JP2003183718A - Method for controlling elution of fluorine from steel smelting slag - Google Patents
Method for controlling elution of fluorine from steel smelting slagInfo
- Publication number
- JP2003183718A JP2003183718A JP2002224479A JP2002224479A JP2003183718A JP 2003183718 A JP2003183718 A JP 2003183718A JP 2002224479 A JP2002224479 A JP 2002224479A JP 2002224479 A JP2002224479 A JP 2002224479A JP 2003183718 A JP2003183718 A JP 2003183718A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- slag
- elution
- suppressing
- steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002893 slag Substances 0.000 title claims abstract description 142
- 239000011737 fluorine Substances 0.000 title claims abstract description 108
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 108
- 238000010828 elution Methods 0.000 title claims abstract description 51
- 238000003723 Smelting Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 28
- 239000010959 steel Substances 0.000 title claims abstract description 28
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000000843 powder Substances 0.000 claims abstract description 28
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims description 40
- 238000007670 refining Methods 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 29
- 229910001868 water Inorganic materials 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 10
- 238000009628 steelmaking Methods 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 235000012255 calcium oxide Nutrition 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000004572 hydraulic lime Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000000203 mixture Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 230000007613 environmental effect Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000002689 soil Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 6
- 239000010436 fluorite Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007922 dissolution test Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101001024616 Homo sapiens Neuroblastoma breakpoint family member 9 Proteins 0.000 description 1
- 102100037013 Neuroblastoma breakpoint family member 9 Human genes 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- -1 calcium aluminate compound Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
- C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- 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)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、フッ素を含有する
鉄鋼スラグからのフッ素溶出抑制方法に係わり、詳しく
は、土壌、海、河川等にフッ素を溶出する可能性のある
鉄鋼製錬スラグを、土木、建築材料等として有効利用で
きるように、含有するフッ素の溶出を抑制する技術に関
する。TECHNICAL FIELD The present invention relates to a method for suppressing the elution of fluorine from a steel slag containing fluorine, and more specifically, a steel smelting slag that may elute fluorine into soil, sea, rivers, etc. The present invention relates to a technology for suppressing elution of contained fluorine so that it can be effectively used as civil engineering, building materials, and the like.
【０００２】[0002]
【従来の技術】鉄鋼製錬においては、例えば、転炉装入
前に溶銑から脱珪、脱燐、脱硫処理する所謂「溶銑予備
処理」、転炉精錬、取鍋精錬、電気炉精錬等の製鋼工程
に際して、そこで発生するスラグの融点や粘性を下げて
該スラグと溶融メタルとの反応性を向上させるため、装
置に投入する副原料の一部にホタル石（ＣａＦ2）を使
用することがある。そのため、ホタル石が使用された工
程で発生するスラグには、ホタル石の使用量に応じ、不
可避的にフッ素が含有される。また、これらの製鋼スラ
グを製銑工程へ原料の一部としてリサイクルすることが
あるが、その際の高炉で生成するスラグ（以下、高炉ス
ラグという）にも不可避的にフッ素が含まれるようにな
る。2. Description of the Related Art In iron and steel smelting, for example, so-called "hot metal pretreatment" in which hot metal is desiliconized, dephosphorized, and desulfurized before charging into a converter, converter refining, ladle refining, electric furnace refining, etc. In the steelmaking process, it is possible to use fluorite (CaF 2 ) as a part of the auxiliary raw material to be fed into the apparatus in order to lower the melting point and viscosity of the slag generated there and improve the reactivity between the slag and the molten metal. is there. Therefore, fluorine is inevitably contained in the slag generated in the process in which the fluorspar is used, depending on the amount of the fluorspar used. In addition, these steelmaking slags may be recycled to the ironmaking process as a part of the raw materials, and the slag generated in the blast furnace at that time (hereinafter referred to as blast furnace slag) will inevitably contain fluorine. .
【０００３】このようなフッ素を含有する鉄鋼製錬スラ
グ（製鉄所で発生する各種スラグの総称）を、土木材料
として路盤材、土木埋立材等に有効利用すると、雨水、
地下水の作用で該スラグからフッ素が徐々に溶け出し、
周辺の土壌を汚染する可能性がある。そのため、該鉄鋼
製錬スラグからのフッ素の溶出を抑制する試みが従来よ
り幾つかなされている。When such steel smelting slag containing fluorine (general name for various slags generated in steelworks) is effectively used as a civil engineering material for roadbed materials, civil engineering landfill materials, etc., rainwater,
Fluorine gradually dissolves from the slag by the action of groundwater,
May pollute the surrounding soil. Therefore, several attempts have been made in the past to suppress the elution of fluorine from the iron and steel smelting slag.
【０００４】例えば、特開２０００−１８００７３号公
報は、フッ素を含有する製鋼スラグに、その１ｔ当たり
につき１０ｋｇ以上の割合で常温水又は温水を散布した
り、あるいは水蒸気を吹き付ける技術を開示している。
また、特開２０００−３３５９４６号公報は、フッ素固
定剤として、合成したカルシウムアルミネート化合物、
天然のカルシウムアルミネート鉱物及びカルシウムアル
ミネートを含む二次精錬スラグから選ばれた１種又は２
種以上を用い、カルシウムアルミネートを含む平均粒径
が０．５ｍｍ以下の粉末５〜８０重量部と、フッ素を含
む製鋼スラグ１００重量部と、高炉徐冷スラグ等の増容
材（希釈材でもある）３００重量部以下とを混合するこ
とで、フッ素を含む製鋼スラグを安定化処理し、土中埋
立用材料を製造する技術を提案している。For example, Japanese Unexamined Patent Publication No. 2000-180073 discloses a technique of spraying room temperature water or warm water at a rate of 10 kg or more per ton or spraying steam on a steelmaking slag containing fluorine. .
Further, JP-A-2000-335946 discloses a synthesized calcium aluminate compound as a fluorine fixing agent,
One or two selected from secondary refining slag containing natural calcium aluminate mineral and calcium aluminate
5 to 80 parts by weight of a powder containing calcium aluminate and having an average particle size of 0.5 mm or less, 100 parts by weight of steelmaking slag containing fluorine, and a volume increasing material (such as a diluting material) such as blast furnace slowly cooled slag. It proposes a technique for producing a landfill material by stabilizing the steelmaking slag containing fluorine by mixing it with 300 parts by weight or less.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、本出願
人が、これら従来技術を用いてフッ素含有鉄鋼スラグか
らのフッ素の溶出抑制を試みたところ、上記した各技術
には、それぞれ下記のような問題のあることが判明し
た。すなわち、特開２０００−１８００７３号公報記載
の技術に従って、製鋼スラグに、その１ｔあたりにつき
１０ｋｇ以上の割合で常温水又は温水を散布したり、水
蒸気の吹き付け処理をしても、環境庁告示４６号で規定
された溶出試験によるフッ素の溶出量は、処理前の約４
／５程度に低下するにとどまった。その後の調査で、こ
のような結果になった理由は、「この技術によるスラグ
からのフッ素の溶出は、急速に起きるものではなく、持
続性があって完全な溶出にはかなり長期間を要する」こ
とにあった。また、特開２０００−３３５９４６号公報
記載の技術に従い、カルシウムアルミネートを含む平均
粒径が０．５ｍｍ以下の粉末をフッ素を含む製鋼スラグ
に混合したところ、カルシウムアルミネートを含む平均
粒径が０．５ｍｍ以下の粉末をかなり多量に混合しない
と、環境庁告示４６号法に規定された溶出試験によるフ
ッ素の溶出量が環境基準値である０．８ｍｇ／リットル
（後は、記号ｌで表す）以下にならなかった。また、そ
の際の処理物には、０．５ｍｍ以下の粉末が多くなり、
ＪＩＳ Ａ５０１５の表２に規定されている路盤材の粒
度規格を満たさなくなった。従って、この技術で、路盤
材の粒度分布をその粒度規格に合致するようにするに
は、カルシウムアルミネートの他に、希釈の働きをする
増容材を別途大量に混合する必要があり、極めて不経済
になることがわかった。However, when the applicant of the present invention tried to suppress the elution of fluorine from the fluorine-containing steel slag by using these conventional techniques, each of the above techniques had the following problems. It turned out that there is. That is, according to the technique described in Japanese Patent Laid-Open No. 2000-180073, even if room temperature water or warm water is sprayed onto the steelmaking slag at a rate of 10 kg or more per 1 t, or if steam treatment is performed, environmental agency notification 46 The elution amount of fluorine in the elution test specified in 1. is about 4 before the treatment.
It fell to only about / 5. Subsequent investigations showed the reason for this result: "The leaching of fluorine from the slag by this technology is not rapid and it takes a long time to be sustained and complete leaching." I was there. Further, according to the technique described in JP-A-2000-335946, when a powder containing calcium aluminate and having an average particle size of 0.5 mm or less was mixed with steelmaking slag containing fluorine, the average particle size containing calcium aluminate was 0. Unless a large amount of powder with a size of 0.5 mm or less is mixed, the elution amount of fluorine in the elution test stipulated by the Environmental Agency Notification No. 46 is 0.8 mg / liter, which is an environmental standard value (hereinafter, represented by symbol l). It did not go below. In addition, the amount of powder of 0.5 mm or less increases in the processed product at that time,
The particle size specification of the roadbed material specified in Table 2 of JIS A5015 is no longer satisfied. Therefore, with this technology, in order to make the particle size distribution of the roadbed material conform to the particle size standard, it is necessary to separately mix a large amount of a volume increasing material that functions as a diluent in addition to calcium aluminate, It turned out to be uneconomical.
【０００６】本発明は、かかる事情に鑑み、フッ素を含
有する鉄鋼製錬スラグからのフッ素の溶出量を従来より
抑制できる安価なフッ素を含有する鉄鋼スラグからのフ
ッ素溶出抑制方法を提供することを目的としている。In view of such circumstances, the present invention provides a method for suppressing the elution of fluorine from a steel slag containing inexpensive fluorine which can suppress the elution amount of fluorine from a steel smelting slag containing fluorine as compared with the prior art. Has an aim.
【０００７】[0007]
【課題を解決するための手段】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。Means for Solving the Problems The inventor has conducted extensive studies in order to achieve the above object, and realized the results in the present invention.
【０００８】すなわち、本発明は、フッ素を含有する鉄
鋼製錬スラグに、フッ素溶出抑制物質として、高炉スラ
グ微粉末の水和固化体、クロム鉱石溶融還元炉スラグ、
含フッ素物質を使用しない二次精錬より排出される二次
精錬スラグ（以下、フッ素非含有の二次精錬スラグとい
う）及びゴミ固形化燃料の炭化物から選ばれる１種又は
２種以上を混合することを特徴とするフッ素を含有する
鉄鋼スラグからのフッ素溶出抑制方法である。この場
合、前記フッ素を含有する鉄鋼製錬スラグのうちの粒径
２ｍｍ以下のもの１００質量部に対し、前記高炉スラグ
微粉末の水和固化体、クロム鉱石溶融還元炉スラグ、フ
ッ素非含有の二次精錬スラグ及び多孔質の炭化物から選
ばれた１種又は２種以上の粒径が２ｍｍ以下のものの混
合量を５〜４００質量部とするのが良く、また、前記高
炉スラグ微粉末の水和固化体が、高炉スラグ微粉末に水
及び生石灰、消石灰、製鋼スラグ及びアルカリ刺激剤の
うちの１種又は２種以上を加え、混練、固化、破砕して
製造したものであると一層良い。クロム鉱石溶融還元炉
スラグ及びフッ素非含有の二次精錬スラグは、所定の化
学組成範囲内のものを用いると良い。さらに、多孔質の
炭化物が廃棄物固形化燃料の炭化物であることが一層好
ましい。That is, the present invention relates to a smelting slag of iron and steel containing fluorine, which comprises a hydrated solidified blast furnace slag fine powder, a chromium ore smelting reduction furnace slag, as a fluorine elution suppressing substance.
Mixing one or more selected from secondary refining slag discharged from secondary refining that does not use fluorine-containing substances (hereinafter referred to as fluorine-free secondary refining slag) and carbide of waste solidified fuel. Is a method for suppressing the elution of fluorine from a steel slag containing fluorine. In this case, with respect to 100 parts by mass of the steel smelting slag containing fluorine having a particle diameter of 2 mm or less, a hydrated solidified product of the blast furnace slag fine powder, a chromium ore melting reduction furnace slag, and a fluorine-free two The amount of one or more selected from the following refining slag and porous carbides having a particle size of 2 mm or less is preferably 5 to 400 parts by mass, and the blast furnace slag fine powder is hydrated. It is more preferable that the solidified body is manufactured by adding water and one or more kinds of water and quick lime, slaked lime, steelmaking slag and alkali stimulant to fine powder of blast furnace slag, kneading, solidifying and crushing. As the chromium ore smelting reduction furnace slag and the fluorine-free secondary refining slag, those having a predetermined chemical composition range may be used. Furthermore, it is more preferable that the porous carbide is the carbide of the waste solidified fuel.
【０００９】本発明では、フッ素の溶出抑制物質とし
て、産業副生物である安価な物質を利用するようにした
ので、鉄鋼製錬スラグからのフッ素溶出の防止を安価に
行えるという利点があるのにとどまらず、フッ素溶出量
を従来に比較してより低いレベルまで抑制することがで
き、且つそのような効果を半永久的に持続することを可
能とした。In the present invention, an inexpensive substance which is an industrial by-product is used as the substance for suppressing the elution of fluorine, so that there is an advantage that the elution of fluorine from the iron and steel smelting slag can be prevented at a low cost. Not only that, it was possible to suppress the amount of fluorine elution to a lower level as compared with the conventional one, and it was possible to sustain such an effect semipermanently.
【００１０】[0010]
【発明の実施の形態】以下、発明をなすに至った経緯に
沿い、本発明の実施の形態を詳しく説明する。BEST MODE FOR CARRYING OUT THE INVENTION The embodiments of the present invention will be described in detail below along with the background of the invention.
【００１１】本発明の対象とする鉄鋼製錬スラグは、製
錬工程でホタル石等が使用されたため、フッ素を含有す
ることになった鉄鋼製錬スラグであって、例えば、溶銑
予備処理工程で発生した脱珪スラグ、脱燐スラグ、脱硫
スラグや溶鋼の溶製時に発生した転炉スラグ、電気炉ス
ラグ、脱炭プロセス以降の所謂「二次精錬」工程、つま
り溶鋼の真空精錬、取鍋精錬等で発生した二次精錬スラ
グ、ステンレス鋼の溶製で発生するステンレス精錬スラ
グ等である。これらのスラグはいずれもフッ素を含むこ
とが多く、雨水等の水と接触すると、フッ素が水に徐々
に溶解する。The iron and steel smelting slag which is the object of the present invention is a smelting iron and steel slag which contains fluorine because the fluorite is used in the smelting process. Desiliconization slag generated, dephosphorization slag, converter slag generated during melting of desulfurization slag and molten steel, electric furnace slag, so-called "secondary refining" process after decarburization process, that is, vacuum refining of molten steel, ladle refining Secondary refining slag generated by the above, stainless steel refining slag generated by melting of stainless steel, and the like. All of these slags often contain fluorine, and when they come into contact with water such as rainwater, the fluorine gradually dissolves in the water.
【００１２】そこで、発明者は、図１に示すように、底
部に貫通孔１を設けた筒状容器２からなる溶出試験装置
を製作し、この装置内にフッ素を含む溶銑予備処理スラ
グに種々の物質を混合したものを充填し、上から水をか
け、前記貫通孔１から留出する水中への該混合物からの
フッ素の溶出状況を調査した。なお、この試験に用いた
溶銑予備処理スラグの最大粒径は４０ｍｍであり、また
混合した物質は、いずれも粒度を２ｍｍ以下とした。こ
こで、前記溶出試験装置は、内径１００ｍｍφ、深さ１
８０ｍｍの円筒状容器である。また、試験方法は、この
溶銑予備処理スラグと２ｍｍ以下の物質を所定量混合し
てから、その混合物（１．５ｋｇ程度）３に上方から１
００ｍｍφの面積に対する約２年分の降雨量に相当する
２５リットルの蒸留水４を７日間にわたって連続的に送
水し、下部から流れ出る水（流出水５という）のフッ素
濃度を調べた。Therefore, the inventor manufactured an elution test apparatus comprising a cylindrical container 2 having a through hole 1 at the bottom thereof as shown in FIG. 1, and various kinds of molten iron pretreatment slag containing fluorine were manufactured in the apparatus. The mixture of the substances of No. 1 was filled, water was poured from above, and the elution state of fluorine from the mixture into the water distilled from the through hole 1 was investigated. The maximum particle size of the hot metal pretreatment slag used in this test was 40 mm, and all the mixed substances had a particle size of 2 mm or less. Here, the dissolution test apparatus has an inner diameter of 100 mmφ and a depth of 1
It is an 80 mm cylindrical container. In addition, the test method was to mix a predetermined amount of this hot metal pretreatment slag with a substance of 2 mm or less, and then add 1 to the mixture (about 1.5 kg) from above.
Twenty-five liters of distilled water 4 corresponding to the rainfall of about two years for an area of 00 mmφ was continuously fed over 7 days, and the fluorine concentration of the water flowing out from the lower part (called outflow water 5) was examined.
【００１３】混合した物質を、高炉スラグ微粉末の固化
体、クロム鉱石溶融還元炉スラグ、フッ素非含有で、且
つＡｌ2Ｏ3の含有量が５〜２１ｍａｓｓ％の二次精錬ス
ラグ及び廃棄物固形化燃料の炭化物とした実験例の結果
を、図２，図３，図４，図５及び図６にそれぞれ示す。
これらの図より、溶銑予備処理スラグに何も混合しない
と、約２年分の降雨量に相当する多量の蒸留水４を供給
しても、該溶銑予備処理スラグからフッ素が溶出し続け
ることが明らかである。これに対して、高炉スラグ微粉
末の固化体、クロム鉱石溶融還元炉スラグ、フッ素非含
有の二次精錬スラグ及び廃棄物固形化燃料の炭化物を混
合した場合には、フッ素の溶出が抑制されることがわか
る。この理由を詳細に調べたところ、フッ素を含む溶銑
予備処理スラグから溶出したフッ素が、高炉スラグ微粉
末の固化体、クロム鉱石溶融還元炉スラグ等と化学反応
及び／又は吸着反応することがわかった。そこで、これ
らの物資をフッ素溶出抑制物質（以下、溶出抑制物質と
いう）としてフッ素を含有する鉄鋼製錬スラグ（以下、
含フッ素スラグという）に混合することで、本発明を完
成させたのである。The mixed substances are solidified blast furnace slag powder, chromium ore smelting reduction furnace slag, fluorine-free secondary refining slag having an Al 2 O 3 content of 5 to 21 mass% and solid waste. The results of the experimental examples in which the carbonized fuel is used are shown in FIGS. 2, 3, 4, 5, and 6, respectively.
From these figures, if nothing is mixed with the hot metal pretreatment slag, even if a large amount of distilled water 4 corresponding to the rainfall for about two years is supplied, fluorine will continue to be eluted from the hot metal pretreatment slag. it is obvious. On the other hand, when solidified blast furnace slag fine powder, chromium ore smelting reduction furnace slag, fluorine-free secondary refining slag and carbide of waste solidified fuel are mixed, the elution of fluorine is suppressed. I understand. A detailed examination of the reason revealed that the fluorine eluted from the hot metal pretreatment slag containing fluorine chemically reacts and / or adsorbs with the solidified blast furnace slag powder, the chromium ore smelting reduction furnace slag, etc. . Therefore, these materials are used as a fluorine elution suppressing substance (hereinafter, referred to as an elution suppressing substance), and a steel smelting slag containing fluorine (hereinafter,
The present invention has been completed by mixing it with fluorine-containing slag).
【００１４】ここで、溶出抑制物質の一つである高炉ス
ラグ微粉末の固化体は、高炉スラグ微粉末に水を加え、
混練、固化、破砕して製造したものである。この固化体
を得るには、高炉スラグ微粉末に水を加え混練する際
に、高炉スラグ微粉末に対し０．１〜１０質量％の消石
灰、あるいは生石灰、微粉の製鋼スラグ及びセメント等
のアルカリ刺激剤のうちの１種又は２種以上を添加す
る。また、使用する高炉スラグ微粉末は、高炉水砕スラ
グを粉砕したものであり、その粒径や比表面積は特に限
定しないが、ブレーン法による比表面積が３０００〜５
０００ｃｍ2／ｇであることが好ましい。さらに、水和
して得た固化体の強度等の物理的持性も特に限定しな
い。水和固化体の物理的特性とフッ素の溶出抑制効果と
は特に相関性が見られず、固まってさえいれば、十分だ
からである。逆に圧縮強度が１０Ｎ／ｍｍ2よりも高く
なると破砕し難くなるために、好ましくない。さらに、
高炉微粉末に対して内割りで最大５０質量％のフライア
ッシュを配分しても良い。フライアッシュは、ＪＩＳ
Ａ ６２０１に規格化されているＩ〜ＶＩ種を用いると
好ましい。Here, the solidified body of the blast furnace slag fine powder, which is one of the dissolution suppressing substances, is prepared by adding water to the blast furnace slag fine powder.
It is produced by kneading, solidifying and crushing. To obtain this solidified body, when water is added to the blast furnace slag fine powder and kneading, 0.1 to 10% by mass of slaked lime, or quick lime, steel slag of fine powder, and alkali stimulation of cement, etc. are added to the blast furnace slag fine powder. One or more of the agents are added. The blast furnace slag fine powder used is crushed granulated blast furnace slag, and its particle size and specific surface area are not particularly limited, but the specific surface area by the Blaine method is 3000 to 5
It is preferably 000 cm 2 / g. Further, the physical properties such as strength of the solidified product obtained by hydration are not particularly limited. This is because there is no particular correlation between the physical properties of the hydrated and solidified product and the effect of suppressing the elution of fluorine, and it is sufficient if it solidifies. On the contrary, if the compressive strength is higher than 10 N / mm 2, it is difficult to crush, which is not preferable. further,
A maximum of 50% by mass of fly ash may be distributed in the blast furnace fine powder. Fly ash is JIS
It is preferable to use the I to VI types standardized in A6201.
【００１５】また、同様に本発明で使用するクロム鉱石
溶融還元炉スラグは、クロム鉱石を転炉型の溶融還元炉
によって溶融状態で還元する際に発生するスラグであ
り、化学組成は、おおよそＣａＯ：３３〜５０ｍａｓｓ
％、ＳｉＯ2：１１〜２５ｍａｓｓ％、Ａｌ2Ｏ3：１０
〜２７ｍａｓｓ％、ＭｇＯ：１０〜２７ｍａｓｓ％、Ｔ
ｏｔａｌ Ｆｅ：０．３〜５ｍａｓｓ％である。なお、
この範囲内であれば、フッ素の溶出抑制効果はほとんど
変わらない。Similarly, the chromium ore smelting reduction furnace slag used in the present invention is a slag generated when chromium ore is reduced in a molten state by a converter-type smelting reduction furnace, and its chemical composition is approximately CaO. : 33-50 mass
%, SiO 2: 11~25mass%, Al 2 O 3: 10
~ 27 mass%, MgO: 10-27 mass%, T
total Fe: 0.3 to 5 mass%. In addition,
Within this range, the effect of suppressing the elution of fluorine hardly changes.
【００１６】同様に本発明で使用する二次精錬スラグ
は、転炉精錬（主として脱炭精錬）や電気炉精錬を実施
した以降の工程で生じたスラグであり、ＲＨ法、ＶＯＤ
法、ＬＦ法等種々の二次精錬工程において発生するスラ
グである。本発明では、これらの二次精錬において、ホ
タル石等の含フッ素物質をスラグ改質材として使用せず
に精錬を行うと、このような二次精錬法におけるスラグ
は、Ａｌ脱酸、Ａｌ昇熱のための金属Ａｌの添加、ある
いは脱酸、脱Ｓ等において高い精錬能を有する高塩基度
スラグの溶融促進・低粘性化のためのバンド頁岩等のＡ
ｌ2Ｏ3源の添加によって、Ａｌ2Ｏ3の含有量が５〜１３
ｍａｓｓ％及び１３〜２１ｍａｓｓ％に大別できる。そ
して、Ａｌ2Ｏ3の含有量がこの範囲内であれば、フッ素
の溶出抑制効果は十分に認められることもわかった。Similarly, the secondary refining slag used in the present invention is a slag produced in the steps subsequent to the converter refining (mainly decarburization refining) and the electric furnace refining, and the RH method and VOD.
Slag that is generated in various secondary refining processes such as the method and the LF method. In the present invention, in these secondary refining, when refining is carried out without using a fluorine-containing substance such as fluorite as a slag modifier, the slag in such a secondary refining method is Al deoxidized and Al promoted. A of band shale, etc. for promoting melting and reducing viscosity of high basicity slag which has high refining ability in addition of metallic Al for heat or deoxidation and de-S
With the addition of a source of 1 2 O 3, the content of Al 2 O 3 is 5 to 13
It can be roughly divided into mass% and 13 to 21 mass%. It was also found that when the content of Al 2 O 3 is within this range, the effect of suppressing the elution of fluorine is sufficiently observed.
【００１７】さらに、多孔質の炭化物としては、安価で
多量に入手できる廃棄物固形化燃料の炭化物を用いるの
が好ましい。該廃棄物固形化燃料は、産業廃棄物の有効
利用の観点で最近開発されている都市ゴミ（生ゴミを含
む）を粉砕、乾燥してから成形（例えば、円筒状等）し
たものであり、本発明では、それを蒸し焼きにして炭化
したものを使用するのが良い。この炭化物の化学組成
は、ゴミの種類により大きく変わるが、主成分は炭素で
あり、多孔質であって比表面積は１００〜５００ｍ2／
ｇである。なお、フッ素の溶出抑制効果は、ゴミの種類
によって大きく変わるものではない。Further, as the porous carbide, it is preferable to use the carbide of the waste solidified fuel which is inexpensive and can be obtained in a large amount. The waste solidified fuel is obtained by crushing municipal waste (including raw garbage) recently developed from the viewpoint of effective utilization of industrial waste, drying it, and then molding (for example, cylindrical), In the present invention, it is preferable to use the one that is steamed and carbonized. The chemical composition of this carbide varies greatly depending on the type of dust, but the main component is carbon, which is porous and has a specific surface area of 100 to 500 m 2 /
It is g. The effect of suppressing the elution of fluorine does not change greatly depending on the type of dust.
【００１８】加えて、本発明では、これらの物質を１種
又は２種以上を、含フッ素スラグに混合するが、いずれ
を選択するかについては、特に定めない。混合効果や経
済性を事前に調査し、決定すれば良いからである。In addition, in the present invention, one or more of these substances are mixed with the fluorine-containing slag, but which one is selected is not particularly specified. This is because the effects of mixing and economics should be investigated and determined in advance.
【００１９】ところで、これらの溶出抑制物質の含フッ
素スラグへの混合量は、本発明では、該スラグのフッ素
溶出量に応じて決めるのが好ましい。例えば、環境庁告
示４６号による溶出試験において２ｍｇ／ｌのフッ素が
溶出する含フッ素スラグを、本発明に係る溶出抑制物質
と混合することで環境基準値以下である０．８ｍｇ／ｌ
以下にするには、該溶出抑制物質を約５質量部以上混合
する必要があり、１０ｍｇ／ｌのフッ素が溶出するスラ
グでは、含フッ素スラグ１００質量部に対して約２０質
量部以上混合する必要がある。具体的には、前記含フッ
素スラグのうちの粒径２ｍｍ以下のもの１００質量部に
対し、前記高炉スラグ微粉末の水和固化体、クロム鉱石
溶融還元炉スラグ及び廃棄物固形化燃料の炭化物から選
ばれた１種又は２種以上の粒径が２ｍｍ以下のものの混
合量を５〜４００質量部とするのが良い。その理由は、
溶出抑制物質の混合量が、５質量部未満では溶出の抑制
効果が小さく、４００質量部を超えると、経済的でなく
なるためである。By the way, in the present invention, the amount of these elution suppressing substances mixed with the fluorine-containing slag is preferably determined according to the amount of fluorine elution of the slag. For example, a fluorine-containing slag capable of eluting 2 mg / l of fluorine in an elution test according to the Environmental Agency Notification No. 46 is mixed with the elution suppressing substance according to the present invention to be 0.8 mg / l or less, which is an environmental standard value or less.
In order to achieve the following, it is necessary to mix the elution suppressing substance in an amount of about 5 parts by mass or more, and in a slag in which 10 mg / l of fluorine is eluted, it is necessary to mix about 20 parts by mass or more with respect to 100 parts by mass of the fluorine-containing slag. There is. Specifically, from 100 parts by mass of the fluorine-containing slag having a particle size of 2 mm or less, a hydrated solidified body of the blast furnace slag fine powder, a chrome ore smelting reduction furnace slag, and a carbide of waste solidified fuel are used. It is preferable that the mixing amount of one or more selected particles having a particle diameter of 2 mm or less is 5 to 400 parts by mass. The reason is,
This is because if the mixing amount of the dissolution inhibiting substance is less than 5 parts by mass, the effect of suppressing dissolution is small, and if it exceeds 400 parts by mass, it becomes uneconomical.
【００２０】また、対象となる含フッ素スラグと前記溶
出抑制物質との混合物の粒径を２ｍｍ以下としたのは、
粒径２ｍｍ以下のものが溶出に及ぼす影響が圧倒的に大
きく、スラグからのフッ素の溶出は実質的に、そのよう
な粒径のものに支配されており、しかも環境庁告示４６
号法による溶出試験も粒径２ｍｍ以下の粒子で行なうた
めである。なお、本発明では、粒径が２ｍｍを超える粒
子を含むことを制限するものではない。例えば、含フッ
素スラグと溶出抑制物質とを混合して路盤材として使用
する場合、該路盤材は、通常粒径４０ｍｍ以下又は２５
ｍｍ以下で、粒度分布がＪＩＳ Ａ ５０１５により規
定されており、粒径２ｍｍを超える粒子を含むのは当然
だからである。The particle size of the mixture of the target fluorine-containing slag and the dissolution inhibiting substance is set to 2 mm or less,
The particle size of 2 mm or less has an overwhelming effect on elution, and the elution of fluorine from the slag is substantially controlled by such particle size.
This is because the dissolution test by the No. method is also performed on particles having a particle size of 2 mm or less. Note that the present invention does not limit inclusion of particles having a particle size of more than 2 mm. For example, when a fluorine-containing slag and an elution suppressing substance are mixed and used as a roadbed material, the roadbed material usually has a particle diameter of 40 mm or less or 25
This is because the particle size distribution is specified by JIS A 5015 when the size is less than or equal to mm, and it is natural that particles including a particle size exceeding 2 mm are included.
【００２１】[0021]
【実施例】本発明に係る含フッ素スラグからのフッ素溶
出抑制方法を実際に行った。その含フッ素スラグとして
は、環境庁告示４６号によるフッ素の溶出量が２．１ｍ
ｇ／ｌ（試料Ａ）及び１０．５ｍｇ／ｌ（試料Ｂ）で、
粒径を４０ｍｍ以下に破砕した溶銑予備処理スラグを用
いた。溶出抑制物質としては、表１に示す組成の高炉ス
ラグ微粉末の固化体、クロム鉱石溶融還元炉スラグ、フ
ッ素非含有の二次精錬スラグ（試料Ｃ，Ｄ，Ｅ）及び廃
棄物固形化燃料の炭化物（比表面積１４０ｍ 2／ｇ）を
用いた。高炉スラグ微粉末の固化体は、ブレーン法によ
る比表面積が４０００ｃｍ2／ｇの高炉スラグ微粉末９
９質量部に、消石灰：１質量部、水道水：４０質量部を
加えて混練・打設・破砕したものである。これらの含フ
ッ素スラグと溶出抑制物質とを表１に示す質量比で混合
した後、環境庁告示４６号による溶出試験を行い、フッ
素の溶出量を調べた。なお、混合は、連続式混合装置を
用い、１水準当りの全混合物の量は１００〜１０００ト
ンである。[Examples] Fluorine dissolution from fluorine-containing slag according to the present invention
The output control method was actually performed. As the fluorine-containing slag
Has a fluorine elution amount of 2.1 m according to the Environmental Agency Notification No. 46.
g / l (Sample A) and 10.5 mg / l (Sample B),
Uses hot metal pretreatment slag crushed to a particle size of 40 mm or less
I was there. As the elution suppressing substance, blast furnace soot having the composition shown in Table 1 is used.
Solidified lag powder, chromium ore smelting reduction furnace slag, flux
Secondary refining slag containing no fluorine (Samples C, D, E) and waste
Waste solidified fuel carbide (specific surface area 140 m 2/ G)
Using. The solidified blast furnace slag powder is produced by the Blaine method.
With a specific surface area of 4000 cm2/ G blast furnace slag fine powder 9
To 9 parts by mass, slaked lime: 1 part by mass, tap water: 40 parts by mass
In addition, it is kneaded, cast, and crushed. These include
Fluorine slag and elution suppressing substance are mixed in the mass ratio shown in Table 1.
After that, perform a dissolution test according to the Environmental Agency Notification No. 46, and
The elution amount of the element was examined. For mixing, use a continuous mixer.
The total amount of the mixture per level is 100 to 1000 tons.
It is
【００２２】[0022]
【表１】 [Table 1]
【００２３】実施成績を表２及び表３に一括して示す。
これらの表より、本発明に係るフッ素含有鉄鋼スラグの
安定化方法を適用して、含フッ素スラグ１００重量部に
溶出抑制物質を５〜４００重量部を混合することで、混
合物全体が土壌環境基準である０．８ｍｇ／ｌ以下をク
リアすることが明らかである。The results of implementation are collectively shown in Tables 2 and 3.
From these tables, by applying the method for stabilizing a fluorine-containing steel slag according to the present invention, by mixing 5 to 400 parts by weight of the elution suppressing substance with 100 parts by weight of the fluorine-containing slag, the entire mixture is a soil environmental standard. It is clear that the value of 0.8 mg / l or less is cleared.
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【表３】 [Table 3]
【００２６】また、溶出抑制物質を複数種混合添加した
場合の実施成績を表４に一括して示す。これら混合物の
添加により、混合物全体が土壌環境基準である０．８ｍ
ｇ／１以下をクリアすることが明らかである。Table 4 collectively shows the results of implementation when a plurality of types of dissolution inhibiting substances were mixed and added. With the addition of these mixtures, the entire mixture is 0.8m, which is the soil environmental standard.
It is clear that it clears g / 1 or less.
【００２７】[0027]
【表４】 [Table 4]
【００２８】これに対して、その他の物質を、含フッ素
スラグに混合する試験も行った。その際、混合物を路盤
材、仮設材として使用する場合を想定し、その周辺土壌
を含フッ素スラグに混合する物質とした。さらに、Ａｌ
2Ｏ3の含有量が３ｍａｓｓ％のフッ素非含有の二次精錬
スラグ（試料Ｅ）についても合わせて評価した。その結
果を表５に一括して示す。表５より明らかなように、こ
れらの例による混合物は、混合する物質が関東ローム
層、黒土等の所謂「土」である場合、増容効果を若干示
すが、土壌環境基準にはほど遠い結果である。また、混
合する物質が川砂、山砂等の所謂「砂」である場合に
は、溶出抑制効果がまったく無く、さらに増容材として
の効果も期待できないことも確認された。さらに、高炉
徐冷スラグも溶出抑制物質に代えて使用し難いことがわ
かった。Ａｌ2Ｏ3の含有量が低い二次精錬スラグは、上
記土壌環境基準はクリアできないが、溶出抑制効果は見
られる。On the other hand, a test of mixing other substances with the fluorine-containing slag was also conducted. At that time, assuming that the mixture was used as a roadbed material or a temporary construction material, the surrounding soil was used as a substance to be mixed with the fluorine-containing slag. Furthermore, Al
A fluorine-free secondary refining slag (Sample E) having a 2 O 3 content of 3 mass% was also evaluated. The results are collectively shown in Table 5. As is clear from Table 5, when the substances to be mixed are so-called “soil” such as Kanto loam layer and black soil, the volume increase effect is slightly shown, but the results are far from the soil environmental standard. is there. It was also confirmed that when the substance to be mixed is so-called "sand" such as river sand and mountain sand, there is no elution suppressing effect and no effect as a volume increasing material can be expected. Further, it was found that blast furnace slowly cooled slag is also difficult to use in place of the dissolution inhibiting substance. Secondary refining slag with a low content of Al 2 O 3 cannot satisfy the above-mentioned soil environmental standards, but an elution suppressing effect is seen.
【００２９】また、上記の例において示すことのなかっ
たＡｌ2Ｏ3の含有量が２１ｍａｓｓ％を超えるようなフ
ッ素非含有の二次精錬スラグは、フッ素の溶出抑制効果
はあるが、それ自体が発生することが稀で、本来の二次
精錬用スラグの機能・効用を超えて、意図的にＡｌ2Ｏ3
分を添加しなくては入手できない。さらに、そのような
スラグ発生量を増やすのは、経済的に引き合うものでは
ない。Fluorine-free secondary refining slag having an Al 2 O 3 content of more than 21 mass%, which has not been shown in the above example, has an effect of suppressing the elution of fluorine, but is itself. Rarely generated, beyond the original function and effect of secondary refining slag, intentionally Al 2 O 3
Not available without the addition of minutes. Furthermore, increasing the amount of such slag generated is not economically attractive.
【００３０】[0030]
【表５】 [Table 5]
【００３１】[0031]
【発明の効果】以上述べたように、本発明により、フッ
素を含有する鉄鋼製錬スラグからのフッ素の溶出を効果
的で、且つ経済的に抑制できることとなった。As described above, according to the present invention, it has become possible to effectively and economically suppress the elution of fluorine from a steel-smelting slag containing fluorine.
【図１】フッ素溶出試験を行った試験装置を示す横断面
図である。FIG. 1 is a cross-sectional view showing a test device that has been subjected to a fluorine elution test.
【図２】含フッ素スラグに混合する物質を高炉微粉末の
水和固化体とした場合の実験装置から流出する水中のフ
ッ素濃度と積算送水量との関係を示す図である。FIG. 2 is a diagram showing the relationship between the concentration of fluorine in water flowing out from the experimental apparatus and the cumulative amount of water fed when the substance mixed with the fluorine-containing slag is a hydrated solidified body of blast furnace fine powder.
【図３】含フッ素スラグに混合する物質をクロム鉱石溶
融還元炉スラグとした場合に、実験装置から流出する水
中のフッ素濃度と積算送水量との関係を示す図である。FIG. 3 is a diagram showing a relationship between a fluorine concentration in water flowing out from an experimental apparatus and an integrated water supply amount when a substance mixed with a fluorine-containing slag is a chromium ore smelting reduction furnace slag.
【図４】含フッ素スラグに混合する物質をフッ素非含有
で、Ａｌ2Ｏ3含有量が５ｍａｓｓ％の二次精錬スラグと
した場合の実験装置から流出する水中のフッ素濃度と積
算送水量との関係を示す図である。FIG. 4 shows the fluorine concentration in the water flowing out from the experimental apparatus and the cumulative amount of water transferred when the substance to be mixed with the fluorine-containing slag is fluorine-free and the secondary refining slag has an Al 2 O 3 content of 5 mass%. It is a figure which shows a relationship.
【図５】含フッ素スラグに混合する物質をフッ素非含有
で、Ａｌ2Ｏ3の含有量が２１ｍａｓｓ％の二次精錬スラ
グとした場合の実験装置流出水中フッ素濃度と積算送水
量との関係を示す図である。FIG. 5 shows the relationship between the fluorine concentration in the experimental equipment effluent and the cumulative amount of water fed when the substance to be mixed with the fluorine-containing slag is fluorine-free and the secondary refining slag has an Al 2 O 3 content of 21 mass%. FIG.
【図６】含フッ素スラグに混合する物質を廃棄物固形化
燃料の炭化物とした場合の実験装置から流出する水中の
フッ素濃度と積算送水量との関係を示す図である。FIG. 6 is a diagram showing a relationship between a fluorine concentration in water flowing out from an experimental apparatus and an integrated water supply amount when a substance mixed with a fluorine-containing slag is a carbide of a waste solidified fuel.
１ 貫通孔 ２ 筒状容器 ３ 混合物 ４ 蒸留水 ５ 流出水 1 through hole 2 cylindrical containers 3 mixture 4 distilled water 5 runoff water
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２１Ｃ 1/02 Ｃ２１Ｃ 7/00 Ｊ 5/54 Ｂ０９Ｂ 3/00 ３０４Ｃ 7/00 Ｚ 5/00 Ｊ (72)発明者 高木 正人 千葉県千葉市中央区川崎町１番地 川崎製 鉄株式会社技術研究所内 (72)発明者 宇田川 悦郎 千葉県千葉市中央区新浜町１番地 川鉄鉱 業株式会社技術研究所内 Ｆターム(参考） 4D004 AA43 AB08 AC05 BA02 CA04 CA34 CA45 CC11 CC13 DA03 DA10 4G012 JD02 JD03 JE02 4K013 CF01 4K014 AE01 CE01 4K070 AB11 BC13 BC14 EA10 EA14─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C21C 1/02 C21C 7/00 J 5/54 B09B 3/00 304C 7/00 Z 5/00 J (72 ) Masato Takagi, 1 Kawasaki-cho, Chuo-ku, Chiba, Chiba Prefecture, Technical Research Laboratory, Kawasaki Steel Co., Ltd. (72) Etsuro Udagawa, Niihama-cho, Chuo-ku, Chiba, Chiba Prefecture, F-Term, Technical Research Laboratory, Kawatetsu Mining Co., Ltd. (Reference) 4D004 AA43 AB08 AC05 BA02 CA04 CA34 CA45 CC11 CC13 DA03 DA10 4G012 JD02 JD03 JE02 4K013 CF01 4K014 AE01 CE01 4K070 AB11 BC13 BC14 EA10 EA14
Claims (5)
ッ素溶出抑制物質として、高炉スラグ微粉末の水和固化
体、クロム鉱石溶融還元炉スラグ、含フッ素物質を使用
しない二次精錬より排出される二次精錬スラグ及び多孔
質の炭化物から選ばれる１種又は２種以上を混合するこ
とを特徴とするフッ素を含有する鉄鋼製錬スラグからの
フッ素溶出抑制方法。1. A smelting slag containing fluorine, which is discharged from a hydrated solidified product of blast furnace slag fine powder, a smelting reduction furnace for chromium ore slag, and a secondary refining that does not use a fluorine-containing substance, as a substance for suppressing the elution of fluorine. A method for suppressing elution of fluorine from fluorine-containing steel smelting slag, which comprises mixing one or more selected from secondary refining slag and porous carbide.
うちの粒径２ｍｍ以下のもの１００質量部に対し、前記
高炉スラグ微粉末の水和固化体、クロム鉱石溶融還元炉
スラグ、含フッ素物質を使用しない二次精錬より排出さ
れる二次精錬スラグ及び多孔質の炭化物から選ばれた１
種又は２種以上の粒径が２ｍｍ以下のものの混合量を５
〜４００質量部とすることを特徴とする請求項１記載の
フッ素を含有する鉄鋼スラグからのフッ素溶出抑制方
法。2. A hydrated solidified product of the blast furnace slag fine powder, a chromium ore smelting reduction furnace slag, and a fluorine-containing substance with respect to 100 parts by mass of a particle size of 2 mm or less of the fluorine-containing iron and steel smelting slag. 1 selected from secondary refining slag and porous carbide discharged from secondary refining that does not use
5 or more kinds of particles having a particle size of 2 mm or less
To 400 parts by mass, the method for suppressing the elution of fluorine from fluorine-containing steel slag according to claim 1.
高炉スラグ微粉末に水及び生石灰、消石灰、製鋼スラグ
及びアルカリ刺激剤のうちの１種又は２種以上を加え、
混練、固化、破砕して製造したものであることを特徴と
する請求項１又は２記載のフッ素を含有する鉄鋼スラグ
からのフッ素溶出抑制方法。3. A hydrated solidified body of the blast furnace slag fine powder,
Add one or more of water and quick lime, slaked lime, steelmaking slag and alkali stimulant to blast furnace slag fine powder,
The method for suppressing the elution of fluorine from a steel slag containing fluorine according to claim 1 or 2, which is produced by kneading, solidifying and crushing.
より排出される二次精錬スラグは、Ａｌ2Ｏ3の含有量が
５〜２１ｍａｓｓ％の範囲であることを特徴とする請求
項１〜３のいずれか記載のフッ素を含有する鉄鋼スラグ
からのフッ素溶出抑制方法。4. The secondary refining slag discharged from the secondary refining which does not use the fluorine-containing substance, wherein the content of Al 2 O 3 is in the range of 5 to 21 mass%. 3. A method for suppressing elution of fluorine from a steel slag containing fluorine according to any one of 3 above.
料の炭化物であることを特徴とする請求項１〜４のいず
れか記載のフッ素を含有する鉄鋼スラグからのフッ素溶
出抑制方法。5. The method for suppressing elution of fluorine from a steel slag containing fluorine according to claim 1, wherein the porous carbide is a carbide of waste solidified fuel.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005239509A (en) * | 2004-02-27 | 2005-09-08 | Nippon Steel & Sumikin Stainless Steel Corp | Method for controlling elution of fluorine from steel slag and underground burying material |
| JP2006241429A (en) * | 2005-02-07 | 2006-09-14 | Fujita Corp | Soil-improving material and engineering method for improving soil |
| JP2007022818A (en) * | 2005-07-12 | 2007-02-01 | Nippon Steel Corp | Method of treating fluorine-containing steel making slag |
| JP2008195568A (en) * | 2007-02-13 | 2008-08-28 | Sumitomo Metal Ind Ltd | Method for inhibiting fluorine elution from slag |
| JP2009040652A (en) * | 2007-08-10 | 2009-02-26 | Jfe Steel Kk | Treatment method of steel making slag |
| JP2009040650A (en) * | 2007-08-10 | 2009-02-26 | Jfe Steel Kk | Treatment method of steel slag |
| JP2009040653A (en) * | 2007-08-10 | 2009-02-26 | Jfe Steel Kk | Treatment method of granulated blast furnace slag |
| JP2010138053A (en) * | 2008-12-15 | 2010-06-24 | Sanyo Special Steel Co Ltd | Method of reducing fluorine elution from steel making slag product |
| JP2012062225A (en) * | 2010-09-16 | 2012-03-29 | Kobe Steel Ltd | Method for producing recycled slag |
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2002
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005239509A (en) * | 2004-02-27 | 2005-09-08 | Nippon Steel & Sumikin Stainless Steel Corp | Method for controlling elution of fluorine from steel slag and underground burying material |
| JP2006241429A (en) * | 2005-02-07 | 2006-09-14 | Fujita Corp | Soil-improving material and engineering method for improving soil |
| JP2007022818A (en) * | 2005-07-12 | 2007-02-01 | Nippon Steel Corp | Method of treating fluorine-containing steel making slag |
| JP2008195568A (en) * | 2007-02-13 | 2008-08-28 | Sumitomo Metal Ind Ltd | Method for inhibiting fluorine elution from slag |
| JP2009040652A (en) * | 2007-08-10 | 2009-02-26 | Jfe Steel Kk | Treatment method of steel making slag |
| JP2009040650A (en) * | 2007-08-10 | 2009-02-26 | Jfe Steel Kk | Treatment method of steel slag |
| JP2009040653A (en) * | 2007-08-10 | 2009-02-26 | Jfe Steel Kk | Treatment method of granulated blast furnace slag |
| JP2010138053A (en) * | 2008-12-15 | 2010-06-24 | Sanyo Special Steel Co Ltd | Method of reducing fluorine elution from steel making slag product |
| JP2012062225A (en) * | 2010-09-16 | 2012-03-29 | Kobe Steel Ltd | Method for producing recycled slag |
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