基于树脂富集-电催化还原-膜汽提协同的水中硝氮资源化提取

doi:10.16085/j.issn.1000-6613.2023-1993

摘要/Abstract

摘要：

针对低浓度硝氮污染及氮资源化技术需求，本文采用电重构策略合成了泡沫Fe₂O_3-_x 催化阴极，构建了高效、低能耗的离子交换工艺-电催化硝氮还原-氨氮汽提回收的耦合反应体系，利用树脂富集低浓度NO₃^--N，促进NO₃^--N向NH₄⁺-N转化，并利用气体氨的汽提作用，实现水中NO₃^--N高效去除和产物氨氮的同步回收。离子交换树脂的富集效应获得的高浓度硝酸盐再生剂用于高效电催化还原产氨，随后利用硝酸根还原反应产生的氢氧根再生阴离子交换树脂，从而在避免投入大量药剂的同时实现了高效的电催化还原。离子交换工艺的引入不仅提升了IE-EC-MC系统电催化还原NO₃^-的能力，还显著降低了系统能耗。结果表明，电流密度为20mA/cm²时，经处理NO₃^--N去除率达98%，氨氮回收率、产氨速率和法拉第效率分别为81%、0.67mg N/(cm²·h)和53%，氨回收能耗仅为19.78kWh/kg (NH₄)₂SO₄。本研究为低浓度硝氮污染及氮资源化工艺提供了新思路。

关键词: 电化学, 离子交换, 硝氮还原, 低浓度, 氨氮回收

Abstract:

In view of the low concentration of nitrate pollution and the technical requirements of nitrogen recycling, the foam Fe₂O_3-_x catalytic cathode was synthesized by the electric reconfiguration strategy, and a coupling reaction system of high-efficiency and low-energy-consumption ion exchange process-electro catalytic nitrate reduction-ammonia nitrogen stripping recovery was constructed. The enrichment effect of the ion exchange resin could obtain a high concentration of nitrate regenerator for efficient electrocatalytic reduction of ammonia, and then the hydroxide generated by the nitrate reduction reaction was used to regenerate the anion exchange resin, thus avoiding the use of a large number of agents while achieving efficient electrocatalytic reduction. The introduction of ion exchange technology improved the electrocatalytic NO₃^- reduction capability of the IE-EC-MC system, and significantly reduced the energy consumption of the system. The results showed that at a current density of 20mA/cm², the NO₃^--N removal rate after treatment reached 98%, and the ammonia nitrogen recovery rate, ammonia production rate, and Faraday efficiency were 81%, 0.67mg N/(cm²·h), and 53%, respectively. The energy consumption for ammonia recovery was only 19.78kWh/kg (NH₄)₂SO₄. This study provided new ideas for low concentration nitrate pollution and nitrogen resource utilization processes.

Key words: electrochemistry, ion exchange, nitrate reduction, low concentration, ammonia recovery

中图分类号:

X523

刘亦菲, 郭晓彬, 程梓绅, 江波. 基于树脂富集-电催化还原-膜汽提协同的水中硝氮资源化提取[J]. 化工进展, 2024, 43(12): 7042-7048.

LIU Yifei, GUO Xiaobin, CHENG Zikun, JIANG Bo. Resource extraction of nitrate in water based on resin enrichment-electrocatalytic reduction-membrane stripping synergy system[J]. Chemical Industry and Engineering Progress, 2024, 43(12): 7042-7048.

图/表 7

图1 带有离子交换柱（左）、电解池（中）和膜接触器（右）的IE-EC-MC系统示意图

图2 泡沫铁、Fe2O3、Fe2O3-x 在不同的扫描速率下的循环伏安曲线和在0.785V下的电容电流随扫描速率的变化曲线（Ia为响应电流，Ic为电容电流）

图3 不同电极的硝氮催化还原性能

表1 制备阴极与其他阴极的硝酸盐氮还原活性对比

阴极材料	硝酸盐浓度 /mg N⋅L^-1	电流密度 /mA⋅cm^-2	反应时间/h	去除率/%	参考文献
Fe₂O_3-_x	100	20	2	98	本研究
Al	50	15	3	65	[11]
Cu/Ti	50	30	1.5	70	[12]
Cu/Zn	100	40	3	90	[13]
Fe	100	20	3	95	[14]

图4 IE-EC-MC系统再生剂中NO3--N的浓度和不同体系所取得的法拉第效率和产氨速率

表2 不同方法氨回收性能的比较

方法	NO₃^-去除效率/%	TAN 回收率/%	添加酸或碱	能耗 /kWh·kg^-1(NH₄)₂SO₄	参考文献
IE-EC-MC 系统	98	81	不添加	19.78	本研究
ES	98	28	添加	—	[15]
带电隔膜法	99.90	78.6~85	不添加	21.8~33.5	[16]
电萃取	100	—	添加	19~57	[17]
双极膜法	—	78	添加	—	[18]

图5 不同电流密度下法拉第效率、产氨速率和能耗

参考文献 18

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