OPTIMIZATION OF EOSIN DYE REMOVAL USING SYNTHESIZED

ZEOLITE Y

BY

OKUNBOR GREAT OSAGIE

17BB004957/1700385

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.

JULY,2022.

i
 DECLARATION

I, Okunbor Great Osagie, with matriculation number 17BB004957, 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.

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 CERTIFICATION

This is to certify that the project entitled “OPTIMIZATION OF EOSIN DYE REMOVAL

USING SYNTHESIZED ZEOLITE Y” 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)

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

possible, and in memory of my ever-lovely parents who put me on track for this journey.

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 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. J.E Okunbor and Mrs. S.U Okunbor, my brother Ehimare Okunbor

and sister Adesua Okunbor for their constant prayers and guidance over the years. My sincere

appreciation goes to my supervisor Engr. John Adeoye for their constructive criticism, inspiring

guidance, valuable 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 encouragement.

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 ABSTRACT
This study is aimed at the adsorptive removal of Eosin dye from aqueous solution by using

synthesized Zeolite Y. The adsorbent was obtained, characterized and, the adsorptive capability

for the removal of dye was determined by optimizing the process parameters (Time,

Temperature, pH, Adsorbate concentration, Adsorbent dosage) using the Central Composite

Design (CCD) in the Response Surface Methodology (RSM). The results gotten shows a

maximum % removal of 98.5 % was obtained at the optimized conditions of 0.1 g, 60 min, 20◦c,

20mg/l, 2 for adsorbent dosage, time, temperature, adsorbate concentration and pH respectively.

The ANOVA of the regression model showed that the model is highly significant with R 2 of

0.8590. Based on the CCD, quadratic models and 2 factor interactions (2FI) were developed

correlating the adsorption variables to the response (% removal). The model prediction was in

good agreement with the experimental results and Zeolite Y was found to be effective in

removing the Eosin dye from aqueous solution.

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 TABLE OF CONTENTS
DECLARATION ii

CERTIFICATION iii

ACKNOWLEDGMENT v

ABSTRACT vi

LIST OF TABLES x

LIST OF FIGURES xi

INTRODUCTION 1

CHAPTER 1 1

1.1 Background of Study 1

1.2 Research Questions 3

1.3 Problem Statement 3

1.4 Significance of Research 4

1.5 Aims and Objectives 4

1.6 Delineation of Research 4

CHAPTER TWO 5

LITERATURE REVIEW 5

2.1 Introduction 5

2.2 Dyes and Wastewater 5

2.2.1 Sources of dyes 6

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 2.2.2 Characteristics of textile dye effluent 7

2.3 Removal Of Dyes 9

2.3.1 Efficiency of dye removal 11

2.4 Adsorption 12

2.4.1 Advantages of adsorption 13

2.4.2 Types of adsorptions 14

2.4.3 Factors affecting adsorption 14

2.5 Adsorbents 16

2.6 Zeolites 17

2.6.1 Properties of zeolites 18

2.7 History Of Eosin Dye 18

2.7.1 Properties of eosin dye 19

2.7.2 Uses of Eosin Dye 20

2.8 Equilibrium Models 20

2.9 Adsorption Thermodynamics 21

2.9.1 Langmuir Adsorption Isotherm 22

2.9.2 Freundlich adsorption isotherm 23

2.10 Adsorption kinetics 24

CHAPTER THREE 25

RESEARCH METHODOLOGY 25

viii
 3.1 Materials 25

3.2 Instrumentation/Apparatus 25

3.3 Design of Experiments 25

3.4 Methodology 26

3.5 Methodology Block Flow Diagram 28

CHAPTER FOUR 29

DISCUSSION OF RESULTS 29

4.1 Characterization Of Zeolite 29

4.1.1 Brunauer–Emmett–Teller (BET) analysis 29

4.1.2 Surface Morphology and Composition / Energy Dispersive Spectroscopy 29

4.1.3 X-ray Diffraction Analysis 30

4.1.4 Fourier Transform Infrared Spectroscopy (FTIR) Analysis 35

4.1.5 X-Ray Florescence 35

4.2 Design Of Experiment 40

4..2.1 Response surface plots 44

CHAPTER FIVE 50

CONCLUSION AND RECOMMENDATION 50

5.1 Conclusion 50

5.2 Recommendation 50

REFERENCES 51

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 LIST OF TABLES
Tables Title Page
2.1 Characteristics of dye effluent 7
2.2 Metals present in dye effluent from textile industry 9
2.3 properties of eosin dye 19
3.1 Experimental ranges for the Central Composite Design. 26
4.1 FTIR Analysis for Zeolite Y Eosin Dye Before Adsorption 37
4.2 FTIR Analysis for Zeolite Y Eosin Dye After Adsorption 38
4.3 Physiochemical Analysis of Zeolite Y produced from Arobieye Kaolin 39
4.4 Experimental design matrix for Eosin dye removal onto Zeolite Y 41
4.5 ANOVA for Quadratic model 43

x
 LIST OF FIGURES
Figures Title Page
3.1 Adsorption process for removal of Eosin dye from aqueous solution. 28
4.1a SEM of zeolite Y before adsorption 31
4.1b SEM of zeolite Y after adsorption 31
4.2 EDX of Zeolite Y before adsorption 32
4.3 EDX of Zeolite Y after adsorption 33
4.4 XRD Analysis of Zeolite Y 34
4.5 Plot of FTIR analysis for before and after 36
4.6 Diagnostic plot of Residuals vs Run Number 45
4.7 Diagnostic plot of Residuals vs Time 46
4.8 3D response surface plot for pH and Temperature 47
4.9 3D response surface plot for Adsorbent and pH 48
4.10 3D response surface plot for Adsorbate and pH 49

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 INTRODUCTION

CHAPTER 1
1.1 Background of Study
The wastewater containing dyes, generated by the textile, printing and papermaking industries,

pose major hazard to the environment and the public health. Many of the dyes used in these

industries are generally toxic, nondegradable, stable, and even carcinogenic. Basic dyes are the

brightest class of soluble dyes used in the textile industry (Chunfeng et al., 2009). Their

tinctorial value is very high: less than 1×10ˉ6 (1 ppm) of the dye produces an obvious coloration.

The coloration of water inhibits sunlight penetration into the stream so as to reduce the

photosynthetic reaction (Chunfeng et al., 2009). During the last few years, various methods,

such as aerobic and anaerobic microbial degradations, electrochemical treatment, hydrogen

peroxide catalysis, chemical oxidation, reverse osmosis, coagulation, and flocculation, have

been investigated for the removal of these dyes (Chunfeng et al., 2009). Most of these methods

suffer from several disadvantages, such as high capital, operational costs, and problem of

unsuccessful removal of the coloration from wastewater. Wastewater containing various dyes

are very difficult to treat using conventional treatment methods due to their complex aromatic

structure and the fact that dyes are generally stable under the influence of light and oxidizing

agents and reactive dyes are resistant to aerobic digestion. Adsorption techniques using solid

absorbents are well established for treating industrial wastewater. Currently, activated carbon is

the most popular adsorbent used for the removal of dyes, as well as other organic and inorganic

pollutants from wastewater because of its significant effectiveness (Shahadat & Isamil, 2018).

Considering discharged volume, this has encouraged research into developing the low-cost and

effective adsorbents to purify water contaminated with dyes.

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Eosin yellow (EY) is an anionic xanthen dye which is widely used for producing ink,

pharmaceutical and textile products. The dye causes eye and skin irritation inhibit protein-

protein interaction and triggers Geno-toxicity in man (Velusamy et al., 2021). Eosin yellow

(EY) is an acidic dye where on dissolution, the sodium ion enters the aqueous solution ensuring

the negatively charged oxygen group provides the dye with an overall negative charge (Okey-

Onyesolu et al., 2018). Analytical grade eosin dye (99.99% purity) used in this study was

supplied by Merck and used without further purification (Oyelude et al., 2017). The negative

charge of the dye should repel that of ionic adsorbent. Eosin yellow (EY) is most commonly

used for coloring among all other dyes of its category. Eosin yellow (EY) is an important acid

dye widely used for printing calico, dyeing, printing cotton and tannin, indicating oxidation-

reduction, and dyeing leather, and in purified zinc free form, it is used as an antiseptic and for

other medicinal purpose but can have various harmful effects (Okey-Onyesolu et al., 2018). The

dye causes eye burns, which may be responsible for permanent injury to the eyes of human and

animals. If swallowed or inhaled can cause chronic effect like cancer, the dye cause irritation to

the gastrointestinal tract with symptoms of nausea, vomiting, and diarrhea. It may cause

methemoglobinemia, cyanosis, convulsions, tachycardia, and dyspnea, if inhaled. It is likely to

cause irritation to the skin (Senthilkumaar et al., 2005). It is therefore vital that any wastewater

containing EY be properly treated before disposal.

Adsorption, using activated carbon or graphene, is a popular physicochemical technique for

treating dye-containing wastewaters because of its simplicity and efficacy of operation

(Velusamy et al., 2021). However, commercial activated carbon and graphene are expensive,

possess poor selectivity properties and require expensive regeneration after their adsorptive

2
power is exhausted (Kanchi et al., 2017). These challenges prompted researchers to investigate

effective and cheaper adsorbents as substitutes for these materials.

1.2 Research Questions

In order to achieve the aim of this research (optimization and thermodynamic study of eosin

dye from aqueous solution by synthesized zeolite Y), some questions need to be addressed and

are listed below;

1) Why the use of zeolite over other adsorbents?

2) Why use adsorption technique to remove Eosin dye?

3) Why carry out optimization?

1.3 Problem Statement

At present, water pollution caused by dyes has become one of the most important problems in

the world. High concentration of dyeing wastewater discharge has caused a series of problems

(Xia et al., 2018). Due to the increasingly strict laws and restrictions on the organic content of

industrial effluents, it is of great importance to remove dyes from wastewater before its

discharge.

Eosin Y enters the environment through human activities, and it is very toxic. Adsorption is the

most effective, but expensive method of removing the dye from aqueous solutions. Various

materials have been studied as adsorbents for Eosin dye so far such as magnetite nanoparticles

(Kumari, & Shekhar, 2018), chitosan (Han and Miao, 2008; Liu et al., 2021). Currently, more

and more attention has been paid to the use of inexpensive materials as adsorbent by simple

treatment with Zeolite Y being a promising choice in this study because it is environment

friendly (Yadanaparthi et al., 2009).

3
1.4 Significance of Research
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). Zeolite Y synthesis has proffered cheaper route and lower reaction temperature and has

a wide range of adsorb dye due to its porous size.

Optimization of Eosin dye gives us the best performance parameter (pH, time, temperature,

initial dye concentration, and adsorbent weight or dosage) to which we can obtain the optimum

condition.

1.5 Aims and Objectives

Widespread contamination of soil and groundwater by synthetic organic chemicals (e.g., dyes)

has been recognized as an issue of growing importance in recent years. Among them, textile

industry ranks first in the usage of dyes for coloration of fiber.

Therefore, the study is to optimize Eosin dye solution by synthesized zeolite, where the

objectives are to;

1) Characterize Zeolite Y before and after adsorption

2) Study the parameter variable on the adsorption of dye on prepared adsorbent (zeolite Y)

3) Establish the Best condition.

1.6 Delineation of Research

This study is aimed at investigating the best parameter in which the adsorption of Eosin dye

from aqueous solution using Zeolite Y as the adsorbent can be obtained, characterizing the

adsorbent (Zeolite Y) in terms of SEM, EDS, FTIR, XRD. Zeolite Y was chosen because, it

possesses a wider inner cavities which allows adsorption to take place more effectively and

efficiently (Kwon et al., 2010).

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 CHAPTER TWO

LITERATURE REVIEW
2.1 Introduction
The colouring industry is a large-scale and one of the most important industries across the world.

However, its wastewater in the environment is considered as a harmful source of pollution for

creatures due to variety of dyes present in it. Mutagenic and carcinogenic of some dyes have

been proved (Kaykhaii et al., 2018). Dysfunction of kidney, liver, brain, reproductive system

and central nervous system are some effects of dyes on human being. Therefore, removal of

dyes from environmental is of important consideration. Researchers are looking for low-cost

methods to remove these dyes from the aquatic environment. It is estimated that textile

industries release approximately 100 tons of dyes and pigments to the water streams annually

(Kaykhaii et al., 2018). Plant materials are mainly comprised of cellulose materials that can

adsorb heavy metal cations in aqueous solution. Numerous waste biomass sources are available

in nature in which adsorption properties have been reported e.g. rice husk, saw dust, tea and

coffee waste, orange peel peanut shells, activated carbon, dry tree leaves and barks (Kakkar et

al., 2018).

2.2 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

(Bhardwaj & Devangan, 2017). Textile industries ranked first in the use of dyes for fibre

coloration out of all the industries that use dyes (Wong et al., 2013). 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

5
properties, depolarization of waste water from material and assembling businesses is a

significant test for natural supervisors (Morley & Steele). 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 (Kandisa et al., 2016).

2.2.1 Sources of dyes

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

bugs, creatures and minerals (Ahsan et al., 2020). 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 sulphate, ochre. Enterprises like

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

(Al-Gheethi et al., 2022). 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 (Singh et al., 2021). 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 (Burcham, 2013). 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 (Gray, 2004).

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2.2.2 Characteristics of textile dye effluent
Dye effluent of textile industry is mainly generated from bleaching, washing processes. Textile

dye effluents are very difficult to treat because of high fluctuation in pH, colour, temperature,

total dissolved solid (TDS), total suspended solid (TSS) and dissolved solid. Classification of

the dye effluents are carried out in three types according to their chemical oxidation demand

(COD), colour intensity; high, average and low concentration dye effluents. High concentration

dye effluent has COD greater than 1500ppm and negligible light permeability. Average

concentration dye effluent has COD in between 800-1500ppm whereas lower concentration dye

effluent has less than 800ppm COD content. Generally, wastewater treatment is work on upper

and lower concentration level (Ushakumary & Madhu, 2013).

Table 2.1: Characteristics of dye effluent

Category BOD (ppm) COD (ppm) pH Temperature

(°C)

High 500 1500 10 28

Average 270 970 9 28

Low 100 460 10 31

Main characteristics of dye effluent are discussed below;

1. Colour
Conjugated double bonds in chromospheres group present in dyes are responsible for colour.

Colour present in dyes effluent is not only creating negative aesthetic effect but also inhibits the

self-purification potential of dye effluent by reducing the photochemical synthesis of 𝑶𝟐 and

disturb the aquatic ecosystem. Colour present in dye effluent absorbs the sunlight which is most

necessary aquatic plant to sustain and reducing the aquatic plant which leads to minimise the

7
dissolve oxygen in wastewater. 1-2 ppm concentration of dye colour is tolerable limits but more

than that of are resisting to oxidizing species, photochemical degradation, and biodegradation.

Decolorization of dye effluent is most tricky job for most of the textile industry wastewater

treatment plan (Gosavi & Sharma, 2014).

2. Dissolved solids:

Dissolved solid in dye effluents are also important characteristics of textile industry effluent.

Common salt is used in dye processes which tremendously increase total dissolve solid (TDS)

in dye effluents. Conventional methods are not sufficient for treating the high TDS dye

effluents. High TDS dye effluents has potential to disturb the ground and surface water quality

of water. High TDS water cannot be used as raw water for industry as well as not suitable for

irrigation purpose (Gosavi & Sharma, 2014).

3. Chlorine:

Chlorine salt is used in textile industry result in residual Cl2 in textile effluent. Chlorine present

in dyes effluent which reduces the dissolve oxygen (DO) in water body as well as chlorine

react with other compound and form complex chlorine salt. Chlorine is very harmful for

microbe which used in biodegradation processes (Quader, 2010).

4. Organic materials:

Organic pollutants arise in dye effluent from organic compound are used in textile processing.

Organic dyes, acid, enzymes, tallow and sizing material etc. are contributed to organic

pollutants in dye effluents. Presence of organic pollutants in dye effluents are measured in

analysis of BOD and COD. Most of the valuable oxygen is consumed to decompose the

organic pollutants in dye effluent (De & Mondal, 2012).

5. Toxic metals:

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Metals may act as primary or secondary pollutants and it’s very toxic in nature to the aquatic

life. Dye effluent contains metals result from textile processing. That metal creates adverse

impact on treatment processes. Removal of metals from dye effluent is very difficult to the

conventional process12. Metals reacts with other compound in dye effluent and form complex

metal salt which is very difficult to remove from dye effluents. Most of the toxic metals in dye

effluent are chromium (Cr), cadmium (Cd), nickel (Ni), zinc (Zn), copper (Cu), lead (Pb),

ferrous (Fe) etc (Gosavi & Sharma, 2014).

Table2.2: Metals present in dye effluent from textile industry

Metals Mg/L

Cr 19.2

Cd 16.7

Ni 8.5

Zn 15.8

Cu 47.7

Pb 32.2

Fe 7.5

2.3 Removal Of Dyes

Most of the dye effluent is generated from preparation processes rather than dying operation in

textile industry. Dye effluent is mainly consisting of dyes, salt, sizing agent, moderant and

surfactants (Rashid et al., 2020). Normal wastewater treatment plants are not suitable for

removing the reactive dyes from textile effluent due to their retardation towards the aerobic and

9
short period anaerobic treatment. Three methods are mainly used for treatment of textile

effluent, these methods have been detail categorized on the basis of their working principle

involved (Shindhal et al., 2021). The physical removal of dye from textile effluent is used in

physical treatment whereas chemical treatment involved the chemical method for removal of

dyes while biodegradation of dye is involved in biological treatment (Gosavi & Sharma, 2014).

1. Physical treatment:

Physical methods like adsorption, ion-exchange and irradiation, filtration are most applicable

methods in treatment of textile wastewater plants. These methods are widely used in industry

to its high dye removal potential and low operating cost. Some adsorbent likes activated carbon

and coal, fly ash, silica, wood, clay material, agriculture wastes and cotton waste are used in

dye effluent treatment processes. Irradiation process is more suitable for decolorization at low

volume with wide range, but very high dissolved oxygen is required for degradation of dye in

textile effluents. Ion exchange has huge limitation for removal of dyes in textile effluents. Ion

exchange is very specific in nature for dyes and other impurity present in wastewater which has

responsible for reduces the capability of processes (Gosavi & Sharma, 2014).

2. Chemical treatment:

Physical methods are not suitable for complete removal of dye from textile effluent, because it

requires further treatment for remove the solid waste from textile effluent that add extra cost to

the treatment. Chemical methods have their own drawbacks but it is commonly used for their

easiness and cost benefits. Chemical methods like flocculation and coagulation technique are

commonly used for remove the organic pollutants. Coagulation technique are very effective for

degrade the insoluble dyes but not so well for soluble dyes in textile effluent. The major

10
drawbacks of these methods are generation of mud and extra cost required for remove such

mud. It leads to the increase the total operating cost of the process (Gosavi & Sharma, 2014).

3. Biological treatment:

Physical and chemical methods are not much applicable for removing the dyes from textile

effluent, because of the high cost, low efficiency, highly specific in nature. Biological methods

are a green technique to remove dye from textile effluent with minimum cost and optimum

operating time. Biological method can effectively remove the chemical oxygen demand (COD)

and turbidity but not much effective for decolorization of textile effluent. For decolorization of

textile effluent, series arrangement of anaerobic followed by an aerobic treatment is the most

suitable arrangement for decolorization in biological treatment (Gosavi & Sharma, 2014).

2.3.1 Efficiency of dye removal

Chemical dye removal methods had the highest dye removal percentages, ranging from 88.8%

to 99.9% (Katheresan et al., 2018). 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 (Jones, 1988). 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

11
methods have a removal percentage ranging from 86.8 to 99% with the adsorption method

ranking highest on the list (Hasanbeigi & Price, 2015). 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 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 (Katheresan et al., 2018).

2.4 Adsorption
Adsorption can be a potential alternative to traditional treatment processes of metal ions

removal (Ushakumary & Madhu, 2013). Adsorption has emerged as promising technique for

metal removal. The processes can occur at an interface between any two phases, such as, liquid-

liquid, gas-liquid, or liquid-solid interfaces (Barakat, 2011). Moreover, adsorption is coming to

be regarded as a practicable separation method for purification or bulk separation in newly

developed material production processes of, for example, high- tech materials and biochemical

and biomedical products (Dąbrowski, 2001). Surface characteristics and pore structures of

adsorbents are the main properties in determining adsorption equilibrium and rate properties

which are needed for plant design. New adsorbents are continuously being developed,

introducing new applications for adsorption technology. Adsorption equilibrium is the

fundamental factor in designing adsorption operations (Suzuki & Suzuki, 1990). When

adsorption takes place with suspended adsorbent particles in a vessel, adsorbate is transported

from the bulk fluid phase to the adsorption sites in the adsorbent particle (Meshko et al., 2001).

12
In this type of situation, changes in the amount adsorbed or concentration in the fluid phase can

be predicted by solving the set of differential equations describing the mass balances in the

particle, at the outer surface and between the particle and the fluid phase. Determination of

diffusion parameters should be done with a simple kinetic system. These discussions are also

applicable to the analysis and design of adsorption operation in a vessel or differential reactor.

Another powerful technique for determining the rate parameters involved in an adsorption

packed column gives the basic relations used for calculation of breakthrough curves. Adsorption

has been proved to be an excellent way to treat industrial waste effluents, offering significant

advantages like the low-cost, availability, profitability, ease of operation and efficiency

(Demirbas, 2008). The use of microbial bio-sorbents for removal of toxic heavy metals from

waste waters offers a relatively low-cost method with potential for metal recovery. Adsorption

has distinct advantages over the conventional methods: the process does not produce sludges

requiring further disposal, it could be highly selective, more efficient, easy to operate, can

handle large volumes of waste waters containing low metal concentrations (Volesky, 1987).

The metal sequestering ability of microorganisms such as yeast, bacteria, fungi and algae have

been investigated and reported. Adsorption technology based on the utilization of dead biomass

offers certain major advantages such as lack of toxicity constraints, non-requirement of nutrient

supply, and recovery of bound metal species by desorption (Gadd, 1990).

2.4.1 Advantages of adsorption

1. Metals at low concentration can be selectively removed.

2. Effluent discharge concentration meets the govt. regulation.

3. System operates over the broad pH ranges (2-9).

4. System is effective over a temperature range of 4-90◦c

13
5. System offers low capital investment and low operation cost.

6. Convert metal pollutant to metal product

7. System offers simple design; easy operation

Adsorption is a good weapon in the fight against toxic metals threatening our environment

(Ushakumary & Madhu, 2013).

2.4.2 Types of adsorptions

There are two types of adsorption phenomena, physical adsorption and chemical adsorption.

1. Physical adsorption

(Vander Waals adsorption) Physical adsorption is the result of intermolecular forces of

attraction between molecules of the solid adsorbent and the substance adsorbed. It is a readily

reversible phenomenon. In industrial adsorption operations this reversibility is used for the

recovery of adsorbent for reuse, for recovery of adsorbed substance or for the fractionation of

the mixtures (Basu).

2. Chemisorption
Chemisorption is the result of chemical interaction between the solid adsorbent and the

adsorbed substance. The adhesive force and the heat liberated are much greater those that found

in physical adsorption. The process is frequently irreversible. Some substances which under

condition of low temperature undergo only physical adsorption substantially. But they exhibit

chemisorption at high temperatures and sometimes both the phenomena may occur at the same

time. Chemisorption is of particular importance in catalysis (Ushakumary & Madhu, 2013).

2.4.3 Factors affecting adsorption

The following are factors that affect adsorption;

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 1. Effect of pH

The pH value of the metal solution plays an important role in the whole adsorption process and

particularly on the adsorption capacity. The pH of the solution would affect both aqueous

chemistry and surface binding sites of the adsorbents. The effect of pH in turn depends on the

charge on the adsorbent surface. If the adsorbent surface is negatively charged, at lower pH, the

large number of H+ ions present neutralizes the negatively charged adsorbent surface, thereby

reducing hindrance to the diffusion, and a better adsorption is obtained. If the surface charge of

the adsorbent is positively charged, the H+ ions may compete effectively with the cations of the

solution causing a decrease in the amount of metal ion adsorbed (BOGALE, 2021).

2. Effect of contact time

The amount adsorbed on to the adsorbent is in a state of dynamic equilibrium with the amount

desorbed from the adsorbent. The time required to attain this state of equilibrium is termed as

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

adsorption capacity of the adsorbent under the operating conditions (Ramakrishna &

Viraraghavan, 1997).

3. Effect of concentration

Whatever be the mechanism of adsorption from the solution, it is certain that the extent depends

mainly on the available surface of the adsorbent. The process of adsorption is almost invariably

reversible and a definite equilibrium is reached in a short time dependent on the concentration

of the solution and quantity of the adsorbent (Stuart et al., 1985).

4. Effect of temperature and pressure

Increase of temperature and decrease of pressure increase the extent of adsorption. This fact

that heat is absorbed in the process of adsorption is implied in the Le Chatliers principles. As in

15
the case of the heat of the solution the different heats of adsorption, viz, the differential and

integral heat must be distinguished. If accurate values were to be obtained the results would

probably throw much light on the adsorption phenomena. Many attempts have been made to

determine heats of adsorption experimentally (Poyet et al., 2021).

5. Effect of surface area (particle size)

The adsorbents with smaller particle size have a higher ability in the adsorption process with

large external surface. Therefore, more metal ions could be removed than the large particles.

The adsorption increases as the particle size decreases, because the surface area increases when

the particle size decreases. Such an effect is probably due to the inability of the large ions to

penetrate all the initial pore structure of the adsorbent (Feng et al., 2012).

2.5 Adsorbents
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 (Afroze & Sen, 2018). 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 (Suraweera, 2013). Adsorbents can be gotten

from different natural just as anthropogenic sources which have been executed for treatment of

waste water defiled with dyes (Senthil Kumar & Saravanan, 2018). Adsorption mechanisms

require a suitable adsorbent material with a high removal capacity. Normally, the materials

chosen for such applications are those with a high degree of porosity, high cationic exchange

capacity (CEC), specific surface area, environmental capability, availability and cost-

effectiveness (Lin & Juang, 2009). Additionally, to be economically advantageous, the material

16
must have low economic value. The advantages of using natural materials for groundwater

clean-up are the low cost and the potential to remove multiple contaminants. The type of

adsorbent material and the treatment system that should be used depend on the contaminant

types that need to be removed, their concentrations and the removal capacity of the system

(Upadhyayula et al., 2009).

2.6 Zeolites
Zeolites are hydrated, crystalline microporous aluminosilicates, whose structures enclose

channels and/or cavities of molecular dimensions (0.3–1.5 nm diameter) (Moliner et al., 2014).

Zeolites are noted for their lability toward ion-exchange and reversible dehydration. They have

a system structure that encases interconnected cavities involved by huge metal cations

(decidedly charged particles) and water molecules (Gili & Hila, 2021). It has been studied that

more than 40 different types of Zeolites are available in the nature (Mumpton & Fishman, 1977).

However, researchers observed that clinoptilolite is easily available and commonly used

Zeolite, which is a heulandite mineral group (Armbruster, 2001). Because of its low cost, high

surface area, and high ion exchange capability zeolites become adsorbents (attractive

adsorbents). Zeolites are having different cavity structures since they are highly porous this is

the reason sorption mechanism in Zeolites is complex, researchers studied and observed that

Zeolites removing trace elements also such as phenols, heavy metals, etc. (Kandisa et al., 2016).

Considering the set of possible adsorbent materials, zeolites have been studied more intensely

than other materials. In recent years, research on the interactions between contaminated water

and zeolite has been of great interest for the application of zeolites as catalysts and adsorbents

because the chemical and physical properties of natural zeolites are advantageous for the

retention of different chemical compounds, including heavy metals, and because zeolites have

17
low economic value (Liu et al., 2021). The three-dimensional framework of zeolites contains

large central cavities and channels, which can selectively exchange cations and water, which is

why zeolites have been referred to as “molecular sieves” (Rocha & Zuquette, 2020).

2.6.1 Properties of zeolites

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

properties, mineralogical and morphological characteristics, thermal characteristics etc.

1. Physical properties

Bulk density and specific gravity are the most basic physical properties of zeolites, and they

are related to porosity (the measurement of pore volume in zeolites) and cation exchange power

(Wang et al., 2006) Specific surface area, void depth, pore radius, particle size, and other

physical properties of zeolites are also common.

2. Chemical properties

Water molecules and/or cations are trapped in the pores and cages of zeolites, which are made

up of aluminum oxide, calcium oxide, iron oxide, magnesium oxide, potassium oxide, silicon

oxide, and sodium oxide (Wu et al., 2006). Some chemical properties of zeolites, such as cation

exchange ability, adsorption properties, pH, and loss on acid immersion, are said to be

dependent on the chemical composition of the synthesized products.

2.7 History Of Eosin Dye

Eosin is a class of fluorescent red dye. It is an artificial derivative of fluorescein consisting of

two closely related compounds, eosin Y and eosin B. Eosin Y is far more commonly used. It is

a tetra Bromo derivate of fluorescein and has a slightly yellowish cast (so is also known as Eosin

Yellowish) (Rostami & Niazi, 2013). Eosin Y can be further divided into water-soluble and

ethanol-soluble eosin Y (Lai et al., 2012). In 1879 Paul Ehrlich published his technique for

18
staining blood films and his method for differential blood cell counting using coal tar dyes and

mentions the eosinophil for the first time (Kay, 2015). Eosin is a bright red synthetic dye

produced by the action of bromine on fluorescein and stains basic proteins due to its acidic

nature. It was discovered in 1874 by Heinrich Caro, Director of the German chemical company

Bardiche Anillin- und Soda-Fabrik. Ehrlich introduced the term ‘eosinophil’ to describe cells

with granules (which he called alpha-granules) having an affinity for eosin and other acid dyes.

He also observed black-staining, indulinophilic, beta-granules in bone marrow-derived

eosinophils, which were probably immature crystalloid granules in eosinophil myelocytes.

Ehrlich described the features of the alpha-granule and the cell's distribution in various species

and tissues. He speculated correctly that the alpha-granule contents were secretory products and

described several causes of eosinophilia including asthma, various skin diseases, helminths and

reactions to medications (De Keijzer & van Bommel, 2017).

2.7.1 Properties of eosin dye

Eosin Y, also called C.I. 45380 or C.I. Acid Red 87, is a member of the triarylmethane dyes. It

is produced from fluorescein by bromination (Ahel, 2017). The table 2.3 shows the properties

of eosin dye.

Table 2.3: properties of eosin dye

Chemical formula C20H6Br4Na2O5

Molar mass 647.89052

Appearance Red powder

Density 1.018 g·cm−3

Melting point 295.5 °C (563.9 °F; 568.6 K)

19
2.7.2 Uses of Eosin Dye
Eosin Y is commonly used as the red dye in red inks. It is commonly used in histology, most

notably in the H&E (Hematoxylin and Eosin) stain. It is also widely used in the Papanicolaou

stain (or Pap stain used in the Pap test) and the Romanowsky type cytologic stains and it is also

used as a photosensitizer in organic synthesis. (Karthik et al., 2017)

2.8 Equilibrium Models

During adsorption a rapid equilibrium is established between adsorbed metal ions and

adsorbent. The equilibrium metal uptake q is calculated using the following equation:

(Ci − Cf )
q= V ………………… 2.1
M

Where , V is the volume of the solution, Ci and Cf are initial and equilibrium concentrations

and M is the dry mass of adsorbent (Can & Jianlong, 2007). The most widely used isotherm

equation for modeling the equilibrium is the Langmuir equation which is valid for monolayer

sorption on to a surface with a finite number of identical sites and is given by equation 2.2:

𝑞max 𝑏𝑐𝑓
𝑞= ……………. 2.2
(1+𝑏𝑐𝑓 )

Where 𝑞𝑚𝑎𝑥 is the maximum amount of the metal ion per unit weight of the adsorbent to form

a complete monolayer on the surface bound at high 𝐶𝑓 and b is a constant related to the affinity

of the binding sites 𝑞𝑚𝑎𝑥 represents a practical limiting adsorption capacity when surface is

fully covered with metal ions and assists in the comparison of adsorption performance

particularly in cases where the adsorbent did not reach its full saturation in experiments. 𝑞𝑚𝑎𝑥

𝐶𝑓
and b can be determined from the linear plot of versus 𝐶𝑓 (Babu & Gupta, 2008). The
𝑞

linearized form of this model equation is given as:

20
 Cf Cf
= + 1/bqmax ………………. 2.3
q q

The empirical Freundlich model also considers mono molecular layer coverage of solute by the

adsorbent. However, it assumes the adsorbent has a heterogeneous surface so that binding sites

are not identical. This model takes the following form for a single component adsorption

(Azouaou et al., 2010)

1/n
q = kcf ………………. 2.4

Where K and n are the Freundlich constants characteristic of the system. K and n are indicators

of adsorption capacity and adsorption intensity respectively. Through the Freundlich isotherm

is more widely used, it provides no information on the monolayer adsorption capacity, in

contrast to the Langmuir model (AKSU, 2012)

1
log 𝑞 = log 𝑘 + log 𝐶𝑓 …………… 2.5
𝑛

Langmuir and Freundlich isotherms are insufficient to explain the physical and chemical

characteristics of adsorption. The Langmuir isotherm constants do not explain the chemical or

physical properties of the adsorption process. However, the mean adsorption energy (E)

calculated from the D-R isotherm provides important information about these properties.

Dubinin – Radushkevich (D-R) isotherm is commonly used to describe the adsorption isotherms

of single solute systems (Azouaou et al., 2010).

2.9 Adsorption Thermodynamics

The concept of thermodynamics assumed that in an isolated system, where energy cannot be

gained or lost, the entropy change is the driving force. In environmental engineering practice,

both energy and entropy factors must be considered in order to determine what processes will

occur spontaneously. The Gibbs free energy change, ∆G is the fundamental criterion of

21
spontaneity. Reaction occurs spontaneously at a given temperature if ∆G is a negative

quantity. The free energy of the sorption reaction considering the sorption equilibrium

constant is given by the following equation (Chen et al., 2010)

𝛥𝐺 = −𝑅𝑇 𝑙𝑛 𝑏 …………… 2.6

Where ∆G is the changes in Gibbs free energy, R (8.314 J/mol K) is the universal gas

constant, T (K) the absolute temperature and b (L/mol) the thermodynamic equilibrium

constant. Considering the relationship between free energy and the equilibrium constant,

change in equilibrium constant can be obtained in the differential form as follows (Ho &

Ofomaja, 2005)

𝑑𝑙𝑛𝑏
= 𝛥𝐻/𝑅𝑇 2 …………….. 2.7
𝑑𝑇

After integration,

𝛥𝐻
ln 𝑏 = − + 𝑌 ………………. 2.8
𝑅𝑇

Where Y is a constant, the above equation can be rearranged to obtain;

−𝑅𝑇 𝑙𝑛 𝑏 = 𝛥𝐻 − 𝑇𝑅𝑌 ………………. 2.9

Let 𝛥𝑆 = 𝑅𝑌

∆G, can be represented as follows;

𝛥𝐺 = 𝛥𝐻 − 𝑇𝛥𝑆 …………… 2.10

2.9.1 Langmuir Adsorption Isotherm

The Langmuir adsorption isotherm has been effectively applied to many pollutant adsorptions

processes and has been the most widely used isotherm for the adsorption of a solute from a

liquid solution. Basic assumptions of the Langmuir theory are;

22
 1. Surface is homogeneous that is adsorption energy is unvarying over all sites.

2. Adsorption on surface is localized that is adsorbed molecules or atoms are

adsorbed at definite localized sites.

3. Every site can accommodate only one atom or molecule.

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

qe= (QO ×Kl ×Ce )

……………… 2.11
1 + Kl × Ce

Where:

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

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

𝑄𝑜 = maximum monolayer coverage capacity (mg/g)

𝐾𝐿 = Langmuir isotherm constant (L/mg)

2.9.2 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 different

energy. The Freundlich model is:

1
ln 𝑞𝑒 = 𝐾𝑓 + 𝑛 𝑙𝑛 𝐶𝑒 ……………… 2.12

Where,

𝑞𝑒 = amount of the adsorbate per unit weight of adsorbent(mg/g).

𝐾𝑓 = is a constant relating the adsorption capacity (Freundlich constants)

1
= is an empirical parameter relating the adsorption intensity (which varies with the
𝑛

heterogeneity of the material).

23
2.10 Adsorption kinetics
The pseudo-first-order and pseudo second-order models are employed to examine adsorption

kinetic data and to investigate the mechanism of adsorption.

• 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).

d𝑞𝑡
= 𝑘(𝑞𝑒 − 𝑞𝑡 ) ……………. 2.13
𝑑𝑡

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

k = constant of pseudo first-order adsorption.

The pseudo second order kinetic equation is given as:

d𝑞𝑡
= 𝑘(𝑞𝑡 − 𝑞𝑒 )2 ……………. 2.14
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 (Bulut et al., 2008).

24
 CHAPTER THREE

RESEARCH 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. Eosin Yellow Dye

3.2 Instrumentation/Apparatus
The following instruments and apparatus were used during the course of this experiment.

Electronic weighing balance, magnetic stirrer, 250ml Volumetric flask, measuring cylinder of

different sizes (1000ml and 100ml), Whiteman Filter paper, glass Funnel, Stuart Shaking

Incubator, Ultraviolet Spectrophotometer

3.3 Design of Experiments

The central composite design (CCD) in response surface methodology was used to carry out the

optimization of the studied parameters. The desirability (D) function was employed to obtain

the optimum conditions to achieve better response in terms of the dye removal efficiency

(Adewoye et al., 2017). Five independent variables; the adsorbent dosage, the time and the

temperature, the pH, and the concentration of the adsorbate were used in designing the

experimental matrix. Each numeric factor was varied over 5 levels: plus, and minus alpha (axial

points), minimum and maximum (factorial points) and the CenterPoint. The minimum and

maximum values for each factor investigated are presented in Table 3.1

25
Table 3.1: Experimental ranges for the Central Composite Design.
Factors Variables Units Minimum Maximum

A Time Mins 20 60

B Temperature ◦C 20 60

C pH 2 12

D Adsorbate Conc. Mg/l 20 60

E Adsorbent Dosage g 0.1 0.5

Design expert version 12.0(Stat – Ease, Inc., Minneapolis, MN 55413, USA) statistical software

was used for the model fitting and for the evaluation of the statistical significance of the dye

adsorption efficiencies. The dye removal efficiency was calculated using;

𝑐𝑜 −𝑐𝑖
% 𝑅𝑒𝑚𝑜𝑣𝑎𝑙 = × 100 ……………. 3.1
𝑐𝑜

where, 𝒄𝒐 is the initial concentration

and 𝒄𝑖 is the final concentration.

3.4 Methodology
The experiment was carried out in the Chemical Analysis Laboratory Landmark University.

The adsorbate, Eosin Yellow dye was acquired from Landmark agricultural laboratory for the

adsorption experiment without further purification. The dye solution was prepared in the

laboratory in stock solutions by weighing 1g of Eosin Yellow dye into a standard volumetric

flask and making up to the 1000cm3 mark with distilled water. From the stock, lower

concentrations of 20, 30, 40, 50 and 60 mg/l were prepared by serial dilution method. Each

Eosin Yellow dye concentration was agitated on the magnetic stirrer for a time interval of 20,

26
40, and 60 minutes continuously. The temperature was varied at 20, 40, and 60oC for each of

the dye concentrations. The adsorbent dosage to be used are 0.1g, 0.3g, 0.5g were measured

using the weighing balance. The solution was filtered using filter paper for estimation of zeolite

Y residue. The Filtrate sample was preserved and analyzed using the ultraviolet

spectrophotometer at 510nm. The adsorbent used was analyzed using Scanning Electron

Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), Brunauer Emmet Teller

(BET), X-Ray Diffraction Analysis (XRD) and Energy Dispersive X-Ray Analysis (EDX).

27
3.5 Methodology Block Flow Diagram

Fig 3.1: Adsorption process for removal of Eosin dye from aqueous solution.

28
 CHAPTER FOUR

DISCUSSION OF RESULTS

4.1 Characterization Of Zeolite

The adsorbent Zeolite Y is characterized before and after adsorption using FTIR, SEM-EDX,

XRD and BET analysis.

4.1.1 Brunauer–Emmett–Teller (BET) analysis

The physicochemical properties analysis of the synthesized zeolite Y was investigated. The

porosity of zeolite Y is well developed with a higher surface area, pore size, and a larger average

pore diameter, which are advantageous for Eosin dye adsorption. This indicated that zeolite Y

used was mesoporous, with a relatively large surface area and pore size. The surface area and

pore size of zeolite Y was reduced after loading due to the adsorbate on the adsorbent. This

implies that adsorption process really took place. Accordingly, the surface area, pore size, total

pore volume and average pore diameter of Zeolite Y was 445.36 𝑚2 /g, 30.5342 Å, 0.603567

𝑐𝑚3 /g and 5.42094nm.

4.1.2 Surface Morphology and Composition / Energy Dispersive Spectroscopy

The identification and recognition of the surface properties and composition of the prepared

adsorbent are germane in comprehending the role and function of the adsorbent on adsorption

processes. The presence of elements and composition was evaluated using SEM-EDS with

model JOEL-JSF7600F. Figures 4.1a and 4.1b shows the surface of the adsorbent before and

after loading respectively. The image has various pores sizes to adsorb Eosin yellow dye onto

his surface. From figure 4.1a, the bright spots show the rough and porous surface of the

adsorbent, which is one of the factors increasing adsorption capacity. In figure 4.1b, it is clearly

seen that the pores, caves and surfaces of the adsorbent were covered by dye.

29
The Energy Dispersive Spectroscopy (EDS) illustrated in Figure 4.2 below shows the presence

of elements such as carbon, calcium, aluminum, silicon, Sulphur, iron and oxygen. Oxygen

(40.26) had the highest weight concentration. Silicon and oxygen had the highest peak in the

EDS spectrum while the other elements such as aluminum, Potassium, Sulphur, calcium, and

iron showed relatively low peaks signifying their relatively minute amounts present in the

composition of the zeolite Y. Figure 4.3 shows the presence of elements such as oxygen, silicon,

carbon, aluminum and sodium. Oxygen (58.03) had the highest weight concentration.

4.1.3 X-ray Diffraction Analysis

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 (Farrell, 2013). Identification of phases is achieved by

comparison of the acquired data to that in reference databases. 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 XRD analysis carried out on the zeolite Y after adsorption is shown in fig 4.4.

30
Fig 4.1a: SEM of zeolite Y before adsorption Fig 4.1b: SEM of zeolite Y after adsorption

31
Fig4.2: EDX of Zeolite Y before adsorption

32
 Element Element Element Atomic Weight
Number Symbol Name Conc. Conc.
8 O Oxygen 66.49 58.03
14 Si Silicon 10.89 16.68
6 C Carbon 8.57 5.62
13 Al Aluminum 7.46 10.99
11 Na Sodium 6.27 7.86

Fig 4.3: EDX of Zeolite Y after adsorption

33
Fig 4.4 XRD Analysis of Zeolite Y

34
4.1.4 Fourier Transform Infrared Spectroscopy (FTIR) Analysis
In order to find out which functional groups were responsible for the Eosin dye adsorption on

the synthesized zeolite Y, FTIR analysis of the before and after adsorption was carried out. The

FTIR spectra results for before and after adsorption of Eosin dye are shown in Figure 4.5, and

then presented in Table 4.1 and 4.2.

4.1.5 X-Ray Florescence

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 4.4;

35
Fig 4.5: Plot of FTIR analysis for before and after

36
Table 4.1: FTIR Analysis for Zeolite Y Eosin Dye Before Adsorption
S/N PEAK ASSIGNMENT FUNCTIONAL
WAVELENGTH
(cm-1) GROUP

1 3458 Stretching vibrations Alcohols, Water

of hydroxyl group

O–H

2 2882 C–H stretching Alkanes

vibration

3 1638 CC Stretch Alkenes

4 1007 Si-O-Si

5 726 C-H bending Alkene

vibration

6 566 Si–O and Al–O Inorganic

bending vibration

modes

37
Table 4.2: FTIR Analysis for Zeolite Y Eosin Dye After Adsorption

S/N PEAK ASSIGNMENT FUNCTIONAL

WAVELENGTH GROUP

(cm-1)

1 3458 Stretching vibrations Water

of hydroxyl group

O–H

2 2893 C–H stretching Alkanes

vibration

3 1645 CC Stretch Alkenes

4 1005 Si-O-Si

5 566 Si–O and Al–O Inorganic

bending vibration

modes

38
Table 4.3: Physiochemical Analysis of Zeolite Y produced from Arobieye Kaolin
Oxide Synthesis Zeolite Na Y 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 ratio) 3.46

39
4.2 Design Of Experiment
The design of experiments comprising of the studied factors, their ranges and the response (dye

removal efficiency) is presented in Table 4.5. The response in terms of dye removal efficiency

was in the range of 68.50 % to 99.77 %.

The experimental data were analyzed using CCD and the final empirical model equations

showing the relationship between the adsorption process variables and the response was

developed as shown in equation below.

Final Equation in Terms of Coded Factors;

% Removal = 96.21 +1.16A + 2.25B - 5.15C + 0.6633D -3.14E – 0.2756AB – 1.67AC – 1.85AD

+ 0.9231AE – 1.75BC – 1.38BD +2.44BE + 2.43CD + 5.54CE – 0.8444DE + 2.29𝐴2 + 2.80𝐵 2

-13.46𝐶 2 – 7.74𝐷2 + 2.70𝐸 2 ……………………... 4.1

Where A, B, C, D, E represents Time, Temperature, pH, Adsorbate concentration, Adsorbent

dosage respectively. The equation in terms of coded factors can be used to make predictions

about the response for given levels of each factor. By default, the high levels of the factors are

coded as +1 and the low levels are coded as -1. The coded equation is useful for identifying

the relative impact of the factors by comparing the factor coefficients. The developed

polynomial model equation shows that, (A), (B), (D) have a positive influence on the removal

of Eosin dye from the wastewater onto the Zeolite Y. It also reveals that the interactions of the

(AE), (BE), (CD), (CE) all have positive influence on the adsorbance. Of all the terms in the

model, only (D2), (C2 ) , (DE), (BD), (BC), (AD), (AC), (E) and (C) have negative influence

on the adsorption of Eosin dye on Zeolite Y. The adequacy and significance of the developed

model was evaluated using F-test and analysis of variance (ANOVA) as shown in Table 4.6

40
 Table 4.4: Experimental design matrix for Eosin dye removal onto Zeolite Y.
Std Run Factor 1 Factor 2 Factor 3 Factor 4 Factor 5 %Removal
A: Time B: Temperature C: pH D: E: Adsorbent %
Adsorbate
27 1 40 40 7 40 0.3 96.88
15 2 20 60 12 60 0.1 79.12
3 3 20 60 2 20 0.1 68.77
24 4 40 40 7 60 0.3 82.78
6 5 60 20 12 20 0.5 96.12
20 6 40 60 7 40 0.3 90.73
31 7 40 40 7 40 0.3 96.88
23 8 40 40 7 20 0.3 93.15
14 9 60 20 12 60 0.1 98.91
18 10 60 40 7 40 0.3 98.59
16 11 60 60 12 60 0.5 81.28
30 12 40 40 7 40 0.3 96.88
8 13 60 60 12 20 0.1 69.26
10 14 60 20 2 60 0.5 75.7
28 15 40 40 7 40 0.3 96.88
25 16 40 40 7 40 0.1 98.87
4 17 60 60 2 20 0.5 73.07
22 18 40 40 12 40 0.3 98.23
2 19 60 20 2 20 0.1 99.77
5 20 20 20 12 20 0.1 98.63
7 21 20 60 12 20 0.5 77.67
11 22 20 60 2 60 0.5 80.26
21 23 40 40 2 40 0.3 98.77
13 24 20 20 12 60 0.5 82.52

41
26 25 40 40 7 40 0.5 97.94
19 26 40 20 7 40 0.3 73.75
9 27 20 20 2 60 0.1 97.64
17 28 20 40 7 40 0.3 97.4
12 29 60 60 2 60 0.1 78.67
1 30 20 20 2 20 0.5 68.5
29 31 40 40 7 40 0.3 96.88
32 32 40 40 7 40 0.3 96.88

42
Table 4.5: ANOVA for Quadratic model
Source Sum of Squares df Mean Square F-value p-value

Model 3241.66 20 162.08 3.35 0.0218 significant

A-Time 24.17 1 24.17 0.4997 0.4943

B-Temperature 91.53 1 91.53 1.89 0.1963

C-pH 477.51 1 477.51 9.87 0.0094

D-Adsorbate 7.92 1 7.92 0.1637 0.6935

E-Adsorbent 177.85 1 177.85 3.68 0.0815

AB 1.22 1 1.22 0.0251 0.8769

CE 490.29 1 490.29 10.13 0.0087

Residual 532.14 11 48.38

Lack of Fit 532.14 6 88.69

Pure Error 0.0000 5 0.0000

Cor Total 3773.80 31

43
The Model F-value of 3.35 implies the model is significant. There is only a 2.18% chance that

an F-value this large could occur due to noise.P-values less than 0.0500 indicate model terms

are significant. In this case C, CE, C² are significant model terms. Values greater than 0.1000

indicate the model terms are not significant.

Std. Dev. 6.96 R² 0.8590

Mean 88.67 Adjusted R² 0.6026

C.V. % 7.84 Adeq Precision 6.0112

Adeq Precision measures the signal to noise ratio. A ratio greater than 4 is desirable. The ratio

of 6.0112 in table 4.7 indicates an adequate signal.

4..2.1 Response surface plots

The interactive effects of the process variables on the Eosin dye removal (%) was studied by

plotting three-dimensional surface curves against any two-independent variable while keeping

the other variable constant (% Removal). A plot showing the residual against the run numbers

and against time (variable A) are shown in figures 4.6 and 4.7 respectively. The 3D curves are

shown in fig 4.8 – 4.10. The graph showed the relationship between the variables and the %

removal of eosin dye of the designed experiment.

44
Fig4.6: Diagnostic plot of Residuals vs Run Number

45
Fig 4.7: Diagnostic plot of Residuals vs Time

46
Fig4.8: 3D response surface plot for interaction of pH and Temperature

47
Fig4.9: 3D response surface plot for Adsorbent and pH

48
Fig4.10: 3D response surface plot for Adsorbate and pH

49
 CHAPTER FIVE

CONCLUSION AND RECOMMENDATION

5.1 Conclusion
The objectives of this research work were achieved. As the study shows the characterization of

the adsorbent Zeolite Y using Brunauer Emmet Teller (BET) surface analysis, Fourier Infrared

Spectroscopy (FT-IR), Energy Dispersive X-Ray analysis (EDX), X-Ray Diffraction Analysis

(XRD) and scanning electron morphology (SEM). The Zeolite Y used in this experiment shows

significant adsorption capacity for the removal of Eosin dye from aqueous solution under

suitable experimental conditions. The best condition for the removal of Eosin dye was at 99.77%

which was achieved at conditions of 0.1g, 60min, 20◦c, 20mg/l, for adsorbent dosage, time,

temperature, adsorbate concentration respectively and a pH of 2. The ANOVA response shows

the reliability of the data with a good correlation coefficient R2 of 0.8590.

5.2 Recommendation
The following recommendations were considered during the course of this experiment;

1. The studies should be carried out using the adsorbent on a large scale for the treatment

of industrial wastewater.

2. The technical viability for mass production of adsorbent should be evaluated in

adsorption studies.

3. The adsorbent should be clearly reported and discussed to offer insight into cost-

effectiveness for commercialization and practical application.

50
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