PDF(10059 KB)
PDF(10059 KB)
PDF(10059 KB)
Cu-Fe/SAC粒子反应器除磷研究
Phosphorus Removal Using Cu-Fe/SAC Particle Reactor
天然水体磷污染治理一直是社会关注的难题,降雨冲刷造成的高负荷磷冲击是河湖(库)磷超标的主要来源,开发雨污水高效除磷技术十分迫切。研发了铜-铁/海藻硅酸钠凝胶类碳微球(Cu-Fe/SAC)粒子反应器,以Cu-Fe/SAC为粒子电极,利用Cu-Fe/SAC良好的吸附性能及导电性能,在交变电场作用下,依次通过电吸附富集磷➝颗粒态磷固化➝电解吸释放磷➝颗粒态磷沉淀,在微纳曝气辅助下,极大提升了雨污水中总磷(TP)去除效率。探索了不同影响因素下,粒子反应器除磷最佳参数,并开展了验证试验,探讨了除磷机理。试验结果表明,雨污水除磷最佳参数为:电流密度5 mA/cm2,Cu-Fe/SAC填充量12 g/L,曝气强度120 mL/min,经30 min反应时间,雨污水TP去除率达90.6%,处理后雨污水TP含量满足《地表水环境质量标准》(GB 3838—2002)中Ⅲ类水标准。
[Objective] High phosphorus loads caused by rainfall runoff are a major source of phosphorus exceedances in rivers, lakes, and reservoirs. While many researchers have studied phosphorus removal using three-dimensional electrode electrocoagulation, such studies are limited to simulated or domestic wastewater and suffer from long processing times. This study proposes a phosphorus removal technology using a Cu-Fe/sodium silicate-alginate carbon microsphere (Cu-Fe/SAC) particle reactor. Taking combined sewer runoff from the Huandi River as the research object, the study explains the phosphorus removal mechanism of the particle reactor through optimization of operational parameters and validation experiments, providing a new approach for rapid phosphorus removal from high-impact rainwater-sewage mixtures. [Methods] The Cu-Fe/SAC material was characterized using Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), and X-ray Diffraction (XRD) for morphology, while pore size distribution was determined by Discrete Fourier Transform (DFT). The experimental setup of the particle reactor was innovatively equipped with key components such as micro-nano aeration membranes and a pulse power supply. Using simulated wastewater, the study investigated phosphorus removal efficiency under different current densities, Cu-Fe/SAC filling amounts, and micro-nano aeration intensities. It also compared the phosphorus removal performance of different reactors under optimal conditions and validated the performance of the particle reactor on actual rain-sewage mixtures under optimal conditions. [Results] Characterization and pore distribution results indicated that Cu-Fe/SAC has a high specific surface area and moderate average pore size, with copper and iron uniformly loaded onto the SAC carbon microspheres as an alloy. Phosphorus removal experiments with simulated wastewater showed that the optimal conditions for the particle reactor were: current density of 5 mA/cm2, Cu-Fe/SAC filling amount of 12 g/L,and aeration intensity of 120 mL/min. Under these optimal conditions, after the same reaction time, the phosphorus removal efficiencies of three electrochemical devices ranked as: Cu-Fe/SAC particle reactor > three-dimensional electrode electrocoagulation (with SAC particle electrodes) > two-dimensional electrode electrocoagulation. Furthermore, validation experiments with actual rain-sewage mixtures showed that under optimal conditions and 30 minutes of reaction, the reactor achieved a total phosphorus (TP) removal rate of 90.6%. [Conclusions] The Cu-Fe/SAC microspheres developed in this study demonstrate excellent surface morphology, pore structure, and electrical conductivity, which enhance the efficiency of pollutant contact-adsorption and electron transfer. Using Cu-Fe/SAC as particle electrodes, the particle reactor achieves optimal phosphorus removal conditions, and under these optimal conditions, after 30 minutes of treatment, the total phosphorus (TP) removal rate in rain-sewage is verified, and the treated water meets the Class III water quality standard for surface water (GB 3838—2002). The phosphorus removal mechanism involves: under an alternating electric field, polarized particle electrodes first enrich and immobilize low-concentration phosphate ions via electro-adsorption, forming particulate phosphorus; then, during electro-desorption, the phosphates are released into the solution at high concentrations and, assisted by micro-nano aeration, rapidly react with precipitated high-concentration metal ions (Fe2+, Fe3+, and Cu2+), forming phosphate precipitates and thus achieving high-efficiency phosphorus removal.
粒子反应器 / 粒子电极 / 三维电极 / 雨污水 / 除磷
particle reactor / particle electrode / three-dimensional electrode / combined rain-sewage / phosphorus removal
| [1] |
曹晓峰, 冀泽华, 兰华春, 等. 气候变化背景下我国湖库型水源富营养化控制与饮用水安全保障策略[J]. 中国工程科学, 2022, 24(5): 34-40.
全球气候变化背景下湖库型水源面临不同程度的富营养化与蓝藻水华问题，对饮用水安全供给产生重要影响。本文通过分析我国现阶段湖库富营养化与湖库型水源地水质现状，从水源保护、净化工艺、管网配送与保障机制等方面，研判了全球气候变化背景下我国湖库型饮用水水源富营养化应对与饮用水安全保障面临的问题与挑战，提出四条针对性的饮用水安全保障策略建议：加强湖库型饮用水水源地环境保护与生态修复力度、推动全过程饮用水安全保障的科技支撑体系建设、构建基于大数据融合的饮用水安全保障智慧化监管平台、加快推动湖库型饮用水源水质安全保障体制机制创新，以期为气候变化影响下我国未来饮用水安全保障提供借鉴。
(
Lake and reservoir ecosystems face varying degrees of eutrophication and cyanobacterial bloom against the background of global climate change, which threatens the safety of drinking water supply. In this study, we reviewed the current status of eutrophication and water quality of lake and reservoir water sources in China, and explored the challenges from the aspects of water source protection, purification process, pipe network distribution, and guarantee mechanism. Four targeted suggestions were recommended for guaranteeing drinking water safety: (1) strengthening environmental protection and ecological restoration of lake and reservoir drinking water sources, (2) promoting the construction of a scientific and technological support system for guaranteeing drinking water safety in the entire process, (3) building an intelligent supervision platform based on big data fusion, and (4) accelerating the system and mechanism innovation for guaranteeing lake and reservoir drinking water safety. |
| [2] |
|
| [3] |
潘涛, 李安峰, 杜兵. 废水污染控制技术手册[M]. 北京: 化学工业出版社, 2013: 942-943.
(
|
| [4] |
杨欣妍. 石墨烯改性陶粒电解反应器净化河水氮磷污染物研究[D]. 南京: 南京大学, 2019.
(
|
| [5] |
|
| [6] |
丁红, 王艺洁, 武福平. 废铁屑-Ti(RuO2)三维电极高效处理高氮磷低C/N污水[J]. 环境工程学报, 2021, 15(3):847-856.
(
|
| [7] |
|
| [8] |
程水林, 杨敏鸽, 王俊勃, 等. 电化学去除污水中磷的工艺研究[J]. 工业水处理, 2021, 41(4): 113-116.
采用正交试验法研究不同电极、电压、电流对电化学去除污水中磷的影响。结果表明：磷的去除率随电压的增加而增大，电流的影响不显著。对于磷质量浓度为0.500 mg/L的中水，最佳电解条件为：铁作正极、铝作负极，电压25 V，电流0.5 A，电解时间40 min，磷去除率为96.0%。电解磷质量浓度为12.97 mg/L的废水，最佳电解条件为：铁作正极、铝作负极，电压30 V，电流1 A，电解时间为60 min，磷去除率为96.77%以上。处理后水中磷的浓度可达到国家排放标准和回用要求。
(
The effects of different electrodes, voltage and current on the electrochemical removal of phosphorus from wastewater were studied by orthogonal experiment. The results showed that the removal rate of phosphorus increased with the increase of voltage, and the effect of current was not significant. When the phosphorus mass concentration of reclaimed water was 0.500 mg/L, the optimum electrolysis conditions were as follows: positive iron, negative aluminum, voltage 25 V, current 0.5 A, electrolysis time 40 min. The removal rate of phosphorus was 96.0%. When the phosphorus mass concentration of wastewater was 12.97 mg/L, the optimum electrolytic conditions were as follows: positive iron, negative aluminum, voltage 30 V, current 1 A, electrolysis time 60 min. The removal rate of phosphorus was 96.77%. The concentration of phosphorus in the treated water could reach the national emission standard and reuse requirements. |
| [9] |
|
| [10] |
|
| [11] |
凌定勋, 曾敏, 李科林, 等. 三维电极-铁屑内电解-水解酸化-BAF工艺处理火炸药废水的研究[J]. 给水排水, 2011, 37(5):138-141.
(
|
| [12] |
陈芳艳, 王春玲, 陈存键, 等. 三维电极电化学氧化法深度处理DOP生产废水的研究[J]. 环境工程学报, 2012, 6(2):540-544.
(
|
| [13] |
程笑婕, 柏永生, 张凯, 等. 电化学除磷过程的条件优化与机理研究[J]. 中国给水排水, 2020, 36(3): 86-91.
(
|
| [14] |
于洋, 陈立波, 刘治中, 等. 电化学法去除工业垃圾渗滤液中的总磷[J]. 工业水处理, 2022, 42(11): 145-152.
采用电絮凝-电化学氧化组合工艺对工业垃圾渗滤液中的总磷（TP）进行去除。首先考察了电极材质、电极间距、电解电压、电解时间、曝气时长、反应体系pH等反应条件对电絮凝TP去除效果的影响，并综合经济性得到电絮凝除磷的最佳工艺条件为：铁、铝电极，脉冲电源，电极间距1.0 cm，铁电极电解电压2.0 V，电解20 s倒极，铝电极电解电压2.5 V，电解10 s倒极，反应体系pH 7~8，电解总时间15 min，电絮凝结束后无需采用曝气辅助除磷。在此最佳条件下，TP为11~15 mg/L的渗滤液样本经电絮凝处理后残余TP降至1.0~1.3 mg/L，TP去除率可达91.7%。将电絮凝工艺同Ti/RuO<sub>2</sub>-IrO<sub>2</sub>电极电化学氧化工艺组合，用于处理TP为14.7 mg/L的渗滤液，处理后渗滤液残余TP为0.2 mg/L，满足工业垃圾渗滤液TP≤0.3 mg/L的直接排放标准。同时，处理后渗滤液COD及氨氮也大幅下降，表明电絮凝-电化学氧化组合工艺对渗滤液样本中氨氮、COD也具有一定的处理能力。
(
The total phosphorus（TP） in industrial landfill leachate was removed by the combined process of electroflocculation and electrochemical oxidation. In this paper，the effects of electrode materials，electrode spacing，electrolysis voltage，electrolysis time，aeration time，pH of reaction system and other reaction conditions on the removal of TP by electro-flocculation were investigated. Additional considertion of economy，the optimum technological conditions of electro-flocculation were as follows：Iron and aluminum electrodes，pulse power supply，1.0 cm of electrode spacing，2.0 V of electrolysis voltage of iron electrodes and 20 s of electrolysis time，2.5 V of electrolysis voltage of aluminum electrodes and 10 s of electrolysis time，pH of the reaction system 7-8，the total electrolysis time 15 min. There was no need to use aeration-assisted phosphorus removal after the electro-flocculation. Under the optimum condition，the residual TP in the leachate samples with TP of 11-15 mg/L was reduced to 1.0-1.3 mg/L after electroflocculation，and the TP removal rate could reach 91.7%. The electro-flocculation process was combined with the Ti/RuO2-IrO2 electrode electrochemical oxidation process to treat the leachate with TP of 14.7 mg/L. The residual TP in the leachate after treatment was 0.2 mg/L，which met the direct discharge standard of TP≤0.3 mg/L of industrial waste leachate. At the same time，the COD and ammonia nitrogen of the leachate also was decreased significantly after treatment，indicating that the combined process of electro-flocculation and electrochemical oxidation also had a certain ability to treat ammonia nitrogen and COD in the leachate samples. |
| [15] |
|
| [16] |
刘晨阳, 单悦, 李久义, 等. 海藻酸钠基吸附材料制备及其脱氮除磷研究进展[J]. 现代化工, 2024, 44(2): 25-31, 36.
综述了海藻酸钠基生物质材料的研究进展，包括种类、制备方法、脱氮除磷效果以及吸附机理等内容，为其开发、应用及氮、磷污染控制提供参考。
(
This paper comprehensively elaborates on the research progress on sodium alginate based biomass materials, including their types, preparation methods, denitrification and phosphorus removal effects, and adsorption mechanisms, aiming to provide reference for their development and application, and uses in controlling nitrogen and phosphorus pollution.
|
| [17] |
GB 3838—2002, 地表水环境质量标准[S]. 北京: 中国环境科学出版社, 2002.
(GB 3838—2002, Environmental Quality Standards for Surface Water[S]. Beijing: China Environmental Science Press, 2002. (in Chinese))
|
| [18] |
张雨婷, 林莉, 贾迪, 等. 微电流电解产H2O2抑制铜绿微囊藻生长研究[J]. 长江科学院院报, 2023, 40(9): 24-31.
为了探究微电流电解过程对铜绿微囊藻生长的影响,以铂钛作为阳极,碳黑聚四氟乙烯(C/PTFE)气体扩散电极为阴极,在微电流电解体系中可产生对铜绿微囊藻生长具有选择性抑制作用的活性物质H<sub>2</sub>O<sub>2</sub>。探究不同电解时间、电流密度和气体流量对藻细胞生长的影响,结果表明:微电流电解的最佳条件为100 mL细胞密度为5×10<sup>5</sup>个/mL 的藻液在10 mA/cm<sup>2</sup>的电流密度下以0.4 L/min的气体流量电解60 min。藻细胞光密度OD<sub>680</sub>从0.035降至0.003,表明藻细胞的生长完全受到抑制。测定电解处理前后藻细胞的叶绿素荧光参数F<sub>v</sub>/F<sub>m</sub>、Y(Ⅱ)、Y(NO)等可知,电解处理后藻细胞的光合作用机制已遭到完全破坏。测定电解过程中产生H<sub>2</sub>O<sub>2</sub>的质量浓度为79 mg/L,并且经过6次循环实验后,C/PTFE气体扩散电极产生H<sub>2</sub>O<sub>2</sub>质量浓度仍为首次使用产生H<sub>2</sub>O<sub>2</sub>质量浓度的66%(52 mg/L),说明C/PTFE气体扩散电极的稳定性良好,具有较大的应用前景。该研究可为微电流电解抑制蓝藻水华提供新手段。
(
Platinum titanium served as the anode, while a carbon black polytetrafluoroethylene (C/PTFE) gas diffusion electrode was utilized as the cathode in order to facilitate the production of H<sub>2</sub>O<sub>2</sub> through low-amperage electrolysis, with the aim of inhibiting the growth of Microcystis aeruginosa. Through a series of experimental investigations involving varying electrolysis time, current density, and gas flow, the optimal conditions for inhibiting <i>Microcystis aeruginosa</i> were determined. Specifically, the optimal configuration involved the electrolysis of 100 mL of 5×10<sup>5</sup> cells/mL algae solution at a current density of 10 mA/cm<sup>2 </sup>and a gas flow rate of 0.4 L/min for a duration of 60 minutes. Following electrolysis, the optical density (OD<sub>680</sub>) of the algae cells decreased from 0.035 to 0.003, indicating the complete inhibition of algae cell growth. Additionally, the measurement of chlorophyll fluorescence parameters, such as <i>F</i><sub>v</sub>/<i>F</i><sub>m</sub>, <i>Y</i>(Ⅱ), and <i>Y</i>(NO), demonstrated the substantial disruption to the photosynthetic mechanism of the algae, further indicating the complete decay of the algae population. The concentration of H<sub>2</sub>O<sub>2 </sub>generated during electrolysis was determined to be 79 mg/L. Furthermore, even after six cycles of reuse, the C/PTFE cathode maintained 66% (52 mg/L) of the initial H<sub>2</sub>O<sub>2</sub> concentration, highlighting the excellent stability and promising application potential of the C/PTFE electrode. This study presents a novel approach to effectively inhibit cyanobacterial blooms through low-amperage electrolysis, offering a new avenue for remediation.
|
| [19] |
Diclofenac (DIC) is a new type of contaminant that has been widely detected in the water environment, posing threats to the ecological environment and human health. However, the conventional wastewater treatment process has a very limited ability to reduce DIC. In this research, persulfate is added to electro-Fenton with the three-dimensional particle electrode (TDE) process whose particle electrodes were formed from manganese slag with loaded active substance (Cu: Fe = 1:1) to construct a three-dimensional electro-Fenton-persulfate (3D electro-Fenton-PS) process to investigate the removal rate of DIC under the optimum working conditions. The effects of different persulfate addition, activator addition and different activators on the removal rate of DIC were researched, respectively. The removal rate of DIC reached 96.3% when the persulfate and the Fe addition were 1.50 mM and 3.00 mM, respectively. The results showed that and OH existed simultaneously in the reaction system, and the removal of DIC was the result of the two free radicals. Moreover, degradation pathways and mechanism of DIC were also discussed. The study may provide a new theoretical basis and technical support for the treatment of DIC in municipal wastewater.Copyright © 2018 Elsevier Ltd. All rights reserved.
|
| [20] |
|
/
| 〈 |
|
〉 |
