JP3972013B2 - Solidification / insolubilization treatment method for contaminated soil - Google Patents
Solidification / insolubilization treatment method for contaminated soil Download PDFInfo
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- JP3972013B2 JP3972013B2 JP2003081975A JP2003081975A JP3972013B2 JP 3972013 B2 JP3972013 B2 JP 3972013B2 JP 2003081975 A JP2003081975 A JP 2003081975A JP 2003081975 A JP2003081975 A JP 2003081975A JP 3972013 B2 JP3972013 B2 JP 3972013B2
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- contaminated soil
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Description
【０００１】
【発明の属する技術分野】
本発明は、汚染土壌の固化・不溶化処理方法に関するもので、特にシアン、フッ素のように、セメント系固化材のみではその不溶化が不十分となる汚染土壌の固化・不溶化処理方法に関するものである。
【０００２】
【従来の技術】
従来の重金属類に汚染された土壌の処理方法は、軟弱地盤の固化処理にも使用されているセメント或いはセメントを主成分としたセメント系固化材を汚染土壌に添加・混練し、該汚染土壌からの重金属類の溶出量を埋立処分基準（概ね、土壌環境基準の３０倍程度）以下になるように固化・不溶化した後、該固化物を管理型処分場に廃棄（埋立て）する場合が多かった。
【０００３】
しかし、このような管理型処分場への埋立て処理については、年々、その用地を確保することが難しくなっており、その施設建設には多くの費用がかかるため、管理型処分場での処理に頼らない原位置での処理対策が強く望まれている。また、管理型処分場への埋立て処理にあたっては、汚染土壌の掘削、積込み、搬送、埋立て等の多くの作業工程を要し、また、その各作業途中における重金属類の周囲への飛散も懸念されるものであった。更に、汚染土壌の種類によっては、セメント系固化材のみでは不溶化が不十分となることも生じていた。
【０００４】
そこで、近年、種々の固化材を重金属類に汚染された土壌に添加・混練した場合の固化・不溶化効果について研究が成され、例えばマグネシウム系固化材については、重金属類、特にセメント系固化材のみではその不溶化が困難であったシアン、フッ素を含む汚染土壌に対しても、かなりの固化・不溶化効果が期待できるとの試験結果が報告されている（非特許文献１）。
【０００５】
【非特許文献１】
第５回地盤改良シンポジウム論文集（２００２年１１月）、２６５頁
〜２７０頁
【０００６】
【発明が解決しようとする課題】
しかしながら、本発明者等による試験によれば、マグネシウム系固化材を用いてシアン、フッ素を含む汚染土壌を固化・不溶化した場合、汚染土壌の固化効果、特に高含水汚染土壌に対する固化効果に問題を有するものであることが判明した。
これは、例えば河川・海岸付近の高含水土壌で自然由来にて蓄積されるフッ素を含有した高含水汚染土壌等に対しては、マグネシウム系固化材のみでは十分な強度と長期耐久性を有する土壌に固化・不溶化することができず、改良土としての使用が困難であることを意味するものであった。
【０００７】
そこで、本発明の目的は、重金属類、特にシアン、フッ素を含む高含水汚染土壌をも、不溶化すると共に、所定以上の強度を有する土壌に固化する、汚染土壌の固化・不溶化処理方法を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者らは、上記した目的を達成すべく鋭意研究を重ねた結果、重金属類に対して不溶化効果の高いマグネシウム系固化材と、強度発現性の良いセメント系固化材とを併用すると共に、両者を時間差をおいてシアン及び／又はフッ素を含む汚染土壌に添加・混練することにより、該汚染土壌を不溶化できると共に、所定以上の強度を有する土壌に固化することができることを見出し、本発明を完成させた。
【０００９】
即ち、本発明は、シアン及び／又はフッ素を含む汚染土壌に、マグネシウム系固化材を添加・混練した後、３時間以上経過後において更にセメント系固化材を添加・再混練することを特徴とする、汚染土壌の固化・不溶化処理方法とした。
【００１０】
ここで、上記セメント系固化材の汚染土壌への添加・再混練時期は、先に汚染土壌に添加・混練したマグネシウム系固化材によるシアン及び／又はフッ素の不溶化効果を十二分に発揮させる観点から、マグネシウム系固化材の添加・混練時期から３時間以上経過後とした。
【００１１】
また、上記本発明に係る汚染土壌の固化・不溶化処理方法は、特にマグネシウム系固化材のみでは十分な固化強度が得られない高含水率、具体的には含水率１００％以上の高含水汚染土壌の処理に好ましいものである。
【００１２】
【発明の実施の形態】
以下、上記した本発明に係る汚染土壌の固化・不溶化処理方法を、詳細に説明する。
【００１３】
先ず、上記した本発明において使用するマグネシウム系固化材としては、例えば酸化マグネシウム単独、或いは酸化マグネシウムを主材料とし、副材料として天然石膏（無水石膏、半水石膏、二水石膏）、副産石膏（燐酸石膏、フッ酸石膏、排煙脱硫石膏、石膏ボード廃材等）等の中から選ばれた１種類、若しくは２種類以上を混合したものが挙げられ、上記酸化マグネシウムとしては、重焼マグネシアは水和活性に乏しいことから、例えばマグネサイト（炭酸マグネシウム）を８００℃前後で焼成して得られる軽焼マグネシアを用いることが好ましい。
【００１４】
上記マグネシウム系固化材の汚染土壌への添加・混練量は、汚染土壌に含まれるシアン及び／又はフッ素の初期溶出量（マグネシウム系固化材の添加・混練前のシアン及び／又はフッ素の溶出量）と該汚染土壌の含水率を勘案しつつ、シアン及び／又はフッ素の不溶化効果と経済性とを考慮し、２０〜４００ｋｇ／ｍ３の範囲内でその添加量を決定することが好ましい。これは、マグネシウム系固化材の不溶化効果は、シアン及び／又はフッ素の初期溶出量により大きく変化するためであり、また、セメント系固化材の添加・再混練時期の混練物（一次混練物）の硬さは、汚染土壌の含水率の影響を大きく受けるためである。
【００１５】
また、上記した本発明において使用するセメント系固化材としては、セメント単独、或いはセメントを主材料とし、副材料として天然石膏（無水石膏、半水石膏、二水石膏）、副産石膏（燐酸石膏、フッ酸石膏、排煙脱硫石膏、石膏ボード廃材等）、高炉スラグ、フライアッシュ、石炭灰、石灰石微粉末、シリカヒューム等の中から選ばれた１種類、若しくは２種類以上を混合した、従来から軟弱地盤の固化処理等に使用されているセメント系材料が広く使用できる。また、上記セメントとしては、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント等の各種ポルトランドセメント、或いは高炉セメント、フライアッシュセメント、シリカセメント等の混合セメント、更にはアルミナセメント、超速硬セメント、アウイン系セメントやその他急硬性セメント等のカルシウムアルミネートを用いたセメント、超微粒子セメント、油井セメント、焼却灰を原料としたエコセメント等の特殊セメントを用いることができる。
【００１６】
上記セメント系固化材の汚染土壌への添加・混練量は、やはり汚染土壌に対する固化効果と経済性とを考慮し、２０〜４００ｋｇ／ｍ３、更に好ましくは５０〜３００ｋｇ／ｍ３の範囲内でその添加量を決定することが好ましい。
【００１７】
本発明に係る汚染土壌の固化・不溶化処理方法は、先に上記マグネシウム系固化材を汚染土壌に添加・混練した後、時間差をおいて更に上記セメント系固化材を汚染土壌に添加・再混練する。
上記セメント系固化材の汚染土壌への添加・再混練時期は、先に汚染土壌に添加・混練したマグネシウム系固化材によるシアン及び／又はフッ素の不溶化効果を十二分に発揮させる観点から、マグネシウム系固化材の添加・混練時期から３時間以上経過後とする。更には、上記マグネシウム系固化材と上記セメント系固化材とを時間差をおいて汚染土壌に添加・混練する作業性及び経済性等をも勘案すると、セメント系固化材の汚染土壌への添加・再混練時期は、先のマグネシウム系固化材の添加・混練時期から３時間以上経過後であって、且つ３６時間以内とすることが好ましい。
【００１８】
上記マグネシウム系固化材、及びセメント系固化材の汚染土壌への添加・混練方法は、特に限定されるものはなく、深層用スラリー系機械攪拌混合、深層用粉体系機械攪拌混合、深層用高圧噴射攪拌混合、バックホウ混合、スタビライザー混合、特殊バックホウ混合、処理ヤード混合、プラント混合等の従来の方法にて行うことができる。
【００１９】
本発明の汚染土壌の固化・不溶化処理方法は、種々の重金属類、例えば鉛、ヒ素、六価クロム、セレン、シアン、フッ素、ホウ素等を含有した汚染土壌の処理に適用できるものであるが、中でも、セメント系固化材のみではその固化・不溶化が困難であるシアンやフッ素を含有した汚染土壌の処理に好ましく適用でき、また、低含水率の土壌であれば、マグネシウム系固化材のみの添加・混練でも十分な固化強度が得られる場合もあるため、マグネシウム系固化材のみ、或いはセメント系固化材のみでは固化・不溶化が達成し難い高含水率、具体的には含水率１００％以上の高含水汚染土壌の処理に本発明に係る汚染土壌の固化・不溶化処理方法は好適に使用できるものである。このように、本発明の方法を用いると、従来の方法ではその固化・不溶化が困難であったシアン及び／又はフッ素を含む高含水汚染土壌の処理をも可能となるため、処理可能な対象汚染土壌の範囲を格段に広げられる。
【００２０】
【試験例】
次に、上記した本発明に係るシアン及び／又はフッ素汚染土壌の固化・不溶化処理方法を見出した試験例を記載する。
【００２１】
−対象土−
試験において使用した対象土の物性を、表１に示す。
【００２２】
【表１】
−固化・不溶化に使用した固化材−
酸化マグネシウム：小野田化学社製の軽焼マグネシア
普通セメント：太平洋セメント社製の普通ポルトランドセメント
早強セメント：太平洋セメント社製の早強ポルトランドセメント
カルシウムアルミネート：太平洋マテリアル社製のカルシウムアルミネート
石 膏：第一セメント社製の天然無水石膏
【００２４】
−固化・不溶化処理−
上記対象土に対し、上記固化材を各々表２に示した条件で添加・混練し、対象土の固化・不溶化処理を行った。
なお、固化材の対象土への添加は粉体状のまま行い、混練はハンドミキサを用いて固化材と対象土が均質になるまで十分に行った。また、１次混合終了後から２次混合までの間は、温度２０℃の恒温室内に対象土を入れ、乾燥しないように表２に示した各々の時間差の間、対象土を静置した。
【００２５】
【表２】
−処理結果−
上記固化材の添加・混練が終了した試料を、一軸圧縮試験用の供試体作製のため、内径５ｃｍ、高さ１０ｃｍの型枠に充填した。供試体の作製方法は、ＪＧＳ０８２１「安定処理土の締固めをしない供試体作製」に準じて行い、供試体の養生は、温度２０℃の恒温室内にて材齢７日及び２８日まで養生を行った。また、一軸圧縮試験は、型枠から脱型した供試体に対し、ＪＩＳ Ａ １１２６「土の一軸圧縮試験方法」に準じて行った。また、シアン、フッ素の溶出試験は、前記一軸圧縮試験後の供試体を用い、環境省告示第４６号法に準じて溶出試験を行った。
なお、上記材齢の計算は、１次混合を終了した時から数えるものとしたため、２次混合を行った試験例では、１次混合からの時間差分だけ実質的に材齢時間が短くなっている。
上記試験結果を、表３に示す。
【００２７】
【表３】
上記試験例から、マグネシウム系固化材をセメント系固化材と時間差をおいてシアン及び／又はフッ素を含む汚染土壌に添加・混練することにより、マグネシウム系固化材にシアン、フッ素の不溶化効果があるため、該汚染土壌を不溶化できると共に、セメント系固化材の強度発現性により所定以上の強度を有する土壌に固化することができることが判明した。
また、セメント系固化材の汚染土壌への添加・再混練時期は、先に汚染土壌に添加・混練したマグネシウム系固化材の添加・混練時期から３時間以上経過後であることが、シアン及び／又はフッ素の不溶化効果を考慮した場合には好ましいことが判明した。
【００２９】
【発明の効果】
以上に詳述した本発明に係る汚染土壌の固化・不溶化処理方法によれば、シアン及び／又はフッ素を含む高含水汚染土壌をも不溶化できると共に、所定以上の強度を有する土壌に固化することができ、汚染土壌の処理対象範囲が広げられ、最終処分場の延命又は縮小にもつながり、経費節減及び自然環境保護に貢献できる効果がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for solidifying / insolubilizing contaminated soil, and more particularly to a method for solidifying / insolubilizing contaminated soil in which insolubilization is insufficient with only a cement-based solidifying material such as cyan and fluorine.
[0002]
[Prior art]
The conventional method for treating soil contaminated with heavy metals is to add and knead cement, which is also used for solidification treatment of soft ground, or cement-based solidification material mainly composed of cement, to the contaminated soil. In many cases, the solidified material is solidified and insolubilized so that the elution amount of heavy metals falls below the landfill disposal standard (generally about 30 times the soil environment standard), and then the solidified material is discarded (landfilled) in a managed disposal site. It was.
[0003]
However, landfill treatment at such a managed disposal site has become difficult year after year, and it is difficult to secure the site. There is a strong demand for in-situ treatment measures that do not depend on In addition, landfill processing to a managed-type disposal site requires many work processes such as excavation, loading, transport, and landfill of contaminated soil, and heavy metals are scattered around the work. It was a concern. Furthermore, depending on the type of contaminated soil, insolubilization may be insufficient with only cement-based solidifying material.
[0004]
Therefore, in recent years, research has been conducted on the effect of solidification and insolubilization when various solidification materials are added to and kneaded with soil contaminated with heavy metals. For example, for magnesium-based solidification materials, only heavy metals, especially cement-based solidification materials, have been studied. Therefore, a test result has been reported that a considerable solidification / insolubilization effect can be expected even for contaminated soil containing cyanide and fluorine, which has been difficult to insolubilize (Non-patent Document 1).
[0005]
[Non-Patent Document 1]
Proceedings of the 5th Ground Improvement Symposium (November 2002) pp. 265-270 [0006]
[Problems to be solved by the invention]
However, according to the tests by the present inventors, when a contaminated soil containing cyanide and fluorine is solidified / insolubilized using a magnesium-based solidifying material, there is a problem with the solidification effect of the contaminated soil, in particular, the solidification effect with respect to highly water-contaminated soil. It was found to have.
This is because, for example, highly moisture-contaminated soil containing fluorine that accumulates naturally from high moisture soils near rivers and coasts, etc., soil with sufficient strength and long-term durability only with magnesium-based solidified material This means that it cannot be solidified or insolubilized and is difficult to use as improved soil.
[0007]
Accordingly, an object of the present invention is to provide a method for solidifying and insolubilizing contaminated soil, which insolubilizes highly water-containing contaminated soil containing heavy metals, particularly cyanide and fluorine, and solidifies into soil having a strength of a predetermined level or more. There is.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned object, the present inventors have used a magnesium-based solidifying material having a high insolubilizing effect for heavy metals and a cement-based solidifying material with good strength development, By adding and kneading them to contaminated soil containing cyan and / or fluorine with a time lag, it was found that the contaminated soil can be insolubilized and solidified into soil having a strength of a predetermined level or more. Completed.
[0009]
That is, the present invention includes a feature to contaminated soil containing cyan and / or fluorine, after adding and kneading a magnesium-based solidifying material, further adding and re-kneaded cement-based solidifying material Oite to or more after 3 hours This is a method for solidifying and insolubilizing contaminated soil.
[0010]
Here, the timing of addition and re-kneading of the cement-based solidifying material to the contaminated soil is a viewpoint that sufficiently exhibits the insolubilizing effect of cyan and / or fluorine by the magnesium-based solidifying material previously added and kneaded to the contaminated soil. From the time of addition of the magnesium-based solidifying material / kneading time, 3 hours or more had elapsed .
[0011]
In addition, the method for solidifying and insolubilizing contaminated soil according to the present invention has a high water content, in particular, a high water content contaminated soil with a moisture content of 100% or more, in which sufficient solidification strength cannot be obtained only with a magnesium-based solidified material. It is preferable for the treatment.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the above-described method for solidifying / insolubilizing contaminated soil according to the present invention will be described in detail.
[0013]
First, as the magnesium-based solidifying material used in the present invention, for example, magnesium oxide alone or magnesium oxide as a main material, natural gypsum (anhydrous gypsum, hemihydrate gypsum, dihydrate gypsum), byproduct gypsum as a secondary material, for example. (Phosphoric acid gypsum, hydrofluoric acid gypsum, flue gas desulfurization gypsum, gypsum board waste materials, etc.) and the like, or those mixed two or more types may be mentioned. Because of its poor hydration activity, it is preferable to use light-burned magnesia obtained by baking magnesite (magnesium carbonate) at around 800 ° C., for example.
[0014]
The amount of addition and kneading of the magnesium-based solidification material to the contaminated soil is the initial elution amount of cyan and / or fluorine contained in the contaminated soil (cyan and / or fluorine elution amount before the addition of the magnesium-based solidification material and kneading) In consideration of the water content of the contaminated soil and the insolubilizing effect of cyan and / or fluorine and the economy, it is preferable to determine the amount of addition within the range of 20 to 400 kg / m 3 . This is because the insolubilizing effect of the magnesium-based solidified material varies greatly depending on the initial elution amount of cyan and / or fluorine, and the kneaded material (primary kneaded material) at the time of addition and re-kneading of the cement-based solidified material. This is because the hardness is greatly affected by the moisture content of the contaminated soil.
[0015]
In addition, as the cement-based solidifying material used in the present invention, cement alone or cement as a main material, natural gypsum (anhydrous gypsum, hemihydrate gypsum, dihydrate gypsum), by-product gypsum (phosphate gypsum) as a secondary material. , Fluoric acid gypsum, flue gas desulfurization gypsum, gypsum board waste, etc.), blast furnace slag, fly ash, coal ash, limestone fine powder, silica fume, etc. Therefore, it is possible to use a wide range of cement materials that are used for solidifying soft ground. In addition, as the above cement, various Portland cements such as ordinary Portland cement, early-strength Portland cement, medium-heated Portland cement, or mixed cements such as blast furnace cement, fly ash cement, silica cement, alumina cement, super-hard cement, Cement using calcium aluminate such as Auin-based cement and other quick-hardening cement, ultrafine cement, oil well cement, and special cement such as eco-cement using incinerated ash as raw materials can be used.
[0016]
Adding and kneading of the contaminated soil of the cement-based solidifying material is also considering the solidification effect and economy for contaminated soils, 20~400kg / m 3, more preferably in the range of 50~300kg / m 3 It is preferable to determine the amount of addition.
[0017]
In the method for solidifying / insolubilizing contaminated soil according to the present invention, the magnesium-based solidified material is first added and kneaded to the contaminated soil, and then the cement-based solidified material is further added and re-kneaded to the contaminated soil with a time difference. .
The above-mentioned cement-based solidifying material is added to the contaminated soil and re-kneaded from the viewpoint of sufficiently exhibiting the insolubilizing effect of cyan and / or fluorine by the magnesium-based solidifying material previously added and kneaded to the contaminated soil. 3 hours or more after the addition / kneading time of the system solidifying material . Furthermore, considering the workability and economics of adding and kneading the magnesium-based solidified material and the cement-based solidified material to the contaminated soil with a time lag, the cement-based solidified material is added to the contaminated soil. The kneading time is preferably 3 hours or more after the addition / kneading time of the magnesium-based solidifying material and within 36 hours.
[0018]
The method for adding and kneading the magnesium-based solidified material and cement-based solidified material to the contaminated soil is not particularly limited, and is a slurry-based mechanical stirring and mixing for deep layers, a powder-based mechanical stirring and mixing for deep layers, and a high-pressure jet for deep layers. It can be performed by conventional methods such as stirring and mixing, backhoe mixing, stabilizer mixing, special backhoe mixing, processing yard mixing, and plant mixing.
[0019]
The method for solidifying and insolubilizing contaminated soil of the present invention can be applied to the treatment of contaminated soil containing various heavy metals such as lead, arsenic, hexavalent chromium, selenium, cyanide, fluorine, boron, Among them, it can be preferably applied to the treatment of contaminated soil containing cyanide and fluorine, which is difficult to solidify and insolubilize only with cement-based solidified material. In addition, if the soil has low moisture content, only magnesium-based solidified material can be added. Since sufficient solidification strength may be obtained even by kneading, high moisture content that is difficult to achieve solidification / insolubilization with only magnesium-based solidified material or cement-based solidified material, specifically, high water content of 100% or more. The method for solidifying / insolubilizing contaminated soil according to the present invention can be suitably used for treating contaminated soil. As described above, when the method of the present invention is used, it is possible to treat highly water-contaminated soil containing cyanide and / or fluorine, which has been difficult to solidify and insolubilize by the conventional method. The range of soil can be greatly expanded.
[0020]
[Test example]
Next, the test example which discovered the solidification / insolubilization treatment method of the cyan and / or fluorine contaminated soil according to the present invention described above will be described.
[0021]
-Target soil-
Table 1 shows the physical properties of the target soil used in the test.
[0022]
[Table 1]
-Solidification material used for solidification and insolubilization-
Magnesium oxide: Light burned magnesia made by Onoda Chemical Co., Ltd .: Normal Portland cement made by Taiheiyo Cement Co., Ltd. Early strength cement made by Taiheiyo Cement Co., Ltd. Calcium aluminate made by Taiheiyo Materials Co., Ltd. Natural anhydrous gypsum manufactured by Daiichi Cement Co., Ltd. [0024]
-Solidification / insolubilization treatment-
The above solidified material was added and kneaded to the target soil under the conditions shown in Table 2, respectively, and the target soil was solidified and insolubilized.
The addition of the solidified material to the target soil was performed in the form of powder, and the kneading was sufficiently performed using a hand mixer until the solidified material and the target soil were homogeneous. Further, during the period from the end of the primary mixing to the secondary mixing, the target soil was placed in a constant temperature room at a temperature of 20 ° C., and the target soil was allowed to stand for each time difference shown in Table 2 so as not to dry.
[0025]
[Table 2]
-Processing results-
The sample after the addition and kneading of the solidifying material was filled into a mold having an inner diameter of 5 cm and a height of 10 cm for preparing a specimen for a uniaxial compression test. The specimens were prepared in accordance with JGS0821 “Preparation of specimens without compaction of stabilized soil”, and the specimens were cured in a constant temperature room at a temperature of 20 ° C. until the ages of 7 and 28 days. went. Moreover, the uniaxial compression test was done according to JIS A1126 "Soil uniaxial compression test method" with respect to the specimen removed from the mold. Moreover, the elution test of cyan and fluorine was carried out using the specimen after the uniaxial compression test according to Ministry of the Environment Notification No. 46.
In addition, since the calculation of the material age was counted from the time when the primary mixing was completed, in the test example in which the secondary mixing was performed, the material age time was substantially shortened by the time difference from the primary mixing. Yes.
The test results are shown in Table 3.
[0027]
[Table 3]
From the above test example, the magnesium-based solidified material has an effect of insolubilizing cyanide and fluorine by adding and kneading the magnesium-based solidified material to the contaminated soil containing cyanide and / or fluorine with a time difference from the cement-type solidified material. It has been found that the contaminated soil can be insolubilized and can be solidified to a soil having a predetermined strength or more due to the strength development of the cement-based solidifying material.
In addition, the addition / re-kneading time of the cement-based solidified material to the contaminated soil is 3 hours or more after the addition / kneading time of the magnesium-based solidified material previously added / kneaded to the contaminated soil. Or it was found that it was preferable when the insolubilizing effect of fluorine was taken into consideration.
[0029]
【The invention's effect】
According to the method for solidifying and insolubilizing contaminated soil according to the present invention described in detail above, highly water-containing contaminated soil containing cyanide and / or fluorine can be insolubilized and solidified into soil having a predetermined strength or more. In addition, the scope of treatment of contaminated soil is expanded, leading to the extension or reduction of the life of the final disposal site, and is effective in reducing costs and protecting the natural environment.
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| JP2007077597A (en) * | 2005-09-12 | 2007-03-29 | Chubu Electric Power Co Inc | Pavement material using coal ash as the main raw material |
| JP4990870B2 (en) * | 2008-11-21 | 2012-08-01 | 財団法人福岡県すこやか健康事業団 | Method for insolubilizing casting waste sand containing fluorine and method for producing roadbed material |
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