TABLE OF CONTENTS

Page

LIST OF TABLES i
LIST OF FIGURES ii
LIST OF ABBREVIATIONS iii

CHAPTER

1 INTRODUCTION 1
1.1 Background of study 4
1.2 Problem statement 4
1.3 Significance of the study 4
1.4 Objective of the study 5

2 LITERATURE REVIEW 6
2.1 Dyes 6
2.1.1 Classification of dyes 7
2.1.2 Methylene blue dye 9
2.1.3 Negative impacts of Methylene blue dye 10
2.2 Methods of dye removal 11
2.4 Adsorption 12
2.5 Adsorbent 14
2.5.1 Activated carbon 15
2.5.2 Low-cost adsorbent 16
2.5.3 Agricultural solid waste 17
2.5.4 Etlingera Coccinea plant 19
2.6 Characterization Instrumentation 21
2.6.1 Scanning electron microscopy (SEM) 21
2.6.2 FTIR spectroscopy 23

i
 3 METHODOLOGY 24
3.1 Materials 24
3.1.1 Raw material 24
3.1.2 Chemicals 24
3.1.3 Instruments 25
3.2 Preparation of Etlingera Coccinea waste 26
3.3 Adsorbate preparation 26
3.4 Characterization of adsorbent 27
3.5 Adsorption experiments 27
3.5.1 The effect of particle size 27
3.5.2 The effect of contact time 27
3.5.3 The effect of initial dye concentration 28
3.6 Calculations 29
3.6.1 Percentage of colour removal 29
3.6.2 Adsorption capacity 29
3.7 Equilibrium Isotherm 29

4 RESULT AND DISCUSSIONS 31

4.1 Adsorption equilibrium studies 31
4.1.1 Effect of particle size 31
4.1.2 Effect of contact time 34
4.1.3 Effect of initial dye concentration 37
4.2 Adsorption isotherms 40
4.3 Characterization of adsorbent 44
4.3.1 SEM analysis 44
4.3.2 FTIR analysis 46

5 CONCLUSION AND RECOMMENDATION 49

GANTT CHART 31
CITED REFERENCES 32

ii
 LIST OF TABLES

Table Page

2.1 Properties of dyes classified on their usage 8

2.2 The advantages and disadvantages of different dye removal 11

methods

2.3 Adsorption capacities, qm (mg/g) of methylene blue dye from 18

various agricultural wastes

4.1 Effect of particle size of ECLP adsorbent 32

4.2 Effect of particle size of ECSP adsorbent 33

4.3 Effect of contact time of ECLP adsorbent 35

4.4 Effect of contact time of ECSP adsorbent 35

4.5 Effect of initial dye concentration of ECLP adsorbent 38

4.6 Effect of initial dye concentration of ECSP adsorbent 38

4.7 Isotherm parameters for removal of MB dye by ECLP and ECSP 41

adsorbents.

iii
 LIST OF FIGURES

Figure Page

2.1 Chemical structure of methylene blue dye 9

2.2 Basic terms used in adsorption theory 13

2.3 Etlingera coccinea plant 20

2.4 Etlingera coccinea inner stem 20

2.5 Scanning electron microscopy (SEM) 21

2.6 Morphology structures of ACLP before and after MB loaded 22

2.7 FTIR spectroscopy 23

2.8 FTIR spectroscopy of raw and MB loaded ACLP 24

4.1 Effect of ECLP and ECSP adsorbents particle size on MB dye 33

adsorption

4.2 Effect of ECLP adsorbent contact time on MB dye adsorption 35

4.3 Effect of ECSP adsorbent contact time on MB dye adsorption 36

4.4 Effect of ECLP adsorbent initial dye concentration on MB dye 39

adsorption

4.5 Effect of ECSP adsorbent initial dye concentration on MB 39

adsorption

4.6 Langmuir isotherm of ECLP adsorbent 45

4.7 Freundlich isotherm of ECLP adsorbent 46

4.8 Langmuir isotherm of ECSP adsorbent 48

iv
 LIST OF ABBREVIATIONS

MB : Methylene Blue

ECW : Etlingera Coccinea Waste

LCA : Low-Cost Adsorbent

SEM : Scanning Electron Microscopy

FTIR : Fourier Transform Infrared Spectroscopy

UV : Ultraviolet

ACLP : Ageratum Conyzoides Leaf Powder

ECLP : Etlingera Coccinea Leaf Powder

ECSP : Etlingera Coccinea Stem Powder

v
 ABSTRACT

REMOVAL OF METHYLENE BLUE DYE USING Etlingera Coccinea WASTE AS

ADSORBENT

This study was conducted to investigate the potential of Etlingera Coccinea wastes
(ECW) as adsorbent to remove methylene blue (MB) dye from wastewater. The ECW
were collected, washed, dried, crushed, ground and sieved to different particle sizes.
Three different parameters were used such as effect of particle size (<125, 125 -250, 250-
500 and 500 µm), contact time (10-50 minutes) and initial dye concentration (5-30 ppm)
to study their effect towards adsorption process. The amount of MB dye removed from
the aqueous solution revealed to be increased when using smaller particle size, longer
contact time with adsorbent and lower concentration of methylene blue dye. The
Langmuir and Freundlich equilibrium models were studied and the maximum adsorption
capacity, qmax was 0.1744 mg/g. The equilibrium data for ECLP adsorbent was found to
fit well with Freundlich model which describes multilayer formation and for ECSP
adsorbent was found to fit well with Langmuir model which describes monolayer
formation during the adsorption from 5 ppm to 30 ppm. FTIR and SEM analysis for
characterization of adsorbents gave result on functional group and porous structure of
ECLP and ECSP adsorbents that directly affect the adsorption process of MB onto the
adsorbents.

vi
 ABSTRAK

PEMBUANGAN WARNA”METHYLENE BLUE” MENGGUNAKAN SISA Etlingera

coccinea SEBAGAI PENJERAP

Kajian ini dijalankan untuk menyelidik potensi sisa Etlingera coccinea (ECW) untuk
menjerap “methylene blue” (MB) daripada air yang tercemar. ECW telah dikumpulkan,
dicuci, dikeringkan, dihancurkan, dikisar dan disaring kepada pelbagai saiz. Tiga
parameter yang berbeza seperti saiz zarah (<125, 125 -250, 250-500 and 500 µm), masa
sentuhan (10–50 minit) dan kepekatan awal pewarna (5–30 ppm) telah digunakan untuk
mengkaji kesan mereka terhadap proses penjerapan. Jumlah pewarna MB dikeluarkan
daripada larutan pewarna telah terbukti meningkat apabila menggunakan saiz zarah
penjerap yang lebih kecil, masa sentuhan yang lebih lama dan kepekatan MB yang lebih
rendah. Model Langmuir dan Freundlich telah dikaji dan kapasiti maksima penjerapan
adalah 0.1744 mg/g. Data keseimbangan untuk penjerap ECLP didapati sesuai dengan
model Freundlich yang menyifatkan pembentukan berlapis and untuk pnjerap ECSP
didapati sesuai dengan model Langmuir yang menyifatkan pembentukan satu lapisan
semasa penjerapan daripada 5 ppm sehingga 30 ppm. Analisis FTIR dan SEM untuk
pencirian bahan penjerap memberi keputusan tentang kumpulan fungsi dan struktur
berliang permukaan penjerap yang memberi kesan secara langsung terhadap proses
penjerapan MB ke penjerap.

vii
 CHAPTER 1

INTRODUCTION

1.1 Background of study

Water pollution is a serious environmental problem that raises concern

around the world. It is mainly caused by the addition of chemical, physical, or

biological substances in certain concentrations, either naturally or of man-made

origin (Metcalf et al., 2003; Forgacs et al. 2004). Numerous Malaysian industrial

sectors, such as textile, paper, paint, pharmaceuticals, food, leather, cosmetics,

tannery, printing and plastic industries employ wide varieties of dye to colour

their products (Wong et al., 2013). Wastewater from textile industry has been

acknowledged as one of the major contribution of wastewater pollution in

Malaysia, considering the volume discharged and the effluent composition.

According to Ferrero (2007), there are more than 100,000 types of

commercially available dyes and more than 700,000 tons of dyes are produced

every year. Numerous varieties of dyes exist, including acidic, basic, disperse,

azo, diazo, anthraquinone based and metal complex dyes (Ezechi et al., 2015).

Among of all the available dyes, methylene blue (MB) dye is one of the most

commonly used in industries such as textiles (dying cotton, wood, and silk) and

pharmaceuticals (Man, Akinbile, & Jun, 2015).

MB dye is a non-biodegradable heterocyclic aromatic chemical compound

with molecular formula of C16H18N3SCl.3H2O which contains three water

1
molecules in hydrated form and based on the various dye classification, MB dye

is classified as a highly toxic cationic dye (Reddy et al., 2015; Ezechi et al.,

2015). MB dye is hazardous to human beings and can cause harmful effects such

as rise of heartbeat, vomiting, shock, cyanosis, jaundices, quadriplegia, tissue

necrosis and even cancer (Reddy et al., 2012). Moreover, their presence can cause

severe problems to the aquatic life, food web and causes damage to the aesthetic

nature of the environment. The colour of the dyes prevent the visible light to

reach to the aquatic life in waters and thereby interfere with the growth of bacteria

and hinder photosynthesis in aquatic plants that is essential for sustaining in

aquatic life. Therefore, it is necessary for wastewater contaminated with MB dye

to be given some treatments before discharge.

Several techniques have been applied to remove MB dyes from

wastewater such as physical, biological and chemical treatments. Chemical

process includes chemical flocculation-coagulation, oxidation, ion exchange and

chemical precipitation. Nonetheless, these techniques cannot be used because of

the expensive costs and cannot be done on a large scale. As for biological

treatment, although it can degrade different pollutants from wastewater, but it

requires large land area and incapable of obtaining satisfactory colour elimination

(Mohammed, Shitu, & Ibrahim, 2014). For physical treatment, two main

processes involved which are adsorption and membrane separation (Brodin and

Theliander, 2012). Membrane separation method is able to remove all types of

dyes from wastewater. However, this technique is unfavorable because of its high

production of concentration sludge. Hence, adsorption is the preferred method as

2
it gives the best results and can be used to remove various types of coloring

materials.

Activated carbon is the most extensively used adsorbent due to its

effectiveness and high adsorption capacity. Nevertheless, it use is still limited

because of its non-regenerability and required additional pretreatment that cause

high operating costs. Biosorption represents a low cost alternative technology for

MB dye treatment as it use adsorbent form natural waste products such as

agricultural and bio waste materials (Lee et al., 2016). The benefits of these

materials include low cost, high efficiency, minimization of chemical or

biological sludge, no additional pretreatment requirement, regeneration of sorbent

and possibility of effluent recovery (Am, Wm, & Oudah, 2015).

Nowadays, the research of adsorbents from untreated plant wastes has

been intensively studied due to relatively cheap, easy availability, eco-friendly,

easy to handle and high adsorption capacities. Moreover, plant wastes materials

often cause dumping space problem for industrial sectors and also to the farmers.

Thus, by generating the wastes into natural adsorbents, it can bring benefits for

both industrial sectors and environment. In this study, Etlingera Coccinea wastes

will be used as adsorbent material for removing MB dye from aqueous solution.

Etlingera Coccinea plant (known as “tuhau” in Sabah) is a member of

Zingiberaceae family. It is a well-known ginger species in Sabah, Malaysia. It has

a strong odour and regarded as a delicacy by the Kadazan Dusun people in Sabah.

However, only the inner stems are eaten and the rest of plant such as leaves and

the outer stems are possibly remain as an agriculture wastes that will cause

3
 potential disposal problems since they exist in large quantities and have no

practical utility. Even though direct open burning in fields is a common option for

disposal, but it will cause serious air pollution problem. Thus, the use of Etlingera

Coccinea wastes as adsorbents will be a good alternative from both economic and

environmental point of view.

1.2 Problem statement

The presence of methylene blue (MB) dyes in wastewater is very

dangerous and has negative effects not only to aquatic life, but to human beings

and environment as well. Thus, effluents containing MB dyes must be treated

using adsorbents before discharge for decolorizing purposes. In conjunction,

agricultural waste materials often cause a disposal problem especially for farmers

and industrial sectors. Hence, the alternative use of agricultural wastes as

adsorbents will be helpful for both industrial and economic point of view.

1.3 Significance of the study

This study will investigate the regeneration of Etlingera Coccinea’s

wastes (ECW) to natural adsorbents for removal of MB dye in aqueous solution.

This study will especially bring benefit to farmers and industrial sectors. Instead

of dispose the agricultural wastes, they can be regenerate to natural adsorbents

thereby reduce disposal problem and the dumping space can be used for other

purposes. On the other hand, the process of regenerating ECW into natural

adsorbents is simple with no use of chemicals hence offers low cost procedure

4
 and safe to human beings. In addition, the data from this study will give

information of adsorption capacity of adsorbent thus validate the use of ECW as

natural adsorbents. Furthermore, this study also will bring awareness that

untreated wastewater infested with MB dyes will give harmful effects to human,

aquatic life as well to the environment. When the wastewater has been treated, the

quality of the water will be suitable with the nature of the environment.

1.4 Objective of the study

The objectives of this study include:

i. To prepare a natural adsorbent from Etlingera Coccinea’s wastes into powder

form.

ii. To investigate the adsorption capacity of untreated Etlingera Coccinea’s wastes

of methylene blue dye in aqueous solution according to the effect of particle

size, contact time, initial dye concentration and pH.

iii. To study on Langmuir and Freundlich models for equilibrium process on

adsorption of MB dye solution using ECW powder.

5
 CHAPTER 2

LITERATURE REVIEW

2.1 Dyes

Dyes are natural or synthetic coloured organic substances that can attach

themselves to surfaces or fabrics to impart colour. There are two key components

of dye molecules: the auxochromes which render the molecule soluble in water

and give enhanced affinity toward the fibers and the chromophores that in charge

for producing colour (Gupta & Suhas, 2009). Even though there are many natural

dyes available, their usage in industries are lack of interests due to costly

production and the colours produced are neither bright nor durable as compared to

synthetic dyes.

Synthetic dyes are broadly used as coloring agents for products of several

industries such as textiles, leather, cosmetic, paper, printing materials and plastics

(Sharma et al., 2010). They are widely used due to reasonably cost and offered a

wide range of new colours, which imparted better properties to the dyed materials.

In addition, the colours produced from synthetic dyes are resistant to heat, light

and biological degradation (Umpuch & Jutarat, 2013). However, it is estimated

that 1-2% of dye production is lost during the usage of the dyes and 5-10% are

discharged to the environment (Forgacs et al., 2004; Khan et al., 2012).

6
 Due to their non-biodegradable nature, their discharge into wastewater

causes a significant source of pollution such as water pollution which raises

concern around the world. The effluents containing these dyes will give

undesirable colour to the water body which result in reduction of sunlight

penetration that interfere with photochemical and biological processes which are

essential for aquatic life (Soni et al., 2012), and indirectly affect the whole

ecosystem. Moreover, synthetic dyes containing hazardous compounds such as

allergic dermatitis, mutagenic and carcinogenic that can cause side effects on

aquatic bio systems even at low concentrations (Pourjavadi & Abedin-

Moghanaki, 2016).

2.1.1 Classification of dyes

Commercial dyes can be categorized in several ways. It can be classified

in terms of structure, colour and application methods (Clarke & Anliker, 1980).

Nevertheless, according to Gupta (2009), classification based on application is

often favourable due to the complexities of the colour nomenclature from the

chemical structure system. Yet, dyes can also be classified in terms of their

properties with their application in industries. Table 2.1 below shows the

properties of dyes classified based on their applications in industries.

7
Table 2.1: Properties of dyes classified on their applications in industries

Dyes Description Chemical types Applications

Acid Water soluble Azo (including Wool, paper, nylon,
premetallized), leather, silk and inks.
anthraquinone,
xanthene, nitro, nitroso
and triphenylmethane.
Basic Water soluble Diazahemicyanine, Inks, paper,
dyes yield cyanine, hemicyanine, polyester, treated
coloured cations triaylmethane, oxazine, nylon and
in solution; very thiazine and acridine. polyacrylonitrile.
bright dyes
Direct Water-soluble, Polyazo compounds, Cotton, leather,
anionic phthalocyanine, paper, rayon and
compounds; can oxazine, and stilbene. nylon.
be applied
directly to
cellulosics
without mordants
(or metals like
chromium and
copper)
Disperse water-insoluble Benzodifuranone, azo, Plastics, acetate,
nonionic dyes anthraquinone, nitro, polyamide and
and styryl. acrylic polyester.
Reactive Water-soluble, Anthraquinone, Wool, cotton, nylon
anionic formazan, and silk.
compounds; phthalocyanine, azo,
largest dye class oxazine and basic.
Sulphur Organic Indeterminate structures Cotton and rayon.
compounds
containing sulfur
or sodium sulfide
Vat Water-insoluble; Indigoids and Wool and cotton.
oldest dyes; more anthraquinone
chemically (including polycyclic
complex quinones).
Source: Christie (2007) and Hunger (2003)

Nonetheless, among all the types of synthetic dyes available, methylene blue dye

is one of the most popular dye used in textile industries (Man, Akinbile, & Jun,

2015).

8
2.1.2 Methylene blue dye

Methylene blue (MB) or tetramethylthionine chloride is a basic dye with

the structure of heterocyclic aromatic chemical compound and has a molecular

formula of C16H18N3SCl.3H2O (Nasuha, Hameed, & Din, 2010). It appears as a

solid, odorless and dark green powder at room temperature. When MB is

dissolved in water, in its oxidized state, a deep blue colour solution is formed

while it is colourless when in its reduced form. According to Banat et al. (1996),

MB is regarded as a highly toxic cationic dye.

Figure 2.1 Chemical structure of methylene blue dye

MB is one of the popular dyes used in industries which involve in dyeing

cottons, textile, wools, leather, momentary hair colorant, coating for paper stock,

pulp and paper and as analytical reagent due to their ease of applicability, stability

and good fastness to materials (Han et al., 2006; Shanna et al., 2010). MB has also

found use in medical applications for staining tissues and as an antidote for

cyanide poisoning (Reddy et al., 2012).

However, due to its non-biodegradable nature, the MB dyes that leaked

into the water bodies gets accumulated which lead to water pollution and causes a

9
 treat to aquatic life. Other than that, the presence of MB dyes in water can affect

human health in various ways. Thus, the effluents related to these industries must

be properly treated before discharge to the water resources.

2.1.3 Negative impacts of MB dyes

The presence of MB dyes in effluent is highly visible even in very little

concentration due to its high intensity of colours. The colours of the dyes interfere

with the transmission of sunlight into streams thus prevent the visible light to

reach to the aquatic life in waters and thereby decrease the photosynthetic activity

that needed for sustaining in aquatic life (Ravindhranath & Reddy, 2014).

The exposure of MB dyes toward human can still generate negative effects

on human health even though the dye is not strongly hazardous. Based on (Reddy,

Verma, & Subrahmanyam, 2015) studies, they stated that the exposure of MB dye

to the eyes can cause irritation, watering and burning sensation to eyelids and

even worse can lead to permanent damage to humans and animals. In addition,

high exposure to skin can cause dryness, redness and discoloration. Ingestion may

lead to irritation of gastrointestinal tract along with symptoms of nausea,

vomiting, dizziness and headache. On top of that, it may give rise to convulsions,

cyanosis, confusion and sweating. If inhaled, it can cause cancer and mutations

due to its degradation products like benzidine, toluidine and other aromatic

compounds which cause some biological and chemical changes in body. Hence,

specific methods for removal of MB dyes from wastewater streams are desired.

10
2.2 Methods of dye removal

Numerous methods have been studied to treat dye bearing effluents which

are biological, chemical and physical treatments (Ghoreishi and Haghighi, 2003).

Despite of the availability of many techniques to remove dye contaminants from

wastewater, each of these methods has its own limitations. Table 2.2 shows the

advantages and disadvantages of different dye removal methods.

Table 2.2: Advantages and disadvantages of dye removal methods

Methods Advantages Disadvantages
Biological treatments
Aerobic Capable of breakdown Recalcitrant to biological
organic compounds and breakdown for some dyes.
degrading various types
Anaerobic of dyes. Anaerobic breakdown
Allows azo and other yields methane and
Combined aerobic- water soluble dyes to be hydrogen sulfide.
anaerobic decolorized. Low biodegradability of
Decolorize aromatic the dyes, less flexibility in
amines and reduction of design and operation,
azo bond. longer times required.
Chemical treatments
Oxidation Simplicity of application Hydrogen peroxide agent
needs to activate by some
Ozonation Ozone can be applied in means.
its gaseous state and does Short half-life (20
not increase the volume minutes).
of wastewater.
Coagulation- Satisfactory removal of
flocculation disperse, sulfur and vat
dyes. High production of
Photochemical No production of sludge concentrated sludge.
and foul odors are greatly Formation of by-products.
reduced.

11
 Physical treatments
Adsorption by Good removal of wide Very expensive
activated carbon variety of dyes.
Membrane separation Remove all dye types. Concentrated sludge
Ion exchange No adsorbent loss during production.
regeneration. Ineffective for all dyes.
Electrokinetic Economically feasible
coagulation Effective oxidation at lab High sludge production.
Irradiation scale Requires a lot of dissolved
oxygen.
Sources: Robinson et al. (2001) and Gupta (2009)

12
2.4 Adsorption

Adsorption technique appears to offer the most effective method for colour

removal of dyes from wastewater among all the physical treatments exist. This

technique is very famous due to its simplicity, ease of operation, efficiency,

inactivity towards toxic substances and comparable low cost of application in

discoloration process. According to Worch (2012), adsorption can be defined as

an enrichment of chemical species from a fluid phase on the surface of a liquid or

a solid. Figure 2.1 shows the basic terms used in adsorption theory for colour

removal of dyes from wastewater.

A highly porous solid material that offers the surface for adsorption is called

adsorbent, whereas, the species that will be adsorbed are known as adsorbate

(Worch, 2012). In this process, an adsorbate (soluble dye) from the liquid phase

(wastewater) is transported to the surface of adsorbent, to which it binds

chemically or physically (Zaharia and Seteu, 2012). The adsorbed species can

released from the surface and transferred back into the liquid phase by altering the

properties of the liquid phase such as concentration, temperature and pH and this

reverse process is known as desorption (Worch, 2012). The surface area is a key

quality parameter of adsorbents since adsorption involving a surface process.

Figure 2.2 Basic terms used in adsorption theory

13
2.5 Adsorbent

The interesting part of adsorption method is, the adsorbents can be chosen

from a wide variety of materials. According to (Bocchiaro & Zamperini,

n.d.)Mohamed (2016), different types of adsorbents are categorized into synthetic

adsorbents and natural adsorbents. Synthetic adsorbents include agricultural

product and wastes, household wastes, industrial wastes, sewage sludge and

polymeric adsorbents. Each adsorbent has its own characteristics such as pore

structure, porosity and nature of its adsorbing surfaces. Natural adsorbents are

charcoal, clays, clay minerals, zeolites and ores. These natural materials are

relatively cheap, abundant in supply and have significant potential for

modification and ultimately enhancement of their adsorption capabilities. Zaharia

and Seteu (2012) stated that, the adsorbent selection must fulfill these following

requirements; ease of regeneration, high capacity and selectivity of adsorption,

mechanical strength and most importantly abundantly available at low cost.

14
2.5.1 Activated carbon

Undoubtedly, many studies have shown that commercially activated

carbon is the most broadly used as an adsorbent for colored effluents treatment

because of its high capacity, micro-pore structures, high degree of surface

reactivity and has a very porous structure with a large surface area ranging from

500 to 2000 m2g-1(Carrott et al., 1991). Besides the ability of removal different

types of dyes, activated carbon can also remove other organic and inorganic

pollutants, and many other chemicals from effluents (Gupta & Suhas, 2009).

However, despite the excellent characteristics of activated carbon, their

use is limited because it is expensive. Furthermore, after the use of activated

carbons, they are no longer capable of adsorbing the dyes since it become

exhausted. Hence, regeneration of activated carbon must be done for further use

in water treatment and a number of methods like thermal, chemical, oxidation and

electrochemical (Freeman, 1989; Hemphill et al., 1997) are used for this purpose

which leads additional of costs. Not only that, regeneration process results in a

loss of carbon and slightly decrease in adsorption capacity of the new product

compare to the virgin activated carbon (Gupta & Suhas, 2009). Although many

studies have been introduced the preparation of activated carbon from agricultural

wastes, we cannot denied that it is still costly due to use of high thermal energy.

Hence, due to this problem, attention has been shifted towards low-cost

alternative adsorbents from natural waste products such as agricultural wastes and

bio wastes materials from large scale industrial operations which may replace

activated carbons in pollution control through adsorption process.

15
2.5.2 Low-cost adsorbents

Low-cost adsorbents (LCAs) are generally referred as natural materials or

non-hazardous wastes produced from industry and agriculture which cost less and

can be used as such or after some minor treatment. Numerous studies protocol for

the development, utilization and application of low-cost adsorbents generally

adopted by researchers has been suggested by Gupta et al., (1990). LCAs are

usually called substitutes for activated carbons as reported in literature due to their

similarity in application for dye removal from effluents. However, in a broad and

clearer way they are basically substitutes for all expensive adsorbents.

There are several factors need to be considered when select the materials for

the development of low-cost adsorbents. According to Yagub et al. (2014), the

materials should be freely available, non-hazardous in nature, without any or

minor pretreatment and most importantly inexpensive. Based on previous study,

there are many low cost adsorbents that have been used for the removal of dyes

and many of them have been tested and proposed for dye removal.

16
2.5.3 Agricultural solid wastes

Many attempts have been made to find economical and easily available

adsorbents to remove dyes from effluents such as agricultural solid wastes. The

productions of agricultural by-products are available in huge quantities around the

world, thus create enormous amount of wastes. Agricultural and industrial sectors

dispose of large amounts of untreated wastes, which may pollute the land, water

and air, and as a result damage to ecosystem. Besides that, improper treatment of

these wastes causes similar problems (Mannan and Ganapathy, 2004).

Within the last few years, Noeline et al., (2005) stated that many ideas

have been introduced in order to properly dispose of these wastes, such as

intensive use of adsorbents for pollutant removal especially for dye removal

where it showed high adsorption capacity. Agricultural wastes are renewable,

available in large amounts and less expensive as compared to other materials used

as adsorbents. Agricultural wastes are better than other adsorbents because the

agricultural wastes are usually used without or with a minimum processing

(washing, drying, grinding) and thus reduce production costs by using a cheap

raw material and eliminating energy costs associated with thermal treatment

(Franca et al., 2009). It can be clearly seen that the use of agricultural wastes for

the treatment of dye effluents is not only essential to the environment in clearing

the solid water disposal problems to farmers and agro industries, but also to the

economy.

17
 Table 2.3 shows some of the previous studies adsorption capacity of

methylene blue dye from various agricultural wastes. The equilibrium data were

analyzed using the Langmuir and Freundlich isotherm models. These agricultural

wastes have been proven to be an effective adsorbent for the removal of MB via

adsorption from aqueous solution based on the results showed.

Table 2.3: Adsorption capacities, qm (mg/g) of methylene blue dye from various
agricultural wastes.

Adsorbent Maximum References

adsorption capacity
(mg/g)
Guava leaf powder 185.2 Ponnusami et al. (2008)
Poplar leaf 135.35 Han et al., (2012)
Pineapple stem 119.05 Hameed et al., (2009)
Pineapple leaf powder 78.22 Chakraborty et al., (2012)
Pine tree leaves 71.94 Saeed et al., (2010)
Sources: Yagub et al. (2014) and Bharathi & Ramesh (2013)

18
2.5.4 Etlingera Coccinea plant

Etlingera Coccinea plant is a member of ginger family, Zingiberaceae and

it is found growing in many places throughout Southeast Asia. In Sabah, E.

Coccinea is a commonly known as “tuhau” to the Kadazan Dusun community.

According to Poulsen (2006), this plant has a distribution across the Thailand,

Peninsular Malaysia, Sumatra, Java and Borneo. There are several factors that

influenced the distribution of E. Coccinea plant such as water and soil texture.

Poulsen (2006) stated that E. Coccinea plant grown in areas near rivers or in

humid areas (adequate water resources). Besides that, the sandy soil composition

and high content in clays at an altitude 30 to 1150 meters enhance the growth of

E. Coccinea plant. In addition, this plant is easily grown in the forest. According

to Poulsen (2003), the height of this species can reach beyond five meters and

able to dominate an area thus causes competition to other plant species due to its

wide leaves structures that block sunlight from reach to the lower plant species.

This plant is a well-known ginger species in Sabah and among the gingers,

E. coccinea has a strong pungent odour. Despite the strong odour, E. Coccinea is

regarded as a delicacy by the locals in Sabah. Available all year round in most

markets or vegetable markets all across Sabah, it is either made as condiments or

pickles. However, only the inner stems are eaten and the rest of the plants are

regarded as agricultural wastes such as leaves, outer stems and roots. Indirectly,

these wastes possess dumping space problems to the local farmers in Sabah.

19
 However, several previous studies have only evaluated the phytochemical

characterization and biological activities of E. Coccinea species and there have been

no reports on the use of this plant as an adsorbent. Hence, the use of E. coccinea

wastes as adsorbent will be a good alternative to overcome the disposal problem and

may be a turning point as a source of income to the local farmers in Sabah. Figures

below are the pictures of E. coccinea.

Figure 2.3 Etlingera coccinea plant

Figure 2.4 Etlingera coccinea inner stem

20
2.6 Characterization instrumentation

Characterization of adsorbent is really important to determine its

adsorption capacity and porosity level. Adsorbent will be characterized by using

two instruments which are scanning electron microscopy (SEM) and Fourier

Transform Infrared (FTIR) spectroscopy.

2.6.1 Scanning electron microscopy (SEM)

Scanning electron microscopy (SEM) is one of the most versatile

instruments which used to analyze and visualize the microstructure morphology

(texture, shape and size) of the bulk samples of solid materials. A beam of

electrons is scanned across the surface of the sample and the images will be used

to estimate the size and shape particles of the samples (Gobin et al., 2006).

Figure 2.5 Scanning electron microscopy

21
 ACLP (raw) ACLP (MB loaded)
Figure 2.6 Morphology structures of ACLP before and after MB loaded. Adapted
from (Ezechi et al., 2015).

The SEM images of raw ACLP and MB loaded ACLP is presented in

Figure 2.5. Based on Ezechi et al., (2015) study, the adsorption pores were evenly

distributed on the surface of raw ACLP. He stated that, adsorbents with such

morphology could enable the adsorption of pollutants from wastewater due to the

trapping of particles on their irregular surface. Furthermore, ACLP has adequate

morphological properties as adsorbent due to the irregular pores on its surface.

The functional groups on the surface of raw ACLP significantly interacted with

the reactive groups of MB solution. As a result, the binding sites on the surface of

raw ACLP were occupied by MB molecules.

22
2.6.2 FTIR spectroscopy

FTIR analysis is used to determine the characteristic functional groups

responsible for the adsorption of MB dye. According to previous study reported

by Ezechi et al., (2015), the IR spectrum of the sample that was recorded

operating in the range 4000 – 400 cm-1 using potassium bromide (KBr) pellets

method.

Figure 2.7: FTIR spectroscopy

23
 Figure 2.8: FTIR spectroscopy of raw and MB loaded ACLP. Adapted
from Ezechi et al., (2015)

The FTIR spectra of ACLP are shown in Figure 2.6. The band at 621 cm−1

indicates the presence of amine groups (Ricordel et al., 2001). The peak between

1061 and 1248 cm−1 indicates the presence of aliphatic amines with C-N groups

bonded on the adsorbent. The medium and strong peaks between 1416 and 1517

cm−1 show the presence of aromatics (C-C) and nitro (N-O) compounds. The IR

spectra at 1617 cm−1 indicates amine peak. The transmittance in the 1637 and

2048 cm−1 region could be attributed to the vibration of the C=O stretch in

aldehydes and ketones. The stretching between 2048 and 2915 cm−1 indicates

alkane peaks whereas the peak at 3232 and 3542 cm−1 indicates alcohols and

phenols groups (Srivastava et al., 2006). The presence of polar groups on the

surface of ACLP provides considerable interaction with adsorbate cations (Ho et

al., 2001). The specific interaction between the adsorbent and reactive groups of

the dye molecules was significantly observed in the disappearance and broadening

of some peaks. The FTIR spectra reveal the bond frequencies and active sites

where the interaction of functional groups occurred.

24
 CHAPTER 3

METHODOLOGY

3.1 Materials

3.1.1 Raw material

The raw material, Etlingera coccinea (tuhau) wastes were obtained free of

charges from local farm-land located in Ranau, Sabah.

3.1.2 Chemicals

Methylene blue powder was purchased from HmbG chemicals.

Hydrochloric acid and sodium hydroxide were purchased from Sigma Aldrich.

3.1.3 Instruments

The instruments used were FTIR-2000 by PerkinElmer, Scanning electron

microscope and UV-Vis spectrophotometer.

25
3.2 Preparation of Etlingera Coccinea wastes (ECW)

The ECW were obtained free of charges from local farm-land located in

Ranau, Sabah. The wastes were washed with distilled water thoroughly to remove

dust, dirt and any unwanted particles. The leaves and stems were cut into small

pieces about 1-3 cm. Then, the ECW were dried under sunlight and further dried

in a hot air oven at 70°C for overnight (12 hours) to remove moisture contents

until weight constant was obtained. After that, the dried ECW were ground to fine

powder by using a grinder and were sieved into three different sizes such as <150,

150-250 and 250-350 µm. The material was stored in an air tight container and

used as adsorbent without any further treatment.

3.3 Preparation of adsorbate

Methylene blue dye was used as an adsorbate to determine the adsorption

potential of ECW as adsorbent. A stock solution of 1000 ppm of MB dye was

prepared by dissolving 1 g of dye powder in 1 L distilled water. The stock of dye

solution was diluted into 5, 10, 15, 20, 25 and 30 ppm as initial needed

concentration. Then, the sample was observed via UV-Vis spectrophotometer at

⋏max of 668 nm.

26
3.4 Characterization of adsorbent

FTIR-2000 by PerkinElmer was used to identify the different functional

groups available on the adsorbent sites and their effect on dye adsorption.

Potassium bromide (KBr) disc method was used and the spectra were recorded in

the scanning range from 4000-400 cm-1 (mid IR region). Analysis was applied on

the sample before and after methylene blue (MB) adsorption. The surface

morphology and texture of the adsorbent analyzed by using Scanning Electron

Microscope (SEM) operated at 20kV accelerating voltage before and after

methylene blue adsorption.

3.5 Adsorption experiments

The adsorption experiments were carried out to analyze the effect of

important parameters such as particle size, contact time and initial dye

concentration on the adsorption of MB. All experiments were carried out in 250

mL of conical flask by mixing ECW powder in 100 mL of dye solution and

agitated at constant and optimum speed at 150 rpm and constant temperature at

room temperature.

27
3.5.1 The effect of particle size

The effect of particle size was studied on the different sizes of adsorbent.

100 mL of 20 ppm of MB solution was added into three different flasks. Then, 1 g

of ECW powder of different sizes (<150, 150-250, and 250-350 µm) were added

into the flasks. The flasks were agitated at constant speed for 30 minutes. The

mixture was filtered using filter paper and observed via UV-Vis spectrometer at

λmax 658.8 nm.

3.5.2 The effect of contact time

The mixture of 100 mL of 20 ppm MB and 1g of adsorbent were agitated

at constant speed at different time 10, 20, 30, 40 and 50 minutes. Then, the

mixture was filtered using filter paper and was observed via UV-Vis spectrometer

at λmax 658.8 nm.

3.5.3 The effect of initial dye concentration

The adsorption isotherm was studied on different concentration of MB. 1g

of adsorbent was added into 100 mL of 5, 10, 15, 20, 25, and 30 ppm of MB

solution. The flasks were agitated at constant speed for 30 minutes until

equilibrium. The mixture was filtered using filter paper and observed via UV-Vis

spectrometer at λmax 658.8 nm.

28
3.6 Calculations

3.6.1 Percentage of colour removal

−
( %) = × %

Where, C0 is the liquid-phase concentration of dye at initial concentration,

(mg/L), and Ce is the liquid-phase concentration of dye at equilibrium, (mg/L)

3.6.2 Adsorption capacity

The amount of MB adsorbed on ECW was calculated by the mass balance

relationship:

( − )×
=

Where C0 is the initial dye concentration (mgL-1), Ce is the concentration of dye at

equilibrium (mgL-1), V is the volume of dye solution (L), m is the amount of

adsorbent (g).

29
3.7 Equilibrium Isotherm

The Langmuir and Freundlich models were used to study the equilibrium process

on adsorption of dye solution using Etlingera coccinea powder. The linearized

equation for the Langmuir sorption isotherm model is as follows;

= +
×

Where Ce (mg/L) is the equilibrium concentration of dye solution, qe (mg/g) is the

amount of the dye sorbed at equilibrium, qmax (mg/g) is the monolayer capacity of

adsorbent, KL is the Langmuir adsorption constant.

A graph was plotted between Ce/qe and Ce, and the values of qmax and KL were

calculated from the slope and the intercept respectively.

The linearized Freundlich equation is as follows.

= +

Where KF and n = Freundlich constants. A graph was plotted between lnqe and

lnCe, and the values of KF and n were calculated from the slope and the intercept.

30
 CHAPTER 4

RESULTS AND DISCUSSION

4.1 Adsorption equilibrium studies

Several batch adsorption experiments were carried out using ECLP

(E.Coccinea’s leaf powder) and ECSP (E.Coccinea’s stem powder) as adsorbents

and aqueous solution of methylene blue as adsorbate. The adsorption experiments

were carried out under agitation to study the effects of varying adsorbent particle

size, initial MB dye concentration and contact time. The studies were carried out

by varying one of the parameters while keeping others constant. The

concentration of dye was monitored using UV-Visible spectrophotometer at λmax

658.8 nm.

4.1.1 Effect of particle size

Adsorption of MB dyes on ECLP and ECSP adsorbent were studied using

different particle sizes and keeping the other parameters as constant. Adsorbent

particle size is an important factor in sorption kinetics because it determines the

time required for transport of sorbate within the pore to the adsorbent sites (Tunc

et al., 2009). For ECLP adsorbent, there are four different particle sizes used (<

125 µm, 125 µm, 250 µm and 500 µm) and for ECSP adsorbent there are only

three different particle sizes used (< 125 µm, 125 µm and 250 µm). Figure 4.1

31
shows the effect of variation particle sizes on the percentage removal of MB dye.

It has been observed that as the particle size decreases, the percentage of MB dye

removal increases.

It can be seen from Figure 4.1 that as the particle size decreases, the

percentage of MB dye removal increases from 81.88% to 95.71% for ECLP

adsorbent and 93.92% to 97.04% for ECSP adsorbent. The greater sorption at

smaller particle size is due to the fact that smaller particle size provides large

surface area for adsorption which results in the higher removal of dye. Moreover,

smaller particles move faster in solution than the larger particles. For larger

particles, the diffusion resistance to mass transport is higher and most of the

internal surface of the particle may be not fully used for sorption and as a result,

the amount of dye adsorbed is lesser (Hassan et al., 2017). According to the

obtained results, particle size below 125 µm has been chosen for the subsequent

experiments.

Table 4.1: Effect of particle size ECLP adsorbent

Samples Absorbance Concentration % dye removal

Blank 0.0000 0.0000 0.0
< 125 µm 0.1156 0.8579 95.71
125 µm 0.2122 2.1651 89.17
250 µm 0.3074 3.4533 82.73
500 µm 0.3200 3.6238 81.88

32
Table 4.2: Effect of particle size ECSP adsorbent

Samples Absorbance Concentration % dye removal

Blank 0.0000 0.0000 0.0
< 125 µm 0.0959 0.5913 97.04
125 µm 0.1145 0.8430 95.79
250 µm 0.1420 1.2152 93.92

Effect of adorbents particle size on MB adsorption

98
96
94
92
% dye removal

90
88 ECLP

86 ECSP

84
82
80
0 100 200 300 400 500 600
particle size (µm)

Figure 4.1: Effect of ECLP and ECSP adsorbents particle size on MB dye
adsorption (experimental conditions: initial dye concentration, 20 mg/L ; contact
time, 30 minutes; agitation speed, 150 rpm)

33
4.1.2 Effect of contact time

Contact time is an important parameter to determine the equilibrium time

and kinetics of adsorption process. The effect of contact time for the adsorption of

MB dye by ECLP and ECSP were studied at different time for a period of 50

minutes by keeping the other parameters as constant. It can be seen from Figure

4.2 and Figure 4.3 that the percentage of dye removal increases with increasing

contact time and thereafter proceeds at slower rate till a plateau is obtained at 30

minutes for both ECLP and ECSP adsorbent. According to Reddy (2016), the

plateau state represents a dynamic equilibrium in which the amount of dye

adsorbed onto the adsorbent is in equilibrium with the MB dye present in the

solution. It can be inferred that the rapid sorption rate at the initial stage is due to

the presence of abundance available active adsorption sites on the external surface

of adsorbent which resulted in higher removal of MB dye (Enenebeaku et al.,

2015).

However, after 30 minutes the sorption rate became slower and the

percentage dye removal decreases as the external surface has been occupied by

the molecules of the dye and some of the remaining vacant surface sites available

are difficult to be occupied probably caused by the repulsive forces between the

solute molecules on the adsorbents and the bulk phase (Kallel et al., 2016).

34
Table 4.3: Effect of contact time ECLP adsorbent

Samples Absorbance Concentration % dye removal

Blank 0.0000 0.0000 0.0000
10 mins 0.1283 1.0298 94.85
20 mins 0.1186 0.8985 95.51
30 mins 0.1104 0.7876 96.06
40 mins 0.1107 0.7916 96.04
50 mins 0.1112 0.7984 96.01

Table 4.4: Effect of contact time ECSP adsorbent

Samples Absorbance Concentration % dye removal

Blank 0.0000 0.0000 0.0000
10 mins 0.0701 0.2422 100.12
20 mins 0.0567 0.06089 100.29
30 mins 0.0668 0.1976 100.32
40 mins 0.0696 0.2355 100.10
50 mins 0.0681 0.2152 100.22

Effect of ECLP adsorbent contact time on MB adsorption

96.5

96
dye removal (%)

95.5

95

94.5

94
0 10 20 30 40 50 60
time(mins)

Figure 4.2: Effect of ECLP adsorbent contact time on MB dye adsorption

(experimental conditions: particle size, <125µm; initial dye concentration, 20
mg/L; agitation speed, 150 rpm)

35
 Effect of ECSP adsorbent contact time on MB adsorption

100.9

100.7
dye removal (%)
100.5

100.3

100.1

99.9

99.7

99.5
0 10 20 30 40 50 60
time (mins)

Figure 4.3: Effect of ECSP adsorbent contact time on MB dye adsorption

(experimental conditions: particle size, <125µm; initial dye concentration, 20
mg/L; agitation speed, 150 rpm)

36
4.1.3 Effect of initial dye concentration

The influence of initial dye concentration in equilibrium uptake of MB

dye by ECLP and ECSP adsorbents were presented in Figure 4.4. The initial dye

concentrations were varied from 5 mg/L to 30 mg/L while keeping the other

parameters as constant. It can be observed from Figure 4.4 and Figure 4.5 that the

percentage removal of dye decreases with increase in initial dye concentration.

This is due to the fact that at lower concentration, the ratio of the dye molecule to

the adsorbent sites is higher, therefore all the dye molecules present in the

solution interact with the binding sites of the adsorbent which cause an increase in

the colour removal. However, all adsorbents have limited number of binding sites

which become saturated at a certain concentration (Tsai and Chen, 2010). As such

at higher concentrations, more MB dye molecules are left unabsorbed in the

solution due to the saturation of binding sites resulting in decreased of dye

removal percentage.

Under the same conditions, the adsorption capacity increases with increase

in initial dye concentration as shown in the Figure 4.4 and Figure 4.5. This is due

to the increasing in concentration gradient which acts as increasing driving force

to overcome all mass transfer resistances of the dye molecules between the

aqueous and solid phase, leading to an increasing equilibrium sorption until

saturation is achieved. In the present study, adsorption rate was greater for higher

initial MB concentrations as the mass transfer driving force increased. Similar

results are reported by other researchers (Ghaedi et al., 2014; Chowdhurry et al.,

2011).

37
Table 4.5: Effect of initial dye concentration ECLP adsorbent

Samples Absorbance Concentration % dye Adsorption

(mg/L) removal capacity, qe
(mg/g)
Blank 0.0000 0.0000 0.00 0.00
5 ppm 0.0545 0.03112 99.38 0.4969
10 ppm 0.0767 0.3315 96.69 0.9669
15 ppm 0.1036 0.6955 95.36 1.4305
20 ppm 0.1188 0.9012 95.49 1.9099
25 ppm 0.1286 1.0338 95.84 2.3966
30 ppm 0.1475 1.2896 95.70 2.8710

Table 4.6: Effect of initial dye concentration ECSP adsorbent

Samples Absorbance Concentration % dye Adsorption

(mg/L) removal capacity, qe
(mg/g)
Blank 0.0000 0.0000 0.00 0.00
5 ppm 0.0253 -0.3640 107.28 0.5364
10 ppm 0.0317 -0.2774 102.77 1.0277
15 ppm 0.0433 -0.1204 100.80 1.5120
20 ppm 0.0487 -0.0474 100.24 2.0047
25 ppm 0.0535 0.0176 99.93 2.4982
30 ppm 0.0867 0.4678 98.44 2.9532

38
 100 3.5
99.5
3
99
98.5 2.5

% dye removal
98

qe (mg/g)
2
97.5
1.5 %
97
mg/g
96.5 1
96
0.5
95.5
95 0
0 5 10 15 20 25 30 35
concentration (mg/L)

Figure 4.4: Effect of ECLP adsorbent initial dye concentration on MB adsorption

(experimental conditions: particle size, <125µm; contact time, 30 minutes;
agitation speed, 150 rpm)

108 3.5
107
3
106
105 2.5
% dye removal

104 qe (mg/g)
103 2

102 1.5
101 %
100 1
99
0.5
98
97 0
0 5 10 15 20 25 30 35
initial dye concentration (mg/L)

Figure 4.5: Effect of ECSP adsorbent initial dye concentration on MB adsorption

(experimental conditions: particle size, <125µm; contact time, 30 minutes;
agitation speed, 150 rpm)

39
4.2 Adsorption isotherms

Adsorption isotherm is used to describe the relationship between the

amount of MB dye adsorbed and its equilibrium concentration. The most common

models used to represent the data of adsorption from solution are Langmuir and

Freundlich isotherms. In this analysis, both models were used. The Langmuir

isotherm model assumes a monolayer formation on the surface of the adsorbent

which implies no further adsorption can take place once a dye molecule occupies

adsorption sites (Hameed, 2009). Freundlich isotherm model assumes a multilayer

adsorption surface that has unequal available sites with different energies of

adsorption (Yagub et al., 2014).

The applicability of these isotherm models to the adsorption study was

judged by the correlation coefficient, R2 value of each plot that indicate which

models can be chosen to give the best-fit. The higher the R2 value, the better the

fit.

All calculated isotherm constants by both models for both adsorbents are

listed in Table 4.7. The R2 values between the isotherm models have been

compared. From the data, Freundlich isotherm for ECLP has higher R2 value

which is 0.9092 compared to Langmuir. Even though the KF value of Freundlich

lowers than Langmuir model which describes greater adsorption uptake, but the

value of n (indicative of favorability) is 0.48, which is close to the unity and

indicates the favorability of the adsorption process (Santhi et al., 2009).

Therefore, Freundlich model is a good model to describe the adsorption data for

ECLP adsorbent.

40
Table 4.7: Isotherm parameters for removal of MB dye by ECLP and ECSP
adsorbents.

Adsorbents Langmuir isotherm parameters Freundlich isotherm

parameters
qmax KL R2 KF n R2
(mg/g) (L / mg) (L / mg)
ECLP 0.1744 3.5765 0.6554 0.2139 0.4843 0.9092
ECSP -0.0873 1.1765 0.6862 - - -

As for ECSP adsorbent, Freundlich model did not provide a good fit to

experimental data. This is because, the calculated values of equilibrium

concentration of dye solution (Ce) are negative as shown in the Table 4.8. Thus,

lnCe cannot be calculated and a graph of Freundlich isotherm cannot be plotted for

ECSP adsorbent. Therefore, Langmuir model is a good model to describe the

adsorption data for ECSP adsorbent.

Table 4.8: Calculated values data of ECSP adsorbent for Freundlich model
purpose

Ce (mg/L) lnCe qe (mg/g) lnqe

-0.3640 - 0.5364 -0.6229
-0.2774 - 1.0277 0.02732
-0.1204 - 1.5120 0.4134
-0.0474 - 2.0047 0.6955
0.0176 -4.0399 2.4982 0.9156
0.4678 -0.7597 2.9532 1.0829

41
 Langmuir adsorption isotherm (ECLP adsorbent)
0.6

0.5

0.4
Ce/qe

0.3
y = 0.2796x + 0.1744
R² = 0.6554
0.2

0.1

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Ce (mg/L)

Figure 4.6: Langmuir isotherm of ECLP adsorbent (experimental conditions:

particle size, <125µm; initial dye concentration, 20 mg/L; contact
time, 30 minutes; agitation speed, 150 rpm)

Freundlich adsorption isotherm (ECLP adsorbent)

1
0.5
0
-1 -0.5 -0.5 0 0.5 1 1.5

-1
ln qe

-1.5
-2 y = 2.0648x - 1.5421
-2.5 R² = 0.9092

-3
-3.5
-4
ln ce

Figure 4.7: Freundlich isotherm of ECLP adsorbent (experimental conditions:

particle size, <125µm; initial dye concentration, 20 mg/L; contact time, 30
minutes; agitation speed, 150 rpm)

42
 Langmuir adsorption isotherm (ECSP adsorbent)
0.4

0.2

0
-0.6 -0.4 -0.2 0 0.2 0.4 0.6
Ce/qe

-0.2
y = 0.85x - 0.0873
R² = 0.6862
-0.4

-0.6

-0.8
Ce (mg/L)

Figure 4.8: Langmuir isotherm of ECSP adsorbent (experimental conditions:

particle size, <125µm; initial dye concentration, 20 mg/L; contact time, 30
minutes; agitation speed, 150 rpm)

43
4.3 Characterization of adsorbent

4.3.1 SEM analysis

Scanning electron microscopy (SEM) was used to observe the

morphological structure of the adsorbents. Figure 4.6 illustrates the SEM images

of the ECLP and ECSP adsorbents before and after the adsorption of MB dye.

The SEM analysis (Figure 4.6 (a) and (c)) shows that both of the adsorbents

before MB dye loaded have a rough and porous surface morphology with

different sizes of pores and shapes which provide large surface area for MB-

surface interaction, indicating a good possibility for MB dye to be trapped and

adsorbed into the surface of the adsorbents. Generally, the pores will became

saturated after the adsorption process due to the entering of MB dye molecules

into the pores. However, Figure 4.6 (b) and (d) shows that the pores for both

adsorbents after MB dye adsorption became empty with no dye molecules

adsorbed into it. This is due to the heating process during drying the adsorbents in

an oven after adsorption analysis and caused the dye molecules left the adsorption

sites.

44
 (a). ECLP (raw) (b). ECLP (MB loaded)

(c). ECSP (raw) (d). ECSP (MB loaded)

Figure 4.6: (a) ECLP (raw), (b) ECLP (MB loaded), (c) ECSP (raw) and (d).
ECSP (MB loaded)

45
4.3.2 FTIR analysis

FTIR is an important technique to determine the functional groups available

on the adsorbent sites, which are capable of adsorbing dyes. The FTIR spectra of

ECLP before and after dye sorption are shown in Figure 4.7. As depicted in

Figure 4.7, the infrared spectra revealed the presence of various functional groups

detected on the surface of ECLP adsorbent, indicating the complex nature of the

material examined.

MB LOADED

RAW

Figure 4.7: FTIR spectra of ECLP adsorbent before and after adsorption of MB
dye.

For ECLP raw sample, the broad peak observed at 3288.92 cm−1 corresponds

to the -OH group. The peak at 2922.67 cm-1 might be due to symmetric and

antisymmetric stretching of C-H bond of methyl and methylene groups. Sharp

band at 1729.62 cm−1 is due to C=O stretching and strong band at 1608.67 cm−1

46
may be attributed to carbonyl group stretching whereas the peak at 1313 cm−1

was due to bending vibration of C-H of methyl group. Characteristic changes

observed in the FTIR spectrum of ECLP adsorbent after adsorption of MB dye

indicated that some peaks were shifted and the decrease in intensity at peak

3288.92 cm−1 also detected. These changes observed in the spectrum proved that

there were interactions between dye molecules with the functional groups of

ECLP adsorbent in the adsorption process.

47
 Figure 4.8 shows the FTIR spectra of ECSP adsorbent sample before and

after the adsorption of MB dye. Similar with ECLP raw sample, the broad peak

observed at 3291.93 cm−1 represents the -OH stretching vibrations of carboxylic

groups. The peak at 2919.96 cm-1 corresponds to the symmetric and

antisymmetric stretching of C-H bond of methyl and methylene groups. Sharp

band at 1627.20 cm−1 is due to C=O stretching and peak at 1313 cm−1 was due to

bending vibration of C-H of methyl group. Characteristic changes observed in the

FTIR spectrum of ECSP adsorbent after adsorption of MB dye indicated that

some peaks were shifted and new peak formed at 1729.43 cm-1 was also detected.

These changes observed in the spectrum proved that there were interactions

between dye molecules with the functional groups of ECLP adsorbent in the

adsorption process.

RAW

MB LOADED

Figure 4.8: FTIR spectra of ECSP adsorbent before and after adsorption of MB.

48
 CHAPTER 5

CONCLUSION AND RECOMMENDATIONS

In this study, the efficiency of ECLP and ECSP adsorbents for the removal

of MB dye were investigated. It was found that adsorption is affected by various

parameters such as particle size, contact time and initial dye concentration. The

particle size below 125 µm was found resulted in higher percentage removal of

the dye molecule for both adsorbents. The equilibrium time for the adsorption of

MB onto both adsorbents were found to be 30 minutes, after which there was no

increase in MB adsorption. The adsorption study also revealed that the percentage

removal of the dye molecule decreased with increase in initial dye concentration.

Adsorption isotherm study indicated that Freundlich model gave the best fit to the

experimental data for ECLP adsorbent while Langmuir model for ECSP

adsorbent. Thus, it was concluded that ECLP and ECSP adsorbents can be

effectively used as a low cost and efficient adsorbent without any pretreatment or

modification for the treatment of dye effluents or waste water.

For further research, the adsorption capacity for these adsorbents can be

maximized by using more parameters. Other than that, the adsorption capacity

also can be increased by activate the adsorbents through heating and modification

by treating with chemical to activate the surface of adsorbent to adsorb more dyes.

49
 GANTT CHART

Plan schedule (September 2016 – June 2017)

2016 2017

Activities Sept Oct Nov Dec Jan Feb Mac Apr May June

Introduction

Literature review

Methodology

Preparation of

adsorbent

Lab work

Characterization of

adsorbent

Thesis writing

50
 CITED REFERENCES

Am, E., Wm, A. E., & Oudah, A. A. A. (2015). Methylene Blue Dye Removal from
Aqueous Solution Using Several Solid Stationary Phases Prepared from Papyrus
Plant. Journal of Analytical & Bioanalytical Techniques, (13).

A.S. Franca, L.S. Oliveira, M.E. Ferreira, Kinetics and equilibrium studies of methylene
blue adsorption by spent coffee grounds, Desalination 249 (2009) 267–272.

B.F.Noeline,D.M.Manohar, T.S. Anirudhan, Kinetic and equilibriummodelling of lead

(II) sorption from water and wastewater by polymerized banana stem in a batch
reactor, Sep. Pur. Tech. 45 (2005) 131–140.

Bharathi, K. S, Ramesh, S. T. (2012) Equilibrium, thermodynamic and kinetic studies on

adsorption of a basic dye by Citrulluslanatus rind. Iran J. Energy. Environ. 3(1):
23–34.

Bocchiaro, P., & Zamperini, A. (n.d.). World â€TM s largest Science , Technology &
Medicine Open Access book publisher The Visible Light Activity of the TiO 2
and TiO 2 : V 4 + Photocatalyst.

Bouaziz, F., Koubaa, M., Kallel, F., Chaari, F., Driss, D., Ghorbel, R. E., & Chaabouni,
S. E. (2015). Efficiency of almond gum as a low-cost adsorbent for methylene
blue dye removal from aqueous solutions. Industrial Crops and Products, 74,
903-911.

Brodin, F. W., and Theliander, H. (2012). “Absorbent materials based on kraft pulp:
Preparation and material characterization,” BioResources 7(2), 1666-1683.

Carrott, P.J.M., Ribeiro Carrott, M.M.L., Roberts, R.A., 1991. Physical adsorption of
gases by microporous carbons. Colloids Surf. 58, 385–400.

Christie, R.M., 2007. Environmental Aspects of Textile Dyeing. Woodhead, Boca Raton,
Cambridge.

Clarke E, Anliker R. Organic dyes and pigments. Handb Environ Chem 1980;3:181–215
[Part A].

Ezechi, E. H., Kutty, S. R. B. M., Malakahmad, A., & Isa, M. H. (2015). Characterization
and optimization of effluent dye removal using a new low cost adsorbent:
Equilibrium, kinetics and thermodynamic study. Process Safety and
Environmental Protection, 98, 16–32.

Ferrero, F. (2007). “Dye removal by low cost adsorbents: Halzenut shells in comparison
with wood sawdust,” J. Hazard. Mater. 142(1-2), 144-152.

51
Forgacs, E., Cserhati, T., and Oros, G. (2004). “Removal of synthetic dyes from
wastewater: A review,” Environ. Inter. 30(7), 953-971.

Freeman, H.M., 1989. Standard Handbook of Hazardous Waste Treatment and Disposal,
second ed. McGraw-Hill, New York.

Ghoreishi S.M. and Haghighi R., Chemical catalytic reaction and biological oxidation for
treatment of non- biodegradable textile effluent, Chem. Eng. J., 95, 163–169
(2003)

Gupta V. Application of low-cost adsorbents for dye removal—a review. J Environ

Manage 2009;90(8):2313–42.

Gupta, V. K., & Suhas. (2009). Application of low-cost adsorbents for dye removal - A
review. Journal of Environmental Management, 90(8), 2313–2342.
https://doi.org/10.1016/j.jenvman.2008.11.017

Hemphill, L., Ramaiah, V., Valentine, M., 1977. Thermal regeneration of activated
carbon 32nd Purdue Industrial Waste Conference, Purdue University, pp. 116–
126.

Ho, Y.-S., Chiang, C.-C., Hsu, Y.-C., 2001. Sorption kinetics for dye removal from
aqueous solution using activated clay. Sep. Sci. Technol. 36, 2473–2488

Hunger, K., 2003. Industrial Dyes: Chemistry, Properties, Applications. Wiley-VCH,

Weinheim; [Cambridge].

I.M. Banat, P. Nigam, D. Singh, R. Marchant, “Microbial decolourization of textile-dye-

containing effluents: a review”, Bioresour. Technol., vol. 58, 1996, pp.217–227.

Khan, T. A., Dahiya,s., Ali, I. (2012) Removal of direct red 81 dye from aqueous solvent
by native and citric acid modified bamboo sawdust: kinetic study and equilibrium
isotherm analysis. Gazi university Journal of Science (GUJS), 25:59-87

Lee, L. Y., Gan, S., Yin Tan, M. S., Lim, S. S., Lee, X. J., & Lam, Y. F. (2016). Effective
removal of Acid Blue 113 dye using overripe Cucumis sativus peel as an eco-
friendly biosorbent from agricultural residue. Journal of Cleaner Production, 113,
194–203.

Man, H. C. B., Akinbile, C. O., & Jun, C. X. (2015). Coconut husk adsorbent for the
removal of methylene blue dye from wastewater. BioResources, 10(2), 2859–
2872.
M.A. Mannan, C. Ganapathy, Concrete from an agricultural waste-oil palm shell (OPS),
Build. Environ. 39 (2004) 441–448.

52
Metcalf, E., Tchobanoglous, G., Franklin, B., and Stensel, H. D. (2003). “Wastewater
Engineering: Treatment and Reuse,” 4th Ed., McGraw-Hill, New York.

Mohammed, M. a, Shitu, A., & Ibrahim, A. (2014). Removal of Methylene Blue Using
Low Cost Adsorbent : A Review. Research Journal of Chemical Sciences, 4(1),
91–102.

Nasuha, N., Hameed, B. H., & Din, A. T. M. (2010). Rejected tea as a potential low-cost
adsorbent for the removal of methylene blue. Journal of Hazardous Materials,
175(1–3), 126–132.

Pourjavadi, A., & Abedin-Moghanaki, A. (2016). Ultrafast and efficient removal of

cationic dyes using a magnetic nanocomposite based on functionalized cross-
linked poly(methylacrylate). Reactive and Functional Polymers, 105, 95–102.

Poulsen, A.D., 2003. The Ginger Genus Etlingera. Borneo: Natural History Publications
& Royal Botanic Garden Edinburgh.

Poulsen, A.D., 2006. Etlingera Of Borneo. Borneo: Natural History Publications & Royal
Botanic Garden Edinburgh.

Rafatullah, M., Sulaiman, O., Hashim, R., & Ahmad, A. (2010). Adsorption of methylene
blue on low-cost adsorbents: A review. Journal of Hazardous Materials, 177(1–3),
70–80.

Ravindhranath, K., & Sreenivasa Reddy, B. (2014). Leaves and barks of some plants as
bio-adsorbents in the control of methylene blue dye from waste waters. International
Journal of ChemTech Research, 6(14), 5612–5624.

Reddy , K . Venkata Ramana and K . Ravindhranath * Department of Engg . Chemistry

and Post Graduate Chemistry , Bapatla Engineering College , BAPATLA- 422101
, . (2012), 215–224.

Reddy, P. M. K., Verma, P., & Subrahmanyam, C. (2015). Bio-waste derived adsorbent
material for methylene blue adsorption. Journal of the Taiwan Institute of
Chemical Engineers, 58, 500–508.

Ricordel, S., Taha, S., Cisse, I., Dorange, G., 2001. Heavy metals removal by adsorption
onto peanut husks carbon: characterization, kinetic study and modeling. Sep.
Purif. Technol. 24, 389–401.

Sharma, P., Kaur, R., Baskar, C., & Chung, W. J. (2010). Removal of methylene blue
from aqueous waste using rice husk and rice husk ash. Desalination, 259(1–3),
249–257.

53
Srivastava, V.C., Mall, I.D., Mishra, I.M., 2006. Characterization of mesoporous rice
husk ash (RHA) and adsorption kinetics of metal ions from aqueous solution onto
RHA. J. Hazard. Mater. 134, 257–267.

Soni M., Sharma A.K. and Srivastava J.K., Adsorptive Removal of Methylene Blue Dye
from an Aqueous Solution Using Water Hyacinth Root Powder as a Low
Adsorbent, Int. J. Chem. Sci. Appl., 3, 338–345 (2012)

Umpuch, C., Jutarat, B. (2013) Adsorption of organic dyes from aqueous solution by
surfactant modified corn straw. Inter. J. Chem. Eng. Applications, 4(3):134 – 139.

Worch, E. (2012). Adsorption Technology in Water Treatment: Fundamentals, Processes,

and Modeling.

Wong, Y., Atiqah, N., and Senan, M. (2013). “Removal of methylene blue and malachite
green dye using different form of coconut fibre as absorbent,” J. Basic Appl. Sci.
9, 172-177.

Yagub, M. T., Sen TK, AngH. Equilibrium, kinetics, and thermodynamics ofmethylene
blue adsorption by pine tree leaves.Water Air Soil Pollut 2012;223(8):5267–82.

Yagub, M. T., Sen, T. K., Afroze, S., & Ang, H. M. (2014). Dye and its removal from
aqueous solution by adsorption: A review. Advances in Colloid and Interface
Science, 209, 172–184.

Zaharia, C., and Suteu, D. (2012). Organic Pollutants Ten Years After the Stockholm
Convention – Environmental and Analytical Update, T. Puzyn and A. Mostrag-
Szlichtyng (eds.), InTech, Rijeka, Croatia.

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 APPENDICES

APPENDIX A

Adsorption experiment of ECLP adsorbent (particle size).

Before MB dye adsorption onto ECLP adsorbent (concentration; 20 ppm)

After MB dye adsorption onto ECLP adsorbent.

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APPENDIX B

Adsorption experiment of ECLP adsorbent (contact time).

Before MB dye adsorption onto ECLP adsorbent (concentration; 20 ppm)

After MB dye adsorption onto ECLP adsorbent.

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APPENDIX C

Adsorption experiment of ECLP adsorbent (initial dye concentration).

Before MB dye adsorption onto ECLP adsorbent (concentration; 5, 10, 15, 20, 25 and 30
ppm)

After MB dye adsorption onto ECLP adsorbent.

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APPENDIX D

Adsorption experiment of ECSP adsorbent (particle size).

Before MB dye adsorption onto ECSP adsorbent (concentration; 20 ppm)

After MB dye adsorption onto ECSP adsorbent.

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APPENDIX E

Adsorption experiment of ECSP adsorbent (contact time).

Before MB dye adsorption onto ECSP adsorbent (concentration; 20 ppm)

After MB dye adsorption onto ECSP adsorbent.

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APPENDIX F

Adsorption experiment of ECSP adsorbent (initial dye concentration).

Before MB dye adsorption onto ECSP adsorbent (concentration; 5, 10, 15, 20, 25 and 30
ppm)

After MB dye adsorption onto ECSP adsorbent.

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APPENDIX G

Absorbance reading of MB dye standard.

Calibration curve:

61
APPENDIX H

Absorbance reading at λmax = 658.8 nm.

Different particle size of ECLP adsorbent

Different contact time of ECLP adsorbent

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Initial dye concentration of ECLP adsorbent

Different particle size of ECSP adsorbent

63
 Different contact time of ECSP adsorbent

Initial dye concentration of ECSP adsorbent

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APPENDIX I

Calculation for MB dyes concentration after adsorption of adsorbent;

Based on standard calibration curve,

y = 0.0739x + 0.0522

Where; y = absorbance value

x = concentration of MB after adsorption

For example; Particle size <125 µm

0.1156 = 0.0739x + 0.0522

0.0739x = 0.0634
x = 0.8579 ppm

Calculation of percentage dye removal of adsorbent;

−
( %) = × %

= [(20 – 0.8579)/ 20] x 100 %

= 95.71 %

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APPENDIX J

Calculation for plotting Langmuir isotherm

( )× ( )
Amount of MB adsorbed, ( )= ( )

For example; 5 ppm initial dye concentration of ECLP adsorbent

( )× ( )
Amount of MB adsorbed, q ( )= ( )

= [(20 – 0.03112) x 0.1L] / 0.1 g

= 0.4969 mg/g

Calculation for qmax and KL from equation obtained on graph for Langmuir isotherm;

= +
×

Since in the equation, y = mx + c

qmax =

and

KL = ×

From Langmuir graph, y = 0.2796x + 0.1744

So, qmax = 0.1744

KL = 3.5765

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APPENDIX K

Calculation for plotting Freundlich isotherm

( )× ( )
Amount of MB adsorbed, ( )= ( )

For example; 5 ppm initial dye concentration of ECLP adsorbent

( )× ( )
Amount of MB adsorbed, q ( )= ( )

= [(20 – 0.03112) x 0.1L] / 0.1 g

= 0.4969 mg/g

Calculation for KF and n from equation obtained on graph for Freundlich isotherm;

= +

Since in the equation, y = mx + c

KF = eC
and

n=

From Langmuir graph, y = 2.0648x – 1.5421

So, KF = 0.2139
n = 0.4843

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APPENDIX L

Grinder

Siever

68