JP6595311B2 - Method for suppressing elution of hexavalent chromium - Google Patents
Method for suppressing elution of hexavalent chromium Download PDFInfo
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Description
本発明は、不溶化材、及び六価クロムの溶出の抑制方法に関する。 The present invention relates to an insolubilizing material and a method for suppressing elution of hexavalent chromium.
近年、工場、事業所、産業廃棄物処理場の跡地等において、土壌が六価クロム等の重金属類で汚染されていることが、しばしば報告されている。このように土壌が六価クロム等の重金属類で汚染されると、その汚染が地下水にまで広がり、人体や穀物にまで影響を及ぼすという安全衛生上の問題がある。また、土壌の汚染濃度が環境基準値を超える場合には、跡地をそのまま利用できなくなり、土地を有効利用することができないという問題もある。
そこで、汚染土壌中の重金属類を不溶化して、これらの重金属類が土壌から溶出することを抑制、防止するための技術が種々提案されている。
In recent years, it has often been reported that soil is contaminated with heavy metals such as hexavalent chromium in sites such as factories, offices, and industrial waste disposal sites. Thus, when soil is contaminated with heavy metals such as hexavalent chromium, there is a safety and health problem that the contamination spreads to the groundwater and affects the human body and grains. Further, when the soil contamination concentration exceeds the environmental standard value, there is a problem that the site cannot be used as it is and the land cannot be used effectively.
Therefore, various techniques for insolubilizing heavy metals in contaminated soil and suppressing or preventing these heavy metals from eluting from the soil have been proposed.
例えば、特許文献１には、セメント系固化材及び酸化マグネシウムからなることを特徴とする土壌用固化材が記載されている。該固化材によれば、六価クロムを溶出することなく、土壌を固化することができる。
また、特許文献２には、酸化マグネシウムと高炉スラグ粉末とを含有し、有害物質を不溶化し得る不溶化材であって、前記高炉スラグ粉末の配合割合が、前記酸化マグネシウム１００質量部に対して５〜９００質量部であり、前記不溶化材中の全酸化マグネシウムの質量に対するく溶性苦土（Ｃ−ＭｇＯ）の割合が、８５質量％以上であることを特徴とする不溶化材が記載されている。該不溶化材によれば、土壌等に含まれる六価クロムを不溶化することができる。
For example, Patent Document 1 describes a soil solidifying material comprising a cement-based solidifying material and magnesium oxide. According to the solidifying material, the soil can be solidified without eluting hexavalent chromium.
Patent Document 2 discloses an insolubilizing material containing magnesium oxide and blast furnace slag powder and capable of insolubilizing harmful substances, and the blending ratio of the blast furnace slag powder is 5 parts by mass with respect to 100 parts by mass of the magnesium oxide. There is described an insolubilizing material characterized in that the proportion of soluble magnesia (C-MgO) is 85 mass% or more with respect to the total mass of magnesium oxide in the insolubilizing material. According to the insolubilizing material, hexavalent chromium contained in soil or the like can be insolubilized.
本発明の目的は、六価クロムを含む焼却灰等の被処理物からの六価クロムの溶出を抑制することができる不溶化材を提供することである。 The objective of this invention is providing the insolubilization material which can suppress the elution of hexavalent chromium from to-be-processed objects, such as incineration ash containing hexavalent chromium.
本発明者は、上記課題を解決するために鋭意検討した結果、六価クロムの溶出を抑制するための不溶化材であって、高炉スラグ粉末および亜硫酸水素ナトリウムを含む不溶化材によれば、上記目的を達成できることを見出し、本発明を完成した。
すなわち、本発明は、以下の［１］〜［８］を提供するものである。
［１］ 六価クロムの溶出を抑制するための不溶化材であって、高炉スラグ粉末および亜硫酸水素ナトリウムを含むことを特徴とする不溶化材。
［２］ 上記高炉スラグ粉末１００質量部当たりの上記亜硫酸水素ナトリウムの量が、１〜２００質量部である前記［１］に記載の不溶化材。
［３］ 硫酸第一鉄を含み、かつ、上記高炉スラグ粉末１００質量部当たりの上記硫酸第一鉄の量が、２００質量部以下である前記［１］又は［２］に記載の不溶化材。
［４］ さらに、セメントを組み合わせてなる前記［１］〜［３］のいずれかに記載の不溶化材。
［５］ 前記［４］に記載の不溶化材を用いて、六価クロムを含む被処理物からの六価クロムの溶出を抑制するための六価クロムの溶出の抑制方法であって、上記被処理物、上記セメント、および水を混合して、混練物を得る第一の添加工程と、上記混練物、および上記セメント以外の不溶化材の材料を混合して、不溶化処理物を得る第二の添加工程と、を含むことを特徴とする六価クロムの溶出の抑制方法。
［６］ 上記被処理物１００質量部当たり、上記セメントの量が５〜３０質量部、上記水の量が１０〜６０質量部、および、上記セメント以外の不溶化材の材料の合計量が０．５〜２０質量部である前記［５］に記載の六価クロムの溶出の抑制方法。
［７］ 上記被処理物が、焼却灰、飛灰、土壌、または汚泥である前記［５］又は［６］に記載の六価クロムの溶出の抑制方法。
［８］ 上記被処理物が、ペーパースラッジの焼却灰である前記［５］〜［７］のいずれかに記載の六価クロムの溶出の抑制方法。
As a result of intensive studies to solve the above problems, the present inventor is an insolubilizing material for suppressing elution of hexavalent chromium, and according to the insolubilizing material containing blast furnace slag powder and sodium hydrogen sulfite, The present invention has been completed.
That is, the present invention provides the following [1] to [8].
[1] An insolubilizing material for suppressing elution of hexavalent chromium, comprising blast furnace slag powder and sodium hydrogen sulfite.
[2] The insolubilized material according to [1], wherein the amount of the sodium hydrogen sulfite per 100 parts by mass of the blast furnace slag powder is 1 to 200 parts by mass.
[3] The insolubilizing material according to [1] or [2], including ferrous sulfate, and an amount of the ferrous sulfate per 100 parts by mass of the blast furnace slag powder is 200 parts by mass or less.
[4] The insolubilized material according to any one of [1] to [3], further comprising cement.
[5] A method for suppressing elution of hexavalent chromium for suppressing elution of hexavalent chromium from an object to be treated containing hexavalent chromium using the insolubilizing material according to [4], A first addition step of mixing a treated product, the cement, and water to obtain a kneaded product, and a second addition step for obtaining an insolubilized treated product by mixing the kneaded product and a material of an insolubilizing material other than the cement. An addition step, and a method for suppressing elution of hexavalent chromium.
[6] The amount of the cement is 5 to 30 parts by mass, the amount of water is 10 to 60 parts by mass, and the total amount of the insolubilizing material other than the cement is 0.1 per 100 parts by mass of the workpiece. The method for suppressing elution of hexavalent chromium according to the above [5], which is 5 to 20 parts by mass.
[7] The method for suppressing elution of hexavalent chromium according to [5] or [6], wherein the object to be treated is incineration ash, fly ash, soil, or sludge.
[8] The method for suppressing elution of hexavalent chromium according to any one of [5] to [7], wherein the object to be treated is incinerated ash of paper sludge.
本発明の不溶化材によれば、六価クロムを含む焼却灰等の被処理物からの六価クロムの溶出を抑制することができる。 According to the insolubilizing material of the present invention, elution of hexavalent chromium from an object to be treated such as incinerated ash containing hexavalent chromium can be suppressed.
本発明において、六価クロムの溶出を抑制する対象となる被処理物としては、例えば、焼却灰（例えば、ペーパースラッジを焼却してなる焼却灰等）、飛灰、土壌、汚泥等が挙げられる。 In the present invention, examples of the object to be treated for suppressing elution of hexavalent chromium include incineration ash (for example, incineration ash obtained by incineration of paper sludge), fly ash, soil, sludge, and the like. .
本発明の不溶化材は、六価クロムの溶出を抑制するための不溶化材であって、高炉スラグ粉末および亜硫酸水素ナトリウムを含むものである。
高炉スラグ粉末としては、高炉で銑鉄を製造する際に副生する溶融状態のスラグを、水で急冷・破砕して得られる水砕スラグや、徐冷・破砕して得られる徐冷スラグ等が挙げられる。
本発明の不溶化材における、高炉スラグ粉末１００質量部当たりの亜硫酸水素ナトリウム（ＮａＨＳＯ3）の量は、好ましくは１〜２００質量部、より好ましくは５〜１００質量部、さらに好ましくは８〜５０質量部、特に好ましくは１０〜３０質量部である。該量が１質量部以上であれば、六価クロムの溶出量をより小さくすることができる。該量が２００質量部以下であれば、コストが過大になることを防ぐことができる。
The insolubilizing material of the present invention is an insolubilizing material for suppressing elution of hexavalent chromium, and contains blast furnace slag powder and sodium bisulfite.
Examples of blast furnace slag powder include granulated slag obtained by quenching and crushing molten slag produced as a by-product when producing pig iron in the blast furnace, and slow cooling slag obtained by slow cooling and crushing. Can be mentioned.
The amount of sodium hydrogen sulfite (NaHSO 3 ) per 100 parts by mass of blast furnace slag powder in the insolubilized material of the present invention is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, and even more preferably 8 to 50 parts by mass. Parts, particularly preferably 10 to 30 parts by mass. When the amount is 1 part by mass or more, the elution amount of hexavalent chromium can be further reduced. If the amount is 200 parts by mass or less, the cost can be prevented from becoming excessive.
本発明の不溶化材は、硫酸第一鉄を含んでいてもよい。硫酸第一鉄を含むことで、六価クロムの溶出量をより小さくすることができる。
本発明の不溶化材における、高炉スラグ粉末１００質量部当たりの硫酸第一鉄（ＦｅＳＯ4）の量は、ｐＨの観点からは、好ましくは２００質量部以下、より好ましくは１００質量部以下、さらに好ましくは５０質量部以下、特に好ましくは３０質量部以下である。該量が２００質量部以下であれば、不溶化処理を行った後の被処理物のｐＨが酸性に近づくことを防ぐことができる。
高炉スラグ粉末１００質量部当たりの硫酸第一鉄の量は、六価クロムの溶出の抑制の観点からは、好ましくは５質量部以上、より好ましくは１０質量部以上、特に好ましくは２０質量部以上である。
The insolubilizing material of the present invention may contain ferrous sulfate. By including ferrous sulfate, the elution amount of hexavalent chromium can be further reduced.
From the viewpoint of pH, the amount of ferrous sulfate (FeSO 4 ) per 100 parts by mass of blast furnace slag powder in the insolubilized material of the present invention is preferably 200 parts by mass or less, more preferably 100 parts by mass or less. Is 50 parts by mass or less, particularly preferably 30 parts by mass or less. If this quantity is 200 mass parts or less, it can prevent that pH of the to-be-processed object after performing insolubilization processing approaches acidity.
The amount of ferrous sulfate per 100 parts by mass of blast furnace slag powder is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more from the viewpoint of suppressing elution of hexavalent chromium. It is.
本発明の不溶化材は、上述した不溶化材の材料（高炉スラグ粉末、亜硫酸水素ナトリウム、硫酸第一鉄）に、さらに、セメントを組み合わせてなるものでもよい。セメントを組み合わせることで、六価クロムの溶出の抑制効果をより長期間継続させることができる。
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、低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や、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や、アルミナセメントや、エコセメント等を使用することができる。中でも、六価クロムの溶出の抑制効果をより長期間継続させることができる観点から、高炉セメントが好ましい。
The insolubilizing material of the present invention may be a material obtained by further combining cement with the insolubilizing material (blast furnace slag powder, sodium hydrogen sulfite, ferrous sulfate). By combining the cement, the effect of suppressing the elution of hexavalent chromium can be continued for a longer period of time.
As cement, various portland cements such as ordinary portland cement, early-strength portland cement, medium heat portland cement, low heat portland cement, mixed cements such as blast furnace cement, fly ash cement, silica cement, alumina cement, eco cement, etc. Can be used. Among them, blast furnace cement is preferable from the viewpoint that the effect of suppressing elution of hexavalent chromium can be continued for a longer period of time.
六価クロムを含む被処理物と本発明の不溶化材を混合することで、被処理物からの六価クロムの溶出を抑制することができる。
具体的には、セメントを含まない本発明の不溶化材を用いる場合における六価クロムの溶出の抑制方法としては、被処理物に不溶化材をそのまま添加して混合するドライ添加方法や、不溶化材に水を加えてスラリーとした後に、該スラリーを被処理物に添加して混合するスラリー添加方法等が挙げられる。不溶化材がスラリーの状態であれば、被処理物への浸透性が向上し、六価クロムの溶出の抑制効果がより向上する。
セメントを組み合わせてなる不溶化材を用いる場合における六価クロムの溶出の抑制方法の一例としては、被処理物、セメント、および水を混合して、混練物を得る第一の添加工程と、混練物、およびセメント以外の不溶化材の材料（高炉スラグ粉末、亜硫酸水素ナトリウム、硫酸第一鉄）を混合して、不溶化処理物を得る第二の添加工程と、を含む方法が挙げられる。
By mixing the workpiece containing hexavalent chromium and the insolubilizing material of the present invention, elution of hexavalent chromium from the workpiece can be suppressed.
Specifically, as a method for suppressing the elution of hexavalent chromium when using the insolubilizing material of the present invention that does not contain cement, a dry addition method in which the insolubilizing material is directly added to the object to be treated and mixed, or an insolubilizing material is used. Examples include a slurry addition method in which water is added to form a slurry, and then the slurry is added to the object to be processed and mixed. If the insolubilizing material is in a slurry state, the permeability to the object to be processed is improved, and the effect of suppressing the elution of hexavalent chromium is further improved.
An example of a method for suppressing elution of hexavalent chromium in the case of using an insolubilized material in combination with cement includes a first addition step of mixing a workpiece, cement, and water to obtain a kneaded product, and a kneaded product And a second addition step of mixing an insolubilizing material other than cement (blast furnace slag powder, sodium hydrogen sulfite, ferrous sulfate) to obtain an insolubilized product.
セメント以外の不溶化材の材料の合計の添加量（具体的には、高炉スラグ粉末、亜硫酸水素ナトリウム、硫酸第一鉄の合計の添加量）は、被処理物の六価クロムの含有量によっても異なるが、被処理物１００質量部当たり、好ましくは０．５〜２０質量部、より好ましくは１〜１０質量部、特に好ましくは２〜５質量部である。該量が０．５質量部以上であれば、六価クロムの溶出量をより小さくすることができる。該量が２０質量部以下であれば、コストが過大になるのを防ぐことができる。 The total addition amount of insolubilizing materials other than cement (specifically, the total addition amount of blast furnace slag powder, sodium hydrogen sulfite, and ferrous sulfate) depends on the hexavalent chromium content of the workpiece. Although it is different, it is preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass per 100 parts by mass of the workpiece. When the amount is 0.5 parts by mass or more, the elution amount of hexavalent chromium can be further reduced. If the amount is 20 parts by mass or less, the cost can be prevented from becoming excessive.
セメントの添加量は、被処理物１００質量部当たり、好ましくは５〜３０質量部、より好ましくは７〜２０質量部、特に好ましくは８〜１５質量部である。
上記セメントの添加量が５質量部以上であれば、六価クロムの溶出の抑制効果をより長期間継続させることができる。上記セメントの添加量が３０質量部以下であれば、コストが過大になるのを防ぐことができる。
The amount of cement added is preferably 5 to 30 parts by mass, more preferably 7 to 20 parts by mass, and particularly preferably 8 to 15 parts by mass per 100 parts by mass of the workpiece.
If the addition amount of the cement is 5 parts by mass or more, the effect of suppressing the elution of hexavalent chromium can be continued for a longer period. If the addition amount of the cement is 30 parts by mass or less, the cost can be prevented from becoming excessive.
水の添加量は、被処理物１００質量部当たり、好ましくは１０〜６０質量部、より好ましくは２０〜５０質量部、特に好ましくは３０〜４５質量部である。
上記水の添加量が１０質量部以上であれば、作業性が向上する。上記水の添加量が６０質量部以下であれば、処理後の被処理物の強度（例えば、一軸圧縮強さ）が向上する。
The amount of water added is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass, and particularly preferably 30 to 45 parts by mass per 100 parts by mass of the workpiece.
If the amount of water added is 10 parts by mass or more, workability is improved. When the amount of water added is 60 parts by mass or less, the strength (for example, uniaxial compressive strength) of the processed object after the treatment is improved.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
使用材料は、以下に示すとおりである。
（１）高炉スラグ粉末：高炉水砕スラグ粉末、デイ・シイ社製、商品名「セラメント」
（２）亜硫酸水素ナトリウム：大東化学社製、規格「一般」
（３）硫酸第一鉄：硫酸第一鉄・１水塩、富士チタン工業社製
（４）ペーパースラッジの焼却灰：六価クロムの溶出量（平成３年８月２３日環境庁告示第４６号「土壌の汚染に係る環境基準について」の別表の「六価クロム」に準拠した溶出試験方法によって測定された溶出量）０．２６ｍｇ／リットル、ｐＨ（上記溶出試験方法によって得られた溶出検液のｐＨ）１１．１
（５）高炉セメント：太平洋セメント社製、商品名「高炉セメントＢ種」
（６）水：上水道水
［不溶化材Ａ〜Ｄの作製］
上記材料を、表１に示す配合に従って混合して、不溶化材Ａ〜Ｄを作製した。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
The materials used are as shown below.
(1) Blast Furnace Slag Powder: Blast Furnace Granulated Slag Powder, manufactured by Dai Shi Co., Ltd., trade name “CERAMENT”
(2) Sodium bisulfite: Daito Chemical Co., Ltd., Standard “General”
(3) Ferrous sulfate: Ferrous sulfate monohydrate, manufactured by Fuji Titanium Industry Co., Ltd. (4) Incinerated ash of paper sludge: Hexavalent chromium elution amount (August 23, 1991, Environment Agency Notification No. 46 Elution amount measured by the elution test method in accordance with “Hexavalent Chromium” in the separate table of the “Environmental Standards Concerning Soil Contamination”, 0.26 mg / liter, pH (elution test obtained by the above elution test method) PH of the liquid) 11.1
(5) Blast furnace cement: Taiheiyo Cement Co., Ltd., trade name “Blast furnace cement type B”
(6) Water: tap water [production of insolubilized materials A to D]
The said material was mixed according to the mixing | blending shown in Table 1, and insolubilization material AD was produced.
［実施例１］
ペーパースラッジの焼却灰と高炉セメントと水を混合した後、得られた混合物に、さらに不溶化材Ｂを加えて混合し、不溶化処理物を得た。なお、各材料の量は、表２に示す配合量に従った。
得られた不溶化処理物について、平成３年８月２３日環境庁告示第４６号「土壌の汚染に係る環境基準について」の別表の「六価クロム」に準拠して溶出試験を行い、得られた検出溶液を用いて、材齢４日及び１０日における六価クロムの溶出量およびｐＨを測定した。六価クロムの溶出量は、「ＪＩＳ Ｋ ０１０２：２０１３（工場排水試験方法）」に準拠して吸光光度法によって測定した。
[Example 1]
After incineration ash of paper sludge, blast furnace cement and water were mixed, insolubilizing material B was further added to the obtained mixture and mixed to obtain an insolubilized product. In addition, the quantity of each material followed the compounding quantity shown in Table 2.
The obtained insolubilized product was obtained by conducting a dissolution test in accordance with “hexavalent chromium” in the separate table of Environmental Agency Notification No. 46 “Environmental Standards Concerning Soil Contamination” on August 23, 1991. The elution amount and pH of hexavalent chromium at a material age of 4 and 10 days were measured using the detected solution. The elution amount of hexavalent chromium was measured by an absorptiometry in accordance with “JIS K 0102: 2013 (factory drainage test method)”.
［実施例２］
不溶化材Ｂの代わりに不溶化材Ｃを用いる以外は、実施例１と同様にして不溶化処理物を得た。得られた不溶化処理物を用いて、実施例１と同様にして、六価クロムの溶出量およびｐＨを測定した。
［実施例３］
不溶化材Ｂの代わりに不溶化材Ｄを用いる以外は、実施例１と同様にして不溶化処理物を得た。得られた不溶化処理物を用いて、実施例１と同様にして、六価クロムの溶出量およびｐＨを測定した。
[Example 2]
An insolubilized material was obtained in the same manner as in Example 1 except that the insolubilized material C was used instead of the insolubilized material B. Using the obtained insolubilized product, the elution amount and pH of hexavalent chromium were measured in the same manner as in Example 1.
[Example 3]
An insolubilized product was obtained in the same manner as in Example 1 except that the insolubilizing material D was used instead of the insolubilizing material B. Using the obtained insolubilized product, the elution amount and pH of hexavalent chromium were measured in the same manner as in Example 1.
［比較例１］
ペーパースラッジの焼却灰と高炉セメントと水を、表２に示す配合量に従って混合し、混合物を得た。得られた混合物を用いて、実施例１と同様にして、材齢４日及び１０日における六価クロムの溶出量およびｐＨを測定した。
［比較例２〜３］
不溶化材Ｂの代わりに不溶化材Ａを用いる以外は、実施例１と同様にして不溶化処理物を得た。得られた不溶化処理物を用いて、実施例１と同様にして、六価クロムの溶出量およびｐＨを測定した。
結果を表２に示す。
[Comparative Example 1]
Paper sludge incineration ash, blast furnace cement and water were mixed according to the blending amounts shown in Table 2 to obtain a mixture. Using the obtained mixture, the elution amount and pH of hexavalent chromium at the age of 4 days and 10 days were measured in the same manner as in Example 1.
[Comparative Examples 2-3]
An insolubilized material was obtained in the same manner as in Example 1 except that insolubilized material A was used instead of insolubilized material B. Using the obtained insolubilized product, the elution amount and pH of hexavalent chromium were measured in the same manner as in Example 1.
The results are shown in Table 2.
表２から、本発明の不溶化材（実施例１〜３）によれば、六価クロムの溶出量を小さく（０．００２ｍｇ／リットル以下に）することができる。特に、材齢が４日であっても、六価クロムの溶出量が小さいことがわかる。
一方、比較例１〜３では、六価クロムの溶出量が実施例１〜３と比べて大きい（０．０１２〜０．１３０ｍｇ／リットル）ことがわかる。
From Table 2, according to the insolubilizing material of the present invention (Examples 1 to 3), the elution amount of hexavalent chromium can be reduced (0.002 mg / liter or less). In particular, it can be seen that the elution amount of hexavalent chromium is small even when the age is 4 days.
On the other hand, in Comparative Examples 1-3, it turns out that the elution amount of hexavalent chromium is large (0.012-0.130 mg / liter) compared with Examples 1-3.
Claims (2)
上記被処理物、上記セメント、および水を混合して、混練物を得る第一の添加工程と、
上記混練物、および上記セメント以外の不溶化材の材料を混合して、不溶化処理物を得る第二の添加工程と、を含み、
上記被処理物１００質量部当たり、上記セメントの量が５〜３０質量部、上記水の量が１０〜６０質量部、および、上記セメント以外の不溶化材の材料の合計量が０．５〜２０質量部であることを特徴とする六価クロムの溶出の抑制方法。 An insolubilizing material for suppressing elution of hexavalent chromium, using a blast furnace slag powder , cement, and an insolubilizing material containing only sodium bisulfite in an amount of 1 to 200 parts by mass per 100 parts by mass of the blast furnace slag powder , A method for suppressing elution of hexavalent chromium for suppressing elution of hexavalent chromium from the incinerated ash of paper sludge, which is an object to be treated containing hexavalent chromium,
A first addition step of mixing the workpiece, the cement, and water to obtain a kneaded product;
A second addition step of mixing the kneaded material and a material of an insolubilizing material other than the cement to obtain an insolubilized material, and
The amount of the cement is 5 to 30 parts by mass, the amount of water is 10 to 60 parts by mass, and the total amount of insolubilizing materials other than the cement is 0.5 to 20 per 100 parts by mass of the workpiece. A method for suppressing elution of hexavalent chromium, characterized by comprising parts by mass .
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