Fairus Muhamad Darus, Harnie Jamilah Hashim, Rusdin Laiman, dan Mohd Nizam Yusoff. 2005.

Use
Of Palm Oil Fiber, An Agricultural Waste For Removal Of Methylene Blue From Aqueous Solution.
Dlm: Jamaluddin Jahi, Kadir Ariffin, Azahan Awang, Kadaruddin Aiyub & Muhammad Rizal Razman
(Eds). Prosiding Seminar Kebangsaan Pengurusan Persekitaran 2005. 4 – 5 Julai 2005. ms 301 - 308.
Bangi. UKM. ISBN: 983-2975-47-6

USE OF PALM OIL FIBER, AN AGRICULTURAL WASTE FOR

REMOVAL OF METHYLENE BLUE FROM AQUEOUS SOLUTION

Fairus Muhamad Darus, Harnie Jamilah Hashim, Rusdin Laiman and Mohd Nizam Yusoff
Environmental Technology Programme
Faculty of Applied Sciences, Universiti Teknologi MARA, Shah Alam

Abstract

Adsorption of dye is an alternative technology to remove colour from wastewater.

Activated carbon prepared from low cost palm oil fiber has been utilized as the
adsorbent for the removal of basic dyes from aqueous solution. A basic dye, Methylene
Blue has been used as the adsorbate. Experiments were conducted at different pH,
different adsorbent dose, different initial concentration of dye and different contact
time. The most effective of color removal was optimum at pH 7 and the percentage
removal increased with the increase in carbon dose. While the percentage removal
decreased with increasing of initial dye concentration. The adsorption equilibrium for
color reached at 90 minutes of contact time. The results indicated that palm oil fiber
could be employed as low cost alternatives to commercial activated carbon in
wastewater treatment for dye removal.

Abstrak

Penjerapan warna adalah teknologi alternatif untuk menyahwarna dari air sisa buangan.
Karbon teraktif yang dihasilkan daripada sabut kelapa sawit pada kos rendah telah
dikenal pasti sebagai penjerap untuk menyahwarna pewarna beralkali dari larutan
berair. Pewarna beralkali, Methylene Blue telah digunakan sebagai larutan. Kajian
dibuat pada pH yang berbeza, sukatan karbon yang berbeza, nilai kepekatan warna pada
permulaan kajian berbeza dan pada masa pertembungan yang berbeza. Penyahwarnaan
pewarna yang efektif adalah pada pH 7 dan peratus penyahwarnaan meningkat dengan
peningkatan sukatan karbon. Sementara itu peratus penyahwarnaan pewarna menurun
dengan peningkatan kepekatan pewarna pada permulaan kajian. Keseimbangan
Penjerapan untuk warna telah dikenal pasti pada minit ke 90. Keputusan menunjukkan
sabut kelapa sawit boleh dijadikan alternatif kepada karbon teraktif yang boleh
dikomersil bagi merawat air sisa buangan khususnya untuk penyahwarnaan pewarna.

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1. Introduction

Water pollution is now emerging as a major problem in the developing world and its
abatement has always been issued in our environmental concern today. The problem of
removing pollutants from water and wastewater has grown with rapid industrialization.
In Malaysia, 97 % of the effluent discharged is mainly from three industrial categories,
which are food industry, chemical industry and textiles industry (Azira et al., 2004;
Ong et al., 2004).
Among various industrial processes, dyes from textile industries produce a large
amount of colour effluent which is unacceptable under Malaysia environmental
regulations besides other parameters such as COD, BOD, dissolved oxygen, total iron,
and others (Tan et al., 2000). The discharging of dyes effluents into natural streams and
rivers are causing severe problems, as dyes impart toxicity to aquatic life, thus
damaging the aesthetic nature of the environment because dyes used in industry are
mostly stable to light and oxidation, as well as resistant to aerobic digestion.
Dyes and pigments are not commonly used in textile industries but also many
other industries such as plastics, paper, food, cosmetics, paints, leather, art and craft,
printing inks and rubber. The various treatment methods for the removal of colour and
dye are coagulation using alum, lime, ferric sulfate, ferric chloride, chemical oxidation
using chlorine and ozone, membrane separation processes, adsorption and so on.
Among these methods, adsorption currently appears the best treatment in order to
remove colour from wastewater (Walker et al., 1998; Chern et al., 2001; Namasivayam
et al., 2001a; Yang et al., 2001; Annadurai et al., 2002a; Robinson et al., 2002b; Gupta
et al., 2003; Janos et al., 2003; Rozada et al., 2003).
Dyes and colour discharged into rivers that meant for public water supply may
not meet the drinking water quality standards. Dyes and their degradation products may
be carcinogen and toxic if these effluents are treated inefficiently before discharging to
the rivers or streams, they could bring negative impact to human health (Kadirvelu et
al., 2003; Pala et al., 2003).
In this study, palm oil fiber has been chosen as activated carbon. By using this
agricultural waste, it may reduce solid waste disposal problem and also minimize the
cost of activated carbon production. The use of palm oil fiber for removing pollutants
will benefit the environment. Contaminated streams and rivers will be cleaned and new
market will be opened for the palm oil fiber. This study will provide useful information
about the efficiency of activated carbon prepared from palm oil fiber in the adsorption
of dyes from textile wastewater.

2. Methodology

In this study, a physical chemical treatment was applied in order to remove the colour.
Experimental variables considered were (i) different initial concentration of dye; (ii)
pH; (iii) dose of adsorbent; and (iv) contact time between adsorbent and dye solution.

2.1 Preparation of activated carbon from palm oil fiber

The raw material used for activated carbon (AC) preparation was palm oil fiber (POF).
To manufacture the AC, dewatered POF was mixed with concentrated H2SO4 (17.5M)
(1:2 v/w) and dried in air at room temperature for 24 hours. 300g of dried material was

302
put into an oven, heated at 180oC for 24 hours. The samples were then allowed to cool
at room temperature in an inert atmosphere. The product resulting from the activation
step was blend in order to form a granular AC and washed with 3M NaOH per 100 g of
product. The carbon product then was vacuum-filtered through Whatman 2 V filter
paper and washed repeatedly with distilled water to remove all traces of the acid and
alkaline i.e until the pH of the rinsed water was constant. The product was wet-screed
and dried at 80oC overnight.

2.2 Aqueous solution

In preparation of aqueous solution, a stock solution of Methylene blue (MB) (1000

mg/l) was prepared and diluted to the required initial concentration. Adsorption
experiments were carried out at room temperature (27±1 oC).

2.3 Adsorption experiments

For adsorption analysis, a duplicate sample and control were prepared for further
treatment studies. The initial and final concentration of MB was obtained by measuring
at 663 nm using spectrophotometer. 100 ml of MB solution of known initial
concentration was shaken at the constant agitation speed (200 rpm) with required dose
of AC prepared from different weight of POF (0.2, 0.4, 0.8, 1.2, 1.6 and 2 g) from 30
to180 min of contact time in incubator. The initial pH of the solutions (pH 7.2) were
adjusted to the required value (range: 3-9) by adding 1M NaOH or 1M H2SO4 solution.

2.4 Separation techniques

For separation between adsorbent and solution, the sample was centrifuged at 200 rpm
at predetermined times. After centrifugation, the samples were removed and its
supernatant was measured by using UV-spectrophotometer. The final concentration
was measured by using UV-spectrophotometer to determine the colour removed from
synthetic wastewater.

2.5 Analysis of the data

Data was analyzed by calculating the percentage removal of dye and the amount
adsorbed (in mg/g) by using this following relationships:

Percentage removal = 100 (Ci . Cf) / Ci

Amount adsorbed (qe) = (Ci . Cf) / m

where Ci and Cf initial and final concentration (in mg/L) of dye respectively, and m is
the mass of activated carbon (in mg/L). Blank containing no dye was used for each
series of experiments as controls. The average values of duplicates runs were obtained
and analyzed.

3. Result and discussion

3.1 Effect of pH on dye removal in aqueous solution

Although pore size distribution and the relative size of adsorbate have a significant
effect on adsorption capacity, the chemical nature of the adsorbent also plays a major

303
role. In order to know the role of surface chemistry on the adsorption capacity of dyes,
the effects of pH have been studied. The experiments have been carried out at different
pH (pH 3 – 9) and different dye concentration (50, 70 and 100 mg/L) and constant
carbon dosage of 2.0 g. The results are shown in Figure 1. The percentage of removal
for dyes was optimum at pH 7 with 120 minutes contact time for three different dye
concentrations. The lower adsorption of Methylene Blue, a cationic dye, at strong pH is
probably due to the presence of excess H+ ions competing with the dye cation for the
adsorption sites (Kannan et al., 2001; Annadurai et al., 2002b; Janos et al., 2003). As
the pH of the system increases, the number of positively charged sites decreases and the
number of negatively charged sites increases. The negatively charged sites favor the
adsorption of dye cation due to electrostatic attraction.

50 mg/L 70 mg/L 100 mg/L

120

99.2
100
90.4
Amount Removal (%)

80 71.4 86.2
69.2

60 67.4

40

20

0
3 4 5 6 7 8 9
pH

Figure 1: Effect of pH on dye removal using AC prepared from POF

(dose = 2 g, temp = 27 ± 1 oC, time: 120 min, particle size: < 105 µm)

3.2 Effect of different initial dye concentration

The results in Figure 2 showed that the concentration of dyes decrease after treatment
with AC prepared from POF. Removal of dye by adsorption using AC prepared from
POF at 50 mg/L initial dye concentration was 78.6% and 99.4% for 1 and 2 g adsorbent
dosage respectively. The amount of dye removed decreased when initial dye
concentration increased to 100 mg/L with 54.8% and 84.5% for 1 and 2 g adsorbent
dose respectively. The result showed the significant decrease on amount of dye removal
when the initial dye concentration increased from 50 mg/L to 100 mg/L. Increase in the
initial dye concentration of Methylene Blue decreased the percent removal of AC
prepared from POF that remained constant after equilibrium time. The process was
found to be very rapid initially and a large amount of dye was removed within a few
minutes. It is clear that the removal of dye was dependent on the concentration of dye
(Namasivayam et al., 2001a; 2001b). As the initial dye concentration is increased, the
percent removal is lower. This is due to limitation of the adsorbent mass where the
binding site of adsorbent/solute ratio is smaller (Azira et al., 2004). When the dye
concentration increased it shows that the amount of adsorbent dose must be increased
because dye concentration influenced the percentage of dye removal (Robinson et al.,
2002a; Garg et al., 2003).

304
 1g 2g
120

99.4
100
84.5

Amount Removal (%)

80
78.6

60

54.8
40

20

0
50 60 70 80 90 100
Concentration (mg/L)

Figure 2: Effect of different initial dye concentration on dye removal using AC prepared from POF
(pH = 7.2, temp = 27 ± 1 oC, time: 120 min, particle size: < 105 µm)

3.3 Effect of adsorbent dose and contact time

The removal percentage increased when the AC prepared from POF dose was increased
from (0.2-2.0 g/100 ml) at 50, 70 and 100 mg/L dye concentration (Figure 3). The
removal percentage of dyes increased with the increasing in adsorbent dosage. At 2.0 g
of adsorbent, a maximum removal of 99.8%, 92.4% and 86.4% was obtained for 50
mg/L, 70 mg/L and 100 mg/L respectively and a minimum removal of 70.2% for 50
mg/L, 70 mg/L and 100 mg/L dye concentration respectively. At 0.2 g of adsorbent a
minimum removal of 70.2%, 50.2% and 32.3% was obtained for 50, 70 and 100 mg/L
of dye concentration at constant pH of 7.2. The result showed a significant increase of
amount dye removal in different adsorbent dosage (0.2 - 2.0 g). Varying the adsorbent
mass may affect the porosity of the adsorbent suspension. A larger mass of adsorbent
could adsorb larger amount of dyes due to the availability of more surface area of the
adsorbent (Namasivayam et al., 1996; 2001a; 2001b). The increases in the adsorption
with the dose can be attributed to increase surface area and the availability of more
adsorption.

305
 50 mg/L 70 mg/L 100 mg/L
120

99.8
100
92.4

Amount Removal (%)

86.4
80
70.2

60
50.2

40 32.2

20

0
0.2 0.4 0.8 1.2 1.6 2
Adsorbent Dose (g)

Figure 3: Effect of adsorbent dose on dye removal using AC prepared from POF
(pH = 7.2, temp = 27 ± 1 oC, time: 120 min, particle size: < 105 µm)

The removal percentage increased with the increase of contact time and remains
constant after the equilibrium time that was presented in Figure 4. Removal of dyes
from AC prepared from POF increased rapidly in the beginning but then slowed down
until the equilibrium time. The equilibrium time for the dyes MB with different initial
concentration for 50, 70 and 100 mg/L were 90 min respectively. The result showed
that the amount of dye removal remain constant after the equilibrium time. It shows
that the removal of dyes from AC prepared from POF was increased with the increase
in agitation and reached equilibrium after 90 min for the dye concentration of 50, 70
and 100 mg/L. Removal of dye by adsorption on AC prepared from POF increased
rapidly in the beginning and then slowly decreased until the equilibrium time.

50 mg/L 70 mg/L 100 mg/L

110

105
99.4
Amount Removal (%)

100
96.6
95 92.8

90
89.1
85
81.1
80

75
73.4
70
30 60 90 120 150 180
t (min)

Figure 4: Effect of contact time on dye removal using AC prepared from POF
(dose = 2.0 g, pH = 7.2, temp = 27 ± 1 oC, particle size: < 105 µm)

306
4. Conclusion

Methylene Blue is found to be adsorbed strongly on the surface of carbons. In overall,

the adsorption can be influenced by many factors, such as adsorbent dose and particle
size, different initial dye concentration, agitation speed, contact time, temperature, pH
and ionic strength of the aqueous solution. Generally, the percent of removal increase
with the increasing of pH, adsorbent dose, contact time and agitation speed. This study
revealed that activated carbon from waste palm oil is an effective adsorbent for the
removal of dyes in aqueous solution. Activated carbon (AC) prepared from palm oil
fiber (POF) could also be employed as a low costs alternative for the removal of colour
and dyes in water and wastewater, particularly for the removal of Methylene Blue.
This treatment is economical as palm oil fiber is freely available in palm industries.

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