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Open AccessDOI: 10.7524/j.issn.0254-6108.2025041804Original Research

Degradation Efficiency of EDTMPS by BDD Anode Electrochemical Advanced Oxidation System

North China Electric Power University, Department of Environmental Science and Engineering

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Degradation Efficiency of EDTMPS by BDD Anode Electrochemical Advanced Oxidation System
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Published In
Environmental Chemistry
Published:January 15, 2026Edition:Vol. 45, Issue 8 • pp. 100-112Citation:WANG Anshan et al. (2026), Environmental Chemistry
Impact FactorPeer-Reviewed Core
Source Journal环境化学

Key Takeaways & Executive Findings

  • • • Optimal EDTMPS degradation of 99.48% was achieved at 50 °C, 300 mL·min−1, 7.0 V, pH 10, and 0.05 mol·L−1 Na2SO4, demonstrating near-complete removal under moderate conditions. • • The presence of chloride ions enhanced degradation rates compared to chloride-free systems, though the improvement was marginal; EPR confirmed the generation of chlorine radicals in addition to hydroxyl and sulfate radicals. • • In a coexisting system with benzotriazole (BTA), degradation efficiencies for EDTMPS and BTA were comparable under conditions of 0.05 mol·L−1 Na2SO4, 40 °C, 390 mL·min−1, 7.0 V, and pH 8, indicating non-selective oxidation. • • The degradation mechanism involves both direct anodic oxidation and indirect oxidation via reactive radicals, with indirect oxidation playing a dominant role, leading to complete mineralization into CO2, PO4^3−, and N2.

Abstract

Ethylene diamine tetra (methylene phosphonic acid) sodium (EDTMPS), an organic phosphonate scale and corrosion inhibitor, is widely used in industrial recirculating cooling water systems. Its efficient degradation in blowdown water is critical for water reuse. This study employed a plate-frame electrochemical advanced oxidation (EAOP) system with a boron-doped diamond (BDD) anode to degrade EDTMPS. The effects of operating conditions (temperature, voltage, liquid flow rate) and water quality parameters (pH, electrolyte concentration, chloride ion concentration) were systematically investigated. Optimal degradation efficiency of 99.48% was achieved at 50 °C, 300 mL·min−1, 7.0 V, pH 10, and 0.05 mol·L−1 Na2SO4. Electron paramagnetic resonance (EPR) characterization of chloride-containing systems indicated that reactive species included hydroxyl radicals, sulfate radicals, and possibly chlorine radicals. In a coexisting system with benzotriazole (BTA), EAOPs degraded EDTMPS and BTA with comparable efficiencies. The results demonstrate that BDD-based EAOPs is effective for removing organic phosphonates from low-chloride, low-hardness cooling water, offering a promising approach for blowdown water treatment and reuse.

1. Introduction

Industrial recirculating cooling water systems operate at high concentration cycles, demanding high stability to prevent corrosion and scaling. Organic phosphonate inhibitors like EDTMPS are widely used due to their excellent scale and corrosion inhibition, but their strong C–P bonds and stable phosphonic groups render them resistant to natural degradation. In blowdown water, EDTMPS not only hampers water reuse but also contributes to eutrophication if discharged. Conventional degradation methods—photolysis, chemical oxidation, and biodegradation—suffer from slow kinetics, low efficiency, and potential toxic byproducts, creating a critical bottleneck for sustainable water management.

Electrochemical advanced oxidation processes (EAOPs) offer a promising alternative, generating strong oxidants such as hydroxyl and sulfate radicals in situ. This study employs a boron-doped diamond (BDD) anode in a plate-frame reactor to degrade EDTMPS, systematically optimizing operational and water quality parameters. The work specifically addresses the challenge of treating low-chloride, low-hardness cooling water, where conventional methods falter. By identifying optimal conditions and elucidating the radical mechanisms, this research provides a viable pathway for efficient EDTMPS removal, enabling safe discharge or reuse of blowdown water.

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Cite This Research Paper
WANG Anshan, ZHANG Yulin, ZHANG Jie, LI Lehuan, ZHANG Yuling (2026). Degradation Efficiency of EDTMPS by BDD Anode Electrochemical Advanced Oxidation System. Environmental Chemistry. https://doi.org/10.7524/j.issn.0254-6108.2025041804
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Frequently Asked Questions

What are the optimal operating conditions for maximum EDTMPS degradation, and how sensitive is the process to variations in these parameters?

The optimal conditions were 50 °C, 300 mL·min−1 flow rate, 7.0 V, pH 10, and 0.05 mol·L−1 Na2SO4, achieving 99.48% degradation. The process is sensitive: deviations in temperature, voltage, or pH can reduce efficiency, as these parameters directly influence radical generation and mass transfer.

How does the presence of chloride ions affect the degradation mechanism and efficiency?

Chloride ions slightly enhanced degradation rates compared to chloride-free systems. EPR analysis revealed the formation of chlorine radicals in addition to hydroxyl and sulfate radicals, which may contribute to oxidation. However, the improvement was marginal, suggesting that chloride radicals play a secondary role under the tested conditions.

What is the degradation mechanism of EDTMPS in this BDD-based EAOP system?

EDTMPS degradation occurs via both direct anodic oxidation and indirect oxidation by reactive radicals. Indirect oxidation, primarily by hydroxyl and sulfate radicals, is dominant, leading to complete mineralization into CO2, PO4^3−, and N2. Direct electron transfer at the anode surface is a minor pathway.

Can this process effectively treat coexisting pollutants like benzotriazole (BTA) in cooling water?

Yes, under conditions of 0.05 mol·L−1 Na2SO4, 40 °C, 390 mL·min−1, 7.0 V, and pH 8, EDTMPS and BTA were degraded with comparable efficiencies, indicating non-selective oxidation. This suggests the process can handle multi-contaminant streams, though the degradation rates were lower than the optimal single-solute case.

What are the practical implications for scaling up this technology to industrial cooling water systems?

The BDD anode demonstrated high efficiency (99.48%) under moderate conditions (50 °C, 7 V), suggesting energy and cost feasibility. However, scale-up must consider electrode fouling, mass transfer limitations, and the impact of real water matrices. The study used synthetic low-chloride, low-hardness water; pilot tests with actual blowdown water are necessary to validate performance and economic viability.

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