ENVIRONMENTAL ENGINEERING SCIENCE

Volume 29, Number 9, 2012

ª Mary Ann Liebert, Inc.
DOI: 10.1089/ees.2011.0181

Decolorization and Organic Removal from Palm Oil Mill Effluent

by Fenton’s Process
Aroon Kongnoo,1,2 Thunwadee Suksaroj,1,2 Punyanich Intharapat,1,2
Thanakrit Promtong,1 and Chaisri Suksaroj 2,3,*
1
Faculty of Environmental Management; 2National Center of Excellence for Environmental and Hazardous Waste Management;
3
Department of Civil Engineering, Faculty of Engineering; Prince of Songkla University, Hat Yai, Thailand.

Received: April 7, 2011 Accepted in revised form: November 27, 2011

Abstract
Decolorization and organics removal in palm oil mill effluent (POME) were investigated with the Fenton
process. Decolorization efficiency obtained was 66.5% at 5 min and > 90.0% at 30 min of reaction time. The
process removed 82.0% of soluble chemical oxygen demand at 1 h of reaction time with optimized conditions:
[H2O2] = 50 mM, [Fe2 + ] = 1.0 mM, and pH = 3.0 – 0.2. The kinetics rate constants (k) of decolorization and dis-
solved organic carbon removal were found at 6.20 · 10 - 2 min - 1 and 2.19 · 10 - 4 (mg/L) - 1 min - 1, respectively.
However, the UV irradiation did not obviously enhance the decolorization and organic removal of POME.
Humic and fulvic acid-like substances were identified at Ex/Em of 315/415 and 260/445 nm, respectively. By
fluorescence excitation-emission matrix (FEEM), spectroscopy could create colors in POME. Reduction of FEEM
intensity was 98.61%, which was related to the decolorization.

Key words: oxidation; decolorization; kinetics; Fenton; palm oil mill effluent

Introduction tion, and adsorption processes are being considered in further

decolorization of the organic pigments. The AOPs offer

O il Palm (Elaeis guineensis) is one of the most common

economic crops in tropical regions. It is a very important
agricultural-based industry, notably in Southern Thailand,
greater efficiency due to their ability to diminish various
pollutants such as aniline, phenol, and dimethyl sulfoxide in
the wastewater (Li et al., 2010; Huang et al., 2011a, 2011b).
Malaysia, and Indonesia. Extraction of palm oil involves a They are based on the generation of hydroxyl radicals (•OH)
number of processes that require large quantities of water. It that have powerful oxidizing capabilities. Among the AOPs,
usually requires an estimated 1.5 m3 of water to process a ton Fenton’s reagent is an attractive one, because the ferrous ions
of fresh fruit bunch, and half of this amount becomes palm oil (Fe2 + ) and hydrogen peroxide (H2O2) are widely available
mill wastewater (POMW). Raw POMW is a thick brownish and easy to handle, and excess decomposition is not harmful
liquid discharged at a high temperature (80C–90C) and to the environment. The Fenton process involves several se-
contains organic pigments, such as anthocyanins, carotene, quential reaction steps as follows (Yoon et al., 2001):
polyphenols, lignin, and tannin. It is characterized by a low
pH of 3.5–5.0, a chemical oxygen demand (COD) of 40,000–
Fe2 þ þ H2 O2 /Fe3 þ þ OH  þ•OH
50,000 mg L - 1, a biochemical oxygen demand (BOD5) of (1)
20,000–30,000 mg L - 1, and a high total suspended solids (TSS) k1 ¼ (5376) M  1 s  1
of 5000–54,000 mg L - 1 (Ahmad et al., 2003). Fe2 þ þ •OH/Fe3 þ þ OH 
Biodegradation system is the most popular method used (2)
for POMW treatment, but it does not always decolorize ef- k2 ¼ (3:24:3) · 108 M  1 s  1
fectively that result nondischargeable palm oil mill effluent •OH þ Org:/Org: Org. . . /CO2 þ H2 O
(POME). Therefore, the physical-chemical methods such as (3)
advanced oxidation processes (AOPs), separation, precipita- k3  107  1010 M  1 s  1
H2 O2 þ•OH/H2 O þ HO2
(4)
k4 ¼ (1:24:5) · 107 M  1 s  1
*Corresponding author: Department of Civil Engineering, Faculty of
Engineering, Prince of Songkla University, Hat Yai, Songkhla 90112, •OH þ•OH/H2 O2
Thailand. Phone: + 66-7428-7116; Fax: + 66-7445-9396; E-mail: schaisri@ (5)
eng.psu.ac.th k5 ¼ 5:3 · 109 M  1 s  1

855
856
Fe3 þ þ H2 O2 /Fe-OOH2 þ þ H þ
1 1
(6)
k6 ¼ 0:0010:020 M s
2þ • þ 3þ
Fe þ HO2 þ H /Fe þ H2 O2
6 1 1
(7)
k7 ¼ 1:2 · 10 M s
•
Fe3 þ þ HO2 /Fe2 þ þ O2 þ H 
(8)
k8 ¼ 1:0 · 104 M  1 s  1
• The photo-Fenton reaction was performed under 6 Watt
H2 O2 þ HO2 /•OH þ H2 O þ O2
(9)
k9 ¼ 0:5  0:09 M  1 s  1
•
•OH þ HO2 /H2 O þ O2
(10)
k10 ¼ 1:0 · 1010 M  1 s  1
This process has shown a promising applicable prospect in
the treatment of several kinds of organic or dye pigments
contaminating wastewaters, including those discharges from
livestock (Lee and Shoda, 2008), azo dye (Meriç et al., 2004)
and olive oil mills (Ugurlu and Kula, 2007).
The purposes of this study are to investigate the Fenton
process expressed in terms of the decolorization, organics
removal efficiencies, and their kinetics in order to determine
optimal conditions for the Fenton’s reagent.
Materials and Methods
Palm oil mill effluent
POME grab samples were collected from the final pond of
the stabilization pond wastewater treatment system in a palm
oil factory located in Trang province, Thailand. They were
placed in a thermal-resistant plastic container and were then
refrigerated at a temperature lower than 4C.
Reagents
Analytical-grade chemicals used during experiments in-
cluded a H2O2 solution (30% w/w), sodium hydroxide
(NaOH), and 98% of sulfuric acid (H2SO4). Ferrous sulfate
hepthahydrate (FeSO4$7H2O) was used as a source of Fe2 + .
Deionized water was used throughout the study.
Experimental setup
The experiments were performed in a stirred glass batch
reactor containing 250 mL of POME at 26C – 1C and under
atmospheric pressure. POME samples were filtrated through
a Whatman grade GF/C glass microfiber filters in order to
remove suspended particles before the experiment. The pH of
the samples was adjusted by adding H2SO4, and NaOH was
constantly controlled throughout the experiment.
Oxidation by Fenton reagents
A predetermined amount of catalytic FeSO4$7H2O was
added to the reactor, and the mixture was vigorously stirred
until it dissolved. The Fenton oxidation began with the ad-
dition of a H2O2 solution. Samples were withdrawn from the
reactor at predetermined time intervals. For the analysis of
soluble chemical oxygen demand (SCOD), excess amounts of
NaOH were added (to adjust pH to 7–10) after 1 h of reaction
in order to terminate the Fenton reaction by ferric hydroxo
complexes (Fe(OH)3) precipitation, followed by heating for
KONGNOO ET AL.
1 h and then left overnight at an ambient temperature in order
to withdraw the residual H2O2 (Kang et al., 1999). The samples
were then (I) filtrated through GF/C before analyzing color
and SCOD, and (II) filtrated through a GF/F glass microfiber
filters before measuring the fluorescence excitation-emission
matrix (FEEM).
The Fenton condition used was estimated from pretest
experiments and other researches (Meriç et al., 2004).
UV lamp power (UVP model UVGL-58) providing wave-
lengths ranging from 254 to 365 nm.
Analytical methods
BOD5, COD, TSS, oil and grease, dissolved organic carbon
(DOC), and pH were analyzed according to the Standard
Methods 5210B, 5220A, 2540D, 5520B, 5310B, and 4500H, re-
spectively (APHA, 2005). Duplications of all analyses were
carried out for each filtered POME sample. The [H2O2] was
measured with the potassium permanganate method
(Mendham et al., 2000). Decolorization of POME was deter-
mined by measuring the absorption intensity of the samples at
wavelengths of 475 nm (Prasongsuka et al., 2009) using UV-
visible spectrophotometry. FEEMs were measured using a
spectrofluorometer. The FEEM spectra of deionized water
was subtracted from the FEEM spectra of all samples, and
converted to quinine sulfate units (QSU). 10 QSU is equivalent
to the fluorescence spectra of 10 lg L - 1 quinine sulfate solu-
tion at 450 nm with an excitation wavelength of 345 nm.
Results and Discussion
POMW and POME characteristics
The characteristics of POMW and POME are presented in
Table 1. The POME remained organic with a low BOD5/
COD. The absorbance spectrum of the POME at a wave-
length range of 200 to 800 nm is presented in Fig. 1, of which
the peak intensity was not evident. This characteristic cor-
responded to the spectrum of natural water containing or-
ganic matters. The UV absorbance at 254 nm (UV-254) value
was not available. This indicated that the POME contained
high quantities of organic matter, especially of aromatic
structures. The FEEM peak intensities of POME were iden-
tified at Ex/Em of 315/415 nm (peak A), and 260/445 nm
(peak B) as shown in Fig. 2. The appearance of fluorescent
peaks A and B indicated respectively the existence of humic
Table 1. The Characterization of Palm Oil Mill
Wastewater and Palm Oil Mill Effluent
Parameter POMW POME
Color Dark brown Brown
pH 4.2–4.8 6.8–9.1
BOD5 (mg L - 1) 21,500–70,500 12–382
COD (mg L - 1) 37,726–166,483 120–638
DOC (mg L - 1) – 121–140
TSS (mg L - 1) 5166–50,050 4–278
Oil & grease (mg L - 1) 1132–14,346 1.5–14.0
POMW, palm oil mill wastewater; POME, palm oil mill effluent;
BOD5, biochemical oxygen demand; COD, chemical oxygen de-
mand; DOC, dissolved organic carbon; TSS, total suspended solids.
DECOLORIZATION OF PALM OIL MILL EFFLUENT BY FENTON’S PROCESS
FIG. 1. Absorbance spectra of POME at a wavelength range
of 200 to 800 nm. POME, palm oil mill effluent.
and fulvic acid-like substances, respectively (Musikavong
et al., 2007), which caused colors in the POME, and not only
from tannin and lignin.
The role of H2O2 and Fe2 + dosage
The effect of [H2O2] in the range of 10 to 150 mM was in-
vestigated at a pH value of 3 – 0.2, [Fe2 + ], 1.0 mM, and 5 min
reaction time decolorization, and 1 h for SCOD removal. The
relationships between the decolorization and SCOD removal
efficiencies are shown in Figs. 3 and 4. It was found that
the decolorization and SCOD removal of POME depended
on the initial [H2O2]. The optimum efficiencies for both de-
colorization and SCOD removal were obtained at 50 mM of
[H2O2]. This indicated that •OH increased with increasing of
initial [H2O2] up to a certain limit (Burbano et al., 2005). This is
due to the decrease of [•OH] as demonstrated in Equations (4),
(5), and (10), respectively. The decolorization was faster than
the SCOD removal, because the breakdown of bond cleavage
in the chromophore group by the reaction of •OH is rather fast
and easier than the transfromation of organic substances to
FIG. 2. FEEM patterns of POME. Peak A: humic acid-like
substances; Peak B: fulvic acid-like substances. FEEM,
fluorescence excitation-emission matrix.
857
FIG. 3. Effect of [H2O2] and [Fe2 + ] on the decolorization
(conditions: pH = 3.0 – 0.2; reaction time 5 min; at 475 nm).
H2O2, hydrogen peroxide; Fe2 + , ferrous ions.
carbondioxide, as Fe2 + is a catalytic agent in the Fenton pro-
cess that generates the •OH. The [H2O2] 50 mM with [Fe2 + ]
varying from 0.2 to 2.5 mM were studied and shown in Figs. 3
and 4. It is indicated that the color and SCOD removal effi-
ciency increased with initial Fe2 + concentrations in the range
of 0.2 to 1.0 mM. Above 1 mM of [Fe2 + ], the reaction was
inhibited. This is because •OH and • HO2 were suppressed by
Fe2 + and Fe3 + with a high k value, resulting in less reaction
with organic matter, as demonstrated by Equations (2), (7),
and (8) (Wongniramaikul et al., 2007). Therefore, the optimum
[H2O2] and [Fe2 + ] were, respectively, 50 and 1.0 mM for color
and SCOD removal of the POME.
The role of pH
The effects of pH on the POME color removal at various
times are presented in Fig. 5. The operation at pH 3 – 0.2 with
50–75 mM of [H2O2] and 1.0 mM of [Fe2 + ] yielded the maxi-
mum reaction rate. The color and SCOD removal efficiencies
of the POME decreased from 58.5% to 34.2% with an in-
creasing of pH value. This is because increasing in pH value
above 3.0 leads to the precipitation of Fe(OH3), resulting in the
inhibition of catalytic oxidation (Neamtu et al., 2003).
FIG. 4. Effect of [H2O2] and [Fe2 + ] on the SCOD removal
(conditions: pH = 3.0 – 0.2; reaction time 1 h). SCOD, soluble
chemical oxygen demand.
858
FIG. 5. Effect of pH on the decolorization at various times
(conditions: [H2O2] 50 mM; [Fe2 + ] 1.0 mM; pH = 3.0 – 0.2; at
475 nm).
The role of UV irradiation
The effect of UV on the POME decolorization is shown in
Fig. 6. The color removal efficiencies obtained by using UV at
wavelengths of 254 and 365 nm were 81.0 and 80.9%, re-
spectively. Although the UV can stimulate the oxidation re-
action according to Equation (11), the organic substances can
be oxidized not only by production of Fe2 + but also by reac-
tive oxidants of •OH as shown in Equation (12) (Sun et al.,
2009). In this study, the use of differing UV wavelengths
yielded no significant changes in decolorization. This is be-
cause oxidation reaction in the presence of UV wavelength
254 nm generated a small amount of •OH, whereas no •OH
was produced by the 365 nm UV.
H2 O2 þ hv/2•OH (11)
Fe3 þ þ H2 O þ hv/•OH þ Fe2 þ þ H þ (12)
Monitoring of color, SCOD, and organic
substances by FEEM spectroscopy
Results were shown in Fig. 7. It was found that the effi-
ciencies of humic and fulvic acid-like substances reduction
FIG. 6. Effect of UV and oxidation processes on the de-
colorization (conditions: [H2O2] 50 mM; [Fe2 + ] 1.0 mM;
pH = 3 – 0.2; at 475 nm).
KONGNOO ET AL.
FIG. 7. Removal efficiency of color, SCOD, humic, and
fulvic acid-like substances (conditions: [H2O2]/[Fe2 + ] = 0.5–
150; pH = 3 – 0.2; and reaction time 1 h.).
were 93.7% to 99.6%, respectively, which corresponded to the
decrease of color in the POME at 475 nm. This is due to the
breakdown of bond cleavage of organic pigments by •OH, but
it was different from the reduction of SCOD, because most of
the humic and fulvic acid-like structures were broken down
but only certain organic molecule can be oxidized and re-
leased as carbon dioxide (Wu et al., 2010).
Kinetics studies
The kinetics of the POME decolorization reaction based on
the relationship between color intensity and reaction time by
using the first oxidation step (Lu et al., 1999) was examined. It
was found that the color reduction was a pseudo-first-order
reaction. A calculation of k was obtained with a good rela-
tionship (R2 ‡ 0.8) for all [H2O2]/[Fe2 + ] ratios (Fig. 8). The k
increased with the increasing of [H2O2]/[Fe2 + ] ratios up to a
certain limit with a color removal efficiency of 61.11%. The
DOC value after treatment decreased with the increase of the
treatment period (Fig. 9). The DOC removal efficiencies were
37.0%, 64.0%, and 85.0% at the treatment periods of 15,
60 min, and 24 h, respectively. The DOC removal reaction
found was of a pseudo-second-order form. This is due to
the remaining organic matter in the POME after oxidation;
the organic removal reaction then was slower than the
FIG. 8. Decolorization kinetics of POME.
DECOLORIZATION OF PALM OIL MILL EFFLUENT BY FENTON’S PROCESS
FIG. 9. DOC decrease of POME (conditions: [H2O2] 50 mM;
[Fe2 + ] 1.0 mM; pH = 3.0 – 0.2). DOC, dissolved organic
carbon.
decolorization. The k of DOC removal reaction calculated was
2.19 · 10 - 4 (mg/L) - 1 min - 1.
Conclusions
The optimum Fenton conditions for color and organic
matter removal of POME obtained from this study were pH
3 – 0.2 and [H2O2] = 50 mM with [Fe2 + ] = 1.0 mM. Under
these conditions, more than 90% of color removal at 30 min
and 82.0% of SCOD removal at 1 h was obtained. The k value
of decolorization and DOC removal was 6.20 · 10 - 2 min - 1,
and 2.19 · 10 - 4 (mg/L) - 1 min - 1, respectively. The presence
of UV showed no effect on decolorization. The existence of
humic and fulvic acid-like substances caused colors in
the POME, and not only from tannin and lignin. The re-
duction of FEEM intensity peak was highly related to the
color reduction.
Acknowledgments
The authors appreciate combined financial supports from
the Faculty of Engineering, Prince of Songkla University
(PSU), Thailand (contract reference number ENG-53-2-7-02-
0002-S-1), the Green Technology Research Unit, and the PSU
Graduate School. In addition, kind suggestions from Assoc.
Prof. Dr. Jin Anotai are greatly acknowledged.
Author Disclosure Statement
No competing financial interests exist.
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