芬顿法处理废水中氨基三亚甲基膦酸同步回收磷研究  

Study on treatment of amino trimethylene phosphonic acid from wastewater and simultaneous phosphorus recovery by Fenton process

作　　者：于莹 黎佳茜 任帅康 吴瑞 温硕钊 刘明亮 张娟娟 YU Ying;LI Jiaxi;REN Shuaikang;WU Rui;WEN Shuozhao;LIU Mingliang;ZHANG Juanjuan(Institute of Water Ecology and Environment,Chinese Research Academy of Environmental Sciences;Business Division of Solar Energy,Beijing Sunda Solar Energy Technology Co.,Ltd.;College of Environmental and Municipal Engineering,Lanzhou Jiaotong University)

机构地区：[1]中国环境科学研究院水生态环境研究所 [2]北京市太阳能研究所有限公司太阳能事业部 [3]兰州交通大学环境与市政工程学院

出　　处：《环境工程技术学报》2025年第2期594-602,共9页Journal of Environmental Engineering Technology

基　　金：中央级公益性科研院所基本科研业务费专项(2024YSKY-10);生态环境部预算工作“入河入海排污口监督管理”项目(102144220260000009095);国家自然科学基金项目(22106173)。

摘　　要：去除与回收工业废水中常用阻垢剂氨基三亚甲基膦酸(ATMP)对水体保护与磷(P)资源可持续利用具有重要意义。采用Fenton法对废水中ATMP进行处理,首先比较了硫酸亚铁(FeSO_(4))、过氧化氢(H_(2)O_(2))、Fenton法(FeSO_(4)+H_(2)O_(2))对ATMP的处理效果,并进一步探究Fenton法处理ATMP体系中FeSO_(4)浓度、H_(2)O_(2)浓度、溶液初始pH、ATMP初始浓度以及共存离子等因素对ATMP处理效果的影响。结果表明:在ATMP初始浓度为1.0 mmol/L(以P计),采用Fenton法(FeSO_(4)和H_(2)O_(2)投加量均为1.5 mmol/L),溶液初始p H为3的反应条件下,ATMP的氧化处理效果较好,反应30 min后,体系中总磷(TP)去除率能达到95%,且去除的TP以磷酸铁(FePO_(4))沉淀的形式生成从而实现P回收。共存金属阳离子(Ca^(2+)或Mg^(2+))对ATMP的氧化降解无影响,共存无机阴离子(HCO_(3)^(-)或NO_(3)^(-))和共存有机阴离子(C_(5)H_(7)O_(5)COO^(-)或CH_(3)COO^(-))对体系中TP去除有抑制作用。自由基淬灭实验和电子自旋共振波谱测试结果表明,羟基自由基在Fenton法氧化处理ATMP的过程中起着关键性作用。综上所述,Fenton法可以有效实现对ATMP的氧化并最终生成正磷酸盐(PO_(4)^(3-)),同时在特定条件下PO_(4)^(3-)与三价铁离子结合生成FePO_(4)沉淀,实现P的资源化回收。本研究可为含有机膦酸盐ATMP废水的资源化处理提供参考。Removal and recovery of amino trimethylene phosphonic acid(ATMP)commonly used as scale inhibitor in industrial wastewater is of great significance for water protection and sustainable utilization of phosphorus resources.The Fenton method was used to treat ATMP in wastewater.The treatment performance of ATMP by ferrous sulfate(FeSO_(4)),hydrogen peroxide(H_(2)O_(2)),and Fenton methods(FeSO_(4)+H_(2)O_(2))was compared.Furthermore,the effects of FeSO_(4)concentration,H_(2)O_(2)concentration,initial solution pH,initial ATMP concentration,and coexisting ions on the treatment of ATMP in the Fenton method system were investigated.The results showed that when the initial concentration of ATMP was 1.0 mmol/L(in P),the dosage of FeSO_(4)was 1.5 mmol/L,the dosage of H_(2)O_(2)was 1.5 mmol/L,and the initial solution pH was 3,the oxidation treatment effect of ATMP was relatively high.The total phosphorus(TP)removal rate was as high as 95%after 30 min of reaction time,and the removed TP was generated in the form of ferric phosphate(FePO_(4))precipitation for phosphorus recovery.The coexisting metal cations(Ca^(2+)or Mg^(2+))had no effect on the oxidative degradation of ATMP.while HCO_(3)^(-)NO_(3)^(-)the coexisting inorganic anions(or)and organic anions(C_(5)H_(7)O_(5)COO^(-)or CH_(3)COO^(-))had inhibitory effects on the removal of TP.The radical quenching experiments and electron spin resonance(ESR)spectroscopy results proved that hydroxyl radicals(·OH)played a key role in the oxidation of ATMP by Fenton method.In PO_(4)^(3-)summary,the Fenton method could effectively oxidize ATMP to,and facilitate phosphorus recovery by PO_(4)^(3-)forming ferric phosphate(FePO_(4))precipitates via the combination of and Fe3+under certain conditions.This study could provide reference for the resourceful treatment of industrial wastewater containing ATMP.

关 键 词：氨基三亚甲基膦酸(ATMP) 芬顿(Fenton) 磷回收 磷酸铁 羟基自由基 

分 类 号：X52[环境科学与工程—环境工程]