JP2005007256A - Contaminated soil insolubilization solidification agent - Google Patents
Contaminated soil insolubilization solidification agent Download PDFInfo
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- JP2005007256A JP2005007256A JP2003172725A JP2003172725A JP2005007256A JP 2005007256 A JP2005007256 A JP 2005007256A JP 2003172725 A JP2003172725 A JP 2003172725A JP 2003172725 A JP2003172725 A JP 2003172725A JP 2005007256 A JP2005007256 A JP 2005007256A
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- soil
- solidifying agent
- insolubilizing
- iron powder
- contaminated soil
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は重金属や塩素化合物等の有害物質によって汚染された土壌の有害物質を不溶化し、かつ土壌を固化せしめる汚染土壌不溶化固化剤に関するものである。
【0002】
【従来の技術】
従来は、この種の汚染土壌は、現場においてセメントあるいはセメントを含む固化剤を注入混合して該汚染土壌を固化せしめ、有害物質を固化せしめられた土壌中に封じ込める方法(例えば特許文献1,2)、汚染土壌を現場から採取除去して新しく非汚染土壌に入れ替える方法、汚染土壌を加熱処理する方法(例えば特許文献3,4)等によって処理されている。
【0003】
【特許文献1】
特開2002−18413号公報
【特許文献2】
特開2001−334135号公報
【特許文献3】
特開2000−288510号公報
【特許文献4】
特開平11−646号公報
【0004】
【発明が解決しようとする課題】
セメントあるいはセメントを含む固化剤で汚染土壌を現場で不溶化固化する場合には、セメントに含まれている6価クロムにより土壌固化物が汚染されるおそれがある。更にセメントの高アルカリにより固化土壌中に封じ込められた有害物質が、固化土壌中から再溶出するおそれもある。
更に現場から汚染土壌を採取除去する方法では、採取した汚染土壌を処理するのに管理型処分場で行わねばならないと云う問題点がある。
更に汚染土壌を加熱処理する方法では、汚染土壌を掘削採取し、処理後埋め戻しを行う作業や加熱のための熱源の費用、設備費等が莫大になる。
【0005】
【課題を解決するための手段】
本発明は上記従来の課題を解決するための手段として、MgOと、鉄粉とを含有する汚染土壌不溶化固化剤を提供するものである。
上記不溶化固化剤には、更に硫酸塩、塩酸塩、スルファミン酸、リン酸、水溶液のPHが7以下であるリン化合物からなる組から選ばれる一種または二種以上の助剤が添加されることが望ましく、更に水溶性ガム類、水溶性繊維素誘導体、粘土質からなる組から選ばれる一種または二種以上の粘度付与剤が添加されることが望ましい。
【0006】
【作用】
本発明では、MgOと鉄粉は土壌中の汚染物質を還元して不溶化し、更にMgOは土壌を固化して固化土壌中に不溶化した有害物質を封じ込める。
MgOに上記助剤を添加すると、土壌中の有害物質の不溶化が促進される。また土壌固化物のゲル強度も向上する。
更に粘度付与剤を添加すると、土壌に混合した不溶化固化剤中の鉄粉の沈降が防止される。
以下に本発明を詳細に説明する。
【0007】
【発明の実施の形態】
〔MgO〕
本発明に使用するMgOとしては、低温焼成品と、高温焼成品のいづれでもよいが、反応性の点からみて低温焼成品(軽焼マグネシウム)の使用が望ましい。
上記軽焼マグネシウムは純分90質量%以上の炭酸マグネシウムを700〜1000℃の温度で焼成することによって得られる。
【0008】
〔鉄粉〕
本発明に使用する鉄粉は、純鉄粉の他、炭素鋼、クロム鋼、ニッケル鋼、モリブデン鋼、マンガン鋼、クロム−モリブデン鋼、マンガン−クロム鋼等の鉄基合金の粉末も含まれる。該鉄粉の粒径は、通常70〜100μm程度とされる。
【0009】
〔助剤〕
土壌の種類、有害物質の種類によっては、MgOと鉄粉のみでは有害物質の不溶化や土壌の固化に長時間を要したり、不充分であつたりする場合がある。そのような場合には有害物質の不溶化および土壌の固化を促進するために助剤を添加する。
上記助剤としては、硫酸塩、塩酸塩、リン酸、スルファミン酸、水溶液のPHが7以下であるリン化合物、あるいはこれら化合物の二種以上の混合物が使用され、上記硫酸塩としては硫酸第一鉄、硫酸マグネシウム、硫酸アルミニウム等が例示され、上記塩酸塩としては塩化第一鉄、塩化第二鉄、塩化マグネシウム、塩化アルミニウム、ポリ塩化アルミニウム等が例示され、水溶液のPHが7以下のリン化合物としては、過燐酸マグネシウム、過燐酸カルシウム、重過燐酸カルシウム等が例示される。
【0010】
〔粘度付与剤〕
土壌に本発明の不溶化固化剤を混合した場合、該不溶化固化剤中の鉄粉が土壌固化剤に沈降分離してしまう場合がある。このような場合には有害物質の不溶化が不充分になる。そこで本発明では鉄粉の沈降分離を防止するために粘度付与剤を混合することが望ましい。上記粘度付与剤としては、グアガム、トラガントガム、アラビアガム等の水溶性ガム類、メチルセルロース、エチルセルロース、メトキシセルロース、エトキシセルロース、カルボキシメチルセルロース等の水溶性繊維素誘導体、ベントナイト、バーミキュライト、ワラストナイト、ゼオライト等の粘土質が使用され、これらは二種以上併用されてもよい。
上記粘度付与剤は助剤を使用して土壌を早期に固化出来るようにした場合には、必ずしも使用する必要はない。
【0011】
〔配合〕
本発明の不溶化固化剤にあっては、通常MgO100質量部に対して鉄粉は1〜50質量部添加される。また助剤を添加する場合には、通常MgO100質量部、鉄粉1〜50質量部に対して5〜200質量部が添加され、更に粘度付与剤を添加する場合には、通常MgO100質量部、鉄粉1〜50質量部、あるいはMgO100質量部、鉄粉1〜50質量部、助剤5〜200質量部に対して、通常0.3〜10質量部添加される。
【0012】
〔土壌処理〕
本発明の不溶化固化剤を使用して土壌を処理する方法としては、現場において汚染土壌中に本発明の不溶化固化剤の水溶液を注入したり、あるいは現場から掘削採取した汚染土壌に本発明の不溶化固化剤を混合してもよい。この場合、MgOと鉄粉、あるいは助剤や粘度付与剤を全部混合してから土壌に注入あるいは混合してもよいし、一部を混合し、他は別にして土壌に注入あるいは混合してもよいし、各組成を混合することなく別々に土壌に注入あるいは混合してもよい。
【0013】
〔実施例1〕
現場から採取した粘度質砂(含水比72.4%、含土率58.0%、砂分49.1%、シルト分24.5%、粘土分26.4%、密度1.55g/cm3 )の重金属汚染土壌1m3 に下記配合の不溶化固化剤Aを15(質量/容量)%(以下単に%と云う)添加し、攪拌混合した原土および7日後の固化土壌の重金属溶出量、PH値および一軸圧縮強度を測定した。その結果を表1に示す。
固化剤Aの配合
軽焼酸化マグネシウム 100質量部
鉄粉 50質量部
【0014】
【表1】
【0015】
表1によれば、本発明の不溶化固化剤Aによる処理によって、土壌に含まれる鉛、砒素は土壌環境基準以下の溶出量にまで不溶化されることが認められる。また土壌の固化強度も充分であることが認められる。
【0016】
〔実施例2〕
実施例1の土壌に水を加えて含水比122%、含土率45%、密度1.38g/cm3 の重金属汚染粘土質試料を作成した。該試料1m3 に下記配合組成の不溶化固化剤Bを15%添加し、攪拌混合した原土および7日後の固化土壌の重金属溶出量、PH値および一軸圧縮強度を測定した。そ結果を表2に示す。
固化剤Bの配合
軽焼酸化マグネシウム 100質量部
鉄粉 50質量部
硫酸第一鉄 20質量部
【0017】
【表2】
【0018】
表2によれば、本発明の不溶化固化剤Bによる処理によって、土壌に含まれる鉛、砒素は土壌環境基準以下の溶出量にまで不溶化されることが認められる。また土壌の固化強度も充分であることが認められる。
【0019】
〔実施例3〕
現場から採取した粘性土(含水比116%、含土率46%、砂分20%、シルト分25.9%、粘土分53.1%、密度1.427g/cm3 )1m3 に、下記配合組成の不溶化固化剤Cを15%添加し、攪拌混合した原土および28日後の固化土壌のトリクロロエチレンの溶出量、PH値および一軸圧縮強度を測定した。その結果を表3に示す。
固化剤Cの配合
軽焼酸化マグネシウム 100質量部
鉄粉 30質量部
硫酸第一鉄 20質量部
グアガム 5質量部
【0020】
【表3】
【0021】
表3によれば、本発明の不溶化固化剤Cによる処理によって、土壌に含まれるトリクロロエチレンは土壌環境基準以下の溶出量にまで不溶化されることが認められる。また土壌の固化強度も充分であることが認められる。
【0022】
〔比較例1〕
実施例1で使用した汚染土壌に、軽焼酸化マグネシウム10%を単独添加および鉄粉5%を単独添加してから、それぞれ攪拌混合し固化させた。
28日後の固化土壌の鉛および砒素の溶出量、固化強度を測定し、結果を表4および表5に示す。
【0023】
【表4】
【0024】
【表5】
表4、表5をみると軽焼酸化マグネシウムおよび鉄粉を単独添加した場合は、鉛および砒素の不溶化が充分でなく、またMgOを省き鉄粉のみ使用した場合〔表5〕は固化強度も充分でないことが認められる。
【0025】
〔比較例2〕
実施例3で使用したトリクロロエチレンで汚染した土壌に対して軽焼酸化マグネシウム10%を単独添加、および鉄粉5%を単独添加し、それぞれ攪拌混合し固化させた。28日後の原土および軽焼酸化マグネシウムおよび鉄粉のそれぞれの固化土壌のトリクロロエチレンの溶出量、固化強度を測定し、その結果を表6および表7に示す。
【0026】
【表6】
【0027】
【表7】
【0028】
表6、表7をみれば、MgOまたは鉄粉を単独添加した場合トリクロロエチレンの不溶化が充分でなく、またMgOを省き鉄粉のみ使用した場合〔表7〕は、固化強度も充分でないことが認められる。
【0029】
【発明の効果】
本発明にあっては、土壌を強固に固化せしめ、かつ該土壌中に含まれている 有害物質を不溶化して該土壌固化物に完全に封じ込めることが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a contaminated soil insolubilizing solidifying agent that insolubilizes soil harmful substances contaminated by harmful substances such as heavy metals and chlorine compounds and solidifies the soil.
[0002]
[Prior art]
Conventionally, this kind of contaminated soil is made by injecting and mixing cement or a cement-containing solidifying agent in the field to solidify the contaminated soil and contain the harmful substances in the solidified soil (for example, Patent Documents 1 and 2). ), Collecting contaminated soil from the site and replacing it with new non-contaminated soil, and heating the contaminated soil (for example, Patent Documents 3 and 4).
[0003]
[Patent Document 1]
JP 2002-18413 A [Patent Document 2]
JP 2001-334135 A [Patent Document 3]
JP 2000-288510 A [Patent Document 4]
Japanese Patent Laid-Open No. 11-646
[Problems to be solved by the invention]
When the contaminated soil is insolubilized and solidified on site with cement or a solidifying agent containing cement, there is a possibility that the soil solidified material is contaminated by hexavalent chromium contained in the cement. In addition, harmful substances contained in the solidified soil due to the high alkali of the cement may re-elute from the solidified soil.
Further, the method of collecting and removing contaminated soil from the site has a problem that it must be carried out at a managed disposal site in order to treat the collected contaminated soil.
Furthermore, in the method of heat treating the contaminated soil, the work of excavating and collecting the contaminated soil and backfilling after the treatment, the cost of the heat source for heating, the equipment cost, etc. become enormous.
[0005]
[Means for Solving the Problems]
The present invention provides a contaminated soil insolubilizing solidifying agent containing MgO and iron powder as means for solving the above conventional problems.
The insolubilizing solidifying agent may be further added with one or more auxiliary agents selected from the group consisting of sulfates, hydrochlorides, sulfamic acids, phosphoric acids, and phosphorus compounds whose aqueous solution has a pH of 7 or less. It is desirable to further add one or more viscosity-imparting agents selected from the group consisting of water-soluble gums, water-soluble fiber derivatives, and clays.
[0006]
[Action]
In the present invention, MgO and iron powder reduce and insolubilize contaminants in the soil, and MgO solidifies the soil and contains harmful substances insolubilized in the solidified soil.
When the auxiliary agent is added to MgO, insolubilization of harmful substances in the soil is promoted. Moreover, the gel strength of the soil solidified material is also improved.
Furthermore, when a viscosity imparting agent is added, sedimentation of iron powder in the insolubilized solidifying agent mixed in the soil is prevented.
The present invention is described in detail below.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
[MgO]
MgO used in the present invention may be either a low-temperature fired product or a high-temperature fired product, but it is desirable to use a low-temperature fired product (light-fired magnesium) from the viewpoint of reactivity.
The lightly burned magnesium can be obtained by baking magnesium carbonate having a pure content of 90% by mass or more at a temperature of 700 to 1000 ° C.
[0008]
[Iron powder]
The iron powder used in the present invention includes powders of iron-based alloys such as carbon steel, chromium steel, nickel steel, molybdenum steel, manganese steel, chromium-molybdenum steel, and manganese-chromium steel in addition to pure iron powder. The particle size of the iron powder is usually about 70 to 100 μm.
[0009]
[Auxiliary]
Depending on the type of soil and the type of toxic substances, MgO and iron powder alone may take a long time to insolubilize toxic substances or solidify the soil, or may be insufficient. In such a case, an auxiliary agent is added to promote insolubilization of harmful substances and solidification of soil.
Examples of the auxiliary agent include sulfate, hydrochloride, phosphoric acid, sulfamic acid, a phosphorus compound whose aqueous solution has a pH of 7 or less, or a mixture of two or more of these compounds. Examples include iron, magnesium sulfate, aluminum sulfate, etc. Examples of the hydrochloride include ferrous chloride, ferric chloride, magnesium chloride, aluminum chloride, polyaluminum chloride, etc. Examples thereof include magnesium perphosphate, calcium perphosphate, and heavy perphosphate.
[0010]
(Viscosity imparting agent)
When the insolubilizing solidifying agent of the present invention is mixed with soil, the iron powder in the insolubilizing solidifying agent may settle and separate into the soil solidifying agent. In such a case, insolubilization of harmful substances becomes insufficient. Therefore, in the present invention, it is desirable to mix a viscosity-imparting agent in order to prevent sedimentation of iron powder. Examples of the viscosity-imparting agent include water-soluble gums such as guar gum, tragacanth gum, and gum arabic, water-soluble fiber derivatives such as methyl cellulose, ethyl cellulose, methoxy cellulose, ethoxy cellulose, and carboxymethyl cellulose, bentonite, vermiculite, wollastonite, zeolite, and the like These clays are used, and two or more of these may be used in combination.
The viscosity-imparting agent is not necessarily used when an auxiliary agent is used to solidify the soil at an early stage.
[0011]
[Combination]
In the insolubilizing solidifying agent of the present invention, 1 to 50 parts by mass of iron powder is usually added to 100 parts by mass of MgO. Further, when adding an auxiliary agent, usually 100 parts by mass of MgO, 5 to 200 parts by mass with respect to 1 to 50 parts by mass of iron powder is added, and when adding a viscosity imparting agent, usually 100 parts by mass of MgO, Usually, 0.3 to 10 parts by mass is added to 1 to 50 parts by mass of iron powder, or 100 parts by mass of MgO, 1 to 50 parts by mass of iron powder, and 5 to 200 parts by mass of an auxiliary.
[0012]
[Soil treatment]
As a method of treating soil using the insolubilizing solidifying agent of the present invention, the insolubilizing solidification agent of the present invention is injected into the contaminated soil at the site, or the contaminated soil excavated and collected from the site is insolubilized according to the present invention. A solidifying agent may be mixed. In this case, you may mix or mix MgO and iron powder, or all the auxiliaries and viscosity-imparting agents and then inject or mix them, or mix some of them and inject or mix them separately. Alternatively, each composition may be injected or mixed separately into the soil without mixing.
[0013]
[Example 1]
Viscous sand collected from the field (water content 72.4%, soil content 58.0%, sand content 49.1%, silt content 24.5%, clay content 26.4%, density 1.55 g / cm 3 ) 15 m (volume / volume)% (hereinafter simply referred to as%) of insolubilizing solidifying agent A having the following composition was added to 1 m 3 of heavy metal contaminated soil of 3 ), and the amount of heavy metal leaching in the solid soil and the solidified soil after 7 days after stirring and mixing, The PH value and uniaxial compressive strength were measured. The results are shown in Table 1.
Mixing of solidifying agent A Lightly burned magnesium oxide 100 parts by mass Iron powder 50 parts by mass
[Table 1]
[0015]
According to Table 1, it is recognized that the treatment with the insolubilizing solidifying agent A of the present invention insolubilizes lead and arsenic contained in the soil to an elution amount below the soil environmental standard. It can also be seen that the soil solidification strength is sufficient.
[0016]
[Example 2]
Water was added to the soil of Example 1 to prepare a heavy metal-contaminated clayey sample having a water content of 122%, a soil content of 45%, and a density of 1.38 g / cm 3 . Sample 1 m 3 insolubilization solidifying agent B having the following composition composition was added 15%, heavy metal elution amount of solidified soil after the original soil and 7 days stirred mixture was measured PH value and unconfined compressive strength. The results are shown in Table 2.
Mixing of solidifying agent B Lightly burned magnesium oxide 100 parts by mass Iron powder 50 parts by mass Ferrous sulfate 20 parts by mass
[Table 2]
[0018]
According to Table 2, it is recognized that the treatment with the insolubilizing solidifying agent B of the present invention insolubilizes lead and arsenic contained in the soil to an elution amount below the soil environmental standard. It can also be seen that the soil solidification strength is sufficient.
[0019]
Example 3
1 m 3 of viscous soil collected from the field (water content ratio 116%, soil content 46%, sand content 20%, silt content 25.9%, clay content 53.1%, density 1.427 g / cm 3 ) 15% of the insolubilizing solidifying agent C having the blending composition was added, and the trichlorethylene elution amount, PH value and uniaxial compressive strength of the raw soil mixed with stirring and the solidified soil after 28 days were measured. The results are shown in Table 3.
Mixing of solidifying agent C Lightly burned magnesium oxide 100 parts by mass Iron powder 30 parts by mass Ferrous sulfate 20 parts by mass Gua gum 5 parts by mass
[Table 3]
[0021]
According to Table 3, it is recognized that the treatment with the insolubilizing solidifying agent C of the present invention insolubilizes trichlorethylene contained in the soil to an elution amount equal to or lower than the soil environmental standard. It can also be seen that the soil solidification strength is sufficient.
[0022]
[Comparative Example 1]
After adding 10% of lightly burned magnesium oxide and 5% of iron powder alone to the contaminated soil used in Example 1, each was stirred and mixed to solidify.
The elution amount and solidification strength of lead and arsenic in the solidified soil after 28 days were measured, and the results are shown in Tables 4 and 5.
[0023]
[Table 4]
[0024]
[Table 5]
Tables 4 and 5 show that when lightly burned magnesium oxide and iron powder are added alone, insolubilization of lead and arsenic is not sufficient, and when MgO is omitted and only iron powder is used [Table 5] also shows solidification strength. It is recognized that it is not enough.
[0025]
[Comparative Example 2]
To the soil contaminated with trichlorethylene used in Example 3, 10% of light-burned magnesium oxide and 5% of iron powder were added alone, and stirred and mixed to solidify. The elution amount and solidification strength of trichlorethylene in the solidified soil of each of the raw soil and light-burned magnesium oxide and iron powder after 28 days were measured, and the results are shown in Tables 6 and 7.
[0026]
[Table 6]
[0027]
[Table 7]
[0028]
Tables 6 and 7 show that trichlorethylene is not sufficiently insolubilized when MgO or iron powder is added alone, and that solidification strength is not sufficient when MgO is omitted and only iron powder is used [Table 7]. It is done.
[0029]
【The invention's effect】
In the present invention, the soil can be solidified, and harmful substances contained in the soil can be insolubilized and completely contained in the soil solidified product.
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Cited By (9)
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JP2006272286A (en) * | 2005-03-30 | 2006-10-12 | Sumitomo Osaka Cement Co Ltd | Grouting material for soil improvement and insolubilization method of soil contaminant using the same |
JP2010163619A (en) * | 2010-02-15 | 2010-07-29 | Sumitomo Osaka Cement Co Ltd | Soil amelioration grouting material and method for insolubilizing soil pollutant using the grouting material |
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JP2006272286A (en) * | 2005-03-30 | 2006-10-12 | Sumitomo Osaka Cement Co Ltd | Grouting material for soil improvement and insolubilization method of soil contaminant using the same |
JP4588512B2 (en) * | 2005-03-30 | 2010-12-01 | 住友大阪セメント株式会社 | Soil-improving injection material and method for insolubilizing soil contaminants using the injection material |
JP2010163619A (en) * | 2010-02-15 | 2010-07-29 | Sumitomo Osaka Cement Co Ltd | Soil amelioration grouting material and method for insolubilizing soil pollutant using the grouting material |
JP2013031795A (en) * | 2011-08-01 | 2013-02-14 | Sumitomo Osaka Cement Co Ltd | Elution-reducing material, and method for production thereof |
CN105008285A (en) * | 2013-03-07 | 2015-10-28 | 株式会社神户制钢所 | Particulate water treatment agent for environment and method for treating water polluted by harmful substances using same |
CN105008285B (en) * | 2013-03-07 | 2017-03-29 | 株式会社神户制钢所 | Particulate-type water-use for environment inorganic agent and the processing method using its water to being polluted by harmful substance |
JP2015183043A (en) * | 2014-03-20 | 2015-10-22 | 太平洋セメント株式会社 | Soil modifying material and method for modifying soil |
JP2016007591A (en) * | 2014-06-26 | 2016-01-18 | 株式会社安藤・間 | Soil cleaning agent and method for cleaning contaminated soil |
JP2018044064A (en) * | 2016-09-14 | 2018-03-22 | 株式会社ジーエルプラン | Agent for reducing pcb and heavy metals |
JP2018103133A (en) * | 2016-12-27 | 2018-07-05 | 日鉄住金セメント株式会社 | Soil treatment material and purification method of heavy metal contaminated soil |
JP2023101945A (en) * | 2022-01-11 | 2023-07-24 | 三友プラントサービス株式会社 | Method for insolubilizing waste gypsum, gypsum composition, and insolubilizing agent |
JP7458654B2 (en) | 2022-01-11 | 2024-04-01 | 三友プラントサービス株式会社 | Method for insolubilizing gypsum dihydrate, method for insolubilizing gypsum hemihydrate, method for producing gypsum composition |
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