基于天然黄铁矿的类Fenton体系处理焦化废水生化出水的研究

doi:10.19965/j.cnki.iwt.2023-0130

摘要/Abstract

摘要：

焦化废水经过生化处理后仍含有大量难降解成分，直接外排会导致自然界水体污染。针对经典Fenton反应存在产生含铁污泥、适用pH范围较窄致使其在实际应用中局限性较大的问题，采用天然黄铁矿作为非均相Fenton反应催化剂对焦化废水生化出水进行处理，并以废水中苯酚作为模型污染物探究其氧化机理。结果表明，该工艺可以在较为宽泛的初始pH条件下对废水COD进行有效去除；废水COD的去除速率与黄铁矿的添加量呈正比，高浓度H₂O₂条件下COD去除速率略有增加，但增加的速度变慢；体系中存在均相和非均相两种催化条件，加入·OH捕获剂后，体系降解效率大幅度降低，证明体系中的主要氧化物种为·OH；苯酚是焦化废水中主要的有机污染物，检测了使用黄铁矿的类Fenton工艺降解苯酚过程中的中间产物，苯酚首先被氧化成对苯酚，随后很快转化为对苯醌，最终被氧化成小分子酸。

关键词: 黄铁矿, 焦化废水生化出水, Fenton反应催化剂, 羟基自由基

Abstract:

After biochemical treatment，coking wastewater still has a large number of refractory components，and direct discharge will lead to natural water pollution. The classical Fenton reaction has problems such as the generation of iron-containing sludge and the narrow pH application range，which is limited in practical applications. Natural pyrite was used as a heterogeneous Fenton reaction catalyst to treat the biochemical effluent of coking wastewater，and phenol in the wastewater was used as a model pollutant to explore its oxidation mechanism. The results indicated that the process could effectively remove COD from wastewater under relatively broad initial pH conditions. The removal rate of COD in wastewater was proportional to the amount of pyrite added，and the removal rate of COD increased slightly under the condition of high concentration of H₂O₂，but the increase rate slowed down. There were two catalytic conditions in the system，homogeneous and heterogeneous. After adding ·OH scavenger，the degradation efficiency of the system significantly decreased，indicating that the main free radical in the system was ·OH. Phenol was the main organic pollutant in coking wastewater，and the intermediate products of phenol degradation by Fenton-like using pyrite were detected，and phenol was first oxidized to p-phenol，then quickly converted to p-benzoquinone，and finally oxidized to small molecule acids.

Key words: pyrite, biochemical effluent of coking wastewater, Fenton reaction catalyst, hydroxyl radicals

中图分类号:

X703.1

李曼, 祁丽, 彭静波. 基于天然黄铁矿的类Fenton体系处理焦化废水生化出水的研究[J]. 工业水处理, 2024, 44(3): 81-88.

Man LI, Li QI, Jingbo PENG. Study on the treatment of coking wastewater biochemical effluent by Fenton-like system based on natural pyrite[J]. Industrial Water Treatment, 2024, 44(3): 81-88.

https://www.iwt.cn/CN/Y2024/V44/I3/81

图/表 13

图1 不同体系对焦化废水生化出水COD的去除效果

Fig.1 The removal effects of different systems on COD in biochemical effluent of coking wastewater

图2 pH对焦化废水生化出水处理效果的影响

Fig.2 Effect of pH on the treatment effect of biochemical effluent of coking wastewater

图3 黄铁矿投加量对焦化废水生化出水处理效果的影响

Fig.3 Effect of pyrite dosage on the treatment effect of biochemical effluent of coking wastewater

图4 H₂O₂投加量对焦化废水生化出水处理效果的影响

Fig.4 Effect of H₂O₂ dosage on the treatment effect of biochemical effluent of coking wastewater

图5 5次循环实验的废水COD去除效果

Fig.5 COD removal effects of wastewater in 5 cycles

图6 重复实验前后黄铁矿表征

Fig.6 Pyrite characterization before and after repeating the experiment

图7 苯酚降解过程中铁离子质量浓度的变化

Fig.7 Changes in iron ions mass concentration during phenol degradation

图8 自由基捕获剂对苯酚降解的影响

Fig.8 Effects of free radical scavengers on phenol degradation

图9 黄铁矿/H₂O₂工艺和经典Fenton工艺对苯酚的降解效果

Fig.9 Degradation effects of pyrite/H₂O₂ process and classical Fenton process on phenol

表1 苯酚降解过程中的中间产物

Table 1 Intermediate products in the degradation of phenol

保留时间	分子式	相对分子质量
3.208	C₆H₁₂O	100
3.773	C₅H₈O	84
4.305	C₆H₁₂O	100
7.888	C₄H₆O₄	118
13.697	C₆H₈O₂	108
13.897	C₆H₁₀O₂	110
15.450	C₆H₆O	94

表2 苯酚分子上各原子电荷分布及福井函数

Table 2 Charge distribution of each atom on phenol molecule and Fukui function

原子符号	q_k （Ｎ）	q_k （Ｎ-1）	q_k （Ｎ+1）	亲电性	亲核性
C1	-0.058 7	-0.118 5	0.085 2	0.025 76	0.455 34
C2	-0.039	-0.167 4	0.026 8	0.055 33	0.208 26
C3	-0.059 7	-0.187 3	0.031 9	0.054 96	0.289 81
C4	0.073 7	0.021 5	0.173 9	0.022 49	0.316 88
C5	-0.073 1	-0.195 6	0.009	0.052 8	0.259 76
C6	-0.041 5	-0.173	0.033 6	0.056 66	0.237 73
H7	0.041 7	-0.004 8	0.099 3	0.020 01	0.182 34
H8	0.045	-0.019 3	0.090 4	0.027 67	0.143 94
H9	0.047 3	-0.016	0.095 3	0.027 29	0.151 95
H10	0.038 7	-0.023	0.085 4	0.026 59	0.147 78
H11	0.044 4	-0.020 7	0.091 4	0.028 07	0.148 75
O12	-0.197 7	-0.244 3	-0.051 7	0.020 05	0.462 04
H13	0.178 9	0.148 2	0.229 4	0.013 25	0.159 65

图10 苯酚分子的福井函数

Fig.10 Fukui function of phenol molecule

图11 苯酚可能的降解路径

Fig.11 Possible degradation pathways of phenol

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