Kinetics of microwave-enhanced oxidation of phenol by hydrogen peroxide

doi:10.1007/s11783-010-0251-9

Front Envir Sci Eng Chin

2011, Vol. 5

Issue (1) : 57-64 https://doi.org/10.1007/s11783-010-0251-9

RESEARCH ARTICLE

Kinetics of microwave-enhanced oxidation of phenol by hydrogen peroxide

Deming ZHAO^1,2, Jie CHENG², Michael R. HOFFMANN²(

)

1. College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, China; 2. W. M. Keck Laboratories, California Institute of Technology, Pasadena, CA 91125, USA

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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

Corresponding Author(s): HOFFMANN Michael R.,Email:mrh@caltech.edu

Issue Date: 05 March 2011

Cite this article:

Deming ZHAO,Jie CHENG,Michael R. HOFFMANN. Kinetics of microwave-enhanced oxidation of phenol by hydrogen peroxide[J]. Front Envir Sci Eng Chin, 2011, 5(1): 57-64.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-010-0251-9
https://academic.hep.com.cn/fese/EN/Y2011/V5/I1/57

Fig.1 A schematic diagram of basic experimental setup. 1) Microwave oven; 2) HO addition port; 3) reactor; 4) temperature control bath; 5) sample outlet; 6) circulation pump

Fig.2

Fig.3 Pseudo-first-order rate constants and pseudo-zero-order constants vs pH during MW/HO oxidation at 30°C, = 1.0 L, [CHOH] = 1.1mmol·L, and [HO] = 8.8 mmol·L

Fig.4 Pseudo-first-order rate constants and pseudo-zero-order constants vs [CHOH] during the combined MW/HO oxidation at 30°C, = 1.0 L, and [HO] = 8.8 mmol·L

Fig.5 Pseudo-first-order rate constants and pseudo-zero-order constants versus [HO] during MW/HO oxidation, at 30°C, = 1.0 L, [CHOH] = 1.1 mmol·L

Fig.6 First-order plots of ln([CHOH]/[ CHOH]) versus time over first 90 min of reaction time, and (a) the pseudo-first kinetics rate constants at different initial pH values of 3(□), 5(○), 7(?), 9(?), and 11() at 30°C, = 1.0 L, [CHOH] = 1.1 mmol·L, and [HO] = 8.8 mmol·L; (b) initial hydrogen peroxide [HO] = 1.5 mmol·L (□), 2.9 mmol·L (○), 5.9 mmol·L (?), 8.8 mmol·L (?), 11.8 mmol·L (), 14.7 mmol·L (), and 17.6 mmol·L (◇) at 30°C, = 1.0 L, pH = 5 for [CHOH] = 1.1 mmol·L; (c) the initial phenol concentration of 0.5 mmol·L (□), 1.1 mmol·L (○), 2.1 mmol·L (?), and 4.3 mmol·L (?)at 3 0°C, = 1.0 L, pH = 5 with [HO] = 8.8 mmol·L; and pseudo first-order constants in different initial pH values, initial hydrogen peroxide, and initial phenol concentration, and the special signs above columns in accordance with the annotated signs in figures (a)-(d)

Fig.7 [CHOH]/[CHOH] versus time profiles over the first 90 min of reaction MW alone (□), for HO alone (○), and for the combined MW/HO oxidation (?) at 30°C, = 1.0 L, [CHOH] = 1.1 mmol·L, and [HO] = 8.8 mmol·L

Fig.8 [CHOH]/[CHOH] versus time data profiles compared to kinetic model results for the MW/HO oxidation system at 30°C, = 1.0 L, [CHOH] = 1.1 mmol·L, pH = 5, and [HO] = 8.8 mmol·L (□) and for the same conditions with [CHOH] = 0.5 mmol·L (○)

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