JP2003320376A - Treatment method for fluorine-containing wastewater and chemical agent used therein - Google Patents
Treatment method for fluorine-containing wastewater and chemical agent used thereinInfo
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- JP2003320376A JP2003320376A JP2003050152A JP2003050152A JP2003320376A JP 2003320376 A JP2003320376 A JP 2003320376A JP 2003050152 A JP2003050152 A JP 2003050152A JP 2003050152 A JP2003050152 A JP 2003050152A JP 2003320376 A JP2003320376 A JP 2003320376A
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- Prior art keywords
- rare earth
- ion
- earth element
- drug
- solution
- 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.)
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- 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の除去方法および除去剤に関する
ものである。TECHNICAL FIELD The present invention relates to a method for removing dissolved fluorine ions contained in water to be treated and a removing agent.
【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、水中に塩化カルシウム又は
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（特許文献１参照）。この方法では、被処
理水中のフッ素イオンを高濃度（１００ｍｇ／ｌ以上）
から中濃度（１０〜２０ｍｇ／ｌ）になるまで除去する
ことは可能であるものの、フッ化カルシウムの溶解度が
約１５ｍｇ／ｌであるためフッ素イオンを平成１３年度
に制定された新たな排水基準である８ｍｇ／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。2. Description of the Related Art Conventionally, the most common method for removing the fluorine ions contained in the water to be treated is the calcium coagulation precipitation method in which calcium chloride or slaked lime is added to the water to precipitate the fluorine ions as calcium fluoride. Has been performed (see Patent Document 1). In this method, the concentration of fluorine ions in the water to be treated is high (100 mg / l or more)
Although it is possible to remove it to a medium concentration (10 to 20 mg / l), since the solubility of calcium fluoride is about 15 mg / l, the fluoride ion is a new drainage standard established in 2001. Removal up to some 8 mg / l or less is almost impossible even with the use of large amounts of calcium salt.
【０００３】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８ｍｇ／ｌ以下には除去できないので、
フッ素イオンを低濃度（８ｍｇ／ｌ以下）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。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（特許文献２参照）、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／又は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。また、フッ素を特異的に吸着す
るフッ素吸着樹脂を使用する方法があるが（特許文献３
参照）、高価な吸着樹脂を使用しなければならない。In the calcium coagulation-precipitation method, as described above, fluorine ions cannot be removed to 8 mg / l or less,
Several methods have been studied as methods for removing fluoride ions to a low concentration (8 mg / l or less). Further, there is an aluminum method in which an aluminum hydroxide-forming agent is added to form a sparingly water-soluble gel-like aluminum hydroxide and fluorine ions in water are adsorbed and removed by the aluminum hydroxide gel (see Patent Document 2). ), A large amount of aluminum compound must be added in this treatment method, and since flocs having good sedimentation and / or dehydration properties cannot be obtained, dehydration is difficult and a large amount of sludge is generated. . There is also a method of using a fluorine-adsorbing resin that specifically adsorbs fluorine (Patent Document 3).
), Expensive adsorbent resins must be used.
【０００４】一方、水溶液中でフッ素と希土類元素を反
応させて得られる化合物、例えばフッ化ランタン（Ｌａ
Ｆ３）は、水に溶けないのでフッ素を８ｍｇ／ｌ以下に
除去するのに有効であると考えられ、希土類化合物とア
ルカリ土類金属化合物及びアルカリ金属化合物からなる
水溶性組成物を加える方法が提案されている（特許文献
４参照）。しかし、一般に希土類元素とフッ素が反応し
て生成する結晶のフロックは細かく、さらに凝集剤を添
加しても沈降性の良いフロックが得られず、また、緻密
な脱水性の良いフロックが得られないという問題があ
る。沈降性の良いフロックが得られないと固液分離のた
め砂ろ過や膜処理等の新たな処理設備を必要とし、コス
トの面でも設置場所の確保の点でも大きな問題となって
いる。On the other hand, a compound obtained by reacting fluorine with a rare earth element in an aqueous solution, such as lanthanum fluoride (La)
F 3 ) is insoluble in water and is therefore considered to be effective in removing fluorine to 8 mg / l or less. A method of adding a water-soluble composition consisting of a rare earth compound, an alkaline earth metal compound and an alkali metal compound is It has been proposed (see Patent Document 4). However, generally, the flocs of crystals formed by the reaction of rare earth elements and fluorine are fine, and even if a flocculant is added, flocs with good sedimentation cannot be obtained, and dense flocs with good dehydration cannot be obtained. There is a problem. If flocs with good sedimentation cannot be obtained, solid-liquid separation requires new treatment equipment such as sand filtration and membrane treatment, which is a major problem in terms of cost and securing the installation site.
【０００５】[0005]
【特許文献１】特開２００１−５４７９１号公報[Patent Document 1] Japanese Unexamined Patent Publication No. 2001-54791
【特許文献２】特開平９−２７６８７５号公報[Patent Document 2] Japanese Patent Laid-Open No. 9-276875
【特許文献３】特開平７−１９５０７１号公報[Patent Document 3] Japanese Patent Laid-Open No. 7-195071
【特許文献４】特開平３−１８６３９３号公報[Patent Document 4] Japanese Patent Laid-Open No. 3-186393
【０００６】[0006]
【発明が解決しようとする課題】本発明は、該水中から
溶存フッ素イオンを新たな排水基準の８ｍｇ／ｌ以下に
除去でき、しかも実排水の処理においても重力沈降のみ
の簡単な方法で固液分離を可能とする効率的な処理方
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。DISCLOSURE OF THE INVENTION The present invention is capable of removing dissolved fluorine ions from the water to 8 mg / l or less, which is a new standard for waste water, and is a solid-liquid method by a simple method of gravity sedimentation even when treating actual waste water. It is an object of the present invention to provide an efficient treatment method that enables separation and a fluorine ion remover used therefor.
【０００７】[0007]
【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。すなわち、本発明は、（１）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、該水
中に希土類元素イオン及び無害性多価金属イオンを存在
させた状態で、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分離させるこ
とを特徴とするフッ素イオンの除去方法、（２）該被処
理水中に、カルシウム化合物を添加する（１）項に記載
の除去方法、（３）該無害性多価金属イオンがアルミニ
ウムイオンで、該アルミニウムイオンを存在させるため
にアルミニウム化合物を添加する（１）項に記載の除去
方法、（４）該無害性多価金属イオンが硫酸アルミニウ
ムによって供給される（１）〜（３）のいずれか１項に
記載の除去方法、（５）該無害性多価金属イオンが鉄イ
オンである（１）又は（２）項に記載の除去方法、
（６）該希土類元素イオンが、希土類元素の酸化物、水
酸化物、炭酸塩、リン酸塩、酢酸塩又はハロゲン化物の
水溶液、塩酸溶液又は硫酸溶液として被処理水中に添加
される（１）〜（５）のいずれか１項に記載の除去方
法、（７）凝集剤を添加する（１）〜（６）のいずれか
１項に記載の除去方法、The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides (1) a method for removing dissolved fluorine ions contained in water to be treated, in which a rare earth element ion and a harmless polyvalent metal ion are present in the water, and the pH is adjusted to 5 to 9. A method for removing fluoride ions, characterized by precipitating and separating the dissolved fluoride ions as a sparingly soluble substance by adjustment, (2) a method for removing calcium ions in the water to be treated (1) (3) The harmless polyvalent metal ion is an aluminum ion, and an aluminum compound is added to allow the aluminum ion to be present, (4) The removal method according to item (4), wherein the harmless polyvalent metal ion is The removal method according to any one of (1) to (3), which is supplied by aluminum sulfate, (5) the harmless polyvalent metal ion is an iron ion (1) or (2). Method of removing described in,
(6) The rare earth element ion is added to the water to be treated as an aqueous solution of a rare earth element oxide, hydroxide, carbonate, phosphate, acetate or halide, hydrochloric acid solution or sulfuric acid solution (1) To (5), the removal method according to any one of (5), (7) the removal method according to any one of (1) to (6) of adding a coagulant,
【０００８】（８）（１）〜（７）のいずれか１項に記
載の方法に使用される薬剤であって、供給される希土類
元素イオンが薬剤として構成されるものであり、その薬
剤が、希土類元素の酸化物、水酸化物、炭酸塩、リン酸
塩、酢酸塩又はハロゲン化物の水溶液、塩酸溶液又は硫
酸溶液からなる群から選択される少なくとも一種からな
ることを特徴とする薬剤、（９）（１）〜（４）、及び
（６）〜（７）のいずれか１項に記載の方法に使用され
る薬剤であって、供給される希土類元素イオンおよびア
ルミニウムイオンが薬剤として構成されるものであり、
その薬剤が、（ｉ）希土類元素の酸化物、水酸化物、炭
酸塩、リン酸塩、酢酸塩又はハロゲン化物の水溶液、塩
酸溶液又は硫酸溶液からなる群から選択される少なくと
も一種と（ii）硫酸アルミニウム溶液、ポリ塩化アルミ
ニウム溶液又はそれらの混合物との混合物からなること
を特徴とする薬剤、および（１０）（１）、（２）、及
び（５）〜（７）のいずれか１項に記載の方法に使用さ
れる薬剤であって、供給される希土類元素イオンおよび
鉄イオンが薬剤として構成されるものであり、その薬剤
が、（ｉ）希土類元素の酸化物、水酸化物、炭酸塩、リ
ン酸塩、酢酸塩又はハロゲン化物の水溶液、塩酸溶液又
は硫酸溶液からなる群から選択される少なくとも一種と
（ii）塩化第二鉄溶液、ポリ鉄溶液又はそれらの混合物
との混合物からなることを特徴とする薬剤を提供するも
のである。(8) A drug used in the method according to any one of (1) to (7), wherein the supplied rare earth element ion is constituted as a drug, and the drug is , A drug comprising at least one selected from the group consisting of an aqueous solution of a rare earth element oxide, hydroxide, carbonate, phosphate, acetate or halide, a hydrochloric acid solution or a sulfuric acid solution, ( 9) A drug used in the method according to any one of (1) to (4) and (6) to (7), wherein the supplied rare earth element ion and aluminum ion are constituted as a drug. Is something
The agent is (i) at least one selected from the group consisting of oxides, hydroxides, carbonates, phosphates, acetates or halides of rare earth elements, hydrochloric acid solutions or sulfuric acid solutions; and (ii) A drug characterized by comprising a mixture with an aluminum sulfate solution, a polyaluminum chloride solution or a mixture thereof, and (10) (1), (2), and any one of (5) to (7). A drug used in the method as described, wherein the supplied rare earth element ion and iron ion are constituted as a drug, and the agent is (i) a rare earth element oxide, hydroxide or carbonate. , A mixture of at least one selected from the group consisting of an aqueous solution of phosphate, acetate or halide, a hydrochloric acid solution or a sulfuric acid solution, and (ii) a ferric chloride solution, a polyiron solution or a mixture thereof. The present invention provides a drug characterized by the above.
【０００９】[0009]
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明では、多価陰イオン及び／又は無害性多価
金属イオンと希土類元素イオンを被処理水中に存在させ
ｐＨを５〜９に調整する。被処理水へ添加する際の希土
類元素イオンは本発明の目的を達成できればいかなる状
態であってもよいが希土類元素含有溶液として添加する
のが好ましく、希土類元素の酸化物、水酸化物、炭酸
塩、リン酸塩、酢酸塩又はハロゲン化物の水溶液、塩酸
溶液又は硫酸溶液として被処理水へ添加するのが好まし
い。その濃度は特に限定されるものではないが、操作性
を考慮すると、例えば希土類元素酸化物の塩酸溶液の場
合は、塩酸溶液中の希土類元素を酸化物として好ましく
は１０〜６０質量％、より好ましくは３０〜５０質量％
である。また、本発明のフッ素イオン除去剤（以下、単
に除去剤という）は、希土類元素イオンからなるもの、
希土類元素イオンとアルミニウムイオン、並びに希土類
元素イオンと鉄イオンからなるものである。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the present invention, a polyvalent anion and / or a harmless polyvalent metal ion and a rare earth element ion are present in the water to be treated to adjust the pH to 5-9. Rare earth element ions when added to the water to be treated may be in any state as long as the object of the present invention can be achieved, but it is preferable to add as a rare earth element-containing solution, oxides, hydroxides, carbonates of rare earth elements. , Phosphate, acetate or halide solution, hydrochloric acid solution or sulfuric acid solution is preferably added to the water to be treated. The concentration is not particularly limited, but in consideration of operability, for example, in the case of a hydrochloric acid solution of a rare earth element oxide, the rare earth element in the hydrochloric acid solution is preferably 10 to 60% by mass as an oxide, and more preferably Is 30 to 50% by mass
Is. Further, the fluorine ion removing agent of the present invention (hereinafter, simply referred to as a removing agent) comprises a rare earth element ion,
It is composed of rare earth element ions and aluminum ions, and rare earth element ions and iron ions.
【００１０】希土類元素イオンの中でもランタンイオ
ン、セリウムイオンの使用が好ましく、ランタンイオン
の使用がより好ましい。また、本発明において除去剤主
体として用いる希土類元素含有溶液は、希土類元素の混
合物の溶液もしくは、希土類元素の単独又は混合液の形
態で用いることができる。ランタンとセリウム及び／又
はイッテルビウムとの混合溶液の使用が好ましく、ラン
タンとセリウムとの混合溶液がより好ましい。好ましい
具体例としては、ランタンとセリウムとイッテルビウム
との塩酸溶液（濃度は酸化物として５０質量％、その中
の組成は、ランタン９５質量％、セリウム４．９質量
％、イッテルビウム０．１質量％）である。Among the rare earth element ions, lanthanum ions and cerium ions are preferably used, and lanthanum ions are more preferably used. In addition, the rare earth element-containing solution used mainly as a removing agent in the present invention can be used in the form of a solution of a mixture of rare earth elements, or a single or mixed solution of rare earth elements. The use of a mixed solution of lanthanum and cerium and / or ytterbium is preferable, and a mixed solution of lanthanum and cerium is more preferable. As a preferred specific example, a hydrochloric acid solution of lanthanum, cerium, and ytterbium (concentration is 50 mass% as an oxide, and the composition thereof is 95 mass% lanthanum, 4.9 mass% cerium, and 0.1 mass% ytterbium). Is.
【００１１】本発明において、希土類元素イオンの添加
量は、被処理水中のフッ素イオンの濃度にもよるが、フ
ッ素イオン１モル当たり好ましくは０．０１〜１０モ
ル、より好ましくは０．１〜１０モル、さらに好ましく
は０．１〜５モルである。希土類元素イオンの添加量が
少なすぎると沈殿物ができにくくなってフッ素の除去率
が低下してしまい、一方、多すぎると希土類元素が被処
理水中に残ってしまいその除去が必要となる。In the present invention, the amount of the rare earth element ion added depends on the concentration of the fluorine ion in the water to be treated, but is preferably 0.01 to 10 moles, more preferably 0.1 to 10 moles per 1 mole of the fluorine ion. The amount is more preferably 0.1 to 5 mol. If the amount of the rare earth element ion added is too small, precipitates are less likely to be formed and the removal rate of fluorine decreases, while if it is too large, the rare earth element remains in the water to be treated and must be removed.
【００１２】本発明では、希土類元素イオンに加えて、
無害性多価金属イオンを被処理水中に存在させることが
好ましい。無害性多価金属イオンとは、IIIＢ族、VIII
族の多価金属イオンであり、アルカリ土類金属（IIＡ
族）イオン以外のものをいう。具体的には、アルミニウ
ムイオン、鉄イオン等が挙げられ、本発明においては、
アルミニウムイオンの使用がより好ましい。また、無害
性多価金属イオンとは、上水処理でも用いられる意味で
無害である多価金属イオンをいう。無害性多価金属イオ
ンを被処理水中に存在させるには、無害性多価金属化合
物を添加する。それらには、具体例として、アルミニウ
ム化合物として硫酸アルミニウム、塩化アルミニウム、
ポリ塩化アルミニウム等が挙げられ、本発明の場合、硫
酸アルミニウムの使用が特に好ましい。また、鉄化合物
等として塩化第二鉄、硫酸第二鉄、ポリ鉄などが挙げら
れる。In the present invention, in addition to the rare earth element ion,
The harmless polyvalent metal ion is preferably present in the water to be treated. Harmless polyvalent metal ions are IIIB group, VIII
Alkaline earth metal (IIA)
Group) means anything other than ions. Specific examples thereof include aluminum ion and iron ion, and in the present invention,
The use of aluminum ions is more preferred. Further, the harmless polyvalent metal ion means a polyvalent metal ion which is harmless in the sense that it is also used in water treatment. In order to make harmless polyvalent metal ions present in the water to be treated, a harmless polyvalent metal compound is added. Specific examples thereof include aluminum sulfate as an aluminum compound, aluminum chloride,
Examples include polyaluminum chloride, and in the case of the present invention, use of aluminum sulfate is particularly preferable. Further, examples of the iron compound and the like include ferric chloride, ferric sulfate, polyiron and the like.
【００１３】本発明において、無害性多価金属イオンの
添加量は、被処理水中のフッ素イオンの濃度にもよる
が、フッ素イオン１モル当たり好ましくは０．０１〜２
０モル、より好ましくは０．０５〜５モル、さらに好ま
しくは０．１〜３モルである。無害性多価金属イオンの
添加量が少なすぎるとフロックの形成が悪くなり、多す
ぎるとスラッジの量が多くなる等の問題がある。In the present invention, the addition amount of the harmless polyvalent metal ion depends on the concentration of the fluorine ion in the water to be treated, but is preferably 0.01 to 2 per mol of the fluorine ion.
It is 0 mol, more preferably 0.05 to 5 mol, and further preferably 0.1 to 3 mol. If the amount of the harmless polyvalent metal ion added is too small, the formation of flocs becomes poor, and if it is too large, the amount of sludge increases.
【００１４】本発明の特徴の一つは、除去剤への希土類
元素イオンの供給源として、高度に精製分離された高価
な希土類化合物を用いることは必要ではないことであ
る。すなわち、本発明で使用される除去剤（以下、除去
剤［Ｉ］ともいう）は、精製された希土類元素で調製す
る必要はない。例えば、希土類元素を含有している鉱石
から礫、及び鉛等の重金属や放射性元素を除いたものを
塩酸に溶解させた後に粗精製したものを使用することが
できる。このときの塩酸濃度は、０．１〜１２規定が好
ましく、より好ましくは５〜１２規定、さらに好ましく
は８〜１２規定であり、希土類元素イオンの濃度は、特
に限定されるものではないが、操作性を考慮すると、酸
化物として好ましくは１０〜６０質量％、より好ましく
は２０〜５０質量％、さらに好ましくは３０〜５０質量
％である。溶解時間は、完全に溶解すればよく、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。One of the features of the present invention is that it is not necessary to use a highly purified and expensive rare earth compound as a source of rare earth element ions to the scavenger. That is, the removing agent used in the present invention (hereinafter, also referred to as removing agent [I]) does not need to be prepared with a purified rare earth element. For example, an ore containing a rare earth element, from which gravel and heavy metals such as lead and radioactive elements have been removed, is dissolved in hydrochloric acid, and then roughly purified can be used. The hydrochloric acid concentration at this time is preferably 0.1 to 12 N, more preferably 5 to 12 N, further preferably 8 to 12 N, and the concentration of the rare earth element ion is not particularly limited, Considering operability, the oxide content is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, and further preferably 30 to 50% by mass. The dissolution time is not particularly limited as long as it is completely dissolved, but 0.5 hours to 2 hours is sufficient.
【００１５】得られた希土類溶液と硫酸アルミニウム溶
液もしくはポリ塩化アルミニウム溶液と混合することに
より除去剤（以下、除去剤［II］ともいう）を調製する
ことが出来る。アルミニウムイオンは、単独又は混合液
の形態で用いることができる。混合液としては、硫酸ア
ルミニウム又はポリ塩化アルミニウムとの混合液の使用
が好ましい。希土類溶液と硫酸アルミニウムもしくはポ
リ塩化アルミニウム溶液との混合割合は、希土類溶液中
の希土類１モルに対して、好ましくは硫酸アルミニウム
もしくはポリ塩化アルミニウム中のアルミニウム０．１
〜５モル、より好ましくは０．５〜３モル、さらに好ま
しくは１〜２モルの割合である。A removing agent (hereinafter also referred to as a removing agent [II]) can be prepared by mixing the obtained rare earth solution with an aluminum sulfate solution or a polyaluminum chloride solution. Aluminum ions can be used alone or in the form of a mixed solution. As the mixed liquid, it is preferable to use a mixed liquid with aluminum sulfate or polyaluminum chloride. The mixing ratio of the rare earth solution and the aluminum sulfate or polyaluminum chloride solution is preferably 0.1 mol of aluminum in the rare earth solution or 1 mol of the rare earth in the rare earth solution.
The amount is -5 mol, more preferably 0.5-3 mol, still more preferably 1-2 mol.
【００１６】得られた希土類溶液と塩化第二鉄溶液もし
くはポリ鉄溶液と混合することにより除去剤（以下、除
去剤［III］ともいう）を調製することが出来る。鉄イ
オンは、単独又は混合液の形態で用いることができる。
混合液としては、塩化第二鉄溶液又はポリ鉄溶液との混
合液の使用が好ましい。希土類溶液と塩化第二鉄溶液又
はポリ鉄溶液との混合割合は、希土類溶液中の希土類１
モルに対して、好ましくは塩化第二鉄溶液又はポリ鉄溶
液中の鉄０．１〜５モル、より好ましくは０．５〜３モ
ル、さらに好ましくは１〜２モルの割合である。A scavenger (hereinafter also referred to as scavenger [III]) can be prepared by mixing the obtained rare earth solution with a ferric chloride solution or a polyiron solution. The iron ions can be used alone or in the form of a mixed solution.
As the mixed solution, it is preferable to use a mixed solution with a ferric chloride solution or a polyiron solution. The mixing ratio of the rare earth solution and the ferric chloride solution or the polyiron solution is 1% of the rare earth solution in the rare earth solution.
The amount of iron in the ferric chloride solution or the polyiron solution is preferably 0.1 to 5 mol, more preferably 0.5 to 3 mol, and further preferably 1 to 2 mol per mol.
【００１７】本発明の除去剤を用いて排水中に溶存する
フッ素イオンを除去する場合、その排水が酸性や中性の
場合、除去剤の添加後、沈殿が生じるようにｐＨ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、より好ましくは７〜８の
範囲である。ｐＨが低すぎるとフロックが生成せず、高
すぎるとアルミニウムを使用した場合フロックが再溶解
してしまう。When the fluorine ion dissolved in the waste water is removed by using the removing agent of the present invention, when the waste water is acidic or neutral, it is preferable to adjust the pH so that precipitation may occur after adding the removing agent. . Its pH is generally in the range 5-9, preferably in the range 6-8, more preferably in the range 7-8. If the pH is too low, no flocs will be produced, and if it is too high, the flocs will be redissolved when aluminum is used.
【００１８】被処理水のｐＨをアルカリ性領域や酸性領
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 an alkaline range or an acidic range, a pH adjusting agent is used. Examples of such a pH adjusting agent include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, An alkaline substance such as calcium hydroxide or an acidic substance such as hydrochloric acid, sulfuric acid or nitric acid is used.
【００１９】本発明における、希土類元素イオンの存
在、ｐＨ調整の順序は、いずれの順序でもよい。希土類
元素イオンを存在させてからｐＨ調整をしてもよいし、
先にｐＨ調整を行った後に希土類元素イオンを存在させ
てもよい。In the present invention, the order of existence of rare earth element ions and pH adjustment may be any order. The pH may be adjusted after the rare earth ion is present,
The rare earth element ions may be allowed to exist after the pH is adjusted first.
【００２０】本発明においては、カルシウム化合物を併
用することが好ましい。まず従来のカルシウム凝集沈殿
法により被処理水中のフッ素イオンを中濃度になるまで
除去し、その後に本発明の除去方法を適用することで、
本発明で用いられる除去剤の使用量を減らすことができ
る。カルシウム化合物としては塩化カルシウム、硫酸カ
ルシウム、硝酸カルシウム、酢酸カルシウム等が挙げら
れる。カルシウム化合物は、ｐＨ調整の前に被処理水中
に添加することが好ましい。カルシウム化合物の添加量
は、被処理水中のフッ素イオンの濃度にもよるが、フッ
素イオン１モル当たり好ましくは０．０１〜２０モル、
より好ましくは０．０２〜５モル、さらに好ましくは
０．０５〜３モルである。In the present invention, it is preferable to use a calcium compound in combination. First by removing the fluorine ions in the water to be treated to a medium concentration by the conventional calcium coagulation precipitation method, by applying the removal method of the present invention after that,
The amount of the remover used in the present invention can be reduced. Examples of the calcium compound include calcium chloride, calcium sulfate, calcium nitrate, calcium acetate and the like. The calcium compound is preferably added to the water to be treated before pH adjustment. The addition amount of the calcium compound depends on the concentration of the fluorine ion in the water to be treated, but is preferably 0.01 to 20 moles per 1 mole of the fluorine ion,
The amount is more preferably 0.02 to 5 mol, and further preferably 0.05 to 3 mol.
【００２１】さらに本発明においては、凝集剤を併用す
ることが好ましい。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、
塩化第一鉄、塩化第二鉄、硫酸第一鉄、硫酸第二鉄、ポ
リ硫酸第一鉄、ポリ硫酸第二鉄等の無機系凝集剤の他、
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／又はその塩
等のアニオン性有機系凝集剤が包含される。Further, in the present invention, it is preferable to use a coagulant together. The aggregating agent in this case is used for floc aggregating, and in such a thing,
In addition to inorganic flocculants such as ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, ferrous polysulfate, and ferric polysulfate,
Cationic modified polyacrylamide, polyacrylic acid dimethylaminoethyl ester, polymethacrylic acid dimethylaminoethyl ester, polyethyleneimine, cationic organic flocculant such as chitosan, nonionic organic flocculant such as polyacrylamide, polyacrylic Anionic organic flocculants such as acids, copolymers of acrylamide and acrylic acid and / or salts thereof are included.
【００２２】一連の工程終了後、被処理水を固液分離処
理する。この固液分離は常法により行うことができ、例
として、濾過分離、遠心分離、沈降分離等が挙げられ
る。After completion of the series of steps, the water to be treated is subjected to solid-liquid separation treatment. This solid-liquid separation can be performed by a conventional method, and examples thereof include filtration separation, centrifugation, sedimentation separation and the like.
【００２３】[0023]
【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。EXAMPLES Next, the present invention will be described in more detail by way of examples.
【００２４】参考例１
希土類元素化合物の粗精製品を１２Ｎの塩酸溶液に溶解
して調製した溶液（希土類元素の濃度は酸化物として５
０質量％である。希土類元素の組成は、ランタン９５質
量％、セリウム４．９質量％、イッテルビウム０．１質
量％）を除去剤［Ｉ］とした。Reference Example 1 A solution prepared by dissolving a crude refined product of a rare earth element compound in a 12N hydrochloric acid solution (the concentration of the rare earth element is 5 as an oxide.
It is 0 mass%. The composition of the rare earth element was lanthanum 95% by mass, cerium 4.9% by mass, ytterbium 0.1% by mass) as the removing agent [I].
【００２５】参考例２
塩化ランタン水溶液（Ｌａ2Ｏ3として３２．５質量％）
と硫酸アルミニウム水溶液（硫酸バンド ６７質量％）
を１：１で混合し撹拌した。これを除去剤［II］とし
た。Reference Example 2 Aqueous lanthanum chloride solution (32.5% by mass as La 2 O 3 )
And aluminum sulfate aqueous solution (sulfate band 67 mass%)
Were mixed 1: 1 and stirred. This was designated as a remover [II].
【００２６】参考例３
塩化ランタン水溶液（Ｌａ2Ｏ3として３２．５質量％）
と塩化第二鉄水溶液（工業用、３７．５質量％）を１：
０．９で混合し撹拌した。これを除去剤［III］とし
た。Reference Example 3 Lanthanum chloride aqueous solution (32.5 mass% as La 2 O 3 )
And ferric chloride aqueous solution (for industrial use, 37.5 mass%) 1:
The mixture was mixed at 0.9 and stirred. This was designated as a remover [III].
【００２７】実施例１
フッ素濃度２０ｍｇ／ｌ（１．０５ｍＭ）、ｐＨ２．９
のフッ酸排水（５００ｍｌ）に除去剤［II］を、ランタ
ンおよびアルミニウムいずれも０．３５ｍＭとなるよう
に添加し撹拌した。その後、水酸化ナトリウム溶液でｐ
Ｈ７に調整し５分間撹拌した後、固液分離し、処理水中
のフッ素濃度をイオンクロマトグラフ（日本ダイオネク
ス（株）製、カラムIon Pac AS11（商品名））で測定し
たところ、４．３ｐｐｍであった。得られたスラッジは
沈降性が良く、重力による沈降分離のみで固液分離する
ことができた。Example 1 Fluorine concentration 20 mg / l (1.05 mM), pH 2.9
The removing agent [II] was added to the hydrofluoric acid waste water (500 ml) of (3) so that both lanthanum and aluminum had a concentration of 0.35 mM, and the mixture was stirred. After that, p with sodium hydroxide solution
After adjusting to H7 and stirring for 5 minutes, solid-liquid separation was performed, and the fluorine concentration in the treated water was measured by ion chromatography (column Ion Pac AS11 (trade name) manufactured by Nippon Dionex Co., Ltd.) to be 4.3 ppm. there were. The sludge obtained had good sedimentation properties, and solid-liquid separation was possible only by sedimentation separation by gravity.
【００２８】実施例２
フッ素濃度１００ｍｇ／ｌ（５．２６ｍＭ）、ｐＨ２．
３のフッ化ナトリウムモデル排水に除去剤［II］をラン
タンおよびアルミニウムいずれも１．７５ｍＭとなるよ
うに添加し撹拌した。その後、水酸化ナトリウム溶液で
ｐＨ７に調整し５分間撹拌した後、固液分離し、処理水
中のフッ素濃度を測定したところ、３．６ｐｐｍであっ
た。得られたスラッジは沈降性が良く、重力による沈降
分離のみで固液分離することができた。Example 2 Fluorine concentration 100 mg / l (5.26 mM), pH 2.
The remover [II] was added to the sodium fluoride model waste water of No. 3 so that both lanthanum and aluminum had a concentration of 1.75 mM, and the mixture was stirred. Thereafter, the pH was adjusted to 7 with a sodium hydroxide solution, the mixture was stirred for 5 minutes, solid-liquid separated, and the fluorine concentration in the treated water was measured. As a result, it was 3.6 ppm. The sludge obtained had good sedimentation properties, and solid-liquid separation was possible only by sedimentation separation by gravity.
【００２９】実施例３
フッ素濃度１００ｍｇ／ｌ（５．２６ｍＭ）、ｐＨ２．
３のフッ化ナトリウムモデル排水に除去剤［III］をラ
ンタンおよび鉄としていずれも１．７５ｍＭとなるよう
に添加し撹拌した。その後、水酸化ナトリウム溶液でｐ
Ｈ７に調整し５分間撹拌した後、固液分離し、処理水中
のフッ素濃度を測定したところ、６．８ｐｐｍであっ
た。得られたスラッジは沈降性が良く、重力による沈降
分離のみで固液分離することができた。Example 3 Fluorine concentration 100 mg / l (5.26 mM), pH 2.
The remover [III] was added to the sodium fluoride model waste water of No. 3 as lanthanum and iron so as to be 1.75 mM, and stirred. After that, p with sodium hydroxide solution
After adjusting to H7 and stirring for 5 minutes, solid-liquid separation was performed, and the fluorine concentration in the treated water was measured and found to be 6.8 ppm. The sludge obtained had good sedimentation properties, and solid-liquid separation was possible only by sedimentation separation by gravity.
【００３０】実施例４
フッ素濃度１００ｍｇ／ｌ（５．２６ｍＭ）、ｐＨ２．
３のフッ化ナトリウムモデル排水に除去剤［III］をラ
ンタンおよび鉄としていずれも１．７５ｍＭとなるよう
に添加し撹拌した。硫酸ナトリウム水溶液を硫酸根とし
て１．７５ｍＭとなるように添加し撹拌した。その後、
水酸化ナトリウム溶液でｐＨ６に調整し５分間撹拌した
後、固液分離し、処理水中のフッ素濃度を測定したとこ
ろ、７．２ｐｐｍであった。得られたスラッジは沈降性
が良く、重力による沈降分離のみで固液分離することが
できた。Example 4 Fluorine concentration 100 mg / l (5.26 mM), pH 2.
The remover [III] was added to the sodium fluoride model waste water of No. 3 as lanthanum and iron so as to be 1.75 mM, and stirred. An aqueous solution of sodium sulfate was added as sulfate radicals to a concentration of 1.75 mM, and the mixture was stirred. afterwards,
After adjusting the pH to 6 with a sodium hydroxide solution and stirring for 5 minutes, solid-liquid separation was performed and the fluorine concentration in the treated water was measured and found to be 7.2 ppm. The sludge obtained had good sedimentation properties, and solid-liquid separation was possible only by sedimentation separation by gravity.
【００３１】実施例５
フッ素濃度２０ｍｇ／ｌ（１．０５ｍＭ）、ｐＨ２．９
のフッ化ナトリウムモデル排水に除去剤［II］をランタ
ンおよびアルミニウムいずれも０．３５ｍＭとなるよう
に添加し撹拌した。その後、水酸化ナトリウム溶液でｐ
Ｈ７に調整し５分間撹拌した後、固液分離し、処理水中
のフッ素濃度を測定したところ、３．５ｐｐｍであっ
た。得られたスラッジは沈降性が良く、重力による沈降
分離のみで固液分離することができた。Example 5 Fluorine concentration 20 mg / l (1.05 mM), pH 2.9
The removing agent [II] was added to the sodium fluoride model waste water so that the concentration of both lanthanum and aluminum was 0.35 mM, and the mixture was stirred. After that, p with sodium hydroxide solution
After adjusting to H7 and stirring for 5 minutes, solid-liquid separation was performed, and the fluorine concentration in the treated water was measured and found to be 3.5 ppm. The sludge obtained had good sedimentation properties, and solid-liquid separation was possible only by sedimentation separation by gravity.
【００３２】実施例６
フッ素濃度９９．７３ｍｇ／ｌ、ｐＨ３．２の実排水１
リットルに塩化カルシウム（３５％）を５ｍｌ／ｌ添加
し、次に除去剤［Ｉ］を０．１ｍｌ／ｌ、硫酸バンド
（工業品；酸化アルミニウムとして８％）を０．２８ｍ
ｌ／ｌ添加した。その後、水酸化ナトリウム溶液でｐＨ
８に調整し５分間撹拌した後、固液分離し、処理水中の
フッ素濃度をイオンクロマトグラフ（日本ダイオネクス
（株）製、カラムIon Pac AS11（商品名））で測定した
ところ、６．８ｐｐｍであった。得られたスラッジは沈
降性が良く、重力による沈降分離のみで固液分離するこ
とができた。Example 6 Actual wastewater 1 having a fluorine concentration of 99.73 mg / l and a pH of 3.2
To the liter, 5 ml / l of calcium chloride (35%) was added, then 0.1 ml / l of the removing agent [I] and 0.28 m of a sulfuric acid band (industrial product; 8% as aluminum oxide).
1 / l was added. Then pH with sodium hydroxide solution
After adjusting to 8 and stirring for 5 minutes, solid-liquid separation was carried out, and the fluorine concentration in the treated water was measured by an ion chromatograph (manufactured by Nippon Dionex Co., Ltd., column Ion Pac AS11 (trade name)) and found to be 6.8 ppm. there were. The sludge obtained had good sedimentation properties, and solid-liquid separation was possible only by sedimentation separation by gravity.
【００３３】比較例１
除去剤［Ｉ］を添加しないこと以外は実施例６と同様に
して処理を行った結果、フッ素の濃度は１７．９ｐｐｍ
であった。Comparative Example 1 As a result of the same treatment as in Example 6 except that the removing agent [I] was not added, the fluorine concentration was 17.9 ppm.
Met.
【００３４】[0034]
【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除去する
ことができる。本発明の方法によれば、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を８ｐ
ｐｍ以下にすることができる。According to the method of the present invention, dissolved fluorine ions contained in water as water to be treated can be efficiently removed. According to the method of the present invention, the dissolved fluorine ion contained in the treated water after removing the fluorine ion is 8 p
It can be pm or less.
フロントページの続き (72)発明者 和田 愼二 茨城県つくば市東１−１−１ 独立行政法 人産業技術総合研究所つくばセンター内 (72)発明者 湯川 恭啓 茨城県つくば市千現２−１−６ 三菱商事 株式会社環境・開発プロジェクト本部環 境・ジェラニック事業ユニット環境資源研 究所内 Ｆターム(参考） 4D015 BA19 BA23 BB05 CA17 DA13 DA15 DA16 DB02 DB03 DB15 DB24 DB32 EA32 FA01 FA11 FA28 4D038 AA08 AB40 AB41 AB42 BB13 BB18 Continued front page (72) Inventor Shinji Wada 1-1-1 Higashi 1-1-1 Tsukuba City, Ibaraki Prefecture Inside the Tsukuba center (72) Inventor, Yasuhiro Yukawa 2-1-6 Sengen, Tsukuba-shi, Ibaraki Mitsubishi Corporation Environment & Development Project Co., Ltd. Sakai / Jeronic Business Unit Inside the laboratory F-term (reference) 4D015 BA19 BA23 BB05 CA17 DA13 DA15 DA16 DB02 DB03 DB15 DB24 DB32 EA32 FA01 FA11 FA28 4D038 AA08 AB40 AB41 AB42 BB13 BB18
Claims (10)
を除去する方法において、該水中に希土類元素イオン及
び無害性多価金属イオンを存在させた状態で、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
性物質として沈殿分離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 the pH is set to 5 in the state where rare earth element ions and harmless polyvalent metal ions are present in the water.
A method for removing fluoride ions, wherein the dissolved fluoride ions are precipitated and separated as a hardly soluble substance by adjusting to 9 to 9.
加する請求項１記載の除去方法。2. The removal method according to claim 1, wherein a calcium compound is added to the water to be treated.
イオンで、該アルミニウムイオンを存在させるためにア
ルミニウム化合物を添加する請求項１又は２に記載の除
去方法。3. The removal method according to claim 1, wherein the harmless polyvalent metal ion is an aluminum ion, and an aluminum compound is added to allow the aluminum ion to exist.
ウムによって供給される請求項１〜３のいずれか１項に
記載の除去方法。4. The removal method according to claim 1, wherein the harmless polyvalent metal ion is supplied by aluminum sulfate.
る請求項１又は２に記載の除去方法。5. The removing method according to claim 1, wherein the harmless polyvalent metal ion is an iron ion.
化物、水酸化物、炭酸塩、リン酸塩、酢酸塩又はハロゲ
ン化物の水溶液、塩酸溶液又は硫酸溶液として被処理水
中に添加される請求項１〜５のいずれか１項に記載の除
去方法。6. The rare earth element ion is added to the water to be treated as an aqueous solution of a rare earth element oxide, hydroxide, carbonate, phosphate, acetate or halide, hydrochloric acid solution or sulfuric acid solution. Item 6. The removal method according to any one of Items 1 to 5.
か１項に記載の除去方法。7. The removing method according to claim 1, wherein a flocculant is added.
法に使用される薬剤であって、供給される希土類元素イ
オンが薬剤として構成されるものであり、その薬剤が、
希土類元素の酸化物、水酸化物、炭酸塩、リン酸塩、酢
酸塩又はハロゲン化物の水溶液、塩酸溶液又は硫酸溶液
からなる群から選択される少なくとも一種からなること
を特徴とする薬剤。8. A drug used in the method according to any one of claims 1 to 7, wherein the supplied rare earth ion is constituted as a drug, and the drug is
A drug comprising at least one selected from the group consisting of an aqueous solution of a rare earth element oxide, hydroxide, carbonate, phosphate, acetate or halide, hydrochloric acid solution or sulfuric acid solution.
項に記載の方法に使用される薬剤であって、供給される
希土類元素イオンおよびアルミニウムイオンが薬剤とし
て構成されるものであり、その薬剤が、（ｉ）希土類元
素の酸化物、水酸化物、炭酸塩、リン酸塩、酢酸塩又は
ハロゲン化物の水溶液、塩酸溶液又は硫酸溶液からなる
群から選択される少なくとも一種と（ii）硫酸アルミニ
ウム溶液、ポリ塩化アルミニウム溶液又はそれらの混合
物との混合物からなることを特徴とする薬剤。9. Any one of claims 1 to 4 and 6 to 7
The drug used in the method according to the item (1), wherein the supplied rare earth element ion and aluminum ion are constituted as a drug, and the agent is (i) a rare earth element oxide, a hydroxide, Consists of a mixture of at least one selected from the group consisting of aqueous solutions of carbonates, phosphates, acetates or halides, hydrochloric acid solutions or sulfuric acid solutions, and (ii) aluminum sulfate solutions, polyaluminum chloride solutions or mixtures thereof. A drug characterized by the following.
１項に記載の方法に使用される薬剤であって、供給され
る希土類元素イオンおよび鉄イオンが薬剤として構成さ
れるものであり、その薬剤が、（ｉ）希土類元素の酸化
物、水酸化物、炭酸塩、リン酸塩、酢酸塩又はハロゲン
化物の水溶液、塩酸溶液又は硫酸溶液からなる群から選
択される少なくとも一種と（ii）塩化第二鉄溶液、ポリ
鉄溶液又はそれらの混合物との混合物からなることを特
徴とする薬剤。10. A drug used in the method according to any one of claims 1, 2 and 5 to 7, wherein the supplied rare earth element ion and iron ion are constituted as a drug. And the agent is (i) at least one selected from the group consisting of oxides, hydroxides, carbonates, phosphates, acetates or halides of rare earth elements, hydrochloric acid solutions or sulfuric acid solutions ( ii) A drug characterized by comprising a mixture with a ferric chloride solution, a polyiron solution or a mixture thereof.
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| JP2002-50484 | 2002-02-26 | ||
| JP2002050484 | 2002-02-26 | ||
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| JP4289451B2 JP4289451B2 (en) | 2009-07-01 |
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Cited By (6)
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|---|---|---|---|---|
| JP2004042041A (en) * | 2002-07-08 | 2004-02-12 | Asahi Glass Co Ltd | Method of refining by-product salt, by-product salt, and snow melting agent |
| JP2006116389A (en) * | 2004-10-20 | 2006-05-11 | Miyoshi Oil & Fat Co Ltd | Fixing method for boron and fluorine and fixing agent composition |
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| CN114988547A (en) * | 2022-06-15 | 2022-09-02 | 江苏中电创新环境科技有限公司 | Fluorine removal agent, preparation method thereof and method for deep fluorine removal by adopting fluorine removal agent |
| CN115259475A (en) * | 2022-08-23 | 2022-11-01 | 四川大学 | Method for removing fluorine by rare earth auxiliary precipitation |
| CN117534169A (en) * | 2024-01-09 | 2024-02-09 | 中国科学院合肥物质科学研究院 | Deep defluorination material and preparation method and application thereof |
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2003
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004042041A (en) * | 2002-07-08 | 2004-02-12 | Asahi Glass Co Ltd | Method of refining by-product salt, by-product salt, and snow melting agent |
| JP4525014B2 (en) * | 2002-07-08 | 2010-08-18 | 旭硝子株式会社 | By-product salt purification method, by-product salt and snow melting agent |
| JP2006116389A (en) * | 2004-10-20 | 2006-05-11 | Miyoshi Oil & Fat Co Ltd | Fixing method for boron and fluorine and fixing agent composition |
| JP6008455B1 (en) * | 2015-04-13 | 2016-10-19 | 株式会社日本海水 | How to handle hazardous substances |
| CN114988547A (en) * | 2022-06-15 | 2022-09-02 | 江苏中电创新环境科技有限公司 | Fluorine removal agent, preparation method thereof and method for deep fluorine removal by adopting fluorine removal agent |
| CN115259475A (en) * | 2022-08-23 | 2022-11-01 | 四川大学 | Method for removing fluorine by rare earth auxiliary precipitation |
| CN115259475B (en) * | 2022-08-23 | 2023-06-16 | 四川大学 | Method for removing fluorine by rare earth-assisted precipitation |
| CN117534169A (en) * | 2024-01-09 | 2024-02-09 | 中国科学院合肥物质科学研究院 | Deep defluorination material and preparation method and application thereof |
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