次氯酸钠耦合过氧化氢法降解氨基三亚甲基膦酸研究  

Degradation of nitrilotris-methylenephosphonic acid via sodium hypochlorite coupled with hydrogen peroxide method

作　　者：郭振杰 刘雪瑜[3] 黎佳茜 李一兵 张娟娟[2,3] 赵旭 GUO Zhenjie;LIU Xueyu;LI Jiaxi;LI Yibing;ZHANG Juanjuan;ZHAO Xu(School of Civil and Transportation Engineering,Hebei University of Technology,Tianjin 300401;Key Laboratory of Drinking Water Science and Technology,Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences,Beijing 100085;Institute of Water Ecology and Environmental,Chinese Research Academy of Environmental Sciences,Beijing 100012)

机构地区：[1]河北工业大学,土木与交通学院,天津300401 [2]中国科学院生态环境研究中心,饮用水科学与技术重点实验室,北京100085 [3]中国环境科学研究院,水生态环境研究所,北京100012

出　　处：《环境科学学报》2024年第2期117-124,共8页Acta Scientiae Circumstantiae

基　　金：国家自然科学基金(No.22106173,22276210)。

摘　　要：针对工业废水中典型有机磷污染物氨基三亚甲基膦酸(NTMP)难降解问题,采用次氯酸钠(NaClO)、过氧化氢(H_(2)O_(2))、NaClO耦合H_(2)O_(2)法对NTMP氧化降解为正磷酸盐(PO_(4)^(3-))的效果进行比较.结果发现,NaClO耦合H_(2)O_(2)法可以显著提高NTMP氧化为PO_(4)^(3-)的效率.考察了NaClO投加量、H_(2)O_(2)投加量、初始溶液pH、反应温度、共存无机阴离子(SO_(4)^(2-)、NO_(3)^(-)、HCO_(3)^(-))和共存有机物腐殖酸(HA)对反应体系氧化NTMP为PO_(4)^(3-)效率的影响.结果表明,当NaClO和H_(2)O_(2)投加量分别为10 mmol·L^(-1),初始溶液pH为5,反应60 min时,1 mmol·L^(-1)(以P计)的NTMP全部被氧化降解生成PO_(4)^(3-).适当升温可以提高反应速率,但过高的温度(45~65℃)会降低NTMP降解效率;SO_(4)^(2-)、NO_(3)^(-)、HCO_(3)^(-)对NTMP氧化降解无明显影响,但HA可明显抑制NTMP的氧化降解,且随着HA浓度的增加这种抑制作用也逐渐增强.自由基淬灭实验和电子自旋共振波谱(ESR)分析证明,该体系中ClO^(-)、·OH、·O_(2)-、^(1)O_(2)是体系氧化降解NTMP的活性物种,其中非自由基^(1)O_(2)作用显著.本研究结果可以为含有机磷的工业废水处理提供参考.Nitrilotris-methylenephosphonic acid(NTMP)degradation poses challenges in industrial wastewater.the oxidation efficiency of NTMP to orthophosphate(PO_(4)^(3-))via varies methods including sodium hypochlorite(NaClO),hydrogen peroxide(H_(2)O_(2))and NaClO coupled with H_(2)O_(2) method were compared.It was found that NaClO coupled with H_(2)O_(2) method could significantly enhance the oxidation efficiency of NTMP to PO_(4)^(3-).The effects of different operating parameters including the dosage of NaClO and H_(2)O_(2),initial solution pH,reaction temperature,coexisting inorganic anions(SO_(4)^(2-),NO_(3)^(-),and HCO_(3)-)and humic acids(HA)on the oxidation efficiency of NTMP to PO_(4)^(3-)was investigated in the NaClO coupled with H_(2)O_(2) system.The results indicated that NTMP was completely oxidized to PO_(4)^(3-)in 60 min when the initial concentration of NTMP was 1.0 mmol·L^(-1)(measured in P),with NaClO and H_(2)O_(2) dosages of 10 mmol·L^(-1) each,and an initial solution pH of 5.It was proved that temperature variation showed a slight favorable impact on the oxidation of NTMP,but a high temperature(45~65℃)would inhibit the oxidation of NTMP.Besides,SO_(4)^(2-),NO_(3)^(-),and HCO_(3)-did not significantly affect the oxidation of NTMP.However,the oxidation of NTMP was obviously inhibited in the presence of HA,especially at higher concentration.The radical quenching experiments and electron spin resonance(ESR)spectroscopy results proved that ClO^(-),·OH,·O_(2)^(-),and ^(1)O_(2) contribute to the oxidation of NTMP to PO_(4)^(3-)in the NaClO coupled with H_(2)O_(2) system,among which,the contribution of non-radical ^(1)O_(2) was considerable.This study offers insights into the treatment of industrial wastewater containing organophosphate.

关 键 词：次氯酸钠 过氧化氢 氨基三亚甲基膦酸 高级氧化工艺 正磷酸盐 

分 类 号：X703[环境科学与工程—环境工程]