JP2006320816A - Treatment material of organohalogen compound - Google Patents
Treatment material of organohalogen compound Download PDFInfo
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- JP2006320816A JP2006320816A JP2005145247A JP2005145247A JP2006320816A JP 2006320816 A JP2006320816 A JP 2006320816A JP 2005145247 A JP2005145247 A JP 2005145247A JP 2005145247 A JP2005145247 A JP 2005145247A JP 2006320816 A JP2006320816 A JP 2006320816A
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- 150000002896 organic halogen compounds Chemical class 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 17
- -1 aromatic organohalogen compound Chemical class 0.000 claims abstract description 7
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000008422 chlorobenzenes Chemical class 0.000 claims abstract description 5
- 150000002013 dioxins Chemical class 0.000 claims abstract description 5
- 239000011812 mixed powder Substances 0.000 claims description 10
- 150000003071 polychlorinated biphenyls Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 54
- 238000000034 method Methods 0.000 description 30
- 238000000354 decomposition reaction Methods 0.000 description 20
- 239000002689 soil Substances 0.000 description 17
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 15
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003673 groundwater Substances 0.000 description 9
- 150000004045 organic chlorine compounds Chemical class 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000005695 dehalogenation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012569 microbial contaminant Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- Fire-Extinguishing Compositions (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
Description
本発明は、有機ハロゲン化合物で汚染された物質（特に土壌、地下水など）を浄化するのに有用な有機ハロゲン化合物処理材に関するものである。 The present invention relates to an organic halogen compound treatment material useful for purifying substances contaminated with organic halogen compounds (especially soil, groundwater, etc.).
トリクロロエチレンなどの揮発性有機塩素化合物は、半導体工場や金属加工工場における脱脂洗浄剤として、またドライクリーニングの洗浄剤として広く使用されている。しかしこれら有機塩素化合物は、過去より排出・投棄されることがあった。有機塩素化合物は自然界において分解を受けにくいため、土壌中や地下水中に徐々に蓄積され、土壌や地下水を汚染し社会問題となっている。 Volatile organic chlorine compounds such as trichlorethylene are widely used as degreasing cleaners in semiconductor factories and metal processing factories and as cleaning agents for dry cleaning. However, these organochlorine compounds have been discharged and dumped from the past. Since organochlorine compounds are not easily decomposed in nature, they are gradually accumulated in soil and groundwater, and contaminate soil and groundwater, which is a social problem.
土壌中や地下水中の汚染物質を無害化する処理方法としては、汚染土壌を掘削除去しロータリーキルン等で燃焼除去する熱分解法、地下水中に溶解した汚染物質を真空ポンプによって吸引し回収除去するガス吸引法、地下水を汲み上げ抽出除去する揚水曝気法、微生物の汚染物質分解能を利用した微生物法などが知られている。 Treatment methods for detoxifying pollutants in soil and groundwater include pyrolysis, which excavates and removes contaminated soil and burns and removes it using a rotary kiln, etc. A suction method, a pumped-water aeration method that draws and removes groundwater, and a microbial method that utilizes the microbial contaminant resolution are known.
しかしながら、熱分解法では土壌掘削に大がかりな設備が必要となり、熱処理後の土壌を埋め戻して再利用する場合には高コストとなる。ガス吸引法では、気化している汚染物質しか回収することができず、さらには回収後に汚染物質を分解処理する必要が生じる。揚水曝気でも水に溶解する汚染物質しか回収することができず、しかも回収後に汚染物質を分解する必要がある。微生物法では、土壌条件によっては適用することができない場合があり、さらには微生物による分解反応であるため、高濃度汚染の場合には他の方法に比べて処理期間が長くなったり、分解反応が途中までしか進行しないこともある。 However, the pyrolysis method requires large-scale equipment for soil excavation, and the cost becomes high when the soil after heat treatment is backfilled and reused. In the gas suction method, only vaporized contaminants can be recovered, and further, it is necessary to decompose the contaminants after recovery. Even with pumped aeration, only pollutants that dissolve in water can be recovered, and the contaminants need to be decomposed after recovery. The microbial method may not be applied depending on the soil conditions. Furthermore, since it is a decomposition reaction by microorganisms, in the case of high-concentration contamination, the treatment period becomes longer or the decomposition reaction does not occur compared to other methods. Sometimes it only progresses halfway.
大がかりな設備や回収後の分解操作が不要であって安定して有機塩素化合物を無害化できる方法として、鉄粉を使用して有機塩素化合物を還元分解する方法が提案されている。この方法では、鉄粉が酸化されることによって発生する電子を利用して、有機塩素化合物を還元分解している。しかし本来、鉄粉による有機塩素化合物の分解効率はそれほど高くないため、実用化の為に種々の方法が提案されている。 As a method capable of stably detoxifying an organic chlorine compound without requiring a large-scale facility or a decomposition operation after recovery, a method of reducing and decomposing an organic chlorine compound using iron powder has been proposed. In this method, an organic chlorine compound is reductively decomposed using electrons generated by oxidation of iron powder. However, since the decomposition efficiency of organochlorine compounds by iron powder is not so high, various methods have been proposed for practical use.
例えば、特許文献１では、難分解性ハロゲン化炭化水素を含有する被処理水と鉄粉を添加して振盪することによってハロゲン化炭化水素を分解するに際して、被処理水から予め溶存酸素を除去し、ｐＨ６．５〜９．５に調整しておくことを提案している。しかしこの方法では、溶存酸素の除去やｐＨ調整などの複雑な操作が必要となるため、汚染現場での原位置処理に適用するのが困難である。
For example, in
特許文献２には、有機塩素化合物を含有する汚染水を、鉄や鋼のヤスリ屑に通すことによって分解・無害化するに際して、前記鉄や鋼のヤスリ屑を活性炭と混合しておき、この混合物層に汚染水を通すことを提案している。しかしこの方法では、高価な活性炭を使用する必要があるため、処理費用が高くなる。
In
近年、鉄粉そのものの反応性を高め、汚染土壌・汚染水の前処理や活性炭などを必要としない方法が提案されている。例えば、特許文献３には、炭素含有量が０．１重量％以上であって、比表面積が５００ｃｍ2／ｇ以上である鉄粉と土壌とを混合し、土壌中の有機塩素系化合物を分解する方法が開示されている。前記比表面積が大きな鉄粉としては、鉄鉱石を還元することによって得られる鉄粉（海綿状鉱石還元鉄粉）が使用されている。しかしこの方法は、比表面積を小さくすると反応性が低下するため、海綿状鉱石還元鉄粉以外には実質的に使用することができない。 In recent years, a method has been proposed in which the reactivity of iron powder itself is increased and pretreatment of contaminated soil and contaminated water and activated carbon are not required. For example, in Patent Document 3, iron powder having a carbon content of 0.1% by weight or more and a specific surface area of 500 cm 2 / g or more is mixed with soil to decompose organochlorine compounds in the soil. A method is disclosed. As the iron powder having a large specific surface area, iron powder (sponge-like ore reduced iron powder) obtained by reducing iron ore is used. However, this method cannot be used for anything other than spongy ore reduced iron powder because the reactivity decreases when the specific surface area is reduced.
また特許文献４は、金属鉄による有機ハロゲン化合物の分解反応が金属銅によって著しく促進されることに着目し、銅含有鉄粉を用いることを提案している。しかし前記銅は原料コストが高く、さらには銅含有鉄粉を製造する際には硫酸銅水溶液等の銅イオン溶液中に鉄粉を混合し、得られる沈殿物を回収するという煩雑な製造工程を必要とするため製造コストも高くなる。
ところで鉄粉としては上述のような海綿状鉄粉の他、アトマイズ鉄粉も知られている。アトマイズ鉄粉とは、アトマイズ法によって溶鋼を粉砕した後（表面が黒く酸化されているため、黒粉と称される）、この黒粉を完全に還元して製造されるものであり（前記黒粉に対して、白粉と称される場合がある）、さらに表面にバインダーとしての樹脂をコートすることによって、粉末冶金の用途に利用されている。上述のような海綿状鉄粉ではなく、粉末冶金用鉄粉（アトマイズ鉄粉）を土壌浄化用途に利用する方法も提案されている。 By the way, as iron powder, atomized iron powder is known in addition to the above-described spongy iron powder. Atomized iron powder is produced by pulverizing molten steel by the atomizing method (referred to as black powder because the surface is oxidized black) and then completely reducing this black powder (the black In some cases, the powder is called white powder), and is further used for powder metallurgy by coating the surface with a resin as a binder. There has also been proposed a method in which iron powder for powder metallurgy (atomized iron powder) is used for soil purification instead of the spongy iron powder as described above.
例えば、特許文献５は、Ｎｉ表面で生成する水素によって分解反応（含ハロゲン有機汚染物質の還元反応、金属の酸化反応）が促進されることに着目し、粉末冶金用鉄粉にＮｉを０．０１〜４．０質量％含有させることを提案している。しかしながら、この技術においても、表面に酸化物が形成されると浄化反応性が低下するとしている。 For example, Patent Document 5 pays attention to the fact that decomposition reaction (reduction reaction of halogen-containing organic pollutants, metal oxidation reaction) is promoted by hydrogen generated on the Ni surface, and Ni is reduced to 0.1% in iron powder for powder metallurgy. It is proposed to contain 01-4.0 mass%. However, even in this technique, the purification reactivity decreases when oxides are formed on the surface.
本発明者らは、有機ハロゲン化合物を効果的に分解処理するための技術についてかねてより研究を重ねており、その研究の一環として特許文献６のような技術を提案している。この技術において、有機ハロゲン化合物を効果的に処理する浄化用鉄粉の様々な形態を例示しており、その一つの形態として、「目開き３００μｍの篩を通過する割合が９０％以上、Ｈ２による還元減量が０．１〜１．０％、組織がマルテンサイトまたは焼戻しマルテンサイトである鉄粉」と、「Ｎｉ含有量が４０％以上で、目開き４５μｍの篩を通過する割合が９０％以上であるＮｉ含有粉」を混合した混合粉末（浄化用鉄粉）が有用な浄化効果を発揮し得ることを示している。
上記のような技術によって、トリクロロエチレン等の有機ハロゲン化合物を、効果的に分解・除去できるようになったのであるが、こうした技術においても更なる改善が望まれているのが実情である。即ち、上記技術によっては、トリクロロエチレン等の有機ハロゲン化合物については、効果的に分解できたのであるが、他の有機ハロゲン化合物についてはその種類によっては、分解除去できないことがあった。例えば、有機ハロゲン化合物のうちでも、芳香族系の有機ハロゲン化合物であるクロロベンゼン類、クロロフェノール類、ダイオキシン類およびポリ塩化ビフェニル類については、上記のような技術によってもトリクロロエチレンほど効果的に分解除去できないのが実情である。また、トリクロロエチレンの分解除去についても更に効率良く分解除去できることが望まれている。 Although the organic halogen compounds such as trichlorethylene can be effectively decomposed and removed by the above-described techniques, further improvements are desired in these techniques. That is, depending on the technique, organic halogen compounds such as trichlorethylene could be effectively decomposed, but other organic halogen compounds could not be decomposed and removed depending on the type. For example, among organic halogen compounds, aromatic organic halogen compounds such as chlorobenzenes, chlorophenols, dioxins, and polychlorinated biphenyls cannot be decomposed and removed as effectively as trichloroethylene by the above-described techniques. Is the actual situation. In addition, it is desired that trichlorethylene can be decomposed and removed more efficiently.
本発明は上記の様な事情に着目してなされたものであって、その目的は、その種類の如何に拘らず有機ハロゲン化合物を効率よく分解できる有機ハロゲン化合物処理材を提供することにある。 The present invention has been made paying attention to the above-described circumstances, and an object thereof is to provide an organic halogen compound treatment material capable of efficiently decomposing an organic halogen compound regardless of the type.
上記目的を達成することのできた本発明の有機ハロゲン化合物処理材とは、鉄粉とＮｉ含有粉を混合した混合粉末で構成される有機ハロゲン処理材であって、前記Ｎｉ含有粉は、平均粒径：０．８μｍ以下である点に要旨を有するものである。 The organic halogen compound treatment material of the present invention that has achieved the above object is an organic halogen treatment material composed of a mixed powder obtained by mixing iron powder and Ni-containing powder, and the Ni-containing powder has an average particle size. Diameter: It has a gist in that it is 0.8 μm or less.
本発明の有機ハロゲン化合物処理材において、前記Ｎｉ含有粉は、Ｎｉ含有量が５０質量％以上のものであることが好ましい。また、前記Ｎｉ含有粉の混合割合は、混合粉末全体に対して０．０１〜２０質量％であることが好ましい。 In the organic halogen compound treatment material of the present invention, the Ni-containing powder preferably has a Ni content of 50% by mass or more. Moreover, it is preferable that the mixing rate of the said Ni containing powder is 0.01-20 mass% with respect to the whole mixed powder.
本発明の有機ハロゲン化合物処理材では、トリクロロエチレンは勿論のこと、クロロベンゼン類、クロロフェノール類、ダイオキシン類およびポリ塩化ビフェニル類（ＰＣＢ類）の少なくともいずれかの芳香族の有機ハロゲン化合物であっても効果的に分解できるものとなる。 The organohalogen compound-treated material of the present invention is effective even if it is an aromatic organic halogen compound of at least one of chlorobenzenes, chlorophenols, dioxins and polychlorinated biphenyls (PCBs) as well as trichloroethylene. Can be decomposed automatically.
本発明の有機ハロゲン化合物処理材は、平均粒径：０．８μｍ以下であるＮｉ含有粉と、鉄粉とを混合した混合粉末で構成したので、有機ハロゲン化合物をその種類の如何に係わらず効果的に分解できるようになり、こうした処理材は有機ハロゲン化合物に汚染された土壌や地下水を浄化するために有用に利用できる。 The organohalogen compound-treated material of the present invention is composed of a mixed powder in which an Ni-containing powder having an average particle size of 0.8 μm or less and an iron powder are mixed. Therefore, the organohalogen compound is effective regardless of the type. These treatment materials can be used effectively to purify soil and groundwater contaminated with organic halogen compounds.
本発明者らは、前記課題を解決するために鋭意研究を重ねた。その結果、鉄粉とＮｉ含有粉を混合した混合粉末で構成される有機ハロゲン化合物処理材において、鉄粉に混合されるＮｉ含有粉の粒径をより微細なものとすれば、様々な有機ハロゲン化合物を効率よく分解できることを見出し、本発明を完成した。 The inventors of the present invention have made extensive studies to solve the above problems. As a result, in the organic halogen compound treatment material composed of a mixed powder in which iron powder and Ni-containing powder are mixed, if the particle size of Ni-containing powder mixed with iron powder is made finer, various organic halogens can be obtained. The present inventors have found that the compound can be efficiently decomposed and completed the present invention.
本発明にかかる有機ハロゲン処理材は、有機ハロゲン化合物の分解（脱ハロゲン化）に利用されるものであるが、この処理材に含まれる鉄粉による脱ハロゲン作用の基本原理について詳細に説明すると、以下の通りである。 The organic halogen treatment material according to the present invention is used for decomposition (dehalogenation) of an organic halogen compound, and the basic principle of the dehalogenation action by the iron powder contained in this treatment material will be described in detail. It is as follows.
鉄粉の表面に有機ハロゲン化合物が付着すると、鉄粉表面において金属側と有機ハロゲン化合物側（環境側）の条件の差異によってアノード分極とカソード分極が生じる。このため電子の流れが生じ、アノード側では鉄の溶出（酸化）が起こって電子を放出し、カソード側では前記電子による還元作用によって脱ハロゲン反応（分解）が生じる。従ってトータルとして、下記式（１）に示す化学反応が起こる。
Ｆｅ＋Ｈ2Ｏ＋ＲＸ → Ｆｅ2+＋ＯＨ-＋ＲＨ＋Ｘ- …（１）
（式中、Ｒは有機基を示し、Ｘは塩素原子などのハロゲン原子を示す）
When the organic halogen compound adheres to the surface of the iron powder, anodic polarization and cathodic polarization occur due to the difference in conditions between the metal side and the organic halogen compound side (environment side) on the iron powder surface. For this reason, an electron flow occurs, iron elution (oxidation) occurs on the anode side to release electrons, and a dehalogenation reaction (decomposition) occurs on the cathode side due to the reduction action of the electrons. Therefore, as a total, a chemical reaction represented by the following formula (1) occurs.
Fe + H 2 O + RX → Fe 2+ + OH − + RH + X − (1)
(Wherein R represents an organic group and X represents a halogen atom such as a chlorine atom)
本発明の有機ハロゲン化合物処理材では、上記のような鉄粉とＮｉ含有粉とを混合したものであるが、このＮｉ含有粉は、鉄粉と水が反応して発生する水素[上記（１）式]を使って、Ｎｉ含有粉が有機ハロゲン化合物からのハロゲンの還元的引き抜きを触媒する作用を発揮するものと考えられる。 The organohalogen compound-treated material of the present invention is a mixture of iron powder and Ni-containing powder as described above. This Ni-containing powder is hydrogen generated by the reaction of iron powder and water [above (1 It is considered that the Ni-containing powder exerts an action of catalyzing the reductive extraction of the halogen from the organic halogen compound using the formula].
鉄粉自体も、有機ハロゲン化合物のうちでも比較的分解し易いトリクロロエチレン類（トリクロロエチレン、テトラクロロエチレン、ジクロロエチレン、モノクロロエチレン等）等に対しては、分解能力が発揮されるのであるが、Ｎｉ含有粉を混合することによって分解反応が促進されることになる。特に、その平均粒径が０．８μｍ以下となるＮｉ含有粉を鉄粉に混合した場合には、有機ハロゲン化合物に対する分解効果が著しく高まり、トリクロロエチレン類等の分解が促進されるものは勿論のこと、非常に難分解性である芳香族系の有機ハロゲン化合物（例えば、クロルベンゼン類、クロロフェノール類、ダイオキシン類、ＰＣＢ類等）についても、常温、常圧の条件下で十分に分解（還元）できたのである。 Iron powder itself is also capable of decomposing trichloroethylenes (trichloroethylene, tetrachloroethylene, dichloroethylene, monochloroethylene, etc.) that are relatively easily decomposed among organic halogen compounds, but mixed with Ni-containing powder. By doing so, the decomposition reaction is promoted. In particular, when Ni-containing powder having an average particle size of 0.8 μm or less is mixed with iron powder, the decomposition effect on organic halogen compounds is remarkably enhanced and the decomposition of trichlorethylenes and the like is promoted. Aromatic organic halogen compounds (eg chlorobenzenes, chlorophenols, dioxins, PCBs, etc.) that are extremely difficult to decompose are also sufficiently decomposed (reduced) under normal temperature and normal pressure conditions. It was done.
上記のような微細Ｎｉ含有粉を鉄粉と併用することによって、上記のような効果が得られた理由については、その全てを解明し得た訳ではないが、おそらくＮｉ含有粉を微細化することによって、水素を使った還元的ハロゲン引き抜き反応の触媒作用が高まったためであると考えることができた。また、こうした観点からすれば、Ｎｉ含有粉の平均粒径は０．５μｍ以下であることが好ましい。 The reason why the above effect was obtained by using the fine Ni-containing powder as described above in combination with the iron powder is not necessarily all of the reason, but perhaps the Ni-containing powder is refined. Therefore, it was considered that the catalytic action of the reductive halogen abstraction reaction using hydrogen was enhanced. From this point of view, the average particle size of the Ni-containing powder is preferably 0.5 μm or less.
上記Ｎｉ含有粉は、Ｎｉの純度がある程度低くても有機ハロゲン化物を分解（還元）することができるものの、Ｎｉ含有量が少なすぎると触媒効果が不十分となる。従ってＮｉ含有量は、５０質量％以上であることが好ましく、より好ましくは７０質量％以上（１００質量％を含む）である。尚、Ｎｉ含有粉は、超高圧アトマイズ法、カーボニル法などによって製造することができる。 Although the Ni-containing powder can decompose (reduce) the organic halide even if the purity of Ni is low to some extent, if the Ni content is too small, the catalytic effect becomes insufficient. Therefore, the Ni content is preferably 50% by mass or more, more preferably 70% by mass or more (including 100% by mass). The Ni-containing powder can be produced by an ultra-high pressure atomization method, a carbonyl method, or the like.
一方、本発明で用いる鉄粉の種類については、特に限定されないが、代表的なものとしてアトマイズ鉄粉が挙げられる。この鉄粉の平均粒径が小さ過ぎると製造コストが高くなり、大き過ぎると有機ハロゲン化合物の分解効果が低くなるので、１μｍ〜５ｍｍ程度が適当である。また、この鉄粉には、実質的にＦｅからなるものであるが、微量の他の成分（Ｃ，Ｍｎなど）、不可避的不純物（Ｐ，Ｓなど）、およびその他の成分を含有していてもよい。 On the other hand, although it does not specifically limit about the kind of iron powder used by this invention, Atomized iron powder is mentioned as a typical thing. If the average particle size of the iron powder is too small, the production cost is increased. If the average particle size is too large, the decomposition effect of the organic halogen compound is decreased. Therefore, about 1 μm to 5 mm is appropriate. The iron powder is substantially composed of Fe, but contains trace amounts of other components (C, Mn, etc.), inevitable impurities (P, S, etc.), and other components. Also good.
前記Ｎｉ含有粉の混合割合は、混合粉末全体に対して０．０１〜２０質量％程度が好ましく、より好ましくは０．０５〜１０質量％程度である。Ｎｉ含有粉の混合割合が低過ぎると、Ｎｉ含有粉の添加効果が小さくなり、過剰になると効果が飽和してコストアップに繋がって好ましくない。 The mixing ratio of the Ni-containing powder is preferably about 0.01 to 20% by mass, more preferably about 0.05 to 10% by mass with respect to the entire mixed powder. If the mixing ratio of the Ni-containing powder is too low, the effect of adding the Ni-containing powder is reduced, and if it is excessive, the effect is saturated and the cost is increased, which is not preferable.
本発明の有機ハロゲン化合物処理材は、有機ハロゲン化物によって汚染された物質を浄化するのに有用である。例えば、有機ハロゲン化合物によって汚染された土壌と混合することにより、または有機ハロゲン化合物によって汚染された地下水を混合または透過させることにより、これら土壌や地下水を浄化することができる。そのため大規模な処理装置が不要となり、汚染現場（原位置）で処理することもできる。また上記浄化処理（土壌浄化処理、地下水浄化処理など）に際しては、他の浄化方法（例えば、微生物法など）と組み合わせてもよい。 The organic halogen compound treatment material of the present invention is useful for purifying substances contaminated by organic halides. For example, these soils and groundwater can be purified by mixing with soil contaminated with organic halogen compounds, or by mixing or permeating groundwater contaminated with organic halogen compounds. Therefore, a large-scale processing apparatus is not necessary, and processing can be performed at the contamination site (original position). Further, the purification treatment (soil purification treatment, groundwater purification treatment, etc.) may be combined with other purification methods (for example, microbial methods, etc.).
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
実施例１
［試験材料］
（ａ）鉄粉:一般的なアトマイズ鉄粉（平均粒径：６５μｍ）
（ｂ）Ｎｉ含有粉
（１）平均粒径：１０μｍのＮｉ粉（ニッケル粉１）
（２）平均粒径：５μｍのＮｉ粉（ニッケル粉２）
（３）平均粒径：０．５μｍのＮｉ粉（ニッケル粉３）
尚、Ｎｉ粉の平均粒径は、「マイクロトラック粒子径分布測定装置Ｘ−１００」［商品名：日機装（株）製］を使って測定したものである。
（ｃ）有機ハロゲン化合物（被処理物）として、土壌や地下汚染で社会問題となっているトリクロロエチレンを使用した。
（ｄ）上記鉄粉とＮｉ粉末を混合し、下記の各種混合粉末を調製して試料（試料１〜８）とした。
（１）試料１：上記アトマイズ鉄粉のみ
（２）試料２：鉄粉に１質量％のＮｉを加えて製造したＮｉ合金アトマイズ鉄粉
（平均粒径６５μｍ）
（３）試料３：アトマイズ鉄粉に、ニッケル粉１を混合したもの（混合割合：
１質量％）
（４）試料４：アトマイズ鉄粉に、ニッケル粉２を混合したもの（混合割合：
１質量％）
（５）試料５：アトマイズ鉄粉に、ニッケル粉３を混合したもの（混合割合：
１質量％）
（６）試料６：アトマイズ鉄粉に、ニッケル粉１を混合したもの（混合割合：
０．１質量％）
（７）試料７：アトマイズ鉄粉に、ニッケル粉２を混合したもの（混合割合：
０．１質量％）
（８）試料８：アトマイズ鉄粉に、ニッケル粉３を混合したもの（混合割合：
０．１質量％）
Example 1
[Test material]
(A) Iron powder: general atomized iron powder (average particle size: 65 μm)
(B) Ni-containing powder (1) Average particle diameter: 10 μm Ni powder (nickel powder 1)
(2) Ni powder (nickel powder 2) having an average particle diameter of 5 μm
(3) Average particle diameter: 0.5 μm Ni powder (nickel powder 3)
In addition, the average particle diameter of Ni powder is measured using "Microtrack particle diameter distribution measuring apparatus X-100" [trade name: manufactured by Nikkiso Co., Ltd.].
(C) Trichlorethylene, which is a social problem due to soil and underground pollution, was used as the organic halogen compound (object to be treated).
(D) The above iron powder and Ni powder were mixed, and the following various mixed powders were prepared as samples (
(1) Sample 1: Atomized iron powder only (2) Sample 2: Ni alloy atomized iron powder produced by adding 1% by mass of Ni to iron powder
(Average particle size 65μm)
(3) Sample 3: Atomized iron powder mixed with nickel powder 1 (mixing ratio:
1% by mass)
(4) Sample 4: Atomized iron powder mixed with nickel powder 2 (mixing ratio:
1% by mass)
(5) Sample 5: Atomized iron powder mixed with nickel powder 3 (mixing ratio:
1% by mass)
(6) Sample 6: Atomized iron powder mixed with nickel powder 1 (mixing ratio:
0.1% by mass)
(7) Sample 7: Atomized iron powder mixed with nickel powder 2 (mixing ratio:
0.1% by mass)
(8) Sample 8: Atomized iron powder mixed with nickel powder 3 (mixing ratio:
0.1% by mass)
［試験方法］
容量１２５ｍｌのバイアル瓶に２．５ｇの試料を添加し、１０ｍｇ／Ｌのトリクロロエチレン水溶液を１２５ｍＬ添加して密栓した。このときブランクとして、容量１２５ｍｌのバイアル瓶に、１０ｍｇ／Ｌのトリクロロエチレン水溶液を１２５ｍＬ添加して密栓したものも準備した（試料を添加しない系）。
[Test method]
A 2.5 g sample was added to a 125 ml capacity vial, and 125 mL of a 10 mg / L trichlorethylene aqueous solution was added and sealed. At this time, a blank was prepared by adding 125 mL of a 10 mg / L aqueous trichlorethylene solution to a 125 mL vial (sealing system in which no sample was added).
鉄粉が適度に流動するように攪拌しながら、２５℃で反応させた。そして、２４時間後および４８時間後に、水中のトリクロロエチレンの濃度をガスクロマトグラフ質量分析装置にて測定し、（試験系における水中のトリクロロエチレン濃度：Ａ）を、（ブランクにおける水中のトリクロロエチレン濃度：Ｂ）で除した値（Ａ／Ｂ）を、トリクロロエチレン残存率として算出した。 It was made to react at 25 degreeC, stirring so that iron powder might flow moderately. Then, after 24 hours and 48 hours, the concentration of trichlorethylene in water was measured with a gas chromatograph mass spectrometer, and (trichloroethylene concentration in water in the test system: A) was (trichloroethylene concentration in water in the blank: B) The divided value (A / B) was calculated as the residual rate of trichlorethylene.
［試験結果］
試料１〜５による分解試験結果を図１に、試料１、６〜８による分解試験結果を図２に、夫々示す。これらの結果から明らかな様に、平均粒径：０．８μｍ以下のＮｉ粉を含む試料５、８で処理したものは、トリクロロエチレンが効率良く分解されていることが分かる。
[Test results]
FIG. 1 shows the results of the decomposition
実施例２
［試験材料］
（ａ）鉄粉:一般的なアトマイズ鉄粉（平均粒径：６５μｍ：実施例１で使用したものと同じ）
（ｂ）Ｎｉ含有粉
（１）平均粒径：５μｍのＮｉ粉（前記ニッケル粉２と同じもの）
（２）平均粒径：０．５μｍのＮｉ粉（前記ニッケル粉３と同じもの）
（ｃ）有機ハロゲン化合物（被処理物）として、モノクロロベンゼン、ペンタクロロフェノールを使用した。
（ｄ）上記鉄粉とＮｉ粉末を混合し、下記の各種混合粉末を調製して試料（試料１、２、４、５）とした。
（１）試料１：上記アトマイズ鉄粉のみ
（２）試料２：鉄粉に１質量％のＮｉを加えて製造したＮｉ合金アトマイズ鉄粉
（平均粒径６５μｍ）
（３）試料４：アトマイズ鉄粉に、ニッケル粉２を混合したもの（混合割合：
１質量％）
（４）試料５：アトマイズ鉄粉に、ニッケル粉３を混合したもの（混合割合：
１質量％）
Example 2
[Test material]
(A) Iron powder: general atomized iron powder (average particle diameter: 65 μm: the same as that used in Example 1)
(B) Ni-containing powder (1) Average particle diameter: 5 μm Ni powder (same as the nickel powder 2)
(2) Ni powder having an average particle diameter of 0.5 μm (the same as the nickel powder 3)
(C) Monochlorobenzene and pentachlorophenol were used as the organic halogen compound (object to be treated).
(D) The above iron powder and Ni powder were mixed to prepare the following various mixed powders, which were used as samples (
(1) Sample 1: Atomized iron powder only (2) Sample 2: Ni alloy atomized iron powder produced by adding 1% by mass of Ni to iron powder
(Average particle size 65μm)
(3) Sample 4: Atomized iron powder mixed with nickel powder 2 (mixing ratio:
1% by mass)
(4) Sample 5: Atomized iron powder mixed with nickel powder 3 (mixing ratio:
1% by mass)
［試験方法］
容量１２５ｍｌのバイアル瓶に２．５ｇの試料を添加し、１０ｍｇ／Ｌのモノクロロベンゼン水溶液またはペンタクロロフェノール水溶液を１２５ｍＬ添加して密栓した。このときブランクとして、容量１２５ｍｌのバイアル瓶に、１００ｍｇ／Ｌのモノクロロベンゼン水溶液またはペンタクロロフェノール水溶液を１２５ｍＬ添加して密栓したものも準備した（試料を添加しない系）。
[Test method]
A sample of 2.5 g was added to a vial with a capacity of 125 ml, and 125 mL of a 10 mg / L monochlorobenzene aqueous solution or a pentachlorophenol aqueous solution was added and sealed. At this time, a blank was prepared by adding 125 mL of a 100 mg / L monochlorobenzene aqueous solution or a pentachlorophenol aqueous solution to a 125 ml capacity vial (system in which no sample was added).
鉄粉が適度に流動するように攪拌しながら、２５℃で反応させた。そして、７日後および１４日後に、水中のモノクロロベンゼンまたはペンタクロロフェノールの濃度をガスクロマトグラフ質量分析装置にて測定し、実施例１と同様にして夫々の残存率を算出した。 It was made to react at 25 degreeC, stirring so that iron powder might flow moderately. Then, after 7 days and 14 days, the concentration of monochlorobenzene or pentachlorophenol in water was measured with a gas chromatograph mass spectrometer, and the residual ratio was calculated in the same manner as in Example 1.
［試験結果］
モノクロロベンゼンの分解試験結果を図３に、ペンタクロロフェノールの分解試験結果を図４に、夫々示す。これらの結果から明らかな様に、平均粒径：０．８μｍ以下のＮｉ粉を含む試料５で処理したものは、モノクロロベンゼンやペンタクロロフェノール等の難分解性の有機ハロゲン化合物を対象とした場合であっても、効率良く分解できることが分かる。
[Test results]
The decomposition test results of monochlorobenzene are shown in FIG. 3, and the decomposition test results of pentachlorophenol are shown in FIG. As is apparent from these results, the sample treated with Sample 5 containing Ni powder having an average particle size of 0.8 μm or less is intended for a hard-to-decompose organic halogen compound such as monochlorobenzene or pentachlorophenol. However, it turns out that it can decompose | disassemble efficiently.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009072742A (en) * | 2007-09-25 | 2009-04-09 | Dowa Eco-System Co Ltd | Powder for decomposing organic chlorine compound, decomposing agent for organic chlorine compound, and purification method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1046283A (en) * | 1996-05-17 | 1998-02-17 | Kobe Steel Ltd | Composite powder for high strength sintered steel, and its production |
| JP2003136051A (en) * | 2001-11-01 | 2003-05-13 | Dowa Mining Co Ltd | Metal powder for decomposing organic halogen compound and method for cleaning soil using the same |
| JP2004058051A (en) * | 2002-06-07 | 2004-02-26 | Toda Kogyo Corp | Iron composite particle powder for cleaning soil and underground water containing aromatic halogen compound, its manufacturing method, cleaning agent containing the iron composite particle powder, its manufacturing method, and method of cleaning soil and underground water containing aromatic halogen compound |
| JP2004082106A (en) * | 2002-06-26 | 2004-03-18 | Kobe Steel Ltd | Iron-based cleaning powder |
-
2005
- 2005-05-18 JP JP2005145247A patent/JP4786936B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1046283A (en) * | 1996-05-17 | 1998-02-17 | Kobe Steel Ltd | Composite powder for high strength sintered steel, and its production |
| JP2003136051A (en) * | 2001-11-01 | 2003-05-13 | Dowa Mining Co Ltd | Metal powder for decomposing organic halogen compound and method for cleaning soil using the same |
| JP2004058051A (en) * | 2002-06-07 | 2004-02-26 | Toda Kogyo Corp | Iron composite particle powder for cleaning soil and underground water containing aromatic halogen compound, its manufacturing method, cleaning agent containing the iron composite particle powder, its manufacturing method, and method of cleaning soil and underground water containing aromatic halogen compound |
| JP2004082106A (en) * | 2002-06-26 | 2004-03-18 | Kobe Steel Ltd | Iron-based cleaning powder |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009072742A (en) * | 2007-09-25 | 2009-04-09 | Dowa Eco-System Co Ltd | Powder for decomposing organic chlorine compound, decomposing agent for organic chlorine compound, and purification method |
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