JP2011046985A - Decomposition material for organic halogen compound and method for producing the same - Google Patents
Decomposition material for organic halogen compound and method for producing the same Download PDFInfo
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- Powder Metallurgy (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
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 is the method of biodegrading with anaerobic microorganisms, bringing iron powder into contact with water, and reducing the organic halogen compounds with hydrogen generated when the 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と記載する場合あり。）−ニッケル（以下、Ｎｉと記載する場合あり。）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 Patent Document 1. The metal powder for decomposing organohalogen compounds described in Patent Document 1 is “at least two kinds of metals of iron (hereinafter sometimes referred to as Fe) —nickel (hereinafter sometimes referred to as Ni). It has a phase mainly composed of elements, a phase mainly composed of Fe as a base metal phase, a phase mainly composed of Ni as an adhering metal phase, and the adhering metal phase adheres to the base metal phase. It becomes a form of Ni-adhered Fe particles, and these particles are aggregated ”(see Patent Document 1 [0016]).
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、共に鉄粉とニッケル粉を用いるという点で共通している。
鉄粉とニッケル粉を用いることにより、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が知られている。
鉄粉のみの場合よりもニッケルが存在することにより有機ハロゲン化合物の分解能が高くなるのは、標準電極電位において鉄が卑、ニッケルが貴になる関係にあることが要因の一つであると考えられている。
すなわち、分解材が水と接触したときに、これらの粒子表面は局部的にカルバニ電池反応による電位差が生じ、鉄が電子を失うことにより他へ自由電子を供給するアノード反応（Ｆｅ→Ｆｅ2＋＋２ｅ−）が、鉄粉のみの場合に比べて加速し、有機ハロゲン化合物の分解反応に供される自由電子の供給量が増大するためであると考えられている。
The inventions disclosed in Patent Documents 1 and 2 are common in that both iron powder and nickel powder are used.
It is known that the use of iron powder and nickel powder is effective for purification of soil contaminated with organic halogen compounds.
The reason why the organohalogen compounds have a higher resolution due to the presence of nickel than in the case of iron powder alone is considered to be due to the fact that iron is base and nickel is noble at the standard electrode potential. It has been.
That is, when the decomposed material comes into contact with water, a potential difference due to the carbani cell reaction is locally generated on the surface of these particles, and the anodic reaction (Fe → Fe 2+ + 2e) in which iron loses electrons and supplies free electrons to others - ) Is accelerated compared to the case of using only iron powder, and it is considered that the amount of free electrons supplied to the decomposition reaction of the organic halogen compound increases.
しかしながら、鉄粉とニッケル粉の用い方によって分解材としての分解作用には大きな違いがあり、どのような用い方をするかについて種々の研究がなされている。 However, there is a great difference in the decomposition action as a decomposition material depending on how iron powder and nickel powder are used, and various studies have been conducted on how to use them.
この点、特許文献１においては、鉄粉の表面にニッケル粒子を点在するように付着させるというものである。
しかしながら、上記のような態様では、実際に分解材として使用する際、土壌と混合するときに鉄粉からニッケルが剥離し、局部電池反応の効果が低下することが考えられる。また、分解材として使用している期間が長くなると、鉄粉が溶解して鉄粉表面に付着していたニッケル粉が鉄粉から分離してしまう。ニッケル粉が鉄粉から分離すると、上述したアノード反応促進効果が少なくなり、有機ハロゲン化合物の分解効果も少なくなる。
In this respect, in Patent Document 1, nickel particles are adhered to the surface of iron powder so as to be scattered.
However, in the above aspect, when actually used as a decomposition material, it is considered that nickel is peeled off from the iron powder when mixed with soil, and the effect of the local cell reaction is lowered. Moreover, when the period used as a decomposition material becomes long, iron powder melt | dissolves and the nickel powder which adhered to the iron powder surface will isolate | separate from iron powder. When the nickel powder is separated from the iron powder, the effect of promoting the anode reaction described above is reduced, and the decomposition effect of the organic halogen compound is also reduced.
他方、特許文献２のものでは、鉄粉と少量のニッケル粉をメカニカルアロイング法により合金化して鉄―ニッケル合金とするものであり、特許文献１のように分解材の使用中にニッケルが鉄から分離するということはない。
しかしながら、特許文献２のものでは、合金化により鉄とニッケルの場合よりも標準電位差が小さくなり、分解速度が低下するという問題がある。
また、特許文献２のものでは、鉄粉とニッケル粉の混合粉を最低でも３０分程度アトライターミルなどで混合しなければならず、製造時間とコストを要するという問題もある。
On the other hand, in Patent Document 2, iron powder and a small amount of nickel powder are alloyed by a mechanical alloying method to form an iron-nickel alloy. Like Patent Document 1, nickel is iron during use of the decomposition material. There is no separation from.
However, the thing of patent document 2 has the problem that a standard potential difference becomes smaller than the case of iron and nickel by alloying, and a decomposition rate falls.
Moreover, in the thing of patent document 2, the mixed powder of iron powder and nickel powder must be mixed with an attritor mill etc. for about 30 minutes at least, and there also exists a problem that manufacturing time and cost are required.
以上のように、上記特許文献１のものでは、分解材として長期使用の点で問題があり、他方特許文献２のものでは反応速度の点で満足できるものではなかった。 As described above, the above-mentioned Patent Document 1 has a problem in terms of long-term use as a decomposition material, while the Patent Document 2 is not satisfactory in terms of reaction rate.
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、長期使用してもその効果が持続する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 in order to solve such problems, and is a decomposition material excellent in the decomposition rate for soil and / or groundwater contaminated with an organic halogen compound, and its effect is maintained even after long-term use, and its production It aims to provide a method.
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.
上記課題を解決するため、発明者は、鉄の溶出があってもニッケルが鉄粉から分離せず、かつ合金化した場合のように標準電位差が小さくなることがないようにするにはいかにすべきかを鋭意検討し、鉄粉の表面をニッケルで覆うことにより、鉄の腐食があっても両者が分離しないようにできるとの知見を得て本発明を完成したものであり、具体的には以下の構成からなるものである。
なお、上記の説明では、鉄とニッケルを例に挙げて説明したが、ニッケルに代えて鉄よりも貴な金属であれば同様な効果があることを確認しており、ニッケル以外の鉄より貴な金属の例としては、パラジウム（Ｐｄ）、白金（Ｐｔ）、ロジウム（Ｒｈ）、ルテニウム（Ｒｕ）、銅（Ｃｕ）、コバルト（Ｃｏ）が挙げられる。
In order to solve the above-mentioned problems, the inventor has found out how to prevent the nickel from being separated from the iron powder even when iron is eluted, and to prevent the standard potential difference from becoming small as in the case of alloying. The present invention has been completed with the knowledge that it is possible to prevent the two from separating even if there is iron corrosion by intensively studying the surface and covering the surface of the iron powder with nickel. It consists of the following composition.
In the above description, iron and nickel have been described as examples, but it has been confirmed that a similar effect can be obtained if a metal is noble rather than iron instead of nickel, and is more noble than iron other than nickel. Examples of such metals include palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), copper (Cu), and cobalt (Co).
（１）本発明に係る有機ハロゲン化合物の分解材は、鉄粉の表面を鉄より貴な金属で被覆してな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 characterized in that the surface of the iron powder is coated with a metal nobler than iron.
（２）また、上記（１）に記載のものにおいて、前記鉄よりも貴な金属の鉄粉表面に対する表面被覆面積比率が30％〜95％であることを特徴とするものである。 (2) Further, in the above (1), the ratio of the surface coating area to the surface of the iron powder of a metal nobler than the iron is 30% to 95%.
（３）また、上記（１）又は（２）に記載のものにおいて、鉄100重量部、鉄よりも貴な金属0.1〜10重量部であることを特徴とするものである。 (3) Further, in the above-described (1) or (2), 100 parts by weight of iron and 0.1 to 10 parts by weight of a metal nobler than iron are characterized.
（４）また、上記（１）乃至（３）のいずれか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。 (4) Further, in any of the above (1) to (3), the metal nobler than iron is nickel.
（５）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、鉄より貴な金属粉と鉄粉を機械的に接触させて前記鉄粉の表面を前記鉄より貴な金属で被覆することを特徴とするものである。 (5) In the method for producing an organic halogen compound decomposition material according to the present invention, a metal powder nobler than iron and iron powder are mechanically contacted to coat the surface of the iron powder with a metal nobler than iron. It is characterized by.
（６）また、上記（５）に記載のものにおいて、前記機械的な接触は、前記鉄粉と前記鉄よりも貴な金属粉をミキサーで混合することによって行うことを特徴とするものである。 (6) Further, in the above (5), the mechanical contact is performed by mixing the iron powder and a metal powder nobler than the iron with a mixer. .
（７）また、上記（５）又は（６）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。 (7) Further, in the above (5) or (6), the particle diameter of the metal powder nobler than iron includes 0.1 to 1 μm in an amount of 90% or more.
（８）また、上記（５）乃至（７）に記載のものにおいて、前記鉄粉の粒径が500μｍ未満であることを特徴とするものである。 (8) Further, in the above (5) to (7), the iron powder has a particle size of less than 500 μm.
（９）また、上記（５）乃至（８）のいずれかに記載のものにおいて、前記鉄粉表面に対するニッケルの表面被覆面積比率が30％〜95％であることを特徴とするものである。 (9) Moreover, in the thing in any one of said (5) thru | or (8), the surface coverage area ratio of the nickel with respect to the said iron powder surface is 30%-95%, It is characterized by the above-mentioned.
（１０）また、上記（５）乃至（９）のいずれか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。 (10) Further, in any of the above (5) to (9), the metal nobler than iron is nickel.
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、迅速に長期間に亘って分解除去でき、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 quickly decomposed and removed from the soil and / or groundwater contaminated with the organic halogen compound over a long period of time, and also manufactured at low cost. Therefore, it is extremely useful industrially.
［実施の形態１］
本実施の形態に係る有機ハロゲン化合物の分解材１は、図１に示すように、鉄粉３の表面をニッケル５で被覆してなることを特徴とするものである。図１においては、後述する表面被覆面積比率の説明のため、鉄粉断面の輪郭線を実線Ａで示し、鉄粉を被覆しているニッケルの輪郭線を破線Ｂで示している。
上記のように構成される本実施の形態の分解材１は、有機ハロゲン化合物のハロゲン原子を水素原子に置換、水素化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 organohalogen compound decomposition material 1 according to the present embodiment is characterized in that the surface of the iron powder 3 is coated with nickel 5 as shown in FIG. In FIG. 1, the outline of the cross section of the iron powder is indicated by a solid line A, and the outline of nickel covering the iron powder is indicated by a broken line B for the explanation of the surface coverage area ratio described later.
The decomposition material 1 of the present embodiment configured as described above exhibits a purifying action by substituting and hydrogenating a halogen atom of an organic halogen compound with a hydrogen atom.
＜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30nm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30nm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。
<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 30 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 30 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.
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。 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を被覆している。被覆とは、鉄粉の表面に薄膜化したニッケルが貼り付いている状態をいう。
ニッケルの表面被覆面積比率としては30％〜95％であることが好ましい。表面被覆面積比率が30％未満になると、鉄粉の腐食によりニッケルが鉄粉から分離し易くなることと、上記触媒反応活性点が減少し、有機ハロゲン化合物の分解能が低下するからである。他方、表面被覆面積比率が95％を超えると鉄の露出が少なくなり、粒子表面での局部的なカルバニ電池反応が生じ難くなり、分解材として使用する際の初期段階において鉄露出度が小さく分解速度が遅くなるからである。
<Nickel>
Nickel coats the surface of the iron powder. The coating means a state in which the thinned nickel is attached to the surface of the iron powder.
The surface coverage area ratio of nickel is preferably 30% to 95%. This is because when the surface coating area ratio is less than 30%, nickel is easily separated from the iron powder due to the corrosion of the iron powder, the catalytic reaction active sites are reduced, and the resolution of the organic halogen compound is lowered. On the other hand, when the surface coating area ratio exceeds 95%, iron exposure is reduced, and local carbani cell reaction on the particle surface is less likely to occur, and the iron exposure level is reduced in the initial stage when used as a decomposition material. This is because the speed becomes slow.
鉄粉の表面を覆うニッケルの厚みは特に限定するものではないが、ニッケルの被覆厚が厚くなっても有機ハロゲン化合物の分解速度には影響は与えない。また、ニッケルの膜厚が厚くなることにより物理的に剥離しやすくなるため、例えば分解材を使用する際に鉄粉同士が擦れ合う、または土壌粒子と擦れ合うときに剥がれ易くなる。さらに、高価なニッケルの使用量も増える。また、さらにニッケルの膜厚が厚くなると、ニッケルの量が増え、ニッケルの量が増えるとニッケルの溶出量が増え、環境上好ましくない。以上の観点から厚みは、薄くするのが好ましく、例えば100nm以下にするのが好ましい。 The thickness of nickel covering the surface of the iron powder is not particularly limited, but even if the nickel coating thickness is increased, the decomposition rate of the organic halogen compound is not affected. Moreover, since it becomes easy to peel physically when the film thickness of nickel becomes thick, when using a decomposition material, it will become easy to peel, for example, when iron powders rub against each other or to rub against soil particles. Furthermore, the amount of expensive nickel used also increases. Further, when the thickness of nickel is further increased, the amount of nickel is increased, and when the amount of nickel is increased, the elution amount of nickel is increased, which is not environmentally preferable. From the above viewpoint, the thickness is preferably thin, for example, 100 nm or less.
ニッケルの膜厚は実際に測定することもできるが、鉄粉粒径、Ｎｉ添加量、表面被覆面積比率から推測できる。表１に鉄粉表面を１００％被覆した場合の、鉄粉粒径とニッケル添加量〔重量部〕によるニッケル膜厚〔nm〕を示す。 Although the film thickness of nickel can be actually measured, it can be estimated from the iron powder particle size, the amount of Ni added, and the surface coating area ratio. Table 1 shows the nickel film thickness [nm] depending on the iron powder particle size and nickel addition amount [parts by weight] when the surface of the iron powder is 100% coated.
表１は、鉄粉表面をニッケルで１００％被覆した場合の膜厚を示しているが、ニッケルの鉄粉に対する表面被覆面積比率は実際には３０〜９５％であるので、表１に示した膜厚よりも実際には少し厚くなる。 Table 1 shows the film thickness when the surface of the iron powder is 100% coated with nickel, but the surface coverage area ratio of nickel to the iron powder is actually 30 to 95%, so it is shown in Table 1. Actually it is a little thicker than the film thickness.
後述の実施例３に示すように、ニッケルの添加量が１重量部を超えるとニッケル溶出量が指数関数的に増大する。一方、ニッケル膜厚が薄くても有機ハロゲン化合物の分解性能に影響を与えない。したがって、ニッケル溶出量を出来るだけ少なくする観点からニッケルの添加量は１重量部以下にするのが好ましい。ニッケルの添加量を１重量部にした場合、ニッケル膜厚は表１から100nmを超えるケースが多い。したがって、膜厚を100nm以下にして、かつニッケル溶出量を抑制するためにはニッケルの添加量を１重量部よりも少ない量にするのが好ましい。
なお、ニッケル膜厚はニッケルの粒径、ニッケル添加量、被覆方法によって制御することができるが、この点は分解材の製造方法に関する実施の形態２で詳細に説明する。
As shown in Example 3 described later, when the amount of nickel added exceeds 1 part by weight, the nickel elution amount increases exponentially. On the other hand, even if the nickel film thickness is small, the decomposition performance of the organic halogen compound is not affected. Therefore, from the viewpoint of reducing the nickel elution amount as much as possible, the amount of nickel added is preferably 1 part by weight or less. When the amount of nickel added is 1 part by weight, the nickel film thickness often exceeds 100 nm from Table 1. Therefore, in order to reduce the film thickness to 100 nm or less and suppress the nickel elution amount, it is preferable that the amount of nickel added is less than 1 part by weight.
The nickel film thickness can be controlled by the particle size of nickel, the amount of nickel added, and the coating method, and this point will be described in detail in Embodiment 2 relating to the method for producing a decomposed material.
鉄粉表面をニッケルで被覆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おり、この塩素の存在によって反応速度が速くなるという効果がある。
As a specific method for coating the surface of the iron powder with nickel, there is a method of mixing and stirring the iron powder and the nickel fine powder with an Eirich mixer and a Henschel mixer, which are mainly used for mixing and granulation. It is not limited.
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 produced by the CVD method, chlorine gas is reattached to the surface of the nickel metal as HCl in the produced nickel fine powder, and the presence of this chlorine has the effect of increasing the reaction rate. .
なお、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、塩素により鉄が腐食するため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。 In addition, it is preferable that the quantity of the chlorine adhering to metallic nickel is 0.1-3 mass% with respect to 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 corroded by chlorine 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。
なお、ニッケル微粉の粒径は、実施の形態２で説明するように、鉄粉表面を被覆させることを考慮して、鉄粉の粒径の1/10〜1/5000にするのが好ましい。（1/5000は、0.1μmのNi粉と500μmの鉄粉の比）さらに、ニッケル微粉の粒径が鉄粉粒径の1/100〜1/5000にするのがより好ましい。なお、ニッケル微粉と鉄粉の粒径比率に関しては、実施の形態２で詳細に説明する。
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.
In addition, it is preferable that the particle diameter of the nickel fine powder is 1/10 to 1/5000 of the particle diameter of the iron powder in consideration of covering the surface of the iron powder as described in the second embodiment. (1/5000 is the ratio of 0.1 μm Ni powder to 500 μm iron powder) Further, it is more preferable that the particle size of the nickel fine powder is 1/100 to 1/5000 of the iron powder particle size. The particle diameter ratio between the nickel fine powder and the iron powder will be described in detail in the second embodiment.
ニッケルで鉄粉を被覆することで前記局部的な反応に加え、オレフィンなどの不飽和炭化水素化合物の水素化触媒として作用するため有機ハロゲン化合物の分解に寄与する。主な触媒作用として、金属のイオン化により発生する水素分子がニッケル表面上で解離されて活性な水素原子となり、その水素原子が不飽和炭化水素化合物などに付加される脱塩素化、水素化反応が考えられる。 By covering the iron powder with nickel, in addition to the local reaction, it acts as a hydrogenation catalyst for unsaturated hydrocarbon compounds such as olefins, thereby contributing to the decomposition of organic halogen compounds. The main catalytic action is the dechlorination and hydrogenation reaction in which hydrogen molecules generated by metal ionization are dissociated on the nickel surface to become active hydrogen atoms, which are added to unsaturated hydrocarbon compounds. Conceivable.
上記のように構成された本実施の形態の分解材１によれば、ニッケル５が鉄粉３と合金化することなく、鉄粉表面を覆うように付着しているので、分解材としての初期の反応性に優れると共に鉄粉の溶出があってもニッケルが鉄粉と分離し難いので長期に亘ってその効果が持続する。
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、分解材としての初期の分解速度に優れると共に、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 1 of the present embodiment configured as described above, the nickel 5 adheres so as to cover the surface of the iron powder without being alloyed with the iron powder 3, so that the initial as the decomposition material In addition to being excellent in reactivity, even if there is elution of iron powder, it is difficult to separate nickel from iron powder, so that the effect lasts for a long time.
In this embodiment, since chlorine adheres to nickel, it is excellent in the initial decomposition rate as a decomposition material, and iron powder may be corroded by chlorine during storage before using the decomposition material. Excellent storage stability. 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 terms 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）、ルテニウム（Ｒｕ）、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. , Ruthenium (Ru), 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、ニッケル微粉と鉄粉を機械的に接触させて前記鉄粉の表面をニッケルで被覆するようにニッケルを圧着させる工程（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 organic halogen compound decomposition material manufacturing method according to the present embodiment includes a step of pressing nickel so that nickel fine powder and iron powder are mechanically contacted to coat the surface of the iron powder with nickel (crimping step). And have.
＜鉄粉＞
本実施の形態で使用する鉄粉は、実施の形態で説明した鉄粉を用いることができる。すなわち、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。また、鉄粉表面が酸化膜で覆われていない鉄粉が好ましく、鉄粉表面が酸化膜で覆われている場合には鉄粉表面の酸化膜厚を30nm以下にするのが好ましい。
鉄粉粒径としては、その上限値は、実施の形態１で説明したように、分解材としての反応性の観点や輸送の観点から500μm未満が望ましい。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>
The iron powder used in this embodiment can be the iron powder used in this embodiment. That is, atomized iron powder, sponge iron powder, reduced iron powder, and electrolytic iron powder can be used. Moreover, the iron powder whose iron powder surface is not covered with an oxide film is preferable, and when the iron powder surface is covered with an oxide film, the oxide film thickness on the iron powder surface is preferably 30 nm or less.
As described in Embodiment 1, the upper limit of the iron powder particle size is preferably less than 500 μm from the viewpoint of reactivity as a decomposition material and from the viewpoint of transportation. 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.
＜ニッケル微粉＞
ニッケル微粉の粒径は、鉄粉表面を被覆させることを考慮して、鉄粉の粒径の1/10〜1/5000にするのが好ましい。（1/5000は、0.1μmのNi粉と500μmの鉄粉の比）さらに、ニッケル微粉の粒径が鉄粉粒径の1/100〜1/5000にするのがより好ましい。なお、粒径比率はニッケル微粉と鉄粉のすべてにおいて当該粒径比率であることを意味するのではなく、使用するニッケル微粉と鉄粉の50質量％以上が当該粒径比率であればよい。つまり、ニッケル微粉と鉄粉の粒径比率が1/100〜1/5000であるとは、仮にニッケル微粉の平均粒径が0.4μmの場合、鉄粉の少なくとも50質量％以上の粒径が40μm以上であることを意味する。
ニッケル微粉の粒径を鉄粉の粒径に比較して小さく設定しているのは、ニッケル微粉と鉄粉をアイリッヒミキサーなどで混合したときに、ニッケル微粉が鉄粉によって扁平化されて鉄粉の表面に薄く広い面積で被覆でき、表面被覆面積比率を大きくすることができるようにするためである。
<Nickel fine powder>
The particle size of the nickel fine powder is preferably set to 1/10 to 1/5000 of the particle size of the iron powder in consideration of covering the surface of the iron powder. (1/5000 is the ratio of 0.1 μm Ni powder to 500 μm iron powder) Further, it is more preferable that the particle size of the nickel fine powder is 1/100 to 1/5000 of the iron powder particle size. The particle size ratio does not mean that the particle size ratio is the same for all of the nickel fine powder and the iron powder, but 50 mass% or more of the nickel fine powder and the iron powder to be used may be the particle size ratio. In other words, the particle size ratio between nickel fine powder and iron powder is 1/100 to 1/5000. If the average particle diameter of nickel fine powder is 0.4 μm, the particle diameter of at least 50 mass% of iron powder is 40 μm. That means that.
The particle size of the nickel fine powder is set smaller than the particle size of the iron powder because when the nickel fine powder and iron powder are mixed with an Eirich mixer etc., the nickel fine powder is flattened by the iron powder. This is because the surface of the powder can be covered with a thin and wide area, and the surface coverage area ratio can be increased.
なお、ニッケル微粉の製造方法は特に問わないが、一つの好ましい態様を示すと以下のようなＣＶＤ法によるものが挙げられる。
ＣＶＤ法によるニッケル微粉製造方法を具体的に示すと、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ことなく、初期の反応速度を向上させることができる。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。
In addition, although the manufacturing method in particular of nickel fine powder is not ask | required, the thing by the following CVD methods will be mentioned if one preferable aspect is shown.
Specifically, a method for producing nickel fine powder by CVD method is described. A molar ratio of a gas obtained by sublimating nickel chloride in three gases of nickel chloride sublimated gas, hydrogen gas and nitrogen gas is 0.10 to 0. The nickel fine powder is produced by a gas 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 the initial reaction rate can be improved without adding chlorine. 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。
ミキサーのアジテータ（ミキサー内の羽）の回転数は1500〜5000rpm、パンの回転速度は20〜150rpm、混合時間は２〜１５分である。
アジテータとパンの回転により、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表面に貼り付けられるようにして付着して鉄粉表面を覆う。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。
被覆方法は、粉砕メディアを入れないで鉄粒子同士のせん断摩擦力を利用してニッケル粒子を鉄粉表面に膜状に被覆する方法がよい。粉砕メディアを入れても被覆可能であるが、処理時間によって鉄粉の粒径、粒形が変化するため制御が煩雑になる。
なお、鉄粉を被覆するニッケルの厚みは鉄粉やニッケル微粉の粒径、鉄粉に対するニッケル微粉の添加量、加工条件によって制御することができ、前述したように、ニッケルの厚みは薄い方が好ましいので、100nm以下にするのが好ましい。
<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.
The rotational speed of the mixer agitator (wings in the mixer) is 1500 to 5000 rpm, the rotational speed of the pan is 20 to 150 rpm, and the mixing time is 2 to 15 minutes.
By rotating the agitator and pan, the iron powder and nickel fine powder in the mixer are mixed and stirred while receiving centrifugal force. At this time, nickel is stuck to the iron powder surface by the shear frictional force of the iron powder having a large particle size. It adheres and covers the iron powder surface. 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.
The coating method is preferably a method in which the nickel particles are coated on the surface of the iron powder in a film shape by using the shear frictional force between the iron particles without using a grinding medium. Although it can be coated even if pulverized media is added, the particle size and particle shape of the iron powder change depending on the processing time, so the control becomes complicated.
The thickness of nickel covering the iron powder can be controlled by the particle size of the iron powder or nickel fine powder, the amount of nickel fine powder added to the iron powder, and the processing conditions. As described above, the thickness of nickel should be thinner. Since it is preferable, it is preferable to set it to 100 nm or less.
ニッケル膜厚を100nm以下にするための好ましいニッケル微粉の粒径について説明する。
表２に、ニッケル微粉の粒径と、ニッケル添加量と鉄粒子（鉄粒子径70μm）１個当たりのニッケルの粒子量の関係を示す。
The preferable particle diameter of the nickel fine powder for making the nickel film thickness 100 nm or less will be described.
Table 2 shows the relationship between the particle size of nickel fine powder, the amount of nickel added, and the amount of nickel particles per iron particle (iron particle diameter 70 μm).
表２に示されるように、ニッケル粒径が５μmの場合、ニッケル添加量が0.2重量部では鉄粒子１個当たりのニッケル粒子個数は５個になる。ニッケル膜厚を100nm以下にするには、５個のニッケル粒子についてその粒径５μmの１/５０以下まで圧延して鉄粒子表面上に被覆させる必要がある。しかしながら、70μmの鉄粒子のせん断摩擦力によって粒径５μmのニッケル粒子をその１/５０以下まで圧延するのは難しい。
これに対して、ニッケル粒径が0.2μmの場合、添加量が0.2重量部では鉄粒子１個当たりのニッケル粒子個数は86,000個である。同様に、ニッケル膜厚を100nm以下にするには、86,000個のニッケル粒子についてその粒径0.2μmの１/２以下まで圧延して鉄粒子表面上に被覆させればよい。この場合、70μmの鉄粒子のせん断摩擦力によって粒径0.2μmのニッケル粒子をその１/２以下まで圧延するのは比較的容易である。
よって、ニッケル微粉の粒子径は小さいほど良い。もっとも、現在製造可能な最小のニッケル粒子径は概ね0.1μm以上であるため、ニッケル微粉の粒径としては0.1μm以上であってできるだけ小さい粒径が好ましい。
As shown in Table 2, when the nickel particle size is 5 μm, the number of nickel particles per iron particle is 5 when the amount of nickel added is 0.2 parts by weight. In order to reduce the nickel film thickness to 100 nm or less, it is necessary to roll the five nickel particles to 1/50 or less of the particle size of 5 μm and coat the surface of the iron particles. However, it is difficult to roll 5 μm nickel particles to 1/50 or less due to the shear frictional force of 70 μm iron particles.
On the other hand, when the nickel particle size is 0.2 μm, the number of nickel particles per iron particle is 86,000 when the addition amount is 0.2 parts by weight. Similarly, in order to make the nickel film thickness 100 nm or less, 86,000 nickel particles may be rolled to 1/2 or less of 0.2 μm in particle diameter and coated on the iron particle surface. In this case, it is relatively easy to roll nickel particles having a particle size of 0.2 μm to 1/2 or less of them by the shear frictional force of 70 μm iron particles.
Therefore, the smaller the particle diameter of the nickel fine powder, the better. However, since the smallest nickel particle diameter that can be produced at present is approximately 0.1 μm or more, the particle diameter of the nickel fine powder is preferably 0.1 μm or more and the smallest possible particle diameter.
アイリッヒミキサーを使用し、ニッケル粒子径：0.2μm、ニッケル添加量：0.2重量部、鉄粉平均粒径：100μmを処理するのに、アジテータの回転速度、パンの回転速度がそれぞれ3000rpm、80rpmとした場合、
５分間の処理により、ニッケル表面被覆面積率が５５％、膜厚を100nm以下に制御できる。
なお、ニッケルの添加量を増やす、またニッケル粒子径を大きくした場合には、処理時間の延長により膜厚を100nm以下に制御できる。
Using an Eirich mixer to process nickel particle size: 0.2μm, nickel addition amount: 0.2 parts by weight, iron powder average particle size: 100μm, agitator rotation speed and bread rotation speed are 3000rpm and 80rpm respectively. if you did this,
By the treatment for 5 minutes, the nickel surface coverage area ratio can be controlled to 55% and the film thickness to 100 nm or less.
When the amount of nickel added is increased or the nickel particle diameter is increased, the film thickness can be controlled to 100 nm or less by extending the processing time.
また、圧着工程において鉄粉表面に付着させるニッケルの表面被覆面積比率は30〜95％が好ましい。
表面被覆面積比率の制御は、鉄粉やニッケル微粉の粒径、鉄粉に対するニッケル微粉の添加量、加工条件によって制御することができる。
Moreover, the surface coverage area ratio of nickel to be adhered to the iron powder surface in the crimping step is preferably 30 to 95%.
The surface coverage area ratio can be controlled by the particle size of iron powder or nickel fine powder, the amount of nickel fine powder added to the iron powder, and the processing conditions.
ＣＶＤ法によって製造した0.1〜1μmが90％以上の粒度のニッケル微粉を、鉄粉100重量部に対して0.1〜10重量部添加し、アイリッヒミキサーによって1500〜3000ｒｐｍで２〜１５分混合することによりニッケルの表面被覆面積比率を30〜95％の範囲で制御することができる。
加工時間を長くすれば、またニッケル微粉量を増やせば、さらにニッケル微粉の粒径が細かければ表面被覆面積比率は増加する。
Add 0.1 to 10 parts by weight of nickel fine powder with a particle size of 0.1 to 1 μm of 90% or more manufactured by CVD method to 100 parts by weight of iron powder, and mix for 2 to 15 minutes at 1500 to 3000 rpm with an Eirich mixer. Thus, the nickel surface coating area ratio can be controlled in the range of 30 to 95%.
If the processing time is lengthened and the amount of nickel fine powder is increased, the surface coating area ratio is increased if the particle diameter of the nickel fine powder is further reduced.
例えば、ＣＶＤ法によって製造した平均粒径0.2μｍのニッケル微粉、0.2重量部、3000rpmで10分間混合すると表面被覆面積比率は90％程度となる。
ニッケルによって表面被覆された鉄粉の断面を電子顕微鏡で観察したところ、ニッケルと鉄粉の境界は明確であり、両者は合金化されていないことが確認された。特許文献２の場合には、混合ミルの中に鉄粉とニッケル粉に加えて鋼球等の粉砕メディアを仕込んでいるが、本実施の形態ではこのような粉砕メディアの仕込みがない点で特許文献２の場合とは製造方法及びその製造された物において明確に相違している。
For example, if the nickel fine powder having an average particle diameter of 0.2 μm manufactured by the CVD method is mixed with 0.2 parts by weight at 3000 rpm for 10 minutes, the surface coating area ratio becomes about 90%.
When the cross section of the iron powder surface-coated with nickel was observed with an electron microscope, the boundary between nickel and iron powder was clear, and it was confirmed that the two were not alloyed. In the case of Patent Document 2, grinding media such as steel balls are charged in a mixing mill in addition to iron powder and nickel powder. In this embodiment, there is no patent in that such grinding media is not charged. It is clearly different from the case of Document 2 in the manufacturing method and the manufactured product.
なお、ニッケルの表面被覆面積比率は、鉄粉の断面を、成分分析装置ＥＰＭＡやＥＤＸを取り付けた電子顕微鏡ＳＥＭで測定する。すなわち、鉄粉断面の周長（Ａ）（図１参照）と、外周ニッケル被覆部長（Ｂ）（図１参照）との比、Ｂ／Ａ×１００で求めることができる。なお、１個では不十分なので複数の粒子で同様な分析を行い平均値より表面被覆面積比率を求める。 In addition, the surface coating area ratio of nickel measures the cross section of iron powder with the electron microscope SEM which attached the component analyzer EPMA and EDX. That is, it can be determined by the ratio of the perimeter of the iron powder cross section (A) (see FIG. 1) to the perimeter nickel coating portion length (B) (see FIG. 1), B / A × 100. Since one particle is insufficient, the same analysis is performed with a plurality of particles, and the surface coverage area ratio is obtained from the average value.
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１〜３０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.
Moreover, it can process also with mills, such as a vibration mill and a rotation ball mill, and processing time is less than 1 to 30 minutes.
以上のように本実施の形態の製造方法によれば、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、鉄粉の表面をニッケルで被覆することが簡易な方法で、かつ短時間で実現でき、分解材としての初期の反応性に優れると共に長期に亘ってその効果が持続する分解材を容易に製造できる。
また、本実施の形態では、ＣＶＤ法によって製造したニッケル微粉を用いているので、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が付着しており、HClの存在により分解材としての初期の分解速度に優れる分解材が容易に製造できる。
As described above, according to the manufacturing method of the present embodiment, 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, so the surface of the iron powder is made of nickel. It is possible to easily produce a decomposing material that can be coated in a simple method and in a short time, has excellent initial reactivity as a decomposing material, and maintains its effect over a long period of time.
In this embodiment, since nickel fine powder produced by the CVD method is used, an appropriate amount of HCl adheres to nickel produced in the nickel fine powder production process, and the presence of HCl causes an initial decomposition material. A decomposition material having an excellent decomposition rate can be easily produced.
上記の実施の形態で示した分解材は、鉄粉表面をニッケルで被覆するというものであるが、どのような製造方法によるのが好ましいかを確認するために、（１）ニッケル添加量と反応速度の関係、（２）混合時間と反応速度及び表面被覆面積比率の関係、（３）ニッケル添加量とニッケル溶出量との関係、（４）鉄粉表面をニッケルで被覆した場合と鉄粉表面にニッケルが点在する場合の分解材としての耐久性の比較を調査した。これらの調査結果を以下の実施例１〜４において説明する。 The decomposition material shown in the above embodiment is to coat the iron powder surface with nickel. In order to confirm what kind of manufacturing method is preferable, (1) nickel addition amount and reaction (2) Relationship between mixing time, reaction rate and surface coating area ratio, (3) Relationship between nickel addition amount and nickel elution amount, (4) When iron powder surface is coated with nickel and iron powder surface Comparison of durability as a decomposition material in the case where nickel is scattered in the steel was investigated. These investigation results will be described in Examples 1 to 4 below.
＜ニッケル添加量と反応速度の関係＞
試験方法は以下の通りである。
＜試験方法＞
・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 ：平均粒径：0.2μm[0.05重量部〜90重量部、及びニッケル微粉のみ]
・混合攪拌条件 ：アイリッヒミキサーによって3.000rpm、６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(DCE)、トリクロロエチレン(TCE)、
テトラクロロエチレン(PCE)各10mg/lの模擬地下水を30mLを加え、
空隙を窒素で置換した後ＰＴＦＥ栓で密栓した。
25℃で72時間静置した後、地下水を採取し、GC-MSヘッドスペース法
によって、各有機ハロゲン化合物の濃度を定量した。
<Relationship between nickel addition and reaction rate>
The test method is as follows.
<Test method>
・ Raw iron powder: Finished reduced iron powder [100 parts by weight, average particle size 100 μm]
Nickel fine powder: Average particle size: 0.2 μm [0.05 to 90 parts by weight, and nickel fine powder only]
-Mixing and stirring conditions: Mixing and disassembling test method: 3.000 rpm, 6 minutes by Eirich mixer: 1.5 g of cleaning agent is put in a 50 mL vial,
Cis-1,2-dichloroethylene (DCE), trichlorethylene (TCE),
Add 30 mL of simulated groundwater of 10 mg / l each of tetrachlorethylene (PCE),
The space was replaced with nitrogen and then sealed with a PTFE stopper.
After standing at 25 ° C for 72 hours, groundwater is collected and the GC-MS headspace method is used.
Was used to quantify the concentration of each organic halogen compound.
試験結果を表３及び図２に示す。図２においては、縦軸が見かけ反応速度［1/hr］で、横軸がニッケル（Ni）添加量（重量部）である。なお、横軸については、鉄粉を用いることなくニッケル微粉のみの場合も示している。 The test results are shown in Table 3 and FIG. In FIG. 2, the vertical axis represents the apparent reaction rate [1 / hr], and the horizontal axis represents the amount of nickel (Ni) added (parts by weight). In addition, about the horizontal axis, the case where only nickel fine powder is shown, without using iron powder is also shown.
表３、図２のグラフに示されるように、ニッケルの添加量が増えるに従って反応速度は大きくなり、特に添加量が0.1重量部以上で反応速度が大きくなる。
しかし、ニッケルの添加量が10重量部を超えると反応速度は鈍る。これは、ニッケルの添加量が増えることで鉄粉表面を覆うニッケルの量が増え、10重量部を越えると鉄粉の露出が極端に小さくなるためと推察される。
この試験結果から、ニッケルの添加量としては、0.1重量部〜10重量部が好ましい。
As shown in the graphs of Table 3 and FIG. 2, the reaction rate increases as the addition amount of nickel increases, and the reaction rate increases particularly when the addition amount is 0.1 parts by weight or more.
However, the reaction rate decreases when the amount of nickel added exceeds 10 parts by weight. This is presumably because the amount of nickel covering the surface of the iron powder increases as the amount of nickel added increases, and when the amount exceeds 10 parts by weight, the exposure of the iron powder becomes extremely small.
From this test result, the amount of nickel added is preferably 0.1 to 10 parts by weight.
なお、表３、図２から分かるように、ニッケル100％であっても有機ハロゲン化合物を分解することができる。これはNi-Feの局所電池反応による分解ではなく、ニッケル自身がオレフィンの水素化触媒機能を有するためで 、ニッケル表面で水素分子が活性な水素原子となり、この水素原子が塩素化エチレンの塩素と置換すると同時に水素化によりオレフィンの2重結合が単結合（パラフィン）となり、すなわちエタンなどの飽和炭化水素へと分解するものと推察される。
このことから、鉄粉表面にニッケルを広い範囲で被覆することでNi-Feの局所電池反応とニッケルの水素化触媒反応の両反応が進行すると考えられ、これによって高い反応速度が得られることが確認された。
As can be seen from Table 3 and FIG. 2, the organohalogen compound can be decomposed even when nickel is 100%. This is not the decomposition of Ni-Fe due to local cell reaction, but nickel itself has a function of hydrogenating olefins, so that hydrogen molecules become active hydrogen atoms on the nickel surface. It is presumed that the double bond of olefin becomes a single bond (paraffin) by hydrogenation at the same time as the substitution, that is, decomposes into a saturated hydrocarbon such as ethane.
From this, it is considered that both the local battery reaction of Ni-Fe and the hydrogenation catalytic reaction of nickel proceed by coating nickel on the iron powder surface in a wide range, and this can provide a high reaction rate. confirmed.
＜混合時間と反応速度及び表面被覆面積比率の関係＞
試験方法は以下の通りである。
・原料鉄粉 ：仕上げ還元鉄粉［100重量部、平均粒径100μm］
・金属ニッケル ：0.2重量部 ニッケル微粉［平均粒径：0.2μm］、
ニッケル試薬:10μm
・混合攪拌条件 ：アイリッヒミキサーによって3.000rpm、1分〜30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(DCE)、トリクロロエチレン(TCE)
各10mg/lの模擬地下水を30mLを加え、空隙を窒素で置換した後
ＰＴＦＥ栓で密栓した。
25℃で72時間静置した後、地下水を採取し、GC-MSヘッドスペース法
によって、各有機ハロゲン化合物の濃度を定量した。
・表面被覆面積比率の測定法： ２０粒の鉄粉粒子を樹脂加工し、研磨機により鉄粉断
面を出した。この断面をＥＰＭＡにより鉄とニッケルの
面分析を行い、上記、鉄粉断面の周長(A)(図１参照)
と、外周ニッケル被覆部長（Ｂ）（図１参照）との比、
Ｂ／Ａ×１００より計算した。
<Relationship between mixing time, reaction rate, and surface coating area ratio>
The test method is as follows.
・ Raw iron powder: Finished reduced iron powder [100 parts by weight, average particle size 100 μm]
-Metallic nickel: 0.2 parts by weight Nickel fine powder [average particle size: 0.2 μm]
Nickel reagent: 10 μm
-Mixing and stirring conditions: 3.000 rpm by Eirich mixer, mixing for 1 to 30 minutes-Decomposition test method: Put 1.5 g of the cleaning agent into a 50 mL vial,
Cis-1,2-dichloroethylene (DCE), trichlorethylene (TCE)
After adding 30 mL each of 10 mg / l simulated groundwater and replacing the voids with nitrogen
Sealed with a PTFE stopper.
After standing at 25 ° C for 72 hours, groundwater is collected and the GC-MS headspace method is used.
Was used to quantify the concentration of each organic halogen compound.
・ Surface coating area ratio measurement method: Resin processing of 20 iron powder particles and cutting iron powder with a polishing machine
I put a face. This cross section is made of iron and nickel by EPMA.
A surface analysis is performed and the perimeter of the iron powder cross section (A) (see Fig. 1)
And the ratio of the outer peripheral nickel coating part length (B) (see FIG. 1),
Calculated from B / A × 100.
試験結果を表４及び図３に示す。図３においては、縦軸が見かけ反応速度［1/hr］で、横軸が混合時間（min）を示している。なお、表４には反応速度に加え、表面被覆面積比率も記載した。 The test results are shown in Table 4 and FIG. In FIG. 3, the vertical axis represents the apparent reaction rate [1 / hr], and the horizontal axis represents the mixing time (min). In Table 4, in addition to the reaction rate, the surface coverage area ratio is also shown.
表４、図３のグラフに示されるように、0.2μmのニッケル微粉を用いた場合、混合時間が長くなることで反応速度は向上している。これは、混合時間が長くなると鉄粉表面へのニッケル被覆率が高くなるためであり、ニッケル被覆率が高くなれば前記、Ni-Fe局所電池＋水素化触媒反応の効率が上がるためであると推察される。
また、混合時間が10分を超えると反応速度はそれ以上を向上していないことから、10分程度の混合時間でニッケルによる被覆が好適な状態になることが窺える。
他方、10μmのニッケル試薬ではアイリッヒミキサーで30分間混合しても反応速度は向上していない。これは、鉄粉表面にニッケルが被覆されず、また粒径の大きなニッケルは比表面積が小さいため同一添加量での水素化触媒反応の効率が悪いためであると推察される。
As shown in the graphs of Table 4 and FIG. 3, when 0.2 μm fine nickel powder is used, the reaction rate is improved by increasing the mixing time. This is because the nickel coverage on the iron powder surface increases as the mixing time increases, and the efficiency of the Ni-Fe local battery + hydrogenation catalyst reaction increases as the nickel coverage increases. Inferred.
In addition, when the mixing time exceeds 10 minutes, the reaction rate does not improve any further, so that it is possible that the coating with nickel becomes suitable in a mixing time of about 10 minutes.
On the other hand, with a 10 μm nickel reagent, the reaction rate does not improve even when mixed for 30 minutes with an Eirich mixer. This is presumably because nickel is not coated on the iron powder surface, and nickel having a large particle size has a small specific surface area, so that the efficiency of the hydrogenation catalyst reaction with the same addition amount is poor.
混合時間とニッケル被覆の状態を確認するため、混合時間4分と10分のものについてEPMA（Electron
Probe Micro Analyzer）による断面のニッケル濃度分布と、表面のSEM像を確認した。図４が混合時間４分のもので、図４（ａ）がEPMAで図４（ｂ）がSEM像である。また、図５が混合時間10分のもので、図５（ａ）がEPMAで図５（ｂ）がSEM像である。
図４（ａ）の粒子が鉄粉を示し、鉄粉の周囲の写真において色が薄くなった部分がニッケルである。図４（ａ）から分かるように、混合時間４分であっても、ある程度のニッケル被覆が行われている。しかし、鉄粉の凹部は鉄粉同士によるせん断摩擦が生じないためニッケルはコーティングされていない。
また、図４（ｂ）から分かるように、混合時間4分では一部のニッケル粒子が被覆コーティングされずに鉄粉表面に点在しているが、大部分は鉄粉表面に被覆コーティングされている。
In order to check the mixing time and the condition of nickel coating, EPMA (Electron
The cross-section nickel concentration distribution and surface SEM image were confirmed by Probe Micro Analyzer. FIG. 4 shows a mixing time of 4 minutes, FIG. 4 (a) is EPMA, and FIG. 4 (b) is an SEM image. FIG. 5 shows a mixing time of 10 minutes, FIG. 5 (a) is an EPMA, and FIG. 5 (b) is an SEM image.
The particle | grains of Fig.4 (a) show iron powder, and the part where the color became thin in the photograph around iron powder is nickel. As can be seen from FIG. 4A, a certain amount of nickel coating is performed even when the mixing time is 4 minutes. However, the concave portion of the iron powder is not coated with nickel because shear friction between the iron powders does not occur.
In addition, as can be seen from FIG. 4 (b), some nickel particles are scattered on the surface of the iron powder without being coated in the mixing time of 4 minutes, but most are coated on the surface of the iron powder. Yes.
図５（ａ）から分かるように、混合時間10分では、被覆率90％程度のニッケル被覆が行われている。
また、図５（ｂ）から分かるように、点在するニッケル粒子はなく、全てのニッケル粒子が鉄粉表面の被覆に供されている。
As can be seen from FIG. 5 (a), nickel coating with a coverage of about 90% is performed at a mixing time of 10 minutes.
Further, as can be seen from FIG. 5B, there are no scattered nickel particles, and all the nickel particles are used for coating the iron powder surface.
＜ニッケル添加量とニッケル溶出量の関係＞
試験方法は以下の通りである。
・試料 実施例１で調整したバイアル瓶より72時間静置した後の液相中のニッケル溶解量
を測定した。
・サンプリング方法：バイアル瓶より0.45μmのメンブランフィルターでろ過した地下水
を測定に用いた。
・測定方法：ICP-MS（誘導結合プラズマ質量分析計）により地下水中のニッケル含有量
を定量した。
試験結果を表５及び図６に示す。図６においては、縦軸がニッケル溶出量［mg/L］で、横軸が水素還元鉄粉100重量部に対するニッケル添加量［重量部］を示している。
<Relationship between nickel addition and nickel elution>
The test method is as follows.
Sample The amount of nickel dissolved in the liquid phase after standing for 72 hours from the vial prepared in Example 1 was measured.
・ Sampling method: Groundwater filtered through 0.45μm membrane filter from vial
Was used for the measurement.
・ Measurement method: Nickel content in groundwater by ICP-MS (Inductively Coupled Plasma Mass Spectrometer)
Was quantified.
The test results are shown in Table 5 and FIG. In FIG. 6, the vertical axis represents the nickel elution amount [mg / L], and the horizontal axis represents the nickel addition amount [parts by weight] with respect to 100 parts by weight of the hydrogen-reduced iron powder.
表５、図６から分かるように、ニッケル添加量1重量部までは分解反応速度はほとんど変わらないが、ニッケル添加量が1重量部を超えるとニッケルの溶出量が指数関数的に増大する。ニッケルの溶出は環境上好ましくないので、この意味からは添加量は１重量部以下とするのが好ましい。
また、ニッケルは鉄粉に比べて高価であるため、反応速度が高く保たれる範囲内ではできるだけ少量の方が良い。この点、実施例１に示されるように、ニッケル添加量は1重量部〜10重量部の範囲では大きな差異がないので、環境面やコスト面を考慮するとニッケル添加量は1重量部以下にするのが好ましい。
As can be seen from Table 5 and FIG. 6, the decomposition reaction rate hardly changes up to 1 part by weight of nickel, but when the amount of nickel added exceeds 1 part by weight, the elution amount of nickel increases exponentially. Since elution of nickel is unfavorable for the environment, the amount added is preferably 1 part by weight or less in this sense.
Also, since nickel is more expensive than iron powder, it is better to use as little amount as possible within a range where the reaction rate is kept high. In this respect, as shown in Example 1, since the nickel addition amount is not significantly different in the range of 1 to 10 parts by weight, the nickel addition amount should be 1 part by weight or less in consideration of environmental and cost aspects. Is preferred.
＜ニッケルの被覆と点在の耐久性の比較＞
［試料調整方法］
・ニッケル被覆鉄粉：金属ニッケル微粉（0.2μm）を鉄粉に0.2重量部添加し、
アイリッヒミキサーで10分間混合。
鉄粉表面のほぼ全面がニッケルでコーティングされる。
・ニッケル点在鉄粉：金属ニッケル微粉（0.2μm）を鉄粉に0.2重量部添加し、
アイリッヒミキサーで１分間混合。
鉄粉表面にニッケル粒子が点在し、完全には被覆されていない。
［試験方法］
上記鉄粉1.5ｇを50mlバイアル瓶に入れ、10mg/LのDCE汚染地下水を30ml添加し、空隙を窒素置換した後、PTFE栓で密栓して20℃で静置した。7日後に地下水を捨て、再度、10mg/LのDCE汚染地下水を30ml添加し、空隙を窒素置換した後、PTFE栓で密栓して20℃で静置した。そして、72時間後に地下水の一部を採取して、GC-MSでDCEを定量した。
同様に31日、93日静置したバイアル瓶の地下水を捨て、再度、10mg/LのDCE汚染地下水を30ml添加し、空隙を窒素置換した後、PTFE栓で密栓して20℃で静置した。72時間後に地下水の一部を採取してGC-MSでDCEを定量した。
<Comparison of nickel coating and dotted durability>
[Sample preparation method]
・ Nickel coated iron powder: Add 0.2 parts by weight of nickel metal fine powder (0.2μm) to iron powder,
Mix for 10 minutes with an Eirich mixer.
Almost the entire surface of the iron powder is coated with nickel.
-Nickel interspersed iron powder: Add 0.2 parts by weight of metallic nickel fine powder (0.2μm) to iron powder,
Mix for 1 minute with an Eirich mixer.
Nickel particles are scattered on the surface of the iron powder and are not completely covered.
[Test method]
The iron powder 1.5 g was put into a 50 ml vial, 30 ml of 10 mg / L DCE-contaminated groundwater was added, and the space was replaced with nitrogen, and then sealed with a PTFE stopper and allowed to stand at 20 ° C. Seven days later, the groundwater was discarded, and 30 ml of 10 mg / L DCE-contaminated groundwater was added again, and the air gap was replaced with nitrogen, and then sealed with a PTFE stopper and allowed to stand at 20 ° C. Then, 72 hours later, a part of groundwater was collected and DCE was quantified by GC-MS.
Similarly, the groundwater in the vials that were allowed to stand on the 31st and 93rd was discarded, and 30 ml of 10 mg / L DCE-contaminated groundwater was added again, and the air gap was replaced with nitrogen. . A portion of groundwater was collected after 72 hours and DCE was quantified by GC-MS.
実験結果を表６及び図７に示す。図７において、縦軸は反応速度（1/hr）を示している。 The experimental results are shown in Table 6 and FIG. In FIG. 7, the vertical axis indicates the reaction rate (1 / hr).
表６、図７から分かるように、ニッケルで被覆した鉄粉は日数が増しても反応速度はほとんど低下していない。これに対して、ニッケルが点在する鉄粉は、日数が増すと極端に反応速度が低下している。このような違いは以下のような現象であると推察される。
鉄粉にニッケルを付着させることでNi-Feの局所電池反応により鉄が腐食する。ニッケルが点在する鉄粉の場合、ニッケル粒子の周囲の鉄の腐食が進行するとニッケル粒子が鉄から剥離し、局所電池反応の効果が得られなくなる。このため、腐食が進行するにしたがって反応速度が極端に低下している。これに対して、鉄粉をニッケルで被覆した場合は、ニッケルが鉄粉を包み込んでいるため、鉄粉の腐食が進行してもニッケルが鉄粉から分離してしまうことはなく、局所電池反応の効果が持続する。
また、ニッケルが点在する場合は、被覆の場合に比べて比表面積が小さいため水素化触媒効果も少なくなるため、この点でも被覆の場合に比較して反応速度が遅い要因である。
As can be seen from Table 6 and FIG. 7, the reaction rate of the iron powder coated with nickel hardly decreases even when the number of days increases. On the other hand, the reaction speed of the iron powder interspersed with nickel is extremely reduced as the number of days increases. Such a difference is assumed to be the following phenomenon.
By attaching nickel to the iron powder, iron corrodes due to the local battery reaction of Ni-Fe. In the case of iron powder interspersed with nickel, when corrosion of iron around the nickel particles proceeds, the nickel particles peel from the iron, and the effect of the local battery reaction cannot be obtained. For this reason, the reaction rate is extremely reduced as corrosion progresses. On the other hand, when iron powder is coated with nickel, nickel wraps the iron powder, so even if the corrosion of the iron powder proceeds, the nickel does not separate from the iron powder, and the local battery reaction The effect of lasts.
Further, when nickel is scattered, the hydrogenation catalyst effect is reduced because the specific surface area is smaller than that in the case of coating, so that the reaction rate is also slow in this respect as compared with the case of coating.
実施例４の比較試験によって鉄粉の表面を被覆する本発明に係る有機ハロゲン化合物の分解材が、特許文献１に記載された鉄粉表面にニッケルを点在させるものに比較して分解材として長期に亘って効果が持続することが実証された。 The decomposition material of the organohalogen compound according to the present invention that coats the surface of the iron powder by the comparative test of Example 4 is a decomposition material as compared with the material in which nickel is scattered on the iron powder surface described in Patent Document 1. It has been demonstrated that the effect lasts for a long time.
１ 分解材
３ 鉄粉
５ ニッケル
1 Decomposition material 3 Iron powder 5 Nickel
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| JP2003339902A (en) * | 2002-05-29 | 2003-12-02 | Dowa Mining Co Ltd | Decomposing agent for organic halogen compound and method for manufacturing the same |
| JP2005034696A (en) * | 2003-07-16 | 2005-02-10 | Tosoh Corp | Treatment method for making object to be treated contaminated by organic halogen compound harmless |
| JP2007301548A (en) * | 2007-02-16 | 2007-11-22 | Dowa Holdings Co Ltd | Metal powder for decomposing organic halogen compound and method for cleaning soil using the same |
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| JP2005034696A (en) * | 2003-07-16 | 2005-02-10 | Tosoh Corp | Treatment method for making object to be treated contaminated by organic halogen compound harmless |
| JP2007301548A (en) * | 2007-02-16 | 2007-11-22 | Dowa Holdings Co Ltd | Metal powder for decomposing organic halogen compound and method for cleaning soil using the same |
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