JP2005254082A - Method for controlling elution of hexavalent chromium from steel slug and material for land burial of the slug - Google Patents
Method for controlling elution of hexavalent chromium from steel slug and material for land burial of the slug Download PDFInfo
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- JP2005254082A JP2005254082A JP2004066710A JP2004066710A JP2005254082A JP 2005254082 A JP2005254082 A JP 2005254082A JP 2004066710 A JP2004066710 A JP 2004066710A JP 2004066710 A JP2004066710 A JP 2004066710A JP 2005254082 A JP2005254082 A JP 2005254082A
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000010828 elution Methods 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 29
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 27
- 239000010959 steel Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000009933 burial Methods 0.000 title abstract 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 40
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 23
- 239000010935 stainless steel Substances 0.000 claims abstract description 23
- 239000002699 waste material Substances 0.000 claims abstract description 14
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000292 calcium oxide Substances 0.000 claims abstract description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010459 dolomite Substances 0.000 claims abstract description 6
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 6
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002893 slag Substances 0.000 claims description 58
- 239000002689 soil Substances 0.000 claims description 18
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 230000001629 suppression Effects 0.000 claims description 3
- 238000007670 refining Methods 0.000 abstract description 11
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000011575 calcium Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004067 bulking agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 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
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- IQDXNHZDRQHKEF-UHFFFAOYSA-N dialuminum;dicalcium;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IQDXNHZDRQHKEF-UHFFFAOYSA-N 0.000 description 2
- 238000007922 dissolution test Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Processing Of Solid Wastes (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
- Road Paving Structures (AREA)
Abstract
Description
本発明は、ステンレス鋼の溶解・精錬の際に発生するステンレス鋼スラグからの六価クロムの溶出を抑制する技術に関する。 The present invention relates to a technique for suppressing elution of hexavalent chromium from stainless steel slag generated during melting and refining of stainless steel.
ステンレス鋼の溶解・精錬の際に発生するステンレス鋼スラグには数％のクロム酸化物を含有し、操業条件によっては六価クロムが発生する場合がある。 Stainless steel slag generated during melting and refining of stainless steel contains several percent of chromium oxide, and hexavalent chromium may be generated depending on operating conditions.
このような六価クロムを含有する鉄鋼スラグを、路盤材、土木埋立て材等に利用する場合には、該スラグから雨水、地下水に徐々に溶け出し、周辺の土壌を汚染させないことが絶対条件である。そのため、該鉄鋼スラグからの六価クロムの溶出を制御する技術が必要である。 When steel slag containing such hexavalent chromium is used for roadbed materials, civil engineering landfill materials, etc., it is an absolute condition that the slag gradually dissolves into rainwater and groundwater and does not contaminate the surrounding soil. It is. Therefore, a technique for controlling the elution of hexavalent chromium from the steel slag is necessary.
例えば、特許文献１は、ステンレス鋼の精錬時に発生した、酸化クロムを含有する塩基度１．３〜４．０の溶融スラグ中に、スラグ中硫黄濃度が０．２０質量％以上となるように０価またはマイナス価数を有する硫黄含有物質を添加する方法を提案している。また、特許文献２は、カルシウムアルミネートやカルシウムシリケートやカルシウムアルミニウムシリケートを含む粉末と、例えば石膏粉末、硫酸マグネシウム粉末、および硫酸ナトリウムの１種または２種以上からなる硫酸根を含む粉末の混合物を固定剤として用いて、カルシウムアルミネートやカルシウムシリケートやカルシウムアルミニウムシリケートを含む平均粒径が２ｍｍ以下の粉末５０〜１５０質量部と、硫酸根を含む粉末２０〜８０質量部と、クロムを含む産業廃棄物１００質量部と徐冷高炉スラグ、高炉水砕スラグ、コンクリート屑または石炭灰など増容材９００質量部以下とを混合して、クロムを含む産業廃棄物を安定化処理し、土中埋設用材料を製造する方法を提案している。 For example, Patent Document 1 discloses that a sulfur concentration in a slag is 0.20% by mass or more in a molten slag containing chromium oxide and having a basicity of 1.3 to 4.0 generated during refining of stainless steel. A method of adding a sulfur-containing substance having zero or negative valence is proposed. Patent Document 2 discloses a mixture of a powder containing calcium aluminate, calcium silicate, or calcium aluminum silicate, and a powder containing a sulfate group composed of one or more of gypsum powder, magnesium sulfate powder, and sodium sulfate, for example. Industrial waste containing calcium aluminate, calcium silicate or calcium aluminum silicate, 50 to 150 parts by weight of powder with an average particle size of 2 mm or less, 20 to 80 parts by weight of powder containing sulfate radical, and chromium as a fixing agent 100 parts by mass of slag, slow-cooled blast furnace slag, blast furnace granulated slag, 900 parts by mass or less of a bulking agent such as concrete scrap or coal ash are mixed to stabilize the industrial waste containing chromium, and buried in the soil Proposes a method of manufacturing the material.
しかし、これらの各技術にはそれぞれ下記のような問題がある。すなわち、特許文献１に記載された技術は、精錬時に製鋼スラグに硫黄含有物質を添加することによって、排滓、冷却後のステンレス鋼スラグ中から六価クロムの溶出が起こらないように、改質する方法を提案している。しかし、精錬時に硫黄含有物質を添加スラグにて改質する方法は、精錬中に硫黄含有物質を添加すると脱硫ができず溶鋼中の硫黄濃度を下げることができない。精錬後に硫黄含有物質を添加すると、条件によっては脱硫した硫黄が上昇する場合があり、またスラグに添加した硫黄含有物質が均質に混合できない場合は六価クロムを制御する本来の改質ができなくなり問題がある。また、特許文献２記載の技術においても、クロムを含む製鋼スラグ１００質量部に対して、希釈を目的とした増容材を９００質量部以下と大量に混合した上に、更にカルシウムアルミネートなどを含む固定剤を０〜１５０質量部、硫酸根を含む粉末２０〜８０質量部と混合することで六価クロムが抑制できるものである。この技術は、六価クロムを含まない増容材、およびスラグなどの六価クロム固定剤が同一製造敷地内で調達、あるいは容易に且つ安価に調達できない場合は、処理が必要な六価クロムを含むスラグの量に対して必要とする増容材、六価クロム固定剤が多量に必要となり効率が悪く経済的でない。 However, each of these technologies has the following problems. That is, the technique described in Patent Document 1 is modified by adding a sulfur-containing material to steelmaking slag during refining so that elution of hexavalent chromium does not occur from the exhausted and cooled stainless steel slag. Proposed method to do. However, the method of reforming a sulfur-containing substance with added slag at the time of refining cannot be desulfurized if the sulfur-containing substance is added during refining, and the sulfur concentration in the molten steel cannot be lowered. If sulfur-containing substances are added after refining, desulfurized sulfur may increase depending on the conditions. If the sulfur-containing substances added to the slag cannot be mixed homogeneously, the original modification to control hexavalent chromium cannot be performed. There's a problem. Also, in the technique described in Patent Document 2, with respect to 100 parts by mass of steel-making slag containing chromium, after adding a large amount of a volume-increasing material for dilution to 900 parts by mass or less, calcium aluminate or the like is further added. Hexavalent chromium can be suppressed by mixing the containing fixative with 0 to 150 parts by mass and 20 to 80 parts by mass of the powder containing sulfate radicals. In this technology, a hexavalent chromium containing no hexavalent chromium and a hexavalent chromium fixing agent such as slag can be procured on the same production site, or if it cannot be procured easily and inexpensively, hexavalent chromium that needs to be processed is obtained. A large amount of bulking agent and hexavalent chromium fixing agent required for the amount of slag to be contained are required, which is inefficient and not economical.
本発明は、かかる事情に鑑み、ステンレス鋼スラグからの六価クロムの溶出量を完全に防止する効率的、且つ安価な方法を提供することを目的としている。 In view of such circumstances, an object of the present invention is to provide an efficient and inexpensive method for completely preventing the elution amount of hexavalent chromium from stainless steel slag.
発明者は、上記目的を達成するため鋭意研究を重ね、その成果を本発明に具現化した。 The inventor has intensively studied to achieve the above object, and the results have been embodied in the present invention.
その要旨構成は次の通りである。
（１）ステンレス鋼スラグに、アルカリ土類金属を含む化合物又は／および混合物を混合することを特徴とする鉄鋼スラグからの六価クロム溶出抑制方法。
（２）アルカリ土類金属を含む化合物が、酸化カルシウム、水酸化カルシウム、硫酸カルシウム、酸化マグネシウム、水酸化マグネシウム、ドロマイトの１種以上であることを特徴とする上記鉄鋼スラグからの六価クロム溶出抑制方法。
（３）アルカリ土類金属を含む混合物が、コンクリート廃材であることを特徴とする上記鉄鋼スラグからの六価クロム溶出抑制方法。
（４）ステンレス鋼スラグとアルカリ土類金属を含む化合物又は／および混合物の混合割合は、予め任意に混合して六価クロムの溶出量を確認して決定することを特徴とする上記鉄鋼スラグからの六価クロム溶出抑制方法。
（５）ステンレス鋼スラグに、アルカリ土類金属を含む化合物又は／および混合物を混合されていることを特徴とする土中埋設用材料。
（６）アルカリ土類金属を含む化合物が、酸化カルシウム、水酸化カルシウム、硫酸カルシウム、酸化マグネシウム、水酸化マグネシウム、ドロマイトの１種以上であることを特徴とする上記土中埋設用材料。
（７）アルカリ土類金属を含む混合物が、コンクリート廃材であることを特徴とする上記土中埋設用材料。
（８）コンクリート廃材のアルカリ土類金属を含む化合物又は／および混合物の含有量が、粉体にしたコンクリート廃材１に対し１０の水に溶解した時のｐＨで１１．５から１２．５であることを特徴とする上記土中埋設用材料。
The gist composition is as follows.
(1) A method for suppressing elution of hexavalent chromium from steel slag, comprising mixing a compound or / and a mixture containing an alkaline earth metal with stainless steel slag.
(2) Hexavalent chromium elution from the steel slag, wherein the compound containing an alkaline earth metal is at least one of calcium oxide, calcium hydroxide, calcium sulfate, magnesium oxide, magnesium hydroxide and dolomite Suppression method.
(3) The method for suppressing elution of hexavalent chromium from the steel slag, wherein the mixture containing an alkaline earth metal is a waste concrete material.
(4) The mixing ratio of the compound or / and the mixture containing stainless steel slag and alkaline earth metal is determined by confirming the elution amount of hexavalent chromium by arbitrarily mixing in advance. Of hexavalent chromium elution suppression method.
(5) A material for embedding in soil, characterized in that a compound or / and a mixture containing an alkaline earth metal is mixed with stainless steel slag.
(6) The material for embedding in soil as described above, wherein the compound containing an alkaline earth metal is at least one of calcium oxide, calcium hydroxide, calcium sulfate, magnesium oxide, magnesium hydroxide and dolomite.
(7) The material for embedding in soil as described above, wherein the mixture containing an alkaline earth metal is a concrete waste material.
(8) The content of the alkaline earth metal-containing compound or / and mixture in the concrete waste material is 11.5 to 12.5 at a pH when dissolved in 10 water with respect to the concrete waste material 1 in powder form. The material for embedding in soil as described above.
本発明では、ステンレス鋼スラグから六価クロムの溶出量を環境汚染の恐れの無いレベルまで抑制し路盤材、埋立て材、海洋土木などの土中埋設物に有効利用することができる。且つアルカリ土類金属を含む混合物として、産業副生物である安価な物質をも利用するようにした利点がある。 In the present invention, the elution amount of hexavalent chromium from the stainless steel slag can be suppressed to a level at which there is no fear of environmental pollution, and can be effectively used for underground objects such as roadbed materials, landfill materials, and marine civil engineering. In addition, as a mixture containing an alkaline earth metal, there is an advantage that an inexpensive substance which is an industrial byproduct is also used.
以下、本発明の実施の形態を詳しく説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明の対象とするステンレス鋼スラグは、ステンレス鋼の溶解・精錬の際に発生するステンレス鋼スラグであって、例えば電気炉スラグ、精錬スラグ、転炉スラグ、二次精錬スラグ等である。これらのスラグは六価クロムを含む場合があり、発生したスラグのまま、路盤材あるいは埋立て材として使用した場合、雨水等の水と接触して、六価クロムが水に徐々に溶解し、土壌を汚染することがある。 The stainless steel slag targeted by the present invention is a stainless steel slag generated during melting and refining of stainless steel, such as an electric furnace slag, a refining slag, a converter slag, and a secondary refining slag. These slags may contain hexavalent chromium, and when used as roadbed materials or landfills with the generated slag, they come into contact with water such as rainwater, and hexavalent chromium gradually dissolves in the water. May contaminate the soil.
ここに本発明にかかる六価クロムの抑制方法について説明する。発明者らは六価クロムの溶出を抑制する物質を見出すために、六価クロムが溶出する鉄鋼スラグに種々の物質を混合して溶出試験を繰り返したところ、六価クロムの溶出量は、溶出溶液のｐＨと強い関係が有り、ｐＨが高く成る程溶出量が抑制できることが分かった。図１に六価クロムの溶出量とｐＨとの関係を示す。溶出溶液のｐＨが１１．５を超えると土壌環境基準である六価クロムの溶出量の０．０５ｍｇ／ｌ以下となり、１２．２以上でほぼ分析下限の０．０２ｍｇ／ｌ以下となることが分かった。またｐＨは混合する物質の量を増加してもおよそ１２．５以上は上がらなかった。 Here, the method for suppressing hexavalent chromium according to the present invention will be described. In order to find a substance that suppresses elution of hexavalent chromium, the inventors mixed various substances with steel slag from which hexavalent chromium is eluted and repeated elution tests. It was found that there is a strong relationship with the pH of the solution, and that the amount of elution can be suppressed as the pH increases. FIG. 1 shows the relationship between the elution amount of hexavalent chromium and pH. When the pH of the elution solution exceeds 11.5, the elution amount of hexavalent chromium, which is the soil environment standard, is 0.05 mg / l or less, and when it is 12.2 or more, the analysis lower limit is approximately 0.02 mg / l or less. I understood. Further, the pH did not rise above 12.5 even when the amount of the substance to be mixed was increased.
そこで、六価クロムの溶出機構を調査するために鉄鋼スラグとアルカリ土類金属を含む物質、およびこれらを１対１に混合した混合材のそれぞれの六価クロム、Ｃａ、Ｓの溶出量を分析し、併せてｐＨも測定した。表１に鉄鋼スラグとアルカリ土類金属を含む物質を混合した時の調査結果を示す。鉄鋼スラグの六価クロムの溶出量は０．４８ｍｇ／ｌ、ｐＨは１０．８であり、アルカリ土類金属を含む物質の六価クロムの溶出量は０．０２ｍｇ／ｌ以下、ｐＨは１２．１であったが、これらを１対１に混合した混合材の六価クロムは０．０３ｍｇ／ｌとそれぞれの六価クロムの溶出量の平均値よりも大幅に低減している。またｐＨは１２．０とアルカリ土類金属を含む物質とほぼ同じ値を示した。アルカリ土類金属であるＣａの溶出量は鉄鋼スラグの２６ｍｇ／ｌからアルカリ物質を混合することによって、１８１ｍｇ／ｌと大きく上昇している。また、Ｓも鉄鋼スラグの２ｍｇ／ｌ、アルカリ土類金属を含む物質が６ｍｇ／ｌに対して、これらを１対１に混合した混合材は１４ｍｇ／ｌと混合したそれぞれの材料のＳ溶出量よりも大きくなっていた。これらのことから、鉄鋼スラグにアルカリ土類金属を含む物質、例えば水溶性のＣａを含む物質を混合することによって、混合材のＣａ濃度が上昇してｐＨを上昇させ、（Ｍｎ、Ｃｒ、Ｃａ）ＳなどのＳを含む鉱物相を溶解して溶液中のＳ濃度が高くなると考えられる。六価クロムは高くなった溶液中のＳにより水に溶解しない三価クロムに還元されたものと考えられる。 Therefore, in order to investigate the elution mechanism of hexavalent chromium, the amount of elution of hexavalent chromium, Ca, and S in each of the materials containing steel slag and alkaline earth metals and a mixture of these in a one-to-one relationship was analyzed. In addition, pH was also measured. Table 1 shows the results of the investigation when a material containing steel slag and alkaline earth metal was mixed. The elution amount of hexavalent chromium in steel slag is 0.48 mg / l, pH is 10.8, the elution amount of hexavalent chromium of substances containing alkaline earth metals is 0.02 mg / l or less, and the pH is 12. Although it was 1, the hexavalent chromium of the mixed material in which these were mixed one-on-one was 0.03 mg / l, which is significantly lower than the average value of the elution amount of each hexavalent chromium. The pH was 12.0, which was almost the same value as the substance containing alkaline earth metal. The amount of Ca, which is an alkaline earth metal, is greatly increased to 181 mg / l by mixing an alkaline substance from 26 mg / l of steel slag. In addition, S is 2 mg / l of steel slag, 6 mg / l of substances containing alkaline earth metals, and mixed materials in which these are mixed in a one-to-one relationship are 14 mg / l. It was bigger than that. From these facts, by mixing a substance containing an alkaline earth metal, for example, a substance containing water-soluble Ca, into the steel slag, the Ca concentration of the mixed material is increased to raise the pH, and (Mn, Cr, Ca It is considered that the S concentration in the solution is increased by dissolving a mineral phase containing S such as S). Hexavalent chromium is considered to have been reduced to trivalent chromium that does not dissolve in water due to S in the solution.
発明者らが調査した結果、六価クロムの溶出を抑制するためには、アルカリ土類金属を含む化合物又は／および混合物を混合するのがよい。アルカリ土類金属を含む化合物が、酸化カルシウム、水酸化カルシウム、硫酸カルシウム、酸化マグネシウム、水酸化マグネシウム、ドロマイトなどの水溶性の化合物であれば１種以上複数の化合物を選択することができる。また、アルカリ土類金属を含む混合物は、コンクリート、モルタルなどのセメントを使用して製造した構造物・建築物から発生するコンクリート廃材がアルカリ土類金属を含有しており利用することができる。これらのアルカリ土類金属を含む化合物又は／および混合物の含有量は、化合物あるいは混合物を２ｍｍ以下に粉砕した材料１質量に対して１０倍の水に溶解した時のｐＨが１１．５から１２．５であることが望ましい。 As a result of investigations by the inventors, in order to suppress the elution of hexavalent chromium, it is preferable to mix a compound or / and a mixture containing an alkaline earth metal. If the compound containing an alkaline earth metal is a water-soluble compound such as calcium oxide, calcium hydroxide, calcium sulfate, magnesium oxide, magnesium hydroxide, or dolomite, one or more compounds can be selected. Moreover, the mixture containing an alkaline earth metal can be utilized because the concrete waste generated from a structure or building manufactured using cement such as concrete or mortar contains an alkaline earth metal. The content of the compound or / and mixture containing these alkaline earth metals is such that the pH when the compound or mixture is dissolved in 10 times as much water as 1 mass of the material obtained by grinding the compound or mixture to 2 mm or less is 11.5 to 12. 5 is desirable.
鉄鋼スラグとアルカリ土類金属を含む化合物又は／および混合物の混合比は、鉄鋼スラグの六価クロムの溶出量とアルカリ土類金属を含む化合物又は／および混合物に含まれるアルカリ土類金属により経済的な最適値があり、鉄鋼スラグとコンクリートなどの廃材との混合比における実施対応については、簡単な事前調査が必要である。ロット単位で、鉄鋼スラグとコンクリート廃材などの六価クロムの溶出量を把握し、これらを基に任意に３水準程度の混合比を変えて溶出試験を行なって、目標とする六価クロム溶出管理値以下となる混合を決定する事ができる。 The mixing ratio of a compound or / and mixture containing steel slag and alkaline earth metal is economical due to the elution amount of hexavalent chromium in steel slag and the alkaline earth metal contained in the compound or / and mixture containing alkaline earth metal. There is an optimal value, and a simple preliminary survey is necessary for implementation measures in the mixing ratio of steel slag and waste materials such as concrete. By grasping the elution amount of hexavalent chromium such as steel slag and concrete waste in lot units, the elution test is performed by arbitrarily changing the mixing ratio of about 3 levels based on these, and the target hexavalent chromium elution control Mixtures below the value can be determined.
これらの方法により、ステンレス鋼スラグに、アルカリ土類金属を含む化合物又は／および混合物を混合することにより、土中埋設物として土壌を汚染させる恐れはなく、路盤材、埋立て、海洋土木に使用することができる。 By using these methods, stainless steel slag is mixed with compounds or / and mixtures containing alkaline earth metals, so there is no risk of soil contamination in the soil, and it is used for roadbed materials, landfills and marine civil engineering. can do.
本発明に従い、ステンレス鋼スラグからの六価クロムの溶出を抑制した。表２に調査した供試材の組成分析値とそれらの溶出量の結果を示す。溶出試験は環境庁告示４６号で行なった。溶出試験に供した試料の粒度は環境庁告示４６号法に従い、２ｍｍ以下に調整した。試料の六価クロムの溶出量は０．４４ｍｇ／ｌであった。アルカリ土類金属を含む混合物は３種類を準備した。 According to the present invention, elution of hexavalent chromium from the stainless steel slag was suppressed. Table 2 shows the composition analysis values of the test materials investigated and the results of their elution amounts. The dissolution test was conducted according to Notification No. 46 of the Environment Agency. The particle size of the sample subjected to the dissolution test was adjusted to 2 mm or less in accordance with the Environmental Agency Notification No. 46 method. The elution amount of hexavalent chromium in the sample was 0.44 mg / l. Three types of mixtures containing alkaline earth metals were prepared.
これらの試料を用いて混合比を変化させて溶出試験を行なった。混合材の六価クロム溶出量の目標は、土壌環境基準である０．０５ｍｇ／ｌ以下をクリアすることとした。表３に本発明の実施例をまとめて示す。鉄鋼スラグ試料とアルカリ土類金属を含む化合物を用いて実施した例を本発明例１〜１３に示す。鉄鋼スラグそのままでは六価クロムが０．４４ｍｇ／ｌ溶出するが、アルカリ土類金属を含む化合物を混合することにより目標の土壌環境基準である０．０５ｍｇ／ｌ以下をクリアした。 Using these samples, the elution test was performed while changing the mixing ratio. The target for the elution amount of hexavalent chromium in the mixed material was to clear the soil environment standard of 0.05 mg / l or less. Table 3 summarizes the examples of the present invention. The example implemented using the compound containing a steel slag sample and an alkaline-earth metal is shown to this invention examples 1-13. Hexavalent chromium was eluted at 0.44 mg / l with steel slag as it was, but the target soil environment standard of 0.05 mg / l or less was cleared by mixing a compound containing an alkaline earth metal.
鉄鋼スラグ試料とコンクリート廃材を用いて実施した例を本発明例１４〜１７に示す。いずれも目標の土壌環境基準を満足することができた。 The example implemented using the steel slag sample and concrete waste material is shown to Examples 14-17 of this invention. All were able to satisfy the target soil environmental standards.
鉄鋼スラグ試料とアルカリ土類金属を含む化合物およびコンクリート廃材を用いて実施した例を本発明例１８〜２２に示す。いずれも目標の土壌環境基準を満足することができた。 The example implemented using the steel slag sample, the compound containing alkaline-earth metal, and a concrete waste material is shown to Examples 18-22 of this invention. All were able to satisfy the target soil environmental standards.
この発明は、ステンレス鋼スラグからの六価クロムの溶出を効果的に抑制する方法に関し、この技術によってステンレス鋼スラグを土中埋設用材料へ適用できる。 The present invention relates to a method for effectively suppressing elution of hexavalent chromium from stainless steel slag, and the stainless steel slag can be applied to an underground material by this technique.
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| JP2015202479A (en) * | 2014-04-16 | 2015-11-16 | 株式会社神戸製鋼所 | Method for suppressing elution of fluorine and/or hexavalent chromium |
| JP2016209846A (en) * | 2015-05-13 | 2016-12-15 | 株式会社神戸製鋼所 | Elution suppression method of hexavalent chromium, production method of material for civil engineering and port, production method of underground burying material, material for civil engineering and port and underground burying material |
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