ADSORPTION OF METHYL ORANGE FROM AQUEOUS

SOLUTION BY ZEOLITE Y SYNTHESIZED FROM KAOLIN

BY

ETEMIRE OGHENEFEJIRO JESHURUN EDITOR

15BB003937/1500092

AN UNDERGRADUATE RESEARCH PROJECT SUBMITTED TO

THE DEPARTMENT OF CHEMICAL ENGINEERING

LANDMARK UNIVERSITY, OMU-ARAN KWARA STATE.

THE PROJECT WAS SUBMITTED TO THE DEPARTMENT OF

CHEMICAL ENGINEERING, LANDMARK UNIVERSITY, OMU-
ARAN KWARA STATE.

IN PARTIAL FULFILMENT OF THE REQUIREMENT FOR AN

AWARD OF THE DEGREE OF BACHELOR OF ENGINEERING
(B.Eng.) IN CHEMICAL ENGINEERING.

24th SEPTEMBER 2021.

 DECLARATION

I, Etemire OgheneFejiro Jeshurun Editor, with matriculation number

15BB003937, hereby declare that this research project was carried out by me and

conducted solely under the supervision of and Engr. John Adeoye, Department of

Chemical Engineering, College of Engineering, Landmark University, Omu-Aran

Kwara State. All materials are fully acknowledged in the references.

ii
 CERTIFICATION

This is to certify that the project entitled “ADSORPTION OF METHYL ORANGE FROM

AQUEOUS SOLUTION BY ZEOLITE Y SYNTHESIZED FROM KAOLIN” is an

authentic work done to meets the regulations governing the awards of the degree of bachelor

of engineering in chemical engineering of Landmark University, Omu-Aran, Kwara state.

______________________________ ______________________________

ENGR J.B. ADEOYE DATE

(PROJECT SUPERVISOR)

______________________________ _____________________________

ENGR OSHIN A. TEMITOPE DATE

(PROJECT COORDINATOR)

______________________________ ______________________________

DR B.S. FAKINLE DATE

(HEAD OF DEPARTMENT)

iii
 DEDICATION
I dedicate this report to the almighty God, without whom none of this would have made

possible Special recognition goes to my parent, for their support and unending care. My

sincere gratitude goes to my supervisor ENGR J.B ADEOYE for his encouragement,

guidance, and patience during this research. work is dedicated to God Almighty, my wisdom,

inspiration, and strength, without whom none of this would have been made possible.

iv
 ACKNOWLEDGMENT
I express my deep gratitude to God almighty who saw me throughout my time in carrying out

this research project and I also want to express my gratitude to my amazing and supportive

family, my parents, Engr. and Mrs. Etemire Editor for their love, unending support, and

constant prayers and guidance over the years. My sincere appreciation goes to my supervisor

Engr. John Adeoye and Engr Anthony Okojie for their constructive criticism, inspiring

guidance, valuable and indispensable contributions throughout this project work. Also, I

would like to thank the Head of the department of Chemical Engineering, Dr. B.S. Fakinle

for his assistance and encouragement.

I am also grateful to the entire lecturing and technical staff of the Department of Chemical

Engineering, Landmark University.

v
 ABSTRACT
This study was carried out on the removal of Methyl Orange dye from an aqueous solution

using an effective adsorbent Zeolite Y. The uptake capacity of the adsorbent for the removal

of Methyl Orange dye from an aqueous solution was investigated in a batch adsorption

process. The zeolite was synthesized and characterized by Brunauer Emmet Teller (BET)

surface analysis, Fourier Infrared Spectroscopy (FT-IR), Energy Dispersive X-Ray analysis

(EDX), X-Ray Diffraction Analysis (XRD), Transmission Electron Microscopy (TEM),

Thermographic Analysis (TGA) and scanning electron morphology (SEM) for the surface

area of 445.360 m2/g, 30.3542 Å, 0.603567 cm3/g, functional group, and surface morphology.

The operation parameters tested to determine the adsorption efficiency were initial dye

concentration, temperature, adsorbent dosage, pH, agitation speed. The result showed that

adsorption of methyl orange was found to attain an equilibrium position in 60 minutes for the

range of concentration studied. The result also showed that the experimental data fitted best

to Langmuir isotherm with a monolayer adsorption capacity of 150.277 mg/g. The collected

Kinetic data showed that the pseudo second-order model best described the adsorption

process.

vi
 TABLE OF CONTENTS

DECLARATION ii
CERTIFICATION iii
DEDICATION iv
ACKNOWLEDGEMENT v
ABSTRACT vi
CHAPTER ONE 1
INTRODUCTION 1
1.1 Back of Study 1

1.2 Research Problem 4

1.3 Research Question 4

1.4 Significance of Research 5

1.5 Aim and Objectives 5

1.6 Delineation of Research 5

CHAPTER TWO 7
LITERATURE REVIEW 7
2.1.0 Dye and Wastewater 7
2.1.1 Sources of Dye and their Classification 7
2.1.2 Removal of Dye 8
2.1.3 Biological Dye Removal Method 8
2.1.4 Chemical Dye Removal Method 9
2.1.5 Physical Dye Removal Method 9
2.1.6 Efficiency of Dye Removal Method 10
2.2.0 History of Methyl Orange 11
2.2.1 Properties of Methyl Orange 11
2.3.0 Purification of Wastewater 12

vii
2.3.1 Filtration 13
2.3.1.1 Types of Filtration 13
2.3.2 Precipitation 14
2.3.2.1 Limitations of Precipitation 15
2.3.3 Coagulation 16
2.3.3.1 Factors Affecting Coagulation 21
2.3.3.2 Limitations of Coagulations 21
2.3.4 Flocculation 21
2.3.4.1 Flocculant 23
2.3.4.2 Mode of Operation 23
2.3.4.3 Application of Flocculation 24
2.3.5 Ozonation 24
2.3.5.1 Effect of Ozonation 25
2.3.5.2 Operation Maintenance and Cost Consideration 28
2.3.5.3 Application of Ozonation 28
2.3.5.4 Health Aspect of Ozonation 29
2.3.6 Reverse Osmosis 29
2.3.6.1 History of Reverse Osmosis 31
2.3.6.2 Application of Reverse Osmosis 32
2.3.7 Adsorption 32
2.3.7.1 Adsorption Mechanism 36
2.3.7.2 Types of Adsorption 36
2.3.7.3 Factors Affecting Adsorption 37
2.3.7.4 Adsorption Description 38
2.3.7.5 Application of Adsorption 38
2.3.7.6 Adsorption Process 39
2.3.7.7 Adsorbent 40
2.3.7.8 Adsorption Isotherm 40
2.3.7.8.1 Freundlich Adsorption Isotherm 40

viii
2.3.7.8.2 Langmuir Isotherm 45
2.3.7.8.3 Temkin Isotherm 45
2.3.7.8.4 Dubinin Radushkevich Isotherm Model 46
2.3.7.8.5 Brunauer, Emmett and Teller Isotherm 47
2.3.7.9 Adsorption Solution Phase 47
2.4.0 Zeolites 47
2.4.1 Basic of Zeolites 48
2.4.1.1 Natural Zeolites 48
2.4.1.2 Synthetic Zeolites 48
2.4.2 Properties of Zeolites 49
2.4.2.1 Physical Properties 49
2.4.2.2 Chemical Properties 49
2.4.3 Ion Exchange and Adsorption Properties 49
2.4.3.1 Mineralogical Properties 52
2.5.0 Factor Affecting the Removal of Azo Dye 52
2.5.1 Effect of pH 52
2.5.2 Effect of Contact Time 53
2.5.3 Effect of Temperature 53
2.5.4 Effect of Initial Concentration 53
2.5.5 Effect of Adsorbent Dosage 53
2.5.6 Effect of Kinetics 54
2.6.0 Adsorption Kinetics Model 54
2.7.0 Adsorption Thermodynamics Study 56
CHAPTER THREE 57
MATERIALS AND METHODOLOGY 57
3.1 Materials 57
3.2 Instrumentation/Apparatus 57
3.3 Methodology 57
3.4 Methodology Block Flow Diagram 59

ix
CHAPTER FOUR 60
DISCUSSION OF RESULT 60
4.1 Zeolite Y Characterization 60
4.1.1 X-Ray Diffraction Analysis on Zeolites Y 74
4.2 Effect of Operation Parameter on Adsorption 76
4.2.1 Effect of Temperature 76
4.2.2 Effect of Initial Dye Concentration and Adsorption Time 78
4.2.3 Effect of pH 84
4.2.4 Effect of Adsorbent Dosage 86
4.2.5 Effect of Agitation Speed 88
4.3 Adsorption Isotherm 90
4.4 Adsorption Kinetics 94
CHAPTER FIVE 98

CONCLUSION AND RECOMMENDATION 98

5.1 Conclusion 98
5.2 Recommendation 99
REFERENCES 100

x
 LIST OF FIGURES
Figure 1.0 – Methyl Orange Chemical Structure 3
Figure 2.0 – Process of Coagulation, Flocculation and Sedimentation 17
Figure 2.1 - Wastewater Treatment System of Ozonation Process 27
Figure 2.2 – Reverse Osmosis Process 30
Figure 2.3 – Adsorption Process 34
Figure 2.4 – Adsorption Isotherm 42
Figure 2.5 – Freundlich Isotherm 44
Figure 2.6 – Ion Exchange and Adsorption Properties 51
Figure 3.0 – Adsorption of Methyl Orange Block Flow Diagram 59
Figure 4.1.1 – SEM image before adsorption 61
Figure 4.1.2 – SEM image after adsorption 62
Figure 4.1.3 – EDX before Adsorption 64
Figure 4.1.4 – EDX after Adsorption 65
Figure 4.1.5 – Thermographic Analysis 66
Figure 4.1.6 – Transmission Electron Microscope 67
Figure 4.1.7 – FTIR of Synthesized Zeolite Y (Before) 71
Figure 4.1.8 – FTIR of Synthesized Zeolite Y (After) 73
Figure 4.1.9 – X-ray Diffraction Analysis of Synthesized Zeolite Y (before) 75
Figure 4.2.0 – Temperature Effect on Adsorption Capacity of Methyl Orange Dye 77
Figure 4.2.1– Effect of Initial Dye Concentration and Time on Methyl Orange at 293K 79
Figure 4.2.2 – Effect of Initial Dye Concentration and Time on Methyl Orange at 303K 80
Figure 4.2.3 – Effect of Initial Dye Concentration and Time on Methyl Orange at 313K 81
Figure 4.2.4 – Effect of Initial Dye Concentration and Time on Methyl Orange at 323K 82
Figure 4.2.5 – Effect of Initial Dye Concentration and Time on Methyl Orange at 333K 83
Figure 4.2.6 – Effect of pH on Methyl Orange Dye Adsorption 85
Figure 4.2.7 – Effect of Adsorbent Dosage on Methyl Orange Dye Adsorption 87

xi
Figure 4.2.8 – Effect of Agitation Speed on Methyl Orange Dye Adsorption 89
Figure 4.2.9 – Langmuir Isotherm at Different Temperature unto Methyl Orange Dye 92
Figure 4.3.0 – Freundlich Isotherm at Different Temperature unto Methyl Orange Dye 93
Figure 4.3.1 – Pseudo 1st Order Kinetics of Methyl Orange Dye at 293K 96
Figure 4.3.2 – Pseudo 2nd Order Kinetics of Methyl Orange Dye at 293K 97

xii
 LIST OF TABLES
Table 1.0: Settling Time for Particles of Various Diameters 18
Table 1.1: Advantages and Disadvantages of Coagulation 20
Table 1.2: Different Between Absorption and Adsorption 35
Table 1.3: Physiochemical Analysis of Zeolite Y Produced from Arobieye Kaolin 69
Table 1.4: FTIR Analysis Result for Zeolite Y (Before) 70
Table 1.5: FTIR Analysis Result for Zeolite Y (After) 72
Table 1.6: Langmuir and Freundlich Isotherm Model Parameters for the Adsorption of
Methyl Orange Dye
91
Table 1.7: Kinetic Model Constant with the Correction Coefficient for Methyl Orange Dye
Adsorption 95

xiii
xiv
 CHAPTER ONE
1.0 INTRODUCTION

1.1 BACKGROUND OF STUDY

Colored sewage is as a consequence of dye usage in the several industries including dye

manufacturing, textile industry, pulp and paper processing, leather tanning, battery

production, and so on (Politi and Sidiras, 2012). Many dyes and their breakdown products

have wide adverse effects for living organisms. Moreover, the colored wastewater reduces

light penetration and then affects the photosynthetic activity of aquatic organisms (Yang et

al., 2015). Azo dyes are an interesting class of compounds that are widely applied in chemical

applications and industries. Although azo dyes are not strongly toxic, they can cause

hypersensitivity and allergy; therefore, the presence of these dyes in water is highly

undesirable (Deligeer et al., 2011; Ling et al., 2016). Hence, disposal of untreated effluents to

the surrounding environment often leads problems for aquatic life and humans. To prevent

any potential hazards, an effective treatment of these industrial wastewaters is needed before

being discharged into the environment. Furthermore, removal of the azo dyes from the

effluent is difficult because they are not easily degradable or removable by conventional

wastewater treatments (Haris et al., 2010). Response surface methodology (RSM) is a set of

statistical and mathematical technique for designing experiments, building models, evaluating

the relative significance of several independent variables, and determining optimum

conditions for desired responses (Wantala et al., 2012). In literature, RSM based on central

composite design (CCD) has been used in different applications of engineering including

heavy-metal removal, dye removal, biofuel production, etc. (Auta and Hameed, 2011; Betiku

and Taiwo, 2015; Dora et al., 2013; Skorupskaite et al., 2015). However, this is the first study

on the optimization of methyl orange (MO) adsorption. Therefore, we decided to evaluate the

1
MO removal potential under various operating conditions such as pH, initial MO

concentrations, and sorbent dosage. The parameters for maximum removal efficiency are

optimized by using CCD with RSM under (Design Expert. 7.0) software. The

physicochemical characteristics of SBB are evaluated by Fourier transform infrared

spectroscopy (FT-IR) and scanning electron microscopy (SEM). Moreover, Langmuir and

Freundlich isotherms were applied to the equilibrium data to describe the main interactive

mechanisms involved the removal process. Kinetic parameters were also calculated from the

pseudo first-order and pseudo second-order models. Furthermore, thermodynamic parameters

(enthalpy, entropy, and adsorption free energy), were calculated for better description of the

adsorption mechanism. Methyl Orange is C14H14N3NaO3S with melting point 300⁰c [572 ⁰f,

573k]. Various physical–chemical methods have been employed for the removal of dyes from

wastewater, including filtration, flocculation, ozonation, reverse osmosis, adsorption,

precipitation, coagulation, and photo-degradation (Akansha, K et al., 2019). Among these, the

adsorption technique is the most competitive method, with a number of advantages, such as

low cost, high efficiency, and simple operation (Alghamdi, A.A et al., 2019). In this

technique, different adsorbents from various sources are explored to find the best material,

subsequently, a convenient adsorption system is built. These adsorbents are comprised of

microorganisms, activated carbon, zeolite, biomasses, polymers, and polymer-based

adsorbents (Zhao, L. et al., 2010). Among the available adsorbents, activated carbon is the

most effective owing largely to its high surface-area, internal porous structure, and varying

surface functional group, as well as its simplicity, high efficiency, and cost-effectiveness

(Chen, D. et al., 2011).

2
Figure 1.0 Methyl Orange Chemical Structure

3
1.2 RESEARCH PROBLEM

Dye pollution is a global issue owing to the hazardous nature of dyes. It is considerably

visible in the environment, as dyes are commonly highly water-soluble and not readily

degradable under natural conditions, resulting in a relatively long-time residence in the

environment. Therefore, the removal of dyes from various toxic effluents has become of

special concern to environmental specialists. Azo dyes such as methyl red and methyl orange

(MO) are well known to be human carcinogens (Hildenbrand et al., 1999), that pervade aqua

systems from various sources, including textile, pharmaceutical, and printing industries, as

well as medical and chemical labs. Although most dyes are not highly toxic, they should be

recognized as visual pollutants that can reduce light penetration into water, consequently

decreasing the efficiency of photosynthesis and affecting the growth of aquatic organisms

(Huang, J.-H et al., 2008). Moreover, dye pollution presents aesthetic changes that are

harmful in the natural environment. Methyl orange (MO) is an anionic, water-soluble (5 g/L,

H2O, 20oC) azo dye, which can function as a weak acid having an approximate pH of 6.5

when dissolved in water. Besides its use for industrial coloring, it also serves as a pH

indicator in various laboratories, with a red to yellow color-change range of 3.1–4.4. MO is a

sulfonated azo dye, and the functional groups that are responsible for their bright color in

water make them difficult to remediate through conventional methods. Dyes bearing aromatic

amines in their chemical structures are carcinogenic due to the production of benzidine

compounds via biotransformation (Akansha, K et al., 2019).

1.3 RESEARCH QUESTION

In this study there are some questions that comes with it, some are listed below;

 Why the use of Zeolite Y? (why not activated carbon or any other thing?)

 Why use Zeolite Y obtained from Kaolin?

 Why adsorption?

4
1.4 SIGINIFICANCE OF RESEARCH

 To get high water quality that is highly essential for human life, aquatic life and the

whole earth ecology system.

 Achievement of high quality and essential treatment for dyes and generated colored

waste water hereby reducing the danger to the environment.

 Adsorption of dyes from aqueous solution has proven to be an excellent approach to

treating effluents as well as a cost-effective technique compare with other methods

(Lotfi Mouni et al., 2018).

1.5 AIM AND OBJECTIVES

Aim

 This research is aimed to remove methyl orange from aqueous solution using zeolite

Objectives

This aim will be achieved via the following objectives;

i. To evaluate the potential of the synthesized zeolite Y as an adsorbent for adsorption

of dye (methyl orange).

ii. To determine the effect of constant time, pH, concentration, temperature, adsorbent

dosage and adsorbate.

iii. To correlate the equilibrium adsorption data with adsorption isotherm, kinetic study

and thermodynamics of adsorption system.

1.6 DELINEATION OF RESEARCH

The study is aimed specifically at determining if Zeolite Y obtained from Kaolin can be used

to remove Methyl Orange Dye from aqueous solutions via adsorption. The adsorbent Zeolite

Y obtained from Kaolin was pre-prepared whereas the adsorbate Methyl Orange Dye was

5
acquired from Landmark project research laboratory and it was used for the experiment

without further purification. Zeolite Y was chosen because for one thing, it possesses wider

inner cavities which allows adsorption to take place more effectively and efficiently. Zeolite

Y obtained from Kaolin was selected because in Nigeria, Kaolin deposits are found

abundantly in almost every part of the country which points to ease of access and ready

availability.

6
 CHAPTER TWO

2.0 LITERATURE REVIEW

2.1.0 DYES AND WASTEWATER

Dyes are coloured substances that are commonly used to dye goods in the clothing, printing,

rubber, cosmetics, plastics, and leather industries, resulting in a significant amount of

coloured wastewater. Anionic, cationic, and non-ionic dyes are the most common

classifications. Textile industries ranked first in the use of dyes for fibre coloration out of all

the industries that use dyes. Dyeing is the process of attaching chemical compounds to fabrics

or surface shells in order to impart colour. Since colours are water dissolvable and make

exceptionally splendid tones in water with acidic properties, depolarization of waste water

from material and assembling businesses is a significant test for natural supervisors. It is

assessed that the material and assembling businesses use more than 10,000 monetarily

accessible (around the world) colours, with colour utilization in the material business arriving

at 1000 tons each year, and around 10-15% of these colours being released into squander

streams as effluents during colouring measures. (Gopinath R. et al, 2016).

2.1.1 SOURCES OF DYES AND THEIR CLASSIFICATION

Dyes are primarily gotten from characteristic sources with no compound treatment like

plants, bugs, creatures and minerals. Dyes got from plant sources are indigo and saffron, bugs

are cochineal bugs and lac scale creepy crawlies, creature sources are gotten from certain

types of molluscs or shellfish, and minerals are ferrous sulfate, ochre. Enterprises like

material, printing, paper, floor covering, plastic, and cowhide use dyes to give tone to their

7
items. These dyes are constantly left in modern waste and therefore released into the water

body. Dyes discharge into squander water from different modern outlets, like paper, food

shading, beautifying agents, cowhide, drug, dyeing, printing, cover enterprises and so forth.

The textile and dyeing ventures use more amounts of an enormous number of dyes and

delivery these dye poisons into climate as waste water effluents. These dyes are profoundly

poisonous and surprisingly cancer-causing to microbial populaces and mammalian creatures

henceforth these are expected to eliminate from the water effluents before they are delivered

into water bodies. Dyes are steady to light and not naturally degradable; they are impervious

to oxygen consuming assimilation and connote one of the troublesome gatherings to be

eliminated from the modern wastewater (Gopinath R. et al, 2016).

2.1.2 REMOVAL OF DYES

Currently, various dye removal techniques have been discovered in numerous research papers

claiming success in dye removal. Even though quite a number of them can be applied, they

all haven’t been successful or even good enough to be practiced because of their numerous

disadvantages. A proper removal method should be able to effectively remove a large amount

of dye from wastewater within very little time without producing secondary pollution (V.

Katheresan et al, 2018). Existing methods of dye removal can be separated into three

categories namely the biological, chemical, and physical treatments. Although many dye

removal methods have been researched in the past 30 years, only several are truly being

implemented by the concerning industries these days because of limitations posed by

majority of the methods.

2.1.3 BIOLOGICAL DYE REMOVAL METHODS

In many nations, the normal natural technique is the usually and broadly used dye evacuation

strategy to treat dye wastewater. By and large known as the ordinary strategy, a mix of high-

8
impact and anaerobic cycle is done before dye effluents are delivered to the climate. This

technique was picked as the go-to dye expulsion strategy fundamentally in light of the fact

that it is modest and can be cultivated without any problem. Indeed, this treatment alone is

inadequate to totally eliminate dangerous particles from material dye wastewater which is the

reason shaded water is as yet found in the climate. Albeit the regular technique treats the

synthetic oxygen request present in the wastewater, it doesn't make the water sans dye or

poisonous free. Other than this technique, other traditional organic dye expulsion strategies

are adsorption by microbial biomass, green growth debasement, catalyst corruption,

contagious societies, microbial societies just as unadulterated and blended culture.

2.1.4 CHEMICAL DYE REMOVAL METHODS

Chemical dye removal are techniques using science or its speculations in achieving dye

expulsion. Customary chemical dye removal methods are progressed oxidation measure,

electrochemical obliteration, Fenton response dye removal, oxidation, ozonation,

photochemical and bright illumination. The majority of the chemical dye removal methods

are exorbitant contrasted with biological and physical dye removal methods with a special

case for the electrochemical debasement dye evacuation strategy. Chemical dye removal

methods are additionally monetarily ugly, requires explicit gear and requires high electrical

energy. High electrical energy is needed to control hardware or reactors in which chemical

dye evacuation happens. Other than that, chemical just as reagent utilization for an enormous

scope is an issue ordinarily detailed by clients of chemical dye eliminating strategies. Another

unwanted attribute of this technique is the age of harmful optional contamination coming

about toward the finish of a chemical dye expulsion measures introducing an extra removal

issue.

2.1.5 PHYSICAL DYE REMOVAL METHODS

9
Physical dye removal methods are normally direct methods ordinarily cultivated by the mass

exchange component. Customary physical dye removal methods are adsorption, coagulation

or flocculation, particle trade, illumination, layer filtration, nano filtration or ultra-filtration

and opposite assimilation. Among the three methods (biological, chemical and physical),

parts of physical dye removal are the most generally utilized methods. These methods are

frequently picked for its effortlessness and proficiency. By a long shot, this method requires

minimal measure of chemicals contrasted with the biological or chemical dye removal

methods (Sung Hwa Jhung et al, 2018). This method doesn't manage living creatures

subsequently is viewed as more unsurprising than the other two dye removal methods.

2.1.6 EFFICIENCY OF DYE REMOVAL METHODS

Chemical dye removal methods had the highest dye removal percentages, ranging from

88.8% to 99.9%. Chemical dye removal methods, on the other hand, frequently have

unacceptable drawbacks. Aside from that, chemical dye removal methods, with the exception

of emerging electrochemical destruction technologies, are pH-dependent and, in most cases,

generate secondary emissions. Chemical dye removal methods should not be considered for

dye removal if necessary due to the high weightage of drawbacks. Biological and physical

methods of dye removal are both effective. The enzyme degradation method ranks first on the

list of biological dye removal methods, with a removal percentage ranging from 76 to 90.1

percent. The enzymatic dye degradation method is a good and effective way to get rid of dye.

This technique is low-cost, efficient, non-toxic, and, most importantly, reusable. Its only

downside is the unpredictability of enzyme processing, but this can be easily remedied by

selecting the right raw material and extraction process. Physical dye removal methods have a

removal percentage ranging from 86.8 to 99% with the adsorption method ranking highest on

the list. The adsorption dye removal method is an excellent dye removal method that can

quickly degrade almost any dye or dye mixture. The adsorption process, like the enzyme

10
degradation method, can be repeated several times before the adsorbent is exhausted. The

only drawback to this method is that some adsorbents can be very expansive due to the

method's inherently high performance. This problem can be addressed by using low-cost raw

materials to create alternative adsorbents. Given the effectiveness of both enzyme

degradation and adsorption in dye removal, incorporating these approaches into a single dye

removal technique should be considered in the future.

2.2.0 HISTORY OF METHYL ORANGE

Methyl orange (MO) is one of the most common indicators used in analytical chemistry to

determine pH and titration thresholds. Analytical chemistry requires both qualitative data to

accurately describe the composition, chemical properties, and molecular structures of

substances.MO is commonly used as a qualitative pH indicator. Its preferred IUPAC

[International Union of Pure and Applied Chemistry] name is sodium 4-{[4-(dimethylamino)

phenyl] diazinyl} benzene-1-sulfonate. These are technical names that indicate the

composition and molecular structure of the substance. MO is an organic compound that

doesn’t permanently react with acids or bases, but instead changes colour from red to orange

and finally yellow in an aqueous acidic solution. It’s effective pH range as an indicator in

aqueous solutions is from pH 3.1 to 4.4. The gradual change in colour is only effective in

aqueous acidic solution. Beyond the range, it’s impossible to know if the solution is still

acidic, neutral, or basic. The accuracy of MO varies depending on several factors such as

temperatures and any solvents that are present. For instance, this indicator has a pKa of 3.47

in water at 25oC. Temperature is a crucial factor in determining the accuracy because the

speed of the molecules in a solution is dependent on the temperature. Acidic solutions tend to

dissociate better ions in solution have higher temperature. MO has an organic compound of

11
carbon, hydrogen, nitrogen, sodium, oxygen and Sulphur. Its chemical formula is

C14H14N3NaO3S (Sandberg et al., 1972).

2.2.1 PROPERTIES OF METHYL ORANGE

i. It has a density of 1.28g/cm3

ii. It has molar mass of 327.33g/mol
iii. It has an appearance of orange or yellow solid
iv. It has a melting point of 300oC and boiling point (Decomposes)
v. It is soluble in water and insoluble in diethylether
vi. It has a pH of 3.0 to 4.4, pink to yellow

2.3 PURIFICATION OF WASTEWATER

Purification of water can be achieved by using a variety of methods including coagulation,

flocculation, ozonation, reverse osmosis, and adsorption [Goncalves et al., 2013]. The

method of choice is determined by the type of contaminant to be removed. Several water

contaminants/pollutants are chemicals that are useful in industries like pharmaceutical, food,

laboratory printing and textile industries [Kaur, and Datta, 2011; Negrulescu, 2014; Raha et

al., 2012; Kim et al., 2012; Bernal et al., 2013]. Organic compounds are major pollutants used

in the mentioned industries especially the synthetic dyes. A variety of azo dyes find use in the

food and textile industries. However, most of these dyes are highly carcinogenic even when

present in minute quantities. Methyl orange is a carcinogenic water-soluble azo dye which is

widely used in textile industries, in manufacturing printing paper, and in research

laboratories. It is also metabolized into aromatic amines by intestinal microorganisms [Yang

et al., 2012; Zhang and Fang, 2006]. Methyl orange is stable, shows low biodegradability and

is soluble in water hence it is difficult to remove from aqueous solutions by common water

purification/treatment methods [Suciu et al., 2012]. Clays contain minerals which are

responsible for their properties. Clay minerals are widely used in several industries and fields

such as in polymers nano-composites adsorbents fields, in heavy metal ion adsorption,

ceramics, and paper fillings [Chen et al., 2012; Du, J.Y 2011; Michalkova and Leszczynski,

12
2011]. These minerals are made up of tetrahedral and octahedral layers and hence they are

characterized by the ratio of this sheets/ layers in the structure. A clay made up of 2

tetrahedral sheets and 1 octahedral sheet it is referred to as a 2:1 clay type (3 sheets) while

those with 1 octahedral sheet and 1 tetrahedral sheet are called 1:1 (2 sheets) clay types

[Rajkumar and Behera, 2012; Srivastava and Ingle, 2011; Nasser, 2014; Novikova, 2013;

Tian and Chen, 2011; Ozkan and Oyman, 2010; Perri, 2014]. Clay minerals in soil may play

a role in scavenging of pollutants from water. The commonly used clays include

montmorillonite, semectites kaolinite and illite.

2.3.1 FILTRATION

Filtration is one of the core stages of water and wastewater treatment every industry

professional should know about and understand. Filtration is the process in which solid

particles in a liquid or gaseous fluid are removed by the use of a filter medium that allows the

fluid to pass through while retaining the solid particles. Filtration may mean the use of a

physical barrier, chemical, and/or a biological process. The removal of particles takes place

with processes including: straining, flocculation, sedimentation and surface capture. Basic

requirements for filtration are: a filter medium (thin or thick barriers); a fluid with suspended

solids; a driving force to cause the fluid to flow; and the filter that holds the filter medium,

contains the fluid, and permits the application of force. In the water industry, clarified water

is the goal of the filtration process. Filtration primarily is used for storm water, wastewater,

and drinking water applications, but it also has uses in industrial manufacturing, power

plants, food and beverage production facilities, mining and other heavy-duty applications.

Water can remove or reduce the concentration of suspended particles, parasites, bacteria,

algae, viruses, fungi, and more chemical and biological contaminants. In order for water to be

filtered, it can only pass through the filter medium if some driving force is applied, which

may be caused by gravity, centrifugation, application of pressure on the fluid above the filter,

13
or other processes that use pumps, valves and pipes to produce enough pressure to push the

water through the filter.

2.3.1.1 Types of Filtration

There are different types of water filters, such as strainers, precoat filters, slow sand filters,

rapid gravity and pressure filters, membrane filters, and granular media filters.

1. Strainers and Straining Filtration

Straining is a very simple method of filtration in which water is poured through a piece of

cloth, and can remove some of the suspended silt and solids, destroying some pathogens in

the process.

2. Gravity Filtration

Gravity filtration is a method of filtering impurities by using gravity to pull liquid through a

filter. This form of filtration occurs through beds of granular media and consists of

interception, straining, flocculation, and sedimentation.

3. Membrane Filtration

Membrane filters utilize microfiltration and ultrafiltration, which can be effective in

eliminating bacteria and/or act as pre-treatment before nanofiltration or reverse osmosis must

occur. 

4. Media Filtration

Media filtration systems promote the filtration of water through a prescribed filter medium,

including:

o Sand filters;
o Granular activated carbon;
o Woven or nonwoven fabric; and
o Metal screens.

5. Pressure Filtration

14
Pressure filters are contained in a steel pressure vessel. Perforated pipes or a steel plate with

nozzles collect the filtered water and for distribution of the wash water and air scour (Cristina

Tuser, 2021).

2.3.2 PRECIPITATION

Metals do not degrade in the environment. They can be very toxic to humans and animals;

therefore, municipalities and industries must remove them from wastewater. Chemical

precipitation is the most common technology used to remove dissolved (ionic) metals from

solutions, such as process wastewaters containing toxic metals. The ionic metals are

converted to an insoluble form (particle) by the chemical reaction between the soluble metal

compounds and the precipitating reagent. The particles formed by this reaction are removed

from solution by settling and/or filtration. The effectiveness of a chemical precipitation

process is dependent on several factors, including the type and concentration of ionic metals

present in solution, the precipitant used, the reaction conditions (especially the pH of the

solution), and the presence of other constituents that may inhibit the precipitation reaction.

The most widely used chemical precipitation process is hydroxide precipitation in which

metal hydroxides are formed by using calcium hydroxide (lime) as the precipitant. Each

dissolved metal has a distinct pH value at which the optimum hydroxide precipitation occurs

- from 7.5 for chromium to 11.0 for cadmium. When considering the cost of precipitating

agents and alkali requirements, lime is the most cost-effective option to remove metals from

wastewaters.

2.3.2.1 Limitations of Precipitation

Precipitation may be difficult for contaminated water with multiple metals. As the

precipitation process for one metal is enhanced, the additive may prevent precipitation of

another. The precipitant that is removed must be tested for leaching prior to land disposal.

There is concern that, after disposal, metals will leach from precipitants, due to changing

15
environmental conditions such as moisture and pH. If the process is aimed at removing

radionuclides, the amounts of radionuclides that can be removed depend on the precipitant,

the concentration of radionuclides present in the aqueous waste, and the pH of the solution. In

all cases, the radioactive precipitant must be disposed of carefully. Hexavalent chromium

requires extra treatment prior to coagulation and flocculation. The addition of chemicals must

be carefully controlled so that unacceptable concentrations in treatment effluent will not

occur. Discharged treated water often requires pH adjustment. If the process is targeting

radioactive substances, treatability studies should be conducted to select the best ion

exchange materials and to determine the best operating parameters for chemical precipitation.

Application of this technology can be used to remediate groundwater containing heavy

metals, including their radioactive isotopes. Precipitation is used mainly to convert dissolved

metals into particulates that can be removed by coagulation and filtration.

2.3.3 COAGULATION
Many water treatment plants use a combination of coagulation, sedimentation, filtration and

disinfection to provide clean, safe drinking water to the public. Worldwide, a combination of

coagulation, sedimentation and filtration is the most widely applied water treatment

technology, and has been used since the early 20th century. The coagulation process involves

adding iron or aluminum salts, such as aluminum sulphate, ferric sulphate, ferric chloride or

polymers, to the water. These chemicals are called coagulants, and have a positive charge.

The positive charge of the coagulant neutralizes the negative charge of the dissolved and

suspended particles in the water. When this reaction occurs, the particles bind together, or

coagulate (this process is sometimes also called flocculation). The larger particle binds

together, or floc, are heavy and quickly settle to the bottom of the water supply. The settling

process is called sedimentation. The following diagram illustrates the basic reactions and

processes that occur during coagulation.

16
Table 1.0 below shows the length of time that is required for particles of different sizes to

settle through the water;

Figure 2.0 Process of Coagulation, Flocculation and Sedimentation

Table 1.0 Settling time for particles of various diameters (Peterson, H.G. 2001.)

Diameter of Type of Particle Settling time through 1m of

17
 Particle water

10 mm Gravel 1 Second

1 mm Sand 10 Seconds

0.1 mm Fine Sand 2 Minutes

10 microns Protozoa, Algae and 2 Hours

Clay
1 micron Bacteria, Algae 8 Days

0.1 micron Viruses, Colloids 2 Years

10 nm Viruses, Colloids 20 Years

1 nm Viruses, Colloids 200 Years

In a water treatment facility, the coagulant is added to the water and it is rapidly mixed, so

that the coagulant is circulated throughout the water. The coagulated water can either be

filtered directly through a medium filter (such as sand and gravel), a microfiltration or

ultrafiltration membrane, or it can be moved to a settling tank. In a settling tank, clarifier, the

heavy particles settle to the bottom and are removed, and the water moves on to the filtration

step of the treatment process. Coagulation can successfully remove a large amount of organic

18
compounds, including some dissolved organic material, which referred to as Natural Organic

Matter (NOM) or Dissolved Organic Carbon (DOC). Coagulation can also remove suspended

particles, including inorganic precipitates, such as iron. A large amount of DOC can give

water an unpleasant taste and odour as well as a brown discolouration. While coagulation can

remove particles and some dissolved matter, the water may still contain pathogens, in an

international report published in 1998, it was found that coagulation and sedimentation can

only be removed between 27 and 84 percent of viruses and between 32 and 87 percent of

bacteria. Usually, the pathogens that are removed from the water are removed because they

are attached to the dissolved substances that are removed by coagulation [world health

organization, 2007].

Table 1.1 Advantages and Disadvantages of Coagulation

Advantages Disadvantages

Simplicity and cost effectiveness Input of chemicals required

Separates many kinds of particles from Qualified personnel required for design and

water system maintenance

Enhance filtration process Transfer of toxic compounds into solid

phase and formation of sludge that has to be

treated subsequently

19
 Uses abundant and low chemicals Relative time-consuming process

2.3.3.1 Factor Affecting Coagulation

Coagulation is affected by the type of coagulant used, its dose and mass; pH and

initial turbidity of the water that is being treated; and properties of the pollutants present. The

effectiveness of the coagulation process is also affected by pretreatments like oxidation

[Jiang, 2015; Chekli et al., 2016; Ramavandi, 2014; Ayekoe et al., 2016].

2.3.3.2 Limitations of Coagulation

Coagulation itself results in the formation of floc but flocculation is required to help the floc

further aggregate and settle. The coagulation-flocculation process itself removes only about

60%-70% of Natural Organic Matter (NOM) and thus, other processes like oxidation,

filtration and sedimentation are necessary for complete raw water or wastewater treatment

[Ayekoe et al., 2016]. Coagulant aids (polymers that bridge the colloids together) are also

often used to increase the efficiency of the process [Oladoja, 2016].

2.3.4 FLOCCULATION
Flocculation goes hand in hand with coagulation in wastewater treatment. Once the waste

particles have clumped together using coagulation, flocculating agents in wastewater

treatment are used to remove the clumps. Flocculants are lightweight, medium weight and

heavy polymers that cause the destabilized clumps of particles to agglomerate and drop out of

20
the solution, removing them from the filtered water. The weight used depends on the type of

particle. Flocculants are like a high-tech rope that ties all of the coagulated clumps together.

Flocculants come in various charges, charge densities, molecular weights and forms, and they

have also been around for centuries. Natural polymers, such as crushed nuts, have been used

as flocculants since prehistoric times by some central African tribes. Flocculation is a water

treatment process where solids form larger clusters, or flocs, to be removed from water. This

process can happen spontaneously, or with the help of chemical agents. It is a common

method of stormwater treatment, wastewater treatment, and in the purification of drinking

water. One of the requirements for treated water leaving wastewater plants is the removal of

suspended solids. Small solid particles affect the colour of the water and carry impurities into

our natural water sources like rivers and the ocean. Phosphorus content must also be limited

in wastewater as a release of phosphorus into rivers promotes algae growth. Uncontrolled

releases of phosphorus have been known to cause mass die-offs of fish and other aquatic life.

Some industrial applications generate high levels of phosphorus in their wastewater, which

may even require pre-treatment before releasing it to wastewater treatment plants. It involves

adding chemicals to the wastewater in sequence and allowing tiny solid particles to collect

together in a larger mass called a floc. As a treatment of wastewater, flocculation is carried

out in stages.

 Stage One
Suspended solid particles in wastewater are negatively charged. In the first stage of

flocculation, a coagulant like aluminium sulphate is added to the wastewater. The positively

charged coagulant molecules neutralize the negatively charged solid particles suspended in

the water. Neutralising these particles paves the way for them to flocculate together into a

larger mass.

 Stage Two

21
The wastewater must be agitated with mixers. High energy mixing is required initially to

ensure that the coagulant spreads throughout the water. When flocculation is in progress the

mixing energy is reduced to prevent the mass of particles from separating again.

 Stage Three
Once floc is beginning to form, a polymer chemical is added to the wastewater. Polymers

bridge the flocculant from micro to macro flocculant, meaning that the mass of particles

collecting together gets bigger. This chemical also binds the collected mass together so that it

does not easily disintegrate even when the water is slightly agitated.

 Stage Four
After flocculation is complete, the large solid masses can be removed from the wastewater

stream. This is done either through settling where the floc drops to the bottom for removal or

through the use of filters which capture the floc in the filter material. Care must be taken

when cleaning the filters to ensure that the phosphorus rich floc is contained and treated.

2.3.4.1 Flocculant

Flocculants are substances that promote the agglomeration of fine particles present in a

solution, creating a floc, which then floats to the surface (flotation) or settles to the bottom

(sedimentation). This can then be more easily removed from the liquid. Flocculants can be

organic or inorganic, and come in various charges, charge densities, molecular weights, and

forms. Organic polymeric flocculants are most widely used today, due to their ability to

promote flocculation with a relatively low dosage. Although, their lack of biodegradability

and the associated dispersion of potentially harmful monomers into water supplies is causing

the focus to shift to biopolymers, which are more environmentally friendly. The problem with

these is they have a shorter shelf-life, and require a higher dosage than organic polymeric

flocculants. To combat this, combined solutions are being developed, where synthetic

polymers are grafted onto natural polymers, to create tailored flocculants for water treatment

that deliver the optimum benefits of both.

22
2.3.4.2 Mode of Operation

Flocculants can either be applied on their own, or in combination with coagulants, depending

on the charge and chemical composition of the solution being separated. Coagulants work by

destabilizing particles present in a stable solution, causing them to aggregate, and allowing

them to be bonded together by flocculants. The flocculants join the particles together into

flocs, which are then separated from the solution, once they have either fallen as sediment or

floated to the surface. The appropriate combination of organic or inorganic flocculants and

coagulants will depend on the type of substances being removed from the water, as well as

the method of separation being used by the water treatment facility (i.e. sedimentation or

floatation etc). While both coagulation and flocculation are both common processes used in

the treatment and purification of water, they are in fact very different. Coagulation is a

chemical process, whereby the chemical properties of the solution are altered to promote

coagulation. Coagulate means to curdle, and coagulants initiate the same process that

naturally occurs in milk, when the pH of the liquid changes and the milk solids clump

together. Coagulants are usually salts, which break down to release positive or negative

charges. Flocculation, on the other hand, is a physical process that causes particles to floc

together, first forming a cloud and then a precipitate. Flocculants are often polymers, which

induce the settling of particles into larger and larger flakes or flocs. Physical agitation or

other techniques are often required to promote flocculation, while coagulation will occur as

soon as the coagulant has been added to the solution, without any physical processes being

required [Adamson and Gast, 1997; Fuhrmann et al., 2019; Han et al., 2003; Rivas et al.,

2010; Brungard, 2018; Beverly, 2015].

2.3.4.3 Application of Flocculation

i. Jar test
ii. Water treatment process
iii. Brewing
iv. Cheese industry

23
 v. Biology
vi. Physical chemistry
vii. Surface chemistry

2.3.5 OZONATION

Ozonation (also referred to as ozonisation) is a chemical water treatment technique based on

the infusion of ozone into water. Ozone is a gas composed of three oxygen atoms (O3), which

is one of the most powerful oxidants. Ozonation is a type of advanced oxidation process,

involving the production of very reactive oxygen species able to attack a wide range of

organic compounds and all microorganisms. The treatment of water with ozone has a wide

range of applications, as it is efficient for disinfection as well as for the degradation of

organic and inorganic pollutants. Ozone is produced with the use of energy by subjecting

oxygen (O2) to high electric voltage or to UV radiation. The required amounts of ozone can

be produced at the point of use but the production requires a lot of energy and is therefore

costly. Ozone (O3) has been used in water treatment since the late 19 th century. Today it is

applied for the disinfection of drinking water, for the removal of effluents from wastewater

treatment plants in a process called ozonation (or ozonisation) as well as for the degradation

of organic and inorganic pollutants in wastewater. Ozone is an excellent disinfectant and can

even be used to inactivate microorganisms such as protozoa, which are very resistant to

conventional disinfectants (VON GUNTEN 2003). However, ozone is an unstable gas that

transforms to oxygen hence no residual disinfection effect takes place with ozonation.

Ozonation is an efficient treatment to reduce the amounts of micropollutants released in the

aquatic systems by wastewater treatment plants (MARGOT et al. 2011). Although no residual

by-products are generated by ozone itself, some concerns are raised regarding oxidation by-

products when water containing both organics and ions, such as bromide, iodide and chlorine

ions, are treated with ozonation. A typical ozonation system consists of an ozone generator

and a reactor where ozone is bubbled into the water to be treated.

24
2.3.5.1 Effect of Ozonation

The effectiveness of ozone results from its powerful oxidising effect on chemicals and

microorganisms caused by the generation of reactive oxygen species during ozone

transformation to oxygen. Ozone directly attacks the surface of microorganisms and destroys

their cell walls. The cells thus lose their cytoplasm and can no longer reactivate themselves

(Stucki et al. 2005). Ozone can induce an oxidative degradation of many organics and leaves

more biodegradable compounds (Derco et al. 2001). Besides, ozone can oxidise metallic ions

such as Fe (II), Mn (II) or As (III) producing insoluble solid oxides that can be easily

separated from water by filtration or sedimentation.

25
Figure 2.1 Wastewater Treatment System of Ozonation Process

26
2.3.5.2 Operation Maintenance and Cost Consideration

Ozone generation uses a significant amount of electrical power. Constant attention must thus

be given to the system to ensure that power is available. Moreover, ozone should not be

released from the system and connections in or surrounding the ozone generator should not

be leaking. The operator must monitor the appropriate subunits on a regular basis to ensure

that they are not overheated. Therefore, the operator must check for leaks routinely since a

very small leak can cause unacceptable ambient ozone concentrations. The cost of ozone

disinfection systems depends on the manufacturer, the site, the capacity of the plant, and the

characteristics of the wastewater to be disinfected. Ozonation costs are generally high in

comparison to other disinfection techniques (EPA 1999). For the removal of micropollutants

in wastewater, the additional operation costs for ozonation combined with sand filtration are

around 3-4 Swiss cents/m3 (Margot et al. 2011).

2.3.5.3 Application of Ozonation

Ozonation has been successfully applied for water disinfection and can kill most bacteria

viruses and protozoa. However, there is no residual disinfection effect and ozonation is more

expensive than chlorination. Ozonation is a suitable process to degrade organic pollutants

(e.g. for micropollutants removal and landfill leachate pre-treatment) and oxidise metallic

ions (e.g. iron manganese). Design and construction need skilled staff and high-tech

equipment. Sophisticated generators consuming high-amounts of electricity are required to

produce ozone. Although operation and maintenance costs are relatively low, precise

monitoring and dosing adjustment of ozone is needed to ensure the efficiency of the treatment

(Nabi Bidhendi et al. 2006).

27
2.3.5.4 Health Aspect of Ozonation

There are significant health and safety concerns for operators regarding the production and

application of ozone. However, far less is known about ozonation and the effect of ozone on

human health (WHO 2009). There are also concerns regarding by-product formation during

the disinfection of drinking water containing bromide ions (Von Gunten 2003).

2.3.6 REVERSE OSMOSIS

Reverse Osmosis (RO) is a water purification methodology that removes ions, molecules and

other large particles from drinking water using a semipermeable membrane. The process of

removing salt from seawater or desalination is done by reverse osmosis.

28
Figure 2.2 Reverse Osmosis Process

29
2.3.6.1 History of Reverse Osmosis

The process of RO by using semipermeable membrane was observed first in 1748 by a

French clergyman and physicist jean Antoine Nollet. The university of California at los

Angeles was the first to investigate in 1950, desalination of seawater using semipermeable

membranes. In the 1950s, researchers from both the university of California and the

university of Florida successfully produced fresh water from seawater. Cape coral, Florida in

1977 became the first municipality in the US to use the reverse osmosis process on a large

scale. By the end of 2001, around 15,200 desalination plants came into operation worldwide

and 20 percent of them were in the US. Reverse Osmosis (RO) is the process of forcing a

solvent to a region of low soluble concentration from high solute concentration region

through a semipermeable membrane by applying pressure. The typical single pass seawater

RO system consists of;

 Intake: To setup RO system you need an intake pump at the source of the water to be

purified.

 Pre-treatment: This step includes removal of solids, sediments, carbonic acid from

the water so as to protect the membrane. This step also includes dosing of oxidizing

biocides like chlorine to kill bacteria.

 High Pressure Pump: This is required to let the water pass through the membrane.

Pressure for brackish water typically ranges from 225 to 376 psi and in the case of

seawater it ranges from 800-1180psi.

 Membrane: In membrane assembly thereis apressure vessel with a membrane,

allowing feed water to be pressed against the membrane. RO system membranes are

made in a range of configurations, but the two most common configuration are spiral-

wound and hollow-fiber.

30
  Energy recovery: This is used to reduce the energy consumption. Much amount of

energy inputs of the high -pressure pump can be recovered by the concentrate flow

and efficient energy recovery device.

 Remineralization and pH Adjustment: Stabilization of desalination wateros done to

protect downstream pipelines and storage, generally by adding lime or caustic soda to

prevent corrosion. Liming material is used to maintain pH between 6.8 to 8.1 so that

meets the potable water specifications.

 Disinfection: RO is an effective blockade of pathogens, but post- treatment assures

secondary protection against downstream and membranes problems. To sterilize

pathogen which has bypassed the RO process, disinfection by means of UV lamps can

be employed.

2.3.6.2 Application of Reverse Osmosis

i. Drinking water purification

ii. Water and wastewater purification

iii. Food industry

iv. Maple syrup and Hydrogen production

v. Reef Aquariums

2.3.7 ADSORPTION

Adsorption is defined as the deposition of molecular species onto the surface. The molecular

species that gets adsorbed on the surface is known as adsorbate and the surface on which

adsorption occurs is known as adsorbent. Common examples of adsorbents are clay, silica

gel, colloids, metals etc. For the adsorption process, two components are required;

 Adsorbate: Substance that is deposited on the surface of another substance. For

example, H2, N2 and O2 gases.

31
  Adsorbent: Surface of a substance on which adsorbate adsorbs. For

example, Charcoal, Silica gel, Alumina.

Adsorption is a surface phenomenon. The process of removal of adsorbent from the surface

of adsorbate is known as desorption.

32
Figure 2.3 Adsorption Process

33
Table 1.2 Difference Between Absorption and Adsorption

ABSORPTION ADSORPTION

Substance penetrates the surface Surface phenomenon

It occurs at uniform rate Rate increase initially than it decreases

It is unaffected by temperature It is affected by temperature

It is an endothermic process It is an exothermic process

It is same throughout the material Concentration on the surface of adsorbent is

different from that in the bulk

Greater molecular interaction Less molecular interaction

It is not spontaneous Adsorption of gas on solid is spontaneous

Complete deposition of a substance in Deposition of a substance on the surface

another substance

34
2.3.7.1 Adsorption Mechanism

The amount of heat evolved when one mole of the adsorbate is adsorbed on adsorbent is

called enthalpy of adsorption. Adsorption is an exothermic process and enthalpy change is

always negative. When adsorbate molecules are adsorbed on the surface, freedom of

movement of molecules become restricted and this results in decrease in entropy. Adsorption

is a spontaneous process at constant pressure and temperature; thus, Gibb’s free energy is

also decreased.

2.3.7.2 Types of Adsorption

There are two types of Adsorption – Physical Adsorption or Physisorption and Chemical

Adsorption or Chemisorption.

1. Physical Adsorption: It involves adsorption of gases on solid surface via weak van

der Waal’s forces.

Characteristics of Physical Adsorption

 There is no specificity in case of physical adsorption. Every gas is adsorbed on the

surface of the solid.

 Nature of the adsorbate. Easily liquefiable gases are strongly adsorbed physically.

 Physical adsorption is reversible in nature. If pressure is increased volume of gas

decreases as a result more gas is adsorbed. So, by decreasing the pressure, gas can be

removed from the solid surface. Low temperature promotes physical adsorption and

high temperature decreases the rate of adsorption.

 More surface area more is the rate of adsorption. Porous substances and finely divided

metals are good adsorbents.

 Physical adsorption is an exothermic process.

 No activation energy is needed.

35
2. Chemical Adsorption: When the gas molecules or atoms are held to the solid surface via

chemical bonds, this type of adsorption is chemical adsorption or chemisorption.

Characteristics of Chemical Adsorption

 This type of adsorption is specific as compared to physical adsorption. Adsorption

occurs only if there is formation of chemical bonds between the adsorbate and

adsorbent.

 Chemical adsorption is irreversible.  It is an exothermic process but the process occurs

slowly at low temperature. Chemisorption is accompanied by increase in temperature.

High pressure promotes chemisorption.

 Chemisorption increases with increase in surface area.

 Due to chemical bond formation enthalpy of chemisorption is high.

 Activation energy is needed.

 It results in unimolecular layer.

2.3.7.3 Factors Affecting Adsorption

Temperature is an important factor that affects the adsorption. Adsorption occurs best at low

temperature. As adsorption is an exothermic process, low temperature will derive the forward

reaction. Adsorption increases with increase in pressure up to certain extent until saturation is

reached. After saturation, has achieved no more adsorption will occur irrespective of the

pressure applied. The relationship between the extent of adsorption and temperature at any

constant pressure is called Adsorption Isobar.

 As adsorption is a surface phenomenon, surface area will increase the rate of

adsorption.

 Easily liquefiable gases are easily adsorbed.

36
2.3.7.4 Adsorption Description

Adsorption emerged as one of the favoured dye removal techniques among the various tried

and tested dye removal methods due to its outstanding ability to remove almost any form of

dyestuff. This system can also be used to treat drinking water or industrial wastewater. Since

conventional methods are ineffective at fully extracting synthetic dyes from dye wastewater,

it is common knowledge that synthetic dyes cannot be extracted from dye wastewater using

conventional methods (V. Katheresan et al, 2018). Adsorption could be defined as the ability

of all strong substances to draw in to their surfaces atoms of gases or arrangements with

which they are in contact. Solids that are utilized to adsorb gases or disintegrated substances

are called adsorbents; the adsorbed particles are normally alluded to by and large as the

adsorbate. Adsorption alludes to the gathering of particles by the outside surface or inward

surface (dividers of vessels or cleft) of solids or by the outside of fluids. Absorption

(assimilation), with which it is frequently confounded, alludes to measures in which a

substance enters into the real inside of crystals, of blocks, of amorphous (formless) solids, or

of fluids. Now and again the word sorption is utilized to demonstrate the interaction of the

taking up of a gas or fluid by a strong without determining whether the cycle is adsorption or

retention (Britannica, 2013).

2.3.7.5 Applications of Adsorption

 High vacuum can be created using adsorption strategy. For creating vacuum activated

charcoal is used.

 Gas masks used in coal mines are based on adsorption principle. These gas masks are

used to adsorb poisonous gases. This makes the air purified for breathing.

 Silica and aluminum gels are used to adsorb moisture to reduce humidity.

 Noble gases can be separated using charcoal as an adsorbent.

 Adsorption of drugs are used to kill germs.

37
  Chromatographic analysis is based on phenomenon of adsorption.

 Sugar is decolorized by treating sugar solution with charcoal powder. The latter

adsorbs the undesirable colors present.

 Adsorption also plays an important role in paint industry. The paint should not contain

dissolved gases, as otherwise the paint does not adhere well to the surface to be

painted and thus will have a poor covering power.

 This method is also used in the formation of the stable emulsions in cosmetics and

syrups.

 The cleaning action of soaps and detergents are also due to adsorption.

2.3.7.6 Adsorption Process

An adsorption interaction includes the exchange of broke up solutes from fluid stage to the

outside of an additional strong stage which is likewise called adsorbent (Ghosh, 2006).The

collection and grouping of toxins from fluid arrangements by the utilization of biological

materials, like chitin, chitosan, yeasts, parasites or bacterial biomass, as adsorbent is named

bio sorption (Crini, 2006). Adsorption can be either physical or chemical in nature. Physical

adsorption takes after the condensation of gases to fluids and relies upon the physical, or van

der Waals, power of fascination between the strong adsorbent and the adsorbate atoms. There

is no chemical explicitness in physical adsorption, any gas having a tendency to be adsorbed

on any strong if the temperature is adequately low or the pressing factor of the gas adequately

high. In chemical adsorption, gases are held to a strong surface by chemical powers that are

explicit for each surface and each gas. Chemical adsorption happens normally at higher

temperatures than those at which physical adsorption happens; besides, chemical adsorption

is commonly a slower interaction than physical adsorption and, as most chemical responses,

much of the time includes an energy of initiation. (Britannica, 2013).

38
2.3.7.7 Adsorbent

Adsorption is a process that is relatively inexpensive. Adsorption has certain benefits over

customary strategies like minimization of chemical and natural slop, ease, high effectiveness,

and recovery of adsorbents. To be economically suitable, an adsorbent ought to have high

selectivity to encourage snappy partitions, good vehicle and dynamic attributes, warm and

chemical solidness, mechanical strength, protection from fouling, recovery limit and low

dissolvability in the fluid in contact. Adsorbents can be gotten from different natural just as

anthropogenic sources which have been executed for treatment of waste water defiled with

dyes.

2.3.7.8 Adsorption Isotherm

Adsorption isotherm is a graph or a relation between the amounts of adsorbate adsorbed on

the surface of adsorbent and pressure at a constant temperature. Adsorption isotherms explain

the equilibrium relationships between adsorbent and adsorbate and the mass of the adsorbed

component per unit mass of adsorbent and the concentration of adsorbate in the medium

under a given set of conditions (temperature and concentration). It also determines the

equilibrium distribution of metal ions and how selective retention takes place when two or

more adsorbent components are present. The term “isotherm” can be defined as a curve

explaining the retention of a substance on a solid at various concentrations. Several isotherm

models are available to describe the mechanism of the adsorption process and the equilibrium

adsorption distribution. Some of the isotherms used in adsorption studies are Langmuir,

Freundlich, and Temkin isotherms. Different adsorption isotherm was studied by different

scientists;

2.3.7.8.1 Freundlich Adsorption Isotherm

The Freundlich model is the most popular adsorption model for a single solute system. The

model has found broad acceptance because of its accuracy and broad applicability. The

Freundlich model assumes a heterogeneous adsorption surface and dynamic sites with

39
different energy. Freundlich proposed an empirical relationship between amount of gas

adsorbed by unit mass of adsorbent and pressure at a particular temperature. Following

equation was proposed for freundlich adsorption isotherm-

x/m=k.p1/n(n>1)

40
Figure 2.4 Adsorption Isotherm

X is the mass of the gas adsorbed

M is the mass of the adsorbent
P is the pressure

41
K and n constants which depends on the nature of the adsorbent and the gas at a particular

temperature. Taking log of the above equation, the following equation will be observed

Log x/m =log k+1/n log p

x/m is plotted on the y axis and log p is on x axis. If straight line is observed than only

Freundlich isotherm is verified.

42
Figure 2.5 Freundlich Adsorption Isotherm

Slope gives 1/n and intercept gives log k. the value of 1/n varies from 0 to 1.
If 1/n is 0, adsorption is independent of pressure.
If 1/n is 1, adsorption changes with pressure.

43
2.3.7.8.2 Langmuir Isotherm

In 1916, Langmuir proposed the theory of adsorption of a gas on the surface of the solid to be

made up of elementary sites each of which would adsorb one gas. It is assumed that all

adsorption sites are equivalent and the ability of a gas molecule to get bound to any one site is

independent of whether or not the neighboring sites are occupied. Additionally, it is also

assumed that dynamic equilibrium exists between adsorbed and non-adsorbed gas molecule.

Following principles can be obtained from Langmuir adsorption isotherm 

 The gas adsorbed behaves ideally in a vapor phase.

 Only monolayer adsorption takes place.

 The surface of the solid is homogeneous.

 There is no lateral interactive force between the adsorbate molecule.

 The adsorbed gas molecules are localized.

This model can be written in non-linear form (Langmuir) as

qe=¿Q × K L × Ce
o
¿
1+ K L × Ce

Where: Ce = the equilibrium concentration of adsorbate (mg/L-1)

qe = the amount of metal adsorbed per gram of the adsorbent at equilibrium (mg/g).

Qo= maximum monolayer coverage capacity (mg/g)

KL = Langmuir isotherm constant (L/mg).

2.3.7.8.3 The Temkin isotherm

This isotherm contains a factor that explicitly taking into the account of adsorbent–adsorbate

interactions. By ignoring the extremely low and large value of concentrations, the model

assumes that heat of adsorption (function of temperature) of all molecules in the layer would

decrease linearly rather than logarithmic with coverage (Dada et al, 2012). As implied in the

equation, its derivation is characterized by a uniform distribution of binding energies (up to

some maximum binding energy) was carried out by plotting the quantity sorbed q e against

44
lnCe and the constants were determined from the slope and intercept. The model is given by

the;

RT
Qe= ln ⁡( A T Ce )
b

Qe=
RT
br
ln A T +
RT
b ( )
lnC e

AT =Temkin isotherm equilibrium binding constant (L/g).

bT = Temkin isotherm constant

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

T= Temperature at 298K.

2.3.7.8.4 Dubinin–Radushkevich isotherm model

Dubinin–Radushkevich isotherm is generally applied to express the adsorption mechanism

with a Gaussian energy distribution onto a heterogeneous surface (Gunay et al, 2007),

(Dabrowski, 2001). The model has often successfully fitted high solute activities and the

intermediate range of concentrations data well

q e=¿ (q ) exp (−k

s ad ε )¿
2

2
ln q e =ln ( q s ) −k ad ε

Where qe, qs, Kad , Ɛ are qe = amount of adsorbate in the adsorbent at equilibrium(mg/g); qs

= theoretical isotherm saturation capacity (mg/g); Kad = Dubinin–Radushkevich isotherm

constant (mol2/kJ2) and Ɛ =Dubinin–Radushkevich isotherm constant. The approach was

usually applied to distinguish the physical and chemical adsorption of metal ions with its

mean free energy, E per molecule of adsorbate (for removing a molecule from its location in

the sorption space to the infinity) can be computed by the relationship (Dubinin, 1960),

(Hobson 1969).

45
 E=
(√ 1
2 B DR )
Where BDR is denoted as the isotherm constant.

2.3.7.8.5 BET Isotherm (after Brunauer, Emmett, and Teller)

The BET theory was proposed by Brunauer, Emmett and Teller in the year 1938. This theory

explains the formation of multilayer adsorption during physisorption. This theory also talks

about the uniformity in the sites of adsorption of solid surfaces. It assumes that when

adsorption occurs at one site it will not affect adsorption at neighboring sites.

2.3.7.9 Adsorption Solution Phase

Solids also adsorb from solutions. For example, when a solution of acetic acid in water is

mixed with charcoal, some of the acid is adsorbed by the charcoal.

Characteristics of adsorption from the solution phase:

 Adsorption decreases with increase in temperature.

 More surface area more is the rate of adsorption.

 Adsorption also depends on concentration of solute in a solution.

 Adsorption also depends on nature of adsorbate and nature of adsorbent.

Freundlich explains the adsorption from solution phase using concentration of the solution

instead of pressure- x/m =kC1/n

Taking log of the above equation, the following reaction will be obtained-

Log x/m = log k+1/n log C

x/m against log C will give straight line.

2.4 ZEOLITES

46
Zeolites are natural or synthetic crystalline aluminosilicates which have a repeating pore

network and release water at high temperature. They are manufactured by hydrothermal

synthesis of sodium aluminosilicate or another silica source in an autoclave followed by ion

exchange with certain cations (Na+, Li+, Ca2+, K+, NH4+). Nonpolar (siliceous) zeolites are

synthesized from aluminum-free silica sources or by dealumination of aluminum-containing

zeolites. The dealumination process is done by treating the zeolite with steam at elevated

temperatures, typically greater than 500 °C (1000 °F). This high temperature heat treatment

breaks the aluminum-oxygen bonds and the aluminum atom is expelled from the zeolite

framework.

2.4.1 BASICS OF ZEOLITES

2.4.1.1 Natural zeolites

Zeolites in nature often, formed as crystals in small cavities of basaltic rocks over the years

or as volcanic tuffs or glass altered by the interaction with saline water. These natural zeolites

are formed in a number of geological environments such as alkaline deserts, lake sediments,

ash ponds and marine sediments at relatively low temperature, under natural conditions. They

are crystallized in geologically young metamorphic rocks in mountainous regions. The most

general formula of natural zeolites is as depicted below (Jha .B. et al, 2011).

(Li, Na, K)p (Mg, Ca, Sr, Ba)q [Al (p+2q) Si n-(p+2q) O2n]

Natural zeolites such as Clinoptilolite (i.e., popularly known as Clino zeolites) and Chabazite

have applications in various diversified fields such as water treatment, fertilizer application

for soil amendment and plant growth by establishing better retention of nutrients.

2.4.1.2 Synthetic Zeolites

These zeolites are synthesized by chemical processes, which result in a more uniform and

purer state as compared to the natural types in terms of their lattice structures, sizes of pores

and cages in their frameworks. The principal raw materials useful for synthesis of synthetic

47
zeolites can be pure chemicals rich in silica and alumina, minerals available on the earth or

by-products of industries. The type of zeolites formed is a function of the temperature,

pressure, concentration of the reagent solutions, pH, process of activation and ageing period,

SiO2 and Al2O3 contents of the raw materials (Scott. J et al, (2001).

2.4.2 PROPERTIES OF ZEOLITES

The various properties of zeolites include: physical, chemical, ion exchange and adsorption

properties, mineralogical and morphological characteristics, thermal characteristics etc.

2.4.2.1 Physical Properties

The most general physical properties of the zeolites are bulk density and specific gravity

which can correlate with their porosity (i.e., the measure of the pore volume in zeolite) and

the cation exchange capacity (Kumar et al, (2001). Other common physical property of

zeolites includes specific surface area, void volume, pore radius, particle size etc.

2.4.2.2 Chemical properties

Zeolites consist of aluminum oxide, calcium oxide, iron oxide, magnesium oxide, potassium

oxide, silicon oxide and sodium oxide within their structure with water molecules and/or

cations in the pores and the cages (Wu et al, (2006). The cation exchange capacity, adsorption

properties, pH, and loss on acid immersion of zeolites are some of the chemical properties

which are reported to depend on the chemical composition of the synthesized products.

2.4.3 Ion Exchange and Adsorption Properties

Zeolites usually gain cations (viz., Na+,K + and NH4+) during the synthesis process or by

interaction with the surrounding medium by virtue of their ion exchange or adsorption

characteristics (Fansuri et al, 2008). The cations are accommodated to balance the negative

charge developed on the surfaces of pores in zeolites. This can be attributed to the

replacement of Si atom by Al atom in some of the [SiO4]4− tetrahedra and its conversion

into the [AlO4]5−tetrahedron which is interconnected to other [SiO4]4− tetrahedron by

48
oxygen atom. As for example, ion exchange process can be described by exposing a sodium

zeolite to a waste water sample or a fresh solution containing other metal cations (e.g.

NH4+). In fact, the sodium ions of the zeolite can be exchanged by ammonium ions provided

they are not excluded from the zeolite pores due to higher molecular size. Based on the

findings of the previous researchers, a typical ion exchange process of waste water treatment

by zeolite application at room temperature is simulated below by allowing ammonium

chloride solution to pass through a zeolite sample, as depicted in Fig. 2.6.

49
Figure 2.6 Ion Exchange and Adsorption Properties

50
2.4.3.1 Mineralogical Properties

X-ray diffraction (XRD) analysis has been a useful tool to check the presence of minerals

such as (mullite, hematite, magnetite and α-quartz) as the main crystalline phase in fly ash

and its zeolites(raw material used for synthesis of synthetic zeolite from by-product of

industries), in addition to the presence of amorphous glassy phase (Querol et al, 2007).

Furthermore, micrographs obtained by scanning electron microscopy (SEM) have been found

to be a useful tool for demonstrating the shape and grain size of constituent minerals.

2.5 FACTORS AFFECTING THE REMOVAL OF AZO DYE

Various factors influence the adsorption capacity of potential adsorbents during the

adsorption process. In the previous researches have assumed that the efficiency of any

adsorbent is strongly influenced by the physiochemical characteristics of the solutions such as

pH, temperature, initial concentration, contact time and also adsorbent dose. A large portion

of adsorption studies data have been compiled to investigate the relationship of these

parameters.

2.5.1 Effect of pH

The pH of the solution was clearly an important parameter that controlled the adsorption

process (Azouaou et al., 2010; Babu and Gupta 2008; Gupta and Rastogi, 2007; Hao Chen et

al., 2010; Waranusantigul et al., 2003). The effect of pH in turn depends on the charge on the

adsorbent surface. The initial pH of dye solution is one of the most important factors in

wastewater treatment because it influences the chemistry of dye molecules and adsorbent in

aqueous solution, which has a significant impact on adsorption capability. The initial pH of

an aqueous solution affects not only site dissociation, but also the dyes' solution chemistry:

pH influences hydrolysis, complexation by organic and/or inorganic ligands, redox reactions,

and precipitation. Preparing an adsorbent-adsorbate solution with a fixed dye concentration

51
and adsorbent dose but a different pH by adding NaOH (1 M) or HCl (1 M) solutions can be

used to assess the effect of solution pH on adsorption.

2.5.2 Effect of Contact Time

The removal efficiency increased with an increase in contact time before equilibrium is

reached. The amount adsorbed at the equilibrium time reflects the maximum adsorption

capacity of the adsorbent under the operating conditions (Azouaou et al., 2010; Maria

Martinez et al., 2006; Mohammad Mehdi et al., 2011).

2.5.3 Effect of Temperature

Temperature is a key element in the adsorption process. The equilibrium potential of the

adsorbent for a given adsorbate changes as the temperature changes. Preparing an adsorbent-

adsorbate solution with a set dye concentration and adsorbent dose but different temperatures

can be used to investigate the effect of temperature on the adsorption of dye phase.

2.5.4 Effect of Initial Concentration

The concentration of dye solutes is well understood to play a role in the adsorption process.

The amount of dye removal adsorption is strongly affected by the initial dye concentration.

The immediate relationship between the dye concentration and the available sites on an

adsorbent surface determines the effect of initial dye concentration. Preparing an adsorbent-

adsorbate solution with a set adsorbent dose and different initial dye concentrations for

different time periods and shaking until equilibrium can be used to investigate the effect of

initial dye concentration. Different initial concentrations and a fixed concentration were used

to calculate adsorption capacity. The initial and final concentrations of the solutions were

measured by Atomic absorption spectrophotometer. These data were used to calculate the

adsorption capacity of the adsorbent (Azouaou et al., 2010; Mausumi et al., 2006;

Mohammad Mehdi et al., 2011).

2.5.5 Effect of Adsorbent Dosage

52
The amount of adsorbent used is also an important factor to consider when optimizing a

biosorption device. Preparing an adsorbent-adsorbate solution with various amounts of

adsorbents applied to a fixed initial dye concentration and fixed initial solution pH and then

shaking until equilibrium time can be determined. In general, as the adsorbent dosage is

increased, the amount of dye removed increases. The increase in surface area caused by the

increase in adsorbent mass increases the number of active adsorption sites for adsorption,

resulting in a higher percentage removal at higher adsorbent dosages.

2.5.6 Effect of Kinetics

The kinetics of dye adsorption onto adsorbent materials is needed in order to select the best

operating conditions for the full-scale batch process. The solute uptake rate is defined by

adsorption dynamics, and this rate clearly regulates the adsorbate uptake residence time at the

solid-solution interface. This solute uptake rate is the most important factor in adsorption

system design since it specifies the residence time needed to complete the adsorption reaction

and can be measured using kinetic analysis. As a result, the adsorption rate is a significant

consideration when selecting an adsorbent; the adsorbent should have a high adsorptive

capacity.

2.6 ADSORPTION KINETICS MODEL

The prediction of adsorption rate gives important information for designing batch adsorption

systems (Prasanna, 2007). The kinetics of adsorption was studied by using three kinetic

models, first order, second order and intra particle diffusion models, but we are only

considering the first and second order. These models take into account the adsorbed

quantities that will enable us in determining the reactor volume (Azouaou, 2010; Gupta and

Rastogi, 2007).

The pseudo-first-order and pseudo second-order models are employed to examine adsorption

kinetic data and to investigate the mechanism of adsorption.

53
  Pseudo-first order

One of the major characteristics to define the efficiency of adsorption is its kinetics. The

pseudo-first-order-kinetic model has been widely used to predict adsorption kinetics. The

pseudo first-order model is presented by the following equation (Ho, 2004).

d qt
=k 1 ( qe −q t )
dt

qe and qt = the amounts of lead (II) adsorbed at equilibrium and time in mg/g

kl = constant of pseudo first-order adsorption.

 The pseudo second order kinetic equation is given as:

d qt
=k 2(qt −q e )2
dt

The pseudo second order model is based on the assumption that the rate limiting step may

stem from the chemical adsorption involving valence forces through the sharing or exchange

of electrons between the adsorbent and adsorbate. The kinetics in most cases follows the first

order equation, where qt and qe are the adsorption capacity at equilibrium and at time t

respectively, and k is the rate constant of the pseudo first order adsorption process. The

integrated linear form of the first order equation is expressed as follows;

k1
log [ qt −qⅇ ] =log [ qt ]− t
2 ⋅303

Plot of log(qe-q) vs t gives a straight line for first order adsorption kinetics and the rate

constant k is computed from the plot.

The sorption data was also studied by second order kinetics;

d qt
=k 2(qt −q e )
dt

Where k2 is the second order rate constant. After integration.

1 1
= + k2 t
qt −q e q t

54
2.7 ADSORPTION THERMODYNAMIC STUDY

Thermodynamic considerations of an adsorption process are necessary to conclude whether

the process is spontaneous or not. The thermodynamic parameters obtained for the adsorption

process were calculated using Equ. (16) and (17) (Alemayehua et al., 2011).

v c0 −cⅇ
kd = ×
M cⅇ

Δs ΔH
k d= −
R RT

where Kd is the distribution coefficient of metal ions on the adsorbent obtained from

multiplication of the adsorption yield by the ratio of solution volume to mass of

adsorbent(V/m), H (kJ/mol) is adsorption enthalpy, S (kJ·mol‒1·K‒1) is adsorption

entropy. The values of S and H were evaluated from the slope and intercept of the

diagram.

55
 CHAPTER THREE

3.0 MATERIALS AND METHODOLOGY

3.1 MATERIALS

The reagents used in this work are all of analytical grade and were used without further

purification. The reagents are;

1. Distilled water

2. Methyl Orange dye

3.2 INSTRUMENTATION/APPARATUS

 Electronic weighing balance

 Magnetic stirrer

 Volumetric flask

 Measuring cylinder

 Whitman Filter paper

 Funnel

 Conical flask

 Ultraviolet Spectrophotometer

3.3 METHODOLOGY

The experiment was carried out at the project research laboratory in Landmark University.

The adsorbate, Methyl Orange dye was acquired from Landmark agricultural laboratory and

it was used for the adsorption experiment without further purification. The dye solution

prepared in the lab were stock solutions of methyl orange dye prepared by weighing 1g of

methyl orange dye into a standard volumetric flask and making up to the 1000cm 3 mark with

56
distilled water. From this stock, lower concentrations of 20, 30, 40, 50 and 60 mg/l were

prepared by serial dilution method. Each methyl orange dye concentration was agitated on the

magnetic stirrer for a time interval of 2, 4, 6, 8, 10, 15, 20, 30, 45, 60, 75, 90 minutes

continuously. The temperature was varied for 20, 30, 40, 50, 60oC for each of the dye

concentrations. Each solution will be agitated on a flat orbital mechanical shaker at 120 rpm

for different time interval. After the experiment, the mixture will draw out by a syringe into

the sample bottle. The solution will then be analysed using ultraviolet-visible

spectrophotometer at 463nm to determine the quantity of methyl orange remaining in the

solution. The adsorbent dosage was maintained at 0.2g. Water samples (200 mL) were

filtered using Whitman No. 41 (0.45 μm pore size) filter paper for estimation of zeolite Y

residue. Filtrate (200 mL) sample was preserved and analysed using the ultraviolet

spectrophotometer. The adsorbent used was analyzed using Scanning Electron Microscopy

(SEM), Fourier Infrared Spectroscopy (FTIR), Brunauer Emmet Teller (BET), X-Ray

Diffraction Analysis (XRD), Thermogravimetric Analysis (TGA), Transmission Electron

Microscopy (TEM) and Energy Dispersive X-Ray Analysis (EDX).

57
3.4 METHODOLOGY BLOCK FLOW DIAGRAM

Figure 3.0 Adsorption of Methyl Orange Block Flow Diagram

58
 CHAPTER FOUR

4.0 DISCUSSION OF RESULT

4.1 ZEOLITE Y CHARACTERIZATION
Structural characterization of zeolite Y was investigated using SEM. Fig. 4.1.1 and 4.1.2

show the SEM image before and after adsorption, the image has various pores sizes to adsorb

Methyl Orange dye onto his surface. From figure 4.1.1, the bright spots show the rough and

porous surface of the adsorbent, which is one of the factors increasing adsorption capacity. In

figure 4.1.2, it is clearly seen that the pores, caves and surfaces of the adsorbent were covered

by dye. Also, the surface area was estimated using Brunauer–Emmett–Teller (BET).

Accordingly, the surface area, pore volume and average pore diameter of Zeolite Y for before

and after adsorption were 445.389 + 6.4420 m2 /g, 442.607 + 6.4420 m2 /g;

59
Figure 4.1.1 SEM image before adsorption

60
Figure 4.1.2 SEM image after adsorption

61
EDX was used as well to investigate the viability of Zeolite Y for adsorption. Figures 4.1.3

and 4.1.4 EDX images before and after adsorption and the elemental composition of Zeolite

Y. The major elements present in Zeolite Y are Silicon, Aluminium and Oxygen. After

adsorption there was a significant decrease in silicon; but an increase in the aluminium and

oxygen.

62
 Figure 4.1.3 EDX before adsorption Figure 4.1.3 EDX before adsorption

Figure 4.1.3 EDX before adsorption

63
Figure 4.1.4 EDX after adsorption

64
Figure 4.1.5 Thermogravimetric Analysis

65
Figure 4.1.6 Transmission Electron Microscope

66
TEM in fig (4.1.5) allows you to observe details as small as individual atoms, giving

unprecedented levels of structural information at the highest possible resolution. As it goes

through objects it can also give you information about internal structures, which SEM cannot

provide. While Thermogravimetric analysis (TGA)in fig (4.1.6) is an analytical technique

used to determine a material's thermal stability and its fraction of volatile components by

monitoring the weight change that occurs as a sample is heated at a constant rate.

Physiochemical analysis of zeolite Y reveals that the mineral analysis of zeolite Y was rich in

silica and alumina, while other minerals are present in small quantities as impurities as

reported in Table 1.3.

The FTIR spectra of zeolite Y from Arobieye clay is shown in Fig 4.1.7 and Fig 4.1.8. It was

observed that certain functional groups are present on the surface of zeolite Y which could

influence the adsorption potential of the material.

67
Table 1.3: Physiochemical Analysis of Zeolite Y produced from Arobieye Kaolin
Oxide Synthesis Zeolite NaY Concentration wt% Molar

SiO2 37.57 0.6262

Al2O3 18.44 0.1809

Fe2O3 2.03

CaO 3.14

MgO 0.23

SO3 7.30

Na2O 33.27

K2O 0.07

TiO2 1.39

P2O5 0.07

Mn2O3 0.02

Si/Al (Mol 3.46

ratio)

68
Table 1.4 FTIR Analysis Result for Zeolite Y (Before)

RUN PEAK TRANSMITTANCE ASSIGNMENT FUNCTIONAL

WAVELENGTH % GROUP
(cm-1)
1 3480.72 56.00 Stretching Water of
vibrations of crystallization
hydroxyl group
(O–H)
2 1710.18 77.12 C–H stretching Alkanes
vibration
3 1550.31 60.00 CH3 asymmetric Alkanes
deformation of the
connection of the
in CH2 group
4 1318.25 60.02 C–OH asymmetric Carboxyl group
Stretching
vibrations in
carboxyl group
5 1100.28 16.00 Asymmetric Si–O– Complex Band
Si and Si–O–Al
stretching
vibrations
6 780.13 64.18 OH− bending Carboxyl group
vibration of
carboxylic
functional group
7 571.46 56.90 Si–O and Al–O Inorganic
bending vibration
modes

69
Figure 4.1.7 FTIR of Zeolite Y (Before)

70
Table 1.5 FTIR Analysis Result for Zeolite Y Methyl Orange Dye (After)

RUN PEAK TRANSMITTANCE ASSIGNMENT FUNCTIONAL

WAVELENGTH GROUP
(cm-1) %
1 3480.72 56.92 Stretching vibrations of Water of
hydroxyl group (O–H) crystallization
2 1742.30 72.18 C–H stretching vibration Alkanes

3 1552.50 72.36 O-H symmetric Carboxylic acid

stretching vibrations of
Carboxylic group
4 1498.55 72.50 NH4+ symmetric NH4+ functional
stretching vibrational group
mode
5 1100.28 16.90 Asymmetric Si–O–Si and Complex band
Si–O–Al stretching
vibrations
6 800.15 65.17 OH− bending vibration of Carboxyl group
carboxylic functional
group
7 702.04 68.15 Si-O-Al symmetric Complex band
stretching vibrations of
bridge bonds
8 541.76 52.08 Si–O and Al–O bending Inorganic
vibration modes

71
Figure 4.1.8 FTIR of Zeolite Y (After)

4.1.1 X-Ray Diffraction Analysis on Zeolite Y

72
X-Ray Diffraction, frequently abbreviated as XRD, is a non-destructive test method used to

analyze the structure of crystalline materials. XRD analysis, by way of the study of the

crystal structure, is used to identify the crystalline phases present in a material and thereby

reveal chemical composition information. Identification of phases is achieved by comparison

of the acquired data to that in reference databases. X-ray diffraction is useful for evaluating

minerals, polymers, corrosion products, and unknown materials. In most cases, the samples

analyzed at Element are analyzed by powder diffraction using samples prepared as finely

ground powders. This test method is performed by directing an x-ray beam at a sample and

measuring the scattered intensity as a function of the outgoing direction. Once the beam is

separated, the scatter, also called a diffraction pattern, indicates the sample’s crystalline

structure. The Rietveld refinement technique is then used to characterize the crystal structure

which most likely provided the observed pattern. 

73
Figure 4.1.9 X-Ray Diffraction Analysis of the synthesized zeolite Y (before)

4.2 EFFECT OF OPERATION PARAMETERS ON ADSORPTION

74
4.2.1 Effect of Temperature

The effect of temperature on the adsorption of Methyl Orange dye was carried out at various

temperatures of 20, 30, 40, 50, 60 oC for 120 minutes using concentrations of 20, 30, 40, 50,

60 mg/l and constant adsorbent dosage of 0.2g. The results are represented in the figure

(4.1.7). Increase in temperature of the adsorption process led to a significant decrease in the

adsorption capacity Methyl Orange dye, which indicates that the adsorption is exothermic.

75
 20 mg/l 30 mg/l 40 mg/l 50 mg/l 60 mg/l

30.00

25.00

20.00
Qe (mg/l)

15.00

10.00

5.00

0.00
290 295 300 305 310 315 320 325 330 335 340

Temperature K

Adsorption Capacity Against Temperature

Figure 4.2.0 Temperature effect on adsorption capacity of methyl orange dye

(time=60mins, V=200mg/l, W=0.2g)

76
4.2.2 Effect of Initial Dye Concentration and Adsorption Time

The initial dye concentration (20-60 mg/l) and time (0-120 min) effect on Methyl Orange dye

adsorption was investigated to determine the dependent on initial dye concentration in

aqueous phase and the dye adsorption capacity of the adsorbent. The uptake of the methyl

orange dye increased with increasing initial concentration. The fast adsorption at the initial

stage was due to the initial concentration between the adsorbate sites in the solution and

number of vacant sites available on the adsorbent surface. From the figure, the attainment of

equilibrium is as a result of decrease in adsorption sites on the adsorbent with time resulting

to the limited mass transfer of the adsorbate molecules from the bulk liquid to the external

surface of the adsorbent. Equilibrium position was achieved faster at lower concentrations

(20mg/L) because more binding sites were available on the surface of the adsorbent. The plot

shows that at 20mg/l, equilibrium was attained at 60 mins respectively for Methyl Orange

dye respectively at 293k.

77
 Qt 20mg/l Qt 30mg/l Qt 40mg/l Qt 50mg/l Qt 60mg/l

40

35

30

25
Qt (mg/l)

20

15

10

0
0 10 20 30 40 50 60 70 80 90 100

Time (min)

Effect of initial temperature against time at [293k, agitation speed

=120rpm, v=200ml,w=0.20g]

Figure 4.2.1 Effect of initial dye concentration and time on Methyl Orange dye at 293K

78
 Qt 20mg/l Qt 30mg/l Qt 40mg/l Qt 50mg/l Qt 60mg/l

40

35

30

25
Qt (mg/l)

20

15

10

0
0 10 20 30 40 50 60 70 80 90 100

Time (min)

Effect of initial temperature against time at [303k, agitation speed

=120rpm, v=200ml,w=0.20g]

Figure 4.2.2 Effect of initial dye concentration and time on Methyl Orange dye at 303K

79
 Qt 20mg/l Qt 30mg/l Qt 40mg/l Qt 50mg/l Qt 60mg/l

45

40

35

30

25
Qt (mg/l)

20

15

10

0
0 10 20 30 40 50 60 70 80 90 100

Time (min)

Effect of initial temperature against time at [313k, agitation speed

=120rpm, v=200ml,w=0.20g]

Figure 4.2.3 Effect of initial dye concentration and time on Methyl Orange dye at 313K

80
 Qt 20mg/l Qt 30mg/l Qt 40mg/l Qt 50mg/l Qt 60mg/l

45

40

35

30

25
Qt (mg/l)

20

15

10

0
0 10 20 30 40 50 60 70 80 90 100

Time (min)

Effect of initial temperature against time at [ 323K, agitation

speed= 120 rpm, v=200ml, w=0.20g]

Figure 4.2.4 Effect of initial dye concentration and time on Methyl Orange dye at 323K

81
 Qt 20mg/l Qt 30mg/l Qt 40mg/l Qt 50mg/l Qt 60mg/l

60

50

40

30
Qt (mg/l)

20

10

0
0 10 20 30 40 50 60 70 80 90 100

Time (min)

Effect of initial temperature against time at [333K, agitation

speed= 120rpm, v=200ml, w=0.20g]

Figure 4.2.5 Effect of initial dye concentration and time on Methyl Orange dye at 333K

4.2.3 Effect of pH

82
The pH of the solution is an important key factor in the adsorption process, because it affects

the existence form of functional groups on the surface of adsorbent, and also affects the

existence morphology and solubility of dye molecules in aqueous solution. A solution pH

effect was conducted to establish the maximum percentage uptake of methyl orange dye onto

the adsorbent (Zeolite Y) in an aqueous solution. An adjustment in the pH solution range was

achieved with the aid of 0.1 M HCl and NaOH. Figure 4.2.3 shows the relationship curve

between pH value and adsorption rate (%Removal) of methyl orange Y. When the pH value

is 2.5 the adsorption rate is maximum, the adsorption rate reaches 95.22%. However, at pH

value of 10.0, the adsorption rate is at its minimum with a value of 27.96%. This indicates

that the adsorption of methyl orange is the best under acidic relatively strong conditions.

With the increase of pH value, the adsorption rate of methyl orange Y showed a decreasing

trend.

83
 Effect of pH
44.00

42.00

40.00
Percentage Removal

38.00

36.00

34.00

32.00
2 3 4 5 6 7 8 9 10 11

Mass (g)

Figure 4.2.6 pH effect on Methyl Orange dye adsorption by Zeolite Y (C o=30 mg/l,

temperature= 303 K, Time=60 minutes, W=0.1 g, V=100ml)

4.2.4 Effect of Adsorbent Dosage

84
The adsorbent dose determines the adsorbent capacity for a given initial concentration of

methyl orange dye. In the experiment performed on 100 ml samples with a concentration of

30 mg/l, temperature of 303K, contact time was 60 minutes and doses of 0.1, 0.2, 0.3, 0.4, 0.5

g were performed. It was found that the removal rate in Methyl Orange dye increases with

increasing the amount of adsorption. The Methyl Orange dye removal increased from 5.27%

to 32.57% by increasing the dose from 0.1 to 0.5 g.

85
 Adsorbent Dosage
50.00

45.00

40.00

35.00

30.00
Percentage Removal

25.00

20.00

15.00

10.00

5.00

0.00
0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55

Mass (g)

Figure 4.2.7 Adsorbent dosage on Methyl Orange dye adsorption by Zeolite Y (C o=30

mg/l, temperature= 303 K, Time=60 minutes, V=100ml)

86
4.2.5 Effect of Agitation Speed

The agitation speed determines the adsorbent capacity for a given initial concentration of

methyl orange dye. In the experiment performed on 100 ml samples with a concentration of

30 mg/l, temperature of 303K, contact time was 60 minutes and agitation speed of 20, 40, 60,

80, 100g were performed. It was found that the removal rate in Methyl Orange dye increases

at 40g and reduces at 100g of adsorption. The Methyl Orange dye removal increased from

41% and decreases at 37% the agitation speed from 20 to 100g.

87
 Agitation Speed
42.00

41.00

40.00

39.00
Percentage Removal

38.00

37.00

36.00

35.00

34.00
10 20 30 40 50 60 70 80 90 100 110

Mass (g)

Figure 4.2.8 Agitation Speed on methyl orange dye adsorption by zeolite Y (co=30mg/l,

temperature=303K, time=60mins, V=100ml)

88
4.3 ADSORPTION ISOTHERM

Several isotherms are available for equilibrium modeling of adsorption processes. In this

study, Freundlich and Langmuir were employed to calculate the adsorption capacity. The

Freundlich isotherm is based on the assumption that adsorption occurs on a heterogeneous

surface. The linear form of the Freundlich isotherm model is also given by;

ln qe = ln KF + (1 /n) ln Ce

where KF and n are Freundlich constants determined from slope and intercept.

The Langmuir isotherm model assumes a monolayer adsorption in which all the adsorbed

ions do not interact with each other and once dye occupies a site, no further adsorption can

take place on that site. The linearized form is of the Langmuir isotherm model is a given by;

Ce 1
=[ ]+¿).
q e Qmax . kl

Where, qe is metal concentration on the zeolite at equilibrium (mg of dye/g of zeolite); Qmax

(mg/g) and KL (1/mg) are Langmuir constants maximum adsorption capacity corresponding

to complete coverage of available adsorption sites and a measure of adsorption energy

(equilibrium adsorption constant), respectively. These constants are found from the slope and

intercept of Ce/qe vs. Ce linear plot so that Qmax = 1/ slope and K L = slope/intercept. Table

1.6 shows the adsorption isotherm model parameter for methyl orange dye unto zeolite Y.

Figures 4.2.9 and 4.3.0 showed the graph of Langmuir and Freundlich isotherm for methyl

orange dye at different temperatures.

89
Table 1.6 Langmuir and Freundlich isotherm model parameters for the adsorption of

Methyl Orange dye.

ISOTHERM PARAMETER
S S 293K 303K 313K 323K 333K
Langumir Qo(mg/g) 12.0627 12.3609 11.9617 18.5874 20.6186
  B(l/mg) -0.4621 0.1458 0.4985 0.3273 0.0227
  R² 0.9540 0.9522 0.9876 0.9979 0.9562
  RL -0.1213 0.2554 0.0912 0.1325 0.6877
Freundich Kf 3.4086 0.2486 1.9338 8.7899 0.1473
  1/n 0.6272 1.3168 0.8894 0.2082 1.1897
  R² 0.8705 0.9133 0.9215 0.7958 0.9255

90
 5

4.5
f(x) = 0.0485313412324912 x + 2.13574297717664
R² = 0.956192839736214
4

3.5 20oC
f(x) = 0.0809151637733811 x + 0.555049456258392 Linear (20oC)
R² = 0.952192485687553 30oC
3
Linear (30oC)
40oC
2.5 Linear (40oC)
Ce/Qe 50oC
f(x) = 0.0537590844516626 x + 0.164424651297545 Linear (50oC)
2 = f(x)
R²f(x) = 0.0836306074656298
0.997858979556855
= 0.082888611924292 x + 0.116714882413975
x − 0.179448131938205 60oC
R² =R²0.954018717613596
= 0.987614098627223
Linear (60oC)
1.5

0.5

0
0 5 10 15 20 25 30 35 40 45 50

Ce

Figure 4.2.9 Langmuir isotherm at different temperatures unto Methyl Orange dye

91
 4

3.5 f(x) = 0.889394874961408 x + 0.659536894103118

R² = 0.921503137542625
f(x) = 0.627206980850197 x + 1.22625865815564
f(x) = 1.31675645807432 x − 1.39184555877884
R² = 0.87047941050002
R² = 0.913255179420411 20
3 Oc
f(x) = 0.208200675349735 x + 2.17356198745779 Lin
R² = 0.795779414461083 ear
(20
ln Qe 2.5 f(x) = 1.18974949611287 x − 1.91545580190037 Oc)
R² = 0.925529956686946 30
Oc
Lin
ear
2 (30
Oc)
40
Oc
1.5 Lin
ear
(40
Oc)
1 50
OC

0.5

0
1.5 2 2.5 3 3.5 4

ln Ce

Figure 4.3.0 Freundlich isotherm at different temperatures unto Methyl Orange dye

92
4.4 ADSORPTION KINETICS

The prediction of kinetics is necessary for the design of sorption systems and reaction rate

controlling step, as chemical reaction occurs. In this research, using pseudo-first-order and

pseudo-second-order, the adsorption kinetics of Methyl Orange dye was studied. The

lagergren pseudo first order considers the rate of occupation of the adsorption site which is

proportional to the number of unoccupied sites. The First-order and Second-order Equation

are given respectively;

K1
log ( q e −q t ) =log qe − t
2.303

A plot of log (qe – qt) versus t will give a straight line from which k 1 and qe can be evaluated

from the slope and intercept.

t 1 1
= − t
qt k 2 q e q e
2

A plot of t/qt versus t will give a straight line from which k 2 and qe can be evaluated. The

second order pseudo model gives the best description of the mechanism of methyl orange dye

unto zeolite Y. Apart from it having the highest R 2 of 0.9991 as shown in Table 1.7, the

adsorption capacity calculated from this model was very close to the experimental values.

Figures 4.3.1 and 4.3.2 show the graph of the pseudo-first order and pseudo Second-order

Model of methyl orange dye at 293K.

93
Table 1.7 Kinetic models constants with the correction coefficients for Methyl Orange

dye adsorption

Kinetic Model Parameters          

      293K      
30mg/
  Co(mg/L) 20mg/L L 40mg/L 50mg/L 60mg/L
Pseudo-First Order qoexpt 12.80 15.63 20.76 24.39 32.53
  R² 0.9645 0.8017 0.9287 0.6074 0.7364
  qecal 11.8304 7.2011 10.1508 7.6860 9.8175
  K1 0.0792 0.0419 0.0716 0.0481 0.0813
Pseudo-Second
Order R² 0.9786 0.9894 0.9982 0.9968 0.9991
  qecal 15.1745 17.3913 21.7865 25.8398 33.8983
  qoexpt 12.80 15.63 20.76 24.39 32.53
  K2 0.0073 0.0130 0.0179 0.0170 0.0199

94
 2.00
20
mg/
L
Lin
1.50 ear
(20
mg/
L)
30
1.00 f(x) = − 0.0344203881270621 x + 1.07299024362968 mg/
f(x)==0.964534553538302
R² − 0.0310504496171208
0.0353133282785655 x + 1.00645468205572
0.991991262359976
R² ==0.928749519803452 L
f(x) 0.736421083554758
− 0.0208974393828426 x + 0.885692932048936
f(x) = − 0.018242070924321 x + 0.857411892840851 Lin
R²
R² == 0.607381987581892
0.801693317801654
Log (Qe-Qt)

ear
(30
0.50 mg/
L)
40
mg/
0.00 L
0 5 10 15 20 25 30 35 40 45 50 Lin
ear
(40
mg/
-0.50 L)

-1.00

Time (mins)

Figure 4.3.1 Pseudo first order kinetic plot for adsorption of Methyl Orange dye at

293K

95
 7

Qt
f(x) = 0.0658571052174473 x + 0.59749380603404 20mg/
R² = 0.97858086360462 L
6 Linear
(Qt
20mg/
L)
f(x) = 0.0575496162438408 x + 0.255219314261107
R² = 0.98944888799107 Linear
5 (Qt
20mg/
L)
Qt
T/Qt

30mg/
f(x) = 0.0459427636683622 x + 0.117498171199634
4 R² = 0.998196403527096 L
Linear
(Qt
f(x) = 0.0386891098863663 x + 0.0878803559853147 30mg/
R² = 0.996848634540164 L)
3 Qt
40mg/
f(x) = 0.0295459048262814 x + 0.0436671463652429 L
R² = 0.999143092067913 Linear
(Qt
2 40mg/
L)
Qt
50mg/
L
1 Linear
(Qt
50mg/
L)

0
0 10 20 30 40 50 60 70 80 90 100

Time (mins)

Figure 4.3.2 Pseudo second order kinetic plot for adsorption of Methyl Orange dye at

293K

96
 CHAPTER FIVE

5.0 CONCLUSION AND RECOMMENDATION

5.1 CONCLUSION

The objectives of this research work were successfully investigated and achieved. As the

study shows, the characterization of the adsorbent zeolite Y using BET (Brunauer Emmett

Teller), TEM (Transmission Electron Microscope), TGA (Thermogravimetric Analysis),

XRD (X-ray diffraction) Electron Dispersed Spectrum (EDS), Scanning Electron Microscope

(SEM) before and after adsorption process. Adsorption of Methyl Orange dye was

investigated under several parameters such as effect of time, temperature, adsorbent dosage,

agitation speed and pH. The results obtained show that the kaolin could be applied as a good

adsorbent for methyl orange dye removal from an aqueous solution. It is observed that the

adsorption of methyl orange by kaolin is described by the Langmuir model with R2 (0.9979)

which is higher than the value that given by the Freundlich model R2 (0.9255).

The adsorbent dose and contact time showed an increase in adsorption capacity until

equilibrium was obtained. Langmuir, Freundlich models were the equilibrium models tested

for the adsorption of methyl orange dye unto zeolite Y, result gotten indicated that the

Langmuir isotherm model best described the adsorption process as the experimental data

fitted well to the Langmuir model. The adsorption process of methyl orange dye conformed

to the pseudo second order model rather than the pseudo first order. The research showed that

zeolite Y is a good adsorbent for Methyl Orange dye from aqueous solution.

97
5.2 RECOMMENDATION

I recommend that studies should be carried out using the adsorbent on a pilot scale for the

treatment of industrial wastewater. I also recommend that studies should be done on the

adsorbent for possible modifications of the adsorbent in order to increase the adsorption

capacity.

98
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