Synergistic effect of cathodic and anodic reactions for degradation of organophosphorus scale inhibitor and recovery of calcium phosphate

doi:10.16085/j.issn.1000-6613.2020-1147

Abstract

Abstract:

To bridge the gap between phosphonates being too much as the antiscalant used in industrial cooling water systems and phosphorus being too little as a resource, the electrochemical treatment process was developed for the recovery of phosphorus from the phosphonate wastewater. In this reaction system, boron doped diamond (BDD) mediated anodic oxidation was effective for the oxidative release of ortho-phosphate (o-PO₄) from phosphonates. At the same time, OH^- was generated by H₂O reduction at the cathode and created a basic environment near the cathode, where calcium phosphate would become highly supersaturated precipitated. In this study, the effects of operation parameters on ethylene diamine tetra(methylene phosphonic acid) (EDTMP) degradation and the recovery of phosphorus were investigated. It was found that the degradation of EDTMP was mainly attributed to the production of ?OH during the BDD mediated anodic oxidation process, which was much more favorable at higher current density. TOC removal efficiency, o-PO₄-P concentration and phosphorus recovery efficiency were increased from 14% to 72%, 6.5mg/L to 9.9mg/L and 21% to 83%, respectively, with current density increasing from 3mA/cm² to 30mA/cm². Phosphorus recovery efficiency was negligibly influenced by the variation of solution pH from 3.0 to 12.0. Increasing Ca²⁺ concentration could increase the recovery of phosphorus. Phosphorus recovery efficiency was enhanced from 46% to 83% with elevating Ca²⁺ concentration from 25mg/L to 100mg/L. In electrochemical reaction system, phosphorus was recovered at the cathode surface in the form of amorphous calcium phosphate with Ca/P molar ratio of 0.6.

Key words: electrochemistry, degradation, organophosphorus, recovery, calcium phosphate

摘要：

为解决工业循环水系统中有机磷阻垢剂添加引发的磷污染和磷资源短缺等问题，本文构建了电化学阴-阳极协同反应体系，利用硼掺杂金刚石（BDD）阳极氧化反应实现有机磷的降解，同时阴极电解反应营造的局域强碱性氛围有利于磷酸钙在阴极的富集。以乙二胺四亚甲基膦酸（EDTMP）为目标阻垢剂，研究了不同参数对EDTMP降解和无机磷回收性能的影响，结果表明：BDD阳极电化学反应产生的强氧化性?OH是氧化EDTMP的主要活性物种，增加电流密度有利于EDTMP的降解，电流密度从3mA/cm²增加到30mA/cm²时，总有机碳（TOC）去除率从14%增加到72%，无机磷产量从6.5mg/L增加到9.9mg/L，磷回收效率从21%同步增加到83%。初始pH（3.0～12.0）对磷回收效率影响较小。Ca²⁺浓度增加有利于水体中磷的回收，Ca²⁺浓度从25mg/L增加到100mg/L时，磷回收效率相应地从46%提升到83%。电化学反应体系内，磷主要以非晶态的磷酸钙形式在阴极表面富集，沉积物种Ca/P物质的量之比约为0.6。

关键词: 电化学, 降解, 有机磷, 回收, 磷酸钙

CLC Number:

LIU Yijie, CAI Limin, WANG Xiaohui, QI Yuanfeng, JIANG Bo. Synergistic effect of cathodic and anodic reactions for degradation of organophosphorus scale inhibitor and recovery of calcium phosphate[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2867-2872.

刘奕捷, 蔡利民, 王晓慧, 齐元峰, 江波. 电化学阴阳极协同降解有机磷及同步回收磷酸钙[J]. 化工进展, 2021, 40(5): 2867-2872.

Figures/Tables 10

References 14

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