JP2009040652A - Treatment method of steel making slag - Google Patents
Treatment method of steel making slag Download PDFInfo
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- JP2009040652A JP2009040652A JP2007209158A JP2007209158A JP2009040652A JP 2009040652 A JP2009040652 A JP 2009040652A JP 2007209158 A JP2007209158 A JP 2007209158A JP 2007209158 A JP2007209158 A JP 2007209158A JP 2009040652 A JP2009040652 A JP 2009040652A
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- 239000002893 slag Substances 0.000 title claims abstract description 99
- 238000009628 steelmaking Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 79
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011737 fluorine Substances 0.000 claims abstract description 78
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 42
- 239000011707 mineral Substances 0.000 claims abstract description 42
- 238000010828 elution Methods 0.000 claims abstract description 34
- 239000011575 calcium Substances 0.000 claims abstract description 32
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 230000007613 environmental effect Effects 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 4
- 230000001629 suppression Effects 0.000 claims description 4
- 238000007922 dissolution test Methods 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 3
- -1 aluminum compound Chemical class 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- HUSUHZRVLBSGBO-UHFFFAOYSA-L calcium;dihydrogen phosphate;hydroxide Chemical compound O.[Ca+2].OP([O-])([O-])=O HUSUHZRVLBSGBO-UHFFFAOYSA-L 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Furnace Details (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
Abstract
Description
本発明は、製鋼スラグに含まれるフッ素を固定化し、スラグからのフッ素の溶出を効果的に抑制することができるスラグ処理方法に関するものである。 The present invention relates to a slag treatment method capable of fixing fluorine contained in steelmaking slag and effectively suppressing elution of fluorine from the slag.
従来、製鋼スラグは、コンクリート骨材や路盤材料、港湾土木材料などの土木材料として広く利用されている。
鉄鋼製造プロセスの精錬工程では、ＣａＯなどの精錬剤の滓化促進剤としてフッ化カルシウム（ＣａＦ２）を主成分とするホタル石が使用されることがあり、このような精錬工程で発生するスラグはフッ素を含有している。また、スラグには、上記のようなフッ素源以外に、高炉装入原料を通じて不可避的にフッ素が混入することもある。
Conventionally, steelmaking slag has been widely used as a civil engineering material such as a concrete aggregate, a roadbed material, and a harbor civil engineering material.
In the refining process of the steel manufacturing process, fluorite containing calcium fluoride (CaF 2 ) as a main component is sometimes used as a hatching accelerator for refining agents such as CaO. Slag generated in such a refining process Contains fluorine. In addition to the above fluorine source, fluorine may be inevitably mixed into the slag through the raw material charged in the blast furnace.
このようなフッ素含有スラグを骨材や土木材料として利用した場合、スラグが水（例えば、雨水、地下水など）に接するとスラグ中のフッ素が水に溶け出し、水質や土壌などを汚染する可能性がある。このような問題に対して、スラグからのフッ素の溶出を抑制するための方法が幾つか提案されている。
例えば、特許文献１には、製鋼スラグ融体にアルミニウム化合物を添加し、凝固過程において安定なＣａＯ−Ａｌ2Ｏ3−Ｆ系化合物を生成させることでフッ素を固定するとともに、製鋼スラグの雨水や地下水などへの溶解に際して、製鋼スラグから溶出するカルシウムイオンやアルミニウムイオンを用いて、スラグから溶出するフッ素を捕捉する方法が提案されている。
When such fluorine-containing slag is used as an aggregate or civil engineering material, if the slag comes into contact with water (for example, rainwater, groundwater, etc.), the fluorine in the slag may dissolve in the water and contaminate water quality and soil. There is. Several methods for suppressing the elution of fluorine from the slag have been proposed for such problems.
For example, in Patent Document 1, an aluminum compound is added to a steelmaking slag melt, and fluorine is fixed by generating a stable CaO—Al 2 O 3 —F-based compound in the solidification process. A method of capturing fluorine eluted from slag by using calcium ions or aluminum ions eluted from steelmaking slag during dissolution in groundwater or the like has been proposed.
また、特許文献２には、フッ素を含む製鋼スラグに、カルシウムアルミネートを含む粉末からなるフッ素固定剤と、高炉徐冷スラグなどからなる増容材を添加し、フッ素を固定化する方法が提案されている。
また、特許文献３には、フッ素を含有する製鋼スラグに、燐含有化合物や燐含有鉱物などのような燐含有物を添加し、スラグからのフッ素の溶出を抑制するようにした方法が提案されている。
Patent Document 3 proposes a method in which phosphorus-containing materials such as phosphorus-containing compounds and phosphorus-containing minerals are added to steel-containing slag containing fluorine to suppress elution of fluorine from the slag. ing.
しかしながら、特許文献１の方法は、スラグの凝固プロセスにおける処理であるため、アルミニウム化合物を添加するための設備が必要となるほか、生成するスラグ量も増加するため、経済性やスラグ処理の面で問題がある。
また、特許文献２の方法は、フッ素固定剤（カルシウムアルミネートを含む粉末）をかなり多量に混合しないと、フッ素の溶出量を環境基準値以下に抑えることができず、経済性に大きな問題がある。
また、特許文献３の方法も、フッ素の溶出を十分に抑制することができない。また、効果を高めようとして多量の燐含有物を添加すると、本来の用途に必要な一軸圧縮強度などの性能が悪化するおそれがある。
However, since the method of Patent Document 1 is a treatment in a slag solidification process, an equipment for adding an aluminum compound is required, and the amount of slag to be generated increases, so that it is economical and slag treatment. There's a problem.
In addition, the method of Patent Document 2 has a large problem in terms of economy because the amount of fluorine eluted cannot be suppressed below the environmental standard value unless a fluorine fixing agent (powder containing calcium aluminate) is mixed in a considerably large amount. is there.
Also, the method of Patent Document 3 cannot sufficiently suppress the elution of fluorine. Further, when a large amount of phosphorus-containing material is added to enhance the effect, performance such as uniaxial compressive strength necessary for the original use may be deteriorated.
したがって本発明の目的は、製鋼スラグからのフッ素溶出を効果的に抑制することができ、しかも特別な設備を用いることなく低コストに実施可能なスラグ処理方法を提供することにある。 Accordingly, an object of the present invention is to provide a slag treatment method that can effectively suppress fluorine elution from steelmaking slag and that can be carried out at low cost without using special equipment.
上記課題を解決するため、本発明は以下を要旨とするものである。
［1］製鋼スラグにフッ素の溶出抑制処理を施す方法において、
フッ素含有量が０．１５mass％以上、リン含有量が０．３mass％以上の製鋼スラグ（Ａ）に対して、カルシウムを含有する鉱物（Ｂ）を添加し、製鋼スラグ（Ａ）の含有成分と鉱物（Ｂ）が含有するカルシウムによりフッ素を含む難溶性化合物を生成させることを特徴とする製鋼スラグの処理方法。
［2］上記［1］の処理方法において、鉱物（Ｂ）の粒径１０ｍｍ以下の割合が５０mass％以上であることを特徴とする製鋼スラグの処理方法。
In order to solve the above problems, the present invention has the following gist.
[1] In a method of applying fluorine elution control to steelmaking slag,
Calcium-containing mineral (B) is added to steelmaking slag (A) having a fluorine content of 0.15 mass% or more and a phosphorus content of 0.3 mass% or more, and the components of steelmaking slag (A) A method for treating steelmaking slag, wherein a sparingly soluble compound containing fluorine is produced by calcium contained in a mineral (B).
[2] A method for processing steelmaking slag according to the above [1], wherein the proportion of the mineral (B) having a particle size of 10 mm or less is 50 mass% or more.
［3］上記［1］又は［2］の処理方法において、鉱物（Ｂ）が、ＣａＯ、Ｃａ（ＯＨ）２、３ＣａＯ・ＳｉＯ２、２ＣａＯ・ＳｉＯ２、ＣａＳＯ４の中から選ばれる１種以上を含有することを特徴とする製鋼スラグの処理方法。
［4］上記［1］〜［3］のいずれかの処理方法において、鉱物（Ｂ）は、フッ素含有量が０．２mass％未満であって、平成３年８月２３日環境庁告示第４６号（平成１３環告１６）に準拠した溶出試験により測定されるＣａ溶出量が１００ｍｇ／Ｌ以上であることを特徴とする製鋼スラグの処理方法。
［5］フッ素含有量が０．１５mass％以上、リン含有量が０．３mass％以上の製鋼スラグ（Ａ）と、カルシウムを含有する鉱物（Ｂ）とからなり、製鋼スラグ（Ａ）の含有成分と鉱物（Ｂ）が含有するカルシウムにより生成したフッ素を含む難溶性化合物を含有することを特徴とする製鋼スラグ。
[3] In the processing method of the above-mentioned [1] or [2], mineral (B) is, CaO, Ca (OH) 2 , 3CaO · SiO 2, 2CaO · SiO 2, CaSO 1 or more selected from among 4 A method for treating steelmaking slag, comprising:
[4] In the processing method according to any one of [1] to [3] above, the mineral (B) has a fluorine content of less than 0.2 mass%, and is notified by the Environment Agency Notification No. 46 on August 23, 1991. No. (Heisei 13 notification 16), the amount of Ca elution measured by the elution test is 100 mg / L or more, The processing method of the steelmaking slag characterized by the above-mentioned.
[5] A steelmaking slag (A) having a fluorine content of 0.15 mass% or more and a phosphorus content of 0.3 mass% or more and a mineral (B) containing calcium, and the components of the steelmaking slag (A) Steelmaking slag characterized by containing a sparingly soluble compound containing fluorine produced by calcium contained in the mineral (B).
本発明によれば、製鋼スラグ（Ａ）の含有成分（フッ素およびリン）と鉱物（Ｂ）が含有するカルシウムによってフッ素を含む難溶性化合物が生成し、製鋼スラグ（Ａ）のフッ素が固定されるので、製鋼スラグ（Ａ）からのフッ素の溶出を効果的に抑制することができる。特に、本発明では、被処理スラグである製鋼スラグ（Ａ）が含有するリンを利用して難溶性化合物を生成させるので、被処理スラグである製鋼スラグ（Ａ）自身の粒子表面がフッ素を含む化合物の析出サイトとして機能するため、高いフッ素固定効果が得られる。 According to the present invention, a hardly soluble compound containing fluorine is generated by the components (fluorine and phosphorus) of the steelmaking slag (A) and calcium contained in the mineral (B), and the fluorine of the steelmaking slag (A) is fixed. Therefore, the elution of fluorine from the steelmaking slag (A) can be effectively suppressed. In particular, in the present invention, since the poorly soluble compound is generated using phosphorus contained in the steelmaking slag (A) which is the treated slag, the particle surface of the steelmaking slag (A) itself which is the treated slag contains fluorine. Since it functions as a precipitation site for the compound, a high fluorine fixing effect can be obtained.
本発明の処理方法は、製鋼スラグにフッ素の溶出抑制処理を施す方法であり、フッ素含有量が０．１５mass％以上、リン含有量が０．３mass％以上の製鋼スラグ（Ａ）に対して、カルシウムを含有する鉱物（Ｂ）を添加し、製鋼スラグ（Ａ）の含有成分と鉱物（Ｂ）が含有するカルシウムによりフッ素を含む難溶性化合物を生成させるものである。
なお、製鋼スラグ（Ａ）のフッ素含有量には、スラグ粒子からその表面に存在（付着）する水に溶出したフッ素分も含まれる。
The treatment method of the present invention is a method of applying a fluorine elution suppression treatment to steelmaking slag, and with respect to steelmaking slag (A) having a fluorine content of 0.15 mass% or more and a phosphorus content of 0.3 mass% or more, A mineral (B) containing calcium is added, and a sparingly soluble compound containing fluorine is produced by the components contained in the steelmaking slag (A) and the calcium contained in the mineral (B).
The fluorine content of the steelmaking slag (A) includes the fluorine content eluted from the slag particles to the water existing (attached) on the surface.
本発明において、被処理スラグとなる製鋼スラグ（Ａ）のフッ素含有量を０．１５mass％以上とするのは、このような製鋼スラグは、通常、フッ素溶出量（環境庁告示第４６号に準拠した溶出試験によるフッ素溶出量）が土壌環境基準を上回るので、フッ素溶出の抑制処理を施す必要があるからである。
製鋼スラグ（Ａ）のリン含有量を０．３mass％以上とするのは、本発明ではスラグ中のリンを利用してフッ素を含む難溶性化合物を生成させるためである。製鋼スラグ（Ａ）は、フッ素を固定する難溶性化合物を形成するべきカルシウムが不足したスラグであり、一般には、平成３年８月２３日環境庁告示第４６号（平成１３環告１６）に準拠した溶出試験により測定されるＣａ溶出量が１００ｍｇ／Ｌ未満のスラグである。
製鋼スラグ（Ａ）としては、フッ素含有量が０．１５mass％以上、リン含有量が０．３mass％以上のものであれば種類を問わないが、一般には、脱燐スラグに該当するものが多い。
In the present invention, the steel content of the steelmaking slag (A) to be treated is made to have a fluorine content of 0.15 mass% or more. Such steelmaking slag is usually in accordance with fluorine elution amount (according to Environment Agency Notification No. 46). This is because the fluorine elution amount by the elution test performed exceeds the soil environmental standard, and it is necessary to perform a fluorine elution suppression treatment.
The reason why the phosphorus content of the steelmaking slag (A) is 0.3 mass% or more is that, in the present invention, phosphorus in the slag is used to produce a sparingly soluble compound containing fluorine. Steelmaking slag (A) is a slag that lacks calcium to form a sparingly soluble compound that fixes fluorine, and in general, the Environment Agency Notification No. 46 (2001 notification 16) on August 23, 1991 The amount of Ca elution measured by a compliant dissolution test is less than 100 mg / L.
The steelmaking slag (A) is not particularly limited as long as it has a fluorine content of 0.15 mass% or more and a phosphorus content of 0.3 mass% or more, but generally there are many that fall under dephosphorization slag. .
本発明では、鉱物（Ｂ）に含まれるカルシウムが製鋼スラグ（Ａ）のフッ素およびリンとともに難溶性化合物を生成し、スラグにフッ素を固定する。すなわち、鉱物（Ｂ）から供給されるＣａと製鋼スラグ（Ａ）中のＰの溶液反応により、水には難溶解性であるがフッ素との反応活性が高いリン酸水素カルシウム水和物が生成し、この水和物とフッ素とが反応し、フッ素が固定される。このフッ素を固定した反応生成物（難溶性化合物）は、Ｃａ５（ＰＯ４）３Ｆ（フルオロアパタイト、Ｃａ10（ＰＯ４）6Ｆ２と表記されることもある）若しくはそれに類する組成物であると考えられ、この反応生成物は水への溶解度が低いため、フッ素固定機能が長期間にわたって持続し、スラグからのフッ素溶出を長期間にわたって効果的に抑制することができ、また環境へのＰの流失も防止することができる。 In the present invention, calcium contained in the mineral (B) generates a hardly soluble compound together with fluorine and phosphorus of the steelmaking slag (A), and fixes fluorine to the slag. That is, a solution reaction of Ca supplied from mineral (B) and P in steelmaking slag (A) produces calcium hydrogen phosphate hydrate that is hardly soluble in water but highly reactive with fluorine. The hydrate reacts with fluorine to fix the fluorine. This fluorine-fixed reaction product (slightly soluble compound) is Ca 5 (PO 4 ) 3 F (fluoroapatite, sometimes expressed as Ca 10 (PO 4 ) 6 F 2 ) or a similar composition. This reaction product has low solubility in water, so the fluorine fixing function can be maintained over a long period of time, and the elution of fluorine from the slag can be effectively suppressed over a long period of time. The loss of P can also be prevented.
ここで、被処理スラグである製鋼スラグ（Ａ）が含有するリンを利用して難溶性化合物を生成させるのが本発明の大きな特徴であり、これにより、スラグ粒子表面がフッ素を含む化合物の析出サイトとして機能し、高いフッ素固定効果が得られるものと考えられる。
鉱物（Ｂ）に含まれるカルシウム化合物としては、ＣａＯ、Ｃａ（ＯＨ）２、３ＣａＯ・ＳｉＯ２、２ＣａＯ・ＳｉＯ２、ＣａＳＯ４などが挙げられ、鉱物（Ｂ）としては、これらカルシウム化合物の１種以上を含むものが好ましい。鉱物（Ｂ）としては、例えば、水酸化カルシウム、酸化カルシウム、カルシウムシリケート、カルシウムシリケート水和物、セメント、石膏、塩化カルシウム、高炉水砕スラグ微粉末、その他の鉄鋼スラグなどが挙げられ、これらの１種以上を添加することができる。
Here, it is a major feature of the present invention that a poorly soluble compound is generated using phosphorus contained in the steelmaking slag (A), which is a slag to be treated, and as a result, precipitation of a compound containing fluorine on the slag particle surface is achieved. It is considered that it functions as a site and a high fluorine fixing effect can be obtained.
The calcium compound contained in the mineral (B), CaO, Ca ( OH) 2, etc. 3CaO · SiO 2, 2CaO · SiO 2, CaSO 4 , and examples of the mineral (B), 1 species of these calcium compounds What contains the above is preferable. Examples of the mineral (B) include calcium hydroxide, calcium oxide, calcium silicate, calcium silicate hydrate, cement, gypsum, calcium chloride, ground granulated blast furnace slag, and other steel slag. One or more can be added.
また、通常、製鋼スラグ（Ａ）に対する鉱物（Ｂ）の添加量は比較的少なくて済むため、それ鉱物（Ｂ）自身が含有するフッ素の影響は相対的に小さい。但し、鉱物（Ｂ）自体がフッ素溶出源とならないようにするため、フッ素含有量は０．２mass％未満であることが好ましい。フッ素含有量が０．２mass％以上では、鉱物（Ｂ）自身からのフッ素溶出の影響が大きくなる。また、鉱物（Ｂ）は、カルシウムの供給源として、平成３年８月２３日環境庁告示第４６号（平成１３環告１６）に準拠した溶出試験により測定されるＣａ溶出量が１００ｍｇ／Ｌ以上、好ましくは２００ｍｇ／Ｌ以上であることが望ましい。Ｃａ溶出量が１００ｍｇ／Ｌ未満では、十分なカルシウム供給源とならず、効果が少ない。 Moreover, since the amount of mineral (B) added to steelmaking slag (A) is usually relatively small, the influence of fluorine contained in the mineral (B) itself is relatively small. However, the fluorine content is preferably less than 0.2 mass% so that the mineral (B) itself does not become a fluorine elution source. When the fluorine content is 0.2 mass% or more, the influence of fluorine elution from the mineral (B) itself becomes large. Further, the mineral (B) has a Ca elution amount of 100 mg / L as a calcium supply source as measured by an elution test in accordance with Environmental Agency Notification No. 46 (Heisei 13 notification 16) on August 23, 1991. As mentioned above, Preferably it is 200 mg / L or more. When the Ca elution amount is less than 100 mg / L, the calcium supply source is not sufficient and the effect is small.
鉱物（Ｂ）のカルシウムを有効に活用するには、鉱物（Ｂ）の粒径がある程度小さい方が好ましく、この意味で、鉱物（Ｂ）は粒径１０ｍｍ以下の割合が５０mass％以上であることが好ましい。
また、製鋼スラグ（Ａ）の粒径は特に規定しないが、用途に適した粒度分布となるように、粒度を適宜調整することが好ましい。
製鋼スラグ（Ａ）に対する鉱物（Ｂ）の添加量は特に制限はないが、製鋼スラグ（Ａ）のフッ素含有量およびリン含有量、鉱物（Ｂ）のＣａ溶出量などに応じて、製鋼スラグ（Ａ）のフッ素を適切に固定できるよう、添加量が選定される。
また、本発明では、被処理スラグである製鋼スラグ（Ａ）のフッ素含有量を０．１５mass％以上とし、この製鋼スラグ（Ａ）に添加する鉱物（Ｂ）の好ましいフッ素含有量を０．２mass％未満とするものであるが、本発明の効果をより有効に生じさせるには、鉱物（Ｂ）のフッ素含有量を０．１５mass％未満とすることがより好ましい。
In order to effectively use calcium of the mineral (B), it is preferable that the particle size of the mineral (B) is small to some extent. In this sense, the proportion of the mineral (B) having a particle size of 10 mm or less is 50 mass% or more. Is preferred.
In addition, the particle size of the steelmaking slag (A) is not particularly defined, but it is preferable to adjust the particle size appropriately so as to obtain a particle size distribution suitable for the application.
The amount of mineral (B) added to steelmaking slag (A) is not particularly limited, but depending on the fluorine content and phosphorus content of steelmaking slag (A), the amount of Ca elution of mineral (B), etc. The addition amount is selected so that the fluorine of A) can be appropriately fixed.
Moreover, in this invention, the fluorine content of steelmaking slag (A) which is a to-be-processed slag shall be 0.15 mass% or more, and the preferable fluorine content of the mineral (B) added to this steelmaking slag (A) is 0.2 mass. However, in order to produce the effect of the present invention more effectively, it is more preferable that the fluorine content of the mineral (B) is less than 0.15 mass%.
本発明の処理方法では、基本的に製鋼スラグ（Ａ）に対して鉱物（Ｂ）を添加・混合するだけでよく、これにより元々スラグなどに含まれている水分を介して上述した機構に基づく反応が生じ、フッ素を含む難溶性化合物が生成し、スラグにフッ素が固定される。また、反応を供用前に進行させるために、製鋼スラグ（Ａ）および／または鉱物（Ｂ）或いはそれらの混合物（製鋼スラグ（Ａ）・鉱物（Ｂ）の混合中を含む）に水を添加してもよい。但し、添加水の一部が流失しないような限度行うことが好ましい。
混合は重機による混合、混合プラントによる混合など任意の方法で行うことができる。養生は必ずしも必要ではないが、１日以上、望ましくは３日以上養生することにより、供用前にフッ素固定を進行させることができる。
本発明の処理法によれば、製鋼スラグ（Ａ）と鉱物（Ｂ）とからなり、且つ上記難溶性化合物を含有するフッ素溶出抑制処理スラグが得られる。
In the treatment method of the present invention, it is basically only necessary to add and mix the mineral (B) to the steelmaking slag (A), and based on the above-described mechanism through the moisture originally contained in the slag. Reaction occurs, a sparingly soluble compound containing fluorine is generated, and fluorine is fixed to the slag. In addition, water is added to steelmaking slag (A) and / or mineral (B) or a mixture thereof (including during the mixing of steelmaking slag (A) and mineral (B)) in order to allow the reaction to proceed before in-service. May be. However, it is preferable to perform the limit so that a part of the added water is not lost.
Mixing can be performed by any method such as mixing by a heavy machine or mixing by a mixing plant. Although curing is not necessarily required, fluorine fixation can be promoted before use by curing for 1 day or longer, preferably 3 days or longer.
According to the treatment method of the present invention, a fluorine elution suppression treatment slag comprising a steelmaking slag (A) and a mineral (B) and containing the hardly soluble compound is obtained.
本実施例におけるスラグのフッ素溶出量およびカルシウム溶出量は、いずれも平成３年８月２３日環境庁告示第４６号（平成１３環告１６）に準拠した溶出試験による溶出量であり、スラグを２ｍｍの篩目で篩った篩下材（２ｍｍ篩下材）について測定した溶出量である。
製鋼スラグ（Ａ）として、フッ素溶出量が１．２ｍｇ／Ｌ、カルシウム溶出量が１２ｍｇ／Ｌである脱燐スラグ（ＳｉＯ２：２５．１mass％、ＣａＯ：３４．２mass％、Ｐ：１．４mass％、Ｆ：０．５０mass％）の２ｍｍ篩い下材を用い、鉱物（Ｂ）として、水酸化カルシウム粉を用いた。製鋼スラグ（Ａ）１００質量部に対して水酸化カルシウム２質量部を添加し、均一に混合した。添加・混合してから３日後に測定したスラグのフッ素溶出量は０．６８ｍｇ／Ｌであり、土壌環境基準（０．８ｍｇ／Ｌ以下）を満足した。また、同じくスラグのカルシウム溶出量は１０００ｍｇ／Ｌであった。
The slag fluorine elution amount and calcium elution amount in this example are both elution amounts based on the elution test in accordance with Environmental Agency Notification No. 46 (Heisei 13 notification 16) on August 23, 1991, and the slag It is the elution amount measured about the sieving material (2 mm sieving material) sieved with the 2 mm sieve mesh.
As the steelmaking slag (A), dephosphorization slag (SiO 2 : 25.1 mass%, CaO: 34.2 mass%, P: 1.4 mass) having a fluorine elution amount of 1.2 mg / L and a calcium elution amount of 12 mg / L. %, F: 0.50 mass%), and calcium hydroxide powder was used as the mineral (B). 2 parts by mass of calcium hydroxide was added to 100 parts by mass of the steelmaking slag (A) and mixed uniformly. The fluorine elution amount of slag measured 3 days after the addition and mixing was 0.68 mg / L, which satisfied the soil environmental standard (0.8 mg / L or less). Similarly, the calcium elution amount of slag was 1000 mg / L.
Claims (5)
フッ素含有量が０．１５mass％以上、リン含有量が０．３mass％以上の製鋼スラグ（Ａ）に対して、カルシウムを含有する鉱物（Ｂ）を添加し、製鋼スラグ（Ａ）の含有成分と鉱物（Ｂ）が含有するカルシウムによりフッ素を含む難溶性化合物を生成させることを特徴とする製鋼スラグの処理方法。 In the method of applying elution suppression treatment to steelmaking slag,
Calcium-containing mineral (B) is added to steelmaking slag (A) having a fluorine content of 0.15 mass% or more and a phosphorus content of 0.3 mass% or more, and the components of steelmaking slag (A) A method for treating steelmaking slag, wherein a sparingly soluble compound containing fluorine is produced by calcium contained in a mineral (B).
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