JP4110259B2 - Manufacturing method of copper-containing iron powder - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は，銅含有鉄粉の製法に係り，特に有機ハロゲン化合物の分解剤として好適な銅含有鉄粉の製法に関する。
【０００２】
【従来の技術】
トリクロロエチレン等の有機ハロゲン化合物で汚染された土壌や地下水を浄化する技術開発が進んでいるが，その基本は，分解能が高く且つ無害の有機ハロゲン化合物分解剤を使用することにある。その代表的な分解剤の例として鉄粉がある。例えば同一出願人に係る特開平１１−２３５５７７号公報において，トリクロロエチレン等の有機塩素系化合物で汚染された土壌に対して比表面積が５００ｃｍ2／ｇ以上でＣ（炭素）を０.１重量％以上含有する鉄粉を混合すると，該土壌中のトリクロロエチレンなどを効果的に分解できると教示している。
【０００３】
同じく同一出願人に係る特開２０００−５４７０号公報には有機塩素化合物で汚染された土壌または地下水に銅含有鉄粉を添加混合すると有機塩素化合物を効率良く分解できると記載されており，銅を含有する鉄粉は銅を含有しない鉄粉よりも，有機塩素系化合物の分解速度が速くなることが明らかとなった。この銅含有鉄粉についてさらに研究を進め，特願２０００−２５７７９６号では，銅含有鉄粉中の銅の含有形態を改善することにより，一層効率よく有機ハロゲン化合物が分解できることを開示した。
【０００４】
【発明が解決しようとする課題】
本発明の課題は，特願２０００−２５７７９６号に提案した銅含有鉄粉からなる有機ハロゲン化合物分解剤を有利に製造しようとする点にある。
【０００５】
【課題を解決するための手段】
本発明によれば，鉄粉に銅含有粉を混合し，この混合物に酸を添加し，ついで液分を分離することからなる銅含有鉄粉の製法を提供する。より具体的には，５０重量％が１５０μｍのふるいを通過する粒度を有する海綿状鉄粉と，平均粒径が１０μｍ以下の銅含有粉とを混合し，次いで酸を添加して攪拌し，液分を分離することからなる有機ハロゲン化合物分解用の銅含有鉄粉の製法を提供する。ここで，銅含有粉は，酸化銅粉，塩化銅粉，硝酸銅粉，硫化銅粉，塩化アンモニウム銅粉またはこれらの水和物から選ばれる少なくとも１種であることができ，銅含有鉄粉中の銅含有量は０.０１〜２０重量％であるのが好ましい。
【０００６】
この製法によって，鉄を主成分とする海面状粒子の表層部に銅が部分的に分布し，鉄と銅の両者が表面に顕れている粒子からなる有機ハロゲン化合物分解剤を得ることができる。この分解剤は，多孔質な鉄粒子の表面に銅が部分的に存在し，鉄と銅が同時に表面に顕れているので，水の存在下で，有機ハロゲン化合物の分解反応が効率よく進行する。
【０００７】
【発明の実施の形態】
本発明の銅含有鉄粉の製法は，要するところ，鉄粉と銅含有粉とを，該鉄粉粒子表面近傍に銅含有粉が均一に存在するように機械的に混合する工程（換言すれば鉄粉の粒子表面に銅含有粉を付着させるか鉄粉の粒子表面近傍に銅含有粉を配置する工程）と，次いで，酸を添加して銅含有粉を金属銅として鉄粉表面に析出させる工程と，必要に応じて液分を分離する工程とからなる。
【０００８】
使用する鉄粉としては，特開平１１−２３５５７７号公報に記載されているのと同様の鉄粉を用いるのがよい。すなわち，５０重量％が１５０μｍのふるいを通過する粒度を有し且つ比表面積が５００ｃｍ2／ｇ以上である海綿状の鉄粉を使用することができる。このような鉄粉としては，同和鉄粉工業株式会社製の商品名Ｅ−２００が挙げられる。
【０００９】
鉄粉の粒子表面に銅を接合する方法として，本発明では銅含有粉を原料として使用し，このものを該鉄粉の表面に先ず機械的に付着させてから，酸を添加して化学的に接合させる。銅原料としての銅含有粉は，平均粒径が１０μｍ以下の酸化銅粉（酸化第一銅または酸化第二銅）または塩化銅粉が好適であり，さらに硝酸銅粉，硫化銅粉，塩化アンモニウム銅粉もしくはそれらの水和物等であって常温で固体のものが好ましい。
【００１０】
鉄粉の粒子表面に銅含有粉を機械的に付着させるには，各種の攪拌機（ミキサー）等を用いて鉄粉と銅含有粉とを機械的に混合するのが便利である。とくに，攪拌軌跡がサイクロイド曲線を描くような攪拌機を用いるのがよい。サイクロイド曲線をもつ攪拌は，例えば公転するインペラーを用いた攪拌によって実現できる。たのような機械的混合によって，鉄粉に銅含有粉を均一に混ぜ合わせると共に，銅含有粉の薄い皮膜を鉄粉の各粒子の表面に付着させるか，もしくは各鉄粒子の近傍に銅含有粉を配置させる。このためには，銅含有粉が微粉であればあるほど好都合であり，海綿状鉄粒子にその微粉が付着または配置されやすくなり且つ酸に溶けやすくなる。銅含有粉の配合量としては，最終の銅含有鉄粉における鉄に対しての銅の重量割合で銅含有量が０.０１〜２０重量％の範囲となるようにすればよい。
【００１１】
機械的攪拌によって，鉄粒子の表面に銅含有粉が付着した複合粉が得られたら，この複合粉に酸を添加して掻き混ぜる。酸の添加は，機械的混合に用いた攪拌機内で行ってもよいが，別の攪拌機内に該複合粉を移行させて，酸の添加と掻き混ぜを行ってもよい。実際には，加熱手段付の攪拌機内で酸の添加と掻き混ぜを行うのが，後の液分の分離のためには都合がよい。酸としては，用いる銅含有粉の溶解度が高いものが好ましいが，工業的には硫酸を使用するのが適当である。酸の濃度は特に限定されないが，０.２〜３０％の水溶液を使用するのがよい。
【００１２】
鉄粒子表面に銅含有粉が付着した複合粉に酸を添加すると，銅含有粉が溶解すると同時に銅が鉄粉表面に析出して，鉄粒子表面に銅が接合した銅含有鉄粉になる。特に海綿状鉄粒子に銅含有粉が付着した複合粉の場合には，酸の添加によって，海綿状鉄粒子の所々に銅が析出した銅含有鉄粉が得られる。残存する液分は加熱蒸発や真空蒸発などの乾燥処理を行うことにより除去できる。とくに鉄と銅の両者が粒子表面に露出している銅被着鉄粉は，有機ハロゲン化合物の分解能力が非常に高い。すなわち，非常に大きな表面積をもつ鉄粒子の表面に銅が部分的に存在することにより鉄と銅の両者が表面に顕れていると，有機ハロゲン化合物の分解を著しく促進することができる。
【００１３】
本発明によって得られる銅含有鉄粉は，有機ハロゲン化合物の分解用として使用される場合には，その粒子の形状構造的な特徴として，粒内に貫通孔を有した，好ましくは比表面積３００ｃｍ2／ｇ以上を示すポーラスな粒子であること，そして，その大きさも５０重量％が１５０μｍのふるいを通過するようなものであること，さらには組成的な特徴として，鉄を主成分とする粒子の表層部に銅が部分的に存在し且つ鉄と銅の両者が表面に顕れている粒子からなること，そして銅含有量は好ましくは０.０１〜２０重量％であること，が望ましい。
【００１４】
この場合，粒子の表面に顕れている鉄と銅は，両者または一方が金属である場合が理想的であるが，必ずしも金属鉄と金属銅である必要はなく，鉄の酸化物，銅の酸化物の層が存在していても，有機ハロゲン化合物の分解反応は十分に速く進行する。その理由については必ずしも明らかではないが，金属鉄，第一鉄イオン，金属銅および第一銅イオンなどの標準電極電位が互いに相違することにより，この粒子が水と接触したときに，粒子の表面では幾種類もの局部電池や酸化還元反応が生成してイオン・電子の移動が生じ，このことが鉄粉による有機ハロゲン化合物の分解機能（脱ハロゲン反応や脱ハロゲン化水素置換反応）を助成するのではないかと考えられる。
【００１５】
鉄中の銅含有量は０.０１〜２０重量％であればよく，銅含有量が０.０１重量％未満では銅存在の効果が殆んど現れず，逆に２０重量％を超えると，鉄量が相対的に低くなり，鉄が表面に存在する割合も低下して好ましくない。代表的な鉄中の銅含有量は０.０１〜８重量％，好ましくは０.０５〜５重量％，さらに好ましくは０.０５〜３重量％である。銅を含有する鉄粒子は０.１重量％以上５重量％以下の炭素を含有していることが好ましい。
【００１６】
本発明に従って製造した銅含有鉄粉は，各種の有機ハロゲン化合物の分解に適する。例えばジクロロメタン，四塩化炭素，1,2-ジクロロエタン, 1,1-ジクロロエチレン, シス-1,2-ジクロロエチレン, 1,1,1-トリクロロエタン, 1,1,2-トリクロロエタン, トリクロロエチレン, テトラクロロエチレン, 1,3-ジクロロプロペン，トランス-1,2-ジクロロエチレン, トリハロメタン，ＰＣＢ，ダイオキシンを分解することができる。
【００１７】
したがって，このような有機ハロゲン化合物で汚染された地下水を対象として，本発明に従う銅含有鉄粉からなる分解剤で浄化処理を行う場合には，浄化処理のための反応壁を地中に造成，この地中反応壁に本発明に従う分解剤を装填するのがよい。地中に造成する反応壁は地下水が銅含有鉄粉と接することができるように設置するが，それには，汚染を受けている土壌深部の地下水の易透過層をカバーするように，そして易透過層下方に位置する難透過層にまで反応壁下縁が達するか，または埋設されるように該反応壁を地中に設置するのがよく，また，反応壁の透水係数が近隣の土質と比較して同じレベルか，若しくはそれより高くなるように透水性の良好な反応壁に構成するのが好ましい。このため，例えば透水性の砂質材料等を母材とし，この母材中に銅含有鉄粉を０.１〜３０重量％程度の範囲で分散させた反応壁を地中に造成するのがよい。
【００１８】
反応壁の造成は，連続した壁体とすることもできるが，柱状のものを複数本連接させたり，間隔を開けて（例えば平面的に見たときに円柱状の反応層を千鳥状に配置する）たて込むなどの処法でもよく，このような柱状の埋設物の施設はボーリングマシーン等を利用して行うことができる。いずれにしても，本発明に従う銅含有鉄粉を使用する場合は，単に鉄粉を使用する場合に比べると，分解反応効率が格段に良好であるので，反応壁の厚み等の規模は半減若しくはそれ以下としても同等の効果をあげることができる。
【００１９】
このような反応壁を造成することのほか，従来の鉄粉を使用する方法と同じような手段により，有機ハロゲン化合物で汚染された土壌や地下水を浄化することができる。例えば，掘削後の土壌に対し，土壌改良機やバックホーなどの重機を用いて，本発明に従う銅含有鉄粉を混合する方法や，汚染されたサイト付近に本発明の銅含有鉄粉を配置し，この分解剤表面に汚染土壌や地下水を拡散濃縮させる方法などが有利に採用できる。
【００２０】
【実施例】
〔実施例１〕
比表面積がほぼ２００００ｃｍ2／ｇ，炭素含有量が０.２重量％の鉄粉であって，その５０重量％以上が１５０μｍのふるいを通過する粒度を有する鉄粉（同和鉄粉工業株式会社製の商品名Ｅ−２００）１００ｇと，酸化銅粉（日興ファインケミカルズ株式会社製のＣｕＯ粉）１.２７ｇ（Ｃｕ 0.8ｇに相当）を，容量３００ミリリットルのサンプルミキサー（イカリ状のインペラーを有するもの）に装填した。
【００２１】
両者を装填したあと１分間の攪拌を行った時点で，攪拌を続けながら，１モル／リットルの硫酸５ミリリットルを該ミキサーに添加し，２０秒間攪拌を続けた。その後，ミキサーから内容物を取出し，乾燥炉で１０５℃に保持して液分を蒸発分離した。
【００２２】
得られた粉体０.５ｇをイオン交換水５０ミリリットルと共に，容量１００ミリリットルのパイアル瓶に入れ，フッ素樹脂（登録商標テフロン）コーテングを施したブチルゴムのセプタムとアルミキャップで密封した。この密封瓶を３セット用意した。
【００２３】
次いで，各々の密封瓶内に，ジクロロメタン（ＤＣＭ），シス−ジクロロエチレン（cis-ＤＣＥ) ，パークロロエチレン (ＰＣＥ）を，それぞれ１μリットルづつ，マイクロシリンジを用いて注入し，試験期間１５日まで，各有機ハロゲン化合物の濃度を経日的に追跡し，分解速度定数と半減期を求めた。それらの結果を表１に示した。
【００２４】
【表１】
〔実施例２〕
酸化銅粉に代えて，塩化銅粉（ＣｕＣｌ2２Ｈ2Ｏ）を２.７５ｇ（Ｃｕ 0.8ｇに相当) を使用した以外は，実施例１を繰り返した。有機ハロゲン化合物としてシス−ジクロロエチレン（cis-ＤＣＥ) を用いて，実施例１と同様の試験を行った。その結果を表２に示した。
【００２６】
【表２】
〔実施例３〕
本例は，実施例１の試験を実操業規模にスケールアップしたものである。すなわち，比表面積がほぼ２００００ｃｍ2／ｇ，炭素含有量が０.２重量％の鉄粉であって，その５０重量％以上が１５０μｍのふるいを通過する粒度を有する鉄粉（同和鉄粉工業株式会社製の商品名Ｅ−２００）８００Ｋｇと，平均粒径７μｍの酸化銅粉１０Ｋｇを，有効攪拌容積が４００リットルの万能混合攪拌機に装填し，インペラーを公転させながらインペラーを回転させてサイクロイド曲線の攪拌軌跡が発生するようにして，３０分攪拌を行った。ついで，攪拌を続けながら，１モル／リットルの硫酸４０Ｋｇを該攪拌機内に添加し，３０分間攪拌を続けた。その後，攪拌機内の材料温度が１０５℃となるように保って攪拌を続け，液分を機外に排出した。
【００２８】
得られた粉体について，実施例１と同様にしてシス−ジクロロエチレン（cis-ＤＣＥ) ，パークロロエチレン (ＰＣＥ）の分解試験を行った。その結果を表３に示した。
【００２９】
【表３】
【発明の効果】
以上説明したように，本発明によると，有機ハロゲン化合物を効率よく分解できる銅含有鉄粉を経済的に且つ操業性よく製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing copper-containing iron powder, and more particularly to a method for producing copper-containing iron powder suitable as a decomposition agent for organic halogen compounds.
[0002]
[Prior art]
Technological development to purify soil and groundwater contaminated with organic halogen compounds such as trichlorethylene is progressing, but the basis is to use a high-resolution and harmless organic halogen compound decomposing agent. A typical example of the decomposition agent is iron powder. For example, in Japanese Patent Application Laid-Open No. 11-235577 related to the same applicant, the specific surface area is 500 cm 2 / g or more and C (carbon) is 0.1 wt% or more with respect to soil contaminated with an organic chlorine-based compound such as trichlorethylene. It teaches that trichloroethylene and the like in the soil can be effectively decomposed by mixing the contained iron powder.
[0003]
Similarly, Japanese Patent Laid-Open No. 2000-5470 related to the same applicant describes that an organic chlorine compound can be efficiently decomposed by adding and mixing copper-containing iron powder to soil or groundwater contaminated with an organic chlorine compound. It became clear that the iron powder contained contained the organochlorine compounds at a faster decomposition rate than the iron powder containing no copper. Further research has been conducted on this copper-containing iron powder, and Japanese Patent Application No. 2000-257796 discloses that an organic halogen compound can be decomposed more efficiently by improving the copper content in the copper-containing iron powder.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to advantageously produce an organic halogen compound decomposing agent comprising a copper-containing iron powder proposed in Japanese Patent Application No. 2000-257796.
[0005]
[Means for Solving the Problems]
According to the present invention, there is provided a method for producing copper-containing iron powder comprising mixing copper-containing powder with iron powder, adding an acid to the mixture, and then separating the liquid. More specifically, 50% by weight of a sponge iron powder having a particle size passing through a 150 μm sieve and a copper-containing powder having an average particle size of 10 μm or less are mixed, and then an acid is added and stirred. Provided is a method for producing a copper-containing iron powder for decomposing an organic halogen compound, comprising separating a fraction. Here, the copper-containing powder may be at least one selected from copper oxide powder, copper chloride powder, copper nitrate powder, copper sulfide powder, ammonium chloride copper powder or hydrates thereof, and copper-containing iron powder The copper content is preferably 0.01 to 20% by weight.
[0006]
By this production method, it is possible to obtain an organohalogen compound decomposing agent composed of particles in which copper is partially distributed in the surface layer portion of sea surface particles mainly composed of iron and both iron and copper appear on the surface. In this decomposition agent, copper is partially present on the surface of the porous iron particles, and iron and copper appear on the surface at the same time, so the decomposition reaction of the organic halogen compound proceeds efficiently in the presence of water. .
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The method for producing the copper-containing iron powder of the present invention is, as necessary, a step of mechanically mixing the iron powder and the copper-containing powder so that the copper-containing powder is uniformly present in the vicinity of the surface of the iron powder particles (in other words, A step of attaching copper-containing powder to the surface of the iron powder particle or placing the copper-containing powder near the surface of the iron powder particle), and then adding an acid to deposit the copper-containing powder as metallic copper on the iron powder surface It consists of a process and the process of isolate | separating a liquid component as needed.
[0008]
As the iron powder to be used, it is preferable to use the same iron powder as described in JP-A-11-235577. That is, a spongy iron powder having a particle size of 50% by weight passing through a 150 μm sieve and a specific surface area of 500 cm 2 / g or more can be used. Examples of such iron powder include trade name E-200 manufactured by Dowa Iron Powder Industry Co., Ltd.
[0009]
As a method for bonding copper to the surface of iron powder particles, the present invention uses copper-containing powder as a raw material, which is first mechanically adhered to the surface of the iron powder, and then added with an acid. To be joined. The copper-containing powder as the copper raw material is preferably copper oxide powder (cuprous oxide or cupric oxide) or copper chloride powder having an average particle size of 10 μm or less, and copper nitrate powder, copper sulfide powder, ammonium chloride Copper powder or hydrates thereof, which are solid at room temperature, are preferable.
[0010]
In order to mechanically adhere the copper-containing powder to the surface of the iron powder particles, it is convenient to mechanically mix the iron powder and the copper-containing powder using various agitators (mixers). In particular, it is preferable to use a stirrer whose agitating locus draws a cycloid curve. Stirring with a cycloid curve can be realized, for example, by stirring using a revolving impeller. The copper-containing powder is uniformly mixed with the iron powder by mechanical mixing such as that of the iron powder, and a thin film of copper-containing powder is adhered to the surface of each particle of the iron powder, or copper is contained in the vicinity of each iron particle. Place the powder. For this purpose, the finer the copper-containing powder is, the more convenient it is, and it becomes easier for the fine powder to adhere to or be arranged on the spongy iron particles and to dissolve in the acid. The blending amount of the copper-containing powder may be such that the copper content is in the range of 0.01 to 20% by weight with the weight ratio of copper to iron in the final copper-containing iron powder.
[0011]
When a composite powder with copper-containing powder attached to the surface of iron particles is obtained by mechanical stirring, acid is added to this composite powder and stirred. The acid may be added in a stirrer used for mechanical mixing, or the composite powder may be transferred to another stirrer to add the acid and stir. In practice, it is convenient to add the acid and stir in a stirrer equipped with heating means for the subsequent separation of the liquid. As the acid, those having high solubility of the copper-containing powder to be used are preferable, but industrially, it is appropriate to use sulfuric acid. The concentration of the acid is not particularly limited, but it is preferable to use a 0.2 to 30% aqueous solution.
[0012]
When an acid is added to the composite powder having the copper-containing powder adhered to the surface of the iron particles, the copper-containing powder dissolves and at the same time, copper is deposited on the iron powder surface, resulting in a copper-containing iron powder having copper bonded to the iron particle surface. In particular, in the case of composite powder in which copper-containing powder adheres to sponge-like iron particles, copper-containing iron powder in which copper is deposited in places of sponge-like iron particles can be obtained by adding acid. The remaining liquid can be removed by performing a drying process such as heat evaporation or vacuum evaporation. In particular, copper-coated iron powder with both iron and copper exposed on the particle surface has a very high ability to decompose organic halogen compounds. That is, if both iron and copper appear on the surface due to the partial presence of copper on the surface of iron particles having a very large surface area, the decomposition of the organic halogen compound can be remarkably accelerated.
[0013]
When the copper-containing iron powder obtained by the present invention is used for decomposing an organic halogen compound, it has a through-hole in the grain, and preferably has a specific surface area of 300 cm 2 as a feature of the shape and structure of the grain. / G or more porous particles, and the size of the particles is such that 50% by weight passes through a 150 μm sieve. It is desirable that the surface layer part is made of particles in which copper is partially present and both iron and copper appear on the surface, and the copper content is preferably 0.01 to 20% by weight.
[0014]
In this case, it is ideal that both or one of the iron and copper appearing on the surface of the particle is a metal, but it is not always necessary that the iron and copper be metallic, and the iron oxide and copper oxidation are not necessarily required. Even in the presence of an object layer, the decomposition reaction of the organic halogen compound proceeds sufficiently quickly. The reason for this is not always clear, but the standard electrode potentials of metallic iron, ferrous ions, metallic copper and cuprous ions are different from each other, so that when the particles come into contact with water, the surface of the particles Then, several types of local batteries and oxidation-reduction reactions are generated, and ions and electrons move, which assists the decomposition function of organic halogen compounds (dehalogenation reaction and dehydrohalogenation reaction) by iron powder. It is thought that.
[0015]
The copper content in iron may be 0.01 to 20% by weight, and if the copper content is less than 0.01% by weight, the effect of the presence of copper hardly appears. Conversely, if the copper content exceeds 20% by weight, The amount of iron is relatively low, and the proportion of iron present on the surface is also unfavorable. The copper content in typical iron is 0.01 to 8% by weight, preferably 0.05 to 5% by weight, more preferably 0.05 to 3% by weight. The iron particles containing copper preferably contain 0.1 wt% or more and 5 wt% or less of carbon.
[0016]
The copper-containing iron powder produced according to the present invention is suitable for the decomposition of various organic halogen compounds. For example, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, 1,1-dichloroethylene, cis-1,2-dichloroethylene, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, tetrachloroethylene, 1,3 -Decomposes dichloropropene, trans-1,2-dichloroethylene, trihalomethane, PCB, and dioxin.
[0017]
Therefore, when purifying the groundwater contaminated with such organic halogen compounds with a decomposing agent comprising copper-containing iron powder according to the present invention, a reaction wall for the purification treatment is created in the ground. This underground reaction wall may be loaded with a decomposition agent according to the present invention. The reaction wall built in the ground is installed so that the groundwater can come into contact with the copper-containing iron powder, covering the easily permeable layer of the groundwater deep in the contaminated soil, and easily permeable. It is better to install the reaction wall in the ground so that the lower edge of the reaction wall reaches or is buried under the impervious layer located below the layer, and the permeability coefficient of the reaction wall is compared with the nearby soil quality. Thus, it is preferable that the reaction walls have good water permeability so as to be at the same level or higher. For this reason, for example, a water-permeable sandy material or the like is used as a base material, and a reaction wall in which copper-containing iron powder is dispersed in the base material in a range of about 0.1 to 30% by weight is formed in the ground. Good.
[0018]
The reaction wall can be formed as a continuous wall, but a plurality of columnar ones can be connected or spaced apart (for example, cylindrical reaction layers can be arranged in a staggered pattern when viewed in plan view). It is also possible to use a method such as vertical installation, and such columnar buried facilities can be carried out using a boring machine or the like. In any case, when the copper-containing iron powder according to the present invention is used, the decomposition reaction efficiency is much better than when only the iron powder is used. Even if it is less than that, the same effect can be obtained.
[0019]
In addition to creating such a reaction wall, soil and groundwater contaminated with organic halogen compounds can be purified by means similar to those using conventional iron powder. For example, a method of mixing copper-containing iron powder according to the present invention with a heavy machine such as a soil conditioner or a backhoe, or placing the copper-containing iron powder of the present invention near a contaminated site. Therefore, a method of diffusing and concentrating contaminated soil and groundwater on the surface of the decomposer can be advantageously employed.
[0020]
【Example】
[Example 1]
Iron powder having a specific surface area of approximately 20000 cm 2 / g and a carbon content of 0.2% by weight, of which 50% by weight or more passes through a 150 μm sieve (made by Dowa Iron Powder Co., Ltd.) Product name E-200) 100g, copper oxide powder (CuO powder made by Nikko Fine Chemicals Co., Ltd.) 1.27g (equivalent to Cu 0.8g), 300ml sample mixer (having squid-like impeller) Loaded.
[0021]
At the time of stirring for 1 minute after charging both, 5 ml of 1 mol / liter sulfuric acid was added to the mixer while continuing stirring, and stirring was continued for 20 seconds. Thereafter, the contents were taken out from the mixer and kept at 105 ° C. in a drying furnace to evaporate and separate the liquid.
[0022]
0.5 g of the obtained powder was put together with 50 ml of ion-exchanged water into a 100 ml capacity trial bottle, and sealed with a butyl rubber septum coated with fluororesin (registered trademark Teflon) and an aluminum cap. Three sets of this sealed bottle were prepared.
[0023]
Then, into each sealed bottle, 1 μL each of dichloromethane (DCM), cis-dichloroethylene (cis-DCE), and perchlorethylene (PCE) was injected using a microsyringe until the test period of 15 days was reached. The concentration of each organic halogen compound was traced over time, and the decomposition rate constant and half-life were obtained. The results are shown in Table 1.
[0024]
[Table 1]
[Example 2]
Example 1 was repeated except that 2.75 g (corresponding to Cu 0.8 g) of copper chloride powder (CuCl 2 2H 2 O) was used in place of the copper oxide powder. The same test as in Example 1 was performed using cis-dichloroethylene (cis-DCE) as the organic halogen compound. The results are shown in Table 2.
[0026]
[Table 2]
Example 3
In this example, the test of Example 1 is scaled up to the actual operation scale. That is, an iron powder having a specific surface area of approximately 20000 cm 2 / g and a carbon content of 0.2% by weight, of which 50% by weight passes through a 150 μm sieve. Company product name E-200) 800 Kg and 10 Kg of copper oxide powder with an average particle size of 7 μm are loaded into a universal mixing stirrer with an effective stirring volume of 400 liters, and the impeller is rotated while revolving the impeller to obtain a cycloid curve Stirring was carried out for 30 minutes so that a stirring locus was generated. Subsequently, while stirring was continued, 40 kg of 1 mol / liter sulfuric acid was added into the stirrer, and stirring was continued for 30 minutes. Thereafter, stirring was continued while keeping the material temperature in the stirrer at 105 ° C., and the liquid was discharged out of the apparatus.
[0028]
The obtained powder was subjected to cis-dichloroethylene (cis-DCE) and perchlorethylene (PCE) decomposition tests in the same manner as in Example 1. The results are shown in Table 3.
[0029]
[Table 3]
【The invention's effect】
As described above, according to the present invention, the copper-containing iron powder capable of efficiently decomposing an organic halogen compound can be produced economically and with good operability.
Claims (5)
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| JP2002051939A JP4110259B2 (en) | 2002-02-27 | 2002-02-27 | Manufacturing method of copper-containing iron powder |
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| JP2002051939A JP4110259B2 (en) | 2002-02-27 | 2002-02-27 | Manufacturing method of copper-containing iron powder |
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| JP4774478B2 (en) * | 2004-10-01 | 2011-09-14 | Ｄｏｗａエコシステム株式会社 | Soil or groundwater purification methods |
| JP5876634B2 (en) * | 2008-07-08 | 2016-03-02 | Ｄｏｗａエコシステム株式会社 | Organochlorine pesticide decomposer and purification method |
| JP2010240636A (en) * | 2009-03-19 | 2010-10-28 | Dowa Eco-System Co Ltd | Decomposer for organohalogen compound, method for producing the same and method for purifying soil or water |
| JP2013107943A (en) * | 2011-11-17 | 2013-06-06 | Dowa Eco-System Co Ltd | Decomposing agent and cleaning method of organochlorine-based agricultural chemical |
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