JP5070254B2 - Charcoal-metal composite for water treatment and molded product for charcoal-metal composite - Google Patents
Charcoal-metal composite for water treatment and molded product for charcoal-metal composite Download PDFInfo
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- JP5070254B2 JP5070254B2 JP2009173760A JP2009173760A JP5070254B2 JP 5070254 B2 JP5070254 B2 JP 5070254B2 JP 2009173760 A JP2009173760 A JP 2009173760A JP 2009173760 A JP2009173760 A JP 2009173760A JP 5070254 B2 JP5070254 B2 JP 5070254B2
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- metal
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- carbon
- charcoal
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- 239000003610 charcoal Substances 0.000 claims description 69
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- 238000000465 moulding Methods 0.000 claims description 12
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- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- 229940100445 wheat starch Drugs 0.000 description 1
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- 239000011592 zinc chloride Substances 0.000 description 1
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- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明は、水処理用炭−金属複合体及び炭−金属複合体用成型体に関する。さらに詳しくは排水等に含まれる有害物質を除去するために最適な水処理用炭−金属複合体及びこれを調製するための炭−金属複合体用成型体に関する。 The present invention relates to a water treatment charcoal-metal composite and a molded article for charcoal-metal composite. More specifically, the present invention relates to a water treatment charcoal-metal composite that is optimal for removing harmful substances contained in waste water and the like, and a charcoal-metal composite molding for preparing the same.
有害元素汚染物質に含まれる有害元素を吸着するための有害元素吸着剤であって、ｐＨが２．５〜３．０の酸を用いて酸化鉄を処理して得られる粒状の調製酸化鉄からなる有害元素吸着剤が知られている（特許文献１）。 A harmful element adsorbent for adsorbing harmful elements contained in harmful element pollutants, from granular prepared iron oxide obtained by treating iron oxide with an acid having a pH of 2.5 to 3.0 A harmful element adsorbent is known (Patent Document 1).
また、排水に含まれるリン、ホウ素、フッ素、ヒ素等を吸着除去するために、有機高分子樹脂（エチレンビニルアルコール共重合体、ポリアクリロニトリル、ポリスルホン、ポリビニルフッ化ビニリデン等）及び無機イオン吸着体（金属酸化物を含むむの）を含んでなる外表面に開口する連通孔を有する多孔性の成型体であって、連通孔を形成するフィブリルの内部に空隙を有し、かつ、該空隙の少なくとも一部はフィブリルの表面で開口しており、該フィブリルの外表面及び内部の空隙表面に、細孔容積が０．０５〜０．２５ｍｌ／ｇである無機イオン吸着体が担持されている多孔性成型体が知られている（特許文献２）。 In addition, in order to adsorb and remove phosphorus, boron, fluorine, arsenic, etc. contained in wastewater, organic polymer resins (ethylene vinyl alcohol copolymer, polyacrylonitrile, polysulfone, polyvinylidene fluoride, etc.) and inorganic ion adsorbents ( A porous molded body having a communication hole that opens to the outer surface of the fibril that forms the communication hole, and at least one of the voids. Some are open at the surface of the fibril, and the porous surface in which the inorganic ion adsorbent having a pore volume of 0.05 to 0.25 ml / g is supported on the outer surface and inner void surface of the fibril A molded body is known (Patent Document 2).
調製酸化鉄からなる有害元素吸着剤や、吸着体が担持されている多孔性成型体では、多量の排水を処理するには多量の吸着剤が必要となるという問題がある。また、この他、吸着剤の製造に危険性の高い強酸を使用したり、特殊な製造装置が必要であるという問題がある。
本発明の目的は、水に含まれる多量の有害物質を少量で除去することができ、容易に製造することができる有害物質除去剤を提供することである。
A harmful element adsorbent made of prepared iron oxide or a porous molded body carrying an adsorbent has a problem that a large amount of adsorbent is required to treat a large amount of waste water. In addition, there is a problem that a strong acid with high risk is used for the production of the adsorbent, and a special production apparatus is required.
An object of the present invention is to provide a harmful substance removing agent that can remove a large amount of harmful substances contained in water in a small amount and can be easily produced.
本発明の炭−金属複合体用成形体の特徴は、水溶性コーティング剤（ＡＣ）でコーティングされた金属粒子（ＭＰ）及び炭粒子（ＣＰ）と、バインダー（Ｖ）とを含有してなり、
金属粒子（ＭＰ）が、マグネシウム、アルミニウム、亜鉛、鉄、ニッケル、錫、鉛又は銅からなる金属粒子であり、
金属粒子（ＭＰ）に繊維状の金属粒子を含有してなる点を要旨とする。
Charcoal present invention - characterized metal complex-body compacts, water-soluble coating agent coated (AC) metal particles (MP) and charcoal particles (CP), Ri greens contain a binder (V) ,
The metal particles (MP) are metal particles made of magnesium, aluminum, zinc, iron, nickel, tin, lead or copper,
The gist is that the metal particles (MP) contain fibrous metal particles .
本発明の炭−金属複合体の特徴は、上記の炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした点を要旨とする。 The charcoal-metal composite according to the present invention is characterized in that water is allowed to act on the above-described molded body for a charcoal-metal composite so that the water-soluble coating agent (AC) is eluted into water and the metal particles (MP) and The gist is that the carbon particles (CP) can come into contact with each other.
本発明の炭−金属複合体の製造方法の特徴は、上記の水処理用炭−金属複合体を製造する方法であって、
方法（１−２１）〜（１−２４）のいずれかの方法で製造する点を要旨とする。
A feature of the method for producing a charcoal-metal composite of the present invention is a method for producing the above-described carbon-metal composite for water treatment,
The gist is that it is produced by any one of methods (1-21) to (1-24).
（１−２１）コーティング混合粒子を得るために、金属粒子（ＭＰ）、炭粒子（ＣＰ）及び水溶性コーティング剤（ＡＣ）とを均一混合する工程（１）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（２）；並びに混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程（３）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（４）を含む方法。 (1-21) Step (1) of uniformly mixing metal particles (MP), charcoal particles (CP) and water-soluble coating agent (AC) in order to obtain coating mixed particles; coating mixed particles and binder (V) To obtain a mixed particle slurry (2); and molding the mixed particle slurry to obtain a carbon-metal composite molded body (3); and a carbon-metal composite molded body Step (4) of obtaining a charcoal-metal composite in which water-soluble coating agent (AC) is eluted into water by allowing water to act so that metal particles (MP) and charcoal particles (CP) can come into contact with each other. Including methods.
（１−２２）金属粒子（ＭＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング金属粒子を得る工程（１）；炭粒子（ＣＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング炭粒子を得る工程（２）；コーティング金属粒子及びコーティング炭粒子を均一混合してコーティング混合粒子を得る工程（３）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（４）；混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程（５）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（６）を含む方法。 (1-22) Step (1) of uniformly mixing metal particles (MP) and water-soluble coating agent (AC) to obtain coated metal particles; and uniformly mixing carbon particles (CP) and water-soluble coating agent (AC). Step (2) for obtaining coated carbon particles by coating Step (3) for uniformly mixing coating metal particles and coating carbon particles to obtain coating mixed particles; Mixing coating mixed particles and binder (V) to obtain mixed particle slurry (4); forming a mixed particle slurry to obtain a molded body for a carbon-metal composite (5); and water acting on the molded body for a carbon-metal composite, thereby providing a water-soluble coating. A method comprising a step (6) of obtaining a charcoal-metal composite by eluting the agent (AC) into water so that the metal particles (MP) and the charcoal particles (CP) can come into contact with each other.
（１−２３）金属粒子（ＭＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング金属粒子を得る工程（１）；コーティング金属粒子及び炭粒子（ＣＰ）を均一混合してコーティング混合粒子を得る工程（２）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（３）；混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程（４）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（５）を含む方法。 (1-23) Step (1) for uniformly mixing metal particles (MP) and water-soluble coating agent (AC) to obtain coated metal particles; coating metal particles and carbon particles (CP) are uniformly mixed and coated mixed particles (2); mixing the coating mixed particles and the binder (V) to obtain a mixed particle slurry (3); molding the mixed particle slurry to obtain a molded body for a carbon-metal composite (4); and by allowing water to act on the molded body for the carbon-metal composite, the water-soluble coating agent (AC) can be eluted into the water so that the metal particles (MP) and the carbon particles (CP) can come into contact with each other. A method comprising a step (5) of obtaining a carbon-metal composite.
（１−２４）炭粒子（ＣＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング炭粒子を得る工程（１）；コーティング炭粒子及び金属粒子を均一混合してコーティング混合粒子を得る工程（２）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（３）；混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程（４）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（５）を含む方法。 (1-24) Step of uniformly mixing carbon particles (CP) and water-soluble coating agent (AC) to obtain coated carbon particles (1); Step of uniformly mixing coating carbon particles and metal particles to obtain coated mixed particles (2): mixing the coating mixed particles and the binder (V) to obtain a mixed particle slurry (3); molding the mixed particle slurry to obtain a carbon-metal composite molded body (4) And by allowing water to act on the molded body for the carbon-metal composite, the water-soluble coating agent (AC) was eluted into the water so that the metal particles (MP) and the carbon particles (CP) could come into contact with each other. A method comprising a step (5) of obtaining a carbon-metal composite.
本発明の水処理用炭-金属複合体は、使用量が少なくても多量の有害物質を除去することができる。
本発明の炭−金属複合体用成型体は、水を作用させることによって、容易に炭−金属複合体を調製できる。
本発明の炭−金属複合体用成型体の製造方法によると、炭−金属複合体用成型体を容易に製造できる。また、危険性の高い強酸等や、特殊な製造装置を使用せずに製造できるため、安全性の面及びコストの面にも優れている。
The charcoal-metal composite for water treatment of the present invention can remove a large amount of harmful substances even if the amount used is small.
The carbon-metal composite molded body of the present invention can easily prepare a carbon-metal composite by allowing water to act.
According to the method for producing a molded body for a carbon-metal composite of the present invention, the molded body for a carbon-metal composite can be easily manufactured. Further, since it can be produced without using a highly dangerous strong acid or the like or a special production apparatus, it is excellent in terms of safety and cost.
金属（Ｍ）としては、水と激しく反応する金属でなければ制限はないが、イオン化傾向等の観点から、マグネシウム、アルミニウム、亜鉛、鉄、ニッケル、錫、鉛又は銅が好ましく、さらに好ましくはマグネシウム、アルミニウム、亜鉛又は鉄、イオンの電荷の観点等からさらに好ましくはアルミニウム又は鉄である。 The metal (M) is not limited unless it is a metal that reacts violently with water, but magnesium, aluminum, zinc, iron, nickel, tin, lead, or copper are preferable, and magnesium is more preferable from the viewpoint of ionization tendency and the like. Aluminum, iron or iron, and aluminum or iron are more preferable from the viewpoint of ionic charge.
炭（Ｃ）としては、有機物｛竹、木、ヤシガラ、籐及び鶏糞等｝を蒸し焼きにして得られる炭化物であれば制限なく使用できる。 The charcoal (C) can be used without limitation as long as it is a charcoal obtained by steaming an organic substance {bamboo, wood, coconut shell, rattan, chicken dung, etc.}.
炭（Ｃ）の原料となる有機物としては、炭化できる物であれば制限がないが、品質等の観点から、竹及び木が好ましい。竹及び木のうち、環境保護等の観点から、廃材（建築廃材、家具廃材、使用済み割りばし、廃パレット）、植木剪定材及びこれらの破砕物を圧縮成形した圧縮成型体等を用いることができる。 The organic substance that is the raw material for the charcoal (C) is not limited as long as it can be carbonized, but bamboo and wood are preferable from the viewpoint of quality and the like. Of bamboo and wood, from the viewpoint of environmental protection, waste materials (construction waste materials, furniture waste materials, used crackers, waste pallets), planted pruning materials, and compression molded bodies obtained by compression molding these crushed materials can be used. .
炭（Ｃ）は、縦型炭化炉で製造されることが好ましい。炭化温度（℃）としては、５００〜１０００程度が好ましく、さらに好ましくは７００〜８００程度である。 Charcoal (C) is preferably produced in a vertical carbonization furnace. As carbonization temperature (degreeC), about 500-1000 are preferable, More preferably, it is about 700-800.
炭（Ｃ）自身は、必ずしも多孔質である必要はないが、多孔質であることにより、有害物質を吸着できるため、多孔質であることが好ましい。 The charcoal (C) itself does not necessarily need to be porous, but it is preferable that the charcoal (C) is porous because it can adsorb harmful substances.
炭（Ｃ）の精練度は、０〜６程度が好ましく、さらに好ましくは０〜５、特に好ましくは０〜４、最も好ましくは０〜３である。 The refining degree of the charcoal (C) is preferably about 0 to 6, more preferably 0 to 5, particularly preferably 0 to 4, and most preferably 0 to 3.
精錬度とは、炭化の度合いを表した数字であり、精錬計｛たとえば、株式会社三陽電機製作所製の木炭精錬計｝で測定試料表面の２点間の電気抵抗値（Ω／ｃｍ）を測定し、この電気抵抗値の指数部分の数字を精錬度としたものである。この精錬度が低い程、電気抵抗が小さく、グラファイト構造を多く含むということができる。 The degree of refining is a number representing the degree of carbonization. The refining meter {for example, a charcoal refining meter manufactured by Sanyo Electric Co., Ltd.) is used to calculate the electrical resistance value (Ω / cm) between two points on the surface of the measurement sample. The number of exponents of this electrical resistance value was measured and used as the degree of refinement. It can be said that the lower the refining degree, the smaller the electrical resistance and the more the graphite structure.
本発明において、金属（Ｍ）と炭（Ｃ）とは接触している必要がある。金属（Ｍ）単独、炭（Ｃ）単独、又は金属（Ｍ）と炭（Ｃ）とが非接触の場合、本発明の効果が発現しないこと、水処理が進行するにつれて金属（Ｍ）が目減りしていること、精錬度の大きな炭（Ｃ）を用いると、本発明の効果が発現しがたいこと等から、金属（Ｍ）と炭（Ｃ）とが電気的に接触することにより、金属（Ｍ）が水へ溶出し｛金属（Ｍ）はイオンとして溶出していると考えられる。異種金属と接触することによる金属（Ｍ）の腐食が生じていると考えられる。｝、本発明の効果が発現しているものと考えられる。したがって、金属（Ｍ）と炭（Ｃ）との接触は、電荷の授受ができる程度に接触していれば足りると考えられる。 In the present invention, the metal (M) and the charcoal (C) need to be in contact with each other. When metal (M) alone, charcoal (C) alone, or metal (M) and charcoal (C) are non-contact, the effect of the present invention is not exhibited, and metal (M) decreases as water treatment proceeds. When the charcoal (C) having a high degree of refining is used, the effect of the present invention is difficult to be manifested. Therefore, the metal (M) and the charcoal (C) are in electrical contact with each other, (M) is eluted in water {Metal (M) is considered to be eluted as ions. It is considered that corrosion of the metal (M) due to contact with a different metal occurs. }, It is considered that the effects of the present invention are manifested. Accordingly, it is considered that the contact between the metal (M) and the charcoal (C) is sufficient as long as the contact can be performed to transfer and receive electric charges.
上記に記載したように、本発明の効果の発現機構の考察から、金属（Ｍ）及び炭（Ｃ）と水との接触面積を大きくすることが、水処理を高い効率で行うことができるものと考えられる。
したがって、金属（Ｍ）及び炭（Ｃ）の形状は、大きな塊であるよりも、板状、波板状、棒状又は粒子状等であることが好ましい。さらに好ましくは金属（Ｍ）が金属粒子（ＭＰ）であり、炭（Ｃ）が炭粒子（ＣＰ）であることである。
As described above, from the consideration of the manifestation mechanism of the effect of the present invention, increasing the contact area between metal (M) and charcoal (C) and water can perform water treatment with high efficiency. it is conceivable that.
Therefore, it is preferable that the shapes of the metal (M) and the charcoal (C) are a plate shape, a corrugated plate shape, a rod shape, or a particle shape, rather than a large lump. More preferably, the metal (M) is metal particles (MP) and the charcoal (C) is charcoal particles (CP).
金属（Ｍ）及び炭（Ｃ）の含有量は特に制限はないが、有害物質の除去等の観点から次の範囲が好ましい。
金属（Ｍ）の含有量（重量％）は、金属（Ｍ）及び炭（Ｃ）の重量に基づいて、１０〜９０が好ましく、さらに好ましくは２０〜８０、特に好ましくは２４〜７０である。
炭（Ｃ）の含有量（重量％）は、金属（Ｍ）及び炭（Ｃ）の重量に基づいて、１０〜９０が好ましく、さらに好ましくは２０〜８０、特に好ましくは３０〜７６である。
The contents of the metal (M) and charcoal (C) are not particularly limited, but the following ranges are preferable from the viewpoint of removing harmful substances.
The content (% by weight) of the metal (M) is preferably 10 to 90, more preferably 20 to 80, and particularly preferably 24 to 70, based on the weight of the metal (M) and the charcoal (C).
As for content (weight%) of charcoal (C), 10-90 are preferable based on the weight of a metal (M) and charcoal (C), More preferably, it is 20-80, Most preferably, it is 30-76.
本発明の炭−金属複合体は、水処理の過程で、金属（Ｍ）及び炭（Ｃ）が常に非接触とならなければ、どのような形態であってもよく、たとえば、以下のような形態が含まれる。 The charcoal-metal composite of the present invention may have any form as long as the metal (M) and the charcoal (C) are not always in contact with each other during the water treatment. Includes form.
（１）金属粒子（ＭＰ）及び炭粒子（ＣＰ）を一体成型した形態（１）
（２）金属粒子（ＭＰ）及び炭粒子（ＣＰ）を網容器（多数の孔を持つ容器又は袋、及び布袋等を含む。以下同じである。）内に保持した形態（２）
（３）金属粒子（ＭＰ）及び炭粒子（ＣＰ）を水の流入口及び排出口をもつカートリッジ内に保持した形態（３）
（４）板状の金属（Ｍ）及び炭粒子（ＣＰ）を水の流入口及び排出口をもつ容器内に保持した形態（４）
（５）金属粒子（ＭＰ）及び炭粒子（ＣＰ）を水の流入口及び排出口をもつ容器内に保持した形態（５）
（６）金属（Ｍ）製の網容器内に炭粒子（ＣＰ）を保持した形態（６）
（７）金属（Ｍ）製の網容器内に炭粒子（ＣＰ）及び金属粒子（ＭＰ）を保持した形態（７）
（８）炭（Ｃ）製の網容器内に金属粒子（ＭＰ）を保持した形態（８）
（９）炭（Ｃ）製の網容器内に炭粒子（ＣＰ）及び金属粒子（ＭＰ）を保持した形態（９）
(1) Form in which metal particles (MP) and carbon particles (CP) are integrally molded (1)
(2) Form (2) in which metal particles (MP) and charcoal particles (CP) are held in a net container (including a container or bag having a large number of holes, and a cloth bag, the same applies hereinafter).
(3) Form in which metal particles (MP) and charcoal particles (CP) are held in a cartridge having a water inlet and outlet (3)
(4) Form in which plate-like metal (M) and charcoal particles (CP) are held in a container having a water inlet and outlet (4)
(5) Form in which metal particles (MP) and charcoal particles (CP) are held in a container having a water inlet and outlet (5)
(6) Form in which carbon particles (CP) are held in a metal (M) net container (6)
(7) Form (7) in which carbon particles (CP) and metal particles (MP) are held in a metal (M) net container
(8) Form in which metal particles (MP) are held in a net container made of charcoal (C) (8)
(9) Form in which charcoal particles (CP) and metal particles (MP) are held in a net container made of charcoal (C) (9)
金属粒子（ＭＰ）及び炭粒子（ＣＰ）を一体成型した形態（１）は、以下の方法等により得ることができる。 Form (1) in which metal particles (MP) and charcoal particles (CP) are integrally molded can be obtained by the following method or the like.
炭粒子（ＣＰ）と半溶融させた金属粒子（ＭＰ）とを混合・成型して、冷却する方法（１−１０）
水溶性コーティング剤（ＡＣ）でコーティングされた金属粒子（ＭＰ）及び炭粒子（ＣＰ）と、バインダー（Ｖ）とを混合・成型して、バインダー（Ｖ）を固化した後水溶性コーティング剤（ＡＣ）を水へ溶出する方法（１−２０）
Method of mixing and molding carbon particles (CP) and semi-molten metal particles (MP) and cooling (1-10)
The metal particles (MP) and carbon particles (CP) coated with the water-soluble coating agent (AC) and the binder (V) are mixed and molded to solidify the binder (V), and then the water-soluble coating agent (AC) ) In water (1-20)
方法（１−１０）としては、具体的に以下の方法等が適用できる。 As the method (1-10), the following methods can be specifically applied.
炭粒子（ＣＰ）と金属粒子（ＭＰ）とを混合しながら、加熱し金属粒子を半溶融させて（金属粒子の表面付近を溶融させて）、成型した後（必要により加圧成型する。以下同じである）、冷却する方法（１−１１） While mixing the carbon particles (CP) and the metal particles (MP), the metal particles are heated to semi-melt (melt the vicinity of the surface of the metal particles) and then molded (pressure-molded as necessary. The same), cooling method (1-11)
半溶融させた金属粒子（ＭＰ）と炭粒子（ＣＰ）とを混合し、成型した後、冷却する方法（１−１２） Method of cooling after semi-melted metal particles (MP) and carbon particles (CP) are mixed, molded, and cooled (1-12)
成型用の型に、炭粒子（ＣＰ）及び金属粒子（ＭＰ）の混合物を充填し、この混合物に通電することにより金属粒子を半溶融させた後、冷却する方法（１−１３）｛特開２００２−３５９５５号公報等｝ A method in which a molding die is filled with a mixture of carbon particles (CP) and metal particles (MP), the metal particles are semi-molten by energizing the mixture, and then cooled (1-13). 2002-35955 etc.}
金属粒子（ＭＰ）を溶融する加熱温度は、各金属の溶融温度及び金属粒子の大きさ等により適宜決定される。加熱雰囲気は、炭粒子（ＣＰ）の発火を防ぐために、不活性ガス雰囲気下で行うことが好ましい。 The heating temperature for melting the metal particles (MP) is appropriately determined depending on the melting temperature of each metal, the size of the metal particles, and the like. The heating atmosphere is preferably performed in an inert gas atmosphere in order to prevent ignition of the carbon particles (CP).
方法（１−２０）としては、具体的に以下の方法等が適用できる。 As the method (1-20), the following methods can be specifically applied.
コーティング混合粒子を得るために、金属粒子（ＭＰ）、炭粒子（ＣＰ）及び水溶性コーティング剤（ＡＣ）とを均一混合する工程（１）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（２）；並びに混合粒子スラリーを成型して（必要に応じて加圧する。以下同じである。）、炭−金属複合体用成型体を得る工程（３）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（４）を含む方法（１−２１） Step (1) of uniformly mixing metal particles (MP), carbon particles (CP) and water-soluble coating agent (AC) to obtain coating mixed particles; mixing coating mixed particles and binder (V); Step (2) for obtaining a mixed particle slurry; and Step (3) for obtaining a molded body for a carbon-metal composite by molding the mixed particle slurry (pressing as necessary. The same applies hereinafter); By allowing water to act on the molded body for the carbon-metal composite, the water-soluble coating agent (AC) is eluted into water so that the metal particles (MP) and the carbon particles (CP) can come into contact with each other. A method (1-21) comprising a step (4) of obtaining a metal composite
金属粒子（ＭＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング金属粒子を得る工程（１）；炭粒子（ＣＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング炭粒子を得る工程（２）；コーティング金属粒子及びコーティング炭粒子を均一混合してコーティング混合粒子を得る工程（３）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（４）；混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程（５）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（６）を含む方法（１−２２） Step (1) of uniformly mixing metal particles (MP) and water-soluble coating agent (AC) to obtain coated metal particles; and uniformly mixing carbon particles (CP) and water-soluble coating agent (AC) Obtaining step (2); uniformly mixing the coating metal particles and the coated carbon particles to obtain coating mixed particles (3); mixing the coating mixed particles and the binder (V) to obtain a mixed particle slurry (4) ); Molding the mixed particle slurry to obtain a carbon-metal composite molded body (5); and by allowing water to act on the carbon-metal composite molded body, water-soluble coating agent (AC) A method (1-22) comprising a step (6-22) of obtaining a charcoal-metal composite which is eluted in water to allow the metal particles (MP) and the charcoal particles (CP) to come into contact with each other.
金属粒子（ＭＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング金属粒子を得る工程（１）；コーティング金属粒子及び炭粒子（ＣＰ）を均一混合してコーティング混合粒子を得る工程（２）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（３）；混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程（４）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（５）を含む方法（１−２３） Step (1) of uniformly mixing metal particles (MP) and water-soluble coating agent (AC) to obtain coated metal particles; Step of uniformly mixing coating metal particles and carbon particles (CP) to obtain coated mixed particles (2) ); Mixing the coating mixed particles and the binder (V) to obtain a mixed particle slurry (3); molding the mixed particle slurry to obtain a carbon-metal composite molded body (4); By allowing water to act on the molded body for the carbon-metal composite, the water-soluble coating agent (AC) is eluted into water so that the metal particles (MP) and the carbon particles (CP) can come into contact with each other. Method (1-23) including the step (5) of obtaining a metal composite
炭粒子（ＣＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング炭粒子を得る工程（１）；コーティング炭粒子及び金属粒子を均一混合してコーティング混合粒子を得る工程（２）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（３）；混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程（４）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（５）を含む方法（１−２４） Step (1) for uniformly mixing carbon particles (CP) and water-soluble coating agent (AC) to obtain coated carbon particles; Step (2) for uniformly mixing coating carbon particles and metal particles to obtain coated mixed particles (Coating) Step (3) for mixing mixed particles and binder (V) to obtain a mixed particle slurry; Step (4) for forming a mixed particle slurry to obtain a molded body for a carbon-metal composite; and Carbon-metal A charcoal-metal composite in which a water-soluble coating agent (AC) is eluted into water by allowing water to act on the composite molded body so that the metal particles (MP) and the carbon particles (CP) can come into contact with each other. (1-24) including the step (5) of obtaining
水溶性コーティング剤（ＡＣ）は、水に容易に溶解でき、金属粒子（ＭＰ）及び炭粒子（ＣＰ）をコーティングできれば制限なく、合成水溶性高分子｛ポリアクリル酸、ポリエチレンオキシド（ポリエチレングリコール）、ポリビニルピロリドン、ポリビニルアルコール及びこれらのポリマーを構成するモノマー及びその他のモノマーを組合わせた共重合体等｝、半合成高分子｛ヒドロキシエチルセルロース（ＨＥＣ）、カルボキシメチルセルロース（ＣＭＣ）、ヒドロキシエチルメチルセルロース（ＨＥＭＣ）、ヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、メチルセルロース（ＭＣ）、エチルセルロース、ペクチン酸及び水溶性ゼラチン等｝及び天然高分子｛でんぷん、寒天、カラギーナン、アルギン酸ソーダ、グアーガム、ペクチン、デキストリン、ゼラチン、カゼイン、コラーゲン、米粉、小麦でんぷん及び生ふ等｝が含まれる。 The water-soluble coating agent (AC) can be easily dissolved in water and can be coated with metal particles (MP) and charcoal particles (CP) without any limitation, and a synthetic water-soluble polymer {polyacrylic acid, polyethylene oxide (polyethylene glycol), Polyvinyl pyrrolidone, polyvinyl alcohol, copolymers of these polymers and copolymers combining other monomers, etc.}, semi-synthetic polymers {hydroxyethylcellulose (HEC), carboxymethylcellulose (CMC), hydroxyethylmethylcellulose (HEMC) , Hydroxypropyl methylcellulose (HPMC), methylcellulose (MC), ethylcellulose, pectic acid and water-soluble gelatin, etc.} and natural polymers {starch, agar, carrageenan, sodium alginate, guar gum, pec Emissions, dextrin, gelatin, casein, collagen, rice flour include wheat starch and raw Fu etc.}.
これらの水溶性コーティング剤（ＡＣ）のうち、環境負荷等の観点から、半合成高分子及び天然高分子が好ましく、さらに好ましくは天然高分子、特に好ましくはでんぷんである。 Of these water-soluble coating agents (AC), semi-synthetic polymers and natural polymers are preferable from the viewpoint of environmental impact and the like, more preferably natural polymers, and particularly preferably starch.
水溶性コーティング剤（ＡＣ）のコーティング厚みは、炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できれば制限がない｛コーティング混合粒子とバインダー（Ｖ）と混合して得た混合スラリーを成型する際、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが水溶性コーティング剤（ＡＣ）を介して近接していればよい。｝。 The coating thickness of the water-soluble coating agent (AC) is such that the water-soluble coating agent (AC) is eluted into water by allowing water to act on the molded body for the carbon-metal composite. There is no limitation as long as it can contact (CP). {When forming a mixed slurry obtained by mixing coating mixed particles and binder (V), metal particles (MP) and carbon particles (CP) are water-soluble coating agents ( AC). }.
水溶性コーティング剤（ＡＣ）は、水溶液又は溶媒溶液として用いることができる。この場合の濃度としては、水溶性コーティング剤（ＡＣ）の種類によって、溶液粘度等を考慮して適宜決定される。
溶媒としては、水性溶媒及びこれと水との混合物が含まれる。水性溶媒としては、炭素数１〜４のアルコール（メタノール、エタノール、イソプロピルアルコール及びｎ−ブチルアルコール等）、炭素数３〜５のケトン（アセトン、メチルエチルケトン及びジメチルスルホキシド等）、炭素数３〜５のアミド（ジメチルホルムアミド及びＮ−メチルピロリドン等）、炭素数３〜５のエステル（酢酸メチル、酢酸エチル及びプロピオン酸メチル等）及びこれらの混合物が含まれる。
The water-soluble coating agent (AC) can be used as an aqueous solution or a solvent solution. The concentration in this case is appropriately determined depending on the type of water-soluble coating agent (AC) in consideration of the solution viscosity and the like.
The solvent includes an aqueous solvent and a mixture thereof with water. Examples of the aqueous solvent include alcohols having 1 to 4 carbon atoms (such as methanol, ethanol, isopropyl alcohol and n-butyl alcohol), ketones having 3 to 5 carbon atoms (such as acetone, methyl ethyl ketone and dimethyl sulfoxide), and those having 3 to 5 carbon atoms. Amides (such as dimethylformamide and N-methylpyrrolidone), esters having 3 to 5 carbon atoms (such as methyl acetate, ethyl acetate and methyl propionate) and mixtures thereof are included.
金属粒子（ＭＰ）としては、水と激しく反応する金属でなければ制限はないが、イオン化傾向等の観点から、マグネシウム、アルミニウム、亜鉛、鉄、ニッケル、錫、鉛又は銅からなる金属粒子が好ましく、さらに好ましくはマグネシウム、アルミニウム、亜鉛又は鉄からなる金属粒子、イオンの電荷の観点等からさらに好ましくはアルミニウム又は鉄からなる金属粒子である。 The metal particle (MP) is not limited unless it is a metal that reacts violently with water, but metal particles made of magnesium, aluminum, zinc, iron, nickel, tin, lead or copper are preferable from the viewpoint of ionization tendency and the like. More preferred are metal particles made of magnesium, aluminum, zinc or iron, and more preferred are metal particles made of aluminum or iron from the viewpoint of ionic charge.
金属粒子（ＭＰ）の重量平均粒子径（ｍｍ）は、成型性及び有害物質の除去等の観点から、０．１〜２０程度が好ましく、さらに好ましくは０．２〜１０程度、特に好ましくは０．５〜５程度である。 The weight average particle diameter (mm) of the metal particles (MP) is preferably about 0.1 to 20, more preferably about 0.2 to 10, particularly preferably 0 from the viewpoints of moldability and removal of harmful substances. About 5-5.
重量平均粒子径は、測定試料の粒度分布を測定し、対数確率紙｛横軸：粒径、縦軸：累積含有量（重量％）｝に、累積含有量と粒子径との関係をプロットし、累積含有量が５０重量％に対応する粒子径を求めることにより得られる。粒度分布は、ＪＩＳ Ｚ８８１５−１９９４に準拠して測定され、ふるいを目開きの狭いふるいを下にして重ね、一番上の最も目開きの広いふるいの上に、測定試料を入れ、ふるい振動機にて篩い分けし、各ふるいの上に残った測定試料の重量を測定し、最初の測定試料の重量に基づく各ふるいの上に残った測定試料の重量％を求めることによって測定される。 The weight average particle size is measured by measuring the particle size distribution of the measurement sample, and plotting the relationship between the cumulative content and the particle size on logarithmic probability paper {horizontal axis: particle size, vertical axis: cumulative content (wt%)}. The particle size corresponding to a cumulative content of 50% by weight is obtained. The particle size distribution is measured in accordance with JIS Z8815-1994, and the sieve is placed with the narrowest sieve on the bottom, the measurement sample is placed on the top sieve with the widest mesh, and the sieve vibrator And the weight of the measurement sample remaining on each sieve is measured, and the weight percentage of the measurement sample remaining on each sieve is determined based on the weight of the first measurement sample.
なお、金属粒子（ＭＰ）の大きさに関して、炭−金属複合体を形成した際、金属粒子と有害物質を含む水との接触性を良好にするため、小さな金属粒子を含有することが好ましく、一方、有害物質の除去効果を長期間維持するため、大きな金属粒子を含有することが好ましい。すなわち、上記理由から、大きな金属粒子と小さな金属粒子との両方を含むことが好ましく、金属粒子の大きさを均一にしないことが好ましい。 As for the size of the metal particles (MP), when forming a carbon-metal composite, it is preferable to contain small metal particles in order to improve the contact between the metal particles and water containing harmful substances, On the other hand, in order to maintain the effect of removing harmful substances for a long period of time, it is preferable to contain large metal particles. That is, for the above reasons, it is preferable to include both large metal particles and small metal particles, and it is preferable not to make the sizes of the metal particles uniform.
金属粒子（ＭＰ）の形状に特に制限はないが、炭−金属複合体を形成した際、金属粒子と有害物質を含む水との接触性を良好にするため、不定形状の金属粒子及び／又は繊維状の金属粒子を含むことが好ましく、さらに好ましくは繊維状の金属粒子を含むことである。繊維状の金属粒子を含有すると、上記理由に加えて、繊維状の金属粒子同士の接触や、繊維状の金属粒子と炭粒子（ＣＰ）との接触が増大し、繊維状の金属粒子と炭粒子（ＣＰ）との接触が確実になるため好ましいと考えられる。 There are no particular restrictions on the shape of the metal particles (MP), but when forming a charcoal-metal composite, in order to improve the contact between the metal particles and water containing harmful substances, the irregularly shaped metal particles and / or It is preferable to include fibrous metal particles, and more preferably to include fibrous metal particles. When the fibrous metal particles are contained, in addition to the above reasons, the contact between the fibrous metal particles and the contact between the fibrous metal particles and the carbon particles (CP) increase, and the fibrous metal particles and the carbon particles are increased. It is considered preferable because contact with the particles (CP) is ensured.
繊維状の金属粒子を含有する場合、繊維状の金属粒子の長さ（ｍｍ）は、０．１〜２０程度が好ましく、さらに好ましくは０．２〜１０程度、特に好ましくは０．５〜５程度である。この場合、繊維状の金属粒子の太さ（直径）は、１μｍ〜５ｍｍ程度が好ましく、さらに好ましくは２μｍ〜４ｍｍ程度、特に好ましくは１０μｍ〜１ｍｍ程度である。 When the fibrous metal particles are contained, the length (mm) of the fibrous metal particles is preferably about 0.1 to 20, more preferably about 0.2 to 10, particularly preferably 0.5 to 5. Degree. In this case, the thickness (diameter) of the fibrous metal particles is preferably about 1 μm to 5 mm, more preferably about 2 μm to 4 mm, and particularly preferably about 10 μm to 1 mm.
以上のような金属粒子（ＭＰ）は、工業的に得ることができ、また、工業製品を必要により混合することにより調製できるが、より安価に入手するために、金属製品や金属部品等を製造する際に発生する切削粉や、回収金属｛回収アルミニウム缶、回収スチール缶、その他の回収金属屑等；必要によりシュレッターで破砕してもよい｝を用いることができる。切削粉や回収金属を用いる場合、水不溶性の切削油剤や油等が付着しているときこれを洗浄する必要があり、水溶性の切削油剤等が付着しているときはそのまま用いてもよいし洗浄して用いてもよい。 The metal particles (MP) as described above can be obtained industrially, and can be prepared by mixing industrial products as necessary, but in order to obtain them at a lower cost, metal products and metal parts are manufactured. In this case, cutting powder generated at the time of recovery, recovered metal {recovered aluminum can, recovered steel can, other recovered metal scraps, etc .; When cutting powder or recovered metal is used, it is necessary to wash the water-insoluble cutting fluid or oil if it is attached. If water-soluble cutting fluid is attached, it may be used as it is. You may wash | clean and use.
炭粒子（ＣＰ）の原料となる有機物の大きさは、ヤシガラ等のように元々小さなものそのまま炭化させ、竹や木等のように大きなものは２〜１０ｃｍ程度以内の大きさ破砕してから炭化させる。 The size of the organic material used as the raw material for the carbon particles (CP) is carbonized as it is originally small, such as coconut shells, and the large one, such as bamboo or wood, is crushed to a size within 2 to 10 cm before carbonization. Let
炭粒子（ＣＰ）は、破砕等により粒子を小さくしてもよく、さらに、スクリーン（金網等）により篩い分けしてもよい。 The carbon particles (CP) may be reduced in size by crushing or the like, and further sieved by a screen (such as a wire mesh).
バインダー（Ｖ）は、水溶性コーティング剤（ＡＣ）でコーティングされた金属粒子（ＭＰ）及び炭粒子（ＣＰ）を成型することができるものであれば制限なく使用でき、有機バインダー及び無機バインダーが含まれる。 The binder (V) can be used without limitation as long as it can form metal particles (MP) and carbon particles (CP) coated with a water-soluble coating agent (AC), and includes an organic binder and an inorganic binder. It is.
有機バインダーとしては、エポキシ樹脂、アクリル樹脂及びウレタン樹脂等が挙げられる。
無機バインダーとしては、セメント、石膏及び粘土等が挙げられる。
これらのバインダー（Ｖ）のうち、無機バインダーが好ましく、さらに好ましくはセメントである。
Examples of the organic binder include epoxy resin, acrylic resin, and urethane resin.
Examples of the inorganic binder include cement, gypsum, and clay.
Of these binders (V), inorganic binders are preferable, and cement is more preferable.
バインダー（Ｖ）の含有量は、混合粒子スラリーを成型して、炭−金属複合体用成型体を得ることができれば制限がないが、成型体の強度が確保できればできるだけ少ないことが好ましく、次の範囲であることが望ましい。
バインダー（Ｖ）の含有量（重量％）は、金属粒子（ＭＰ）及び炭粒子（ＣＰ）の重量に基づいて、３０〜８０が好ましく、さらに好ましくは４０〜７０、特に好ましくは５０〜６０である。
The content of the binder (V) is not limited as long as the mixed particle slurry can be molded to obtain a molded body for a carbon-metal composite, but is preferably as small as possible if the strength of the molded body can be secured. A range is desirable.
The content (% by weight) of the binder (V) is preferably 30 to 80, more preferably 40 to 70, particularly preferably 50 to 60, based on the weight of the metal particles (MP) and the carbon particles (CP). is there.
バインダー（Ｖ）として、セメントを用いる場合、ハロゲン化アルカリ金属、ハロゲン化アルカリ土類金属、アルカリ土類金属水酸化物、酸化アルカリ土類金属、ハロゲン化アンモニウム、遷移金属酸化物、第１３属元素の酸化物及び遷移金属ハロゲン化物からなる群より選ばれる少なくとも１種をセメントに含有させることが好ましい。これらの無機化合物を含有すると、セメントに混入させる水の量を少なくすることができ、セメントが固化する前に、水溶性コーティング剤（ＡＣ）が水へ溶出してしまうことを防止できる。また、これらの無機化合物を含有すると、含有しない場合に比べて、強度を増すことができる。 When cement is used as the binder (V), an alkali metal halide, an alkaline earth metal halide, an alkaline earth metal hydroxide, an alkaline earth metal oxide, an ammonium halide, a transition metal oxide, a Group 13 element It is preferable that the cement contains at least one selected from the group consisting of oxides and transition metal halides. When these inorganic compounds are contained, the amount of water mixed into the cement can be reduced, and the water-soluble coating agent (AC) can be prevented from being eluted into water before the cement is solidified. Moreover, when these inorganic compounds are contained, the strength can be increased as compared with the case where they are not contained.
ハロゲン化アルカリ金属としては、塩化リチウム、塩化カリウム、塩化ナトリウム、臭化ナトリウム及びヨウ化リチウム等が挙げられる。
ハロゲン化アルカリ土類金属としては、塩化マグネシウム、塩化カルシウム及び臭化マグネシウム等が挙げられる。
アルカリ土類金属水酸化物としては、水酸化マグネシウム及び水酸化カルシウム等が挙げられる。
酸化アルカリ土類金属としては、酸化マグネシウム等が挙げられる。
ハロゲン化アンモニウムとしては、塩化アンモニウム及び臭化アンモニウム等が挙げられる。
遷移金属酸化物としては、酸化第一鉄、酸化第二鉄及び酸化亜鉛等が挙げられる。
第１３属元素の酸化物としては、酸化ホウ素及び酸化アルミニウム等が挙げられる。
遷移金属ハロゲン化物としては、塩化第二鉄、塩化ニッケル、塩化第二銅及び塩化亜鉛等が挙げられる。
Examples of the alkali metal halide include lithium chloride, potassium chloride, sodium chloride, sodium bromide and lithium iodide.
Examples of the alkaline earth metal halide include magnesium chloride, calcium chloride and magnesium bromide.
Examples of the alkaline earth metal hydroxide include magnesium hydroxide and calcium hydroxide.
Examples of the alkaline earth metal oxide include magnesium oxide.
Examples of the ammonium halide include ammonium chloride and ammonium bromide.
Examples of transition metal oxides include ferrous oxide, ferric oxide, and zinc oxide.
Examples of Group 13 element oxides include boron oxide and aluminum oxide.
Examples of transition metal halides include ferric chloride, nickel chloride, cupric chloride, and zinc chloride.
水溶性コーティング剤（ＡＣ）を金属粒子（ＭＰ）及び／又は炭粒子（ＣＰ）にコーティングする方法としては、公知の方法を適用でき、たとえば、回転するコーティングパンを使用する方法、及び流動層を使用する方法が挙げられる。これらの他、水溶性コーティング剤（ＡＣ）の水溶液又は溶媒溶液に、金属粒子（ＭＰ）及び／又は炭粒子（ＣＰ）を浸漬した後、コーティング粒子を金網等ですくいあげる方法、同じく浸漬した後、コーティング粒子を濾別する方法等も適用できる。 As a method of coating the water-soluble coating agent (AC) on the metal particles (MP) and / or the carbon particles (CP), a known method can be applied. For example, a method using a rotating coating pan, and a fluidized bed The method to use is mentioned. In addition to these, after immersing the metal particles (MP) and / or carbon particles (CP) in an aqueous solution or solvent solution of the water-soluble coating agent (AC), scooping the coating particles with a wire mesh, etc. Also, a method of separating the coating particles by filtration can be applied.
混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程において、必要に応じて加圧しながら成型してもよい。
加圧する場合、圧力は、混合粒子スラリーの粘度等を考慮して、適宜決定される。
In the step of forming the mixed particle slurry to obtain a molded body for a carbon-metal composite, it may be molded while applying pressure as necessary.
When pressurizing, the pressure is appropriately determined in consideration of the viscosity of the mixed particle slurry.
炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させるためには、炭−金属複合体用成型体に水を注いでもよいし、水の中に炭−金属複合体用成型体を浸漬してもよく、水中に炭−金属複合体用成型体を浸漬してもよい。 In order to elute the water-soluble coating agent (AC) into water by allowing water to act on the molded body for the charcoal-metal composite, water may be poured into the molded body for the charcoal-metal composite. The molded object for charcoal-metal composites may be immersed in the inside, and the molded object for charcoal-metal composites may be immersed in water.
炭−金属複合体用成型体に含まれる水溶性コーティング剤（ＡＣ）を水へ溶出させることによって、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようになる。すなわち、炭−金属複合体用成型体から、炭−金属複合体が調製できる。 By eluting the water-soluble coating agent (AC) contained in the carbon-metal composite molded body into water, the metal particles (MP) and the carbon particles (CP) can come into contact with each other. That is, a charcoal-metal composite can be prepared from a molded body for a charcoal-metal composite.
金属粒子（ＭＰ）及び炭粒子（ＣＰ）を網容器内に保持した形態（２）は、金属粒子（ＭＰ）及び炭粒子（ＣＰ）を混合して、網容器内に入れて、金属粒子（ＭＰ）及び炭粒子（ＣＰ）が網容器外に出てこないようにすることにより得ることができる。 In the form (2) in which the metal particles (MP) and the charcoal particles (CP) are held in the net container, the metal particles (MP) and the charcoal particles (CP) are mixed and put in the net container, MP) and carbon particles (CP) can be obtained by preventing them from coming out of the net container.
網容器としては、網状の容器（たとえば、ステンレス製金網で調製した容器や袋）の他、多数の孔を持つ容器（ステンレス製パンチングメタルで調製した容器）又は袋（たとえば、多数の穴を開けたポリエチレン製の袋）、及び布袋（たとえば、不織布で調製した袋、木綿で調製した袋）等を含む。 As a net container, in addition to a net-like container (for example, a container or bag prepared with a stainless steel wire mesh), a container having a large number of holes (a container prepared with stainless steel punching metal) or a bag (for example, having a large number of holes opened) Polyethylene bags), and cloth bags (for example, bags made of nonwoven fabric, bags made of cotton).
金属粒子（ＭＰ）及び炭粒子（ＣＰ）を水の流入口及び排出口をもつカートリッジ内に保持した形態（３）は、金属粒子（ＭＰ）及び炭粒子（ＣＰ）を混合して、水の流入口及び排出口をもつカートリッジ内に入れて、密閉することにより得ることができる。 In the form (3) in which the metal particles (MP) and the charcoal particles (CP) are held in the cartridge having the water inlet and outlet, the metal particles (MP) and the charcoal particles (CP) are mixed to It can be obtained by sealing in a cartridge having an inlet and an outlet.
水の流入口及び排出口をもつカートリッジは、公知のものが適用できる。なお、水の流入口及び排出口には、金属粒子（ＭＰ）及び炭粒子（ＣＰ）が流出しないように、フィルター又は網を設けることが好ましい。 A known cartridge can be used as the cartridge having the water inlet and outlet. In addition, it is preferable to provide a filter or a net | network in the inflow port and discharge port of water so that a metal particle (MP) and charcoal particle (CP) may not flow out.
板状の金属（Ｍ）及び炭粒子（ＣＰ）を水の流入口及び排出口をもつ容器内に保持した形態（４）は、水の流入口及び排出口をもつ容器内に、板状の金属（Ｍ）及び炭粒子（ＣＰ）を混合状態で入れることにより得ることができる。 In the form (4) in which the plate-like metal (M) and the carbon particles (CP) are held in a container having a water inlet and outlet, the plate-like metal (M) and charcoal particles (CP) It can be obtained by putting the metal (M) and the carbon particles (CP) in a mixed state.
水の流入口及び排出口をもつ容器は、板状の金属（Ｍ）及び炭粒子（ＣＰ）を保持できれば制限がない。なお、水の流入口及び排出口には、炭粒子（ＣＰ）が流出しないように、フィルター又は網を設けることが好ましい。 The container having the water inlet and outlet is not limited as long as it can hold plate-like metal (M) and charcoal particles (CP). In addition, it is preferable to provide a filter or a net | network in the inflow port and discharge port of water so that charcoal particle (CP) may not flow out.
板状の金属（Ｍ）は、表面積を増大させるために、表面に模様を設けたり、板に孔を空けたり、板自体を網目状にしたり、板自体を波板状にしたり、板自体を螺旋状に丸めたり、これらを組合わせたりしてもよい。
板の大きさ（厚みも含む）は、容器内に収納できれば制限ない。
In order to increase the surface area, the plate-like metal (M) is provided with a pattern on the surface, a hole is formed in the plate, the plate itself is made into a mesh shape, the plate itself is made into a corrugated plate, They may be rounded into a spiral shape or a combination thereof.
The size (including thickness) of the plate is not limited as long as it can be stored in the container.
金属粒子（ＭＰ）及び炭粒子（ＣＰ）を水の流入口及び排出口をもつ容器内に保持した形態（５）は、金属粒子（ＭＰ）及び炭粒子（ＣＰ）を混合して、水の流入口及び排出口をもつ容器内に入れることにより得ることができる。 In the form (5) in which the metal particles (MP) and the charcoal particles (CP) are held in a container having an inlet and an outlet for water, the metal particles (MP) and the charcoal particles (CP) are mixed to form water. It can be obtained by placing it in a container having an inlet and an outlet.
水の流入口及び排出口をもつ容器は、金属粒子（ＭＰ）及び炭粒子（ＣＰ）を保持できれば制限がない。なお、水の流入口及び排出口には、金属粒子（ＭＰ）及び炭粒子（ＣＰ）が流出しないように、フィルター又は網を設けることが好ましい。 The container having the water inlet and outlet is not limited as long as it can hold metal particles (MP) and charcoal particles (CP). In addition, it is preferable to provide a filter or a net | network in the inflow port and discharge port of water so that a metal particle (MP) and charcoal particle (CP) may not flow out.
金属（Ｍ）製の網容器内に炭粒子（ＣＰ）を保持した形態（６）は、金属（Ｍ）製の網容器内に炭粒子（ＣＰ）を入れることにより得ることができる。 The form (6) in which the carbon particles (CP) are held in the metal (M) net container can be obtained by putting the carbon particles (CP) in the metal (M) net container.
金属（Ｍ）製の網容器の形状や大きさは、炭粒子（ＣＰ）を保持することができれば制限がない。しかし、水処理の進行と共に、金属（Ｍ）が徐々に目減りするため、肉厚にすることが好ましい。 The shape and size of the metal (M) net container are not limited as long as the carbon particles (CP) can be retained. However, since the metal (M) gradually decreases as the water treatment proceeds, it is preferable to increase the thickness.
金属（Ｍ）製の網容器内に炭粒子（ＣＰ）及び金属粒子（ＭＰ）を保持した形態（７）は、金属（Ｍ）製の網容器内に炭粒子（ＣＰ）及び金属粒子（ＭＰ）を入れることにより得ることができる。 In the form (7) in which the carbon particles (CP) and the metal particles (MP) are held in the metal (M) net container, the carbon particles (CP) and the metal particles (MP) are stored in the metal (M) net container. ) Can be obtained.
網容器の金属（Ｍ）の種類と、金属粒子（ＭＰ）の種類とは、同じでも異なってもよいが、網容器の金属（Ｍ）のイオン化傾向が、金属粒子（ＭＰ）のイオン化傾向よりも小さいことが好ましい｛網容器の金属（Ｍ）が、金属粒子（ＭＰ）よりも水に溶出しにくいことが好ましい。｝。 The type of metal (M) in the net container and the type of metal particles (MP) may be the same or different, but the ionization tendency of the metal (M) in the net container is more than the ionization tendency of the metal particles (MP). It is preferable that the metal (M) of the mesh container is less likely to elute into water than the metal particles (MP). }.
炭（Ｃ）製の網容器内に金属粒子（ＭＰ）を保持した形態（８）は、炭（Ｃ）製の網容器内に金属粒子（ＭＰ）を入れることにより得ることができる。 The form (8) which hold | maintained the metal particle (MP) in the net container made from charcoal (C) can be obtained by putting a metal particle (MP) in the net container made from charcoal (C).
炭（Ｃ）製の網容器の形状や大きさは、金属粒子（ＭＰ）を保持することができれば制限がない。炭（Ｃ）製の網容器は、炭を網目状にくみ上げてもよく、炭の原料である有機物を網目状に加工してから炭化してもよい。 The shape and size of the net container made of charcoal (C) are not limited as long as the metal particles (MP) can be held. The net container made of charcoal (C) may draw up the charcoal in a mesh shape, or may carbonize after processing the organic material which is the raw material of charcoal into a net shape.
炭（Ｃ）製の網容器内に炭粒子（ＣＰ）及び金属粒子（ＭＰ）を保持した形態（９）は、炭粒子（ＣＰ）及び金属粒子（ＭＰ）を混合して、炭（Ｃ）製の網容器内に入れることにより得ることができる。 In the form (9) in which the carbon particles (CP) and the metal particles (MP) are held in the net container made of carbon (C), the carbon particles (CP) and the metal particles (MP) are mixed, and the carbon (C) It can be obtained by placing it in a net container.
本発明の炭−金属複合体は、この内部に水が自由に出入りできる隙間を設けることが好ましい。すなわち、本発明の炭−金属複合体は多孔質であることが好ましい。 It is preferable that the carbon-metal composite of the present invention is provided with a gap through which water can freely enter and exit. That is, the carbon-metal composite of the present invention is preferably porous.
本発明の炭−金属複合体の形態によって、水に浸漬したり、炭−金属複合体の内部に水を導いたりすることができる。
金属粒子（ＭＰ）及び炭粒子（ＣＰ）を一体成型した形態（１）；金属粒子（ＭＰ）及び炭粒子（ＣＰ）を網容器内に保持した形態（２）；金属（Ｍ）製の網容器内に炭粒子（ＣＰ）を保持した形態（６）；金属（Ｍ）製の網容器内に炭粒子（ＣＰ）及び金属粒子（ＭＰ）を保持した形態（７）；炭（Ｃ）製の網容器内に金属粒子（ＭＰ）を保持した形態（８）；並びに炭（Ｃ）製の網容器内に炭粒子（ＣＰ）及び金属粒子（ＭＰ）を保持した形態（９）の場合、水に浸漬することが好ましい。なお、これらを容器に保持して、水をこの容器に導いてもよい。
Depending on the form of the charcoal-metal composite of the present invention, it is possible to immerse in water or guide water into the charcoal-metal composite.
Form (1) in which metal particles (MP) and charcoal particles (CP) are integrally molded; Form (2) in which metal particles (MP) and charcoal particles (CP) are held in a net container; Net made of metal (M) Form (6) in which carbon particles (CP) are held in a container; Form (7) in which carbon particles (CP) and metal particles (MP) are held in a metal (M) net container; In the case of the form (8) in which the metal particles (MP) are held in the mesh container of the above; It is preferable to immerse in water. In addition, these may be hold | maintained at a container and water may be guide | induced to this container.
金属粒子（ＭＰ）及び炭粒子（ＣＰ）を水の流入口及び排出口をもつカートリッジ内に保持した形態（３）；板状の金属（Ｍ）及び炭粒子（ＣＰ）を水の流入口及び排出口をもつ容器内に保持した形態（４）；並びに金属粒子（ＭＰ）及び炭粒子（ＣＰ）を水の流入口及び排出口をもつ容器内に保持した形態（５）の場合、流入口から水を流入させることにより、水を処理する。 Form (3) in which metal particles (MP) and charcoal particles (CP) are held in a cartridge having a water inlet and outlet; plate-like metal (M) and charcoal particles (CP) in water inlet and In the case of the form (4) held in the container having the discharge port; and the form (5) in which the metal particles (MP) and the carbon particles (CP) are held in the container having the water inlet and the discharge port, the inlet Treat the water by letting it in.
本発明の炭−金属複合体で処理する水のｐＨは、金属（Ｍ）又は金属粒子（ＭＰ）の種類等によって適正な範囲があると考えられる。たとえば、金属（Ｍ）又は金属粒子（ＭＰ）がアルミニウム又はアルミニウム粒子の場合、６〜８が好ましく、さらに好ましくは６．５〜７．５である。すなわち、水のｐＨは中性であることが好ましい。一方、金属（Ｍ）又は金属粒子（ＭＰ）が鉄又は鉄粒子の場合、９〜１１が好ましく、さらに好ましくは９．５〜１０．５である。 The pH of water to be treated with the carbon-metal composite of the present invention is considered to have an appropriate range depending on the type of metal (M) or metal particles (MP). For example, when the metal (M) or the metal particles (MP) is aluminum or aluminum particles, 6 to 8 is preferable, and 6.5 to 7.5 is more preferable. That is, the pH of water is preferably neutral. On the other hand, when the metal (M) or the metal particles (MP) is iron or iron particles, 9 to 11 is preferable, and 9.5 to 10.5 is more preferable.
本発明の炭−金属複合体で処理した水は、固液分離して（沈殿槽等を経て）から排出又は次工程へ移行することが好ましい。 It is preferable that the water treated with the carbon-metal composite of the present invention is solid-liquid separated (through a precipitation tank or the like) and then discharged or transferred to the next step.
本発明の炭−金属複合体が除去できる有害物質としては、ヒ素、フッ素、ホウ素、リン、アンチモン、亜鉛、クロム、ニッケル、銅、鉛及び／又はケイ素等の元素を含むものの他に、コロイド、エマルション、色素等も含まれる。 Hazardous substances that can be removed by the carbon-metal composite of the present invention include arsenic, fluorine, boron, phosphorus, antimony, zinc, chromium, nickel, copper, lead and / or silicon, colloid, Emulsions, pigments and the like are also included.
以下、特記しない限り、部は重量部と意味し、％は重量％を意味する。
＜実施例１＞
木質廃パレット（南洋材）を破砕して得たチップ（最長長さ２〜１０ｃｍ）を、縦型炭化炉（草・木チップ連続製炭機、ＴＹＰＥ１８０ｋｇ／Ｈｒ、村井鉄工所）で炭化させた後（７００〜８００℃、３０〜４０分間）、目開き２．８ｍｍの金網を通過させて、最長長さ０．１〜２．８ｃｍの炭粒子（ＣＰ１）を得た。炭粒子（ＣＰ１）の精練度は３であった。
アルミニウム加工工場から排出されたアルミニウム切削屑（繊維状の切削屑を多く含む）を目開き２．８ｍｍの金網を通過させて、金属粒子（ＭＰ１）を得た。金属粒子（ＭＰ１）の重量平均粒子径は１００μｍであった。
水溶性コーティング剤（ＡＣ１）｛コーンスターチ、フエキ糊、不易糊工業株式会社、「フエキ」は同社の登録商標である｝３００部及び水１０００部からなる水溶液に、金属粒子（ＭＰ１）１５０部を均一混合した後、目開き６３μｍの金網で濾過して、コーティング金属粒子を得た。引き続いて、このコーティング金属粒子と、炭粒子（ＣＰ１）４００部とを均一混合した後、約２５℃で約１２時間風乾して、顆粒状のコーティング混合粒子（ＣＭ１）を得た。
Hereinafter, unless otherwise specified, parts means parts by weight and% means% by weight.
<Example 1>
Chips (longest length: 2 to 10 cm) obtained by crushing wood waste pallets (southern wood) were carbonized in a vertical carbonization furnace (grass / wood chip continuous charcoal machine, TYPE 180 kg / Hr, Murai Iron Works). Later (700 to 800 ° C., 30 to 40 minutes), a wire mesh having a mesh opening of 2.8 mm was passed through to obtain carbon particles (CP1) having a maximum length of 0.1 to 2.8 cm. The scouring degree of the carbon particles (CP1) was 3.
The aluminum cutting waste (which contains a lot of fibrous cutting waste) discharged from the aluminum processing factory was passed through a metal mesh having an opening of 2.8 mm to obtain metal particles (MP1). The weight average particle diameter of the metal particles (MP1) was 100 μm.
Water-soluble coating agent (AC1) {Corn Starch, Fuchi Glue, Non-Gai Kogyo Co., Ltd., "Fueki" is a registered trademark of the company}} Uniformly distribute 150 parts of metal particles (MP1) in an aqueous solution consisting of 300 parts and 1000 parts of water. After mixing, the mixture was filtered through a wire mesh having an opening of 63 μm to obtain coated metal particles. Subsequently, the coated metal particles and 400 parts of carbon particles (CP1) were uniformly mixed and then air-dried at about 25 ° C. for about 12 hours to obtain granular coating mixed particles (CM1).
コーティング混合粒子（ＣＭ１）２２００部、炭粒子（ＣＰ１）３００部、普通ポルトランドセメント１５００部、無機化合物水溶液｛塩化カルシウム２部、塩化カリウム２部、塩化第二鉄２部、酸化マグネシウム２部、塩化マグネシウム２部、塩化アンモニウム２部、水２５００部を均一混合した水溶液）２０部及び水７００部とを均一混合して、混合粒子スラリー（ＭＰＳ１）を得た。この混合粒子スラリー（ＭＰＳ１）を内径５０ｍｍ深さ３０ｍｍの型に注いで、およそ１ｋｇ／ｃｍ２の圧力を加えた後、２４時間静置して、本発明の炭−金属複合体用成型体（１）を得た。 Coated mixed particles (CM1) 2200 parts, charcoal particles (CP1) 300 parts, ordinary Portland cement 1500 parts, inorganic compound aqueous solution {calcium chloride 2 parts, potassium chloride 2 parts, ferric chloride 2 parts, magnesium oxide 2 parts, chloride A mixed particle slurry (MPS1) was obtained by uniformly mixing 20 parts of an aqueous solution (2 parts of magnesium, 2 parts of ammonium chloride, and 2500 parts of water) and 700 parts of water. The mixed particle slurry (MPS1) is poured into a mold having an inner diameter of 50 mm and a depth of 30 mm, and after applying a pressure of about 1 kg / cm 2 , the mixture is allowed to stand for 24 hours to form a molded body for a carbon-metal composite of the present invention ( 1) was obtained.
２０個の炭−金属複合体用成型体（１）を目開き１５０μｍの金網製の容器に入れ、これをアンチモン元素濃度２ｐｐｍの工場排水（１）（流量６０００リットル／日）の流路（シックナーの直前）に浸漬させて、アンチモン元素濃度を１、６、８日後に測定し、この結果を次表に示した。
なお、アンチモン元素濃度は、ＪＩＳ Ｋ０１０２：２００８「工業排水試験方法」の「６２．２ 水素化物発生原子吸光法」で定量した。
Twenty molded bodies for carbon-metal composite (1) are put into a wire mesh container with an opening of 150 μm, and this is put into a factory drain (1) (flow rate of 6000 liters / day) with an antimony element concentration of 2 ppm (thickener). The antimony element concentration was measured after 1, 6 and 8 days, and the results are shown in the following table.
The antimony element concentration was quantified by “62.2 Hydride generation atomic absorption method” in JIS K0102: 2008 “Industrial wastewater test method”.
重金属元素を含む工場排水（２）５００ｍｌを１リットルガラス瓶に採取し、この中に、本発明の炭−金属複合体用成型体（１）を１個入れ、重金属元素濃度を１８、２４、４８、１４４時間後に測定し、この結果を次表に示した。
なお、銅元素濃度はＪＩＳ Ｋ０１０２：２００８「工業排水試験方法」の「５２．２ フレーム原子吸光法」で、また、全クロム元素濃度は同ＪＩＳの「６５．１．２ フレーム原子吸光法」で、また、ニッケル元素濃度は同ＪＩＳの「５９．２ フレーム原子吸光法」で、また、亜鉛元素濃度は同ＪＩＳの「５３．１ フレーム原子吸光法」で、また、鉛元素濃度は同ＪＩＳの「５４．１ フレーム原子吸光法」で定量した。
Collect 500 ml of industrial wastewater (2) containing heavy metal elements in a 1 liter glass bottle, and put one molded body for charcoal-metal composites (1) of the present invention into this, and the concentration of heavy metal elements is 18, 24, 48 The measurement was made after 144 hours, and the results are shown in the following table.
The copper element concentration is “52.2 flame atomic absorption method” of JIS K0102: 2008 “Industrial drainage test method”, and the total chromium element concentration is “65.1.2 Flame atomic absorption method” of the same JIS. The nickel element concentration is the same JIS “59.2 flame atomic absorption method”, the zinc element concentration is the same JIS “53.1 flame atomic absorption method”, and the lead element concentration is the same JIS. The quantity was determined by “54.1 flame atomic absorption method”.
＜実施例２＞
水溶性コーティング剤（ＡＣ１）｛コーンスターチ、フエキ糊、不易糊工業株式会社、「フエキ」は同社の登録商標である｝３００部及び水１０００部からなる水溶液に、金属粒子（ＭＰ１）１５４０部を均一混合した後、目開き６３μｍの金網で濾過して、コーティング金属粒子を得た。引き続いて、このコーティング金属粒子と、炭粒子（ＣＰ１）６６０部とを均一混合した後、約２５℃で約１２時間風乾して、顆粒状のコーティング混合粒子（ＣＭ２）を得た。
<Example 2>
Water-soluble coating agent (AC1) {Corn Starch, Fuchi Glue, Non-Gai Gin Kogyo Co., Ltd., "Fueki" is a registered trademark of the same company} 1540 parts of metal particles (MP1) uniformly in an aqueous solution consisting of 300 parts and 1000 parts of water After mixing, the mixture was filtered through a wire mesh having an opening of 63 μm to obtain coated metal particles. Subsequently, the coated metal particles and 660 parts of carbon particles (CP1) were uniformly mixed, and then air-dried at about 25 ° C. for about 12 hours to obtain granular coating mixed particles (CM2).
コーティング混合粒子（ＣＭ２）２２００部、普通ポルトランドセメント１１００部、無機化合物水溶液｛塩化カルシウム２部、塩化カリウム２部、塩化第二鉄２部、酸化マグネシウム２部、塩化マグネシウム２部、塩化アンモニウム２部、水２５００部を均一混合した水溶液）２０部及び水７００部とを均一混合して、混合粒子スラリー（ＭＰＳ２）を得た。この混合粒子スラリー（ＭＰＳ２）を内径５０ｍｍ深さ３０ｍｍの型に注いで、およそ１ｋｇ／ｃｍ２の圧力を加えた後、２４時間静置して、本発明の炭−金属複合体用成型体（２）を得た。 Coated mixed particles (CM2) 2200 parts, ordinary Portland cement 1100 parts, inorganic compound aqueous solution {calcium chloride 2 parts, potassium chloride 2 parts, ferric chloride 2 parts, magnesium oxide 2 parts, magnesium chloride 2 parts, ammonium chloride 2 parts 20 parts of water and an aqueous solution in which 2500 parts of water were uniformly mixed) and 700 parts of water were uniformly mixed to obtain a mixed particle slurry (MPS2). The mixed particle slurry (MPS2) is poured into a mold having an inner diameter of 50 mm and a depth of 30 mm, and after applying a pressure of about 1 kg / cm 2 , the mixture is allowed to stand for 24 hours to form a molded body for a carbon-metal composite of the present invention ( 2) was obtained.
亜鉛元素濃度５ｐｐｍの工場排水（３）５００ｍｌを１リットルガラス瓶に採取し、この中に、本発明の炭−金属複合体用成型体（２）を１個入れ、亜鉛元素濃度を１、２日後に測定し、この結果を次表に示した。
なお、亜鉛元素濃度は、ＪＩＳ Ｋ０１０２：２００８「工業排水試験方法」の「５３．１ フレーム原子吸光法」で定量した。
Collect 500 ml of industrial wastewater (3) with a zinc element concentration of 5 ppm in a 1 liter glass bottle, and put one molded body (2) for the charcoal-metal composite of the present invention into it. This was measured later and the results are shown in the following table.
The zinc element concentration was quantified by “53.1 flame atomic absorption method” in JIS K0102: 2008 “Industrial Wastewater Test Method”.
重金属元素を含む工場排水（４）５００ｍｌを１リットルガラス瓶に採取し、この中に、本発明の炭−金属複合体用成型体（２）を１個入れ、重金属元素濃度を１８、２４、４８、１４４時間後に測定し、この結果を次表に示した。
なお、銅元素濃度はＪＩＳ Ｋ０１０２：２００８「工業排水試験方法」の「５２．２ フレーム原子吸光法」で、また、全クロム元素濃度は同ＪＩＳの「６５．１．２ フレーム原子吸光法」で、また、ニッケル元素濃度は同ＪＩＳの「５９．２ フレーム原子吸光法」で、また、亜鉛元素濃度は同ＪＩＳの「５３．１ フレーム原子吸光法」で定量した。
Collect 500 ml of industrial wastewater (4) containing heavy metal elements in a 1 liter glass bottle, and put one molded body (2) for charcoal-metal composites of the present invention into this, and the concentration of heavy metal elements is 18, 24, 48 The measurement was made after 144 hours, and the results are shown in the following table.
The copper element concentration is “52.2 flame atomic absorption method” of JIS K0102: 2008 “Industrial drainage test method”, and the total chromium element concentration is “65.1.2 Flame atomic absorption method” of the same JIS. The nickel element concentration was quantified by “59.2 flame atomic absorption method” of JIS, and the zinc element concentration was quantified by “53.1 flame atomic absorption method” of JIS.
＜実施例３＞
備長炭（精錬度２）を破砕してから、目開き２．８ｍｍの金網を通過させて、最長長さ０．１〜２．８ｃｍの炭粒子（ＣＰ２）を得た。
アルミニウム箔（箔地）を裁断して、金属粒子（ＭＰ２）｛１ｃｍ×１ｃｍ×０．４ｍｍ厚｝を調製した。
炭粒子（ＣＰ２）３０ｇ及び金属粒子７０ｇを均一混合して、３００ｍｌガラス瓶に充填して、本発明の炭−金属複合体（１）を得た。
<Example 3>
Bincho charcoal (refining degree 2) was crushed and then passed through a wire mesh having an opening of 2.8 mm to obtain charcoal particles (CP2) having a maximum length of 0.1 to 2.8 cm.
Aluminum foil (foil) was cut to prepare metal particles (MP2) {1 cm × 1 cm × 0.4 mm thickness}.
30 g of carbon particles (CP2) and 70 g of metal particles were uniformly mixed and filled in a 300 ml glass bottle to obtain a carbon-metal composite (1) of the present invention.
亜ヒ酸水溶液（三酸化二ヒ素を水に溶解して調製した）２００ｇを、本発明の炭−金属複合体（１）に注いで、ヒ素元素濃度を６時間後に測定し、この結果を次表に示した。
なお、ヒ素元素濃度は、ＪＩＳ Ｋ０１０２：２００８「工業排水試験方法」の「６１．３ 水素化物発生ＩＣＰ発光分光分析法」で定量した。
200 g of an aqueous arsenous acid solution (prepared by dissolving arsenic trioxide in water) was poured into the carbon-metal composite (1) of the present invention, and the arsenic element concentration was measured after 6 hours. Shown in the table.
The arsenic element concentration was quantified by “61.3 Hydride Generation ICP Emission Spectroscopy” in JIS K0102: 2008 “Industrial Wastewater Test Method”.
＜実施例４＞
２０ｃｍ×２０ｃｍ×深さ９ｃｍのポリカーボネート製水槽に、金属（Ｍ１）（８ｃｍ×１７ｃｍ×０．２６ｃｍ厚のアルミニウム板）４枚（９５ｇ）を等間隔で配置し、炭粒子（ＣＰ１）３００ｇを充填して、本発明の炭−金属複合体（２）を得た。
<Example 4>
In a 20cm x 20cm x 9cm deep water tank made of polycarbonate, 4 pieces of metal (M1) (8cm x 17cm x 0.26cm thick aluminum plate) (95g) are arranged at equal intervals and filled with 300g of charcoal particles (CP1). Thus, the carbon-metal composite (2) of the present invention was obtained.
ケイ酸水溶液（ケイ酸を水に溶解して調製した）２０００ｇを、本発明の炭−金属複合体（２）に注いで、送液ポンプで１００ｍｌ／分の流量で全体に循環させた。ケイ素元素濃度を３、５、１２、２０日後に測定し、この結果を次表に示した。
なお、ケイ素元素濃度は、ＪＩＳ Ｋ０１０２：２００８「工業排水試験方法」の「４７．３ ＩＣＰ発光分光分析法」に準拠して、波長２５１．６１２ｎｍで定量した。
2000 g of an aqueous silicic acid solution (prepared by dissolving silicic acid in water) was poured into the charcoal-metal composite (2) of the present invention, and circulated through the liquid feed pump at a flow rate of 100 ml / min. The silicon element concentration was measured after 3, 5, 12, and 20 days, and the results are shown in the following table.
The silicon element concentration was quantified at a wavelength of 251.612 nm in accordance with “47.3 ICP emission spectroscopic analysis” of JIS K0102: 2008 “Industrial drainage test method”.
＜実施例５＞
回収アルミニウム缶の蓋及び底の部分を切り落とした後、側面を切断して平面に伸ばして、シュレッターで裁断して、２．５ｍｍ×３０ｍｍの金属粒子（ＭＰ３）を得た。
水溶性コーティング剤（ＡＣ１）｛コーンスターチ、フエキ糊、不易糊工業株式会社、「フエキ」は同社の登録商標である｝３００部及び水１０００部からなる水溶液に、金属粒子（ＭＰ３）１５４０部を均一混合した後、目開き６３μｍの金網で濾過して、コーティング金属粒子を得た。引き続いて、このコーティング金属粒子と、炭粒子（ＣＰ２）６６０部とを均一混合した後、約２５℃で約１２時間風乾して、顆粒状のコーティング混合粒子（ＣＭ３）を得た。
<Example 5>
After the lid and bottom of the recovered aluminum can were cut off, the side surfaces were cut and stretched to a flat surface, and cut with a shredder to obtain 2.5 mm × 30 mm metal particles (MP3).
Water-soluble coating agent (AC1) {Corn Starch, Fue Glue, Non-Gai Gin Kogyo Co., Ltd., "Fueki" is a registered trademark of the same company} 1540 parts of metal particles (MP3) uniformly in an aqueous solution consisting of 300 parts and 1000 parts of water After mixing, the mixture was filtered through a wire mesh having an opening of 63 μm to obtain coated metal particles. Subsequently, the coating metal particles and 660 parts of carbon particles (CP2) were uniformly mixed, and then air-dried at about 25 ° C. for about 12 hours to obtain granular coating mixed particles (CM3).
コーティング混合粒子（ＣＭ３）２２００部、普通ポルトランドセメント１１００部、無機化合物水溶液｛塩化カルシウム２部、塩化カリウム２部、塩化第二鉄２部、酸化マグネシウム２部、塩化マグネシウム２部、塩化アンモニウム２部、水２５００部を均一混合した水溶液）２０部及び水７００部とを均一混合して、混合粒子スラリー（ＭＰＳ３）を得た。この混合粒子スラリー（ＭＰＳ３）を内径５０ｍｍ深さ３０ｍｍの型に注いで、およそ１ｋｇ／ｃｍ２の圧力を加えた後、２４時間静置して、本発明の炭−金属複合体用成型体（３）を得た。 Coated mixed particles (CM3) 2200 parts, ordinary Portland cement 1100 parts, inorganic compound aqueous solution {calcium chloride 2 parts, potassium chloride 2 parts, ferric chloride 2 parts, magnesium oxide 2 parts, magnesium chloride 2 parts, ammonium chloride 2 parts 20 parts of an aqueous solution in which 2500 parts of water were uniformly mixed) and 700 parts of water were uniformly mixed to obtain a mixed particle slurry (MPS3). The mixed particle slurry (MPS3) is poured into a mold having an inner diameter of 50 mm and a depth of 30 mm, and after applying a pressure of about 1 kg / cm 2 , the mixture is allowed to stand for 24 hours to form a molded body for a carbon-metal composite of the present invention ( 3) was obtained.
２０個の炭−金属複合体用成型体（３）を目開き１５０μｍの金網製の容器に入れ、これをアンチモン元素濃度２ｐｐｍの工場排水（１）（流量６０００リットル／日）の流路（シックナーの直前）に浸漬させて、アンチモン元素濃度を１、６、８日後に測定し、この結果を次表に示した。
なお、アンチモン元素濃度は、上記と同様にして定量した。
Twenty molded bodies for carbon-metal composite (3) are put into a wire mesh container having an opening of 150 μm, and this is put into a factory drain (1) (flow rate of 6000 liters / day) with an antimony element concentration of 2 ppm (thickener). The antimony element concentration was measured after 1, 6 and 8 days, and the results are shown in the following table.
The antimony element concentration was quantified in the same manner as described above.
＜比較例１＞
特許文献１の実施例１に準拠して、比較用の有害元素吸着剤を調製した。
比較用の有害元素吸着剤（Ｈ１）１ｋｇを目開き１５０μｍの金網製の容器に入れ、これをアンチモン元素濃度２ｐｐｍの工場排水（１）（流量６０００リットル／日）の流路（シックナーの直前）に浸漬させて、アンチモン元素濃度を１、６、８日後に測定し、この結果を次表に示した。
なお、アンチモン元素濃度は、上記と同様にして定量した。
<Comparative Example 1>
In accordance with Example 1 of Patent Document 1, a comparative harmful element adsorbent was prepared.
1 kg of comparative harmful element adsorbent (H1) is placed in a wire mesh container with an opening of 150 μm, and this is a factory wastewater (1) (flow rate of 6000 liters / day) with an antimony element concentration of 2 ppm (immediately before thickener) The antimony element concentration was measured after 1, 6 and 8 days, and the results are shown in the following table.
The antimony element concentration was quantified in the same manner as described above.
重金属元素を含む工場排水（２）５００ｍｌを１リットルガラス瓶に採取し、この中に、比較用の有害元素吸着剤（Ｈ１）を２００ｇ入れ、重金属元素濃度を１８、２４、４８、１４４時間後に測定し、この結果を次表に示した。
なお、重金属元素濃度は、上記と同様にして定量した。
Industrial wastewater containing heavy metal elements (2) 500 ml was collected in a 1 liter glass bottle, 200 g of comparative harmful element adsorbent (H1) was put in it, and heavy metal element concentrations were measured after 18, 24, 48 and 144 hours. The results are shown in the following table.
The heavy metal element concentration was quantified in the same manner as described above.
本発明の炭−金属複合体又は本発明の炭−金属複合体用成型体を用いると、少ない量で多量の排水を処理しても、有害物質の除去能力は低下しなかった。すなわち、本発明の炭−金属複合体又は本発明の炭−金属複合体用成型体は、少量で多量の有害物質を除去することができた。一方、比較用の有害元素吸着剤は、多量の排水から有害物質を除去することはできなかった。すなわち、引用文献１や２の吸着による除去手段であると、有害物質を初期に除去できたとしても、吸着が飽和状態に至ると、もはや有害物質を吸着除去することができないものと考えられる。 When the charcoal-metal composite of the present invention or the molded product for the charcoal-metal composite of the present invention was used, the ability to remove harmful substances did not decrease even when a large amount of wastewater was treated in a small amount. That is, the charcoal-metal composite of the present invention or the molded product for the charcoal-metal composite of the present invention was able to remove a large amount of harmful substances in a small amount. On the other hand, the harmful element adsorbent for comparison could not remove harmful substances from a large amount of waste water. That is, with the removal means by adsorption described in the cited documents 1 and 2, even if the harmful substance can be removed at the initial stage, it is considered that the harmful substance can no longer be removed by adsorption when the adsorption reaches a saturated state.
Claims (8)
金属粒子（ＭＰ）が、マグネシウム、アルミニウム、亜鉛、鉄、ニッケル、錫、鉛又は銅からなる金属粒子であり、
金属粒子（ＭＰ）に繊維状の金属粒子を含有してなることを特徴とする炭−金属複合体用成形体。 Water-soluble coating agent and coated with (AC) metal particles (MP) and charcoal particles (CP), Ri greens contain a binder (V),
The metal particles (MP) are metal particles made of magnesium, aluminum, zinc, iron, nickel, tin, lead or copper,
A molded article for a carbon-metal composite comprising metal particles (MP) containing fibrous metal particles .
方法（１−２１）〜（１−２４）のいずれかの方法で製造することを特徴とする水処理用炭−金属複合体の製造方法。
（１−２１）コーティング混合粒子を得るために、金属粒子（ＭＰ）、炭粒子（ＣＰ）及び水溶性コーティング剤（ＡＣ）とを均一混合する工程（１）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（２）；並びに混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程（３）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（４）を含む方法。
（１−２２）金属粒子（ＭＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング金属粒子を得る工程（１）；炭粒子（ＣＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング炭粒子を得る工程（２）；コーティング金属粒子及びコーティング炭粒子を均一混合してコーティング混合粒子を得る工程（３）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（４）；混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程（５）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（６）を含む方法。
（１−２３）金属粒子（ＭＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング金属粒子を得る工程（１）；コーティング金属粒子及び炭粒子（ＣＰ）を均一混合してコーティング混合粒子を得る工程（２）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（３）；混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程（４）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（５）を含む方法。
（１−２４）炭粒子（ＣＰ）及び水溶性コーティング剤（ＡＣ）を均一混合してコーティング炭粒子を得る工程（１）；コーティング炭粒子及び金属粒子を均一混合してコーティング混合粒子を得る工程（２）；コーティング混合粒子とバインダー（Ｖ）とを混合して、混合粒子スラリーを得る工程（３）；混合粒子スラリーを成型して、炭−金属複合体用成型体を得る工程（４）；並びに炭−金属複合体用成型体に水を作用させることによって、水溶性コーティング剤（ＡＣ）を水へ溶出させて、金属粒子（ＭＰ）と炭粒子（ＣＰ）とが接触できるようにした炭−金属複合体を得る工程（５）を含む方法。 A method for producing a water treatment charcoal-metal composite according to claim 6 or 7 ,
A method for producing a carbon-metal composite for water treatment, which is produced by any one of methods (1-21) to (1-24).
(1-21) Step (1) of uniformly mixing metal particles (MP), charcoal particles (CP) and water-soluble coating agent (AC) in order to obtain coating mixed particles; coating mixed particles and binder (V) To obtain a mixed particle slurry (2); and molding the mixed particle slurry to obtain a carbon-metal composite molded body (3); and a carbon-metal composite molded body Step (4) of obtaining a charcoal-metal composite in which water-soluble coating agent (AC) is eluted into water by allowing water to act so that metal particles (MP) and charcoal particles (CP) can come into contact with each other. Including methods.
(1-22) Step (1) of uniformly mixing metal particles (MP) and water-soluble coating agent (AC) to obtain coated metal particles; and uniformly mixing carbon particles (CP) and water-soluble coating agent (AC). Step (2) for obtaining coated carbon particles by coating Step (3) for uniformly mixing coating metal particles and coating carbon particles to obtain coating mixed particles; Mixing coating mixed particles and binder (V) to obtain mixed particle slurry (4); forming a mixed particle slurry to obtain a molded body for a carbon-metal composite (5); and water acting on the molded body for a carbon-metal composite, thereby providing a water-soluble coating. A method comprising a step (6) of obtaining a charcoal-metal composite by eluting the agent (AC) into water so that the metal particles (MP) and the charcoal particles (CP) can come into contact with each other.
(1-23) Step (1) for uniformly mixing metal particles (MP) and water-soluble coating agent (AC) to obtain coated metal particles; coating metal particles and carbon particles (CP) are uniformly mixed and coated mixed particles (2); mixing the coating mixed particles and the binder (V) to obtain a mixed particle slurry (3); molding the mixed particle slurry to obtain a molded body for a carbon-metal composite (4); and by allowing water to act on the molded body for the carbon-metal composite, the water-soluble coating agent (AC) can be eluted into the water so that the metal particles (MP) and the carbon particles (CP) can come into contact with each other. A method comprising a step (5) of obtaining a carbon-metal composite.
(1-24) Step of uniformly mixing carbon particles (CP) and water-soluble coating agent (AC) to obtain coated carbon particles (1); Step of uniformly mixing coating carbon particles and metal particles to obtain coated mixed particles (2): mixing the coating mixed particles and the binder (V) to obtain a mixed particle slurry (3); molding the mixed particle slurry to obtain a carbon-metal composite molded body (4) And by allowing water to act on the molded body for the carbon-metal composite, the water-soluble coating agent (AC) was eluted into the water so that the metal particles (MP) and the carbon particles (CP) could come into contact with each other A method comprising a step (5) of obtaining a carbon-metal composite.
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