JP2006212508A - Treatment method of fluorine-containing water - Google Patents
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本発明は、フッ素含有水の処理方法に関し、特に、フッ素含有排水からフッ素を除去する方法に関する。 The present invention relates to a method for treating fluorine-containing water, and more particularly to a method for removing fluorine from fluorine-containing wastewater.
フッ素は、化学工業の他、半導体製造や金属表面処理などにおいて大量に使用され、近年その使用量が著しく増大している。このような化学工業の工場などから排出されるフッ素含有排水をそのまま海域などに排出すると海域を汚染するので、フッ素含有排水を海域などに排出する前にフッ素の量をできるだけ低減する必要がある。特に、水質汚濁防止法施行令では、排水中のフッ素含有量の基準は、海域に排出する場合には１５ｍｇ／Ｌ以下、海域以外に排出する場合には８ｍｇ／Ｌ以下であることが規定されているため、フッ素含有排水中のフッ素含有量を８ｍｇ／Ｌ以下に低減する必要がある。 In addition to the chemical industry, fluorine is used in large quantities in semiconductor manufacturing, metal surface treatment, and the like, and in recent years, the amount used has increased significantly. If the fluorine-containing wastewater discharged from such a chemical industry factory is discharged into the sea as it is, the sea area is contaminated. Therefore, it is necessary to reduce the amount of fluorine as much as possible before discharging the fluorine-containing wastewater into the sea. In particular, the Ordinance for Enforcement of Water Pollution Control Law stipulates that the standard for fluorine content in wastewater is 15 mg / L or less when discharged into the sea area and 8 mg / L or less when discharged outside the sea area. Therefore, it is necessary to reduce the fluorine content in the fluorine-containing wastewater to 8 mg / L or less.
従来、フッ素含有排水中のフッ素含有量を低減する方法として、排水にカルシウム化合物を添加して難溶性のフッ化カルシウムとして固定した後、固液分離を行う方法が知られているが、この方法では、処理水中のフッ素濃度を２０ｍｇ／Ｌ程度にしか低減することができない。そのため、二次処理としてアルミニウム化合物を添加し、中和領域で生成するゲル状の水酸化アルミニウムにフッ素を吸着させて沈降分離する方法が提案されているが、この方法では、生成するゲル状の水酸化アルミニウムの脱水性が悪く、また、多量のアルミニウム化合物を添加しなければフッ素を除去することができないので、含水率の高い水酸化アルミニウムスラッジが多量に発生して産業廃棄物の量が増大するという問題がある。 Conventionally, as a method for reducing the fluorine content in fluorine-containing wastewater, a method of solid-liquid separation after adding a calcium compound to the wastewater and fixing it as hardly soluble calcium fluoride is known. Then, the fluorine concentration in the treated water can be reduced only to about 20 mg / L. For this reason, a method has been proposed in which an aluminum compound is added as a secondary treatment, and fluorine is adsorbed to gelled aluminum hydroxide formed in the neutralization region and separated by settling. Aluminum hydroxide is poorly dehydrated, and fluorine cannot be removed unless a large amount of aluminum compound is added. Therefore, a large amount of aluminum hydroxide sludge with a high water content is generated, increasing the amount of industrial waste. There is a problem of doing.
このような問題を解消するため、フッ素を含有する排水に、カルシウムを含む物質、アルミニウムを含む物質および硫酸根を含む物質を添加することにより、排水中に不溶性のエトリンガイトやモノサルフェートを生成させ、これらの物質中にフッ素を固定し、排水から分離することによって排水中のフッ素を除去する方法が提案されている（例えば、特許文献１参照）。 In order to solve such problems, by adding a substance containing calcium, a substance containing aluminum, and a substance containing sulfate radical to wastewater containing fluorine, insoluble ettringite and monosulfate are generated in the wastewater, A method of removing fluorine in waste water by fixing fluorine in these substances and separating it from waste water has been proposed (for example, see Patent Document 1).
この特許文献１には、排水中のフッ素の固定化メカニズムが以下のように説明されている。排水中でカルシウムを含む物質からはＣａ２＋イオン、アルミニウムを含む物質からはｐＨ値が５．１以上でＡｌＯ２ ２−イオンが溶出し、硫酸根を含む物質からはＳＯ４ ２−イオンが溶出し、これらの溶出イオンが互いに反応してエトリンガイトおよび／またはモノサルフェートを生成する。この生成反応の過程でエトリンガイトおよび／またはモノサルフェートの生成に寄与する硫酸イオン（ＳＯ４ ２−）の一部がフッ素イオン（Ｆ−）と置換または取り込まれることにより、エトリンガイトおよび／またはモノサルフェート中にフッ素が固定され、排水中のフッ素が低減される。 This Patent Document 1 describes a mechanism for fixing fluorine in waste water as follows. Substances containing calcium in waste water elute Ca 2+ ions, substances containing aluminum elute AlO 2 2- ions with a pH value of 5.1 or higher, and substances containing sulfate radicals elute SO 4 2- ions. These eluted ions react with each other to produce ettringite and / or monosulfate. A part of sulfate ion (SO 4 2− ) that contributes to the formation of ettringite and / or monosulfate in the course of this formation reaction is substituted or taken in by fluorine ion (F − ), so that in ettringite and / or monosulfate Fluorine is fixed to the water, and fluorine in the waste water is reduced.
しかし、特許文献１に提案された方法では、排水中でエトリンガイトなどを生成させながらフッ素濃度を低減するので、エトリンガイトを十分に生成させるために長時間を要し、また、その生成反応のための反応槽などを備えた廃水処理設備が必要になり、いわゆるバッチ処理を行うためにはその設備が必要になる。 However, in the method proposed in Patent Document 1, the fluorine concentration is reduced while producing ettringite and the like in the waste water. Therefore, it takes a long time to sufficiently produce ettringite, and for the production reaction. A wastewater treatment facility equipped with a reaction tank or the like is necessary, and the facility is necessary for performing so-called batch treatment.
したがって、本発明は、このような従来の問題点に鑑み、フッ素含有水中のフッ素含有量を簡易且つ効率的に低減することができ、特に、フッ素含有水中のフッ素含有量を８ｍｇ／Ｌ以下に安定して維持することができる、フッ素含有水の処理方法を提供することを目的とする。 Therefore, in view of such a conventional problem, the present invention can easily and efficiently reduce the fluorine content in fluorine-containing water, and in particular, the fluorine content in fluorine-containing water is 8 mg / L or less. It aims at providing the processing method of fluorine-containing water which can be maintained stably.
本発明者らは、上記課題を解決するために鋭意研究した結果、フッ素含有水にエトリンガイトを添加することにより、フッ素含有水中のフッ素含有量を簡易且つ効率的に低減することができ、特に、フッ素含有水中のフッ素含有量を８ｍｇ／Ｌ以下に安定して維持することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors can easily and efficiently reduce the fluorine content in fluorine-containing water by adding ettringite to fluorine-containing water. The inventors have found that the fluorine content in the fluorine-containing water can be stably maintained at 8 mg / L or less, and have completed the present invention.
すなわち、本発明によるフッ素含有水の処理方法は、フッ素含有水にエトリンガイトを添加することを特徴とする。このフッ素含有水の処理方法において、エトリンガイトが粒状物または粉末であるのが好ましく、その平均粒径が１〜５００μｍであるのが好ましい。また、エトリンガイトをＣａ（ＯＨ）２とＡｌ２（ＳＯ４）３から生成するのが好ましい。 That is, the method for treating fluorine-containing water according to the present invention is characterized in that ettringite is added to fluorine-containing water. In this method for treating fluorine-containing water, the ettringite is preferably in the form of granules or powder, and the average particle size is preferably 1 to 500 μm. Ettringite is preferably produced from Ca (OH) 2 and Al 2 (SO 4 ) 3 .
本発明によれば、フッ素含有水中のフッ素含有量を簡易且つ効率的に低減することができ、特に、フッ素含有水中のフッ素含有量を８ｍｇ／Ｌ以下に安定して維持することができる。 According to the present invention, the fluorine content in fluorine-containing water can be reduced easily and efficiently, and in particular, the fluorine content in fluorine-containing water can be stably maintained at 8 mg / L or less.
本発明によるフッ素含有水の処理方法の実施の形態では、フッ素含有排水などのフッ素含有水に粒状や粉状などのエトリンガイトを添加することにより、フッ素含有水中のフッ素を除去する。この処理方法は、高濃度のフッ素を含有する排水に適用することができる。 In the embodiment of the method for treating fluorine-containing water according to the present invention, fluorine in the fluorine-containing water is removed by adding ettringite in the form of particles or powder to fluorine-containing water such as fluorine-containing wastewater. This treatment method can be applied to waste water containing a high concentration of fluorine.
エトリンガイト自体は安定した物質であるため、固体のエトリンガイトをフッ素含有排水に直接添加しても、排水中でほとんど分解せずにフッ素とほとんど反応しないと考えられていたが、本発明者らは、フッ素含有水に粒状や粉状などのエトリンガイトを添加することによりフッ素含有水中のフッ素濃度を短時間で低減することができることを見出し、特に、塊状のエトリンガイトを製造した後に粒状物や粉末にしてフッ素含有水に添加することにより、フッ素含有水中のフッ素濃度を短時間で低減することができることを見出した。この理由は明確ではないが、固体のエトリンガイトは安定物質であるにもかかわらず、水中では、エトリンガイトの表面に存在するカルシウムがフッ素と結合することによって生成するＣａＦ２の再溶解が、エトリンガイト自体の安定性によって抑制されるためであると考えられる。なお、フッ素含有水に固体のエトリンガイトを添加すれば、大規模な槽などの設備を新たに設ける必要がなくなり、フッ素含有水にエトリンガイトを連続的に添加することにより処理系内でフッ素含有水を連続的に処理することができる。 Since ettringite itself is a stable substance, it was thought that even when solid ettringite was added directly to fluorine-containing wastewater, it hardly decomposed in the wastewater and hardly reacted with fluorine. It has been found that the fluorine concentration in fluorine-containing water can be reduced in a short time by adding ettringite in granular or powder form to fluorine-containing water. It has been found that the fluorine concentration in fluorine-containing water can be reduced in a short time by adding to the water. Although the reason for this is not clear, in spite of the fact that solid ettringite is a stable substance, in water, the re-dissolution of CaF 2 produced by the binding of calcium present on the surface of ettringite with fluorine causes ettringite's own It is thought that this is because it is suppressed by stability. If solid ettringite is added to fluorine-containing water, there is no need to newly install large-scale tanks and other equipment, and fluorine-containing water can be added to the treatment system by continuously adding ettringite to fluorine-containing water. Can be processed continuously.
本発明によるフッ素含有水の処理方法の実施の形態は、フッ素を含有する排水の処理に適用することができるが、フッ素を含有するガスや土壌などにも適用することができると考えられる。特に、２０ｍｇ／Ｌ以上の高い濃度のフッ素を含有する排水に適用すると、薬剤などの使用量を抑えることができ、さらに高い濃度の１００〜５００ｍｇ／Ｌのフッ素を含有する排水に適用する場合にも特別な排水処理設備を設ける必要がなく、コスト面で有利である。なお、排水中のフッ素濃度は、ＪＩＳ
Ｋ０１０２の３４．２の方法により求められる値である。
The embodiment of the method for treating fluorine-containing water according to the present invention can be applied to the treatment of wastewater containing fluorine, but is also considered to be applicable to gas or soil containing fluorine. In particular, when applied to wastewater containing fluorine at a high concentration of 20 mg / L or more, the amount of chemicals used can be suppressed, and when applied to wastewater containing fluorine at a higher concentration of 100 to 500 mg / L. However, there is no need to provide a special wastewater treatment facility, which is advantageous in terms of cost. The fluorine concentration in the wastewater is JIS
This is a value obtained by the method of K4.22 34.2.
また、フッ素を含有する排水としては、例えば、半導体工場などのガラスエッチング排水、石炭燃焼排ガスの排煙脱硫装置から排出される排煙脱硫排水や排煙脱硝排水、廃棄物焼却炉などの排煙洗浄排水などが挙げられ、一般に、これらの排水は重金属やカルシウム塩なども含有している。 Examples of wastewater containing fluorine include glass etching wastewater from semiconductor factories, flue gas desulfurization wastewater and flue gas denitration wastewater discharged from coal combustion exhaust gas, and waste incinerators. Examples of the wastewater include washing wastewater, and these wastewaters generally contain heavy metals and calcium salts.
本発明によるフッ素含有水の処理方法の実施の形態において使用するエトリンガイトは、Ｃａ６Ａｌ２（ＳＯ４）３（ＯＨ）２・２６Ｈ２Ｏの組成を有する。特に、塊状のエトリンガイトを粉砕して粒状物または粉末にすれば、フッ素含有水に添加し易くなり、作業上の取扱いが容易になるとともに、反応性も向上する。粒状物または粉末の粒径は、排水中の分散などに影響するため、大き過ぎても小さ過ぎても好ましくなく、所定の粒径に制御するのが好ましい。この粒径は、１〜５００μｍであるのが好ましく、工業上１〜３００μｍ程度であるのがさらに好ましい。エトリンガイトは、Ｃａ、ＡｌおよびＳＯ４を主成分とする化合物であり、Ｃａはフッ素と反応してフッ素を固定化する作用を有し、さらにエトリンガイトのＣａ、ＡｌおよびＳＯ４によってフッ素の再溶解を防いでいる。 The ettringite used in the embodiment of the method for treating fluorine-containing water according to the present invention has a composition of Ca 6 Al 2 (SO 4 ) 3 (OH) 2 .26H 2 O. In particular, if lumped ettringite is pulverized into a granular material or powder, it can be easily added to fluorine-containing water, the handling on the work is facilitated, and the reactivity is improved. Since the particle size of the granular material or powder affects the dispersion in the waste water, it is not preferable that it is too large or too small, and it is preferable to control the particle size to a predetermined particle size. The particle size is preferably 1 to 500 μm, more preferably about 1 to 300 μm industrially. Ettlingite is a compound mainly composed of Ca, Al and SO 4. Ca reacts with fluorine to immobilize fluorine. Further, ettringite Ca, Al and SO 4 can re-dissolve fluorine. It is preventing.
エトリンガイトの添加量は、フッ素含有水中のフッ素濃度に応じて適宜決定される。例えば、フッ素含有水中のフッ素濃度が１００ｍｇ／Ｌの場合には、エトリンガイトの添加量は０．１モル程度でよいが、実用的には、エトリンガイトの添加量が０．１〜１０重量％程度であれば十分にフッ素濃度を低減することができる。特に、エトリンガイトの添加量が１重量％以上になると、エトリンガイトが分解しないため、後工程でろ過し易くなり、固液分離が容易になる。 The amount of ettringite added is appropriately determined according to the fluorine concentration in the fluorine-containing water. For example, when the fluorine concentration in the fluorine-containing water is 100 mg / L, the addition amount of ettringite may be about 0.1 mol, but practically, the addition amount of ettringite is about 0.1 to 10% by weight. If present, the fluorine concentration can be sufficiently reduced. In particular, when the amount of ettringite added is 1% by weight or more, ettringite is not decomposed, so that it is easy to filter in a subsequent step, and solid-liquid separation is facilitated.
エトリンガイトの添加方法としては、エトリンガイトを排水処理設備の配管などの流路や貯水槽に直接噴霧または添加する方法でもよいし、エトリンガイトをスラリー状にして噴霧または添加する方法でもよい。また、エトリンガイトの粒状物または粉末を貯蔵するタンクから気流搬送などにより直接処理設備に供給する方法でもよいし、エトリンガイトを水または排水と混合してスラリー状にしてポンプにより処理設備に供給する方法でもよい。また、エトリンガイトを粒状物または粉末にすれば、様々な添加方法が考えられ、様々な処理設備に対応することができる。 The method for adding ettringite may be a method in which ettringite is directly sprayed or added to a flow path such as a pipe of a wastewater treatment facility or a water storage tank, or a method in which ettringite is sprayed or added in a slurry state. In addition, a method of supplying ettringite granules or powder directly to the processing facility by airflow conveyance or the like may be used, or a method of mixing ettringite with water or waste water to form a slurry and supplying it to the processing facility by a pump. Good. Moreover, if ettringite is made into a granular material or a powder, various addition methods can be considered and it can respond to various processing facilities.
このようにフッ素含有水にエトリンガイトを添加して所定時間経過した後、固液分離を行うことによりフッ素含有水中のフッ素を除去することができる。また、エトリンガイトがフッ素含有水中で不安定である場合には、フッ素含有水にアルミニウム化合物を加え、ＮａＯＨなどのアルカリで中和してｐＨ６．５付近に調整し、この溶液を固液分離して、残渣中にエトリンガイトを生成させればよい。このようにして生成したエトリンガイトをフッ素含有水に添加し、固液分離してフッ素を除去することができる。なお、アルミニウム化合物を添加して中和する前に、予めカルシウム塩などを添加して中和を行うと、より効果的である。 Thus, after adding ettringite to fluorine-containing water and elapse of a predetermined time, fluorine in the fluorine-containing water can be removed by performing solid-liquid separation. When ettringite is unstable in fluorine-containing water, an aluminum compound is added to the fluorine-containing water, neutralized with an alkali such as NaOH to adjust the pH to around 6.5, and this solution is separated into solid and liquid. Ettringite may be generated in the residue. The ettringite produced in this manner can be added to fluorine-containing water and separated into solid and liquid to remove fluorine. It is more effective to neutralize by adding calcium salt or the like before adding the aluminum compound and neutralizing.
フッ素含有水にエトリンガイトを添加した後にフッ素を固定化するために要する時間は極めて短時間でよい。フッ素含有水にエトリンガイトを添加する場合、フッ素を固定化する反応速度が速いため、添加時間は短時間でよい。フッ素含有排水の流路などにエトリンガイトを添加する場合でも、排水が装置内を流れている間に十分に反応することができる。反応は１〜５程度で終了するが、長くても１０分程度で十分に反応する。 The time required to immobilize fluorine after adding ettringite to fluorine-containing water may be very short. When ettringite is added to fluorine-containing water, the reaction time for immobilizing fluorine is fast, so the addition time may be short. Even when ettringite is added to the flow path of fluorine-containing wastewater, it can react sufficiently while the wastewater flows through the apparatus. The reaction is completed in about 1 to 5, but the reaction is sufficient in about 10 minutes at the longest.
連続的に排水処理を行う場合でも、各工程間の流量や処理作業の安定を図るために排水を一時的に貯水するバッファ槽に排水が滞留する時間が数分間程度であれば、十分に反応してフッ素を固定化することができる。したがって、既存の装置にさらに反応槽などを設置する必要がなく、さらに付加的なポンプ、計装設備、配管などを設ける必要がなく、現状の装置をそのまま使用することができる。また、処理液中のフッ素の再溶解も少なく、安定してフッ素を固定化することができる。 Even when continuous wastewater treatment is performed, if the time that the wastewater stays in the buffer tank that temporarily stores the wastewater is around several minutes in order to stabilize the flow rate between each process and the treatment work, the reaction will be sufficient. Thus, fluorine can be immobilized. Therefore, it is not necessary to install a reaction tank or the like in the existing apparatus, and it is not necessary to provide an additional pump, instrumentation equipment, piping, or the like, and the current apparatus can be used as it is. In addition, there is little re-dissolution of fluorine in the treatment liquid, and fluorine can be immobilized stably.
以下、本発明によるフッ素含有水の処理方法の実施例について詳細に説明する。 Hereinafter, the Example of the processing method of the fluorine-containing water by this invention is described in detail.
まず、所定のモル比になるように秤量したＣａ（ＯＨ）２とＡｌ２（ＳＯ４）３をポリエチレンの容器に入れ、十分な量のイオン交換水を加えて数回振って、そのまま室温で６日間放置した後、一部を吸引ろ過し、乾燥し、粉砕することによって、エトリンガイト（Ｃａ６Ａｌ２（ＳＯ４）３（ＯＨ）２・２６Ｈ２Ｏ）の粉末を得た。得られたエトリンガイト粉末は、粉末Ｘ線回折を用いて同定した。また、得られたエトリンガイト粉末の粒径をレーザー回折法で測定したところ、平均粒径は１００μｍであった。 First, Ca (OH) 2 and Al 2 (SO 4 ) 3 weighed so as to have a predetermined molar ratio are put in a polyethylene container, a sufficient amount of ion-exchanged water is added and shaken several times, and left at room temperature. after standing for 6 days, a portion was filtered off with suction, dried, by grinding to obtain a powder of ettringite (Ca 6 Al 2 (SO 4 ) 3 (OH) 2 · 26H 2 O). The obtained ettringite powder was identified using powder X-ray diffraction. Moreover, when the particle diameter of the obtained ettringite powder was measured by a laser diffraction method, the average particle diameter was 100 μm.
また、ＮａＦを水に加えてフッ素濃度が３００ｍｇ／Ｌになるように調整したフッ化物イオン溶液を用意し、この溶液に所定量のエトリンガイトを添加した。エトリンガイトの添加量は、湿った状態で溶液に対して１．３重量％（実施例１）および２．６重量％（実施例２）とした。エトリンガイトを添加してから５分後、３０分後および６０分後に、それぞれの溶液から所定量をサンプリングし、吸引ろ過し、ろ液中のフッ素濃度を測定した。また、実施例２の残渣についてＸＲＤ測定を行った。 Further, a fluoride ion solution prepared by adding NaF to water to adjust the fluorine concentration to 300 mg / L was prepared, and a predetermined amount of ettringite was added to this solution. The amount of ettringite added was 1.3% by weight (Example 1) and 2.6% by weight (Example 2) based on the solution in a wet state. 5 minutes, 30 minutes and 60 minutes after the addition of ettringite, a predetermined amount was sampled from each solution, suction filtered, and the fluorine concentration in the filtrate was measured. Further, XRD measurement was performed on the residue of Example 2.
エトリンガイトを添加した後の溶液中のフッ素濃度の経時変化を図１に示す。図１に示すように、実施例１および２では、いずれも５〜３０分経過後にフッ素濃度が１ｍｇ／Ｌ程度まで減少した。また、実施例２において所定時間経過後の残渣のＸＲＤ測定の結果を図２に示す。図２に示すように、実施例２の残渣がＣａＦ２とエトリンガイトを含むことがわかる。ＣａＦ２の溶解度は８ｍｇ／Ｌであり、溶液中のフッ素濃度がこの溶解度よりも低いので、エトリンガイトによりフッ素が固定化されているのがわかる。 FIG. 1 shows the change over time in the fluorine concentration in the solution after the addition of ettringite. As shown in FIG. 1, in Examples 1 and 2, the fluorine concentration decreased to about 1 mg / L after 5 to 30 minutes had elapsed. Moreover, the result of the XRD measurement of the residue after predetermined time progress in Example 2 is shown in FIG. As shown in FIG. 2, it can be seen that the residue of Example 2 contains CaF 2 and ettringite. Since the solubility of CaF 2 is 8 mg / L and the fluorine concentration in the solution is lower than this solubility, it can be seen that fluorine is immobilized by ettringite.
Claims (4)
The method for treating fluorine-containing water according to any one of claims 1 to 3, wherein the ettringite is produced from Ca (OH) 2 and Al 2 (SO 4 ) 3 .
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