JPH10244259A - Water treatment method - Google Patents
Water treatment methodInfo
- Publication number
- JPH10244259A JPH10244259A JP9049039A JP4903997A JPH10244259A JP H10244259 A JPH10244259 A JP H10244259A JP 9049039 A JP9049039 A JP 9049039A JP 4903997 A JP4903997 A JP 4903997A JP H10244259 A JPH10244259 A JP H10244259A
- Authority
- JP
- Japan
- Prior art keywords
- water
- cation exchange
- treated
- membrane separation
- exchange resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はフッ化物イオン
（Ｆ）及びカルシウムイオン（Ｃａ）を含有する水、或
いは、Ｆを含有する水及びＣａを含有する水を処理して
高純度水を製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention processes high-purity water by treating water containing fluoride ions (F) and calcium ions (Ca), or water containing F and water containing Ca. About the method.
【０００２】[0002]
【従来の技術】従来、純水の製造手段としては、イオン
交換樹脂によるイオン交換法又は逆浸透（ＲＯ）膜分離
装置によるＲＯ膜分離法があるが、イオン交換法では、
イオン交換樹脂の再生のために酸又はアルカリを多量に
必要とすることから、ＲＯ膜分離法が採用される場合が
多い。2. Description of the Related Art Conventionally, as a means for producing pure water, there is an ion exchange method using an ion exchange resin or an RO membrane separation method using a reverse osmosis (RO) membrane separation apparatus.
Since a large amount of acid or alkali is required for regeneration of the ion exchange resin, the RO membrane separation method is often employed.
【０００３】しかし、ＲＯ膜分離法は、膜で不純物を分
離する方法であるため、原水中にＳＳが混入したり、膜
濃縮水中の塩類濃度が高くなり、溶解度を超える濃度と
なって塩類が析出したりすると、膜表面にこれらが沈積
し、膜の目詰りで通水が不可能となる。特に、原水中に
ＣａとＦが含まれている場合には、難溶性のＣａＦ2が
生成することになるが、このＣａＦ2 の溶解度は８ｐｐ
ｍ（Ｆ換算）と低いため、濃縮によるＣａＦ2 の析出で
ＲＯ膜を閉塞させ易い。即ち、例えば、原水のＦ濃度が
５ｐｐｍの場合、純水（透過水）回収率９０％でＲＯ膜
分離処理すると、濃縮水のＦ濃度は５０ｐｐｍとなり、
また、純水回収率９５％でＲＯ膜分離処理すると濃縮水
のＦ濃度は１００ｐｐｍとなり、Ｃａが共存するとＣａ
Ｆ2 の析出でＲＯ膜が閉塞し、通水は不可能となる。[0003] However, since the RO membrane separation method is a method of separating impurities by a membrane, SS is mixed in the raw water or the salt concentration in the membrane concentrated water becomes high, and the concentration exceeds the solubility, and the salt is removed. When they are deposited, they are deposited on the surface of the membrane, and clogging of the membrane makes it impossible to pass water. In particular, if it contains Ca and F in the raw water, but will produce the CaF 2 hardly soluble, the solubility of the CaF 2 is 8pp
m (in terms of F), the RO film is easily clogged by the precipitation of CaF 2 by concentration. That is, for example, when the F concentration of the raw water is 5 ppm, when the RO membrane separation treatment is performed at a pure water (permeated water) recovery rate of 90%, the F concentration of the concentrated water becomes 50 ppm,
Further, when the RO membrane separation treatment is performed at a pure water recovery rate of 95%, the F concentration of the concentrated water becomes 100 ppm.
The RO film is blocked by the deposition of F 2 , and water cannot be passed.
【０００４】このため、従来においては、原水中にＣａ
及びＦが含まれている場合には、ＲＯ膜分離を行わず、
イオン交換樹脂によるイオン交換法が採用されている。
或いは、Ｃａをソーダライム法でＣａＣＯ3 として沈殿
分離させた後、Ｆ等の塩類をＲＯ膜で分離する方法が採
用されている。For this reason, conventionally, in the raw water, Ca
And F is contained, RO membrane separation is not performed,
An ion exchange method using an ion exchange resin is employed.
Alternatively, a method is employed in which Ca is precipitated and separated as CaCO 3 by the soda lime method, and then salts such as F are separated by an RO membrane.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、イオン
交換樹脂のみで処理する方法では、前述の如く、再生の
ための酸やアルカリを多量に必要とするため、工業的に
不利である。However, the method of treating with only an ion exchange resin is industrially disadvantageous as described above because it requires a large amount of acid or alkali for regeneration.
【０００６】また、Ｃａを沈殿分離した後ＲＯ膜分離す
る方法では、 Ｃａの沈殿分離のための薬注条件やｐＨ管理が難し
い。 沈殿槽を必要とする。 ＣａＣＯ3 の汚泥が発生する。 ＲＯ膜分離処理の原水中にＮａ，ＣＯ3 等のイオン
が増加するため、膜負荷が大きくなり、ＲＯ膜分離装置
を大型化する必要がある。 Ｆが濃縮されたＲＯ膜濃縮水の処理の問題がある。 といった欠点がある。Further, in the method of separating Ca by precipitation and then RO membrane separation, it is difficult to control chemical injection conditions and pH for precipitation and separation of Ca. Requires a settling tank. CaCO 3 sludge is generated. Since ions such as Na and CO 3 increase in the raw water for the RO membrane separation treatment, the membrane load increases, and it is necessary to increase the size of the RO membrane separation apparatus. There is a problem in the treatment of RO membrane concentrated water in which F is concentrated. There are drawbacks.
【０００７】本発明は上記従来の問題点を解決し、Ｆ及
びＣａを含有する水或いはＦを含有する水及びＣａを含
有する水を効率的に処理して純水を製造する方法を提供
することを目的とする。The present invention solves the above-mentioned conventional problems, and provides a method for producing pure water by efficiently treating water containing F and Ca or water containing F and Ca. The purpose is to:
【０００８】[0008]
【課題を解決するための手段】請求項１の水処理方法
は、フッ化物イオン及びカルシウムイオンを含有する水
を処理する方法において、該水をカチオン交換樹脂と接
触させ、次いで逆浸透膜分離処理して透過水を第１処理
水とする第１工程と、該カチオン交換樹脂の再生排液と
該逆浸透膜分離処理の濃縮水とを混合してＣａＦ2 を生
成させ、このＣａＦ2 を分離して分離水を第２処理水と
する第２工程とを有することを特徴とする。According to a first aspect of the present invention, there is provided a method for treating water containing fluoride ions and calcium ions, the method comprising contacting the water with a cation exchange resin, and then subjecting the water to reverse osmosis membrane separation. and a first step of the permeate from the first treated water, by mixing a concentrate of the regeneration effluent and the reverse osmosis membrane separation process of the cation exchange resin to produce a CaF 2, the CaF 2 separation And using the separated water as the second treated water.
【０００９】請求項２の水処理方法は、フッ化物イオン
を含有するＦ含有水とカルシウムイオンを含有するＣａ
含有水とを処理する方法において、該Ｃａ含有水をカチ
オン交換樹脂と接触させて第１処理水を得る第１工程
と、該Ｆ含有水を逆浸透膜分離処理して透過水を第２処
理水とする第２工程と、該カチオン交換樹脂の再生排液
と該逆浸透膜分離処理の濃縮水とを混合してＣａＦ2 を
生成させ、このＣａＦ2を分離して分離水を第３処理水
とする第３工程とを有することを特徴とする。なお、Ｃ
ａ含有水はＣａＦ2 として析出するレベル以下の濃度で
あればＦを含有していても良い。According to a second aspect of the present invention, there is provided the water treatment method, wherein the F-containing water containing fluoride ions and the Ca-containing water containing calcium ions.
In the method for treating water containing water, a first step of contacting the water containing Ca with a cation exchange resin to obtain a first treated water, and a second treatment of separating the permeated water by subjecting the F containing water to a reverse osmosis membrane separation treatment A second step of forming water, mixing the regenerated effluent of the cation exchange resin with the concentrated water of the reverse osmosis membrane separation treatment to generate CaF 2 , separating the CaF 2 and subjecting the separated water to third treatment And a third step of forming water. Note that C
The a-containing water may contain F as long as it has a concentration equal to or lower than the level at which it precipitates as CaF 2 .
【００１０】本発明の方法では、被処理水中のＣａをカ
チオン交換樹脂で除去し、Ｆ、その他の塩類をＲＯ膜で
分離することにより純水を得る。このカチオン交換樹脂
の再生により排出される、Ｃａを多量に含む再生排液
と、ＲＯ膜分離処理で得られるＦを多量に含む濃縮水と
を混合することでＣａＦ2 を析出させ、これを分離除去
することにより、再生排液及び濃縮水についても放流可
能な処理水にまで容易に処理することができる。In the method of the present invention, pure water is obtained by removing Ca in the water to be treated with a cation exchange resin and separating F and other salts with an RO membrane. CaF 2 is precipitated by mixing a regenerated effluent containing a large amount of Ca, which is discharged by regeneration of the cation exchange resin, and a concentrated water containing a large amount of F obtained by RO membrane separation treatment, and separated. By removing, even the regenerated effluent and the concentrated water can be easily processed into treated water that can be discharged.
【００１１】[0011]
【発明の実施の形態】以下、図面を参照して本発明の実
施の形態を説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００１２】図１は請求項１の水処理方法の実施の形態
を示す系統図、図２は請求項２の水処理方法の実施の形
態を示す系統図である。なお、図２において、図１に示
す部材と同一機能を奏する部材には同一符号を付してあ
る。FIG. 1 is a system diagram showing an embodiment of the water treatment method of the first aspect, and FIG. 2 is a system diagram showing an embodiment of the water treatment method of the second aspect. In FIG. 2, members having the same functions as those shown in FIG. 1 are denoted by the same reference numerals.
【００１３】図１に示す方法は、Ｃａ及びＦを共に含有
する水（以下、Ｃａ・Ｆ含有水ということがある。）を
処理する方法であって、Ｃａ・Ｆ含有水はまずｐＨ調整
槽１で必要に応じて酸又はアルカリのｐＨ調整剤を添加
して後段のＲＯ膜分離装置３の通水条件であるｐＨ５〜
８にｐＨ調整される。The method shown in FIG. 1 is a method for treating water containing both Ca and F (hereinafter sometimes referred to as Ca.F containing water). In step 1, an acid or alkali pH adjuster is added as needed to adjust the pH of the RO membrane
The pH is adjusted to 8.
【００１４】ｐＨ調整された水は、次いでカチオン交換
塔２に通水され、カチオン交換樹脂によりＣａが除去さ
れる。カチオン交換塔２の流出水は次いでＲＯ膜分離装
置３に導入される。そしてＲＯ膜でＦ、その他の塩類が
分離された透過水を純水（第１処理水）として回収す
る。一方、濃縮水は混合槽４に導入される。The pH-adjusted water is then passed through a cation exchange tower 2 to remove Ca by a cation exchange resin. The effluent from the cation exchange column 2 is then introduced into the RO membrane separation device 3. Then, the permeated water from which F and other salts have been separated by the RO membrane is recovered as pure water (first treated water). On the other hand, the concentrated water is introduced into the mixing tank 4.
【００１５】混合槽４には、カチオン交換塔２から排出
されるカチオン交換樹脂の再生排液が導入され、Ｆが濃
縮され、高濃度にＦを含むＲＯ膜分離装置３の濃縮水
と、カチオン交換樹脂の再生によりＣａを多量に含む再
生排液とが混合される。In the mixing tank 4, a regenerated effluent of the cation exchange resin discharged from the cation exchange tower 2 is introduced, F is concentrated, and the concentrated water of the RO membrane separation device 3 containing F at a high concentration is mixed with the cation exchange resin. By the regeneration of the exchange resin, the regeneration wastewater containing a large amount of Ca is mixed.
【００１６】本発明においては、カチオン交換塔２の再
生液としてはＮａＣｌ水溶液を用いるのが、中性の再生
排液が得られるため有利である。即ち、再生排液が中性
であれば、ＲＯ膜分離装置３の濃縮水もｐＨ５〜８のほ
ぼ中性域であるため、これらを混合すれば、ｐＨ調整を
行うことなく、ＣａＦ2 の沈殿に好適なｐＨ域（ｐＨ６
〜８）とすることができる。従って、カチオン交換塔２
のカチオン交換樹脂としてはＮａ型弱酸性カチオン交換
樹脂又はＮａ型強酸性カチオン交換樹脂を用いる。In the present invention, it is advantageous to use an aqueous solution of NaCl as the regenerating solution for the cation exchange column 2 because a neutral regenerating effluent can be obtained. That is, if the regenerated effluent is neutral, the concentrated water in the RO membrane separation device 3 is also in a substantially neutral range of pH 5 to 8, and if these are mixed, the CaF 2 precipitates without pH adjustment. PH range (pH 6
To 8). Therefore, the cation exchange column 2
As the cation exchange resin, a Na type weakly acidic cation exchange resin or a Na type strongly acidic cation exchange resin is used.
【００１７】ＲＯ膜分離装置３の濃縮水とカチオン交換
樹脂の再生排液とは混合槽４で混合された後、凝集槽５
でポリアクリルアミド系ポリマー等の高分子凝集剤が添
加され、これにより、ＣａＦ2 が析出沈殿する。このＣ
ａＦ2 は沈殿槽６で分離される。After the concentrated water of the RO membrane separation device 3 and the regenerated effluent of the cation exchange resin are mixed in the mixing tank 4, the coagulation tank 5
, A polymer coagulant such as a polyacrylamide polymer is added, whereby CaF 2 precipitates and precipitates. This C
aF 2 is separated in the sedimentation tank 6.
【００１８】沈殿槽６でＣａＦ2 を分離して得られる分
離水は、放流可能な排出基準（一般的にはＦ濃度１５ｐ
ｐｍ以下）にまで十分にＦ濃度を低減したものとなり、
処理水として系外に排出し放流することができる。The separated water obtained by separating CaF 2 in the sedimentation tank 6 is discharged according to a discharge standard (generally, an F concentration of 15 p
pm or less).
It can be discharged outside the system as treated water and discharged.
【００１９】なお、この場合、ＦをＣａＦ2 として十分
に除去するには、再生排液中のＣａが不足する場合に
は、混合槽４に別途Ｃａ源を添加してＣａの不足分を補
う。この場合、Ｃａ源としてＣａＣｌ2 を添加すれば、
ｐＨ調整を行う必要がないが、Ｃａ（ＯＨ）2 を用いた
場合には更にＨＣｌ又はＨ2 ＳＯ4 等の酸を添加して系
内のｐＨを６〜８程度に調整する必要がある。In this case, in order to sufficiently remove F as CaF 2 , if Ca in the regenerated effluent is insufficient, a Ca source is separately added to the mixing tank 4 to make up for the insufficient Ca. . In this case, if CaCl 2 is added as a Ca source,
Although not necessary to perform the pH adjustment, it is necessary to further adjust the 6 to 8 the pH in acid added systems such as HCl or H 2 SO 4 in the case of using Ca (OH) 2.
【００２０】図１に示す方法は、Ｆを含む地下水やＦを
含む排水を予めＣａ塩を添加して沈殿処理を行ない、こ
れをそのまま放流又は雑用水として再利用あるいは純水
として回収等、多目的のため一次処理を行なったＣａ及
びＦを含む排水の処理等に有効である。In the method shown in FIG. 1, groundwater containing F or wastewater containing F is subjected to a precipitation treatment by adding Ca salt in advance, and this is discharged as it is or reused as miscellaneous water or recovered as pure water. Therefore, it is effective for the treatment of wastewater containing Ca and F which has been subjected to the primary treatment.
【００２１】図２に示す方法は、Ｃａを含むがＦをほと
んど含まない通常の工水、水道水、あるいはＣａ塩を使
用した排水処理水等のＣａ含有水と、ＩＣ製造工程から
排出されるような、ＨＦ，ＮＨ4 Ｆ等のＦとＨＮＯ3 等
の酸を含み、Ｃａを含まないＦ含有水とがそれぞれ分別
されて排出される場合に好適な方法であり、この場合に
は、図２に示す如く、Ｃａ含有水のみをカチオン交換塔
２で処理し、Ｆ含有水はカチオン交換塔２に通水するこ
となく、直接ＲＯ膜分離装置３で処理する。このように
することにより、Ｃａ含有水とＦ含有水とを混合して処
理する場合に比べて、カチオン交換塔２の通水量が低減
されるため、カチオン交換塔２を小型化することができ
る。In the method shown in FIG. 2, Ca-containing water such as ordinary industrial water containing tap water, tap water, or treated waste water using Ca salt, which contains Ca but hardly contains F, is discharged from the IC manufacturing process. Such a method is suitable for a case in which F such as HF and NH 4 F and F-containing water containing an acid such as HNO 3 and containing no Ca are separated and discharged, respectively. As shown in FIG. 2, only Ca-containing water is treated in the cation exchange column 2, and F-containing water is treated directly in the RO membrane separation device 3 without passing through the cation exchange column 2. By doing so, the amount of water passing through the cation exchange tower 2 is reduced as compared with the case where the Ca-containing water and the F-containing water are mixed and treated, so that the cation exchange tower 2 can be downsized. .
【００２２】図２に示す方法では、Ｃａ含有水及びＦ含
有水をそれぞれｐＨ調整槽１Ａ，１Ｂに導入して、前述
の如く、ＲＯ膜分離装置３の通水条件であるｐＨ５〜８
にｐＨ調整する。In the method shown in FIG. 2, Ca-containing water and F-containing water are introduced into the pH adjusting tanks 1A and 1B, respectively, and the pH of the RO membrane separation apparatus 3 is adjusted to pH 5 to 8 as described above.
Adjust the pH to.
【００２３】そして、Ｆ含有水はそのまま滞留槽７へ送
られる。一方、Ｃａ含有水はカチオン交換塔２に通水し
てＣａを除去して第１処理水とされ、滞留槽７へ送られ
る。Ｆ含有水と第１処理水とが混合された水は、この滞
留槽７からＲＯ膜分離装置３に導入され、ＲＯ膜でＦ及
びその他の塩類を除去して得られる透過水を純水（第２
処理水）として回収する。Then, the F-containing water is sent to the retention tank 7 as it is. On the other hand, the Ca-containing water is passed through the cation exchange tower 2 to remove Ca and becomes the first treated water, which is sent to the retention tank 7. The water in which the F-containing water and the first treated water are mixed is introduced into the RO membrane separation device 3 from the retention tank 7, and the permeated water obtained by removing F and other salts with the RO membrane is purified water ( Second
(Treated water).
【００２４】このＲＯ膜分離装置３の濃縮水とカチオン
交換塔２の再生排液は、図１に示す方法と同様に、混合
槽４に導入されて混合された後、凝集槽５で高分子凝集
剤の添加を受けて凝集処理され、次いで沈殿槽６でＣａ
Ｆ2 が沈殿分離され、分離水は処理水（第３処理水）と
して系外へ排出される。The concentrated water of the RO membrane separation device 3 and the regenerated effluent of the cation exchange column 2 are introduced into a mixing tank 4 and mixed, as in the method shown in FIG. Coagulation treatment is performed by adding a coagulant, and then Ca
F 2 is precipitated and separated, and the separated water is discharged out of the system as treated water (third treated water).
【００２５】この方法においても、再生排液中のＣａの
みでは、濃縮水中のＦをＣａＦ2 として十分に除去する
ことができない場合には、別途ＣａＣｌ2 などのＣａ源
を混合槽４に添加する。Ｃａ（ＯＨ）2 を使用する場合
はＨＣｌ又はＨ2 ＳＯ4 でｐＨ６〜８に調整する必要が
ある。これは混合槽で行なってもよいが、混合槽の次工
程にｐＨ調整槽を設置した方が運転管理は容易となる。Also in this method, when F in the concentrated water cannot be sufficiently removed as CaF 2 only by Ca in the regenerated effluent, a Ca source such as CaCl 2 is separately added to the mixing tank 4. . When using Ca (OH) 2 has to be adjusted to pH6~8 with HCl or H 2 SO 4. This may be carried out in a mixing tank, but operation management is easier if a pH adjusting tank is provided in the next step of the mixing tank.
【００２６】[0026]
【実施例】以下に、実施例を挙げて本発明をより具体的
に説明する。The present invention will be described below more specifically with reference to examples.
【００２７】実施例１ Ｃａ及びＦを含む下記水質の地下水を原水として図１に
示す方法で処理を行った。Example 1 Groundwater of the following quality containing Ca and F was treated as raw water by the method shown in FIG.
【００２８】原水水質 ｐＨ：６．２ Ｃａ：１２ｍｇ／Ｌ Ｆ ：６．５ｍｇ／Ｌ このＣａ・Ｆ含有水を直接カチオン交換樹脂としてレバ
チットＣＮＰ−８０（バイエル社製）を１．０Ｌ充填し
たカチオン交換塔２にＳＶ２０／ｈｒで通水した。 Raw water quality pH: 6.2 Ca: 12 mg / L F: 6.5 mg / L Cation filled with 1.0 L of Levatit CNP-80 (manufactured by Bayer) using the Ca.F-containing water directly as a cation exchange resin. Water was passed through the exchange tower 2 at SV 20 / hr.
【００２９】次いで、カチオン交換塔２の流出水（水質
は表１に示す通り。）をＲＯ膜分離装置３に導入し、透
過水を純水として回収すると共に、濃縮水を混合槽４に
送給した。このＲＯ膜分離装置３は、ＲＯ膜としてポリ
アミド系材質のスパイラル型のものを用いたものであ
り、ＲＯ膜分離は水回収率８０％で操作圧１０〜１５気
圧の条件で行った。Next, the effluent from the cation exchange tower 2 (the water quality is as shown in Table 1) is introduced into the RO membrane separation device 3, and the permeated water is recovered as pure water, and the concentrated water is sent to the mixing tank 4. Paid. The RO membrane separator 3 uses a spiral type RO membrane made of a polyamide material as the RO membrane. The RO membrane separation was performed at a water recovery of 80% and an operating pressure of 10 to 15 atm.
【００３０】得られた純水及び濃縮水の水質は表１に示
す通りであり、高純度の純水が得られた。The quality of the obtained pure water and concentrated water is as shown in Table 1, and high-purity pure water was obtained.
【００３１】カチオン交換塔２は１０重量％ＮａＣｌ水
溶液により、４０００ＢＶに１回の頻度で再生レベル１
００ｇ−ＮａＣｌ／Ｌ−樹脂，ＳＶ５／ｈｒの条件で再
生処理した。再生により得られた表１に示す水質の再生
排液は、混合槽４に送給した。The cation exchange column 2 is regenerated with a 10% by weight aqueous solution of NaCl once every 4000 BV.
Regeneration treatment was performed under the conditions of 00g-NaCl / L-resin and SV5 / hr. The regenerated wastewater of the quality shown in Table 1 obtained by the regeneration was fed to the mixing tank 4.
【００３２】混合槽４では、再生排液と濃縮水とを１：
８０の容量比で混合し、その後、ＣａＣｌ2 ３００ｍｇ
／Ｌ（ａｓ Ｃａ）及び凝集槽５でポリマー（クリフロ
ックＰＡ３６７（栗田工業（株）製））を１ｍｇ／Ｌ添
加した後、沈殿槽６でＣａＦ2 を分離した。In the mixing tank 4, the regenerated effluent and the concentrated water are mixed at 1:
Mix at a volume ratio of 80, then add 300 mg of CaCl 2
/ L (as Ca) and 1 mg / L of polymer (Cryfloc PA367 (manufactured by Kurita Kogyo Co., Ltd.)) were added in the flocculation tank 5, and then CaF 2 was separated in the precipitation tank 6.
【００３３】沈殿槽６の分離水の水質は表１に示す通り
であり、放流可能な処理水が得られた。The quality of the separated water in the sedimentation tank 6 was as shown in Table 1, and treated water that could be discharged was obtained.
【００３４】[0034]
【表１】 [Table 1]
【００３５】実施例２ 半導体工場の総合廃水処理設備から排出されるＣａを含
む下記水質の排水とエッチング工程から排出されるＦを
含む下記水質の排水を原水として図２に示す方法で処理
を行った。Example 2 The wastewater of the following quality containing Ca discharged from the integrated wastewater treatment facility of a semiconductor factory and the wastewater of the following quality containing F discharged from the etching step are treated as raw water by the method shown in FIG. Was.
【００３６】Ｃａ系原水水質 ｐＨ：９．５ Ｃａ：６０ｍｇ／Ｌ Ｆ ：０．１ｍｇ／Ｌ以下Ｆ系原水水質 ｐＨ：３．１ Ｆ ：３２．６ｍｇ／Ｌ Ｃａ：０．１ｍｇ／Ｌ以下 このＣａ含有水及びＦ含有水をそれぞれｐＨ調整槽１
Ａ，１ＢでＨＣｌ又はＮａＯＨを添加してｐＨ６．０に
調整した後、Ｃａ含有水はカチオン交換樹脂としてレバ
チットＣＮＰ−８０（バイエル社製）を１．０Ｌ充填し
たカチオン交換塔２にＳＶ２０／ｈｒで通水した。 Ca-based raw water quality pH: 9.5 Ca: 60 mg / L F: 0.1 mg / L or less F-based raw water quality pH: 3.1 F: 32.6 mg / L Ca: 0.1 mg / L or less The Ca-containing water and the F-containing water are each stored in a pH adjusting tank 1
After adjusting the pH to 6.0 by adding HCl or NaOH with A and 1B, the Ca-containing water was placed in a cation exchange column 2 packed with 1.0 L of Levatit CNP-80 (manufactured by Bayer) as a cation exchange resin, and the SV20 / hr was added. Water was passed.
【００３７】このカチオン交換塔２の流出水（水質は表
２に示す通り。）とｐＨ調整したＦ含有水を滞留槽７を
経てＲＯ膜分離装置３に導入し、透過水を純水として回
収すると共に、濃縮水を混合槽４に送給した。滞留槽７
へ流入するカチオン交換塔処理水とＦ含有水の比率は
２：１であった。このＲＯ膜分離装置３は、ＲＯ膜とし
てポリアミド系材質のスパイラル型のものを用いたもの
であり、ＲＯ膜分離は水回収率９０％で操作圧１０〜１
５気圧の条件で行った。The effluent (water quality is as shown in Table 2) of the cation exchange tower 2 and the F-containing water whose pH has been adjusted are introduced into the RO membrane separation device 3 through the retention tank 7, and the permeated water is recovered as pure water. At the same time, the concentrated water was fed to the mixing tank 4. Retention tank 7
The ratio of the cation exchange tower treated water and the F-containing water flowing into the reactor was 2: 1. The RO membrane separation apparatus 3 uses a spiral type of a polyamide material as the RO membrane. The RO membrane separation is performed at a water recovery rate of 90% and an operating pressure of 10 to 1%.
The test was performed under the condition of 5 atm.
【００３８】得られた純水及び濃縮水の水質は表２に示
す通りであり、高純度の純水が得られた。The quality of the obtained pure water and concentrated water is as shown in Table 2, and high-purity pure water was obtained.
【００３９】カチオン交換塔２は１０重量％ＮａＣｌ水
溶液により、７００ＢＶに１回の頻度で再生レベル１０
０ｇ−ＮａＣｌ／Ｌ−樹脂，ＳＶ５／ｈｒの条件で再生
処理した。再生により得られた表２に示す水質の再生排
液は、混合槽４に送給した。The cation exchange column 2 is regenerated with a 10 wt% aqueous solution of NaCl once every 700 BV.
Regeneration treatment was performed under the conditions of 0 g-NaCl / L-resin and SV5 / hr. The regenerated wastewater of the water quality shown in Table 2 obtained by the regeneration was fed to the mixing tank 4.
【００４０】混合槽４では、再生排液と濃縮水とを１：
１０の容量比で混合し、その後、凝集槽５でポリマー
（クリフロックＰＡ３６７（栗田工業（株）社製））を
１ｍｇ／Ｌ添加した後、沈殿槽６でＣａＦ2 を分離し
た。In the mixing tank 4, the regenerated effluent and the concentrated water are mixed at 1:
After mixing at a volume ratio of 10 and then adding 1 mg / L of polymer (Cryfloc PA367 (manufactured by Kurita Kogyo Co., Ltd.)) in the flocculation tank 5, CaF 2 was separated in the precipitation tank 6.
【００４１】沈殿槽６の分離水の水質は表２に示す通り
であり、放流可能な処理水が得られた。The quality of the separated water in the sedimentation tank 6 was as shown in Table 2, and the treated water that could be discharged was obtained.
【００４２】[0042]
【表２】 [Table 2]
【００４３】[0043]
【発明の効果】以上詳述した通り、Ｃａをカチオン交換
樹脂で除去し、Ｆ、その他の塩類をＲＯ膜で分離除去す
る本発明の水処理方法によれば、 ＣａＦ2 によるＲＯ膜の閉塞がない。 従来のイオン交換樹脂法に比べて、イオン交換樹脂
の再生のための薬剤量は大幅に低減される。 ＣａをＣａＣＯ3 として沈殿分離した後、ＲＯ膜分
離処理する従来法に比べて、ＣａＣＯ3 汚泥発生がな
く、しかも、ＲＯ膜の負荷の増大もないため、装置を小
型化できる。 といった効果が奏され、Ｃａ・Ｆ含有水或いは、Ｃａ含
有水及びＦ含有水を低コストにて、安定かつ効率的に処
理することができる。As described above in detail, according to the water treatment method of the present invention in which Ca is removed by a cation exchange resin and F and other salts are separated and removed by an RO membrane, the RO membrane is blocked by CaF 2. Absent. Compared with the conventional ion exchange resin method, the amount of drug for regenerating the ion exchange resin is greatly reduced. Compared to the conventional method of separating RO by Ca as CaCO 3 and separating the RO membrane, CaCO 3 sludge is not generated and the load on the RO membrane is not increased, so that the apparatus can be downsized. Thus, Ca-F-containing water or Ca-containing water and F-containing water can be treated stably and efficiently at low cost.
【００４４】しかもカチオン交換樹脂の再生排液とＲＯ
膜分離処理の濃縮水とを混合し、生成したＣａＦ2 を分
離するのみで、これらを放流可能な処理水にまで処理す
ることができ、再生排液や濃縮水の処理も効率的に行え
る。In addition, the regenerated effluent of the cation exchange resin and the RO
By merely mixing the concentrated water of the membrane separation treatment and separating the generated CaF 2 , it is possible to treat the treated water into a treated water that can be discharged, and the regenerated wastewater and the concentrated water can be efficiently treated.
【図１】請求項１の水処理方法の実施の形態を示す系統
図である。FIG. 1 is a system diagram showing an embodiment of a water treatment method according to claim 1;
【図２】請求項２の水処理方法の実施の形態を示す系統
図である。FIG. 2 is a system diagram showing an embodiment of a water treatment method according to claim 2;
１，１Ａ，１Ｂ ｐＨ調整槽 ２ カチオン交換塔 ３ ＲＯ膜分離装置 ４ 混合槽 ５ 凝集槽 ６ 沈殿槽 ７ 滞留槽 1, 1A, 1B pH adjustment tank 2 Cation exchange tower 3 RO membrane separation device 4 Mixing tank 5 Coagulation tank 6 Sedimentation tank 7 Retention tank
Claims (3)
含有する水を処理する方法において、 該水をカチオン交換樹脂と接触させ、次いで逆浸透膜分
離処理して透過水を第１処理水とする第１工程と、 該カチオン交換樹脂の再生排液と該逆浸透膜分離処理の
濃縮水とを混合してＣａＦ2 を生成させ、このＣａＦ2
を分離して分離水を第２処理水とする第２工程とを有す
ることを特徴とする水処理方法。1. A method for treating water containing fluoride ions and calcium ions, wherein the water is brought into contact with a cation exchange resin, and then subjected to reverse osmosis membrane separation treatment to obtain permeated water as first treated water. a step, to generate CaF 2 by mixing a concentrate of the regeneration effluent and the reverse osmosis membrane separation process of the cation exchange resin, the CaF 2
And treating the separated water as second treated water.
水とカルシウムイオンを含有するカルシウム含有水とを
処理する方法において、 該Ｃａ含有水をカチオン交換樹脂と接触させて第１処理
水を得る第１工程と、 該Ｆ含有水を逆浸透膜分離処理して透過水を第２処理水
とする第２工程と、 該カチオン交換樹脂の再生排液と該逆浸透膜分離処理の
濃縮水とを混合してＣａＦ2 を生成させ、このＣａＦ2
を分離して分離水を第３処理水とする第３工程とを有す
ることを特徴とする水処理方法。2. A method for treating fluoride-containing water containing fluoride ions and calcium-containing water containing calcium ions, comprising: contacting the Ca-containing water with a cation exchange resin to obtain a first treated water. One step, a second step in which the F-containing water is subjected to reverse osmosis membrane separation treatment to make permeated water a second treated water, and a regenerated effluent of the cation exchange resin and concentrated water in the reverse osmosis membrane separation treatment. Mixing to form CaF 2 , and this CaF 2
And treating the separated water as third treated water.
をＦ含有水と共に逆浸透膜分離処理することを特徴とす
る水処理方法。3. The water treatment method according to claim 2, wherein the first treated water is subjected to a reverse osmosis membrane separation treatment together with F-containing water.
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|---|---|---|---|
| JP04903997A JP3622407B2 (en) | 1997-03-04 | 1997-03-04 | Water treatment method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04903997A JP3622407B2 (en) | 1997-03-04 | 1997-03-04 | Water treatment method |
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| Publication Number | Publication Date |
|---|---|
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| JP3622407B2 JP3622407B2 (en) | 2005-02-23 |
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ID=12819954
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006095425A (en) * | 2004-09-29 | 2006-04-13 | Kurita Water Ind Ltd | Method for purifying biological treatment water-containing water of waste water and apparatus for purifying the same |
| JP4543482B2 (en) * | 2000-03-06 | 2010-09-15 | 栗田工業株式会社 | Fluorine-containing water treatment method |
| JP2020018992A (en) * | 2018-08-03 | 2020-02-06 | オルガノ株式会社 | Method and apparatus for treating silica/hardness component-containing water |
| JP2020124668A (en) * | 2019-02-04 | 2020-08-20 | 株式会社東芝 | Water treatment system and water treatment method |
-
1997
- 1997-03-04 JP JP04903997A patent/JP3622407B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4543482B2 (en) * | 2000-03-06 | 2010-09-15 | 栗田工業株式会社 | Fluorine-containing water treatment method |
| JP2006095425A (en) * | 2004-09-29 | 2006-04-13 | Kurita Water Ind Ltd | Method for purifying biological treatment water-containing water of waste water and apparatus for purifying the same |
| JP2020018992A (en) * | 2018-08-03 | 2020-02-06 | オルガノ株式会社 | Method and apparatus for treating silica/hardness component-containing water |
| JP2020124668A (en) * | 2019-02-04 | 2020-08-20 | 株式会社東芝 | Water treatment system and water treatment method |
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| Publication number | Publication date |
|---|---|
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