very difficult to remove due to high affinity towards surfaces, consist of
residual dyes and chemicals demanding high amount of oxygen and complex
degradable materials which cannot be accepted by the natural environment (Siti Zuraida
et al., 2013). Strong and persistent colors of textile waste discharge are more difficult to
treat because of the complex compounds or composition and their concentrations.
The large quantity of non-biodegradable organic matter in the effluents makes
the textile wastewater too strong and much polluted to be received by the water bodies
without prior treatment. The high concentration of color pigments is the major factor of
the high turbidity of the textile effluent whereas the aquatic environment will be
affected by the deficiency of oxygen caused by high COD of the discharged effluent.

1.1.1

Dye Removal Methods.

Researchers and scientists have tried and implemented a lot of methods to treat
wastewater from textile industry which contain high concentration of dyes. The
techniques include physical, biological and chemical treatments. It is difficult to treat
dye effluents by conventional treatment processes because the dye molecules are
difficult to degrade due to their complex-structured polymers that cause them nonbiodegradable. After the treatments are finished, the formed precipitation is difficult to
be disposed off. Moreover, those methods consume a lot of money. For example, one of
the weaknesses of biological dye treatment is that the design and operation are less
flexible. Moreover, biological treatment requires a larger land area which is limited and
the purchase of extra lots are costly. Longer time is also needed for decolorizationfermentation process.
Thus, coagulation and flocculation method is chosen in this study because it is
commonly used in wastewater treatment. Moreover, this method is proven to be
effective and the operations are simple. The best materials for this method must be
known. Therefore, three materials have been used in this study. They are alum,
magnesium chloride and calcium chloride. The effect of dye pH and dosage of
coagulants on the percentage of dye removal also have been studied. The color
reduction of the dye in this study was assessed by UV-Vis photometry method.

1.2

Problem Statements
Recently, the advancement of industry in this country shows the increasing

usage of dyes especially for the textile, leather and paper industries. A considerably
large amount of water per day is required by those aforementioned industries for the
finishing and coloring processes. Other than that, they also produce large quantity of
dye wastewater too. If the untreated dye effluents are directly discharged into the water
bodies, the ecosystem stability will be broken because they contains high concentration
of COD and color. Because of the more stringent environmental laws and standards, the
dye effluents become the main environmental concern that must be solved. Even though
there are a lot of effective dye treatment processes in removing COD and color, they
still have a few considerable weaknesses.
3

Thus, we need to come up with more efficient and cost-saving methods to treat
the dye wastewater before discharge into the water bodies. On the other hand, there are
a few potential materials to be made as coagulants for coagulation and flocculation
method in treating textile dyes. Therefore, a study of coagulation and flocculation using
a few typical coagulants need to be conducted to identify each of their performances for
treatment of textile dye effluents.

1.3

Research Objectives
Generally, the main objective of this research is to evaluate the performances of

different types of coagulants for the treatment of reactive black 5 dye by using
coagulation and flocculation method. In details, the objectives of the research are:i)

To examine and verify the characteristics of Reactive Black 5 dye.

ii)

To determine the optimum conditions of the treatment in which the color

removal efficiency achieves the highest percentage.

iii)

To determine the most efficient coagulant in the removal of Reactive Black 5

dye in wastewater.

1.4

Research Scope
The scope of the study is bounded to the following; the azo dye, reactive black 5

(RB5) is used in this research. This research is focused on comparison of types of

coagulants in coagulation and flocculation process for dye color removal. The efficiency
of the coagulation is affected by the pH of the dye, dosage of the coagulants used and
the initial concentrations of dye solutions. These different conditions of treatment yield
different end results. Therefore, the relationship between them on the efficiency of the
treatment is studied. UV-Vis photometry studies are conducted to get the efficiency of
4

dye removal. A few tests such as UV-Vis wavelength scan and FT-IR analysis are also
done to identify the dye characteristics to fulfill the first objective of the research.

1.5

Organization of Thesis
A short introduction of textile industries wastewater and dye removal method

which is used in this study are included in Chapter 1. The problem statement, objectives
and scope of study are included in this chapter to explain the research direction.
Chapter 2 tells about the relation between dyes and the environment and also the
introductory explanation of the textile dyes. Also, the various dye treatment methods
including biological, chemical and physical methods with their application on removing
or reducing COD to the permissible level are justified in this chapter as well based on
some references published by the previous researchers.
Chapter 3 is about the materials, instruments and methods used in the
experiments. The experimental procedures and analytical methods are explained in this
chapter starting from the sample preparation to the final sample testing.
Then, Chapter 4 is the details about the results obtained from several
experiments in this research. The relevant data are presented as graphs and tables with
comprehensible explanations.
In Chapter 5, the conclusions are explained based on the results in Chapter 4
together with the objectives achievements and the recommendations for further
researches.

CHAPTER 2

LITERATURE REVIEW

2.1

Textile Industries Effluent

A developing global population causes fast spreading of industries which leads

to pollutions all over the world (Xin et al., 2012). More than 10000 types of dyes with
amount exceeding 700000 tons are produced by industries annually. Unfortunately more
than five percents are released into water bodies (Gong et al., 2005). A lot of dyes have
been released as wastewater effluents (Forgacs et al., 2004) that caused critical pollution
because the dyes do not degrade easily (Rai et al., 2005).
Dyes are colored substances that when they are in contacts with fibers,
everlasting colors will be given that is resistant to detergents, light and water. There are
two important components for a dye compound (Rai et al., 2005):
i)

Chromophores: Groups which are functioning to produce colors because they

are capable of absorbing light in the near ultraviolet region. Some crucial
chromophores are nitroso (N=O), nitro (-NO2), nitrogen (-N=N-), thioketones
(C=S), carbonyl (C=O), imine (-C=N) and (CH-CH)n.

ii)

Auxochromes: Dye molecules are attached to the fiber when stable chemical
bonds exist. These chemical bonds are comprised of acidic or basic groups that
occur naturally. Those auxochromes are hydroxide (-OH), carboxyl (-COOH),
sulphonic (-SO3H) [all basic] and primary amide (-NH2), tertiary amide (-NR2)
and secondary amide (-NHR) [all acidic].

2.2

Health Effect of Dye Effluent

Other than affecting human aesthetic view, the discharge of untreated textile dye

effluent will also cause a lot of health problems because of the mutagenic and
carcinogenic characteristics of the dye components (Arslan et al., 2000). In 1999,
Platzek et al. have shown that human skin bacteria is a factor of formation of a
carcinogenic amine from Direct Blue 14 azo dye. They have conducted a study on how
the bacteria living beneath or on human skin were able to metabolize the azo dyes by
measuring the reduction of the amines contained. The type of dye used was Direct Blue
(DB14). They have used a standardized test subject to determine the skin bacteria
reductive capacity using collections of bacterial strains and the freshly isolated bacteria
from healthy human skin.
From their experiment, Platzek et al. have concluded that in the liver of
mammals, azo compounds are biochemically used by cytosolic and microsomal
enzymes such as reductive cleavage to the amines as proven by their research. In their
experiment using skin bacteria, they have shown the cleavage of Direct Blue 14 azo dye
to the corresponding aromatic amine o-tolidine reduction product. The cleavage
formation means that the azo dye also has the same carcinogenic and mutagenic action
towards human cells.

2.3

Effect of Dye Effluent Towards Environment

When the textile coloring process is carried out by the industry, a considerably

large percentage of the dye does not bind to the fibre and it is gone to the wastewater
stream. In other word, dye effluent from textile industries brings a huge volume of dyes
and other chemical additives that become the main factor of water pollution (Ramesh et
al., 2007). Untreated dyes will affect the chemical and biological properties in aquatic
system by reducing sunlight penetration and causing distruption to the photosynthetic
activities (Reddy, 2012) of the plants or microorganisms containing chlorophylls.
7

According to Alves and Pereira (2012), color is typically the first thing to be
noted by human eyes in wastewater because a very small quantity of artificial dyes in
water of less than one part per million is easily can be visioned. This will affect the
aesthetical value, water transparency and gas solubility of the contaminated water
bodies. The dye particles reflect the sunlight from entering the water. This causes light
penetration reduction, leading to inhibition of aquatic organisms growth and getting in
the way of photosynthesis.

2.4

Law and Legislation on Textile Industrial Effluent Discharge

The release of industrial wastewater into the water bodies has been a major

concern of the current Department Of Environment (DOE) Malaysia. One of the

pollutant of industrial effluent is dye which comes mainly from textile industries or any
kind of industries using dyes as colorants. Due to the aesthetic, health and
environmental impacts of the dye pollution, DOE has establised a set of regulations
regarding the discharge of industrial effluents into the water bodies especially the inland
waters.
As stated in Section 25 of Environmental Quality Act 1973, there should be no
person discharging environmentally damaging pollutants, wastes or substances into any
inland waters. In this context, inland water is the water contained in water bodies other
than the sea such as the rivers, drains, lakes, stream, etc. Under the Subsection 2(a),
someone is to be believed to discharge the aforementioned pollutants into inland water
if s/he puts any waste into any water bodies or in a place where the waste might get in
contact with the water. In this case, the waste is the textile dye effluent.
According to Environmental Quality (Industrial Effluent) Regulations 2009,
industrial effluent is any waste in the form of wastewater or liquid produced from
manufacturing process. In this research, the waste is in the form of textile dye effluent
containing azo dyes as its constituent which is discharged from textile industries.
Chemical oxygen demand (COD) is an important parameter in consideration of this
8

regulation. Regulation 11 and 12 are about the tolerable situations for the discharge of
industrial effluent including dye for COD and any other parameters.
Regulation 11 prohibits the discharge of industrial effluent including textile dyes
containing parameters other than COD of which their concentrations exceed the
permissible limits in the Fifth Schedule (refer to Table 2.1) for standard A and standard
B. In this case, standard A means that the discharge is done into any inland water bodies
within the water catchment areas specified in Sixth Schedule whereas standard B is into
any other downstream inland waters not listed in Sixth Schedule. Meanwhile,
Regulation 12 is about the acceptable circumstances for discharge of textile dye effluent
for COD parameter which is referred in Seventh Schedule (refer to Table 2.1).
Table 2.1: Simplified Fifth and Seventh Schedule Tolerable situations
for industrial effluent discharge of standards A & B
Parameters
(i) Temperature
(ii) pH value
(iii) Biochemical oxygen demand, BOD5 at 20C
(iv) Color
(iv) Chemical oxygen demand, COD

2.5

Unit
C
mg/L
mg/L
mg/L

Standard
A
B
40
40
6.0-9.0 5.5-9.0
20
50
100
200
80
250

Azo Dyes
According to Babu et al. (2007), azo dyes form the biggest and most essential

class of commercial dyes which are used in textile industry. Azo dyes are diminished
from other types of dye by the existence of one or more azo groups (-N=N-) (Carliel et
al., 1996). Depending on the number of azo bonds presents, they can further be
classified into monoazo, diazo and triazo dyes (Yadav, 2008). The azo groups are bound
to the aromatic and heterocyclic compounds which are the factors of color intensity and
are less biodegradable because of different molecular structure and bonding (Wang et
al., 2011).

Azo dyes can further be categorized into acid, basic, direct, disperse and reactive
depending on the bonds classification (Lim, 2009). The details of each of category of
dyes are simplified in Table 2.2.
Table 2.2: The classification of dyes and chemical types (Hunger, 2003).
Class

Applied on

Application method

Acid

Wool, paper, nylon, Neutral to acidic

leather and silk.
dyebaths.

Basic

Polyyacrylonitrile,
polyester, inks,
modified nylon and
paper.
Rayon, cotton,
paper, nylon and
leather.

Direct

Disperse

Polyamide, acrylic,
plastics, polyester
and acetate.

Reactive

Silk, cotton, wool

and nylon

Acidic dyebaths.

Neutral
or almost alkaline
baths containing
additional electrolyte.
Fine aqueous dispersions
by high temperature; dye
is padded on material to
be colored and then baked
on thermofix.
Reactive sites on dye
chemical compound reacts
with functional groups on
material (fiber) to bind
dye under factor of heat
and alkalinity.

Types of chemical
presents
Azo, xanthene,
triphenylmethane,
azine, nitroso, nitro
and anthraquinone.
Diazahemicynanine
, diphenylmethane,
azo, oxazine and
acridine.
Anthraquinone, azo,
styryl,
benzodifuranone
and nitro.
Anthraquinone, azo,
styryl,
benzodifuranone
and nitro.
Azo, anthraquinone,
formazan,
phthalocyanine,
basic and oxazine.

Among all of these dyes, reactive dyes are the most typically-used group in
textile industry. Unfortunately, it is highly problematic to remove reactive dyes from the
textile effluent. This is caused by their high water solubility. Other than that, the
degradation of reactive dyes are also due to the strong bonding between the reactive
groups and surface groups of the textile fibers or materials to be colored (Lim, 2009).
This is also supported by Tabak et al. (2009) in their research who have stated that the
hydrolysis of reactive groups of such dyes when they are in water phase has caused
lower fixation degree which has become the factor of difficult degradation.

10

2.6

Treatment Methods of Textile Effluent

In general, the methods of dye removal from wastewater can be categorized into

physical, biological and chemical treatments. All methods have their own advantages
and disadvantages either technically or economically. Traditional methods of
wastewater treatment cannot be used for dye removal in textile effluent because of the
very obstinate chemical structure. Table 2.3 shows the biological, physical and chemical
treatments of dye removal from wastewater together with their benefits and weaknesses.

2.6.1

Physical Methods
The main concept in physical methods of dye removal is to transform the dye

pollutant from liquid into solid phase. However, there are several disadvantages of
physical treatments. First of all, the unwanted sludge generation makes it a non-fully
effective method. Secondly, the generated sludge will give economical side effect due to
the cost for its disposal. Other than that, the dyes are not actually destroyed; they just
change their molecules to another phase. Lastly, this method will be truly effective if
and only if the dye effluent to be treated is in small amount (Vijayaraghavan et al.,
2012).

2.6.1.1 Membrane Filtration

Membrane filtration is a physical treatment method which efficaciously separate
the dye particles from the textile wastewater. Membrane is a permeable medium which
acts as barrier to control certain species of chemicals from moving. Various dyes are
proven to be removed effectively except for the disperse dyes which cause production
of concentrated dye sludge on the membrane.

11

Table 2.3: Benefits and weaknesses of current dye removal methods

(Robinson et al., 2001).
Methods
Benefits
Weaknesses
Physical methods
Membrane
- Can remove all types of dyes
- Sludge produced is
filtration
concentrated
Absorption by - Can remove a wide variety of - Activated carbon is too costly
activated carbon
dyes
Chemical methods
Ozonation
- O3 can be used in gaseous - Short half-life for about 20
state
min only.
- Volume of wastewater and
sludge does not increase
Oxidative
- Simple application
- H2O2 agent needs to be
processes
activated by some methods
Biological methods
Aerobic
- Biogas generation which can - Costly
be used as energy source
- Decolorisation is less efficient
- Effective removal of
biochemical oxygen demand
from low to medium range
Application of - Natural source for flocculant - Not practicable due to
bioflocculant
material, making it cost- complex method.
effective.

Another main disadvantage of membrane filtration is the high maintenance cost

because of the occasional membrane replacement. The membrane needs to be replaced
when it is clogged and saggy. A research done by Ahmad et al. (2002) has shown that
the removal of dye by membrane filtration is affected by the dye concentration. The
higher the dye concentration, the higher the percentage of removal which is measured
by the amount of dye rejected by the membrane when the effluent is flowing through.

2.6.1.2 Absorption by Activated Carbon

12

Absorption is the gathering of certain material at the interface between two

different physical phases. There are two terms associated with this method which are
absorbate and absorbent. Absorbate is the substance that gathers at the interface whereas
absorbent is the solid at which the absorption happens on its surface (Rowski, 2001).
For this method, the absorbate is the dye molecules to be removed whereas the
absorbent is the activated carbon to be used.
In a study conducted by Lacerda et al. (2015), they have used the lignocellulosic
waste to produce activated carbon for the removal of rhodamine B (RhB) dye from
aqueous solution using different operating parameters such as dosage of absorbent, pH,
starting concentration of dye and temperature of solution. From their experiments, they
found out that the removal percentage of dye increases when more activated carbon is
used. Other than that, they also discovered that the absorption occurs at a high rate until
it finally stops after two hours when reaching equilibrium state.
Unfortunately, the high maintenance cost becomes the major limitation of this
treatment method which is caused by the requirement to reactivate carbon after certain
periods of time. Other than that are the unwanted dye sludge formation and the spent
carbon regeneration (Lim, 2009). For the latter, it is good if the activated carbon could
be regenerated after treatment which can save the cost but it is becoming a problem only
when the regeneration is not needed.

2.6.2

Chemical Methods
In the removal of dyes from textile industrial wastewater, chemical methods are

extensively utilized. Despite of its usefulness in removal of dyes, the problem of dye
sludge disposal is the major issue. Besides, different types of chemicals used can induce
secondary pollutions problem (Pereira and Alves, 2012). As an instance, Azbar et al.
(2004) has stated that conventional treatment method such as the coagulation has the
potential to produce undesirable dye sludge and fails to treat solutions with very soluble
dyes.

13

Thus researchers have came up with two prominent chemical methods of dye
treatment which are ozonation and oxidative processes as substitutions to the old
treatment methods to fulfill the needs to decolorize the textile industrial wastewater
before being released into the water bodies by eliminating dye pollutants. (Muhammad
et al., 2008).

2.6.2.1 Ozonation
Ozone,O3 is a great oxidizing agent to the point of self-decomposition into the
hydroxyl free radicals in aqueous phase. It is efficient in breaking down the bonds of
dye which symbolize the color intensity that becomes the factor of stubborn removal.
Other than treatment of textile effluent, ozone can also be used for taste and odour
removal, microbial removal and promoting the ability of organic compounds to degrade
biologically (Yang et al., 2012).
Based on the study conducted by Zhang et al. (2013), they have used the
ozonation method for reduction of Reactive Red 2 (RR2) azo dye. In their study, they
have utilized ferrous as catalyst in the ozonation process in a semi-batch reactor. They
learned that Fe(II) could promote the degradation effectiveness of RR2 dye. Next, they
have discovered that the more alkaline the dye solutions, the higher the dye removal
efficiency. Subsequently, it is shown that the dye degradation effectiveness increased
with the temperature rise.

2.6.2.2 Oxidative Processes

Oxidative process means any set of steps of dye removal which utilize the
oxidation method. Yang et al. (1998) has stated that chemical oxidation is used to be the
most potential method for treatment of textile industry effluent using reactive azo dyes
as its colorant. Advanced oxidation process (AOP) is one of the oxidative processes in
textile effluent. Latest advancement in the removal of dyes from wastewater has
14

demanded that the AOP needs to be improved which generation of greatly reactive
groups such as the hydroxyl radicals (Malik et al., 2015).
A set of experiments by Nisar et al. (2011) has been done to compare the variety
of oxidative treatments for Reactive Black 5 (RB5) dye removal. They have used the
UV-Vis spectrophotometry to determine the initial and final absorbances of RB5 so that
the removal efficiency could be acquired. By adjusting the initial dye concentration as
the first parameter in their study, they found out that the removal efficiency increased
when the dye samples used were more concentrated.

2.6.3

Biological Methods
Biological treatment methods of dye removal are the application of natural-

occuring processes that involve microorganisms such as viruses, bacteria, yeasts, fungi,
etc to transform organic substances into liquidous or gaseous by-products. Despite the
fact that they are able to remove biodegradable organic compound, most of the synthetic
organic groups are persistant because of their complex bonding and structures (Yadav,
2008). Moreover, certain dyes cannot be removed by biological means (Hayelom,
2014).
On the other hand, biological methods are cheap and non-harmful to the
environment because there are no production of unwanted by-products compared to
chemical and physical methods. There are two types of biological dye removal methods
which are aerobic treatment and bioflocculant application.

2.6.3.1 Aerobic Treatment

15

Aerobic process is one which occurs with the presence of oxygen, O 2. For
thetreatment of textile dye effluent, it is a process which utilizes microorganisms such
as bacteria to break down the azo bonds of the dye molecules. Nevertheless, the ability
of aerobic microbes to break down the bonds are less than that of anaerobic ones. Once
again, Yadav (2008) has proved that an aerobic system is able to merely remove about
ten to thirty percentages of reactive azo dyes from wastewater which is can be
concluded as not too effective.
However, a recent research done by Tan et al. (2016) has proved the efficiency
of aerobic treatment in remediation of textile industrial effluent. In their investigation,
they have used recently isolated Scheffersomyces spartinae which is a salt-tolerant yeast
to degrade, decolorize and detoxificate azo dyes. Six types of azo dyes have been used.
The results show an average of 97.05% color removal with an average of 16 hours 10
minutes of reactions that took place.

2.6.3.2 Bioflocculant Application

Flocculation of dye is another effective method of dye removal from textile
wastewater. When flocculation happens, the dye particles are attracted to each other to
form lumps. These lumps which are also known as flocs are going to settle down to the
bottom of the equipment in which the dye-polluted solution is contained in. Then the
clear supernatant is taken out as the treated wastewater to be discharged safely.
A research done by Buthelezi et al. (2012) has demonstrated that bioflocculants
produced from native bacterial segregates are able to remove dye from wastewater
effluent. In their research, they have used six different bacteria isolates to decolorize
three contrasting colors of dyes produced by mixing several different types of dyes.
They found out that the removal percentage of dye is strongly affected by pH of
different dye mixtures.

16

CHAPTER 3

RESEARCH METHODOLOGY

3.1

Introduction
This chapter is about the materials and methods used in the experiments that

have been done. The dye, chemicals and instruments used are discussed here together
with the experimental and analytical methods. The flow of methodology is shown in
Figure 3.1.

17

Figure 3.1: General flow of methodology

3.2

Materials used

3.2.1

Reactive Black 5 (RB5)

The dye used was Reactive Black 5 (RB5) obtained from Sigma-Aldrich
which was used without further purification. The properties of RB5 is shown in Table
3.1.

Table 3.1: Properties of RB5 dye

Color index name
Color
Molecular Formulae
Molecular Weight (g/mol)
Class
Maximum wavelength Absorption, max (nm )
Solubility in water

Reactive Black 5 (RB5)

Black
C26H21N5Na4O19S6
991.82 g/mol
Diazo (-N=N-)
597
550 mg/mL

RB5 is a common dye used in textile coloring and finishing industries. The
compositions of RB5 are azo bonds (-N=N-), benzene rings, sulphonic acid and
hydroxyl groups. The chemical structure of RB5 is shown in Figure 3.2.

Figure 3.2: Reactive Black 5 chemical structure (Yuen et al., 2005)

The composition of RB5 has been tested by Fourier Transform-Infrared
analysis and the result is shown in Chapter 4.

3.2.2

Chemicals and Reagents Used

18

Table 3.2 shows the list of chemicals and reagents used in the experiments
other than the dye to be tested.
Table 3.2: Chemicals and reagents used in experiments
Chemicals
Aluminium sulphate 18-

Molecular formula
Al2(SO)318HO

Manufacturer
HmbG Chemicals

hydrate/alum
Magnesium chloride 6-hydrate
Calcium chloride 2-hydrate
pH buffer solutions
Sodium hydroxide
Hydrochloric acid
Potassium dichromate
Mercury(II) sulfate
Distilled water

MgCl2.6HO
CaCl2.2HO
NaOH
HCl
K2Cr2O7
HgSO4
-

HmbG Chemicals
HmbG Chemicals
HANNA Instruments
HmbG Chemicals
Fischer Scientific
Fischer Scientific
HmbG Chemicals
UltraPure water purifier

3.3

Experimental Procedure
In this part, every step in the project is explained one by one starting from the

materials preparation to the data measurement.

3.3.1

Preparation of Materials and Equipments

Four stock solutions have been prepared with concentrations as shown in Table

3.3.
First of all, one gram of RB5 powder is measured using an electronic
measurement balance. Then, the measured RB5 powder is transferred into 1L flatbottomed flask using a steel spatula. Next, 1L of distilled water is added up to the mark.
The mixture is shaken well to make a stock solution of 1000 ppm Reactive Black 5. The
prepared stock solution of RB5 is transferred into a 1L translucent bottle and is kept in a
place without light radiation or exposure.
19

Table 3.3: Stock solutions concentrations

Stock solution
Reactive Black 5
Aluminium sulphate (alum)
Magnesium chloride
Calcium chloride
Hydrochloric acid
Sodium hydroxide

Function
Sample to be tested
Coagulant
Coagulant
Coagulant
pH adjustment
pH adjustment

Initial concentration
1000 mg/L
20000 mg/L
20000 mg/L
20000 mg/L
0.1 M
0.1 M and 1 M

The same steps are also done for the preparation of coagulants and sodium
hydroxide alkaline solution. The difference is the mass of each material to be diluted in
the distilled water. For the coagulants, 20 g of each material is diluted whereas for the
preparation of 1M of NaOH, 40 g of it is diluted instead. The calculation for the amount
of sodium hydroxide powder to be added is shown below.
Molecular weight of NaOH
Required NaOH concentration
1M
1 mol/L40 g/mol

=
=
=
=

40 g/mol
1M
1 mol/L
40 g/L

Volume of NaOH to be diluted = 40 g in 1L distilled water

For the preparation of 0.1M NaOH solution, 40 g is divided by 10. It means

that only 4 gram is dissolved. The purpose of making NaOH solution of two different
concentrations is so that the increment of dye solutions pH can be little or big. The more
concentrated the NaOH solution, the higher the pH change that it makes to the dye
solutions.
Hydrochloric acid, HCl solution is prepared to lower the pH of dye solutions.
8.33 mL of 6M HCl stock solution obtained from Fischer Scientific is diluted with
491.67 mL distilled water to make a 500 mL 0.1M HCl. The calculation of this amount
is shown in Equation 3.1. The dilution process is done in a fume hood while wearing a
thick glove because the concentrated hydrochloric acid is volatile which is harmful to
the respiratory system if it is exposed to the air.

20

C1V1 = C2V2
12M x mL = 0.1M 500 mL
x = 0.1 500
6

(3.1)

= 8.33 mL
= Amount of HCl to be diluted
500-8.33 = 491.67 mL
= Amount of distilled water to dilute the HCl
stock (Simply distilled water is added into
the 500 mL volumetric flask to the ring
graduation marking without measuring
491.67 mL distilled water first).
Before using the glasswares and bottles, all of them are washed with running
water followed by rinsing with distilled water. This is to remove all the impurities such
as dusts and chemical residues that might affect the purity and concentration of the
prepared stock solutions. Secondly, the equilibrium of the measuring balance is adjusted
by rotating the screws below the balance until the bubble is centered in the circular
indicator. Next, a safety mask is worn to avoid the inhalation of RB5 powder because of
its carcinogenic characteristic (Arslan et al., 2000) that can cause cancer if inhaled. A
pair of gloves is also worn to avoid the skin from being in contact with the dye because
of the persistent color that might be difficult to be washed off when it is too
concentrated.
3.3.2

Preparation of Diluted RB5 Solutions

The next stage is the preparation of diluted RB5 solutions. Using the stock

RB5 solution prepared, an amount of it is dissolved in a certain amount of distilled

water according to the desired final concentration and volume of diluted dye. For
example,

20 ppm of RB5 solution is to be prepared. Based on Equation 3.2, the

amount of RB5 stock needed to produce a 20 ppm RB5 in 500 mL solution is 10 mL.
M1V1 = M2V2
(3.2)
1000 ppm x mL = 20 ppm 500 mL
x = 10 mL
= Amount of RB5 stock to be diluted
21

For the preparation of dye solutions, about five or six beakers are needed
depending on the requirement of the experiment. As an example, five beakers are
required to make five 500 mL RB5 solutions of 20 ppm each. First of all, 10 mL RB5
stock solution is pipetted out from its bottle using the 10 mL micropipette as shown in
Figure 3.3. Then, the stock is transferred into a 500mL volumetric flask. Thirdly,
distilled water is added to the circular marking on the neck of the flask. Next, the
solution is shaken vigorously so that the dye is well diluted. The well-diluted dye is then
transferred into the beaker. The steps are repeated for the preparation of other solutions
to be put in separated beakers. The beakers filled with dye solutions are sealed with
aluminium foil at the top and are kept in a place without light penetration if they are
going to be used for the next day.
Once again, all the equipments are washed and rinsed with distilled water
before use. For the 1-10 mL micropipette, it is adjusted to 10 mL or any reading that is
required for preparation of dye solution. After adjustment of volume to be taken, the
knob of the micropipette is pressed several times to let out all the air to prevent entrance
of bubbles in the dye stock solution. After that, the knob is pressed to the first stop and
the tip is immersed into the stock solution. Then the knob is released to let the liquid in.
Subsequently, the tip is pressed all the way down to the second stop so that the liquid
gets into the flask to be added with distilled water.

Figure 3.3: 1-10 mL micropipette used for measuring volumes bigger than 1 mL

22

3.4

Characterization Tests of Reactive Black 5

In this part, two characteristics test for Reactive Black 5 dyes are explained

which are maximum wavelength absorbance and functional groups that exist in the RB5
molecules to fulfill the first objective of the research.

3.4.1

Wavelength Scan
The main purpose of wavelength scan is to know which wavelength is

absorbed the most by the color of reactive black 5 dye. The instrument used is UV-Vis
U-2810 Spectrophotometer manufactured by Hitachi company as shown in Figure 3.4.
First of all, 20 ppm of RB5 dye solution is prepared as shown in step 3.3.2. Preparation
of small amount of 50 mL is enough because this analysis does not use much volume of
sample. Secondly, two blank samples which are the distilled water are filled up into two
separate cuvettes for the baselining process. The cuvettes are inserted into the cuvette
holders of the UV-Vis instrument followed by closing the sliding lid of the sample
scanning compartment. The scanning range is set up from 200-800 nm. The scanning is
started with the scanning speed of 100 nm min-1.

Figure 3.4: UV-Vis U-2810 spectrophotometer used for wavelength scan and
photometry
When the baseline correction is done, the cuvette at the front holder is taken
out. The blank inside is wasted out into an empty beaker and the empty cuvette is filled
23

up with the prepared dye solution. The dye sample is also put into the front holder. The
next step is the scanning of the RB5 wavelength. The graph is being displayed on the
monitor as the scanning is going on. After a period of six minutes, the scanning stopped
and the sample cuvette is taken out of the UV-Vis spectrophotometer. The graph formed
is analyzed to determine the maximum wavelength absorbance and it is discussed
comprehensively in Chapter 4.

3.4.2

Fourier Transform Infrared Analysis

Fourier Transform Infrared (FT-IR) analysis is done as shown in Figure 3.5.

First of all, the baseline correction is done by using only a little bit of distilled water as a
blank sample. After the baseline correction is finished, the dye sample is used and the
scanning is let to happen for varying wavelength starting from the infrared to the visible
color regions. The result is plotted on the monitor as a graph with transmittance (%T)
versus wavelength axes. Further explanations about the result is explained in Chapter 4.

Figure 3.5: FTIR spectrophotometer used for recognizing functional groups

3.4.3

Chemical Oxygen Demand Determination

24

Chemical Oxygen Demand (COD) test is done for 200 mg/L RB5 solution.
The purpose of this experiment is to determine the amount of oxygen that is consumed
by the chemical process that takes place when the dye particles react with the
surrounding environment. First of all, 200 mg/L RB5 solution is prepared by diluting
100 mL of RB5 stock with 400 mL distilled water to make a 500 mL solution.
Next, five COD vials are prepared for preparation of dye solution for COD test
together with two vials for blank samples. 2 mL dye sample is mixed together with 3
mL potassium dichromate and subsequently is added with a little bit of mercury(II)
sulfate powder. The opening of the vial is closed with the cap and the vial is shaken
vigorously to mix the components inside well. Five vials of samples for COD are
prepared. All of them are heated for two hours at 150C using the COD reactor HI
839800 as shown in Figure 3.6.

Figure 3.6: Heating COD samples using the reactor

The vials are let to cool down in a day. The next step is the measurement of
COD using DO meter DR2800. For the calibration of the equipment, three blank
samples are used. Firstly, a blank sample is put inside the DO scanner followed by
pressing the Zero button. Then, the COD of the other two blank samples are also
25

measured. The best blank is known when there are no negative values when it is zeroed
with other blanks as samples. After zeroing is done, the dye sample vials are inserted
one after the another for COD measurements.

3.4.4

pH Measurement
As for the purpose of fulfilling the requirement of the first objective, pH of

RB5 dye is determined. The pH of 50 ppm of RB5 has been measured using the pH
meter by HANNA Instrument. This method is explained more in part 3.3.4.

3.5

pH Adjustment of Diluted RB5

pH meter by HANNA Instruments is the instrument used to measure the

change of pH in the dye solutions. First of all, a pair of identical magnets are prepared
to stir the dye solutions. Secondly, the cap is unscrewed from the tip of the pH meter.
The tip was then rinsed with distilled water to wash off the ORP storage solution so that
it will not be mixed in the dye solutions. Two pH buffer solutions are prepared for the
pH meter calibration. For the neutral calibration, the start calibration button is pressed
followed by immersing the tip part of the pH probe in the pH 7.01 solution. After the
reading is obtained, the confirmed button is pressed. The same steps are also done for
the acidic calibration using the pH 4.01 buffer solution. A good calibration is shown
when good condition and fast response are displayed on the screen.
Next, a magnet is put into the dye solution. If the pair of magnets obtained is
of different sizes, the smaller one is put inside. The beaker is put on top of the hotstirrer
plate. The stirring knob is turned clockwise to the sixth or seventh scale, depending on
the volume of dye solution in which the pH adjustment is to be done. The more content
of dye in the beaker, the faster the stirring should be and vice versa. Using a dropper, a
small drop of 0.1 M NaOH is put into the dye solution to make a small increase of pH
whereas 1 M NaOH is used to increase the dye solution from its initial pH up to pH 11.
26

The same steps are done for HCl to lower the pH of the RB5 diluted solutions. The
whole process of pH adjustment is shown in Appendix A.
The small drop does not mean that the whole acid or alkali sucked into the
dropper is to be ejected into the dye solution. A very small pH change is influenced by a
very little amount of acid or alkali. To ensure that only a very little amount of pH
regulator is added, 100-1000 L micropipette is used because of the ability to measure
down till 0.1 mL. However, there are two micropipette tips used which one is for alkali
and the other one is for acid. This is to avoid the mixing of those two pH regulators
together that might neutralize them thus giving error for the pH change of the dye
solution. Before putting the magnet into the dye solution, it is checked whether there are
dusts, contaminants or even iron powders that might get attracted to it because these
foreign things affect the coagulation process.

3.6

Coagulant Dosing
After pH adjustment is done, coagulant is dosed into the dye solutions to

prepare the solution for removal of dye during the jar test. There are three types of
coagulants used in the experiments, i.e. aluminium sulfate (alum), magnesium chloride
(MgCl2) and calcium chloride (CaCl2). Initially, the amount of dosages are kept the
same for experiments that aim to find the optimum pH of coagulations. After the
optimum pH is known, the amount of dosages are variated from as small as 200 ppm
alum to the biggest dosage which is 4000 ppm of MgCl2 and CaCl2 coagulants.
For example, a 500 mL dye solution at pH 12 is dosed with 2000 ppm MgCl 2.
Therefore, 50 mL of stock MgCl2 is injected into the dye solution. The process is started
with taking that amount of stock MgCl2 from the storage bottle using 1-10 mL
micropipette. Then it is transferred into the dye solution. For this amount, 10 mL of
dosage is repeated five times until 50 mL of coagulant MgCl 2 is transferred into the dye
solution. The calculation for the volume of coagulant MgCl 2 to be used is shown in
below which is based on Equation 3.2.

27

20000 ppm x mL = 2000 ppm 500 mL

x = 50
= 50 mL MgCl2 is added into the dye
solution for jar test.

3.7

Jar Test
The purpose of this stage is to coagulate the dye solutions which have been

dosed with the coagulants. Jar test JLT6 has been used in this experiment. Conceptually,
fast agitation is done for a short period of time for the sake of coagulation followed by
slow agitation at much longer time for flocculation. For the fast agitation, the dye
solutions are mixed for 3 min at 120 rpm (Yeap et al., 2014). It is followed by slow
agitation for 40 min at 60 rpm. The formed flocs (if available) are let to settle down by
gravity for a day. After using the jar test equipment, the paddles are rinsed with tap
water filled in a beaker to remove any residual dye solutions. It is followed by wiping
the paddles with a tissue so that rust does not form on them.

3.8

UV-Vis Photometry
The purpose of this activity is to measure the concentration of dye that has

been reduced to know the percentage of dye removal. First of all, a set of standard
samples is made by varying the RB5 solution from 10-50 ppm. This is so that a standard
curve could be generated for the testing of other samples. This measurement is done by
inserting the sample of 10 ppm first followed by 20 ppm until 50 ppm into the UV-Vis
spectrophotometer. The graph plotted in Figure 3.7 is standard graph obtained with
linearity of R2=0.997 which is acceptable and usable.

28

Figure 3.7: Standard calibration graph for RB5 at maximum wavelength absorption.
Six essential things have been prepared before doing the UV-Vis
spectrophotometry which are the samples, cuvettes, distilled water, empty beaker,
dropper and tissue that are shown in Figure 3.8. First of all, the photometry method is
selected together with the value of the maximum wavelength absorbed as what has been
done in step 3.3.3.1. Secondly, two cuvettes consisting of distilled water blanks are
inserted into the UV-Vis holders. The methodology flow is continued with the zeroing
of the instrument. After the zeroing step, the cuvette from the sample side is taken out to
be replaced with that of the treated dye sample. The absorbance of wavelength is read
by the spectrophotometer and the result is displayed on the PC screen. The data are all
recorded and analyzed in Chapter 4.

Figure 3.8: Preparation for UV-Vis test

29

30

CHAPTER 4

RESULT AND DISCUSSIONS

4.1

Introduction

In this chapter, all the results from the experiments that have been done are
shown starting from the RB5 dye sample characterization analyses to the measurement
of dye removal efficiency using different types of coagulants with variated conditions.

4.2.

Characterization Tests of Reactive Black 5

In this subchapter, the results from the four characterization tests are shown and

discussed which involve the measurement of maximum wavelength absorbed by RB5

sample, identification of functional groups, COD determination and pH measurement.
The discussion is in term of the data obtained in the experiments and comparison with
the results gained by previous researches if available.

4.2.1. Wavelength Scanning of Reactive Black 5

In order to identify which visible color wavelength is absorbed the most by the
chromophores groups in the Reactive Black 5 dye, a wavelength scanning has been
31

done in the range of ultraviolet wavelength (200nm) to the visible color wavelength
(800nm). Figure 4.1 shows the wavelength scan that has been plotted for the scanning
of 20 ppm RB5.

Figure 4.1: Wavelength scan of 20 ppm Reactive Black 5

From the graph, it can be seen that there are several noticeable peaks which
show how much each of them are absorbed by the dye molecules. The obvious peaks
occur at the following wavelengths: 356 nm, 388 nm and 597 nm which are seen in the
visible region only. It is seen that visible light of 597 nm wavelength is the one that is
absorbed the most as it shows 0.433 absorbance value which is corresponding to 20
mg/L of RB5 solution tested. This result is in compliance with the theoretical value as
shown in Table 3.1.

4.2.2

Functional Groups Identification by FT-IR Analysis

Infrared spectrophotometry is a test in which infrared rays are bombarded into

the materials to be tested at varying wavelengths starting from 4000 cm -1 to 650 cm-1.
Different functional groups only react to certain ranges of wavelength. The term react
here means that the groups are in excited state and will vibrate only when certain
wavelengths of infrared are passing through them. The stronger a certain groups vibrate,
the longer the percentage of transmittance shown on the graph. The strength of vibration
is also influnced by the percentage composition of the functional groups in the tested
material.
32

Identification of functional groups existing in RB5 has been done. The scanning
of the liquid solution of RB5 using infrared ray started from 4000.0 cm -1 down to 650.0
cm-1. The graph in Figure 4.2 shows the transmittance percentage which is the amount
of infrared ray that goes through the RB5 sample which is shown at the vertical axis
against the horizontal axis which shows the wavelength range of infrared ray.
These detected functional groups are further classified whether as chromophores
or auxochromes. Further information about these two categories has been explained in
Chapter 2.1. Table 4.1 shows the functional groups that exist in the sample of RB5
together with the bonds and the functional groups that are represented.

Figure 4.2: FT-IR spectrophotometry of RB5 dye solution

Table 4.1: Result of FT-IR analysis of Reactive Black 5 dye (Webspectra, 2000).
Wavelength at
which
maximum
atomic
vibration
occurs (cm-1)
3306.17
2124.92
1637.65
667.84

Available dye
bonds

Functional groups

Types of group

O-H
-N=NN-H
C-Br

Alcohol, phenol
Azo
1 amine
Alkyl halides

Auxochrome
Chromophore
Chromophore
N/A
33

The result shows the important functional groups that exist in the RB5 dye. The
types of groups available are auxochrome and chromophore of which their functions are
to hold the dye molecules to the molecules of fibres and absorbs the visible light,
respectively. Next, the presence of the C-Br bond is due to the usage of potassium
bromide, KBr powder to make the excitement of particles more obvious. Contrariwise,
there are no sulphonyl groups, RSO3- and RSO2R present in the infrared spectral
analysis. This might be happening due to presence of impurities during the
bombardment of infrared ray that blocks it from reaching the sulphonyl groups which
are supposed to be shown in the graph. It may also be caused by the error of choosing
smoothing effect when the graph is plotted.

4.2.3

Chemical Oxygen Demand Determination

The purpose of doing chemical oxygen demand (COD) analysis for RB5 dye is

to know how much oxygen will be used up during chemical reactions that happen when
the dye reacts with the solution or materials it makes contact with. For this experiment,
200 mg/L of RB5 without pH modification has been used for COD test. Five RB5
solutions of identical pH and concentration have been tested to determine the COD
contents as shown in Table 4.2.

Table 4.2: COD sampling for 200 mg/L Reactive Black 5 without pH modification
Sample
1
2
3
4
5

COD content (mg/L)

203.6
243.4
231.3
221.2
215.6

34

The result shows that the range of COD content is between 203-243 mg/L with
average of 223.02 mg/L per sample. This is almost in compliance with the finding of
Lee et al., (2011) who have stated that the range of COD for 200 mg/L Terasil Red R is
from 278-412 mg/L. The slight difference of reading might be caused by the impurities
of potassium dichromate as a COD reagent which has been exposed to surrounding air
before the COD sample preparation is done.

4.2.1.4

pH Determination of RB5
pH means the potential of H+ ions to react with the functional groups that exist

in chemicals. All dyes produced so far have different initial pH, depending on their ionic
properties. For Reactive Black 5 azo dye, the initial pH without any further purification
or pH adjustment is experimentally proven to be at pH 5.60. It can be said that RB5 is
moderately acidic (5.4<pH<6.0) as stated by USDA (1993). This property is further
supported by the known theory that the lower the pH of a molecule, the higher the
hydrogen ions concentration that are attached to it and vice versa. As what has been
shown in Figure 3.2, H+ ions do exist because they are a part of the phenol rings.
Therefore, phenol rings are the main factor of the dye molecule acidic nature.

4.3

Coagulation Studies of Different Types of Coagulants

Several experiments have been conducted to know the most effective type of

coagulant by variating the pH of dye solution and dosage of coagulants for the
coagulation and flocculation method. The chosen materials that are used as coagulants
in this study are alum, MgCl2 and CaCl2. The efficiency of each coagulant for different
operating conditions is calculated using Equation 4.1.
Color removal efficiency = C0 C1
100%
C0

(4.1)
,
35

where

C0

= Initial dye concentration (mg/L

C1

or abs)
= Final dye concentration (mg/L
or abs)

4.3.1

Determination of Optimum pH
The purpose of these experiments is to find the optimum pH at which the

coagulants yield the best dye removal percentages. The RB5 dye color removal from a
20 mg/L dye solution by various types of coagulant solutions has been studied at
different pH starting from as small as pH 2 to a big alkalinity value of pH 12. Figure 4.3
shows the graph of pH of dye solution versus the color removal efficiency of dye using
alum as the single inorganic coagulant when the dosage is kept at 200 mg/L.

Treatment of 20 ppm RB5 solution with 200 ppm alum at different pH

60.00%
50.00%
40.00%

Color reduction efficiency

30.00%
20.00%
10.00%
0.00%
1

9 10 11

pH of dye solution

Figure 4.3: Color removal of RB5 using 200 mg/L alum at different pH
From the graph, it can be seen that the optimum pH for removal of RB5 dye in
20 mg/L of its concentration is pH 4. It means that alum works the best if and only if
the working operation is extremely acidic. However, there are no visible formation of
dye flocs for this treatment. This is due to the nature of alum as a good coagulant but
not an effective flocculant. Here we can state that alum is able to gather the dye
particles together but fails to create a bigger, settleable flocs.
36

In Figure 4.4, it is shown that the optimum pH for magnesium chloride to

function well as an effective coagulant is pH 11. At pH 11, the removal efficiency is just
48.44% which is not as much as what have been predicted. Therefore, it is totally
recommended to increase the dosage of MgCl2 due to the increasing trendline of the
graph.

Treatment of 20 ppm RB5 solution using 600 ppm MgCl2 at different pH

60.00%
50.00%
40.00%

Color removal efficiency

30.00%
20.00%
10.00%
0.00%
pH 3

pH 4

pH 6

pH 8

pH 10 pH 11

pH of dye solution

Figure 4.4: Color removal of 20 mg/L RB5 dye using 600 ppm MgCl2 at different pH
The third single coagulant used in this study is the calcium chloride inorganic
salt, CaCl2. The usage of CaCl2 is considered rare and novel because there have been no
research up to this date which reported that CaCl 2 alone is used as a single coagulant in
dye removal from wastewater. However, CaCl2 is once hybridized with polyacrylamide
(PAM) in the research by Lee et al., (2010) who have produced the CaCl 2-PAM hybrid
polymer to flocculate kaolin in water. Therefore, this usage of CaCl 2 is for the sake of
seeing its feasibility in

removing dye color of wastewater whether it is slightly

applicable or not.
From the graph shown in Figure 4.5, it seems that the optimum pH which
shows the highest percentage of dye removal is at pH 5. The low percentage of removal
is caused by the low dosage of CaCl2 used. Therefore, the range of CaCl2 dosage is
increased for the next stage which is the determination of optimum dosage of CaCl2.
37

Color removal efficiency for RB5 treatment with 100 ppm CaCl2 at different pH
5.00
4.00

Color removal efficiency (%)

3.00
2.00
1.00
0.00

10 11 12

pH of dye solution

Figure 4.5: Color removal of 35 mg/L RB5 using 100 mg/L CaCl2 at different pH

Figure 4.6 shows the combined graphs for the determination of optimum pH
for the different types of coagulants. From the graph, Table 4.3 is made to show the
summarization of optimum pH of different types of coagulants together with the
removal efficiencies. Due to the low efficiencies of dye removal, the next batch of
experiment uses higher range of coagulant dosage.

Comparison of optimum pH with different types of coagulants

60
50
40

Dye removal efficiency (%)

30
20
10
0

10

12

pH of dye solution
Alum

MgCl2

CaCl2

Figure 4.6: Comparison of optimum pH with different types of coagulants

38

Table 4.3: Comparison of optimum pH with different types of coagulants (pH variant)
Dosage
Dye removal
Type of coagulant
Optimum pH
(mg/L)
efficiency
Alum
200
4
51.38 %
MgCl2
600
11
48.44 %
CaCl2
100
5
4.306 %

4.3.2

Determination of Optimum Dosage of Coagulant

This batch of experiments is aimed to find the optimum dosage of coagulants

after their optimum pH values of dye solutions are known.

Based on Figure 4.7, a range of 50-300 mg/L of alum has been tested for the
dye removal efficiency with the pH is at its optimum value which is pH 4. It can be seen
that the highest dosage of alum yields the highest percentage of dye removal which is
34.14%. Unfortunately, this is still below the targetted removal which is supposed to be
higher than 50%. Therefore, 6000 ppm of alum will be used for the next batch of
experiment in which the aim is to find the optimum initial dye concentration based on
the prediction of the trend in the graph.

Removal efficiency of RB5 using different alum dosages at pH4

Color removal efficiency

40.00%
35.00%
30.00%
25.00%
20.00%
15.00%
10.00%
5.00%
0.00%
0

50 100 150 200 250 300 350

Dosage of alum (ppm)

Figure 4.7: Determination of optimum dosage of alum at optimum pH of dye solution
39

The same experiment is also done with MgCl 2 to determine its optimum
coagulant dosage. From the graph in Figure 4.8, it can be stated that the optimum
dosage of MgCl2 is 2000 mg/L with 67.233% color removal. The increment of
efficiency beyond the dosage of 2000 mg/L is neglected because the percentages of dye
color removal of dosages bigger than that are all almost the same. Therefore, 2000 mg/L
dye is the optimum dosage of MgCl2. This optimum dosage is used in the experiment of
determination of optimum initial dye concentration.

Determination of optimum MgCl2 dosage with optimum pH 11 and initial RB5 conentration of 50 mg/L
80
70
60
50

Removal efficiency 40
30
20
10
0
500 1000 1500 2000 2500 3000 3500 4000 4500

Dosage of MgCl2 dosage

Figure 4.8: Determination of optimum dosage of MgCl2 at optimum pH of dye solution

Next, an experiment to find the optimum CaCl2 dosage has also been done
with Figure 4.9 as the graph that vizualizes the experimental result. From the graph, it is
shown that a high removal of RB5 dye can only be yielded when a dosage of 500 mg/L
of CaCl2 is used with pH 5 as the optimum dye concentration.

40

Removal of RB5 dye solution at pH 5 using different CaCl2 dosage

55.000
50.000
45.000

COlor removal efficiency (%)

40.000
35.000
30.000

1000

2000

3000

4000

5000

Dosages of CaCl2 (ppm)

Figure 4.9: Determination of optimum dosage of CaCl2 at optimum pH of dye solution

Table 4.4 shows the summary of optimum coagulant dosage of each type of
coagulant. It can be concluded that the highest dye removal percentage is shown by
500 mg/L calcium chloride at pH 5. Nonetheless, there are a lot of calcium deposites in
the interior side of the beakers after the treatment by using the calcium chloride. The
calcium deposits harden when they are exposed to the air and humidity for several
hours. This is because of the number of molecules attached to one mole of CaCl 2 which
is only two. This leads to the fast hardening of unused calcium when they dry and
conclusively shows the disadvantage of using CaCl2 as the coagulant.

Table 4.4: Comparison of optimum dosages of different types of coagulants for

optimum pH
Type of coagulant
Optimum pH
Optimum Dosage
Dye removal
(mg/L)
efficiency
Alum
4
300
34.142 %
MgCl2
11
2000
67.233 %
CaCl2
5
500
50.343 %

41

4.3.3

Determination of Optimum Initial RB5 Dye Concentration

Another important factor in determining the successfulness of dye removal

from water solution is the initial dye concentrations. The importance of this factor is to
test for the feasibility of a certain type of coagulant to treat dye of varying
concentrations given the optimum pH of dye solutions and dosage of coagulant. Figure
4.10 shows different initial dye concentrations with optimum pH and coagulants. In this
scope of experiment, only MgCl2 is used because CaCl2 causes build-up of coagulant
residue as explained in subheading 4.3.2 and alum does not show enough potential as a
good coagulant due to low removal percentages.
An experiment of determining the optimum initial dye concentration for usage
of MgCl2 has been done with optimum pH 11 and optimum 2000 mg/L dosage. The
result is vizualised as a graph in Figure 4.10. From the graph, it is shown that the
removal of RB5 dye is the highest when the initial dye concentration is only 20 mg/L.
This is because more dosage of MgCl2 will be needed when the dye is more
concentrated and vice versa.
A picture showing the removal of dye is shown in Figure 4.11. The picture
shows the condition of the treated water after three days of jar test. The dye particles are
clumped and settle down to the bottom of the beaker as time goes by. More details about
the flocculation and settling down of dye flocs are seen in Appendix B.

Removal of RB5 with different initial dye concentration at optimum conditions of pH 11 and 2000 mg/L dosage
100
80
60

Removal efficiency (%)

40
20
0
15 20 25 30 35 40 45 50 55 60 65

Initial dye concentrations (mg/L)

42

Figure 4.10: Removal of RB5 with different initial dye concentration at optimum
conditions of pH 11 and 2000 mg/L dosage

Figure 4.11: Settling down of dye particles after three days by using 2000 mg/L MgCl2
at optimum pH 11.

43

CHAPTER 5

CONCLUSION AND RECOMMENDATION

5.1

Objective Achievement
All objectives in this project have been achieved. The first objective which is

testing and verifying the properties of Reactive Black 5 dye has been accomplished.
This is because the four important characteristics of RB5 which are maximum
wavelength absorbed, functional groups compositions, chemical oxygen demand and
pH tests have been done and compared with the theoretical values from the previous
researches.
The second objective that has been completed is to know the optimum
conditions at which the coagulation and flocculation performance is the highest. The
optimum pH of dye solution and dosage of coagulants for each type of coagulant have
been found by experiments. Their results are shown in Chapter 4 with tables of
summarization. It is found out that the optimum pH for treatment with alum, MgCl 2 and
CaCl2 are 4, 11 and 5 respectively. Meanwhile, the optimum dosages of coagulant are
300 mg/L, 2000 mg/L and 500 mg/L for alum, MgCl2 and CaCl2 respectively.
Last but not least, the most efficient type of coagulant is inorganic salt
magnesium chloride which manages to show up to 97% dye color removal under pH 11
condition and 2000 mg/L dosage. This theory is supported with the finding by
Mohamed et al. (2014) who have stated that MgCl2 has given the same result twice for
removal of reactive dyes.

44

5.2

Overall Conclusion
From the experiments done, it can be concluded that magnesium chloride is

the most efficient coagulant for the treatment when the optimum conditions are met, i.e
the dosage used is only 2000 mg/L at pH 11. These optimum conditions are almost the
same as the findings by Mohamed et al. (2014) which have stated that the optimum pH
for treatment with MgCl2 is 10.0-12.0 with the optimum dosage of 3000 mg/L.
The main advantage of coagulation and flocculation method is its
applicability of operation and commercial value. It can be applied anywhere when
necessary i.e. when a factory wants to reduce the concentration of dye to the water
bodies.
On the other hand, this method has several disadvantages. The first one is the
chemical cost to be used in the coagulation and flocculation. For example, it is
expensive to buy chemical such as MgCl2 and CaCl2 especially when they need to be
imported from the other country. The second one is as stated before for the treatment
using calcium chloride. The unreacted calcium will build up on the surface of the beaker
where the treatment is done.
Last but not least, this method produces dye sludge which cause problem when
there is a need for disposal. The concentrated dye sludge as shown in Figure 5.1 is also
difficult to be washed if it does not be disposed of within less than a week as the dye
particles bind to the molecule of the glass or whatever container that holds them in.

5.3

Recommendations
There are several recommendations that should be followed to improve further

researches for this project in the future. The first one is the addition of several
parameters. In this research, only three parameters are used which are the pH of dye
solution, dosages of coagulants and initial dye concentration. The new parameters that
45

should be added are the mixing speed and settling time of jar tests. The third one is the
temperature in which the experiment should be conducted. This is because these
parameters will likely effect the results in term of color removal efficiencies.

Figure 5.1: Formation of dye sludge after a complete settle down.

The next recommendation is to remove a mixture of dyes rather than using

single dye which is only RB5 azo dye in this project. The mixture of dye is to simulate
the real textile industrial dye effluent which contains more than one types of dye. The
mixtures of dyes should contain reactive, disperse, basic, acid, direct and vat dyes of
different mixing ratio. For example, dye sample 1 contains equal concentration of each
type of dye whereas for dye sample 2, the concentrations differ for each type and so on.
One of the weakness of this project is the abundance of chemical used in the
jar tests. For example, up till 4 g/L of MgCl 2 is used for the jar test which can effect the
operating cost in real-life situation. To cater for this, less amount of coagulant should be
used while maintaining the high color removal by adding polymer such as
polyacrylamide (PAM) or polyaluminium chloride (PAC) because these materials have
the potential to bind up with the inorganic coagulant particles and together they bind the

46

dye molecules to form larger flocs. The larger the flocs formed, the faster the dye
particles will settle down and thus improving the color removal percentages.
The last one is the methods of assessing the color removal of dye. Rather than
only doing the UV-Vis photometry to measure the reduction of dye concentration, FTIR
analysis and final COD analysis should be conducted too. For the FTIR analysis, the
importance is to know which chemical functional groups will disappear from the
solution after complete settling down of dye particles when the jar test is done. For the
COD analysis, the purpose is to know the final COD content of the clear supernatant to
know whether the treated water complies with the standards in regulations before
discharge into the water bodies.

47

48

REFERENCES

Ahmad, A., Harris, W. and Seng, O. (2016). Removal of dye from wastewater of textile
industry using membrane technology. Jurnal Teknologi, 36, pp.31-44.

Al-Kdasi, A., Idris, A. and Saed, K. (2004). Treatment of textile wastewater by

advanced oxidation processes a review. The International Journal of Hazardous
Matter, 6(3), pp.222-230.
Arslan, I., Balcioglu, I., Tuhkanen, T. and Bahnemann, D. (2002). H 2O2/Uv-C And
Fe21/H2O2/Uv-C Versus Tio2/Uv-A Treatment For Reactive Dye Wastewater. Journal of
Environmental Engineering, 126(10), pp.903-911.
Azbar, N., Yonar, T. and Kestioglu, K. (2004). Comparison of various advanced
oxidation processes and chemical treatment methods for COD and color removal from a
polyester and acetate fiber dyeing effluent. Chemosphere, 55(1), pp.35-43.
Buthelezi, S., Olaniran, A. and Pillay, B. (2012). Textile Dye Removal from Wastewater
Effluents Using Bioflocculants Produced by Indigenous Bacterial Isolates. Molecules,
17(12), pp.14260-14274.
Carliel, C. (2000). Treatment of exhausted reactive dye bath effluent using anaerobic
digestion laboratory and full-scale trials. Water SA, 22(3), p.225.
da Silva Lacerda, V., Lpez-Sotelo, J., Correa-Guimares, A., Hernndez-Navarro, S.,
Snchez-Bscones, M., Navas-Gracia, L., Martn-Ramos, P. and Martn-Gil, J. (2015).
Rhodamine B removal with activated carbons obtained from lignocellulosic
waste. Journal of Environmental Management, 155, pp.67-76.

49

Dbrowski, A. (2001). Adsorption from theory to practice. Advances in Colloid and

Interface Science, 93(1-3), pp.135-224.
Dargo Beyene, H. (2014). The Potential of Dyes Removal from Textile Wastewater by
Using Different Treatment Technology, a Review. International Journal of
Environmental Monitoring and Analysis, 2(6), p.347.
Department of Environment, Malaysia, (1973). Environmental Quality Act. Kuala
Lumpur: Department of Environment Malaysia.
Forgacs, E., Cserhti, T. and Oros, G. (2004). Removal of synthetic dyes from
wastewaters: a review.Environment International, 30(7), pp.953-971.
Gong, R., Li, M., Yang, C., Sun, Y. and Chen, J. (2005). Removal of cationic dyes from
aqueous solution by adsorption on peanut hull. Journal of Hazardous Materials, 121(13), pp.247-250.
Hunger, K. (2016). Industrial Dyes-Chemistry, Properties, Applications. Weinheim:
Wiley-VCH, p.4.
Lee, K., Teng, T., Morad, N., Poh, B. and Hong, Y. (2010). Flocculation of kaolin in
water using novel calcium chloride-polyacrylamide (CaCl 2-PAM) hybrid
polymer. Separation and Purification Technology, 75(3), pp.346-351.
Lee, K., Teng, T., Morad, N., Poh, B. and Mahalingam, M. (2011). Flocculation activity
of novel ferric chloridepolyacrylamide (FeCl3-PAM) hybrid polymer. Desalination,
266(1-3), pp.108-113.
Ling, L. (2009). Treatment of a reactive dye, a disperse dye, and their mixtures using
h2o2/pyridine/cu(ii) system. Master of Science Thesis, 1(1).
Malik, R., Rana, P., Tomer, V., Chaudhary, V., Nehra, S. and Duhan, S. (2016). Nano
gold supported on ordered mesoporous WO3/SBA-15 hybrid nanocomposite for
oxidative decolorization of azo dye. Microporous and Mesoporous Materials, 225,
pp.245-254.
Muhammad, A., Shafeeq, A., Butt, M., Rizvi, Z., Chughtai, M. and Rehman, S. (2008).
Decolorization and removal of cod and bodfrom raw and biotreated textile dye bath
50

effluent through advanced oxidation processes (AOPS). Brazilian Journal of Chemical

Engineering, 25(3), pp.453-459.
Nisar, M., Nosheen, S., Noreen, A., Majeed, I., Saleem, A. and Ahmad Sheikh, M.
(2011). Comparison of various oxidative treatments for removal of reactive black
CNN. Journal of Environmental Science and Technology, 5(11), pp.916-923.
Pereira, L. and Alves, M. (2011). DyesEnvironmental Impact and
Remediation. Environmental Protection Strategies for Sustainable Development,
pp.111-162.
Platzek, T., Lang, C., Grohmann, G., Gi, U. and Baltes, W. (1999). Formation of a
carcinogenic aromatic amine from an azo dye by human skin bacteria in vitro. Human
& Experimental Toxicology, 18(9), pp.552-559.
Radin Mohamed, R., Mt. Nanyan, N., Abd Rahman, N., A Ibrahim Kutty, N. and Mohd.
Kassim, A. (2014). Colour Removal of Reactive Dye from Textile Industrial Wastewater
using Different Types of Coagulants. Asian Journal of Applied Sciences, 2(5), pp.650657.
Rai, H., Singh, J., Bansal, T., Vats, P. and Banerjee, U. (2005). Removal of Dyes from
the Effluent of Textile and Dyestuff Manufacturing Industry: A Review of Emerging
Techniques With Reference to Biological Treatment. Critical Reviews in Environmental
Science and Technology, 35(3), pp.219-238.
Ramesh, B., A,K, P., S, R. and Kumar, P. (2007). Cotton Textile Processing Waste
Generation and Effluent Treatment. Journal of Cotton Science, 11, pp.141-153.
Robinson, T., McMullan, G., Marchant, R. and Nigam, P. (2001). Remediation of dyes
in textile effluent: a critical review on current treatment technologies with a proposed
alternative.Bioresource Technology, 77(3), pp.247-255.
Sivaramakrishna, L., Reddy, S. and Reddy, V. (2016). The use of an agricultural waste
material, Jujuba seeds for the removal of anionic dye (Congo red) from aqueous
medium. Journal of Hazardous Materials, 203, pp.118127.

51

National Department of Agriculture United States. (2016). Soil Survey Manual Chapter
Three.
[online]
Available
at:
http://www.nrcs.usda.gov/wps/
cid=nrcs142p2_054253 [Accessed 11 April 2016].
Tabak, A., Eren, E., Afsin, B. and Caglar, B. (2009). Determination of adsorptive
properties of a Turkish Sepiolite for removal of Reactive Blue 15 anionic dye from
aqueous solutions. Journal of Hazardous Materials, 161(2-3), pp.1087-1094.
Tan, L., He, M., Song, L., Fu, X. and Shi, S. (2016). Aerobic decolorization,
degradation and detoxification of azo dyes by a newly isolated salt-tolerant yeast
Scheffersomyces spartinae TLHS-SF1. Bioresource Technology, 203, pp.287-294.
Verma, A. and Dash, R. (2012). Decolorization and COD Reduction Efficiency of
Magnesium over Iron based Salt for the Treatment of Textile Wastewater Containing
Diazo and Anthraquinone Dyes. International Journal of Environmental, Chemical,
Ecological, Geological and Geophysical Engineering, 6, pp.365-372.
Vijayaraghavan, J. and Basha, S. (2013). Review on efficacious methods to decolorize
reactive azo dye.Journal of Urban and Environmental Engineering, 7(1).
Wang, Z., Xue, M., Huang, K. and Liu, Z. (2011). Textile Dyeing Wastewater
Treatment. Advances in Treating Textile Effluent.
Xu, X., Li, M. and Yuan, Y. (2012). Treatment of Direct Blending Dye Wastewater and
Recycling of Dye Sludge. Molecules, 17(12), pp.2784-2795.
Yang, D., Wang, B., Ren, H. and Yuan, J. (2012). Effects and mechanism of ozonation
for degradation of sodium acetate in aqueous solution. Water Science and Engineering,
5(2), pp.155163.
Yang, Y., D.T, W. and Bahorsky, M. (2001). Decolorization of Dyes Using UV/H 2O2
Photochemical Oxidation. Journal of Researchgate, 1(1), pp.23-41.
Yeap, K., Teng, T., Poh, B., Morad, N. and Lee, K. (2014). Preparation and
characterization of coagulation/flocculation behavior of a novel inorganicorganic
hybrid polymer for reactive and disperse dyes removal. Chemical Engineering Journal,
243, pp.305-314.

52

Yuen, C., Ku, S., Choi, P., Kan, C. and Tsang, S. (2005). Determining Functional
Groups of Commercially Available Ink-Jet Printing Reactive Dyes Using Infrared
Spectroscopy. Textile and Apparel, 9(2), pp.26-38.
Zhang, X., Dong, W. and Yang, W. (2013). Decolorization efficiency and kinetics of
typical reactive azo dye RR2 in the homogeneous Fe(II) catalyzed ozonation
process. Chemical Engineering Journal, 233, pp.14-23.
Zuraida, S., C.R, N. and Ku Hamid, K. (2013). Removal of Synthetic Dyes from
Wastewater by Using Bacteria, Lactobacillus delbruckii. International Refereed Journal
of Engineering and Science, 2(5), pp.1-7.

53

Appendix B: Flocculation and settling down of dye flocs

Appendix B(i): Settling down of dye flocs of different initial dye concentrations

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Appendix B(ii): After four days of jar test=Complete settling down

55