ABSTRACT
This research investigates the removal of the dyes, methyl orange (MO) and methyl blue (MB) from aqueous environment using two biosorbent materials, namely, orange and yam peels. Samples of orange and yam peels were analysed using UV-Visible spectrophotometer. These two selected biosorbents were studied under varying experimental conditions such as: contact time, temperature, pH, dye concentrations among others. The kinetics of sorption were well correlated using the pseudo first and second order constants ranging from 0.742gmg-1min for methyl orange and 5.741gmg-1min for methyl blue. The results of these experiments were modeled using Langmuir and Freundlich isotherm, some of the RL values at all four temperatures used did not fall between 0-1 while all KF values for Freundlich isotherm model fell between 1-10 this implies that these two locally available adsorbents, fitted completely into Freundlich but partly into Langmuir model. Other parameters like sorption capacity, sorption maximum were also determined. The calculated sorption maximum capacities are 46.67% (1.67mg/g), for yam peel and 42.04% (1.57mg/g) for orange peel at 318K. It was observed that sorption increases with increase in temperature in Kelvin for the two biosorbents studied. The isotherm models evaluated showed that the two biosorbents have significant potentials as adsorbents for the removal of methyl orange and methyl blue colours from aqueous environments.The results obtained shows that modified and unmodified powdered orange and yam peels, MOP, MOP, UOP and UYP are promising and cheap adsorbent that can be used for the removal of the methyl orange and methyl blue from solutions. It is therefore recommended that, modified and unmodified orange peel and yam peel should be used to adsorb waste water and solutions contaminated with dyes for industrial and domestic usage, they are easy and cheap to afford.
TABLE OF CONTENT
Title page i
Declaration ii
Certification iii
Dedication iv
Acknowledgement v
Table of contents vii
List of tables x
List of figures xi
List of abbreviations xii
Abstract
CHAPTER
1: INTRODUCTION
1.1 Background
of the study 1
1.2 Aims
and Objectives of the study 2
1.3 Justification
of the study 3
1.4 Significance
of the study 3
1.5 Scope
of the work 3
CHAPTER
2: LITERATURE REVIEW
2.0 Literature
review 4
2.1 Adsorption 4
2.2 Dyes
6
2.3 Definition
of dye 8
2.4 History of dyes 9
2.5
Methyl blue dye 10
2.6 Methyl
orange dye 11
2.7 Reasons
why dyes are coloured 11
2.8 Mechanism
for dye colour alteration 12
2.9 Basic adsorption isotherms 12
2.9.1 Freundlich
isotherm 13
2.9.2 Langmuir
adsorption isotherm 13
2.9.3 BET
adsorption isotherm 14
2.9.4 SIPS
Isotherm 15
2.10 Adsorption
kinetics 15
2.10.1 Adsorption kinetic models 16
2.11 Adsorption
diffusion models 18
2.12 Liquid
film diffusion model 18
2 .12.1Linear driving force rate law 18
2.12.2 Film
diffusion mass transfer rate equation 19
2.13 Intra-particle
diffusion model 19
2.14 Reasons
for the use of adsorption process in wastewater treatment 20
2.15 Driving
force for adsorption process 20
2.16 Adsorption
in wastewater treatment 20
2.17 Adsorption
as a physical process 21
2.18 Common
adsorbents 21
2.19 Factors
affecting adsorption, process 22
2.20 Adsorption
equilibrium 23
2.21 Dye
removal methods 23
2.22 Natural
adsorbent 25
2.23 Agro/industrial
wastes identification 25
2.24 Agro
– wastes in effluents treatment 26
2.25 Sources
of waste water 27
2.26 Industrial
applications of adsorption 27
2.27 Adsorption
in biological system 28
2.28 Desorption study 28
2.29 Point of zero charge 29
2.30 Detoxification 29
CHAPTER
3: MATERIALS AND METHODS
3.0 Materials
and methods 31
3.1 Materials 31
3.2 Methods 32
3.3 Modification
of Adsorbent 32
3.3.1 Modification
of orange peel 32
3.3.2 Modification
of yam peel 33
3.4 Blank
adsorption experiment 33
3.5
Adsorption equilibrium and kinetic studies 33
3.6
Analytical Measurements 34
3.7 Biosorptionequillibrium
experiment 35
3.8
Effect of biosorbent dose on biosorption 35
3.9 Effect of biosorbent initial
concentration on biosorption 37
3.10 Influence of contact time on biosorption 38
3.11 Effect of pH on biosorption 39
3.12
Effect of temperature on biosorption 39
3.13
Separation factor (Rl) 40
3.14 Adsorption
isotherm studies 41
3.15 Point
of zero charge 42
3.16 Fourier
transform-infra red (FT-IR) 43
3.17 Statistical analysis 43
CHAPTER
4: RESULTS AND DISCUSSION
4.0 Results and
discussion
4.1 Results of adsorbent
dose 44
4.1.1 Interpretation of statistical analysis 49
4.2 Results of contact
time effect on adsorption 50
4.3 Results of initial
dye concentration 55
4.4 Results of pH
depended study of MO and MB adsorption 61
4.5 Results of
temperature depended study of MO and MB adsorption 67
4.6 Results of point of zero charge 73
4.7 Results of separation factor 74
4.8 Results of adsorption isotherm studies 75
4.9. Results
of pseudo first (1st) and second (2nd)
order for
kinetic study of MO and MB
biosorption by OP and YP 80
4.10. Results of Forrier Transform
Infra-red (FT-IR) study of YP and OP 85
4.11. Interpretation of statistical analysis 96
CHAPTER
5: CONCLUSION AND RECOMMENDATION
5.1 Conclusion 97
5.2 Recommendation 98
REFFERENCES
99
Appendices 108
LIST
OF TABLES
2.1 Classification of dyes 9
2.2 Advantages and disadvantages of dye removal
method 23
2.3 Agricultural produce table 26
3.1 List of materials and their sources 31
3.2 List of materials and their sources. 32
4.1 Results of MO
sorption on MOP adsorbent doses 44
4.2 Results of MO
sorption on UOP adsorbent doses 44
4.3 Results of MB
sorption on MOP adsorbent doses 45
4.4 Results of MB
sorption on UOP adsorbent doses 45
4.5 Results of MO
sorption on MYP adsorbent doses 46
4.6 Results of MO
sorption on UYP adsorbent doses 46
4.7 Results of MB
sorption on MYP adsorbent doses 47
4.8 Results of MB
sorption on UYP adsorbent doses 48
4.9 Results of contact
time of MO on MOP 49
4.10 Results of contact
time of MO on UOP 50
4.11 Results of contact
time of MB on MOP 51
4.12 Results of contact
time of MB on UOP 52
4.13 Result of contact time
of MO on MYP 53
4.14 Results of contact
time of MO on UYP 53
4.15 Results of contact
time for MB on MYP 54
4.16 Effect of contact time
for MB on UYP 54
4.17 Results of initial dye
(MO) concentrations adsorbed on MOP 56
4.18 Results of initial dye
(MO) concentrations adsorbed on UOP 57
4.19 Results of initial dye
(MB) concentrations adsorbed on MOP 58
4.19 Results of initial dye
(MB) concentrations adsorbed on MOP 58
4.21 Results of initial dye
(MO) concentrations adsorbed on MYP 59
4.22 Results of initial dye
(MO) concentrations adsorbed on UYP
59
4.23 Results of initial dye
(MB) concentrations adsorbed on MYP 60
4.24 Results of initial dye
(MB) concentrations adsorbed on UYP 60
4.25 Results of pH
dependent study of MO biosorption by MOP 62
4.26 Results of pH
dependent study of MO biosorption by UOP 62
4.27 Results of pH
dependent study of MB biosorption by UOP 63
4.28 Results of pH
dependent study of MB biosorption by UOP 63
4.29 Results of pH
dependent study of MO biosorption by MYP 64
4.30 Results of pH
dependent study of MO biosorption by UYP 64
4.31 Results of pH
dependent study of MB biosorption by UYP 64
4.32 Results of pH
dependent study of MB biosorption by UYP 64
4.33 Results of effect of
temperature on the adsorption of MO on MOP
67
4.34 Results of effect of
temperature on the adsorption of MO on UOP
67
4.35 Results of effect of
temperature on the adsorption of MB on MOP
68
4.36 Results of effect of
temperature on the adsorption of MB on UOP
69
4.37 Results of effect of
temperature on the adsorption of MO on MYP
70
4.38 Results of effect of temperature on the
adsorption of MO on UYP 70
4.39 Results of effect of
temperature on the adsorption of MB on MYP
72
4.40 Results of effect of
temperature on the adsorption of MB on UYP 72
4.41 Point of zero charge
(pHpzc) 73
4.42 Results
of FT – IR Spectra characteristics of UYP and UOP before
and after MO and MB dye adsorption 88
4.43 The FT – IR Spectra
characteristics of activated YP and OP before
and after dye adsorption 93
a1 Adsorption isotherm parameters 105
a1 Kinetic model parameters of adsorption
of MO on to YP 106
a2 Kinetic model parameters of adsorption
of MO on to OP 106
a3 Kinetic model parameters of adsorption
of MB on to YP 107
a4 Kinetic model parameters of adsorption
of MB on to OP 107
a5 Intra-particle diffusion of MO and MB on
OP and YP 108
LIST
OF FIGURES
2.1 Structure
of methyl blue 10
2.2 Structure
of methyl orange 11
4.1 Results
of biosorbent dose of MOP and UOP on MO 45
4.2 Results
of biosorbent dose of MOP and UOP on MB 46
4.3 Results
of biosorbent dose of MYP and UYP on MO 47
4.4 Results
of biosorbent dose of MYP and UYP on MB 48
4.5 Combined result of
contact time of MO on MOP and UOP 51
4.6 Combined result of contact time of MB on MOP and UOP
52
4.7 Combined result of contact time of MO on MYP and UYP
54
4.8 Combined result of contact time of MB on MYP and UYP
55
4.9 Combined
plot for effect of contact time 56
4.10 Plot
of initial dye concentration of MO adsorbed on MOP and UOP
57
4.11 Plot
of initial dye concentration of MB adsorbed on MOP and UOP
58
4.12 Plot of initial dye concentration of MO adsorbed on MYP and
UYP 59
4.13 Plot of initial dye concentration of MB adsorbed on MYP and
UYP 61
4.14 Results of pH
dependent study of MO biosorption by MOP and UOP 62
4.15 Results of pH
dependent study of MB biosorption by MOP and UOP 63
4.16 Results of pH
dependent study of MB biosorption by MYP and UYP 65
4.17 Combined results of pH dependent study of MO and MB biosorption
By MOP, UOP, MYP, and UYP
66
4.18 Plot of results of temperature dependent
studies on the rate of
biosorption of MO on MOP and UOP
68
4.19 Plot of results of temperature dependent
studies on the rate of
biosorption of MB on MOP and UOP
69
4.20 Plot of results of temperature dependent
studies on the rate of
biosorption of MO on MYP and UYP 70
4.21 Plot of results of temperature dependent
studies on the rate of
biosorption of MB on MYP and UYP 72
4.22 Point
of zero charge (pHzpc) profile for OP and YP biomass
74
4.23 Separation factor (Rl) profile
for biosorption of MO and MB as a
function of initial dye
concentration 75
4.24 Langmuir
isotherm for biosorption of MO dye stuffs by OP
76
4.25 Langmuir
isotherm for biosorption of MO dye stuffs by YP
77
4.26 Langmuir
isotherm for biosorption of MB dye by OP
77
4.27 Langmuir
isotherm for biosorption of MB by YP
78
4.28 Freundlich
isotherm for biosorption of MO dye stuffs by OP
78
4.29 Freundlich
isotherm for biosorption of MO dye stuffs by YP
79
4.30 Freundlich
isotherm for biosorption of MB dye stuffs by OP
79
4.31 Freundlich
isotherm for biosorption of MB dye stuffs by YP
80
4.32 Pseudo-first
order plot for kinetic study of MO biosorption by OP 81
4.33 Pseudo-second
order plot for kinetic study of MO biosorption by OP 82
4.34 Pseudo
first order plot for kinetic study of MO biosorption by YP 82
4.35 Pseudo
second order plot for kinetic study of MO biosorption by YP 83
4.36 Pseudo
first order plot for kinetic study of MB biosorption by OP 83
4.37 Pseudo
second order plot for kinetic study of MB biosorption by OP 84
4.38 Pseudo
first order plot for kinetic study of MB biosorption by YP 84
4.39 Pseudo
second order plot for kinetic study of MB biosorption by YP 85
4.40 FT-IR spectrum of unmodified orange peel
before dye adsorption 86
4.41 FT-IR spectrum of unmodified orange peel after MO dye adsorption 86
4.42 FT-IR spectra of unmodified orange peel after MB dye adsorption 87
4.43 FT-IR
spectra of unmodified yam peel after MO dye adsorption 87
4.44 FT-IR spectra of modified yam peel after MB
dye adsorption 88
4.45 FT-IR spectrum of modified YP and OP before
dye adsorption 89
4.46 FT-IR spectrum of modified OP fibre after
MO adsorption 92
4.47 FT-IR spectrum of activated YP after MO
adsorption
93
4.48 FT-IR spectra of activated OP after MB
adsorption
94
4.49 FT-IR spectra of
activated YP after MB adsorption
94
CHAPTER 1
INTRODUCTION
1.1 BACKGROUND
OF THE STUDY
Colour is visible in the dark and in the light. The presence of
even minute amounts of coloured pollutants in water bodies makes it undesirable
due to its appearance. Adsorption of colour from textile and manufacturing
waste water is currently one of the major problems for environmental managers
(Ho and Chiang, 2001). Dyes may significantly affect photosynthetic activity in
aquatic plants due to their light absorption. (Hameed and El-Khaiary, 2008).
The adsorption of dye-bearing effluents is a major challenge due to the
difficulty in treating such wastewaters by conventional adsorbent treatment
method (Hameed, 2008a). Some of the commonly used methods for colour removal are
biological oxidation and chemical precipitation while some commonly adsorbents
are silca gel, charcoal activated carbon, clay, rice husk, maize cub, to
mention but few. Azo dyes are dyes containing =N=N= ammine functional group,
they are very important compounds; they have wide application and used in many
industrial fields (Haqueet al.,2010).
The presence of dyes in water is not desirable
because of their toxic nature to the aquatic life and the environment.
Therefore, the removal of such compounds from waste water is a vital task
(Clarke et al., 2001).
Activated carbon, Silca gel and Charcoal have been commercially
available and have long been used as adsorbents in industries to remove colours
from dyed materials due to their superior adsorption capacities (Haqueet al.,2010).
Theproperties of activated carbon depend on the preparation conditions as well
as the chemical nature of the activated carbon surface used (Kannan, et al.,2002).
The term adsorption kinetic means the rate of molecular uptake
from the adsorbent solution to the adsorbent surfaces after overcoming all of
the intra and intermolecular forces that tries to preclude the adsorption
process (Knabel, 2003).
The kinetic data are valuable for determining the period required
to reach equilibrium and assessing the adsorbent performance for effluent
material adsorption. These data explains the mechanism of adsorption which is
essential for improving the efficiency of such processes. For these reasons, great
attention has been paid recently toward the development of such studies (Abia
and Igwe, 2005).
However, the presence of very low concentrations of dyes in
aqueous effluents (less than 1ppm for some dyes) is slightly visible and
obstructs penetration of sunlight into the water bodies; this has a deleterious
effect on photosynthesis and aquatic life (Arami et al., 2005).
Dyes are of different chemical varieties such as acidic, basic and
dispersed, examples are azo-, diazo-, anthraquinone-based and metal complex
types. The highest rates of dye toxicity have been found amongst the basic and
diazo direct dyes (Robinson et al.,
2001).
The removal of dyestuffs from effluents is of great importance in
many countries worldwide for environmental and water reuse concerns (Choy et al., 1999).
Due
to the low biodegradability of dyes, conventional biological treatment
processes are not very effective in treating dye wastewaters; therefore, they
are usually treated by either physical or chemical processes (Azhar et al., 2005).
1.2 AIM
AND OBJECTIVES OF THE STUDY
The study is aimed at the removal of dyes using low cost
adsorbents.
The
objectives of this study are to;
- Determine the rate of adsorption
of dyes on orange and yam peels.
- Ascertain the
quantity/amount of the adsorbates - dye effluents that could be adsorbed
by these adsorbents (yam and orange peels)
- Investigate the effect
of chemically modified yam and orange peels on the rate of dye adsorption
of dye
- Compare the rate of
adsorption of the modified yam and orange peels to the unmodified
- Establish the sorption
isotherm that best fit the adsorption mechanism
- Adsorption optimization through pH, concentration,
temperature, time and material dosage studies.
1.3 JUSTIFICATION
OF THE STUDY
To
determine the efficiency of yam and orange peels can serve as adsorbents of dyes
in aqueous solutions in the treatment of industrial water before discharge. The
research finding will go a long way in reducing high cost of waste water
treatment before discharge. It will also provide alternative source of
treatment for industries, hence reducing pollution in our environment which is
of great concern.
1.4 SIGNIFICANCE
OF THE STUDY
The outcome of this study will encourage environmentalists to
device an indigenous method/materials for solving environmental pollution
problems through the use of biodegradable materials like yam peel and orange
peel to treat water bodies polluted with dye by sorption method.
1.5 SCOPE
OF THE WORK/STUDY
This work covers the use of biodegrable materials like yam peel and
orange peel for the removal of dye polluted aqueous environment. This also
includes the sorption Isotherm modelling of data generated thereof using models
like Freundlich and Langmuir model, among others.
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