Kinetics of microwave-enhanced oxidation of phenol by hydrogen peroxide

Abstract

Aqueous solutions of phenol were oxidized by hydrogen peroxide assisted by microwave (MW) irradiation. A simple kinetic model for the overall degradation of phenol in the presence of excess H₂O₂ is proposed in which the degradation rate of phenol is expressed as a linear function of the concentrations of phenol and H₂O₂. A detailed parametric study showed that the degradation rate of phenol increased with increasing [H₂O₂] until saturation was observed. Phenol degradation followed apparent zero-order kinetics under MW radiation or H₂O₂ oxidation. However, after 90 min of irradiation, the observed kinetics shifted to pseudo first order. The overall reaction rates were significantly enhanced in the combined MW/H₂O₂ system, mainly because microwave could accelerate H₂O₂ to generate hydroxyl radical (^·OH) and other reactive oxygen intermediates. The observed synergetic effects of the MW/H₂O₂ process resulted in an increased in the net reaction rate by a factor of 5.75. When hydrogen peroxide is present in a large stoichiometric excess, the time required to achieve complete mineralization is reduced significantly.

Keywords

microwave (MW) irradiation / hydrogen peroxide / phenol / synergetic effects / kinetic model

References

[1] Wu Z L, Ondruschka B, Cravotto G. Degradation of phenol under combined irradiation of microwaves and ultrasound. Environmental Science & Technology, 2008, 42(21): 8083–8087

[2] Stöffler B, Luft G. Oxidative degradation of p-toluenesulfonic acid using hydrogen peroxide. Chemosphere, 1999, 38(5): 1035–1047

[3] Zazo J A, Casas J A, Molina C B, Quintanilla A, Rodriguez J J. Evolution of ecotoxicity upon Fenton’s oxidation of phenol in water. Environmental Science & Technology, 2007, 41(20): 7164–7170

[4] Zazo J A, Casas J A, Mohedano A F, Gilarranz M A, Rodríguez J J. Chemical pathway and kinetics of phenol oxidation by Fenton’s reagent. Environmental Science & Technology, 2005, 39(23): 9295–9302

[5] Zhao D M, Shi H X, Lei L C, Wang D H. Degradation of phenol in aqueous solution by US/H₂O₂ combination process. Zhejiang Daxue Xuebao, Gongxueban, 2004, 38(2): 240–243 (in Chinese)

[6] Han D H, Cha S Y, Yang H Y. Improvement of oxidative decomposition of aqueous phenol by microwave irradiation in UV/H₂O₂ process and kinetic study. Water Research, 2004, 38(11): 2782–2790

[7] Edalatmanesh M, Dhib R, Mehrvar M. Kinetic modeling of aqueous phenol degradation by UV/H₂O₂ process. International Journal of Chemical Kinetics, 2008, 40(1): 34–43

[8] Rosenfeldt E J, Linden K G, Canonica S, von Gunten U. Comparison of the efficiency of ^*OH radical formation during ozonation and the advanced oxidation processes O₃/H₂O₂ and UV/H₂O₂. Water Research, 2006, 40(20): 3695–3704

[9] Gogate P R, Pandit A B. A review of imperative technologies for wastewater treatment I: Oxidation technologies at ambient conditions. Advances in Environmental Research, 2004, 8(3-4): 501–551

[10] Glaze W H, Kang J W, Chapin D H. The chemistry of water treatment processes involving ozone. Ozone Science and Engineering, 1987, 9(4): 335–352

[11] Lesko T, Colussi A J, Hoffmann M R. Sonochemical decomposition of phenol: evidence for a synergistic effect of ozone and ultrasound for the elimination of total organic carbon from water. Environmental Science & Technology, 2006, 40(21): 6818–6823

[12] Weavers L K, Malmstadt N, Hoffmann M R. Kinetics and mechanism of pentachlorophenol degradation by sonication, ozonation, and sonolytic ozonation. Environmental Science & Technology, 2000, 34(7): 1280–1285

[13] Destaillats H, Hung H M, Hoffmann M R. Degradation of alkylphenol ethoxylate surfactants in water with ultrasonic irradiation. Environmental Science & Technology, 2000, 34(2): 311–317

[14] Weavers L K, Ling F H, Hoffmann M R. Aromatic compound degradation in water using a combination of sonolysis and ozonolysis. Environmental Science & Technology, 1998, 32(18): 2727–2733

[15] Mills G, Hoffmann M R. Photocatalytic degradation of pentachlorophenol on titanium dioxide particles- identification of intermediates and mechanism of reaction. Environmental Science & Technology, 1993, 27(8): 1681–1689

[16] Willberg D M, Lang P S, Höchemer R H, Kratel A, Hoffmann M R. Degradation of 4-chlorophenol, 3,4-dichloroaniline, and 2,4,6-trinitrotoluene in an electrohydraulic discharge reactor. Environmental Science & Technology, 1996, 30(8): 2526–2534

[17] Wu Z C, Zhou M H. Partial degradation of phenol by advanced electrochemical oxidation process. Environmental Science & Technology, 2001, 35(13): 2698–2703

[18] Jung K S, Kwon J H, Son S M, Shin J S, Lee G D, Park S S. Characteristics of the copper phthalocyanines synthesized at various conditions under the classical and microwave processes. Synthetic Metals, 2004, 141(3): 259–264

[19] Abramovitch R A, Zhou H B, Davis M, Peters L. Decomposition of PCB's and other polychlorinated aromatics in soil using microwave energy. Chemosphere, 1998, 37(8): 1427–1436

[20] Caddick S. Microwave assisted organic reactions. Tetrahedron, 1995, 51(38): 10403–10432

[21] Tai H S, Jou C J G. Application of granular activated carbon packed-bed reactor in microwave radiation field to treat phenol. Chemosphere, 1999, 38(11): 2667–2680

[22] Lai T L, Lee C C, Wu K S, Shu Y Y, Wang C B. Microwave-enhanced catalytic degradation of phenol over nickel oxide. Applied Catalysis B: Environmental, 2006, 68(3-4): 147–153

[23] Horikoshi S, Hidaka H, Serpone N. Environmental remediation by an integrated microwave/UV-illumination method. 1. Microwave-assisted degradation of rhodamine-B dye in aqueous TiO₂ dispersions. Environmental Science & Technology, 2002, 36(6): 1357–1366

[24] Horikoshi S, Hidaka H, Serpone N. Hydroxyl radicals in microwave photocatalysis. Enhanced formation of OH radicals probed by ESR techniques in microwave-assisted photocatalysis in aqueous TiO₂ dispersions. Chemical Physics Letters, 2003, 376(3-4): 475–480

[25] Kataoka S, Tompkins D T, Zeltner W A, Anderson M A. Photocatalytic oxidation in the presence of microwave irradiation: observations with ethylene and water. Journal of Photochemistry and Photobiology A Chemistry, 2002, 148(1-3): 323–330

[26] Zhao D M, Jin N R, Wu C X. Degradation of phenol aqueous solution using MW/H₂O₂ system. Huagong Xuebao (Chinese Edition), 2007, 58(7): 1736–1740 (in Chinese)

[27] Zhao D M, Fei K F. Synergetic kinetics of phenol degradation in water by using microwave/H₂O₂ system. Huagong Xuebao (Chinese Edition), 2008, 59(1): 101–105 (in Chinese)

[28] Bari S S, Bose A K, Chaudhary A G, Manhas M S, Raju V S, Robb E W. Reactions accelerated by microwave radiation in the undergraduate organic laboratory. Journal of Chemical Education, 1992, 69(11): 938–939

[29] Pougnet M A B. Modification of a commercial microwave-oven for applications in the chemical laboratory. Review of Scientific Instruments, 1993, 64(2): 529–531

[30] Horikoshi S, Hidaka H, Serpone N. Environmental remediation by an integrated microwave/UV-illumination method II: Characteristics of a novel UV-VIS–microwave integrated irradiation device in photodegradation processes. Journal of Photochemistry and Photobiology A Chemistry, 2002, 153(1-3): 185–189

[31] Liu X T, Quan X, Bo L L, Chen S, Zhao Y Z. Simultaneous pentachlorophenol decomposition and granular activated carbon regeneration assisted by microwave irradiation. Carbon, 2004, 42(2): 415–422

[32] Park M, Komarneni S, Roy R. Microwave-hydrothermal decomposition of chlorinated organic compounds. Materials Letters, 2000, 43(5-6): 259–263

[33] Shi H X, Zhao D M, Lei L C, Wang D H. Synergetic kinetics of phenol degradation in water using ultrasonic/H₂O₂ system. Huagong Xuebao (Chinese Edition), 2003, 54(10): 1436–1441 (in Chinese)

[34] De A K, Chaudhuri B, Bhattacharjee S, Dutta B K. Estimation of ^·OH radical reaction rate constants for phenol and chlorinated phenols using UV/H₂O₂ photo-oxidation. Journal of Hazardous Materials, 1999, 64(1): 91–104

[35] Sanz J, Lombrana J I, De Luis A M, Ortueta M, Varona F. Microwave and Fenton’s reagent oxidation of wastewater. Environmental Chemistry Letters, 2003, 1(1): 45–50

[36] Sawyer D T. Oxygen Chemistry: The International Series of Monographs on Chemistry. New York: Oxford University Press, 1991

[37] Haag W R, Yao C C D. Rate constants for reaction of hydroxyl radicals with several drinking-water ontaminants. Environmental Science & Technology, 1992, 26(5): 1005–1013

[38] Shen Y S, Ku Y, Lee K C. The effect of light absorbance on the decomposition of chlorophenols by ultraviolet radiation and UV/H₂O₂ processes. Water Research, 1995, 29(3): 907–914

[39] Apak R, Hugül M. Photooxidation of some mono-, di-, and tri-chlorophenols in aqueous solution by hydrogen peroxide/UV combinations. Journal of Chemical Technology and Biotechnology, 1996, 67(3): 221–226

[40] Christensen H, Sehested K, Corfitzen H. Reactions of hydroxyl radicals with hydrogen peroxide at ambient and elevated temperatures. Journal of Physical Chemistry, 1982, 86(9): 1588–1590

[41] Zhou M H, Wu Z C, Shi Y, Li W, Zhong Z T, Ye Q. Synergetic kinetics of phenolic wastewater treatment using UV/H₂O₂ systems. Gaoxiao Huaxue Gongcheng Xuebao, 2002, 16(5): 536–541 (in Chinese)

[42] Joglekar H S, Samant S D, Joshi J B. Kinetics of wet air oxidation of phenol and substituted phenols. Water Research, 1991, 25(2): 135–145

[43] Esplugas S, Giménez J, Contreras S, Pascual E, Rodríguez M. Comparison of different advanced oxidation processes for phenol degradation. Water Research, 2002, 36(4): 1034–1042

[44] Tryba B, Morawski A W, Inagaki M, Toyoda M. The kinetics of phenol decomposition under UV irradiation with and without H₂O₂ on TiO₂, Fe–TiO₂ and FecC–TiO₂ photocatalysts. Applied Catalysis B: Environmental, 2006, 63(3-4): 215–221

RIGHTS & PERMISSIONS

Higher Education Press and Springer-Verlag Berlin Heidelberg