多孔炭流动电极对氮磷钾钙离子的电容去离子性能

    Capacitive deionization performance of porous carbon flow electrode for nitrogen, phosphorus, potassium and calcium ions

    • 摘要: 针对流动电极电容去离子(flow electrode capacitive deionization, FCDI)技术的的电极材料吸附性能欠佳和电解液不统一的问题,该研究以多孔炭为流动电极,探讨不同多孔炭理化特性和电容去离子性能,探究不同电解液和不同初始离子浓度的去离子性能,并利用动力学模型解析电容去离子过程。结果表明,ZnCl2活化后,PC-1Zn-600的含氧官能团(C=O和O=C-O)增加,比表面积提升至1137.23 m2/g,平均孔径为1.70 nm,对称电容器中PC-1Zn-600的比电容达72.30 F/g,还具有最小的电阻(2.53 Ω),而经过100次的CDI(capacitive deionization,CDI)吸附/解吸循环后,PC-1Zn-600的去除量保持率仍有73.83%。在210 min时,PC-1Zn-600为电极材料对氨氮、P、K和Ca去除率分别达到了84.98%、79.97%、72.79%和91.21%。对于3种电解液(进液、K2SO4和H2O),当电解液为H2O时,处理氨氮和P的效果较好,去除率分别达91.69%和75.55%,并且回收能耗更低。随着初始离子浓度的增加,FCDI的离子去除率降低,但随着时间延长至210~570 min以上,FCDI对氮磷钾钙离子的去除率都可以接近100%。流动电极电容去离子过程更适合伪一级动力学模型(R2>0.96),建议FCDI处理高离子浓度运行时间6~9 h以上;FCDI的离子迁移过程由双电层和离子交换膜控制,进液界面与离子交换膜的接触面积以及离子交换膜的性质是FCDI处理高浓度离子的关键因素。研究可为流动电极电容去离子的工业化应用提供参考。

       

      Abstract: Flow electrode capacitive deionization (FCDI) is a promising technology for continuous desalination and energy-efficient water purification. However, the performance of FCDI is influenced by various factors, including the choice of electrode materials and the electrolyte composition. In this study, porous carbon was synthesized by activating biochar with different mass ratios of ZnCl2. We evaluated the physicochemical properties and capacitive deionization performance of the resulting porous carbon materials, assessed the deionization efficiency under varying electrolytes and initial ion concentrations, and analyzed the capacitive deionization process using kinetic models. The study identifies key factors affecting the FCDI process and explores its potential for application in environments with high ion concentrations. The results demonstrated that ZnCl2 activation significantly enhanced the physicochemical and capacitive deionization properties of the porous carbon. When the mass ratio of ZnCl2 to porous carbon was 1 (PC-1Zn-600), the specific surface area of the material increased to 1137.23 m² g−1, and the pore diameter was reduced to 1.70 nm. Additionally, the concentration of oxygen-containing functional groups (e.g., C=O, O=C-O) increased. The specific capacitance of PC-1Zn-600 and PC-2Zn-600 improved to 72.30 F g−1 and 169.98 F g−1, respectively, compared to that of PC-600 (25.74 F g−1), representing a 1.81-fold and 5.60-fold increase, respectively. Furthermore, the electrical resistance of PC-1Zn-600 was reduced to 2.53 Ω. Compared to PC-600 and PC-2Zn-600, the removal efficiencies of ammonia nitrogen, Phosphorus (P), Potassium (K), and Calcium (Ca) ions using the PC-1Zn-600 flow electrode reached 84.98%, 79.9%, 72.79%, and 91.21%, respectively, after 210 minutes. Among the three electrolytes tested (feed solution, K2SO4, and H2O), the H2O electrolyte was the most effective for removing ammonia nitrogen and phosphorus, with removal rates of 91.69% and 75.55%, respectively. Compared to the K2SO4 electrolyte, H2O showed lower energy consumption for ion recovery and did not require the addition of chemicals, offering both low cost and high performance potential for practical applications. As the initial ion concentrations increased, the flow capacitive deionization (FCDI) process showed a slower removal rate in the short term. However, after 6–9 hours of operation, even with high initial concentrations of ammonia nitrogen (1000 mg/L), phosphorus (150 mg/L), potassium (1500 mg/L), and calcium (150 mg/L), removal efficiencies reached 99.33%, 98.15%, 98.50%, and 98.22%, respectively. These removal rates were comparable to those observed at lower ion concentrations (e.g., 100 mg/L ammonia nitrogen, 50 mg/L phosphorus, 500 mg/L KCl, and 50 mg/L CaCl2), demonstrating the ability of FCDI to effectively treat high-concentration solutions. Therefore, it is recommended that the operation time for FCDI treatment of high-ion concentration solutions be extended to at least 6–9 hours. Additionally, the first-stage kinetic model (R2 > 0.96) was found to be well-suited for the FCDI deionization process, indicating that the process is primarily governed by electrostatic interactions. The migration process of ammonia nitrogen and potassium ions included three stages: a double-layer membrane stage, an ion-exchange membrane stage, and an equilibrium stage. For phosphorus and calcium ions, the process consisted of a double-layer membrane stage followed by an ion-exchange membrane stage, with the ion-exchange membrane stage acting as the rate-limiting step. Thus, optimizing the contact area between the influent solution and the ion-exchange membrane, as well as improving the properties of the ion-exchange membrane, are critical factors for enhancing the efficiency of FCDI in treating highly concentrated solutions.

       

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