JP2002059174A - Method of removing fluoride ion and removing agent for the same - Google Patents
Method of removing fluoride ion and removing agent for the sameInfo
- Publication number
- JP2002059174A JP2002059174A JP2000252746A JP2000252746A JP2002059174A JP 2002059174 A JP2002059174 A JP 2002059174A JP 2000252746 A JP2000252746 A JP 2000252746A JP 2000252746 A JP2000252746 A JP 2000252746A JP 2002059174 A JP2002059174 A JP 2002059174A
- Authority
- JP
- Japan
- Prior art keywords
- water
- treated
- containing hydrophilic
- hydrophilic polymer
- carboxyl group
- 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.)
- Pending
Links
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、被処理水中に含ま
れる溶存フッ素イオンを除去する方法及びフッ素イオン
除去剤に関するものである。The present invention relates to a method for removing dissolved fluoride ions contained in water to be treated and a fluoride ion remover.
【０００２】[0002]
【従来の技術】従来から、被処理水中に含まれるフッ素
イオンの除去方法としては、その水中に石灰又は消石灰
等を添加して、フッ素イオンをフッ化カルシウムとして
沈殿させるカルシウム凝集沈殿法が最も一般的に行われ
てきた。この方法では、被処理水中の高濃度（１００ｍ
ｇ／Ｌ以上）のフッ素イオンを中濃度（１０〜２０ｍｇ
／Ｌ）になるまで除去することは可能であるものの、低
濃度（１０ｍｇ／ｌ以下）まで除去することは、大量の
カルシウム塩を使用しても殆んど不可能である。カルシ
ウム凝集沈殿法では、前記のようにフッ素イオンを１０
ｍｇ／Ｌ以下には除去できないので、フッ素イオンを低
濃度に除去する方法としていくつかの方法が検討されて
いる。そのような方法として、吸着剤を用いる吸着法が
提案されているが、この方法の場合、吸着剤コストがか
なり高く、かつ処理条件の制約が厳しい上、吸着剤の再
生等の問題があり、ほとんど実用には供されていない。
また、水酸化アルミニウム形成剤を添加し、難水溶性の
ゲル状の水酸化アルミニウムを生成させるとともに、水
中のフッ素イオンをその水酸化アルミニウムゲルに吸着
除去するアルミニウム法があるが、この処理方法では大
量のアルミニウム化合物を加えなければならず、しかも
沈降性及び脱水性のよいフロックが得られないため、脱
水が困難であり、また大量のスラッジが発生する問題が
ある。2. Description of the Related Art Conventionally, the most common method of removing fluoride ions contained in water to be treated is a calcium coagulation precipitation method in which lime or slaked lime is added to the water to precipitate fluoride ions as calcium fluoride. Has been done. In this method, a high concentration (100 m
g / L or more) of fluorine ions at a medium concentration (10 to 20 mg).
/ L), but it is almost impossible to remove to a low concentration (10 mg / l or less) even by using a large amount of calcium salt. In the calcium coagulation sedimentation method, as described above, 10
Since it cannot be removed at mg / L or less, several methods have been studied as a method for removing fluorine ions at a low concentration. As such a method, an adsorption method using an adsorbent has been proposed, but in this method, the adsorbent cost is considerably high, and the processing conditions are severely restricted, and there are problems such as regeneration of the adsorbent, It is hardly practical.
There is also an aluminum method in which an aluminum hydroxide-forming agent is added to generate a hardly water-soluble gelled aluminum hydroxide, and fluorine ions in water are adsorbed and removed by the aluminum hydroxide gel. Since a large amount of an aluminum compound must be added, and flocs having good sedimentation and dehydration properties cannot be obtained, there is a problem that dehydration is difficult and a large amount of sludge is generated.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、水中から溶
存フッ素イオンを効率よくかつ低められたスラッジ発生
量で除去するための方法及びそれに用いるフッ素イオン
の除去剤を提供することをその課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for efficiently removing dissolved fluorine ions from water with a reduced amount of sludge generated, and a fluorine ion remover used in the method. I do.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、被処理水中に含まれ
る溶存フッ素イオンを除去する方法において、（ｉ）ア
ルミニウムイオンと（ii）カルボキシル基含有親水性高
分子物質及び／又はその加水分解生成物の存在下で、該
被処理水のｐＨを５〜９に調整することによって、該溶
存フッ素イオンを難溶性物質として沈殿させることを特
徴とするフッ素イオンの除去方法が提供される。また、
本発明によれば、被処理水中に含まれる溶存フッ素イオ
ンを除去する薬剤であって、（ｉ）アルミニウム化合物
と（ii）カルボキシル基含有親水性高分子物質及び／又
はその加水分解生成物とからなることを特徴とするフッ
素イオン除去剤が提供される。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, in the method for removing dissolved fluorine ions contained in the water to be treated, the presence of (i) aluminum ion and (ii) a carboxyl group-containing hydrophilic polymer substance and / or a hydrolysis product thereof A method for removing fluorine ions is provided, wherein the pH of the water to be treated is adjusted to 5 to 9 to precipitate the dissolved fluorine ions as a hardly soluble substance. Also,
According to the present invention, there is provided an agent for removing dissolved fluoride ions contained in water to be treated, comprising: (i) an aluminum compound and (ii) a carboxyl group-containing hydrophilic polymer substance and / or a hydrolysis product thereof. A fluorine ion removing agent is provided.
【０００５】[0005]
【発明の実施の形態】本発明のフッ素イオン除去剤（以
下、単に除去剤とも言う）は、（ｉ）アルミニウム化合
物と（ii）カルボキシル基含有親水性高分子物質及び／
又はその加水分解生成物との混合物からなるものであ
る。アルミニウム化合物には、水中で加水分解してゲル
状の水酸化アルミニウムを生成するものであればよく、
従来公知の各種のものを用いることができる。このよう
なものとしては、例えば、塩化アルミニウムやポリ塩化
アルミニウム、硫酸アルミニウム、硝酸アルミニウム、
アルミン酸ソーダ等が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The fluoride ion remover of the present invention (hereinafter also simply referred to as a remover) comprises (i) an aluminum compound, (ii) a carboxyl group-containing hydrophilic polymer substance and / or
Or a mixture with a hydrolysis product thereof. The aluminum compound may be any compound that hydrolyzes in water to produce a gel-like aluminum hydroxide,
Conventionally known various types can be used. Such materials include, for example, aluminum chloride and polyaluminum chloride, aluminum sulfate, aluminum nitrate,
And sodium aluminate.
【０００６】カルボキシル基含有親水性高分子物質に
は、各種の水溶性高分子物質が包含される。このような
高分子物質としては、アルギン酸、ジエランガム、キサ
ンタンガム、ペクチン、ペクチン酸、ペクチニン酸、ア
ニオン化でんぷん、アルギン酸プロピレングリコールエ
ステル、カルボキシメチルセルロース、デンプングリコ
ール酸、繊維素グリコール酸等の多糖類及びそれらの金
属塩等が挙げられる。The carboxyl group-containing hydrophilic polymer substance includes various water-soluble polymer substances. Such high-molecular substances include polysaccharides such as alginic acid, dielan gum, xanthan gum, pectin, pectic acid, pectinic acid, anionized starch, propylene glycol alginate, carboxymethylcellulose, starch glycolic acid, cellulose glycolic acid, and the like. Metal salts and the like.
【０００７】本発明では、特に、アルギン酸ナトリウム
やアルギン酸カルシウムの使用が好ましいが、このもの
を用いる場合には、アルギン酸を構成しているマンヌマ
ロン酸（Ｍ）とグルロン酸（Ｇ）の含有比率（モル比）
［Ｍ］／［Ｇ］が、０．１〜４．０、好ましくは０．１
〜３の範囲にあるものの使用が好ましい。グルロン酸の
含有比率が多いもの程、フロック形成性にすぐれてい
る。In the present invention, it is particularly preferable to use sodium alginate or calcium alginate. In the case of using these, the content ratio (molar ratio) of mannumaric acid (M) and guluronic acid (G) constituting alginic acid is preferably used. ratio)
[M] / [G] is 0.1 to 4.0, preferably 0.1
It is preferable to use those in the range of ~ 3. The higher the content of guluronic acid, the better the floc-forming property.
【０００８】本発明において除去剤主体として用いる前
記カルボキシル基含有親水性高分子物質は、単独又は混
合物の形態で用いることができる。混合物としては、ア
ルギン酸又はその塩を含有する混合物の使用が好まし
い。In the present invention, the carboxyl group-containing hydrophilic high-molecular substance used as the main remover can be used alone or in the form of a mixture. As the mixture, it is preferable to use a mixture containing alginic acid or a salt thereof.
【０００９】本発明において除去剤主体として用いる前
記カルボキシル基含有親水性高分子物質の好ましい混合
物の具体例としては、（ｉ）アルギン酸又はその塩と、
（ii）ジエランガム、キサンタンガム、ペクチン、ペク
チン酸、ペクチニン酸及びそれらの塩の中から選ばれる
少なくとも１種の親水性高分子物質との混合物を挙げる
ことができる。その混合比を示すと、例えば、アルギン
酸ナトリウムと他のアニオン基含有親水性高分子物質と
の混合物を用いる場合、アルギン酸ナトリウム（Ａ）と
他のアニオン基含有親水性高分子物質（Ｂ）との重量比
［Ａ］／［Ｂ］は、１〜１００、好ましくは２〜５０で
ある。Specific examples of the preferred mixture of the carboxyl group-containing hydrophilic polymer substance used as a remover in the present invention include (i) alginic acid or a salt thereof;
(Ii) Mixtures with at least one hydrophilic polymer selected from dielan gum, xanthan gum, pectin, pectic acid, pectinic acid and salts thereof. When the mixture ratio is shown, for example, when a mixture of sodium alginate and another anion group-containing hydrophilic polymer is used, the mixture of sodium alginate (A) and another anion group-containing hydrophilic polymer (B) is used. The weight ratio [A] / [B] is 1 to 100, preferably 2 to 50.
【００１０】本発明の除去剤を好ましく製造するには、
先ず、カルボキシル基を含有する親水性高分子物質を水
に溶かすが、よく溶けない場合は、アルカリ物質を含む
水中において加熱し、加水分解させるとともに水中に溶
解させる。例えば、アルカリ性物質としての水酸化ナト
リウムを含む水中にアルギン酸ナトリウムを存在させ、
加熱し、そのアルギン酸ナトリウムを溶解させる。この
ときの加熱温度は、沸騰しない７０℃以上から１００℃
未満が好ましく、より好ましくは、７５℃から９０℃、
さらに好ましくは８０℃から８５℃である。加熱時間
は、カルボキシル基含有親水性物質が溶解すればよく、
特に限定されないが、０．５時間から２時間程度で十分
である。次に、得られたカルボキシル基含有親水性高分
子物質及び／又はその加水分解生成物を含有する水溶液
にアルミニウム化合物を混合することにより本発明の除
去剤を製造することが出来る。In order to preferably produce the removing agent of the present invention,
First, a hydrophilic polymer substance containing a carboxyl group is dissolved in water. If the substance is not well dissolved, the carboxyl group is heated in water containing an alkaline substance, hydrolyzed, and dissolved in water. For example, sodium alginate is present in water containing sodium hydroxide as an alkaline substance,
Heat to dissolve the sodium alginate. The heating temperature at this time is from 70 ° C. or higher which does not boil to 100 ° C.
Less than, more preferably from 75 ° C to 90 ° C,
More preferably, the temperature is from 80 ° C to 85 ° C. The heating time only needs to dissolve the carboxyl group-containing hydrophilic substance,
Although not particularly limited, about 0.5 to 2 hours is sufficient. Next, the remover of the present invention can be produced by mixing an aluminum compound with the obtained aqueous solution containing a carboxyl group-containing hydrophilic polymer substance and / or a hydrolysis product thereof.
【００１１】アニオン基含有親水性高分子物質及び／又
はその加水分解生成物とアルミニウム化合物の割合は、
特に制約されないが、一般的には、アニオン基含有親水
性高分子物質及び／又はその加水分解生成物１重量部に
対して、アルミニウム化合物１〜１００００重量部、好
ましくは５〜５０００重量部、より好ましくは、５〜１
０００重量部の割合である。[0011] The ratio of the anionic group-containing hydrophilic polymer substance and / or its hydrolysis product to the aluminum compound is as follows:
Although not particularly limited, generally, 1 to 10,000 parts by weight of an aluminum compound, preferably 5 to 5,000 parts by weight, based on 1 part by weight of a hydrophilic polymer substance containing an anion group and / or a hydrolysis product thereof, Preferably, 5-1
000 parts by weight.
【００１２】本発明により被処理水中のフッ素イオンを
除去するには、除去剤の存在下でｐＨを５〜９に調整す
ればよい。In order to remove fluorine ions in the water to be treated according to the present invention, the pH may be adjusted to 5 to 9 in the presence of a removing agent.
【００１３】本発明の除去剤を用いて被処理水中に溶存
するフッ素イオンを除去する場合、その被処理水が酸性
やアルカリ性の場合、除去剤の添加後、沈殿が生じるよ
うにｐＨを調整するのが好ましい。そのｐＨは、一般的
には、５〜９の範囲、好ましくは６〜８の範囲である。When fluorine ions dissolved in the water to be treated are removed using the removing agent of the present invention, if the water to be treated is acidic or alkaline, the pH is adjusted so that precipitation occurs after the addition of the removing agent. Is preferred. The pH is generally in the range from 5 to 9, preferably in the range from 6 to 8.
【００１４】被処理水のｐＨを中性領域に調節する場
合、ｐＨ調節剤が用いられるが、このようなｐＨ調節剤
としては、水酸化ナトリウム、水酸化カリウム、炭酸ナ
トリウム、炭酸カリウム、水酸化カルシウム等のアルカ
リ性物質、もしくは塩酸、硫酸、硝酸等の酸性物質が用
いられる。When the pH of the water to be treated is adjusted to a neutral range, a pH adjuster is used. Examples of such a pH adjuster include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and hydroxide. An alkaline substance such as calcium or an acidic substance such as hydrochloric acid, sulfuric acid or nitric acid is used.
【００１５】本発明の除去剤においては、凝集剤を併用
するのが好ましい。この場合の凝集剤は、フロックの凝
集に用いられているものであり、このようなものには、
ポリアクリルアミドのカチオン化変性物、ポリアクリル
酸ジメチルアミノエチルエステル、ポリメタクリル酸ジ
メチルアミノエチルエステル、ポリエチレンイミン、キ
トサン等のカチオン性有機系凝集剤、ポリアクリルアミ
ド等のノニオン性有機系凝集剤、ポリアクリル酸、アク
リルアミドとアクリル酸との共重合体及びその塩等のア
ニオン性有機系凝集剤が包含される。凝集剤の使用量
は、水中における濃度で、１〜２０ｍｇ／Ｌ、好ましく
は３〜１０ｍｇ／Ｌである。In the removing agent of the present invention, it is preferable to use a coagulant in combination. The flocculant in this case is used for floc flocculation.
Cationically modified polyacrylamide, dimethylaminoethyl polyacrylate, dimethylaminoethyl polymethacrylate, cationic organic coagulants such as polyethyleneimine and chitosan, nonionic organic coagulants such as polyacrylamide, polyacryl Anionic organic coagulants such as acids, copolymers of acrylamide and acrylic acid, and salts thereof are included. The amount of the coagulant used is 1 to 20 mg / L, preferably 3 to 10 mg / L, in water.
【００１６】前記ｐＨ調節工程終了後のフロックを含む
被処理水は、固液分離処理される。この場合の固液分離
方法としては、慣用の方法、例えば、濾過分離、遠心分
離、沈降分離等が挙げられる。The water to be treated containing flocs after the completion of the pH adjusting step is subjected to a solid-liquid separation treatment. The solid-liquid separation method in this case includes a conventional method, for example, filtration separation, centrifugation, sedimentation separation and the like.
【００１７】本発明で用いる被処理水は、溶存フッ素イ
オン（Ｆ-）を含むものであり、各種の工場排水が用い
られる。被処理水中のフッ素イオン濃度は、フッ素原子
（Ｆ）として、１０ｍｇ／Ｌ以上、特に１５ｍｇ／Ｌ以
上である。その上限値は５０ｍｇ／Ｌ程度である。The water to be treated used in the present invention contains dissolved fluorine ions (F − ), and various types of industrial wastewater are used. The concentration of fluorine ions in the water to be treated is 10 mg / L or more, particularly 15 mg / L or more, as fluorine atoms (F). Its upper limit is about 50 mg / L.
【００１８】[0018]
【発明の効果】本発明の方法によれば、被処理水として
の水中に含まれる溶存フッ素イオンを、効率よくかつ低
められたスラッジ発生量で除去することができる。本発
明によれば、被処理水中のフッ素イオンを低められたス
ラッジ量でほぼ完全に除去することができ、フッ素イオ
ンを除去した後の処理水に含まれる溶存フッ素イオンは
１０ｐｐｍ以下、好ましくは８ｐｐｍ以下である。According to the method of the present invention, dissolved fluorine ions contained in the water to be treated can be removed efficiently and with a reduced amount of sludge. According to the present invention, fluorine ions in the water to be treated can be almost completely removed with a reduced amount of sludge, and the dissolved fluorine ions contained in the treated water after removing the fluorine ions are 10 ppm or less, preferably 8 ppm. It is as follows.
【００１９】[0019]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。Next, the present invention will be described in more detail with reference to examples.
【００２０】参考例１ ５００ｍｌのビーカーで、１ＮのＮａＯＨ３００ｍｌに
３０ｇのアルギン酸ナトリウムを添加した後、７５℃〜
８５℃に加熱し３０分以上１時間以内の時間攪拌する。
攪拌し終わった溶液を常温（２５〜３５℃）まで放冷し
た後、１０Ｌのビーカーで、前記常温のアルギン酸ナト
リウム溶液３００ｍｌとアルミン酸ソーダ（Ａｌ2Ｏ3
１９．７〜２０．３％）５７００ｍｌを混合した。この
ようにして本発明の除去剤を得た。REFERENCE EXAMPLE 1 In a 500 ml beaker, 30 g of sodium alginate was added to 300 ml of 1N NaOH, and the mixture was heated to 75 ° C.
Heat to 85 ° C. and stir for 30 minutes to 1 hour.
After the stirred solution was allowed to cool to room temperature (25 to 35 ° C.), 300 ml of the room temperature sodium alginate solution and sodium aluminate (Al 2 O 3 ) were placed in a 10 L beaker.
(19.7-20.3%) 5700 ml were mixed. Thus, the removing agent of the present invention was obtained.
【００２１】実施例１ フッ素濃度が３４．８５ｍｇ／Ｌ，ｐＨ８．５の実際の
工場排水に対して以下の処理を施した。 （１）既存処理Ａ 硫酸を添加してｐＨ７．５に調整後、塩化カルシウムを
５００ｍｇ／Ｌ添加して３分攪拌し、次ぎに硫酸バンド
０．５７ｍｇ／Ｌ添加し３分攪拌をした。これに水酸化
ナトリウムを加えてｐＨ７．５に調整し、高分子凝集剤
を２４ｍｇ／Ｌ添加して生成したスラッジの抜き取りを
行った。得られた処理水に硫酸バンド０．５７ｍｇ／Ｌ
添加し３分間攪拌後水酸化ナトリウムでｐＨを７．５に
調整し、これに高分子凝集剤を６ｍｇ／Ｌ添加し、最終
的な処理水を得た。処理水のフッ素濃度をイオンクロマ
トグラフで分析したところ、その濃度は８．８１ｍｇ／
Ｌで得られたスラッジは２９２．５ｍｇ／Ｌであった。 （２）本発明処理 上記工場排水に本発明除去剤を０．３ｍｌ／Ｌ添加し３
分間攪拌後、硫酸でｐＨ７に調整した。これに高分子凝
集剤を６ｍｇ／Ｌ添加し、最終処理水を得た。処理水の
フッ素濃度をイオンクロマトグラフで分析したところ、
その濃度は７．３５ｍｇ／Ｌで得られたスラッジは２１
４．０ｍｇ／Ｌであった。Example 1 The following treatment was performed on actual factory wastewater having a fluorine concentration of 34.85 mg / L and a pH of 8.5. (1) Existing treatment A After adjusting the pH to 7.5 by adding sulfuric acid, 500 mg / L of calcium chloride was added and the mixture was stirred for 3 minutes, and then 0.57 mg / L of a sulfuric acid band was added and stirred for 3 minutes. The pH was adjusted to 7.5 by adding sodium hydroxide thereto, and sludge generated by adding a polymer coagulant at 24 mg / L was extracted. 0.57 mg / L of sulfuric acid band was added to the obtained treated water.
After adding and stirring for 3 minutes, the pH was adjusted to 7.5 with sodium hydroxide, and a polymer coagulant was added at 6 mg / L to obtain final treated water. When the fluorine concentration of the treated water was analyzed by ion chromatography, the concentration was 8.81 mg /
The sludge obtained in L was 292.5 mg / L. (2) Treatment of the present invention 0.3 ml / L of the remover of the present invention was added to the above-mentioned factory wastewater.
After stirring for minutes, the pH was adjusted to 7 with sulfuric acid. 6 mg / L of a polymer flocculant was added thereto to obtain final treated water. When the fluorine concentration of the treated water was analyzed by ion chromatography,
The sludge obtained at a concentration of 7.35 mg / L was 21
It was 4.0 mg / L.
【００２２】実施例２ フッ素濃度１５．０６ｍｇ／Ｌ、カルシウム濃度１００
０ｍｇ／Ｌ、ｐＨ３．１のモデル排水に本発明除去剤を
０．２ｍｌ／Ｌ添加し３分間攪拌後、硫酸でｐＨ７に調
整した。これに高分子凝集剤を６ｍｇ／Ｌ添加し、最終
処理水を得た。処理水のフッ素濃度をイオンクロマトグ
ラフで分析したところ、その濃度は４．４ｍｇ／Ｌであ
った。Example 2 Fluorine concentration 15.06 mg / L, calcium concentration 100
0.2 ml / L of the remover of the present invention was added to 0 mg / L, model wastewater of pH 3.1, stirred for 3 minutes, and adjusted to pH 7 with sulfuric acid. 6 mg / L of a polymer flocculant was added thereto to obtain final treated water. When the fluorine concentration of the treated water was analyzed by ion chromatography, the concentration was 4.4 mg / L.
【００２３】比較例１ 実施例２のモデル排水に塩化カルシウム１０００ｍｇ／
Ｌを添加し、水酸化ナトリウムでｐＨ１２．７に調整し
たところ、得られた処理水のフッ素濃度は１３．５ｍｇ
／Ｌであった。Comparative Example 1 Calcium chloride 1000 mg /
L was added and the pH was adjusted to 12.7 with sodium hydroxide, and the fluorine concentration of the resulting treated water was 13.5 mg.
/ L.
【００２４】比較例２ 実施例２のモデル排水に水酸化カルシウム１０００ｍｇ
／Ｌを添加し、ｐＨ１２．９に調整したところ、得られ
た処理水のフッ素濃度は１３．７ｍｇ／Ｌであった。Comparative Example 2 1000 mg of calcium hydroxide was added to the model waste water of Example 2.
/ L was added to adjust the pH to 12.9, and the fluorine concentration of the resulting treated water was 13.7 mg / L.
【００２５】参考例２ アルギン酸ナトリウム水溶液（濃度１０００ｍｇ／Ｌ）
を調製し、これをポリ塩化アルミニウム溶液（Ａｌ2Ｏ3
１０％）と容積比１：８で混合し攪拌したところ均一に
分散した。この混合液を除去剤（ＩＩ）とした。Reference Example 2 An aqueous solution of sodium alginate (concentration: 1000 mg / L)
Was prepared, and this was mixed with a polyaluminum chloride solution (Al 2 O 3
10%) and stirred at a volume ratio of 1: 8, and the mixture was uniformly dispersed when stirred. This mixed solution was used as a removing agent (II).
【００２６】実施例３ 実施例２のモデル排水に除去剤（ＩＩ）を５００ｍｇ／
Ｌ添加し、水酸化ナトリウムでｐＨ８に調整した。１０
分間攪拌した後、アニオン性高分子凝集剤５ｍｇ／Ｌ添
加し、固液分離した。得られた処理水のフッ素濃度は
６．７ｍｇ／Ｌであった。Example 3 The remover (II) was added to the model wastewater of Example 2 in an amount of 500 mg /
L was added, and the pH was adjusted to 8 with sodium hydroxide. 10
After stirring for 5 minutes, 5 mg / L of an anionic polymer flocculant was added, followed by solid-liquid separation. The fluorine concentration of the obtained treated water was 6.7 mg / L.
───────────────────────────────────────────────────── フロントページの続き (71)出願人 000005979 三菱商事株式会社 東京都千代田区丸の内２丁目６番３号 (74)上記３名の代理人 100074505 弁理士 池浦 敏明 (72)発明者 辰巳 憲司 茨城県つくば市小野川16番３ 工業技術院 資源環境技術総合研究所内 (72)発明者 和田 愼二 茨城県つくば市小野川16番３ 工業技術院 資源環境技術総合研究所内 (72)発明者 湯川 恭啓 茨城県つくば市千現２−１−６ 三菱商事 プロジェクト開発部環境資源研究所内 Ｆターム(参考） 4D038 AA08 AB42 BB18 4D062 BA19 CA20 DB03 DB04 DB07 DB12 DB15 DB32 DC06 DC07 DC08 EA14 EA16 EA32 FA01 FA02 FA12 FA19 FA28 ──────────────────────────────────────────────────続 き Continuation of the front page (71) Applicant 000005979 Mitsubishi Corporation 2-6-3 Marunouchi, Chiyoda-ku, Tokyo (74) The above three agents 100074505 Patent Attorney Toshiaki Ikeura (72) Inventor Kenji Tatsumi Ibaraki 16-3 Onogawa, Tsukuba, Japan Prefectural Institute of Advanced Industrial Science and Technology (72) Inventor Shinji Wada 16-3 Onogawa, Tsukuba, Ibaraki Pref.Research Institute of Natural Resources and Environmental Science (72) Inventor Yasuhiro Yukawa Ibaraki 2-1-6 Sengen, Tsukuba City Mitsubishi Corporation Project Development Department Environmental Resource Research Laboratory F-term (reference) 4D038 AA08 AB42 BB18 4D062 BA19 CA20 DB03 DB04 DB07 DB12 DB15 DB32 DC06 DC07 DC08 EA14 EA16 EA32 FA01 FA02 FA12 FA19 FA28
Claims (5)
を除去する方法において、（ｉ）アルミニウムイオンと
（ii）カルボキシル基含有親水性高分子物質及び／又は
その加水分解生成物の存在下で、該被処理水のｐＨを５
〜９に調整することによって、該溶存フッ素イオンを難
溶性物質として沈殿させることを特徴とするフッ素イオ
ンの除去方法。1. A method for removing dissolved fluorine ions contained in water to be treated, wherein (i) aluminum ions and (ii) a carboxyl group-containing hydrophilic polymer substance and / or a hydrolysis product thereof, The pH of the water to be treated is 5
A method for removing fluorine ions, wherein the dissolved fluoride ions are precipitated as a hardly soluble substance by adjusting the value to ~ 9.
が、（ｉ）アルギン酸もしくはその塩又は（ii）アルギ
ン酸もしくはその塩と他のアニオン基含有親水性高分子
物質との混合物からなる請求項１の除去方法。2. The carboxyl group-containing hydrophilic high molecular substance comprises (i) alginic acid or a salt thereof or (ii) a mixture of alginic acid or a salt thereof and another anionic group-containing hydrophilic high molecular substance. Removal method.
かの除去方法。3. The method according to claim 1, wherein a coagulant is added.
を除去する薬剤であって、（ｉ）アルミニウム化合物と
（ii）カルボキシル基含有親水性高分子物質及び／又は
その加水分解生成物とからなることを特徴とするフッ素
イオン除去剤。4. An agent for removing dissolved fluoride ions contained in water to be treated, comprising (i) an aluminum compound and (ii) a carboxyl group-containing hydrophilic polymer substance and / or a hydrolysis product thereof. A fluorine ion remover, characterized in that:
が、（ｉ）アルギン酸もしくはその塩又は（ii）アルギ
ン酸もしくはその塩と他のアニオン基含有親水性高分子
物質との混合物からなる請求項４の除去剤。5. The carboxyl group-containing hydrophilic polymer substance comprises (i) alginic acid or a salt thereof or (ii) a mixture of alginic acid or a salt thereof and another anion group-containing hydrophilic polymer substance. Remover.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000252746A JP2002059174A (en) | 2000-08-23 | 2000-08-23 | Method of removing fluoride ion and removing agent for the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000252746A JP2002059174A (en) | 2000-08-23 | 2000-08-23 | Method of removing fluoride ion and removing agent for the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002059174A true JP2002059174A (en) | 2002-02-26 |
Family
ID=18741944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000252746A Pending JP2002059174A (en) | 2000-08-23 | 2000-08-23 | Method of removing fluoride ion and removing agent for the same |
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| Country | Link |
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| JP (1) | JP2002059174A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003080519A1 (en) * | 2002-03-25 | 2003-10-02 | Mitsubishi Gas Chemical Company, Inc. | Method of wastewater treatment |
| KR101082714B1 (en) | 2003-09-16 | 2011-11-15 | 미츠비시 가스 가가쿠 가부시키가이샤 | Method of Treating Wastewater Containing Fluoride Ion |
Citations (6)
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|---|---|---|---|---|
| JPS4932472A (en) * | 1972-07-25 | 1974-03-25 | ||
| JPS51105578A (en) * | 1975-03-14 | 1976-09-18 | Aisin Seiki | SHARYOYOSEKISAIKAJUOTOGATASEIDOYUATSUSEIGYOSOCHI |
| JPS5670893A (en) * | 1979-11-09 | 1981-06-13 | Norihiko Base | Treatment of muddy water |
| JPS5895582A (en) * | 1981-11-30 | 1983-06-07 | Mitsubishi Heavy Ind Ltd | Treatment of fluorine containing waste water |
| JPH10479A (en) * | 1996-06-12 | 1998-01-06 | Kurita Water Ind Ltd | Fluorine removing device |
| WO1999031017A1 (en) * | 1997-12-15 | 1999-06-24 | Japan As Represented By Ministry Of International Trade And Industry, Director-General, Agency Of Industrial Science And Technology | Method of removing harmful ions and remover for use in the same |
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2000
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4932472A (en) * | 1972-07-25 | 1974-03-25 | ||
| JPS51105578A (en) * | 1975-03-14 | 1976-09-18 | Aisin Seiki | SHARYOYOSEKISAIKAJUOTOGATASEIDOYUATSUSEIGYOSOCHI |
| JPS5670893A (en) * | 1979-11-09 | 1981-06-13 | Norihiko Base | Treatment of muddy water |
| JPS5895582A (en) * | 1981-11-30 | 1983-06-07 | Mitsubishi Heavy Ind Ltd | Treatment of fluorine containing waste water |
| JPH10479A (en) * | 1996-06-12 | 1998-01-06 | Kurita Water Ind Ltd | Fluorine removing device |
| WO1999031017A1 (en) * | 1997-12-15 | 1999-06-24 | Japan As Represented By Ministry Of International Trade And Industry, Director-General, Agency Of Industrial Science And Technology | Method of removing harmful ions and remover for use in the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003080519A1 (en) * | 2002-03-25 | 2003-10-02 | Mitsubishi Gas Chemical Company, Inc. | Method of wastewater treatment |
| KR101082714B1 (en) | 2003-09-16 | 2011-11-15 | 미츠비시 가스 가가쿠 가부시키가이샤 | Method of Treating Wastewater Containing Fluoride Ion |
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