电化学高级氧化对HEDP的降解效能研究

doi:10.11949/0438-1157.20220493

摘要/Abstract

摘要：

羟基亚乙基二膦酸（HEDP）是典型的有机膦缓蚀阻垢剂，广泛存在于工业水处理系统中，其常规生物降解率低于5%，已成为工业废水处理回用和外排的制约因素。为此，探索了电化学高级氧化法对HEDP的降解效能，考察了电流密度、Na₂SO₄浓度、pH、温度及溶液流速等关键参数对HEDP降解率的影响；利用电子自旋共振测试，自由基猝灭方法和HEDP降解动力学探讨了HEDP的降解机制。结果表明，电流密度为30 mA/cm²，电解质Na₂SO₄浓度为0.1 mol/L，pH=11，温度为30℃，溶液流速为500 ml/min时HEDP降解率最高，90 min内可达99.7%；研究采用的电化学高级氧化体系产生羟基自由基（·OH）和硫酸根自由基（SO $4 -$ ·），仅·OH可以降解HEDP，·OH与HEDP的反应速率常数k_•_OH，HEDP=（4.28±0.24）×10⁸ L/（mol·s）。

关键词: 电化学高级氧化, 自由基, HEDP, 降解, 动力学

Abstract:

Hydroxyethylidene diphosphonic acid (HEDP) is a typical organic phosphine corrosion and scale inhibitor. It widely exists in industrial water treatment system. Its conventional biodegradation rate is less than 5%. It has become a restrictive factor for industrial wastewater treatment, reuse and efflux. The degradation efficiency of HEDP by electrochemical advanced oxidation method was explored, and the effects of key parameters such as current density, Na₂SO₄ concentration, pH, temperature and solution flow rate on the degradation rate of HEDP were investigated. The degradation mechanism of HEDP was explored by electron spin resonance test, radical quenching method and kinetic experiment. The results showed that the degradation rate of HEDP was the highest when the current density was 30 mA/cm², the concentration of electrolyte Na₂SO₄ was 0.1 mol/L, pH=11, the temperature was 30℃, the solution flow rate was 500 ml/min, and it could reach 99.7% in 90 min. The electrochemical advanced oxidation system used in the study mainly produces hydroxyl radical (·OH) and sulfate radical (SO $4 -$ ·). Only ·OH can degrade HEDP. The reaction rate constant of ·OH and HEDP is (4.28±0.24)×10⁸ L/(mol·s)。

Key words: electrochemical advanced oxidation, radical, HEDP, degradation, kinetics

中图分类号:

X 703.1

靳文章, 张玉玲, 贾晓宇. 电化学高级氧化对HEDP的降解效能研究[J]. 化工学报, 2022, 73(9): 4062-4069.

Wenzhang JIN, Yuling ZHANG, Xiaoyu JIA. Study on degradation efficiency of hydroxyethylidene diphosphonic acid by electrochemical advanced oxidation[J]. CIESC Journal, 2022, 73(9): 4062-4069.

图/表 13

图1 HEDP结构式

Fig.1 HEDP structural formula

图2 装置原理图1—板框;2—氟化橡胶垫;3—BDD阳极;4—质子交换膜;5—钛阴极

Fig.2 Schematic diagram of device

图3 电流密度对HEDP降解率的影响

Fig.3 Effect of current density on degradation rate of HEDP

表1 氧化反应电位

Table 1 Oxidation reaction potential

氧化反应	氧化电位/V
2H₂O $→$ 4H⁺+4e^-+O₂	-1.23
2SO $4 2 -$ $→$ S₂O $8 2 -$ +2e^-	-2.01
H₂O $→$ ·OH+H⁺+e^-	-2.74

表1 氧化反应电位

Table 1 Oxidation reaction potential

氧化反应	氧化电位/V
2H₂O $→$ 4H⁺+4e^-+O₂	-1.23
2SO $4 2 -$ $→$ S₂O $8 2 -$ +2e^-	-2.01
H₂O $→$ ·OH+H⁺+e^-	-2.74

图4 Na2SO4浓度对HEDP降解率的影响

Fig.4 Effect of Na2SO4 concentration on degradation rate of HEDP

图5 pH对HEDP降解率的影响

Fig.5 Effect of pH on degradation rate of HEDP

图6 温度对HEDP降解率的影响

Fig.6 Effect of temperature on degradation rate of HEDP

图7 溶液流速对HEDP降解率的影响

Fig.7 Effect of solution flow rate on degradation rate of HEDP

图8 电解装置循环性能实验结果

Fig.8 Experiment result of cycle performance of electrolysis device

图9 不同反应时间下的EPR谱图(反应条件:电流密度30 mA/cm2,Na2SO4浓度0.10 mol/L, pH=5.6,T=30℃, 溶液流速500 ml/min)

Fig.9 EPR spectra at different reaction times

图10 添加自由基猝灭剂对HEDP降解效果的影响(反应条件:电流密度30 mA/cm2, Na2SO4浓度0.1 mol/L, pH=5.6, T=30℃, 溶液流速500 ml/min)

Fig.10 Effect of free radical quencher on degradation rate of HEDP

图11 HEDP降解的伪一级动力学模拟

Fig.11 Pseudo first order kinetic simulation of HEDP degradation

表2 猝灭剂和HEDP的ck值

Table 2 ck values of quencher and HEDP

猝灭剂种类	猝灭剂浓度/(mmol/L)	c₁k₁	c₂k₂
甲醇	30	2.9×10¹⁰	3.6×10⁷
叔丁醇	70	（2.7×10¹⁰）~（5.4×10¹⁰）	3.6×10⁷

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