JP3438044B2 - Method of removing volatile organic compounds in soil - Google Patents

Method of removing volatile organic compounds in soil

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JP3438044B2
JP3438044B2 JP14193693A JP14193693A JP3438044B2 JP 3438044 B2 JP3438044 B2 JP 3438044B2 JP 14193693 A JP14193693 A JP 14193693A JP 14193693 A JP14193693 A JP 14193693A JP 3438044 B2 JP3438044 B2 JP 3438044B2
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soil
method
inorganic compound
removing
volatile organic
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JPH0741761A (en )
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孝文 坂梨
善成 川崎
守 松本
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株式会社片山化学工業研究所
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【発明の詳細な説明】 【0001】 【産業上の利用分野】この発明は揮発性有機化合物で汚染された土壌からそれらの物質を除去する方法に関する。 BACKGROUND OF THE INVENTION BACKGROUND OF THE INVENTION [0001] relates to a method this invention is to remove these substances from the soil contaminated with volatile organic compounds. 【0002】 【従来の技術】最近トリクロロエチレン、パークロロエチレン等の揮発性有機化合物による土壌汚染が深刻な環境汚染の1つとして問題になっている。 [0004] Recently trichlorethylene, soil contamination by volatile organic compounds perchlorethylene, etc. in question as one of the serious environmental pollution. これはかつてこれらを溶媒や脱脂剤として用いてきた多くの工場から種々の原因で漏出或いは排出されて土壌中に混入したための環境汚染であるが、当時はその様な認識もうすく、また規制も定められていなかったため、かえってその汚染が広がったからである。 Although this is a former environmental pollution for mixed them to be leaked or discharged in a variety of causes of many plant has been used as a solvent or degreasing agents in the soil at that time such recognized thin, also regulated because it was not defined, because the contrary is the contamination spread. 【0003】最近になり、このような物質による人体への有害性が指摘され、規制の対象として全国的な調査が進んでおり次第にその汚染状況が把握されつつある。 [0003] More recently, such harmful to the human body by the substance has been pointed out, gradually the pollution situation is progressing nationwide survey as subject to regulation is being grasped. この汚染土壌の処理対策として天日による土壌の自然乾燥や蒸気による温風乾燥、ロータリーキルン等を用いた機械的処理が行われている。 Hot-air drying by natural drying or steam soil by sun as the process measures the contaminated soil, are made mechanical treatment using a rotary kiln or the like. しかし天日による乾燥は自然の気象条件に影響され、かつ、かなり長期間を要しても土壌の表層の部分しか揮発性有機化合物を除去できない。 However drying with sun is affected by natural weather conditions, and only the surface layer portion of the soil can not be removed volatile organic compound it is quite takes long time. 又機械的処理法も高額の設備費が必要、かつ、一度に大量の土壌を処理できないため、その土壌処理コストは高くつくと考えられる。 The mechanical treatment method also requires expensive equipment costs, and, because it can not handle large amounts of soil at a time, the soil processing cost is considered to be expensive. 【0004】この発明はかかる状況において簡便かつ効果的な揮発性有機化合物で汚染された土壌の新しい処理法を提供しようとするものである。 [0004] in which the present invention seeks to provide a new treatment of contaminated soil in a simple and effective volatile organic compound in such situations. 【0005】 【課題を解決するための手段】すなわちこの発明によれば、揮発性有機化合物が含まれた土壌に、中和反応により発熱しうる酸性の無機化合物(以下、「酸性無機化合 [0005] Means for Solving the Problems That is, according to the present invention, the soil volatile organic compound is included, the inorganic acidic compounds which can be heated by the neutralization reaction (hereinafter, "acidic inorganic compounds
物」とも称す)と塩基性の無機化合物(以下、「塩基性 Things "and also referred) and the basic inorganic compound (hereinafter," basic
無機化合物」とも称す)とを添加混合し、揮発性有機化合物を除去することを特徴とする土壌中の揮発性有機化合物の除去方法が提供される。 Also referred) and adding and mixing an inorganic compound "method of removing volatile organic compounds in the soil and removing the volatile organic compound. 【0006】さらにこの発明によれば、揮発性有機化合物が含まれた土壌に、酸性の無機化合物、塩基性の無機化合物及び濡れ促進剤を混合することを特徴とする土壌中の揮発性有機化合物の除去方法が提供される。 [0006] Further according to the present invention, the soil containing the volatile organic compound, an inorganic compound of an acidic, volatile organic compounds in the soil, which comprises mixing a basic inorganic compound and a wetting accelerator the method of removal is provided. 【0007】この発明の方法で除去される揮発性有機化合物とは、常圧で沸点150℃以下の炭化水素誘導体、 [0007] The volatile organic compounds are removed in the method of this invention, the hydrocarbon derivative having a boiling point 0.99 ° C. or less at atmospheric pressure,
すなわち、炭化水素及びその水素の1個以上がハロゲン原子、水酸基、アミノ基等で置換された化合物で、土壌に人為的に含有されたものを意味する。 That is, one or more halogen atoms of the hydrocarbon and hydrogen, hydroxyl, a compound substituted with an amino group or the like, it refers to those artificially contained in the soil. 例えば、ベンゼン、トルエン、n−ヘキサン、シクロヘキサン、クロロホルム、四塩化炭素、1,1-ジクロロエタン、1,2-ジクロロエタン、1,1,1-トリクロロエタン、1,1,2-トリクロロエタン、トリクロロエチレン、テトラクロロエチレン、 For example, benzene, toluene, n- hexane, cyclohexane, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichlorethylene, tetrachlorethylene,
1,1,1,2-テトラクロロエタン、1,1,2,2-テトラクロロエタン、メチルアミン、ジメチルアミン、トリメチルアミン等が挙げられる。 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, methylamine, dimethylamine, trimethylamine, and the like. これらの中で、常圧で沸点120℃ Among these, the boiling point 120 ° C. at atmospheric pressure
以下のものが除去効率の点で好ましい。 Preferable in terms of removal efficiency as follows. 【0008】この発明に用いる酸性の無機化合物としては、1重量%水溶液のpHが3以下を示すものが好ましい。 [0008] As the inorganic compound of an acidic used in the present invention, it is preferable the pH of 1% by weight aqueous solution exhibits a 3 below. それより酸度の低い酸では中和反応速度が比較的遅く又発熱量も低いため、土壌中の揮発性有機化合物の除去能力が充分でない。 Because it lower relatively slow also calorific neutralization reaction rate at low acidity acid removal capacity of volatile organic compounds in the soil is not sufficient. かくしてこの発明で用いる酸性無機化合物の具体例としては、硫酸、塩酸、リン酸、硫酸水素ナトリウム、硫酸水素カリウム、 リン酸水素二ナト Thus Examples of acidic inorganic compounds used in the present invention may include sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydrogen sulfate, potassium hydrogen sulfate, phosphate dibasic isocyanatomethyl
リウム 、スルファミン酸、五酸化リン、無水硫酸、塩化アルミニウム、五塩化リン、三塩化リン、硫酸バン土等が挙げられる。 Potassium, sulfamic acid, phosphorus pentoxide, sulfur trioxide, aluminum chloride, phosphorus pentachloride, phosphorus trichloride, sulfuric acid alum and the like. これらの中で、価格、安全性、取扱い性などの点で、硫酸、リン酸、硫酸水素ナトリウム、スルファミン酸、塩化アルミニウム、硫酸バン土が好ましく、特に硫酸、リン酸、硫酸水素ナトリウムがより好ましい。 Among these, price, safety, in terms of handling property, sulfuric acid, phosphoric acid, sodium bisulfate, sulfamic acid, aluminum, aluminum sulfate preferably chloride, in particular sulfuric acid, phosphoric acid, preferably more sodium hydrogen sulfate . 【0009】この発明に用いる塩基性無機化合物としては、1重量%水溶液ないし懸濁液のpHが10以上を示すものが好ましい。 [0009] Examples of the basic inorganic compound used in the present invention, pH of 1% by weight aqueous solution or suspension is preferably exhibits a 10 or greater. 例えば(a)生石灰、消石灰、酸化ナトリウム、水酸化ナトリウム、酸化カリウム、水酸化カリウム、酸化マグネシウム、水酸化マグネシウム、酸化バリウム、水酸化バリウム、酸化リチウム、水酸化リチウム、水ガラス、ケイ酸ナトリウム等、及び(b)炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、過酸化ナトリウム、過酸化カリウム等が挙げられる。 For example (a) quick lime, slaked lime, sodium oxide, sodium hydroxide, potassium oxide, potassium hydroxide, magnesium oxide, magnesium hydroxide, barium oxide, barium hydroxide, lithium oxide, lithium hydroxide, water glass, sodium silicate, etc. , and (b) sodium carbonate, potassium carbonate, calcium carbonate, sodium peroxide, and peroxide potassium. これらの化合物のうち生石灰、消石灰、水酸化ナトリウム、炭酸ナトリウムが、価格、安全性及び取扱い上好ましい。 Quicklime Of these compounds, calcium hydroxide, sodium hydroxide, sodium carbonate, price, on the safety and handling preferred. 【0010】また、これらの化合物のうち、(a)群の化合物は、上記酸性無機化合物1モル当り1kcal以上の中和熱を発生する化合物であり、また(b)群の化合物は、中和反応の結果、発熱と同時に気体を発生させうる化合物である。 [0010] Among these compounds, (a) group compound is a compound generating the acidic inorganic compound per mole 1kcal more heat of neutralization, and (b) group of compounds are neutralized result of the reaction, a compound capable simultaneously to generate gas and heat. この発明に用いる酸性無機化合物及び塩基性無機化合物は、常温で固体のものについては、通常、粉末、フレーク、小塊状、顆粒のものが適している。 Acidic inorganic compound and the basic inorganic compound used in this invention, for those solid at room temperature, usually, a powder, flakes, small lumps, those granules are suitable. 土壌の含水率にもよるが、比較的含水率の低い土壌(約13重量%以下)または砂質の土壌に対しては、粉末状或いは顆粒状のものが好ましく、含水率が比較的高いか、粘土質の多い土壌の場合はフレーク状又は塊状のものを用いるのが好ましい。 Depending on the moisture content of the soil, or relatively with respect to the soil with a low water content soil (about 13 wt% or less) or sandy, preferably in powder form or granular form, a relatively high water content , in the case of a lot of clay soil preferable to use those flake or bulk. 【0011】また、これらの化合物のうち、常温で液体または濃厚水溶液のものについては、安全性及び取扱い上、水で10〜80重量%前後に希釈して用いてもよい。 [0011] Among these compounds, the ones of the liquid or concentrated aqueous solution at room temperature, may be diluted safety and handling, 10 to 80% by weight before and after the water. 特にリン酸、硫酸、塩酸等は希溶液とするのが好ましい。 In particular phosphoric acid, sulfuric acid, that hydrochloric acid is a dilute solution preferred. 上記酸性無機化合物と塩基性無機化合物とを揮発性有機化合物が含まれた土壌に添加混合することにより、土壌の水分中で中和反応が行われ、発熱し、それにより土壌中の揮発性有機化合物が揮散され、土壌外へ放出される。 By admixing the above acidic inorganic compound and the basic inorganic compound to the soil containing the volatile organic compound, it is carried out the neutralization reaction in the soil moisture, fever, volatile organic thereby soil compounds are volatilized and released into the soil outside. 【0012】また、この発明で用いる酸性無機化合物及び塩基性無機化合物は、単独で添加しても土壌中の水と反応して発熱するものも含まれているが、これらを単独で用いると土壌が酸性又はアルカリ性の何れか一方に極端に偏り土質を損なうことになる。 Further, the acidic inorganic compound and the basic inorganic compound used in this invention has also included those which generate heat by reacting with water alone in the soil by the addition, use of these alone the soil There would impair the extremely uneven soil to either acidic or alkaline. このような土質の偏りをなくすため、この発明は酸性無機化合物と塩基性の無機化合物の組合わせを添加し、中和反応により発熱させ、土壌中の揮発性有機化合物を追い出すと同時に土質を略中性にすることができる。 To eliminate bias in such soil, the present invention is the addition of a combination of an acidic inorganic compound and the basic inorganic compound, substantially by heating, the soil at the same time drive off volatile organic compounds in the soil by the neutralization reaction it can be in neutral. 【0013】処理される土壌は、含水率が10〜30重量%(通常はこの範囲である)の場合に特に顕著な効果がえられる。 [0013] Soil to be treated, the water content is 10 to 30 wt% (usually this range is) particularly remarkable effect when the will be obtained. したがって、土壌の含水率が10重量%未満の場合は、処理前後に水を散布、攪拌して含水率を1 Therefore, if the water content of the soil is less than 10 wt%, before and after processing to spray water, the water content was stirred for 1
0重量%以上にするのが好ましい。 Preferably 0 wt% or more. また、混合時の土壌温度は、15℃以上、好ましくは30℃以上に保持する。 Also, the soil temperature at the time of mixing is, 15 ° C. or higher, preferably held at 30 ° C. or higher. 【0014】上記酸性無機化合物及び塩基性無機化合物の土壌に対する添加比率は、両剤の合計量として、土壌1kgに対し150〜0.10g(すなわち150〜0.1g/k [0014] addition ratio to soil of the acidic inorganic compound and the basic inorganic compound, the total amount of both agents, 150~0.10G to soil 1 kg (i.e. 150~0.1g / k
g)が適切で、60〜10g/kgがより好ましい。 g) is appropriate, 60~10g / kg is more preferable. 15 15
0gより多いと土質に対する影響が大きくなり好ましくない。 Effects on soil and more than 0g large unfavorably. また、0.10gより少ないと中和反応の進行が遅く又発熱量も少ない。 Also, progress is slow addition calorific value of the neutralization reaction is less than 0.10g small. 【0015】さらに、酸性無機化合物と塩基性の無機化合物の添加比率は、酸性無機化合物の酸としての当量1 Furthermore, the addition ratio of the acidic inorganic compound and the basic inorganic compound, eq 1 as an acid acidic inorganic compound
に対し塩基性の無機化合物の塩基としての当量3〜0.3 Equivalents as base of the basic inorganic compound to from 3 to 0.3
がよく、この範囲を越えると土壌の酸性又はアルカリ性が強くなり土質を損なう恐れがある。 C., acidic or alkaline soils exceeds this range may impair strongly become soil. 上記酸性の無機化合物及び塩基性無機化合物の土壌への添加方法については、同時に添加するか、または一方を添加後、他の一方を添加する方法のいずれかを用いてもよい。 For a method of adding to the soil of the acidic inorganic compound and the basic inorganic compound, after addition of either, or one added simultaneously, it may be used any method of adding the other one. いずれにしても揮発性有機化合物の除去効果の点からは、酸性無機化合物と塩基性無機化合物が土壌に均一になるように混合するのが好ましい。 From the viewpoint of the effect of removing the volatile organic compounds in any event, the acidic inorganic compound and the basic inorganic compound is preferably mixed uniformly to soil. 無機化合物と土壌との混合方法に特に限定はなく、土壌の表面に無機化合物を散布し、物理的手段を用いて攪拌することによりその場で攪拌してもよく、土壌と土壌の間に無機化合物または無機化合物含有土壌をサンドウィッチ形式に挟み込む方法もまた好ましい。 There is no particular limitation on the method of mixing the inorganic compound and the soil, the inorganic compound is sprayed on the surface of the soil, it may also be agitated in situ by stirring using a physical means, inorganic between soil and soil how to sandwich the compound or an inorganic compound containing soil sandwich format is also preferred. 【0016】一般に、液状のものと固形のものを添加する際は液状のものを先に添加するのが経験上好ましい。 [0016] In general, when adding those things and solid of liquid on the experience to add to the previous ones of liquid preferred.
また、場合によっては土壌を採取し、別の場所や容器内で均一混合してもよい。 In some cases collected soil may be mixed uniformly in a different place or in a container. この反応に用いられる中和反応は、土壌の含水率にもよるが、水中の場合と比較して土壌中においての反応であるため、反応速度がかなり緩やかになる。 Neutralization reaction used in this reaction depends on the water content of the soil, since the reaction of the soil as compared with the case of water, the reaction rate is quite moderate. 特に酸性無機化合物及び塩基性無機化合物の何れか一方は両方が固形の場合にその傾向が見られる。 This trend is particularly seen when both either the acidic inorganic compound and the basic inorganic compound is a solid.
その様な場合土中に含まれる水分と接触して速やかに溶解させて中和反応を促進させることが必要で、例えば、 Neutralization reaction is necessary to accelerate the dissolving rapidly in contact with the moisture contained in the soil such a case, for example,
次の(1)、(2)の手段を用いてもよい。 The following (1), may be used a means (2). 【0017】(1)濡れ促進剤の使用無機化合物が固形の場合、濡れ促進剤を用いるのが好ましい。 [0017] (1) When using an inorganic compound wetting enhancer is a solid, it is preferable to use a wetting enhancer. ここで濡れ促進剤とは、潮解性を有する化合物で、具体的には塩化リチウム、塩化カルシウム、塩化マグネシウム、塩化マンガン、塩化鉄、塩化アルミニウム等の塩化物;硝酸アルミニウム、硝酸カルシウム、硝酸マンガン等の硝酸塩;亜リン酸水素アンモニウム、亜リン酸水素カリウム等の亜リン酸塩;水酸化ナトリウム、 Here, the wetting accelerator, a compound having deliquescence, specifically lithium chloride, calcium chloride, magnesium chloride, manganese chloride, iron chloride, and aluminum chloride; aluminum nitrate, calcium nitrate, manganese nitrate, etc. ammonium hydrogen phosphite, phosphite such as potassium phosphite hydrogen; nitrate sodium hydroxide,
水酸化カリウム等の水酸化物;及び酢酸カリウム等が挙げられる。 Hydroxides such as potassium hydroxide; and potassium acetate. これらの中で価格、実用性の点から塩化カルシウム、塩化マグネシウム、水酸化ナトリウム等が好ましい。 Price Of these, calcium chloride from the viewpoint of practicality, magnesium chloride, and sodium hydroxide are preferred. 【0018】濡れ促進剤の添加比率は土壌に対し50〜 [0018] The addition ratio of wet accelerator 50 to the soil
0.5g/kgが適当でより好ましくは10〜2g/kgである。 0.5 g / kg is more preferably suitable are 10~2g / kg. 固形の無機化合物が混合された土壌に、濡れ促進剤を添加すると、濡れ促進剤は、固形の酸性又は塩基性の無機化合物の一部と互いに土中で接触する状態となる。 The soil inorganic compound solid is mixed, the addition of a wetting accelerator, wetting enhancer is in a state in contact with the soil together with part of acidic or basic inorganic compound solid.
濡れ促進剤はその潮解性の為に次第に土中の水を呼び込み、初めは自身の分子の回りに水分子を集めるがそのうち、集まって来た水分子に溶解し、流動性をもってその近くに接していた酸性又は塩基性の化合物の固体の表面をぬらす。 Wet accelerator attract gradually soil of water because of its deliquescent, the beginning of which is collecting the water molecules around its own molecule, was dissolved in came together water molecules, with a liquidity close to the contact with the wets the solid surface of the optionally acidic or basic compound. また同時に水に濡れた該促進剤は別の酸性又は塩基性の化合物とも接触を拡げて行く。 The accelerator wet simultaneously water also goes spread the contact with another acidic or basic compound. こうして、濡れ促進剤は、自ら呼び込んだ水で固形の無機化合物の表面を濡らしてその固形の無機化合物の水への溶解を助長するだけでなく、その近くに存在する別の固形の無機化合物とも接触し自身が媒介する形で異なる固形の無機化合物同士が水で濡れながら接触し中和反応を促進するものと推察される。 Thus, wetting enhancer not only facilitates the dissolution in water of inorganic compound in the solid wet the surface of the inorganic compound solid at himself attracted waters, inorganic compounds both of another solid present in the vicinity inorganic compounds between different solid in the form of contact with itself mediated is presumed to facilitate contact and neutralization reaction while wet with water. 【0019】(2)物理的手段の使用中和反応を促進させる物理的手段としては、過剰に到らぬ程度に無機化合物添加後の土壌に散水したり、または転圧を施したりする。 [0019] (2) As the physical means to promote the use neutralization physical means, excessive or watering to soil after addition inorganic compound to the extent that it became too, or or subjected to roller compaction. ここで転圧とは物理的な手段による圧縮を意味し、ローラー等で圧迫する等の手段を用いてもよい。 Here refers to compression by physical means and compaction may be used means such as squeezing with a roller or the like. また、時々土壌を攪拌する方法も適宜利用しうる。 Also be utilized appropriately a method of occasionally agitating the soil. 土壌より除去される揮発性有機化合物は、そのまま大気中に放散すると、大気汚染につながるので、適当な方法で補捉し、焼却又は物理化学的な分解処理を行うのが適当である。 Volatile organic compounds are removed from the soil, when it is released into the atmosphere, so leading to air pollution, and Ho捉 in a suitable manner, it is appropriate to carry out the incineration or physicochemical degradation process. 【0020】この揮発性有機化合物を捕捉する方法としては、特に限定されない。 [0020] As a method of capturing the volatile organic compound is not particularly limited. その具体例としは、密閉系内で、揮発有機化合物が含まれる土壌に酸性及び塩基性無機化合物を混合し、生じた揮発性有機化合物を、 a)活性炭に吸着させる、 b)高沸点(bp160℃以上)の親水性有機溶媒、例えばグリコール、灯油、芳香族炭化水素(例、トリメチルベンゼン)に溶解吸収させる、 c)酸化性の酸、例えば濃硫酸中に通気し、酸化分解する、またはd)紫外線照射により分解する等の方法がある。 Is as its specific examples, in a closed system, the soil was mixed with acidic and basic inorganic compound include volatile organic compounds, the resulting volatile organic compounds, a) is adsorbed on activated carbon, b) a high-boiling hydrophilic organic solvent (Bp160 ° C. or higher), such as glycols, kerosene, aromatic hydrocarbons (e.g., trimethylbenzene) are dissolved absorbed, c) oxidizing acid, was bubbled for example in concentrated sulfuric acid, oxidative decomposition, or d) a method such as decomposed by ultraviolet irradiation. 【0021】上記の方法で、活性炭に吸着させる場合について、さらに説明すると、密閉系例えば密閉容器に、 [0021] In the above method, the case of adsorption on activated carbon, To further illustrate, a closed system for example a closed container,
排気管を配設し、排気管の中間または末端に活性炭を充填した吸着部を設けたものを用いることができる。 The exhaust pipe is disposed, it can be used provided with a suction unit filled with activated carbon in the middle or end of the exhaust pipe. さらにこの密閉容器に、空気導入管を配設し、この導入管にファンを介して空気を強制的に導入すると一層効果的な捕捉を行うことができる。 Further in this sealed container, disposed an air inlet pipe, through the fan to the inlet pipe can be performed forcibly more effectively capture the introduction of air. また、排気管の末端に空気の吸引手段を付設してもよい。 It may also be attached to a suction device of the air at the end of the exhaust pipe. 【0022】 【実施例】次にこの発明を以下の実施例及び比較例によりさらに具体的に説明する。 [0022] [Embodiment] Next will be described more specifically by the following examples and comparative examples of this invention. 実施例1 幅250mm、奥行400mm、高さ120mmの合成樹脂製の容器にトリクロロエチレンで汚染された土壌約10.0kg EXAMPLE 1 Width 250 mm, depth 400 mm, contaminated with trichlorethylene to a synthetic resin container made of a height of 120mm soil about 10.0kg
(含水率18.5重量%)を入れ、酸性無機化合物として、 The (water content 18.5 wt%) was placed, as an acidic inorganic compounds,
フレークの硫酸水素ナトリウム及び85重量%リン酸及び20重量%硫酸を用いた。 With sodium hydrogen sulfate and 85 wt% phosphoric acid and 20% by weight sulfuric acid flakes. 又塩基性無機化合物として、平均粒度5mmに砕いた生石灰、粉末状の炭酸ナトリウム、フレークの苛性ソーダを用いた。 Also as the basic inorganic compound, lime crushed to an average particle size of 5 mm, powdered sodium carbonate with caustic soda flake. 混合法としては双方がフレーク、固体又は粉末の際は同時に添加しよくかきまぜた。 Both the mixing method flakes, when in solid or powder was stirred well added simultaneously. また、酸性無機化合物が液状のときはまず液状物質を先に添加し、ついで塩基性無機化合物を添加しかきまぜた。 Further, the acidic inorganic compound is added to the first previously a liquid substance when the liquid and then stirred by adding a basic inorganic compound. 経時的に土壌の温度を測定しながら8時間放置し、その後、土壌中のトリクロロエチレン濃度及び土壌のpHを測定した。 Over time it left for 8 hours while measuring the temperature of the soil, followed by measuring the pH of trichlorethylene concentration and soil in the soil. 結果を表1に示す。 The results are shown in Table 1. 【0023】(トリクロロエチレンの濃度測定方法)土壌5gを50mlの遠沈管に採取し手早く秤量の後、水1 [0023] (A method for measuring the concentration of trichlorethylene) after the collected quickly weighed the soil 5g to the centrifuge tube of 50ml, water 1
0ml及びn−ヘキサン10mlを速やかに加え蓋をして振盪機を用いて10分間振盪抽出する。 Shaking extracted for 10 minutes with 0ml and n- hexane 10ml rapidly added shaker with a lid. ついで、n−ヘキサン層中のトリクロロエチレンの濃度をガスクロマトグラフィーにより求める。 Then, the concentration of trichlorethylene in n- hexane layer obtained by gas chromatography. 【0024】同時に土壌中の水分含有量を測定し、土壌絶乾量に対するトリクロロエチレン濃度を求めた(本法は社団法人日本環境測定分析協会発行の「環境と測定技術Vol.16,No.5, 1989 ,31-34に記載の測定方法に準ずる)。 【0025】(土壌のpHの測定)土壌1kgを採取しこれを10 lの純水中に入れて1分間攪拌後5分間放置し、その上澄液100mlを取ってそのpHを測定し土壌のpHとした。 【0026】 【表1】 [0024] at the same time to measure the moisture content in the soil was determined trichlorethylene concentration for soil bone dry weight (present method of Japan Environmental Measurement Analysis Association issued "environment and measurement techniques Vol.16, No.5, 1989, pursuant to the measuring method described in 31-34). [0025] (measurement of pH of the soil) was left soil 1kg was taken take this into pure water 10 l 1 minute after stirring 5 minutes, the and the pH of the soil to measure the pH by taking the supernatant 100ml. [0026] [Table 1] 【0027】 【表2】 [0027] [Table 2] 【0028】実施例2 トリクロロエチレンの含有量が50mg/kg、含水率が1 The content of the Example 2 Trichlorethylene is 50 mg / kg, moisture content 1
2.6重量%の土壌を用い、実施例1と同様の方法によりテストした。 With 2.6 wt% of the soil was tested in the same manner as in Example 1. 但し今回は土壌の含水率の低さを考え、濡れ促進剤を併用したものについてもその効果を調べた。 However, this time considering the low moisture content of the soil, was examined the effect also that a combination of wet accelerator.
その結果を表2に示す。 The results are shown in Table 2. 【0029】 【表3】 [0029] [Table 3] 【0030】 【表4】 [0030] [Table 4] 【0031】実験結果の考察表1の結果を見るに、無処理の場合でも8時間で土中のトリクロロエチレンの3割が飛散するが大部分は残存していることが分かる。 [0031] To view the results of the Discussion Table 1 experimental results, most 30% is scattered in the soil in 8 hours even in the case of untreated trichlorethylene It can be seen that remains. また、比較例1〜6を見ると何れもブランクよりはトリクロロエチレンが除去されていることが認められるが、これは各化合物の水との溶解熱や反応熱の為トリクロロエチレンの飛散を促したものである。 Moreover, those it is recognized that trichlorethylene than any blank when looking at Comparative Example 1-6 is removed, which is urged scattering of trichlorethylene for heat of solution or heat of reaction with water of each compound is there. 但し生石灰を除き8時間後においてもその除去率は5〜7割の間にありなお3〜4割のトリクロロエチレンが存在する。 However its removal rate even after 8 hours except quicklime is between 5-7 percent Incidentally 30-40% of trichlorethylene is present. 生石灰は自身の高い水との反応熱から単独でもよい効果を挙げているが、テストNo2〜8と比較すると、(これらは何れも固体換算で生石灰と同じ合計量4重量%を含むが)No2〜8の何れもが4時間経過した時点で除去率が90重量%を超え8時間後には99重量%を超えており生石灰単独より優れている。 Although lime cites a good effect solely from reaction heat with high own water, when compared with the test No2~8, (including the same total amount of 4 wt% and quicklime both these solid terms) No2 any 8 of the removal rate at the time of the lapse of 4 hours is better than quicklime alone and after 8 hours more than 90% by weight greater than 99 wt%. 又No1を見ると2重量%の濃度でも生石灰単独とほぼ同等の効果を挙げていることが分かる。 Also it can be seen that given substantially the same effect as quicklime alone at a concentration of 2 wt% Looking No1. さらにテスト後の土壌のpH Furthermore, the pH of the soil after the test
を見ると、比較例の1〜6は何れも強い酸性又はアルカリ性を示しているのに対しテストNo1〜8は何れも6〜 Looking at, any test No1~8 whereas shows 1-6 Any strong acid or alkaline Comparative Example 6
8のpH値を示し何れも土質を損なわないことが分かる。 Both a pH value of 8 can be seen that does not impair the soil. 【0032】表2の結果を見るにテストNo9〜12が酸性化合物と塩基性化合物の組合わせにより比較的良い結果が表われており、8時間経過後でトリクロロエチレンが9割以上除去されている。 The relatively good results have we table by a combination of test No9~12 acidic compound and the basic compound in view the results in Table 2, are removed trichlorethylene 90% or more after 8 hours. 一方テストNo1〜8のように濡れ促進剤が併用されると、No9とNo1,2,5,8 On the other hand, if wetting enhancer as tested No1~8 are used in combination, No9 and No1,2,5,8
或いはNo10とNo3,4或いはNo11とNo6或いはNo1 Or No10 and No3,4 or No11 and No6 or No1
2とNo7との対比で示される様に、何れも濡れ促進剤を用いたものが中和反応を促進し除去率を上げ、100% 2 and as shown by comparison with No7, those both with wet enhancer raised promote removal rate neutralization reaction, 100%
に近い数字から分かるように、殆んど完璧に除去が行われることが分かる。 As can be seen from figures close to, it can be seen that the perfect removal is carried out almost.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl. 7識別記号 FI F24J 1/00 (56)参考文献 特開 平4−347176(JP,A) 特開 平4−135689(JP,A) 特開 昭57−145092(JP,A) 特開 昭63−162592(JP,A) 特開 昭61−91283(JP,A) 特開 平5−76618(JP,A) 特開 昭52−90469(JP,A) 特開 昭54−130350(JP,A) 特開 平5−168727(JP,A) 特開 平3−178675(JP,A) (58)調査した分野(Int.Cl. 7 ,DB名) C09K 17/00 - 17/52 A62D 3/00 ZAB B09C 1/00 - 1/10 C09K 3/00 ────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. 7 identifications FI F24J 1/00 (56) references Patent Rights 4-347176 (JP, a) Patent Rights 4-135689 (JP, a) JP open Akira 57-145092 (JP, A) JP Akira 63-162592 (JP, A) JP Akira 61-91283 (JP, A) Patent Rights 5-76618 (JP, A) JP Akira 52-90469 ( JP, a) JP Akira 54-130350 (JP, a) JP flat 5-168727 (JP, a) JP flat 3-178675 (JP, a) (58 ) investigated the field (Int.Cl. 7, DB name) C09K 17/00 - 17/52 A62D 3/00 ZAB B09C 1/00 ​​- 1/10 C09K 3/00

Claims (1)

  1. (57)【特許請求の範囲】 【請求項1】 揮発性有機化合物が含まれた土壌に、中和反応により発熱しうる酸性の無機化合物と塩基性の無機化合物とを添加混合し、揮発性有機化合物を除去することを特徴とする土壌中の揮発性有機化合物の除去方法。 (57) to the Claims 1 Soil volatile organic compound is included, and an inorganic compound of an inorganic compound and the basic acid that can generate heat admixed by neutralization reaction, volatile method of removing volatile organic compounds in the soil, characterized in that the removal of organic compounds. 【請求項2】 濡れ促進剤をさらに添加する請求項1記載の除去方法。 2. A wet removal method according to claim 1, wherein the promoter is further added. 【請求項3】 酸性の無機化合物が1重量%水溶液のp Wherein the inorganic acidic compounds is 1 wt% aqueous solution of p
    Hが3以下を示す酸性の無機化合物である請求項1記載の除去方法。 Removing method of claim 1, wherein H is an inorganic compound of an acidic showing a 3 below. 【請求項4】 塩基性の無機化合物が1重量%水溶液ないし懸濁液のpHが10以上を示す塩基性の無機化合物である請求項1記載の除去方法。 4. A method for removing of claim 1 wherein the pH of the basic inorganic compound is 1% by weight aqueous solution or suspension is a basic inorganic compound showing 10 or more. 【請求項5】 酸性の無機化合物が燐酸、硫酸または硫酸水素ナトリウムである請求項1〜4のいずれかに記載の除去方法。 5. The acidic inorganic compound phosphate, method for removing according to any one of claims 1 to 4 is sulfuric acid or sodium hydrogen sulfate. 【請求項6】 塩基性の無機化合物が酸化カルシウム、 6. The basic inorganic compound is calcium oxide,
    水酸化カルシウム、水酸化ナトリウムまたは炭酸ナトリウムである請求項1〜5のいずれかに記載の除去方法。 Calcium hydroxide, the method of removing according to claim 1 which is sodium hydroxide or sodium carbonate. 【請求項7】 濡れ促進剤が、塩化カルシウム、塩化マグネシウムまたは水酸化ナトリウムである請求項2記載の除去方法。 7. A wetting accelerator, calcium chloride, a method of removing according to claim 2, wherein magnesium chloride or sodium hydroxide. 【請求項8】 揮発性有機化合物の除去が、土壌を攪拌、転圧または散水して行われる請求項1記載の除去方法。 Removal of 8. The volatile organic compounds, stirred soil, compaction or removing method according to claim 1 wherein, taken in watering. 【請求項9】 揮発性有機化合物の除去が密閉系で行い、揮発する有機化合物を捕捉する請求項1記載の除去方法。 9. performs removal of volatile organic compounds in a closed system, the method for removing of claim 1, wherein capturing the organic compound to be volatilized. 【請求項10】 捕捉が活性炭に吸着させることである請求項9記載の除去方法。 10. A method for removing of claim 9, wherein capture is to adsorb on the activated carbon.
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