JPWO2019244856A1 - Improvement method for heavy metal insolubilized solidifying material and contaminated soil - Google Patents

Improvement method for heavy metal insolubilized solidifying material and contaminated soil Download PDF

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JPWO2019244856A1
JPWO2019244856A1 JP2020525731A JP2020525731A JPWO2019244856A1 JP WO2019244856 A1 JPWO2019244856 A1 JP WO2019244856A1 JP 2020525731 A JP2020525731 A JP 2020525731A JP 2020525731 A JP2020525731 A JP 2020525731A JP WO2019244856 A1 JPWO2019244856 A1 JP WO2019244856A1
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solidifying material
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智彦 金沢
智彦 金沢
奈那 西川
奈那 西川
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Nippon Steel Cement Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/02Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/06Calcium compounds, e.g. lime
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/02Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/10Cements, e.g. Portland cement
    • EFIXED CONSTRUCTIONS
    • E02HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02DFOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
    • E02D3/00Improving or preserving soil or rock, e.g. preserving permafrost soil
    • E02D3/12Consolidating by placing solidifying or pore-filling substances in the soil

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  • Treatment Of Sludge (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

重金属で汚染された軟弱土壌類の強度を向上させると共に、ヒ素及び鉛の溶出量を抑制し得る重金属不溶化固化材、及び軟弱土壌又は汚泥の改良工法を提供する。重金属を含有する軟弱土壌又は汚泥を固化して改良土壌にする共に改良土壌からのヒ素及び鉛の溶出を抑制する重金属不溶化固化材であって、セメント、高炉スラグ及び石膏からなるセメント系固化材と、消石灰又は軽焼ドロマイトを含み、セメント系固化材と消石灰又は軽焼ドロマイトの合計に対し、消石灰又は軽焼ドロマイトの配合量が10〜55質量%であることを特徴とする重金属不溶化固化材、及びその重金属不溶化固化材を使用する軟弱土壌又は汚泥の改良工法。Provided are a heavy metal insolubilized solidifying material capable of improving the strength of soft soil contaminated with heavy metals and suppressing the elution amount of arsenic and lead, and an improvement method for soft soil or sludge. A heavy metal insolubilizing material that solidifies soft soil or sludge containing heavy metals into improved soil and suppresses the elution of arsenic and lead from the improved soil, and is a cement-based solidifying material consisting of cement, blast furnace slag, and gypsum. A heavy metal insolubilizing and solidifying material containing 10 to 55% by mass of slag or lightly burned sludge with respect to the total amount of the cement-based solidifying material and the slag or lightly burned dolomite. And a method for improving soft soil or sludge using its heavy metal insolubilized solidifying material.

Description

本発明は、建設汚泥や浚渫土等の軟弱土壌に含まれる重金属の溶出を抑制でき、適切な強度の土壌に改良可能な重金属不溶化固化材、特にヒ素や鉛を含有する軟弱土壌の重金属溶出量を低減し得る不溶化固化材に関する。 INDUSTRIAL APPLICABILITY The present invention can suppress the elution of heavy metals contained in soft soils such as construction sludge and dredged soil, and can improve the elution of heavy metals into soils of appropriate strength. With respect to insolubilized solidifying materials that can reduce.

現場工事において、建設汚泥や浚渫土等の軟弱土壌に、ヒ素や鉛等の重金属有害物質が含まれていることが報告されている。ヒ素や鉛等の重金属は、環境基準で規制された汚染物質であり、直接摂取することや溶出した水を摂取することで人体に影響を及ぼすおそれがあり、溶出基準値を上回ると、土壌の不溶化処理や吸着工法、遮蔽処理等の措置を行う必要がある。
加えて、建設汚泥や浚渫土等の軟弱土壌の場合、再生利用するために、固化処理によって所定強度の土壌に改良する必要がある。
In on-site construction, it has been reported that soft soil such as construction sludge and dredged soil contains heavy metal toxic substances such as arsenic and lead. Heavy metals such as arsenic and lead are pollutants regulated by environmental standards, and there is a risk of affecting the human body by ingesting them directly or by ingesting eluted water. It is necessary to take measures such as insolubilization treatment, adsorption method, and shielding treatment.
In addition, in the case of soft soil such as construction sludge and dredged soil, it is necessary to improve the soil to a predetermined strength by solidification treatment in order to recycle it.

ヒ素や鉛に汚染された土壌の不溶化処理方法として、例えば、Ca/Mg系塩基性物質を添加した後、鉄の硫酸塩/塩酸塩を添加する方法(特許文献1)、焼石膏とAl化合物とCa/Mg含有化合物を混合使用する方法(特許文献2)によって、中性域で不溶化固化することが提案されている。
しかし、特許文献1,2に記載されている方法は、土壌からのヒ素や鉛の溶出を抑制することは可能であるものの、不溶化後における改良土壌の強度発現性が低く、軟弱土壌の再生利用には不十分である。
ヒ素含有汚泥の処理について、不溶化剤による不溶化処理工程、固化材による固化処理工程、及び乾燥剤による乾燥処理工程からなる三工程の処理方法(特許文献3)が提案されているが、工程が煩雑であり、現場施工に不向きである。また、ヒ素汚染土壌を200〜700℃で加熱処理した後、Ca化合物と水を添加する処理方法(特許文献4)も提案されているが、こうした高温加熱処理も、現場での施工に適さない。
As a method for insolubilizing soil contaminated with arsenic or lead, for example, a method of adding a Ca / Mg-based basic substance and then an iron sulfate / hydrochloride (Patent Document 1), gypsum plaster and an Al compound. It has been proposed to insolubilize and solidify in the neutral region by a method of mixing and using a compound containing Ca / Mg and (Patent Document 2).
However, although the methods described in Patent Documents 1 and 2 can suppress the elution of arsenic and lead from the soil, the strength development of the improved soil after insolubilization is low, and the soft soil is recycled. Is not enough.
Regarding the treatment of arsenic-containing sludge, a three-step treatment method (Patent Document 3) consisting of an insolubilization treatment step using an insolubilizer, a solidification treatment step using a solidifying material, and a drying treatment step using a desiccant has been proposed, but the steps are complicated. Therefore, it is not suitable for on-site construction. Further, a treatment method (Patent Document 4) in which a Ca compound and water are added after heat-treating arsenic-contaminated soil at 200 to 700 ° C. has also been proposed, but such high-temperature heat treatment is also not suitable for on-site construction. ..

他方、セメントは、軟弱土壌のセメント系固化材として汎用されており、重金属の不溶化にも有効である。しかし、粘土分の多い土壌や重金属含有量の多い土壌に対しては、従来のセメント系固化材ではヒ素や鉛の不溶化には十分とはいえず、重金属の溶出環境基準を満たすためにセメント系固化材の添加量を多くすると、改良土壌の強度が過剰になり軟弱土壌の再生利用に支障を来す懸念がある。 On the other hand, cement is widely used as a cement-based solidifying material for soft soil, and is also effective for insolubilizing heavy metals. However, for soils with a high clay content and soils with a high heavy metal content, conventional cement-based solidifying materials are not sufficient for insolubilizing arsenic and lead, and cement-based materials are used to meet the heavy metal elution environmental standards. If the amount of the solidifying material added is increased, the strength of the improved soil becomes excessive, and there is a concern that the regeneration of the soft soil may be hindered.

特許文献5〜9は、各種のセメント系固化材又は不溶化材を開示する。すなわち、特許文献5は、石膏と、生石灰又はセメントと、高炉スラグ微粉末とを混合した主材と、主材による土壌の強アルカリ化を抑制するpH調整剤とからなる汚染土壌の不溶化材を開示する。特許文献6は、土壌用セメント系固化材に、消石灰と軽焼ドロマイトとを所定比で配合してなるセメント系固化材用添加材、及び火山灰質土壌改良方法を開示する。特許文献7は、セメントクリンカ、石膏及び消石灰を含んでなる土壌固化材において、消石灰として粒子径30μm以上の粒子を5〜40体積%含有する消石灰を用いることを開示する。特許文献8は、ポルトランドセメントと高炉スラグと石膏とを所定割合で含む重金属汚染土壌用セメント系処理材、及び重金属汚染土壌の固化不溶化処理方法を開示する。特許文献9は、セメント系固化材にセメント焼成炉プレヒーターから抽出されたセメント原料粉末(プレヒーター原料)を混合して用いる地盤改良工法を開示する。プレヒーター原料中には、セメント原料中の石灰石が熱分解して生成した生石灰が多く含まれる。 Patent Documents 5 to 9 disclose various cement-based solidifying materials or insolubilizing materials. That is, Patent Document 5 describes an insolubilizing material for contaminated soil, which comprises a main material obtained by mixing gypsum, quicklime or cement, and fine powder of blast furnace slag, and a pH adjuster that suppresses strong alkalinization of the soil by the main material. Disclose. Patent Document 6 discloses an additive for a cement-based solidifying material obtained by blending slaked lime and light-burned dolomite in a predetermined ratio with a cement-based solidifying material for soil, and a method for improving volcanic ash soil. Patent Document 7 discloses that in a soil solidifying material containing cement clinker, gypsum and slaked lime, slaked lime containing 5 to 40% by volume of particles having a particle diameter of 30 μm or more is used as the slaked lime. Patent Document 8 discloses a cement-based treatment material for heavy metal-contaminated soil containing Portland cement, blast furnace slag, and gypsum in a predetermined ratio, and a method for solidifying and insolubilizing heavy metal-contaminated soil. Patent Document 9 discloses a ground improvement method using a cement-based solidifying material mixed with cement raw material powder (preheater raw material) extracted from a cement firing furnace preheater. The preheater raw material contains a large amount of quicklime produced by thermal decomposition of limestone in the cement raw material.

特開2006−205169号公報Japanese Unexamined Patent Publication No. 2006-20516 特開2010−207659号公報Japanese Unexamined Patent Publication No. 2010-2076559 特開2005−103429号公報Japanese Unexamined Patent Publication No. 2005-103429 特開2006−167617号公報Japanese Unexamined Patent Publication No. 2006-167617 特開2012−055819号公報Japanese Unexamined Patent Publication No. 2012-055819 特開2011−256324号公報Japanese Unexamined Patent Publication No. 2011-256324 特開2010−159347号公報Japanese Unexamined Patent Publication No. 2010-159347 特開2007−222694号公報Japanese Unexamined Patent Publication No. 2007-222694 特開2000−120059号公報Japanese Unexamined Patent Publication No. 2000-120059

本発明は、ヒ素及び鉛を含有する軟弱汚染土壌のヒ素及び鉛の溶出量を抑制し、かつ改良土壌として適切な強度発現性を示し得る重金属不溶化固化材、及び汚染土壌類の改良工法を提供することを目的とする。 The present invention provides a heavy metal insolubilized solidifying material capable of suppressing the elution amount of arsenic and lead in a softly contaminated soil containing arsenic and lead and exhibiting appropriate strength development as an improved soil, and an improvement method for contaminated soil. The purpose is to do.

本発明者は、上記課題を解決するために、特定のセメント系固化材に消石灰を組み合わせることによって、上記課題を解決し得ることを見出した。 The present inventor has found that the above problems can be solved by combining slaked lime with a specific cement-based solidifying material in order to solve the above problems.

すなわち、本発明は、重金属としてヒ素及び鉛を含有する軟弱土壌又は汚泥を固化して改良土壌にする共に改良土壌からのヒ素及び鉛の溶出を抑制する重金属不溶化固化材であって、セメント、高炉スラグ及び石膏からなるセメント系固化材と、消石灰又は軽焼ドロマイトを含み、セメント系固化材と消石灰又は軽焼ドロマイトの合計に対し、消石灰の配合量が10〜55質量%であることを特徴とする重金属不溶化固化材である。 That is, the present invention is a heavy metal insolubilizing solidifying material that solidifies soft soil or sludge containing arsenic and lead as heavy metal into improved soil and suppresses elution of arsenic and lead from the improved soil, and is a cement or blast furnace. It contains a cement-based solidifying material composed of slag and gypsum and slaked lime or light-baked dolomite, and is characterized in that the amount of slaked lime blended is 10 to 55% by mass with respect to the total of the cement-based solidifying material and slaked lime or light-burning dolomite. It is a heavy metal insolubilizing and solidifying material.

上記消石灰としては、平均粒径が20μm以下であり、CaOを72.5質量%以上含有するものが適する。上記軽焼ドロマイトとしては、CaO・MgOを93.0質量%以上含有するものであり、粉末度は5000cm/g〜7000cm/gが適する。また、上記セメント系固化材としては、セメントを25〜90質量%、高炉スラグを5〜50質量%、石膏を5〜25質量%含有するものが適する。As the slaked lime, one having an average particle size of 20 μm or less and containing 72.5% by mass or more of CaO is suitable. As the light burnt dolomite, and those containing CaO · MgO 93.0 wt% or more, fineness suitable is 5000cm 2 / g~7000cm 2 / g. Further, as the cement-based solidifying material, one containing 25 to 90% by mass of cement, 5 to 50% by mass of blast furnace slag, and 5 to 25% by mass of gypsum is suitable.

上記重金属不溶化固化材は、上記セメント系固化材と消石灰又は軽焼ドロマイトの合計100質量部に対し、アルカリ金属及び/又はアルカリ土類金属の塩化物及び/又は硫酸塩を2〜20質量部配合することができる。 The heavy metal insolubilized solidifying material contains 2 to 20 parts by mass of alkali metal and / or alkaline earth metal chloride and / or sulfate in a total of 100 parts by mass of the cement-based solidifying material and slaked lime or lightly baked dolomite. can do.

上記重金属不溶化固化材は、軟弱土壌又は汚泥を、一軸圧縮強さ100〜3000kN/mの改良土壌にするために、ヒ素と鉛の溶出量を各0.01mg/L以下の改良土壌にするために好適に使用される。The heavy metal insolubilized solidifying material makes the soft soil or sludge into an improved soil with a uniaxial compressive strength of 100 to 3000 kN / m 2 and an elution amount of arsenic and lead of 0.01 mg / L or less, respectively. Is preferably used for this purpose.

また、本発明は、ヒ素及び鉛を含有する軟弱土壌又は汚泥を改良して強度を高める共に上記重金属の溶出を抑制する軟弱土壌又は汚泥の改良工法であって、上記の重金属不溶化固化材を土壌又は汚泥に混合することを特徴とする軟弱土壌又は汚泥の改良工法である。
軟弱土壌又は汚泥を、一軸圧縮強さ100〜3000kN/mの改良土壌にしたり、ヒ素溶出量0.01mg/l以下、又は鉛溶出量0.01mg/l以下の改良土壌にする場合に好適な工法である。
Further, the present invention is a method for improving soft soil or sludge containing arsenic and lead to increase strength and suppress elution of the heavy metal, wherein the heavy metal insolubilized solidifying material is used as soil. Alternatively, it is a method for improving soft soil or sludge, which is characterized by being mixed with sludge.
Suitable for soft soil or sludge to be improved soil with uniaxial compressive strength of 100 to 3000 kN / m 2 , or improved soil with arsenic elution amount of 0.01 mg / l or less or lead elution amount of 0.01 mg / l or less. It is a construction method.

本発明の重金属不溶化固化材によれば、簡易に、ヒ素及び鉛を含有する軟弱土壌又は汚泥類を適切な強度の改良土壌に固化でき、かつ、ヒ素及び鉛の溶出量を環境指定基準以下に抑制できる。 According to the heavy metal insolubilized solidifying material of the present invention, soft soil containing arsenic and lead or sludge can be easily solidified in improved soil having an appropriate strength, and the amount of arsenic and lead eluted is below the environmental designation standard. Can be suppressed.

本発明の重金属不溶化固化材は、重金属としてヒ素及び鉛を含有する軟弱土壌又は汚泥(以下、両者を軟弱土壌類又は土壌ともいう。)を固化して改良土壌にする共に、改良土壌からのヒ素と鉛の溶出を抑制する重金属不溶化固化材である。この重金属不溶化固化材は主成分としてセメント系固化材と消石灰又は軽焼ドロマイト(以下、消石灰類ともいう。)を含む。 The heavy metal insolubilized solidifying material of the present invention solidifies soft soil or sludge containing arsenic and lead as heavy metals (hereinafter, both are also referred to as soft soil or soil) to make improved soil, and arsenic from the improved soil. It is a heavy metal insolubilizing and solidifying material that suppresses the elution of lead. This heavy metal insolubilized solidifying material contains a cement-based solidifying material and slaked lime or light-burned dolomite (hereinafter, also referred to as slaked limes) as main components.

セメント系固化材と消石灰類の配合割合は、両者の合計に対し、消石灰類の配合量が10〜55質量%であり、好ましくは20〜50質量%である。消石灰類が10質量%未満では、改良土壌の強度が過剰となり、ヒ素や鉛の不溶化も不十分となり易く、再生利用に支障を来す懸念がある。消石灰類の添加量が55質量%を超えると改良土壌の強度が不充分となるだけでなく、pHが高くなることから、鉛の溶出量が増加する。 The blending ratio of the cement-based solidifying material and the slaked limes is such that the blending amount of the slaked limes is 10 to 55% by mass, preferably 20 to 50% by mass, based on the total of both. If the amount of slaked lime is less than 10% by mass, the strength of the improved soil becomes excessive, and the insolubilization of arsenic and lead tends to be insufficient, which may hinder recycling. If the amount of slaked lime added exceeds 55% by mass, not only the strength of the improved soil becomes insufficient, but also the pH becomes high, so that the amount of lead eluted increases.

セメント系固化材は、セメントを母材とする固化性の材料であって、軟弱土壌類を効率良く安定化するために、セメントに高炉スラグや石膏を有効成分として添加したものである。セメント系固化材100質量%中に、セメントを25〜90質量%、高炉スラグを5〜50質量%、及び石膏を5〜25質量%含有することがより好ましい。
セメントとしては、JIS規格品(JIS R 5210〜5214)あるいは、ポルトランドセメントを製造する際の中間原料であるクリンカーを使用できる。すなわち、ポルトランドセメント、高炉セメント、シリカセメント、フライアッシュセメント、エコセメント及び混合セメントが挙げられるが、好ましくはポルトランドセメント、高炉セメントである。
高炉スラグとしては、徐冷スラグ、水砕スラグが挙げられるが、潜在水硬性を有する水砕スラグが適する。
石膏としては、無水石膏が適する。
なお、高炉セメントなどセメント中に高炉スラグや石膏を含むものも存在するが、本発明のセメント系固化材としてセメントに配合される高炉スラグや石膏は、これとは別に加える量であると理解される。
セメント系固化材の製造は、それぞれの粉末を混合、あるいは混合粉砕のいずれも使用できる。セメント系固化材の粒径は、ブレーン比表面積が4000cm/g以上、好ましくは5000cm/g以上である。
セメント系固化材に消石灰又は軽焼ドロマイトを配合した重金属不溶化固化材の粒径は、消石灰を配合する場合、ブレーン比表面積が7000cm/g以上、好ましくは8000cm/g以上である。軽焼ドロマイトを配合する場合、ブレーン比表面積が5000cm/g以上、好ましくは6000cm/g以上である。上限は特に限定されないが、粉砕限界の観点から、12000cm/g程度である。
The cement-based solidifying material is a solidifying material using cement as a base material, and is obtained by adding blast furnace slag or gypsum as an active ingredient to cement in order to efficiently stabilize soft soils. It is more preferable that the cement-based solidifying material contains 25 to 90% by mass of cement, 5 to 50% by mass of blast furnace slag, and 5 to 25% by mass of gypsum in 100% by mass of the cement-based solidifying material.
As the cement, JIS standard products (JIS R 5210 to 5214) or clinker, which is an intermediate raw material for producing Portland cement, can be used. That is, Portland cement, blast furnace cement, silica cement, fly ash cement, eco-cement and mixed cement are mentioned, but Portland cement and blast furnace cement are preferable.
Examples of the blast furnace slag include slow cooling slag and granulated slag, and granulated slag having latent hydraulic slag is suitable.
Anhydrous gypsum is suitable as the gypsum.
Although some cements such as blast furnace cement contain blast furnace slag and gypsum, it is understood that the amount of blast furnace slag and gypsum blended in cement as the cement-based solidifying material of the present invention is an amount to be added separately. To.
In the production of the cement-based solidifying material, either the respective powders can be mixed or mixed and pulverized can be used. The grain size of the cement-based solidifying material is such that the specific surface area of the brain is 4000 cm 2 / g or more, preferably 5000 cm 2 / g or more.
The particle size of the heavy metal insolubilized solidifying material obtained by blending slaked lime or light-baked dolomite with the cement-based solidifying material is such that the brain specific surface area is 7000 cm 2 / g or more, preferably 8000 cm 2 / g or more when slaked lime is blended. When blending the light burned dolomite, Blaine specific surface area of 5000 cm 2 / g or more, preferably 6000 cm 2 / g or more. The upper limit is not particularly limited, but from the viewpoint of the pulverization limit, it is about 12000 cm 2 / g.

消石灰又は軽焼ドロマイトの配合割合は、重金属不溶化固化材において10〜55質量%の範囲とすることがよい。
消石灰としては、JIS規格品(JIS R 9001)を使用できる。好ましくは特号であり、CaO分を72.5質量%以上含有するものが適する。また、消石灰には、土壌と混合した際に消石灰となり得る化合物を含む。好ましくは生石灰である。
また、消石灰の平均粒径(d50)は、好ましくは20μm以下、より好ましくは10μm以下である。
軽焼ドロマイトとしては、JIS規格品(JIS R 9001)を使用できる。好ましくは特号であり、CaO・MgO分を93.0質量%以上、MgO分を30.0質量%以上含有するものが適する。
粉末度(比表面積)は、好ましくは5000〜7000cm/gである。ここで、粉末度は、軽焼ドロマイトをセメント固化材等と混合、粉砕した後の数値である。
The blending ratio of slaked lime or light-baked dolomite may be in the range of 10 to 55% by mass in the heavy metal insolubilized solidifying material.
As slaked lime, a JIS standard product (JIS R 9001) can be used. It is preferably a special item, and one containing 72.5% by mass or more of CaO content is suitable. In addition, slaked lime contains a compound that can become slaked lime when mixed with soil. Quicklime is preferable.
The average particle size (d50) of slaked lime is preferably 20 μm or less, more preferably 10 μm or less.
JIS standard products (JIS R 9001) can be used as light-baked dolomite. It is preferably a special item, and those containing CaO / MgO content of 93.0% by mass or more and MgO content of 30.0% by mass or more are suitable.
The degree of powderness (specific surface area) is preferably 5000 to 7000 cm 2 / g. Here, the degree of powder is a value after mixing and crushing lightly baked dolomite with a cement solidifying material or the like.

本発明の重金属不溶化固化材は、ヒ素、鉛の溶出量を抑制するために、上記セメント系固化材と消石灰類に加えて、アルカリ金属及び/又はアルカリ土類金属の塩化物及び/又は硫酸塩を配合するとよい。
塩化物としては、好ましくは塩化カルシウム、又は塩化ナトリウムが挙げられ、硫酸塩としては、好ましくは硫酸マグネシウム、硫酸ナトリウム、又は硫酸カルシウムが挙げられ、これらを単独又は二種以上を混合して使用できる。
塩化物及び/又は硫酸塩は、上記セメント系固化材と消石灰類の合計100質量部に対し、2〜20質量部を配合することがよく、好ましくは7〜15質量部である。
In order to suppress the elution amount of arsenic and lead, the heavy metal insolubilized solidifying material of the present invention contains chlorides and / or sulfates of alkali metals and / or alkaline earth metals in addition to the cement-based solidifying materials and slaked limes. It is good to mix.
Chloride is preferably calcium chloride or sodium chloride, and sulfate is preferably magnesium sulfate, sodium sulfate, or calcium sulfate, which can be used alone or in admixture of two or more. ..
The chloride and / or sulfate is preferably added in an amount of 2 to 20 parts by mass, preferably 7 to 15 parts by mass, based on 100 parts by mass of the total of the cement-based solidifying material and slaked limes.

本発明の重金属不溶化固化材には、必要によりコンクリート混和材や無機粉末などその他の成分を配合し得る。また、重金属不溶化固化材は配合成分を事前に混合してもよく、施工現場で同時に混合してもよいが、事前に混合しておけば、製品の品質安定性が優れる。 The heavy metal insolubilizing and solidifying material of the present invention may contain other components such as a concrete admixture and an inorganic powder, if necessary. Further, the heavy metal insolubilized solidifying material may be mixed in advance with the compounding components or may be mixed at the same time at the construction site, but if they are mixed in advance, the quality stability of the product is excellent.

本発明の重金属不溶化固化材は、軟弱土壌又は汚泥を処理して改良土壌とするために使用される。
軟弱土壌としては、一般に泥土と言われ、建設ないし浚渫等により発生する土壌のうち流動性を呈する状態のものであって、強度としては、コーン指数200kN/m2未満であるか、あるいは一軸圧縮強さが概ね50kN/m2以下の土壌がある。
汚泥としては水槽、川、池、湖沼、海底等に堆積したものがあるが、これらは水分量が多く、流動性が大きいので、陸地に放置してある程度乾燥させるか、水分量の少ない土壌と混合して事前処理して含水量を調整することがよい。
The heavy metal insolubilizing and solidifying material of the present invention is used for treating soft soil or sludge into improved soil.
The soft soil is generally called muddy soil, which is a soil generated by construction or dredging that exhibits fluidity, and its strength is less than 200 kN / m 2 in cone index or uniaxial compression. There is soil with a strength of approximately 50 kN / m 2 or less.
Some sludge is deposited in water tanks, rivers, ponds, lakes, seabeds, etc., but since these have high water content and high fluidity, they can be left on land to dry to some extent, or soil with low water content can be used. It is advisable to mix and pre-treat to adjust the water content.

土壌の状態としては、含水比が10〜200質量%、好ましくは20〜50質量%の土壌であることがよい。重金属不溶化固化材が固化して強度を発現するためには適当な水分が必要であるが、過剰であると強度向上効果が劣る。
また、湿潤密度としては、1〜3g/cm、好ましくは1.5〜2.50g/cmの土壌に適する。
加えて、重金属としてヒ素と鉛を含む軟弱土壌類が対象である。ヒ素と鉛の含有量は特に限定されないが、土壌1kg当たり、各1.0mg以上、好ましくは10.0mg以上含むことがよい。上限には制限はないが、200mg程度以下であれば、固化後の改良土壌において、排出基準値(0.01以下)の溶出量に低減できる。
特に、粘土を多く含む軟弱土壌において、本発明の固化材や改良工法は有効である。土壌は通常、粘土と砂とから構成されるが、粘土が多い土壌は粘性土、逆に砂が多い土壌は砂質土と言われる。本発明は、粘土と砂の合計量に対して粘土を50質量%以上含む粘性土、又は粘土を30質量%以上含む砂質土を処理するのに有効である。
The soil condition is preferably a soil having a water content of 10 to 200% by mass, preferably 20 to 50% by mass. Appropriate water content is required for the heavy metal insolubilized solidifying material to solidify and develop strength, but if it is excessive, the strength improving effect is inferior.
As the wet density, 1 to 3 g / cm 3, preferably suitable for soil 1.5~2.50g / cm 3.
In addition, soft soils containing arsenic and lead as heavy metals are targeted. The contents of arsenic and lead are not particularly limited, but may be 1.0 mg or more, preferably 10.0 mg or more, respectively, per 1 kg of soil. There is no limit to the upper limit, but if it is about 200 mg or less, it can be reduced to the elution amount of the emission standard value (0.01 or less) in the improved soil after solidification.
In particular, the solidifying material and the improved method of the present invention are effective in soft soil containing a large amount of clay. Soil is usually composed of clay and sand, but clay-rich soil is called cohesive soil, and sand-rich soil is called sandy soil. The present invention is effective for treating cohesive soil containing 50% by mass or more of clay or sandy soil containing 30% by mass or more of clay with respect to the total amount of clay and sand.

本発明の重金属不溶化固化材を使用して軟弱土壌類の不溶化固化処理する場合、処理対象の軟弱土壌類1mに対し、重金属不溶化固化材を、10〜300kg、好ましくは30〜200kg、特に好ましくは50〜150kg使用することがよい。また、重金属不溶化固化材に含まれる消石灰類の添加量としては、軟弱土壌類1mに対し、5〜55kgの範囲が好ましい。より好ましくは10〜55kgの範囲である。If insolubilized solidification of soft soil such using a heavy metal insolubilization solidifying material of the present invention, with respect to soft soils such 1 m 3 to be processed, heavy metal insolubilization solidifying material, 10~300Kg, preferably 30~200Kg, particularly preferably It is recommended to use 50 to 150 kg. The amount of slaked lime contained in the heavy metal insolubilized solidifying material is preferably in the range of 5 to 55 kg with respect to 1 m 3 of soft soil. More preferably, it is in the range of 10 to 55 kg.

本発明の重金属不溶化固化材は、軟弱土壌類を一軸圧縮強さ100〜3000kN/mの改良土壌にすることが可能となる。特に、一軸圧縮強さ300〜2000kN/mの改良土壌、さらに800〜1800kN/mの改良土壌にすることが可能となる。
本発明の重金属不溶化固化材は、上述のとおり軟弱土壌類を所定強度に固化できると共に、ヒ素と鉛の溶出量を低減できる。好ましくはヒ素又は鉛の溶出量の少なくともいずれかを環境基準値(0.01mg/L以下)にすることも可能となる。なお、溶出量の測定は実施例の条件に従う。
The heavy metal insolubilizing and solidifying material of the present invention makes it possible to turn soft soils into improved soils having a uniaxial compressive strength of 100 to 3000 kN / m 2. In particular, improved soil uniaxial compressive strength 300~2000kN / m 2, it is possible to further the improved soil 800~1800kN / m 2.
As described above, the heavy metal insolubilizing and solidifying material of the present invention can solidify soft soils to a predetermined strength and reduce the amount of arsenic and lead eluted. Preferably, at least one of the elution amount of arsenic or lead can be set to an environmental standard value (0.01 mg / L or less). The elution amount is measured according to the conditions of Examples.

以下、実施例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、特に断りのない限り部は質量部であり、%は質量%である。 Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the following Examples. Unless otherwise specified, parts are parts by mass, and% is% by mass.

重金属不溶化固化材に使用した材料を次に示す。
普通ポルトランドセメント(OPC) 日鉄セメント社製、ブレーン比表面積3340 cm2/g
高炉スラグ 日本製鉄社製
無水石膏 タイ産
消石灰特特選 北海道石灰化工社製 (CaO:73.5%,平均粒径:4.8μm)
軽焼ドロマイト 黒崎播磨社製 (CaO・MgO:97.0%、MgO:39.5%、粉末度:6140 cm2/g)
The materials used for the heavy metal insolubilizing and solidifying material are shown below.
Ordinary Portland cement (OPC) Made by Nippon Steel Cement, Brain Specific surface area 3340 cm 2 / g
Blast furnace slag Nippon Steel's anhydrous gypsum Thai slaked lime special selection Hokkaido calcification company (CaO: 73.5%, average particle size: 4.8 μm)
Lightly baked dolomite manufactured by Krosaki Harima Co., Ltd. (CaO / MgO: 97.0%, MgO: 39.5%, powderiness: 6140 cm 2 / g)

上記OPC単体をセメント系固化材(I)とした。セメント(I)とも言う。
上記OPC57.0質量部、高炉スラグ34.7部及び石膏8.3部を、混合、粉砕して、ブレーン比表面積6310cm2/gのセメント系固化材(II)とした。セメント(II)とも言う。
The above OPC alone was used as a cement-based solidifying material (I). Also called cement (I).
The above OPC 57.0 parts by mass, blast furnace slag 34.7 parts and gypsum 8.3 parts were mixed and pulverized to obtain a cement-based solidifying material (II) having a brain specific surface area of 6310 cm 2 / g. Also called cement (II).

下記の土壌材料及び重金属化合物(試薬)を使用し、温度50度で2日間乾燥させた土と蒸留水に重金属試薬を溶解させたものを、ソイルミキサーで3分間混合することで、含水比、重金属量を調整した模擬汚染土壌を作成した(土壌A〜E)。
荒木田土 あかぎ園芸製
砕砂 白老産
8号珪砂 東北珪砂社製
ひ酸水素二ナトリウム七水和物(特級) 関東化学社製
硝酸鉛(II) 関東化学社製
Using the following soil materials and heavy metal compounds (reagents), the soil and distilled water dried at a temperature of 50 ° C. for 2 days are mixed with the heavy metal reagent in distilled water for 3 minutes to obtain a water content ratio. Simulated contaminated soil with adjusted heavy metal content was prepared (soils A to E).
Arakida soil Akagi gardening made crushed sand Shiraoi
No. 8 silica sand Tohoku silica sand company disodium hydrogen arsenate heptahydrate (special grade) Kanto Chemical Co., Inc. lead nitrate (II) Kanto Chemical Co., Ltd.

土壌A〜Eの配合組成、土質、含水比、密度及び重金属含有量を表1に示す。
表1において、湿潤密度の単位は(g/cm3)であり、ヒ素、鉛の含有量(上段)の単位は(mg/kg)であり、ヒ素、鉛の溶出量(下段)の単位は(mg/L)である。配合量は部である。
なお、溶出量の測定は、環境省告示46号に準拠して検液を作製し、ICP発光分光分析法によって測定した。
Table 1 shows the composition, soil quality, water content, density and heavy metal content of soils A to E.
In Table 1, the unit of wet density is (g / cm 3 ), the unit of arsenic and lead content (upper) is (mg / kg), and the unit of arsenic and lead elution (lower) is. (mg / L). The blending amount is a part.
The elution amount was measured by preparing a test solution in accordance with Notification No. 46 of the Ministry of the Environment and measuring by ICP emission spectroscopic analysis.

Figure 2019244856
Figure 2019244856

参考例1〜4
土壌A〜Dに、セメント系固化材(II)を100kg/m3となるように混合して、7日後及び28日後のヒ素溶出量と一軸圧縮強さを測定した。結果を表2に示す。
Reference examples 1 to 4
Cement-based solidifying material (II) was mixed with soils A to D so as to be 100 kg / m 3, and the amount of arsenic elution and uniaxial compressive strength after 7 days and 28 days were measured. The results are shown in Table 2.

Figure 2019244856
Figure 2019244856

表2から、土壌中の砂の量が増えるほどヒ素の溶出量は減少し、参考例4の土壌Dでは、セメント系固化材においても環境基準値以下までヒ素の不溶化が可能であることが分かる。しかし、粘土(荒木田土)が増えるほどヒ素溶出量が増加し、セメント系固化材では不溶化が困難であることが分かる。 From Table 2, it can be seen that the elution amount of arsenic decreases as the amount of sand in the soil increases, and in the soil D of Reference Example 4, even the cement-based solidifying material can insolubilize arsenic to below the environmental standard value. .. However, as the amount of clay (Arakida soil) increases, the amount of arsenic eluted increases, and it can be seen that insolubilization is difficult with cement-based solidifying materials.

実施例1〜8、比較例1〜5
上記土壌Eに対し、セメント系固化材(II)と消石灰を配合してなる重金属不溶化固化材を混合処理して、7日後の溶出量と一軸圧縮強さを測定した。結果を表3に示す。なお、表3には、重金属不溶化固化材のブレーン比表面積も示す。
Examples 1-8, Comparative Examples 1-5
A heavy metal insolubilized solidifying material obtained by blending a cement-based solidifying material (II) and slaked lime was mixed with the soil E, and the elution amount and uniaxial compressive strength after 7 days were measured. The results are shown in Table 3. Table 3 also shows the brain specific surface area of the heavy metal insolubilized solidifying material.

Figure 2019244856
Figure 2019244856

表3から、消石灰を配合しないと、ヒ素の不溶化が不十分となり、消石灰量が増えるとともに、ヒ素の溶出量も減少するが、鉛の溶出量が増加することが分かる。また、セメント系固化材(II)に代えて、OPC単独のセメント系固化材(I)を使用した場合は、鉛又はヒ素の不溶化が不十分となることが分かる。このことから、セメント系固化材(II)に含まれている高炉スラグが溶出量の抑制に有効であることが分かる。すなわち、OPC、高炉スラグ、石膏と消石灰(10〜55質量%)とすることで、ヒ素と鉛の溶出量を環境基準値以下とすることができる。 From Table 3, it can be seen that if slaked lime is not added, the insolubilization of arsenic becomes insufficient, the amount of slaked lime increases, the amount of arsenic eluted also decreases, but the amount of lead eluted increases. Further, it can be seen that when the cement-based solidifying material (I) of OPC alone is used instead of the cement-based solidifying material (II), the insolubilization of lead or arsenic becomes insufficient. From this, it can be seen that the blast furnace slag contained in the cement-based solidifying material (II) is effective in suppressing the elution amount. That is, by using OPC, blast furnace slag, gypsum and slaked lime (10 to 55% by mass), the amount of arsenic and lead eluted can be kept below the environmental standard value.

実施例9〜14
上記模擬土壌Eに対し、セメント系固化材(II)と消石灰に加えて塩化物を配合してなる重金属不溶化固化材を混合処理して、7日後の溶出量と一軸圧縮強さを測定した。結果を表4に示す。なお、表4には、重金属不溶化固化材のブレーン比表面積も示す。
Examples 9-14
The simulated soil E was mixed with a heavy metal insolubilized solidifying material prepared by blending chloride in addition to cement-based solidifying material (II) and slaked lime, and the elution amount and uniaxial compressive strength after 7 days were measured. The results are shown in Table 4. Table 4 also shows the brain specific surface area of the heavy metal insolubilized solidifying material.

Figure 2019244856
Figure 2019244856

実施例15〜20
上記模擬土壌Eに対し、セメント系固化材(II)と消石灰に加えて硫酸塩を配合してなる重金属不溶化固化材を混合処理して、7日後の溶出量と一軸圧縮強さを測定した。結果を表5に示す。なお、表5には、重金属不溶化固化材のブレーン比表面積も示す。
Examples 15-20
The simulated soil E was mixed with a heavy metal insolubilized solidifying material prepared by blending a cement-based solidifying material (II), slaked lime, and a sulfate, and the elution amount and uniaxial compressive strength after 7 days were measured. The results are shown in Table 5. Table 5 also shows the brain specific surface area of the heavy metal insolubilized solidifying material.

Figure 2019244856
Figure 2019244856

表4、5から、セメント系固化材(II)と消石灰に加えて塩化物又は硫酸塩を配合してなる重金属不溶化固化材を使用することにより、鉛溶出量を更に抑制できることが分かる。 From Tables 4 and 5, it can be seen that the amount of lead elution can be further suppressed by using a heavy metal insolubilized solidifying material in which chloride or sulfate is blended in addition to the cement-based solidifying material (II) and slaked lime.

実施例21〜27
上記土壌E(表3と同条件の土壌)に対し、セメント系固化材(II)と軽焼ドロマイトを配合してなる重金属不溶化固化材を混合処理して、7日後の溶出量と一軸圧縮強さを測定した。結果を表6に示す。なお、表6には、重金属不溶化固化材のブレーン比表面積も示す。
Examples 21-27
The above soil E (soil under the same conditions as in Table 3) is mixed with a heavy metal insolubilized solidifying material, which is a mixture of cement-based solidifying material (II) and light-baked dolomite, and the amount of elution and uniaxial compressive strength after 7 days. Was measured. The results are shown in Table 6. Table 6 also shows the brain specific surface area of the heavy metal insolubilized solidifying material.

Figure 2019244856
Figure 2019244856

表6から、軽焼ドロマイトにおいても消石灰と同様に、ヒ素、鉛の不溶化効果が認められ、ヒ素や鉛の溶出量を抑制することができる。 From Table 6, the insolubilizing effect of arsenic and lead is observed in light-baked dolomite as well as slaked lime, and the elution amount of arsenic and lead can be suppressed.

本発明によれば、簡易に、ヒ素及び鉛を含有する軟弱土壌又は汚泥類を適切な強度の改良土壌に固化でき、かつ、ヒ素及び鉛の溶出量を環境指定基準以下に抑制できる。よって、重金属で汚染された軟弱土壌類の強度を向上させると共に、ヒ素及び鉛の溶出量を抑制し得る重金属不溶化固化材、及び軟弱土壌又は汚泥の改良工法として、非常に有用である。 According to the present invention, soft soil containing arsenic and lead or sludge can be easily solidified in improved soil having an appropriate strength, and the amount of arsenic and lead eluted can be suppressed below the environmental designation standard. Therefore, it is very useful as a heavy metal insolubilized solidifying material capable of improving the strength of soft soil contaminated with heavy metals and suppressing the elution amount of arsenic and lead, and as a method for improving soft soil or sludge.

Claims (11)

重金属としてヒ素及び鉛を含有する軟弱土壌又は汚泥を固化して改良土壌にする共に改良土壌からのヒ素及び鉛の溶出を抑制する重金属不溶化固化材であって、セメント、高炉スラグ及び石膏からなるセメント系固化材と、消石灰又は軽焼ドロマイトを含み、セメント系固化材と消石灰又は軽焼ドロマイトの合計に対し、消石灰又は軽焼ドロマイトの配合量が10〜55質量%であることを特徴とする重金属不溶化固化材。 A heavy metal insolubilizing solidifying material that solidifies soft soil or sludge containing arsenic and lead as heavy metals into improved soil and suppresses the elution of arsenic and lead from the improved soil. Cement consisting of cement, blast furnace slag and gypsum. A heavy metal containing a system-based solidifying material and slaked lime or light-burned dolomite, and the amount of slaked lime or light-burned dolomite is 10 to 55% by mass based on the total amount of the cement-based solidifying material and slaked lime or light-burned dolomite. Insolubilized solidifying material. 消石灰が、平均粒径が20μm以下であり、CaOを72.5質量%以上含有する請求項1に記載の重金属不溶化固化材。 The heavy metal insolubilizing and solidifying material according to claim 1, wherein the slaked lime has an average particle size of 20 μm or less and contains CaO in an amount of 72.5% by mass or more. 軽焼ドロマイトが、CaO・MgOを93.0質量%以上含有し、粉末度が5000〜7000cm/gである請求項1に記載の重金属不溶化固化材。The heavy metal insolubilizing and solidifying material according to claim 1, wherein the light-baked dolomite contains CaO / MgO in an amount of 93.0% by mass or more and has a powderiness of 5000 to 7000 cm 2 / g. セメント系固化材が、セメント25〜90質量%、高炉スラグを5〜50質量%及び石膏を5〜25質量%含有する請求項1又は2に記載の重金属不溶化固化材。 The heavy metal insolubilizing material according to claim 1 or 2, wherein the cement-based solidifying material contains 25 to 90% by mass of cement, 5 to 50% by mass of blast furnace slag, and 5 to 25% by mass of gypsum. セメント系固化材と消石灰又は軽焼ドロマイトの合計100質量部に対し、アルカリ金属及び/又はアルカリ土類金属の塩化物及び/又は硫酸塩を2〜20質量部配合してなる請求項1に記載の重金属不溶化固化材。 The first aspect of claim 1, wherein 2 to 20 parts by mass of alkali metal and / or alkaline earth metal chloride and / or sulfate is added to a total of 100 parts by mass of the cement-based solidifying material and slaked lime or lightly baked dolomite. Heavy metal insolubilizing and solidifying material. 軟弱土壌又は汚泥を、一軸圧縮強さ100〜3000kN/mの改良土壌にするために使用される請求項1に記載の重金属不溶化固化材。The heavy metal insolubilizing and solidifying material according to claim 1, which is used to turn soft soil or sludge into improved soil having a uniaxial compressive strength of 100 to 3000 kN / m 2. 軟弱土壌又は汚泥を、ヒ素溶出量0.01mg/l以下、又は鉛溶出量0.01mg/l以下の改良土壌にするために使用される請求項1に記載の重金属不溶化固化材。 The heavy metal insolubilizing and solidifying material according to claim 1, which is used to turn soft soil or sludge into improved soil having an arsenic elution amount of 0.01 mg / l or less or a lead elution amount of 0.01 mg / l or less. ヒ素及び鉛を含有する軟弱土壌又は汚泥を改良して強度を高める共に上記重金属の溶出を抑制する軟弱土壌又は汚泥の改良工法であって、請求項1に記載の重金属不溶化固化材を土壌又は汚泥に混合することを特徴とする軟弱土壌又は汚泥の改良工法。 It is an improvement method for soft soil or sludge containing arsenic and lead to improve strength and suppress elution of the heavy metal, and the heavy metal insolubilized solidifying material according to claim 1 is used as soil or sludge. A method for improving soft soil or sludge, which is characterized by mixing with. 軟弱土壌又は汚泥に対し、消石灰又は軽焼ドロマイトの添加量が5〜55kg/mになるように、重金属不溶化固化材を土壌又は汚泥に混合する請求項8に記載の軟弱土壌又は汚泥の改良工法。The improvement of soft soil or sludge according to claim 8, wherein a heavy metal insolubilized solidifying material is mixed with the soil or sludge so that the amount of slaked lime or light-burned dolomite added to the soft soil or sludge is 5 to 55 kg / m 3. Construction method. 軟弱土壌又は汚泥を、一軸圧縮強さ100〜3000kN/mの改良土壌にする請求項8に記載の軟弱土壌又は汚泥の改良工法。The method for improving soft soil or sludge according to claim 8, wherein the soft soil or sludge is made into improved soil having a uniaxial compressive strength of 100 to 3000 kN / m 2. 軟弱土壌又は汚泥を、ヒ素溶出量0.01mg/l以下、又は鉛溶出量0.01mg/l以下の改良土壌にする請求項8に記載の軟弱土壌又は汚泥の改良工法。 The method for improving soft soil or sludge according to claim 8, wherein the soft soil or sludge is made into improved soil having an arsenic elution amount of 0.01 mg / l or less or a lead elution amount of 0.01 mg / l or less.
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