高铁酸钾氧化降解间甲酚的动力学分析

doi:10.11894/iwt.2019-0380

摘要/Abstract

摘要：

以焦化废水中典型污染物间甲酚为对象，采用烧杯实验，确定水溶液中高铁酸钾〔Fe（Ⅵ）〕氧化降解间甲酚的最佳反应条件，并建立化学反应动力学模型。实验结果表明，当Fe（Ⅵ）和间甲酚的物质的量比为8，溶液pH=9，温度为14℃时，反应180 s后间甲酚的去除率为91.84%。前30 s的反应过程符合准一级反应动力学模型，反应速率常数k=0.062 7，磷酸盐会抑制Fe（Ⅵ）对间甲酚的氧化降解。

关键词: 间甲酚, Fe (Ⅵ), 速率常数, 焦化废水

Abstract:

A series of beaker experiments were carried out to study the optimal reaction conditions for the oxidative degradation of typical m-cresol in the coking wastewater by potassium ferrate[Fe(Ⅵ)]. Then the chemical reaction kinetic model was established. The experimental results showed that when the molar ratio of Fe(Ⅵ) to m-cresol was 8, the solution pH was 9, and the temperature was 14℃, the removal rate of m-cresol after the reaction for 180 s was 91.84%. The reaction process in the first 30 s conformed to the pseudo-first-order reaction kinetics model, and the reaction rate constant k was 0.062 7. Phosphate inhibited the oxidative degradation of m-cresol by Fe(Ⅵ).

Key words: m-cresol, Fe(Ⅵ), rate constant, coking wastewater

中图分类号:

X703
X784

张静,李亚男,王乐心,吴康迎,冯雪枫. 高铁酸钾氧化降解间甲酚的动力学分析[J]. 工业水处理, 2020, 40(3): 73-77.

Jing Zhang,Ya'nan Li,Lexin Wang,Kangying Wu,Xuefeng Feng. Kinetic analysis of oxidative degradation of m-cresol by potassium ferrate[J]. Industrial Water Treatment, 2020, 40(3): 73-77.

https://www.iwt.cn/CN/Y2020/V40/I3/73

图/表 8

参考文献 33

1	杜婷, 冯柏林, 李花, 等. 工业含酚废水的处理研究[J]. 广州化工, 2014, 42 (8): 26- 28. doi: 10.3969/j.issn.1001-9677.2014.08.010
2	单明军, 吕艳丽, 丛蕾. 焦化废水处理技术[M]. 北京: 化学工业出版社, 2007: 32- 33.
3	任源, 韦朝海, 吴超飞, 等. 焦化废水水质组成及其环境学与生物学特性分析[J]. 环境科学学报, 2007, 27 (7): 1094- 1100. doi: 10.3321/j.issn:0253-2468.2007.07.004 URL
4	Zhang J , Zhu L , Shi Z Y , et al. Rapid removal of organic pollutants by activation sulfite with ferrate[J]. Chemosphere, 2017, 186, 576- 579. doi: 10.1016/j.chemosphere.2017.07.102
5	Patel G B , Agnew B J , Dicaire C J . Inhibition of pure cultures of methanogens by benzene ring compounds[J]. Applied and Environmental Microbiology, 1991, 57 (10): 2969- 2974. doi: 10.1128/AEM.57.10.2969-2974.1991
6	Sharma N K , Philip L , Murty Bhallamudi S . Aerobic degradation of phenolics and aromatic hydrocarbons in presence of cyanide[J]. Bioresource Technology, 2012, 121, 263- 273. doi: 10.1016/j.biortech.2012.06.039 URL
7	Tay J H , He Y X , Yan Y G . Anaerobic biogranulation using phenol as the sole carbon source[J]. Water Environment Research, 2000, 72 (2): 189- 194. doi: 10.2175/106143000X137275
8	Fedorak P M , Hrudey S E . Anaerobic treatment of phenolic coal conversion wastewater in semicontinuous cultures[J]. Water Research, 1986, 20 (1): 113- 122. URL
9	王伟.厌氧强化工艺处理煤制气废水中酚类化合物效能的研究[D].哈尔滨:哈尔滨工业大学, 2011. URL
10	Sharma V K , Chen L , Zboril R . Review on high valent FeⅥ (Ferrate):A sustainable Green oxidant in organic chemistry and transformation of pharmaceuticals[J]. ACS Sustainable Chemistry & Engineering, 2016, 4 (1): 18- 34. URL
11	Sharma V K , Zboril R , McDonald T J . Formation and toxicity of brominated disinfection byproducts during chlorination and chloramination of water:A review[J]. Journal of Environmental Science and Health, Part B, 2014, 49 (3): 212- 228. doi: 10.1080/03601234.2014.858576 URL
12	Sharma V K . Oxidation of inorganic contaminants by ferrates (Ⅵ, Ⅴ, and Ⅳ)-kinetics and mechanisms:A review[J]. Journal of Environmental Management, 2011, 92 (4): 1051- 1073. doi: 10.1016/j.jenvman.2010.11.026 URL
13	Peings V , Frayret J , Pigot T . Mechanism for the oxidation of phenol by sulfatoferrate(Ⅵ):Comparison with various oxidants[J]. Journal of Environmental Management, 2015, 157, 287- 296. URL
14	Luo Z Y , Li X M , Zhai J . Kinetic investigations of quinoline oxidation by ferrate(Ⅵ)[J]. Environmental Technology, 2016, 37 (10): 1249- 1256. doi: 10.1080/09593330.2015.1111424
15	Song Y , Jiang J , Ma J , et al. Oxidation of inorganic compounds by aqueous permanganate:Kinetics and initial electron transfer steps[J]. Separation and Purification Technology, 2017, 183, 350- 357. doi: 10.1016/j.seppur.2017.04.015
16	Sun S F , Liu Y L , Ma J , et al. Transformation of substituted anilines by ferrate(Ⅵ):Kinetics, pathways, and effect of dissolved organic matter[J]. Chemical Engineering Journal, 2018, 332, 245- 252. doi: 10.1016/j.cej.2017.08.116
17	Huang Z S , Wang L , Liu Y L , et al. Impact of phosphate on ferrate oxidation of organic compounds:an underestimated oxidant[J]. Environmental Science & Technology, 2018, 52 (23): 13897- 13907. URL
18	宾月景, 祝万鹏, 蒋展鹏, 等. 催化湿式氧化处理H-酸溶液的反应动力学[J]. 环境科学, 2000, 21 (3): 77- 80. URL
19	Wagner W F , Gump J R , Hart E N . Factors affecting stability of aqueous potassium ferrate(Ⅵ) solutions[J]. Analytical Chemistry, 1952, 24 (9): 1497- 1498. doi: 10.1021/ac60069a037
20	Han Q , Wang H J , Dong W Y , et al. Degradation of bisphenol A by ferrate(Ⅵ) oxidation:Kinetics, products and toxicity assessment[J]. Chemical Engineering Journal, 2015, 262, 34- 40. doi: 10.1016/j.cej.2014.09.071
21	Sharma V K . Ferrate(Ⅵ) and ferrate(Ⅴ) oxidation of organic compounds:Kinetics and mechanism[J]. Coordination Chemistry Reviews, 2013, 257 (2): 495- 510. doi: 10.1016/j.ccr.2012.04.014 URL
22	Wood R H . The heat, free energy and entropy of the ferrate(Ⅵ) ion[J]. Journal of the American Chemical Society, 1958, 80 (9): 2038- 2041. doi: 10.1021/ja01542a002
23	MacHala L , Zboril R , Sharma V K , et al. Mossbauer characterization and in situ monitoring of thermal decomposition of potassium ferrate(Ⅵ), K₂FeO₄ in static air conditions[J]. The Journal of Physical Chemistry B, 2007, 111 (16): 4280- 4286. doi: 10.1021/jp068272x
24	Lee Y , Kissner R , von Gunten U . Reaction of ferrate(Ⅵ) with ABTS and self-decay of ferrate(Ⅵ):kinetics and mechanisms[J]. Environmental Science & Technology, 2014, 48 (9): 5154- 5162.
25	Li C , Li X Z , Graham N . A study of the preparation and reactivity of potassium ferrate[J]. Chemosphere, 2005, 61 (4): 537- 543. doi: 10.1016/j.chemosphere.2005.02.027 URL
26	Sarma R , Angeles-Boza A M , Brinkley D W , et al. Studies of the diiron(Ⅵ) intermediate in ferrate-dependent oxygen evolution from water[J]. Journal of the American Chemical Society, 2012, 134 (37): 15371- 15386. doi: 10.1021/ja304786s URL
27	Sharma V K , Yngard R A , Cabelli D E , et al. Ferrate(Ⅵ) and ferrate(Ⅴ) oxidation of cyanide, Thiocyanate, and copper(Ⅰ) cyanide[J]. Radiation Physics and Chemistry, 2008, 77 (6): 761- 767. doi: 10.1016/j.radphyschem.2007.11.004 URL
28	Song Y R , Ma J W . Oxidation of inorganic contaminants by ferrates (Ⅵ):A review[J]. Applied Mechanics and Materials, 2013, 361/362/363, 662- 665.
29	Shao B B , Dong H Y , Sun B , et al. Role of ferrate(Ⅳ) and ferrate (Ⅴ) in activating ferrate(Ⅵ) by calcium sulfite for enhanced oxidation of organic contaminants[J]. Environmental Science & Technology, 2019, 53 (2): 894- 902.
30	Kralchevska R P , Prucek R , Kolarík J , et al. Remarkable efficiency of phosphate removal:Ferrate(Ⅵ)-induced in situ sorption on coreshell nanoparticles[J]. Water Research, 2016, 103, 83- 91. doi: 10.1016/j.watres.2016.07.021
31	Chen G , Lam W W Y , Lo P K , et al. Mechanism of water oxidation by ferrate(Ⅵ) at ph 7-9[J]. Chemistry-a European Journal, 2018, 24 (70): 18735- 18742. doi: 10.1002/chem.201803757
32	Goff H , Murmann R K . Mechanism of isotopic oxygen exchange and reduction of ferrate(Ⅵ) ion (FeO₄^2-)[J]. Journal of the American Chemical Society, 1971, 93 (23): 6058- 6065. doi: 10.1021/ja00752a016
33	Wagner W F , Gump J R , Hart E N . Factors affecting stability of aqueous potassium ferrate(Ⅵ) solutions[J]. Analytical Chemistry, 1952, 24 (9): 1497- 1498. doi: 10.1021/ac60069a037

[Fe（Ⅵ）]₀/（mmol·L^-1）	动力学方程	R²	k_obs/s^-1
3.235	y=-0.020 27x	0.974 42	0.020 27
4.621	y=-0.046 79x	0.921 55	0.046 79
7.394	y=-0.076 29x	0.966 94	0.076 29
9.242	y=-0.126 12x	0.989 69	0.126 12
13.863	y=-0.112 52x	0.996 49	0.112 52

[Fe（Ⅵ）]₀/（mmol·L^-1）	动力学方程	R²	k_obs/s^-1
3.235	y=-0.020 27x	0.974 42	0.020 27
4.621	y=-0.046 79x	0.921 55	0.046 79
7.394	y=-0.076 29x	0.966 94	0.076 29
9.242	y=-0.126 12x	0.989 69	0.126 12
13.863	y=-0.112 52x	0.996 49	0.112 52

pH	动力学方程	R²	k_obs/s^-1
5	y=-0.024 72x	0.933 21	0.024 72
6	y=-0.020 92x	0.938 56	0.020 92
7	y=-0.033 09x	0.932 69	0.033 09
8	y=-0.051 14x	0.932 61	0.051 14
9	y=-0.076 29x	0.966 94	0.076 29

pH	动力学方程	R²	k_obs/s^-1
5	y=-0.024 72x	0.933 21	0.024 72
6	y=-0.020 92x	0.938 56	0.020 92
7	y=-0.033 09x	0.932 69	0.033 09
8	y=-0.051 14x	0.932 61	0.051 14
9	y=-0.076 29x	0.966 94	0.076 29

pH环境	动力学方程	R²	k_obs/s^-1
磷酸盐pH=8	y=-0.042 73x	0.935 98	0.042 73
磷酸盐pH=9	y=-0.023 54x	0.988 27	0.023 54
硼砂盐pH=8	y=-0.051 14x	0.932 61	0.051 14
硼砂盐pH=9	y=-0.076 29x	0.966 94	0.076 29
无缓冲溶液pH=8	y=-0.011 70x	0.956 23	0.011 70
无缓冲溶液pH=9	y=-0.008 33x	0.955 86	0.008 33

选择文件类型/文献管理软件名称

选择包含的内容