Fe~(2+)/H_2O_2体系降解MB机制及影响因素研究
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摘要
以亚甲基蓝(MB)作为目标污染物,实验研究了Fe~(2+)/H_2O_2体系降解MB的活性物质,明确了主要反应条件对MB降解的影响特性。结果表明:HO_2·没有直接降解MB的能力;Fe~(2+)/H_2O_2体系对MB的降解能力主要来自于·OH;Fe~(2+)/H_2O_2体系降解MB可分为快速反应阶段和匀速反应阶段。快速反应阶段的MB降解率随温度升高而下降。体系对MB降解能力随H_2O_2初始浓度增加呈现先升高后减弱的趋势,本实验条件下,最佳H_2O_2初始浓度为5 mmol·L~(-1)。体系对MB降解能力随Fe~(2+)初始浓度的增加而单调增加。MB降解速率随MB初始浓度的增加而增加,但MB降解率随其初始浓度呈现先增大后减小的趋势。保证·OH生成速率及其有效利用是提高体系氧化能力及H_2O_2利用率的关键。
Using methylene blue(MB) as the target pollutant, the active substances of MB degradation in Fe~(2+)/H_2O_2 system were studied experimentally. The influence characteristics of main reaction conditions on MB degradation were clarified. The results showed that HO_2· had no ability to directly degrade MB and the capacity of the Fe~(2+)/H_2O_2 system for MB degradation mainly came from ·OH radicals. The degradation of MB by Fe~(2+)/H_2O_2 system can be divided into a rapid reaction stage and a uniform reaction stage. The MB degradation ratio in the rapid reaction phase decreased with the increase in temperature. The degradation ability of MB in the system increased first and then decreased with the increase of the initial concentration of H_2O_2. Under this experimental conditions, the optimal initial concentration of H_2O_2 was 5 mmol·L~(-1). The degradation capacity of MB in the system increased monotonously with the inerease of Fe~(2+)initial concentration. The degradation rate of MB increased with the increase of initial concentration of MB, but the degradation ratio of MB increased first and then decreased with it. Ensuring the rate of ·OH production and its effective utilization are key to improving the oxidizing ability of the system and the utilization of H_2O_2.
Using methylene blue(MB) as the target pollutant, the active substances of MB degradation in Fe~(2+)/H_2O_2 system were studied experimentally. The influence characteristics of main reaction conditions on MB degradation were clarified. The results showed that HO_2· had no ability to directly degrade MB and the capacity of the Fe~(2+)/H_2O_2 system for MB degradation mainly came from ·OH radicals. The degradation of MB by Fe~(2+)/H_2O_2 system can be divided into a rapid reaction stage and a uniform reaction stage. The MB degradation ratio in the rapid reaction phase decreased with the increase in temperature. The degradation ability of MB in the system increased first and then decreased with the increase of the initial concentration of H_2O_2. Under this experimental conditions, the optimal initial concentration of H_2O_2 was 5 mmol·L~(-1). The degradation capacity of MB in the system increased monotonously with the inerease of Fe~(2+)initial concentration. The degradation rate of MB increased with the increase of initial concentration of MB, but the degradation ratio of MB increased first and then decreased with it. Ensuring the rate of ·OH production and its effective utilization are key to improving the oxidizing ability of the system and the utilization of H_2O_2.
引文
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[23] Christensen H, Sehested K, Corfitzen H. Reactions of hydroxyl radicals with hydrogen peroxide at ambient and elevated temperatures[J]. The Journal of Physical Chemistry, 1982, 86(9):1588-1590.
[24] Elliot A J, Buxton G V. Temperature dependence of the reactions·OH+O2-·and·OH+HO2·in water up to 200℃[J]. Journal of the Chemical Society, Faraday Transactions, 1992, 88(17):2465-2470.
[25] Sehested K, Rasmussen O L, Fricke H. Rate constants of OH with HO2, O2-, and H2O2+from hydrogen peroxide formation in pulseirradiated oxygenated water[J]. The Journal of Physical Chemistry,1968, 72(2):626-631.
[26]赵海谦,高杏存,王忠华,等. Fe2+/H2O2体系O2生成路径[J].化工学报, 2016, 67(6):2625-2630.Zhao H Q, Gao X C, Wang Z H, et al. O2generation path in Fe2+/H2O2system[J]. CIESC Journal, 2016, 67(6):2621-2630.
[2] Tekin H, Bilkay O, Ataberk S S, et al. Use of Fenton oxidation to improve the biodegradability of a pharmaceutical wastewater[J].Journal of Hazardous Materials, 2006, 136(2):258-265.
[3] Diagne M, Oturan N, Oturan M A. Removal of methyl parathion from water by electrochemically generated Fenton's reagent[J].Chemosphere, 2007, 66(5):841-848.
[4] Kurt U, Apaydin O, Gonullu M T. Reduction of COD in wastewater from an organized tannery industrial region by electroFenton process[J]. Journal of Hazardous Materials, 2007, 143(1):33-40.
[5] Hermosilla D, Cortijo M, Huang C P. Optimizing the treatment of landfill leachate by conventional Fenton and photo-Fenton processes[J]. Science of the Total Environment, 2009, 407(11):3473-3481.
[6] Chen L W, Ma J, Li X C, et al. Strong enhancement on Fenton oxidation by addition of hydroxylamine to accelerate the ferric and ferrous iron cycles[J]. Environmental Science&Technology,2011, 45(9):3925-3930.
[7] Thompson K M, Griffith W P, Spiro M. Mechanism of bleaching by peroxides(1):Kinetics of bleaching of phenolphthalein by hydrogen peroxide at high pH[J]. Journal of the Chemical Society,Faraday Translations, 1993, 89:1203-1209.
[8] Taher A M, Cates D M. Bleaching cellulose(Ⅰ):A free radical mechanism[J]. Textile Chemist&Colorist, 1975, 7(12):30-34.
[9] Dannacher J, Schlenker W. The mechanism of hydrogen peroxide bleaching[J]. Textile Chemist and Colorist, 1996, 28(11):24-28.
[10] Spiro M, Griffith W P. The mechanism of hydrogen peroxide bleaching[J]. Textile Chemist and Colorist, 1997, 29(11):12-13.
[11] Zhou W, Gao J H, Zhao H Q, et al. The role of quinone cycle in Fe2+-H2O2system in the regeneration of Fe2+[J]. Environmental Technology, 2017, 38(15):1887-1896.
[12] Abbot J, Brown D G. Kinetics of iron-catalyzed decomposition of hydrogen peroxide in alkaline solution[J]. International Journal of Chemical Kinetics, 1990, 22(9):963-974.
[13] Lin S S, Gurol M D. Catalytic decomposition of hydrogen peroxide on iron oxide:kinetics, mechanism, and implications[J].Environmental Science&Technology, 1998, 32(10):1417-1423.
[14]赵海谦,高继慧,周伟,等. Fe2+/H2O2体系内各种自由基在氧化NO中的作用[J].化工学报, 2015, 66(1):449-454.Zhao H Q, Gao J H, Zhou W, et al. Roles of varied radicals in NO oxidation by Fe2+/H2O2system[J]. CIESC Journal, 2015, 66(1):449-454.
[15] Huang W, Brigante M, Wu F, et al. Assessment of the Fe(III)–EDDS complex in Fenton-like processes:from the radical formation to the degradation of bisphenol A[J]. Environmental Science&Technology, 2013, 47(4):1952-1959.
[16] Munoz M, de Pedro Z M, Casas J A, et al. Preparation of magnetite-based catalysts and their application in heterogeneous Fenton oxidation—a review[J]. Applied Catalysis B:Environmental, 2015, 176:249-265.
[17]郭幸斐,王姚武,张宏伟,等.类芬顿试剂对亚甲基蓝的降解研究[J].环境科学与技术, 2016, 39(5):38-41.Guo X F, Wang Y W, Zhang H W, et al. Study on the degradation of methylene blue by Fenton-like reagent[J]. Environmental Science&Technology, 2016, 39(5):38-41.
[18] Ogata F, Nakamura T, Kawasaki N. Improvement of the homogeneous Fenton reaction for degradation of methylene blue and acid orangeⅡ[J]. Chemical and Pharmaceutical Bulletin,2018, 66(5):585-588.
[19] Zheng J, Gao Z, He H, et al. Efficient degradation of acid orange 7in aqueous solution by iron ore tailing Fenton-like process[J].Chemosphere, 2016, 150:40-48.
[20]姜成春,庞素艳,马军,等.钛盐光度法测定Fenton氧化中的过氧化氢[J].中国给水排水, 2006, 22(4):88-91.Jiang C C, Pang S Y, Ma J, et al. Spectrophotometric determination of hydrogen peroxide in Fenton reaction with titanium oxalate[J]. China Water&Wastewater, 2006, 22(4):88-91.
[21] de Laat J, Gallard Hé. Catalytic decomposition of hydrogen peroxide by Fe(Ⅲ)in homogeneous aqueous solution:mechanism and kinetic modeling[J]. Environmental Science&Technology,1999, 33(16):2726-2732.
[22] Buxton G V, Greenstock C L, Helman W P, et al. Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals(·OH/·O-)in aqueous solution[J].Journal of Physical and Chemical Reference Data, 1988, 17(2):513-886.
[23] Christensen H, Sehested K, Corfitzen H. Reactions of hydroxyl radicals with hydrogen peroxide at ambient and elevated temperatures[J]. The Journal of Physical Chemistry, 1982, 86(9):1588-1590.
[24] Elliot A J, Buxton G V. Temperature dependence of the reactions·OH+O2-·and·OH+HO2·in water up to 200℃[J]. Journal of the Chemical Society, Faraday Transactions, 1992, 88(17):2465-2470.
[25] Sehested K, Rasmussen O L, Fricke H. Rate constants of OH with HO2, O2-, and H2O2+from hydrogen peroxide formation in pulseirradiated oxygenated water[J]. The Journal of Physical Chemistry,1968, 72(2):626-631.
[26]赵海谦,高杏存,王忠华,等. Fe2+/H2O2体系O2生成路径[J].化工学报, 2016, 67(6):2625-2630.Zhao H Q, Gao X C, Wang Z H, et al. O2generation path in Fe2+/H2O2system[J]. CIESC Journal, 2016, 67(6):2621-2630.
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