高铁酸钾氧化自絮凝处理实际化学镀镍废槽液

doi:10.19965/j.cnki.iwt.2021-0688

摘要/Abstract

摘要：

化学镀镍工艺广泛应用于工业生产领域，并产生大量废水。此类废水一般由预处理工艺废水、镀件清洗水、废镀液及其他废水组成，成分复杂，具有微生物毒性，如直接排放会对自然环境造成严重污染。采用高铁酸钾（K₂FeO₄）对含高浓度Ni和COD的化学镀镍废槽液进行处理，探讨K₂FeO₄浓度、废水初始pH对废水处理效果的影响。结果表明，K₂FeO₄最适浓度为5 mmol/L，最佳废水初始pH为3，对络合态Ni的破络效率最高可达99%，COD去除率最高达80%。超高效液相色谱-质谱（UPLC-MS）表征结果显示，废水中的Ni主要以苹果酸-Ni形态存在。K₂FeO₄处理化学镀镍废槽液的机理可能为：K₂FeO₄先与废水中的还原物质反应得到还原产物Fe（Ⅲ），再与Ni-有机络合物发生置换使Ni游离，同时，Fe（Ⅲ）的絮凝作用可降低废水的COD。

关键词: K₂FeO₄, 化学镀镍槽液, 破络合

Abstract:

Electroless nickel plating process is widely used in industrial fields and generates a large amount of wastewater. This type of wastewater generally consists of pretreatment process wastewater， cleaning water， waste plating solution and other wastewater with complex composition and microbial toxicity， which will cause serious pollution to the natural environment if discharged directly. Potassium ferrate（K₂FeO₄） was used to treat bath waste of electroless nickel plating containing high concentrations of Ni and COD. The effects of K₂FeO₄ concentration and initial pH of wastewater on treatment were investigated. The results showed that the optimum concentration of K₂FeO₄ was 5 mmol/L and the optimal initial pH of the wastewater was 3. The complex-breaking efficiency of K₂FeO₄ was up to 99% for complexed Ni and the removal rate of COD was up to 80%. UPLC-MS characterization showed that Ni in the wastewater mainly existed in the form of malic acid-Ni. The reaction mechanism of K₂FeO₄ for bath waste of electroless nickel plating may be as follows： K₂FeO₄ reacts with the reducing substances in the wastewater to form reduction product Fe（Ⅲ）， and then replaces with Ni-organic complex. Meanwhile， the flocculation effect of Fe（Ⅲ） can reduce COD of the wastewater.

Key words: potassium ferrate, electroless nickel plating bath, breaking complexation

中图分类号:

X703

熊秀琴, 谢观生, 余真, 赖玲, 邵鹏辉, 杨利明, 石慧, 罗旭彪. 高铁酸钾氧化自絮凝处理实际化学镀镍废槽液[J]. 工业水处理, 2022, 42(4): 78-83.

Xiuqin XIONG, Guansheng XIE, Zhen YU, Ling LAI, Penghui SHAO, Liming YANG, Hui SHI, Xubiao LUO. Treatment of actual electroless nickel plating bath waste by potassium ferrate oxidation and self-flocculation[J]. Industrial Water Treatment, 2022, 42(4): 78-83.

https://www.iwt.cn/CN/Y2022/V42/I4/78

图/表 7

表1 化学镀镍废槽液的水质

Table 1 Quality of bath waste from electroless nickel plating

项目	Cr	Mn	Ag	Pd	Cd	Ni	Co	Cu	Fe	pH	TOC
数值	未检出	未检出	未检出	未检出	未检出	4 868	1.475	未检出	未检出	4.61	17 000
项目	F^-	Cl^-	NO₃ ^-	PO₄ ^3-	SO₄ ^2-	Br^-	NO₂ ^-	NH₃-N	COD	浊度	色度
数值	10 913	14 736	4 226	67 910	69 191	未检出	未检出	4 878	48 152	0.57	50

图1 不同氧化剂对废水的处理效果（a）H₂O₂；（b）KMnO₄；（c）Na₂S₂O₈；（d）NaClO；（e）K₂FeO₄

Fig. 1 Treatment effects of different oxidants on wastewater

图2 K₂FeO₄浓度对废水处理效果的影响（a）络合态Ni；（b）游离态Ni；（c）COD

Fig. 2 Treatment effect of K₂FeO₄ concentration on wastewater

图3 初始pH对废水处理效果的影响（a）游离态Ni；（b）络合态Ni；（c）COD

Fig. 3 Treatment effect of initial pH on wastewater

图4 UPLC-MS谱图（a）总离子流图；（b）苹果酸质谱图；（c）柠檬酸质谱图；（d）EDTA质谱图；（e）柠檬酸铵质谱图

Fig. 4 Spectra of UPLC-MS

图5 不同条件下模拟废水和废槽液的Ni去除情况（a）过Na柱后Ni的剩余量；（b）投加K₂FeO₄后Ni去除率；（c）不同pH下废槽液的Ni去除率；（d）不同pH下苹果酸-Ni配水的Ni去除率

Fig. 5 Removal of Ni from simulated wastewater and bath waste under different conditions

图6 UV-Vis谱图及CV曲线（a）废槽液与K₂FeO₄反应；（b）苹果酸-Ni与K₂FeO₄反应；（c）苹果酸-Ni与Fe₂（SO₄）₃反应的CV曲线

Fig. 6 UV-Vis spectrum and CV curve

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