JP5833425B2 - Earthwork materials - Google Patents
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- JP5833425B2 JP5833425B2 JP2011276979A JP2011276979A JP5833425B2 JP 5833425 B2 JP5833425 B2 JP 5833425B2 JP 2011276979 A JP2011276979 A JP 2011276979A JP 2011276979 A JP2011276979 A JP 2011276979A JP 5833425 B2 JP5833425 B2 JP 5833425B2
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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
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Investigation Of Foundation Soil And Reinforcement Of Foundation Soil By Compacting Or Drainage (AREA)
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Description
本発明は、底質を使用し、埋め戻し材などに利用される土工材料に関し、詳細には底質に含まれる有害物質の溶出量を土壌環境基準以下に抑制した土工材料に関する。 The present invention relates to an earthwork material that uses bottom sediment and is used as a backfill material, and more particularly to an earthwork material in which the amount of toxic substances contained in the bottom sediment is suppressed to a soil environment standard or less.
底質とは海域、港湾、河川、水路、湖沼などの水底の土砂やヘドロ等のことである。底質の粒度組成としては一般に粒径６３μｍ以上の砂質と粒径６３〜５μｍのシルトおよび粒径５μｍ以下の粘土から構成されており、ヘドロなどではシルトや粘土などの微粒子の割合が多い。また、底質には有機物や硫化物、さらには重金属などが含まれていることも多い。そのため、特に海域や河川等の底質の浚渫工事で発生する浚渫土、あるいは津波等で陸上に滞留した底質の堆積土などにおいては、その処理方法が大きな課題となっている。廃棄物の低減という側面からは、底質の浚渫土や堆積土を埋め戻し材などの土木材料として有効利用していくのが望ましいが、そのためには、底質からの有害物質の溶出という環境安全面の問題を解決する必要がある。具体的には、底質に含まれる主な有害物質であるふっ素、ほう素、砒素、鉛の溶出量が土壌環境基準（環境庁告示第４６号）を超える恐れがあることが、その有効利用の妨げとなっている。表１に土壌環境基準（環境庁告示第４６号）に規定されているふっ素、ほう素、砒素、鉛の溶出量を示す。 Sediment refers to sediment, sludge, etc. at the bottom of sea areas, harbors, rivers, waterways, lakes and marshes. The particle size composition of the bottom is generally composed of sand having a particle size of 63 μm or more, silt having a particle size of 63 to 5 μm, and clay having a particle size of 5 μm or less, and sludge or the like has a large proportion of fine particles such as silt and clay. In addition, the bottom sediment often contains organic substances, sulfides, and heavy metals. For this reason, particularly in dredged soil generated by dredging work on bottom sediments in the sea area, rivers, etc., or sediment sediment soil deposited on land due to tsunami or the like, the treatment method has become a major issue. From the aspect of waste reduction, it is desirable to effectively use the dredged soil and sediment in the bottom sediment as a civil engineering material such as backfill material. Safety issues need to be solved. Specifically, the effective use of the fact that the amount of elution of fluorine, boron, arsenic, and lead, which are the main harmful substances in sediments, may exceed the soil environmental standards (Environment Agency Notification No. 46) It is an obstacle. Table 1 shows the amount of elution of fluorine, boron, arsenic, and lead specified in the soil environmental standards (Environment Agency Notification No. 46).
この課題を解決するため、従来は、底質を洗浄することにより、有害物質を除去する方法が用いられてきた（特許文献１）。しかし、この方法では、洗浄により重金属などの有害物質を含んだ排水が発生し、その排水処理も必要となることから処理工程が複雑になり経済性に劣るという問題があった。そのため、有害物質を含む底質をより効率的かつ経済的に土工材料として有効利用する技術が望まれており、具体的には、底質に含まれる有害物質を不溶化して溶出を防止することで、洗浄等の処理を行うことなく土工材料に利用できる技術が求められていた。 In order to solve this problem, conventionally, a method of removing harmful substances by washing the bottom sediment has been used (Patent Document 1). However, this method has a problem in that wastewater containing harmful substances such as heavy metals is generated by washing, and the wastewater treatment is required, so that the treatment process becomes complicated and the economy is inferior. Therefore, there is a demand for a technology that effectively uses the sediment containing hazardous substances as an earthwork material more efficiently and economically. Specifically, insoluble substances contained in the sediment are insolubilized to prevent elution. Therefore, a technique that can be used for earthwork materials without performing treatment such as washing has been demanded.
従来、ふっ素の不溶化技術としては、消石灰などのカルシウム塩を使用して難溶性のふっ化カルシウムを生成させる方法、硫酸アルミニウムなどのアルミニウム塩を使用して水酸化アルミニウムが生成される過程でふっ素を吸着・不溶化する方法、硫酸マグネシウムなどのマグネシウム塩を使用して水酸化マグネシウムが生成される過程でふっ素を吸着・不溶化する方法などが知られている。また、ほう素の不溶化技術としては、硫酸アルミニウムなどのアルミニウム塩の使用、あるいは、硫酸アルミニウムと消石灰を併用することで、ふっ素を吸着・不溶化する方法が知られている。また、砒素の不溶化技術としては、硫酸アルミニウムなどのアルミニウム塩を使用して水酸化アルミニウムが生成される過程で砒素を吸着・不溶化する方法、塩化第二鉄などの鉄塩を使用して水酸化鉄が生成される過程で砒素を吸着・不溶化する方法などが知られている。また、鉛の不溶化技術としては、アルカリ沈殿法による水酸化物としての不溶化処理が知られている。
しかし、これらの方法では不溶化の効果が低いため、底質からのこれらの有害物質の溶出量を前記土壌環境基準以下に抑制することは困難であった。
Conventionally, fluorine insolubilization techniques include the use of calcium salts such as slaked lime to produce sparingly soluble calcium fluoride, and the process in which aluminum hydroxide is produced using aluminum salts such as aluminum sulfate. There are known methods for adsorption and insolubilization, methods for adsorption and insolubilization of fluorine in the process of producing magnesium hydroxide using a magnesium salt such as magnesium sulfate. Further, as a boron insolubilization technique, a method is known in which fluorine is adsorbed and insolubilized by using an aluminum salt such as aluminum sulfate or using aluminum sulfate and slaked lime in combination. As arsenic insolubilization technology, arsenic is adsorbed and insolubilized in the process of producing aluminum hydroxide using aluminum salt such as aluminum sulfate, and iron salt such as ferric chloride is used for hydroxylation. A method of adsorbing and insolubilizing arsenic in the process of iron generation is known. As a lead insolubilization technique, an insolubilization treatment as a hydroxide by an alkali precipitation method is known.
However, since these methods have a low insolubilizing effect, it has been difficult to suppress the amount of these harmful substances eluted from the sediment below the soil environmental standard.
また、底質とは異なるが、汚染土壌において特定の有害物質の溶出を抑制する方法が提案されている。 Moreover, although it differs from sediment, the method of suppressing the elution of a specific harmful substance in contaminated soil is proposed.
例えば、特許文献２には、砒素や６価クロムをキレート剤であるジチオカルバミン酸塩で捕捉・不溶化する技術が報告されている。しかし、この技術は、ジチオカルバミン酸塩は砒素などの不溶化には有用あるが、ふっ素やほう素の溶出抑制には効果が認められないため、ふっ素、ほう素および鉛などの重金属類を有害物質として含む、底質の溶出抑制にこの技術を適用することはできない。 For example, Patent Document 2 reports a technique for capturing and insolubilizing arsenic and hexavalent chromium with dithiocarbamate as a chelating agent. However, although this technique is useful for insolubilizing arsenic and the like, dithiocarbamate is not effective in suppressing the elution of fluorine and boron, so heavy metals such as fluorine, boron and lead are used as harmful substances. This technology cannot be applied to the suppression of sediment dissolution.
また、特許文献３には、汚染土壌に水硬性結合材であるセメントまたは石灰を添加することで、汚染土壌に含まれるふっ素やほう素の溶出を抑制する技術が報告されている。しかし、この技術では、重金属類の溶出防止には効果が認められないことから、ふっ素、ほう素および重金属類を有害物質として含む底質の溶出抑制にこの技術を適用することはできない。 Patent Document 3 reports a technique for suppressing elution of fluorine and boron contained in contaminated soil by adding cement or lime which is a hydraulic binder to the contaminated soil. However, since this technique is not effective in preventing the elution of heavy metals, this technique cannot be applied to the suppression of the elution of sediment containing fluorine, boron and heavy metals as harmful substances.
本発明の課題は、底質を使用した土工材料において、底質に含まれる有害物質であるふっ素、ほう素および重金属類（砒素、鉛）の溶出量を土壌環境基準以下に抑制できる経済的かつ効率的な土工材料の処方を提供することにある。 The object of the present invention is to reduce the amount of elution of fluorine, boron and heavy metals (arsenic and lead), which are harmful substances contained in sediment, to an earthwork material that uses sediment, which is economical and It is to provide an efficient earthwork material formulation.
本発明者は、検討を重ねた結果、ふっ素、ほう素及び重金属類（砒素、鉛）から選ばれる１種以上を含む底質を土工材料として使用するに際し、底質とカルシウムアルミネート、硫酸アルミニウム、石灰及びアルカリ金属リン酸塩とを組み合わせることで、該土工材料を水と混合して得られる混合物からの有害物質の溶出量を土壌環境基準以下に抑制でき、しかもその溶出抑制効果が、混合物を作成してから短時間で発揮されることを見出した。また、該土工材料の配合にセメントを加えることで、有害物質の溶出抑制効果がさらに高まることを見出し、本発明を完成させるに至った。 As a result of repeated studies, the present inventor, when using a sediment containing at least one selected from fluorine, boron and heavy metals (arsenic, lead) as an earthwork material, the sediment, calcium aluminate, aluminum sulfate. In addition, by combining lime and alkali metal phosphate, the elution amount of harmful substances from the mixture obtained by mixing the earthwork material with water can be suppressed below the soil environment standard, and the elution suppression effect is a mixture. It has been found that it can be demonstrated in a short time after creating. In addition, the present inventors have found that the addition of cement to the blending of the earthwork material further increases the effect of suppressing the elution of harmful substances, thereby completing the present invention.
すなわち、本発明は、次の［１］〜［７］に係るものである。 That is, the present invention relates to the following [1] to [7].
［１］（Ａ）ふっ素、ほう素、砒素及び鉛から選ばれる１種以上の溶出量が土壌環境基準を超える底質、（Ｂ）カルシウムアルミネート、（Ｃ）硫酸アルミニウム、（Ｄ）石灰、及び（Ｅ）アルカリ金属リン酸塩を含有する土工材料。
［２］（Ａ）底質１００質量部に対して（Ｂ）カルシウムアルミネート０．２〜２質量部、（Ｃ）硫酸アルミニウム０．１〜１質量部、（Ｄ）石灰０．０５〜１０質量部、及び（Ｅ）アルカリ金属リン酸塩０．０１〜０．１質量部を含有する［１］の土工材料。
［３］（Ｂ）カルシウムアルミネートの主成分が非晶質の１２ＣａＯ・７Ａｌ2Ｏ3である［１］又は［２］の土工材料。
［４］アルカリ金属リン酸塩が、リン酸カリウムである［１］〜［３］のいずれかの土工材料。
［５］さらに、セメントを含有する［１］〜［４］のいずれかの土工材料。
［６］セメントが、白色ポルトランドセメントである［５］の土工材料。
［７］ふっ素、ほう素、砒素及び鉛の溶出量が、土壌環境基準以下に抑制されたものである［１］〜［６］のいずれかの土工材料。
[1] (A) Bottom sediment in which one or more elution amounts selected from fluorine, boron, arsenic and lead exceed soil environmental standards, (B) calcium aluminate, (C) aluminum sulfate, (D) lime, And (E) an earthwork material containing an alkali metal phosphate.
[2] (A) 0.2 to 2 parts by mass of calcium aluminate, (C) 0.1 to 1 part by mass of aluminum sulfate, and (D) 0.05 to 10 parts of lime with respect to 100 parts by mass of the sediment. [1] The earthwork material which contains a mass part and 0.01-0.1 mass part of (E) alkali metal phosphate.
[3] The earthwork material according to [1] or [2], wherein the main component of (B) calcium aluminate is amorphous 12CaO · 7Al 2 O 3 .
[4] The earthwork material according to any one of [1] to [3], wherein the alkali metal phosphate is potassium phosphate.
[5] The earthwork material according to any one of [1] to [4], further containing cement.
[6] The earthwork material according to [5], wherein the cement is white Portland cement.
[7] The earthwork material according to any one of [1] to [6], wherein an elution amount of fluorine, boron, arsenic, and lead is suppressed to a soil environment standard or less.
本発明の底質を使用した土工材料は、経済的な処方で底質に含まれる有害物質であるふっ素、ほう素および重金属類（砒素、鉛）の溶出量を土壌環境基準（環境庁告示第４６号）以下に抑制できるため環境安全性が高い。しかも、その溶出抑制効果は該土工材料を水と混合してから２４時間以内に発揮されるため、混合後の養生期間を長く設ける必要なく埋め戻し材などに使用することができる。さらに、本発明の土工材料は水と混合後の溶出抑制効果が長期間保たれるため、混合物を長期間保管することができ、セメント製品用混和材などとして使用する際に便利である。よって、本発明は底質の有効利用の促進に極めて有用な技術である。 The earthwork material using the bottom sediment of the present invention is an economical prescription, and the amount of elution of fluorine, boron and heavy metals (arsenic, lead), which are harmful substances contained in the bottom sediment, is determined based on the soil environment standards (Environment Agency Notification No. 1). No. 46) Environmental safety is high because it can be suppressed to the following. And since the elution inhibitory effect is exhibited within 24 hours after mixing the earthwork material with water, it can be used as a backfill material or the like without the need for a long curing period after mixing. Furthermore, since the earthwork material of the present invention maintains the elution suppression effect after mixing with water for a long period of time, the mixture can be stored for a long period of time, which is convenient when used as an admixture for cement products. Therefore, the present invention is an extremely useful technique for promoting effective utilization of sediment.
本発明の土工材料に用いる（Ａ）底質とは、海域、港湾、河川、水路、湖沼などの水底の土砂やヘドロ等であり、ふっ素、ほう素、砒素及び鉛から選ばれる１種以上の溶出量が土壌環境基準（環境庁告示第４６号）を超える底質である。底質としては、前記の土砂やヘドロ等を陸上に上げたもの、すなわち、海域や河川等の浚渫工事で発生する浚渫土あるいは津波等で陸上に滞留した堆積土が特に適している。底質は、通常、砂質（粒径６３μｍ以上）、シルト（粒径６３〜５μｍ）及び粘土（粒径５μｍ以下）を含有し、これらの含有比率は問わない。 (A) Sediment used in the earthwork material of the present invention is sediment, sludge, etc. in the bottom of sea areas, harbors, rivers, waterways, lakes, etc., and one or more selected from fluorine, boron, arsenic and lead. Sediment whose elution amount exceeds the soil environment standard (Environment Agency Notification No. 46). As the sediment, the above-mentioned sediment, sludge, or the like raised to the land, that is, dredged soil generated by dredging work in the sea area, rivers, or the like, or accumulated soil staying on land due to a tsunami or the like is particularly suitable. The sediment usually contains sand (particle size 63 μm or more), silt (particle size 63-5 μm) and clay (particle size 5 μm or less), and the content ratio thereof is not limited.
本発明の土工材料に用いる（Ｂ）カルシウムアルミネートはＣａＯ原料とＡｌ2Ｏ3原料を熱処理することにより得られる物質である。カルシウムアルミネートは化学成分としてＣａＯとＡｌ2Ｏ3からなる結晶質やガラス化が進んだ構造の水和活性物質であれば何れのものでも良く、ＣａＯとＡｌ2Ｏ3に加えて他の化学成分が加わった化合物、固溶体、ガラス質物質又はこれらの混合物等でもよい。前者としては例えば１２ＣａＯ・７Ａｌ2Ｏ3、ＣａＯ・Ａｌ2Ｏ3、３ＣａＯ・Ａｌ2Ｏ3、ＣａＯ・２Ａｌ2Ｏ3、ＣａＯ・６Ａｌ2Ｏ3等が挙げられ、後者としては例えば、４ＣａＯ・３Ａｌ2Ｏ3・ＳＯ3、１１ＣａＯ・７Ａｌ2Ｏ3・ＣａＦ2、Ｎａ2Ｏ・８ＣａＯ・３Ａｌ2Ｏ3等が挙げられる。好ましくは、有害物質の溶出抑制効果に優れていることから、熱処理後のクリンカを急冷してガラス化率を９０％以上にした非晶質の１２ＣａＯ・７Ａｌ2Ｏ3を主成分とするものが好ましい。また、カルシウムアルミネートの粉末度はブレーン比表面積として２０００ｃｍ2／ｇ以上のものが好ましい。 (B) Calcium aluminate used in the earthwork material of the present invention is a substance obtained by heat-treating a CaO raw material and an Al 2 O 3 raw material. Calcium aluminate may be any hydrated active substance having a crystallized structure composed of CaO and Al 2 O 3 or a vitrified structure as a chemical component, and other chemicals in addition to CaO and Al 2 O 3. A compound added with a component, a solid solution, a glassy substance, or a mixture thereof may be used. The former example 12CaO · 7Al 2 O 3, CaO · Al 2 O 3, 3CaO · Al 2 O 3, CaO · 2Al 2 O 3, CaO · 6Al 2 O 3 and the like, and as the latter example, 4CaO · 3Al 2 O 3 · SO 3, 11CaO · 7Al 2 O 3 · CaF 2, Na 2 O · 8CaO · 3Al 2 O 3 and the like. Preferably, since it is excellent in the elution suppression effect of harmful substances, the main component is amorphous 12CaO · 7Al 2 O 3 in which the clinker after heat treatment is rapidly cooled to a vitrification ratio of 90% or more. preferable. The fineness of calcium aluminate is preferably 2000 cm 2 / g or more in terms of Blaine specific surface area.
本発明の土工材料に用いる（Ｃ）硫酸アルミニウムとしては、化学成分としてＡｌ2（ＳＯ4）3・ｎＨ2Ｏで表される水和物、あるいはＡｌ2（ＳＯ4）3で表される無水塩の何れでも良い。好ましくは、有害物質の溶出抑制効果に優れていることからｎが１４〜１８の水和物が好ましい。 The aluminum sulfate (C) used for the earthwork material of the present invention includes a hydrate represented by Al 2 (SO 4 ) 3 .nH 2 O as a chemical component, or an anhydrous represented by Al 2 (SO 4 ) 3. Any salt may be used. Preferably, a hydrate having n of 14 to 18 is preferable because it has an excellent effect of suppressing the dissolution of harmful substances.
本発明の土工材料に用いる（Ｄ）石灰としては、化学成分としてＣａＯで表される酸化カルシウムを主成分とするもの、あるいは化学成分としてＣａ（ＯＨ）2で表される水酸化カルシウムを主成分とするものが使用でき、これら両方を含むものであっても良い。好ましくは、有害物質の溶出抑制効果に優れていることから酸化カルシウムの含有量が多い石灰が好ましい。石灰の粉末度はブレーン比表面積として２０００ｃｍ2／ｇ以上のものが好ましい。 The (D) lime used for the earthwork material of the present invention is mainly composed of calcium oxide represented by CaO as a chemical component, or calcium hydroxide represented by Ca (OH) 2 as a chemical component. Can be used, and both of them may be included. Preferably, lime having a high calcium oxide content is preferable because it is excellent in the elution suppressing effect of harmful substances. The fineness of lime is preferably 2000 cm 2 / g or more as the Blaine specific surface area.
本発明の土工材料に用いる（Ｅ）アルカリ金属リン酸塩としては、リン酸ナトリウムやリン酸カリウムなどの易溶性の塩が使用できる。本発明では、アルカリ金属リン酸塩を配合することにより、短い養生期間でも良好な溶出抑制効果が得られる。アルカリ金属リン酸塩としては下記式（１）〜（３）で表されるリン酸カリウムが好ましく、養生期間の短縮効果に優れていることから下記式（２）で表されるリン酸二水素カリウムがより好ましい。 As the (E) alkali metal phosphate used in the earthwork material of the present invention, a readily soluble salt such as sodium phosphate or potassium phosphate can be used. In this invention, a favorable elution inhibitory effect is acquired by a short curing period by mix | blending an alkali metal phosphate. As the alkali metal phosphate, potassium phosphate represented by the following formulas (1) to (3) is preferable, and dihydrogen phosphate represented by the following formula (2) because it is excellent in the effect of shortening the curing period. Potassium is more preferred.
Ｋ2ＨＰＯ4 （１）
ＫＨ2ＰＯ4 （２）
Ｋ3ＰＯ4 （３）
K 2 HPO 4 (1)
KH 2 PO 4 (2)
K 3 PO 4 (3)
本発明の土工材料は、（Ａ）底質１００質量部に対して（Ｂ）カルシウムアルミネート０．２〜２質量部、（Ｃ）硫酸アルミニウム０．１〜１質量部、（Ｄ）石灰０．０５〜１０質量部、（Ｅ）アルカリ金属リン酸塩０．０１〜０．１質量部の配合割合とするのが、底質に含まれるふっ素、ほう素、砒素、鉛の溶出量を土壌環境基準（環境庁告示第４６号）以下に抑制する効果及び経済性の点から好ましい。カルシウムアルミネート、硫酸アルミニウム及び石灰の含有量は、有害物質の溶出抑制効果の点から上記範囲が好ましい。また石灰の含有量は、上記範囲とすることにより、養生期間が短くても良好な溶出抑制効果が得られる点で好ましい。アルカリ金属リン酸塩の含有量は、十分な溶出抑制効果を得るために必要な養生期間を短くする点で上記範囲が好ましい。アルカリ金属リン酸塩の含有量（質量）をカルシウムアルミネートの１／４０〜１／１０程度にすると短い養生期間で良好な溶出抑制効果が得られ、しかも経済的であるため好ましい。 The earthwork material of the present invention is (A) 0.2 to 2 parts by mass of calcium aluminate, (C) 0.1 to 1 parts by mass of aluminum sulfate, (D) 0 to lime with respect to 100 parts by mass of sediment. 0.05 to 10 parts by mass, and (E) 0.01 to 0.1 parts by mass of alkali metal phosphate, the amount of elution of fluorine, boron, arsenic and lead contained in the sediment is determined by soil It is preferable from the viewpoint of the effect of suppressing the environmental standard (Environment Agency Notification No. 46) or less and economical efficiency. The content of calcium aluminate, aluminum sulfate and lime is preferably within the above range from the viewpoint of the elution suppressing effect of harmful substances. Moreover, content of lime is preferable at the point by which a favorable elution inhibitory effect is acquired even if a curing period is short by setting it as the said range. The content of the alkali metal phosphate is preferably within the above range in terms of shortening the curing period necessary for obtaining a sufficient elution suppression effect. It is preferable that the content (mass) of the alkali metal phosphate is about 1/40 to 1/10 that of calcium aluminate because a good elution suppressing effect can be obtained in a short curing period and it is economical.
本発明の土工材料にセメントを配合すると底質に含まれるふっ素、ほう素、砒素、鉛の溶出をより効果的に抑制することができる。本発明の土工材料に用いられるセメントは、ポルトランドセメント、混合セメント、特殊セメント、及びエコセメントが挙げられる。ポルトランドセメントとは、普通ポルトランドセメント、早強ポルトランドセメント、超早強ポルトランドセメント、中庸熱ポルトランドセメント、耐硫酸塩ポルトランドセメント、白色ポルトランドセメント、低熱ポルトランドセメント及びそれらの低アルカリ型のポルトランドセメント等を言う。混合セメントとは、高炉セメント、フライアッシュセメント、シリカセメント等を言う。特殊セメントとは、セメント系固化材、アルミナセメント、超速硬セメント、アウイン系セメント、超微粒子セメント、油井セメント等を言う。エコセメントとは、都市ごみ焼却残渣などの廃棄物を主原料として製造されたセメントを言う。より好ましくは白色ポルトランドセメントが良く、白色ポルトランドセメントは鉛や６価クロムなど有害な重金属類をほとんど含まないため、本発明の土工材料に特に好適に使用できる。
底質１００質量部に対してセメントを０．５〜１０質量部配合するのが良く、より好ましい配合割合は２〜５質量部である。セメントを配合すると、カルシウムアルミネート、硫酸アルミニウム、石灰、アルカリ金属リン酸塩の配合割合が少なくても良好な溶出防止効果が得られるため、経済的である。
When cement is added to the earthwork material of the present invention, elution of fluorine, boron, arsenic and lead contained in the sediment can be more effectively suppressed. Examples of the cement used in the earthwork material of the present invention include Portland cement, mixed cement, special cement, and ecocement. Portland cement means normal Portland cement, early-strength Portland cement, ultra-early strong Portland cement, moderately hot Portland cement, sulfate-resistant Portland cement, white Portland cement, low heat Portland cement, and their low alkali type Portland cement. . Mixed cement refers to blast furnace cement, fly ash cement, silica cement and the like. Special cements include cement-based solidified materials, alumina cements, ultrafast cements, Auin-based cements, ultrafine particle cements, oil well cements, and the like. Eco-cement refers to cement manufactured using waste such as municipal waste incineration residue as the main raw material. More preferably, white Portland cement is good, and since white Portland cement hardly contains harmful heavy metals such as lead and hexavalent chromium, it can be used particularly suitably for the earthwork material of the present invention.
It is good to mix | blend 0.5-10 mass parts cement with respect to 100 mass parts of bottom sediments, and a more preferable mixture ratio is 2-5 mass parts. When cement is blended, it is economical because a good elution preventing effect can be obtained even if the blending ratio of calcium aluminate, aluminum sulfate, lime, and alkali metal phosphate is small.
本発明の土工材料の用途は特に限定されず、盛土材、埋め戻し材、裏込材、土壌改良材、道路資材、コンクリートなどのセメント製品用混和材などに有効活用できる。また、本発明の土工材料の製造方法についても特に限定はされず、一般的な製造方法を用いることができる。本発明の土工材料は水と混合後、２４時間以内に溶出抑制効果を発揮するため、養生期間を長く設ける必要なく使用することができ、例えば埋め戻し材として使用する場合は、現場でパン型ミキサーや強制二軸ミキサーなどの一般的なミキサーを用いて本発明の土工材料を水と混合し、スラリー状または塊状の混合物に加工した直後に埋め戻し作業を行うことができる。また、本発明の土工材料は水と混合後、長期間溶出抑制効果が保たれるため、混合物を長期間保管しておいて、適宜、セメント製品用混和材などに使用することができる。 The use of the earthwork material of the present invention is not particularly limited, and can be effectively used as an embedding material for cement products such as embankment material, backfill material, backing material, soil improvement material, road material, and concrete. Moreover, it does not specifically limit about the manufacturing method of the earthwork material of this invention, A general manufacturing method can be used. Since the earthwork material of the present invention exhibits the elution suppression effect within 24 hours after mixing with water, it can be used without the need for a long curing period. For example, when used as a backfill material, The backfilling operation can be performed immediately after the earthwork material of the present invention is mixed with water using a general mixer such as a mixer or a forced biaxial mixer and processed into a slurry-like or massive mixture. In addition, since the earthwork material of the present invention maintains the effect of suppressing elution for a long time after mixing with water, the mixture can be stored for a long period of time and appropriately used as an admixture for cement products.
次に実施例を挙げて本発明をさらに詳細に説明する。 EXAMPLES Next, an Example is given and this invention is demonstrated still in detail.
（Ａ）底質（略号：ＢＳ）：表２に示す粒度構成、含水率、強熱減量の海底浚渫土を使用した。環境庁告示第４６号による底質からの有害物質（ふっ素、ほう素、砒素、鉛）の溶出量を表３に示す。 (A) Bottom sediment (abbreviation: BS): The submarine soil having a particle size constitution, moisture content, and loss on ignition shown in Table 2 was used. Table 3 shows the amount of toxic substances (fluorine, boron, arsenic, lead) eluted from sediments according to Environmental Agency Notification No. 46.
（Ｂ）カルシウムアルミネート
ＣａＯ原料としてＣａＯ含有量９７質量％の生石灰（粉末試薬）、Ａｌ2Ｏ3原料としてバン土頁岩（Ａｌ2Ｏ3含有量８８質量％、Ｆｅ2Ｏ3含有量１質量％）、Ｆｅ2Ｏ3原料としてヘマタイト（Ａｌ2Ｏ3含有量３質量％、Ｆｅ2Ｏ3含有量９３質量％）を用い、表４に示す配合で混合し、電気炉を用いて１５５０±５０℃で２時間加熱した。加熱後は、常温近傍まで炉内で自然冷却（徐冷）したクリンカと、１５５０℃前後から炉外に取り出し、直ちに冷却用圧搾空気を吹き付けて急冷したクリンカを得た。これらのクリンカについては、粉末エックス線回折によって生成結晶相の存在量を定量し、残部をガラス相とみなしてガラス相生成量を計算し、クリンカ総量との比（質量比）よりクリンカのガラス化率を算定した。この値を表４に示す。これらのクリンカをボールミルでブレーン比表面積５０００±５００ｃｍ2／ｇとなるように粉砕して用いた。
(B) calcium aluminate CaO material as CaO content 97 mass% of quicklime (powdered reagent), Al 2 O 3 raw material as alum shale (Al 2 O 3 content of 88 wt%, Fe 2 O 3 content of 1 mass %), Hematite (Al 2 O 3 content 3 mass%, Fe 2 O 3 content 93 mass%) was used as the Fe 2 O 3 raw material, mixed in the formulation shown in Table 4, and 1550 ± using an electric furnace Heated at 50 ° C. for 2 hours. After heating, a clinker that was naturally cooled (slowly cooled) in the furnace to near room temperature and a clinker that was taken out of the furnace from around 1550 ° C. and immediately cooled with blown compressed air were obtained. For these clinker, the abundance of the generated crystal phase is quantified by powder X-ray diffraction, the remaining phase is regarded as the glass phase, the glass phase generation amount is calculated, and the vitrification rate of the clinker is calculated from the ratio (mass ratio) with the clinker total amount. Was calculated. This value is shown in Table 4. These clinkers were pulverized with a ball mill to a specific surface area of 5000 ± 500 cm 2 / g.
（使用材料）
（Ｃ）硫酸アルミニウム１４−１８水和物（略号：ＡＬＳ）：関東化学社製 粉末試薬
（Ｄ）酸化カルシウム（略号：ＣＡＯ）：関東化学社製 粉末試薬
（Ｅ）リン酸二水素カリウム（略号：ＰＫ）：関東化学社製 粉末試薬
（Ｆ）普通ポルトランドセメント（略号：ＯＰＣ）：太平洋セメント社製
（Ｆ）白色ポルトランドセメント（略号：ＷＰＣ）：太平洋セメント社製「ホワイトセメント」
(Materials used)
(C) Aluminum sulfate 14-18 hydrate (abbreviation: ALS): Powder reagent manufactured by Kanto Chemical Co., Inc. (D) Calcium oxide (abbreviation: CAO): Powder reagent manufactured by Kanto Chemical Co., Inc. (E) Potassium dihydrogen phosphate (abbreviation) : PK): Kanto Chemical Co., Inc. Powder Reagent (F) Ordinary Portland Cement (abbreviation: OPC): Taiheiyo Cement (F) White Portland Cement (abbreviation: WPC): Taiheiyo Cement “White Cement”
表５に示す割合で上記使用材料を配合し、本発明の土工材料および比較品の土工材料を得た。 The above materials were blended in the proportions shown in Table 5 to obtain the earthwork material of the present invention and a comparison earthwork material.
（溶出量の測定）
表５に示す土工材料１０００ｇに水６００ｇを加え、モルタルミキサーで３分間混合し、混合物を調製した。該混合物をビニール袋内に封入して２０℃の温度で養生し、養生期間３、６、２４時間経過後に、環境庁告示第４６号に準じた方法でふっ素、ほう素、砒素、鉛の溶出量を測定した。溶出量の測定結果を表７に示す。また、該混合物をビニール袋内に封入して２０℃の温度で２４時間養生した後、ビニール袋から該混合物を取り出して温度２０℃、湿度６０％の環境で保管し、１ヶ月経過後に環境庁告示第４６号に準じた方法でふっ素、ほう素、砒素、鉛の溶出量を測定した。溶出量の測定結果を表８に示す。
(Measurement of elution amount)
600 g of water was added to 1000 g of the earthwork material shown in Table 5 and mixed for 3 minutes with a mortar mixer to prepare a mixture. The mixture is sealed in a plastic bag and cured at a temperature of 20 ° C. After the curing period of 3, 6, and 24 hours, elution of fluorine, boron, arsenic, and lead is performed in accordance with the Environmental Agency Notification No. 46. The amount was measured. Table 7 shows the measurement results of the elution amount. The mixture is sealed in a plastic bag and cured at a temperature of 20 ° C. for 24 hours, and then the mixture is taken out from the plastic bag and stored in an environment at a temperature of 20 ° C. and a humidity of 60%. The amount of elution of fluorine, boron, arsenic and lead was measured by a method according to Notification No. 46. Table 8 shows the measurement results of the elution amount.
〔環境庁告示第４６号に準じた溶出量測定方法〕
（１）所定期間養生後の試料を粗砕し、ふるい２ｍｍ通過分を採取混合する。
（２）容積１０００ｍＬのポリ容器に試料５０ｇを計りとり、溶媒（純水１Ｌに０．５ｍｏｌ塩酸を加えてｐＨ６．１に調整したもの）５００ｇを加え、振とう機（振とう回数２００回／分）で６時間振とうする。
（３）ポリ容器を３０分静置した後、試料液の上澄みを孔径０．４５μｍのメンブレンフィルターでろ過して検液とする。
（４）採取した検液の成分を表６に示す方法で測定する。
[Measurement method of elution volume according to Environmental Agency Notification No. 46]
(1) Roughly crush the sample after curing for a predetermined period, collect and mix the sieve 2 mm passage.
(2) Weigh 50 g of sample in a 1000 mL capacity plastic container, add 500 g of solvent (adjusted to pH 6.1 by adding 0.5 mol hydrochloric acid to 1 L of pure water), and shaker (number of shakes 200 times / Shake for 6 hours.
(3) After allowing the polycontainer to stand for 30 minutes, the supernatant of the sample solution is filtered through a membrane filter having a pore diameter of 0.45 μm to obtain a test solution.
(4) The components of the collected test solution are measured by the method shown in Table 6.
表７の結果より、本発明の土工材料は全て、養生期間が２４時間以内でふっ素、ほう素、砒素、鉛の溶出量が土壌環境基準（環境庁告示第４６号）の規定値未満に抑制されていることが分かる。特に、本発明６、７、８、１１、１２、１３、１６、１８、１９、２０、２１、２２、２３の土工材料は、ふっ素、ほう素、砒素、鉛の溶出量が養生期間３時間で土壌環境基準の規定値未満に抑制されており、溶出抑制効果が短時間に発揮されることが分かる。一方、比較例として示した土工材料（比較品１〜１０）は本発明の土工材料に比べ、溶出抑制効果が劣っており、特に養生期間が６時間以内での溶出量が多いことが分かる。比較品１０の土工材料では、養生期間を２４時間とした場合のほう素と砒素の溶出量が土壌環境基準未満に抑制されているものの、ふっ素および鉛の溶出量は土壌環境基準を超過しており、底質の溶出抑制を図るには性能が不十分である。 From the results in Table 7, all the earthwork materials of the present invention have a curing period of 24 hours or less, and the amount of elution of fluorine, boron, arsenic, and lead is suppressed below the specified value of the soil environment standard (Environment Agency Notification No. 46). You can see that. In particular, the earthwork materials according to the present invention 6, 7, 8, 11, 12, 13, 16, 18, 19, 20, 21, 22, 23 have an elution amount of fluorine, boron, arsenic, lead of 3 hours. It can be seen that the elution suppression effect is demonstrated in a short time. On the other hand, it can be seen that the earthwork materials (comparative products 1 to 10) shown as comparative examples are inferior to the earthwork material of the present invention in terms of the elution suppression effect, and that the amount of elution is particularly large within a curing period of 6 hours or less. In the earthwork material of comparative product 10, the elution amount of boron and arsenic when the curing period is 24 hours is suppressed below the soil environmental standard, but the elution amount of fluorine and lead exceeds the soil environmental standard. Therefore, the performance is insufficient to suppress the dissolution of sediment.
表７の結果より、結晶質のカルシウムアルミネート（ＣＡ−１）を使用した本発明の土工材料（本発明１）は、非晶質カルシウムアルミネート（ＣＡ−２）を使用して配合割合が同一の本発明の土工材料（本発明４）に比べてふっ素、ほう素、砒素、鉛の溶出量が多くなっており、カルシウムアルミネートとしては非晶質のものが好ましいことが分かる。 From the results shown in Table 7, the earthwork material of the present invention (invention 1) using crystalline calcium aluminate (CA-1) was mixed with amorphous calcium aluminate (CA-2). Compared to the same earthwork material of the present invention (Invention 4), the amount of elution of fluorine, boron, arsenic and lead is larger, and it can be seen that an amorphous material is preferable as the calcium aluminate.
表７の結果より、普通ポルトランドセメント（ＯＰＣ）を使用した本発明の土工材料（本発明９）は、白色ポルトランドセメント（ＷＰＣ）を使用して配合割合が同一の本発明の土工材料（本発明１２）に比べてふっ素、ほう素および鉛の溶出量が多くなっており、セメントとしては白色ポルトランドセメントが好ましいことが分かる。 From the results shown in Table 7, the earthwork material of the present invention (invention 9) using ordinary Portland cement (OPC) is the earthwork material of the present invention (invention 9) having the same blending ratio using white Portland cement (WPC). Compared with 12), the amount of elution of fluorine, boron and lead is increased, and it can be seen that white Portland cement is preferable as the cement.
表７の結果より、本発明の土工材料では、石灰の配合量を増やすと溶出抑制効果が向上することが分かる。また、本発明の土工材料では、リン酸塩の配合量を増やすと溶出抑制効果が向上し、養生時間が短くても溶出量を少なく抑えられることが分かる。 From the results of Table 7, it can be seen that, in the earthwork material of the present invention, when the amount of lime is increased, the elution suppression effect is improved. Moreover, in the earthwork material of this invention, when the compounding quantity of a phosphate is increased, it turns out that the elution inhibitory effect improves and even if the curing time is short, the elution amount can be restrained small.
表８の結果より、実施例として示す本発明の土工材料（本発明品４、５、１１、１２、１５、２０、２２、２３）は、温度２０℃、湿度６０％の環境で１ヶ月間保管した後も、ふっ素、ほう素、砒素、鉛の溶出量が土壌環境基準（環境庁告示第４６号）の規定値未満に抑制されていることが分かる。一方、比較例として示した土工材料のうち比較品６、９は、ふっ素、ほう素、砒素、鉛の溶出量が土壌環境基準を超過しており、比較品６は保管前（２０℃で２４時間養生した時点）より溶出量が増加していた。比較品１０は、ほう素および砒素の溶出量は土壌環境基準の規定値未満であったが、ふっ素および鉛の溶出量が土壌環境基準を超過していた。 From the results of Table 8, the earthwork materials of the present invention (the products of the present invention 4, 5, 11, 12, 15, 20, 22, 23) shown as examples are one month in an environment of temperature 20 ° C. and humidity 60%. It can be seen that the amount of elution of fluorine, boron, arsenic, and lead is suppressed to less than the value specified in the soil environmental standards (Environment Agency Notification No. 46) even after storage. On the other hand, among the earthwork materials shown as comparative examples, comparative products 6 and 9 have an elution amount of fluorine, boron, arsenic, and lead exceeding the soil environmental standards, and comparative product 6 was stored before storage (24 at 20 ° C. The amount of elution increased from the time curing. In comparative product 10, the elution amounts of boron and arsenic were less than the prescribed values of the soil environment standard, but the elution amounts of fluorine and lead exceeded the soil environment standard.
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