REMOVAL OF CONGO RED BY USING ADSORPTION ONTO PALM OIL WASTE

MUBARAK BIN AMIR

FACULTY OF CHEMICAL ENGINEERING

UNIVERSITI TEKNOLOGI MARA
PULAU PINANG
REMOVAL OF CONGO RED BY USING ADSORPTION ONTO PALM OIL WASTE

MUBARAK BIN AMIR

This report is submitted in partial fulfillment of the requirements needed for

the award of Diploma of Chemical Engineering

FACULTY OF CHEMICAL ENGINEERING

UNIVERSITI TEKNOLOGI MARA
PULAU PINANG

MAY 2008
 DECLARATION

“I hereby declare that this report is the result of my own work except for quotations
and summaries which have been duly acknowledged.”

Mubarak Bin Amir 12 May

2008
2005491176

ii
 SUPERVISOR’S CERTIFICATION

“I hereby declare that I have read this thesis and in my opinion this project report is
sufficient in terms of scope and quality for the award of the Diploma of Chemical
Engineering.”

Signature : ……………………………………
Name : ……………………………………
Date : ……………………………………

iii
iv
 Accepted:

Signed :…………………………
Date :…………………………

Coordinator
Puan Siti Aminah Binti Mohd Ali
Faculty of Chemical Engineering
Universiti Teknologi MARA
Pulau Pinang

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 ACKNOWLEDGEMENT

I would like to express my sincere gratitude and appreciation to my

supervisor, Puan Ainnie Rahayu Bte Abdullah of Department of Applied Sciences,
UiTMPP for her support and invaluable advice with a continuous stream of
suggestions, feedback, and encouragement that have guided me throughout the
whole period of my final year project. I especially would like to thank her for always
being accessible and making research her top priority. I would also like to thank Dr.
Nor Aziyah Bte Bakhari of Department of Applied Sciences, UiTMPP for her
constructive comments, suggestions and salient advice. The Laboratory’s
technicians of Environmental, Geotechnic and Chemistry for their help in finishing of
this project. I would like to thank the faculty and staff in the Faculty of Chemical
Engineering for their continuous support and high quality education. I would like to
thank all the present students of Chemical Engineering, especially Abdul Hakim Bin
Mohd Fadzil, Mohd Shafiq Bin Yusof and Mohd Syafiq Rahman Bin Abd Rahman for
their friendship and contributions to my project. In particular, I want to give my
special thanks to Mr. Hazreeq Bin Ramli of Engineering Faculty of Universiti Putra
Malaysia for his detailed and thoughtful comments, tremendous help, analytical
method development and friendship that made my introduction to laboratory life a
wonderful experience. Many thanks to all students of Chemical Engineering for
creating a stimulating and supportive environment, and all my friends at Universiti
Teknologi MARA, who have made another part of my life full of joy and excitement.
I would like to thank Abdul Hakim Bin Mohd Fadzil for his kindness and friendship
while completing my report, and especially for embarking on my life’s journey with
me. Finally, my sincere warmhearted gratitude goes to my parents for their endless
love, understanding, patience and support. Without them, none of my
accomplishments would have been possible. To them, I dedicate this report.

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 ABSTRACT

Dyes are usually present in trace quantities in the treated effluents of many
industries. The effectiveness of adsorption for dye removal from wastewaters has
made it an ideal alternative to other expensive treatment methods. This study
investigates the potential use of palm oil waste for the removal of Congo red, an azo
dye from simulated wastewater. The effects of varying parameter such as
adsorbent dosage, initial dye concentration and contact time were studied by batch
adsorption procedure. The results showed that as the amount of the adsorbent was
increased, the percentage of dye removal increased accordingly. As the amount of
adsorbent dosage was increased from 0.5g/100mL to 2.0g/100mL, the percent of
dye removal was increased by 60.4% from 33.2% to 83.9% at 300 minutes leading
to the optimum contact time. Higher adsorption percentages were observed at
lower concentrations of Congo red. For instance, the percent of dye removal was
found to be 65.0% at the initial dye concentration of 10mg/L instead of 53.0% at the
initial dye concentration of 50mg/L at optimum contact time of 300 minutes. Palm oil
waste showed an average performance in terms of efficiency of dye removal
compared to some other agricultural wastes, thus making it an interesting option for
dye removal from dilute industrial effluents.

vi
 CONTENTS

TITLE PAGE
AUTHOR’S DECLARATION ii
SUPERVISOR’S CERTIFICATION iii
COORDINATOR’S CERTIFICATION iv
ACKNOWLEDGEMENT v
ABSTRACT vi
LIST OF TABLES ix
LIST OF FIGURES x
LIST OF PLATES xi

CHAPTER 1 INTRODUCTION
1.1 General Overview 1
1.2 Problem Statement 2
1.6 Objectives of Project 4

CHAPTER 2 LITERATURE REVIEW

2.1 Dyes 5
2.1.1 Congo Red 6
2.1.1 (a) Behavior in Solution 7
2.1.1 (b) Dyeing Activity 7
2.2 Treatment of Dyes 7
2.2.1 Physical Treatment 8
2.2.2 Chemical Treatment 8
2.2.3 Biological Treatment 9
2.3 Adsorption 11
2.3.1 Types of Adsorption 12
2.3.1 (a) Physical Adsorption 12
2.3.1 (b) Chemical Adsorption 13
2.3.2 Factors Influencing Adsorption 13
2.3.2 (a) Effect of Contact Time 13
2.3.2 (b) Effect of Initial Concentration 14
2.1.2 (c) Effect of Adsorbent Molecular Size 14
2.1.2 (d) Effect of pH 14

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 2.1.2 (e) Effect of Temperature 15
2.1.2 (f) Effect of Adsorbent Characteristic 15
2.1.2 (g) Effect of Solubility of Adsorbent 15
2.4 Adsorbent 16
2.4.1 Activated Carbon 16
2.4.2 Non-Conventional Activated carbon 17
2.4.2 (a) Palm Oil and Palm Oil Waste 17

CHAPTER 3 METHODOLOGY
3.1 Experimental Work 19
3.2 Chemicals 19
3.3 Apparatus and Equipments 19
3.4 Adsorbent Preparation 20
3.5 Preparation of Anionic Dye Solutions 22
3.6 Procedure 22
3.6.1 Weight of Adsorbent 22
3.6.2 Contact Time 23
3.6.3 Shaking Speed 23
3.7 Adsorption Studies 24

CHAPTER 4 RESULTS AND DISCUSSIONS

4.1 Preliminary Result 26
4.1.1 Color Observation 26
4.2 Experimental Results 27
4.2.1 Effect of Contact Time 31
4.2.2 Effect of Initial Concentration 33

CHAPTER 5 CONCLUSION AND RECOMMENDATIONS

5.1 Summary and Conclusion 35
5.2 Recommendations / Future Work 36

REFERENCES 38

LIST OF TABLES

viii
TABLE TITLE PAGE
2.1 Different Techniques Used For Dye Decolorization 10
2.2 Comparison for Adsorption of Some Dyes on Various Adsorbents 17
4.1 Tabular Data of the First Trial 26
4.2 Tabular Data of the Second Trial 26
4.3 Tabular Data of the Third Trial 27
4.4 Average to the Triplicate Trial 27
4.5 Effect of Adsorbent Dose on the Dye Adsorption 30
4.6 Effect of Congo Red Concentration on the Dye Adsorption 32

LIST OF FIGURES

ix
FIGURE TITLE PAGE
2.1 Chemical Structure of CR Dye 06
2.2 Micropores 10
2.3 Activated Carbon Pore Structures 15
2.4 Palm Oil Wastes 16
4.2 Effect of Adsorbent Dosage on Removal of CR 29
4.3 Removal of CR as a Function of Equilibrium Time 31

LIST OF PLATES

x
PLATE TITLE PAGE
3.1 Raw Material of Palm Oil Waste 18
3.2 Palm Oil Waste Washed With Water and Remove the 18
Precipitate Before Drying in Multi Point at 110°C
3.3 Final Products after Drying Process 19
3.4 Dryer Multi Point 19
3.5 Auto Sieve Shaker D408 ENDECOTTS 19
3.6 Orbital Shaker SK-600 21
3.7 UV/VIS Spectrophotometry (Shimadzu UV-160 A) 22
3.8 Delta 320 pH Meter 23
4.1 Comparison of Color Changes Before (left) and 25
After (right) Treatment

xi
 CHAPTER 1

INTRODUCTION

1.1 GENERAL OVERVIEW

The use of chemicals such as alum, ferric, chloride, polymer flocculants and coal
based activated carbon as conventional wastewater treatment are not practically
and cost effective for many developing countries. In Malaysia, for instance, to be
one of the world’s fast developing countries, the problems such as wastewater
treatment might be the government vital focus towards industrial areas. An
economically viable alternative for the removal of pollutants by adsorbent that is
easily available and for sure inexpensive and affordable by the industries would
cater the needs of wastewater treatment. For instance, the vast of agricultural areas
such as palm oil plantation, rubber plantation and many others across the country
has its own advantage due to the waste produced. In this project, the use of palm
oil waste for the removal of Congo Red (CR) by using adsorption method from
wastewater was adapted to suit the effective in cost and more practical means to the
scenario in Malaysia.

The major problem in the treatments of waters that contain azo-dyes is due
to the high stability of these species. Dyes are resistant to light and oxidation
agents moderately, thus they cannot be completely treated by conventional methods
of anaerobic digestion (Panswed et. al, 1986). Some procedures can be used for
treating waters containing dyes, for instance, coagulation and flotation (Malik PK et.
al, 2003), ozonization (Koch M et. al, 2002), membrane separation (Deo Mall I et. al,
2005) and adsorption by activated carbon (Namasivayam C et. al, 2003). The
adsorption process at solid or liquid interface has been extensively employed for
several reasons, mainly due to its efficiency and economy (Espantaleon et. al,
2003). Nevertheless, the used of activated carbon adsorption is the most popular
physico-chemical treatment for the removal of dissolved organics from wastewaters.
Adsorption studies for dye removal have been carried out using activated carbon

1
made from non-conventional sources as adsorbents (MM. Howlader et. al, 1999)
where in this project; palm oil waste was fully utilized.

Many industries such as paper, food, cosmetics, textiles etc. use dye in
order to colour their products. The presence of these dyes in water even at very low
concentration is highly visible and undesirable. Colour is the first contaminant to be
recognized. Textile dyeing operations are generally small-scale processes that use
highly variable colorant formulations and fresh water quantities, depending upon the
required characteristics of the final product. Azo dyes are the most widely used
colorants, accounting for up to 70 % of the overall colorant production (Chiang et. al,
2000). The wastewaters generated from dyeing operations contain unreacted
organic colorants and inorganic fixing agents that result in strong color coupled with
variable ionic strength and pH. Aside from being an aesthetic problem, colorant
substances are often biologically-recalcitrant and may cause both acute and chronic
health disorders to organisms exposed to them.

Adsorption methods offer a good potential to remove colour from

wastewater. In the present project this method was employed for removal of Congo
red and it was found to be very useful and cost effective for a better removal of dye
and the results were recorded. The operating variables such as adsorbent dose,
adsorbate concentration, pH etc were optimised.

1.2 PROBLEM STATEMENT

Synthetic dyes are extensively used in many industries such as the textile, leather
tanning, paper production, food technology, hair colorings, etc. Wastewaters
discharged from these industries are usually polluted by dyes. Congo red (CR) is
most commonly used for the dyeing of cotton, silk, paper, leather and also in
manufacturing of paints and printing inks. Congo red is widely used in distilleries for
coloring purposes (Khattri et. al., 1999). Congo red has properties that make it
difficult to remove from aqueous solutions and also toxic to major microorganisms
(Papinutti et. al., 2006). Congo red when discharged into receiving streams will
affect the aquatic life and causes detrimental effects in liver, gill, kidney, intestine,
gonads and pituitary gonadotrophic cells (Srivastava et. al., 2004). Therefore, the
treatment of effluent containing such dye is of interest due to its esthetic impacts on
receiving waters.

2
 Dyes are common constituents of effluents discharged by various
industries, particularly the textile industry. The presence of small amounts of dyes in
water is highly visible and undesirable (Crini, 2006). Recently, an increasing interest
has been focused on removing dyes from water due to its refractory biodegradation
and toxic nature, which affects the aquatic biota and food web (Gregory et al.,
1991). Adsorption technique is quite popular due to its simplicity as well as the
availability of a wide range of adsorbents and it is proved to be an effective and
attractive process for removal of non-biodegradable pollutants (including dyes) from
wastewater (Aksu, 2005).

The common adsorbent, activated carbon, has good capacity of removal of

pollutants (Walker and Weatherley, 1997) and (Walker and Weatherley, 1998). But
its main disadvantages are the high price of treatment and difficult regeneration,
which increases the cost of wastewater treatment. Thus, there is a demand for
other adsorbents, which are of inexpensive material and does not require any
expensive additional pretreatment step. So the adsorption process will become
economically viable. A successful adsorption process not only depends on dye
adsorption performance of the adsorbents, but also on the constant supply of the
materials for the process. So it is preferable to use low cost adsorbents, such as an
industrial waste, natural ores, and agricultural byproducts. This has resulted in a
search for developing other adsorbents based on solid wastes. Such low cost
adsorbents have given satisfactory performance at the laboratory scale for treatment
of colored effluents (Sivaraj et al., 2001).

3
1.3 OBJECTIVES OF PROJECT

The project was focused on the dye removal by palm oil waste, one of an
agricultural (non-conventional) adsorbent. It was conducted by evaluating the
adsorption capacity of palm oil waste with the relevant parameters. The specific
objectives of this project are as follows:

i. To study the effects of contact time on Congo red removal.

ii. To study the effects of initial dye concentration on Congo red removal.
iii. To study the effects of adsorbent dosage on Congo red removal.

4
 CHAPTER 2

LITERATURE REVIEW

2.1 DYES

A dye can generally be described as a colored substance that has an affinity to the
substrate to which it is being applied. The dye is generally applied in an aqueous
solution, and may require a mordant to improve the fastness of the dye on the fiber.
Both dyes and pigments appear to be colored because they absorb some
wavelengths of light preferentially. In contrast with a dye, a pigment generally is
insoluble, and has no affinity for the substrate. Some dyes can be precipitated with
an inert salt to produce a lake pigment. Archaeological evidence shows that,
particularly in India and the Middle East, dyeing has been carried out for over 5000
years. The dyes were obtained from animal, vegetable or mineral origin, with no or
very little processing. By far the greatest source of dyes has been from the plant
kingdom, notably roots, berries, bark, leaves and wood, but only a few have ever
been used on a commercial scale.

Dyes are recalcitrant by design and not readily amendable to common

treatment methods, imposing a challenge for closing industrial water systems.
Extensive research in the field of biological azo dye decolorization has shown
promising results (Cervantes et. al, 2001; Dos Santos et. al, 2003). However,
industrial textile wastewater presents the additional complexity of dealing with
unknown quantities and varieties of many kinds of dyes (Bisschops and Spanjers,
2003), as well as low BOD/COD ratios, which may affect the efficiency of the
biological decolorization. Many microorganisms are able to anaerobically reduce
azo dyes producing anaerobically recalcitrant aromatic amines (Chung et al., 1995).
However, many of these amines are readily mineralized aerobically, so an
anaerobic-aerobic treatment strategy has been proposed as a feasible treatment
strategy (Tan et. al, 2000).

5
2.1.1 Congo Red

Different adsorbent materials have been used to removes dyes from waters. In this
work, the palm oil waste was used as adsorbent to remove Congo red (that in this
work was simply designated as CR) from synthetic wastewater. Congo Red, (1-
naphthalenesulfonic acid, 3,3’ – (4,4’ – biphenylenebis (azo)) bis (4 – amino -)
disodium salt) [C.I. = 22120, chemical formula = C32H22N6Na2O6S2, FW = 696.7, λmax
= 500 nm] is a benzidine-based anionic disazo dye. This dye is known to
metabolize to benzidine, a known human carcinogen. It is widely used in textiles,
paper, rubber and plastic industries. Due to its structural stability, CR is difficult to
biodegrade. The chemical structure of the CR dye contains NH2 and SO3 functional
groups as illustrated in Figure 2.1 below. In the environment view-point, the removal
of color from aquatic systems caused by the presence of synthetic dyes that majorly
contains azo-aromatic groups is tremendously important due to its carcinogenic,
mutagenic and toxic effects (Gregory AR et. al, 1991). For drinking purpose and
other uses, colored waters are strictly objectionable an aesthetic grounds for human
daily lives.

In addition, the presence of dye on natural water systems restraints sunlight

diffusion into the water, thus, reduces the photosynthetic process of aquatic plants
(Gong R et. al, 2005). Discharge of wastewater into natural streams and rivers from
the industries using dyes poses severe environmental problems where even small
quantities of dyes can color large water bodies that finally obstruct the natural
process of photosynthesis. CR represent one of the problematic groups; they are
emmited into wastewaters from various industries branches, mainly from the dye
manufacturing and textile finishing (Janos et. al, 2003) and also from food colouring,
cosmetics, paper and carpet industries (Indra DeoMall et. al, 2004).

Figure 2.1 Chemical structure of CR dye

6
2.1.1 (a) Behavior in Solution

Due to a color change from blue to red at pH 3.0-5.2, Congo red can be used as a
pH indicator. Since this color change is an approximate inverse of that of litmus, it
can be used with litmus paper in a simple parlor trick: add a drop or two of Congo
red to both an acid solution and a base solution. Dipping red litmus paper in the red
solution will turn it blue, while dipping blue litmus paper in the blue solution will turn it
red. Congo red has a propensity to aggregate in aqueous and organic solutions.
The proposed mechanisms suggest hydrophobic interactions between the aromatic
rings of the dye molecules, leading to a pi-pi stacking phenomenon. Although these
aggregates are present under various sizes and shapes, the "ribbon-like micelles" of
a few molecules seem to be the predominant form (even if the "micelle" term is not
totally appropriate here). This aggregation phenomenon is more important for high
Congo red concentrations, at high salinity and/or low pH.

2.1.1 (b) Dyeing Activity

As suggested by its intense red color, Congo red has important spectrophotometric
properties. Indeed, its UV-visible absorption spectrum shows a characteristic,
intense peak around 498 nm in aqueous solution, at low dye concentration. Congo
red molar extinction coefficient is about 45000 [L]/[mol].[cm] in these conditions.
Aggregation of the dye tends to red-shift the absorption spectrum, whereas binding
to cellulose fibres or amyloid fibrils has the opposite effect. Congo red also shows a
fluorescent activity when bound to amyloid fibrils, which tends to be used as a
sensitive diagnosis tool for amyloidosis, instead of the traditional histological
birefringence test.

2.2 TREATMENT OF DYES

Many processes have been used and/or researched for dye treatment from
wastewater. A brief description of dye treatment of each process compiled from
literature is summarized in Table 2.1. However, not all processes work for all
colored wastewaters (Hao et al., 2000; Robinson et al., 2001; Naim and Abd, 2002).
Some studies have reported successful decolorization using different treatment
schemes, despite the fact that the treated wastewater still has low color intensity.

7
Only a few cases have being reported with complete decolorization and dye
mineralization (Hao et al., 2000; Robinson et al., 2001; Naim and Abd, 2002).

2.2.1 Physical Treatment

Activated carbon is the most used method of dye decolorization by adsorption, and
is very effective for adsorbing cationic, mordant and acid dyes (Nasser and El-
Geundi, 1991; Raghavachraya, 1997). Numerous other adsorbents, such as peat,
wood chips, fly ash, and brown coal have been used as dye adsorbents (Nigam et
al., 2000; Robinson et al., 2001). However, although adsorption can efficiently
decolorize textile effluents, its application has been limited by the high cost of
adsorbents and the large volume of wastewater normally involved (Robinson et al.,
2001; Naim and Abd, 2002). Nanofiltration removed up to 99% of a variety of
reactive dyes in laboratory studies (Wu et al., 1998) and has been successfully
applied in a pilot-scale study (Chen et al., 1997). Rozzi and coworkers (1999)
employed a microfiltration unit followed by a nanofiltration unit or a reverse osmosis
membrane process for a potential textile wastewater reuse. Nonetheless, the use of
membrane processes for large flow rates is prohibitively costly, in addition to the
common problems of membrane processes with respect to flux decline, irreversible
fouling, and required treatment and disposal of the concentrate (Van’t Hul et al.,
1997; Hao et al., 2000; Naim and Abd, 2002).

2.2.2 Chemical Treatment

Chemical oxidation is the most frequently used decolorization process in research

and applied in industry, partly due to the diversity of chemical processes that can be
effective. Chemical oxidation removes the dye from the dye-containing effluent by
oxidation resulting in aromatic ring cleavage of the dye molecules (Raghavacharya,
1997; Robinson et al., 2001). Recently, many advanced oxidation processes, such
as the Fenton’s reagent (H2O2 and Fe2+), UV light with or without catalysis (e.g.,
TiO2), H2O2, and ozone (O3), have been evaluated for the decolorization of textile
wastewater (Hao et al., 2000; Robinson et al., 2001; Naim and Abd, 2002).

8
2.2.3 Biological Treatment

Many researchers have demonstrated the biological decolorization of dyes by pure

and mixed cultures of fungi and bacteria. The use of ligninolytic fungi is one of the
possible alternatives studied for the biodegradation of dyes. Fungi can mineralize
xenobiotic compounds to CO2 and H2O through their highly oxidative and non-
specific ligninolytic system, which is also responsible for the decolorization and
degradation of a wide range of dyes (Fu and Viraraghavan 2001; McMullan et al.,
2001; Wesemberg et al., 2003; Pinheiro et al., 2004). Since degradation of dyes by
the white-rot fungi was first reported by Glenn and Gold (1983), white-rot fungi have
been the most widely studied, dye-decolorizing microorganisms. Fungi such as
Phanerochaete chrysosporium, Pleurotus, Bjerkandera, Trametes, Poyporus,
Phelinus, Iperx lacteus, Funalia trogii, and Thelephora sp., have been investigated
for the decolorization and mineralization of various dyes (Fu and Viraraghavan
2001; Selvam et al., 2003; Wesemberg et al., 2003; Yesilada et al., 2003).

9
 Table 2.1: Different techniques used for dye decolorization

INFLUENT DYE CONC. TREATMENT

PROCESS DYE COMMENTS
(COLOR MEASUREMENT) PROCESS
Adsorption Orange Red, Crystal 200 mg/L Sorption capacity of Equilibrium capacity various with dyes and
Violet and Methylene (respective αmax) different activated carbons; correlated well with mesophore
Blue carbons and large micropore volumea
Membrane Various dyes to Integration of the area Polysulfone nanofiltration 99% color removal by a particular polyamide
simulate textile waste under A400-700 membrane with total membrane at 20°C and 180 psib
area of 10 m2
Fenton and Reactive Orange 4 100-400 mg/L Varying pH, Fe2+, H2O2 98% color removal; photo-Fenton process is
photo-Fenton (respective αmax) and UV light intensity more efficientc
Photocatalytic Orange II 50 mg/L TiO2 catalysts supported Over 95% color removal; TiO2 supported on
(TiO2) (respective αmax) on three different absorbents is more efficient than that of bare
absorbents TiO2
Ozonation and Reactive Blue 19 30 mg/L Varying ozone, and First-order rate constants increased by
ultrasound- (respective αmax) ultrasound enhanced 200% for ultrasonic power inputs compared
enhanced ozone operational to ozonation alonec
ozonation conditions
a
Krupa and Cannon, 1996
b
Wu et al., 1998
c
Muruganandham and Swaminathan, 2004

10
2.3 ADSORPTION

The use of solids for removing substances from either gaseous or liquid solutions
has been widely used since biblical times. This process, known as adsorption,
involves nothing more than the preferential partitioning of substances from the
gaseous or liquid phase onto the surface of a solid substrate. From the early days
of using bone char for decolorization of sugar solutions and other foods, to the later
implementation of activated carbon for removing nerve gases from the battlefield, to
today's thousands of applications, the adsorption phenomenon has become a useful
tool for purification and separation. Adsorption phenomena are operative in most
natural physical, biological, and chemical systems, and adsorption operations
employing solids such as activated carbon and synthetic resins are used widely in
industrial applications and for purification of waters and wastewaters.

The process of adsorption involves separation of a substance from one

phase accompanied by its accumulation or concentration at the surface of another.
The adsorbing phase is the adsorbent, and the material concentrated or adsorbed at
the surface of that phase is the adsorbate. Adsorption is thus different from
absorption, a process in which material transferred from one phase to another (e.g.
liquid) interpenetrates the second phase to form a "solution". The term sorption is a
general expression encompassing both processes. Physical adsorption is caused
mainly by van der Waals forces and electrostatic forces between adsorbate
molecules and the atoms which compose the adsorbent surface. Thus adsorbents
are characterized first by surface properties such as surface area and polarity. A
large specific surface area is preferable for providing large adsorption capacity, but
the creation of a large internal surface area in a limited volume inevitably gives rise
to large numbers of small sized pores between adsorption surfaces.

The size of the micropores determines the accessibility of adsorbate

molecules to the internal adsorption surface (see Figure 2.2), so the pore size
distribution of micropores is another important property for characterizing
adsorptivity of adsorbents. Especially materials such as zeolite and carbon
molecular sieves can be specifically engineered with precise pore size distributions
and hence tuned for a particular separation. Surface polarity corresponds to affinity
with polar substances such as water or alcohols. Polar adsorbents are thus called
"hydrophillic" and aluminosilicates such as zeolites, porous alumina, silica gel or
silica-alumina are examples of adsorbents of this type. On the other hand, nopolar

11
adsorbents are generally "hydrophobic". Carbonaceous adsorbents, polymer
adsorbents and silicalite are typical nonpolar adsorbents. These adsorbents have
more affinity with oil or hydrocarbons than water.

Figure 2.2 Micropores

2.3.1 Types of Adsorption

Most adsorption processes in wastewater treatment are combination of neither

purely physical nor purely chemical processes. It is difficult to distinguish between
these two processes and such distinction is not necessary in order to analyzed and
design the adsorption processes (Benefield, 1982). Adsorption processes occurs in
both conditions whether steady or unsteady state. The primary force driving the
interaction between the adsorbate and the adsorbent is the electrostatic attraction
and repulsion between molecules of the adsorbate and the adsorbent. This driving
force can be either physical or chemical (Alley, 2000).

2.3.1 (a) Physical Adsorption

Physical adsorption or physisorption is a result of intermolecular forces such as Van

der Waals and dipole forces between the adsorbent and the adsorbate. The
adsorbed molecule is not affixed to the adsorbent during physical adsorption but it is
free to move about the surface of the adsorbent (The, 1999). Physical adsorption is
a readily reversible reaction and includes both mono and multilayer coverage of
adsorbate molecular on the adsorbent’s surface (Alley, 2000).

12
2.3.1 (b) Chemical Adsorption

Chemical adsorption or chemisorption is occurred as a result of a chemical reaction

between the adsorbate molecule and the adsorbent (Benefield, 1982). Chemical
adsorption creates high stronger forces, which involves the actual chemical bonding
of the adsorbents surface to a solute, compare to those lead formation of chemical
compounds. The adsorbed molecules make a layer over the surface that is only
one molecule thick and are relatively not free to move from one surface site to
another surface (The, 1999). Abu Foul (2007) cited that this type of adsorption is
thought to occur on the sides and corners of the micro-crystallites that compromise
the activated carbon.

2.3.2 Factors Influencing Adsorption

Molecules of solute are removed from solution and taken up by the adsorbent during
the process of adsorption. The majority of molecules are adsorbed onto the large
surface area within the pores of adsorbent particles and relatively few are adsorbed
on the outside surface. These transfer process continue until equilibrium is
achieved (Benefield et al., 1982). Many factors affect the rate at which adsorption
reaction occurs and the extent to which a particular material can be adsorbed.
These factors included contact time, initial concentration, adsorbent, characteristics,
size of adsorbate molecules, solubility of the adsorbate, pH and temperature (Abu
Foul, 2007).

2.3.2 (a) Effect of Contact Time

In general, adsorption increases with the increase in contact time until equilibrium is
reached (Sag and Aktay, 2002). Contact time in the adsorption system affects the
rate adsorption, which is controlled by either, film diffusion or pore diffusion. If the
contact time is relatively small, the surface film of liquid around the particle will be
thick and film diffusion will likely be the rate-limiting step. If adequate contact time is
provided, film diffusion rate will increase to the point that pore diffusion becomes the
rate-limiting step (Benefield et al., 1982).

13
2.3.2 (b) Effect of Initial Pollutant Concentration

Effect of initial pollutant concentration is one of the factors that influence the rate of
the adsorption. Generally, the rate of adsorption decreases as initial pollutants
concentration increases. This is because the adsorption sites adsorb the available
molecules more quickly at low concentrations (Alley, 2000; Sag and Aktay, 2002).

2.3.2 (c) Effect of Adsorbent Molecular Size

Molecular size would logically be important in adsorption; since the molecules must
enter the micropores of an adsorbent so as to be adsorbed. Research has shown
that within a homologous series of aliphatic acids, aldehydes, or alcohol, adsorption
usually increases as the size of molecule increase (Benefield et al., 1982).
Substances of the highest molecular weight are most easily adsorbed. The rates
are reciprocally with the square of the particle diameter (Eckenfelder, 1989).

2.3.2 (d) Effect of pH

The pH at which adsorption is carried out has been shown to have a strong
influence on the extent of adsorption. This is partly due to the fact that hydrogen
ions themselves are strongly adsorbed and partly that pH influences the ionization,
of many compounds. Organic acids are more adsorbed at low pH, whereas the
adsorption of organic bases is favored by high pH. In general, metal adsorption
increases as pH increases (Seco et al., 1999; Evans et al., 2002).

Isa et al., (2006) suggested that the optimum pH value for the adsorption of
colour occurred at acidic conditions. This is due to the positive charge dominating
the surface of the adsorbent which slightly increase the electrostatic attraction
between the negatively charged dye species and the positively charged surface of
the adsorbent (Namasivayam and Kavitha, 2002). In removal of COD, lower PH
values give greater removal. At lower value of pH, the precipitation of solids will
increase which improves the removal efficiency of COD. Removal of iron at acidic
condition is better than at alkaline conditions. Higher removal of iron efficiency at
pH over 10 may be contributed by the effect of adsorption and precipitation (Isa et
al. 2004).

14
2.3.2 (e) Effect of Temperature

In adsorption process, temperature does take affect in rate of adsorption and the
extent to which adsorption occurs. Generally adsorption rates increase with
increase in temperature. However since the adsorption is generally an exothermic
process, the degree of adsorption will increase at lower temperature and increase at
lower temperature and decrease at higher temperature (Benefield et al., 1982).
According to Kobya, (2004) adsorption capacity of activated carbon increased with
increasing temperature.

2.3.2 (f) Effect of Adsorbent Characteristic

Adsorbent molecular size is an important factor in adsorption since molecule must

pass through the micropores of an adsorbent as to be adsorbed. Researches have
proved that adsorption usually increases as the size of molecule increases within a
homologous series of aliphatic acids, aldehydes or alcohol (Benefield et. al, 1982).

Particle size, chemical structure and surface area are important properties
of media with respect to its use as an adsorbent. Adsorption rate increases as
adsorbent particle size decreases (Benefield et al., 1982). Generally the total
adsorptive capacity of adsorbents depends on its total surface area (Sag and Aktay,
2002).

2.3.2 (g) Effect of Solubility of The Adsorbent

In adsorption process, a molecule must be separated from the solvent before

attached to the adsorbent surface. Generally, soluble compounds are more difficult
to adsorb rather than insoluble compounds because of the strong affinity for their
soluble. However, there are exceptions since many compounds are difficult adsorb
even though in slightly soluble. Some compounds which are very soluble may be
adsorbed readily (Benefield at al., 1982).

15
2.4 ADSORBENT

Adsorbents are the material used to adsorb the adsorbate. There are several types
of adsorbents that have been used which are activated carbon, zeolite, organic
polymers, palm ash, limestone, clay mineral, sepiolite, Indian rosewood, chitosan,
commercial activated carbon, activated carbon prepared from agricultural waste,
fungus Aspergillus’s, limestone and activated carbon, sand and activated carbon
and also sulphur and limestone (Abu Foul, 2007).

2.4.1 Activated Carbon

Activated carbon is an adsorbent that contain highly porous carbonaceous

substance. It is a common term of products that consist primarily of elemental
carbon. Because of its inherent properties, large surface area, microporous
structure, high adsorption capacity and surface reactivity, activated carbon becomes
well-liked adsorbent for the removal of organic and inorganic pollutants from
leachate (Kurniawan et al., 2006). Activated carbon macropores have an effective
radius of 5000 to 20000 Angstroms (Angstroms = 10-10m) and open directly to the
outer surface of the carbon particle. Transitional pores with radius of 40 to 200
Angstroms develop off the macropores, whereas the micropores with an effective
radius of 18 to 20 Angstroms develop off transitional pores (Benefield et al., 1982).
Micropores are the most important property in the adsorption process. Figure 2.3
show the sample and structure of activated carbon.

Figure 2.3 Activated carbon pore structures (Source: Impregnated Activated Carbon for
Environment Protection, 1997)

16
2.4.2 Non-Conventional Activated Carbon

Due to the low-cost factor, an agricultural or non-conventional activated carbon has

been tested for the efficiency as an adsorbent. The use of agricultural wastes such
as wood (H.M. Asfour et. al, 1985), Fuller’s earth and fired clay (G. McKay et. al,
1985), fly ash (S.K. Khare et. al, 1987), biogas waste slurry (C. Namasivayam et. al,
1992), waste Fe(III)/Cr(III) hydroxide (C. Namasivayam et. al, 1994), waste orange
peel (C. Namasivayam et. al, 1996), banana pith (C. Namasivayam et. al, 1992),
peat (G. McKay et. al, 1982), chitin (G. McKay et. al, 1983), chitosan (R.S. Juang et.
al, 1997) and silica (G. McKay et. al, 1984) was reported with favor results as
expected. Comparison for adsorption of some dyes on various adsorbents is shown
in Table 2.2 below.

Table 2.2: Comparison for adsorption of some dyes on various adsorbents

Adsorbent(s) Dye(s) References
Duckweed Methylene blue (Waranusantigul et. al., 2003)
Sewage Sludge Basic red 46 (Martin et. al., 2003)
Waste newspaper Basic blue 9 (Okada et. al., 2003)
Rice husk Malachite green (Guo et. al., 2003)
Acid yellow 36 (Malik et. al., 2003)
Acid blue (Mohamed et. al., 2004)
Sugarcane bagasse Acid orange 10 (Tsai et. al., 2001)
Coir pith Congo red (Namasivayam et. al., 2002)
Straw Basic blue 10 (Kannan et. al., 2001)

2.4.2 (a) Palm Oil and Palm Oil Waste

The oil-palm (Elaeis guineensis Jacq.) was originally planted in West Africa, where
local people have used it to make foodstuffs, medicines and wine. At the present
time, oil-palm exists in a wild, semi-wild and cultivated state in the three land areas
of equatorial tropics: Africa, South-East Asia and America (Hartley et. al, 1988).
Today large scales of oil-palm plantations are mostly for the production of palm oil,
which is extracted from the flesh part of the palm fruit (mesocarp), and kernel oil,
which is obtained from the innermost nut. Agricultural wastes like the palm oil waste
are discarded in the agricultural sector in Malaysia as illustrated in Figure 2.4. As
one of the biggest producer and exporter of palm oil in the world, the abundant of
resources might be an advantage to the needs of this project.

17
 Figure 2.4 Palm oil wastes

Palm oil wastes are the main biomass resources in ASEAN countries. In
Malaysia and Indonesia, the two largest palm oil producing countries in the world,
there were 30 M ton and 8.2 M ton of palm oil wastes (empty fruit bunch, fiber, palm
oil shell) generated respectively in year 2000, and they are increasing at spectacular
pace with the rapidly expanding of food and manufacturing industries. To treat this
tremendous amount of wastes, novel technologies with improved efficiencies and
reduced environmental impacts need to be established timely. In Malaysia itself, the
annual production is around 14 million tons from more than 38,000 square
kilometers of land, making it the largest exporter of palm oil in the world. To fully
utilize this abundant resource, in the present study I was analyzed by experimental
observation, the use of palm oil waste as the non-conventional adsorbent to remove
dye from wastewaters.

CHAPTER 3

18
 METHODOLOGY

3.1 EXPERIMENTAL WORK

The present work was conducted in Environmental Laboratory and Geotechnic

Laboratory of Faculty of Civil Engineering, Ground Floor of Perdana Complex and
Chemistry Laboratory 2 and 3 Applied Sciences Department, 2nd Floor of Perdana
Complex, UiTM Penang. The experimental work consists of several phases which
are to determine the effect of shaking time, contact time and weight of adsorbent in
decolorization of dye from simulated wastewater.

3.2 CHEMICALS

i. Palm oil waste (collected from nearby palm oil plantation in Nibong Tebal).
ii. Congo Red (Sigma Aldrich Corp.).

3.3 APPARATUS AND EQUIPMENTS

NO. APPARATUS/EQUIPMENTS
1 Conical Flasks (250ml)
2 Volumetric Flasks (1000ml)
3 Volumetric Flasks (500ml)
4 Pipette
5 pH meter
6 UV/VIS Spectrophotometer
7 Orbital Shaker
8 Dryer Multi Point
9 Weight Container
3.4 ADSORBENT PREPARATION

Palm oil waste was collected from nearby palm oil plantation factory in Nibong
Tebal, Penang by the Department of Applied Sciences, UiTM Penang. It was dried
under sunlight until all the moisture has evaporated. The material was ground to
fine powder. The crush palm oil waste was then washed with water; the precipitated
was removed by hand before it is being dry using dryer multi point (model P3500) at

19
110°C. The processes to get a dry palm oil waste are illustrated in plate 3.1, 3.2
and 3.3 below. The raw was subjected to carbonization at 110°C for 3 days using
dryer multi point (see plate 3.4) under closed condition. The carbonized material
was taken out and being sieved by Auto Sieve Shaker (Model: D408 ENDECOTTS)
(see plate 3.5) to approximately 150 μm and the resulting material ready to be used
for adsorption studies. No other chemicals were used to treat the palm oil waste for
adsorption enhancements.

Plate 3.1 Raw material of Palm oil waste

Plate 3.2 Palm oil waste washed with water and removed the precipitate before
drying in multi point at 110°C

20
 Plate 3.3 Final products after drying process

Plate 3.4 Dryer Multi Point

Plate 3.5 Auto Sieve Shaker D408 ENDECOTTS

3.5 PREPARATION OF ANIONIC DYE SOLUTIONS

The anionic dye, Congo red (CR) was manufactured by Sigma Aldrich Corporation,
Germany and supplied by Faculty of Chemical Engineering, UiTM Penang. The dye
was come with analytical grade and it was used without any further purification. It is
a hazardous dye and fully safety conditions were applied throughout the
experimental works. The stock solution was prepared by dissolving accurately
weighted dye in distilled water in the concentration of 500 mg/L. It was done by

21
weighting 0.5 g of Congo red (CR) on the top loading balance (Model X3-100) then
the weighted dye was dissolved in 1L of distilled water in a 1L Volumetric flask. The
solution was then properly agitated for favour dissolving distributions. The stock
solution was saved for dilution process with certain determined concentrations which
was obtained by successive dilutions. The dilution process was done in three
different samples where each sample contains of 10, 25 and 50 ml of stock solution
where each determined concentrations were added with 490, 475 and 450 ml of
distilled water respectively. The chemical formula of M1V1 = M2V2 has been applied
throughout the dilution process in order to get a correct value of respective desired
concentration. Each sample was then saved for further experimental works by
labeling each of the different concentrations.

3.6 PROCEDURE

Three main parameters that have been used throughout this work were the weight
of adsorbent, contact time and shaking speed. It was done by a certain procedures
that lead to the successive adsorption studies.

3.6.1 Weight of Adsorbent

To determine the effect of weight of adsorbent in the treatment of wastewater for

removal of Congo red (CR), three different amount of palm oil waste which are 0.5g,
1.0g, and 2.0g was introduced into 250ml conical flasks each containing 100ml of
stock solutions. The flasks were then shaken at room temperature using the orbital
shaker SK-600. Plate 3.6 shows the orbital shaker used to shaken the stock
solutions and palm oil waste.

22
 Plate 3.6 Orbital Shaker SK-600

3.6.2 Contact Time

The aim of this experiment was to determine the optimum contact time (shaking
time) for Congo red removal. In order to assess the effect of contact time in the
removal of Congo red, the palm oil waste was tested with various predetermined
contact times. The set of three conical flasks consist of different weight of adsorbent
that were then shaken by the orbital shaker with 60, 180 and 300 minutes of contact
time for each set.

3.6.3 Shaking Speed

Throughout the present work, shaking speed was set to be constant at 150rpm with
all different weight of adsorbent. The samples were then brought to the
Environmental Laboratory for UV check. This has been done by using UV/VIS
Spectrophotometry (Shimadzu UV-160 A) to measure the adsorbance after shake
as illustrated in plate 3.7. The experiments were carried out in triplicate and being
averaged to get the consistency of results.

23
 Plate 3.7 UV/VIS Spectrophotometry (Shimadzu UV-160 A)

3.7 ADSORPTION STUDIES

The dye solutions were prepared from stock solutions (500 mg/L) to desired
concentration. The adsorption experiments were carried out by a batch method.
100 mL of solution containing amount of palm oil waste and dye solution were taken
in a 250 mL conical flask. A different amount of adsorbent was then introduced with
4 sets of different volumetric flask. Each set contains 0, 0.5, 1.0 and 2.0 g of
adsorbents and agitated at constant speed of 150rpm at room temperature over a
period of time. The sets which contain with no adsorbents have not been shaking
and it is used for pH checking (see plate 3.8) and colour different observation. The
CR concentration of supernatant was measured after the treatment by using UV
spectrophotometer, at the maximum wavelength of Congo red at 500 nm
(λ = 500nm) (Shimadzu UV-160 A). Calibration curves were plotted between
absorbance and concentration of the standard dye solutions.

24
 Plate 3.8 Delta 320 pH meter

The removal efficiency (E) of adsorbent on Congo red was defined as:

E (%) = [(C0 – Ci) / C0] x 100 3.1

Where E (%) is the removal efficiency of dye adsorbed per unit weight of palm oil
waste; C0 the initial concentration of CR (mg/L); Ci the concentration of CR in
solution at equilibrium time (mg/L).

Blank runs, with only the sorbate in 100 ml of distilled water, were
conducted simultaneously at similar conditions to account for colour changes
adsorbed by glass containers. The experimental parameters studied are adsorbed
amount (0.5, 1.0 and 2.0 g/100mL), contact time (60, 180 and 300 min), and initial
dye concentration (10, 25 and 50 mg/L).

25
 CHAPTER 4

RESULTS AND DISCUSSIONS

4.1 PRELIMINARY RESULT

The preliminary result of the present work was observed by its color observation.
The color change of the simulated wastewater depicted the successfulness of the
work done.

4.1.1 Color Observation

Color observation is one of the vital parameter in determination of the experimental

success. Besides, by implementing the color observation, we can evaluate how far
the effectiveness and relevancy of the adsorbent that has been used. From the
present experiment, the color of simulated wastewater by the mixture of Congo red
with distilled water before and after treatment by the adsorbent presence was
observed and it showed that the color was clearer after the treatment rather than
before treatment (see plate 4.1). The bright red color of Congo red is depicting its
carcinogenic, toxic and mutagenic effect (Gregory et al., 1991; McKay et al., 1985).
The color changes show that the palm oil waste effective to be an adsorbent in
removing of dye from wastewater.

26
 Plate 4.1 Comparison of color changes before (left) and after (right) treatment

4.2 EXPERIMENTAL RESULTS

This experiment was conducted in order to determine the effect of process

parameters which is shaking time, adsorbent dose and initial dye concentration.
The effect of pH could not be determined due to the time constraint factors. Three
experimental trial results of removal of Congo red by adsorption onto palm oil waste
with effect of process parameters were done. Average value of the triplicate trials
result was then calculated in order to get an average value. Percent of dye removal
was then finally calculated. The tabular data of the present experiment are shown in
the table 4.1, 4.2, 4.3 and 4.4.

27
 Table 4.1 Tabular data of the first trial
CONCENTRATION, PALM OIL WASTE, ABSORBANCE
mg/L (g)
1h 3h 5h
0.0 0.733 0.733 0.733
0.5 0.420 0.398 0.288
10
1.0 0.549 0.509 0.476
2.0 0.500 0.450 0.320
0.0 1.173 1.173 1.173
0.5 0.860 0.800 0.676
25
1.0 0.989 0.880 0.743
2.0 0.940 0.821 0.700
0.0 1.906 1.906 1.906
0.5 1.593 1.447 1.076
50
1.0 1.722 1.709 1.432
2.0 1.673 1.655 1.300

Table 4.2 Tabular data of the second trial

CONCENTRATION, PALM OIL WASTE, ABSORBANCE
mg/L (g)
1h 3h 5h
0.0 0.733 0.733 0.733
0.5 0.397 0.300 0.288
10
1.0 0.553 0.511 0.496
2.0 0.501 0.449 0.211
0.0 1.173 1.173 1.173
0.5 0.780 0.700 0.654
25
1.0 0.845 0.811 0.543
2.0 0.913 0.875 0.361
0.0 1.906 1.906 1.906
0.5 1.300 1.223 1.200
50
1.0 1.488 1.421 1.361
2.0 1.329 1.275 1.087

Table 4.3 Tabular data of the third trial

CONCENTRATION, PALM OIL WASTE, ABSORBANCE
mg/L (g)
1h 3h 5h
0.0 0.733 0.733 0.733
0.5 0.455 0.400 0.286
10
1.0 0.629 0.651 0.457
2.0 0.511 0.491 0.400
0.0 1.173 1.173 1.173
0.5 0.568 0.540 0.497
25
1.0 0.575 0.570 0.488
2.0 0.958 0.900 0.843
50 0.0 1.906 1.906 1.906

28
 0.5 1.590 1.520 1.432
1.0 0.996 0.884 0.655
2.0 0.990 0.876 0.598

Table 4.4 Average to the triplicate trials

CONCENTRATION, PALM OIL WASTE, ABSORBANCE
mg/L (g)
1h 3h 5h
0.0 0.733 0.733 0.733
0.5 0.424 0.375 0.257
10
1.0 0.577 0.398 0.352
2.0 0.504 0.380 0.334
0.0 1.173 1.173 1.173
0.5 0.736 0.614 0.463
25
1.0 0.797 0.703 0.497
2.0 0.937 0.845 0.510
0.0 1.906 1.906 1.906
0.5 1.319 1.197 0.896
50
1.0 1.402 1.203 0.901
2.0 1.564 1.241 1.031

To achieve the objective of this experiment which is to determine the effect

of process parameters on Congo red removal in simulated wastewater by using
adsorption, the experimental data that obtained was analyzed by constructing a
graph of percent of dye removal versus adsorbent dose which is the palm oil waste
for each set of experiments. The graph shows that the percent of dye removal
increased as the weight of palm oil waste increasing and the percent removal mostly
depicted removal of more than 30%. Even though the adsorbent that has been
used is palm oil waste instead of activated carbon, the results of dye removal is still
acceptable. This is support by an article by A.G Liew et al., (2005), which they had
found that about 36.9% of methyl red dye was removed by using 0.6 g/100ml of
sugarcane baggase as the adsorbent. The agricultural non-conventional adsorbents
was proved that it can be a good adsorbent to remove of dye from wastewater
instead of conventional adsorbent such as alum, ferric and chloric.

29
4.2.1 Effect of Contact Time

The variation of Congo red adsorbed with time is shown in Figure 4.2 below. It was
observed that with a fixed amount of palm oil waste, the amount of Congo red
adsorbed increases with time and then attained a constant value after 200 min. The
time to reach equilibrium conditions appears to be independent of initial Congo red
concentrations. As shown in Table 4.5, we can conclude that with a fixed amount of
palm oil waste, the amount of Congo red adsorbed increases with time. During the
experiment, maximum contact time of 300 min shows the efficiency of percent
removal of Congo red decrease. This happened as the aggregation of dye
molecules with the increase in contact time makes it almost impossible to diffuse
deeper into the adsorbent structure at highest energy sites (Indra Deo Mall et. al.,
2004).

30
 T he Graph of Percent of Dye Removal vs. Contact T ime

100
Percent Dye Removal (%)
80

60 0.5(g/100ml)
1(g/100ml)
40 2(g/100ml)
20

0
0 50 100 150 200 250 300 350

T ime (minute)

Figure 4.2 Effect of adsorbent dosage on removal of CR by palm oil waste

This aggregation negates the influence of contact time as the mesopores

get filled up and start offering resistance to diffusion of aggregated dye molecules in
the adsorbents. This factor also has been studied by Indra Deo Mall et al., (2004)
where they have extent the contact time up to 7 days and it was observed that the
Congo red removal by baggase fly ash was only increases by about 0.5% over
those that have been obtained for 240 min of contact time. This is the reason why
an insignificant enhancement in adsorption is effected as the number of contact time
increase. Since the difference in the adsorption values at 60 min and 300 min is
very small, the experiments were conducted for 300 min of contact time only. The
adsorption curve is single, smooth and continuous leading to saturation and
indicated the possible mono-layer coverage on the surface of adsorbents by the dye
coverage on the surface of adsorbents by the dye molecules (Wong and Yu, 1999;
Malik, 2003).

As we look from the graph, the lowest percent of removal of Congo red is
when 0.5 g of adsorbent is used. The percent adsorption increased and equilibrium
time decreased with increasing adsorbent doses. The adsorption increased from
33.2 to 83.9%, as the palm oil waste treated dose was increased from 0.5 g to 2.0 g
at equilibrium time (60 min). The maximum dye removal was achieved within 90-
120 min after which Congo red concentration in the test solution was almost
constant. Increase in the adsorption with adsorbent dose can be attributed to the
increase in adsorbent area and availability of more adsorption sites.

31
 Table 4.5 Effect of adsorbent dose on the dye adsorption
Adsorbent dose, Percent (%) dye removal with time (min)
60 min 180 min 300 min
(g)
0.5 33.2 35.1 37.9
1.0 61.4 62.3 64.6
2.0 83.9 84.5 92.1

4.2.2 Effect of Initial Concentration

The Graph of Percent of Dye Removal vs. Contact Time

70
Percent of Removal (%)

60
50
10(mg/L)
40
25(mg/L)
30
50(mg/L)
20
10
0
0 50 100 150 200 250 300 350

Time (min)

Figure 4.3 Removal of CR as a function of equilibrium time

32
The percentage of Congo red adsorption with varying amounts of palm oil waste is
presented in Figure 4.3 above. In general, the increase in adsorbent dosage
increased the percent removal of adsorbate. This is consistent with the expectation
that higher adsorbent dosages will result in more adsorption process as more pores
available to adsorb the contaminants. The graph shows the removal of Congo red
by palm oil waste at different adsorbent doses (0.5 – 2.0 g/100mL) for the dye
concentrations of 10, 25 and 50 mg/L at different time intervals of 60, 180 and 300
min. Results are shown in Table 4.6. It is evidence that the percent adsorption
efficiency of palm oil waste decreased with the increase in initial dye concentration
in the solution. The percent of dye uptake is 65.0% by the influence of initial
concentration of 10mg/L at 300 min.

After while the initial concentration was increased to 25mg/L, the percent of
dye uptake was decreased by 6.92% to 60.5% and the percent decrease of dye up
taken by initial concentration was increment by 18.46% to 53.0% of removal was
observed by the influence of 50mg/L of initial concentration. The graph is not
perfectly obeying the general where it should be. As we can see from the graph, for
concentration of 10 mg/L, for 180 contact time, the trend is decrease where the line
should be higher than 25 mg/L line. This might be due to some experimental error
that occurred. To be compared, the percent removal of dye with initial concentration
of 10 mg/L is the highest instead of 25 and 50 mg/L of initial concentration in the
solution. In the process of dye adsorption, initially dye molecules have to encounter
the boundry layer effect before diffusing from boundry layer film onto adsorbent
surface. This is followed by the diffusion of dye into the porous structure of the
adsorbent. This phenomenon will relatively take longer contact time. The graph of
dye uptake is a single, smooth and continuous curve leading to saturation,
suggesting the possible monolayer coverage of dye on the surface of the adsorbent
(Garg et al., 2004).

Table 4.6 Effect of Congo red concentration on the dye adsorption

Initial dye Percent (%) dye removal with time (min)
concentration,
60 min 180 min 300 min
(mg/L)
10 42.1 48.9 65.0
25 37.3 47.7 60.5
50 30.8 37.2 53.0

33
 CHAPTER 5

CONCLUSION AND RECOMMENDATIONS

5.1 SUMMARY AND CONCLUSION

This experiment was conducted to determine the effect of process parameters which
is contact time, weight of adsorbent and initial concentrations on removal of Congo
red from wastewater by using adsorption technique. Adsorbent that has been used
was palm oil waste as replacement of conventional method due to high in cost.

34
 Palm oil waste is a common biomass waste material and easily available at
a small price. The removal of Congo red from simulated wastewater using a non-
conventional treatment of palm oil waste has been investigated under different
experimental conditions in batch mode basis. The adsorption of Congo red was
observed to be dependent on the adsorbent dose and Congo red concentration in
the wastewater. The results show that as the amount of the adsorbent was
increased, the percentage of dye removal increased accordingly. It was observed
that with a minimum at least of 30% efficiency of dye removal was established
during the present work that depicted the efficient of palm oil waste as the
adsorbent. Higher adsorption percentages were observed at lower concentrations
of Congo red. This study proved that palm oil waste is an attractive option for dye
removal from dilute industrial effluents. Even though the results obtained were not
favourly fits with the past study conducted, the trend can be considered to obey the
way it should be.

Experimental work that has been done showed that palm oil waste which
was used as an adsorbent was efficient in removing Congo red more than 30%.
The results of percentage dye removal versus weight of activated carbon showed
that the percentage of Congo red removal increasing as the weight of palm oil waste
increased for all parameters. This is due to the increase in adsorbent surface area.
Other parameter investigated which is contact time was also reported that
percentage of dye removal was increased with time and then it attained a constant
value after certain period of time. It might be due to the loosely attached molecule
that re-enter into the adsorbate and thus lowering the percentage of removal
efficiency of the dye. Aggregation of dye molecules with the increase in contact time
makes it almost impossible to diffuse deeper into the adsorbent structure at highest
energy sites (Indra Deo Mall et. al, 2004).

5.2 RECOMMENDATIONS / FUTURE WORK

From result of this experiment of Congo red removal from wastewater by using palm
oil waste as adsorbent, it is recommended to use adsorption isotherm models such
as Langmuir and Freundlich isotherm in order to determine the mathematical
relationships to describe the adsorption behavior of a particular adsorbent-adsorbate
combination. They help in calculating the adsorption capacity of material used.

35
 Time constraint was the main hardship that has been faced due to the late
of chemical supplied. The study might be useful if the adsorbent could be treated
with other chemicals for an enhancement purposes. From the recent study, it was
observed that the adsorbent that has been treated with other chemicals along the
adsorption process can result with a higher percentage of dye removal. This could
be evidence from the study conducted by Liew Abdullah A.G. et. al, (2005) where
sulphuric acid treated sugarcane baggase showed a better performance compared
to untreated sugarcane in the percentage of methyl red.

It was difficult to analyses the effect of pH parameter on percentage of

Congo red removal onto palm oil waste due to the time constraint factors. The pH
effect study has got to be skipping as this might take more time to be done as the
presence of other chemicals is needed to treat the adsorbent in order to investigate
the effect of pH. Effect of initial dye concentration shows a good trend in term of
percentage of dye removal. It was evidenced that the percent adsorption efficiency
of palm oil waste decreased with the increase in initial dye concentration in the
solution. However, this might be improved if the palm oil waste can be treated with
other chemicals to act as the catalyst to the adsorbent to boost up the efficiency on
adsorption capacity.

In this experiment, investigation through the mechanism of adsorption and

the potential rate-controlling processes is not being made. Therefore, for future
studies, adsorption kinetics which is pseudo-first, pseudo-second order and the
intraparticle diffusion models are fully suggested to be made in order to analyze the
adsorption kinetics for all parameters investigate.

For more effective studies on carbon material uses as an adsorbent,

activated carbon is recommended to be part with. This is because activated carbon
might give more accurate value of removal percentage due to its large surface area
that makes it an effective adsorbent. There are slight errors occurred in this
experiment maybe due to improper weighting of adsorbent-adsorbate that makes
the results did not fits the trend where it should be. For that reason, accurate
measurement of adsorbent or adsorbate must be done in accurately to have a
correct and more precise reading of the dye removal.

36
 REFERENCES

Aksu, Z., and Gonen, F. (2004) Biosorption of phenol by immobilized activated

sludge in a continuous packed bed: prediction of breakthrough curves.
Process Biochem. 39, pp. 599-613.
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