电去离子技术制备超纯水的研究
摘要
电去离子(Electrodeionization,简称EDI)技术是将电渗析和混床离子交换有机结合形成的新型分离过程,具有无污染、能连续生产超纯水的优点,已经成为制备超纯水的主流工艺。水解离机理及膜堆结垢问题是EDI的基础研究及工程应用中的核心问题。本文通过考察膜堆电压、浓水流量、淡水流量等因素对EDI超纯水制备过程及硬度离子脱除性能的研究,主要分析讨论EDI膜堆的水解离情况及影响因素、EDI膜堆的运行模式及操作条件对EDI膜堆结垢的影响,并提出了防止EDI膜堆结垢的方法。
通过考察了不同条件下EDI膜堆的电流-电压特性曲线、浓水和淡水中的pH-电流变化曲线,综合分析了各种影响因素,得出了实验膜堆水解离的基本规律,同时得到了随淡水水质的影响因素。实验结果表明,在较低电压下,阳膜表面先于阴膜表面发生水解离,引起浓水和淡水中的pH的下降；膜堆电流的持续上升及浓、淡水pH的增大,主要是由于阴离子交换膜表面与阴树脂表面的水解离。淡水流量的变化对水解离影响不大,淡水流量过大会使淡水水质变差；浓水流量的增大会抑制水解离的发生；原水电导率增大会使水解离难发生,使淡水水质变差。同时得到了本实验膜堆最佳工作电压为40-45V,最佳水回收率为80%-90%。
通过对硬度脱除的质量平衡分析,证实了EDI膜堆电压对EDI过程的运行模式具有重要影响：在电压较低时,EDI在增强传质模式下运行,树脂保持为盐型；在电压较高时,EDI在电再生模式下运行,树脂床层通过电再生转化为H型和OH型,EDI相当于连续获得再生的混床离子交换。同时对两种不同运行模式下EDI过程的基本特点进行了分析和讨论。本实验中EDI膜堆的两种运行模式的分界电压在25-30V之间。在此研究基础上,本实验装置采用35V以上的膜堆电压,淡水电阻率可达13MΩ·cm以上,硬度的脱除率最高可达到96%；研究发现EDI在增强传质模式下运行,EDI膜堆易发生结垢,原水中硬度大小及CO2含量高使膜堆易发生结垢。
Electrodeionization (EDI) is a novel separation process combining with ion-exchange. The advantage of producing ultra-pure water with EDI is non-pollution and continuous. EDI with reverse osmosis (RO) is an inevitable development tendency to producing ultra-pure water.The mechanism of water dissociation and membrane stack scaling are key problems in the EDI process and its application. In this paper, performances of the EDI process for the production of ultra-pure water and the removal of hardness ions were investigated. The purpose of the study is not only to discuss the rules and influential factors of water dissociation and stack scaling in the EDI process, but also find methods to prevent stack scaling.
Through investigation of the Current-Voltage curses and the pH-Current curses during the EDI process under different condition, this experiment summarizes the mechanism of water dissociation in the EDI process. Under low voltage, the pH value of the concentrated water and dilute water is descending along with the increase of the voltage, because water dissociation on the surface of cation-exchange membrane takes place more early and severely than on the surface of anion exchange membrane; Through an certain point of voltage, the current and pH value of the concentrated water and dilute water are continuously rising with the increase of the voltage due to water dissociation on the surface of anion-exchange membrane and resins. The flow flux of the dilute water affects little on water dissociation, but the resistance of the dilute water will descend with the flow flux of the dilute water increased. However, when the flow flux of the concentrated water increases, water dissociation will became weak. Water dissociation will be difficult to take place as conductivity in the feed water is high. At the same time, this study suggested that the optimum operating voltage was 40-45V and the optimum water recover rate was 80%-90%.
With the mass balance for hardness ions in the EDI process, operating voltage has an important influence on two different working regimes of EDI process. Under low voltage, EDI works in resin-enhanced regime and the resins in the dilute water remain in the salt forms; under high voltage, the resins are electrochemically converted to the hydrogen and hydroxide forms, and deionization is consistent with a model of continuous regenerated mixed resin bed. The characteristics of the two different regimes are discussed. In this experiment, the demarcation voltage of two different working regimes of EDI process was 25-30V. Base on above conclusions, when the voltage was above 35V, the resistivity of dilute water can be above 13MΩ·cm and removal rate of hardness ions can be up to 96%; scaling is easy to occur in the EDI stack working in resin-enhanced regime. Feed water with high concentration of hardness ions and carbon dioxide can result in scaling.
通过考察了不同条件下EDI膜堆的电流-电压特性曲线、浓水和淡水中的pH-电流变化曲线,综合分析了各种影响因素,得出了实验膜堆水解离的基本规律,同时得到了随淡水水质的影响因素。实验结果表明,在较低电压下,阳膜表面先于阴膜表面发生水解离,引起浓水和淡水中的pH的下降；膜堆电流的持续上升及浓、淡水pH的增大,主要是由于阴离子交换膜表面与阴树脂表面的水解离。淡水流量的变化对水解离影响不大,淡水流量过大会使淡水水质变差；浓水流量的增大会抑制水解离的发生；原水电导率增大会使水解离难发生,使淡水水质变差。同时得到了本实验膜堆最佳工作电压为40-45V,最佳水回收率为80%-90%。
通过对硬度脱除的质量平衡分析,证实了EDI膜堆电压对EDI过程的运行模式具有重要影响：在电压较低时,EDI在增强传质模式下运行,树脂保持为盐型；在电压较高时,EDI在电再生模式下运行,树脂床层通过电再生转化为H型和OH型,EDI相当于连续获得再生的混床离子交换。同时对两种不同运行模式下EDI过程的基本特点进行了分析和讨论。本实验中EDI膜堆的两种运行模式的分界电压在25-30V之间。在此研究基础上,本实验装置采用35V以上的膜堆电压,淡水电阻率可达13MΩ·cm以上,硬度的脱除率最高可达到96%；研究发现EDI在增强传质模式下运行,EDI膜堆易发生结垢,原水中硬度大小及CO2含量高使膜堆易发生结垢。
Electrodeionization (EDI) is a novel separation process combining with ion-exchange. The advantage of producing ultra-pure water with EDI is non-pollution and continuous. EDI with reverse osmosis (RO) is an inevitable development tendency to producing ultra-pure water.The mechanism of water dissociation and membrane stack scaling are key problems in the EDI process and its application. In this paper, performances of the EDI process for the production of ultra-pure water and the removal of hardness ions were investigated. The purpose of the study is not only to discuss the rules and influential factors of water dissociation and stack scaling in the EDI process, but also find methods to prevent stack scaling.
Through investigation of the Current-Voltage curses and the pH-Current curses during the EDI process under different condition, this experiment summarizes the mechanism of water dissociation in the EDI process. Under low voltage, the pH value of the concentrated water and dilute water is descending along with the increase of the voltage, because water dissociation on the surface of cation-exchange membrane takes place more early and severely than on the surface of anion exchange membrane; Through an certain point of voltage, the current and pH value of the concentrated water and dilute water are continuously rising with the increase of the voltage due to water dissociation on the surface of anion-exchange membrane and resins. The flow flux of the dilute water affects little on water dissociation, but the resistance of the dilute water will descend with the flow flux of the dilute water increased. However, when the flow flux of the concentrated water increases, water dissociation will became weak. Water dissociation will be difficult to take place as conductivity in the feed water is high. At the same time, this study suggested that the optimum operating voltage was 40-45V and the optimum water recover rate was 80%-90%.
With the mass balance for hardness ions in the EDI process, operating voltage has an important influence on two different working regimes of EDI process. Under low voltage, EDI works in resin-enhanced regime and the resins in the dilute water remain in the salt forms; under high voltage, the resins are electrochemically converted to the hydrogen and hydroxide forms, and deionization is consistent with a model of continuous regenerated mixed resin bed. The characteristics of the two different regimes are discussed. In this experiment, the demarcation voltage of two different working regimes of EDI process was 25-30V. Base on above conclusions, when the voltage was above 35V, the resistivity of dilute water can be above 13MΩ·cm and removal rate of hardness ions can be up to 96%; scaling is easy to occur in the EDI stack working in resin-enhanced regime. Feed water with high concentration of hardness ions and carbon dioxide can result in scaling.
引文
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