JP4845188B2 - Waste water treatment agent and method for reducing fluorine ions in waste water - Google Patents
Waste water treatment agent and method for reducing fluorine ions in waste water Download PDFInfo
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本発明は、フッ素イオンを含有する排水の処理剤に関する。また本発明は、排水中のフッ素イオンを低減させる方法に関する。 The present invention relates to a wastewater treatment agent containing fluorine ions. The present invention also relates to a method for reducing fluorine ions in waste water.
工場排水中にはフッ素イオン（フッ素と称することがある）が含有されていることが多々あり、特に半導体製造時にシリコンウエハーのエッチング剤として多量のフッ酸が使用されている。このフッ酸は、水等で洗浄されるが排水中に高濃度のフッ素が含まれている。そして、環境庁発令の排水基準によれば検液中に８ｍｇ／Ｌ以下、また、土壌基準によれば検液中に０．８ｍｇ／Ｌ以下のフッ素濃度が定められている。
フッ素含有排水中のフッ素を除去する方法としては、フッ素含有排水にカルシウム塩を加えて難溶性のフッ化カルシウムを生成させる方法が提案されている（特許文献１参照）。
Industrial wastewater often contains fluorine ions (sometimes referred to as fluorine), and a large amount of hydrofluoric acid is used as an etchant for silicon wafers, particularly during semiconductor manufacturing. This hydrofluoric acid is washed with water or the like, but contains a high concentration of fluorine in the waste water. And according to the drainage standard issued by the Environment Agency, the fluorine concentration is set to 8 mg / L or less in the test solution, and according to the soil standard, the fluorine concentration is set to 0.8 mg / L or less in the test solution.
As a method for removing fluorine from fluorine-containing wastewater, a method has been proposed in which calcium salt is added to fluorine-containing wastewater to form poorly soluble calcium fluoride (see Patent Document 1).
また、フッ素含有排水に、化学組成式Ｍ１‐ｘ ２＋Ｍｘ ３＋（ＯＨ‐）２＋ｘ‐ｙ（Ａｎ‐）ｙ／ｎ
［式中、Ｍ２＋は、Ｍｇ２＋、Ｎｉ２＋、Ｚｎ２＋、Ｆｅ２＋、Ｃａ２＋およびＣｕ２＋からなる群から選ばれる少なくとも１種の金属イオンを示し、Ｍ３＋は、Ａｌ３＋およびＦｅ３＋からなる群から選ばれる少なくとも１種の金属イオンを示し、Ａｎ‐はｎ価のアニオンを示す。また、０．１≦ｘ≦０．５であり、０．１≦ｙ≦０．５であり、ｎは１または２である。］で表される複合金属水酸化物を加える方法、および
化学組成式Ｍ１‐ｘ ２＋Ｍｘ ３＋Ｏ２‐ｘ／２ ２‐［式中、Ｍ２＋は、Ｍｇ２＋、Ｎｉ２＋、Ｚｎ２＋、Ｆｅ２＋、Ｃａ２＋およびＣｕ２＋からなる群から選ばれる少なくとも１種の金属イオンを示し、Ｍ３＋はＡｌ３＋およびＦｅ３＋からなる群から選ばれる少なくとも１種の金属イオンを示す。また、０．１≦ｘ≦０．５である。］で表される複合金属酸化物を加える方法が提案されている（特許文献２参照）。
しかしながら、フッ素含有排水にカルシウム塩を加えてフッ化カルシウムを生成させる方法は、フッ化カルシウムの溶解度が０．００１６ｇ／１００ｇ（１８℃）と大きく土壌基準をクリアすることができない。また、特許文献２の複合金属水酸化物および複合金属酸化物をフッ素含有排水に添加する方法も土壌基準のフッ素濃度０．８ｍｇ／Ｌ以下をクリアすることが出来ていない。
[ Wherein M 2+ represents at least one metal ion selected from the group consisting of Mg 2+ , Ni 2+ , Zn 2+ , Fe 2+ , Ca 2+, and Cu 2+ , and M 3+ represents from Al 3+ and Fe 3+. comprising represents at least one metal ion selected from the group, an - is an anion of n valence. Further, 0.1 ≦ x ≦ 0.5, 0.1 ≦ y ≦ 0.5, and n is 1 or 2. And a chemical composition formula M 1-x 2+ M x 3+ O 2-x / 2 2− [wherein M 2+ is Mg 2+ , Ni 2+ , Zn 2+. , Fe 2+ , Ca 2+ and Cu 2+ represent at least one metal ion selected from the group consisting of Al 3+ and Fe 3+ . M 3+ represents at least one metal ion selected from the group consisting of Al 3+ and Fe 3+ . Further, 0.1 ≦ x ≦ 0.5. ] Has been proposed (see Patent Document 2).
However, the method of generating calcium fluoride by adding calcium salt to fluorine-containing wastewater has a high solubility of calcium fluoride of 0.0016 g / 100 g (18 ° C.) and cannot clear the soil standard. Further, the method of adding the composite metal hydroxide and composite metal oxide of
本発明は、フッ素イオンの吸着能に優れた排水処理剤を提供することを目的とする。また本発明は、排水中のフッ素イオンを除去する方法を提供することを目的とする。 An object of this invention is to provide the waste water treatment agent excellent in the adsorption capacity of a fluorine ion. Another object of the present invention is to provide a method for removing fluorine ions in waste water.
本発明者らは、フッ素イオン吸着能に優れた物質を鋭意検討した。その結果、特定の複合金属化合物が優れたフッ素吸着能を有することを見出し本発明を完成した。また、かかる複合金属化合物を高濃度のフッ素を含有する排水に添加することにより、処理後液中のフッ素濃度を排水基準の８ｍｇ／Ｌ以下、さらには土壌基準の０．８ｍｇ／Ｌ以下とすることが可能であることを見出し本発明を完成した。 The present inventors diligently studied a substance excellent in fluorine ion adsorption ability. As a result, the inventors have found that a specific composite metal compound has an excellent fluorine adsorbing ability and completed the present invention. Further, by adding such a composite metal compound to waste water containing high concentration of fluorine, the fluorine concentration in the treated liquid is set to 8 mg / L or less of the drainage standard, and further to 0.8 mg / L or less of the soil standard. The present invention has been completed.
即ち、本発明は、下記式（Ｉ）
［Ｍｇ（ＯＨ）２］ｘ・Ａｌ２（ＯＨ）６−２ｙ−ｚ・（ＣＯ３）ｙ・（Ｃｌ）ｚ・ｎＨ２Ｏ （Ｉ）
（式中、ｘ、ｙ、ｚおよびｎは、１≦ｘ≦１２、０≦ｙ≦１、０≦ｚ≦１、０．１≦ｎ≦１０、０．１≦（ｙ＋ｚ）≦１．５を満足する）
で表され、
(１)水酸化マグネシウムスラリー中に、(２)アルミニウム塩水溶液および(３)炭酸アルカリ水溶液または苛性アルカリ水溶液を、
各成分のモル比を、Ｍｇ／Ａｌが０.５〜１５、炭酸アルカリ／Ａｌが０．５〜１．２、苛性アルカリ／Ａｌが１〜２．４になるようにして投入し、
反応終了時点でｐＨ６.０〜９.０となるように反応ｐＨを調整し、温度１０〜５０℃で反応させることにより得られ、
粉末Ｘ線回折法による測定に基づいて、水酸化マグネシウム結晶のパターンが認められる複合金属化合物からなる、フッ素イオンを含有する排水の処理剤である。
また本発明は、フッ素イオンを含有する排水に、下記式（Ｉ）、
［Ｍｇ（ＯＨ）２］ｘ・Ａｌ２（ＯＨ）６−２ｙ−ｚ・（ＣＯ３）ｙ・（Ｃｌ）ｚ・ｎＨ２Ｏ （Ｉ）
（式中、ｘ、ｙ、ｚおよびｎは、１≦ｘ≦１２、０≦ｙ≦１、０≦ｚ≦１、０．１≦ｎ≦１０、０．１≦（ｙ＋ｚ）≦１．５を満足する）
で表され、
(１)水酸化マグネシウムスラリー中に、(２)アルミニウム塩水溶液および(３)炭酸アルカリ水溶液または苛性アルカリ水溶液を、
各成分のモル比を、Ｍｇ／Ａｌが０.５〜１５、炭酸アルカリ／Ａｌが０．５〜１．２、苛性アルカリ／Ａｌが１〜２．４になるようにして投入し、
反応終了時点でｐＨ６.０〜９.０となるように反応ｐＨを調整し、温度１０〜５０℃で反応させることにより得られ、
粉末Ｘ線回折法による測定に基づいて、水酸化マグネシウム結晶のパターンが認められる複合金属化合物を接触せしめることを特徴とする、排水中のフッ素イオンを低減させる方法である。
That is, the present invention relates to the following formula (I)
[Mg (OH) 2] x · Al 2 (OH) 6-2y-z · (CO 3) y · (Cl) z · nH 2 O (I)
(Wherein x, y, z and n are 1 ≦ x ≦ 12, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, 0.1 ≦ n ≦ 10, 0.1 ≦ (y + z) ≦ 1.5. Satisfy)
Represented by
(1) In a magnesium hydroxide slurry , (2) an aqueous solution of aluminum salt and (3) an aqueous alkali carbonate solution or an aqueous caustic solution ,
The molar ratio of each component was set so that Mg / Al was 0.5 to 15, alkali carbonate / Al was 0.5 to 1.2, and caustic alkali / Al was 1 to 2.4.
It is obtained by adjusting the reaction pH so that the pH is 6.0 to 9.0 at the end of the reaction, and reacting at a temperature of 10 to 50 ° C.
It is a wastewater treatment agent containing fluorine ions, which is composed of a composite metal compound in which a magnesium hydroxide crystal pattern is observed based on measurement by a powder X-ray diffraction method.
Moreover, the present invention provides the following formula (I),
[Mg (OH) 2] x · Al 2 (OH) 6-2y-z · (CO 3) y · (Cl) z · nH 2 O (I)
(Wherein x, y, z and n are 1 ≦ x ≦ 12, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, 0.1 ≦ n ≦ 10, 0.1 ≦ (y + z) ≦ 1.5. Satisfy)
Represented by
(1) In a magnesium hydroxide slurry , (2) an aqueous solution of aluminum salt and (3) an aqueous alkali carbonate solution or an aqueous caustic solution ,
The molar ratio of each component was set so that Mg / Al was 0.5 to 15, alkali carbonate / Al was 0.5 to 1.2, and caustic alkali / Al was 1 to 2.4.
It is obtained by adjusting the reaction pH so that the pH is 6.0 to 9.0 at the end of the reaction, and reacting at a temperature of 10 to 50 ° C.
This is a method for reducing fluorine ions in waste water, characterized in that a composite metal compound in which a magnesium hydroxide crystal pattern is observed is brought into contact based on measurement by a powder X-ray diffraction method.
本発明の処理剤は、優れたフッ素イオン吸着能を有する。本発明方法によれば、排水中のフッ素イオンを低減させることができる。また本発明方法によれば、排水中のフッ素イオン濃度を排水基準以下、さらには土壌基準以下にすることができる。また本発明方法によれば、ｐＨ４程度の高濃度フッ素イオン含有排水のｐＨを中和し排水基準内とすることができる。さらに本発明方法によれば、排水中に多量の各種陰イオン（ＳＯ４ ２‐、Ｃｌ‐、ＮＯ３ ‐等）が存在していても選択的にフッ素イオンを吸着することができる。 The treatment agent of the present invention has an excellent fluorine ion adsorption ability. According to the method of the present invention, fluorine ions in waste water can be reduced. Moreover, according to the method of the present invention, the fluorine ion concentration in the wastewater can be reduced below the wastewater standard, and further below the soil standard. Further, according to the method of the present invention, the pH of the high concentration fluorine ion-containing wastewater having a pH of about 4 can be neutralized to be within the wastewater standard. Furthermore, according to the method of the present invention, fluorine ions can be selectively adsorbed even if a large amount of various anions (SO 4 2− , Cl − , NO 3 − etc.) are present in the waste water.
＜排水の処理剤＞
本発明は、下記式（Ｉ）、
［Ｍｇ（ＯＨ）２］ｘ・Ａｌ２（ＯＨ）６−２ｙ−ｚ・（ＣＯ３）ｙ・（Ｃｌ）ｚ・ｎＨ２Ｏ （Ｉ）
（式中、ｘ、ｙ、ｚおよびｎは、１≦ｘ≦１２、０≦ｙ≦１、０≦ｚ≦１、０．１≦ｎ≦１０、０．１≦（ｙ＋ｚ）≦１．５を満足する）
で表される複合金属化合物からなる、フッ素イオンを含有する排水の処理剤である。
式（Ｉ）中、ｘは、１≦ｘ≦１２、好ましくは２≦ｘ≦７を満足する。ｙは、０≦ｙ≦１、好ましくは０．１≦ｙ≦０．８を満足する。ｚは、０≦ｚ≦１、好ましくは０．１≦０．５を満足する。ｎは、０．１≦ｎ≦１０、好ましくは０．５≦ｎ≦５を満足する。
ｙ＋ｚは、０．１≦（ｙ＋ｚ）≦１．５、好ましくは０．１５≦（ｙ＋ｚ）≦１．２を満足する。
<Wastewater treatment agent>
The present invention relates to the following formula (I),
[Mg (OH) 2] x · Al 2 (OH) 6-2y-z · (CO 3) y · (Cl) z · nH 2 O (I)
(Wherein x, y, z and n are 1 ≦ x ≦ 12, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, 0.1 ≦ n ≦ 10, 0.1 ≦ (y + z) ≦ 1.5. Satisfy)
It is the processing agent of the waste_water | drain containing the fluorine ion which consists of a composite metal compound represented by these.
In the formula (I), x satisfies 1 ≦ x ≦ 12, preferably 2 ≦ x ≦ 7. y satisfies 0 ≦ y ≦ 1, preferably 0.1 ≦ y ≦ 0.8. z satisfies 0 ≦ z ≦ 1, preferably 0.1 ≦ 0.5. n satisfies 0.1 ≦ n ≦ 10, preferably 0.5 ≦ n ≦ 5.
y + z satisfies 0.1 ≦ (y + z) ≦ 1.5, preferably 0.15 ≦ (y + z) ≦ 1.2.
ｘが１未満となると、理由は不明であるがフッ素イオン吸着容量が極端に低くなる。また、ｘが１２を超えると式（Ｉ）中の水酸化アルミニウム様物質生成量が極端に少なくなるので、これまたフッ素イオン吸着容量が極端に低くなる。ｙ＋ｚが０．１未満になると、フッ素イオン吸着サイトが極端に少なくなるので、フッ素イオン吸着容量が極端に低くなる。また、ｙ＋ｚは、高いほどフッ素イオン吸着容量は高くなるが、１．５を超える物質は合成することができない。ｎを０．１未満にするためには乾燥時に多大の熱エネルギーを必要とするために経済的に不利である。また、ｎが１０を超えると化合物中の固形分含有量が極端に少なくなり、フッ素イオン吸着容量が低くなる。 When x is less than 1, the reason is unknown, but the fluorine ion adsorption capacity becomes extremely low. In addition, if x exceeds 12, the amount of aluminum hydroxide-like substance in formula (I) is extremely reduced, so that the fluorine ion adsorption capacity is also extremely low. When y + z is less than 0.1, the number of fluorine ion adsorption sites becomes extremely small, and the fluorine ion adsorption capacity becomes extremely low. Moreover, the higher the y + z, the higher the fluorine ion adsorption capacity, but a substance exceeding 1.5 cannot be synthesized. In order to make n less than 0.1, a great deal of heat energy is required during drying, which is economically disadvantageous. On the other hand, when n exceeds 10, the solid content in the compound is extremely reduced, and the fluorine ion adsorption capacity is lowered.
複合金属化合物として、下記式（Ｉ−１）
［Ｍｇ（ＯＨ）２］ｘ・Ａｌ２（ＯＨ）６‐２ｙ・（ＣＯ３）ｙ・ｎＨ２Ｏ (I-1)
（式(I-1)中、ｘ、ｙ、ｎは、１≦ｘ≦１２、０≦ｙ≦１、０．５≦ｎ≦３．０を満足する）
で表される化合物が好ましい。
また下記式（Ｉ−２）
［Ｍｇ（ＯＨ）２］ｘ・Ａｌ２（ＯＨ）６‐２ｙ‐ｚ・（ＣＯ３）ｙ・（Ｃｌ）ｚ・ｎＨ２Ｏ （Ｉ−２）
（式（Ｉ−２）中、ｘ、ｙ、ｚ、ｎは、１≦ｘ≦１２、０≦ｙ≦１、０≦ｚ≦１、０．１≦ｎ≦１０、０．１≦（ｙ＋ｚ）≦１．５を満足する）
で表される化合物が好ましい。この化合物（Ｉ−２）は、上記式（Ｉ−１）で表される化合物のＣＯ３を、塩酸を用いてＣｌにイオン交換することにより製造することができる。
As the composite metal compound, the following formula (I-1)
[Mg (OH) 2 ] x · Al 2 (OH) 6-2 y · (CO 3 ) y · nH 2 O (I-1)
(In the formula (I-1), x, y, and n satisfy 1 ≦ x ≦ 12, 0 ≦ y ≦ 1, and 0.5 ≦ n ≦ 3.0)
The compound represented by these is preferable.
Moreover, following formula (I-2)
[Mg (OH) 2 ] x · Al 2 (OH) 6-2 y -z · (CO 3 ) y · (Cl) z · nH 2 O (I-2)
(In the formula (I-2), x, y, z, and n are 1 ≦ x ≦ 12, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, 0.1 ≦ n ≦ 10, 0.1 ≦ (y + z ) ≦ 1.5
The compound represented by these is preferable. This compound (I-2) can be produced by ion exchange of CO 3 of the compound represented by the above formula (I-1) with Cl using hydrochloric acid.
複合金属化合物は、粉末Ｘ線回折法による測定に基づいて、水酸化マグネシウム結晶のパターンが認められる化合物であり、複合金属化合物と同様な化学組成を有する物質としてハイドロタルサイトが良く知られているが、複合金属化合物は粉末Ｘ線回折法による構造解析からハイドロタルサイトとは全く異なる物質であることが分かる。
すなわち、本発明の式（Ｉ）で表される複合金属化合物は、粉末Ｘ線回折法による測定に基づいて、ハイドロタルサイトの結晶パターンは認められない。また同様の回折法による測定に基づいて水酸化アルミニウム、炭酸マグネシウム、塩化アルミニウムおよび塩化マグネシウムの結晶のパターンも実質的に認められない。
排水処理剤としての複合金属化合物は、排水中において拡散されやすい微粒子であることが好ましく、レーザー光回折散乱法による平均粒径が、好ましくは０．１〜５０μｍ、より好ましくは０．５〜２０μｍである。
A composite metal compound is a compound in which a magnesium hydroxide crystal pattern is recognized based on measurement by a powder X-ray diffraction method, and hydrotalcite is well known as a substance having the same chemical composition as the composite metal compound. However, it can be seen that the composite metal compound is a substance completely different from hydrotalcite from the structural analysis by the powder X-ray diffraction method.
That is, the composite metal compound represented by the formula (I) of the present invention does not have a hydrotalcite crystal pattern based on the measurement by the powder X-ray diffraction method. Also, substantially no crystal pattern of aluminum hydroxide, magnesium carbonate, aluminum chloride and magnesium chloride is observed based on the measurement by the same diffraction method.
The composite metal compound as the waste water treatment agent is preferably fine particles that are easily diffused in the waste water, and the average particle diameter by the laser light diffraction scattering method is preferably 0.1 to 50 μm, more preferably 0.5 to 20 μm. It is.
複合金属化合物は、(１)水酸化マグネシウムスラリーと、(２)アルミニウム塩水溶液および(３)炭酸アルカリ水溶液または苛性アルカリ水溶液とを、反応させることにより製造することが出来る。
(２)アルミニウム塩としては、硫酸アルミニウム、塩化アルミニウム、硝酸アルミニウム等が挙げられる。また(３)炭酸アルカリとしては、炭酸ナトリウム、炭酸カリウム、炭酸アンモニウム等が上げられる。(３)苛性アルカリとしては、水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム等が挙げられる。（１）水酸化マグネシウムスラリーは、Ｍｇ(ＯＨ)２スラリーであれば何の制限もない。
The composite metal compound can be produced by reacting (1) magnesium hydroxide slurry with (2) an aqueous aluminum salt solution and (3) an aqueous alkali carbonate solution or an aqueous caustic solution.
(2) Aluminum salts include aluminum sulfate, aluminum chloride, aluminum nitrate and the like. (3) Examples of the alkali carbonate include sodium carbonate, potassium carbonate, ammonium carbonate and the like. (3) Examples of the caustic alkali include sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like. (1) The magnesium hydroxide slurry is not limited as long as it is a Mg (OH) 2 slurry.
各成分のモル比は、Ｍｇ／Ａｌが好ましくは０.５〜１５、より好ましくは１．０〜４．０になるようにする。炭酸アルカリ／Ａｌが好ましくは０〜１.４、より好ましくは０．５〜１．２になるようにする。苛性アルカリ／Ａｌが好ましくは０〜２.８、より好ましくは１〜２．４になるようにする。
この反応方法の特徴は、(２)アルミニウム塩水溶液の使用量に対する(３)炭酸アルカリまたは苛性アルカリの使用量を理論等量以下とすることである。そして、不足のアルカリ源を水酸化マグネシウムから得ることである。このようにすることにより、単純な水酸化マグネシウムと単純な水酸化アルミニウムの混合物ではなく、非晶質ではあるがアルミニウムとマグネシウムの相互作用を持った水酸化物と、水酸化マグネシウムの混合物の形態となっていると推測される。
この製法では、アルミニウム塩水溶液、炭酸アルカリ水溶液の必要量を同時に、必要量の水酸化マグネシウムスラリー中に投入することにより、式（Ｉ）で表される複合金属化合物を得ることができる。反応ｐＨは、反応終了時点でｐＨ６.０〜９.０となるように調整し、反応温度は１０〜５０℃に調整することが好ましい。Ｃｌの導入は、得られた複合金属化合物を塩酸で洗浄すれば得られる。
The molar ratio of each component is such that Mg / Al is preferably 0.5 to 15, more preferably 1.0 to 4.0. Alkali carbonate / Al is preferably 0 to 1.4, more preferably 0.5 to 1.2. Caustic / Al is preferably 0 to 2.8, more preferably 1 to 2.4.
The feature of this reaction method is that (2) the amount of alkali carbonate or caustic alkali used is less than the theoretical equivalent with respect to the amount of aluminum salt aqueous solution used. And to obtain a deficient alkali source from magnesium hydroxide. By doing so, it is not a simple mixture of magnesium hydroxide and simple aluminum hydroxide, but a form of a mixture of an amorphous hydroxide that has an interaction between aluminum and magnesium, and magnesium hydroxide. It is estimated that
In this production method, the composite metal compound represented by the formula (I) can be obtained by simultaneously adding the required amounts of the aluminum salt aqueous solution and the alkali carbonate aqueous solution into the required amount of magnesium hydroxide slurry. The reaction pH is preferably adjusted to pH 6.0 to 9.0 at the end of the reaction, and the reaction temperature is preferably adjusted to 10 to 50 ° C. The introduction of Cl can be obtained by washing the obtained composite metal compound with hydrochloric acid.
＜排水中のフッ素イオン濃度を低減させる方法＞
本発明は、フッ素イオンを含有する排水に、上記複合金属化合物を接触せしめることを特徴とする、排水中のフッ素イオン濃度を低減させる方法である。半導体製造工場から排出される排水中のフッ素イオンの濃度は通常０．８５〜３００ｍｇ／Ｌであるが、複合金属化合物の添加量を調整することにより高濃度の排水にも対応することができる。
排水と複合金属化合物との接触は、排水を液全体が混ざる程度に攪拌しながら、複合金属化合物を投入することにより行うことができる。かかる接触によりフッ素イオンを処理剤に吸着させることが出来る。接触の時間は５分以内で十分である。
複合金属化合物の使用量は、排水中のフッ素イオン含有量および処理後の排水中のフッ素イオン濃度を幾らに設定するかによって異なるが、一般に、排水１００重量部当り、複合金属化合物が、好ましくは０．１〜１０重量部、より好ましくは１〜５重量部である。１０重量部以上になると、処理後の廃棄物の廃棄費用が高くなり現実的でなくなる。
<Method to reduce fluorine ion concentration in waste water>
The present invention is a method for reducing the concentration of fluorine ions in waste water, wherein the composite metal compound is brought into contact with waste water containing fluorine ions. The concentration of fluorine ions in the wastewater discharged from the semiconductor manufacturing factory is usually 0.85 to 300 mg / L, but it can also be applied to high concentration wastewater by adjusting the amount of the composite metal compound added.
The contact between the waste water and the composite metal compound can be performed by introducing the composite metal compound while stirring the waste water to such an extent that the whole liquid is mixed. By such contact, fluorine ions can be adsorbed to the treatment agent. A contact time of 5 minutes or less is sufficient.
The amount of the composite metal compound used varies depending on how much the fluorine ion content in the wastewater and the fluorine ion concentration in the wastewater after treatment are set. Generally, the composite metal compound is preferably used per 100 parts by weight of the wastewater. 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight. If it is 10 parts by weight or more, the disposal cost of the waste after the treatment becomes high and it is not realistic.
排水に複合金属化合物を投入し、フッ素イオンを除去した上澄み液を速やかに廃棄するために、凝集剤を投入し速やかに複合金属化合物を沈降させることが工業的に有利である。この目的で凝集剤を使用する。凝集剤の種類としては、アニオン系凝集剤のポリアクリルアミド系の化合物が有効である。凝集剤の使用量は、複合金属化合物１重量部当り、好ましくは０．０１〜０．５重量部、より好ましくは０.０５〜０.３重量部である。その際、凝集剤の添加は、複合金属化合物を添加した後でも良く、これらを同時に添加しても良い。即ち、フッ素イオンを含有する排水に、複合金属化合物を接触させると同時に、あるいは接触後に、凝集剤を添加することが好ましい。
排水に、複合金属化合物および凝集剤を接触させる際の温度は、好ましくは４〜６０℃、より好ましくは１０〜２５℃である。例えば冬季を想定した液温４℃と、夏季を想定した４０℃とで、フッ素除去効率は同程度である。
本発明の処理剤を用いると、排水中のフッ素イオン濃度を８ｍｇ／Ｌ以下とすることが可能である。本発明の処理剤を用いると、排水中のフッ素イオン濃度を０．８ｍｇ／Ｌ以下とすることもできる。また、本発明の処理剤を用いると、ｐＨ３以下の排水をｐＨ５．６〜８．６にすることができる。
In order to throw away the composite metal compound into the wastewater and quickly discard the supernatant liquid from which the fluorine ions have been removed, it is industrially advantageous to throw in the composite metal compound quickly by adding a flocculant. A flocculant is used for this purpose. As the type of the flocculant, an anionic flocculant polyacrylamide compound is effective. The amount of the flocculant used is preferably 0.01 to 0.5 parts by weight, more preferably 0.05 to 0.3 parts by weight per part by weight of the composite metal compound. At this time, the flocculant may be added after the composite metal compound is added, or these may be added simultaneously. That is, it is preferable to add the flocculant at the same time or after the contact of the composite metal compound with the waste water containing fluorine ions.
The temperature at which the composite metal compound and the flocculant are brought into contact with the waste water is preferably 4 to 60 ° C, more preferably 10 to 25 ° C. For example, the fluorine removal efficiency is about the same at a liquid temperature of 4 ° C. assuming winter and 40 ° C. assuming summer.
When the treatment agent of the present invention is used, the fluorine ion concentration in the waste water can be 8 mg / L or less. When the treatment agent of the present invention is used, the fluorine ion concentration in the waste water can be 0.8 mg / L or less. Moreover, when the processing agent of this invention is used, pH3 or less wastewater can be pH 5.6-8.6.
以下、実施例により本発明を具体的に説明するが、本発明は以下の実施例によって限定されるものではない。尚、複合金属化合物中のアルミニウム、マグネシウムはキレート法、炭酸イオンはＪＩＳ Ｋ９１０１で、ＣｌイオンはＶＯＬＨＡＲＤ法、Ｘ線回折は理学電気（株）製のＲＩＮＰ２２００Ｖを用いてＣｕ−ｋαにて測定した。
Ｔａｒｇｅｔ：Ｃｕ， Ｆｉｌｔｅｒ：Ｎｉ，Ｖｏｌｔａｇｅ：４０ＫＶ，Ｃｕｒｒｅｎｔ：２０ｍＡ，Ｓｃａｎｎｉｎｇ Ｓｐｅｅｄ：２°／ｍｉｎ．，Ｓｌｉｔ→ＤＳ １°ＲＳ ０．３ｍｍ ＳＳ １°
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by a following example. In the composite metal compound, aluminum and magnesium were measured by a chelate method, carbonate ions were measured by JIS K9101, Cl ions were measured by a VOLHARD method, and X-ray diffraction was measured by Cu-kα using a RINP2200V manufactured by Rigaku Corporation.
Target: Cu, Filter: Ni, Voltage: 40 KV, Current: 20 mA, Scanning Speed: 2 ° / min. , Slit → DS 1 ° RS 0.3mm SS 1 °
＜実施例１＞複合金属化合物Ａの合成
３Ｌ用ビーカーに、水道水６００ｍＬおよび協和化学工業株式会社製の水酸化マグネシウム(キスマＦ)１００ｇを投入し水酸化マグネシウムスラリーとし(２.８６モル／Ｌ)、攪拌下に、０.５２モル／Ｌ硫酸アルミニウム水溶液８５０ｍＬおよび０.７５モル／Ｌ炭酸ナトリウム水溶液１４００ｍＬを、それぞれの定量ポンプを用いて同時に３０分間で投入した。反応温度は２０℃で実施し、また、反応終了後のｐＨは７.８であった。
反応液はろ過水洗し、６０℃で２０時間オーブンにて乾燥し、ラボスケールハンマーミルで粉砕し、複合金属化合物Ａを得た。反応条件の詳細および得られた複合金属化合物Ａの組成を表１に示す。また、得られた複合金属化合物ＡのＸ線回折図を図１に示す。図１から明らかなように、複合金属化合物ＡのＸ線回折パターンは水酸化マグネシウム結晶のパターンのみである。
<Example 1> Synthesis of composite metal compound A In a 3L beaker, 600 mL of tap water and 100 g of magnesium hydroxide (Kisuma F) manufactured by Kyowa Chemical Industry Co., Ltd. were added to form a magnesium hydroxide slurry (2.86 mol / L). ) While stirring, 850 mL of a 0.52 mol / L aluminum sulfate aqueous solution and 1400 mL of a 0.75 mol / L sodium carbonate aqueous solution were added simultaneously for 30 minutes using respective metering pumps. The reaction temperature was 20 ° C., and the pH after completion of the reaction was 7.8.
The reaction solution was washed with filtered water, dried in an oven at 60 ° C. for 20 hours, and pulverized with a lab scale hammer mill to obtain a composite metal compound A. The details of the reaction conditions and the composition of the obtained composite metal compound A are shown in Table 1. Further, an X-ray diffraction diagram of the obtained composite metal compound A is shown in FIG. As is apparent from FIG. 1, the X-ray diffraction pattern of the composite metal compound A is only a magnesium hydroxide crystal pattern.
＜実施例２＞複合金属化合物Ｂの合成
３.５Ｌ容ビーカーに、実施例１と同じ水酸化マグネシウムを用いて２.０モル／Ｌ水酸化マグネシウムスラリーを１Ｌ調製し、攪拌下に、１モル／Ｌ塩化アルミニウム水溶液７７０ｍＬおよび０.７５モル／Ｌ炭酸ナトリウム水溶液１２５０ｍＬを、それぞれの定量ポンプを用いて同時に３０分間で投入した。反応温度は３０℃で実施し、また、反応終了後のｐＨは８.３であった。
反応液はろ過水洗し、６０℃で２０時間オーブンにて乾燥し、ラボスケールハンマーミルで粉砕し、複合金属化合物Ｂを得た。反応条件の詳細および得られた複合金属化合物Ｂの組成を表１に示す。
<Example 2> Synthesis of composite metal compound B In a 3.5 L beaker, 1 L of a 2.0 mol / L magnesium hydroxide slurry was prepared using the same magnesium hydroxide as in Example 1, and 1 mol was stirred. 770 mL of a / L aluminum chloride aqueous solution and 1250 mL of a 0.75 mol / L sodium carbonate aqueous solution were added simultaneously for 30 minutes using each metering pump. The reaction temperature was 30 ° C., and the pH after completion of the reaction was 8.3.
The reaction solution was washed with filtered water, dried in an oven at 60 ° C. for 20 hours, and pulverized with a lab scale hammer mill to obtain a composite metal compound B. The details of the reaction conditions and the composition of the obtained composite metal compound B are shown in Table 1.
＜実施例３＞複合金属化合物Ｃの合成
３.５Ｌ容ビーカーに、実施例１と同じ水酸化マグネシウムを用いて２.５モル／Ｌ水酸化マグネシウムスラリーを１Ｌ調製し、攪拌下に、１モル／Ｌ硝酸アルミニウム水溶液７７０ｍＬおよび０.７５モル／Ｌ炭酸ナトリウム水溶液１２００ｍＬを、それぞれの定量ポンプを用いて同時に３０分間で投入した。反応温度は４０℃で実施し、また、反応終了後のｐＨは８.７であった。反応液はろ過水洗し、６０℃で２０時間オーブンにて乾燥し、ラボスケールハンマーミルで粉砕し、複合金属化合物Ｃを得た。反応条件の詳細および得られた複合金属化合物Ｃの組成を表１に示す。
<Example 3> Synthesis of composite metal compound C In a 3.5 L beaker, 1 L of 2.5 mol / L magnesium hydroxide slurry was prepared using the same magnesium hydroxide as in Example 1, and 1 mol was stirred. 770 mL of a / L aluminum nitrate aqueous solution and 1200 mL of a 0.75 mol / L sodium carbonate aqueous solution were added simultaneously for 30 minutes using each metering pump. The reaction temperature was 40 ° C., and the pH after completion of the reaction was 8.7. The reaction solution was washed with filtered water, dried in an oven at 60 ° C. for 20 hours, and pulverized with a lab scale hammer mill to obtain a composite metal compound C. The details of the reaction conditions and the composition of the obtained composite metal compound C are shown in Table 1.
＜実施例４＞複合金属化合物Ｄの合成
１００ｇの複合金属化合物Ａを１Ｌの純水に懸濁後、ろ過した。続いて、０．５モル／Ｌ塩酸８６０ｍＬを通液した後、１．５Ｌの水道水を通水し、６０℃で２０時間オーブンにて乾燥した。その後、ラボスケール粉砕機で粉砕することにより塩素を含有する化合物Ｄを得た。得られた複合金属化合物Ｄの組成を表１に示す。また、得られた複合金属化合物ＤのＸ線回折図を図２に示す。
<Example 4> Synthesis of composite metal compound D 100 g of composite metal compound A was suspended in 1 L of pure water and filtered. Subsequently, after passing through 860 mL of 0.5 mol / L hydrochloric acid, 1.5 L of tap water was passed through and dried in an oven at 60 ° C. for 20 hours. Then, the compound D containing chlorine was obtained by grind | pulverizing with a laboratory scale grinder. The composition of the obtained composite metal compound D is shown in Table 1. Moreover, the X-ray diffraction pattern of the obtained composite metal compound D is shown in FIG.
＜実施例５＞
１ｇの複合金属化合物Ａを表２に示すイオンを含む半導体製造工場より排出された排水１００ｍＬに添加し、５分間マグネティックスタラーを用いて攪拌した。その後、固液分離し、上澄み液中のｐＨをｐＨメータで、フッ素（Ｆ）イオン濃度をＪＩＳ Ｋ０１０２ ３４．１に準じて測定した。測定結果を表３に示す。
<Example 5>
1 g of the composite metal compound A was added to 100 mL of waste water discharged from the semiconductor manufacturing factory containing the ions shown in Table 2, and stirred for 5 minutes using a magnetic stirrer. Thereafter, solid-liquid separation was performed, and the pH in the supernatant was measured with a pH meter, and the fluorine (F) ion concentration was measured according to JIS K0102 34.1. Table 3 shows the measurement results.
＜実施例６＞
複合金属化合物Ａの使用量を３．５ｇとした以外は、実施例５と同じ操作を実施した。測定結果を表３に示す。
<Example 6>
The same operation as in Example 5 was performed except that the amount of the composite metal compound A used was 3.5 g. Table 3 shows the measurement results.
＜実施例７＞
複合金属化合物Ａの代わりに複合金属化合物Ｂを用いた以外は実施例６と同じ操作を実施した。測定結果を表３に示す。
<Example 7>
The same operation as in Example 6 was performed except that the composite metal compound B was used instead of the composite metal compound A. Table 3 shows the measurement results.
＜実施例８＞
複合金属化合物Ｂの代わりに複合金属化合物Ｃを用いた以外は、実施例６と同じ操作を実施した。測定結果を表３に示す。
<Example 8>
The same operation as in Example 6 was performed except that the composite metal compound C was used instead of the composite metal compound B. Table 3 shows the measurement results.
＜実施例９＞
複合金属化合物Ｂの代わりに複合金属化合物Ｄを用いた以外は、実施例６と同じ操作を実施した。測定結果を表３に示す。
<Example 9>
The same operation as in Example 6 was performed except that the composite metal compound D was used instead of the composite metal compound B. Table 3 shows the measurement results.
＜実施例１０＞
実施例６の方法でＦイオン吸着処理後、住友アルケム（株）製アニオン性高分子凝集剤「スミフロックＦＡ−４０」を５ｐｐｍ添加し、攪拌したところ２０秒で良好なフロックが形成され容易に固液分離できた。上澄み液中のｐＨをｐＨメータで、フッ素（Ｆ）イオン濃度をＪＩＳ Ｋ０１０２ ３４．１に準じて測定した。測定結果を表３に示す。
<Example 10>
After F ion adsorption treatment by the method of Example 6, 5 ppm of anionic polymer flocculant “Sumifloc FA-40” manufactured by Sumitomo Alchem Co., Ltd. was added and stirred. Liquid separation was possible. The pH in the supernatant was measured with a pH meter, and the fluorine (F) ion concentration was measured according to JIS K0102 34.1. Table 3 shows the measurement results.
＜実施例１１＞
表２に示すイオンを含む半導体製造工場より排出された排水に、純水を加えてフッ素イオン濃度を２ｍｇ／Ｌに調整した水溶液を作成した。該水溶液１００ｍＬに、複合金属化合物Ａを０．１ｇ添加し、５分間マグネティックスタラーを用いて攪拌した。その後、固液分離し、上澄み液中のｐＨをｐＨメータで、フッ素（Ｆ）イオン濃度をＪＩＳ Ｋ０１０２ ３４．１に準じて測定した。測定結果を表３に示す。
<Example 11>
An aqueous solution was prepared by adding pure water to waste water discharged from a semiconductor manufacturing factory containing ions shown in Table 2 to adjust the fluorine ion concentration to 2 mg / L. 0.1 g of the composite metal compound A was added to 100 mL of the aqueous solution, and the mixture was stirred for 5 minutes using a magnetic stirrer. Thereafter, solid-liquid separation was performed, and the pH in the supernatant was measured with a pH meter, and the fluorine (F) ion concentration was measured according to JIS K0102 34.1. Table 3 shows the measurement results.
＜実施例１２＞
表２に示すイオンを含む半導体製造工場より排出された排水に、フッ化ナトリウムを加えてフッ素イオン濃度を３００ｍｇ／Ｌに調整した水溶液を作成した。該水溶液１００ｍＬに、複合金属化合物Ａを１１．０ｇ添加し、５分間マグネティックスタラーを用いて攪拌した。その後、固液分離し、上澄み液中のｐＨをｐＨメータで、フッ素（Ｆ）イオン濃度をＪＩＳ Ｋ０１０２ ３４．１に準じて測定した。測定結果を表３に示す。
<Example 12>
An aqueous solution was prepared by adding sodium fluoride to waste water discharged from a semiconductor manufacturing factory containing ions shown in Table 2 to adjust the fluorine ion concentration to 300 mg / L. To 100 mL of the aqueous solution, 11.0 g of the composite metal compound A was added and stirred for 5 minutes using a magnetic stirrer. Thereafter, solid-liquid separation was performed, and the pH in the supernatant was measured with a pH meter, and the fluorine (F) ion concentration was measured according to JIS K0102 34.1. Table 3 shows the measurement results.
＜比較例１＞
消石灰１ｇを、表２に示すイオンを含む半導体製造工場より排出された排水１００ｍＬに添加し、５分間マグネティックスタラーを用いて攪拌した。その後、固液分離し、上澄み液中のｐＨをｐＨメータで、フッ素（Ｆ）イオン濃度をＪＩＳ Ｋ０１０２ ３４．１に準じて測定した。測定結果を表３に示す。
<Comparative Example 1>
1 g of slaked lime was added to 100 mL of waste water discharged from a semiconductor manufacturing factory containing ions shown in Table 2, and stirred for 5 minutes using a magnetic stirrer. Thereafter, solid-liquid separation was performed, and the pH in the supernatant was measured with a pH meter, and the fluorine (F) ion concentration was measured according to JIS K0102 34.1. Table 3 shows the measurement results.
＜比較例２＞
消石灰使用量を３．５ｇとした以外は比較例１と同操作を実施した。測定結果を表３に示す。
<Comparative example 2>
The same operation as Comparative Example 1 was performed except that the amount of slaked lime used was 3.5 g. Table 3 shows the measurement results.
＜比較例３＞
協和化学工業株式会社製ハイドロタルサイト類化合物(ＤＨＴ−４)３.５ｇを、表２に示すイオンを含む半導体製造工場より排出された排水１００ｍＬに添加し、５分間マグネティックスタラーを用いて攪拌した。後、固液分離し、上澄み液中のｐＨをｐＨメータで、フッ素（Ｆ）イオン濃度をＪＩＳ Ｋ０１０２ ３４．１に準じて測定した。測定結果を表３に示す。
<Comparative Example 3>
3.5 g of hydrotalcite compound (DHT-4) manufactured by Kyowa Chemical Industry Co., Ltd. is added to 100 mL of waste water discharged from a semiconductor manufacturing factory containing the ions shown in Table 2, and stirred for 5 minutes using a magnetic stirrer. did. Thereafter, solid-liquid separation was performed, and the pH in the supernatant was measured with a pH meter, and the fluorine (F) ion concentration was measured according to JIS K0102 34.1. Table 3 shows the measurement results.
Claims (15)
［Ｍｇ（ＯＨ）２］ｘ・Ａｌ２（ＯＨ）６−２ｙ−ｚ・（ＣＯ３）ｙ・（Ｃｌ）ｚ・ｎＨ２Ｏ （Ｉ）
（式中、ｘ、ｙ、ｚおよびｎは、１≦ｘ≦１２、０≦ｙ≦１、０≦ｚ≦１、０．１≦ｎ≦１０、０．１≦（ｙ＋ｚ）≦１．５を満足する）
で表され、
(１)水酸化マグネシウムスラリー中に、(２)アルミニウム塩水溶液および(３)炭酸アルカリ水溶液または苛性アルカリ水溶液を、
各成分のモル比を、Ｍｇ／Ａｌが０.５〜１５、炭酸アルカリ／Ａｌが０．５〜１．２、苛性アルカリ／Ａｌが１〜２．４になるようにして投入し、
反応終了時点でｐＨ６.０〜９.０となるように反応ｐＨを調整し、温度１０〜５０℃で反応させることにより得られ、
粉末Ｘ線回折法による測定に基づいて、水酸化マグネシウム結晶のパターンが認められる複合金属化合物からなる、フッ素イオンを含有する排水の処理剤。 Formula (I)
[Mg (OH) 2] x · Al 2 (OH) 6-2y-z · (CO 3) y · (Cl) z · nH 2 O (I)
(Wherein x, y, z and n are 1 ≦ x ≦ 12, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, 0.1 ≦ n ≦ 10, 0.1 ≦ (y + z) ≦ 1.5. Satisfy)
Represented by
(1) In a magnesium hydroxide slurry , (2) an aqueous solution of aluminum salt and (3) an aqueous alkali carbonate solution or an aqueous caustic solution ,
The molar ratio of each component was set so that Mg / Al was 0.5 to 15, alkali carbonate / Al was 0.5 to 1.2, and caustic alkali / Al was 1 to 2.4.
It is obtained by adjusting the reaction pH so that the pH is 6.0 to 9.0 at the end of the reaction, and reacting at a temperature of 10 to 50 ° C.
A treatment agent for wastewater containing fluorine ions, comprising a composite metal compound in which a magnesium hydroxide crystal pattern is observed based on measurement by a powder X-ray diffraction method.
［Ｍｇ（ＯＨ）２］ｘ・Ａｌ２（ＯＨ）６−２ｙ−ｚ・（ＣＯ３）ｙ・（Ｃｌ）ｚ・ｎＨ２Ｏ （Ｉ）
（式中、ｘ、ｙ、ｚおよびｎは、１≦ｘ≦１２、０≦ｙ≦１、０≦ｚ≦１、０．１≦ｎ≦１０、０．１≦（ｙ＋ｚ）≦１．５を満足する）
で表され、
(１)水酸化マグネシウムスラリー中に、(２)アルミニウム塩水溶液および(３)炭酸アルカリ水溶液または苛性アルカリ水溶液を、
各成分のモル比を、Ｍｇ／Ａｌが０.５〜１５、炭酸アルカリ／Ａｌが０．５〜１．２、苛性アルカリ／Ａｌが１〜２．４になるようにして投入し、
反応終了時点でｐＨ６.０〜９.０となるように反応ｐＨを調整し、温度１０〜５０℃で反応させることにより得られ、
粉末Ｘ線回折法による測定に基づいて、水酸化マグネシウム結晶のパターンが認められる複合金属化合物を接触せしめることを特徴とする、排水中のフッ素イオンを低減させる方法。 In wastewater containing fluorine ions, the following formula (I),
[Mg (OH) 2] x · Al 2 (OH) 6-2y-z · (CO 3) y · (Cl) z · nH 2 O (I)
(Wherein x, y, z and n are 1 ≦ x ≦ 12, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, 0.1 ≦ n ≦ 10, 0.1 ≦ (y + z) ≦ 1.5. Satisfy)
Represented by
(1) In a magnesium hydroxide slurry , (2) an aqueous solution of aluminum salt and (3) an aqueous alkali carbonate solution or an aqueous caustic solution ,
The molar ratio of each component was set so that Mg / Al was 0.5 to 15, alkali carbonate / Al was 0.5 to 1.2, and caustic alkali / Al was 1 to 2.4.
It is obtained by adjusting the reaction pH so that the pH is 6.0 to 9.0 at the end of the reaction, and reacting at a temperature of 10 to 50 ° C.
A method for reducing fluorine ions in waste water, which comprises contacting a composite metal compound in which a magnesium hydroxide crystal pattern is observed based on measurement by a powder X-ray diffraction method.
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