JP5414410B2 - Decomposing material for organic halogen compounds and method for producing the same - Google Patents
Decomposing material for organic halogen compounds and method for producing the same Download PDFInfo
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- 239000000463 material Substances 0.000 title claims description 37
- 150000002896 organic halogen compounds Chemical class 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 214
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 147
- 239000000843 powder Substances 0.000 claims description 95
- 229910052759 nickel Inorganic materials 0.000 claims description 94
- 239000002245 particle Substances 0.000 claims description 58
- 229910052751 metal Inorganic materials 0.000 claims description 49
- 239000000460 chlorine Substances 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 47
- 229910052801 chlorine Inorganic materials 0.000 claims description 47
- 238000000354 decomposition reaction Methods 0.000 claims description 40
- 229910052742 iron Inorganic materials 0.000 claims description 32
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000000034 method Methods 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 32
- 238000005229 chemical vapour deposition Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
- 239000002689 soil Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 239000003673 groundwater Substances 0.000 description 10
- KFUSEUYYWQURPO-UPHRSURJSA-N cis-1,2-dichloroethene Chemical group Cl\C=C/Cl KFUSEUYYWQURPO-UPHRSURJSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012808 vapor phase Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000012459 cleaning agent Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003574 free electron Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 238000001784 detoxification Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 as described above Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Processing Of Solid Wastes (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Powder Metallurgy (AREA)
Description
本発明は有機ハロゲン化合物に汚染された土壌及び／又は地下水等を迅速に分解できる有機ハロゲン化合物の分解材及びその製造方法に関する。 The present invention relates to an organic halogen compound decomposition material capable of rapidly decomposing soil and / or groundwater contaminated with an organic halogen compound, and a method for producing the same.
有機ハロゲン化合物は優れた溶解力を持つ脱脂溶剤として、半導体製造業、金属加工業、クリーニング業などで広く使用されてきたが、使用後の有機ハロゲン化合物による土壌及び地下水の汚染が深刻となっている。
有機ハロゲン化合物を無害化する方法として、原位置から汚染土壌そのものを除去する方法、原位置で土壌、または有機塩素系化合物が溶けこんだ地下水を処理して有機ハロゲン化合物を分解する方法、汚染土壌の周辺において汚染土壌から流出する地下水を浄化する方法等が提案されている。
Organohalogen compounds have been widely used in the semiconductor manufacturing industry, metal processing industry, cleaning industry, etc. as degreasing solvents with excellent dissolving power, but contamination of soil and groundwater by organohalogen compounds after use has become serious. Yes.
Methods for detoxifying organohalogen compounds include removing contaminated soil from its original location, treating soil in situ or groundwater in which organochlorine compounds are dissolved, decomposing organohalogen compounds, and contaminated soil A method for purifying groundwater flowing out from contaminated soil in the surrounding area has been proposed.
これらのうち、原位置で汚染土壌を浄化する方法には、嫌気性微生物により生物分解する方法と鉄粉と水分を接触させ、鉄粉が酸化される際に発生する水素によって有機ハロゲン化合物を還元し、分解する方法（以下、鉄粉法）がある。これらの方法の中で、現在、鉄粉法が効果の確実性に優れ、且つ、工場跡地など広大な汚染土壌を処理するのに適していることから主流となりつつある。 Among these methods, the method of purifying contaminated soil in-situ involves biodegrading with anaerobic microorganisms, bringing iron powder into contact with moisture, and reducing organic halogen compounds with hydrogen generated when iron powder is oxidized. Then, there is a method of decomposition (hereinafter referred to as iron powder method). Among these methods, the iron powder method is currently becoming mainstream because it has excellent reliability of effects and is suitable for treating a large amount of contaminated soil such as a factory site.
このような鉄粉法に関する技術として、特許文献１に記載された有機ハロゲン化合物分解用金属粉に関する発明がある。この特許文献１に記載された有機ハロゲン化合物分解用金属粉は、「少なくとも、鉄（以下、Ｆｅと記載する。）−ニッケル（以下、Ｎｉと記載する。）の２種の金属元素を主成分とする相を有し、Ｆｅを主成分とする相を母材金属相とし、Ｎｉを主成分とする相を付着金属相とし、付着金属相は母材金属相に付着してＮｉ付着Ｆｅ粒子の形態となり、この粒子が集合したものである」（特許文献１［００１６］参照）。
As a technique relating to such an iron powder method, there is an invention relating to a metal powder for decomposing organic halogen compounds described in
また、鉄粉法に関する他の技術として、特許文献２に開示された被処理物用無害化処理剤の発明がある。この特許文献２に開示された発明は、「Ｆｅ粉末１００重量部とＮｉ粉末０．０１〜２重量部からなる混合物をメカニカルアロイング法により合金化したＦｅ−Ｎｉ合金からなる有機ハロゲン化合物で汚染された被処理物用無害化処理剤」である（特許文献２、請求項１参照）。 Moreover, there exists invention of the detoxification processing agent for to-be-processed objects disclosed by patent document 2 as another technique regarding an iron powder method. The invention disclosed in Patent Document 2 is “contaminated with an organic halogen compound composed of an Fe—Ni alloy obtained by alloying a mixture of 100 parts by weight of Fe powder and 0.01 to 2 parts by weight of Ni powder by a mechanical alloying method. Detoxification treatment agent for processed material "(refer to Patent Document 2 and Claim 1).
特許文献１、２に開示された発明は、共に鉄粉にニッケル粉を付着させるという点で共通している。
そして、鉄粉にニッケル粉を付着させることにより、有機ハロゲン化合物に汚染された土壌等の浄化に効果があることは認められる。
しかしながら、上記特許文献１、２の発明では、初期の反応速度が十分ではなく、分解速度の点では必ずしも満足できるものではなかった。
The inventions disclosed in
And it is recognized that by attaching nickel powder to iron powder, there exists an effect in the purification | cleaning of the soil contaminated with the organic halogen compound.
However, in the inventions of
また、特許文献１のものでは、ニッケル粉の粒径については特に言及されておらず、他方特許文献２のものではニッケル粉の粒径として１〜10μｍ程度と記載されており、比較的粒径が粗いものを使用している。
しかしながら、ニッケル粉の粒径が粗いと、同じ効果を得るのにニッケル粉の必要量が増えコストが高くなるという問題がある。
また、ニッケル粉の粒径が大きいと鉄粉表面へ付着させにくく、例えば特許文献２においてはＭＡ法に使用するアトライターミルなどを用いて３０分以上の混合が必要とされており、製造に時間を要するという問題もある。
In addition, in
However, if the particle size of the nickel powder is coarse, there is a problem that the required amount of nickel powder increases to increase the cost in order to obtain the same effect.
In addition, when the particle size of nickel powder is large, it is difficult to adhere to the iron powder surface. For example, in Patent Document 2, mixing for 30 minutes or more is required using an attritor mill used in the MA method. There is also the problem of taking time.
本発明はかかる課題を解決するためになされたものであり、有機ハロゲン化合物に汚染された土壌及び／又は地下水等に対する分解速度に優れた分解材及びその製造方法を提供することを目的とする。
また、上記の分解性能に加えて、コストが低減され、また製造が容易な分解材及びその製造方法を提供することを目的としている。
The present invention has been made to solve such problems, and an object of the present invention is to provide a decomposition material excellent in the decomposition rate for soil and / or groundwater contaminated with an organic halogen compound and a method for producing the same.
It is another object of the present invention to provide a decomposed material and a method for manufacturing the same, in which cost is reduced and manufacturing is easy in addition to the above-described decomposition performance.
鉄粉にニッケル粉を付着させることにより、有機ハロゲン化合物に汚染された土壌等の浄化に効果があることは公知の事実である。
しかしながら、従来の分解材では初期の反応速度が十分でなく、この点を改善するべく発明者は研究を行い、その過程で、ニッケル粉の粒径に着目し、その粒径の微細なもの（以下、ニッケル微粉という）を用いて分解材を製造した。
ニッケル微粉として、発明者は、塩化ニッケルを気化し、還元反応を起こさせて気相から粒子を析出させる気相化学反応法（ＣＶＤ法）で製造したものを使用し、このようにして製造されたニッケル微粉を鉄粉に付着させて分解材を製造し、その性能試験を行った。
その過程で、ニッケル微粉として製品として出荷されるものと、製品として出荷される前の、すなわち、ＣＶＤ法によって気相から析出されたものをそのままの状態で使用した場合の比較実験を行った。
そうしたところ、ＣＶＤ法によって気相から析出されたものをそのままの状態で使用したものが初期の反応速度の面で優れていることを発見した。
It is a known fact that nickel powder adheres to iron powder and is effective in the purification of soil contaminated with organic halogen compounds.
However, the initial reaction rate is not sufficient with the conventional decomposed material, and the inventor conducted research to improve this point, and in the process, focused on the particle size of the nickel powder, Hereinafter, the decomposition material was manufactured using nickel fine powder).
As the nickel fine powder, the inventor uses a product produced by a vapor phase chemical reaction method (CVD method) in which nickel chloride is vaporized and a reduction reaction is caused to precipitate particles from the gas phase. Nickel fine powder was adhered to iron powder to produce a decomposed material, and its performance test was conducted.
In that process, a comparison experiment was conducted in which nickel fine powder shipped as a product and before shipping as a product, that is, a product deposited from the gas phase by the CVD method were used as they were.
As a result, it was discovered that what was deposited as it was from the vapor phase by the CVD method was excellent in terms of the initial reaction rate.
そこで、製品として出荷される状態のニッケル微粉とＣＶＤ法によって気相から析出されたものをそのままの状態のものとの違いについて検討した。
通常、ＣＶＤ法によって気相から析出されたニッケル微粉中には塩素ガスがHCｌとして金属ニッケル表面に再付着しているため、これを水洗し、水洗後はデカンターと言われる脱水器で脱水し、不活性ガス雰囲気中で乾燥し、塩素の残留量が数十ppm程度以下になるようにしている。この事実から、発明者は、ニッケル微粉に含まれる塩素がＶＯＣ分解材としての機能をより優れたものにする効果を発揮するとの知見を得た。
Then, the difference between the nickel fine powder in the state shipped as a product and the one deposited from the vapor phase by the CVD method was examined.
Usually, in the nickel fine powder deposited from the vapor phase by the CVD method, chlorine gas is reattached to the surface of the metallic nickel as HCl, so this is washed with water, and after washing with water, dehydrated with a dehydrator called decanter, It is dried in an inert gas atmosphere so that the residual amount of chlorine is about tens of ppm or less. From this fact, the inventor has obtained knowledge that chlorine contained in nickel fine powder exhibits an effect of making the function as a VOC decomposition material more excellent.
つまり、塩素が含まれることにより、分解材を使用する際において塩素が水と反応して生成されるＨＣｌが鉄粉の溶解促進に寄与する。すなわち、ＶＯＣの分解に寄与する自由電子は、Ｆｅ→Ｆｅ2＋＋2e-の反応によるが、この反応は酸性の方が起こりやすいので鉄粉表面（微細領域）に局所的にＨＣｌが存在すると、そこのサイトは塩酸酸性となり鉄の溶解が促進され、ＶＯＣの分解に優れることになり、特に初期の反応性に優れることになる。
もっとも、生成する塩酸の量が多いと、鉄粉表面が錆びてしまい、表面の鉄さび比率が増えるとＦｅ→Ｆｅ2＋＋2e―によるＶＯＣの分解に寄与する自由電子の発生が少なくなるし、あるいは分解材として長期保存を考慮すると、塩素の量には上限がある。
That is, when chlorine is contained, HCl produced by the reaction of chlorine with water contributes to the promotion of dissolution of iron powder when the decomposition material is used. In other words, free electrons that contribute to the decomposition of VOC are due to the reaction of Fe → Fe 2+ + 2e-, but this reaction is more likely to be acidic, so if HCl exists locally on the iron powder surface (fine region), This site becomes acidic with hydrochloric acid, so that the dissolution of iron is promoted, and the decomposition of VOC is excellent. In particular, the initial reactivity is excellent.
However, when the amount of hydrochloric acid is often produced, will rust iron powder surface, iron rust ratio of the surface increases the Fe → Fe 2+ + 2e - occurs in the free electrons that contribute to the degradation of VOC by the to less, or decomposition Considering long-term storage as a material, there is an upper limit on the amount of chlorine.
本発明はかかる知見を基になされたものであり、具体的には以下の構成からなるものである。 The present invention has been made on the basis of such knowledge, and specifically comprises the following constitution.
（１）本発明に係る有機ハロゲン化合物の分解材は、鉄粉の表面に鉄より貴な金属を付着させた有機ハロゲン化合物の分解材であって、前記鉄より貴な金属が、鉄より貴な金属の塩化物を気相中で還元して、塩素が付着した鉄より貴な金属粉を含む金属粉であることを特徴とするものである。
(1) The organic halogen compound decomposition material according to the present invention is an organic halogen compound decomposition material in which a metal noble than iron is attached to the surface of iron powder, wherein the metal noble than iron is nobler than iron. It is characterized in that it is a metal powder containing a metal powder nobler than iron to which chlorine is attached by reducing a chloride of a metal in a gas phase .
（２）また、上記（１）に記載のものにおいて、前記鉄より貴な金属がニッケルであることを特徴とするものである。
( 2 ) Further, in the above (1), the metal nobler than iron is nickel.
（３）また、上記（１）又は（２）のいずれかに記載のものにおいて、前記塩素の濃度が前記鉄より貴な金属に対して0.1〜3質量％であることを特徴とするものである。
( 3 ) Moreover, in the thing in any one of said (1) or ( 2 ), the density | concentration of the said chlorine is 0.1-3 mass% with respect to the noble metal rather than the said iron, It is characterized by the above-mentioned. is there.
（４）本発明に係る有機ハロゲン化合物の分解材の製造方法は、鉄より貴な金属の塩化物を気相中で還元して、塩素が付着した鉄より貴な金属粉を含む金属粉を製造し、これらの金属粉と鉄粉を機械的に接触させて前記鉄粉の上面に前記鉄より貴な金属粉を圧着させることを特徴とするものである。
(4) The method for producing an organohalogen compound decomposition material according to the present invention comprises reducing metal chlorides nobler than iron in a gas phase to produce metal powders containing metal nobler than iron adhering to chlorine. The metal powder is manufactured by mechanically contacting the metal powder and the iron powder, and the metal powder nobler than the iron is pressed onto the upper surface of the iron powder.
（５）また、上記（４）に記載のものにおいて、前記鉄より貴な金属がニッケルであることを特徴とするものである。
( 5 ) Further, in the above ( 4 ), the metal nobler than iron is nickel.
（６）また、上記（４）又は（５）に記載のものにおいて、鉄より貴な金属粉の粒径が0.1〜1μｍを90％以上含むことを特徴とするものである。 ( 6 ) Further, in the above ( 4 ) or ( 5 ), the particle size of the metal powder nobler than iron contains 0.1 to 1 μm in 90% or more.
本発明の有機ハロゲン化合物の分解材よれば、有機ハロゲン化合物に汚染された土壌及び／又は地下水から、有機ハロゲン化合物を確実、且つ、迅速に分解除去でき、さらに、安価に製造できるため、産業上極めて有用である。 According to the organic halogen compound decomposition material of the present invention, the organic halogen compound can be reliably and rapidly decomposed and removed from soil and / or groundwater contaminated with the organic halogen compound, and can be produced at low cost. Very useful.
［実施の形態１］
本発明に係る有機ハロゲン化合物の分解材は、鉄粉の表面に鉄より貴な金属であるニッケルを付着させた有機ハロゲン化合物の分解材であって、前記ニッケルが塩素を付着又は含有していることを特徴とするものである。そして、分解材を介して有機ハロゲン化合物のハロゲン原子を水素原子に置換することによって浄化作用を発揮するものである。
[Embodiment 1]
The organic halogen compound decomposition material according to the present invention is an organic halogen compound decomposition material in which nickel, which is a noble metal than iron, is adhered to the surface of iron powder, and the nickel adheres to or contains chlorine. It is characterized by this. And a purification effect is exhibited by substituting the halogen atom of an organic halogen compound for a hydrogen atom through a decomposition material.
＜鉄粉＞
この浄化剤に使用される鉄粉としては、アトマイズ鉄粉、海綿鉄粉、還元鉄粉、電解鉄粉を使用することができるが、鉄粉表面が酸化膜で覆われていない鉄粉が好ましい。もっとも、鉄粉表面が酸化膜で覆われている場合や酸化膜が厚い場合には、例えば仕上げ還元処理によって鉄粉表面の酸化膜厚を500nm以下にするのが好ましく、酸化膜の厚みは薄いほど好ましい。酸化膜厚が500nm以下であるためには、酸化膜は鉄粉の表面にほぼ均一に形成されると想定できることから鉄粉の酸素濃度で規定することができ、鉄粉の酸素濃度が1質量％以下であればよい。なお、酸化膜の除去に関しては、仕上げ還元処理の他、酸性溶液で表面の酸化膜を除去するようにしてもよい。
また、鉄粉粒径としては、500μm未満が望ましい。500μm未満としたのは、500μm以上の粒径の場合、鉄粉の比表面積が小さくなるため反応性が著しく劣化し、さらに、スラリー状態として土壌と混合する場合には、そのスラリーを圧送する配管、ポンプにおいて詰りや摩耗が発生するためである。また、鉄粉の粒径の下限値としては、45μm以下が45％以下にすることが施行性の観点から望ましい。
<Iron powder>
As the iron powder used in this purification agent, atomized iron powder, sponge iron powder, reduced iron powder, and electrolytic iron powder can be used, but iron powder whose iron powder surface is not covered with an oxide film is preferable. . However, when the iron powder surface is covered with an oxide film or when the oxide film is thick, it is preferable to reduce the oxide film thickness on the iron powder surface to 500 nm or less by, for example, finish reduction treatment, and the thickness of the oxide film is thin. The more preferable. Since the oxide film thickness is 500 nm or less, it can be assumed that the oxide film is formed almost uniformly on the surface of the iron powder, so it can be defined by the oxygen concentration of the iron powder, and the oxygen concentration of the iron powder is 1 mass. % Or less. Regarding the removal of the oxide film, the oxide film on the surface may be removed with an acidic solution in addition to the finish reduction treatment.
The iron powder particle size is preferably less than 500 μm. When the particle size is 500 μm or more, the specific surface area of the iron powder is reduced and the reactivity is significantly deteriorated. Further, when mixing with the soil as a slurry state, the piping for pumping the slurry This is because clogging and wear occur in the pump. Moreover, as a lower limit of the particle size of iron powder, it is desirable from a viewpoint of effectiveness that 45 micrometers or less shall be 45% or less.
＜ニッケル＞
ニッケルは鉄粉の表面にニッケル微粉を機械的に付着させるようにする。付着させるための具体的な方法としては、混合・造粒を主目的としたアイリッヒミキサー、ヘンシェルミキサーにより、鉄粉とニッケル微粉を混合攪拌する方法があるが、これに限られるものではない。
ニッケル微粉としては、塩化ニッケルを気化し、還元反応を起こさせて気相から粒子を析出させる気相化学反応法（ＣＶＤ法）で製造するようにしてもよいが、これに限定されるものではない。
もっとも、ＣＶＤ法によってニッケル微粉を製造した場合には、製造されたニッケル微粉中に塩素ガスがHClとして金属ニッケル表面に再付着しているので、別途塩素を添加する必要がないので好ましい。
<Nickel>
Nickel causes nickel fine powder to mechanically adhere to the surface of the iron powder. Specific methods for adhering include, but are not limited to, a method in which iron powder and nickel fine powder are mixed and stirred by an Eirich mixer and a Henschel mixer mainly used for mixing and granulation.
The nickel fine powder may be manufactured by a vapor phase chemical reaction method (CVD method) in which nickel chloride is vaporized and a reduction reaction is caused to precipitate particles from the gas phase, but is not limited thereto. Absent.
However, when nickel fine powder is manufactured by the CVD method, chlorine gas is reattached to the surface of the metallic nickel as HCl in the manufactured nickel fine powder, and therefore it is preferable because it is not necessary to add chlorine separately.
ニッケル微粉の粒度は、鉄粉表面への機械的な付着させやすさを考慮して、鉄粉の粒度の1/10〜1/1000にするのが好ましい。なお、ＣＶＤ法によってニッケル微粉を製造した場合には、その粒度は、0.1〜1μmで90％以上となる。 The particle size of the nickel fine powder is preferably 1/10 to 1/1000 of the particle size of the iron powder in consideration of the ease of mechanical adhesion to the iron powder surface. In addition, when nickel fine powder is manufactured by CVD method, the particle size will be 90% or more at 0.1-1 micrometer.
＜塩素＞
金属ニッケルに付着している塩素の量は、金属ニッケルに対して0.1〜3質量％であることが好ましい。0.1質量％未満であると、分解材として使用する際に鉄の溶解を促進する効果が少なく、分解材として初期反応の促進効果が期待できない。他方、3質量％を越えると、鉄が酸化して表面が酸化膜で覆われてしまい、Ｆｅ→Ｆｅ2＋＋2e―によるＶＯＣの分解に寄与する自由電子の発生が少なくなるからである。また、分解材として長期保存の観点からも、塩素の量が3質量％を超えると長期保存ができなくなるので好ましくない。
<Chlorine>
The amount of chlorine attached to the metallic nickel is preferably 0.1 to 3% by mass with respect to the metallic nickel. If it is less than 0.1% by mass, the effect of promoting the dissolution of iron is small when used as a decomposition material, and the effect of promoting the initial reaction cannot be expected as the decomposition material. On the other hand, if it exceeds 3 mass%, iron is oxidized and the surface is covered with an oxide film, and the generation of free electrons contributing to the decomposition of VOC by Fe → Fe 2+ + 2e − is reduced. Further, from the viewpoint of long-term storage as a decomposition material, if the amount of chlorine exceeds 3% by mass, long-term storage becomes impossible, which is not preferable.
ＣＶＤ法によってニッケル微粉を製造した場合には、上述したようにニッケルに塩素が付着することになり、別途塩素を添加する必要がない。しかし、ニッケル微粉を製造する方法としては、ＣＶＤ法以外の例えば、金属を直接還元雰囲気下で昇華させて微粉末を作るプラズマＰＶＤ法、Ni塩の水溶液を還元して微粉末を製造する液相法、Ni塩をそのまま水素還元して微粉末を製造する固相法であってもよい。液相法や固相法では出発原料が塩化ニッケルであれば製造された微粉末に塩素が残留するので、ＣＶＤ法と同様に別途塩素を添加する必要がない。 When nickel fine powder is manufactured by the CVD method, chlorine adheres to nickel as described above, and it is not necessary to add chlorine separately. However, as a method for producing nickel fine powder, other than the CVD method, for example, a plasma PVD method in which metal is sublimated directly in a reducing atmosphere to produce fine powder, a liquid phase in which an aqueous solution of Ni salt is reduced to produce fine powder. Alternatively, a solid phase method in which a Ni salt is directly reduced with hydrogen to produce a fine powder may be used. In the liquid phase method or the solid phase method, if the starting material is nickel chloride, chlorine remains in the produced fine powder, so that it is not necessary to add chlorine as in the CVD method.
上記のように構成された本実施の形態の分解材によれば、分解材としての初期の反応性に優れるという効果を奏する。
また、本実施の形態においては、塩素がニッケルに付着しているので、分解材の使用前の保存中には塩素によって鉄粉が腐食することがなく保存性に優れる。他方、分解材の使用状態では、前述したように、塩素が水と反応して鉄粉の溶解促進に寄与する。このように、本実施の形態の分解材は保存性に優れると共に初期反応性に優れるという効果を奏する。
もっとも、塩素は初期反応性に優れるという効果の点からすれば、塩素が鉄粉側に付着するものを排除するものではない。
According to the decomposition material of this Embodiment comprised as mentioned above, there exists an effect that it is excellent in the initial reactivity as a decomposition material.
Moreover, in this Embodiment, since chlorine has adhered to nickel, during storage before use of a decomposition material, iron powder does not corrode by chlorine and is excellent in preservability. On the other hand, in the use state of the decomposition material, as described above, chlorine reacts with water and contributes to the promotion of dissolution of iron powder. Thus, the decomposition material of this Embodiment has the effect that it is excellent in preservability and is excellent in initial stage reactivity.
However, in view of the effect that chlorine is excellent in initial reactivity, it does not exclude the case where chlorine adheres to the iron powder side.
なお、上記の実施の形態においては、鉄より貴な金属の例としてニッケルを例に挙げて説明したが、鉄より貴な金属としては、パラジウム（Ｐｄ）、白金（Ｐｔ）、ロジウム（Ｒｈ）、銅（Ｃｕ）、コバルト（Ｃｏ）が挙げられる。 In the above embodiment, nickel has been described as an example of a noble metal than iron, but as a noble metal than iron, palladium (Pd), platinum (Pt), rhodium (Rh) is used. , Copper (Cu), and cobalt (Co).
［実施の形態２］
本実施の形態２は、分解材の製造方法に関するものである。
本実施の形態に係る有機ハロゲン化合物の分解材の製造方法は、塩化ニッケルを気相中で分解して、塩素が付着したニッケル微粉を含むニッケル微粉を製造する工程と（ニッケル微粉製造工程）、これらの金属粉と鉄粉を機械的に接触させて前記鉄粉の上面に前記鉄より貴な金属粉を圧着させる工程（圧着工程）とを有している。
[Embodiment 2]
The second embodiment relates to a method for manufacturing a decomposed material.
The method for producing an organic halogen compound decomposition material according to the present embodiment includes a step of decomposing nickel chloride in a gas phase to produce nickel fine powder including nickel fine powder to which chlorine is attached (nickel fine powder production step), There is a step (pressure bonding step) of bringing these metal powder and iron powder into mechanical contact with each other and pressing the metal powder nobler than the iron onto the upper surface of the iron powder.
＜ニッケル微粉製造工程＞
ニッケル微粉製造工程をより具体的に示すと、塩化ニッケルを昇華させたガス、水素ガスおよび窒素ガスの３種のガス中で塩化ニッケルを昇華させたガスのモル比が０．１０〜０．２０となるように混合し、１０００〜１２００℃に加熱した反応管内で気相反応によってニッケル微粉を製造する（ＣＶＤ法）。
ＣＶＤ法によってニッケル微粉を製造した場合には、その粒度は、0.1〜1μmで90％以上となる。
ＣＶＤ法によってニッケル微粉を製造した場合には、ニッケル微粉にHClが付着することになり、別途塩素を添加する必要がない。一部、未反応の塩化ニッケルも存在するがニッケル微粉に対し1質量％以下であれば問題ない。
<Nickel fine powder manufacturing process>
More specifically, the nickel fine powder production process has a molar ratio of 0.10 to 0.20 of a gas obtained by sublimating nickel chloride in three kinds of gases including hydrogen chloride and nitrogen gas. Then, nickel fine powder is produced by vapor phase reaction in a reaction tube heated to 1000 to 1200 ° C. (CVD method).
When nickel fine powder is produced by the CVD method, the particle size is 90% or more at 0.1 to 1 μm.
When nickel fine powder is produced by the CVD method, HCl adheres to the nickel fine powder, and there is no need to add chlorine separately. Some unreacted nickel chloride is present, but there is no problem if it is 1% by mass or less based on the nickel fine powder.
＜圧着工程＞
圧着工程には、アイリッヒミキサーなどの混合・造粒を主目的としたミキサーを使用し、鉄粉とニッケル微粉を混合攪拌する。
このとき、ニッケル微粉の粒度は、鉄粉表面への機械的な付着させやすさを考慮して、鉄粉の粒度の1/10〜1/1000にするのが好ましい。すなわち、ニッケル微粉の粒径を小さくすると、圧着工程で鉄粉の表面に薄く広い面積で付着させることができ、ニッケルの鉄粉に対する表面比率を大きくすることができる。
ミキサーのアジテータ（ミキサー内の羽）の回転数は1500〜5000rpm、混合時間は４〜１５分である。
アジテータの回転により、ミキサー内の鉄粉とニッケル微粉が遠心力を受けながら混合攪拌され、このとき粒径の大きい鉄粉のせん断摩擦力によってニッケルが鉄粉に貼り付けられるようにして付着する。このような方法でニッケル微粉を鉄粉の表面に付着させるので、加工前後で粒度がほとんど変わらない。
<Crimping process>
In the crimping step, a mixer mainly for mixing and granulation such as an Eirich mixer is used, and iron powder and nickel fine powder are mixed and stirred.
At this time, the particle size of the nickel fine powder is preferably set to 1/10 to 1/1000 of the particle size of the iron powder in consideration of easy mechanical adhesion to the iron powder surface. That is, when the particle size of the nickel fine powder is reduced, the nickel powder can be attached to the surface of the iron powder in a thin and wide area in the pressure-bonding step, and the surface ratio of nickel to the iron powder can be increased.
The rotational speed of the mixer agitator (wings in the mixer) is 1500 to 5000 rpm, and the mixing time is 4 to 15 minutes.
Due to the rotation of the agitator, the iron powder and the nickel fine powder in the mixer are mixed and stirred while receiving a centrifugal force, and at this time, the nickel is adhered to the iron powder by the shear frictional force of the iron powder having a large particle size. Since nickel fine powder is adhered to the surface of iron powder by such a method, the particle size hardly changes before and after processing.
なお、アイリッヒミキサーに代えて、混合・造粒を目的としたミキサーとしてヘンシェルミキサーがあるが、このようなミキサーを使用することもできる。
また、振動ミルや回転ボールミルのようなミルでも加工でき、加工時間は数〜数十分以内である。
In place of the Eirich mixer, there is a Henschel mixer as a mixer for mixing and granulation, but such a mixer can also be used.
Further, it can be processed by a mill such as a vibration mill or a rotating ball mill, and the processing time is within several to several tens of minutes.
以上のように本実施の形態の製造方法によれば、ニッケル微粉製造工程において製造されたニッケルに適量のHClが付着するので、別途塩素を付着させる必要がない。
また、ミキサーやミル内で混合攪拌される鉄粉のせん断摩擦力によってニッケルを鉄粉に付着させるようにしたので、簡易な方法で短時間での加工ができる。
As described above, according to the manufacturing method of the present embodiment, since an appropriate amount of HCl adheres to the nickel manufactured in the nickel fine powder manufacturing process, it is not necessary to separately attach chlorine.
Further, since nickel is adhered to the iron powder by the shear frictional force of the iron powder mixed and stirred in the mixer or the mill, processing can be performed in a short time by a simple method.
＜実施例１＞
上記の実施の形態で示した分解材は、ニッケル微粉の表面に塩素が付着することによって反応速度が速くなるというものであるが、この点を確認するために以下のように、実施例１とこれに対する比較例１〜３について以下のような実験を行った。
実験条件は以下の通りである。
＜実施例１＞
・原料鉄粉 ：仕上げ還元鉄粉［100重量部、平均粒径100μm］
・塩素量 ：0.54質量％（対ニッケル金属）［金属ニッケル表面に付着］
・ニッケル微粉 ：0.2重量部（平均粒径：0.4μm）
・混合攪拌条件 ：アイリッヒミキサーによって3.000rpm、5分間混合
・分解試験方法 ：浄化剤1.5gを50mLのバイアル瓶に入れ、シス-1,2-ジクロロエチレン
に汚染された地下水30mLを加えてＰＴＦＥ栓で密栓して静置し所定
時間後のシス-1,2-ジクロロエチレン濃度を測定
（測定方法 GC-MSヘッドスペース法）
<Example 1>
The decomposition material shown in the above embodiment is such that the reaction rate is increased due to the adhesion of chlorine to the surface of the nickel fine powder. In order to confirm this point, Example 1 and The following experiments were conducted on Comparative Examples 1 to 3 for this.
The experimental conditions are as follows.
<Example 1>
・ Raw iron powder: Finished reduced iron powder [100 parts by weight,
・ Chlorine content: 0.54 mass% (to nickel metal) [attached to the surface of nickel metal]
・ Nickel fine powder: 0.2 parts by weight (average particle size: 0.4 μm)
・ Mixing and stirring conditions: 3.000 rpm with an Eirich mixer for 5 minutes ・ Decomposition test method: 1.5 g of a cleaning agent is placed in a 50 mL vial and cis-1,2-dichloroethylene is added.
Add 30 mL of contaminated ground water, seal tightly with a PTFE stopper, and leave to stand.
Measure cis-1,2-dichloroethylene concentration after time
(Measurement method GC-MS headspace method)
＜比較例１＞
・塩素量 ：0.01％未満（対ニッケル金属）
・ニッケル微粉 ：0.2重量部（平均粒径：0.4μm）
ニッケル微粉の金属ニッケル表面に存在する塩素量を0.01％未満（対ニッケル金属）とし、他の条件は実施例１と同じ。
＜比較例２＞
・原料鉄粉 ：仕上げ還元鉄粉［100重量部、平均粒径100μm］
・ニッケル微粉 ：0.2重量部（平均粒径：0.4μm）
・塩化ニッケル微粉：0.01重量部
比較例１と同様にニッケル微粉の金属ニッケル表面に存在する塩素量を0.01％未満とし、さらに上記の塩化ニッケルを加えた。その他の条件は実施例１と同じ。
＜比較例３＞
・原料鉄粉 ：仕上げ還元鉄粉［100重量部、平均粒径100μm］
・塩化ニッケル粉 ：0.2重量部（平均粒径：5μm）
・塩化ニッケル ：0.01重量部
ニッケル微粉に代えて上記粒径の異なるニッケル粉を用い、さらに塩化ニッケルを添加した。その他の条件は実施例１と同じ。
＜比較例４＞
・原料鉄粉 ：仕上げ還元鉄粉［100重量部、平均粒径100μm］
・銅粉 ：0.2重量部（平均粒径：5μm）
ニッケル微粉に代えて上記銅粉を添加した。その他の条件は実施例１と同じ。
<Comparative Example 1>
・ Chlorine content: Less than 0.01% (to nickel metal)
・ Nickel fine powder: 0.2 parts by weight (average particle size: 0.4 μm)
The amount of chlorine present on the surface of the nickel metal powder nickel is less than 0.01% (vs. nickel metal), and other conditions are the same as in Example 1.
<Comparative example 2>
・ Raw iron powder: Finished reduced iron powder [100 parts by weight,
・ Nickel fine powder: 0.2 parts by weight (average particle size: 0.4 μm)
Nickel chloride fine powder: 0.01 part by weight In the same manner as in Comparative Example 1, the amount of chlorine present on the surface of the nickel metal in the nickel fine powder was made less than 0.01%, and the above nickel chloride was further added. The other conditions are the same as in Example 1.
<Comparative Example 3>
・ Raw iron powder: Finished reduced iron powder [100 parts by weight,
・ Nickel chloride powder: 0.2 parts by weight (average particle size: 5μm)
Nickel chloride: Nickel powder having a different particle diameter was used instead of 0.01 parts by weight of nickel fine powder, and nickel chloride was further added. The other conditions are the same as in Example 1.
<Comparative Example 4>
・ Raw iron powder: Finished reduced iron powder [100 parts by weight,
・ Copper powder: 0.2 parts by weight (average particle size: 5 μm)
The copper powder was added in place of the nickel fine powder. The other conditions are the same as in Example 1.
実験条件及び結果を表１に示すと共に、実験結果を図１に示す。図１においては、縦軸がcis-DCE濃度（mg/L）で、横軸が時間（hr）である。 The experimental conditions and results are shown in Table 1, and the experimental results are shown in FIG. In FIG. 1, the vertical axis represents cis-DCE concentration (mg / L), and the horizontal axis represents time (hr).
図１のグラフに示されるように、実施例１の金属ニッケル表面に塩素が付着するものについては、他のものに比較して反応速度、特に初期段階の反応速度が際立って速い。このことから、金属ニッケルの表面に塩素を付着させることが分解材としての反応速度を高める効果があることが確認できた。 As shown in the graph of FIG. 1, the reaction rate, especially the initial reaction rate, of the case where chlorine adheres to the surface of the nickel metal of Example 1 is significantly higher than that of the others. From this, it was confirmed that adhering chlorine to the surface of metallic nickel has an effect of increasing the reaction rate as a decomposition material.
次に、金属ニッケルの表面に付着する塩素量の最適範囲を確認するための実験を行った。実験方法は以下の通りである。
＜試料＞
(1)仕上げ還元鉄粉：［100重量部、平均粒径100μm］
(2)金属ニッケル表面上に塩素を0.03〜11％含有（対ニッケル金属）（表２参照）するニッケル微粉（平均粒径：0.4μm）を0.2重量部
上記(1)(2)を混ぜてアイリッヒミキサーで3000rpm、5分間混合して調製。
＜分析試験方法＞
分析試験方法は、実施例１と同様に、浄化剤1.5gを50mLのバイアル瓶に入れ、シス-1,2-ジクロロエチレンに汚染された地下水30mLを加えてＰＴＦＥ栓で密栓して静置し所定時間後のシス-1,2-ジクロロエチレン濃度を測定（測定方法 GC-MSヘッドスペース法）
なお、反応速度の算出方法は下式による。
反応速度Ｋ＝ＬＮ（Ｃ/Ｃｏ）/ｈ
但し、 Ｃ：ｈ時間後の濃度
Ｃｏ：初期濃度
Next, an experiment was conducted to confirm the optimum range of the amount of chlorine adhering to the surface of metallic nickel. The experimental method is as follows.
<Sample>
(1) Finished reduced iron powder: [100 parts by weight,
(2) 0.2 parts by weight of nickel fine powder (average particle size: 0.4 μm) containing 0.03% to 11% chlorine (relative to nickel metal) (see Table 2) on the surface of metallic nickel. Mix (1) and (2) above. Prepared by mixing for 5 minutes at 3000 rpm with an Eirich mixer.
<Analytical test method>
In the same manner as in Example 1, the analytical test method was carried out by putting 1.5 g of the cleaning agent into a 50 mL vial, adding 30 mL of ground water contaminated with cis-1,2-dichloroethylene, sealing it with a PTFE stopper, and allowing it to stand. Measure cis-1,2-dichloroethylene concentration after time (measurement method GC-MS headspace method)
In addition, the calculation method of reaction rate is based on the following formula.
Reaction rate K = LN (C / Co) / h
C: Concentration after h hours
Co: Initial concentration
実験結果を表２及び図２に示す。図２において、横軸はNｉ微粉中の塩素含有量（％）、縦軸は反応速度（1/h）を示している。 The experimental results are shown in Table 2 and FIG. In FIG. 2, the horizontal axis represents the chlorine content (%) in the Ni fine powder, and the vertical axis represents the reaction rate (1 / h).
図２から分かるように、金属ニッケル表面上に付着する塩素量が0.1〜3質量％では、製造直後（Fresh）のもの及び製造後一ヶ月を経過したもののいずれのものでも優れた反応速度を示している。
他方、塩素量が0.1質量％未満のものでは、製造直後（Fresh）のもの及び製造後一ヶ月を経過したもののいずれのものでも反応速度が十分でない。
また、塩素量が3質量％を超えたものでは、製造直後（Fresh）に使用した場合には十分な反応速度を示しているが、製造後一ヶ月経過後に使用すると、製造直後に使用する場合に比較して反応速度が著しく低下していることが分かる。これは、塩素量が多過ぎると鉄粉表面が酸化して酸化被膜で覆われるためであると推察される。
以上の考察から、金属ニッケル表面上に付着する塩素量を0.1〜3質量％にするのが好適である。
As can be seen from FIG. 2, when the amount of chlorine adhering to the surface of the metallic nickel is 0.1 to 3% by mass, the reaction rate is excellent both in the fresh product and the one month after the production. ing.
On the other hand, when the amount of chlorine is less than 0.1% by mass, the reaction rate is not sufficient for either the product immediately after production (Fresh) or the product after one month has passed since production.
In addition, when the chlorine content exceeds 3% by mass, the reaction rate is sufficient when used immediately after production (Fresh). It can be seen that the reaction rate is remarkably reduced as compared with FIG. This is presumably because the iron powder surface is oxidized and covered with an oxide film when the amount of chlorine is too large.
From the above considerations, it is preferable that the amount of chlorine deposited on the surface of the metallic nickel is 0.1 to 3% by mass.
次に、鉄粉表面に対するニッケルの添加量の最適範囲を求める実験を行った。
実験方法は以下の通りである。
＜試料＞
(1)アトマイズ鉄粉：［100重量部、平均粒径100μm］
(2)金属ニッケル表面上に塩素を0.54％含有（対ニッケル金属）するニッケル微粉（平均粒径：0.4μm）を0.05〜5.0重量部（表３参照）
上記(1)(2)を混ぜてアイリッヒミキサーで3000rpm、5〜10分間混合して調製
＜分析試験方法＞
分析試験方法は、実施例１と同様に、浄化剤1.5gを50mLのバイアル瓶に入れ、シス-1,2-ジクロロエチレンに汚染された地下水30mLを加えてＰＴＦＥ栓で密栓して静置し所定時間後のシス-1,2-ジクロロエチレン濃度を測定（測定方法 GC-MSヘッドスペース法）
なお、反応速度の算出方法は下式による。
反応速度Ｋ＝ＬＮ（Ｃ/Ｃｏ）/ｈ
但し、 Ｃ：ｈ時間後の濃度
Ｃｏ：初期濃度
Next, an experiment was performed to find the optimum range of the amount of nickel added to the iron powder surface.
The experimental method is as follows.
<Sample>
(1) Atomized iron powder: [100 parts by weight,
(2) 0.05 to 5.0 parts by weight of nickel fine powder (average particle size: 0.4 μm) containing 0.54% chlorine (as opposed to nickel metal) on the surface of nickel metal (see Table 3)
Prepared by mixing (1) and (2) above and mixing with Eirich mixer at 3000 rpm for 5-10 minutes <Analytical test method>
In the same manner as in Example 1, the analytical test method was carried out by putting 1.5 g of the cleaning agent into a 50 mL vial, adding 30 mL of ground water contaminated with cis-1,2-dichloroethylene, sealing it with a PTFE stopper, and allowing it to stand. Measure cis-1,2-dichloroethylene concentration after time (measurement method GC-MS headspace method)
In addition, the calculation method of reaction rate is based on the following formula.
Reaction rate K = LN (C / Co) / h
C: Concentration after h hours
Co: Initial concentration
実験結果を表３及び図３に示す。図３において、横軸はニッケル微粉添加量（％）、縦軸は反応速度（1/h）を示している。 The experimental results are shown in Table 3 and FIG. In FIG. 3, the horizontal axis represents the amount of nickel fine powder added (%), and the vertical axis represents the reaction rate (1 / h).
図３から分かるように、塩素を0.54質量％含有するニッケル微粉の添加量が0.1質量％以上の範囲（表３のNo.2〜No.7参照）では、高い反応速度を示している。
以上のことから、所定量の塩素を含有するニッケル微粉の添加量としては0.1質量％以上の範囲が好適である。
As can be seen from FIG. 3, the reaction rate is high when the amount of nickel fine powder containing 0.54% by mass of chlorine is 0.1% by mass or more (see No. 2 to No. 7 in Table 3).
From the above, the amount of nickel fine powder containing a predetermined amount of chlorine is preferably in the range of 0.1% by mass or more.
次に、ニッケル微粉の粒度とＶＯＣ分解性能の関係について実験を行った。
実験方法は以下の通りである。
＜試料＞
(1)アトマイズ鉄粉：［100重量部、平均粒径100μm］
(2)表４に示す平均粒径0.1〜10μmで、金属ニッケル表面上に塩素を0.4％含有（対ニッケル金属）するニッケル微粉
なお、粒径0.1〜１μmのニッケル微粉はCVD法にて製造し、分級により平均粒径を調整した。また、粒径5μm及び10μmのニッケル微粉は試薬のニッケル金属を破砕、分級し、希塩酸でニッケル金属にCl相当分として0.4％になるように散布した。
上記(1)(2)を混ぜてアイリッヒミキサーで3000rpm、10分間混合して調製した。
＜分析試験方法＞
分析試験方法は、実施例１と同様に、浄化剤1.5gを50mLのバイアル瓶に入れ、シス-1,2-ジクロロエチレンに汚染された地下水30mLを加えてＰＴＦＥ栓で密栓して静置し所定時間後のシス-1,2-ジクロロエチレン濃度を測定（測定方法 GC-MSヘッドスペース法）
なお、反応速度の算出方法は下式による。
反応速度Ｋ＝ＬＮ（Ｃ/Ｃｏ）/ｈ
但し、 Ｃ：ｈ時間後の濃度
Ｃｏ：初期濃度
Next, an experiment was conducted on the relationship between the particle size of nickel fine powder and the VOC decomposition performance.
The experimental method is as follows.
<Sample>
(1) Atomized iron powder: [100 parts by weight,
(2) Nickel fine powder with an average particle size of 0.1-10 μm shown in Table 4 containing 0.4% chlorine on the nickel metal surface (as opposed to nickel metal) Nickel fine powder with a particle size of 0.1-1 μm is manufactured by the CVD method. The average particle size was adjusted by classification. Nickel fine powders with particle diameters of 5 μm and 10 μm were crushed and classified as reagent nickel metal and sprayed with dilute hydrochloric acid so that the equivalent of Cl was 0.4%.
The above (1) and (2) were mixed and prepared by mixing with an Eirich mixer at 3000 rpm for 10 minutes.
<Analytical test method>
In the same manner as in Example 1, the analytical test method was carried out by putting 1.5 g of the cleaning agent into a 50 mL vial, adding 30 mL of ground water contaminated with cis-1,2-dichloroethylene, sealing it with a PTFE stopper, and allowing it to stand. Measure cis-1,2-dichloroethylene concentration after time (measurement method GC-MS headspace method)
In addition, the calculation method of reaction rate is based on the following formula.
Reaction rate K = LN (C / Co) / h
C: Concentration after h hours
Co: Initial concentration
実験結果を表４及び図４に示す。図４において、横軸はニッケル微粉の粒径（μm）、縦軸は反応速度（1/h）を示している。 The experimental results are shown in Table 4 and FIG. In FIG. 4, the horizontal axis indicates the particle size (μm) of the nickel fine powder, and the vertical axis indicates the reaction rate (1 / h).
表４及び図４から分かるように、添加率が同じであればニッケル微粉の粒径が小さいほど表面被覆率が高く、特にニッケル微粉の平均粒径が0.1〜1.0μmではニッケルの表面被覆率が比較的高く、反応速度にも優れることが確認された。これは、鉄粉とニッケル微粉との粒径の差が大きいことにより、両者の質量差が大きく、混合時にニッケル微粉が効果的に鉄粉表面に付着したものと推認される。
以上のことから、ニッケル微粉の粒径としては0.1〜1.0μmの範囲にするのが好適であることが確認された。
As can be seen from Table 4 and FIG. 4, if the addition rate is the same, the smaller the particle size of the nickel fine powder, the higher the surface coverage, and in particular when the average particle size of the nickel fine powder is 0.1 to 1.0 μm, the surface coverage of nickel is high. It was confirmed that the reaction rate was relatively high and the reaction rate was excellent. This is presumed that due to the large particle size difference between the iron powder and the nickel fine powder, the mass difference between the two is large, and the nickel fine powder effectively adheres to the iron powder surface during mixing.
From the above, it was confirmed that the particle size of the nickel fine powder is preferably in the range of 0.1 to 1.0 μm.
次に、ニッケル微粉の粒度と混合時間との関係について実験を行った。
実験方法は以下の通りである。
＜試料＞
(1)アトマイズ鉄粉：［100重量部、平均粒径100μm］
(2)表５に示す平均粒径0.2μm及び10μmのニッケル微粉
なお、粒径0.2μmのニッケル微粉はCVD法にて製造し、分級により平均粒径を調整した。また、粒径10μmのニッケル微粉は試薬のニッケル金属を破砕、分級した。
上記(1)(2)を混ぜてアイリッヒミキサーで3000rpm、2〜30分間混合して調製した。
Next, an experiment was conducted on the relationship between the particle size of nickel fine powder and the mixing time.
The experimental method is as follows.
<Sample>
(1) Atomized iron powder: [100 parts by weight,
(2) Nickel fine powder having an average particle size of 0.2 μm and 10 μm shown in Table 5 Incidentally, nickel fine powder having a particle size of 0.2 μm was produced by a CVD method, and the average particle size was adjusted by classification. Further, the nickel fine powder having a particle diameter of 10 μm was crushed and classified as a nickel metal reagent.
The above (1) and (2) were mixed and prepared by mixing with an Eirich mixer at 3000 rpm for 2 to 30 minutes.
実験結果を表５及び図５に示す。図５において、横軸はアイリッヒミキサーによる混合時間（min）、縦軸は反応速度定数（1/h）を示している。 The experimental results are shown in Table 5 and FIG. In FIG. 5, the horizontal axis represents the mixing time (min) by the Eirich mixer, and the vertical axis represents the reaction rate constant (1 / h).
表５及び図５から分かるように、平均粒径が0.2μmのニッケル微粉では、約10分の混合時間で-0.12の高い分解反応速度が得られている。これに対して、平均粒径が10μmのニッケル微粉では30分間混合しても-0.01以下の低い分解反応速度しか得られていない。
このことから、添加率が同じであればニッケル微粉の平均粒径が小さいほど短い時間で鉄粉表面への被覆が行われることが確認された。
As can be seen from Table 5 and FIG. 5, with nickel fine powder having an average particle size of 0.2 μm, a high decomposition reaction rate of −0.12 was obtained in a mixing time of about 10 minutes. In contrast, nickel fine powder having an average particle size of 10 μm has only obtained a low decomposition reaction rate of −0.01 or less even when mixed for 30 minutes.
From this, it was confirmed that the coating on the iron powder surface is performed in a shorter time as the average particle diameter of the nickel fine powder is smaller if the addition ratio is the same.
Claims (6)
6. The method for producing a decomposed material of an organic halogen compound according to claim 4 or 5, wherein the particle diameter of the metal powder nobler than iron contains 0.1 to 1 μm in 90% or more.
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