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The 2

nd
International Malaysia-Ireland Joint
Symposium on Engineering, Science and Business 2012
(IMiEJS2012)
647

Organic Pollutants Removal From Diluted Palm Oil Mill Effluent (POME)
Through Sono Fenton nZVI Process.
M. R. Taha
1,a
, A. H. Ibrahim
2,b,*
, A. W. Azhari
2,c
M. A. Wahab
2,d

1
Department of Civil and Structure Engineering, Universiti Kebangsaan Malaysia, 26000, Malaysia
2
School of Environmental Engineering, Universiti Malaysia Perlis, 01000, Malaysia
a
profraihan@gmail.com,
b
abdulhaqi@unimap.edu.my,
c
ayuwazira@unimap.edu.my,
d
mahyun@unimap.edu.my


Keywords: palm oil mill effluent (POME), sono-Fenton, zero valent iron

Abstract. In this study, an advance Fenton process called sono-Fenton-nZVI process was used to
remove organics content from palm oil mill effluent (POME). Factors such as pH, sonication
intensity and sonication time were studied in order to see their effects on organic removal
efficiency. Sono-Fenton-nZVI process very much dependent on the presence of ferrous ion (Fe
2+
).
At pH 2, nZVI particles oxidized rapidly to produce sufficient Fe
2+
which is very crucial in Fenton
process. Through sono-Fenton-nZVI process, 80% of the organic content was removed after 24
hour of silent degradation. However, at higher sonication intensity and longer sonication period the
process was accelerated. Same removal efficiency was achieved after 2 hours instead of 24 hours of
silent degradation. Hence, the application of sono-Fenton-nZVI process seems to be a promising
treatment method to remove the organic pollutants from POME.

INTRODUCTION

Palm oil production is one of the major industries in Malaysia and ranked as worlds second largest
exporter of palm oil after Indonesia. In the year 2010, Malaysia had produced approximately 17.2
million tonnes of crude palm oil (CPO) which were produced from 416 palm oil mills located
throughout the country [1]. All mills operated in the country currently employed wet milling
process which directly used large amount of water. In return, large volumes of waste water were
also produced which usually called as palm oil mill effluent (POME).

Data shows that raw POME contain average of 25,000 mg/l biochemical oxygen demand (BOD)
and 55,250 mg/l of chemical oxygen demand (COD) [2]. While during the high-crop season, the
values of BOD and COD in POME can rise up to 49,000 mg/L and 79,000 mg/L respectively [3].
Study by [2,3] indicates that POME is extremely rich in organic loads and directly poses very high
risk to environmental pollution if it not well treated before being emitted into the water bodies. Due
to extremely high content of organic loadings, several stages of treatment process have been applied
by the mill operators in order to meet the discharge limit impose by the local authority. Currently,
certain mill operators treat their POME up to tertiary/ polishing treatment to ensure the effluent
comply the discharge limit.

In most cases, aerobic process (activated sludge or membrane filters) is employed in
tertiary/polishing treatment plant. An evaluation study on tertiary treatment plant in palm oil mills
by Wahab [4] indicates that COD removal through the treatment process can only removed an
average of 56% of initial COD content. While Johari [5] reported that palm oil mills which
employed activated sludge process for the tertiary treatment also shows similar removal efficiency.
Since the microorganisms are very sensitive to the environmental changes, a very intensive care
should be carried out to ensure the survival of the microorganisms.
The 2
nd
International Malaysia-Ireland Joint
Symposium on Engineering, Science and Business 2012
(IMiEJS2012)
648


Besides using biological approaches, applications of advance oxidation processes (AOPs)
particularly Fenton process to remove COD from different types of wastewater such as olive mill
effluent [6], industrial wastewater [7] and landfill leachate [8, 9] also widely studied. During Fenton
process, hydroxyl radical (OH) produced from the reaction of Fe
2+
and hydrogen peroxide (H
2
O
2
)
attack and degrade the organic compounds hence reduce the COD content in the wastewater.

In Fenton process, the removal efficiency of organic compounds is very much dependent on pH,
dosage of H
2
O
2
and Fe
2+
[10]. Besides hydroxyl radical (OH) that is being produced, Fe
2+
also
being oxidized to ferric ion (Fe
3+
). The reactions occur during the Fenton process are as below:

Fe
2+
+ H
2
O
2
Fe
3+
+ OH + OH

(1)
Fe
3+
+ H
2
O
2
Fe
2+
+ OOH + H
+
(2)

In addition, reaction in Eq. 2 is slower compared to reaction in Eq. 1 where at certain point, the
ferrous ion concentration will be decrease and the production of OH will become less [11].
Consequently removal efficiency of organic compounds from the wastewater will be affected.

To overcome the drawbacks, exposure to ultrasound irradiation is one of the solutions.
Ultrasound irradiation can accelerate Eq. 2 where the level of Fe
2+
concentration can be keep at
adequate level to maintain the fenton process. In addition, OH can also be produced through the
cavitation of water molecules during the sonolysis process hence reduce the volume of H
2
O
2
used in
Fenton process [12]. The reactions can be represent as:

H
2
O +))) OH + H (3)
2OH + 2H H
2
O
2
+ H
2
(4)

In conventional Fenton process, iron sulfate (FeSO
4
) is used as major source of Fe
2+
[13].
Application of nZVI particles in Fenton process as an alternative to iron salt has been proven to
reduce the cost of Fenton process. Nano size ZVI particles will provide more reactive surface area
hence contribute to the success of Fenton process. In addition, the recycling rate of Fe
3+
also
become faster when nZVI particles are used in the Fenton process. The reaction can be represent
through the following reaction [14]:

2 Fe
3+
+ Fe 3Fe
2+
(5)

The objective of this study is to investigate the effects of pH, sonication intensity and sonication
time in Fenton process while utilizing nZVI particles as Fe
2+
source on COD removal of diluted
palm oil mill effluent (POME).

MATERIALS AND METHODS

Chemicals. Hydrogen peroxide (R&M Chemicals, 30%), Sulfuric acid (Merck, 95-97%), Sodium
Hydroxide (Merck, M=40g/mol), nZVI particles (Nanofer Star by NANO IRON, s.r.o., 80%) with
average particle size to 50 nm.

Experimental procedures. Concentrated raw palm oil mill effluent (POME) was diluted 25 times
with distilled water. The average initial CO concentrations of the diluted samples were 1160 mg/L
The 2
nd
International Malaysia-Ireland Joint
Symposium on Engineering, Science and Business 2012
(IMiEJS2012)
649

respectively. pH of the diluted samples were then adjusted to pH 2 and pH 4 using sulfuric acid
(0.5M).

100 ml of sample was then placed in a water-jacketed cylindrical glass reactor. For every 100 ml
sample, 0.06 g of nano zero valent iron and 0.4 ml of hydrogen peroxide was added. The mixture
was then subjected to sonocation using an ultrasonic probe (Sonic Ruptor 250, 20kHz, OMNI
International).
Immediately after the sonication process, 15 ml of samples were taken out and centrifuged at
4000 rpm for 10 minutes and tested for COD content via closed refluxed method. Remaining
samples then were placed in an automatic shaker for silent degradation of COD. COD analysis was
also done after 1 hour, 2 hours and 24 hours of silent degradation.

The experimental design was generated using full factorial design in statistical software called
Design Expert version 7.1 by Stat- Ease Company. The levels and independent variables for the
experimental design are shown in Table 1. Each run was replicated 3 times and average COD
removal was recorded for analysis.

Table 1: Levels and independent variables for the experimental design
Run Sonication intensity
(%)
Sonication time
(min)
pH
1 20 5 2
2 40 5 2
3 20 15 2
4 40 15 2
5 20 5 4
6 40 5 4
7 20 15 4
8 40 15 4

RESULT AND DISCUSSION

Oxidation Of Nano Zero Valent Iron Particles (Nzvi). Nanofer Star are very reactive nZVI
particles, which in the presence of water, will be oxidized into Fe
2+
. With high specific surface area
and ultrasound assisted, the productions of Fe
2+
from nZVI particle occurred rapidly. High
concentration of Fe
2+
will improve the Fenton process through the conversion of H
2
O
2
to OH by
Fe
2+
[15]. Fig. 1 shows the production of Fe
2+
from nZVI particle at different process condition.
Result shows that at pH 2, nZVI particles were oxidized most compared to pH 4. At pH 4, the
production of Fe
2+
was very low. This was in agreement with a study by Kellel and Namkung [14,
16] where Fe
2+
produced from iron by corrosion was increased with the decreasing value of pH.

The 2
nd
International Malaysia-Ireland Joint
Symposium on Engineering, Science and Business 2012
(IMiEJS2012)
650


Fig 1: The Fe
2+
concentration at different silent degradation time and process condition.

At pH 2, combination on high sonocation intensity and longer sonocation time help to boost the
production of Fe
2+
in the samples. This condition can be seen through run 4 where almost 700 mg/L
of Fe
2+
were produced immediately after sonication process. Concentration of Fe
2+
will reduce
gradually due to the reaction of H
2
O
2
to produce OH as mentioned in Eq. 1. However, after 2 hours
of silent degradation, the concentration of Fe
2+
starts to increase back. At this stage, Fe
3+
produced
from Eq. 1 started to react with H
2
O
2
to reproduce Fe
2+
through Eq. 2.

The Effect of pH, Sonication Power And Sonication Time On COD Removal. Immediately after
the sonication process, COD readings in all samples were increased except for run 4. Results based
on the treatment processes is represented in Fig. 2. This phenomenon occurred due to the presence
of remaining H
2
O
2
in the samples which interfered the COD analysis [17]. During the COD
analysis, besides the organic pollutants, the remaining H
2
O
2
was also oxidized by the oxidizing
agent, hence increased the COD reading. It obviously happened in all samples treated at pH 4. At
pH 4, there were very minimal Fe
2+
present to react with H
2
O
2
to produce hydroxyl radical (OH).
Due to that, more H
2
O
2
available in the samples and contribute larger interference to the COD
analysis. The effect of H
2
O
2
concentration on COD reading is represented in Figure 3. As can been
seen in Figure 3, addition of 0.4 ml of hydrogen peroxide into 100 ml of distilled water will rise up
the COD reading up to 1332 mg/L.


Fig 2: COD removal from diluted POME Fig 3: Effetc of H
2
O
2
on COD readings.
samples

As for samples treated at pH 2, it clearly shows that COD removal in all samples were increased
by time. It can be explain by the presence of Fe
2+
in these samples due to the oxidation of nZVI
The 2
nd
International Malaysia-Ireland Joint
Symposium on Engineering, Science and Business 2012
(IMiEJS2012)
651

which later react with H
2
O
2
to OH. Longer silent degradation produced more hydroxyl radical OH
and help to remove COD from POME samples. After 24 hours of silent degradation, 68 - 80% of
COD content was removed through sono-Fenton-nZVI process.

On the other hand, COD reading in samples which were treated at pH 4 went back to their initial
COD content after 24 hours of silent degradation. These indicate no COD removal from the diluted
POME samples. In these samples, all added H
2
O
2
were decomposed into water and oxygen. The
decomposition of H
2
O
2
can be represent in the following equation:

2 H
2
O
2
2 H
2
O

+ O
2
(6)

Sonication intensity or sonication time gave no significant effect on COD removal efficiency of
diluted POME. Figure 2 shows that samples which were treated at pH 4 at various sonication
intensity and sonication time resulted in almost the same COD removal. Similar trends were also
noticed in treatment condition 1, 2, and 3. COD removal efficiency for these three treatment
conditions was not much different. This result matched the finding by R. Chand [18]. Through his
study, samples were treated at two different high ultrasound frequency (300 and 520 kHz). Even
though the samples were treated at two different frequencies, the total organic removal were almost
the same for both samples. However, combination of high power and longer sonication time
boosted the COD removal efficiency. This clearly happened in treatment process 4. At this
treatment condition, the maximum COD removal (80%) can be achieved in 2 hours instead of 24
hours of silent degradation.

CONCLUSION

Application of NZVI particles can be an alternative to the usage of iron sulfate in conventional
Fenton process. In sono-Fenton-nZVI process, pH of the sample plays a major role to the success of
the process. At pH 2, nano zero valent iron particles will produce sufficient Fe
2+
to react with H
2
O
2
and reduce the organic content from the POME sample through the sono-Fenton-nZVI process. In
addition, an exposure to high sonication intensity and longer sonication time will accelerate the
COD removal process. Hence, the application of sono-Fenton-nZVI process seems to be a
promising treatment method to remove organic content from POME.

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nd
International Malaysia-Ireland Joint
Symposium on Engineering, Science and Business 2012
(IMiEJS2012)
652

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