JP2010269244A - Additive and method for cleaning medium contaminated with mineral oil - Google Patents
Additive and method for cleaning medium contaminated with mineral oil Download PDFInfo
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- JP2010269244A JP2010269244A JP2009123093A JP2009123093A JP2010269244A JP 2010269244 A JP2010269244 A JP 2010269244A JP 2009123093 A JP2009123093 A JP 2009123093A JP 2009123093 A JP2009123093 A JP 2009123093A JP 2010269244 A JP2010269244 A JP 2010269244A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- A—HUMAN NECESSITIES
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- 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
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- C09K3/00—Materials not provided for elsewhere
- C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/20—Sludge processing
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Abstract
Description
本発明は、汚染地域の土壌、地下水或いは底質土などといった媒体の中に添加される鉱物油の無害化剤及び本発明の鉱物油の無害化方法に関する。 The present invention relates to a mineral oil detoxifying agent added to a medium such as soil, groundwater or sediment in a contaminated area, and the mineral oil detoxifying method of the present invention.
有害な化学物質によって汚染された環境を浄化する手段として、微生物を利用して浄化する方法(バイオレメディエーション)が注目されている。この方法は、従来の物理的・化学的処理方法に比べて動力・設備等が低コストであり、原位置浄化が容易であることが大きな利点である。
このバイオレメディエーションは、汚染物質を分解する能力の高い外来微生物を添加することによって浄化するバイオオーギュメンテーションと、微生物に栄養源等を供給して増殖力、あるいは汚染物質の代謝力を高めることによって浄化するバイオスティミュレーションに大別される。
As a means for purifying an environment polluted by harmful chemical substances, a method of purifying using microorganisms (bioremediation) has attracted attention. This method has great advantages in that power and equipment are low in cost and easy in-situ purification as compared with conventional physical and chemical treatment methods.
This bioremediation is based on bioaugmentation, which is purified by adding foreign microorganisms that have a high ability to decompose pollutants, and by supplying nutrients to the microorganisms to increase their ability to grow or metabolize pollutants. It is roughly divided into biostimulation to purify.
外来微生物を利用するバイオオーギュメンテーションについては、微生物の変異、域外への拡散などを考慮しながら、現在、実用化の検討が進められている。一方、バイオスティミュレーションは、土着の微生物を利用することができ、また栄養塩類その他の材料を対象となる環境に添加するだけでよいので、多くの汚染サイトの原位置浄化工事において採用されるようになってきている。 Regarding bioaugmentation using foreign microorganisms, practical application is currently under consideration, taking into account mutation of microorganisms, diffusion outside the region, and the like. Biostimulation, on the other hand, can be used in in-situ purification work at many contaminated sites because it can utilize native microorganisms and only add nutrients and other materials to the target environment. It has become like this.
本発明者らは、有機塩素化合物に対する従来のバイオレメディエーション剤の課題を解消すべく、嫌気性微生物による有機塩素化合物の浄化に関して特許文献1及び特許文献2において汚染された土壌、地下水或いは底質土の修復に使用する添加剤を開示している。これらの添加剤は、栄養源、エネルギー源となる材料の水溶性が高く、また生分解性がよいので、土壌中において拡散しやすく、また溶存酸素(DO:Dissolved Oxygen、以下「DO」と表記する)も結合性の酸素(NOX‐のO)も存在しない嫌気状態を造成し有機塩素化合物を分解・浄化するまでの工程が迅速に進行する。 In order to solve the problem of the conventional bioremediation agent for organic chlorine compounds, the present inventors have made soil, groundwater or sediment soil contaminated in Patent Document 1 and Patent Document 2 regarding purification of organic chlorine compounds by anaerobic microorganisms. Additives for use in repairing the skin are disclosed. These additives are highly water-soluble and biodegradable in materials that serve as nutrients and energy sources, so that they easily diffuse in the soil, and dissolved oxygen (DO: Dissolved Oxygen, hereinafter referred to as “DO”). And an anaerobic state in which no binding oxygen (NOx-O) is present, and the process of decomposing and purifying the organochlorine compound proceeds rapidly.
この結果、栄養剤を注入するための井戸の間隔を広く取ることが可能となり、少ない地点から注入することによって広い範囲に効果を及ぼすことが可能である。また妨害物質の影響が及ぶ前に有機塩素化合物を分解・浄化することが可能となり、浄化における作業量の低減、浄化期間の短縮を達成することが可能となった。さらに、環境中における生分解性の高い成分が選択されており、浄化完了後に材料は二酸化炭素及び水になり、現場に残留することはない。 As a result, the interval between wells for injecting nutrients can be widened, and the effect can be exerted over a wide range by injecting from a small number of points. In addition, it became possible to decompose and purify organochlorine compounds before the influence of interfering substances, and it was possible to reduce the amount of work in purification and shorten the purification period. Furthermore, highly biodegradable components in the environment are selected, and after purification is completed, the material becomes carbon dioxide and water, and does not remain on site.
以上のように、従来の有機塩素化合物のバイオレメディエーションにおいては、例えばバイオスティミュレーションを原位置浄化に適用する場合に、嫌気生微生物を利用する技術が主流である。一方、ベンゼン類、ガソリン等に代表される鉱物油については、好気性微生物を利用するバイオレメディエーションが有効である。 As described above, in the conventional bioremediation of organic chlorine compounds, for example, when biostimulation is applied to in-situ purification, a technique using anaerobic microorganisms is mainstream. On the other hand, bioremediation using aerobic microorganisms is effective for mineral oils typified by benzenes and gasoline.
本発明の目的は、土壌、地下水及び底質が鉱物油によって汚染されている場合に、鉱物油を原位置においてかつ効果的に浄化する方法において、汚染物質を土着の微生物によって短期間で浄化するための無害化剤によって、環境に対する負荷が小さく使用前の環境への速やかな復元が可能な鉱物油の無害化剤及び鉱物油の無害化方法を提供することにある。 It is an object of the present invention to purify pollutants in a short period of time by indigenous microorganisms in a method for effectively purifying mineral oil in situ when soil, groundwater and sediment are contaminated with mineral oil. The purpose of the present invention is to provide a detoxifying agent for mineral oil and a detoxifying method for mineral oil that can reduce the environmental load and can be promptly restored to the environment before use.
本発明の鉱物油の無害化剤は、ペプトン、酵母エキス、アルギニン、ヒスチジン、イソロイシン、リシン、トレオニン、バリンの1つ以上とマンガン、亜鉛、鉄、マグネシウム、コバルト、ニッケル、銅、モリブデン、ナトリウム、カリウム、カルシウムとこれらの塩類の1つ以上とチアミン、p−アミノ安息香酸、コリン、アスコルビン酸、パントテン酸、ピリドキシン、リボフラビン、ニコチン酸、ビオチン、イノシトール、葉酸、リポ酸、シアノコバラミンの1つ以上とアンモニウム塩の1つ以上とリン酸塩の1つ以上から構成されることを特徴とする。 The mineral oil detoxifying agent of the present invention includes one or more of peptone, yeast extract, arginine, histidine, isoleucine, lysine, threonine, valine and manganese, zinc, iron, magnesium, cobalt, nickel, copper, molybdenum, sodium, One or more of potassium, calcium and their salts and one or more of thiamine, p-aminobenzoic acid, choline, ascorbic acid, pantothenic acid, pyridoxine, riboflavin, nicotinic acid, biotin, inositol, folic acid, lipoic acid, cyanocobalamin It is characterized by being composed of one or more ammonium salts and one or more phosphates.
また本発明の鉱物油の無害化方法は、対象とする媒体を好気状態にする工程と、ペプトン、酵母エキス、アルギニン、ヒスチジン、イソロイシン、リシン、トレオニン、バリンの1つ以上とマンガン、亜鉛、鉄、マグネシウム、コバルト、ニッケル、銅、モリブデン、ナトリウム、カリウム、カルシウムとこれらの塩類の1つ以上とチアミン、p−アミノ安息香酸、コリン、アスコルビン酸、パントテン酸、ピリドキシン、リボフラビン、ニコチン酸、ビオチン、イノシトール、葉酸、リポ酸、シアノコバラミンの1つ以上とアンモニウム塩の1つ以上とリン酸塩の1つ以上から構成される本発明の鉱物油の無害化剤を供給する工程と、からなることを特徴とする。 The mineral oil detoxification method of the present invention comprises a step of aerobicizing a target medium, one or more of peptone, yeast extract, arginine, histidine, isoleucine, lysine, threonine, valine, manganese, zinc, Iron, magnesium, cobalt, nickel, copper, molybdenum, sodium, potassium, calcium and one or more of these salts and thiamine, p-aminobenzoic acid, choline, ascorbic acid, pantothenic acid, pyridoxine, riboflavin, nicotinic acid, biotin Supplying a detoxifying agent for mineral oil of the present invention comprising at least one of inositol, folic acid, lipoic acid, cyanocobalamin, at least one ammonium salt and at least one phosphate. It is characterized by.
本発明の鉱物油の無害化剤には、さらに脂肪酸ナトリウム、モノアルキル硫酸塩、アルキルポリオキシエチレン硫酸塩、アルキルベンゼンスルホン酸塩、モノアルキルリン酸塩、アルキルジメチルアミンオキシド、アルキルカルボキシベタイン、ポリオキシエチレンアルキルエーテル、脂肪酸ソルビタンエステル、アルキルポリグルコシド、脂肪酸ジエタノールアミド、アルキルモノグリセリルエーテル、脂肪酸カリウム、アルファスルホ脂肪酸エステルナトリウム、直鎖アルキルベンゼンスルホン酸ナトリウム、アルキル硫酸エステルナトリウム、アルキルエーテル硫酸エステルナトリウム、アルファオレフィンスルホン酸ナトリウム、アルキルスルホン酸ナトリウム、しょ糖脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、脂肪酸アルカノールアミド、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、アルキルアミノ脂肪酸ナトリウム、アルキルベタイン、アルキルアミンオキシド、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、ラムノリピッド、マンノシルエリスリトールリピッドの1つ以上を加えることができる。 The mineral oil detoxifying agent of the present invention further includes sodium fatty acid, monoalkyl sulfate, alkyl polyoxyethylene sulfate, alkyl benzene sulfonate, monoalkyl phosphate, alkyl dimethylamine oxide, alkyl carboxybetaine, polyoxy Ethylene alkyl ether, fatty acid sorbitan ester, alkyl polyglucoside, fatty acid diethanolamide, alkyl monoglyceryl ether, fatty acid potassium, sodium alpha sulfo fatty acid ester, sodium alkyl benzene sulfonate, sodium alkyl sulfate ester, sodium alkyl ether sulfate, alpha olefin Sodium sulfonate, sodium alkyl sulfonate, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene Of sorbitan fatty acid ester, fatty acid alkanolamide, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, alkylamino fatty acid sodium, alkyl betaine, alkylamine oxide, alkyltrimethylammonium salt, dialkyldimethylammonium salt, rhamnolipid, mannosylerythritol lipid One or more can be added.
対象とする媒体の透水係数が10−4cm/秒未満の場合は圧力をかけることができる。また対象とする媒体を好気状態にする工程が、対象とする媒体のpH の範囲を5.5〜9.0に管理し、さらにDO濃度が5mg/L以上の水を注入する工程とするのがよい。 When the water permeability coefficient of the target medium is less than 10 −4 cm / second, pressure can be applied. Further, the step of bringing the target medium into an aerobic state is a step of controlling the pH range of the target medium to 5.5 to 9.0 and injecting water having a DO concentration of 5 mg / L or more. It is good.
対象とする媒体を好気状態にする工程が、対象とする媒体のDO濃度が2mg/L以上、酸化還元電位(Oxidation−reduction Potential;ORP、以下「ORP」と表記する)値が0mV以上である好気状態にする工程としてもよい。
[作用]
本発明の鉱物油の無害化剤及びこれを用いる本発明の鉱物油の無害化方法は、対象となる媒体に対して供給した物質を、微生物が栄養源あるいは呼吸源として利用して活性化、増殖して鉱物油を無害化する。
このように、鉱物油を分解する過程で関与する微生物群を構成する各種の微生物全体の働きを考慮して、複数種類の性質の異なる物質を添加剤として供給することで、効率的であって、しかも有害物質が残留しにくいバイオレメディエーション工法が可能となる。
なお、添加剤を構成するそれぞれの物質の配合比は修復対象の土質に合わせて設定することで修復の効果を高めることができる。
The step of bringing the target medium into an aerobic state is that the DO concentration of the target medium is 2 mg / L or more, and the oxidation-reduction potential (ORP, hereinafter referred to as “ORP”) value is 0 mV or more. It is good also as a process of making a certain aerobic state.
[Action]
The mineral oil detoxifying agent of the present invention and the mineral oil detoxifying method of the present invention using the same are activated by using a substance supplied to a target medium as a nutrient source or a respiratory source, Proliferates and detoxifies mineral oil.
In this way, considering the action of all the microorganisms that make up the microbial community involved in the process of decomposing mineral oil, it is efficient by supplying multiple types of substances with different properties as additives. In addition, a bioremediation method in which harmful substances hardly remain can be realized.
In addition, the effect of the restoration can be enhanced by setting the mixing ratio of each substance constituting the additive according to the soil quality to be restored.
本発明の鉱物油の無害化剤及び本発明の鉱物油の無害化方法によれば、鉱物油を迅速かつ低コストで浄化することができる。 According to the mineral oil detoxifying agent of the present invention and the mineral oil detoxifying method of the present invention, mineral oil can be purified quickly and at low cost.
以下、本発明の鉱物油の無害化剤及び本発明の鉱物油の無害化方法を実施するための最良の形態を説明する。 The best mode for carrying out the mineral oil detoxifying agent of the present invention and the mineral oil detoxifying method of the present invention will be described below.
本発明の鉱物油の無害化剤に用いられるアンモニウム塩の1つ以上とは、例えば硫酸アンモニウム、リン酸水素二アンモニウム等の1つ以上であって、係るアンモニウム塩としては構造的にアンモニウム塩として認識若しくは評価される全ての物質を用いることができる。水溶性が高いことが好ましく、対象とする媒体における供給において供給した場所からの移動性が高いことが本発明の効果を高める上で有効である。
また本発明の鉱物油の無害化剤に用いられるリン酸塩の1つ以上とは、例えばリン酸水素二アンモニウム、リン酸水素二カリウム、リン酸二水素カリウム等の1つ以上であって、係るリン酸塩としては構造的にリン酸塩として認識若しくは評価される全ての物質を用いることができる。水溶性が高いことが好ましく、対象とする媒体における供給において供給した場所からの移動性が高いことが本発明の効果を高める上で有効である。
One or more of the ammonium salts used in the mineral oil detoxifying agent of the present invention is one or more of ammonium sulfate, diammonium hydrogen phosphate, etc., and such ammonium salts are structurally recognized as ammonium salts. Alternatively, all substances to be evaluated can be used. It is preferable that the water solubility is high, and that the mobility from the place of supply in the supply in the target medium is high in order to enhance the effect of the present invention.
One or more of the phosphates used in the mineral oil detoxifying agent of the present invention is, for example, one or more of diammonium hydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, and the like, As such a phosphate, all substances structurally recognized or evaluated as phosphates can be used. It is preferable that the water solubility is high, and that the mobility from the place of supply in the supply in the target medium is high in order to enhance the effect of the present invention.
本発明の鉱物油の無害化剤及び本発明の鉱物油の無害化方法が対象とする媒体は、例えば一般的に土着の微生物が存在する土壌、地下水或いは底質があるが、媒体が微生物の生息できる環境であれば、外部から微生物を添加する手法によっても、同等の効果を得ることができる。
本発明の鉱物油の無害化剤は、汚染地域の土壌、地下水或いは底質土などといった媒体の中に添加される。本発明の鉱物油の無害化剤を構成するそれぞれの物質の配合比は媒体の性質に合わせて設定することで修復の効果を高めることができる。
また添加剤の形態は、固体状、液体状、スラリー状などであり、汚染地域の地層などの地質状態や、汚染地域の汚染状況に基づいて決定される。供給方法は、例えば、水に溶解させて媒体に供給する方法が一般的であるが、機械によって媒体と混合する方法などによっても同等の効果を得ることができる。
The medium targeted by the mineral oil detoxifying agent of the present invention and the mineral oil detoxifying method of the present invention is, for example, soil, groundwater or sediment in which indigenous microorganisms are generally present. If the environment can inhabit, the same effect can be obtained by adding microorganisms from the outside.
The mineral oil detoxifying agent of the present invention is added to a medium such as soil in a contaminated area, groundwater or sediment. The effect of the restoration can be enhanced by setting the blending ratio of each substance constituting the mineral oil detoxifying agent of the present invention in accordance with the properties of the medium.
The form of the additive is solid, liquid, slurry, etc., and is determined based on the geological state of the strata in the contaminated area and the contamination status of the contaminated area. As a supply method, for example, a method in which the solution is dissolved in water and supplied to the medium is generally used, but the same effect can be obtained by a method of mixing with the medium by a machine.
本発明が無害化の対象とする物質は、鉱物油であり、例えば、ベンゼン、トルエン、キシレン、エチルベンゼンなどのベンゼン類、ガソリン、灯油、軽油といった物質であるが、一般的に鉱物油、もしくは鉱油として認識される物質であれば、これらに限定されない。
本発明の鉱物油の無害化剤による無害化に利用される微生物とは、汚染土壌に存在し、一般的な微生物と同様の方法で増殖させることができる微生物であり、無機塩、窒素源、その他栄養源を含む無機栄養培地、有機栄養培地等において増殖できる、鉱物油を無害化することのできる微生物である。外来微生物を混合したり、微生物から抽出した遺伝子によって作成した組み換え微生物を使用したり、微生物を単体に固定化した場合も本発明の汚染物質の無害化剤及び無害化方法は適用可能である。
Substances to be detoxified by the present invention are mineral oils, for example, benzenes such as benzene, toluene, xylene, ethylbenzene, gasoline, kerosene, light oil, etc., but generally mineral oil or mineral oil As long as it is a substance recognized as, it is not limited to these.
Microorganisms used for detoxification with the detoxifying agent of mineral oil of the present invention are microorganisms that are present in contaminated soil and can be grown in the same manner as general microorganisms, inorganic salts, nitrogen sources, It is a microorganism capable of detoxifying mineral oil that can be grown in inorganic nutrient media, organic nutrient media, and the like including other nutrient sources. The contaminant detoxifying agent and the detoxifying method of the present invention can also be applied to cases where foreign microorganisms are mixed, recombinant microorganisms prepared from genes extracted from microorganisms are used, or microorganisms are immobilized in a simple substance.
ペプトン、酵母エキス、アルギニン、ヒスチジン、イソロイシン、リシン、トレオニン、バリンの1つ以上とマンガン、亜鉛、鉄、マグネシウム、コバルト、ニッケル、銅、モリブデン、ナトリウム、カリウム、カルシウムとこれらの塩類の1つ以上とチアミン、p−アミノ安息香酸、コリン、アスコルビン酸、パントテン酸、ピリドキシン、リボフラビン、ニコチン酸、ビオチン、イノシトール、葉酸、リポ酸、シアノコバラミンの1つ以上とアンモニウム塩の1つ以上とリン酸塩の1つ以上から構成される添加物は、汚染物質を分解する微生物の活性化、増殖に関る栄養源として有効であり、対象とする汚染物質の種類及び濃度、媒体の種類、利用する微生物種などに応じて使用する物質の種類、添加量が選択される。 One or more of peptone, yeast extract, arginine, histidine, isoleucine, lysine, threonine, valine and one or more of manganese, zinc, iron, magnesium, cobalt, nickel, copper, molybdenum, sodium, potassium, calcium and their salts And one or more of thiamine, p-aminobenzoic acid, choline, ascorbic acid, pantothenic acid, pyridoxine, riboflavin, nicotinic acid, biotin, inositol, folic acid, lipoic acid, cyanocobalamin and one or more ammonium salts and phosphate An additive composed of one or more is effective as a nutrient source for the activation and growth of microorganisms that decompose pollutants, and the type and concentration of the target pollutants, the type of medium, the type of microorganism used The type of substance to be used and the amount added are selected according to the above.
脂肪酸ナトリウム、モノアルキル硫酸塩、アルキルポリオキシエチレン硫酸塩、アルキルベンゼンスルホン酸塩、モノアルキルリン酸塩、アルキルジメチルアミンオキシド、アルキルカルボキシベタイン、ポリオキシエチレンアルキルエーテル、ソルビタン脂肪酸エステル、アルキルポリグルコシド、脂肪酸ジエタノールアミド、アルキルモノグリセリルエーテル、脂肪酸カリウム、アルファスルホ脂肪酸エステルナトリウム、直鎖アルキルベンゼンスルホン酸ナトリウム、アルキル硫酸エステルナトリウム、アルキルエーテル硫酸エステルナトリウム、アルファオレフィンスルホン酸ナトリウム、アルキルスルホン酸ナトリウム、しょ糖脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、脂肪酸アルカノールアミド、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、アルキルアミノ脂肪酸ナトリウム、アルキルベタイン、アルキルアミンオキシド、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、ラムノリピッド、マンノシルエリスリトールリピッドの1つ以上から構成される添加物は、土壌に吸着した鉱物油を水相へと移行しやすくするための物質群であり、脂溶性の物質の水への移動性を高める材料として微生物が対象物質を無害化する際の利用性(バイオアベイラビリティ)を高めるために有効であり、食品工業分野において食品添加物などとして利用されている有害性の低い物質である。 Fatty acid sodium, monoalkyl sulfate, alkyl polyoxyethylene sulfate, alkyl benzene sulfonate, monoalkyl phosphate, alkyl dimethylamine oxide, alkyl carboxybetaine, polyoxyethylene alkyl ether, sorbitan fatty acid ester, alkyl polyglucoside, fatty acid Diethanolamide, alkyl monoglyceryl ether, fatty acid potassium, sodium alphasulfo fatty acid ester, linear sodium alkylbenzene sulfonate, sodium alkyl sulfate ester, sodium alkyl ether sulfate, sodium alpha olefin sulfonate, sodium alkyl sulfonate, sucrose fatty acid ester, Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid Consists of one or more of lucanolamide, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, alkylamino fatty acid sodium, alkylbetaine, alkylamine oxide, alkyltrimethylammonium salt, dialkyldimethylammonium salt, rhamnolipid, mannosylerythritol lipid Additives are a group of substances that make it easier for the mineral oil adsorbed on the soil to migrate to the water phase, and when microorganisms detoxify target substances as materials that enhance the mobility of fat-soluble substances to water. It is effective in enhancing the availability (bioavailability) of the sucrose, and is a less harmful substance that is used as a food additive in the food industry.
酸素は、空気による供給、土壌の混練など、供給方法は問わない。水に溶かしてDOの形態で媒体に供給する方法が、媒体内での拡散、効果の波及の面から好ましい。最も好適な方法として、DO濃度が5mg/L以上の水を注入することによってDO濃度で2mg/L以上、ORP値0mV以上の好気状態にすることが、対象となる汚染物質を分解する好気性微生物の活性化、増殖の観点から好ましい。 There is no limitation on the method of supplying oxygen, such as air supply or soil kneading. A method of dissolving in water and supplying to the medium in the form of DO is preferable from the viewpoint of diffusion in the medium and spreading of the effect. The most preferable method is to inject a water having a DO concentration of 5 mg / L or more into an aerobic state with a DO concentration of 2 mg / L or more and an ORP value of 0 mV or more. It is preferable from the viewpoint of activation and growth of aerobic microorganisms.
本発明の無害化剤あるいは酸素を溶解させた水を媒体へと供給する場合、水のとおりやすさを示す指標である透水係数に応じて注入方法を選定することが望ましい。すなわち、透水係数が10−4cm/秒未満の場合は圧力をかけることによって、透水係数が10−4cm/s以上の場合は自然流下によって供給することが適当である。 When supplying the detoxifying agent of the present invention or oxygen-dissolved water to the medium, it is desirable to select an injection method according to the water permeability coefficient, which is an index indicating the ease of passing water. That is, when the water permeability is less than 10 −4 cm / sec, it is appropriate to apply pressure, and when the water permeability is 10 −4 cm / s or more, it is appropriate to supply by natural flow.
本発明では、微生物を利用することによって鉱物油の無害化を迅速に行う為、一般的に微生物が好適に生息できる環境において適用するか、もしくは環境を形成・管理することが必要である。この観点から、pHを5.5から9.0の範囲に管理することが望ましい。
以上の条件で、本発明は鉱物油を無害化することができる。従って、従来の浄化対策によっては困難、もしくは時間のかかっていた汚染媒体においても環境負荷、短工期、コスト面での負担を小さくし無害化できる浄化方法である。
以下、実施例を用いて本発明の鉱物油の無害化剤及び本発明の鉱物油の無害化方法をより詳細に説明するが、本発明の技術的範囲はこれら実施例に限定されるものではない。
In the present invention, in order to rapidly detoxify mineral oil by using microorganisms, it is generally necessary to apply in an environment in which microorganisms can suitably live or to form and manage the environment. From this viewpoint, it is desirable to control the pH in the range of 5.5 to 9.0.
Under the above conditions, the present invention can render mineral oil harmless. Therefore, it is a purification method capable of reducing the burden on the environmental load, the short construction period, and the cost in a contaminated medium that is difficult or time-consuming by conventional purification measures, and can be made harmless.
Hereinafter, the mineral oil detoxifying agent of the present invention and the detoxifying method of the mineral oil of the present invention will be described in more detail using examples, but the technical scope of the present invention is not limited to these examples. Absent.
本発明の鉱物油の無害化剤及び本発明の鉱物油の無害化方法によって地下水中のベンゼン類を無害化した事例を示す。
ベンゼン類によって汚染された地下水の原位置浄化において、添加剤による浄化効果を実証するため、ベンゼン類による地下水汚染が確認されているサイトにおいてパイロット試験を実施した。パイロット試験現場は、平面領域が縦10m×横10mで、地下水位は2.2m、地表からの対象層厚が5mの範囲である。この試験においては、ベンゼン類(ベンゼン、トルエン、キシレン)の濃度、DO濃度(mg/L)、ORP値(mV)をパラメータとして測定した。
ベンゼン類の濃度は、公定分析法(JIS−K0125)に準拠してガスクロマトグラフ質量分析計を用いて測定した。この試験において使用した添加剤は、酵母エキス2kg、アルギニン2kg、アスコルビン酸1kg、リン酸水素二アンモニウム350kg、塩化カリウム50kg、塩化ナトリウム5kg、リン酸水素二カリウム50kg、しょ糖脂肪酸エステル20kgの混合物である。
Examples of detoxifying benzenes in groundwater by the mineral oil detoxifying agent of the present invention and the mineral oil detoxifying method of the present invention are shown.
In order to demonstrate the purification effect of additives in the in situ purification of groundwater contaminated with benzenes, a pilot test was conducted at a site where groundwater contamination by benzenes was confirmed. The pilot test site has a plane area of 10 m long × 10 m wide, a groundwater level of 2.2 m, and a target layer thickness from the ground surface of 5 m. In this test, the concentration of benzenes (benzene, toluene, xylene), DO concentration (mg / L), and ORP value (mV) were measured as parameters.
The concentration of benzenes was measured using a gas chromatograph mass spectrometer in accordance with an official analysis method (JIS-K0125). The additive used in this test is a mixture of 2 kg of yeast extract, 2 kg of arginine, 1 kg of ascorbic acid, 350 kg of diammonium hydrogen phosphate, 50 kg of potassium chloride, 5 kg of sodium chloride, 50 kg of dipotassium hydrogen phosphate and 20 kg of sucrose fatty acid ester. .
現場において水道水50トンにこの添加剤をタンクにおいて混合しながら注入井戸から地下水に滴下し、同時に水道水に酸素を平均20mg/Lで溶解させて3?/分の流速で地下水に継続的に注入した。当該現場土壌の透水係数は、5.1×10−3cm/秒であったので、井戸への自然流下方式によって注入を実施した。
また、比較例として同一現場内において井戸水に空気を吹き込んで曝気する方法も実施した。
双方の場合において注入井戸から地下水流の下流0.5mと3mの位置に設置した観測井戸において、地下水中のDO濃度(mg/L)を定期的に測定した。
また実施例における地下水中のベンゼン類濃度及びORP値(mV)を定期的に測定した。
以上の実施例1及び比較例における各パラメータの測定結果を表1に示す。
While adding this additive to 50 tons of tap water in the tank while dripping in the tank, it is dropped into the groundwater from the injection well, and at the same time, oxygen is dissolved in tap water at an average of 20 mg / L and continuously into the groundwater at a flow rate of 3? / Min. Injected. Since the hydraulic conductivity of the field soil was 5.1 × 10 −3 cm / sec, the soil was injected by a natural flow method to the well.
Further, as a comparative example, a method of aeration by blowing air into well water in the same site was also carried out.
In both cases, DO concentration (mg / L) in the groundwater was periodically measured in the observation wells installed at positions 0.5 m and 3 m downstream of the groundwater flow from the injection well.
Moreover, the benzene density | concentration and ORP value (mV) in groundwater in an Example were measured regularly.
Table 1 shows the measurement results of the parameters in Example 1 and the comparative example.
表1から添加剤の注入によって汚染地域のDOとORPが微生物による好気分解に好適な条件となって汚染の分解環境が形成され、試験期間中維持されたことが分かる。対象となるベンゼン類は、試験開始から15〜30日後には、環境基準を満足するまで濃度が低減された。一方、比較例に示す従来の技術である曝気法の場合には、注入井戸から0.5mの地点で初期に一時的な酸素濃度の増加が見られたものの、その後は、2mg/Lを下回り、好気性微生物の活動に十分な酸素を供給できなかった。原因として注入井戸において曝気をしたことによって気泡が井戸周囲にたまり、以後の水及び酸素の移動が妨げられたためと考えられる。以上の結果から微生物による地下水中の鉱物油、特にはベンゼン類の浄化に本発明の鉱物油の無害化剤及び本発明の鉱物油の無害化方法が有効であることを実証することができた。 From Table 1, it can be seen that DO and ORP in the contaminated area became a suitable condition for aerobic degradation by microorganisms by the injection of the additive, and the degradation environment of pollution was formed and maintained during the test period. The target benzenes were reduced in concentration until the environmental standards were satisfied 15 to 30 days after the start of the test. On the other hand, in the case of the aeration method, which is the conventional technique shown in the comparative example, a temporary increase in oxygen concentration was initially observed at a point 0.5 m from the injection well, but after that, it was less than 2 mg / L. Insufficient oxygen supply for aerobic microbial activity. This is probably because air bubbles accumulated around the well due to aeration in the injection well, preventing the subsequent movement of water and oxygen. From the above results, it was proved that the mineral oil detoxifying agent of the present invention and the mineral oil detoxifying method of the present invention are effective for the purification of mineral oil in groundwater by microorganisms, especially benzenes. .
本発明の鉱物油の無害化剤及び本発明の鉱物油の無害化方法によって地下水中の鉱物油を無害化した事例を示す。
鉱物油によって汚染された地下水の原位置浄化において、添加剤による浄化効果を実証するため、鉱物油によって地下水汚染が確認されているサイトにおいてパイロット試験を実施した。パイロット試験現場は、平面領域が縦10m×横10mで、地下水位は1.5m、地表からの対象層厚が3mの範囲である。
この試験においては、鉱物油については、全石油系炭化水素(以下、TPHと表記する。)の濃度、DO濃度(mg/L)、ORP値(mV)をパラメータとして測定した。TPH濃度は、水素炎イオン化検出器付きガスクロマトグラフ(以下、GC−FIDと表記する)を使用して測定した。この試験において使用した添加剤は、ペプトン2kg、トレオニン2kg、リボフラビン1kg、リン酸水素二アンモニウム220kg、塩化カリウム30kg、塩化ナトリウム5kg、塩化マグネシウム5kg、燐酸水素二カリウム30kg、ソルビタン脂肪酸エステル20kgの混合物である。
Examples of detoxifying mineral oil in groundwater by the mineral oil detoxifying agent of the present invention and the mineral oil detoxifying method of the present invention are shown.
In order to demonstrate the purification effect of additives in the in situ purification of groundwater contaminated with mineral oil, a pilot test was conducted at a site where groundwater contamination was confirmed by mineral oil. The pilot test site has a plane area of 10 m long × 10 m wide, a groundwater level of 1.5 m, and a target layer thickness from the ground surface of 3 m.
In this test, the mineral oil was measured using the concentrations of total petroleum hydrocarbons (hereinafter referred to as TPH), DO concentration (mg / L), and ORP value (mV) as parameters. The TPH concentration was measured using a gas chromatograph with a flame ionization detector (hereinafter referred to as GC-FID). The additive used in this test was a mixture of 2 kg peptone, 2 kg threonine, 1 kg riboflavin, 220 kg diammonium hydrogen phosphate, 30 kg potassium chloride, 5 kg sodium chloride, 5 kg magnesium chloride, 30 kg dipotassium hydrogen phosphate and 20 kg sorbitan fatty acid ester. is there.
現場において水道水30トンにこの添加剤をタンクにおいて混合しながら注入井戸から地下水に滴下し、同時に水道水に酸素を平均30mg/Lで溶解させて3?/分の流速で地下水に継続的に注入した。当該現場土壌の透水係数は、1.4×10−3cm/秒であったので、井戸への自然流下方式によって注入を実施した。注入井戸から地下水流の下流2mの位置に設置した観測井戸において、定期的にTPH濃度及びDO濃度(mg/L)、ORP値(mV)、pHを測定した。実施例2における各パラメータの測定結果を表2に示す。 While adding this additive to 30 tons of tap water in the tank while dripping in the tank, it is dropped into the groundwater from the injection well, and at the same time, oxygen is dissolved in the tap water at an average of 30 mg / L and continuously into the groundwater at a flow rate of 3? / Min. Injected. Since the hydraulic conductivity of the field soil was 1.4 × 10 −3 cm / sec, injection was performed by a natural flow method to the well. In the observation well installed 2 m downstream of the groundwater flow from the injection well, the TPH concentration, DO concentration (mg / L), ORP value (mV), and pH were measured periodically. Table 2 shows the measurement results of each parameter in Example 2.
表2から添加剤の注入によって汚染地域のDOとORPが微生物による好気分解に好適な条件となって汚染の分解環境が形成され、試験期間中維持されたことが分かる。対象となる鉱物油は、試験開始から30日後には、定量下限以下まで濃度が低減された。以上の結果から本発明の鉱物油の無害化剤及び本発明の鉱物油の無害化方法が、微生物による地下水中の鉱物油の浄化に有効であることを実証することができた。 From Table 2, it can be seen that DO and ORP in the contaminated area became a suitable condition for aerobic decomposition by microorganisms by the injection of the additive, and the degradation environment of pollution was formed and maintained during the test period. The concentration of the target mineral oil was reduced to the lower limit of quantification 30 days after the start of the test. From the above results, it was proved that the mineral oil detoxifying agent of the present invention and the mineral oil detoxifying method of the present invention are effective for purification of mineral oil in groundwater by microorganisms.
Claims (7)
One or more of peptone, yeast extract, arginine, histidine, isoleucine, lysine, threonine, valine and one or more of manganese, zinc, iron, magnesium, cobalt, nickel, copper, molybdenum, sodium, potassium, calcium and their salts And one or more of thiamine, p-aminobenzoic acid, choline, ascorbic acid, pantothenic acid, pyridoxine, riboflavin, nicotinic acid, biotin, inositol, folic acid, lipoic acid, cyanocobalamin and one or more ammonium salts and phosphate A mineral oil detoxifying agent characterized by comprising one or more.
The step of bringing the target medium into an aerobic state is a step of bringing the target medium into an aerobic state where the dissolved oxygen concentration of the target medium is 2 mg / L or more and the oxidation-reduction potential value is 0 mV or more. Item 7. A method for detoxifying a mineral oil according to any one of Items 6.
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JP2010046623A (en) * | 2008-08-22 | 2010-03-04 | Showa Denko Kk | Method of purifying contaminated soil |
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WO2008015688A2 (en) * | 2006-07-31 | 2008-02-07 | Indian Oil Corporation Limited | Method for bio-assisted treatment of hydrocarbon contaminated soil |
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JP2005288276A (en) * | 2004-03-31 | 2005-10-20 | Ecocycle Corp | Additive used in restoring contaminated soil, ground water or sedimentary soil deposit |
WO2005118171A1 (en) * | 2004-06-02 | 2005-12-15 | Ecocycle Corporation | Additive for use to restore polluted soil, groundwater or bottom sediment soil |
JP2010046623A (en) * | 2008-08-22 | 2010-03-04 | Showa Denko Kk | Method of purifying contaminated soil |
Cited By (4)
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CN102807305A (en) * | 2012-08-23 | 2012-12-05 | 中国石油天然气股份有限公司 | Biological agent for treating oily sludge and using method thereof |
JP2020039256A (en) * | 2018-09-06 | 2020-03-19 | 株式会社バイオレンジャーズ | Soil improvement method |
JP7238228B1 (en) | 2022-08-29 | 2023-03-14 | 生態環境部南京環境科学研究所 | Combining rhamnolipids and earthworms to remediate dioxin-contaminated soil |
JP2024032630A (en) * | 2022-08-29 | 2024-03-12 | 生態環境部南京環境科学研究所 | Method for repairing dioxin polluted soil by combining rhamnolipid with earthworm |
Also Published As
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KR20100126152A (en) | 2010-12-01 |
CN101890211A (en) | 2010-11-24 |
BRPI0903995A2 (en) | 2011-02-01 |
JP4944157B2 (en) | 2012-05-30 |
TWI450745B (en) | 2014-09-01 |
TW201041623A (en) | 2010-12-01 |
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