本發明係關於電透析裝置、電透析方法、廢液處理裝置及廢液處理方法。The present invention relates to an electrodialysis device, an electrodialysis method, a waste liquid treatment device, and a waste liquid treatment method.
以往，離子交換體使用於各種用途，舉例而言，使用於純水之製造系統。一般而言，純水之製造系統具有：陽離子交換體填充裝置、去碳酸裝置、陰離子交換體填充裝置，其藉由使原水依序通水至該等裝置，在陽離子交換體填充裝置中去除被處理水中之陽離子成分，在去碳酸裝置中去除碳酸氣體，在陰離子交換體填充裝置中去除被處理水中之陰離子成分，以製造純水。Ion exchangers have been used in various applications, for example, in pure water production systems. Generally speaking, a pure water production system consists of a cation exchanger, a decarbonation unit, and an anion exchanger. Raw water is passed through these units in sequence, with the cation exchanger removing cations, the decarbonation unit removing carbon dioxide, and the anion exchanger removing anions, thereby producing pure water.
但是，陽離子交換體、陰離子交換體當使用某程度之期間時，會成為飽和狀態而無法進行離子交換，因此需要再生飽和之離子交換體的作業。為了完全地再生飽和之離子交換體，需要大量地使用酸液、鹼溶液作為再生液。此外，使用於再生後之酸液、鹼溶液作為廢液(再生廢液)處理，需進行中和等處理。該廢液之中和處理時，亦使用大量之酸或鹼，因此化學品使用量多的廢液中會有鹽濃度上升的問題。因此，由減少化學品使用量及降低處理成本之觀點，且由減輕環境負荷之觀點來看，需要回收廢液(再生廢液)。However, after a certain period of use, cation exchangers and anion exchangers become saturated and no longer perform ion exchange, necessitating the regeneration of the saturated ion exchanger. To completely regenerate the saturated ion exchanger, large quantities of acid or alkaline solutions are required. Furthermore, the regenerated acid or alkaline solution is treated as wastewater (regeneration wastewater) and requires neutralization. Neutralization of this wastewater also requires large quantities of acid or alkaline, leading to increased salt concentrations in wastewater containing high levels of chemicals. Therefore, from the perspective of reducing chemical usage and lowering treatment costs, as well as reducing environmental burdens, wastewater recycling (recycling) is necessary.
在上述再生廢液之回收中，需要去除高濃度之廢酸、廢鹼溶液中微量之雜質、即陽離子(鉀、鈉、鈣、鎂、銨離子等)或陰離子(氯離子、硫酸離子、硝酸離子等)。 就離子之去除方法而言，有電透析，但有人提出藉由電透析處理再生廢液，以回收成為酸及鹼之方法。The recovery of the regeneration wastewater mentioned above requires the removal of trace impurities, namely cations (potassium, sodium, calcium, magnesium, ammonium, etc.) or anions (chloride, sulfate, nitrate, etc.), from the high-concentration waste acid and waste alkali solutions.Electrodialysis is a common method for removing ions, but some have proposed using electrodialysis to treat the regeneration wastewater and recover the acid and alkali.
例如，專利文獻1記載：在將鹽酸及氫氧化鈉所致之離子交換樹脂的再生工序中產生的再生廢液，通液至電透析裝置以分離成鹽酸及氫氧化鈉的處理方法中，在再生廢液中添加具有鈣之析出抑制效果，且防止對鈣膜之附著、水垢化的膜污染防止劑。 [先前技術文獻] [專利文獻]For example, Patent Document 1 describes a method for treating wastewater generated during the regeneration process of an ion exchange resin using hydrochloric acid and sodium hydroxide by passing it through an electrodialysis device to separate it into hydrochloric acid and sodium hydroxide. A membrane fouling inhibitor that inhibits calcium precipitation and prevents calcium adhesion and scaling to the membrane is added to the wastewater.[Prior Art Document][Patent Document]
專利文獻1：日本特開平11-566號公報Patent document 1: Japanese Patent Application Laid-Open No. 11-566
[發明所欲解決之課題] 但是，專利文獻1記載之方法需要新添加膜污染防止劑至再生廢液，化學品使用量增加，有成本升高之問題。 另一方面，在各種工廠，特別是半導體工廠中，使用於SPM沖洗(硫酸-過氧化氫混合物清潔(sulfuric acid-hydrogen peroxide mixture cleaning))等所致之沖洗工序等的大量廢酸液係被排出，大多數之情形係中和後被處理並被放流，吾人希望這樣的廢酸液能夠有其他用途。[Problem to be Solved by the Invention]However, the method described in Patent Document 1 requires the addition of a membrane antifouling agent to the regenerated wastewater, which increases chemical usage and raises costs.On the other hand, in various factories, particularly semiconductor factories, large amounts of waste acid liquid are discharged from cleaning processes such as SPM cleaning (sulfuric acid-hydrogen peroxide mixture cleaning). In most cases, this waste acid liquid is neutralized, treated, and then discharged. It is desirable to find other uses for this waste acid liquid.
本發明之目的在於提供一種：可防止在電透析裝置之離子交換膜面生成水垢，且可在不增加成本之下進行穩定之酸回收的電透析裝置及電透析方法，以及具有該電透析裝置之廢液處理裝置，及使用前述電透析裝置之廢液處理方法。 [解決課題之手段]The present invention aims to provide an electrodialysis device and an electrodialysis method that prevent scale formation on the ion exchange membrane surface of an electrodialysis device and enable stable acid recovery without increasing costs, as well as a wastewater treatment device including the electrodialysis device and a wastewater treatment method using the electrodialysis device.[Means for Solving the Problem]
本發明人用心檢討上述問題，結果發現藉由使用具有特定構造之電透析裝置進行電透析，可由廢液有效地回收酸，因而完成了本發明。The inventors of the present invention have carefully examined the above-mentioned problems and have found that acid can be effectively recovered from wastewater by performing electrodialysis using an electrodialysis device having a specific structure, thereby completing the present invention.
本發明包含以下態樣。 [1]一種電透析裝置，至少具有陽極、陰極、第1雙極膜、陰離子交換膜、陽離子交換膜及第2雙極膜， 在前述陽極與前述陰極之間，由前述陽極之側依序配置前述第1雙極膜、前述陰離子交換膜、前述陽離子交換膜、前述第2雙極膜， 該電透析裝置尚具有： 陽極室，其由前述陽極與前述第1雙極膜界定； 酸回收室，其由前述第1雙極膜與前述陰離子交換膜界定； 去鹽室，其由前述陰離子交換膜與前述陽離子交換膜界定； 廢酸室，其由前述陽離子交換膜與前述第2雙極膜界定；及 陰極室，其由前述第2雙極膜與前述陰極界定， 該電透析裝置係供給水至前述酸回收室，供給酸性溶液至前述去鹽室，供給廢酸至前述廢酸室，以進行電透析處理。 [2]如[1]記載之電透析裝置，其中前述廢酸係由半導體工廠排出之廢酸。 [3]如[1]或[2]記載之電透析裝置，其中前述酸性溶液係陽離子交換體之再生廢液。 [4]如[1]或[2]記載之電透析裝置，其中前述廢酸係硫酸水溶液，前述廢酸之硫酸濃度在1至20質量%之範圍內。 [5]如[1]或[2]記載之電透析裝置，尚具有測量前述廢酸之pH的pH測量機構， 以前述pH測量機構測得之前述廢酸的pH，在全電透析期間中係小於2。 [6]如[1]或[2]記載之電透析裝置，尚具有： 酸性溶液貯存槽，其貯存供給至前述去鹽室之前述酸性溶液； 酸性溶液循環路，其使由前述去鹽室排出之處理酸性溶液返回前述酸性溶液貯存槽，並使其循環； 酸性溶液循環裝置，其使前述酸性溶液在前述酸性溶液貯存槽及前述酸性溶液循環路中流通； 測量電透析處理時之前述陽極與前述陰極間之電流值的電流測量裝置、測量前述水或前述酸性溶液之導電率的導電率測量機構、測量前述水或前述酸性溶液之pH的pH測量機構中的至少1種；及 控制裝置，其控制前述酸性溶液循環裝置之動作，且接收以前述電流測量裝置、前述導電率測量機構、前述pH測量機構中之至少1種測得的值， 前述控制裝置在電透析處理時，使用前述酸性溶液循環裝置而使前述酸性溶液循環，當選自於電流值之斜率、電流、導電率及pH之至少1種的值在預定範圍內時，將循環之前述酸性溶液以預定比率以上與循環系統外之前述酸性溶液置換，或排出至循環系統外。 [7]如[1]或[2]記載之電透析裝置，尚具有： 奈米過濾裝置，其以奈米過濾膜將前述酸性溶液分離成透過液及濃縮液；及 管線，用以供給前述透過液至前述去鹽室。 [8]一種電透析方法，係用於包含硬度成分之酸性溶液的處理，該電透析方法係使用電透析裝置，該電透析裝置至少具有陽極、陰極、第1雙極膜、陰離子交換膜、陽離子交換膜及第2雙極膜，在前述陽極與前述陰極之間，由前述陽極之側依序配置前述第1雙極膜、前述陰離子交換膜、前述陽離子交換膜、前述第2雙極膜， 該電透析裝置尚具有： 陽極室，其由前述陽極與前述第1雙極膜界定； 酸回收室，其由前述第1雙極膜與前述陰離子交換膜界定； 去鹽室，其由前述陰離子交換膜與前述陽離子交換膜界定； 廢酸室，其由前述陽離子交換膜與前述第2雙極膜界定；及 陰極室，其由前述第2雙極膜與前述陰極界定， 該電透析方法具有下列工序： 供給水至前述酸回收室； 供給前述酸性溶液至前述去鹽室；及 供給廢酸至前述廢酸室，進行電透析處理。 [9]一種廢液處理裝置，具有： 陽離子交換裝置，其填充有陽離子交換體； 再生液貯存槽，其貯存前述陽離子交換體之再生液；及 電透析裝置，其處理由被供給前述再生液之前述陽離子交換裝置排出的再生廢液， 前述電透析裝置至少具有陽極、陰極、第1雙極膜、陰離子交換膜、陽離子交換膜及第2雙極膜，在前述陽極與前述陰極之間，由前述陽極之側依序配置前述第1雙極膜、前述陰離子交換膜、前述陽離子交換膜、前述第2雙極膜， 該電透析裝置尚具有： 陽極室，其由前述陽極與前述第1雙極膜界定； 酸回收室，其由前述第1雙極膜與前述陰離子交換膜界定； 去鹽室，其由前述陰離子交換膜與前述陽離子交換膜界定； 廢酸室，其由前述陽離子交換膜與前述第2雙極膜界定； 陰極室，其由前述第2雙極膜與前述陰極界定； 供給水至前述酸回收室之機構； 供給酸性溶液至前述去鹽室之機構；及 供給廢酸至前述廢酸室之機構。 [10]一種廢液處理方法，具有下列工序： 供給陽離子交換體之再生液至填充有前述陽離子交換體之陽離子交換裝置；及 電透析處理由前述陽離子交換裝置排出之再生廢液， 前述電透析處理之工序具有下列工序： 使用電透析裝置，該電透析裝置至少具有陽極、陰極、第1雙極膜、陰離子交換膜、陽離子交換膜及第2雙極膜，在前述陽極與前述陰極之間，由前述陽極之側依序配置前述第1雙極膜、前述陰離子交換膜、前述陽離子交換膜、前述第2雙極膜， 該電透析裝置尚具有： 陽極室，其由前述陽極與前述第1雙極膜界定； 酸回收室，其由前述第1雙極膜與前述陰離子交換膜界定； 去鹽室，其由前述陰離子交換膜與前述陽離子交換膜界定； 廢酸室，其由前述陽離子交換膜與前述第2雙極膜界定；及 陰極室，其由前述第2雙極膜與前述陰極界定， 該電透析裝置進行下列工序： 供給水至前述酸回收室； 供給前述再生廢液至前述去鹽室；及 供給廢酸至前述廢酸室，進行電透析處理。 [發明效果]The present invention includes the following aspects. [1] An electrodialysis device comprising at least an anode, a cathode, a first bipolar membrane, an anion exchange membrane, a cation exchange membrane, and a second bipolar membrane. The first bipolar membrane, the anion exchange membrane, the cation exchange membrane, and the second bipolar membrane are arranged in order from the side of the anode between the anode and the cathode. The electrodialysis device further comprises: an anode chamber defined by the anode and the first bipolar membrane; an acid recovery chamber defined by the first bipolar membrane and the anion exchange membrane; a desalination chamber defined by the anion exchange membrane and the cation exchange membrane; a waste acid chamber defined by the cation exchange membrane and the second bipolar membrane; and a cathode chamber defined by the second bipolar membrane and the cathode. The electrodialysis device supplies water to the acid recovery chamber, supplies an acidic solution to the desalination chamber, and supplies waste acid to the waste acid chamber to perform electrodialysis treatment. [2] The electrodialysis device as described in [1], wherein the waste acid is waste acid discharged from a semiconductor factory. [3] The electrodialysis device as described in [1] or [2], wherein the acidic solution is regenerated waste liquid of a cation exchanger. [4] The electrodialysis device as described in [1] or [2], wherein the waste acid is an aqueous solution of sulfuric acid, and the sulfuric acid concentration of the waste acid is in the range of 1 to 20 mass%.[5] The electrodialysis device as described in [1] or [2], further comprising a pH measuring mechanism for measuring the pH of the waste acid,The pH of the waste acid measured by the pH measuring mechanism is less than 2 during the full electrodialysis period. [6] The electrodialysis apparatus as described in [1] or [2] further comprises:an acidic solution storage tank for storing the acidic solution supplied to the desalination chamber;an acidic solution circulation circuit for returning the treated acidic solution discharged from the desalination chamber to the acidic solution storage tank and circulating the acidic solution;an acidic solution circulation device for circulating the acidic solution in the acidic solution storage tank and the acidic solution circulation circuit;at least one of a current measuring device for measuring the current value between the anode and the cathode during electrodialysis treatment, a conductivity measuring mechanism for measuring the conductivity of the water or the acidic solution, and a pH measuring mechanism for measuring the pH of the water or the acidic solution; and A control device controls the operation of the acidic solution circulation device and receives values measured by at least one of the current measuring device, the conductivity measuring mechanism, and the pH measuring mechanism.During electrodialysis treatment, the control device circulates the acidic solution using the acidic solution circulation device. When at least one value selected from the current slope, current, conductivity, and pH is within a predetermined range, the circulating acidic solution is replaced with the acidic solution outside the circulation system at a predetermined ratio or greater, or the acidic solution is discharged from the circulation system. [7] The electrodialysis device as described in [1] or [2] further comprises: a nanofiltration device which separates the acidic solution into a permeate and a concentrated solution using a nanofiltration membrane; and a pipeline for supplying the permeate to the desalination chamber. [8] An electrodialysis method for treating an acidic solution containing a hardness component, the electrodialysis method using an electrodialysis device, the electrodialysis device having at least an anode, a cathode, a first bipolar membrane, a cationic exchange membrane, a cationic exchange membrane, and a second bipolar membrane, wherein the first bipolar membrane, the cationic exchange membrane, the cationic exchange membrane, and the second bipolar membrane are arranged in order from the side of the anode between the anode and the cathode. The electrodialysis device further comprises: an anode chamber defined by the anode and the first bipolar membrane; An acid recovery chamber defined by the first bipolar membrane and the anion exchange membrane;a desalination chamber defined by the anion exchange membrane and the cation exchange membrane;a waste acid chamber defined by the cation exchange membrane and the second bipolar membrane; anda cathode chamber defined by the second bipolar membrane and the cathode.The electrodialysis method comprises the following steps:supplying water to the acid recovery chamber;supplying the acidic solution to the desalination chamber; andsupplying waste acid to the waste acid chamber for electrodialysis treatment. [9] A waste liquid treatment device comprising:a cation exchange device filled with a cation exchanger;a regeneration liquid storage tank storing a regeneration liquid of the cation exchanger; andan electrodialysis device for treating the regeneration waste liquid discharged from the cation exchange device before being supplied with the regeneration liquid. The electrodialysis device comprises at least an anode, a cathode, a first bipolar membrane, a cationic exchange membrane, a cationic exchange membrane, and a second bipolar membrane. The first bipolar membrane, the cationic exchange membrane, the cationic exchange membrane, and the second bipolar membrane are arranged in this order between the anode and the cathode, starting from the side of the anode.The electrodialysis device further comprises:an anode chamber defined by the anode and the first bipolar membrane;an acid recovery chamber defined by the first bipolar membrane and the cationic exchange membrane;a desalination chamber defined by the cationic exchange membrane and the cationic exchange membrane;A waste acid chamber defined by the cation exchange membrane and the second bipolar membrane; a cathode chamber defined by the second bipolar membrane and the cathode; a mechanism for supplying water to the acid recovery chamber; a mechanism for supplying an acidic solution to the desalination chamber; and a mechanism for supplying waste acid to the waste acid chamber. [10] A waste liquid treatment method comprising the following steps: supplying a regenerated liquid of a cation exchanger to a cation exchange device filled with the cation exchanger; and electrodialysis treatment of the regenerated waste liquid discharged from the cation exchange device. The electrodialysis treatment step comprises the following steps: An electrodialysis device is used, comprising at least an anode, a cathode, a first bipolar membrane, a cationic exchange membrane, a cationic exchange membrane, and a second bipolar membrane. The first bipolar membrane, the cationic exchange membrane, the cationic exchange membrane, and the second bipolar membrane are disposed in this order between the anode and the cathode, starting from the side of the anode.The electrodialysis device further comprises:an anode chamber defined by the anode and the first bipolar membrane;an acid recovery chamber defined by the first bipolar membrane and the cationic exchange membrane;A desalination chamber is defined by the anion exchange membrane and the cation exchange membrane; a waste acid chamber is defined by the cation exchange membrane and the second bipolar membrane; and a cathode chamber is defined by the second bipolar membrane and the cathode.The electrodialysis device performs the following steps:Supplying water to the acid recovery chamber;Supplying the regenerated wastewater to the desalination chamber; andSupplying waste acid to the waste acid chamber for electrodialysis treatment.[Effects of the Invention]
依據本發明可提供一種可防止在離子交換膜面生成水垢，且可在不增加成本之下進行穩定之酸回收的電透析裝置及電透析方法以及廢液處理裝置及廢液處理方法。According to the present invention, an electrodialysis device and an electrodialysis method as well as a waste liquid treatment device and a waste liquid treatment method can be provided, which can prevent scale formation on the ion exchange membrane surface and can perform stable acid recovery without increasing costs.
依據本發明之實施形態，藉由使用具有特定構造之電透析裝置進行酸性溶液之電透析，即使未使用化學品亦可防止水垢之生成，且可抑制成本，並進行穩定之酸回收。 依據本發明實施形態之電透析裝置依序至少具有陽極、陰極、第1雙極膜、陰離子交換膜、陽離子交換膜及第2雙極膜，該電透析裝置尚具有：陽極室，其由前述陽極與前述第1雙極膜界定；酸回收室，其由前述第1雙極膜與前述陰離子交換膜界定；去鹽室，其由前述陰離子交換膜與前述陽離子交換膜界定；廢酸室，其由前述陽離子交換膜與前述第2雙極膜界定；及陰極室，其由前述第2雙極膜與前述陰極界定。在這樣的電透析裝置中，供給水至前述酸回收室，供給酸性溶液至前述去鹽室，供給廢酸至前述廢酸室，以進行電透析處理。 供給至去鹽室之酸性溶液中之Na+等陽離子成分移動至廢酸室中，且Cl-移動至酸回收室，此時H+由雙極膜供給至酸回收室。結果，可由酸回收室回收HCl。 此外，供給至去鹽室之酸性溶液中的Ca2+、Mg2+硬度成分移動至廢酸室，藉由控制廢酸之pH(循環廢酸時廢酸之添加或排出)，即使未添加藥劑亦可防止水垢之產生。 另外，藉由依據在各室處理製得之液體的pH或導電率、電透析裝置之電流值而決定電透析處理之終點的時點，可進行有效之電透析。電透析裝置經過某程度之運轉時間而值穩定下來時，可在該穩定狀態下使電透析結束。 再者，就供給至廢酸室之廢酸而言，係可使用由各種工廠排出之廢酸液，且可有效利用中和處理後放流之廢酸液。例如可使用用於工廠之製造工序等的酸溶液等，具體而言可使用在半導體製造工序之SPM(硫酸-過氧化氫混合物清潔(sulfuric acid-hydrogen peroxide mixture cleaning))沖洗工序、SOM(硫酸及臭氧混合物(sulfuric acid and Ozone Mixture))沖洗工序中產生的廢硫酸等。藉由使用這樣的廢硫酸，不需要準備新的化學品用於電透析裝置之水垢對策，可減少化學品或全體之化學品使用量。According to embodiments of the present invention, by performing electrodialysis of an acidic solution using an electrodialysis device having a specific structure, scale formation can be prevented without using chemicals, while costs can be suppressed and stable acid recovery can be achieved. An electrodialysis device according to an embodiment of the present invention comprises, in order, at least an anode, a cathode, a first bipolar membrane, an anion exchange membrane, a cation exchange membrane, and a second bipolar membrane. The electrodialysis device further comprises: an anode chamber defined by the anode and the first bipolar membrane; an acid recovery chamber defined by the first bipolar membrane and the anion exchange membrane; a desalination chamber defined by the anion exchange membrane and the cation exchange membrane; a waste acid chamber defined by the cation exchange membrane and the second bipolar membrane; and a cathode chamber defined by the second bipolar membrane and the cathode. In such an electrodialysis device, water is supplied to the acid recovery chamber, an acidic solution is supplied to the desalination chamber, and waste acid is supplied to the waste acid chamber for electrodialysis treatment. Cationic components such as Na+ in the acidic solution supplied to the desalination chamber migrate to the waste acid chamber, whileCl- migrates to the acid recovery chamber. At this point, H+ is supplied to the acid recovery chamber via the bipolar membrane. As a result, HCl can be recovered in the acid recovery chamber. Furthermore, hardness components such as Ca2+ and Mg2+ in the acidic solution supplied to the desalination chamber migrate to the waste acid chamber. By controlling the pH of the waste acid (by adding or removing the waste acid during recycling), scale formation can be prevented even without the addition of chemicals. Furthermore, by determining the end point of electrodialysis treatment based on the pH or conductivity of the liquid produced in each chamber and the current flowing through the electrodialysis unit, efficient electrodialysis can be performed. Once the electrodialysis unit has stabilized after a certain period of operation, electrodialysis can be terminated in this stable state. Furthermore, waste acid supplied to the waste acid compartment can be waste acid liquid discharged from various plants, and waste acid liquid discharged after neutralization treatment can be effectively utilized. For example, acid solutions used in factory manufacturing processes can be used. Specifically, waste sulfuric acid generated during SPM (sulfuric acid-hydrogen peroxide cleaning) and SOM (sulfuric acid and ozone mixture) cleaning processes in semiconductor manufacturing can be used. By using this waste sulfuric acid, there's no need to prepare new chemicals for scale reduction in electrodialysis equipment, reducing chemical usage or overall chemical usage.
以下，參照圖式說明本發明之較佳實施形態，但本發明不限於該等實施形態及圖式所示之構成。 圖1顯示依據本發明之一實施形態的一電透析裝置例。在圖1中，電透析裝置100至少具有：陽極1、陰極17、第1雙極膜(以下亦稱為「第1BPM」)3、陰離子交換膜(以下亦稱為「AEM」)5、陽離子交換膜(以下亦稱為「CEM」)7及第2雙極膜9(以下亦稱為「第2BPM」)。在陽極1與陰極17之間，由陽極1之側依序配置第1BPM3、AEM5、CEM7、第2BPM9。該構成具有：陽極室20，其由陽極1與第1BPM3界定；酸回收室22，其由第1BPM3與AEM5界定；去鹽室24，其由AEM5與CEM7界定；廢酸室26，其由CEM7與第2BPM9界定；及陰極室34，其由第2BPM9與陰極17界定。The following describes preferred embodiments of the present invention with reference to the accompanying drawings, but the present invention is not limited to these embodiments and the structures shown in the drawings.Figure 1 shows an example of an electrodialysis device according to one embodiment of the present invention. In Figure 1, the electrodialysis device 100 comprises at least an anode 1, a cathode 17, a first bipolar membrane (hereinafter referred to as "first BPM") 3, an anion exchange membrane (hereinafter referred to as "AEM") 5, a cation exchange membrane (hereinafter referred to as "CEM") 7, and a second bipolar membrane 9 (hereinafter referred to as "second BPM"). Disposed between the anode 1 and the cathode 17 are, in order from the side of the anode 1, the first BPM 3, the AEM 5, the CEM 7, and the second BPM 9. The structure includes: an anode chamber 20, which is bounded by the anode 1 and the first BPM 3; an acid recovery chamber 22, which is bounded by the first BPM 3 and the AEM 5; a desalination chamber 24, which is bounded by the AEM 5 and the CEM 7; a waste acid chamber 26, which is bounded by the CEM 7 and the second BPM 9; and a cathode chamber 34, which is bounded by the second BPM 9 and the cathode 17.
在此，陽極室20係收容陽極1，且隔著第1BPM3設有鄰接陽極室20之酸回收室22。此外，陰極室34係收容陰極17，且隔著第2BPM9設有鄰接陰極室34之廢酸室26。Here, the anode chamber 20 houses the anode 1, and an acid recovery chamber 22 is provided adjacent to the anode chamber 20 via the first BPM 3. Furthermore, the cathode chamber 34 houses the cathode 17, and a waste acid chamber 26 is provided adjacent to the cathode chamber 34 via the second BPM 9.
在上述構成中，陽極室20與酸回收室22由第1BPM3隔開，酸回收室22與去鹽室24由AEM5隔開。此外，去鹽室24與廢酸室26由CEM7隔開，廢酸室26與陰極室34由第2BPM9隔開。即，圖1所示之電透析裝置100係由陽極1側依序配置第1BPM3、AEM5、CEM7、第2BPM9，且以酸回收室22、去鹽室24、廢酸室26之三室作為主構成的三室式電透析裝置。In the above configuration, the anode chamber 20 and the acid recovery chamber 22 are separated by the first BPM 3, and the acid recovery chamber 22 and the desalination chamber 24 are separated by the AEM 5. Furthermore, the desalination chamber 24 and the waste acid chamber 26 are separated by the CEM 7, and the waste acid chamber 26 and the cathode chamber 34 are separated by the second BPM 9. In other words, the electrodialysis device 100 shown in FIG1 is a three-chamber electrodialysis device, with the first BPM 3, AEM 5, CEM 7, and second BPM 9 arranged in this order on the anode 1 side, and the acid recovery chamber 22, desalination chamber 24, and waste acid chamber 26 as the main components.
在此，由陽極1側依序表示構成電透析裝置100之各室時，為陽極-陽極室-(酸回收室-去鹽室-廢酸室)n-陰極室-陰極。在此，以用前述括弧內之「酸回收室-去鹽室-廢酸室」構成之最小重複單位為基本構成(即單元組)，且n(n係1以上之整數)係單元組之重複積層數。此外，圖1係表示n=1之構成，後述之圖2係表示n=2之構成。 單元組之重複積層數通常可設定在n=1至500之範圍，較佳在1至200之範圍。Here, the chambers that make up the electrodialysis device 100 are sequentially represented from the anode 1 side as anode - anode chamber - (acid recovery chamber - desalination chamber - waste acid chamber) n - cathode chamber - cathode. The minimum repeating unit consisting of "acid recovery chamber - desalination chamber - waste acid chamber" within the parentheses is considered the basic configuration (i.e., a cell set), and n (n is an integer greater than 1) represents the number of repeating layers of the cell set. Figure 1 shows a configuration with n = 1, while Figure 2, described later, shows a configuration with n = 2.The number of repeating layers of the cell set can generally be set within the range of n = 1 to 500, preferably within the range of 1 to 200.
由陽極側依序表示構成電透析裝置100之各膜時，為陽極-BPM(AEM-CEM-BPM)n-陰極。在此n(n係1以上之整數)係單元組之重複積層數。此外，圖1係顯示n=1之構成，後述之圖2係顯示n=2之構成。The membranes that make up electrodialysis device 100 are shown in order from the anode side: anode-BPM (AEM-CEM-BPM)n-cathode. Here, n (n is an integer greater than 1) represents the number of repeated layers of the unit. Figure 1 shows a configuration with n=1, while Figure 2, described later, shows a configuration with n=2.
在圖1所示之依據本發明實施形態的電透析裝置100中，供給純水至酸回收室22，供給酸性溶液至去鹽室24，供給廢酸至廢酸室26，進行電透析處理。供給至酸回收室22之純水，通過酸回收室22，被排出作為回收酸液。供給至去鹽室24之酸性溶液，通過去鹽室24，被排出作為去鹽水。供給至廢酸室26之廢酸，通過廢酸室26，被排出作為處理廢酸。供給至酸回收室22之純水，只要是具有所希望的電透析程度之雜質少的高純度水即可，且以具有逆滲透膜處理水以上純度的水為佳。In the electrodialysis apparatus 100 according to an embodiment of the present invention shown in FIG1 , pure water is supplied to the acid recovery chamber 22, an acidic solution is supplied to the desalination chamber 24, and waste acid is supplied to the waste acid chamber 26 for electrodialysis treatment. The pure water supplied to the acid recovery chamber 22 passes through the acid recovery chamber 22 and is discharged as recovered acid solution. The acidic solution supplied to the desalination chamber 24 passes through the desalination chamber 24 and is discharged as desalinated water. The waste acid supplied to the waste acid chamber 26 passes through the waste acid chamber 26 and is discharged as treated waste acid. The pure water supplied to the acid recovery chamber 22 can be any high-purity water with a low impurity content sufficient for the desired electrodialysis level, preferably water having a purity higher than that of water treated by a reverse osmosis membrane.
雙極膜3、9係陽離子交換膜與陰離子交換膜一體形成之膜，通常具有重疊陽離子交換膜與陰離子交換膜之構造。此外，雙極膜係構成為：其陽離子交換膜與陰離子交換膜之重疊界面具有最適合水之解離反應的構造，容易進行水之解離反應。為了達成該目的，一般而言，在重疊不同離子交換膜之界面係導入具有水解離用之觸媒作用的物質(例如重金屬離子、3級胺等)。此外，雙極膜係將陰離子交換膜面側配置在陽極側，將陽離子交換膜面側配置在陰極側。Bipolar membranes 3 and 9 are integrally formed from a cation exchange membrane and an anion exchange membrane, typically having a structure in which the cation exchange membrane and anion exchange membrane are stacked. Furthermore, the bipolar membrane is constructed so that the interface between the overlapping cation exchange membrane and anion exchange membrane is optimally suited for water dissociation, facilitating the water dissociation reaction. To achieve this, a substance that acts as a catalyst for water dissociation (e.g., heavy metal ions, tertiary amines, etc.) is typically introduced at the interface between the stacked ion exchange membranes. In addition, the bipolar membrane is configured with the anion exchange membrane surface side on the anode side and the cation exchange membrane surface side on the cathode side.
此外，雙極膜3、9只要是對於水解離係有效之膜即可，不僅是作成製品販賣者，亦可為重疊陽離子交換膜與陰離子交換膜之構造。Furthermore, the bipolar membranes 3 and 9 may be any membrane effective for hydrolyzing ions, and may be manufactured and sold as products or may be constructed by stacking cation exchange membranes and anion exchange membranes.
用於本發明實施形態之離子交換膜5、7的材質沒有特別限制，可適當使用習知者，只要選擇對鹽之分離有效的膜即可。可舉例如：用聚氯乙烯被覆後加熱、包含苯乙烯及二乙烯苯之糊，然後導入交換基製得之均質膜，或使用例如聚乙烯、聚苯乙烯、酚樹脂、合成橡膠等適當造膜性的結合劑，使離子交換樹脂之粉末成形製得的非均質膜等。The materials used for the ion exchange membranes 5 and 7 in this embodiment of the present invention are not particularly limited; known materials may be used as appropriate, provided that they are effective for salt separation. Examples include homogeneous membranes made by coating with polyvinyl chloride, then heating a paste containing styrene and divinylbenzene, and then introducing an exchange matrix; and heterogeneous membranes made by shaping ion exchange resin powder using a suitable membrane-forming binder such as polyethylene, polystyrene, phenolic resin, or synthetic rubber.
陽極1及陰極17可使用在水電解等電化學工業中使用之電極，且可沒有任何限制地使用這樣的電極。就可用於陽極1及陰極17之電極而言，係可舉例如：鎳電極、鈦製鍍鉑電極及不鏽鋼電極等。 陽極室及陰極室被電極液分別地充滿。就電極液而言，可舉例如：氫氧化鈉溶液、硫酸鈉溶液及純水等。Anode 1 and cathode 17 can be electrodes used in electrochemical industries such as water electrolysis, and such electrodes can be used without limitation. Examples of electrodes that can be used for anode 1 and cathode 17 include nickel electrodes, titanium-plated platinum electrodes, and stainless steel electrodes.The anode chamber and cathode chamber are each filled with an electrode liquid. Examples of the electrode liquid include sodium hydroxide solution, sodium sulfate solution, and pure water.
接著，依據發明實施形態之另一電透析裝置的例子顯示在圖2中。在圖2所示之電透析裝置200中，由陽極1側依序配置：陽極1、陰極17、BPM3(相當於圖1中之第1BPM)、AEM5(相當於圖1中之AEM5)、CEM7(相當於圖1中之CEM7)、BPM11(相當於圖1中之第2BPM9)、AEM13、CEM15、BPM9(相當於圖1中之第2BPM9)。該構成具有：陽極室20，其由陽極1及BPM3界定；酸回收室22，其由BPM3及AEM5界定；去鹽室24，其由AEM5及CEM7界定；廢酸室26，其由CEM7及BPM11界定；酸回收室28，其由BPM11及AEM13界定；去鹽室30，其由AEM13及CEM15界定；廢酸室32，其由CEM15及BPM9界定；及陰極室34，其由BPM9及陰極17界定。此外，在圖2中顯示圖1中之單元組n=2的構成。Next, another example of an electrodialysis device according to an embodiment of the present invention is shown in FIG2 . In the electrodialysis device 200 shown in FIG2 , the following components are arranged in order from the anode 1 side: anode 1, cathode 17, BPM3 (equivalent to the first BPM in FIG1 ), AEM 5 (equivalent to AEM 5 in FIG1 ), CEM 7 (equivalent to CEM 7 in FIG1 ), BPM 11 (equivalent to the second BPM 9 in FIG1 ), AEM 13, CEM 15, and BPM 9 (equivalent to the second BPM 9 in FIG1 ). This configuration includes: an anode chamber 20, which is bounded by anode 1 and BPM3; an acid recovery chamber 22, which is bounded by BPM3 and AEM5; a desalination chamber 24, which is bounded by AEM5 and CEM7; a waste acid chamber 26, which is bounded by CEM7 and BPM11; an acid recovery chamber 28, which is bounded by BPM11 and AEM13; a desalination chamber 30, which is bounded by AEM13 and CEM15; a waste acid chamber 32, which is bounded by CEM15 and BPM9; and a cathode chamber 34, which is bounded by BPM9 and cathode 17. FIG. 2 also shows the configuration of unit group n=2 in FIG. 1.
由純水槽並列地供給純水至各酸回收室(例如，純水槽→酸回收室22→純水槽之循環管線及純水槽→酸回收室28→純水槽之循環管線)。該純水只要是具有所希望的電透析程度之雜質少的高純度水即可，且以具有逆滲透膜處理水以上純度的水為佳。Pure water is supplied in parallel from the pure water tank to each acid recovery chamber (e.g., pure water tank → acid recovery chamber 22 → pure water tank circulation line and pure water tank → acid recovery chamber 28 → pure water tank circulation line). This pure water can be high-purity water with a low impurity content sufficient for electrodialysis, preferably water with a purity higher than that of reverse osmosis membrane-treated water.
並列地供給被處理液、即酸性溶液至各去鹽室(例如，再生廢液貯存槽→去鹽室24→再生廢液貯存槽之循環管線及再生廢液貯存槽→去鹽室30→再生廢液貯存槽之循環管線)。亦可供給陽離子交換體再生廢液作為酸性溶液。例如，在藉由使用鹽酸之陽離子交換體填充塔的再生得到的再生廢液中，包含由離子交換反應產生之NaCl、KCl、CaCl2、MgCl2及HCl等。此外，作為陽離子交換體再生用之酸，並不限於鹽酸，鹽酸以外亦可使用硫酸、硝酸等強酸(無機酸)。The treated liquid, i.e., the acidic solution, is supplied in parallel to each desalination chamber (e.g., the regeneration waste liquid storage tank → desalination chamber 24 → regeneration waste liquid storage tank circulation line and the regeneration waste liquid storage tank → desalination chamber 30 → regeneration waste liquid storage tank circulation line). Cation exchanger regeneration waste liquid can also be supplied as the acidic solution. For example, the regeneration waste liquid obtained by regenerating a cation exchanger packed column using hydrochloric acid contains NaCl, KCl,CaCl₂ ,MgCl₂ , and HCl, which are produced by the ion exchange reaction. Furthermore, the acid used for cation exchanger regeneration is not limited to hydrochloric acid; strong acids (inorganic acids) such as sulfuric acid and nitric acid can also be used in addition to hydrochloric acid.
由廢酸貯存槽並列地供給廢酸至各廢酸室(例如，廢酸貯存槽→廢酸室26→廢酸貯存槽之循環管線及廢酸貯存槽→廢酸室32→廢酸貯存槽之循環管線)。此時，廢酸室中之溶液的pH宜小於2，在1以下更佳。就廢酸而言，例如可使用用於工廠之製造工序等的酸溶液等，具體而言可使用在半導體製造工序之SPM(硫酸-過氧化氫混合物清潔(sulfuric acid-hydrogen peroxide mixture cleaning))沖洗工序、SOM(硫酸及臭氧混合物(sulfuric acid and Ozone Mixture))沖洗工序中產生的廢硫酸等。藉由使用這樣的廢硫酸，不需要為了電透析裝置之水垢對策而準備新的化學品，可減少化學品成本或全體之化學品使用量。 就廢硫酸之硫酸濃度而言，宜在1至20質量%之範圍內，且在1至10質量%之範圍內更佳。藉由硫酸濃度採1質量%以上，可有效地抑制pH之上升，且藉由作成20質量%以下，可防止構件之劣化。 此外，廢酸之硬度宜小於1ppm。該硬度係將鈣與鎂之合計量換算成碳酸鈣量(CaCO3)而得者。 另外，廢酸之供給可為一次，或循環供給。 電透析運轉中，宜在整體運轉期間中調整廢酸濃度，而調整通液量，使廢酸室中之廢酸的pH成為小於2(以≦pH1為佳)。藉由使廢酸室中之廢酸的pH小於2，可避免電透析運轉中生成水垢，可防止膜破損，而穩定地運轉。此外，使廢酸循環時，宜間歇地添加及排出廢酸。因此，除了可使廢酸室中之廢酸的pH小於2以外，亦可將廢酸中累積之雜質(硬度成分等)排出至系統外，而防止過多雜質濃度之上升。Waste acid is supplied in parallel from the waste acid storage tank to each waste acid chamber (e.g., a circulation line from waste acid storage tank → waste acid chamber 26 → waste acid storage tank, and a circulation line from waste acid storage tank → waste acid chamber 32 → waste acid storage tank). The pH of the solution in the waste acid chamber is preferably less than 2, and more preferably below 1. Waste acid can be used, for example, from acid solutions used in factory manufacturing processes. Specifically, waste sulfuric acid generated during the SPM (sulfuric acid-hydrogen peroxide mixture cleaning) and SOM (sulfuric acid and ozone mixture) cleaning processes in semiconductor manufacturing processes can be used. By using such waste sulfuric acid, there is no need to prepare new chemicals for scale countermeasures in electrodialysis equipment, which can reduce chemical costs or the total amount of chemicals used. The sulfuric acid concentration of the waste sulfuric acid is preferably in the range of 1 to 20 mass%, and more preferably in the range of 1 to 10 mass%. By adopting a sulfuric acid concentration of 1 mass% or more, the increase in pH can be effectively suppressed, and by making it 20 mass% or less, the deterioration of components can be prevented. In addition, the hardness of the waste acid is preferably less than 1 ppm. This hardness is obtained by converting the total amount of calcium and magnesium into calcium carbonate (CaCO3 ). In addition, the supply of waste acid can be a single or cyclic supply. During electrodialysis operation, it is advisable to adjust the waste acid concentration and flow rate throughout the entire operation to keep the pH of the waste acid in the waste acid compartment below 2 (preferably ≤ pH 1). By maintaining the pH of the waste acid in the waste acid compartment below 2, scale formation during electrodialysis operation can be avoided, membrane damage can be prevented, and stable operation can be achieved. Furthermore, when circulating the waste acid, it is advisable to intermittently add and remove the waste acid. This not only maintains the pH of the waste acid in the waste acid compartment below 2, but also allows accumulated impurities (such as hardness components) in the waste acid to be discharged outside the system, preventing an excessive increase in impurity concentration.
以下，說明圖1所示之電透析裝置中之電透析實施中的離子移動。此外，雖然顯示鹽酸作為離子交換體再生用之酸的例子，但使用鹽酸以外之酸亦可。The following describes ion migration during electrodialysis in the electrodialysis apparatus shown in FIG1. Although hydrochloric acid is used as the acid for regenerating the ion exchanger, acids other than hydrochloric acid may be used.
在雙極膜(第1及第2BPM3、9)之陽離子交換膜與陰離子交換膜的重疊界面，H2O藉由水解離反應而轉換成H+及OH-。在各電極室中，如圖1所示，被第1BPM3解離而得之OH-供給至陽極室20，被第2BPM9解離而得之H+供給至陰極室34。因此，在陽極室20及陰極室34中使用相同電極液時，例如藉由使電極液在陽極室20與陰極室34之間循環，可使供給之H+及OH-平衡。At the overlapping interface between the cation exchange membrane and the anion exchange membrane of the bipolar membrane (the first and second BPMs 3 and 9),H2O is converted into H+ andOH- through a hydrolysis reaction. In each electrode chamber, as shown in Figure 1, theOH- released by the first BPM 3 is supplied to the anode chamber 20, while the H+ released by the second BPM 9 is supplied to the cathode chamber 34. Therefore, when the same electrode liquid is used in the anode chamber 20 and the cathode chamber 34, for example, by circulating the electrode liquid between the anode chamber 20 and the cathode chamber 34, the supplied H+ andOH- can be balanced.
如圖1所示，在酸回收室22中被供給由陽極側之第1BPM3解離而得之H+，且Cl-由去鹽室24透過AEM5移動過來。結果，H+與Cl-結合而生成鹽酸(HCl)，排出至室外。As shown in Figure 1, H+ dissociated from the first BPM3 on the anode side is supplied to the acid recovery chamber 22, andCl- is transferred from the desalination chamber 24 through the AEM 5. As a result, H+ andCl- combine to form hydrochloric acid (HCl), which is discharged to the outside.
如圖1所示，在去鹽室24中，Cl-透過陽極側之AEM5，移動至酸回收室22，Na+、K+、Ca2+、Mg2+等透過陰極側之CEM7移動至廢酸室26。因此，由酸性溶液生成去鹽水。如此，作為酸性溶液供給之陽離子交換體再生廢液(被處理液)，在電透析後會被排出至室外作為去鹽水。As shown in Figure 1, in the desalination chamber 24,Cl- passes through the anode-side AEM 5 and moves to the acid recovery chamber 22. Na+ , K+ , Ca2+ , Mg2+ , and other elements pass through the cathode-side CEM 7 and move to the waste acid chamber 26. Thus, desalinated water is generated from the acidic solution. In this way, the cation exchanger regeneration wastewater (the treated liquid), which is supplied as the acidic solution, is discharged to the outside as desalinated water after electrodialysis.
如圖1所示，在廢酸室26中Na+、K+、Ca2+、Mg2+等透過陽極側之CEM7，由去鹽室24移動過來，並由陰極側之BPM9供給OH-。如此，供給之廢酸在電透析後，會被排出至室外作為處理廢酸。As shown in Figure 1, in the waste acid chamber 26, Na+ , K+ , Ca2+ , and Mg2+ pass through the CEM7 on the anode side, move from the desalination chamber 24, and are supplied by the BPM9 on the cathode side toOH- . After electrodialysis, the supplied waste acid is discharged outside as treated waste acid.
關於陽極室20及陰極室34，雖然未圖示，但可理想地採用：設置電極液貯存槽，並用泵使電極液在該電極液貯存槽、陽極室20及陰極室34之間循環的方法。電極液可用並列之循環管線(電極液貯存槽→陽極室→電極液貯存槽、電極液貯存槽→陰極室→電極液貯存槽)分別地流至陽極室、陰極室，或用1個循環管線(電極液貯存槽→陽極室→陰極室→電極液貯存槽或電極液貯存槽→陽極室→陰極室→電極液貯存槽)流至陽極室、陰極室。Although not shown in the figure, the anode chamber 20 and the cathode chamber 34 may be provided with an electrode liquid storage tank and a method of circulating the electrode liquid between the electrode liquid storage tank, the anode chamber 20, and the cathode chamber 34 using a pump may be preferably adopted. The electrode liquid can be flowed to the anode chamber and cathode chamber separately using parallel circulation pipelines (electrode liquid storage tank → anode chamber → electrode liquid storage tank, electrode liquid storage tank → cathode chamber → electrode liquid storage tank), or can be flowed to the anode chamber and cathode chamber using one circulation pipeline (electrode liquid storage tank → anode chamber → cathode chamber → electrode liquid storage tank or electrode liquid storage tank → anode chamber → cathode chamber → electrode liquid storage tank).
圖3顯示依據本發明實施形態之一處理離子交換體再生廢液的廢液處理裝置例的概略方塊圖。泵及閥等未圖示。 各液(電解液、酸性溶液(離子交換體再生廢液)、純水、廢酸)對電透析裝置之供給，可透過通至各室(陽極室、酸回收室、去鹽室、廢酸室、陰極室)之各管線(流路)，藉由泵等送液來進行。Figure 3 is a schematic block diagram of an example of a wastewater treatment apparatus for treating ion exchanger regeneration wastewater according to one embodiment of the present invention. Pumps and valves are not shown.The various liquids (electrolyte, acidic solution (ion exchanger regeneration wastewater), pure water, and waste acid) are supplied to the electrodialysis device via pipelines (flow paths) leading to the various chambers (anode chamber, acid recovery chamber, desalination chamber, waste acid chamber, and cathode chamber) using pumps and other means.
在圖3中，在酸液槽(再生液貯存槽)之下游設置填充有陽離子交換體之離子交換體填充塔。用以再生前述陽離子交換體之酸液係貯存在該酸液槽中。In Figure 3, an ion exchanger column filled with cation exchanger is installed downstream of the acid tank (regeneration liquid storage tank). The acid used to regenerate the cation exchanger is stored in the acid tank.
如圖3所示，再生廢液貯存槽係設置在前述陽離子交換體填充塔之下游，通過前述陽離子交換體填充塔，用以再生前述陽離子交換體之酸液係貯存在該再生廢液貯存槽中，作為離子交換體再生廢液。 該陽離子交換體再生廢液，宜係用於半導體工廠之純水製造的陽離子交換體之再生廢液。用於半導體工廠之純水製造的陽離子交換體之再生廢液，其有機成分少，且有機污染風險低，因此可據以進行水垢抑制，而使電透析裝置穩定地運轉。As shown in Figure 3, a regeneration wastewater storage tank is located downstream of the cation exchanger-packed tower. The acid solution used to regenerate the cation exchanger after passing through the cation exchanger-packed tower is stored in the regeneration wastewater storage tank as ion exchanger regeneration wastewater.This cation exchanger regeneration wastewater is preferably cation exchanger regeneration wastewater from pure water production in semiconductor plants. This cation exchanger regeneration wastewater from pure water production in semiconductor plants contains low levels of organic components and has a low risk of organic contamination. Therefore, it can be used to suppress scale and ensure stable operation of the electrodialysis device.
如圖3所示，電透析裝置設置成：連通於再生廢液貯存槽。供給至該電透析裝置之陽離子交換體再生廢液(酸性溶液)，如前述圖1所示，供給至電透析裝置之去鹽室。在電透析裝置之去鹽室處理製得之再生廢液(去鹽水)，再返回再生廢液貯存槽，並被循環處理。 這樣的循環處理可藉由循環裝置進行，該循環裝置由再生廢液貯存槽供給再生廢液(酸性溶液)至電透析裝置之去鹽室，接著由去鹽室返回再生廢液貯存槽，並使其循環。再生廢液之送液可藉由泵進行。該循環裝置可構成為：藉由後述之終點判斷結束電透析時，由再生廢液貯存槽排出循環處理製得之再生廢液(去鹽水)至系統外。就去鹽水之排出目的地而言，例如可合流至既有之排水回收設備或排水處理設備。此外，該循環裝置可構成為：由再生廢液貯存槽排出循環處理製得之再生廢液(去鹽水)後或同時地，供給新的再生廢液至再生廢液貯存槽，進行再生廢液之更換。另外，可構成為：排出循環處理製得之再生廢液的一部份(預定比率以上)，只供給排出部份之新的再生廢液至再生廢液貯存槽。即，可構成為：用新的再生廢液置換循環處理製得之再生廢液的一部份(預定比率以上)。循環處理製得之再生廢液的排出，可藉由設置在連接於再生廢液貯存槽之排出管線之控制閥的開關來控制。新的再生廢液對再生廢液貯存槽之供給，可藉由設置在連接於再生廢液貯存槽之供給管線之控制閥的開關來控制。As shown in Figure 3, the electrodialysis unit is configured to be connected to a regeneration wastewater storage tank. The cation exchanger regeneration wastewater (acidic solution) supplied to the electrodialysis unit is then supplied to the desalination chamber of the electrodialysis unit, as shown in Figure 1. The regeneration wastewater (desalted water) produced by treatment in the desalination chamber of the electrodialysis unit is then returned to the regeneration wastewater storage tank for recirculation.This recirculation process is achieved using a circulation system that supplies regeneration wastewater (acidic solution) from the regeneration wastewater storage tank to the desalination chamber of the electrodialysis unit and then returns it from the desalination chamber to the regeneration wastewater storage tank, where it circulates. The regeneration wastewater is pumped. The circulation device may be configured such that when electrodialysis is terminated by the end point judgment described later, the regenerated waste liquid (desalted water) obtained by the circulation treatment is discharged from the regenerated waste liquid storage tank to the outside of the system. As for the discharge destination of the desalted water, for example, it may be merged with an existing drainage recovery device or drainage treatment device. In addition, the circulation device may be configured such that after or simultaneously with the discharge of the regenerated waste liquid (desalted water) obtained by the circulation treatment from the regenerated waste liquid storage tank, new regenerated waste liquid is supplied to the regenerated waste liquid storage tank to replace the regenerated waste liquid. In addition, the device may be configured such that a portion (above a predetermined ratio) of the regenerated waste liquid obtained by the circulation treatment is discharged and only the new regenerated waste liquid of the discharged portion is supplied to the regenerated waste liquid storage tank. Specifically, the system can be configured to replace a portion (above a predetermined ratio) of the regenerated waste liquid produced by the recycling process with new regenerated waste liquid. The discharge of the regenerated waste liquid produced by the recycling process can be controlled by switching a control valve installed in the discharge line connected to the regenerated waste liquid storage tank. The supply of new regenerated waste liquid to the regenerated waste liquid storage tank can be controlled by switching a control valve installed in the supply line connected to the regenerated waste liquid storage tank.
如圖3所示，純水槽配置成：連通於電透析裝置。純水(只要是雜質少之高純度水即可，且以具有逆滲透膜處理水以上純度的水為佳)貯存在該純水槽中。如前述圖1所示，純水供給至電透析裝置之酸回收室。 電透析裝置通過後之處理製得的純水(回收酸液)，再返回純水槽，並被循環處理。藉由後述之終點判斷結束電透析時，循環處理製得之純水(回收酸液)由純水槽移送至酸液槽，並重新供給純水至純水槽來取代移送之回收酸液。 酸液槽中之酸液，不僅可使用由純水槽移送之回收酸液，亦可視需要由系統外補充酸液而與由純水槽移送之回收酸液混合，並調整濃度來使用，純水槽與酸液槽可共用一個槽。酸液槽中之酸液的酸濃度沒有特別限制，但為了有效地再生離子交換體，宜係1至10質量%，更佳係1至5質量%。As shown in Figure 3, the pure water tank is connected to the electrodialysis unit. Pure water (high-purity water with minimal impurities is acceptable, preferably with a purity higher than that of reverse osmosis membrane-treated water) is stored in the pure water tank. As shown in Figure 1, this pure water is supplied to the acid recovery chamber of the electrodialysis unit.The pure water (recovered acid solution) produced after treatment in the electrodialysis unit is returned to the pure water tank for recirculation. When electrodialysis is terminated, as determined by endpoint determination (described later), the pure water (recovered acid solution) produced by the recirculation process is transferred from the pure water tank to the acid solution tank, where it is then resupplied to replace the transferred recovered acid solution.The acid tank can contain not only recycled acid transferred from the pure water tank, but also acid added from outside the system as needed, mixed with recycled acid transferred from the pure water tank, and adjusted in concentration. The pure water tank and acid tank can share a single tank. There is no specific limit on the acid concentration of the acid tank, but for efficient regeneration of the ion exchanger, it is preferably 1 to 10 mass%, more preferably 1 to 5 mass%.
如圖3所示，廢酸貯存槽配置成：連通於電透析裝置。廢酸(＜pH2，以≦pH1為佳)貯存在廢酸貯存槽中。供給至該電透析裝置之廢酸，如前述圖1所示，供給至電透析裝置之廢酸室。 電透析裝置通過後之處理製得的廢酸(處理廢酸)，再返回廢酸貯存槽，並被循環處理。電透析處理中宜監測：廢酸貯存槽內之液體的pH，並適當進行循環處理製得之廢酸的系統外排出及新的廢酸的添加，使pH成為小於2(以≦pH1為佳)。即，宜用新的廢酸置換循環處理製得之廢酸的一部份。 藉由後述之終點判斷結束電透析時，可將循環處理製得之廢酸(處理廢酸)由廢酸貯存槽排出至系統外，並更換為新的廢酸。就處理廢酸之排出目的地而言，例如可合流至既有之排水處理設備及排水回收設備等。As shown in Figure 3, the waste acid storage tank is connected to the electrodialysis unit. Waste acid (pH < 2, preferably ≤ pH 1) is stored in the waste acid storage tank. Waste acid supplied to the electrodialysis unit is supplied to the waste acid chamber of the electrodialysis unit, as shown in Figure 1.The waste acid produced after treatment in the electrodialysis unit (processed waste acid) is returned to the waste acid storage tank for recirculation. During electrodialysis treatment, the pH of the liquid in the waste acid storage tank should be monitored. Waste acid produced during recirculation should be discharged from the system and fresh waste acid should be added as appropriate to maintain the pH below 2 (preferably ≤ pH 1). Specifically, it is desirable to replace a portion of the waste acid produced by the recycling process with new waste acid.When electrodialysis is terminated through endpoint determination (described later), the waste acid produced by the recycling process (process waste acid) can be discharged from the waste acid storage tank to the outside of the system and replaced with new waste acid. The waste acid can be discharged to, for example, existing wastewater treatment and recovery facilities.
循環時之各液量可非同量，可依據由酸回收室得到之回收酸液的需要濃度設定任意之水量。例如，相較於使純水及再生廢液同量地循環之情形，如果使純水之循環水量比再生廢液之循環水量減少，可得到濃度高之回收酸液(相反地，如果使純水之循環水量比再生廢液之循環水量增加，可得到濃度低之回收酸液)。但是，減少廢酸之液量時招致硬度成分Ca2+、Mg2+之濃縮，因此需要注意。The volumes of each liquid during circulation can vary; any desired volume can be set based on the desired concentration of the recovered acid solution obtained from the acid recovery chamber. For example, compared to circulating equal volumes of pure water and regenerated wastewater, reducing the pure water volume relative to the regenerated wastewater volume will yield a higher-concentration recovered acid solution. (Conversely, increasing the pure water volume relative to the regenerated wastewater volume will yield a lower-concentration recovered acid solution.) However, reducing the waste acid volume will result in a concentration increase in the hardness components Ca2+ and Mg2+ , so this should be considered.
電透析裝置之運轉，可為每次離子交換體之再生處理的間歇運轉，亦可例如圖3地設置再生廢液貯存槽，且連續運轉。連續運轉時，再生廢液之電透析處理終點的時點(處理製得之再生廢液開始排出)可與下一個陽離子交換體之再生的時點(新的再生廢液開始供給)重疊。相較於間歇運轉時，連續運轉可使電透析裝置小型化，使再生廢液之供給流量減少並調整時點。因此，可期望電透析裝置之小型化、起動時間之縮短及處理水水質之穩定等。Electrodialysis equipment can be operated intermittently, with each ion exchanger regenerated, or continuously, with a regenerated wastewater storage tank installed, as shown in Figure 3. During continuous operation, the end of the electrodialysis treatment of the regenerated wastewater (when the resulting regenerated wastewater begins to be discharged) can overlap with the regeneration of the next cation exchanger (when new regenerated wastewater begins to be supplied). Compared to intermittent operation, continuous operation allows for smaller electrodialysis equipment, a reduced regenerated wastewater supply flow rate, and the ability to adjust the timing. Consequently, it is expected that electrodialysis equipment will be smaller, startup time will be shortened, and treated water quality will be more stable.
電透析處理終點之時點的決定方法，可舉例如：只運轉預先設定之時間的方法、觀察在陽極與陰極間流動之電流值變化來決定的方法、及觀察供給至酸回收室之純水或在去鹽室處理製得之再生廢液(去鹽水)的導電率變化來決定的方法(可能在使純水或再生廢液循環時)、觀察在酸回收室處理製得之純水(回收酸液)、在去鹽室處理製得之再生廢液(去鹽水)或在廢酸室處理製得之廢酸(處理廢酸)的pH變化來決定的方法(可能在各個溶液循環時)。Methods for determining the end point of electrodialysis treatment include, for example, a method of operating only for a preset time, a method of determining by observing changes in the current flowing between the anode and cathode, a method of determining by observing changes in the conductivity of pure water supplied to the acid recovery chamber or regenerated waste liquid (desalted water) produced by treatment in the desalination chamber (possibly when the pure water or regenerated waste liquid is circulated), and a method of determining by observing changes in the pH of pure water (recovered acid liquid) produced by treatment in the acid recovery chamber, regenerated waste liquid (desalted water) produced by treatment in the desalination chamber, or waste acid (treated waste acid) produced by treatment in the waste acid chamber (possibly when each solution is circulated).
只運轉預先設定之時間時，可設定成：與離子交換體之再生時點為同時等任意之時間。When running only for a preset time, you can set it to any time, such as the time when the ion exchanger is regenerated.
在觀察電流值變化來決定之方法中，可與電透析裝置及電源裝置串列地連接電流測量裝置，並且每個預定周期發送電流值至控制裝置。電流值在開始電透析時漸漸地上升後，由某時點轉變成下降，然後穩定在比較低之值。在該電流值穩定在比較低之狀態時，即電流值在預定範圍內只繼續預定時間時，使電透析結束。是否在預定範圍內只繼續預定時間，可例如用電流值變化之斜率是否在預定範圍來判斷。In the method of determining the time by observing changes in current values, a current measuring device can be connected in series with the electrodialysis device and power supply device, and the current value can be transmitted to the control device at every predetermined period. The current value gradually rises at the beginning of electrodialysis, then at some point begins to decrease and then stabilizes at a relatively low value. Electrodialysis is terminated when the current value stabilizes at a relatively low level, that is, when the current value remains within a predetermined range for a predetermined time. Whether the current value remains within the predetermined range for a predetermined time can be determined, for example, by determining whether the slope of the current value change is within a predetermined range.
在觀察導電率之變化來決定的方法中，可在各室之出口、再生廢液貯存槽內或純水槽內設置導電率計(導電率測量機構)，每個預定周期發送值至控制裝置。導電率到達預定值(範圍)時，或變化之斜率在預定範圍時，使電透析結束。例如導電率變化之斜率，係純水槽之純水因為如前述地生成鹽酸之影響，所以導電率逐漸地上升，且經過某程度之時間後穩定在高值。此外，再生廢液貯存槽之陽離子交換體再生廢液，因為離子類如前述地移動至鄰接去鹽室之室的影響，所以導電率逐漸地下降，且經過某程度之時間後穩定在低值。In the method of determining the status by observing changes in conductivity, a conductivity meter (conductivity measuring device) can be installed at the outlet of each chamber, in the regeneration wastewater storage tank, or in the pure water tank. The meter transmits values to the control device at predetermined intervals. Electrodialysis is terminated when the conductivity reaches a predetermined value (range), or when the slope of the change is within a predetermined range. For example, the slope of the conductivity change is due to the effect of hydrochloric acid generated in the pure water tank as described above, causing the conductivity to gradually increase and then stabilize at a high value after a certain period of time. In addition, the conductivity of the cation exchanger regeneration wastewater in the regeneration wastewater storage tank gradually decreases due to the influence of ions moving to the adjacent desalination chamber as mentioned above, and after a certain period of time, it stabilizes at a low value.
在觀察pH之變化來決定的方法中，可在各室之出口、再生廢液貯存槽內、純水槽內或廢酸貯存槽內設置pH計(pH測量機構)，每個預定周期發送值至控制裝置。pH達到預定值(範圍)時，或變化之斜率在預定範圍時，使電透析結束。例如pH變化之斜率係純水槽之純水因為如前述地生成鹽酸之影響，所以pH由中性附近逐漸地下降，且經過某程度之時間後穩定在低值。此外，再生廢液貯存槽之陽離子交換體再生廢液，因為離子類如前述地移動至鄰接去鹽室之室的影響，所以pH由酸性側逐漸地上升，且經過某程度之時間時，由初始值穩定在中性側。廢酸貯存槽內之廢酸，因為離子類如前述地由鄰接之去鹽室移動過來，且由雙極膜供給OH-的影響，所以pH由酸性側逐漸地上升。In methods that determine the pH by observing changes in pH, a pH meter (pH measurement device) can be installed at the outlet of each chamber, in the regeneration wastewater storage tank, in the pure water tank, or in the waste acid storage tank. The pH value is transmitted to the control device at predetermined intervals. Electrodialysis terminates when the pH reaches a predetermined value (range), or when the slope of the change falls within a predetermined range. For example, the slope of the pH change in the pure water tank, due to the generation of hydrochloric acid as described above, causes the pH to gradually decrease from near neutral and stabilize at a low value after a certain period of time. Furthermore, the pH of the regenerated wastewater from the cation exchanger in the regenerated wastewater storage tank gradually increases from the acidic side due to the influence of ions migrating to the adjacent desalination chamber as described above, and after a certain period of time, it stabilizes at the neutral side from the initial value. The pH of the waste acid in the waste acid storage tank gradually increases from the acidic side due to the influence of ions migrating from the adjacent desalination chamber as described above and the supply ofOH- by the bipolar membrane.
圖4係顯示依據本發明實施形態之另一處理離子交換體再生廢液之廢液處理裝置例的概略方塊圖。泵及閥等未圖示。 圖4所示之裝置成為在圖3所示之裝置的陽離子交換體填充塔與再生廢液貯存槽之間配置奈米過濾膜(NF)的構成。藉由該構成，供給透過NF之陽離子交換體再生廢液至再生廢液貯存槽。Figure 4 is a schematic block diagram of another example of a wastewater treatment system for treating ion exchanger regeneration wastewater according to an embodiment of the present invention. Pumps, valves, and other components are not shown.The system shown in Figure 4 incorporates a nanofiltration membrane (NF) between the cation exchanger-packed column and the regeneration wastewater storage tank of the system shown in Figure 3. This system supplies cation exchanger regeneration wastewater that has passed through the NF to the regeneration wastewater storage tank.
NF未使Ca2+或Mg2+之類的2價離子透過，且使Cl-及Na+等1價離子透過。因此，在下游之電透析裝置中，得到防止硬度成分累積或在膜面產生水垢之進一步效果。NF does not allow divalent ions such as Ca2+ and Mg2+ to pass through, but allows monovalent ions such asCl- and Na+ to pass through. This further prevents the accumulation of hardness components and the formation of scale on the membrane surface in downstream electrodialysis equipment.
圖5係顯示依據本發明實施形態之又一處理離子交換體再生廢液之廢液處理裝置例的概略方塊圖。泵及閥等未圖示。 在圖5所示之裝置中，相較於圖3之構成，未使由電透析裝置排出之去鹽水(處理製得之再生廢液)循環至再生廢液貯存槽，而是原樣地排出至系統外。此外，相較於圖3之構成，未使由電透析裝置排出之回收酸液循環至純水槽，而是原樣地移送至酸液槽。另外，相較於圖3之構成，未使由電透析裝置排出之處理廢酸循環至廢酸貯存槽，而是原樣地排出至系統外。Figure 5 is a schematic block diagram of another example of a wastewater treatment system for treating ion exchanger regeneration wastewater according to an embodiment of the present invention. Pumps, valves, and other components are not shown.In the system shown in Figure 5, compared to the configuration of Figure 3, the desalinated water (regeneration wastewater produced by treatment) discharged from the electrodialysis unit is not circulated to the regeneration wastewater storage tank but is discharged directly outside the system. Furthermore, compared to the configuration of Figure 3, the recovered acid discharged from the electrodialysis unit is not circulated to the pure water tank but is transferred directly to the acid tank. Furthermore, compared to the configuration of Figure 3, the treated waste acid discharged from the electrodialysis unit is not circulated to the waste acid storage tank but is discharged directly outside the system.
藉由圖5之裝置構成，不需要在電透析終點更換各槽之溶液，而是每離子交換體之再生處理被供給再生廢液，且純水及廢酸分別地供給與各液之排出量同量至電透析運轉中之電透析裝置。此外，廢酸(＜pH2，以≦pH1為佳)不需要監測pH，因此可簡化操作。另外，藉由使各溶液之供給流速與排出流速相同，純水槽及廢酸貯存槽之各槽不一定需要設置。The apparatus shown in Figure 5 eliminates the need to replace the solutions in each tank at the end of electrodialysis. Instead, the regenerated wastewater is supplied to each ion exchanger after regeneration, while pure water and waste acid are supplied to the electrodialysis unit in quantities equal to the discharge volume of each solution. Furthermore, pH monitoring of the waste acid (<pH 2, preferably ≤pH 1) is not required, simplifying operation. Furthermore, by aligning the supply and discharge flow rates of each solution, separate pure water and waste acid storage tanks are no longer necessary.
此外，亦可為如圖3地作成圖5所示之構成的一部份，例如使由電透析裝置排出回收酸液(處理後之純水)及去鹽水(處理製得之再生廢液)循環，且未使處理廢酸循環地原樣排出之類的構成。為了得到電透析裝置之小型化或穩定之處理水質，宜使回收酸液(處理後之純水)及去鹽水(處理製得之再生廢液)循環。Alternatively, a portion of the configuration shown in FIG5 may be constructed as shown in FIG3 , for example, by circulating the recovered acid solution (pure water after treatment) and desalinated water (regenerated wastewater produced by treatment) discharged from the electrodialysis device, while the treated waste acid is discharged as is without being circulated. In order to achieve miniaturization of the electrodialysis device or stable treated water quality, it is desirable to circulate the recovered acid solution (pure water after treatment) and desalinated water (regenerated wastewater produced by treatment).
未使去鹽水(處理製得之再生廢液)循環地原樣排出時之電透析裝置的運轉方法，可與使去鹽水(處理製得之再生廢液)循環時同樣地為每離子交換體之再生處理的間歇運轉，亦可為連續運轉。連續運轉時，電透析處理之終點的時點可與離子交換體之再生的時點(再生廢液開始供給)重疊。相較於間歇運轉時，連續運轉可使電透析裝置小型化，使再生廢液之供給流速減少並調整時點。因此，可期望電透析裝置之小型化、起動時間之縮短及處理水水質之穩定等。When desalinated water (regenerated wastewater produced by treatment) is discharged as is without circulation, the electrodialysis device can be operated intermittently, regenerating each ion exchanger, similar to the desalinated water (regenerated wastewater produced by treatment) circulation method, or it can be operated continuously. In continuous operation, the end of electrodialysis treatment can overlap with the time of ion exchanger regeneration (the start of regenerated wastewater supply). Compared to intermittent operation, continuous operation allows for smaller electrodialysis devices, a reduced regenerated wastewater supply flow rate, and adjusted timing. Consequently, it is expected that the electrodialysis device will be smaller, startup time will be shortened, and treated water quality will be more stable.
變更圖5所示之構成，作成未使回收酸液(處理後之純水)循環地原樣排出之構成時電透析處理之終點的時點成為無再生廢液的時點。 變更圖5所示之構成，作成使回收酸液(處理後之純水)循環至純水槽之構成時電透析處理之終點的時點除了成為無再生廢液的時點以外，亦可用上述純水槽之導電率或pH、運轉時間、電流值來判斷。If the configuration shown in Figure 5 is modified so that the recovered acid solution (treated pure water) is discharged as is without circulation, the end point of electrodialysis treatment becomes the point at which no regenerated wastewater is produced.If the configuration shown in Figure 5 is modified so that the recovered acid solution (treated pure water) is circulated to the pure water tank, the end point of electrodialysis treatment can be determined not only by the point at which no regenerated wastewater is produced but also by the conductivity or pH of the pure water tank, the operating time, or the current value.
變更圖5所示之構成，作成使去鹽水(處理製得之再生廢液)循環且未使回收酸液(處理後之純水)循環地原樣排出之構成時電透析處理之終點的時點可用上述廢酸貯存槽之導電率或pH、運轉時間、電流值來判斷。If the configuration shown in Figure 5 is modified to circulate desalinated water (regenerated wastewater produced by treatment) and to discharge the recovered acid solution (pure water after treatment) as is, the end point of the electrodialysis treatment can be determined by the conductivity or pH of the waste acid storage tank, the operating time, and the current value.
在來自純水製造及半導體製造等之酸性廢液等的水處理中，藉由使用具有依據本發明實施形態之電透析裝置的廢液回收裝置，即使未添加用以防止水垢之化學品，亦可避免在離子交換膜面生成水垢，且可在不增加成本之下，進行利用電透析裝置所致之穩定酸回收。此外，因為可避免在離子交換膜面生成水垢，所以可防止電透析裝置之膜破損，可穩定地運轉且有效率地運轉。 [實施例]In the treatment of acidic wastewater from pure water production and semiconductor manufacturing, for example, a wastewater recovery system using an electrodialysis device according to an embodiment of the present invention can prevent scale formation on the ion exchange membrane surface, even without the addition of anti-scaling chemicals. This allows for stable acid recovery using the electrodialysis device without increasing costs. Furthermore, by preventing scale formation on the ion exchange membrane surface, membrane damage in the electrodialysis device is prevented, enabling stable and efficient operation.[Examples]
以下，顯示實施例進一步說明本發明，但本發明不限於以下實施例。The present invention is further described below with reference to the following embodiments, but the present invention is not limited to the following embodiments.
(實施例1) 在本實施例中，依據使用圖2所示之電透析裝置的本發明實施形態，在以下條件下實施電透析處理。此外，設置對各室之供給液的貯存槽並進行循環處理。 (實驗條件) 實驗裝置：ASTOM公司製之雙極膜電透析裝置(製品名：Acilyzer EX3B) 供給液之水質：記載於表1中 對去鹽室之供給液：純水製造用陽離子交換體填充塔之再生液 對廢酸室之供給液：大約8質量%硫酸 對酸回收室之供給液：純水(逆滲透膜處理水) 電極液：4質量%NaOH 水溫：20至25℃(常溫) 對去鹽室之供給液量及循環流量：850ml、1.4L/min 對廢酸室之供給液量及循環流量：850ml、1.4L/min 對酸回收室之供給液量及循環流量：850ml、1.4L/min 電壓值：10V(一定) pH之測量係用TOA DKK公司(股)製之可攜式pH計(製品名：HM-40P)(玻璃電極法)測量在各供給液之槽內的pH。 導電率之測量係用TOA DKK公司(股)製之導電率計(製品名：AOL-10)測量在各供給液之槽內的導電率。 液中之離子類的測量係用Thermo Fisher Scientific公司(股)製之離子層析儀(製品名：Dionex Integrion)(離子層析法)測量。(Example 1)In this example, electrodialysis treatment was performed under the following conditions using the electrodialysis apparatus shown in Figure 2 according to the embodiment of the present invention. Furthermore, a storage tank for the feed fluid to each chamber was provided, and circulation was performed.(Experimental Conditions)Experimental Apparatus: Bipolar Membrane Electrodialysis Unit (Acilyzer EX3B) manufactured by ASTOMFeed Liquid Quality: As shown in Table 1Feed Liquid to the Desalination Chamber: Regeneration Fluid from a Cation Exchanger Tower for Purified Water ProductionFeed Liquid to the Spent Acid Chamber: Approximately 8% by Mass Sulfuric AcidFeed Liquid to the Acid Recovery Chamber: Pure Water (Reverse Osmosis Membrane Treatment Water)Electrode Liquid: 4% by Mass NaOHWater Temperature: 20 to 25°C (Room Temperature)Feed Liquid Volume and Circulation Flow Rate to the Desalination Chamber: 850 ml, 1.4 L/minFeed Liquid Volume and Circulation Flow Rate to the Spent Acid Chamber: 850 ml, 1.4 L/minFeed volume and circulation flow rate to the acid recovery chamber: 850 ml, 1.4 L/minVoltage: 10 V (constant)pH was measured in each feed tank using a TOA DKK portable pH meter (product name: HM-40P) (glass electrode method).Conductivity was measured in each feed tank using a TOA DKK conductivity meter (product name: AOL-10).Ions in the solution were measured using a Thermo Fisher Scientific ion chromatography instrument (product name: Dionex Integrion) (ion chromatography method).
(實驗結果) 供給至去鹽室處理製得之再生廢液(去鹽水)及供給至酸回收室處理製得之純水(回收酸液)的導電率及pH之轉變(隨著運轉時間經過之值的變化)顯示在圖6中，且電透析裝置之電流值之轉變(隨著運轉時間經過之值的變化)顯示在圖7中。各供給液之水質的轉變顯示在表1中。 如表1所示，可確認藉由電透析，去鹽室中之Na+等陽離子成分移動至廢酸室中，且Cl-移動至酸回收室。此外，可確認由電透析開始經過120分後，去鹽室中之幾乎所有Cl-移動至酸回收室，且可由酸回收室回收HCl(回收酸液)。(Experimental Results) The conductivity and pH changes (value changes over time) of the regenerated wastewater (desalinated water) supplied to the desalination chamber and the pure water (recovered acid solution) supplied to the acid recovery chamber are shown in Figure 6, and the current value of the electrodialysis device (value changes over time) is shown in Figure 7. The changes in the water quality of each feed liquid are shown in Table 1. As shown in Table 1, it can be confirmed that through electrodialysis, cationic components such as Na+ in the desalination chamber are transferred to the waste acid chamber, andCl- is transferred to the acid recovery chamber. In addition, it can be confirmed that after 120 minutes from the start of electrodialysis, almost all of theCl- in the desalination chamber has moved to the acid recovery chamber, and HCl (recovered acid solution) can be recovered in the acid recovery chamber.
此外，藉由上述圖2所示之裝置中的離子移動(表1)，如圖6所示，就在酸回收室處理製得之純水(回收酸液)而言，其導電率上升，在大約90分穩定在高值，pH由中性附近開始經過40分後成為pH＜1。另外，就在去鹽室處理製得之再生廢液(去鹽水)而言，其導電率降低，在大約90分穩定在低值，且pH由1附近開始在大約100分穩定在pH3.5附近。Furthermore, as shown in Figure 6, the ion migration (Table 1) in the apparatus shown in Figure 2 above shows that the conductivity of the pure water (recovered acid solution) produced by treatment in the acid recovery chamber increased, stabilizing at a high value at approximately 90 minutes, and the pH decreased from near neutral to pH <1 after 40 minutes. Furthermore, the conductivity of the regenerated wastewater (desalinated water) produced by treatment in the desalination chamber decreased, stabilizing at a low value at approximately 90 minutes, and the pH decreased from near 1 to near pH 3.5 after approximately 100 minutes.
如圖7所示，在電透析裝置之陽極與陰極間流動之電流值，在開始電透析時由10分附近大幅上升後，由30分附近轉變成下降，然後在110分附近穩定在低值。As shown in Figure 7, the current flowing between the anode and cathode of the electrodialysis device rises sharply around 10 minutes at the start of electrodialysis, then begins to decline around 30 minutes, and then stabilizes at a low value around 110 minutes.
如上所述，在本實施例中，在由開始電透析經過大約110分之時點，去鹽室及酸回收室內之液體的導電率分別地呈穩定的狀態，且在電透析裝置之陽極與陰極間流動之電流值亦穩定在低值。 此外，電透析中未觀察到因水垢生成所致之電流值降低，即使電透析後目視觀察離子交換膜面，亦不能目視到水垢物質。 由以上，可知，依據本發明可防止水垢之生成，可在不增加成本之下，由再生廢液穩定地進行酸回收。As described above, in this embodiment, approximately 110 minutes after the start of electrodialysis, the conductivity of the liquid in the desalination chamber and the acid recovery chamber was stable, and the current flowing between the anode and cathode of the electrodialysis device also remained stable at a low value.Furthermore, no decrease in current due to scale formation was observed during electrodialysis, and even after visual inspection of the ion exchange membrane surface after electrodialysis, no scale was visible.From the above, it can be seen that the present invention can prevent scale formation and enable stable acid recovery from regenerated wastewater without increasing costs.
[表1] (表1)供給液之水質及水質之轉變
(參考例1) 除了供給調整成pH3之硫酸作為對廢酸室之供給液以外，與實施例1同樣地進行電透析。 確認電流值相較於實施例1降低(電流值之尖峰小於2A且整體低地轉變並最終在大約80分成為大約0A)。此外，確認處理水質之惡化(由電透析開始經過120分後酸回收室之Cl-濃度係4000mg/L)。另外，由電透析開始經過120分後確認電透析裝置之內部時，在陽離子交換膜面確認白色之水垢。這考慮係Ca(OH)2及Mg(OH)2等成分析出。(Reference Example 1) Electrodialysis was performed in the same manner as in Example 1, except that sulfuric acid adjusted to pH 3 was supplied as the feed liquid to the waste acid chamber. A decrease in the current value compared to Example 1 was confirmed (the current value peaked at less than 2 A and generally decreased, ultimately reaching approximately 0 A at approximately 80 minutes). Furthermore, deterioration in the treated water quality was confirmed (theCl- concentration in the acid recovery chamber was 4000 mg/L 120 minutes after the start of electrodialysis). Furthermore, when the interior of the electrodialysis device was inspected 120 minutes after the start of electrodialysis, white scale was observed on the cation exchange membrane surface. This is believed to be due to the precipitation of components such as Ca(OH)2 and Mg(OH)2 .
1:陽極 3:第1雙極膜;第1BPM;BPM 5,13:陰離子交換膜(AEM) 7,15:陽離子交換膜(CEM) 9:第2雙極膜;第2BPM;BPM 11:BPM 17:陰極 20:陽極室 22,28:酸回收室 24,30:去鹽室 26,32:廢酸室 34:陰極室 100,200:電透析裝置1: Anode3: 1st bipolar membrane; 1st BPM; BPM5, 13: Anion exchange membrane (AEM)7, 15: Cation exchange membrane (CEM)9: 2nd bipolar membrane; 2nd BPM; BPM11: BPM17: Cathode20: Anode chamber22, 28: Acid recovery chamber24, 30: Desalination chamber26, 32: Waste acid chamber34: Cathode chamber100, 200: Electrodialysis unit
[圖1]係顯示依據本發明實施形態之一電透析裝置例的概略構成圖。 [圖2]係顯示依據本發明實施形態之另一電透析裝置例的概略構成圖。 [圖3]係顯示依據本發明實施形態之一處理離子交換體再生廢液之廢液處理裝置例的概略方塊圖。 [圖4]係顯示依據本發明實施形態之另一處理離子交換體再生廢液之廢液處理裝置例的概略方塊圖。 [圖5]係顯示依據本發明實施形態之又一處理離子交換體再生廢液之廢液處理裝置例的概略方塊圖。 [圖6]係顯示使用圖2所示之電透析裝置之實施例的廢液處理中之導電率及pH值與運轉時間的關係的圖。 [圖7]係顯示使用圖2所示之電透析裝置之實施例的廢液處理中之電流值與運轉時間的關係的圖。[Figure 1] is a schematic diagram showing the configuration of an electrodialysis apparatus according to one embodiment of the present invention.[Figure 2] is a schematic diagram showing the configuration of another electrodialysis apparatus according to another embodiment of the present invention.[Figure 3] is a schematic block diagram showing an example of a wastewater treatment apparatus for treating ion-exchange medium regeneration wastewater according to one embodiment of the present invention.[Figure 4] is a schematic block diagram showing another example of a wastewater treatment apparatus for treating ion-exchange medium regeneration wastewater according to another embodiment of the present invention.[Figure 5] is a schematic block diagram showing yet another example of a wastewater treatment apparatus for treating ion-exchange medium regeneration wastewater according to another embodiment of the present invention. Figure 6 shows the relationship between conductivity and pH value and operating time during wastewater treatment using the embodiment of the electrodialysis apparatus shown in Figure 2.Figure 7 shows the relationship between current value and operating time during wastewater treatment using the embodiment of the electrodialysis apparatus shown in Figure 2.
1:陽極1: Anode
3:第1雙極膜；第1BPM；BPM3: 1st bipolar membrane; 1st BPM; BPM
5:陰離子交換膜(AEM)5: Anion Exchange Membrane (AEM)
7:陽離子交換膜(CEM)7: Cation Exchange Membrane (CEM)
9:第2雙極膜；第2BPM；BPM9: 2nd Bipolar Membrane; 2nd BPM; BPM
17:陰極17: Cathode
20:陽極室20: Anode Chamber
22:酸回收室22: Acid Recovery Room
24:去鹽室24: Desalination Room
26:廢酸室26: Waste Acid Room
34:陰極室34:Cathode chamber
100:電透析裝置100:Electrodialysis device
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2023-194572 | 2023-11-15 |
| Publication Number | Publication Date |
|---|---|
| TW202532352Atrue TW202532352A (en) | 2025-08-16 |
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