JPWO2013161936A1 - Chemical substance decomposition agent composition and chemical substance decomposition treatment method using the same - Google Patents
Chemical substance decomposition agent composition and chemical substance decomposition treatment method using the same Download PDFInfo
- Publication number
- JPWO2013161936A1 JPWO2013161936A1 JP2014512681A JP2014512681A JPWO2013161936A1 JP WO2013161936 A1 JPWO2013161936 A1 JP WO2013161936A1 JP 2014512681 A JP2014512681 A JP 2014512681A JP 2014512681 A JP2014512681 A JP 2014512681A JP WO2013161936 A1 JPWO2013161936 A1 JP WO2013161936A1
- Authority
- JP
- Japan
- Prior art keywords
- chemical substance
- agent composition
- persulfate
- iron
- substance decomposition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Emergency Management (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Business, Economics & Management (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
本発明は、金属腐食性が抑制され、かつ化学物質を十分分解することができるという双方の効果をバランスよく有する化学物質分解処理剤組成物及びそれを用いた化学物質の分解処理方法を提供することを目的とする。上記目的を達成するため、本発明は、（Ａ）過硫酸塩、（Ｂ）珪酸ナトリウム及び（Ｃ）アルカリ金属炭酸塩、アルカリ土類金属炭酸塩並びにこれらの混合物から選択される炭酸塩を含有することを特徴とする化学物質分解剤組成物および該組成物を用いた化学物質の分解処理方法を提供する。The present invention provides a chemical substance decomposition treatment composition having a good balance between the effects of suppressing metal corrosivity and capable of sufficiently decomposing chemical substances, and a chemical substance decomposition treatment method using the same. For the purpose. In order to achieve the above object, the present invention comprises (A) persulfate, (B) sodium silicate and (C) alkali metal carbonate, alkaline earth metal carbonate and a carbonate selected from a mixture thereof. There are provided a chemical substance decomposing agent composition and a chemical substance decomposing method using the composition.
Description
本発明は、化学物質によって汚染された土壌に添加することで、当該化学物質を効率よく分解処理することができる化学物質分解剤組成物及びそれを用いた化学物質の分解処理方法に関する。 The present invention relates to a chemical substance decomposing agent composition capable of efficiently decomposing a chemical substance when added to soil contaminated with the chemical substance, and a chemical substance decomposing method using the same.
従来、有機塩素化合物などの化学物質が洗浄剤などとして半導体工場やクリーニング店（工場）などで広く使用されてきたが、その環境負荷が大きいため、近年はその使用が敬遠されている。しかしながら、既に使用されたこれらの化学物質が、土壌や地下水に混入している場合も多く、土地を再利用するに際し大きな社会問題となっている。そこで様々な手段で、汚染土壌や汚染水を浄化する試みがなされている。 Conventionally, chemical substances such as organic chlorine compounds have been widely used as cleaning agents in semiconductor factories and cleaning shops (factories), but their use has been refrained in recent years due to their large environmental impact. However, these chemical substances that have already been used are often mixed in soil and groundwater, which is a major social problem when reusing land. Therefore, attempts have been made to purify contaminated soil and contaminated water by various means.
汚染土壌や汚染水を物理的に除去する方法や、汚染物質を生物的あるいは化学的に分解する方法が知られているが、物理的な方法により、汚染土壌の搬出を伴う場合は二次的な処理が必要となる欠点がある。また、生物的に汚染物質を分解する方法も検討されているが、環境への負荷が小さいという利点はあるものの、高濃度の汚染物質や有機塩素化合物等の難分解性化合物への適用は難しく、分解に長期間を要するという課題がある。これに対して化学的に分解する方法では、現地で汚染物質の分解が可能であるため二次的な処理は不要であり、高濃度の汚染物質や有機塩素化合物等の難分解性化合物を早期に分解可能なため活発に検討されている。 There are known methods of physically removing contaminated soil and water, and methods of biologically or chemically decomposing contaminants. There is a drawback that requires a special treatment. In addition, biologically degrading pollutants has been studied, but although it has the advantage of low environmental impact, it is difficult to apply to highly degradable compounds such as high concentrations of pollutants and organochlorine compounds. There is a problem that it takes a long time to decompose. On the other hand, the chemical decomposition method does not require secondary treatment because it is possible to decompose pollutants in the field, and high-concentration pollutants and refractory compounds such as organochlorine compounds can be removed early. Since it can be decomposed, it has been actively studied.
化学的に分解する方法としては、過酸化水素や過硫酸塩を用いて汚染物質を酸化分解処理する方法が知られている。分解処理の方法としては、地盤中に注入する方法が一般的であるが、過酸化水素は不安定で分解が早いため地盤中に注入すると直ちに分解してしまい、浄化する範囲が極端に狭くなるという課題がある。一方、過硫酸塩は安定であるため、より多くの検討がなされている（特許文献１〜４を参照）。 As a method of chemically decomposing, a method of oxidatively decomposing a contaminant using hydrogen peroxide or persulfate is known. As a method of decomposition treatment, a method of injecting into the ground is general, but hydrogen peroxide is unstable and decomposes quickly, so when it is injected into the ground, it is immediately decomposed, and the range to be purified becomes extremely narrow. There is a problem. On the other hand, since persulfate is stable, more studies have been made (see Patent Documents 1 to 4).
汚染土壌を掘削搬出することなく原位置において、廉価に浄化するには分解処理剤を汚染地下水に注入したり、また、難透水層などの汚染部位を浄化するには攪拌機により攪拌しながら分解処理剤を注入する後者の方が汚染土壌と分解処理剤がより均一になる点で好ましいとされている。しかしながら、過硫酸塩を用いた分解処理剤は強酸性であるため、攪拌機や注入管等に用いられる金属（特に鋼材）が腐食してしまうという課題があり、低腐食性の分解処理剤が要望されている。 In order to purify the soil at low cost without excavating and transporting the contaminated soil, a decomposition treatment agent is injected into the contaminated groundwater, and to purify contaminated sites such as a poorly permeable layer, the material is decomposed while stirring with a stirrer. The latter, in which the agent is injected, is preferred in that the contaminated soil and the decomposition treatment agent become more uniform. However, since the decomposition treatment agent using persulfate is strongly acidic, there is a problem that the metal (particularly steel) used in the stirrer or the injection tube corrodes, and a decomposition solution with low corrosion resistance is desired. Has been.
よって、本発明の目的は、金属腐食性が抑制され、かつ化学物質を十分分解することができるという双方の効果をバランスよく有する化学物質分解処理剤組成物及びそれを用いた化学物質の分解処理方法を提供することにある。 Therefore, an object of the present invention is to provide a chemical substance decomposition treatment agent composition having a good balance between the effects of suppressing metal corrosiveness and capable of sufficiently decomposing a chemical substance, and chemical substance decomposition treatment using the same. It is to provide a method.
本発明者らは、上記課題を解決すべく鋭意検討した結果、（Ａ）過硫酸塩、（Ｂ）珪酸ナトリウム（Ｂ）並びに（Ｃ）アルカリ金属炭酸塩、アルカリ土類金属炭酸塩及びこれらの混合物から選択される炭酸塩を含有することを特徴とする化学物質分解処理剤組成物を見出し、斯かる組成物が上記目的を達成しうることを知見し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have found that (A) persulfate, (B) sodium silicate (B), and (C) alkali metal carbonate, alkaline earth metal carbonate, and these The present inventors have found a chemical substance decomposition treating agent composition characterized by containing a carbonate selected from a mixture, and have found that such a composition can achieve the above-mentioned object, thereby leading to the present invention.
本発明によれば、高い過硫酸塩濃度においても金属腐食性が抑制され、かつ十分な化学物質分解能を有する化学物質分解剤組成物を提供することができることにある。 According to the present invention, it is possible to provide a chemical substance decomposer composition that suppresses metal corrosiveness even at a high persulfate concentration and has sufficient chemical substance resolution.
本発明の化学物質分解剤組成物は、（Ａ）過硫酸塩、（Ｂ）珪酸ナトリウム並びに（Ｃ）アルカリ金属炭酸塩、アルカリ土類金属炭酸塩およびこれらの混合物から選択される炭酸塩を含有する組成物である。
分解の対象となる化学物質は、有機物であれば種類を選ばず、例えば、ヘキサン、石油エーテル等の脂肪族炭化水素化合物；ベンゼン、トルエン、キシレン、ナフタレン、アントラセン、フェナントレン、ピレン、クリセン等の芳香族炭化水素化合物；灯油、軽油、重油、ガソリン、軽油、潤滑油等の石油製品；ジクロロメタン、クロロホルム、四塩化炭素、ブロモトリフルオロメタン、ブロモクロロジフルオロメタン、ジブロモジフルオロメタン、ジブロモテトラフルオロエタン、トリブロモフルオロメタン、テトラクロロエチレン、トリクロロエチレン、１，１−ジクロロエチレン、１，２−ジクロロエチレン、クロロエチレン、ヘキサクロロエタン、１，１，１−トリクロロエタン、１，１，２−トリクロロエタン、１，１−ジクロロエタン、１，２−ジクロロエタン、１，２−ジクロロテトラフルオロエタン、１，３−ジクロロプロペン、２−クロロ−１，３−ブタジエンが挙げられる。ハロゲン化脂環式化合物としては、例えば、１，２，３，４，５，６−ヘキサクロロシクロヘキサン、アルドドリン（Aldrin）、ディルドリン（Dieldrin）、エンドリン（Endrin）、クロルデン（Chlorden）、ヘプタクロル（Heptachor）、マイレックス（Mirex）、トキサフェン（Toxaphene）が挙げられる。ハロゲン化芳香族化合物としては、例えば、ジクロロジフェニルトリクロロエタン（ＤＤＴ）、２，４−ジクロロフェノール、２，４，５−トリクロロフェノール、２，４，６−トリクロロフェノール、ペンタクロロフェノール、ポリ塩化ビフェニル類（ＰＣＢ）、ダイオキシン類等の有機ハロゲン化合物、上記化合物以外では、遊離シアン酸や鉄シアノ錯体などのシアン化合物等が挙げられる。本発明の化学物質分解剤組成物は、難分解性として知られる有機ハロゲン化合物に対して効果的に使用することができる。The chemical substance decomposer composition of the present invention contains (A) persulfate, (B) sodium silicate, and (C) carbonate selected from alkali metal carbonate, alkaline earth metal carbonate, and mixtures thereof. Composition.
The chemical substance to be decomposed is not limited as long as it is organic, for example, aliphatic hydrocarbon compounds such as hexane and petroleum ether; aromatics such as benzene, toluene, xylene, naphthalene, anthracene, phenanthrene, pyrene and chrysene. Petroleum products such as kerosene, light oil, heavy oil, gasoline, light oil, lubricating oil; dichloromethane, chloroform, carbon tetrachloride, bromotrifluoromethane, bromochlorodifluoromethane, dibromodifluoromethane, dibromotetrafluoroethane, tribromo Fluoromethane, tetrachloroethylene, trichloroethylene, 1,1-dichloroethylene, 1,2-dichloroethylene, chloroethylene, hexachloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1-dichloro Tan, 1,2-dichloroethane, 1,2-dichlorotetrafluoroethane, 1,3-dichloropropene, and a 2-chloro-1,3-butadiene. Examples of the halogenated alicyclic compound include 1,2,3,4,5,6-hexachlorocyclohexane, aldodrine, dieldrin, endrin, chlordane, heptachlor. , Mirex, and Toxaphene. Examples of the halogenated aromatic compound include dichlorodiphenyltrichloroethane (DDT), 2,4-dichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, pentachlorophenol, and polychlorinated biphenyls. (PCB), organic halogen compounds such as dioxins, and cyan compounds such as free cyanic acid and iron cyano complexes may be used in addition to the above compounds. The chemical substance decomposing agent composition of the present invention can be effectively used for an organic halogen compound known to be hardly decomposable.
上記の化学物質が混入した対象物を浄化する目的で、本発明の化学物質分解剤組成物は使用されるが、こうした対象物としては、例えば、土壌、汚泥、工場排水、生活排水、河川水、湖沼水、地下水等が挙げられる。 The chemical substance decomposing agent composition of the present invention is used for the purpose of purifying the object mixed with the above chemical substances. Examples of such objects include soil, sludge, factory effluent, domestic effluent, and river water. , Lake water, groundwater, etc.
＜（Ａ）過硫酸塩＞
本発明の化学物質分解剤組成物に使用される（Ａ）成分の過硫酸塩としては、例えば、過硫酸リチウム、過硫酸ナトリウム及び過硫酸カリウム等が挙げられる。これらの中でも、過硫酸ナトリウム及び過硫酸カリウムが好ましく、経済的に安価で水溶性の高い過硫酸ナトリウムが更に好ましい。上記した過硫酸塩は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。<(A) persulfate>
Examples of the persulfate of the component (A) used in the chemical substance decomposing agent composition of the present invention include lithium persulfate, sodium persulfate, and potassium persulfate. Among these, sodium persulfate and potassium persulfate are preferable, and sodium persulfate that is economically inexpensive and highly water-soluble is more preferable. The persulfate described above may be used alone or in combination of two or more.
＜（Ｂ）珪酸ナトリウム＞
「珪酸ナトリウム」は、一般にＮａ2Ｏ・ｎＳｉＯ2（式中、ｎは０より大きい実数を示す）で表される物質である（式中ｎの値は０より大きい数である。）入手の観点から、ｎ＝０．５〜４の範囲の値であることが好ましい。具体的には、例えば、オルソ珪酸ナトリウム（Ｎａ2Ｏ・１／２ＳｉＯ2・ｘＨ2Ｏ）、セスキ珪酸ナトリウム（Ｎａ2Ｏ・２／３ＳｉＯ2・ｘＨ2Ｏ）、メタ珪酸ナトリウム（Ｎａ2Ｏ・ＳｉＯ2・ｘＨ2Ｏ）等の粉体状のもの（式中、ｘは０以上の数）；１号珪酸ナトリウム（Ｎａ2Ｏ・２ＳｉＯ2・ａｑ）、２号珪酸ナトリウム（Ｎａ2Ｏ・５／２ＳｉＯ2・ａｑ）、３号珪酸ナトリウム（Ｎａ2Ｏ・３ＳｉＯ2・ａｑ）、４号珪酸ナトリウム（Ｎａ2Ｏ・４ＳｉＯ2・ａｑ）等の液体状のもの（式中、ａｑは水溶液であることを示す）が挙げられる。尚、前記、１号〜４号ケイ酸ナトリウムは、ＪＩＳ Ｋ１４０８において規定されるものを指す。<(B) Sodium silicate>
“Sodium silicate” is a substance generally represented by Na 2 O.nSiO 2 (wherein n represents a real number greater than 0) (where n is a number greater than 0). From a viewpoint, it is preferable that it is the value of the range of n = 0.5-4. Specifically, for example, ortho sodium silicate (Na 2 O · 1 / 2SiO 2 · xH 2 O), sodium sesquicarbonate silicate (Na 2 O · 2 / 3SiO 2 · xH 2 O), sodium metasilicate (Na 2 O・ Powder type such as SiO 2 .xH 2 O (wherein x is a number of 0 or more); No. 1 sodium silicate (Na 2 O.2SiO 2 .aq), No. 2 sodium silicate (Na 2 O · 5 / 2SiO 2 · aq) , sodium silicate No. 3 (Na 2 O · 3SiO 2 · aq), 4 No. of sodium silicate (Na 2 O · 4SiO 2 · aq) ones like liquid of (wherein, aq is Indicating an aqueous solution). In addition, said 1st-4th sodium silicate points out what is prescribed | regulated in JISK1408.
本発明の化学物質分解剤組成物に使用される（Ｂ）成分の珪酸ナトリウムとしては、粉体又は液体の何れかでもよいが、取り扱いが容易であるため液体のものが好ましい。具体的には１号珪酸ナトリウム、２号珪酸ナトリウム、３号珪酸ナトリウム等が挙げられ、中でも取り扱いが容易な３号珪酸ナトリウムが好ましい。 The component (B) sodium silicate used in the chemical substance decomposing agent composition of the present invention may be either powder or liquid, but is preferably liquid because it is easy to handle. Specifically, No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate and the like are mentioned, and among them, No. 3 sodium silicate which is easy to handle is preferable.
なお、ＪＩＳ Ｋ１４０８において規定される１号〜３号ケイ酸ナトリウムの詳細を以下の表に示す。 Details of Nos. 1 to 3 sodium silicates defined in JIS K1408 are shown in the following table.
本発明の化学物質分解剤組成物に使用される（Ａ）成分及び（Ｂ）成分の配合比は特に規定されないが、（Ａ）成分１質量部に対して、（Ｂ）成分中のＳｉＯ2として０．００５〜０．２００質量部、好ましくは０．００８〜０．１８０質量部、より好ましくは０．００８〜０．１５０質量部配合すればよい。（Ｂ）成分が０．００５質量部より少ないと金属腐食抑制効果が損なわれる場合があり、０．２００質量部を超えると化学物質の分解が進みにくくなる場合がある。The compounding ratio of the component (A) and the component (B) used in the chemical substance decomposing agent composition of the present invention is not particularly defined, but the SiO 2 in the component (B) with respect to 1 part by mass of the component (A). 0.005 to 0.200 parts by mass, preferably 0.008 to 0.180 parts by mass, more preferably 0.008 to 0.150 parts by mass. If the amount of the component (B) is less than 0.005 parts by mass, the metal corrosion inhibitory effect may be impaired, and if it exceeds 0.200 parts by mass, decomposition of the chemical substance may be difficult to proceed.
本発明の化学物質分解剤組成物には、上記（Ａ）成分及び（Ｂ）成分に加えて、アルカリ金属炭酸塩、アルカリ土類金属炭酸塩から選択される炭酸塩を少なくとも１種用いて、（Ｃ）成分とする。（Ｃ）成分は、中和剤として用いられ過硫酸塩の安定化に寄与する。
＜（Ｃ１）アルカリ金属炭酸塩＞
アルカリ金属炭酸塩（Ｃ１）としては、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム等が挙げられる。
＜（Ｃ２）アルカリ土類金属炭酸塩＞
アルカリ土類金属炭酸塩としては、炭酸マグネシウム、炭酸カルシウム等が挙げられる。
上記した（Ｃ）成分として用いられる化合物は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。The chemical substance decomposer composition of the present invention uses at least one carbonate selected from alkali metal carbonates and alkaline earth metal carbonates, in addition to the components (A) and (B). Component (C) is used. Component (C) is used as a neutralizing agent and contributes to stabilization of persulfate.
<(C1) Alkali metal carbonate>
Examples of the alkali metal carbonate (C1) include sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate.
<(C2) alkaline earth metal carbonate>
Examples of the alkaline earth metal carbonate include magnesium carbonate and calcium carbonate.
The compounds used as the component (C) described above may be used alone or in combination of two or more.
本発明の化学物質分解剤組成物に（Ｃ）成分を併用する場合、（Ｃ）成分の配合量は特に規定されないが、通常（Ａ）成分１質量部に対して、（Ｃ）成分を０．０１〜１質量部、好ましくは０．０５〜０．７質量部配合される。（Ｃ）成分が０．０１質量部より少ないと安定化効果が得られない場合があり、１質量部を超えると化学物質の分解が進みにくくなる場合がある。本発明の（Ｃ）成分において、アルカリ金属炭酸塩（Ｃ１）が好ましく、中でも炭酸ナトリウム又は炭酸水素ナトリウムがより好ましい。 When the component (C) is used in combination with the chemical substance decomposing agent composition of the present invention, the amount of the component (C) is not particularly specified, but the component (C) is usually 0 with respect to 1 part by mass of the component (A). 0.01 to 1 part by mass, preferably 0.05 to 0.7 part by mass. If the amount of component (C) is less than 0.01 parts by mass, the stabilizing effect may not be obtained. In the component (C) of the present invention, an alkali metal carbonate (C1) is preferable, and sodium carbonate or sodium bicarbonate is more preferable.
また、本発明の化学物質分解剤組成物には、上記（Ａ）成分、（Ｂ）成分並びに（Ｃ）成分を加えた組成物に、更に（Ｄ）成分として２価又は３価の鉄イオンを含有させることが出来る。この（Ｄ）成分は、化学物質分解の触媒として作用する。 In addition, the chemical substance decomposing agent composition of the present invention is a composition obtained by adding the above component (A), component (B) and component (C), and further, divalent or trivalent iron ions as component (D). Can be contained. This component (D) acts as a catalyst for chemical substance decomposition.
＜（Ｄ）２価又は３価の鉄イオン＞
本発明の化学物質分解剤組成物に使用される２価又は３価の鉄イオン（Ｄ）のイオン源は、水に溶解あるいは分散するものであれば特に限定されないが、水への溶解性が良好なことから鉄塩を使用することが好ましい。こうした鉄塩としては、例えば、塩化鉄（ＩＩ）、塩化鉄（ＩＩＩ）、過塩酸鉄（ＩＩ）、過塩酸鉄（ＩＩＩ）、臭化鉄（ＩＩ）、臭化鉄（ＩＩＩ）、ヨウ化鉄（ＩＩ）、ヨウ化鉄（ＩＩＩ）、硝酸鉄（ＩＩ）、硝酸鉄（ＩＩＩ）、チオシアン酸鉄（ＩＩ）、チオシアン酸鉄（ＩＩＩ）、酢酸鉄（ＩＩ）、シュウ酸鉄（ＩＩＩ）、硫酸アンモニウム鉄（ＩＩ）、硫酸アンモニウム鉄（ＩＩＩ）、硫酸カリウム鉄（ＩＩＩ）、硫酸鉄（ＩＩ）、硫酸鉄（ＩＩＩ）、フェロシアン化ナトリウム、フェリシアン化ナトリウム、フェロシアン化カリウム、フェリシアン化カリウム、フェロシアン化アンモニウム、フェリシアン化アンモニウム等が挙げられる。<(D) Divalent or trivalent iron ion>
The ion source of the divalent or trivalent iron ion (D) used in the chemical substance decomposing agent composition of the present invention is not particularly limited as long as it is dissolved or dispersed in water, but has solubility in water. It is preferable to use an iron salt because it is good. Examples of such iron salts include iron (II) chloride, iron (III) chloride, iron (II) perhydrochloride, iron (III) perhydrochloride, iron (II) bromide, iron (III) bromide, and iodide. Iron (II), iron (III) iodide, iron (II) nitrate, iron (III) nitrate, iron (II) thiocyanate, iron (III) thiocyanate, iron (II) acetate, iron (III) oxalate , Ammonium iron sulfate (II), ammonium iron sulfate (III), potassium iron sulfate (III), iron sulfate (II), iron sulfate (III), sodium ferrocyanide, sodium ferricyanide, potassium ferrocyanide, potassium ferricyanide, ferrocyanide And ammonium ferricyanide.
有機物質の分解率と経済性の点から、塩化鉄（ＩＩ）、塩化鉄（ＩＩＩ）、硝酸鉄（ＩＩ）、硝酸鉄（ＩＩＩ）、硫酸鉄（ＩＩ）、硫酸鉄（ＩＩＩ）が好ましく、塩化鉄（ＩＩ）、硝酸鉄（ＩＩ）、硫酸鉄（ＩＩ）が更に好ましく、塩化鉄（ＩＩ）及び硫酸鉄（ＩＩ）が最も好ましい。これらの鉄塩は無水塩でもよいし水和物でもよく、水への溶解または分散のしやすさを考慮して、適宜選択すればよい。なお、本発明において水和物とは結晶水を有する塩をいい、例えば、硫酸鉄（ＩＩ）は無水塩の他に、一水和物、四水和物、五水和物及び七水和物が知られている。上記した鉄イオンのイオン源は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 From the viewpoint of the decomposition rate and economical efficiency of organic substances, iron (II) chloride, iron (III) chloride, iron (II) nitrate, iron (III) nitrate, iron (II) sulfate, and iron (III) sulfate are preferable. Iron chloride (II), iron nitrate (II), and iron sulfate (II) are more preferable, and iron chloride (II) and iron sulfate (II) are most preferable. These iron salts may be anhydrous salts or hydrates, and may be appropriately selected in consideration of ease of dissolution or dispersion in water. In the present invention, the hydrate refers to a salt having water of crystallization. For example, iron (II) sulfate is monohydrate, tetrahydrate, pentahydrate and heptahydrate in addition to anhydrous salts. Things are known. The above iron ion source may be used alone or in combination of two or more.
本発明の化学物質分解剤組成物に（Ｄ）成分を併用する場合、（Ｄ）成分の配合量は特に規定されないが、通常（Ａ）成分１質量部に対して、（Ｄ）成分を０．０１〜１質量部、好ましくは０．０５〜０．７質量部、より好ましくは０．１〜０．４質量部配合すればよい。（Ｄ）成分が０．０１質量部より少ないと化学物質分解の促進効果が得られない場合があり、１質量部を超えると（Ａ）成分が短時間で消費されて持続性が損なわれる場合や、配合量に見合った効果が得られない場合がある。 When the component (D) is used in combination with the chemical substance decomposing agent composition of the present invention, the amount of the component (D) is not particularly specified, but the component (D) is usually 0 with respect to 1 part by mass of the component (A). 0.01 to 1 part by mass, preferably 0.05 to 0.7 part by mass, more preferably 0.1 to 0.4 part by mass. When the component (D) is less than 0.01 parts by mass, the chemical substance decomposition promoting effect may not be obtained, and when it exceeds 1 part by mass, the component (A) is consumed in a short time and the sustainability is impaired. In addition, the effect corresponding to the blending amount may not be obtained.
また、本発明の化学物質分解剤組成物には、更に過酸化水素、キレート剤、過硫酸安定化剤（上記（Ｃ）成分の炭酸塩を除く）、コロイダルシリカ等を添加することができる。 Further, hydrogen peroxide, a chelating agent, a persulfuric acid stabilizer (excluding the carbonate of the above component (C)), colloidal silica, and the like can be further added to the chemical substance decomposer composition of the present invention.
本発明の化学物質の分解処理方法は、本発明の化学物質分解剤組成物（以下、「本薬剤」という）を、化学物質に汚染された土壌又は水と接触させ、当該化学物質を分解処理する方法である。 The chemical substance decomposition method of the present invention comprises contacting the chemical substance decomposition agent composition of the present invention (hereinafter referred to as “the present drug”) with soil or water contaminated with a chemical substance, and decomposing the chemical substance. It is a method to do.
本薬剤は、水溶液の状態が好ましく、具体的には、（Ａ）成分である過硫酸塩が１〜２０質量％の水溶液になるように本薬剤を水で希釈し、浄化しようとする土量１ｍ3に対して、水で希釈した本薬剤中の（Ａ）成分である過硫酸塩が０．５〜５０ｋｇになるように本薬剤の水溶液を添加するのが好ましく、１〜４０ｋｇがより好ましく、２〜２０ｋｇが更に好ましい。過硫酸塩が０．５ｋｇ未満の場合は化学物質の分解速度が遅くなる場合や、分解が完全に終了しない場合があり、５０ｋｇを超えると環境に悪影響を与える場合や、添加量に見合った効果が得られない場合がある。また、本薬剤を構成する成分をそれぞれ別々に土壌に注入することも可能である。The drug is preferably in the form of an aqueous solution. Specifically, the volume of soil to be purified by diluting the drug with water so that the persulfate as the component (A) is 1 to 20% by mass. It is preferable to add an aqueous solution of this drug to 0.5 to 50 kg per 1 m 3 so that the persulfate as component (A) in the drug diluted with water is 0.5 to 50 kg, more preferably 1 to 40 kg. 2 to 20 kg is more preferable. If the persulfate is less than 0.5 kg, the decomposition rate of the chemical substance may be slow, or the decomposition may not be completed completely. If it exceeds 50 kg, the environment may be adversely affected, or the effect commensurate with the amount added May not be obtained. Moreover, it is also possible to inject | pour into the soil each component which comprises this chemical | medical agent separately.
次に、化学物質により汚染された土壌を浄化する工法について説明する。汚染された土壌を浄化するには、汚染された土壌を掘り返し、当該土壌に水を加えてスラリー状にしてから分解処理してもよいし、汚染された土壌に本薬剤を直接注入して分解処理してもよい。その場合には、単軸、及び２軸のオーガや、先端に攪拌羽根のついた掘削機や、パワーショベルなどの掘削機などに適用できる。また、圧力噴射機能を備えたボーリング工法も適用できる。この他に、上記に類似する重機との併用や、揚水曝気工法などが挙げられる。これら工法において、重機は化学物質分解剤組成物と接触することとなる。 Next, a method for purifying soil contaminated with chemical substances will be described. In order to purify the contaminated soil, the contaminated soil may be dug up, and water may be added to the soil to form a slurry and then decomposed. Alternatively, the agent is directly injected into the contaminated soil for decomposition. It may be processed. In that case, the present invention can be applied to single-shaft and bi-shaft augers, excavators having a stirring blade at the tip, excavators such as power shovels, and the like. A boring method having a pressure injection function can also be applied. In addition, the combined use with the heavy machinery similar to the above, the pumped water aeration method, etc. are mentioned. In these methods, the heavy machinery comes into contact with the chemical substance decomposer composition.
上記重機の掘削部、配管部等には鉄を主成分とする合金である鋼材が用いられる。本発明の化学物質分解剤組成物は、鋼材の種類を選ばず低腐食性を示す。重機によく用いられる鋼材として炭素鋼材が挙げられ、炭素鋼材としては機械構造用炭素鋼材（ＪＩＳ Ｇ４０５１）や一般構造用圧延鋼材（ＪＩＳ Ｇ３１０１）が挙げられる。具体例として、機械構造用炭素鋼材には、Ｓ３５Ｃ、Ｓ４５Ｃ、Ｓ５５Ｃ等が挙げられ、一般構造用圧延鋼材には、ＳＳ４００、ＳＳ４９０、ＳＳ５４０等が挙げられる。 A steel material, which is an alloy containing iron as a main component, is used for excavation parts, piping parts, and the like of the heavy machinery. The chemical substance decomposer composition of the present invention exhibits low corrosivity regardless of the type of steel material. Examples of steel materials often used in heavy machinery include carbon steel materials, and examples of carbon steel materials include carbon steel materials for mechanical structures (JIS G4051) and rolled steel materials for general structures (JIS G3101). Specific examples of the carbon steel material for mechanical structure include S35C, S45C, and S55C, and examples of the general structural rolled steel material include SS400, SS490, and SS540.
以下、実施例により本発明を更に説明するが、本発明はこれらの実施例によって限定されるものではない。尚、実施例中の「部」や「％」は質量基準によるものである。
下記試験方法に従い、本発明の化学物質分解剤組成物の金属腐食性、及び汚染化合物であるトリクロロエチレン（ＴＣＥ）の分解試験を行った。EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these Examples. In the examples, “parts” and “%” are based on mass.
In accordance with the following test method, the chemical decomposition agent composition of the present invention was subjected to a metal corrosivity and a decomposition test of trichlorethylene (TCE) which is a contaminating compound.
＜金属腐食性＞
表１に記載の薬剤に試験片として、機械構造用炭素鋼材（Ｓ４５Ｃ（ＪＩＳ Ｇ４０５１）；３．２×１５×３０ｍｍ）を室温にて４日浸漬し、試験片の重量測定を行った。結果を表１に示す。尚、表中組成物の数字は各薬剤の水若しくは結晶水を除いた純分の質量％を表す。また、表中の重量減少量の項目は、試験前の試験片重量に対して減少した量を％として表している。<Metal corrosivity>
Carbon steel materials for mechanical structures (S45C (JIS G4051); 3.2 × 15 × 30 mm) were immersed in the chemicals listed in Table 1 for 4 days at room temperature, and the weights of the test pieces were measured. The results are shown in Table 1. In addition, the number of the composition in a table | surface represents the mass% of the pure part except the water or crystallization water of each chemical | medical agent. Moreover, the item of the weight reduction amount in a table | surface represents the quantity reduced with respect to the test piece weight before a test as%.
＜分解試験＞
１２０ｍｌの遮光バイアル瓶に、粉砕及び乾燥した土を１０ｇ、ＴＣＥが２００ｍｇ／ｌの水溶液を５０ｇ入れた。上記金属腐食性試験と同様の各薬剤１．５ｍｌをイオン交換水で５０ｍｌにメスアップして、土とＴＣＥ水溶液の入った遮光バイアル瓶にそれぞれ添加した。その後、遮光バイアル瓶を上下に振って内容物を均一化し、２５℃の恒温槽内に静置した。この時点（分解前）でのＴＣＥ濃度は１００ｍｇ／ｌである。
４日間静置後、遮光バイアル瓶中の上澄み水を１０ｍｌ採取し、ガスクロマトグラフィーを用いて残存ＴＣＥ量をＪＩＳ Ｋ０１２５に準拠して測定した。結果を表１のＴＣＥ濃度に示す。ガスクロマトグラフィーの条件は下記の通りである。<Decomposition test>
In a 120 ml light-shielding vial, 10 g of ground and dried soil and 50 g of an aqueous solution having a TCE of 200 mg / l were placed. 1.5 ml of each drug similar to that in the metal corrosion test was made up to 50 ml with ion-exchanged water, and each was added to a light-shielding vial containing soil and an aqueous TCE solution. Thereafter, the light-shielding vial was shaken up and down to make the contents uniform, and left in a constant temperature bath at 25 ° C. The TCE concentration at this point (before decomposition) is 100 mg / l.
After standing for 4 days, 10 ml of the supernatant water in the light-shielding vial was collected, and the residual TCE amount was measured according to JIS K0125 using gas chromatography. The results are shown in Table 1 for TCE concentration. The conditions for gas chromatography are as follows.
＜ガスクロマトグラフィー条件＞
機器：ＧＣ−２０１４（島津製作所株式会社製）
カラム：Ｉｎｅｒｔ
Ｃａｐ１（内径０．２５ｍｍ、長さ３０ｍ、膜厚１．５μｍ；ＧＬサイエンス社製）
カラム温度：４０℃から２００℃に昇温（５℃／ｍｉｎ）
インジェクション温度：２００℃
ディテクター温度：２５０℃
注入量：０．１ｍｌ
スプリット比：１：５０<Gas chromatography conditions>
Equipment: GC-2014 (manufactured by Shimadzu Corporation)
Column: Inert
Cap1 (inner diameter 0.25 mm, length 30 m, film thickness 1.5 μm; manufactured by GL Sciences)
Column temperature: 40 ° C to 200 ° C (5 ° C / min)
Injection temperature: 200 ° C
Detector temperature: 250 ° C
Injection volume: 0.1ml
Split ratio: 1:50
なお、表１における３号珪酸ナトリウムの二酸化珪素含有量は２９．１０％である。 In Table 1, the silicon dioxide content of No. 3 sodium silicate is 29.10%.
上記比較例の結果より、（Ｂ）成分および（Ｃ）成分を加えることで金属腐食性を著しく抑えられることが確認された。また、実施例１〜５のいずれも良好な化学物質分解能を有することが分かる。さらに、（Ｄ）成分を加えることでより化学物質分解能が増強される。 From the result of the comparative example, it was confirmed that the metal corrosivity can be remarkably suppressed by adding the component (B) and the component (C). Moreover, it turns out that all of Examples 1-5 have a favorable chemical substance resolution | decomposability. Furthermore, the chemical substance resolution is further enhanced by adding the component (D).
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014512681A JPWO2013161936A1 (en) | 2012-04-27 | 2013-04-25 | Chemical substance decomposition agent composition and chemical substance decomposition treatment method using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012103410 | 2012-04-27 | ||
| JP2012103410 | 2012-04-27 | ||
| JP2014512681A JPWO2013161936A1 (en) | 2012-04-27 | 2013-04-25 | Chemical substance decomposition agent composition and chemical substance decomposition treatment method using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPWO2013161936A1 true JPWO2013161936A1 (en) | 2015-12-24 |
Family
ID=49483240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014512681A Pending JPWO2013161936A1 (en) | 2012-04-27 | 2013-04-25 | Chemical substance decomposition agent composition and chemical substance decomposition treatment method using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2013161936A1 (en) |
| CN (1) | CN104245055A (en) |
| TW (1) | TWI566806B (en) |
| WO (1) | WO2013161936A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624634B (en) * | 2015-03-12 | 2016-03-02 | 南京科盛环保技术有限公司 | A kind of chemical oxidation restorative procedure of organic polluted soil |
| CN112567003B (en) * | 2018-08-13 | 2022-08-09 | 三菱瓦斯化学株式会社 | Viscous fluid decomposer and method for producing the same |
| CN111925098B (en) * | 2020-09-16 | 2021-02-12 | 深圳瑞新达新能源科技有限公司 | Sludge wall breaking treatment agent and method and deep dehydration method |
| KR102657465B1 (en) * | 2021-03-04 | 2024-04-16 | (주) 테크윈 | Stabilization method of persulfate solution |
| CN114958379B (en) * | 2022-05-17 | 2023-08-29 | 南京大学 | Composition for treating hexachloroethane in organic contaminated soil and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004160413A (en) * | 2002-11-15 | 2004-06-10 | Japan Organo Co Ltd | Purification method for contamination by chemical substance |
| JP2004202357A (en) * | 2002-12-25 | 2004-07-22 | Japan Organo Co Ltd | Method for purifying organic compound-polluted object |
| JP2004298693A (en) * | 2003-03-28 | 2004-10-28 | Ohbayashi Corp | Soil cleaning method and soil cleaning agent |
| JP2005237778A (en) * | 2004-02-27 | 2005-09-08 | Idemitsu Kosan Co Ltd | Method for treating hardly decomposable organic compound |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA932278B (en) * | 1992-04-17 | 1994-09-30 | Colgate Palmolive Co | Peroxygen bleach composition |
| JP4020512B2 (en) * | 1998-09-29 | 2007-12-12 | 株式会社日立製作所 | Chemical decontamination method and apparatus |
| JP3669238B2 (en) * | 1999-12-27 | 2005-07-06 | 三浦工業株式会社 | Method for decomposing chlorinated organic compounds |
| JP2002136961A (en) * | 2000-10-31 | 2002-05-14 | Miyama Kk | Decontamination method for soil or underground water |
| SE0200964D0 (en) * | 2002-03-27 | 2002-03-27 | Pnb Entreprenad Ab | A soil decontaminatin method |
| WO2003080264A1 (en) * | 2002-03-27 | 2003-10-02 | Detox Ab | A soil decontamination method |
| JP4018947B2 (en) * | 2002-07-17 | 2007-12-05 | 出光興産株式会社 | Method for decomposing persistent materials |
-
2013
- 2013-04-25 CN CN201380021022.XA patent/CN104245055A/en active Pending
- 2013-04-25 WO PCT/JP2013/062197 patent/WO2013161936A1/en active Application Filing
- 2013-04-25 JP JP2014512681A patent/JPWO2013161936A1/en active Pending
- 2013-04-26 TW TW102115040A patent/TWI566806B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004160413A (en) * | 2002-11-15 | 2004-06-10 | Japan Organo Co Ltd | Purification method for contamination by chemical substance |
| JP2004202357A (en) * | 2002-12-25 | 2004-07-22 | Japan Organo Co Ltd | Method for purifying organic compound-polluted object |
| JP2004298693A (en) * | 2003-03-28 | 2004-10-28 | Ohbayashi Corp | Soil cleaning method and soil cleaning agent |
| JP2005237778A (en) * | 2004-02-27 | 2005-09-08 | Idemitsu Kosan Co Ltd | Method for treating hardly decomposable organic compound |
Non-Patent Citations (1)
| Title |
|---|
| 公害資源研究所第２２回研究講演会資料, JPN7016002862, 12 July 1989 (1989-07-12), pages 39 - 47, ISSN: 0003406565 * |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI566806B (en) | 2017-01-21 |
| CN104245055A (en) | 2014-12-24 |
| TW201412357A (en) | 2014-04-01 |
| WO2013161936A1 (en) | 2013-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9814919B2 (en) | Degrading halogenated organic compounds | |
| Zhang et al. | Degradation of p-chloroaniline by pyrite in aqueous solutions | |
| ES2687753T3 (en) | Treatment of environmental pollutants | |
| US7745680B1 (en) | Compositions, methods, and systems for reducing contamination | |
| US7785038B2 (en) | Oxidation of organic compounds | |
| JP5250975B2 (en) | Soil and / or groundwater purification method | |
| JPWO2013161936A1 (en) | Chemical substance decomposition agent composition and chemical substance decomposition treatment method using the same | |
| JP2007209824A (en) | Method for cleaning contaminated soil or contaminated groundwater | |
| JP5817718B2 (en) | Chemical substance treatment agent containing persulfate and silver complex, and chemical substance decomposition method using the same | |
| US7928277B1 (en) | Method for reducing contamination | |
| JP2010082600A (en) | Method of cleaning soil and/or groundwater | |
| JP5666832B2 (en) | Organic substance decomposition treatment method and organic substance decomposition treatment agent kit | |
| JP4167052B2 (en) | Purification method for organic compound contamination | |
| US20140335601A1 (en) | Chemical oxidation and biological attenuation process for the treatment of contaminated media | |
| Han et al. | Kill two birds with one stone: Solubilizing PAHs and activating PMS by photoresponsive surfactants for the cycle remediation of contaminated groundwater | |
| Goi et al. | DDT-contaminated soil treatment with persulfate and hydrogen peroxide utilizing different activation aids and the chemicals combination with biosurfactant | |
| JP5888877B2 (en) | Chemical substance decomposition agent composition and chemical substance decomposition treatment method using the same | |
| JP2005185870A (en) | Additive used for restoration of contaminated soil, ground water or bottom deposit | |
| JP4978292B2 (en) | Method for removing ruthenium etching composition | |
| JP4803346B2 (en) | Composition having organic compound decomposability and decomposition method | |
| JP2004290768A (en) | Method for cleaning soil and ground water polluted with organochlorine compound | |
| JP2010194450A (en) | Method for cleaning organic halide | |
| JP2017043706A (en) | Chemical material decomposition composition and decomposition treatment method of chemical material | |
| JP2002126713A (en) | Method for cleaning contaminated soil | |
| JP2002361228A (en) | Method for treating organic chlorine compound in soil and/or underground water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160205 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160927 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20170321 |