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Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 310–316

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Journal of the Taiwan Institute of Chemical Engineers


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Degradation of acetaminophen in an aerated Fenton reactor


Chia-Chi Su a, Luzvisminda M. Bellotindos b, An-Tzu Chang a, Ming-Chun Lu a,*
a
Department of Environmental Resources Management, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan
b
Office of Research and Extension, Universidad de Zamboanga, Zamboanga City, Philippines

A R T I C L E I N F O A B S T R A C T

Article history: This study investigates the degradation of acetaminophen (ACTP) using a novel Fenton aerated reactor.
Received 25 April 2012 The aerator was used to agitate and sludge was removed from a sludge outlet. The effects of operating
Received in revised form 23 August 2012 parameters such as pH, Fe2+ and H2O2 concentrations on the initial rate of ACTP degradation (r), removal
Accepted 6 November 2012
efficiency and mineralization were studied. The results indicate that a novel Fenton aerated reactor was
Available online 28 December 2012
successfully performed to degrade ACTP. The highest r value was obtained at pH 3. At pH 3, the r value
and ACTP removal efficiency were significantly improved as the [Fe2+]:[H2O2] ratio increased. The
Keywords:
removal efficiencies of ACTP, COD and TOC were 99%, 34% and 14%, respectively, at 40 min, when
Acetaminophen
optimum conditions for 5 mM acetaminophen, 25 mM H2O2 and 0.1 mM Fe2+ were used at pH 3.
Advanced oxidation processes
Degradation ß 2012 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Fenton process
Paracetamol

1. Introduction usually used to relieve pain. About 58–68% of acetaminophen is


excreted from the body during therapeutic use [6]. Recently,
Pharmaceuticals and personal care products (PPCPs) generally advanced oxidation processes (AOPs) and electrochemical treat-
refer to any product that can be used by individuals for personal ments have been successfully used to degrade or remove
health or cosmetic reasons or by agribusiness to promote the growth pharmaceuticals [3,7–10]. The acetaminophen degradation in
or health of livestock. Huge amounts of these chemicals are used aqueous solution has been investigated by ozonation/H2O2/UV
annually for therapeutic purposes and in animal farming. Pharma- [3], ozonation/UV/Fe2+/Cu2+ [11], UV/TiO2 [12], photo-Fenton [8]
ceuticals end up in soil, surface waters and eventually in ground and and Solar/photo-Fenton processes [9]. In the electrochemical
drinking water after their excretion from humans or animals via treatments, solution is decontaminated during the electrolysis by
urine or faeces, through the sewage system and into the influent of the direct reaction of pollutants with adsorbed OH at the anode
wastewater treatment plants [1]. PPCPs have been detected in many surface from oxidation of water in acid and neutral media [7].
surface and ground waters throughout the world and so have However, the efficiency of anodic oxidation was affected by the
attracted increasing attention as an emerging class of environmental type of anode. The effectiveness of AOPs is due to production of
pollutants [2,3]. In very small concentrations, some PPCPs may cause hydroxyl radical (OH), which is a powerful oxidant, highly
disruption of endocrine systems and affect the hormonal control of reactive, and non-selective reagent. One of the AOPs is the Fenton
development in aquatic organisms and wildlife [4,5]. New compos- process which uses hydrogen peroxide and ferrous ions to produce
ite pharmaceuticals and personal care products are continually hydroxyl radicals. In addition, the Fenton method is easy operation
excessively being manufactured and used to protect human and and more efficient with a lower cost than other AOPs [13].
aniline. The wastewater of pharmaceutical manufacturer contained The Fenton process has been known for more than a century
higher concentration toxic chemical substances. Hence, it is and is effective in the treatment of industrial wastewater [14–17].
important to develop an effective method for treating wastewater Fenton process in UV cell was conducted to explore the
with high concentration of pharmaceuticals. degradation of dye wastewater containing non-biodegradable
Acetaminophen (ACTP) is commonly called paracetamol and toxic substances [15]. This study reported that the initial dye
(N-acetyl-para-aminophenol or para-acetyl-amino-phenol). It is degradation rate increased with the increasing ferrous or hydrogen
peroxide concentrations. In the present study a lower concentra-
tion of pharmaceuticals degradation has been explored by Fenton
* Corresponding author. Tel.: +886 6 2660489; fax: +886 6 2663411.
reaction [18–20]. Fenton process has been used successfully to
E-mail addresses: bingb@uz.edu.ph (L.M. Bellotindos), remove a low concentration of pharmaceuticals. The pharmaceu-
mmclu@mail.chan.edu.tw (M.-C. Lu). ticals degradation was significantly affected by H2O2:Fe2+ molar

1876-1070/$ – see front matter ß 2012 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jtice.2012.11.009
C.-C. Su et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 310–316 311

ratio. Nevertheless, no previous studies have been found in the comprised a Plexiglas reservoir with dimensions of 21.5  15 
literature on the removal of wastewater with high concentration 25 cm3 with a volume of 8 L. The Fenton process was performed at
acetaminophen by Fenton process. The Fenton process involves room temperature (around 25 8C) in batch mode.
several reactions, as shown below [7]:
2.2. Experimental method
Fe2þ þH2 O2 ! Fe3þ þ OH þ OH (1)


The distilled water was used to prepare the solutions. 5 mM
OH þ organics ! Products þ CO2 þ H2 O (2)
acetaminophen was used in the study. Then, the pH was adjusted
to a predetermined value (2–4) by adding perchloric acid (HClO4).
Fe3þ þH2 O2 ! FeOOH2þ þHþ (3) Thereafter, ferrous ions (0.01–0.1 mM) were added to the reactor.
A particular amount of H2O2 (1–25 mM) was then added to the
FeOOH2þ !  O2 H þ Fe2þ (4) reactor and the reaction simultaneously started. The aerator at the
bottom of the reactor was used to provide better agitation. At

OH þ Fe2þ ! Fe3þ þOH (5) selected time intervals, a 4 mL sample was taken from the reactor
and immediately injected into a tube containing 16 mL of 1 M

OH þ H2 O2 !  O2 H þ H2 O (6) NaOH solution to terminate the reaction. Each sample was filtered
through a 0.2 mm membrane filter to remove precipitates before
Fe2þ þ O2 H ! HO2  þFe3þ (7) analysis. Each experiment was replicated.

Fe3þ þ O2 H ! O2 þHþ þFe2þ (8) 2.3. Analytical method


The Fenton process generates a very large quantity of ferric
The concentration of acetaminophen was determined with
hydroxide (Fe(OH)3) sludge, which must be separated and
Spectra System model SN4000 HPLC (Thermo Finnigan) equipped
disposed. Generally, conventional Fenton process uses a magnetic
with Asahipak ODP-50 6D column (150 mm  6 mm  5 mm), the
stirrer to provide a vigorous stirring in the laboratory-scale studies
UV1000 UV/V detector set at 220 nm. A mobile phase containing
[21–23]. However, magnetic stirrer is unfeasible for an enlarge-
550 mL of acetonitrile (CH3CN), 11.85 mL of 85% of phosphoric acid
scale reactor. For wastewater treatment in manufacturing plants,
(H3PO4) and 3000 mL of distilled water was used at 1 mL/min.
the aerator may be more feasible for an enlarge-scale reactor than
These analyses were made by injecting 20-mL. The concentration
the stirrer. Therefore, the aerator was used in this study to replace
of H2O2 was determined by iodometric titration with Na2S2O3
the stirrer. So far no investigation designs that how to remove
solution [21]. To prevent the concentration of H2O2 from affecting
sludge after Fenton process. Hence, this work designs a new reactor
the COD measurement, the samples were left overnight to
with aerator and sludge outlet. Sludge is removed from this newly
eliminate any residual hydrogen peroxide that may have otherwise
designed reactor though an added sludge outlet. The degradation
remained in the sample solution. Chemical Oxygen Demand (COD)
of acetaminophen in a new Fenton reactor, which includes a sludge
was determined using a closed reflux titrimetric method from the
outlet and an aerator, is studied in this study. The effects of
Standard Methods [22]. TOC was analyzed using an Elemental liqui
important parameters (pH, ferrous ions and hydrogen peroxide
TOC analyzer.
concentrations) on the initial rate of acetaminophen degradation
and its removal efficiencies are studied in detail.
3. Results and discussion
2. Materials and methods
3.1. Background experiment and comparison
2.1. Material and reactor
The experiment was performed to determine the effect of H2O2
and ACTP concentrations on ACTP degradation as the control
Acetaminophen (C8H9NO2, Merck), hydrogen peroxide (H2O2,
experiment. Fig. 2 (a) indicates that degradation of ACTP at initial
35%, Merck), and ferrous sulfate hepta-hydrated (FeSO47H2O,
concentration of 5 mM without H2O2 was less 3.5% less than
Merck) were reagent-grade and used without further purification.
degradation of 5 mM ACTP with 20 mM H2O2. During the
Fig. 1 shows the aerated Fenton reactor. The Fenton reactor
experiment, the concentration of H2O2 slightly declined (Fig. 2
(b)). Therefore, H2O2 alone had no significant effect on ACTP
degradation. In addition, the effect of stirrer and aerator on ACTP
degrdation was compared and shown in Fig. 3. The result shows
that the difference in the removal of ACTP between stirrer and
aerator could be negligible. In a real case of wastewater treatment,
the aerator may be more feasible for an enlarge-scale reactor built-
up than the stirrer. Hence, the novel configuration of reactor with
an aerator has the potential for treating wastewater in
manufacturing plant. A new reactor with an aerator was used in
following investigation to replace the stirrer.

3.2. Effect of parameters on degradation of acetaminophen

The pH value that is suitable for the Fenton process is 2–4 [23].
In this study, the pH of the solution was controlled at 2–4. Fig. 4(a)
presents the effect of pH on the degradation of ACTP in the Fenton
process. Notably, the ACTP concentration at pH 3 and 4 declined
rapidly in the first 10 min. At pH 2, the ACTP concentration
Fig. 1. Schematic diagram of Fenton reactor. decreased slightly with time. In the first 10 min, the degradations
312 C.-C. Su et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 310–316

Acetaminophen remaining, C/C0


Acetaminophen remaining, C/C0
1.0 1.0
pH 2
0.8 0.8 pH 3
pH 4

0.6 0.6
5 mM ACTP
0.4 5 mM ACTP and 20 mM H2O2 0.4

0.2 0.2
(a)
0.0 0.0
0 10 30 50 70 90 110 130 0 10 30 50 70 90 110 130

1.0
1.0

H2O2 remaining, C/C0


H2O2 remaining, C/C0

0.8
0.8

0.6
0.6
0.4
0.4
0.2
0.2
5 mM ACTP and 20 mMH2O2
(b)
0.0
0.0
0 10 30 50 70 90 110 130 0 10 30 50 70 90 110 130
Time (min) Time (min)
Fig. 2. (a) Acetaminophen and (b) H2O2 removal efficiencies at pH 3. Fig. 4. Effect of pH on degradation of acetaminophen. Experimental conditions:
[acetaminophen] = 5.0 mM, [H2O2] = 15.0 mM and [Fe2+] = 0.1 mM.

of ACTP followed the order pH 3 > pH 4 > pH 2. At the end of the


reaction, they followed the order pH 3 = pH 4 > pH 2. The same (0.449 mM min1) was achieved at pH 3 (Table 1). Hence, the
patterns were observed for the remaining concentration of H2O2 optimum pH for this study should be 3. In addition, Lu et al. [26].
(Fig. 4 (b)). At pH 3 and 4, the concentration of H2O2 decreased reported the Fenton system undewent a two-stage reaction. The
rapidly in the first 15 min, while the H2O2 concentration at pH 2 first stag was the reaction in the first 30 second in which the
decreased with time. In the pH 3 and 4 systems, H2O2 was decomposition rate of dichlorvos was high, and there was a Fe2+/
significantly consumed in the first 40 min. At low pH, Fe2+ is H2O2 reaction. The second stage was a slower Fe3+/H2O2 reaction
probably associated with the formation of Fe(OH)+, whose activity taking place after 30 second. In this study, the ACTP was
is higher than that of Fe2+ in Fenton oxidation. Fe(OH)+ reacts more decomposed rapidly in 5 min, and then the reaction rate was
slowly than Fe2+ with H2O2 and produces fewer OH radicals.
Therefore, the H2O2 was slowly consumed at low pH [24,25]. 1.4
Although, the removal efficiency of acetaminophen at pH 3 and 4
1 mM H2O2 10 mM H2O2
Acetaminophen remaining, C/C0

were same, the highest initial rate of ACTP degradation


1.2 5 mM H2O2 15 mM H2O2
7.5 mM H2O2 25 mM H2O2
1.0 1.0
Acetaminophen remaining, C/C0

0.8 0.8
Stirrer
Aerator 0.6
0.6

0.4
0.4

0.2
0.2
0.0
0.0 0 10 30 50 70 90 110 130
0 20 40 60 80 100 120 Time (min)
Time (min)
Fig. 5. Effect of H2O2 concentration on degradation of acetaminophen. Experimental
Fig. 3. Comparison of stirrer and aerator for the degradation of acetaminophen. conditions: [acetaminophen] = 5.0 mM, [Fe2+] = 0.1 mM at pH 3.
C.-C. Su et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 310–316 313

Table 1
Initial rates of ACTP degradation and ACTP removal efficiencies.

pH [H2O2] (mM) [Fe2+] (mM) [Fe2+]/[H2O2] Initial ratea (mM min1) Acetaminophen removalb (%)

2 15 0.10 0.0067 0.040 84


3 0.0067 0.449 91
4 0.0067 0.403 91
3 1.0 0.10 0.1000 0.053 15
5.0 0.0200 0.238 47
7.5 0.0130 0.347 69
10.0 0.0100 0.332 77
15.0 0.0067 0.449 91
25.0 0.0040 0.479 99
3 5.0 0.01 0.0020 0.026 56
0.10 0.0200 0.238 47
15.0 0.05 0.0033 0.206 71
0.10 0.0067 0.449 91
25.0 0.01 0.0004 0.029 67
0.10 0.0040 0.479 99
a
At 10 min of reaction
b
At the end of reaction

gradually decreased between 2 and 40 min. The ACTP remaining did not significantly decrease. Increasing the H2O2 concentration
was not substantially changed after 30 min. increased the number of OH radicals formed, which reacted with
The effect of hydrogen peroxide on the degradation of ACTP was the organics in the solution according to Eqs. (1) and (2).
studied at initial concentration of 5 mM ACTP and 0.1 mM Fe2+ at Fig. 6 plots the effect of initial Fe2+ concentration on ACTP
pH 3. Various H2O2 concentrations are 1, 5, 7.5, 10, 15 and 25 mM. degradation. In the first 10 min, the degradation efficiency in the
As shown in Fig. 5, increasing the initial H2O2 concentration from 1 0.1 mM Fe2+ system exceeded that in the 0.01 mM Fe2+ system
to 25 mM promoted the ACTP degradation. At all concentrations of when 5 mM H2O2 was used (Fig. 6(a)). After 10 min, the
H2O2, the ACTP degraded rapidly in the first 10 min, but thereafter degradation efficiency in the 0.1 mM Fe2+ system remained

(a) 1.0 1.0


ACTP remaining, C/C0

H2O2 remaining, C/C0

0.8 0.8

0.6 0.6 0.01 mM Fe2+


0.10 mM Fe2+
0.4 0.4

0.2 0.2

0.0 0.0
0 10 30 50 70 90 110 130 0 10 30 50 70 90 110 130
(b) 1.0 1.0
ACTP remaining, C/C0

H2O2 remaining, C/C0

0.8 0.8
0.05 mM Fe2+
0.6 0.6 0.10 mM Fe2+

0.4 0.4

0.2 0.2

0.0 0.0
0 10 30 50 70 90 110 130 0 10 30 50 70 90 110 130
(c) 1.0 1.0
H2O2 remaining, C/C0
ACTP remaining, C/C0

0.8 0.8

0.6 0.6

0.4 0.4 0.01 mM Fe2+


0.10 mM Fe2+
0.2 0.2

0.0 0.0
0 10 30 50 70 90 110 130 0 10 30 50 70 90 110 130
Time (min) Time (min)
Fig. 6. Effect of Fe2+ concentration on degradation of acetaminophen at (a) [H2O2] = 5 mM, (b) [H2O2] = 15.0 mM and (c) [H2O2] = 25 mM, [acetaminophen] = 5.0 mM, pH 3.
314 C.-C. Su et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 310–316

constant. The degradation efficiency in the 0.1 mM Fe2+ system 0.6


increased slowly because the H2O2 in the 0.1 mM Fe2+ system was (a)
exhausted at 10 min. In the 0.01 mM Fe2+ system, little H2O2 0.5
resulted in weak ACTP degradation until H2O2 was exhausted at
90 min. The ACTP degradation efficiencies in the 0.05 and 0.1 mM 0.4

r, mM min-1
Fe2+ systems were obviously improved when 15 mM H2O2 was
used (Fig. 6(b)). For example, the degradation efficiency at 20 min
was 62% at 0.05 mM Fe2+ (Fig. 6 (b)), and 10% and 48% at 0.01 and 0.3
0.1 mM Fe2+, respectively, (Fig. 6 (a)). These results indicate that
the OH radicals were efficiently generated by appropriate 0.2
concentrations of Fe2+ and H2O2. When the H2O2 concentration pH 2
was increased to 25 mM, the ACTP degradation efficiency in the 0.1 pH 3
0.01 mM Fe2+ system apparently decreased. A large amount of pH 4
H2O2 remained in the solution (Fig. 6(c)). Since H2O2 is overdosed,

0.0
OH radicals reacted with a very large amount of H2O2 in solution,
0.000 0.005 0.010 0.015 0.020
reducing the concentration of OH radicals, and thereby reducing
the ACTP degradation efficiency, according to Eqs. (2) and (6). 100
Table 1 lists the ACTP removal efficiency in the Fenton process. The (b)
effects of the pH, Fe2+, and H2O2 concentrations on ACTP
80

Removal efficiency, %
degradation are significant. The following section investigates in
detail the effects of these important parameters on the initial rate
of ACTP degradation and removal efficiency. 60

3.3. Effect of parameters on initial rate of ACTP degradation and ACTP


removal efficiency 40

The degradation of ACTP was most rapid in the initial 10 min.


Therefore, the ACTP concentrations at the first 10 min were used to 20
estimate the initial rate of ACTP degradation (r).
 
D½ACTP ½ACTP0  ½ACTP10 0
r¼ ¼ (9)
Dt t 0  t 10 0.000 0.005 0.010 0.015 0.020
[Fe2+]/[H2O2]
The removal efficiency for acetaminophen was determined as
Fig. 7. Effect of pH on rate of acetaminophen degradation and removal efficiency.
follows.

ACTP removal efficiency ¼ D½ACTP concerning the r value indicated that the ACTP removal efficiency

¼ ½ACTP0  ½ACTP120  100 (10) at pH 2 was improved significantly by increasing the [Fe2+]:[H2O2]
ratio above 0.0007, probably because better agitation by the
where [ACTP]0, [ACTP]10 and [ACTP]120 are the concentrations aerator improved the Fenton process.
of acetaminophen in the solution at time zero, 10 and 120 min, Fig. 8 presents the r values and ACTP removal efficiencies at
respectively. to and t10 are reaction times zero and 10 min, various [Fe2+]:][H2O2] ratios. As [Fe2+]:[H2O2] increased from 0.002
respectively. Fig. 7 (a) plots the effect of pH on the initial rate of to 0.0067 at pH 2, the changes in the r value and ACTP removal
ACTP degradation. At pH 2, the r value increased slightly with the efficiency were insignificant (Fig. 8 (a)-(b)). However, the r value
[Fe2+]:[H2O2] ratio from 0.0007 to 0.002, but further increasing the and ACTP removal efficiency decreased by factors of around 1.6 and
[Fe2+]:[H2O2] ratio reduced the r value. The maximum r value was 1.8, respectively, as [Fe2+]:[H2O2] ratio increased by a factor of five
0.046, obtained at [Fe2+]:[H2O2] = 0.002. At pH 3, the r value to 0.01 (Fig. 8 (c)), mainly because the excess ferrous ion
increased apparently when [Fe2+]:[H2O2] ratio more than 0.002. scavenged OH radicals, according to Eq. (5). Increasing the
The r value reached its maximum value of 0.479 at [Fe2+]:[H2O2] ratio from 0.002 to 0.0067 (3.4 times) at pH 3
[Fe2+]:[H2O2] = 0.004. As [Fe2+]:[H2O2] ratio increased from increased the r value by a factor of around 17.3 and ACTP removal
0.004 to 0.02, the rate of ACTP degradation fell from 0.479 to efficiency by a factor of around 1.6 (Fig. 8 (a)-(b)). This result
0.238 mM min1. At pH 4, the r value significantly increased with implies that the catalyst increases the degradation rate because
the [Fe2+]:[H2O2] ratio from 0.0007 to 0.0067, and decreased to iron activates the hydrogen peroxide to form OH radicals. As
0.246 mM min1 as the ratio increased further to 0.01. The highest [Fe2+]:[H2O2] ratio is increased from 0.002 to 0.0067 (by a factor of
r value (0.403 mM min1) was obtained at [Fe2+]:[H2O2] = 0.0067. around 3.4) at pH 4, the r value and ACTP removal efficiency
Fig. 7 (b) presents the effect of pH on ACTP removal efficiency. At increased by factors of around 3.3 and 1.2, respectively (Fig. 8 (a)-
various pH values, ACTP removal efficiency clearly increased with (b)). When [Fe2+]:[H2O2] ratio was increased to 0.01 (by a factor of
the [Fe2+]:[H2O2] ratio, but the removal efficiency of ACTP around five), the r value was doubled and the ACTP removal
decreases when [Fe2+]:[H2O2] ratio increased further. ACTP efficiency decreased by a factor of around 1.25. As observed in
removal increased from 12% to 81% and 84% at pH 2, when Fig. 8, at pH 3, as [Fe2+]:[H2O2] ratio increased by a factor of around
[Fe2+]:[H2O2] ratio was increased from 0.0007 to 0.002 and 0.0067, 3.4, r increased by a factor of 17.3. As [Fe2+]:[H2O2] increased by
respectively. ACTP removal increased from 56% to 71% and 99% at factors of 3.4 and five at pH 4, the r value increased by factors of 3.3
pH 3, when [Fe2+]:[H2O2] ratio increased from 0.002 to 0.0033 and and two, respectively. ACTP removal efficiency increased by a
0.004, respectively. ACTP removal increased from 53% to 76% and factor of 1.63 at pH 3 and 1.2 at pH 4. The r value increased more
91% at pH 4, when [Fe2+]:[H2O2] ratio increased from 0.0007 to than did the ACTP removal efficiency because a high concentration
0.002 and 0.0067, respectively. A comparison with the results of OH radicals was generated in the first phase of Fenton reaction, as
C.-C. Su et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 310–316 315

thereby reducing the efficiency of degradation. Nevertheless, the


formation of intermediates is one of the causes of low removal
efficiency. The Fe2+ and H2O2 reacted with the OH radicals
according to Eqs. (5) and (6), reducing the concentration of OH
radicals that could react with the organic compounds, and thereby
reducing the removal efficiency.
Under optimal conditions, ACTP degradation in the Fenton
process reached 99% in 40 min, as shown in Fig. 9. All H2O2 was
consumed in 40 min, when the ACTP degradation therefore
stopped, as did the removal of COD and TOC. The removal
efficiencies of COD and TOC fell at 40 min, being only 34% and 14%,
respectively, indicating that not all ACTP was oxidized to carbon
dioxide during this period.

4. Conclusion

A novel Fenton reactor, with an aerator and a sludge outlet,


was used to study the degradation of acetaminophen. The
important parameters, such as pH, and H2O2 and Fe2+ concen-
trations, clearly affected the initial rate of acetaminophen
degradation (r) and acetaminophen removal efficiency. At pH
2, the r value and ACTP removal efficiency did not significantly
change, as [Fe2+]:[H2O2] ratio increased by a factor of 3.4 to
0.0067. Nevertheless, in the pH 3 and 4 systems, the r value
increased by factors of 17.3 and 3.3, respectively, as [Fe2+]:[H2O2]
ratio increased by a factor of 3.4. The ACTP removal efficiencies
increased by a factor of 1.63 at pH 3 and 1.2 at pH 4. The r value
increased more than the ACTP removal efficiency, indicating that
Fenton reaction produced a higher concentration of OH radicals
at the first phase than that at the second one. As a result, the
degradation efficiency of ACTP decreased. The optimal conditions
were at 5 mM of acetaminophen, 25 mM of H2O2, 0.1 mM of Fe2+,
and pH 3 with 99% of ACTP, 34% of COD and 14% of TOC removal,
respectively.

Acknowledgement
2+
Fig. 8. Effect of the [Fe ]:[H2O2] ratio on initial rate of ACTP degradation (r) and
ACTP removal efficiency. The authors would like to thank the National Science Council of
Taiwan, for financially supporting this research under Contract No.
NSC 99-2221-E-041-012-MY3.
described by Eq. (1). As the reaction proceeded, intermediates
were formed by degradation. The intermediates, such as oxalic References
acids, formed complexes with iron, and so precipitated out [27],
reducing the amount of iron available in the Fenton process and [1] Klavarioti M, Mantzavinos D, Kassinos D. Removal of residual pharmaceuticals
from aqueous system by advanced oxidation processes. Environ Int 2009;
35:402–17.
[2] Stumpf M, Ternes TA, Wilken RD, Rodrigues SV, Baumann W. Polar drug
residues in sewage and natural waters in the state of Rio de Janeiro. Brazil
1.0 Sci Total Environ 1999;225:135–41.
[3] Andreozzi R, Caprio V, Marotta R, and Vogna D. Paracetamol oxidation from
aqueous solutions by means of ozonation and H2O2/UV system. Water Res
0.8 2003;37: 993–1004.
[4] Lintelmann L, Katayama A, Kurihara N, Shore L, Wenzel A. Endocrine disruptors
in the environment (IUPAC technical report). Pure Appl Chem 2003;75:631–81.
[5] Esplugas S, Bila DM, Krause LGT, Dezotti M. Ozonation and advanced oxidation
C/C0

0.6 technologies to remove endocrine disrupting chemicas (EDCs) and pharma-


ceuticals and personal care products (PPCPs) in water effluents. J Hazard Mater
2007;149:631–42.
0.4 H 2O 2 [6] Muir N, Nichols JD, Clifford JM, Sykes J. Comparative bioavailability of aspirin
Acetaminophen and acetaminophen following single dose administration of solution and plain
tables. Curr Med Res Opin 1997;13:491–500.
COD [7] Brillas E, Sirés I, Arias C, Cabot PL, Centellas F, Rodrı́guez RM, et al. Minerali-
0.2 TOC zation of paracetamol in aqueous soltuion by anodic oxidation with a boron-
doped diamond electrode. Chemosphere 2005;58:399–406.
[8] Durán A, Monteagudo JM, Carnicer A, Ruiz-Murillo M. Photo-Fenton minerali-
zation of synthetic municipal wastewater effluent containing acetaminophen
0.0 in a pilot plant. Desalination 2011;270:124–9.
0 20 40 60 80 100 120 [9] Radjenovic J, Sirtori C, Petrovic M, Barceló D, Malato S. Solar photocatalytic
degradation of persistent pharmaceuticals at pilot scale: kinetics and charac-
Time, min terization of major intermediate products. Appl Catal B Environ 2009;89:
255–64.
Fig. 9. Degradation and mineralization of acetaminophen. [acetaminophen] = [10] Zhang X, Wu F, Wu XW, Chen P, Deng N. Photodegradation of acetaminophen
5.0 mM, [H2O2] = 25 mM and [Fe2+] = 0.1 mM at pH 3. in TiO2 suspended solution. J Hazard Mater 2008;157:300–7.
316 C.-C. Su et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 310–316

[11] Skourmal M, Canot PL, Centellas F, Arias C, Rodriguez RM, Garrido JA, et al. [19] Gonzalez O, Sans C, Esplugas S. Sulfamethoxazole abatement by photo-Fenton:
Mineralization of paracetamol by ozonation catalyzed with Fe+2, Cu+2, and toxicity, inhibition and biodegradability assessment of intermediates. J Hazard
UVA light. Appl Catal B Environ 2006;66:228–40. Mater 2007;146:459–64.
[12] Yang L, Liya EY, Ray MB. Degradation of paracetamol in aqueous solutions by [20] Kulik N, Trapido M, Goi A, Veressinina Y, Munter R. Combined chemical
TiO2 photocatalysis. Water Res 2008;42:3480–8. treatment of pharmaceutical effluents from medical ointment production.
[13] Esplugas S, Gimenez J, Contreras S, Pascual E, Rodriguez M. Comparison of Chemosphere 2008;70:1525–31.
different advanced oxidation processes for phenol degradation. Water Res [21] Kolthoff IM, Sandell EB, Meehan EJ, and Buckstein S. Quantitative chemical
2002;36:1034–42. analysis, 4th ed. New York: Macmillan; 1969, p. 1862–7.
[14] Chang MW, Chern JM. Decolorization of peach red azo dye, HF6 by [22] APHA. Standard Methods for the Examination of Water and Wastewater. 22 nd
Fenton reaction: initial rate analysis. J Taiwan Inst Chem Eng 2010;41: ed. American Public Health Association, Washington, D.C., USA; 2012.
221–8. [23] Zhang H, Choi HJ, Huang CP. Optimization of Fenton process for the treatment
[15] Ting WP, Lu MC, Huang YH. The reactor design and comparison of Fenton, of landfill leachate. J Hazard Mater 2005;125:166–74.
electro-Fenton and phogoelectro-Fenton processes for mineralization of ben- [24] Gogate PR, Pandit AB. A review of imperative technologies for wastewater
zene sulfonic acid (BSA). J Hazard Mater 2008;156:421–7. treatment I: oxidation technologies at ambient conditions. Adv Environ Res
[16] Liou MJ, Lu MC. Catalytic degradation of nitroaromatic explosives with Fen- 2004;8:501–51.
ton’s reagent. J Mol Catal A Chem 2007;277:155–63. [25] Masomboon N, Ratanatamskul C, Lu MC. Chemical oxidation of 2,6-dimethy-
[17] Kang SF, Liao CH, Chen MC. Pre-oxidation and coagulation of textile waste- laniline in the Fenton process. Environ Sci Technol 2009;43: 8629–34.
water by the Fenton process. Chemosphere 2002;46:923–8. [26] Lu MC, Chen JN, Chang CP. Oxidation of dichlorvos with hydrogen peroxide
[18] Xing M, Deng C, Godefroid B, Yang J. Treatment of pharmaceutical wastewater using ferrous ion as catalyst. J Hazard Mater 1999;B65: 277–88.
containing recalcitrant compounds in a Fenton-coagulation process. J Environ [27] Ting WP, Lu MC, Huang YH. Kinetics of 2,6-dimethylaniline degradation by
Sci 2006;18:459–63. electro-Fenton process. J Hazard Mater 2009;161:1484–90.

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