多孔炭流动电极对氮磷钾钙离子的电容去离子性能分析

    Capacitive deionization performance of the 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 one of the most promising technologies for the continuous desalination and energy-efficient water purification. However, the performance of FCDI is confined to the electrode materials and the electrolyte composition. In this study, the porous carbon was synthesized to activate the biochar with different mass ratios of ZnCl2. A systematic investigation was implemented to evaluate the physicochemical properties and capacitive deionization performance of the resulting porous carbon materials. An assessment was then performed on the deionization efficiency under varying electrolytes and initial ion concentrations. The capacitive deionization was analyzed using kinetic models. The key factors were determined on by the FCDI process. The potential application was given in various environments with the high ion concentrations. The results demonstrated that the ZnCl2 activation was 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 1 137.23 m2/g, and the pore diameter was reduced to 1.70 nm. Additionally, there was the an increase in the concentration of oxygen-containing functional groups (e.g., C=O, O=C-O). The specific capacitance values of PC-1Zn-600 and PC-2Zn-600 were improved to 72.30 F/g and 169.98 F/g, respectively, compared with the PC-600 (25.74 F/g), indicating the 1.81 and 5.60 fold increase, respectively. Furthermore, the electrical resistance of PC-1Zn-600 was reduced to 2.53 Ω. 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 min, compared with the PC-600 and PC-2Zn-600. Among the three electrolytes (feed solution, K2SO4, and H2O), the H2O electrolyte was the most effective to remove ammonia nitrogen and phosphorus, with the removal rates of 91.69% and 75.55%, respectively. The H2O showed the lower energy consumption for the ion recovery, compared with the K2SO4 electrolyte. No addition of chemicals was required to offer both low cost and high performance in practical applications. The FCDI shared the low removal rate in the short term, as the concentrations of initial ion increased. However, the removal efficiencies reached 99.33%, 98.15%, 98.50%, and 98.22%, respectively, even with the high initial concentrations of ammonia nitrogen (1 000 mg/L), phosphorus (150 mg/L), potassium (1500 mg/L), and calcium (150 mg/L), after 6-9 h of operation. The removal rates were comparable to those observed at the lower ion concentrations (e.g., 100 mg/L ammonia nitrogen, 50 mg/L phosphorus, 500 mg/L KCl, and 50 mg/L CaCl2). As such, the FCDI can be expected to effectively treat the high-concentration solutions. Therefore, it is recommended that the operation time for the FCDI treatment of high-ion concentration solutions can 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. The process was primarily governed by electrostatic interactions. The migration of ammonia nitrogen and potassium ions included three stages: double-layer membrane, ion-exchange membrane, and equilibrium stage. In phosphorus and calcium ions, the process consisted of a double-layer membrane followed by an ion-exchange membrane stage, with the ion-exchange membrane stage acting as the rate-limiting step. Thus, the properties of the ion-exchange membrane were improved to optimize the contact area between the influent solution and the ion-exchange membrane. The efficiency of FCDI was then enhanced to treat the highly concentrated solutions.

       

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