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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
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.
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
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
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.
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 (%)
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
0.8 0.8
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
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
0.0 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
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
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
4. Conclusion
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
[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.