Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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A Comparison between the Decomposition of Bisphenol A and the Concentration of Hydrogen Peroxide Formed during Ozone/Catalyst Oxidation Process

오존/촉매 산화공정에서 비스페놀 A의 분해와 생성된 과산화수소의 농도 비교

  • Choi, Jae Won (School of Chemical Engineering, University of Ulsan) ;
  • Lee, Hak Sung (School of Chemical Engineering, University of Ulsan)
  • Received : 2017.08.17
  • Accepted : 2017.09.05
  • Published : 2017.12.10
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Abstract

In this study, the formation of hydroxyl radical and decomposition characteristics of bisphenol A (BPA) was investigated by quantifying hydrogen peroxide formed as a reaction by-product during the formation stage of hydroperoxyl radical. The direct oxidation reaction by ozone only decomposed BPA just like the Criegee mechanism under the condition where radical chain reactions did not occur. Non-selective oxidation reactions occurred under the conditions of pH 6.5 and 9.5 where radical chain reactions do occur, confirming indirectly the formation of hydroxyl radical. The decomposition efficiency of BPA by the added catalysts appeared in the order of $O_3$/PAC ${\geq}$ $O_3/H_2O_2$ > $O_3$/high pH > $O_3$ alone. 0.03~0.08 mM of hydrogen peroxide were continuously measured during the oxidation reactions of ozone/catalyst processes. In the case of $O_3$/high pH process, BPA was completely decomposed in 50 min of the oxidation reaction, but reaction intermediates formed by oxidation reaction were not oxidized sufficiently with 29% of the removal ratio for total organic carbon (TOC, selective oxidation reaction). In the case of $O_3/H_2O_2$ and $O_3$/PAC processes, BPA was completely decomposed in 40 min of the oxidation reaction, and reaction intermediates formed by the oxidation reaction were oxidized with 57% and 66% of removal ratios for TOC, respectively (non-selective oxidation reactions).

본 연구에서는 하이드로퍼옥시 라디칼 생성단계에서 반응 부산물로 생성되는 과산화수소를 정량하여 수산화라디칼의 생성 및 비스페놀 A (BPA)의 분해특성을 조사하였다. 라디칼 연쇄반응이 일어나지 않는 조건에서는 Criegee mechanism과 동일하게 오존에 의한 직접산화반응만이 BPA를 분해시키는 것으로 나타났다. 라디칼 연쇄반응이 일어나는 pH 6.5 및 9.5의 조건에서는 비선택적 산화반응이 일어나 수산화라디칼의 생성을 간접적으로 확인할 수 있었다. 투입된 촉매에 의한 BPA의 분해효율은 $O_3$/PAC ${\geq}$ $O_3/H_2O_2$ > $O_3$/high pH > $O_3$ alone 공정 순으로 나타났다. 오존/촉매공정들의 산화반응 동안에는 0.03~0.08 mM의 과산화수소가 지속적으로 측정되었다. $O_3$/high pH 공정의 경우, BPA가 반응시작 50 min 만에 완전히 분해되었지만, TOC (총유기탄소) 제거율은 29%로 산화반응 중 생성된 중간물질을 충분히 산화시키지 못하는 것으로 나타났다(선택적 산화반응). $O_3/H_2O_2$ 및 $O_3$/PAC 공정에서는 BPA가 반응시작 40 min 만에 완전히 분해되었으며, TOC 제거율은 각각 57% 및 66% 정도로 반응 중간체들을 산화(비선택적 산화반응)시키는 것으로 나타났다.

Keywords

References

  1. W. H. Glaze and J. W. Kang, Advanced oxidation process, description of a kinetic model for the oxidation of hazardous materials in aqueous media with ozone and hydrogen peroxide in a semi-batch reactor, Ind. Eng. Chem. Res., 28, 1573-1580 (1989). https://doi.org/10.1021/ie00095a001
  2. E. Carlsen, A. Giwercman, N. Keiding, and N. E. Skakkebaek, Evidence for decreasing quality of semen during past 50 years, Br. Med. J., 305, 609-613 (1992). https://doi.org/10.1136/bmj.305.6854.609
  3. N. V. Raghavan and S. Steenken, Electrophilic reaction of the hydroxyl radical with phenol. Determination of the distribution of isomeric dihydroxycyclohexadienyl radicals, J. Am. Chem. Soc., 102, 3495-3499 (1980). https://doi.org/10.1021/ja00530a031
  4. W. H. Glaze, J. W. Kang, and D. H. Chapin, The chemistry of water treatment involving ozone, hydrogen peroxide and ultraviolet radiation, Ozone Sci. Eng., 9, 335-352 (1987). https://doi.org/10.1080/01919518708552148
  5. K. H. Barbara, M. Ziolek, and J. Nawrocki, Cataytic ozonation and methods of enhancing molecular ozone reactions in water treatment, Appl. Catal. B, 46, 639-669 (2003). https://doi.org/10.1016/S0926-3373(03)00326-6
  6. H. Allemane, B. Delouane, H. Paillard, and B. Legube, Comparative efficiency of three systems ($O_3$, $O_3/H_2O_2$, $O_3/TiO_2$) for the oxidation of natural organic matter in water, Ozone Sci. Eng., 15, 419-432 (1993). https://doi.org/10.1080/01919512.1993.10555733
  7. B. Gozmen, M. A. Oturan, N. Oturan, and O. Erbatur, Indirect electrochemical treatment of bisphenol A in water via electrochemically generated Fenton's reagent, Environ. Sci. Technol., 37, 3716-3723 (2003). https://doi.org/10.1021/es034011e
  8. V. J. Pereira, H. S. Weinberg, K. G. Linden, and P. C. Singer, UV degradation kinetics and modeling of pharmaceutical compounds in laboratory grade and surface water via direct and indirect photolysis at 254 nm, Environ. Sci. Technol., 41, 1682-1688 (2007). https://doi.org/10.1021/es061491b
  9. J. H. Baxendale and J. A. Wilson, The photolysis of hydrogen peroxide at high light intensities, Trans. Faraday Soc., 53, 344-356 (1957). https://doi.org/10.1039/tf9575300344
  10. J. Staehelln and J. Hoigne, Decomposition of ozone in water: rate of initiation by hydroxide ions and hydrogen peroxide, Environ Sci. Technol., 16, 676-681 (1982). https://doi.org/10.1021/es00104a009
  11. R. E. Buehler, J. Staehelin, and J. Hoigne, Ozone decomposition in water studied by pulse radiolysis. 1. $HO_{2}/O_{2}^{-}$ and $HO_{3}/O_{3}^{-}$ as intermediates, J. Phys. Chem., 88, 2560-2564 (1984). https://doi.org/10.1021/j150656a026
  12. J. Staehelin, R. E. Buehler, and J. Hoigne, Ozone decomposition in water studied by pulse radiolysis. 2. OH and $HO_4$ as chain intermediates, J. Phys. Chem., 88, 5999-6004 (1984). https://doi.org/10.1021/j150668a051
  13. J. Hoigne and H. Bader, Rate constants of reactions of ozone with organic and inorganic compounds in water I: Non-dissociating organic compounds, Water Res., 17, 173-183 (1983). https://doi.org/10.1016/0043-1354(83)90098-2
  14. J. Hoigne and H. Bader, Rate constants of reactions of ozone with organic and inorganic compounds in water-II: Dissociating organic compounds, Water Res., 17, 185-194 (1983). https://doi.org/10.1016/0043-1354(83)90099-4
  15. J. Hoigne and H. Bader, Rate constants of reactions of ozone with organic and inorganic compounds in water III: Inorganic compounds and radicals, Water Res., 19, 993-1004 (1985). https://doi.org/10.1016/0043-1354(85)90368-9
  16. J. Staehelln and J. Hoigne, Decomposition of ozone in water in the presence of organic solutes acting as promoters and inhibitors of radical chain reactions, Environ. Sci. Technol., 19, 1206-1213 (1985). https://doi.org/10.1021/es00142a012
  17. Q. Huang and J. Weber, Transformation and removal of bisphenol A from aqueous phase via peroxidase-mediated oxidative coupling reactions: efficacy, products, and pathways, Environ. Sci. Technol., 39, 6029-6036 (2005). https://doi.org/10.1021/es050036x
  18. W. H. Glaze, Y. Lay, and J. W. Kang,, Advanced oxidation processes - A kinetic model for the oxidation of 1,2- dibromo-3-chloropropane in water by the combination of hydrogen peroxide and UV radiation, Ind. Eng. Chem. Res., 34, 2314-2323 (1995). https://doi.org/10.1021/ie00046a013
  19. J. W. Kang and K. H. Lee, A kinetic model of the hydrogen peroxide UV process for the treatment of hazardous waste chemicals, Environ. Eng. Sci., 14, 183-192 (1997). https://doi.org/10.1089/ees.1997.14.183
  20. E. J. Rosenfeldet and K. G. Linden, Degradation of endocrine disrupting chemicals bisphenol A, ethinyl estradiol, and estradiol during UV photolysis and advanced oxidation processes, Environ. Sci. Technol., 38, 5476-5483 (2004). https://doi.org/10.1021/es035413p
  21. X. Zhang, Y. Ding, H. Tang, X. Han, L. Zhu, and N. Wang, Degradation of bisphenol A by hydrogen peroxide activated with $CuFeO_2$ microparticles as a heterogeneous Fenton-like catalyst: efficiency, stability and mechanism, Chem. Eng. J., 236, 251-262 (2014). https://doi.org/10.1016/j.cej.2013.09.051
  22. S. Y. Mo, H. K. Chang, K. J. Lee, G. E. Jang, and J. R. Sohn, Measurement of the quantity of hydrogen peroxide produced in the ultrasound-irradiated aqueous solution of organic compounds, J. Korean Soc. Environ. Eng., 22, 61-71 (2000).
  23. H. Nomura, S. Koda, K. Yasuda, and Y. Kojima, Quantification of ultrasonic intensity based on the decomposition reaction of porphyrin, Ultrason. Sonochem., 3, S153-S156 (1996). https://doi.org/10.1016/S1350-4177(96)00020-X
  24. J. W. Choi and H. S. Lee, Decomposition characteristics of bisphenol A by a catalytic ozonation process, Appl. Chem. Eng., 26, 463-469 (2015). https://doi.org/10.14478/ace.2015.1057
  25. H. S. Shin, K. W. Kim, and D. S. Rhee, Degradation of humic acids by ozone/high pH, ozone/hydrogen peroxide and ozone/hydrogen carbonate system, Anal. Sci. Technol., 13, 652-658 (2000).
  26. K. W. Kim and D. S. Rhee, Formation of hydrogen peroxide by the ozonation of aqueous humic acid, Anal. Sci. Technol., 13, 659-665 (2000).
  27. M. J. Lundqvist and L. A. Eriksson, Hydroxyl radical reactions with phenol as a model for generation of biologically reactive tyrosyl radicals, J. Phys. Chem. B, 104, 848-855 (2000). https://doi.org/10.1021/jp993011r
  28. S. P. Mezyk, T. Neubauer, W. J. Cooper, and J. R. Peller, Free-radical-induced oxidative and reductive degradation of sulfa drugs in water: absolute kinetics and efficiencies of hydroxyl radical and hydrated electron reactions, J. Phys. Chem. A, 111, 9019-9024 (2007). https://doi.org/10.1021/jp073990k
  29. B. Langlais, D. A. Reckhow, and D. R. Brink, Ozone in Water Treatment: Application and Engineering, 11-54, Lewis Publishers Inc., New York (1991).
  30. H. Paillard1, R. Brunet, and M. Dore, Optimal conditions for applying an ozone-hydrogen peroxide oxidizing system, Water Res., 22, 91-103 (1988). https://doi.org/10.1016/0043-1354(88)90135-2
  31. R. Brunet, M. M. Bourbigot, and M. Dore, Oxidation of organic compounds through the combination ozone-hydrogen peroxide, Ozone Sci. Eng., 6, 163-183 (1984). https://doi.org/10.1080/01919518408551019
  32. U. Jans and J. Hoigne, Activated carbon and carbon black catalyzed transformation of aqueous ozone into OH-radicals, Ozone Sci. Eng., 20, 67-90 (1998). https://doi.org/10.1080/01919519808547291
  33. X. Wang, X. Huang, C. Zuo, and H. Hu, Kinetics of quinoline degradation by $O_3$/UV in aqueous phase, Chemosphere, 55, 733-741 (2004). https://doi.org/10.1016/j.chemosphere.2003.11.019
  34. J. R. Peller, S. P. Mezyk, and W. J. Cooper, Bisphenol A reactions with hydroxyl radicals: diverse pathways determined between deionized water and tertiary treated wastewater solutions, Res. Chem. Intermed., 35, 21-34 (2009). https://doi.org/10.1007/s11164-008-0012-6
  35. F. J. Beltran, J. F. García-Araya, and B. Acedo, Advanced oxidation of atrazine in water-I. Ozonation, Water Res., 28, 2153-2164 (1994). https://doi.org/10.1016/0043-1354(94)90027-2