EVALUATION OF ZEOLITE Y FOR THE ADSORPTIVE

REMOVAL OF EOSIN YELLOW DYE FROM AQUEOUS

SOLUTION

BY

BALOGUN DAVID OLOLADE

16BB004308/1600635

AN UNDERGRADUATE RESEARCH PROJECT SUBMITTED TO

DEPARTMENT OF CHEMICAL ENGINEERING

LANDMARK UNIVERSITY, OMU-ARAN KWARA STATE.

A THESIS SUBMITTED TO THE DEPARTMENT OF

CHEMICAL ENGINEERING, LANDMARK UNIVERSITY, OMU-
ARAN KWARA STATE. IN PARTIAL FULFILMENT OF THE
REQUIREMENT OF THE REQUIREMENTS FOR THE AWARD
OF THE DEGREE OF BACHELOR OF ENGINEERING (B.Eng.)
IN CHEMICAL ENGINEERING.

24th SEPTEMBER, 2021.

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 DECLARATION

I, BALOGUN DAVID OLOLADE, with matriculation number 16BB004308, 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 this research project ‘‘EVALUATION OF ZEOLITE Y FOR THE

ADSORPTIVE REMOVAL OF EOSIN YELLOW DYE FROM AQUEOUS

SOLUTION’’ by BALOGUN DAVID OLOLADE (16BB004308) meets the

regulations governing the awards of the degree of bachelor of engineering in chemical

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

Date:

Engr. J.B ADEOYE

PROJECT SUPERVISOR

Date:

DR. B.S. FAKINLE

HEAD OF DEPARTMENT

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 DEDICATION

This research work is dedicated to God Almighty, my wisdom, inspiration and strength,

without whom none of this would have been made possible.

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 ACKNOWLEDGMENT

I express my deep gratitude to my amazing Family, my parents, Engr. and Mrs Balogun

for their love, unending support and their constant prayers and guidance over the years.

My sincere appreciation goes to my supervisor Engr. John Adeoye for his constructive

criticism, inspiring guidance, valuable and indispensable contributions throughout this

project work. Also, I would like to thank the Head of department Chemical

Engineering, Dr. B.S. Fakinle for his assistance and encouragement.

I’m also grateful to the entire lecturing and technical staff of the department of

Chemical Engineering, Landmark University.

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 ABSTRACT

This study was carried out on the removal of Eosin yellow dye from aqueous

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

for the removal of Eosin yellow dye from 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) and scanning

electron morphology (SEM) for surface area, functional group and surface morphology

with the BET surface area of 445.36 m2/g, 30.5342 Å, 0.603567 cm3/g. 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 eosin yellow dye was found to attain 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 monolayer adsorption capacity of 47.17 mg/g. The collected

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

process.

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 TABLE OF CONTENT

CONTENT PAGE

Cover page
Title page
DECLARATION i
CERTIFICATION ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
TABLE OF CONTENT vi
LIST OF TABLES viii
LIST OF FIGURES ix
CHAPTER ONE
INTRODUCTION 1
1.1 Background of study 1
1.2 Research problems 3
1.3 Problem Statement 4
1.4 Significant of research 4
1.5 Aims and objectives 5
1.6 Delineation of research 5
CHAPTER TWO
LITERATURE REVIEW
2.1 Dyes and Wastewater 6
2.1.1 Sources of dyes and their classification 6
2.2 Removal of Dyes 7
2.2.1 Biological dye removal methods 7
2.2.2 Chemical dye removal methods 7
2.2.3 Physical dye removal methods 8
2.2.4 Efficiency of dye removal methods 9
2.2.5 Adsorption 10
2.2.6 Adsorption process 10

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 2.3 Adsorbents 11
2.4 Zeolite 11
2.4.1 Basics of zeolites 12
2.4.2 Properties of zeolite 13
2.5 Factors affecting removal of dye 14
2.5.1 Influence of pH 14
2.5.2 Influence of initial dye concentration 15
2.5.3 Influence of solution temperature 15
2.5.4 Influence of adsorbent dosage 15
2.5.5 Influence of kinetics 16
2.6 Adsorption equilibrium isotherms 16
2.7.1 Langmuir isotherm 16
2.7.2 Freundlich isotherm 17
2.7.3 Temkin isotherm 17
2.7.4 Dubinin–Radushkevich isotherm model 18
2.7 Adsorption kinetics 19

CHAPTER THREE
MATERIALS AND METHODS 20
3.1 Materials 20
3.2 Methodology 20
CHAPTER FOUR
RESULT AND DISCUSSION 23
4.1 Characterization of zeolite Y 23
4.2 Effects of operation parameters on the adsorption 26
4.3 Adsorption Isotherm Studies 32
4.4 Adsorption Kinetic Studies 34

CHAPTER FIVE
CONCLUSION AND RECOMMENDATION 38
5.1 Conclusion 38
5.2 Recommendation 38
REFERENCES 39

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 LIST OF FIGURES

Fig 4.1a SEM image before adsorption 23

Figure 4.1b SEM image after adsorption 23

Fig 4.1(c): Spectra FTIR of zeolite Y after adsorption 25

Fig 4.1(d): FTIR spectra of zeolite Y before adsorption 25

Fig 4.1(e) EDX before adsorption 26

Fig 4.1(f) EDX after adsorption 26

Figure 4.2.1 Temperature effect on the adsorption capacity of Eosin yellow dye 27

Fig 4.2.2(a) Effect of initial dye concentration and time on EYD at 293K 28

Fig 4.2.2(b) Effect of initial dye concentration and time on EYD dye at 303K 28

Fig 4.2.2(c) Effect of initial dye concentration and time on EYD at 313K 29

Fig 4.2.2(d) Effect of initial dye concentration and time on EYD at 323K 29

Fig 4.2.2(e) Effect of initial dye concentration and time on EYD at 323K 30

Figure 4.2.3 pH effect on Eosin yellow dye adsorption by Zeolite Y 31

Figure 4.2.4 Adsorbent dosage on Eosin yellow dye adsorption by Zeolite Y 32

Figure 4.3(a) Langmuir isotherm at different temperatures unto Eosin yellow dye 34

Figure 4.3(b) Freundlich isotherm at different temperatures unto Eosin yellow dye 34

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 LIST OF TABLES

Table 4.1: Physiochemical Analysis of Zeolite Y produced from Arobieye Kaolin [21]

Table 4.3 Langmuir and Freundlich isotherm model parameters for the adsorption of

Eosin yellow dye

Table 4.4 Kinetic models constants with the correction coefficients for Eosin yellow

dye adsorption

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 CHAPTER 1

INTRODUCTION

Background of Study

A wide range of synthetic dyes are used in the textile, paper, plastic, rubber, food,

pharmaceutical and cosmetic industries and the discharge of dye wastewater is

hazardous to the environmental and ecosystem at large (S. Syafalni et al, 2014). The

presence of these dyes even at very low concentration is very obvious and unwanted,

and may to a large extent affect photosynthetic activity in aquatic life due to reduced

light penetration. Some dyes are also toxic and even carcinogenic (Denise Alves

Fungaro et al, 2009). Recent estimates indicate that approximately 12% of synthetic

dyes used each year is lost during manufacture and processing operation and 20% of

these dyes enter the environment through effluents that result from treatment of residual

industrial wastewaters (Weber and Stickney, 1993). Dyes usually possess complex

aromatic molecular structures enabling them attain more stability and as such causing

them to be difficult to breakdown (biodegrade).

A variety of studies have been carried out to assess the harmful effects of colorants on

the ecosystem. It was discovered that dyes may cause problems in the following ways:

Dyes can have adverse effects on exposed organisms and this depends on the

concentration of the dye and the amount of time the organism was exposed for.

Dyes are intrinsically highly visible; any slight release of effluent may lead to abnormal

coloration of surface water and will as such capture the attention of the public.

Dyes have an inherent ability to reflect sunlight entering the water, this has a

detrimental effect on the growth of bacteria and upsets their biological activity.

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Dyes possess many different and complicated molecular structures, and therefore are

not only difficult treat, but also interfere with municipal waste treatment operations.

Dyes in wastewater undergo chemical and biological changes, consume dissolved

oxygen from the stream and destroy aquatic life.

The methods most often used to remove dyes from wastewater systems include;

physicochemical, chemical, and biological methods, such as flocculation, coagulation,

precipitation, adsorption, membrane filtration, electrochemical techniques, ozonation,

and fungal decolorization. Most of these methods suffer from a number of

disadvantages, such as high capital, operational costs, and problem of unsuccessful

removal of the coloration from wastewater (Wang Chunfeng et al, 2009). 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. Of all the techniques listed above, adsorption in particular is an effective

process for the removal of dyes from aqueous solutions (Denise Alves Fungaro et al,

2009).

Adsorption is a mass transfer operation by which, by attracting the dissolved solution

to its surface, a solid material can selectively extract dissolved parts from an aqueous

solution (Abida Kausar et al, 2018). This method produces on the surface of the

adsorbent a film of the adsorbate. Adsorption techniques using solid adsorbents is a

proven method for treating industrial wastewater (Wang Chunfeng et al, 2009). The

type of adsorbent used in the purification of wastewater plays an important role in the

treatment process. As such, a wide range of adsorbents have been studied and proposed

by various researchers. Some of the commonly used adsorbents include; waste

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biopolymers, activated carbon, diatomite, zeolite, mesoporous silica MCM-48, and clay

minerals were preferred economically in the purification of wastewater as well as their

easy accessibility and availability in nature. (Abukhadra M. R. et al, 2018). Presently,

activated carbon is the most popular adsorbent used for the removal of dyes and other

toxic substances from wastewater because of its success rate, high capacity of

adsorption of organic material, its effectiveness and versatility. However, because it is

a limited natural resource, it has slow adsorption kinetics and low adsorption capacity

of bulky adsorbate due to its microporous nature, disposal problems and also the high

cost and difficulty of regeneration, research into cheap, effective adsorbents such as

clay derivatives has become important (Adeyemo AA et al, 2015).

Natural and synthetic zeolitic materials are a wide class of crystalline materials

with incredible nanoporous properties (microporous) and are primarily made up of

silica tetrahedral units that are closely connected to other alumina tetrahedral units.

Chemical substitution processes between silicon and aluminium ions within their lattice

positions were caused by such open crystalline structures, resulting in a normal

negatively charged surface for all known zeolite minerals. This helps in the formation

of many forms of alkali cations such as Na+, Ca2+, or K+ as a modifier for any excess

in the negative charge of the mineral, thus increasing the efficiency of such structures

as cation exchangers, molecular sieves, or adsorbents in the decontamination of water

contaminants.

1.1 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?

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 • Why adsorption?

1.2 Problem Statement

Water is essential for life on earth. Roughly 2.66% of all the water in the world

(groundwater, lakes and rivers, polar ice and glaciers) is fresh water, but only as little

as 0.6% of this is drinkable (Ugbe and Ikudayisi, 2017).

Due to the outrageous cost of synthetic activated carbon, the adsorption technique for

removal of dye from wastewater is very expensive. Also, because of 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. One pointer to the

gravity of the problem is the fact that two percent (2%) of dyes which are produced are

discharged directly into aqueous effluents (Kysaz et al, 2013). This problem has pushed

so many researchers to find alternatives to activated carbon that are cheap and eco-

friendly. Cheap materials such as clays, ores, charcoal and zeolites are cheaper

alternatives to activated carbon. In this study, Zeolite Y obtained from Kaolin is being

explored and its optimum adsorption capacity for Eosin yellow dye will be determined

as a function of the process variables aforementioned.

1.3 Significance of Research

Water quality is highly essential for excellent human life and the whole earth’s

economic system. Kaolin is one raw material used to produce Zeolite Y. It is abundantly

lying in different parts of the country.

Zeolite Y synthesis has proffered cheaper route and lower reaction temp and has a wide

range of adsorb dye due to its porous size.

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Adsorption has proved to be more cost effective, efficient, and easy to operate and it is

widely considered to be very appropriate for treating wastewater (Kwon et al, 2010,

Yadanaparthi et al, 2019).

1.4 Aims and Objectives

Aim

• To evaluate the potential of Zeolite Y for removal of Eosin yellow dye from

aqueous solution.

Objectives

• To study the respective effects of the process variables (pH, contact time,

agitation speed, particle size of adsorbent, initial dye concentration, adsorbent

dosage and temperature) on the adsorption of dye on the prepared adsorbent.

• To correlate the equilibrium adsorption data with adsorption isotherm, kinetics

study and thermodynamics of adsorption system.

1.5 Delineation of Research

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

be used to remove Eosin Yellow Dye from aqueous solutions via adsorption. The

adsorbent Zeolite Y obtained from Kaolin was pre-prepared whereas the adsorbate

Eosin Yellow Dye was acquired from Landmark agricultural 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.

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 CHAPTER 2

LITERATURE REVIEW

2.1 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 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,
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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 et al, 2016).

2.2 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.

2.2.1 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-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

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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.

2.2.2 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

2.2.3 Physical dye removal methods

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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.

2.2.4 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.

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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 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.

2.2.5 Adsorption

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)

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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).

2.2.6 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).

2.3 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

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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.

2.4 Zeolite

Zeolites are hydrated, crystalline microporous aluminosilicates, whose structures

enclose channels and/or cavities of molecular dimensions (0.3–1.5 nm diameter) (C.

Martinez, A. Corma, 2013). 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 (Britannica, 2021). 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

Natural zeolites: In nature, zeolites often form as crystals in small cavities of basaltic

rocks over time, or as volcanic tuffs or glass altered by saline water interaction. Natural

zeolites are formed in a variety of geological settings, including alkaline deserts, lake

sediments, ash ponds, and marine sediments, at relatively low temperatures. In

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mountainous areas, they crystallize in geologically young metamorphic rocks. The most

basic formula for natural zeolites is shown 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 including Clinoptilolite (also known as Clino zeolites) and Chabazite

have a wide variety of applications, including water treatment, fertilizer application for

soil amendment, and plant growth by enhancing nutrient retention.

Synthetic zeolites: Chemical processes are used to produce these zeolites, which result

in a more uniform and pure state than natural forms in terms of lattice structures, pore

sizes, and cages in their frameworks. Pure chemicals rich in silica and alumina, minerals

found on the surface of the earth, and industrial by-products can all be used to produce

synthetic zeolites. Temperature, strain, reagent solution concentration, pH, activation

process and ageing time, as well as the SiO2 and Al2O3 content of the raw materials, all

influence the type of zeolites developed (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

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 (Kumar et al, 2001). Specific surface area, void depth, pore radius,

particle size, and other physical properties of zeolites are also common.

2.4.2.2 Chemical properties

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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.

2.4.2.3 Ion exchange and adsorption properties

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

contact with the surrounding medium due to their ion exchange or adsorption properties

(Fansuri et al, 2008). The cations are accommodated in zeolites to counteract the

negative charge that develops on the pores' surfaces. This is due to the substitution of

Al atoms for Si atoms in certain [SiO4]4 tetrahedra, resulting in the creation of the

[AlO4]5 tetrahedron, which is connected to other [SiO4]4 tetrahedra by oxygen atoms.

Exposing a sodium zeolite to a waste water sample or a fresh solution containing other

metal cations (e.g. NH4+) may be used to characterize an ion exchange process. In

reality, zeolite sodium ions can be substituted for ammonium ions if they are not

blocked from entering the zeolite pores due to their larger molecular size.

2.4.2.4 Mineralogical properties

In addition to the presence of amorphous glassy phase, X-ray diffraction (XRD)

analysis has been a useful method for testing the presence of minerals such as (mullite,

hematite, magnetite, and -quartz) as the main crystalline phase in fly ash and its zeolites

(raw material used for synthesis of synthetic zeolite from by-products of industries)

(Querol et al, 2007). Scanning electron microscopy (SEM) micrographs have also been

found to be a valuable method for demonstrating the form and grain size of constituent

minerals.

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2.5 Factors affecting removal of dye

Adsorbate/adsorbent interaction, adsorbent surface area and pore structure, chemistry

of the adsorbent surface, existence of the adsorbate, presence of other ions, particle size,

pH, temperature, contact time, and other physico-chemical factors all affect the

adsorption method. As a result, the implications of these parameters must be

considered. The development of industrial-scale dye removal treatment technologies

will be greatly helped by the optimization of such conditions. As a result, some of the

most important factors influencing dye adsorption are discussed in this section.

2.5.1 Influence of pH

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 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 Influence of initial dye 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.

15 | P a g e
2.5.3 Influence of solution 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 Influence of adsorbent dosage

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.

2.5.5 Influence 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 equilibrium isotherms

16 | P a g e
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.

2.6.1 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

• Surface is homogeneous that is adsorption energy is unvarying over all

sites.

• Adsorption on surface is localized that is adsorbed molecules or atoms

are adsorbed at definite localized sites.

• Every site can accommodate only one atom or molecule.

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

𝒒𝒆 = 𝑸𝒐 ×𝑲𝑳 ×𝑪𝒆
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)

17 | P a g e
KL = Langmuir isotherm constant (L/mg).

2.6.2 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 = 𝐥𝐧 𝑲𝒇 + 𝐥𝐧 𝑪𝒆
𝒏

where

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

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

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

heterogeneity of the material).

2.6.3 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 absorbed qe against ln Ce and the constants were determined

from the slope and intercept. The model is given by the

𝑹𝑻
𝑸𝒆 = 𝐥𝐧 (𝑨𝑻 𝑪𝒆 )
𝒃

𝑹𝑻 𝑹𝑻
𝑸𝒆 = 𝒍𝒏𝑨𝑻 + ( ) 𝒍𝒏𝑪𝒆
𝒃𝒓 𝒃

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

18 | P a g e
bT = Temkin isotherm constant

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

T= Temperature at 298K.

2.6.4 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

𝒒𝒆= (𝒒𝒔 )𝒆𝒙𝒑(−𝒌𝒂𝒅 𝜺𝟐 )

𝒍𝒏𝒒𝒆 = 𝒍𝒏(𝒒𝒔 ) − 𝒌𝒂𝒅 𝜺𝟐

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).

𝟏
𝑬= ( )
√𝟐𝑩𝑫𝑹

Where BDR is denoted as the isotherm constant.

2.7 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

19 | P a g e
 used to predict adsorption kinetics. The pseudo first-order model is presented

by the following equation (Ho, 2004).

𝒅𝒒𝒕
= 𝒌𝟏 (𝒒𝒆 − 𝒒𝒕 )
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:

𝒅𝒒𝒕
= 𝒌(𝒒𝒕 − 𝒒𝒆 )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.

20 | P a g e
 CHAPTER 3

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. Eosin yellow dye

3.2 Instrumentation/Apparatus

• Electronic weighing balance

• Magnetic stirrer

• Volumetric flask

• Measuring cylinder

• Whattman 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, Eosin yellow 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 eosin yellow dye prepared

by weighing 1g of Eosin yellow dye into a standard volumetric flask and making up to

the 1000cm3 mark with distilled water. From this stock, lower concentrations of 20, 30,

21 | P a g e
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 2, 4, 6, 8, 10,

15, 20, 30, 45, 60, 75, 90 minutes continuously. The temperature was varied for 293,

303, 313, 323, 333K for each of the dye concentrations. 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 Transform

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

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

22 | P a g e
 CHAPTER 4

RESULTS AND DISCUSSION

4.1 Zeolite Y Characterization

Structural characterization of zeolite Y was investigated using SEM. Fig. 4.1a and 4.1b

show the SEM image before and after adsorption, 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. 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 445.36 m2/g,

30.5342 Å, 0.603567 cm3/g (before) and 442.67 m2/g, 30.5342 Å, 0.603567 cm3/g

(after) respectively;

Fig 4.1(a) SEM image before adsorption Fig 4.1(b) SEM image after

adsorption

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

23 | P a g e
 impurities as reported in Table 4.1. The FTIR spectra of zeolite Y from Arobieye clay

is shown in Fig. 4.1(c) - 4.1(d). It was observed that certain functional groups are

present on the surface of zeolite Y which could influence the adsorption potential of the

material.

Table 4.1: Physiochemical Analysis of Zeolite Y produced from Arobieye Kaolin [21]

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 ratio) 3.46

24 | P a g e
Fig 4.1(c): Spectra FTIR of zeolite Y after adsorption

Fig 4.1(d): FTIR spectra of zeolite Y before adsorption

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

4.1c and 4.1d EDX images before and after adsorption and the elemental composition

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

25 | P a g e
Oxygen. After adsorption there was a significant decrease in silicon; but an increase in

the aluminium and oxygen.

Fig 4.1(e) EDX before adsorption Fig 4.1(f) EDX after adsorption

4.2 Effect of Operation Parameters on the adsorption

4.2.1 Effect of temperature

The effect of temperature on the adsorption of Eosin yellow dye was carried out at

various temperatures of 293, 303, 313, 323, 333K 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 (4.2.1). Increase in temperature of the adsorption process led

to a significant decrease in the adsorption capacity Eosin yellow dye y, which indicates

that the adsorption is exothermic.

26 | P a g e
 Temperature effect on adsorption capacity
35.000

30.000

25.000
20 mg/l
Qe (mg/l)

20.000
30 mg/l
15.000
40 mg/l
10.000
50 mg/l
5.000 60 mg/l
0.000
290 295 300 305 310 315 320 325 330 335
Temp (K)

Figure 4.2.1 Temperature effect on the adsorption capacity of Eosin yellow dye

(time=60min, V=200mg/l, W=0.2g)

4.2.2 Effect of initial dye concentration and adsorption time

The initial dye concentration (20-60 mg/l) and time (0-150 min) effect on Eosin yellow

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

eosin yellow 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 Eosin yellow dye respectively at 293k.

27 | P a g e
 Effect of initial dye concentration and time on Eosin yellow
dye at 293K
45
40
35
30 20 mg/l
Qt (mg/l)

25
30 mg/l
20
15 40 mg/l
10 50 mg/l
5 60 mg/l
0
0 10 20 30 40 50 60 70 80 90 100
Time

Fig 4.2.2(a) Effect of initial dye concentration and time on Eosin yellow dye at 293K

Effect of initial dye concentration and time on Eosin yellow

dye at 303K
40
35
30
25 20 mg/l
Qt (mg/l)

20 30 mg/l
15 40 mg/l
10 50 mg/l
5 60 mg/l
0
0 10 20 30 40 50 60 70 80 90 100
Time

Fig 4.2.2(b) Effect of initial dye concentration and time on Eosin yellow dye at 303K

28 | P a g e
 Effect of initial dye concentration and time on Eosin
yellow dye at 313K
35

30

25
20 mg/l
Qt mg/l)

20
30 mg/l
15
40 mg/l
10
50 mg/l
5 60 mg/l
0
0 20 40 60 80 100
Time

Fig 4.2.2(c) Effect of initial dye concentration and time on Eosin yellow dye at 313K

Effect of initial dye concentration and time on Eosin yellow

dye at 323K
45
40
35
30 20 mg/l
Qt mg/l)

25
30 mg/l
20
15 40 mg/l
10 50 mg/l
5 60 mg/l
0
0 10 20 30 40 50 60 70 80 90 100
Time

Fig 4.2.2(d) Effect of initial dye concentration and time on Eosin yellow dye at 323K

29 | P a g e
 Effect of initial dye concentration and time on Eosin yellow
dye at 333K
50
45
40
35
20 mg/l
Qt (mg/l)

30
25 30 mg/l
20 40 mg/l
15
50 mg/l
10
5 60 mg/l
0
0 20 40 60 80 100
Time (min)

Fig 4.2.2(e) Effect of initial dye concentration and time on Eosin yellow dye at 333K

4.2.3 Effect of pH

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

eosin yellow 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 eosin Y. When the pH value is 2.3 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 eosin Y is the

best under acidic relatively strong conditions implying that the adsorbate is basic and

the reaction is deproteination. With the increase of pH value, the adsorption rate of

eosin Y showed a decreasing trend.

30 | P a g e
 Effect of pH on adsorption rate
100.00
90.00
80.00
70.00
% Removal

60.00
50.00
40.00
30.00
20.00
10.00
0.00
0 2 4 6 8 10 12
pH

Figure 4.2.3 pH effect on Eosin yellow dye adsorption by Zeolite Y (Co=30 mg/l,

temperature= 303 K, Time=60 minutes, W=0.1 g, V=100ml)

4.2.4 Effect of adsorbent dosage

The adsorbent dose determines the adsorbent capacity for a given initial concentration

of eosin yellow 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 Eosin

yellow dye increases with increasing the amount of adsorption. The eosin yellow dye

removal increased from 5.27% to 32.57% by increasing the dose from 0.1 to 0.5 g.

31 | P a g e
 Effect of absorbent dosage on adsorption of eosin yellow
dye
40.00
35.00
30.00
25.00
Removal

20.00
15.00
10.00
5.00
0.00
0 0.1 0.2 0.3 0.4 0.5 0.6
Mass (g)

Figure 4.2.4 Adsorbent dosage on Eosin yellow dye adsorption by Zeolite Y (Co=30

mg/l, temperature= 303 K, Time=60 minutes, V=100ml)

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 (4.1)

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

32 | P a g e
𝐶𝑒⁄ = [1⁄
𝑞𝑒 𝑄𝑚𝑎𝑥. 𝑘𝑙 ] + (𝐶𝑒/𝑄𝑚𝑎𝑥). (4.2)

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

KL = slope/intercept.

Table 4.3 shows the adsorption isotherm model parameter for eosin yellow dye unto

zeolite Y. Figures 4.3 (a) and (b) showed the graph of Langmuir and Freundlich

isotherm for eosin yellow dye at different temperatures.

Table 4.3 Langmuir and Freundlich isotherm model parameters for the adsorption of

Eosin yellow dye

Isotherms Parameters 293K 303K 313K 323K 333K

Langmuir Qo (mg/g) 2.6 52.91 47.17 28.49 21.23

B (L/mg) 6.38 30.75 22.02 14.61 9.02
R2 0.8064 0.9111 0.9847 0.7735 0.96

RL 0.00778 0.00162 0.00227 0.00341 0.00551

Freundlich KF 0.0036 3.2838 5.7586 5.9062 7.3133

1/n 2.5283 0.4737 0.4297 0.447 0.447

R2 0.8804 0.9202 0.9407 0.7503 0.9362

33 | P a g e
 y =3 0.0485x + 0.3092y = 0.0189x + 0.5812y = 0.0212x + 0.4668y = 0.0351x + 0.5128
y = 0.0471x + 0.4247
R² = 0.8066 R² = 0.9111 R² = 0.9847 R² = 0.7735 R² = 0.96
2.5

2
293K
Ce/Qe

1.5 303K
313K
1
323K
0.5 333K

0
0 5 10 15 20 25 30 35 40 45
Ce (mg/l)

Figure 4.3(a) Langmuir isotherm at different temperatures unto Eosin yellow dye

4 y = 2.5283x - 5.6213 y = 0.4737x + 1.189 y = 0.4297x + 1.7507

R² = 0.8804 R² = 0.9202 R² = 0.9407
3.5

2.5 293K
In Qe

2 y = 0.447x + 1.776 303K

R² = 0.7503 y = 0.447x + 1.9897
1.5 R² = 0.9362 313K
323K
1
333K
0.5

0
0 0.5 1 1.5 2 2.5 3 3.5 4
In Ce

Figure 4.3(b) Freundlich isotherm at different temperatures unto Eosin yellow dye

4.4 Adsorption kinetics studies

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 Eosin yellow dye was

studied. The lagergren pseudo first order considers the rate of occupation of the

34 | P a g e
adsorption site which is proportional to the number of unoccupied sites. The First-order

and Second-order Equation are given respectively;

𝐾1
log(𝑞𝑒 − 𝑞𝑡 ) = 𝑙𝑜𝑔𝑞𝑒 − 𝑡 (4.3)
2.303

A plot of log (qe – qt) versus t will give a straight line from which k1 and qe can be

evaluated from the slope and intercept.

𝑡 1 1
= 2
− 𝑡 (4.4. )
𝑞𝑡 𝑘2 𝑞𝑒 𝑞𝑒

A plot of t/qt versus t will give a straight line from which k2 and qe can be evaluated.

The second order pseudo model gives the best description of the mechanism of eosin

yellow dye unto zeolite Y. Apart from it having the highest R2 of 0.996 as shown in

Table 4.4, the adsorption capacity calculated from this model was very close to the

experimental values. Figures 4.4 (a) and (b) show the graph of the pseudo-first order

and pseudo Second-order Model of eosin yellow dye at 293K.

35 | P a g e
Table 4.4 Kinetic models constants with the correction coefficients for Eosin yellow

dye adsorption

Kinetic model Parameters

293K
Co (mg/l) 20 mg/l 30 mg/l 40 mg/l 50 mg/l 60 mg/l
qoexpt
Pseudo-first order 3.65 9.61 18.43 23.92 37.6
(mg/g)
R2 0.9446 0.9623 0.765 0.8933 0.9262
qecal (mg/g) 2.46 8.7 9.99 13.68 34.11
0.0824 0.0686 0.0439 0.1013 0.0872
K1
5 3 9 3 8

Pseudo-second
R2 0.9961 0.9289 0.995 0.9964 0.9936
order

qecal(mg/g) 4.03 13.95 19.53 26.32 42.02

qoexp(mg/g) 3.65 9.61 18.43 23.92 37.6
0.0547 0.0050 0.0112 0.0036
K2 0.0118
5 2 2 8

y =2-0.0358x + 0.3907 y = -0.0298x + 0.9396 y = -0.0191x + 0.9997 y = -0.0379x + 1.5329

R² = 0.9446 R² = 0.9623 R² = 0.765 y = -0.044x + 1.1362 R² = 0.9262
R² = 0.8933
1.5

1
20 mg/l
log (qe-qt)

0.5 30 mg/l

0 40 mg/l
0 5 10 15 20 25 30 35 40 45 50 50 mg/l
-0.5
60 mg/l
-1

-1.5
T (mins)

Fig 4.4 (a): Pseudo first order kinetic plot for adsorption of Eosin yellow dye at

293K

36 | P a g e
 25 y = 0.0717x + 1.0244 y = 0.0512x + 0.2222 y = 0.038x + 0.1287 y = 0.0238x + 0.1541
y = 0.248x + 1.1233 R² = 0.9289 R² = 0.995 R² = 0.9964 R² = 0.9936
R² = 0.9961
20

20 mg/l
log (qe-qt)
15
30 mg/l
10 40 mg/l
50 mg/l
5
60 mg/l

0
0 10 20 30 40 50 60 70 80 90 100
T (mins)

Fig 4.4 (b): Pseudo second order kinetic plot for adsorption of Eosin yellow dye at

293K

37 | P a g e
 CHAPTER 5
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).

Adsorption of Eosin yellow dye was investigated under several parameters such as

effect of time, temperature, adsorbent dosage, pH. 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 eosin

yellow 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 eosin yellow 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 eosin yellow dye removal from aqueous solution.

5.2 Recommendation

I recommend that studies should be carried out using the adsorbent on a large scale for

the treatment of industrial wastewater.

38 | P a g e
REFERENCES

• Ugbe, F. A., & Ikudayisi, V. A. (2017). The kinetics of eosin yellow removal

from aqueous solution using pineapple peels. Edorium Journal of Waste

Management, 2, 5-11.

• Ali, B., & Dikko, Z. T. Geochemical And Geological Characterisation Of

Kaolinite Deposits Around Kaoje, Kebbi State, Nigeria.

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