TWI727046B - Water treatment method and apparatus, and method of regenerating ion exchange resin - Google Patents

Water treatment method and apparatus, and method of regenerating ion exchange resin Download PDF

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TWI727046B
TWI727046B TW106116221A TW106116221A TWI727046B TW I727046 B TWI727046 B TW I727046B TW 106116221 A TW106116221 A TW 106116221A TW 106116221 A TW106116221 A TW 106116221A TW I727046 B TWI727046 B TW I727046B
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water
membrane
ion exchange
reverse osmosis
exchange resin
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TW106116221A
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TW201806875A (en
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中野徹
大江太郎
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日商奧璐佳瑙股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis, ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02Reverse osmosis; Hyperfiltration ; Nanofiltration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis, ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58Multistep processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04Processes using organic exchangers
    • B01J39/05Processes using organic exchangers in the strongly acidic form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • B01J49/53Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for cationic exchangers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/75Regeneration or reactivation of ion-exchangers; Apparatus therefor of water softeners
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis

Abstract

In a water treatment method that uses an ion exchange resin and a reverse osmosis membrane, the ion exchange resin can be regenerated more easily and at lower cost, even when the water being treated contains SO4 2- or CO3 2- . The invention provides a water treatment method including: a softening step of softening a water to be treated, containing SO4 2- and/or CO3 2- , a hardness component, and Na+ and Cl- , using an ion exchange resin; a nanofiltration step of separating the water softened in the softening step into a nanofiltration membrane permeate and concentrate using a nanofiltration membrane; a reverse osmosis step of separating the permeate from the nanofiltration membrane into a reverse osmosis membrane permeate and concentrate using a reverse osmosis membrane; and an ion exchange resin regeneration step of regenerating the ion exchange resin using the concentrate from the reverse osmosis membrane. Also provided is a water treatment apparatus suitable for carrying out this method. The invention also provides a method of regenerating an ion exchange resin containing the above softening step, the above nanofiltration step, the above reverse osmosis step, and a step of regenerating the ion exchange resin using the concentrate from the reverse osmosis membrane.

Description

水處理方法、水處理裝置及離子交換樹脂之再生方法Water treatment method, water treatment device and regeneration method of ion exchange resin

本發明關於適於處理例如電子產業之排水的水處理方法及裝置。又,本發明關於離子交換樹脂之再生方法。The present invention relates to a water treatment method and device suitable for treating, for example, drainage from the electronics industry. Furthermore, the present invention relates to a regeneration method of ion exchange resin.

已知有使用離子交換樹脂與逆滲透膜的水處理方法。專利文獻1揭示使伸銅工業、鍍敷工業、鋼鐵工業或食品工業等之含有游離酸的排水通過離子交換樹脂後,以逆滲透壓法予以分離成濃縮液與膜透過液。A water treatment method using ion exchange resin and reverse osmosis membrane is known. Patent Document 1 discloses that waste water containing free acid in the copper drawing industry, the plating industry, the steel industry, or the food industry is passed through an ion exchange resin and then separated into a concentrated liquid and a membrane permeate by a reverse osmotic pressure method.

又,專利文獻2揭示能減低水之消耗量的蒸氣工廠及其操作方法。該文獻記載使經具備樹脂的軟化容器軟化的水通過具備半透膜的逆滲透裝置,將逆滲透裝置之滲透水供給到鍋爐(boiler),並將逆滲透裝置之濃縮液使用於軟化容器之再生。 [先前技術文獻] [專利文獻]In addition, Patent Document 2 discloses a steam plant and its operation method that can reduce water consumption. This document states that the water softened by a softening vessel equipped with resin is passed through a reverse osmosis device equipped with a semipermeable membrane, the permeated water of the reverse osmosis device is supplied to a boiler, and the concentrated liquid of the reverse osmosis device is used in the softening vessel. regeneration. [Prior Technical Document] [Patent Document]

[專利文獻1] 日本特開昭50-105546號公報 [專利文獻2] 日本特開2013-212504號公報[Patent Document 1] Japanese Patent Laid-Open No. 50-105546 [Patent Document 2] Japanese Patent Laid-Open No. 2013-212504

[發明所欲解決之課題] 依專利文獻2記載之技術,藉由將逆滲透裝置之濃縮液使用於軟化容器(樹脂)之再生,可減少通常用以洗滌軟化容器的原水之使用。[Problem to be Solved by the Invention] According to the technology described in Patent Document 2, by using the concentrated liquid of the reverse osmosis device for the regeneration of the softening vessel (resin), the use of raw water usually used for washing the softening vessel can be reduced.

但,就使用離子交換樹脂與逆滲透膜的水處理方法而言,當被處理水含有硫酸離子SO4 2- 、碳酸離子CO3 2- 時,該等2價陰離子會通過離子交換樹脂而濃縮於逆滲透膜之濃縮水中。若將此濃縮水使用於離子交換樹脂之再生,有CaSO4 、CaCO3 析出之疑慮,故此時應避免將逆滲透膜之濃縮水使用於離子交換樹脂之再生。However, for water treatment methods using ion exchange resins and reverse osmosis membranes, when the water to be treated contains sulfuric acid ions SO 4 2- and carbonate ions CO 3 2- , these divalent anions will be concentrated by the ion exchange resin In the concentrated water of the reverse osmosis membrane. If this concentrated water is used for the regeneration of ion exchange resins, there are concerns about the precipitation of CaSO 4 and CaCO 3. Therefore, at this time, avoid using the concentrated water of the reverse osmosis membrane for the regeneration of ion exchange resins.

另一方面,將用於軟化處理之離子交換樹脂再生的再生劑,一般多使用高濃度NaCl水溶液,但再生劑之成本昂貴,而且由於需要將固體之NaCl溶解的步驟故操作變得煩雜。On the other hand, the regenerating agent used to regenerate the ion exchange resin used for softening treatment generally uses high-concentration NaCl aqueous solution, but the cost of the regenerating agent is expensive, and the operation becomes complicated due to the step of dissolving the solid NaCl.

本發明之目的係提供:一種水處理方法,係使用離子交換樹脂與逆滲透膜的水處理方法,即便在被處理水含有硫酸離子SO4 2- 、碳酸離子CO3 2- 的情況下,仍可以更低成本且更簡易地進行離子交換樹脂之再生。The purpose of the present invention is to provide: a water treatment method using ion exchange resins and reverse osmosis membranes, even when the water to be treated contains sulfuric acid ions SO 4 2- and carbonate ions CO 3 2- The regeneration of ion exchange resin can be carried out at a lower cost and easier.

本發明之另一目的係提供適於實施上述方法的水處理裝置。Another object of the present invention is to provide a water treatment device suitable for implementing the above method.

本發明之又另一目的係提供能夠以更低成本且更簡易地進行離子交換樹脂之再生的離子交換樹脂再生方法,尤其使從使用離子交換樹脂與逆滲透膜的水處理方法得到的逆滲透膜濃縮水,即便在該水處理之被處理水含有硫酸離子SO4 2- 、碳酸離子CO3 2- 的情況下,仍可使用於離子交換樹脂之再生。 [解決課題之手段]Yet another object of the present invention is to provide an ion exchange resin regeneration method that can regenerate ion exchange resins at a lower cost and more easily, especially the reverse osmosis obtained from a water treatment method using ion exchange resins and reverse osmosis membranes. Membrane concentrated water can be used for the regeneration of ion exchange resin even if the water to be treated contains sulfuric acid ions SO 4 2- and carbonate ions CO 3 2-. [Means to solve the problem]

依本發明之一態樣,提供: 一種水處理方法,包括以下步驟: 軟化步驟,使用離子交換樹脂將包含選自於由SO4 2- 及CO3 2- 構成的群組中的1種或2種的2價陰離子、硬度成分、Na+ 、與Cl- 的被處理水軟化; 奈米過濾步驟,使用奈米濾膜將經該軟化步驟軟化的水予以分離成奈米濾膜之透過水與濃縮液; 逆滲透步驟,使用逆滲透膜將該奈米濾膜之透過水予以分離成逆滲透膜之透過水與濃縮水;及 離子交換樹脂再生步驟,使用該逆滲透膜之濃縮水將該離子交換樹脂再生。According to one aspect of the present invention, there is provided: a water treatment method, including the following steps: a softening step, using an ion exchange resin to include one selected from the group consisting of SO 4 2- and CO 3 2- or Two kinds of divalent anions, hardness components, Na + , and Cl - are softened by the treated water; in the nanofiltration step, the water softened by the softening step is separated into the permeate water of the nanofiltration membrane using a nanofiltration membrane. And concentrated liquid; the reverse osmosis step, using a reverse osmosis membrane to separate the permeated water of the nanofiltration membrane into permeated water and concentrated water of the reverse osmosis membrane; and the ion exchange resin regeneration step, using the concentrated water of the reverse osmosis membrane The ion exchange resin is regenerated.

依本發明之另一態樣,提供: 一種水處理裝置,包含: 具備離子交換樹脂的軟化裝置; 具備奈米濾膜的奈米過濾裝置; 具備逆滲透膜的逆滲透裝置; 將該軟化裝置之軟化水出口連接到該奈米過濾裝置入口的管線; 將該奈米過濾裝置之透過水出口連接到該逆滲透裝置之入口的管線;及 將該逆滲透裝置之濃縮液出口連接到該軟化裝置之再生劑入口的管線。According to another aspect of the present invention, there is provided: a water treatment device, comprising: a softening device with ion exchange resin; a nanofiltration device with a nanofiltration membrane; a reverse osmosis device with a reverse osmosis membrane; and the softening device The outlet of the softened water is connected to the pipeline of the inlet of the nanofiltration device; the outlet of the permeate water of the nanofiltration device is connected to the inlet of the reverse osmosis device; and the outlet of the concentrated liquid of the reverse osmosis device is connected to the softening The pipeline of the regenerant inlet of the device.

依本發明之又另一態樣,提供: 一種離子交換樹脂之再生方法,包括以下步驟: 軟化步驟,使用離子交換樹脂將包含選自於由SO4 2- 及CO3 2- 構成的群組中的1種或2種的2價陰離子、硬度成分、Na+ 、與Cl- 的被處理水軟化; 奈米過濾步驟,使用奈米濾膜將經該軟化步驟軟化的水予以分離成奈米濾膜之透過水與濃縮液; 逆滲透步驟,使用逆滲透膜將該奈米濾膜之透過水予以分離成逆滲透膜之透過水與濃縮水; 離子交換樹脂再生步驟,使用該逆滲透膜之濃縮水將離子交換樹脂(可為該軟化步驟中使用的離子交換樹脂,也可為和該軟化步驟中使用的離子交換樹脂不同的離子交換樹脂)再生。 [發明之效果]According to yet another aspect of the present invention, there is provided: a method for regenerating an ion exchange resin, comprising the following steps: a softening step, using an ion exchange resin to include a resin selected from the group consisting of SO 4 2- and CO 3 2- One or two of the divalent anions, hardness components, Na + , and Cl - are softened by the treated water; in the nanofiltration step, the water softened by the softening step is separated into nanometers using a nanofiltration membrane. Permeate water and concentrated liquid of the membrane; reverse osmosis step, use a reverse osmosis membrane to separate the permeated water of the nanofiltration membrane into permeated water and concentrated water of the reverse osmosis membrane; ion exchange resin regeneration step, use the reverse osmosis membrane The concentrated water regenerates the ion exchange resin (the ion exchange resin used in the softening step, or the ion exchange resin different from the ion exchange resin used in the softening step). [Effects of Invention]

依本發明,提供:一種水處理方法,係使用離子交換樹脂與逆滲透膜的水處理方法,即便在被處理水含有硫酸離子SO4 2 、碳酸離子CO3 2- 的情況下,仍可以更低成本且更簡易地進行離子交換樹脂之再生。According to the present invention, there is provided: a water treatment method using ion exchange resin and reverse osmosis membrane, even when the treated water contains sulfuric acid ions SO 4 2 and carbonate ions CO 3 2- Low-cost and simpler regeneration of ion exchange resin.

又,依本發明,提供適於實施上述方法的水處理裝置。Furthermore, according to the present invention, a water treatment device suitable for implementing the above method is provided.

再者依本發明,提供能夠以更低成本且更簡易地進行離子交換樹脂之再生的離子交換樹脂再生方法,尤其,從使用離子交換樹脂與逆滲透膜的水處理方法得到的逆滲透膜濃縮水,即便在該水處理之被處理水含有硫酸離子SO4 2- 、碳酸離子CO3 2- 的情況下,仍可使用於離子交換樹脂之再生。Furthermore, according to the present invention, there is provided an ion exchange resin regeneration method that can regenerate ion exchange resins at a lower cost and more easily, in particular, a reverse osmosis membrane concentration obtained from a water treatment method using ion exchange resins and reverse osmosis membranes Water, even if the water to be treated contains sulfuric acid ions SO 4 2- and carbonate ions CO 3 2- , it can still be used for the regeneration of ion exchange resins.

本發明之水處理方法或離子交換樹脂之再生方法包括:軟化步驟、奈米過濾步驟、逆滲透步驟及離子交換樹脂再生步驟。The water treatment method or ion exchange resin regeneration method of the present invention includes: a softening step, a nanofiltration step, a reverse osmosis step, and an ion exchange resin regeneration step.

[奈米濾膜、逆滲透膜] 關於本發明,將在NaCl濃度500mg/L、pH6.5、溫度25℃、操作壓力1.5MPa之條件下NaCl阻擋率為5%以上且未達93%之膜稱為奈米濾膜(NF),將在同條件下NaCl阻擋率為93%以上之膜稱為逆滲透(RO)膜。[Nanofiltration membrane, reverse osmosis membrane] Regarding the present invention, the NaCl barrier rate will be greater than 5% and less than 93% under the conditions of NaCl concentration of 500 mg/L, pH 6.5, temperature of 25°C, and operating pressure of 1.5 MPa. The membrane is called a nanofiltration membrane (NF), and the membrane with a NaCl barrier rate of over 93% under the same conditions is called a reverse osmosis (RO) membrane.

阻擋率可依下式求得。The blocking rate can be obtained by the following formula.

【數1】

Figure 02_image001
【Number 1】
Figure 02_image001

[軟化步驟] 在軟化步驟中,使用離子交換樹脂將被處理水軟化。被處理水包含2價陰離子、硬度成分、鈉離子Na+ 、與氯離子Cl- 。2價陰離子係選自於由硫酸離子SO4 2- 及碳酸離子CO3 2- 構成之群組中的1種或2種。2價陰離子尤其為SO4 2-[Softening step] In the softening step, an ion exchange resin is used to soften the water to be treated. Treated water contains divalent anion, hardness components, a sodium ion Na +, chloride ions and Cl -. The divalent anion is one or two selected from the group consisting of sulfuric acid ion SO 4 2- and carbonate ion CO 3 2- . The divalent anion is especially SO 4 2- .

硬度成分係水處理之領域中周知者,一般為以Ca2+ 及Mg2+ 為代表的2價陽離子。在軟化步驟,硬度成分之濃度會減低。Hardness components are well-known in the field of water treatment, and are generally divalent cations represented by Ca 2+ and Mg 2+. In the softening step, the concentration of the hardness component will be reduced.

離子交換樹脂,可適宜地使用在軟化處理中使用的公知的離子交換樹脂,尤其可適宜地使用Na型之強酸性陽離子交換樹脂,有凝膠型、多孔型、MR型,可使用其中任一種。離子交換樹脂,例如可使用奧璐佳瑙股份有限公司製Amberjet 1020(商品名,以下同樣)、Amberjet 1024、Amberlite IR124、Amberlite IR120B等。As the ion exchange resin, known ion exchange resins used in softening treatment can be suitably used, especially Na-type strong acid cation exchange resins can be suitably used. There are gel type, porous type, and MR type, any of which can be used. . As the ion exchange resin, for example, Amberjet 1020 (trade name, the same hereinafter) manufactured by Olugano Co., Ltd., Amberjet 1024, Amberlite IR124, Amberlite IR120B, etc. can be used.

[奈米過濾步驟] 在此步驟中,使經軟化步驟軟化的水(軟化水)通過NF膜,得到NF膜之透過水與濃縮水。亦即,使用NF膜將軟化水予以分離成NF膜之透過水(已透過NF膜的液體)、與NF膜之濃縮水(未透過NF膜的液體)。[Nanofiltration step] In this step, the water softened by the softening step (softened water) is passed through the NF membrane to obtain permeated water and concentrated water of the NF membrane. That is, the NF membrane is used to separate the demineralized water into permeated water of the NF membrane (liquid that has passed through the NF membrane) and concentrated water of the NF membrane (liquid that has not passed through the NF membrane).

將NF膜之透過水供給至逆滲透步驟。將NF膜之濃縮水,視2價陰離子之濃度等,而適宜地排放到外界或當作產業廢棄物處理。The permeated water of the NF membrane is supplied to the reverse osmosis step. Depending on the concentration of divalent anions, the concentrated water of the NF membrane can be appropriately discharged to the outside or treated as industrial waste.

NF膜係用以預先將供給至RO膜的液體之2價陰離子(SO4 2- 及/或CO3 2- )濃度減低。藉此,將RO膜之濃縮水用於離子交換樹脂之再生時可防止CaSO4 、CaCO3 析出。是以,宜將2價陰離子盡可能地濃縮於NF膜之濃縮水中。另一方面,宜使1價離子(Na+ 及Cl- )盡可能地透過NF膜,並使其盡可能多量地存在於RO膜之濃縮水中,而作為離子交換樹脂之再生劑利用。The NF membrane is used to reduce the concentration of divalent anions (SO 4 2- and/or CO 3 2- ) in the liquid supplied to the RO membrane in advance. This prevents CaSO 4 and CaCO 3 from separating out when the concentrated water of the RO membrane is used for the regeneration of ion exchange resins. Therefore, it is advisable to concentrate the divalent anions in the concentrated water of the NF membrane as much as possible. On the other hand, desirable that the monovalent ions (Na + and Cl -) NF membrane permeable as possible, and a large amount as it present in the membrane of the RO water and concentrated, using as regenerant an ion exchange resin.

由此觀點,NF膜之NaCl之阻擋率較佳為70%以下,50%以下更佳。又,NF膜之2價陰離子(SO4 2- 及/或CO3 2- )之阻擋率較佳為90%以上,98%以上更佳。From this point of view, the NaCl barrier rate of the NF film is preferably 70% or less, and more preferably 50% or less. In addition, the blocking rate of the divalent anions (SO 4 2- and/or CO 3 2- ) of the NF membrane is preferably 90% or more, and more preferably 98% or more.

NF膜,例如可使用The Dow Chemical Company公司製之NF-245(商品名)。As the NF membrane, for example, NF-245 (trade name) manufactured by The Dow Chemical Company can be used.

[逆滲透步驟] 在此步驟中,使NF膜之透過水通過RO膜,得到RO膜之透過水與濃縮水。亦即,使用RO膜將NF膜之透過水予以分離成RO膜之透過水(已透過RO膜的液體)、與RO膜之濃縮水(未透過RO膜的液體)。[Reverse Osmosis Step] In this step, the permeated water of the NF membrane is passed through the RO membrane to obtain the permeated water and concentrated water of the RO membrane. That is, the RO membrane is used to separate the permeated water of the NF membrane into the permeated water of the RO membrane (liquid that has passed through the RO membrane) and the concentrated water of the RO membrane (liquid that has not passed through the RO membrane).

RO膜之透過水為純度高的水。是以,亦可排放到外界,但較佳係作為回收水而予以再利用。The permeate water of RO membrane is high purity water. Therefore, it can also be discharged to the outside, but it is better to reuse it as recycled water.

在RO膜之濃縮水中濃縮有Na+ 及Cl- 。另一方面,SO4 2- 及CO3 2- 被NF膜擋住,RO膜之濃縮水中的SO4 2- 及CO3 2- 之濃度可減低到非常低。是以,此濃縮水適合作為離子交換樹脂之再生劑,可供給至離子交換樹脂再生步驟。 Na + and Cl - are concentrated in the concentrated water of the RO membrane. On the other hand, SO 4 2- and CO 3 2- are blocked by the NF membrane, and the concentration of SO 4 2- and CO 3 2- in the concentrated water of the RO membrane can be reduced to a very low level. Therefore, this concentrated water is suitable as a regeneration agent for ion exchange resin and can be supplied to the regeneration step of ion exchange resin.

從使RO膜濃縮水中含有更多之Na+ 及Cl- 之觀點,RO膜宜為能在更高壓下使用者。From the point of view that the RO membrane concentrate water contains more Na + and Cl - , the RO membrane is suitable for users under higher pressure.

RO膜,例如可使用The Dow Chemical Company公司製之SW-30HR(商品名)。For the RO membrane, for example, SW-30HR (trade name) manufactured by The Dow Chemical Company can be used.

[離子交換樹脂再生步驟] 在此步驟中,使用RO膜之濃縮水將離子交換樹脂再生。RO膜之濃縮水,可作為在軟化處理中使用的離子交換樹脂之再生劑利用。亦即,將被處理水以軟化步驟、奈米過濾步驟、接著逆滲透步驟予以處理時,可將從該逆滲透步驟得到的RO膜之濃縮水利用於該軟化步驟中使用的離子交換樹脂之再生。水處理方法或水處理裝置,通常採用此形態。[Ion exchange resin regeneration step] In this step, the ion exchange resin is regenerated using RO membrane concentrated water. The concentrated water of RO membrane can be used as a regeneration agent of ion exchange resin used in softening treatment. That is, when the water to be treated is treated in a softening step, a nanofiltration step, and then a reverse osmosis step, the concentrated water of the RO membrane obtained from the reverse osmosis step can be used as the ion exchange resin used in the softening step. regeneration. Water treatment methods or water treatment devices usually adopt this form.

但不限於此,也可將RO膜之濃縮水利用於和該軟化步驟中使用的離子交換樹脂不同的離子交換樹脂之再生。離子交換樹脂之再生方法,可採用前述之形態(將軟化處理中使用的離子交換樹脂再生),也可採用此形態。However, it is not limited to this, and the concentrated water of the RO membrane can also be used to regenerate an ion exchange resin different from the ion exchange resin used in the softening step. The regeneration method of the ion exchange resin can adopt the aforementioned form (regenerate the ion exchange resin used in the softening treatment), and this form can also be adopted.

也可在進行離子交換樹脂之再生之前,視需要對於RO膜之濃縮水添加NaCl而提高NaCl濃度。又,也可將RO膜之濃縮水以蒸發法等其他方法進一步濃縮後,方作為再生劑利用。It is also possible to increase the concentration of NaCl by adding NaCl to the concentrated water of the RO membrane as needed before the regeneration of the ion exchange resin. In addition, the concentrated water of the RO membrane can also be used as a regenerating agent after being further concentrated by other methods such as evaporation.

也可在進行離子交換樹脂之再生之前,視需要對RO膜之濃縮水進行其他處理。例如,為了去除SO4 2- 及CO3 2- ,或為了去除氟離子(F- ),可利用使用離子交換樹脂、氟吸附劑的方法來處理RO膜之濃縮水。或可利用脱碳酸法等來處理RO膜之濃縮水。It is also possible to perform other treatments on the concentrated water of the RO membrane as needed before the regeneration of the ion exchange resin. For example, in order to remove SO 4 2- and CO 3 2-, or to remove fluoride ions (F -), may utilize an ion exchange resin, a fluorine adsorbent way to handle the concentrated water RO membranes. Alternatively, decarbonation method can be used to treat the concentrated water of the RO membrane.

[水處理裝置] 以下,邊參照圖式邊說明本發明,但本發明不限於此。本發明之方法,可利用具有圖1所示之流程的水處理裝置實施。[Water Treatment Apparatus] Hereinafter, the present invention will be described with reference to the drawings, but the present invention is not limited to this. The method of the present invention can be implemented using a water treatment device having the process shown in FIG. 1.

此水處理裝置包含:具備離子交換樹脂的軟化裝置3,具備奈米濾膜的奈米過濾裝置(NF裝置)4,與具備逆滲透膜的逆滲透裝置(RO裝置)5。軟化裝置、奈米過濾裝置、逆滲透裝置之各裝置之結構,可適宜地採用公知的結構。 軟化裝置3之軟化水出口與NF裝置4之入口以管線L2連接而可連通。NF裝置4之透過水出口與RO裝置5之入口以管線L3連接而可連通。RO裝置5之濃縮液出口與軟化裝置3之再生劑入口以管線L6及L7(於該等管線之間設有RO膜濃縮水槽6)連接而可連通。This water treatment device includes a softening device 3 equipped with ion exchange resin, a nanofiltration device (NF device) 4 equipped with a nanofiltration membrane, and a reverse osmosis device (RO device) 5 equipped with a reverse osmosis membrane. The structure of each device of the softening device, the nanofiltration device, and the reverse osmosis device may suitably adopt a well-known structure. The softened water outlet of the softening device 3 and the inlet of the NF device 4 are connected by a pipeline L2 and can be communicated. The permeated water outlet of the NF device 4 and the inlet of the RO device 5 are connected by a pipeline L3 and can be communicated. The outlet of the concentrated liquid of the RO device 5 and the inlet of the regenerant of the softening device 3 are connected by lines L6 and L7 (the RO membrane concentrated water tank 6 is provided between these lines) and can be communicated.

又,此水處理裝置具有被處理水槽1,並於連接被處理水槽1與軟化裝置3的管線(L1)設有泵浦2。被處理水槽1、泵浦2、RO膜濃縮水槽6並非一定需要,可適宜地設置。未設置RO膜濃縮水槽6時,以管線連接RO裝置之濃縮液出口與軟化裝置之再生劑入口。此時,例如可設置多個系統的軟化裝置,在以1個系統進行水處理的期間,將其他系統的離子交換樹脂再生。In addition, this water treatment device has a water tank 1 to be treated, and a pump 2 is provided in a pipeline (L1) connecting the water tank 1 to be treated and the softening device 3. The treated water tank 1, pump 2, and RO membrane concentration water tank 6 are not necessarily required, and can be appropriately installed. When the RO membrane concentrated water tank 6 is not installed, connect the concentrated liquid outlet of the RO device and the regenerant inlet of the softening device with a pipeline. In this case, for example, multiple systems of softening devices can be installed, and while one system is performing water treatment, the ion exchange resins of other systems can be regenerated.

可適宜地以配管構成各管線。因應在水處理運轉與離子交換樹脂再生運轉之間切換等目的,可於各管線適宜地設置閥、儀表控制部。Each pipeline can be appropriately constituted by piping. For the purpose of switching between water treatment operation and ion exchange resin regeneration operation, valves and instrument control units can be appropriately installed in each pipeline.

進行水處理時,被處理水從被處理水槽1通過管線L1而供給至軟化裝置3。此時被處理水因泵浦2而升壓。經軟化的水從軟化裝置3通過管線L2而供給至NF裝置4。NF膜之透過液通過管線L3而供給至RO裝置。NF膜之濃縮水通過管線L4而從水處理裝置排出,適宜地排放到外界或當作產業廢棄物處理。RO膜之透過液通過管線L5而排出於裝置外,可適宜地作為回收水利用或排放到外界。RO膜之濃縮液通過管線L6而供給至RO膜濃縮水槽6。When the water treatment is performed, the water to be treated is supplied from the water tank 1 to be treated to the softening device 3 through the line L1. At this time, the pressure of the water to be treated is boosted by pump 2. The softened water is supplied from the softening device 3 to the NF device 4 through the line L2. The permeate of the NF membrane is supplied to the RO device through the line L3. The concentrated water of the NF membrane is discharged from the water treatment device through the line L4, and is appropriately discharged to the outside or treated as industrial waste. The permeate of the RO membrane is discharged to the outside of the device through the line L5, and can be suitably used as recycled water or discharged to the outside. The concentrated liquid of the RO membrane is supplied to the RO membrane concentrated water tank 6 through the line L6.

將配備於軟化裝置3的離子交換樹脂再生時,RO膜濃縮水從RO膜濃縮水槽6通過管線L7而供給至軟化裝置,利用RO膜濃縮水將離子交換樹脂再生。再生廢液從管線L8排出至水處理裝置外,適宜地排放到外界或當作產業廢棄物處理。When the ion exchange resin provided in the softening device 3 is regenerated, the RO membrane concentrated water is supplied to the softening device from the RO membrane concentrated water tank 6 through the line L7, and the ion exchange resin is regenerated by the RO membrane concentrated water. The regeneration waste liquid is discharged from the pipeline L8 to the outside of the water treatment device, and is appropriately discharged to the outside or treated as industrial waste.

[處理條件] 於表1及表2,針對軟化步驟供給液(被處理水)、NF步驟供給液(軟化水)、RO步驟供給液(NF膜透過水)顯示處理條件之代表例。[Treatment conditions] In Tables 1 and 2, representative examples of processing conditions are shown for the softening step supply liquid (water to be treated), the NF step supply liquid (softened water), and the RO step supply liquid (NF membrane permeated water).

從RO步驟得到的濃縮水中的NaCl濃度,從有效率地將離子交換樹脂再生的觀點,較佳為2質量%以上,更佳為4質量%以上。又,從適當的滲透壓之觀點,較佳為10質量%以下。若採用表1及2所示的代表性的處理條件,其結果易於使RO膜濃縮水中的NaCl濃度在前述較佳的範圍內。From the viewpoint of efficiently regenerating the ion exchange resin, the NaCl concentration in the concentrated water obtained from the RO step is preferably 2% by mass or more, and more preferably 4% by mass or more. Moreover, from the viewpoint of an appropriate osmotic pressure, it is preferably 10% by mass or less. If the representative treatment conditions shown in Tables 1 and 2 are used, the result is that the NaCl concentration in the RO membrane concentrated water is easily within the aforementioned preferable range.

RO膜透過水中的NaCl濃度,從回收再利用的觀點宜為150mg/L以下。The NaCl concentration in the RO membrane permeate water is preferably 150 mg/L or less from the viewpoint of recycling.

【表1】典型的處理條件(之1)

Figure 02_image003
【Table 1】Typical processing conditions (Part 1)
Figure 02_image003

【表2】典型的處理條件(之2)

Figure 02_image005
【Table 2】Typical processing conditions (Part 2)
Figure 02_image005

依本發明,即便在被處理水含有SO4 2- 、CO3 2- 的情況下,仍可將RO膜濃縮液利用於離子交換樹脂之再生。是以,可降低於離子交換樹脂之再生劑所花費的成本,而且可省去溶解固體NaCl的步驟,故運轉管理變得容易。According to the present invention, even when the water to be treated contains SO 4 2- and CO 3 2- , the RO membrane concentrate can still be used for the regeneration of ion exchange resins. Therefore, the cost of the regenerant of the ion exchange resin can be reduced, and the step of dissolving solid NaCl can be omitted, so the operation management becomes easy.

又依本發明,將軟化水以RO膜處理前,先以NF膜處理。相較於直接以RO膜處理軟化水的情形,依本發明可減低RO膜待處理液中的鹽濃度,亦即可減低滲透壓。是以,易於提高於RO膜之濃縮倍率而提高RO膜濃縮液中的NaCl濃度,或可更降低RO膜之操作壓力。According to the present invention, the softened water is treated with NF membrane before it is treated with RO membrane. Compared with the case where the RO membrane is directly used to treat the softened water, the present invention can reduce the salt concentration in the RO membrane to be treated liquid, which can also reduce the osmotic pressure. Therefore, it is easy to increase the concentration ratio of the RO membrane to increase the NaCl concentration in the RO membrane concentrate, or to further reduce the operating pressure of the RO membrane.

又若鋁離子與離子狀二氧化矽共存,有時會促進二氧化矽垢之生成。但依本發明,即便在被處理水中有鋁離子共存的情況下,鋁離子亦可利用離子交換樹脂去除,從而防止鋁離子流入後段的NF膜及RO膜。 [實施例]In addition, if aluminum ions and ionic silica coexist, sometimes the formation of silica scale will be promoted. However, according to the present invention, even when aluminum ions coexist in the water to be treated, the aluminum ions can be removed by the ion exchange resin, thereby preventing the aluminum ions from flowing into the NF membrane and the RO membrane in the subsequent stage. [Example]

以下,根據實施例更詳細地說明本發明,但本發明不限於此。Hereinafter, the present invention will be explained in more detail based on examples, but the present invention is not limited to this.

[實施例1] ・軟化步驟 使用性狀顯示於表3的半導體工廠排放水作為被處理液。對此排放水,使用具備離子交換樹脂的軟化裝置進行軟化處理,去除Ca離子。亦將經軟化處理的水之性狀顯示於表3。[Example 1] ・Softening step The discharged water from a semiconductor factory whose properties are shown in Table 3 was used as the liquid to be treated. The discharged water is softened using a softening device equipped with ion exchange resin to remove Ca ions. The properties of the softened water are also shown in Table 3.

使用的軟化裝置(離子交換裝置)與操作條件如下: 離子交換樹脂:奧璐佳瑙股份有限公司製,Amberjet1020(商品名)、 樹脂量:1L、 使用管柱:Φ(直徑)45mm×H(高度)600mm、 通水量:40L、 SV(空間速度):20(1/h)、 操作溫度、壓力:常溫、常壓(25℃、0.10MPa)。The softening device (ion exchange device) and operating conditions used are as follows: Ion exchange resin: Amberjet1020 (trade name) manufactured by Olugano Co., Ltd., resin volume: 1L, column used: Φ (diameter) 45mm×H( Height) 600mm, water flow: 40L, SV (space velocity): 20 (1/h), operating temperature and pressure: normal temperature, normal pressure (25°C, 0.10MPa).

【表3】排放水性狀

Figure 02_image007
[Table 3] Discharge water state
Figure 02_image007

・NF步驟 使用NF平板膜將表3所示之軟化水濃縮,得到表4所示之濃縮水與透過水。軟化後之水(40L)經2倍濃縮,得到濃縮水20L與透過水20L。・NF step Use the NF flat membrane to concentrate the demineralized water shown in Table 3 to obtain the concentrated water and permeate water shown in Table 4. The softened water (40L) was concentrated twice to obtain 20L concentrated water and 20L permeated water.

使用的NF膜與操作條件如下: NF膜:The Dow Chemical Company公司製NF-245(商品名)Φ75mm平板膜、 操作壓:0.75MPa、 水溫:25℃。The used NF membrane and operating conditions are as follows: NF membrane: NF-245 (trade name) Φ75mm flat membrane manufactured by The Dow Chemical Company, operating pressure: 0.75 MPa, water temperature: 25°C.

・RO步驟 其次,使用RO平板膜將NF膜之透過水進一步地濃縮,得到表4所示之濃縮水與透過水。NF膜透過水(20L)經大約12倍濃縮,得到濃縮水1.7L與透過水18.3L。・RO step Next, use RO flat membrane to further concentrate the permeated water of the NF membrane to obtain the concentrated water and permeated water shown in Table 4. NF membrane permeate water (20L) was concentrated about 12 times to obtain 1.7L of concentrated water and 18.3L of permeated water.

使用的RO膜與操作條件如下: RO膜:The Dow Chemical Company公司製SW30-HR(商品名)Φ75mm平板膜、 操作壓:4.5MPa、 水溫:25℃。The RO membrane used and the operating conditions are as follows: RO membrane: SW30-HR (trade name) Φ75mm flat membrane manufactured by The Dow Chemical Company, operating pressure: 4.5 MPa, water temperature: 25°C.

【表4】實施例1試驗結果

Figure 02_image009
[Table 4] Test results of Example 1
Figure 02_image009

此RO膜濃縮水中,Na+ 及Cl- 的濃度高,可直接作為離子交換樹脂之再生劑利用。另外,將NF膜濃縮水及RO膜透過水廢棄。This RO membrane concentrated water contains high concentrations of Na + and Cl - and can be directly used as a regenerant for ion exchange resins. In addition, the NF membrane concentrated water and RO membrane permeate water are discarded.

[比較例1] 對於表3所示之軟化水(40L),不進行利用NF膜所為之處理,而使用RO平板膜直接予以濃縮。此時使用的RO膜、與RO步驟之操作壓、水溫和實施例1同樣。軟化水經大約8倍濃縮,得到表5所示之濃縮水(5L)與透過水(35L)。[Comparative Example 1] The demineralized water (40L) shown in Table 3 was not treated with NF membrane, but was directly concentrated using RO flat membrane. The RO membrane used at this time is the same as the operating pressure and water temperature of the RO step as in Example 1. The demineralized water was concentrated about 8 times to obtain the concentrated water (5L) and permeated water (35L) shown in Table 5.

【表5】比較例1試驗結果

Figure 02_image011
[Table 5] Test results of Comparative Example 1
Figure 02_image011

在與實施例1同樣的操作壓(4.5MPa)下,因滲透壓之影響僅能達到大約8倍濃縮。和實施例1之RO膜濃縮水比較,比較例1之RO膜濃縮水的Na+ 、Cl- 的濃度稍低。此RO膜濃縮水由於含有高濃度的SO4 2 ,故不適合作為離子交換樹脂之再生劑(離子交換樹脂再生時CaSO4 析出之可能性高)。 [產業利用性]Under the same operating pressure (4.5 MPa) as in Example 1, the concentration can only reach about 8 times due to the influence of osmotic pressure. Compared with the RO membrane concentrated water of Example 1, the RO membrane concentrated water of Comparative Example 1 has a slightly lower concentration of Na + and Cl -. This RO membrane concentrated water contains a high concentration of SO 4 2 , so it is not suitable as a regeneration agent for ion exchange resins ( the possibility of CaSO 4 precipitation during ion exchange resin regeneration is high). [Industrial Utilization]

本發明有助於處理半導體工廠、精糖工廠等工廠排水並回收純度高的水。The invention is helpful for processing wastewater from factories such as semiconductor factories, sugar refineries, etc., and recovering high-purity water.

1‧‧‧被處理水槽 2‧‧‧泵浦 3‧‧‧軟化裝置 4‧‧‧奈米過濾裝置(NF裝置) 5‧‧‧逆滲透裝置(RO裝置) 6‧‧‧RO膜濃縮水槽 L1~L8‧‧‧管線 1‧‧‧The treated water tank 2‧‧‧Pump 3‧‧‧Softening device 4‧‧‧Nano filter device (NF device) 5‧‧‧Reverse Osmosis Device (RO Device) 6‧‧‧RO membrane concentrating water tank L1~L8‧‧‧Pipeline

【圖1】係顯示本發明之水處理裝置之一例的處理流程圖。[Figure 1] is a processing flow chart showing an example of the water treatment device of the present invention.

1‧‧‧被處理水槽 1‧‧‧The treated water tank

2‧‧‧泵浦 2‧‧‧Pump

3‧‧‧軟化裝置 3‧‧‧Softening device

4‧‧‧奈米過濾裝置(NF裝置) 4‧‧‧Nano filter device (NF device)

5‧‧‧逆滲透裝置(RO裝置) 5‧‧‧Reverse Osmosis Device (RO Device)

6‧‧‧RO膜濃縮水槽 6‧‧‧RO membrane concentrating water tank

L1~L8‧‧‧管線 L1~L8‧‧‧Pipeline

Claims (6)

一種水處理方法,包括以下步驟:軟化步驟,使用離子交換樹脂將包含選自於由SO4 2-及CO3 2-構成的群組中的1種或2種的2價陰離子、硬度成分、Na+、與Cl-的排水軟化;奈米過濾步驟,使用奈米濾膜將經該軟化步驟軟化的水予以分離成奈米濾膜之透過水與濃縮液;逆滲透步驟,使用逆滲透膜將該奈米濾膜之透過水予以分離成逆滲透膜之透過水與濃縮水;及離子交換樹脂再生步驟,使用該逆滲透膜之濃縮水將該離子交換樹脂再生;該奈米濾膜的NaCl阻擋率為70%以下,且該奈米濾膜的該2價陰離子之阻擋率為90%以上。 A water treatment method includes the following steps: a softening step, using an ion exchange resin to contain one or two divalent anions selected from the group consisting of SO 4 2- and CO 3 2-, hardness components, The drainage of Na + and Cl - is softened; in the nanofiltration step, the water softened by the softening step is separated into the permeate and concentrated liquid of the nanofiltration membrane by the nanofiltration membrane; in the reverse osmosis step, the reverse osmosis membrane is used Separating the permeated water of the nanofiltration membrane into permeated water and concentrated water of the reverse osmosis membrane; and the ion exchange resin regeneration step, using the concentrated water of the reverse osmosis membrane to regenerate the ion exchange resin; The NaCl barrier rate is below 70%, and the barrier rate of the divalent anion of the nanofiltration membrane is above 90%. 如申請專利範圍第1項之水處理方法,其中,經該軟化步驟軟化的水中,SO4 2-濃度為10mg/L以上10000mg/L以下,CO3 2-含量以CaCO3換算計為10mg/L以下。 For example, the water treatment method of item 1 in the scope of patent application, wherein the SO 4 2- concentration in the water softened by the softening step is 10 mg/L or more and 10,000 mg/L or less, and the CO 3 2- content is 10 mg/L in terms of CaCO 3 Below L. 如申請專利範圍第1或2項之水處理方法,其中,該奈米濾膜之透過水中,SO4 2-濃度未達10mg/L。 For example, the water treatment method of item 1 or 2 in the scope of patent application, wherein the concentration of SO 4 2- in the permeated water of the nanofiltration membrane does not reach 10 mg/L. 如申請專利範圍第1或2項之水處理方法,其中,該2價陰離子為SO4 2-For example, the water treatment method of item 1 or 2 in the scope of patent application, wherein the divalent anion is SO 4 2- . 一種水處理裝置,包含: 具備離子交換樹脂的軟化裝置,其被供給包含選自於由SO4 2-及CO3 2-構成的群組中的1種或2種的2價陰離子、硬度成分、Na+、與Cl-的排水;具備奈米濾膜的奈米過濾裝置;具備逆滲透膜的逆滲透裝置;將該軟化裝置之軟化水出口連接到該奈米過濾裝置入口的管線;將該奈米過濾裝置之透過水出口連接到該逆滲透裝置之入口的管線;及將該逆滲透裝置之濃縮液出口連接到該軟化裝置之再生劑入口的管線;該奈米濾膜的NaCl阻擋率為70%以下,且該奈米濾膜的該2價陰離子之阻擋率為90%以上。 A water treatment device comprising: a softening device provided with an ion exchange resin, which is supplied with one or two divalent anions selected from the group consisting of SO 4 2- and CO 3 2-, and a hardness component , Na + , and Cl - drainage; nanofiltration device with nanofiltration membrane; reverse osmosis device with reverse osmosis membrane; pipeline connecting the softened water outlet of the softening device to the inlet of the nanofiltration device; The pipeline connecting the permeate outlet of the nanofiltration device to the inlet of the reverse osmosis device; and the pipeline connecting the concentrate outlet of the reverse osmosis device to the regenerant inlet of the softening device; the NaCl barrier of the nanofiltration membrane The rate is less than 70%, and the barrier rate of the divalent anion of the nanofiltration membrane is more than 90%. 一種離子交換樹脂之再生方法,包括以下步驟:軟化步驟,使用離子交換樹脂將包含選自於由SO4 2-及CO3 2-構成的群組中的1種或2種的2價陰離子、硬度成分、Na+、與Cl-的排水軟化;奈米過濾步驟,使用奈米濾膜將經該軟化步驟軟化的水予以分離成奈米濾膜之透過水與濃縮液;逆滲透步驟,使用逆滲透膜將該奈米濾膜之透過水予以分離成逆滲透膜之透過水與濃縮水;及離子交換樹脂再生步驟,使用該逆滲透膜之濃縮水將離子交換樹脂再生;該奈米濾膜的NaCl阻擋率為70%以下,且該奈米濾膜的該2價陰離子之阻擋率為90%以上。 An ion exchange resin regeneration method, comprising the following steps: a softening step, using ion exchange resin to contain one or two divalent anions selected from the group consisting of SO 4 2- and CO 3 2-, Hardness components, Na + , and Cl - drainage softening; nanofiltration step, use nanofiltration membrane to separate the water softened by this softening step into permeate water and concentrated liquid of nanofiltration membrane; reverse osmosis step, use The reverse osmosis membrane separates the permeated water of the nanofiltration membrane into permeated water and concentrated water of the reverse osmosis membrane; and the ion exchange resin regeneration step uses the concentrated water of the reverse osmosis membrane to regenerate the ion exchange resin; the nanofiltration The NaCl barrier rate of the membrane is below 70%, and the barrier rate of the divalent anion of the nanofiltration membrane is above 90%.
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