Removal of congo red dye from aqueous

solution using low cost novel pitali fruits peel

A thesis paper on adsorbent

Jashore University of Science and Technology

Jashore University of Science and Technology
A THESIS PAPER
ON

“Removal of congo red dye from aqueous solution using low

cost novel pitali fruits peel adsorbent.’’

Submitted By
Md. Moshiur Rahmam
STUDENT ID: 150527
SESSION: 2015-2016
A dissertation submitted in partial fulfillment of the
requirements for the degree of
B.Sc. in Chemical Engineering.

Supervisor
Dr. Md. Jahangir Alam
Associate Professor,
Dept. of Chemical Engineering,
Jashore University of Science and Technology

Co-supervisor
Prof. Dr. Biplob Kumar Biswas,
Professor,
Dept. of Chemical Engineering,
Jashore University of Science and Technology
June, 2020.

i
 Declaration

I, (Md. Moshiur Rahmam) am presenting this thesis in partial fulfillment of the required
degree of B.Sc. in Chemical Engineering. This thesis paper represent my own unaided
work and no part of this work has not previously been submitted to any university or
institute before for an award or any academic qualification. Furthermore, it represents my
own opinions and not necessarily those of the Jashore University of Science and
Technology.

Signature

……………………………

Md. Moshiur Rahmam

Student ID: 150516

Session: 2015-16

Dept. of Chemical Engineering

Jashore University of Science & Technology,

Jashore – 7408.

ii
 Certification of Approval
Department of Chemical Engineering
Jashore University of Science & Technology,
Jashore – 7408, Bangladesh.

This is to certify that the dissertation submitted by

Titled “Removal of congo red dye from aqueous solution using low cost novel pitali
fruits peel adsorbent.” has been approved by the dissertation committee for the partial
fulfillment of the requirements for the degree of B.Sc. in Chemical Engineering in the
Department of Chemical Engineering, JUST at June, 2020.

Signature……………………………………………
Name of Supervisor: Dr. Md. Jahangir Alam
Associate Professor
Dept. of Chemical Engineering
Jashore University of Science & Technology, Jashore – 7408, Bangladesh
Date……………………………................................

iii
 ACKNOWLEDGEMENTS

I begin with the name of Allah, the most Merciful and Beneficent. I am grateful to
Almighty Allah for the blessings that he has bestowed upon me and for giving me the
strength, peace of mind, wisdom and good health to finish this research.

I would like to express my sincere gratitude to my mentor, philosopher and guide Dr. Md.
Jahangir Alam, Associate Professor, Dept. of Chemical Engineering to accept me as a
student in his laboratory. It is my proud privilege and a great pleasure to work with him. I
am grateful to him for his continuous support, valuable guidance, suggestions, and
encouragement throughout my research work. I am thankful to him for being an excellent
supervisor, a great motivator, intellectual magnet, and most important, never be a
conservative. I appreciate all his contributions of time from his busy schedule, support and
ideas. . I must grateful to my co-supervisor Prof. Dr. Biplob Kumar Biswas,
Department of ChE,JUST, He helped me every moment to the thesis work successfully.
Without his kind co-operation it became very difficult to complete the thesis.
I would like to express my appreciation to Md. Owaleur Rahman, Lecturer, Dept. of
Chemical Engineering for his helpful suggestions, inspirations, support and sharing of his
insights throughout my research.I also wish to express my heartiest thanks to my class
mates, teacher, technical stuff of the department of chemical engineering, Jashore
University of Science and Technology. For their teaching and helping hand during the
period ofthesis work.
I would like to thank “Jashore University of Science and Technology” of Bangladesh for
allowing me to partial fulfillment my Research.
I would like to express thank to my family who have guide me throughout my life. They
have always sacrifices their time and continuously support me to achieve my dreams and
goals.
Finally, I also addressed my thanks to all my lab members and friends for their advice and
supports

iv
This thesis dedicated to my beloved parents, whose love, encouragement
and prays have made me able to get such achievement and integrity

v
vi
 Table of contents

Contents Page No

Abstract 1
CHAPTER 01 - INTRODUCTION

1.1 Background 2
1.2 water pollution 3
1.2.1 What is water pollution 4
1.2.2 Sources of water pollution 6
1.2.2.1 Point source 6
1.2.2.2 Non point source 7
1.2.3 How do we know when water is polluted? 8
1.2.4 The causes of water pollution 8
1.2.4.1 Sewage 9
1.2.4.2Nutrients 10
1.2.4.3 Chemical waste 10
1.2.4.4 Radioactive waste 11
1.2.4.5 Oil pollution 12
1.2.4.6 Plastic 12
1.2.5 Types of Water Pollutants 12
1.2.6 The effects of water pollution 15
1.2.7 Importance of Wastewater Treatment 15
1.2.8 Water Treatment condition of Bangladesh 17
1.3 Scope of the study 18
1.4 Objectives of this Study 18
1.5 Outline of the Dissertation 19
CHAPTER 02 - LITERATURE REVEIW

2.1 Literature review of Dye 20

2.1.1 What is Dye ? 20

1
2.1.2 Classification of Dye 20
2.1.2.1 Natural Dye 20
2.1.2.2 Synthetic Dye 22
2.1.2.3 Acid Dye 22
2.1.2.4 Basic Dye 23
2.1.2.5 Mordant Dye 24
2.1.2.6 Reactive Dye 25
2.1.2.7 Azoic Dye 25
2.1.2.8 Sulphur Dye 25
2.1.2.9 Vat Dye 26
2.1.2.10 Disperse Dye 27
2.1.3 Harmful Effect of Dye 28
2.1.4 Brief Description on Congo Red 29
2.1.4.1 History of Congo Red Dye 29
2.1.4.2 Chemical properties of congo Red 30
2.1.4.3 Congo Red at a glance 30
2.1.4.4 Industrial application of Congo Red 31
2.2 Water treatment Methods 32
2.2.1 Membrane Process 33
2.2.2. Ion-Exchange Process 35
2.2.3 Activated Carbon Process 36
2.2.4 Sedimentation Process 38
2.2.6 Coagulation , Flocculation and Sedimentation Process 40
2.2.7 Adsorption process 42
2.3 Literature Review of Adsorption 43
2.3.1 What is Adsorption ? 43
2.3.2 Why Chosen Adsorption Process ? 44
2.3.3 Types of Adsorption 44
2.3.3.1 Physical Adsorption 44
2.3.3.1.1 Characteristics of Physisorption 45
2.3.3.2 Chemical Adsorption 46
2.3.3.2.1 Characteristics of Chemisorption 47

2
2.3.4 Factors influencing adsorption: 47
2.3.5 Adsorption principles 49
2.3.6 Study of Adsorption Isotherms 50
2.3.6.1 Langmuir Isotherm 50
2.3.6.2 Freundlich Isotherm 51
2.3.6.3 Temkin Isotherm 52
2.3.6.4 Dubinin Radushkevich Isotherm 53
2.3.6.5 Harkin-Jura Isotherm 54
2.3.6.6 Halsey Isotherm 54
2.4 Literature review of Adsorbent 56
2.4.1 What is adsorbent? 56
2.4.2 Types of Adsorbent 56
2.4.2.1 Jute Stick 57
2.4.2.2 Coconut Husk 57
2.4.2.3 Sugarcane Bagasse 58
2.4.2.4 Water Hyacinth 59
2.4.2.5 Mango Seed 60
2.4.2.6 Pine bark 61
2.4.2.7 Fallen Leaves 62
2.4.2.8 Maize Husk 63
2.4.2.9 Rice Husk 64
2.4.2.10 Straw 64
2.4.2.11 Paper Industry Wastes 65
2.4.3 Fruits peel of Pitali (Trewia nudiflora) as an adsorbent 66
2.4.4 Properties of Pitali (Trewia nudiflora 66
2.4.5 Why pitali considered 67
CHAPTER 03: MATERIALS AND METHOD

3.1 Chemicals and Apparatus Used 68

3.2 Preparation Methodology of Adsorbent 71
3.3 Cumulative methodology of the Adsorption process 71
3.4 Preparation of congo red dye solution 72
3.5 Calibration Curve of Congo Red Solution 72

3
 3.6 Optimum Wavelength (λopt) Determination 73
3.7 pH Neutralization of Adsorbent 73
3.8 pH of Dye Solution 73
3.9 Concentration of Dye Solution 74
3.10 Adsorbent Dosages 74
CHAPTER 04: RESULTS AND DISCUSSION

Batch Adsorption Studies

4.1 Effect of pH 75
4.2Effect of Dosages 75
4.3Effect of Concentration 76
4.4 Effect of contact time 78
4.5 Langmuir Isotherm 78
4.6 Freundlich Isotherm 80
4.7 pseudo-second-order kinetic 82
4.8 Frist order Pseudo-First-Order Kinetic Model 83
CHAPTER 05: Conclusions and Recommendations 85

REFERENCES 87

4
 LIST OF FIGURE
NAME PAGE
NO
Figure-1.1 Water pollution 4

Figure-1.2 Water pollution[britinnica.com] 5

Figure-1.3 Water pollution ,point source 6

Figure-1.4 Above: Point-source pollution Below: Nonpoint-source pollution [ 7

US Fish & Wildlife Service Photo Library.]

Figure-2.1Natural Dye (indigo) 21

Figure- 2.2 ACID BLUE 78 23

Figure-2.3 N,N-dimethylcyclohexylamine CAS No. 98-94-2 23

Figure-2.4(1R)-1-phenylethanamine CAS NO. 3886-69-9 23

Figure-2.5mordant dye 24

Figure-2.6Reactive black 39 [Reactive dye] 24

Figure -2.7 Orange colored azo dye 25

Figure-2.8 Partial chemical structure of proposed for Sulfur Black 1 26

Figure-2.9Vat Dye (Vat Blue 36) 27

Figure-2.10Disperse Dye ( Disperse yellow 42) 27

Figure-2.11Congo Red Dye 31

Figure-2.12 Dye Remove process 32

Figure -2.13Membrane Separation Process 34

Figure-2.14Ion Exchange Process 36

Figure-2.15 Activated carbon process 37

Figure-2.16Sedimentation Process 37

Figure-2.17Photocatalytic Water Purification process 38

Figure-2.18 Coagulation , Flocculation ,sedimentation 41

Figure-2.19 water treatment ,adsorption process 42

Figure-2.20physisorption and chemisorption 45

Figure-2.21Chemical adsorption 46

5
Figure -2.22 JUTE STICK 57

Figure-2.23 Coconut Husk 58

Figure-2.24Sugar Cane (wastes) 59

Figure-2.25 Water Hyacinth 60

Figure-2.26Mango Seed 61

Figure-2.27 Pine bark 61

Figure-2.28 Fallen Leaves 62

Figure-2.29 Maize Husk 63

Figure-2.30 Rice Husk 64

Figure-2.31Straw rice 65

Figure-2.32 Wastage Paper 66

Figure -2.33pitali fruits 67

Figure 3.1-Overall Adsorption process methodology by using peels of pitali 71

fruits adsorbent

Figure-3.2 Calibration curve of congo red dye 72

Figure-3.3 pH Neutralization of Adsorbent 73

Figure-3.4 pH effect on Dye Solution 73

Figure-4.1 Effect of different pH on the removal of CR dye by using pitali 75

fruits peel adsorbent

Figure-4.2 Effect of different adsorbent dosages on the removal of CR dye by 76

using pitali fruits peel adsorbent

Figure -4.3 ffect of different time on the removal of CR dye by using pitali 77
fruits peel adsorbent

4.4 ffect of different time (50 ml, 4 pH, 100 ppm,, 225 mg were fixed) on the 88
removal of congo red dye by using pitali fruits peel adsorbent

Figure 4.5 Langmuir Isotherm on the removal of congo red dye by using 79
adsorbent
Figure 4.6 Freundlich Isotherm on the removal of congo red dye by using 81
adsorbent.
Figure 4.7pseudo-second-order kinetic on the removal of congo red dye by 82
using adsorbent
Figure 4.8 pseudo-frist -order kinetic on the removal of congo red dye by 84
using adsorbent

6
 LIST OF TABLE

NAME PAGE NO
Table -1 [Classification of membrane separation processes] 34

Table- 2 Chemicals are used 68

Table- 3 Apparatus are used 69

Table-04 The Langmuir adsorption isotherm and parameters 80

Table-05 The Freundlich adsorption isotherm and parameters 82

Table-06 pseudo-second-order kinetic model parameter 83

Table-07 pseudo-frist -order kinetic model parameter 83

7
 ABSTRACT

Fruit peels as a promising adsorbent to remove dyes has attracted ample attention worldwide.
A novel potential adsorbent derived from the fruit peel of Trewia nudiflora, waste to resource
approaches. The effects of various experimental parameters as initial concentration (50-300
ppm), the initial dose of as prepared adsorbent (0.5-2.0 g), and contacting time of congo red
adsorption on advanced peel adsorbent (APA) surface were evaluated and optimize the
experimental conditions were decided by conducting batch-wise adsorption. Results were
indicating superb synergetic adsorption capacity of the APA for congo red adsorption.
Comparing the Langmuir and Freundlich adsorption isotherm models, the former showed a
higher correlation coefficient (R2) than the latter implying that the former model can be
applied to uptake Congo red dye by APA. In the kinetic adsorption experiment, adsorbed dye
almost reached equilibrium about 8 h for the APA and followed the pseudo-second-order
kinetic model. Thus, the APAs are propriety and competent in terms of capability and
reusability to remove dyes as congo red.

1
 CHAPTER 1

Introduction
1.1 Background
Saving water to save the planet and to make the future of mankind safe is what we need now.
With the growth of mankind, society, science, technology our world is reaching to new high
horizons but the cost which we are paying or will pay in near future is surely going to be too
high. Among the consequences of this rapid growth is environmental disorder with a big
pollution problem. Anthropogenic activities have caused a great harm to the quality of our
lifeline, i.e. water. Because of fast depletion of the freshwater resources, there seems to be a
crisis of the same. Water pollution is a global concern and, it is the high time that we realize
the gravity of the situation. Removing pollutants from water is the crying need of the hour
and developing a cost effective and environmentally safe method to achieve the same is a
challenging task for chemical engineers. After all, it is the future of mankind, which is at
stake. A dye is a colored substance that has an affinity to the substrate to which it is being
applied. Dyes appear to be colored because they absorb some wavelengths of light more than
others. Humans are estimated to use dyes for thousands of years and the earliest use of the
colorant is believed to be by Neanderthal man about 1,80,000 years ago [1, 2]. The year 1856
witnessed a historic discovery of first synthetic dye, Mauvine, by Perkin [3, 4]. In due course
of time, these synthetic dyes gained huge popularity and began to be synthesized on a large
scale. In fact, it has reached to a level of annually, over 7.0x105 and nearly 1000 different
types of dyes are produced worldwide [5].

The UN estimates that the amount of water released as waste annually is about 1,500 km3.
six times more water than exists in all the rivers of the world. (UN WWAP 2009). Therefore
the first logical step in tackling this mammoth of a problem is reclamation of fresh water
from these water which is released as waste [6]. WHO prescribes a limit of 1 microgram/litre
of colouring substances in drinking water. There are more than 300 million cases of water-

2
borne diseases every year, which leads to the death of approximately 8 to 12 million people.
The composition of industrial waste cannot be readily characterized by a typical range of
values because its makeup depends on the type of manufacturing process involved. Sewage,
industrial wastes and agricultural chemicals such as fertilizers and pesticides are the main
causes of water pollution. The development of industries such as paint, coating, smelting and
electric battery manufacturing, alloy preparation, wood preservation, plating, tanning,
corrosion inhibition has been resulted [7]. It was observed that 10–15% of dyes were released
into the environment during their manufacturing and usage. Dyes and pigments present in
wastewater of industries leads to the generation of hazardous affects to the animal and human
health. Dyes have complex aromatic molecular structures and stable towards heat and
oxidizing agent. In addition, most of dyes are toxic and harmful to some
microorganisms. Colored dyes are esthetic carcinogenic and obstruct the light
penetration into aquatic system. Several dyes are toxic to flora and fauna and therefore,
caused health hazard. Congo red is a direct diazo dye and causes allergic reaction. It is
a recalcitrant and metabolized to benzidine which is a human carcinogen. Congo red is
very difficult to remove because it possesses the thermal, physico-chemical and optical
stability due to their aromatic structure. Thus the removal of dyes remains an
important issue for researchers and environmentalists. . Many conventional methods
such as chemical precipitation, ion exchange, electro-dialysis, ultra-filtration
membrane separation, photo-degradation, electrochemical oxidation etc. have been
widely used for the treatment of dyes bearing wastewater. However, due to various
disadvantages associated with conventional methods, adsorption process has been
explored by many researchers [8].

1.2 water pollution

Over two thirds of Earth's surface is covered by water [9]; less than a third is taken up by
land. As Earth's population continues to grow, people are putting ever-increasing pressure
on the planet's water resources. In a sense, our oceans, river and other inland waters are being
"squeezed" by human activities—not so they take up less room, but so their quality is
reduced. Poorer water quality means water pollution. We know that pollution is a human
problem because it is a relatively recent development in the planet's history: before the 19th

3
century Industrial Revolution, people lived more in harmony with their immediate
environment. As industrialization has spread around the globe, so the problem of pollution
has spread with it. When Earth's population was much smaller, no one believed pollution
would ever present a serious problem. It was once popularly believed that the oceans were
far too big to pollute. Today, with around 7 billion people on the planet, it has become
apparent that there are limits pollution is one of the signs that humans have exceeded those
limits.how serious is the problem? According to the environmental campaign organization
WWF: "Pollution from toxic chemicals threatens life on this planet. Every ocean and every
continent, from the tropics to the once-pristine polar regions, is contaminated." [10]

Figure 1.1 water pollution[Britannica.com]

Figure 2 water pollution[Britannica.com]

1.2.1 What is water pollution ?
Figure 3 water pollution[Britannica.com]
Water pollution can be defined in many ways. Usually, it means one or more substances have
built up in water to such an extent that they cause problems for animals or people. Oceans,
lakes, rivers, and other inlandFigure
waters4 water pollution[Britannica.com]
can naturally clean up a certain amount of pollution by
dispersing it harmlessly. If you poured a cup of black ink into a river, the ink would quickly
disappear into the river's much larger volume of clean water. The ink would still be there in
the river, but in such a low concentration that you would not be able to see it. At such low
levels, the chemicals in the ink probably would not present any real problem. However, if
you poured gallons of ink into a river every few seconds through a pipe, the river would
quickly turn black. The chemicals in the ink could very quickly have an effect on the quality

4
of the water. This, in turn, could affect the health of all the plants, animals, and humans
whose lives depend on the river. Thus, water pollution is all about quantities: how much of
a polluting substance is released and how big a volume of water it is released into. A small
quantity of a toxic chemical may have little impact if it is spilled into the ocean from a ship.
But the same amount of the same chemical can have a much bigger impact pumped into a
lake or river, where there is less clean water to disperse it.Water pollution almost always
means that some damage has been done to an ocean, river, lake, or other water source. A
1969 United Nations report defined ocean pollution as

Figure 1.2 water pollution[britinnica.com]

"The introduction by man, directly or indirectly, of substances or energy into the marine
environment (including estuaries) resulting in such deleterious effects as harm to living
resources, hazards to human health, hindrance to marine activities, including fishing,
impairment of quality for use of sea water and reduction of amenities."

Fortunately, Earth is forgiving and damage from water pollution is often reversible. [11]

5
1.2.2 Sources of water pollution

Figure 1.3 water pollution ,point source

1.2.2.1 point sourc

When we think of Earth's water resources, we think of huge oceans, lakes, and rivers. Water
resources like these are called surface waters. The most obvious type of water pollution
affects surface waters. For example, a spill from an oil tanker creates an oil slick that can
affect a vast area of the ocean.Not all of Earth's water sits on its surface, however. A great
deal of water is held in underground rock structures known as aquifers, which we cannot
see and seldom think about. Water stored underground in aquifers is known as groundwater.
Aquifers feed our rivers and supply much of our drinking water.They too can become
polluted, for example, when weed killers used in people's gardens drain into the ground.
Groundwater pollution is much less obvious than surface-water pollution, but is no less of
a problem. In 1996, a study in Iowa in the United States found that over half the state's
groundwater wells were contaminated with weed killers.You might think things would have
improved since then, but, two decades on, all that's really changed is the name of the
chemicals we're using. Today, numerous scientific studies are still finding weed killers in
groundwater in worrying quantities: a 2012 study discovered glyphosate in 41 percent of
140 groundwater samples from Catalonia, Spain; scientific opinion differs on whether this
is safe or not. Surface waters and groundwater are the two types of water resources that
pollution affects.Point source pollution is defined as coming from a single point, such as a
factory or sewage treatment plant. Here are a few examples of point source pollution OR&R

6
worked on. Factories and sewage
treatment plants are two common
types of point sources. Factories,
including oil refineries, pulp and
paper mills, and chemical, electronics
and automobile manufacturers,
typically discharge one or more
pollutants in their discharged waters
(called effluents). Some factories
discharge their effluents directly into
a waterbody. Others treat it
themselves before it is released, and
still others send their wastes to
sewage treatment plants for
treatment. Sewage treatment plants
treat human wastes and send the
treated effluent to a stream or river.
Figure 1.4 Above: Point-source pollution Below:
Another way that some factories and Nonpoint-source pollution [ US Fish & Wildlife
sewage treatment plants handle waste Service Photo Library.]
material is by mixing it with urban runoff in a combined sewer system. Runoff refers to
stormwater that flows over surfaces like driveways and lawns. As the water crosses these
surfaces, it picks up chemicals and pollutants. This untreated, polluted water then runs
directly into a sewer system.When it rains excessively, a combined sewer system may not
be able handle the volume of water, and some of the combined runoff and raw sewage will
overflow from the system, discharging directly into the nearest waterbody without being.

1.2.2.2 Non point source

Nonpoint source pollution generally results from land runoff, precipitation, atmospheric deposition,
drainage, seepage or hydrologic modification. Nonpoint source (NPS) pollution, unlike pollution
from industrial and sewage treatment plants, comes from many diffuse sources. NPS pollution is
caused by rainfall or snowmelt moving over and through the ground. As the runoff moves, it picks
up and carries away natural and human-made pollutants, finally depositing them into lakes, rivers,
wetlands, coastal waters and ground waters [12]. When point-source pollution enters the
environment, the place most affected is usually the area immediately around the

7
source. For example, when a tanker accident occurs, the oil slick is concentrated
around the tanker itself and, in the right ocean conditions, the pollution disperses the further
away from the tanker you go. This is less likely to happen with nonpoint source pollution
which, by definition, enters the environment from many different places at once [13].Other
examples of point source pollution include an oil spill from a tanker, a discharge from a
smoke stack (factory chimney), or someone pouring oil from their car down a drain. A great
deal of water pollution happens not from one single source but from many different scattered
sources. This is called nonpoint-source pollution. Sometimes pollution that enters the
environment in one place has an effect hundreds or even thousands of miles away. This is
known as transboundary pollution. Above: Point-source pollution comes from a single, well-
defined place such as this pipe. Below: Nonpoint-source pollution comes from many sources.
All the industrial plants alongside a river and the ships that service them may be polluting
the river collectively. Other examples of point source pollution include an oil spill from a
tanker, a discharge from a smoke stack (factory chimney), or someone pouring oil from their
car down a drain. A great deal of water pollution happens not from one single source but
from many different scattered sources. This is called nonpoint-source pollution [14].

1.2.3 How do we know when water is polluted?

There are two main ways of measuring the quality of water. One is to take samples of the
water and measure the concentrations of different chemicals that it contains. If the chemicals
are dangerous or the concentrations are too great, we can regard the water as polluted.
Measurements like this are known as chemical indicators of water quality. Another way to
measure water quality involves examining the fish, insects, and other invertebrates that the
water will support. If many different types of creatures can live in a river, the quality is likely
to be very good; if the river supports no fish life at all, the quality is obviously much poorer.
Measurements like this are called biological indicators of water quality.

1.2.4 The causes of water pollution

Most water pollution doesn't begin in the water itself. Take the oceans: around 80 percent of
ocean pollution enters our seas from the land [15]. Virtually any human activity can have an
effect on the quality of our water environment. When farmers fertilize the fields, the
chemicals they use are gradually washed by rain into the groundwater or surface waters
8
nearby. Sometimes the causes of water pollution are quite surprising. Chemicals released by
smokestacks (chimneys) can enter the atmosphere and then fall back to earth as rain, entering
seas, rivers, and lakes and causing water pollution. That's called atmospheric deposition.
Water pollution has many different causes and this is one of the reasons why it is such a
difficult problem to solve.

1.2.4.1 Sewage
With billions of people on the planet, disposing of sewage waste is a major problem.
According to 2015 figures from the World Health Organization (the most recent available at
the time this article was updated in 2019), some 2.1 billion people (28 percent of the world's
population) don't have access to safe drinking water, while 2.3 billion (30 percent of the
world's population) don't have proper sanitation (hygienic toilet facilities); although there
have been great improvements in securing access to clean water, relatively little progress has
been made on improving global sanitation in the last decade. Sewage disposal affects people's
immediate environments and leads to water-related illnesses such as diarrhea that kills
525,000 children under five each year [16]. (Back in 2002, the World Health Organization
estimated that water-related diseases could kill as many as 135 million people by 2020; in
2016, the WHO was still estimating the annual death toll from poor water and sanitation at
close to a million people a year.) In developed countries, most people have flush toilets that
take sewage waste quickly and hygienically away from their homes.Yet the problem of
sewage disposal does not end there. When you flush the toilet, the waste has to go somewhere
and, even after it leaves the sewage treatment works, there is still waste to dispose of.
Sometimes sewage waste is pumped untreated into the sea. Until the early 1990s, around 5
million tons of sewage was dumped by barge from New York City each year [17]. According
to 2002 figures from the UK government's Department for the Environment, Food, and Rural
Affairs (DEFRA), the sewers of Britain collect around 11 billion liters of waste water every
day; there are still 31,000 sewage overflow pipes through which, in certain circumstances,
raw sewage is pumped untreated into the sea [18]. The New River that crosses the border
from Mexico into California once carried with it 20–25 million gallons (76–95 million liters)
of raw sewage each day; a new waste water plant on the US-Mexico border, completed in
2007, substantially solved that problem [19]. Unfortunately, even in some of the richest
nations, the practice of dumping sewage into the sea continues. In early 2012, it was reported

9
that the tiny island of Guernsey (between Britain and France) has decided to continue
dumping 16,000 tons of raw sewage into the sea each day.

In theory, sewage is a completely natural substance that should be broken down harmlessly
in the environment: 90 percent of sewage is water [20].In practice, sewage contains all kinds
of other chemicals, from the pharmaceutical drugs people take to the paper, plastic, and other
wastes they flush down their toilets. When people are sick with viruses, the sewage they
produce carries those viruses into the environment. It is possible to catch illnesses such as
hepatitis, typhoid, and cholera from river and sea water.

1.2.4.2 Nutrients
Suitably treated and used in moderate quantities, sewage can be a fertilizer: it returns
important nutrients to the environment, such as nitrogen and phosphorus, which plants and
animals need for growth. The trouble is, sewage is often released in much greater quantities
than the natural environment can cope with. Chemical fertilizers used by farmers also add
nutrients to the soil, which drain into rivers and seas and add to the fertilizing effect of the
sewage. Together, sewage and fertilizers can cause a massive increase in the growth of algae
or plankton that overwhelms huge areas of oceans, lakes, or rivers. This is known as a
harmful algal bloom (also known as an HAB or red tide, because it can turn the water red).
It is harmful because it removes oxygen from the water that kills other forms of life, leading
to what is known as a dead zone. The Gulf of Mexico has one of the world's most spectacular
dead zones. Each summer, according to studies by the NOAA, it grows to an area of around
5500–6000 square miles (14,000–15,500 square kilometers), which is about the same size as
the state of Connecticut [10].

1.2.4.3 Chemical waste

Detergents are relatively mild substances. At the opposite end of the spectrum are highly
toxic chemicals such as polychlorinated biphenyls (PCBs). They were once widely used to
manufacture electronic circuit boards, but their harmful effects have now been recognized
and their use is highly restricted in many countries. Nevertheless, an estimated half million
tons of PCBs were discharged into the environment during the 20th century [21]. In a classic

10
example of transboundary pollution, traces of PCBs have even been found in birds and fish
in the Arctic. They were carried there through the oceans, thousands of miles from where
they originally entered the environment. Although PCBs are widely banned, their effects will
be felt for many decades because they last a long time in the environment without breaking
down.

Another kind of toxic pollution comes from heavy metals, such as lead, cadmium, and
mercury. Lead was once commonly used in gasoline (petrol), though its use is now restricted
in some countries. Mercury and cadmium are still used in batteries (though some brands now
use other metals instead). Until recently, a highly toxic chemical called tributyltin (TBT) was
used in paints to protect boats from the ravaging effects of the oceans. Ironically, however,
TBT was gradually recognized as a pollutant: boats painted with it were doing as much
damage to the oceans as the oceans were doing to the boats.

The best known example of heavy metal pollution in the oceans took place in 1938 when a
Japanese factory discharged a significant amount of mercury metal into Minamata Bay,
contaminating the fish stocks there. It took a decade for the problem to come to light. By that
time, many local people had eaten the fish and around 2000 were poisoned. Hundreds of
people were left dead or disabled [22].

1.2.4.4 Radioactive waste

People view radioactive waste with great alarm—and for good reason. At high enough
concentrations it can kill; in lower concentrations it can cause cancers and other illnesses.
The biggest sources of radioactive pollution in Europe are two factories that reprocess waste
fuel from nuclear power plants: Sellafield on the north-west coast of Britain and Cap La
Hague on the north coast of France. Both discharge radioactive waste water into the sea,
which ocean currents then carry around the world. Countries such as Norway, which lie
downstream from Britain, receive significant doses of radioactive pollution from Sellafield.
The Norwegian government has repeatedly complained that Sellafield has increased
radiation levels along its coast by 6–10 times. Both the Irish and Norwegian governments
continue to press for the plant's closure [23].

11
1.2.4.6 Oil pollution
When we think of ocean pollution, huge black oil slicks often spring to mind, yet these
spectacular accidents represent only a tiny fraction of all the pollution entering our oceans.
Even considering oil by itself, tanker spills are not as significant as they might seem: only
12 percent of the oil that enters the oceans comes from tanker accidents; over 70 percent of
oil pollution at sea comes from routine shipping and from the oil people pour down drains
on land [24]. However, what makes tanker spills so destructive is the sheer quantity of oil
they release at once — in other words, the concentration of oil they produce in one very
localized part of the marine environment. The biggest oil spill in recent years (and the biggest
ever spill in US waters) occurred when the tanker Exxon Valdez broke up in Prince William
Sound in Alaska in 1989. Around 12 million gallons (44 million liters) of oil were released
into the pristine wilderness—enough to fill your living room 800 times over! Estimates of
the marine animals killed in the spill vary from approximately 1000 sea otters and 34,000
birds to as many as 2800 sea otters and 250,000 sea birds. Several billion salmon and herring
eggs are also believed to have been destroyed [25].

1.2.4.7 Plastic
If you've ever taken part in a community beach clean, you'll know that plastic is far and
away the most common substance that washes up with the waves. There are three reasons
for this: plastic is one of the most common materials, used for making virtually every kind
of manufactured object from clothing to automobile parts; plastic is light and floats easily
so it can travel enormous distances across the oceans; most plastics are not biodegradable
(they do not break down naturally in the environment), which means that things like plastic
bottle tops can survive in the marine environment for a long time. (A plastic bottle can
survive an estimated 450 years in the ocean and plastic fishing line can last up to 600 years.)

1.2.5 Types of Water Pollutants

1.Chemical – when various chemicals are the water pollution causes. The following
chemicals are the most common water pollutants:

• Crude oil and various petroleum products (including gasoline, diesel fuel, kerosene, motor
and lubricating oils, jet fuel). These compounds are lighter than water and thus always sit

12
on top of water forming sheens of “free product”. However, part of these compounds
dissolve in water and, even in small amounts may be harmful and at the same time may
remain unnoticeable by the eye.

• Fertilizers (including nitrates and phosphates) – while small amounts are useful to life,
higher amounts of nitrates and phosphates in water are only beneficial to algae and harmful
microorganisms and are poisonous to human and aquatic life. These contaminants cannot
be seen themselves in water (as they do not form sheens or color the water), but their effects
can. The typical effect of water pollution by fertilizers (usually through agricultural runoff)
is the fast and abundant water growth.

• Chlorinated solvents (including TCE, PCE, 1,1,1-TCA, carbon tetrachloride, Freons)

which sink in water (are denser than water) and are quite persistent and toxic. These
compounds thus, cannot be seen by the eye, in contrast with petroleum products that are
easily seen as sheens on top of water surface.

• Petroleum solvents (including benzene, toluene, xylenes, ethylbenzene)

• Other organic solvents and chemicals (such as acetone, methyl ethyl ketone, alcohols such
as ethanol, isopropanol; or oxygenate compounds such as MTBE)

• Antibiotics and other pharmaceutical products;

• Perchlorate – perchlorate salts are used in rocket fuels, as well as many other applications
such as fireworks, explosives, road flares, inflation bags, etc. This contaminant is usually
associated with military bases, construction sites (when explosives are used). However,
natural formation in arid areas may account for perchlorate in water, too (e.g., in Chile,
Texas or California where natural formation of perchlorate has been observed)

• Trihalomethanes – these are usually byproducts of water chlorination and may pollute
groundwater and surface water via leaking sewer lines and discharges. Examples of such
compounds are: chloroform, bromoform, dichlorobromomethane.

• Metals and their compounds – of higher health risk are the organo-metal compounds which
may form when metals from water react with organic compounds from water. Common
examples include Hg, As, and Cr poisoning of water. Thus, if water is polluted with both
metals and organic compounds the health risk is higher. And so is the effect of water
pollution on aquatic life.

13
• Pesticides/insecticides/herbicides – comprise a large number of individual chemicals that
get into water due to agricultural activities directly (by spraying over large areas) or
indirectly with agriculture runoff. The insecticide DDT is a typical example of such type of
water pollutant.

• PCBs – in spite of their recent ban, their ubiquitous environmental presence makes these
contaminants usually associated with urban runoffs.

2. Radiological – when radioactive materials are the water pollutant causes.

3 Biological – when various microorganisms (e.g., bacterial species and viruses), worms,
and/or algae occurring in a large number are the water pollution causes. This type of
pollution is caused by decaying organic material in water, animal wastes, as well as
improper disposal of human wastes [26].

14
1.2.6 the effects of water pollution
Some people believe pollution is an inescapable result of human activity: they argue that if
we want to have factories, cities, ships, cars, oil, and coastal resorts, some degree of pollution
is almost certain to result. In other words, pollution is a necessary evil that people must put
up with if they want to make progress. Fortunately, not everyone agrees with this view. One
reason people have woken up to the problem of pollution is that it brings costs of its own that
undermine any economic benefits that come about by polluting.Take oil spills, for example.
They can happen if tankers are too poorly built to survive accidents at sea. But the economic
benefit of compromising on tanker quality brings an economic cost when an oil spill occurs.
The oil can wash up on nearby beaches, devastate the ecosystem, and severely affect tourism.
The main problem is that the people who bear the cost of the spill (typically a small coastal
community) are not the people who caused the problem in the first place (the people who
operate the tanker). Yet, arguably, everyone who puts gasoline (petrol) into their car—or
uses almost any kind of petroleum-fueled transport—contributes to the problem in some way.
So oil spills are a problem for everyone, not just people who live by the coast and tanker
operates.Sewage is another good example of how pollution can affect us all. Sewage
discharged into coastal waters can wash up on beaches and cause a health hazard. People
who bathe or surf in the water can fall ill if they swallow polluted water—yet sewage can
have other harmful effects too: it can poison shellfish (such as cockles and mussels) that
grow near the shore. People who eat poisoned shellfish risk suffering from an acute—and
sometimes fatal—illness called paralytic shellfish poisoning. Shellfish is no longer caught
along many shores because it is simply too polluted with sewage or toxic chemical wastes
that have discharged from the land nearby.Pollution matters because it harms the
environment on which people depend. The environment is not something distant and separate
from our lives. It's not a pretty shoreline hundreds of miles from our homes or a wilderness
landscape that we see only on TV. The environment is everything that surrounds us that gives
us life and health. Destroying the environment ultimately reduces the quality of our own
lives—and that, most selfishly, is why pollution should matter to all of us [27].

1.2.7 Importance of Wastewater Treatment

The fact that the simple turn of a tap delivers clean, safe water to our homes is easily taken
for granted. It’s easy to forget that behind the convenience are water treatment plants and

15
hard-working water treatment professionals making sure that the water we and our family
use is safe. In under-developed areas of the world that don’t have water treatment facilities,
waterborne illnesses such as cholera, typhoid and dysentery sicken or kill a large number of
people each year.

Water treatment is a vital industry prerequisite and goes under 4 principle branches which
incorporate boiler water treatment, cooling water treatment, water filtration and the treatment
of wastewater pro-fluent ensure that waterborne bacteria and parasites don’t cause outbreaks
of disease in the United States. It is viewed as that these cover the dominant part of Water
treatment forms in the UK and Internationally. Water treatment is frequently observed as an
additional cost over top of already very expensive industrial procedures and somewhat of a
business extravagance if the cost is right. However, water treatment can be massively
valuable to your business not slightest on the grounds that it can spare us a huge number of
pounds every year in working expenses but because of diminished support it can likewise
build productivity and yield. It is an industry which can rapidly pay for itself and give back
in spades. And the budgetary advantages it is likewise essential to recollect with utilize
comes wear which is the reason it is gigantically vital with immense working plants to have
our apparatus working proficiently and securely as is our task in danger as well as the
wellbeing and prosperity of our workers is as well, proficiency and security come as an
inseparable unit.

Boiler water treatment is a prominent treatment process in modern plants as a result of the
issue caused by scale development and consumption inside the framework which
accompanies stream. This, at best case scenario can cause expanded vitality costs and a
much-diminished level of productivity and a shorter plant life. Even under the least favorable
conditions this can prompt a catastrophic failure with the damage of machinery and more
seriously injury and loss of life. Boilers have to work with incredible pressures as water
heated in to steam expands in volume over 1000 times and has to travel down narrow steam
pipes at over 100 kilometers an hour. Water treatment is an important aspect in making sure
this process is kept safe and efficient. As with Boiler Water, Cooling Water processes also
suffer from scale formation and corrosion but also can be subject to fouling as they easily
become breeding grounds for harmful bacteria such as Legionella. This form of pneumonia
is the cause of Legionnaires Disease which comes with the inhaling of water droplets which
in most cases proves fatal. In addition to this, untreated cooling water will more than likely

16
reduce the efficiency of and shorten your plant's life, this can lead to unreliable and unsafe
plant operation. Left untreated you could be wasting El0,000s in energy, chemicals and water
charges every year. Specialized water treatment chemicals can prevent the build-up of scale
and corrosion thus preventing and reversing the effects on industrial processes.

Chlorine Dioxide has these days become the favorite method of water purification in
industrial and commercial processes; this is because of a number of the advanced and unique
disinfection Properties it carries. These include its powerful, yet selective nature unlike
Chlorine and Bromine C102 is unaffected by changes in pH and is incredibly effective
against biofilms. It can readily permeate and penetrate biofilms that are normally resistant to
most disinfectants and Chlorine. Legionella as stated before is a serious danger should your
water remain untreated and Chlorine Dioxide has been seen to be extremely effective in the
control and disinfection of the Legionella bacteria. As should be obvious water treatment is
a far-reaching industry and there is a requirement for it in most industrial and numerous
business locales, cost and wellbeing are mysteriously connected and in most theaters cost
increments with interest in wellbeing however not with water treatment. Operational
expenses are ensured to diminish in the long haul as your vegetation's is protracted and
support is required less habitually [28].

1.2.8 Water Treatment condition of Bangladesh

Bangladesh is among the countries with the lowest level of wastewater treatment in the Asia
Pacific region. The country treats only 17 percent of its wastewater, says the United Nations
World Water Development Report 2017. On water management system in Dhaka, the report
said only 2% of its water was safely managed. It also stressed the need for improving the
efficiency of wastewater management systems in order to increase the proportion of
wastewater that is safely managed. Prof Mujibur Rahman, who has been monitoring the
discharge of wastewater into the Buriganga river for years, said, “The finding is not too far
away from the reality. Bangladesh is far away from reaching the satisfactory level as the
water treatment issue is still neglected in the country. We have to work really hard for
improving the situation. The issue was very alarming and that the government should give
immediate attention on it to prevent water crisis in future. If we look at Dhaka, there are
rivers around it but you can't use their water. The situation is same in other major cities.Asia
and the Pacific region were experiencing increased competition across key sectors over

17
limited freshwater resources, while an estimated 80–90 percent of all wastewater produced
in the region was released untreated, polluting ground and surface water resources, as well
as coastal ecosystems. The intentional use of wastewater in aquaculture is declining
worldwide due to safety concerns and loss of land areas close to urban markets. Unintentional
waste-fed aquaculture occurs in Bangladesh through fish farming in water bodies containing
faecalis contaminated water. On an average, high-income countries treat about 70 percent of
the municipal and industrial wastewater they generate. That ratio drops to 38 percent in upper
middle-income countries and to 28 percent in lower middle-income countries. In low-income
countries, only 8 percent undergoes treatment of any kind. These estimates support the often-
cited approximation that, globally, over 80 percent of all wastewater is discharged without
treatment.In a world where demands for freshwater are continuously growing, and where
limited water resources are increasingly stressed by over-abstraction, pollution and climate
change, neglecting the opportunities arising from improved wastewater management is
nothing less than unthinkable. Currently, two-thirds of the world's population live in areas
that experience water scarcity for at least one month a year. Referring to the World Economic
Forum 2016 report, water crisis was determined as the global risk of highest concern for
people and economies for the next 10 years. On current trends, the UN programmer forecasts
that water demand -- for industry, energy and an extra billion people -- will increase 50
percent by 2030. The United Nations World Water Development Report is the UN's flagship
report on water. It is published each year with a focus on different strategic water issues. The
title of the 2017 report is “Wastewater: The untapped resource”. The launch of the report is
at the core of the World Water Day celebrations [29].

1.3 Scope of the study

This research paper foucused on:
1. Removal of anionic congored dye by using novel potential adsorbent derived from the
fruit peel of Trewia nudiflora(pitali).
2. Mnimizing pitali waste.
3.water security and savings.
4.Protect environment from water pollution.

1.4 Objectives of this Study

• To treat industrial wastewater containing organic dyes

18
 • To showTrewia nudiflora(pitali) as a potential low-cost adsorbent for water treatment
• To optimize process variables e.g. pH, concentration, dosage and contact time
• To study adsorption isotherm
• To study kinetics of the process
• To mitigate environmental pollution

➢ To determine the effect of different parameter such as:

• pH
• Contac time
• Concentration
• Adsorbent doses

1.5 Outline of the Dissertation

This dissertation has written in several parts mentioning as chapter. The current chapter
(Chapter 1) presents overall introduction of this dissertation, fundamental background of
Trewia nudiflora, water pulution,type of polutant, and details of plant, potentiality of our
work and principle objectives of the present study.

Chapter 2 describes the literature review of the present study. In the literature review, type
of Dye, methods of water treatment, technique and application were presented.

Chapter 3 presents the experimental and prediction method and procedure of adsorption
and characterization.

Chapter 4 presents the results and discussion of our research work.

Chapter 5 presents the conclusions of present study and recommendations for future
progress in this research area.

19
 CHAPTER 2

LITERATURE REVEIW

2.1 literature review of Dye

2.1.1 What is Dye ?

Dye, substance used to impart colour to textiles, paper, leather, and other materials such that
the colouring is not readily altered by washing, heat, light, or other factors to which the
material is likely to be exposed. Dyes differ from pigments, which are finely ground solids
dispersed in a liquid, such as paint or ink, or blended with other materials. Most dyes are
organic compounds (i.e., they contain carbon), whereas pigments may be inorganic
compounds (i.e., they do not contain carbon) or organic compounds. Pigments generally give
brighter colours and may be dyes that are insoluble in the medium employed. Colour has
always fascinated humankind, for both aesthetic and social reasons. Throughout history dyes
and pigments have been major articles of commerce. Manufacture of virtually all commercial
products involves colour at some stage, and today some 9,000 colorants with more than
50,000 trade names are used. The large number is a consequence of the range of tints and
hues desired, the chemical nature of the materials to be coloured, and the fact that colour is
directly related to the molecular structure of the dye [30].

2.1.2 Classification of Dye

Dyes are two types:
• Natural Dye
• Synthetic Dye

2.1.2.1 Natural Dye

Natural dyes are dyes or colorants derived from plants, invertebrates, or minerals. The
majority of natural dyes are vegetable dyes from plant sources—roots, berries, bark, leaves,

20
and wood—and other biological sources such as fungi.Archaeologists have found evidence
of textile dyeing dating back to the Neolithic period. In China, dyeing with plants, barks and
insects has been traced back more than 5,000 years.[1] The essential process of dyeing
changed little over time. Typically, the dye material is put in a pot of water and heated to
extract the dye compounds into solution with the water. Then the textiles to be dyed are
added to the pot, and held at heat until the desired colour is achieved. Textile fibre may be
dyed before spinning or weaving ("dyed in the wool"), after spinning ("yarn-dyed") or after
weaving ("piece-dyed") . Many natural dyes require the use of substances called mordants to
bind the dye to the textile fibres. Mordants (from the Latin verb 'mordere', meaning 'to bite')
are metal salts that can form a stable molecular coordination complex with both natural dyes
and natural fibres. Historically, the most common mordants were alum (potassium aluminum
sulphate - a metal salt of aluminum) and iron (ferrous sulphate). Many other metal salt
mordants were also used, but are seldom used now due to modern research evidence of their
extreme toxicity either to human health, ecological health, or both. These include salts of
metals such as chrome, copper, tin, lead, and others. In addition, a number of non-metal salt
substances can be used to assist with the molecular bonding of natural dyes to natural fibres
- either on their own, or in combination with metal salt mordants - including tannin from oak
galls and a range of other plants/plant parts, 'pseudo-tannins', such as plant-derived oxalic
acid, and ammonia from stale urine. Plants that bio-accumulate aluminum have also been
used, including club mosses, which were commonly used in parts of Europe, but are now
endangered in many areas. The Symplocos genus of plants, which grows in semi-tropical
regions, also bioaccumulates aluminum, and is still popular with natural dyers. Some
mordants, and some dyes themselves, produce strong odors, and large-scale dyeworks were
often isolated in their own districts [31].

Figure 2.1 Natural Dye (indigo)

21
2.1.2.2 Synthetic Dye
Synthetic dyes are manufactured from organic molecules. Before the discovery of synthetic
dyes in 1856, the majority of natural dyes were prepared from plant sources: roots, berries,
bark, leaves, wood, fungi, and lichens. Batches of natural dyes were never exactly alike in
hue and intensity, whereas synthetic dyestuffs can be manufactured consistently. These dyes
are made from synthetic resources such as chemicals, petroleum by-products, and earth
minerals. The first human-made organic aniline dye, mauveine, was discovered by William
Henry Perkin in 1856, the result of a failed attempt in total synthesis of quinine. Since then,
thousands of synthetic dyes have been prepared [32].

2.1.2.3 Acid Dye

Acid dyes are highly water soluble, and have better light fastness than basic dyes.The textile
acid dyes are effective for protein fibers such as silk, wool, nylon and modified acrylics.
They contain sulphonic acid groups, which are usually present as sodium sulphonate salts.
These increase solubility in water, and give the dye molecules a negative charge. In an acidic
solution, the -NH2 functionalities of the fibres are protonated to give a positive charge: -
NH3+. This charge interacts with the negative dye charge, allowing the formation of ionic
interactions. As well as this, Van-der-Waals bonds, dipolar bonds and hydrogen bonds are
formed between dye and fibre. As a group, acid dyes can be divided into two sub-groups:
acid-leveling or acid-milling [33].

22
 Figure 2.2 ACID BLUE 78

2.1.2.4 Basic Dye

Basic dyes are called so since they are salts of organic bases. Basic dyes are also called
cationic dyes because in solution the basic dye molecule ionizes, causing its colored
component to become an action of positively charged radical. Basic dyes are used for dyeing
wool, silk, and acrylic and mod-acrylic fibres.

Figure- 2.3 N,N-dimethylcyclohexylamine CAS No. 98-94-2

Figure- 2.4 (1R)-1-phenylethanamine CAS NO. 3886-69-9

23
2.1.2.5 Mordant Dye
A mordant or dye fixative is a substance used to set (i.e. bind) dyes on fabrics by forming a
coordination complex with the dye, which then attaches to the fabric (or tissue). It may be
used for dyeing fabrics or for intensifying stains in cell or tissue preparations. Although
mordants are still used, especially by small batch dyers, it has been largely displaced in
industry by directs.The term mordant comes from the Latin mordere, "to bite". In the past,
it was thought that a mordant helped the dye bite onto the fiber so that it would hold fast
during washing. A mordant is often a polyvalent metal ion, often chromium(III). The
resulting coordination complex of dye and ion is colloidal and can be either acidic or
alkaline [34].

Figure-09 mordant dye

Figure 2.5 Reactive black 39 [Reactive dye]

24
2.1.2.6 Reactive Dye
In a reactive dye, a chromophore contains a substituent that reacts with the substrate.
Reactive dyes have good fastness properties owing to the covalent bonding that occurs during
dyeing. Reactive dyes are most commonly used in dyeing of cellulose like cotton or flax, but
also wool is dyeable with reactive dyes. eactive dyes are mainly used for dyeing
cellulose fibres such as cotton and viscose, but they are also increasingly gaining importance
for wool and polyamide. The range of available reactive dyes is wide and enables a large
number of dyeing techniques to be used [35] .

2.1.2.7 Azoic Dye

Azo dyes are organic compounds bearing the functional group R−N=N−R′, in which R and
R′ are usually aryl. They are a commercially important family of azo compounds, i.e.
compounds containing the linkage C-N=N-C.Azo dyes are widely used to treat textiles,
leather articles, and some foods. Chemically related to azo dyes are azo pigments, which are
insoluble in water and other solvents [36]. Other azo dyes contain chemical groups that bind
metal ions. Among numerous metal salts used with these dyes, chromium and copper are
most common; often, the metal ion also unites with the fibre, improving the resistance of the
dye to washing. The presence of the metal sometimes produces important changes in shade
[37] [38].

Figure 2.6 Orange colored azo dye

2.1.2.8 Sulphur Dye

Sulfur dyes are the most commonly used dyes manufactured for cotton in terms of volume.
They are inexpensive, generally have good wash-fastness, and are easy to apply. Sulfur dyes
are predominantly black, brown, and dark blue. Red sulfur dyes are unknown, although a

25
pink or lighter scarlet color is available [39].These are water insoluble dyes and have no
affinity for the cellulosics as such, but solubilised when treated with a weak alkaline solution
of sodium sulphide or any other reducing agent to form a leuco compound. These leuco
compounds are water soluble and have affinity for the cellulosic materials such as cotton,
viscose, jute and flex etc. These dyes are absorbed by the cellulosic material in the leuco
form from aqueous solution and when oxidized by suitable oxidizing agents, got converted
into insoluble parent dye, which is fast to normal color fastness parameters [40].

Figure-2.7 Partial chemical structure of proposed for Sulfur Black 1

2.1.2.9 Vat Dye

Vat dyes are a class of dyes that are classified as such because of the method by which they
are applied. Vat dyeing is a process that refers to dyeing that takes place in a bucket or vat.
The original vat dye is indigo, once obtained only from plants but now often produced
synthetically [41]. The vat dyes have high color fastness, which is uncommon in other dye
classes. On the other hand, vat dyes tend to have poor rubbing fastness, but this can be
mitigated with special treatments to the fabric. Indigo is subject to major crocking (i.e.,
rubbing the dye off onto other items) unless it is applied carefully. This means that dipping
many times in a weaker dyebath is more preferred than to dip once in a stronger dyebath.Vat

26
dyes are water insoluble pigments.They are called dyes because chemical reduction ialkaline
solution converts the pigment into a water soluble leuco form with substantivity cotton [42].

Figure-2.9 Vat Dye (Vat Blue 36)

2.1.2.10 Disperse Dye

Disperse dyes were formulated and introduced to permit dyeing of hydrophobic

thermoplastic fibers including nylon, polyester, acrylic, and other synthetics. The disperse
dyes are small polar molecules, usually containing anthraquinone or azo groups which do
not have charged cationic or anionic groups within the structure. The disperse dyes are
sparingly soluble in water and must be dispersed with the aid of a surfactant in the dyebath.
As the small amount of dissolved disperse dye diffuses into the fiber, additional dye
dispersed in solution is dissolved until the disperse dye is nearly completely exhausted onto
the fiber. The dyes were initially known as cellulose acetate dyes; later, however, they were
found to be suitable for dyeing a wide variety of fibres and in 1953 the Society of Dyers and
Colourists renamed them ‘disperse dyes’ [43].

Figure-2.10 Disperse Dye ( Disperse yellow 42)

27
2.1.3 Harmful Effect of Dye
There is no proof to suggest that most of the dyestuffs at present used in textile dyeing
and finishing are risky to human health at the levels of exposure that workers generally face
in the factories. However, with long-term or accidental over exposure, there can be
likely health hazards and all dyes and chemicals must consequently be treated with
care. The most common hazard of reactive dyes is respiratory problems due to the
inhalation of dye particles. Sometimes they can affect a person’s immune system and in
extreme cases this can mean that when the person next inhales the dye their body can react
dramatically. This is called respiratory sensitization and symptoms include itching,
watery eyes, sneezing and symptoms of asthma such as coughing and wheezing [44].
Perhaps the most predominant health problems related to dyeing and finishing processes
arise from exposure to chemicals acting as irritants. These may cause skin irritation, itchy
or blocked noses, sneezing and sore eyes. They include formaldehyde-based resins,
ammonia, acetic acid, some shrink-resist chemicals, some optical whiteners, soda ash,
caustic soda and bleach. Certain reactive, vat and disperse dyes are also recognized as
skin sensitive [45]. Textile industries produce large amounts of liquid wastes. These textile
effluents contain organic and inorganic compounds [46]. During the dyeing processes,
not all dyes that are applied to the fabrics are fixed on them and there is always a portion of
these dyes that remains unfixed to the fabrics and gets washed out. These unfixed dyes are
found to be in high concentrations in textile effluents [47]. The amount of water consumed
and released also varies depending on the type of fabrics produced . Almost 0.08 –0.15 m3
of water is used to produce 1 kg of fabrics. It is estimated that about 1,000 – 3,000
m3 of water is let out after processing about 12 – 20 tons of textiles per day [48]. These
effluents are rich in dyes and chemicals, some of which are non-biodegradable and
carcinogenic and pose a major threat to health and the environment. Several primary,
secondary and tertiary treatment processes like flocculation, trickling filters and
electrodialysis have been used to treat these effluents. However these treatments are not
found effective against the removal of all dyes and chemicals used [49]. The effluents
do not only contain high concentration of dyes used in the industry, but also contain the
chemicals used in the various processing stages. Some trace metals such as Cr, As, Cu
and Zn are present in these effluents and are capable of causing several health
problems including haemorrhage, ulceration of skin, nausea, severe irritation of skin
and dermatitis. Textile effluents are also found to contain other organic and microbial

28
impurities [50]. The usage of cotton has been increasing constantly throughout the past
century [51]. Cotton fibres are mainly dyed using azo dyes which are one of the largest
groups of synthetic colorants used in the industry. Azo dyes are difficult to degrade
by the current conventional treatment processes. They are characterized by the presence
of the nitrogen-nitrogen bond (-N=N-) in the center and hence they are highly electron
deficient [52]. These azo dyes are found to be complex in nature and have been found to
show carcinogenic evidences on reductive cleavage. These dyes are capable of altering
the physical and chemical properties of soil, deteriorating water bodies and causing
harm to the flora and fauna in the environment [53]. It was observed that the toxic nature
of dyes causes death to the soil microorganisms which in turn affect the agricultural
productivity. The presence of very small amount of Azo dyes in water (<1ppm) are
highly visible . This affects aesthetic merit, transparency and water-gas solubility.
Reducing light penetration through water decreases photosynthetic activity, causing
oxygen deficiency and de-regulating the biological cycles of aquatic biota [54]. Many
Azo dyes are also highly poisonous to the ecosystem and mutagens, meaning they can
have acute to chronic effects upon organisms, depending on exposure time and Azo dye
concentration. 1,4-diamino benezene is an aromatic amine whose parent azo dyes can
cause skin irritation, contact dermatitis, chemosis, lacrimation, exopthamlmose, permanent
blindness, rhabdomyolysis, acute tubular necrosis supervene, vomiting gastritis,
hypertension, vertigo and, upon ingestion, oedema of the face, neck, pharynx, tongue and
larynx along with respiratory distress [55] . Aromatic amines can be mobilised by water
or sweat, which encourage their absorption through the skin and other exposed areas, such
as the mouth. Absorption by ingestion is faster and so potentially more dangerous, as
more dye can be absorbed in a smaller time frame . Water soluble Azo dyes become
dangerous when metabolized by liver enzymes [56].

2.1.4 Brief Description on Congo Red

2.1.4.1 History of Congo Red Dye

Congo red was first synthesized in 1883 by Paul Böttiger, who had been employed at
Friedrich Bayer Company in Elberfeld, Germany. He was looking for textile dyes that did
not require a mordant step. The company was not interested in this bright red color, so he
filed the patent under his own name and sold it to the AGFA company of Berlin. AGFA
marketed the dye under the name "Congo red", a catchy name in Germany at the time of

29
the 1884 Berlin West Africa Conference, an important event in the Colonisation of Africa.
The dye was a major commercial success for AGFA. In the following years, for the same
reason, other dyes were marketed using the "Congo" name: Congo rubine, Congo corinth,
brilliant Congo, Congo orange, Congo brown, and Congo blue.[2] Once of economic
significance, Congo red has fallen into disuse as have all benzidine-derived dyes, owing
to their carcinogenic activity [57].

2.1.4.2 Chemical properties of congo Red

Congo red is red-brown powder, soluble in hot water and the cold water 10 times of its
weight; the color of the solution is yellow-red; soluble in ethanol and the solution is
orange; slightly soluble in acetone, while almost insoluble in ether. The solution is dark
blue when in sulfuric acid, turning to light blue accompanied with the appearance of blue
precipitate when diluted.Its aqueous solution will form a blue floc when in concentrated
hydrochloric acid. When added with acetic acid, the precipitate turned blue with a little
purple to a precipitate with some red color. It is insoluble in the concentration of caustic
soda solution; susceptible to acid and salt which means even if its absorption of carbon
dioxide from the air will make the color blue and dark, while dilute soda solution can
restore the original color [58].

2.1.4.3 Congo Red at a glance

Chemical Name : Congo Red

Molecular Formula : C32H22N6O6.2Na

Molecular Weight : 696.7

Color : Red Brown

From : Powder

Composition : Dye content ≥85%

Melting point : >360 OC (lit)

Solubility : H2O 10 mg/ml

Density : 0.995 g/ml at 25 OC

30
Cololur Index : 22120

pH : 6.7 at 20 OC

pH Range : 3(blue)-5.2 (red) [59]

Chemicalstructure:

Figure-2.11 Congo Red Dye

2.1.4.4 Industrial application of Congo Red

❖ It has been widely used in cotton, viscose dyeing. Because it can easily be
transformed into blue when in acid, while there is no appropriate treatment to
improve, the usage amount is gradually decreased since the advent of insoluble azo
dyes and acid-resistant red 4BS, however, the amount used in the paper industry is
quite large. It can also be used as indicators of acid-base, namely Congo red test
paper. The measurable range pH is 3.0 (blue)-5.0 (red). It is also used for biological
staining, analysis reagents.
❖ An indicator frequently used in lab as well as a carcinogenic disperse dyes; used to
standard test.

❖ Used as an acid-base indicator, adsorption indicator and biological stain, etc.

❖ Acid-base indicator, pH 3.0 (blue violet)~5.0 (red); detect the acidity of paper and
hydrochloric acid in the gastric juice; test boric acid, cyanide; biological media
additives; biological staining, such as embryo slices, plant mucin, cellulose, elastic
tissue dyeing.

31
 ❖ Mainly used for dyeing cotton, hemp, silk and other textile and paper products; it
can also be used as an indicator [60].

2.2 Water treatment Methods

Dyeing is the process of adding color to textile products like fibers, yarns and fabrics. Dyeing
is normally done in a special solution containing dyes and particular chemical materials. Dye
molecules are fixed to the fiber by absorption, diffusion, or bonding with temperature and
time being key controlling factors. The bond between dye molecule and fiber may be strong
or weak, depending on the dye used [61].The technologies divided into three categories as
flows:

❖ Biological Methods
❖ Chemical Methods
❖ Physical Methods

Figure-2.12 Dye Remove process

Biological Methods

Biological treatment is often the most economical alternative when compared with other
physical and chemical processes. Biodegradation methods such as fungal decolonization,
microbial degradation, adsorption by microbial biomass and bio remediation systems are

32
commonly applied to the treatment of industrial effluents because many microorganisms
such as bacteria, Yeasts, algae and fungi are able to accumulate and degrade different
pollutants.

Chemical Method
Chemical methods include coagulation or flocculation combined with flotation and filtration,
precipitation-floccution with Fe(ll), Ca(OH)2, electro-flotation, electro kinetics coagulation,
conventional oxidation methods by oxidizing agents, irradiation or electrochemical
processes. These chemical techniques are often expensive and although the dyes are
removed, accumulation of concentrated sludge creates a disposal problem. There is also the
possibility that a secondary pollution will arise because of excessive chemical

Physical method
Different physical methods are also widely used such as membrane, filtration processes
(Nano filtration, reverse osmosis, electrolysis) and adsorption techniques. The major
disadvantage of membrane processes is that they have limited life time before membrane
fouling occurs and the cost of periodic replacement must thus be included in any analysis of
their economic viability. In accordance with the very abundant literature date, liquid —phase
adsorption is one of the most popular methods for the removal of pollutants from wastewater.
This process provides an attractive alternative for the treatment of contaminated water.

2.2.1 Membrane Process

Membrane processes cover a group of separation processes in which the characteristics of a
membrane (porosity, selectivity, electric charge) are used to separate the components of a
solution or a suspension. In these processes the feed stream is separated into two: the fraction
that permeates through the membrane, called the permeate, and the fraction containing the
components that have not been transported through the membrane, usually called
the retentate The size of the components to be separated and the nature and magnitude of the
driving force provide criteria for a classification of the membrane separation processes, as
shown in the table. It should be noted that the boundaries between some of the processes,

33
such as reverse osmosis and ultrafiltration, are arbitrary.

Figure -2.13 Membrane Separation Process

Of the processes listed in table 1 , reverse osmosis and ultafiltration are the most widely used
industrially. Abundant examples of their application can be found in water Desalinization,
the dairy industries and the separation of organic solutes from aqueous solutions. Membrane
processes do not require heating, which makes the process suitable for the treatment of
thermolabile products. In addition the relatively low capital and operating costs involved
make membrane processes an appealing alternative to more conventional separation
processes, particularly when dealing with dilute solutions. In the next sections the principles
and characteristics of the processes listed in Table 1 will be described briefly [62] [63].

Table 1 [Classification of membrane separation processes]

34
2.2.2. Ion-Exchange Process
Ion exchange refers to the interaction of ionic species in aqueous solutions with adsorbent
solid materials. It is distinguished from conventional Adsorption by the nature and
morphology of the adsorbent material which in most cases is either a dynamic polymer
matrix or an inorganic structure containing exchangeable functional groups. All modern ion
exchange resins are polymeric structures, generally based either on styrene or an acrylic
matrix. Polystyrene sulphonic acid cation resins are cross-linked copolymers of styrene
(vinylbenzene), with divinylbenzene (DVB-containing pendant sulphonic acid groups
capable of exchanging cations in solution over the entire pH range. Acrylic cation resins are
made by copolymerizing acrylic or methacrylic acid with DVB. These resins have a high
capacity and will exchange cations in the alkaline pH range 7−14. Polystyrene onion
exchange resins are cross-linked copolymers of polystyrene-DVB, with pendant functional
groups comprising primary, secondary and tertiary amines. Strong base resins operate over
the entire pH range, whereas weak base resins exchange anions in the pH range 0−7.
Polystyrene copolymers possess a gel type structure, swell and contract in aqueous solutions
and are physically robust in most process operations. Macroporous or macroreticular resins
have been developed which have a porous, sintered structure possessing free water channels
within the matrix of about 1,000 Ådiameter. Large molecules can travel freely within these
pores and therefore, these materials are less prone to organic fouling. Inorganic materials are
either naturally-occurring or synthetic materials. Typical examples are natural and synthetic
zeolites; insoluble salts, e.g., hydrous zirconium phosphate; heteropolyacids, e.g.,
ammonium phosphomolybdate; natural clays, e.g., montmorillonite. The largest single
application, measured in terms of ion exchange resin usage, is water treatment, i.e., softening,
demineralization for high pressure boilers and dealkalization.

35
 Figure 18

Figure -2.14 Ion Exchange Process

Enormous advances in ion exchange technology have occurred because of the relentless
requirement for pure and ultrapure water. Other major industrial applications are the
processing and decolorization of sugar solutions and the recovery of uranium from relatively
low-grade mineral ore leach solutions. Ion exchange is also used in the fields of medicine,
pharmaceuticals, chemicals processing, catalysis and laboratory analysis [64] [65] [66] .

2.2.3 Activated Carbon Process

Activated carbon, also called activated charcoal, is a form of carbon processed to have small,
low-volume pores that increase the surface area available for adsorption or chemical
reactions. Activated is sometimes substituted with active.Due to its high degree of
microporosity, one gram of activated carbon has a surface area in excess of 3,000 m2 (32,000
sq ft) as determined by gas adsorption. An activation level sufficient for useful application
may be obtained solely from high surface area. Further chemical treatment often enhances
adsorption properties.Activated carbon is usually derived from charcoal. When derived from
coal it is referred to as activated coal. Activated coke is derived from coke.

Carbon adsorption has numerous applications in removing pollutants from air or water
streams both in the field and in industrial processes such as:

• Spill cleanup
• Groundwater remediation
• Drinking water filtration

36
 Figure-2.15 Activated carbon process

• Air purification
• Volatile organic compounds capture from painting, dry cleaning, gasoline dispensing
operations, and other processes
• Volatile organic compounds recovery (solvent recovery systems, SRU) from flexible
packaging, converting, coating, and other processes.

During early implementation of the 1974 Safe Drinking Water Act in the US, EPA officials
developed a rule that proposed requiring drinking water treatment systems to use granular
activated carbon. Because of its high cost, the so-called GAC rule encountered strong
opposition across the country from the water supply industry, including the largest water
utilities in California. Hence, the agency set aside the rule. Activated carbon filtration is an
effective water treatment method due to its multi-functional nature. There are specific types
of activated carbon filtration methods and equipment that are indicated – depending upon the
contaminants involved.Activated carbon is also used for the measurement of radon
concentration in air [67].
2.2.4.Sedimentation Process
Sedimentation is a physical water treatment process using gravity to remove suspended solids
from

Ffigure -2.16 Sedimentation Process

37
water.Solid particles entrained by the turbulence of moving water may be removed naturally
by sedimentation in the still water of lakes and oceans. Settling basins are ponds constructed
for the purpose of removing entrained solids by sedimentation. Clarifiers are tanks built with
mechanical means for continuous removal of solids being deposited by
sedimentation.Clarification does not remove dissolved species.Sedimentation is the act of
depositing sediment. Sedimentation in potable water treatment generally follows a step of
chemical coagulation and flocculation, which allows grouping particles together into flocs
of a bigger size.This increases the settling speed of suspended solids and allows settling
colloids. Sedimentation has been used to treat wastewater for millennia.Primary treatment of
sewage is removal of floating and settleable solids through sedimentation. Primary clarifiers
reduce the content of suspended solids as well as the pollutant embedded in the suspended
solids. Because of the large amount of reagent necessary to treat domestic wastewater,
preliminary chemical coagulation and flocculation are generally not used, remaining
suspended solids being reduced by following stages of the system. However, coagulation and
flocculation can be used for building a compact treatment plant (also called a "package
treatment plant"), or for further polishing of the treated water.Sedimentation tanks called
"secondary clarifiers" remove flocs of biological growth created in some methods of
secondary treatment including activated sludge, trickling filters and rotating biological
contactors [68].

2.2.5 Photocatalytic Process

Photocatalysis is the acceleration of a photoreaction in the presence of a catalyst. In catalyzed
photolysis, light is absorbed by an adsorbed substrate. In photogenerated catalysis, the
photocatalytic activity (PCA) depends on the ability of the catalyst to create electron–hole

Figure-2.17 Photocatalytic Water Purification process

38
pairs, which generate free radicals (e.g. hydroxyl radicals) able to undergo secondary reactions.
Its practical application was made possible by the discovery of water electrolysis by means of
titanium dioxide. Homogeneous Photocatalysis in which the reactants and the photocatalysts
exist in the same phase. The most commonly used homogeneous photocatalysts include
ozone and photo-Fenton systems (Fe+ and Fe+/H2O2). The reactive species is the •OH
which is used for different purposes. Heterogeneous catalysis has the catalyst in a different
phase from the reactants. Heterogeneous photocatalysis is a discipline which includes a large
variety of reactions: mild or total oxidations, dehydrogenation, hydrogen transfer, 18O2–16O2
and deuterium-alkane isotopic exchange, metal deposition, water detoxification, gaseous
pollutant removal, etc. Most common heterogeneous photocatalysts are transition metal
oxides and semiconductors, which have unique characteristics.Linda Zou et al. (2006)
conducted a photocatalysis study where result reveals that the TiO2–SiO2 pellets with higher
surface area (421.1 m2/g) achieved 100% conversion efficiency for a substantial period of
time (4 h), whereas the catalyst with low surface area only had a very brief period of 100%
degradation efficiency [69]. Michael R et al. (1995) conducted a photocatalysis study
where the investigation indicates, Semiconductor photocatalysis appears to be a promising
technology that has a number of applications in environmental systems such as air
purification, water disinfection, hazardous waste remediation, and water purification. In
addition, the basic research that underlies the application of this technology is forging a new
understanding of the complex heterogeneous photochemistry of metal oxide systems in
multiphasic environments [70]. Disinfection of water by supported titanium dioxide
photocatalysts, a form of solar water disinfection.Oxidation of organic contaminants using
magnetic particles that are coated with titanium dioxide nanoparticles and agitated using a
magnetic field while being exposed to UV light.Decontamination of water with
photocatalysis and adsorption: the removal and destruction of organic contaminants in
groundwater can be addressed through the impregnation of adsorbents with photoactive
catalysts. These adsorbents attract contaminating organic atoms/molecules like
tetrachloroethylene to them. The photoactive catalysts impregnated inside speed up the
degradation of the organics. Adsorbents are placed in packed beds for 18 hours, which would
attract and degrade the organic compounds. The spent adsorbents would then be placed in
regeneration fluid, essentially taking away all organics still attached by passing hot water
counter-current to the flow of water during the adsorption process to speed up the reaction.
The regeneration fluid then gets passed through the fixed beds of silica gel photocatalysts to
remove and decompose the rest of the organics left. Through the use of fixed bed reactors,
39
the regeneration of adsorbents can help increase the efficiency [71].

2.2.6 Coagulation , Flocculation and Sedimentation Process

Groundwater and surface water contain both dissolved and suspended particles. Coagulation
and flocculation are used to separate the suspended solids portion from the water. Suspended
particles vary in source, charge, particle size, shape, and density. Correct application of
coagulation and flocculation depends upon these factors. Suspended solids in water have a
negative charge and since they have the same type of surface charge, they repel each other
when they come close together. Therefore, suspended solids will remain in suspension and
will not clump together and settle out of the water, unless proper coagulation and flocculation
is used. Coagulation and flocculation occurs in successive steps, allowing particle collision
and growth of floc. This is then followed by sedimentation (see Sedimentation Chapter). If
coagulation is incomplete, flocculation step will be unsuccessful, and if flocculation is
incomplete, sedimentation will be unsuccessful.
Coagulant chemicals with charges opposite those of the suspended solids are added to the
water to neutralize the negative charges on non-settlable solids (such as clay and color-
producing organic substances).Once the charge is neutralized, the small suspended particles
are capable of sticking together.These slightly larger particles are called microflocs, and are
not visible to the naked eye. Water surrounding the newly formed microflocs should be clear.
If not, coagulation and some of the particles charge have not been neutralized. More
coagulant chemicals may need to be added.A high-energy, rapid-mix to properly disperse
coagulant and promote particle collisions is needed to achieve good coagulation. Over-
mixing does not affect coagulation, but insufficient mixing will leave this step incomplete.
Contact time in the rapid-mix chamber is typically 1 to 3 minutes. Flocculation, a gentle
mixing stage, increases the particle size from submicroscopic microfloc to visible suspended
particles. Microfloc particles collide, causing them to bond to produce larger, visible flocs
called pinflocs. Floc size continues to build with additional collisions and interaction with
added inorganic polymers (coagulant) or organic polymers. Macroflocs are formed and high
molecular weight polymers, called coagulant aids, may be added to help bridge, bind, and
strengthen the floc, add weight, and increase settling rate. Once floc has reached it optimum
size and strength, water is ready for sedimentation. Design contact times for flocculation
range from 15 or 20 minutes to an hour or more, and flocculation requires careful attention
to the mixing velocity and amount of mix energy. To prevent floc from tearing apart or

40
shearing, the mixing velocity and energy are usually tapered off as the size of floc increases.

Figure 2.18 Coagulation , Flocculation ,sedimentation

Once flocs are torn apart, it is difficult to get them to reform to their optimum size and
strength. The amount of operator control available in flocculation is highly dependent upon
the type and design of the equipment.Some designs incorporate coagulation, flocculation,
and sedimentation a single unit (either upflow solids contact units or sludge blanket units).
Most upflow solids contact units use recirculation of previously formed floes to enhance floc
formation and maximize usage of treatment chemicals. Sludge blanket units force newly
forming flocs to pass upward through a suspended bed of floc.In both styles of units, the
cross-sectional surface of the basin increases from bottom to top,causing water flow to slow
as it rises, and allowing floc to settle out. Combination units generally use higher rise rates
and shorter detention time than conventional treatment. Numerous manufacturers market
proprietary units based on these design concepts. These units are more compact and require
less land for plant site location. On-site pilot plant evaluation, by a qualified engineer familiar
with the water quality, is recommended prior to design. The choice of coagulant chemical
depends upon the type of suspended solid to be removed, raw water conditions, facility
design, and cost of chemical. Final selection of coagulant (or coagulants) should be made
with jar testing and plant scale evaluation. Consideration must be given to required effluent
quality, effect upon down stream treatment process performance, cost,method and cost of
sludge handling and disposal, and cost of the dose required for effective treatment [72].

41
2.2.7 Adsorption process
The adsorption/bio-oxidation process is a two-stage modification of the activated sludge
process used for wastewater treatment. It consists of a high-loaded A-stage and low-loaded
B-stage. The process is operated without a primary clarifier, with the A-stage being an open
dynamic biological system. Both stages have separate settling tanks and sludge recycling
lines, thus maintaining unique microbial communities in both reactors. Principle of operation
The A-stage, or adsorption stage is the most innovative component of the process. It is not
preceded by primary treatment.Simple schematic description of the adsorption/bio-oxidation
process Influent organic matter is removed in the A-stage mainly by flocculation and sorption
to sludge due to the high loading rates (2-10 g BOD • g VSS−1 • d−1) and low sludge age
(typically 4-10 h). Hydrolysis of complex organic molecules occurs improving
biodegradability of the influent of the B-stage. High loading rates and low sludge age favours
development of dynamic biocoenosis with a large fraction of microorganisms present in the
exponential growth phase. Diverse sludge biocoenosis increase variety of organic
compounds that can be degraded in the A-stage and makes the process more stable towards
the shock loads. Altogether, up to 80% of the influent organic matter can be removed in the
A-stage. The required reactor volume and oxygen supply are lower if compared to the
removal in the conventional activated sludge process.

Figure-2.19 water treatment ,adsorption process

The B-stage, or bio-oxidation stage, is a typical low-loaded activated sludge process, where
biodegradation of the remaining organic material occurs. The B-stage can be designed for
nitrogen and/or phosphorus removal by alternating aerobic, anoxic and anaerobic zones in
the reactor [73].

42
Applications for industrial wastewater treatment

• The adsorption/bio-oxidation process is used for treatment of industrial wastewater

with high COD, including wastewater from:
• Pulp and paper industry.
• Textile industry.
• Food industry, including dairy industry.
• Pharmaceutical industry.
• Leather tanning industry [74].

2.3 Literature Review of Adsorption

2.3.1.What is Adsorption ?
Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid
to a surface.This process creates a film of the adsorbate on the surface of the adsorbent. This
process differs from absorption, in which a fluid (the absorbate) is dissolved by or permeates
a liquid or solid (the absorbent), respectively.Adsorption is a surface phenomenon, while
absorption involves the whole volume of the material. The term sorption encompasses both
processes, while desorption is the reverse of it.

IUPAC definition:

Increase in the concentration of a substance at the interface of a condensed and a liquid or

gaseous layer owing to the operation of surface forces.Adsorption of proteins is of great
importance when a material is in contact with blood or body fluids. In the case of blood,
albumin, which is largely predominant, is generally adsorbed first, and then rearrangements
occur in favor of other minor proteins according to surface affinity against mass law selection
(Vroman effect). Adsorbed molecules are those that are resistant to washing with the same
solvent medium in the case of adsorption from solutions. The washing conditions can thus
modify the measurement results, particularly when the interaction energy is low.Similar to
surface tension, adsorption is a consequence of surface energy. In a bulk material, all the
bonding requirements (be they ionic, covalent or metallic) of the constituent atoms of the
material are filled by other atoms in the material. However, atoms on the surface of the
adsorbent are not wholly surrounded by other adsorbent atoms and therefore can attract
adsorbates [75].

43
2.3.2 Why Chosen Adsorption Process ?
Adsorption technique for waste water treatment has become more popular in recent year
owing to their efficiency in the removal of pollutants too stable for biological methods. Dye
adsorption is a result of two mechanism and is influenced by many factors e.g.(dye-
adsorbent interaction,surface area, particle size,temperature,pH ).

The main advantage of this process to choose it are:

Easy to carry out
No reagents are required
Minimum activation steps are required
Easy to operate
Cost effective
High efficiency

2.3.3 Types of Adsorption

There are two types of Adsorption-Physical Adsorption or Physio sorption and Chemical
Adsorption or Chemisorption.

2.3.3.1 Physical Adsorption

Physisorption, also called physical adsorption, is a process in which the electronic structure
of the atom or molecule is barely perturbed upon adsorption. The fundamental interacting
force of physisorption is Harsh force. Even though the interaction energy is very weak (~10–
100 meV), physisorption plays an important role in nature. For instance, the van der Waals
attraction between surfaces and foot-hairs of geckos provides the remarkable ability to climb
up vertical walls. Van der Waals forces originate from the interactions between induced,
permanent or transient electric dipoles.In comparison with chemisorption, in which the
electronic structure of bonding atoms or molecules is changed and covalent or ionic bonds
form, physisorption, generally speaking, can only be observed in the environment of low
temperature (thermal energy at room temperature ~26 meV) and the absence of the
relatively strong chemisorptions. In practice, the categorisation of a particular adsorption as
physisorption or chemisorption depends principally on the binding energy of the adsorbate
to the substrate [76].

44
 Figure-2.20 physisorption and chemisorption

2.3.3.1.1 Characteristics of Physisorption

Energetics and kinetics: Physisorption is an exothermic process. However it is
characterized by low enthalpy values (20– 40 kJ mol-1), due to 45 weak van der Waals forces
of attraction. The activation energy for physisorption is also very low and hence it is
practically a reversible process.

Effect of temperature: Since physical adsorption is an exothermic process, it occurs more

readily at lower temperatures and decreases with increase in temperature (Le-Chatelier’s
Principle).
Effect of pressure: In case of physisorption of gases over solids, the extent of adsorption
increases with increase in pressure as the volume of the gases decrease during adsorption
(Le-Chatelier’s Principle).

Specificity: Since the van der Waals’ forces are universal, a given surface of an adsorbent
does not show any preference for an adsorbate in physisorption i.e. it is not specific with
respect to adsorbent.
Nature of adsorbate: However, the extent of adsorption depends on the nature of gas
(adsorbate). In general, easily liquefiable gases with higher critical temperatures) are readily
adsorbed as the van der Waals’ forces are stronger, especially, near the critical temperatures.

45
Surface area of adsorbent: The extent of adsorption increases with the increase of surface
area of the adsorbent. Hence finely powdered metals and porous substances having large
surface areas perform well as adsorbents [77].

2.3.3.2 Chemical Adsorption

Chemisorption is a kind of adsorption which involves a chemical reaction between the
surface and the adsorbate. New chemical bonds are generated at the adsorbant surface.
Examples include macroscopic phenomena that can be very obvious, like corrosion, and
subtler effects associated with heterogeneous catalysis, where the catalyst and reactants are
in different phases. The strong interaction between the adsorbate and the substrate surface
creates new types of electronic bonds.

In contrast with chemisorption is physisorption, which leaves the chemical species of the
adsorbate and surface intact. It is conventionally accepted that the energetic threshold
separating the binding energy of "physisorption" from that of "chemisorption" is about 0.5
eV per adsorbed species [78].

Figure-2.21 Chemical adsorption

Due to specificity, the nature of chemisorption can greatly differ, depending on the chemical
identity and the surface structural properties. The bond between the adsorbate and adsorbent
in chemisorption is either ionic or covalent.

2.3.3.2.1 Characteristics of Chemisorption

Energetics and kinetics: Chemisorption is also an exothermic process and the enthalpy
values are higher (80-240 kJ mol-1) as it involves formation of chemical bonds. However,

46
the activation energy for chemisorption is high and occurs slowly. Hence it is also called
activated adsorption. It is practically irreversible.

Effect of temperature: Even though chemical adsorption is an exothermic process, it does

not occur slowly at lower temperature due to high kinetic energy barrier. Hence, like most
chemical changes, the extent of chemisorption increases with increase in temperature up to
certain limit and then after that it starts decreasing. It is also observed that, in some cases,
physisorption of a gas adsorbed at low temperature may change into chemisorption at a high
temperatures.

Effect of pressure: The chemisorption is not appreciably affected by small changes in

pressure. However, very high pressures are favourable for chemisorption.

High specificity: Chemisorption is highly specific and occurs only if there is some
possibility of chemical bonding between adsorbent and adsorbate.

Surface area: Like physisorption, chemisorption also increases with increase of surface
area of the adsorbent [79].

2.3.4 Factors influencing adsorption:

Adsorption on a solid is influenced by a number of factors such as,

• Surface area
• Nature of the adsorbate
• Hydrogen ion concentration (pH) of the solution
• Temperature
• Mixed solutes and
• Nature of adsorbate

Surface Area: Adsorption is a surface phenomenon and as such the extent of adsorption is
proportional to specific surface area. Specific surface area can be defined as that portion of
the total surface area that is available for adsorption. Thus the amount of adsorption
accomplished per unit weight of solid adsorbent is greater, if the solid is more finely divided
and more porous. It was found that for porous materials like activated carbon, the breaking
up of large particulars to form smaller ones can in some instances serve to open some tiny,

47
sealed channels in the carbon with might then become available for adsorption thus possibly
yielding dependence of equilibrium capaci6y of particular size. They also showed that both
the rate and extent to adsorption by particulars of a fixed carbon size should vary
approximately linearly with the dosage of adsorbent over a range of doses that do not result
in great differences in the concentrations of solute remaining in bulk solution phase.

Nature of adsorbate: Adsorption increases with decrease in the solubility of the solvent.
Greater the solubility, stronger the solute-solvent. The solubility of the solute is to a large
extent, a controlling factor for adsorption equilibrium. The landelius rule states that an
inverse relationship can be anticipated between the extent of adsorption of a solute and its
48 solubility in the solvent from which adsorption occurs Adsorption increases with
decrease in the solubility of the solvent. Greater the solubility, stronger the solute-solvent
bond and the smaller the extent of adsorption.

Hydrogen ion concentration: The pH of a solution from which adsorption occurs influences
the extent of adsorption. Because, hydrogen and hydroxide ions are adsorbed quite strongly,
the adsorption of other ions is influenced by the pH of the solution. The majority of colored
materials encountered with the industry are negatively charged and ordinarily carbons will
give greater decolourisation with increase in acidity of the solution, the pH of the adsorbent
itself is an important factor, as this may affect the pH of the liquid.

Temperature: Heavy metal removal is usually greater at higher temperature. Temperature

effects on adsorption equilibria are generally not significant over the range of temperature
practically encountered in water and wastewaters. Thus small variations in temperature do
not alter the adsorption process to any significant extent.

Mixed solutes: In the application of adsorption for purification of waters and wastewaters,
the material to be adsorbed commonly will be mixture of many compounds rather than a
single one. The compounds may mutually enhance adsorption, may act relatively a single
one. The compounds may mutually enhance adsorption, may act relatively independently or
may interfere with one another. In mixed solutes, each solute completes in some way with
the adsorption of the other. The degree of mutual inhibition of competing should be related
to the relative size of the molecules being adsorbed, to the relative adsorptive affinities and
the relative concentrations of the solutes. The presence of the 49 other solutes in the mixture
adversely affects adsorptions of the first, leading to much more rapid breakthrough of this
material.

48
Nature of adsorbent: The physiochemical nature of the adsorbent can have profound effects
on both rate and capacity for adsorption. Adsorption by activated carbon is a surface
phenomenon and is affected by the following parameters.

• Surface functional groups

• Structural details

Significant amount of the carbonyl and carboxyl groups are present on activated carbon
surfaces. The behaviours of activated carbon as an adsorbent have to be related to the surface
functionally of the material and the evidence for chemical interaction at the surface between
carbonyl and carboxyl groups and organic absorbates is convincing. The adsorption capacity
of activated carbon may well be accomplished by increasing the concentration of the
appropriate functional group [80].

2.3.5 Adsorption principles

The basic principle of operation for carbon adsorption is the mass transfer and adsorption of
a molecule from a liquid or gas into solid surface. Activated carbon is manufactured in such
a way as to produce extremely porus carbon particles whose internal surface area is very
large .This porous structure attracts and holds organic molecules as well as certain metal and
inorganic molecules. Adsorption occurs because i) The contaminant has low solubility in the
waste ii) The contaminant has greater affinity for the carbon than for the waste iii) A
combination of two Two most common carbon adsorption processes are the granular
activated carbon (GAC) which is used in packed beds, and the powdered activated carbon.
The activated carbon adsorption process is one of the most frequently applied technologies
for the removal of trace organic compounds from an aqueous solution. Adsorption is a
surface phenomenon in which soluble particles from a solution are bonded onto a particular
substrate. One of the most desirable properties of an adsorbent is a high surface to volume
ratio. Activated carbon ratio ranging from 500 to 1000 m2 /g is a good adsorbent for effective
removal of organic compounds [81].

2.3.6 Study of Adsorption Isotherms

To investigate an interaction of adsorbate molecules and adsorbent surface, six well-known

models, the Langmuir, Freundlich, Temkin, Dubinin Radushkevich, Harkin-Jura and Halsey
Isotherms were selected to explicate dye–clay interaction in this study.

49
2.3.6.1 Langmuir Isotherm

In 1916, Irving Langmuir published a new model isotherm for gases adsorbed to solids, which
retained his name. It is a semi-empirical isotherm derived from a proposed kinetic
mechanism. This isotherm was based on different assumptions one of which is that
dynamicequilibrium exists between adsorbed gaseous molecules and the free gaseous
molecules.

It is based on four assumptions:

• The surface of the adsorbent is uniform, that is, all the adsorption sites are
equivalent.
• Adsorbed molecules do not interact.
• All adsorption occurs through the same mechanism.
• At the maximum adsorption, only a monolayer is formed: molecules of adsorbate
do not deposit on other, already adsorbed, molecules of adsorbate, only on the
free surface of the adsorbent [80].

The Langmuir isotherm model deals with a monolayer maximum adsorption capacity of the
adsorbent. This means that each site can take in only one molecule and it assumes constant
adsorption energy for all the active binding sites present on the adsorbent. In addition, the
adsorbed molecules cannot move across the surface or react with neighboring molecules
[82]. Langmuir model is expressed by following equation (2.1). [83].

(2.1)

The linearized form of the Langmuir isotherm can be given by following equation (2.2).
[84]

(2.2)

where,

𝑞𝑒 = The amount of adsorbate adsorbed per unit weight of adsorbent at equilibrium (mg/g)

50
𝐶𝑒 = The dye concentration in the equilibrium solution (mg/L),

𝑞𝑚𝑎𝑥= The maximum adsorption capacity and

𝐾𝑏= The adsorption equilibrium constant (L/mg).

When Ce/qe is plotted against Ce, a straight line with slope 1/qmax and intercept of 1/qmaxKb
is obtained.
The fundamental characteristics of the Langmuir isotherm have been given by the expression
separation factor or equilibrium constant RL, which is defined by following equation (2.3).

(2.3)

where

Co = The initial dye concentration

Kb = The Langmuir constant

Equilibrium constant RL signs the nature of adsorption as (Hameed et al., 2008):

RL > 1 (unfavorable), 0 < RL < 1 (favorable), RL = 0 (irreversible), and RL = 1 (linear) [85].

2.3.6.2 Freundlich Isotherm

The Freundlich equation or Freundlich adsorption isotherm, an adsorption isotherm, is an

empirical relation between the concentration of a solute on the surface of an adsorbent to
the concentration of the solute in the liquid with which it is in contact. In 1909, Herbert
Freundlich gave an expression representing the isothermal variation of adsorption of a
quantity of gas adsorbed by unit mass of solid adsorbent with pressure. This equation is
known as Freundlich adsorption isotherm or Freundlich adsorption equation. The
Freundlich isotherm is the closer relationship that depicts the sorption equation derived
empirically in 1912. Freundlich model is typically used when the surface of the adsorbent
is heterogeneous; Freundlich isotherm is expressed by following equation (2.4) [86].

51
 (2.4)

where, qe = The quantity of adsorbate adsorbed per mass unit of the adsorbent,
Ce = The equilibrium concentration of the adsorbate (mg/L),

KF = The affinity of the adsorbate towards the adsorbent (L/mg)1/n, 1/n = The adsorption
intensity or surface heterogeneity,

The value of 1/n ranges between 0 to 1, the adsorption becoming more heterogeneous as 1/n
value gets closer to zero. To determine the constants KF and 1/n, equation (2.4) can be
described by the linearized form as shown in followed equation (2.5) [86]

(2.5)

A plot of log qe versus log Ce results in a straight line with a slope of (1/n) and an intercept
(log KF).

K and n are constants for a given adsorbate and adsorbent at a particular temperature. At high
pressure 1/n = 0, hence extent of adsorption becomes independent of pressure. It is used in
cases where the actual identity of the solute is not known, such as adsorption of colored
material from sugar, vegetable oil etc.

2.3.6.3 Temkin Isotherms

Temkin isotherm is one of the earliest reported isotherms and assumes the heat of adsorption
decreases linearly with increasing coverage due to the interactions between adsorbate and
adsorbent. The Temkin isotherm has been generally applied in the form as shown in equation
(2.6) [87].

(2.6)

Equation (2.6) can be linearized as

52
𝑞𝑒 = 𝐵𝑙𝑛(𝐴) + 𝐵𝑙𝑛(𝐶𝑒) (2.7)
where
B = RT/b

b = (J/mol) is the Temkin constant related to heat of sorption,

A = The Temkin isotherm equilibrium binding constant (L/g),

R = The universal gas constant (8.314 J/mol K),

T = The absolute solution temperature (⁰K).

The constants A and B are calculated from the intercept and slope of the plot, respectively.

2.3.6.4 Dubinin Radushkevich Isotherm

The Dubinin Radushkevich Isotherm model can explain the physical and chemical
characteristics of adsorption with its mean free energy [88]. D–R model has commonly been
applied in the following equation (2.8)

𝑙𝑛𝑞𝑒 = 𝑙𝑛𝑞𝑚 − 𝛽𝜀2 (2.8)

where β = The activity coefficient related to mean adsorption energy (mol2/J2).

ε = The Polanyi potential.

ε can be written as following equation (2.9)

(2.9)

The mean adsorption energy E (KJ/mol) can be obtained by using the expression

(2.10)

53
The adsorption process is said to be dominated by physisorption for the energy values less
than 8 KJ/mol, by chemical ion exchange mechanism for those between 8 and 16 kJ/mol and
by chemical particle diffusion for the greater than 16 kJ/mol [89].

2.3.6.5 Harkin-Jura Isotherm

The Harkin–Jura [90] equation accounts for multilayer adsorption and can be explained by
the existence of a heterogeneous pore distribution. The Harkins–Jura isotherm can be
expressed in its linear form

(2.11)

where B and A are Harkin–Jura isotherm parameters

Both B and A can be achieved from the slope and the intercept of the linear plot based on
1/qe2 versus logCe.

2.3.6.6 Halsey Isotherm

This model is suitable for multilayer adsorption and heteroporous adsorbents. The Halsey
adsorption isotherm can be given as

(2.12)
Where KH and nH Halsey Constant

Equation (2.12) can be expressed in its linear form

(2.13)

Both KH and nH can be achieved from the slope and the intercept of the linear plot based on
lnqe versus ln(1/Ce).

54
 2.3.7 Adsorption kinetics

Pseudo-First-Order Kinetic Model

It is given by equation is below:

Log (Qe − Qt ) = log Qe − (k1∕2.303)t 4.14

Where: qt and qe are the amount of solute sorbed per mass of sorbent (mg g−1) at any time
and equilibrium, respectively, and k1 is the rate constant of first-order sorption (min−1). The
straight-line plot of log (qe − qt) against t gives log (qe) as slope and intercept equal to
k1/2.303. Hence the amount of solute sorbed per gram of sorbent at equilibrium (qe) and the
first-order sorption rate constant (k1) can be evaluated from the slope and the intercept.
pseudo-second-order kinetic

The pseudo-second-order kinetic rate equation is expressed as,

𝑑𝑞𝑡
= 𝐾2 (𝑞𝑒 − 𝑞𝑡 )2 4.15
𝑑𝑡

Where K2 is the pseudo-second-order rate constant (min g/mg), qe and qt represent the
amount of dye adsorbed (mg/g) at equilibrium and at time t.

Separating the variables:

𝑑𝑞𝑡
(𝑞𝑒 −𝑞𝑡 )2
= 𝐾2 𝑡 4.16

Where K2 is the rate constant of second-order adsorption. For the boundary condition t=0,
t=t

and qt=0, qt=qt the integrated and linear form of equation becomes,

𝑡 1 1
=𝐾 2 +𝑞 𝑡 4.17
𝑞1 2 𝑞𝑒 𝑒

Plots of t/qt versus t gave linear graphs from which qe and k2 were estimated from the slopes
and intercepts of the plot different concentrations.

2.4 Literature review of Adsorbent

2.4.1 What is adsorbent?

55
Adsorbents are materials that are used to remove the trace contaminants from liquids and
gas streams. They are used in industries to vanish away impurities. It is essential to use them
as they protect downstream catalysts and avoid unplanned shutdowns. As these materials
have a great demand in market, manufactures must ensure that they respond to every type of
purification process efficiently. They are used in diverse types of industries including
petrochemical, water treatment, refining and oil organizations. Adsorbents get attached to
other substances without covalent bonding. They are insoluble in nature and play a crucial
role in chemical absorption. A material is good Adsorbent if it has the ability to attract a
definite amount of liquid. Charcoal is one of the best examples of Adsorbents. The whole
process of making a molecular film by Adsorbents over the surface is called adsorption. It is
operative in physical, biological and even chemical processes. The biggest advantage of
using Adsorbents is that it causes waste heat which is used for producing cold water in air
conditioning [91].

2.4.2 Types of Adsorbent

• Most industrial adsorbents fall into one of three classes:

• Oxygen-containing compounds are typically hydrophilic and polar, including
materials such as silica gel and zeolites.
• Carbon-based compounds are typically hydrophobic and nonpolar, including
materials such as activated carbon and graphite.
• Polymer-based compounds are polar or non-polar functional groups in a porous
polymer matrix [92].
2.4.2.1 Jute Stick
Jute stick powder (JSP) has been found to be a promising material for adsorptive removal of
congo red (C.I. 22120) and rhodamine B (C.I. 45170) from aqueous solutions.
Physicochemical parameters like dye concentration, solution pH, temperature and contact
time have been varied to study the adsorption phenomenon. Favorable adsorption occurs at
around pH 7.0 whereas temperature has no significant effect on adsorption of both the dyes.
The maximum adsorption capacity has been calculated to be 35.7 and 87.7mg/g of the
biomass for congo red and rhodamine B, respectively. The adsorption process is in
conformity with Freundlich and Langmuir isotherms for rhodamine B whereas congo red

56
adsorption fits well to Langmuir isotherm only. In both the cases, adsorption occurs very fast
initially and attains equilibrium within 60min. Kinetic results suggest the intra-particle
diffusion of dyes as rate limiting step [93].

Figure -2.22 JUTE STICK

2.4.2.2 Coconut Husk

Coconut coir and husk is a good absorbent. the efficiency of coconut husks (CHs) in
removing methylene blue (MB) dye from wastewaters in Malaysia was carried out. A fixed
bed column adsorber was set up using flow rates of 40 and 80 mL/min, and the adsorbent
(CH) was prepared using the base treatment method with NaOH as activating agent. Three
different column bed depths (10, 20, and 25 cm) and unit weights of adsorbent (103, 213,
and 260 g) were used. Two models, the bed depth service time (BDST) and Thomas models,
were used to validate the adsorption capacity results and breakthrough curve. Changing the
bed depth from 20 to 25 cm did not result in a significant change in adsorption capacity,
therefore a 20-cm bed depth is recommended as the most efficient. Similarly, adsorption
capacity increased as flow rates increased from 40 to 80 mL/min, indicating that a flow rate
of 80 mL/min yielded optimum efficiency. The two models also provided predictions with
good fits of the bed depth effect, the adsorption capacity, and the breakthrough curve of CH
for MB removal [94].

57
 Figure-2.23 Coconut Husk

coconut coir dust (CCD) a low cost agricultural waste material in a batch process was
investigated. Adsorption was studied as a function of amount of adsorbent, pH and
concentration with time. It was found that percentage adsorption varied linearly with the
amount of adsorbent and concentration with time but varies non-linearly with pH. Adsorption
equilibrium data were represented by isotherm, kinetics and thermodynamics models. Three
isotherm models namely Langmuir, Freundlich and Temkin were tested and adsorption was
found to fit well into these models with R2 0.90. The kinetic data were well described by
the pseudo-second order kinetic model. The adsorption process was endothermic with a mean
change in enthalpy (ΔH) (+17.87 KJ mol−1) and spontaneous with a mean free energy
change (ΔG) (−9.69 KJ mol−1). FTIR analyses of the adsorbent suggest that adsorption of
the dye was through a chemical interaction of the functional groups on the surface of the
adsorbent [95] .

2.4.2.3 Sugarcane Bagasse

The main emphasis of the present study was to prepare a low-cost adsorbent using sugarcane
bagasse for the adsorption of methylene blue. Chemical activation using di-potassium
hydrogen phosphate (K2HPO4) was employed for the preparation of activated carbon by
onefactor-at-a time methodology using batch operation. Different process parameters such
as K2HPO4 concentration, impregnation time, temperature, and impregnation ratio were
optimized for the chemical treatment of bagasse. The optimized protocol yielded 136.84

58
mg/g binding capacity in the activated carbon composed of 2 M K2HPO4 solution-
treatedbagasse powder (treated for 6 h with an impregnation ratio of 0.0125 at 30°C
temperature); while sugarcane bagasse without any pretreatment was found to have a binding
capacity of 125.06 mg/g. The methylene blue adsorption capacity of the chemically treated
adsorbent was compared to the commercial activated carbon. Reduction in the characteristic
peak intensities of IR spectroscopy and scanning electron microscopy studies indicates
structural changes in chemically activated bagasse powder. Prepared adsorbent has
tremendous potential for adsorption of harmful dyes and chemicals from polluted water
system [96].

Figure-2.24 Sugar Cane (wastes)

59
2.4.2.4 Water Hyacinth

Figure-2.25 Water Hyacinth

Phytoremediation through aquatic macrophytes treatment system for the removal of

pollutants and contaminants from various natural sources is a well established
environmental protection technique.Water hyacinth (Eichhornia crassipes), a worst invasive
aquatic weed has been utilised for various research activities over the last few decades. The
biosorption capacity of the water hyacinth in minimising various contaminants present in
the industrial wastewater is well studied. The present review quotes the litera tures related
to the biosorption capacity of the water hyacinth in reducing the concentration of dyestuffs,
heavy metals and minimising certain other physiochemical parameters like TSS (total
suspended solids), TDS (total dissolved solids), COD (chemical oxygen demand) and BOD
(biological oxygen demand) in textile wastewater. Sorption kinetics through various
models, factors influencing the biosorption capacity, and role of physical and chemical
modifications in the water hyacinth are also discussed [97].

2.4.2.5 Mango Seed

Mango (Mangifera indica L.), belonging to the family Anacardiaceae, is one among the most
cultivated fruit in the world. Quite a lot of mango wastes are produced annually from
factories. Because mango is a seasonal fruit, and about 20% of fruits are processed for
products including puree, nectar, leather, pickles, and canned slices, among others, that have
worldwide popularity. At present the shell and its kernel are nothing but wastes having no
value. Since it is primarily lingo-cellulosic in nature, it would be interesting to use it as a
feed-stock for making activated carbon for adsorption of water pollutants including Cr (VI)

60
to save the woody biomass currently being used for producing activated carbon on a large
scale [98].

Figure-2.26 Mango Seed

2.4.2.6 Pine bark
Pine bark has a very porous surface. It is considered as a good adsorbent for airborne
pollutants, and therefore used for their biomonitoring and for studying some particular
phenomena such as the deposition of heavy metals from the atmosphere. For liquid phase
pollutants, pine bark is known to adsorb heavy metals. Pine bark qualified as a good natural
adsorbent for lindane and heptachlor, reaching average percentage removals high enough for
it to be considered as a potential alternative to activated carbon or other synthetic materials.
For heptachlor, pine bark adsorbed even more than activated carbon (93.6% versus 75%), in
contrast to lindane (80.6%) [99].

Figure-2.27 Pine bark

61
2.4.2.7 Fallen Leaves

Figure-2.28 Fallen Leaves

The potential of the fallen leaves of Platanus as a natural biosorbent was investigated for
adsorptive removal of methylene blue (MB) from aqueous solutions. Variables, including
solution pH, initial MB concentration, biosorbents dose and ionic strength, were investigate
to determine their effects on biosorption. The removal rate at pH = 7 is the maximum value
(95.23%). The extent of the MB removal increased with initial MB concentration, biosorbent
dose and ionic strength. Furthermore, the fallen leaves could be regenerated through the
desorption of MB in deionized water and reused to adsorb the dye again. The equilibrium
data could be well interpreted by Temkin isotherm followed by Langmuir and Freundlich
isotherms. Lagergren first-order, Ho second-order, and Weber and Morris intraparticle model
were used to explain the behavior of the adsorbent, and the kinetic data fitted well with Ho
second-order model. The values of activation energy were 14.26 kJ/mol, which indicated that
MB biosorption onto the leaves was mainly physical. The thermodynamics parameters: ΔG°,
ΔH°, and ΔS° were evaluated, which indicated the biosorption was a spontaneous,
endothermic process, meanwhile an increase in temperature was advantaged for leaves to
adsorb MB. The results of Fourier transform infrared spectroscopy showed that the
functional groups hydroxyl (–OH) and carboxyl (–COOH) may be potential biosorption sites
for MB dye [100].

62
2.4.2.8 Maize Husk
Adsorption of iron from aqueous solution by using maize husk (Zea mays L.) as a low-cost
adsorbent was studied. Batch experiments were carried out at ambient temperature, 0.075-
0.250 mm of particle size and 100 rpm of agitation speed to determine the influence of initial
pH, adsorbent dose, initial concentration and contact time on the removal of iron. Langmuir
and Freundlich models were applied to describe the adsorption isotherm of iron by maize

Figure 2.29 Maize Husk

husk. The results showed that optimum condition of iron removal were 4 of pH solution, 20
g/L of adsorbent dose, 10 mg/L of Fe concentration and 15 min of contact time of adsorption
with 0.499 mg Fe/g maize husk of adsorption capacity. Experimental data fitted well to
Langmuir's adsorption equilibrium isotherm within the concentration range studied. This
study demonstrated that maize husk, which is an agricultural waste, has potential for iron
removal from groundwater or other polluted waters [101].

63
2.4.2.9 Rice Husk

Rice husk, which is a relatively abundant and inexpensive material, is currently being
investigated as an adsorbent for the removal of various pollutants from water and
wastewaters. Various pollutants, such as dyes, phenols, organic compounds, pesticides,
inorganic anions, and heavy metals can be removed very effectively with rice husk as an
adsorbent. This article presents a brief review on the role of rice husk and rice husk ash in
the removal of various pollutants from wastewater. Studies on the adsorption of various
pollutants by rice husk materials are reviewed and the adsorption mechanism, influencing
factors, favorable conditions, etc., discussed in this article. It is evident from the review that
rice husk and its ash can be potentially utilized for the removal of various pollutants from
water and wastewaters [102].

Figure-2.30 Rice Husk

2.4.2.10 Straw
The aims of the current work are in large part the benefit of rice straw to be used as adsorbent
material and natural source of fiber in Fino bread. The rice straw was subjected to high
temperature for modification process and the chemical composition was carried out and the
native rice straw contained about 41.15% cellulose, 20.46% hemicellulose, and 3.91% lignin
while modified rice straw has 42.10, 8.65, and 5.81%, respectively. The alkali number was
tested and showed an increase in the alkali consumption due to the modification process. The
different concentrations of modified rice straw, aflatoxin B1, and pH were tested for removal
of aflatoxin B1 from aqueous media and the maximum best removal was at 5% modified rice
straw, 5 ng/mL aflatoxin B1, and pH 7. The modified rice straw was added to Fino bread at

64
a level of 5, 10, and 15% and the chemical, rheological, baking quality, staling, and sensory
properties were studied. Modified rice straw induced an increase of the shelf life and the
produced Fino bread has a better consistency [103].

Figure-2.31 Straw rice

2.4.2.11 Paper Industry Wastes

Paper and pulp industries consume huge amount of resources like wood and water every year
and creates large amounts of solid wastes and waste water that have to be treated. Different
forms of wastes are produced such as particle, solid, gas, and water during paper production.
The developed wastes are usually not treated properly and waste water is mostly allowed to
mix with water resources like river. So identification of some suitable methodologies to treat
these wastes in an environmental-friendly way and to extract the energy from these wastes
is the need of the day [104].Many researchers have investigated low-cost adsorption
materials including abundant natural materials such as clay and dried plants..Industrial
wastes are also considered as feasible candidates both in environmental and economic terms.
Agro-industrial wastes and municipal wastes are applied to remove from water. In particular,
agro-industrial wastes are intensively studied because they do not contain the harm element
such as heavy metal and chlorinated organics, which caused secondary pollution in the water.
In addition, there are plenty of bio-materials in agro-industrial wastes. These bio-materials
show high efficiency for the treatment of polluted liquid media. While there have been many
efforts on employing agro-industrial wastes, the paper industry has received relatively little
attention as adsorbent of heavy metal. The paper industry produces a number of by-products
in large quantities, which create serious disposal problems and degrade the surrounding
environment . Currently, they are disposed of through combustion or landfilling. Thus, the

65
use of paper industry wastes as low-cost adsorbents is attractive due to their contribution to
the reduction of costs for waste disposal.In addition, paper industry wastes include a number
of cellu-losic materials, lignin, lime, and so on. Organic substances such as cellulose and
lignin are now considered to be good potential adsorbent materials because they contain
oxygenated functional group [105].

Figure-2.32 Wastage Paper

2.4.3 Fruits peel of Pitali (Trewia nudiflora) as an adsorbent

The fruit peel of Trewia nudiflora is an untried, low cost, locally available biosorbent.The
tree's population is widespread in tropical countries such as Bangladesh.The powder of fruit
peel of Trewia nudiflora is an attractive adsorbent for wastewater treatment. The fruit peel
of Trewia nudiflora is relatively abundant and inexpensive material, is currently being
investigated as an adsorbent for the removal of various pollutants from water and
wastewaters. Various pollutants, such as dyes, phenols, organic compounds, pesticides,
inorganic anions, and heavy metals can be removed very effectively. Over the years, a major
thrust in the research area has been observed on exploring the heavy metal sorption potential
of various agricultural and waste biomass based materials due to their several advantages
like low cost,larger availability and higher efficiencies.Utilizing waste biomass of fruit peels
appear as viable and ecofriendly option for detoxification of harmful contaminants [106].

2.4.4 Properties of Pitali (Trewia nudiflora)

66
Plant contains a pyridine alkaloid, N-methyl-5-carboxamide-2-pyridone. Leaves contain
analkaloid, nudiflorine. Bark yields taraxerone and betasitosterol. Seeds contain an alkaloid
ricinidine. The seeds also contain a maytansinoid compound, trewiasine .6 It exhibited
significantcytotoxic activity against various human cell lines in vitro [107].

Figure -2.33 pitali fruits

2.4.5 Why pitali considered

• Locally available
• High adsorption capacity
• Environment friendly
• Cost effective
• Nonhazardous materials

67
 CHAPTER 3

MATERIALS AND METHODS

3.1 Chemicals and Apparatus Used

For laboratory experiments of adsorption process, some specified chemicals as well as
apparatus such as glass wares and instruments are used.

Table- 2 Chemicals are used

SL
Name of Chemicals View of Chemicals
No.

01 Sodium Hydroxide (NaOH)

02 Phophoric Acid (H3PO4)

03 Distilled Water

68
Table 3 Apparatus are used
SL
Name of apparatus View of apparatus
No.

01 Glass wares

02 Dryer

03 pH meter

04 Rotary flask shaker

69
05 Blender

06 Digital weight balance

07 UV-visible spectrophotometer

Fourier Transform Infra-Red

08
Spectrophotometer

09 Scanning Electron Microscopy

70
3.2 Preparation Methodology of Adsorbent
The endless supply of Pitali fruits are found in Northen part of Bangladesh especilly in
Chapainawabganj district.Because Pitali fruits have no significant application, they are
known as waste materials and are therefore available in large quantities at no cost.First of
all, the pitali fruits are collect from Norendrapur village under chapainawabgonj district.Then
it washed thoroughly to remove dirt and it adhered to unwanted particles. Then cut it into
small pieces and separates from peels.Small pieces were washed with distil water and
immersed in acidic (H3PO4) water for 8 hr. Later small pieces were neutralized by adding
molar solution of NaOH and kept in dryer for 18 hr at 120 oC. Then it was ground separately
using a blender. The powdered materials were sieved to obtain particles of required mesh
size. Then powdered were kept in a ball mill to make more fine particle.Then finaly it kept
in dryer at 100 oC for 5 hr to remove moisture and adsorbent stored into an air tight box.

3.3 Cumulative methodology of the Adsorption process

Getting ready the Congo Red Dye solution in a beaker with different concentrations and pH.
Outpouring the adsorbent powdered into the beaker and first shake gently. The beaker then
kept shaking in a rotary shaker for three hours. After the shaking was complete, filtration
took place and pure water was obtained

Outpouring in stirring frist

adsorbent dye solution gently

Shaking for 3.5

Pure water filtration hr

Figure 3.1-Overall Adsorption process methodology by using peels of pitali fruits

adsorbent

71
3.4 Preparation of congo red dye solution
Congo red (molecular weight: 696.665) is an anionic dye, was purchased from Merket . One
250 mLand five 50 ml beakers are cleaned by washing detergents. Then it is washed by
distilled water. To make various concentration of dye solution e.g. (2 ppm, 4 ppm, 6 ppm,
8ppm and 10 ppm) take 100mL distill water in a beaker. Now 10 gm of Congo red are used
into the beaker to make 100 ppm of dye solution. take 1 mL of 100 ppm solution in each of
five beakers. Now to make 2, 4 , 6, 8, and 10ppm of dye solution add 49ml, 24ml, 15.6ml,
11.5ml and 9ml of distill water is add in six beaker.Then in each beaker add 1ml of 100 ppm
solution.

3.5 Calibration Curve of Congo Red Solution

The synthetic dye sample calibrated in order to find out various optical densities at various
concentration. The calibrated results are very effective to identify the respective color
removal capacities of various adsorbents. Different concentrations of dye solutions are
prepared such as 2ppm, 4ppm, 6ppm, 8ppm, 10ppm. Each concentration is measured for its
absorbance value. These absorbance values are plotted against the concentrations. Then a
linear line is found from the calibration graph. The figure showing the graphical
representation of calibration of Congo red. Dye concentration was determined by using
absorbance values measured at 498 nm with UV-Visible spectrophotometer.

Calibration curve : Absorbance VS Conc.

0.4
0.344
0.35
0.289
0.3
0.25 0.21
Absorbance

0.2
0.139
0.15
0.1 0.057
0.05
0
0 2 4 6 8 10 12
Concentration
Figure-3.2 Calibration curve of congo red dye

72
3.6 Optimum Wavelength (λopt) Determination
Intended for finding optimum wavelength for UV analysis were carried out in this research
work. This is necessary because at the predetermined optimum wavelength, we can achieve
the best absorbance data of adsorption of dye. However, various sample e.g. (2ppm, 4ppm,
6ppm, 8ppm, 10ppm etc) were analyzed for obtaining this. These concentration of dye
solution took place into adsorption process in ambient condition of pressure, temperature,
dosages, time etc. After adsorption process determined value of the absorbance by using
UVvisible Spectrophotometer at various wavelength e.g. (395nm – 600nm) helps to
determine optimum wavelength.The optimum wavelength for congored is 498nm.

3.7 pH Neutralization of Adsorbent

pH neutralization of adsorbent is most important before
mixing with dye solution to get better result when adsorption
process goes through the change of pH of dye solution,
termed as effect of pH. To neutralize the adsorbent, its
beneficial to make the peels of pitali neutralized before
drying and grinding. So for neutralizing peels of pitali , used
100mL 0.01M HCl and 100mL 0.01M NaOH. By using the
droplets of these lower concentration of acid and base make
the peels of pitali neutral, which checked by pH meter.
Figure-3.3 pH Neutralization of
Adsorbent

3.8 pH of Dye Solution

To detect the effect of pH on adsorption process, there used
various pH of dye solution e.g. (pH 3,4,5,6,7,8,9). Mostly
Congo red dye solution with distill water shown around pH
6.2 to pH 7. For getting required pH, we used 100mL 0.01M
HCl and 100mL 0.01M NaOH for decreasing or increasing
the pH of the dye solution. pH points are observed by pH
meter. The color of Congo red dye solution changes blackish
to reddish with the change of pH 3 to pH 9. Then 50mg of
Figure-3.4 pH effect on
adsorbent added into every 50mL,100ppm Congo red dye Dye Solution

73
solutions of various pH e.g. (pH 3, 4, 5, 6, 7, 8, 9) and shaking around 3.5hrs. After that
filtration is completed, determine the optimum pH through the graph of Absorbance Vs pH.

3.9 Concentration of Dye Solution

To observe the effect of concentration on adsorption process, there used various
concentration of dye solution e.g. ( 50ppm,100ppm, 200ppm). To make these concentrations
of Congo red dye solutions taking 50mL distill water in each of six beakers. Now 5mg,
10mg, 20mg, of Congo red are used respectively into six beakers to make above
concentrations of dye solutions. Then 50mg of adsorbent added into every 50mL Congo red
dye solutions of various concentrations e.g. ( 50ppm, 100ppm, 200ppm) at optimum pH and
shaking around 3.5hrs. After that filtration is completed, determine the optimum
Concentration through the graph of Absorbance Vs Concentration.

3.10 Adsorbent Dosages

To observe the effect of dosages on adsorption process, there used various dosages of
adsorbent e.g. (100mg, 125mg, 150mg, 175mg, 200mg, 225mg,250mg, 300mg ) into every
50mL at optimum concentration, optimum pH and shaking around 3.5hrs. After completing
the shaking and completed filtration, determining the optimum dosage through the graph of
Absorbance Vs Dosages.

74
 CHAPTER 4

RESULTS AND DISCUSSION

4 Batch Adsorption Studies

4.1 Effect of pH
pH is an important parameter in the absorption process and it affected the absorption capacity,
dye solubility [109] , solution chemistry and the surface of the adsorbent [110] . The relation
between the initial pH of the solution and the percentage removal of congo red dye are shown
in following Figure 42 The dye removal is not significantly affected by pH over the whole
range explored and the removal percentage for both dyes was steady around 99%. [111]

99.8

99.7
Congored removal%

99.6

99.5

99.4

99.3

99.2
0 2 4 6 8 10
pH

Figure-4.1 Effect of different pH (.5gm, 100ppm, 50ml 3.5 hr were fixed)

on the removal of CR dye by using pitali fruits peel adsorbent.

From above Figure 4.1 the optimum pH considered at 4 for removal of CR dye by using
powdered ESM adsorbent.

4.2 Effect of Dosages:

75
The percent removal of CR increased with the increase in adsorbent dosage due to the
increase in adsorbent surface area as shown in following Figure 42. The maximum removal
rate of around 99% starting from 100 mg adsorbent in dye solution. After this point, further
increase in dosage brought countable staring increase in percent removal.

dose vs congo red removal%

100
95
90
congo red removal%

85
80
75
70
65
60
55
50
100 150 200 250 300
adsorbent dose (mg)

Figure-4.2 Effect of different adsorbent dosages,in mg (50ml, 100 ppm, 4

pH, 3.5 hr were fixed) on the removal of CR dye by using pitali fruits peel
adsorbent.

This may due to the increase of the adsorption sites [112]. From above Figure 4.2 shown
that sufficient adsorbent concentration provides sufficient surface area to interact with
particular amount of dye. So that the optimum 225mg of powdered eggshell membrane
considered as optimum dosage for removal of CR dye by using powdered pitali fruits peel
adsorbent.

4.3 Effect of Concentration

The percentage removal of dye is widely dependent on the initial dye concentration. The
impact of the initial dye concentration factor depends on the immediate relation between
the concentration of the dye and the available binding sites on an adsorbent surface [113].
First an increase in adsorption capacity with increase in dye concentration was observed.
This may be explained by the presence of more dye in solution available for binding onto

76
the active sites of the powdered pitali fruits peel adsorbent. Subsequently, the adsorption
reached to a saturation value from 150ppm at 99% removal, this can be due to the fact that
all adsorbents have a limited number of active sites and at higher concentrations the active
sites became saturated [114].

Concentration vs CR%
101

99
congored removal %

97

95

93

91

89

87

85
0 100 200 300 400 500 600 700
concentration ppm

Figure -4.3 ffect of different concentration of dye(50 ml, 4 pH, 3.5 hr, 225
mg were fixed) on the removal of CR dye by using pitali fruits peel
adsorbent.

From above Figure- 4.3 150 ppm considered as the optimum concentration for removal
of CR dye by using powdered pitali fruits peel adsorbent.

77
4.4 Effect of contact time

The percentage removal of dye is widely dependent on the contact time. Congo red removal
percentage is increase with increasing contact time.

100

90

80

70
cogored removal %

60

50

40

30

20

10

0
10 60 110 160 210 260
contact time (min

Figure 4.4 ffect of different time (50 ml, 4 pH, 100 ppm,, 225 mg were fixed) on
the removal of congo red dye by using pitali fruits peel adsorbent

From above Figure- 4.4 , 210 min considered as the optimum cotact time for removal of
congo red dye by using powdered pitali fruits peel adsorbent.

4.5 Langmuir Isotherm

The Langmuir isotherm model deals with a monolayer maximum adsorption capacity of the
adsorbent. This means that each site can take in only one molecule and it assumes constant
adsorption energy for all the active binding sites present on the adsorbent. In addition, the
adsorbed molecules cannot move across the surface or react with neighboring molecules
[82]. Langmuir model is expressed by following equation (4.1). [83].

78
 (4.1)

The linearized form of the Langmuir isotherm can be given by following equation (4.2).
[84]

(4.2)

where,

𝑞𝑒 = The amount of adsorbate adsorbed per unit weight of adsorbent at equilibrium (mg/g)
𝐶𝑒 = The dye concentration in the equilibrium solution (mg/L),

𝑞𝑚𝑎𝑥= The maximum adsorption capacity and

𝐾𝑏= The adsorption equilibrium constant (L/mg).

Figure 4.5 Langmuir Isotherm on the removal of congo

red dye by using adsorbent.

When Ce/qe is plotted against Ce, a straight line with slope 1/qmax and intercept of 1/qmaxKb
is obtained.

79
The fundamental characteristics of the Langmuir isotherm have been given by the
expression separation factor or equilibrium constant RL, which is defined by following
equation (4.3).

(4.3)

where

Co = The initial dye concentration

Kb = The Langmuir constant

Equilibrium constant RL signs the nature of adsorption as (Hameed et al., 2008):

RL > 1 (unfavorable), 0 < RL < 1 (favorable), RL = 0 (irreversible), and RL = 1 (linear) [85]

Table-04 The Langmuir adsorption isotherm and parameters

qmax R2 kb

43.47 mg/g 0.9926 1150.2

4.6 Freundlich Isotherm

The Freundlich equation or Freundlich adsorption isotherm, an adsorption isotherm, is an

empirical relation between the concentration of a solute on the surface of an adsorbent to
the concentration of the solute in the liquid with which it is in contact. In 1909, Herbert
Freundlich gave an expression representing the isothermal variation of adsorption of a
quantity of gas adsorbed by unit mass of solid adsorbent with pressure. This equation is
known as Freundlich adsorption isotherm or Freundlich adsorption equation. The
Freundlich isotherm is the closer relationship that depicts the sorption equation derived
empirically in 1912. Freundlich model is typically used when the surface of the adsorbent
is heterogeneous; Freundlich isotherm is expressed by following equation (4.4) [86].

(4.4)

80
 where, qe = The quantity of adsorbate adsorbed per mass unit of the adsorbent,

Ce = The equilibrium concentration of the adsorbate (mg/L),

KF = The affinity of the adsorbate towards the adsorbent (L/mg)1/n, 1/n = The adsorption
intensity or surface heterogeneity,

The value of 1/n ranges between 0 to 1, the adsorption becoming more heterogeneous as 1/n
value gets closer to zero. To determine the constants KF and 1/n, equation (2.4) can be
described by the linearized form as shown in followed equation (2.5) [86]

(4.5)

A plot of log qe versus log Ce results in a straight line with a slope of (1/n) and an intercept
(logKF).

K and n are constants for a given adsorbate and adsorbent at a particular temperature. At high
pressure 1/n = 0, hence extent of adsorption becomes independent of pressure. It is used in
cases where the actual identity of the solute is not known, such as adsorption of colored
material from sugar, vegetable oil etc.

Figure 4.6 Freundlich Isotherm on the removal of congo red

dye by using adsorbent.

81
 Table-05 The Freundlich adsorption isotherm and parameters

R2 n KF
0.3815 0.0093 0

4.7 pseudo-second-order kinetic

The pseudo-second-order kinetic rate equation is expressed as,
𝑑𝑞𝑡
= 𝐾2 (𝑞𝑒 − 𝑞𝑡 )2 4.6
𝑑𝑡

Where K2 is the pseudo-second-order rate constant (min g/mg), qe and qt represent the
amount of dye adsorbed (mg/g) at equilibrium and at time t.
Separating the variables:
𝑑𝑞𝑡
(𝑞𝑒 −𝑞𝑡 )2
= 𝐾2 𝑡 4.7

Where K2 is the rate constant of second-order adsorption. For the boundary condition t=0,
t=t
and qt=0, qt=qt the integrated and linear form of equation becomes,
𝑡 1 1
=𝐾 2 +𝑞 𝑡 4.8
𝑞1 2 𝑞𝑒 𝑒

Figure 4.7pseudo-second-order kinetic on the removal of congo red

dye by using adsorbent.

82
Table-06 pseudo-second-order kinetic model parameter

R2 K2 qe
0.9986 0.000586 80.51mg/g

Plots of t/qt versus t gave linear graphs from which qe and k2 were estimated from the slopes
and intercepts of the plot different concentrations. The R2 values were as high as 0.9986 The
good agreement shows that the pseudo-second order kinetic equation fits and the adsorption
data well.

4.8 Pseudo-First-Order Kinetic Model

It is given by equation is below:

Log (Qe − Qt ) = log Qe − (k1∕2.303)t 4.9

Where: qt and qe are the amount of solute sorbed per mass of sorbent (mg g−1) at any time
and equilibrium, respectively, and k1 is the rate constant of first-order sorption (min−1). The
straight-line plot of log (qe − qt) against t gives log (qe) as slope and intercept equal to
k1/2.303. Hence the amount of solute sorbed per gram of sorbent at equilibrium (qe) and the
first-order sorption rate constant (k1) can be evaluated from the slope and the intercept.

Table-07 pseudo-frist -order kinetic model parameter

R2 K1 Qe

0.746 0.0176 4.7mg/g

83
 Figure 4.8 pseudo-frist -order kinetic on the removal of congo red dye
by using adsorbent

In this investigation, we had optimized pH at 4, concentration at 150 ppm, adsorbent dosages

225 mg, and contact time was 210 min.Pitali fruits peel adsorbent was demonstrated as a
cost-effective adsorbent for the removal of congo red dye from aqueous solution. pH, initial
concentration, adsorbent dosages and contact time have been optimized for the maximum
recovery of the dye. It is a reactive dye. So, it becomes more effective at lower pH. Maximum
percent removal of dye has been found at pH 4. Dye concentration also manipulate the
absorbance process. Dye removal percentage decreases with increasing the concentration of
dye. Initial concentration has been optimized at 150 ppm. Amount of the absorbent doses are
directly proportional to the dye removal percentage. Optimum adsorbent dosage has been
found 225 mg. Similarly, with increase of interaction time the dye removal percentage rises.
Time has been optimized at 210 minutes. Kinetic study of the adsorption process was
performed and fitted well with pseudo second-order kinetics and Langmuir Isotherm.

84
 CHAPTER 5

Conclusions and Recommendations

5.1 Conclusion
The chemically modified Pitali fruits peels adsorbent is an effective material that could be
used as low cost adsorbent to remove anion and cationic dyes (like Congo red) from water
and wastewater at low concentration and short time. The dye concentration, the pH of dye
solution, the temperature and the particle size of adsorbent were found as the more effective
factors affecting the adsorption process. There is a need for new researches to develop more
application on Pitali fruits In this paper, investigation of the equilibrium sorption was carried
out at pH 4, 150 ppm, 3.5 hr. Other physico-chemical parameters were determined and two
adsorption isotherm models were studied. The sorption data fitted into Langmuir, Freundlich
isotherms out of which Langmuir Adsorption model was found to be have the highest
regression value and hence the best fit. It could be concluded Pitali fruits peels adsorbent is
a potential and active adsorbent for removal of Congo red dye from its aqueous solution and
industrial waste water remediation.

5.2 Future Work and Recommendation

For the future work, optimization of other parameters such as particle size, adsorbent surface
area, temperature, flowrate, pressure and agitation speed could be carried out in order to
achieve higher percentage of dye removal. Pitali fruits peels adsorbent has been found to be
effect for dye removal. Investigations need to be carried out to know how effective it is for
metal particles removal. Pitali fruits peels adsorbent is optimized at average concentration.
Investigations need to be carried out for lower and higher concentration. The main issue of
adsorption process for dye removal is to utilize the natural adsorbent particles. For this
regard, more and more research should be carried out for a vast use of natural substances.The
environmentally-friendly techniques are to be suggested such as “Green Technology”.But
the main drawback of such kind of work is that there is no application even in pilot plant or

85
commercial use. Attempt should be taken to move the dye adsorption process to an industrial
scale.

86
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