JP2004042011A - Early purification method for petroleum-contaminated soil using burnt lime, and greening method - Google Patents

Early purification method for petroleum-contaminated soil using burnt lime, and greening method

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Publication number
JP2004042011A
JP2004042011A JP2002238650A JP2002238650A JP2004042011A JP 2004042011 A JP2004042011 A JP 2004042011A JP 2002238650 A JP2002238650 A JP 2002238650A JP 2002238650 A JP2002238650 A JP 2002238650A JP 2004042011 A JP2004042011 A JP 2004042011A
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Prior art keywords
method
soil
contaminated
lime
petroleum
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JP2002238650A
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Japanese (ja)
Inventor
Satoshi Matsumoto
Satoru Shibata
Toru Ueda
松本 聰
柴田 悟
植田 徹
Original Assignee
Satoshi Matsumoto
Toru Ueda
松本 聰
植田 徹
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/40Valorisation of by-products of wastewater, sewage or sludge processing

Abstract

PROBLEM TO BE SOLVED: To provide three methods which are (1) a method for decontaminating petroleum-contaminated soil or the like at a low cost, quickly, in an ecologically friendly manner, (2) a method of applying greening thereto using soil, and (3) a design method for performing the two above-mentioned treatments.
SOLUTION: In the decontamination method of petroleum-contaminated soil is characterized in that, after the petroleum-contaminated soil is slurried by adding water, it is combined with three treatments such as (1) burnt lime addition, (2) hydrogen peroxide addition, and (3) warming (normal temperature-100 °C) or pressurization and warming treatment (normal temperature-200°C). Moreover, the method may use alkali salts such as slaked lime, sodium bicarbonate, sodium hydroxide and potassium hydroxide, and alkaline electrolytic water instead of burnt lime.
COPYRIGHT: (C)2004,JPO

Description

【0001】 [0001]
【発明の属する技術分野】 BACKGROUND OF THE INVENTION
本発明は、石油系汚染土壌等の(1)早期浄化法、(2)緑化法、更には、(3)それらの方法を行うためのプラント設計法に関する。 The present invention, such as petroleum contaminated soil (1) early purification method, (2) planting method, furthermore, relates to plant design method for performing (3) those methods.
【0002】 [0002]
【従来の技術】 BACKGROUND OF THE INVENTION
従来の石油系汚染土壌の処理方法は、(1)微生物分解法、(2)堆肥添加法、(3)電極による熱分解法、(4)溶媒洗浄法、(5)磁選処理法、(6)加熱分離法、(7)焼却法、(8)紫外線照射法等を挙げる事ができる。 Processing method of the conventional petroleum contaminated soil, (1) microbial degradation method, (2) Fertilizer addition method, (3) thermal decomposition method by the electrode, (4) a solvent washing method, (5) magnetic separation treatment, (6 ) heating separation method, (7) incineration, and (8) UV irradiation method. しかしながら、これらの浄化法のうち、汚染土壌1m 当たり、2万円以下の経費で済む処理方法は2,3に限定される。 However, among these purification methods, contaminated soil 1 m 3 per treatment method requires only 20,000 yen or less expenses is limited to 2,3. そのうち、微生物分解法は油分が多い土壌には、分解微生物の生育活性が阻害されるため事実上使えない。 Of these, microbial degradation method is the oil is often soil, can not be used practically for growth activity of the degrading microorganisms is inhibited. また、光照射法も土壌スラリーは光を通しにくいので、実験室レベルならともかく、現場の大量土壌に有効照射するのは実際は難しい。 In addition, since the light irradiation method also soil slurry is difficult through the light, anyway if the laboratory level, in practice it is difficult to effective radiation to a large amount soil of the field. また、数百℃で油分を揮発させたり、燃焼させる方法も、ダイオキシン等の有害物質を大気に放出する危険性が無視できない。 Also, or to evaporate the oil a few hundred ° C., a method to burn even can not be ignored risk of releasing toxic substances such as dioxin in the atmosphere. 更に、溶剤抽出法に関しても、処理した後の土壌の再利用を考えていないだけでなく、ガソリンスタンド跡地のような面積が小さい場合はプラントを現場では組み立てられないといった問題点が残る。 Furthermore, with regard solvent extraction method, not only we do not plan to reuse soil after treatment, when the area, such as gas stations site is small problem that not assembled remain on site plant. 本発明は、これらの点に考慮してなされたものであり、(1)石油汚染土壌1m 当たり、2万円以下の経費で行え、(2)短期間で浄化が可能であり、(3)薬剤(生石灰、過酸化水素等)の残留問題が比較的少なく、(4)300℃以上といった大きなエネルギーも使わず、(5)処理後の土壌を緑化等に利用可能、という5点において、従来の技術と比べ一定の競争力があるものと考えられる。 The present invention has been made in view of these points, (1) Oil contaminated soil 1 m 3 per performed at 20,000 yen or less expenses, are possible purification in (2) short term, (3 ) agent (quicklime, remaining problems of hydrogen peroxide, etc.) is relatively small, (4) 300 ° C. energy greater without such or, (5) the soil after treatment available to greening, the five points that, it is believed that there is a certain competitive compared with the prior art.
【0003】 [0003]
本発明の浄化原理は、請求項1に挙げた、アルカリ・過酸化水素法と、請求項3に挙げたフェントン反応法に大別できる。 Purifying the principles of the present invention is listed in claim 1, and an alkali-hydrogen peroxide method can be roughly divided into Fenton reaction method mentioned in claim 3. まず前者に関する関連特許としては、まず米国会社であるコンティニュアム エンバイロンメンタル インコーポレーテッドの「有機汚染物質の処理方法(特表2001−513021)」を挙げる必要がある。 The first patents related to the former, it is necessary to first mention of a US company Continuum the Environmental Inc. "Handling organic pollutants (Kohyo 2001-513021)." しかし、この米国会社の方法では、何よりも、「生石灰等アルカリ剤を加えていない点」が本発明と根本的に異なる。 However, in the US company of the way, more than anything else, "that it does not added to the quicklime such as an alkaline agent" is different to the present invention fundamentally. 本発明の実施例で示したように過酸化水素のみの添加で石油汚染土壌の酸化処理を行う場合は、(ケン化剤としても作用する)生石灰の添加を伴う区と比べ、格段に油状物質分解能力が劣り、特に油分の割合が多い場合は十分に浄化する事はできないし、緑化にも使えない。 When performing the oxidation treatment of oil-contaminated soil with the addition of hydrogen peroxide alone, as shown in the embodiment of the present invention, compared to the wards with the addition of quick lime (also acts as saponification agent), much oil poor decomposition ability, do not be, especially if the proportion of oil is often possible to sufficiently purified, can not be used to greening. また、この特許では、請求項1において「パイプ手段によって連結している連続した独立の処理装置」を用いて「該土壌を処理装置から処理装置に移動させる」方式に限定した上で全ての権利請求を行っているが本発明においては、「パイプ手段によって連結している連続した独立の処理装置」を用いない「単独の処理槽」によっても浄化を行えるため、そういった面でも、この米国会社特許とは競合しないと判断できる。 Also, in this patent, all rights on that limited to "move to the processing unit from the processing unit to the soil" method using "independent of the processing device continuously being connected by a pipe means" in claim 1 in Although the present invention has made the request, since that allows purification by not using the "pipe means to have continuous independent processor connected by" "a single processing tank", even in such a plane, the US company patent it can be determined that does not compete with.
【0004】 [0004]
また、請求項3に関する関連特許(すなわちフェントン反応を用いた浄化)に関しては、株式会社荏原製作所の「固体中のダイオキシン類の分解方法(特開2000−197867)」が挙げられるが、本特許は、対象をあくまでもダイオキシンに限定しており、石油汚染土壌等に関しては請求範囲を広げていないだけでなく、用いる鉄化合物に関しても硫酸第一鉄に限定している。 As for the related patents for claim 3 (i.e. purification using the Fenton reaction), "method for decomposing dioxins in the solid (JP 2000-197867)" of Ebara Corporation but are mentioned, this patent , and by limiting the subject last to dioxin, it is limited to ferrous sulfate regard regarding petroleum contaminated soil or the like not only extends the claims, as iron compound. それに対し、本発明においては、このフェントン反応を石油汚染土壌浄化に適用した結果、良好な結果が得られたので、ダイオキシン以外の全ての有機化合物汚染土壌浄化にも適用しうる新技術としてフェントン反応に特許請求するものである。 In contrast, in the present invention, the Fenton reaction result of applying the oil contaminated soil remediation, and because good results were obtained, Fenton reaction as a new technology that can be applied to all of the organic compounds contaminated soil remediation other than dioxins it is intended to claimed. また、フェントン反応に用いる鉄化合物に関しても硫酸第一鉄に限定せず、硫化鉄等、二価の鉄イオンを供給する全ての鉄化合物に関して請求を行う点が異なっている。 Also, not limited to ferrous sulfate with respect to the iron compound used in the Fenton reaction, iron sulfide, etc., that perform billing is different for all iron compound supplying divalent iron ions. また、同様の特許として、藤堂福蔵氏出願の「ジベンゾ−p−ジオキシンおよびジベンゾフランの処理方法(特開2001−240596)」も挙げる必要があるが、本特許も、特許請求の対象をダイオキシン類のみに限定しており、石油汚染土壌等、ダイオキシン以外の有機化合物に適用できる事は対象外としており、ダイオキシン以外の物質を浄化する限りにおいては、本発明の請求項3とは競合しない。 Further, as the same patent, it is necessary to mention also "dibenzo -p- dioxin and dibenzofuran processing method (JP 2001-240596)" said Fukuzo Todo application, also this patent, dioxins claimed subject matter only It is limited to, petroleum contaminated soil or the like, that can be applied to organic compounds other than dioxins are not eligible, as long as purifying substances other than dioxins, the third aspect of the present invention do not conflict. 更に、二価の鉄イオンの供給源として、特に硫化鉄、酸化鉄や、それを含む火山灰や鉄鋼スラグが有効である事に関しても、触れていないため、そういった点に関しても、本発明の独自性及び権利は主張できるものと考えられる。 Furthermore, as a source of divalent iron ions, especially iron sulfide, and iron oxide, with regard volcanic ash and steel slag containing it to be effective, because it does not touch, with regard such a point, the uniqueness of the present invention and rights are believed to be claimed.
【0005】 [0005]
また、本発明は、石油系汚染土壌の浄化法の原理だけでなく、それを行うためのプラントに関しても特許請求を行っている(請求項6〜9)。 Further, the present invention is not only the principle of purification methods petroleum contaminated soil, also performed claimed respect plant are (claims 6-9) to do it. そのうち、請求項6に示したジュール熱を活用する方式に対する関連特許として、株式会社間組の「汚染土壌の浄化方法(特開2002−1299)」を挙げる必要があるが、この間組の方法では単に導電性物質を添加し加熱するのみなので、比較的分解が容易なトリクロロエチレンなら分解できても、石油汚染土壌に関しては有効な浄化が期待できない。 Among them, as a related patent to Exploiting Joule heat of the claims 6, it is necessary to include a "method of purifying contaminated soil (JP 2002-1299)" sets between Co., simply by this between sets of methods since the addition of conductive material such only heating even be resolved if decomposed relatively easy trichlorethylene, effective cleaning can not be expected with respect to petroleum contaminated soil. また、溶融固化法やアルカリ触媒化学分解法においても同様なプラントを設置するが、両者とも300℃以上の高温を要求し設備がそれだけ大がかりになるのに対し、本発明のプラントでは100℃以下の比較的低温で作用させるためイニシャルコストが安いメリットがある。 Although installing a similar plant also in melting and solidification method or alkali catalyst chemical decomposition method, whereas Both require high temperatures above 300 ° C. facility becomes much large-scale, of 100 ° C. or less in the plant of the present invention relatively initial cost to act at a low temperature is low merit.
【0006】 [0006]
また、請求項7で示した省エネ型プラントに関しての関連特許として、三菱重工株式会社の「焼却灰の処理方法およびその装置(特開2001−137803)」を挙げる必要があるが、この特許はダイオキシン汚染飛灰のみに限定されたものであり、飛灰以外の土壌、底泥や、石油等のダイオキシン以外の有機物質汚染に関しては対象としていない。 Further, as a related patents regarding energy-saving plant shown in claim 7, MHI "ash treatment method and apparatus (JP 2001-137803)" Corporation it is necessary to mention, the patent dioxin pollution fly ash has been limited only to, soil other than fly ash, and sediment, does not cover with respect to organic pollution of non-dioxin such as petroleum. また、焼却場排水のみに限定しており、地熱発電所、温泉等の自然エネルギーや、原子力発電所、精錬所等の工場排水は対象としておらず、それでは十分な省エネルギー効果が期待できない。 Also, are limited only to incineration waste water, geothermal power plants, and natural energy of hot springs, etc., nuclear power plants, industrial wastewater, such as refinery is not intended, So enough energy-saving effect can not be expected.
【0007】 [0007]
最後に、請求項8,9に示した浄化能を有した移動車両・船舶プラントに関しては、従来の技術に特記すべきものを発明者らは知らない。 Finally, with respect to the moving vehicle and ship plant having a purifying capability of the claims 8 and 9, we do not know what particular note in the prior art. 例えば、油回収船は多く建造されていても、その油回収船の中で浄化も同時に行える船舶は現在、存在せず、そのため廃棄物輸送コストがかかる上に、油回収量の制約も大きい。 For example, even if oil recovery vessels are often built, now ship performed simultaneously purifying in the oil recovery vessel, absent, therefore on the take waste transport costs, greater constraints oil recovery amount. 従って、本発明(請求項8,9)によって、環境浄化の機動性を向上させうる事が期待される。 Accordingly, the present invention (Claim 8, 9), it is expected that can improve the mobility of environmental cleanup. また、請求項10に示した浄化処理を部分的に終えた土壌を緑化に用いるという概念の従来の技術も報告されていない。 Further, prior art concept of using the greening partially completed soil purification process of the claims 10 also not been reported. 特に本発明では、請求項1においては、土壌浄化に生石灰等を用いるが、生石灰や消石灰は土壌改良材若しくは肥料として農業で一般的に用いられており、この浄化処理で残留した生石灰、消石灰等や、分解された石油成分を、植物栄養源に用いる方向性を示したのは、本発明が最初であろう。 In particular, in this invention, in claim 1, uses a quicklime, etc. soil remediation, the quicklime and slaked lime are commonly used in agriculture as a soil conditioner or fertilizer, lime remaining in the purification process, slaked lime, etc. and, the decomposed oil component, was indicate the direction of using the plant nutrient sources present invention will be first.
【0008】 [0008]
【発明が解決しようとする課題】 [Problems that the Invention is to Solve
石油系汚染土壌等を、(1)低コストで、迅速に、環境に優しい形で浄化する方法、(2)浄化処理済みの土壌を用いて緑化する方法、(3)前述の2処理を行うためのプラント設計法、の3つを提供する事を課題とする。 Performing petroleum contaminated soil or the like, (1) low cost, quickly, a method of purifying at an environmentally sound fashion, a method of greening with (2) purifying the treated soil, a 2 process (3) described above plant design method for, it is an object of the present invention to provide a three.
【0009】 [0009]
【課題を解決するための手段】 In order to solve the problems]
上記目的を達成するためには、石油系汚染土壌に水を加えスラリー化した上で、生石灰等のアルカリ剤添加と過酸化水素添加と加温加圧処理の3処理を組み合わせればよい。 To achieve the above object, after slurrying adding water to petroleum contaminated soil, it may be combined to 3 treatment alkaline agent addition and the addition of hydrogen peroxide and heating and pressurizing treatment such as quicklime. あるいは、土壌スラリーに硫化鉄、硫酸第一鉄等の二価の鉄イオンを供給しうる鉄化合物、若しくはそれらを含む火山灰、鉄鋼スラグと過酸化水素添加を組み合わせるフェントン反応を用いても良い。 Alternatively, the iron sulfide in the soil slurry, iron compounds capable of supplying a divalent iron ion such ferrous sulfate, or ash containing them, may be used Fenton reaction combining steel slag and the addition of hydrogen peroxide. また、更に必要なら、(1)オゾン、光照射、次亜塩素酸等の各種酸化処理、(2)触媒、(3)曝気、若しくは撹拌、(4)活性炭等炭化素材添加の計4処理のうちの1つ、若しくは複数を組み合わせれば更に分解能を促進させる事ができる。 Further, if necessary, (1) ozone, light irradiation, various oxidation processes, such as hypochlorous acid, (2) catalyst, (3) aeration or stirring, (4) a total of four treatment such as activated carbon carbonized material added one out, or a plurality of further can promote the resolution by combining. また、土壌等の加温処理(常温〜100℃)を行う場合は、スラリー化した汚染土壌等を地中等に設置した容器内に入れた上で、電極を設置し通電により発生したジュール熱を利用できるよう設計されたプラントを用いても良い。 In the case of performing heat treatment of the soil or the like (normal temperature to 100 ° C.), after having placed in a container equippedwith a slurried contaminated soil or the like into the ground or the like, the Joule heat generated by installing the electrode energization it may be using the plant, which is designed so that available. また、地熱発電所、精錬所、原子力発電所、火力発電所、ゴミ等焼却場等の大量の熱を発生するプラントの高熱工業排水あるいは温泉水を用いて、請求項1〜5の方法を用いて浄化を行えるよう設計された省エネ型浄化プラントを設置したり、請求項1〜5の方法を行える設備一式(スラリー等を撹拌可能な装置、過酸化水素等酸化剤添加装置、生石灰等アルカリ剤添加装置、紫外線照射装置、触媒添加装置、加熱装置、加圧装置等)を設置し、原位置で石油等に汚染された土壌や海水等を浄化できるよう設計された移動車両・船舶プラントを用いるのも効果的である。 Further, geothermal power plants, smelters, nuclear power plants, thermal power plants, using a high heat industrial wastewater or hot spring water of the plant that generates a large amount of heat, such as dust incinerator or the like, using the method of claims 1 to 5 established the energy-saving purification plant designed to perform the purification Te or, stirrable device equipment set (slurry or the like that enables the method of claims 1 to 5, and hydrogen peroxide oxidizing agent adding device, lime and the like alkali agent addition device, the ultraviolet irradiation apparatus, catalyst addition, heating device, set up a pressure device, etc.), using a mobile vehicle and ships plant which is designed to purify contaminated soil or sea water or the like such as oil in situ the it is also effective. 更に、これらの方法を用いて部分浄化した土壌等に植栽を行う事を特徴とする植物環境修復法もしくは緑化法や、該土壌等に、植栽を行わずに単に有害物質分解微生物群や堆肥を添加する微生物環境修復法も効果的に働く事が期待される。 Furthermore, and plants environmental restoration method or greening method and performing a planting portion purifying soil or the like using these methods, to the soil or the like, Ya simply harmful substances decomposed microorganisms without planting microbial environmental remediation method in which the addition of compost also is expected to work effectively. また、油状汚染土壌等をこれらの方法を用いて処理した処理物を酸性土壌矯正用の土壌改良材、若しくは肥料として花卉栽培、林業等に用いるのも、資源循環促進、処理コスト回収の両面で有効である。 Further, the oil contaminated soil, etc. Soil improvement material for acid soils correcting treated treated using these methods, or floriculture as a fertilizer, also used in forestry, such as, recycling promotion, both in processing cost recovery It is valid.
【0010】 [0010]
【発明の実施の形態】 DETAILED DESCRIPTION OF THE INVENTION
以下、本発明を更に詳細に説明する。 Hereinafter, more detailed explanation of the present invention. 有機物質を含有する排水に、(1)生石灰等のアルカリ剤添加と、(2)過酸化水素添加と、(3)室温〜100℃の範囲(できれば80℃前後)での加温処理、若しくは加圧加温処理(〜200℃)の計3処理を組み合わせればよい。 In wastewater containing organic matter, (1) an alkali agent and an additive, such as lime, (2) and the addition of hydrogen peroxide, (3) heating process in the range of room temperature to 100 ° C. (before and after 80 ° C. if possible), or it may be combined to a total of 3 treatment pressurizing and heating treatment (to 200 DEG ° C.). この時、加圧せずに単に加温する場合は、撹拌若しくは曝気を行った方が良い。 In this case, when simply warmed without applying pressure, the better it was stirred or aerated. それだけで、生石灰処理のみや、過酸化水素処理のみや、生石灰と過酸化水素を常温処理のみと比較し、石油分解能が格段に高まる。 It only quicklime treatment or only, and only the hydrogen peroxide treatment, compared with quicklime and hydrogen peroxide cold treatment alone, petroleum resolution is increased remarkably. なお、この際、生石灰の添加割合は、石油汚染土壌重量の1〜3割程度、過酸化水素の添加割合は、石油汚染土壌重量の5〜30%を目安に適宜調節すればよい。 At this time, the addition ratio of quicklime, 1-3 percent degree of oil-contaminated soil by weight, addition ratio of hydrogen peroxide may be suitably adjusted to 5-30% of oil contaminated soil weight as a guide. 過酸化水素の添加量が多い程、石油分解能は高まるが、その分、コストが割高になるので、費用対効果を念頭に条件検討を行うべきである。 The more amount of hydrogen peroxide, petroleum resolution is increased, correspondingly, the cost becomes expensive, it should perform conditional consider cost effectiveness in mind. この反応の原理は、過酸化水素添加により発生するヒドロキシラジカルの発生がアルカリ条件、高温条件で高まると同時に、エステル結合を含む油分の場合は同時にケン化効果もあるものと推測できる。 The principle of this reaction, generation of hydroxyl radicals generated by adding hydrogen peroxide under alkaline conditions, at the same time increases at high temperature conditions, when the oil containing an ester bond can presumed that some saponification effect simultaneously. また、ここでアルカリ剤として生石灰を用いるのは、強アルカリ状態にしても、水や空気中の二酸化炭素と反応して、消石灰を経て炭酸カルシウムに自然に中和される効果が期待されると同時に、熱源としても利用できるからである。 Also, where use quicklime as alkali agent will, in strongly alkaline conditions, reacts with carbon dioxide in water or in the air, the effect to be neutralized naturally calcium carbonate through the slaked lime is expected at the same time, because it is also used as a heat source. また、生石灰は過酸化水素と同様、値段が安く、処理経費が安価に抑えられる。 In addition, quicklime as well as hydrogen peroxide, cheaper price, processing cost can be suppressed at low cost. これらアルカリ剤及び過酸化水素の添加は一度に投入するのではなく、一定の時間間隔をおいて追加添加を繰り返す方が、作用時間全体を通してのヒドロキシラジカルの発生効率及び熱発生効率を高める上で望ましい。 The addition of these alkali agents and hydrogen peroxide rather than introduced all at once, who repeats the additional added at regular time intervals, in enhancing the generation efficiency and heat generation efficiency of the hydroxyl radicals throughout the action time desirable. なお、生石灰の代わりに、水酸化ナトリウム等を用いても良いが、その場合は、処理後に酢酸や木酢液等で中和処理を行う必要がある。 Instead of quicklime, it may be used sodium hydroxide, in which case, it is necessary to perform neutralization with acetic acid or vinegar and the like after treatment. また、これらの反応を行う上で、単なる加温処理(常温〜100℃)でも良いが、多少コストがかかっても、浄化時間を早めたい場合は、加温加圧法(〜200℃)の方が効果的なのはパルプ業界の例から考えても明白である。 Further, in carrying out these reactions, but may be simply a heat treatment (room temperature to 100 ° C.), even when a slight cost, if you want to accelerate the purification time, towards the warm pressing process (to 200 DEG ° C.) but effective one is obvious be considered from the example of the pulp industry. 実際、発明者らも石油汚染土壌を通常の高圧滅菌器(オートクレーブ)で127℃2時間処理したものと、単に同時間80℃処理したものとを比較した結果、前者の分解効率の方が優れていた事を確認している。 In fact, as a result of inventors also to those treated 127 ° C. 2 h petroleum contaminated soil normal pressure sterilizer (autoclave), simply by comparing the those treated same time 80 ° C., superior to the former destruction efficiency which was that the has been confirmed.
【0011】 [0011]
また、アルカリ・過酸化水素法にこだわる必要はなく、(鉄汚染がやや気にはなるが)フェントン反応を石油汚染土壌に用いるのも有効である。 Moreover, it is not necessary to stick to alkaline hydrogen peroxide method, (although iron contamination is the vapor slightly) is also effective to use a Fenton reaction petroleum contaminated soil. その場合、石油系汚染土壌に水を加えスラリー化した上で、(1)硫化鉄、硫酸第一鉄等の二価の鉄イオンを供給できる鉄化合物、若しくは鉄化合物を含む火山灰、鉄鋼スラグ等と、(2)過酸化水素との2つを添加した上で、更に必要なら加圧加温(若しくは加温のみ)すれば良い。 In that case, after slurrying adding water to petroleum contaminated soil (1) iron sulfide, ash containing iron compound which can supply divalent iron ions, such as ferrous sulfate or iron compounds, iron and steel slag, etc. If, (2) in terms of the addition of two of hydrogen peroxide may be if further required pressurizing and heating (or under heat only). ダイオキシンの場合は、フェントン方法が有効に働くという特許が既に出願され、その点においては発明者らは特許請求はできないが、今回、発明者らは石油汚染土壌に関してフェントン反応法を実際に試してみたところ良好な浄化が確認できたので、新たな技術として特許請求を行う事とした。 For dioxin, patents that Fenton method works effectively is already filed, but can not claimed inventors at that point, now we actually tried Fenton reaction method with respect to petroleum contaminated soil since the good purification was seen was confirmed, it was to perform the claims as a new technology. また、 Also,
【従来の技術】の欄においても述べたように、鉄化合物の中でも特に硫化鉄が有効である事を発明者らは見出し、それを含んだ火山灰等も土壌浄化に利用できる事を請求項に含めた点が本発明の新規性となろう。 As also mentioned in the column of BACKGROUND ART, inventors to be a particularly iron sulfide is enabled among iron compounds found, that the available volcanic ash in soil remediation containing it to claim points, including will become novelty of the present invention. また、二価鉄イオンの供給源として鉄鋼スラグを挙げ、鉄鋼スラグの有効利用を含めた点も本発明の独自性として権利請求を行えるものと考える。 Also, like the steel slag as a source of divalent iron ions, even point, including effective use of steel slag considered to perform the claimed as the uniqueness of the present invention. なお、このフェントン反応を行う場合、pH6以下の酸性で作用させた方が分解が進む事が期待される。 In this case of the Fenton reaction, it is more an acting at pH6 following acidic that progresses degradation is expected.
【0012】 [0012]
また、アルカリ・過酸化水素法にせよ、フェントン反応法にせよ、石油分解反応を更に促進するためには、一般に促進酸化反応で用いられている手段等を適宜、組み合わせれば良い。 Further, whether alkaline hydrogen peroxide method, whether Fenton reaction method, in order to further promote the oil decomposition reaction is generally the like means used in the accelerated oxidation as appropriate, may be combined. 具体的に言えば、(1)オゾン、光照射、次亜塩素酸等の各種酸化処理、(2)触媒、(3)曝気、若しくは撹拌、(4)活性炭等炭化素材添加の計4処理のうちの1つ、若しくは複数を組み合わせる事が有効である。 Specifically, (1) ozone, light irradiation, various oxidation processes, such as hypochlorous acid, (2) catalyst, (3) aeration or stirring, (4) a total of four treatment such as activated carbon carbonized material added one out, or a plurality of combining is valid. ただ、土壌等を処理する場合は、次亜塩素酸処理で生ずる塩素が、新たな有害物質産生に関わる可能性もあるので、その点は注意は要する。 However, when processing soil or the like, chlorine generated by hypochlorite treatment, because there is a possibility related to new harmful substances production, the point caution required. また、これらの処理を行えば、それだけ経費もかかるので、できるだけ単純なシステムで浄化を行った方がよい。 Further, by performing these processes, since much consuming and cost, it is better to perform cleaning with as simple system. そういった意味で、環境汚染物を浄化する場合は、生石灰と過酸化水素を添加して熱処理する方法が最も単純かつ有効であると考えられる。 In this sense, if the purifying environmental contaminants, a method of heat treatment by adding quicklime and hydrogen peroxide is considered to be the most simple and effective.
【0013】 [0013]
これらの一連の方法を用いれば、単に石油汚染土壌を浄化するだけでなく、土壌、底泥、食品、厨房排水等中のダイオキシン、PCB、環境ホルモン、残留農薬、動植物油脂、エストロゲン、残留化学兵器等の各種有害有機物質や臭気物質を除去する事も可能であり、幅広く環境中、食品中の有害有機物質処理に用いる事ができる。 With these series of methods, not only to clean the oil contaminated soil, soil, sediments, food, dioxin in kitchen wastewater, PCB, environmental hormones, residual agricultural chemicals, animal and vegetable fats, estrogen, residual chemical weapons various it is also possible to remove harmful organic substances and odorous substances etc. widely in the environment, can be used in hazardous organic material treatment in foods.
【0014】 [0014]
なお、広大な敷地で、大量の石油等汚染土壌を処理する必要がある場合、土壌等の加温処理を行う際、スラリー化した汚染土壌等を地中等に設置した容器内に入れた上で、電極を設置し通電により発生したジュール熱(〜100℃)により請求項1〜5の処理を行えるよう設計されたプラントを用いれば、比較的、安価に目的を達成する事ができよう。 In large site, when it is necessary to process a large amount of oil such as contaminated soil, when performing the heating of the soil, etc., on which was placed in a container equippedwith a slurried contaminated soil or the like in the ground, etc. , the use of the plant designed to perform the process of claims 1 to 5 by the Joule heat generated by installing the electrode current (to 100 ° C.), relatively, could be used to achieve the low cost objective. この際、水分が蒸発乾固してしまわないように、簡単なオフガスフードを設置する必要がある。 At this time, as moisture is not would provide an evaporated to dryness, it is necessary to install a simple off-gas hood. また、可能なら、土壌スラリーを撹拌する装置を併せて設置すればより効果的であろう。 Also, if possible, it would be more effective if placed together a device for stirring the soil slurry. ただ、この方法は、ガソリンスタンドや住宅の跡地の浄化といった比較的狭い土地を浄化するには使いにくいので、その際は後述するように「コンクリートミキサー車を改装した浄化機能付き移動車両」を活用した方が浄化の機動性は向上しよう。 However, since this method difficult to use to purify the relatively narrow land such as the purification of the gas station and houses of the site, take advantage of the "concrete purification function with a moving vehicle to a mixer truck was refurbished," as the case will be described later who was tries to improve the mobility of purification.
【0015】 [0015]
また、地熱発電所、精錬所、原子力発電所、火力発電所、ゴミ等焼却場等の大量の熱を発生するプラントの高熱工業排水あるいは温泉水を用いて、請求項1〜5の方法を用いて浄化を行えるよう設計された省エネ型浄化プラントを活用できれば、熱源を節約する事はできるが、その分、汚染土壌等の輸送コストはかかる。 Further, geothermal power plants, smelters, nuclear power plants, thermal power plants, using a high heat industrial wastewater or hot spring water of the plant that generates a large amount of heat, such as dust incinerator or the like, using the method of claims 1 to 5 if utilizing energy-saving purification plant designed to perform the purification Te, but it can save heat source, correspondingly, the cost of transportation, such as contaminated soil according. そういった意味で、請求項1〜5の方法を行える設備一式(スラリー等を撹拌可能な装置、過酸化水素等酸化剤添加装置、生石灰等アルカリ剤添加装置、紫外線照射装置、触媒添加装置、加熱装置、加圧装置等)を設置し、原位置で石油等に汚染された土壌や海水等を浄化できるよう設計された移動車両・船舶プラントを建造するのが環境浄化を機動的に行う上で今後、重要になろう。 In this sense, device stirrable equipment set (slurry or the like that enables the method of claims 1 to 5, and hydrogen peroxide oxidizing agent adding device, lime such as an alkaline agent addition device, the ultraviolet irradiation apparatus, catalyst addition, heating apparatus , established the pressure device or the like), the future in terms of to build a moving vehicle and ships plant which is designed to purify contaminated soil or sea water or the like such as oil in situ is flexibly perform the environmental purification , it will become important. そのためには、既存のコンクリートミキサー車、、タンクローリー車、油回収船等を請求項8に示した方法で改造してもよい。 For this purpose, existing concrete mixer truck ,, tanker truck, an oil recovery vessel, such as may be modified by the method described in claim 8. このようなプラントがあれば、例えば、ダイオキシンで汚染された土壌に、この改造ミキサー車を数台派遣し、数ヶ月かけてその場で分解を行わせた後に、そのまま車で走って、次の汚染場所に移る、といった浄化手法をとる事が可能となり、機動性を持たせた浄化が行える事が期待される。 If there is such a plant, for example, in soil that has been contaminated with dioxin, this remodeling mixer truck was dispatched several units, after having to perform the decomposition in situ over a period of several months, running it in the car, the next Turning to contaminated sites, such as it becomes possible to take a purification technique, it is expected to perform the purification which gave the maneuverability.
【0016】 [0016]
なお、本発明では、特にプラント図等は用意しないが、要は、汚染土壌スラリーや汚染排水を撹拌槽に添加し、その撹拌槽に、生石灰、過酸化水素、触媒などをIC制御等で投入する装置を設置し、その上でその撹拌槽自体をボイラー等で加温(もしくは加圧加温)する装置を付ければよく、また必要なら複数の反応槽に分ければ良いだけなので、わざわざ図面を引くに値しない程、単純であり、そして単純だからこそ組み合わせは多数考えられるが、請求項8の概念に入る限り、それら全てに特許請求を行いたい。 In the present invention, but do not provide particular plant view like, short, the contaminated soil slurry or contaminated waste water was added to a stirred tank, poured into the stirred tank, quicklime, hydrogen peroxide, a catalyst such as an IC control, etc. the device for installing, the stirred tank itself on its good if you stick the device for heating (or pressed and heated) in a boiler or the like, also because only it Wakere the number of reaction vessels if necessary, the bother drawings as unworthy to draw, it is simple, and combinations are many possible precisely because it simple, as long as it enters the concept of claim 8, want to make the claims to all of them.
【0017】 [0017]
また、特に請求項1で示したアルカリ・過酸化水素法で浄化した場合は、生石灰、及び生石灰が水と反応した結果、生じる消石灰は、農業分野で一般に土壌改良材、若しくは肥料として用いられているので、処理土壌そのものを(酸性土壌に対する)土壌改良材、若しくは肥料として用いる事も可能である。 Also, particularly when cleaned with alkaline hydrogen peroxide method indicated in claim 1, quicklime, and the results quicklime reacts with water producing slaked lime is generally used a soil conditioner, or as a fertilizer in agriculture because there, the treated soil itself (to acid soil) soil conditioners, or it is also possible to use as fertilizer. 実際、(実施例ではデータを示さなかったが)発明者らは本方法で浄化した土壌を用いて、コマツナを用いた発芽試験を3週間行ったが、順調な発芽及び植物生育が確認できた。 In fact, (it showed no data in the embodiment) we use the clean soil in this way, was performed 3 weeks germination test using komatsuna was confirmed successful germination and plant growth . これは残存した消石灰や石油成分分解物が植物の栄養源になるためと考えられる。 This may be because the hydrated lime and oil component decomposition product remaining is a nutrient source for plants. また、その場合、仮に処理土壌に若干の過酸化水素が残存していても植物や植物根圏微生物群の多くは過酸化水素を分解する酵素(SOD)を産生するので、特に問題とならず、逆に残存成分を除去する上でも緑化を行った方が効果的であるものと考えられる。 Further, not only the case, if so slight hydrogen peroxide treated soil to produce enzymes that degrade hydrogen peroxide (SOD) Many plants and plant rhizosphere microorganisms be left, in particular the problem , who was greening even on removing the remaining components on the contrary considered to be effective. なお、この技術は汚染地の緑化技術として使えると共に、植物自身あるいは植物の根に自然と(ゆるやかに)共生する土壌微生物群がラッカーゼ等を分泌し、残存している油状物質を分解する植物環境修復、微生物環境修復(ハイブリッド浄化技術)としても利用できる(ハイブリッド浄化)。 It should be noted that, with this technology is used as a green technology of contaminated sites, (gently) nature and the roots of the plant itself or plant soil microorganisms in harmony secrete laccase, etc., break down the oil remaining plant environment repair, it can also be used as a microbial environmental remediation (hybrid purification technology) (hybrid purification). なお、ここで用いる植物種は、浄化対照となる汚染物質によって選択すればよい。 Incidentally, the plant species used herein may be selected by the contaminants to be purified control. 例えば、ダイオキシンの場合は、ラッカーゼ活性が高い漆が効果的に分解する事が出光興産株式会社らにより報告されている(塩素化ダイオキシン汚染土壌または水の浄化法、特開2001−232345)。 For example, in the case of dioxins, that laccase activity is high lacquer is effectively decomposed has been reported by Idemitsu Kosan Co., Ltd., et al. (Chlorinated dioxins contaminated soil or purification method water, JP 2001-232345). また、この汚染土壌地で栽培した植物に油状汚染物が一定割合で蓄積する可能性も考えられるので、その際は、重金属蓄積植物を用いた植物環境修復技術のように、その栽培植物が成長後、刈り取り、産業廃棄物として処理する方法も有効であろう。 Further, since the oil contaminants plants cultivated in the contaminated soil areas are considered possible that accumulate at a constant rate, whereby, as a plant remediation technique using a heavy metal accumulating plants, the crop plants are growing after cutting, a method of as industrial waste will also be effective. また、植栽を行う上で、生石灰処理でアルカリ化した土壌等に、ピートモス等の酸性土壌改良材や堆肥を添加し中性化を早めても良いし、好アルカリ性植物を植栽してもよい。 Further, in carrying out planting, the alkalized soil like in lime treatment may be earlier added to neutralize the acidic soil conditioner and compost such as peat moss, even when planting alkalophilic plants good. 更に、請求項1〜7の方法で浄化した土壌等では土着菌の多くが死滅しているので、外来性の微生物が定着しやすくなる効果も期待される事もあり、植栽を行わずに単に有害物質分解微生物群を添加したり、各種堆肥を添加したりする微生物環境修復技術を組み合わせたハイブリッド浄化法も有効である。 Further, since the purifying soil or the like by the method of claims 1 to 7 dying many indigenous bacteria, also sometimes it expected effect of exogenous microorganisms is easily fixed, without planting simply or added harmful substances degradation microorganisms, hybrid purification method combining the microbial remediation technique or by adding various compost is also effective.
【0018】 [0018]
なお、本処理土壌を植物栽培に用いる場合は、できれば、食用にしない花卉栽培、観葉植物栽培、林業、造園等に用いた方が良いだろう。 In the case of using the present process soil to plant cultivation, if possible, floriculture you do not edible, ornamental plant cultivation, forestry, it would be better used in the landscaping and the like. 万一、有害な有機物質が植物に若干、蓄積しても、人体には影響しにくいからである。 Should be harmful organic substances slightly plants, accumulated, it is not easily affect the human body. また、花卉、観葉植物、木材等は換金できるので、うまく農業経営すれば浄化コストの一部を回収できる効果が期待される。 In addition, flowers, foliage plants, because the wood and the like can be redeemed, effect that can be recovered a part of the purification cost if successful farm management is expected.
【0019】 [0019]
次に、実施例にて本発明をより詳細に説明するが、本発明は下記の例のみに限定されるものではない。 Next, the present invention will be described in Examples in more detail, the present invention is not limited only to the following examples. 本実施例では、石油精製に用いられ廃棄物処理が求められている石油汚染白土をモデル浄化実験に用いた。 In the present embodiment, a petroleum contaminated clay waste treatment used in petroleum refining is sought model purification experiments. 本汚染白土は、油分が10%近くあり、微生物が生育できないためバイオレメディエーション法は利用できない。 This pollution clay, oil There are nearly 10%, the bioremediation method for microorganisms can not grow is not available. また、油分が多すぎるため光分解処理も有効に機能しない。 Moreover, not even photolytic process to function effectively because of too much oil. この厄介な石油汚染白土をわずか2時間程度で油臭及び着色油膜が十分に少ない水準まで浄化できる事を確認できたので以下に詳細に説明する。 This annoying oil odor and coloring oil film oil contaminated clay in only about 2 hours is described in detail below because it was confirmed that can purify up sufficiently small level.
【0020】 [0020]
【実施例】 【Example】
この汚染白土をまず篩い(2mm)にかける事を試みたが、粘度が高く、篩いにかけるのは不可能だった。 Tried to put this pollution clay First to sieve (2mm), high viscosity, it was impossible to sieved. 従って、この汚染白土を1kg秤量し、均質になるよう(ビニール手袋を付けた)手でこねて十分、混合した。 Therefore, this contaminated clay was 1kg weighed (marked with vinyl gloves) homogeneous so as sufficiently knead by hand and mixed. 500ml共栓三角フラスコ15本にそれぞれ50gずつ加え、以下の5区に分け、それぞれ3連で実験を行った。 Additionally 500ml stoppered Erlenmeyer flask 15 present each 50g respectively, divided into the following five wards, respectively experiments in triplicate. (1)石油汚染土壌50gに生石灰(和光一級、037−00775、和光純薬株式会社)5g、過酸化水素水(試薬特級、30%、和光純薬株式会社)50ml. (1) quicklime in petroleum contaminated soil 50g (Wako primary, 037-00775, Wako Pure Chemical Industries, Ltd.) 5g, hydrogen peroxide (reagent grade, 30%, Wako Pure Chemical Industries, Ltd.) 50ml. 、超純粋50mlを加え、80℃、2時間の条件で振とう処理した区。 , Ultrapure 50ml was added, 80 ° C., stirring treatment was ward under conditions of 2 hours. (2)石油汚染土壌50gに生石灰(和光一級、037−00775、和光純薬株式会社)5g、硫酸鉄(II)七水和物(試薬特級、和光純薬株式会社)1g. (2) quicklime in petroleum contaminated soil 50g (Wako primary, 037-00775, Wako Pure Chemical Industries, Ltd.) 5g, iron (II) sulfate heptahydrate (reagent special grade, Wako Pure Chemical Industries, Ltd.) 1g. 、過酸化水素水(試薬特級、30%、和光純薬株式会社)50ml. , Hydrogen peroxide (reagent grade, 30%, Wako Pure Chemical Industries, Ltd.) 50ml. 、超純粋50mlを加え、80℃、2時間の条件で振とう処理した区。 , Ultrapure 50ml was added, 80 ° C., stirring treatment was ward under conditions of 2 hours. (3)石油汚染土壌50gに生石灰(和光一級、037−00775、和光純薬株式会社)5g、硫化鉄(II)(試薬特級、関東化学株式会社)1g. (3) quicklime in petroleum contaminated soil 50g (Wako primary, 037-00775, Wako Pure Chemical Industries, Ltd.) 5g, iron sulfide (II) (special grade reagent, Kanto Chemical Co., Inc.) 1g. 、過酸化水素水(試薬特級、30%、和光純薬株式会社)50ml. , Hydrogen peroxide (reagent grade, 30%, Wako Pure Chemical Industries, Ltd.) 50ml. 、超純粋50mlを加え、80℃、2時間の条件で振とう処理した区。 , Ultrapure 50ml was added, 80 ° C., stirring treatment was ward under conditions of 2 hours. (4)石油汚染土壌50gに生石灰(和光一級、037−00775、和光純薬株式会社)5g、過酸化水素水(試薬特級、30%、和光純薬株式会社)50ml. (4) quicklime in petroleum contaminated soil 50g (Wako primary, 037-00775, Wako Pure Chemical Industries, Ltd.) 5g, hydrogen peroxide (reagent grade, 30%, Wako Pure Chemical Industries, Ltd.) 50ml. 、超純粋50mlを加え、80℃、2時間の条件で振とう処理した区。 , Ultrapure 50ml was added, 80 ° C., stirring treatment was ward under conditions of 2 hours. (5)石油汚染土壌50gに超純粋100mlを加え、80℃、2時間の条件で振とう処理した区。 (5) petroleum contaminated soil 50g ultrapure 100ml addition, 80 ° C., stirring treatment was ward under conditions of 2 hours.
【0021】 [0021]
2時間の80℃処理後、それぞれの三角フラスコの内容物をビーカーに移し、1時間放置後、油臭を確認した。 After 80 ° C. for 2 hours, the contents were transferred to each Erlenmeyer flask to a beaker, allowed to stand for 1 hour, it was confirmed oil odor. 油臭は、2名の臭気判定人により、6段階臭気強度表示法(0:無臭、1:やっと感知できる臭い、2:何の臭いであるかわかる弱い臭い、3:楽に感知できる臭い、4:強い臭い、5:強烈な臭い)を用いて盲目試験を行う事によって判定した。 Oil odor, the odor judgment's two people, 6 stage odor intensity display method (0: odorless, 1: odor barely can be sensed, 2: weak odor that can be seen in whether what the smell, 3: odor easily perceivable, 4 : strong odor, 5: was determined by performing a blind test by using a strong odor). その結果、単に汚染土壌に水を加えた区(5)は、6段階中、最も強い「強烈な臭い」であるのに対し、生石灰と過酸化水素の双方を添加した区(1)に関しては、「何の臭いであるかわかる弱い臭い」まで分解できている事が確認できた。 As a result, simply Gu water was added to the contaminated soil (5), in six stages, whereas the strongest "strong odor", with respect ward (1) with the addition of both quicklime and hydrogen peroxide , things that can be decomposed to the "weak odor can be seen how many of smell" could be confirmed. また、フェントン反応を行った(2)及び(3)に関しては、生石灰・過酸化水素法と比べれば、やや分解が劣る「楽に感知できる臭い」まで分解が進んでいた((2)と(3)の差は区別付かず)。 In addition, with regard to went the Fenton reaction (2) and (3), compared with quicklime, hydrogen peroxide method, had progressed decomposition until slightly decomposition is poor "smell that can be comfortably sense" and ((2) (3 the difference of) are not indistinguishable). 最後に、過酸化水素のみ添加した(4)に関しては、更に分解が進んでおらず「強い臭い」に留まっていた。 Finally, with regard to the alone was added hydrogen peroxide (4), has remained in the "strong smell" not promoted further decomposition. 従って、コンティニュアムエンバイロンメンタルインコーポレーテッドの出願特許「有機汚染物質の処理方法(特表2001−513021)」の方法、すなわち過酸化水素のみ添加し熱処理する方法では、今回の汚染白土の浄化には太刀打ちできない事が明らかとなった。 Thus, the method of application patent Continua smokeless Byron mental Incorporated "method for processing an organic contaminant (Kohyo 2001-513021)", namely the method of adding hydrogen peroxide alone heat treatment, the purification of this contamination clay it can not compete revealed.
【0022】 [0022]
次に、この5区を遠心管に移し、30分間、室温で激しく振とうした後、8000rpmで30分遠心し、試験管の上層における油膜の形成を確認した。 Then transferred to the 5 wards into a centrifuge tube, 30 min, after vigorous shaking at room temperature, centrifuged for 30 minutes at 8000 rpm, to confirm the formation of the oil film in the upper layer of the tube. その結果、単に汚染土壌に水を加えた区(5)に関しては、5ml程度の真っ黒な油膜が確認でき、過酸化水素のみを添加した区(4)に関しても2ml程度の真っ黒な油膜が確認できたが、フェントン反応を行った(2)及び(3)に関しては黒い油膜が0.5ml程度と大幅に減少していた((2)と(3)の差は区別付かず)。 As a result, simply respect Gu water was added to the contaminated soil (5) completely black oil film of about 5ml is confirmed, but also can completely black oil film confirmation about 2ml respect ward (4) with the addition of hydrogen peroxide and it was subjected to Fenton reaction (2) and black oil film with respect to (3) were significantly reduced with about 0.5 ml ((2) and (3 difference) is not adhere distinction). また、生石灰・過酸化水素法を適用した(1)に関しては着色した油膜は全く確認できなかったが、白い油膜が0.5ml程度、確認できる程度まで顕著に分解が進んでいる事が確認できた。 In addition, although not confirmed at all the oil film which is colored with respect to the application of the quicklime, hydrogen peroxide method (1), white oil film is about 0.5ml, it is confirmed that progressed significantly degraded to the extent that can be confirmed It was.
【0023】 [0023]
以上の結果により、生石灰・過酸化水素法を用いる事によって、フェントン反応法や、単に過酸化水素を添加し熱処理する区と比べると格段に石油分解が進んでいる事が実証できたものと考えられる。 From the above results, considered by using the quick lime-hydrogen peroxide method, and Fenton reaction method, simply assumed that was demonstrated that is progressing much oil degradation compared with district heat treating adding hydrogen peroxide It is. また、ここではデータを示さないが、乾燥オーブンで各処理土壌を乾燥させた後、ヘキサン抽出したヘキサン抽出液のOD600も測定したが、上の傾向と矛盾しない結果が得られた。 Although not shown the data here, after drying each treated soil in a drying oven, was also measured OD600 hexane extract was extracted with hexane, it results consistent with the tendency of the above were obtained. なお、本実験では簡易法として油臭と油膜で油分の分解を確認したが、可能なら更にGC−FID法等でより客観的な数値を取得する必要がある。 In the present experiment has been confirmed the decomposition of oil in the oil odor and oil film as a simple method, it is necessary to obtain a more objective numerical value further if possible GC-FID method. しかし、論理さえしっかりしていれば特許が認められる制度となっている日本においては十分の実証データになっているものと考えられる。 However, it is considered that has become enough of empirical data in Japan has become a system that patent is recognized if even firmly logic. GC−FID法を含めた詳細な結果は追って学術誌に投稿したい。 Detailed results, including GC-FID method Otte want to post to academic journals. また、ここではデータを示さないが、80℃2時間の熱処理の代わりに、オートクレーブ(127℃、2時間)を行う実験も行ったが、この場合は、更に分解が進んでいる事が確認できた。 Although not shown the data here, instead of the heat treatment of 80 ° C. 2 h, the autoclave (127 ° C., 2 hours), but also performed experiments to perform, in this case, confirmed that has progressed further decomposition It was.
【0024】 [0024]
【発明の効果】 【Effect of the invention】
実施例で示したように、生石灰及び過酸化水素添加と加圧加熱処理を組み合わせたアルカリ・過酸化水素法か、若しくはフェントン反応法のいずれかを適用する事によって、油分を高濃度に含んだ白土を短時間かつ安価に浄化できる。 As shown in the examples, or quicklime and hydrogen peroxide added and pressurized and alkaline peroxide method combining a heat treatment, or by applying any of the Fenton reaction method, including the oil at a high concentration clay can quickly and inexpensively purify. また、本発明で示した移動車両・船舶プラントを活用する事によって、日本全国の油汚染土壌及び油汚染海水を機動的に浄化できる事が期待される。 In addition, by taking advantage of the moving vehicles and ships the plant shown in the present invention, it is expected that can be flexibly to purify the oil contaminated soil and oil pollution sea of ​​Japan. 更に、特に生石灰を用いたアルカリ・過酸化水素法を用いれば、処理後の土壌を用意に緑化する事が可能となり、ひいては、国民の健康と福祉に貢献する事ができるであろう。 In addition, the use of especially the alkaline hydrogen peroxide method using quicklime, it becomes possible to greening the soil of post-processing to prepare, in turn, will be able to contribute to the public health and welfare.

Claims (11)

  1. 石油系汚染土壌に水を加えスラリー化した上で、(1)生石灰添加、(2)過酸化水素添加、(3)加温(常温〜100℃)、若しくは加圧加温処理(常温〜200℃)の3つの処理を組み合わせる事を特徴とする石油系汚染土壌の浄化法。 On slurried adding water to petroleum contaminated soil (1) lime addition, (2) addition of hydrogen peroxide, (3) warming (room temperature to 100 ° C.), or pressurizing and heating process (room temperature to 200 purification method of petroleum contaminated soil, characterized in that it combines three processes ° C.).
  2. 請求項1において、生石灰の代わりに、消石灰、重曹、水酸化ナトリウム、水酸化カリウム等のアルカリ塩やアルカリ電解水を用いる方法。 According to claim 1, in place of quicklime, a method using slaked lime, baking soda, sodium hydroxide, alkali salts and alkaline electrolyzed water such as potassium hydroxide.
  3. 石油系汚染土壌に水を加えスラリー化した上で、(1)硫化鉄、硫酸第一鉄等の二価の鉄イオンを供給できる鉄化合物、若しくは鉄化合物を含む火山灰、鉄鋼スラグ等と、(2)過酸化水素との2つを添加し、必要なら、更に加圧加温(若しくは加温のみ)する事を特徴とする石油系汚染土壌の浄化法。 On slurried adding water to petroleum contaminated soil, and (1) iron sulfide, iron compound which can supply divalent iron ions, such as ferrous sulfate, or ash containing iron compounds, steel slag or the like, ( 2) purification method of petroleum contaminated soil, characterized in that the addition of two, if necessary, further pressurizing and heating (or under heat only) with hydrogen peroxide.
  4. 請求項1〜3の方法に、(1)オゾン、過酢酸、次亜塩素酸、光照射等の各種酸化処理、(2)触媒、(3)曝気、若しくは撹拌(4)活性炭等炭化素材添加の計4処理のうちの1つ、若しくは複数を組み合わせる浄化法。 The method of claims 1 to 3, (1) ozone, peracetic acid, hypochlorous acid, various oxidation processes of the light irradiation or the like, (2) catalyst, (3) aeration or stirring (4) activated carbon carbonized material added one, or purification method combining a plurality of the four process.
  5. 請求項1〜4に述べた方法を用いて、土壌、底泥、海水、食品、厨房排水等中のダイオキシン、PCB、環境ホルモン、残留農薬、動植物油脂、エストロゲン、残留化学兵器等の各種有害有機物質や臭気物質を除去する方法。 Using the method described in claims 1 to 4, soil, sediments, sea water, food, dioxin in kitchen wastewater, PCB, environmental hormones, residual agricultural chemicals, animal and vegetable fats, estrogen, various harmful organic such as residual chemical weapons a method for removing substances and odorous substances.
  6. 土壌等の加温処理を行う際、スラリー化した汚染土壌等を地中等に設置した容器内(オフガスフード付き)に入れた上で、電極を設置し通電により発生したジュール熱(〜100℃)により請求項1〜5の処理を行えるよう設計されたプラント。 When performing the heating treatment such as soil, the container equippedwith a slurried contaminated soil or the like into the ground or the like on which were placed in (off-gas hood), established the electrode Joule heat generated by energization (to 100 ° C.) plant designed to perform the process of claims 1 to 5 by.
  7. 地熱発電所、精錬所、原子力発電所、火力発電所、ゴミ等焼却場等の大量の熱を発生するプラントの高熱工業排水あるいは温泉水を用いて、請求項1〜5の方法を用いて浄化を行えるよう設計された省エネ型浄化プラント。 Geothermal power plants, smelters, nuclear power plants, thermal power plants, using a high heat industrial wastewater or hot spring water of the plant that generates a large amount of heat, such as dust incinerator or the like, using the method of claims 1 to 5 purification energy-purification plant designed to perform the.
  8. 請求項1〜5の方法を行える設備一式(スラリー等を撹拌可能な装置、過酸化水素等酸化剤添加装置、生石灰等アルカリ剤添加装置、紫外線照射装置、触媒添加装置、加熱装置、加圧装置等)を設置し、原位置で石油等に汚染された土壌や海水等を浄化できるよう設計された移動車両・船舶プラント。 Stirring apparatus capable facilities complete (slurry or the like that enables the method of claims 1 to 5, and hydrogen peroxide oxidizing agent adding device, lime such as an alkaline agent addition device, the ultraviolet irradiation apparatus, catalyst addition, heating device, pressure device etc.) set up, the mobile vehicle and ship plant which is designed to purify contaminated soil or sea water or the like such as oil in situ.
  9. 既存のコンクリートミキサー車、、タンクローリー車、油回収船等を請求項8に示した方法で改造した移動車両・船舶プラント。 Existing concrete mixer truck ,, tanker truck, moving vehicles and ships plant oil recovery vessels like was modified by the method described in claim 8.
  10. 請求項1〜9の方法を用いて部分浄化した土壌等に、更に植栽を行う事を特徴とする植物環境修復法もしくは緑化法。 Parts clarified in soil or the like, plant environmental remediation method or greening method and performing a planting using the method of claims 1-9. 更に、該土壌等に、植栽を行わずに単に有害物質分解微生物群や堆肥を添加する微生物環境修復法。 Furthermore, to the soil or the like, simply microbial remediation method of adding harmful material decomposition microorganisms and compost without planting.
  11. 油状汚染土壌等を請求項1〜9の方法で得た処理物を土壌改良材、若しくは肥料として用い、花卉・果樹栽培、林業等を行う方法。 Using the treated product oil contaminated soil or the like obtained by the method of claims 1-9 soil conditioner or as a fertilizer, flower-fruit cultivation, a method of performing forestry and the like.
JP2002238650A 2002-07-15 2002-07-15 Early purification method for petroleum-contaminated soil using burnt lime, and greening method Pending JP2004042011A (en)

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JP2006026460A (en) * 2004-07-12 2006-02-02 Dowa Mining Co Ltd Method of detoxifying polluted substance
JP2006247483A (en) * 2005-03-09 2006-09-21 Mitsubishi Gas Chem Co Inc Treatment method of contaminated soil
WO2007074776A1 (en) * 2005-12-28 2007-07-05 Osaka University Method for purification of substances contaminated with organic chemicals
JP2007209824A (en) * 2005-10-04 2007-08-23 Dowa Holdings Co Ltd Method for cleaning contaminated soil or contaminated groundwater
JP2009208077A (en) * 2009-06-16 2009-09-17 Hitachi Constr Mach Co Ltd Contamination control method
JP2009291668A (en) * 2008-06-02 2009-12-17 Hiroshima Univ Water area environment improving material and its use
JP2009297708A (en) * 2008-05-15 2009-12-24 Mitsui Eng & Shipbuild Co Ltd Apparatus and method for treating estrogen-containing water
JP2011218251A (en) * 2010-04-05 2011-11-04 Ohbayashi Corp Cleaning method of contaminated ground
KR101206786B1 (en) 2011-12-28 2012-11-30 박우현 Composition and Method for reducing the mal-odor of sludge
KR101474308B1 (en) * 2014-10-21 2014-12-18 한국외국어대학교 연구산학협력단 Apparatus for remediation of contaminated soil
KR101831387B1 (en) * 2015-12-04 2018-02-22 재단법인 포항산업과학연구원 In-situ remediation method for oil-contaminated soil and device for in-situ remediation of oil-contaminated soil

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006026460A (en) * 2004-07-12 2006-02-02 Dowa Mining Co Ltd Method of detoxifying polluted substance
JP2006247483A (en) * 2005-03-09 2006-09-21 Mitsubishi Gas Chem Co Inc Treatment method of contaminated soil
JP2007209824A (en) * 2005-10-04 2007-08-23 Dowa Holdings Co Ltd Method for cleaning contaminated soil or contaminated groundwater
WO2007074776A1 (en) * 2005-12-28 2007-07-05 Osaka University Method for purification of substances contaminated with organic chemicals
US9309164B2 (en) 2005-12-28 2016-04-12 Osaka University Method for purification of substances contaminated with organic chemicals
JP5403531B2 (en) * 2005-12-28 2014-01-29 国立大学法人大阪大学 Method for purifying organic chemical-containing contaminated material
JP2009297708A (en) * 2008-05-15 2009-12-24 Mitsui Eng & Shipbuild Co Ltd Apparatus and method for treating estrogen-containing water
JP2009291668A (en) * 2008-06-02 2009-12-17 Hiroshima Univ Water area environment improving material and its use
JP2009208077A (en) * 2009-06-16 2009-09-17 Hitachi Constr Mach Co Ltd Contamination control method
JP2011218251A (en) * 2010-04-05 2011-11-04 Ohbayashi Corp Cleaning method of contaminated ground
KR101206786B1 (en) 2011-12-28 2012-11-30 박우현 Composition and Method for reducing the mal-odor of sludge
KR101474308B1 (en) * 2014-10-21 2014-12-18 한국외국어대학교 연구산학협력단 Apparatus for remediation of contaminated soil
KR101831387B1 (en) * 2015-12-04 2018-02-22 재단법인 포항산업과학연구원 In-situ remediation method for oil-contaminated soil and device for in-situ remediation of oil-contaminated soil

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