JP5764089B2 - Surface modification method for slag materials - Google Patents
Surface modification method for slag materials Download PDFInfo
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- JP5764089B2 JP5764089B2 JP2012096719A JP2012096719A JP5764089B2 JP 5764089 B2 JP5764089 B2 JP 5764089B2 JP 2012096719 A JP2012096719 A JP 2012096719A JP 2012096719 A JP2012096719 A JP 2012096719A JP 5764089 B2 JP5764089 B2 JP 5764089B2
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- 239000002893 slag Substances 0.000 title claims description 174
- 239000000463 material Substances 0.000 title claims description 50
- 238000002715 modification method Methods 0.000 title description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 125
- 239000010959 steel Substances 0.000 claims description 125
- 238000000034 method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 18
- 230000007613 environmental effect Effects 0.000 description 17
- 239000003513 alkali Substances 0.000 description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 15
- 238000010828 elution Methods 0.000 description 15
- 239000011575 calcium Substances 0.000 description 14
- 239000000292 calcium oxide Substances 0.000 description 13
- 239000013535 sea water Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 241001474374 Blennius Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000003920 environmental process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 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
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
本発明は、例えば、鉄鋼スラグを含むスラグ材を海洋環境修復材として用いるスラグ材の表面改質方法に関する。 The present invention relates to a surface modification method for a slag material using, for example, a slag material containing steel slag as a marine environment restoration material.
近年、海洋では、「海砂採取後の深掘り部による貧酸素海域」や「海藻類の減少による磯焼け」により悪化した環境の修復が望まれており、深掘り部の「埋め戻し材」や「藻場造成」等の材料として、製銑工程や製鋼工程で発生した鉄鋼スラグの利用が期待されている。鉄鋼スラグは、既に路盤材等の陸上利用が進められているが、海洋環境修復材としてスラグを使用する場合、海水浸漬時のｐＨ上昇と白濁生成を抑制し、環境に無害な状態とする必要がある。 In recent years, in the oceans, it has been desired to restore the environment that has deteriorated due to “anoxic areas by deep excavation after sea sand collection” and “burning by reduction of seaweeds”. It is expected that steel slag generated in the ironmaking process and steelmaking process will be used as a material for smelting and seaweed formation. Iron and steel slag is already being used on the road, such as roadbed materials, but when using slag as a marine environment restoration material, it is necessary to suppress the pH increase and cloudiness generation when immersed in seawater, making it harmless to the environment. There is.
鉄鋼スラグには、成分として生石灰などの溶け残りであるｆ−ＣａＯやこのｆ−ＣａＯの水和反応で形成されたＣａ（ＯＨ）２を含んでいる。ｆ−ＣａＯやＣａ（ＯＨ）２は海水などの水分と接触すると、溶解しアルカリ化する。また、海水中にアルカリが溶出してしまうとｐＨ９．５以上でＭｇ（ＯＨ）２の白色沈殿が生じて、環境影響が懸念される。このようなことから、鉄鋼スラグを、海洋で利用するためにはアルカリ溶出を抑制する処理が必要である。鉄鋼スラグ等のアルカリ溶出を抑制する技術として特許文献１〜５に示すものがある。 Steel slag contains, as components, f-CaO, which is an undissolved part of quicklime, and Ca (OH) 2 formed by a hydration reaction of this f-CaO. When f-CaO or Ca (OH) 2 comes into contact with water such as seawater, it dissolves and becomes alkaline. Moreover, if alkali is eluted in seawater, white precipitation of Mg (OH) 2 occurs at a pH of 9.5 or more, and there is a concern about environmental impact. For this reason, in order to use steel slag in the ocean, a process for suppressing alkali elution is necessary. Patent Documents 1 to 5 include techniques for suppressing alkali elution of steel slag and the like.
特許文献１では、鉄鋼スラグ中に存在するＣａＯ分を炭酸化するに際し、鉄鋼スラグに機械攪拌を付与しつつ、ＣＯ２含有ガスを供給して炭酸化反応を行わせしめる鉄鋼スラグの処理方法であって、鉄鋼スラグ中に１０〜４０ｍｍの粒状物を含む状態で機械攪拌している。特許文献２では、セメント、無機系混和材、骨材、混和剤及び水を含むコンクリートを硬化させたコンクリート硬化体の表面を、散水及び／又は強制炭酸化し、コンクリート硬化体の中性化深さを０．５ｍｍ以上にしている。 Patent Document 1 is a method for treating steel slag in which carbonation is performed by supplying a CO 2 -containing gas while giving mechanical stirring to the steel slag when carbonating the CaO component present in the steel slag. The steel slag is mechanically agitated in a state where 10 to 40 mm of granular material is contained. In patent document 2, the surface of the concrete hardening body which hardened the concrete containing cement, an inorganic type admixture, an aggregate, an admixture, and water is watered and / or forced-carbonized, and the neutralization depth of a hardened concrete body is disclosed. Is 0.5 mm or more.
また、特許文献３では、鉄鋼スラグに含まれる遊離ＣａＯ及びＣａ（ＯＨ）２の合計含有量を０．９質量％以下としている。特許文献４では、高炉水砕スラグと刺激剤とを主成分とする固化処理材を水の存在下で廃棄物に混合し、該廃棄物を固化させている。特許文献５では、水分が添加された石材用原料の積み山での原料充填層を形成し、該積み山に炭酸ガスまたは炭酸ガス含有ガスからなる原料ガスを吹き込むことにより、微粉原料中に含まれるＣａＯの炭酸化反応より生成させたＣａＣＯ３をバインダーとして石材用原料の積み山を炭酸固化させている。 Moreover, in patent document 3, the total content of free CaO and Ca (OH) 2 contained in steel slag is 0.9 mass% or less. In patent document 4, the solidification processing material which has a blast furnace granulated slag and a stimulant as a main component is mixed with waste in presence of water, and this waste is solidified. In Patent Document 5, a raw material packed layer is formed in a pile of stone raw materials to which moisture is added, and the raw material gas composed of carbon dioxide or carbon dioxide-containing gas is blown into the pile, thereby being contained in the fine powder raw material. A stack of stone raw materials is carbonized and solidified using CaCO 3 produced by the carbonation reaction of CaO as a binder.
特許文献１〜５では、アルカリ溶出を抑制するために鉄鋼スラグ等の炭酸化処理を行っているものの、これらの技術を用いても鉄鋼スラグの表面全体に適正な炭酸化処理を付与することができず、アルカリ溶出性にバラツキが生じることがあった。
本発明は、上述の問題に鑑みてなされたもので、鉄鋼スラグを含むスラグ材からのアルカリ溶出を十分に抑制することができるスラグ材の表面改質方法を提供することを目的とする。
In Patent Documents 1 to 5, although carbonation treatment of steel slag and the like is performed to suppress alkali elution, an appropriate carbonation treatment can be imparted to the entire surface of the steel slag even if these techniques are used. In some cases, the alkali elution was not uniform.
This invention is made | formed in view of the above-mentioned problem, and it aims at providing the surface modification method of the slag material which can fully suppress the alkali elution from the slag material containing steel slag.
上述の目的を達成するため、本発明においては以下の技術的手段を講じた。
本発明のスラグ材の表面改質方法は、鉄鋼スラグを含むスラグ材を相対湿度が１００％
となる湿潤環境で保持しつつ当該スラグ材の表面全体を濡らす第１工程と、前記第１工程後に前記スラグ材を相対湿度が８０％以下となる乾燥環境で保持しつつ当該スラグ材の表面全体を乾かす第２工程とを有する湿乾処理を３回以上行ってスラグ材の表面を改質することを特徴とする。
In order to achieve the above-described object, the present invention takes the following technical means.
In the surface modification method for slag material of the present invention, the relative humidity of the slag material containing steel slag is 100%.
A first step in which the entire surface of the slag material is wetted while being held in a moist environment, and the entire surface of the slag material is held in a dry environment in which the relative humidity is 80% or less after the first step. The surface of the slag material is modified by performing a wet-drying process having a second step of drying the slag three times or more.
前記第１工程では、前記スラグ材に水分を混合することが好ましい。
前記湿乾処理は、前記前記スラグ材の表面温度が５〜６０℃となる範囲で行うことが好ましい。
In the first step, it is preferable to mix moisture in the slag material.
The wet-drying treatment is preferably performed in a range where the surface temperature of the slag material is 5 to 60 ° C.
本発明によれば、鉄鋼スラグを含むスラグ材からのアルカリ溶出を十分に抑制することができる。 According to the present invention, alkali elution from a slag material including steel slag can be sufficiently suppressed.
以下、本発明に係るスラグ材の表面改質方法について、図をもとに説明する。
製鉄所では、一般的に、高炉で出銑した溶銑に対して脱硫処理及び脱珪処理などの溶銑予備処理を行い、溶銑予備処理の終了後には脱りん処理や脱炭処理を行っている。溶銑などを溶鋼に精錬する様々な精錬処理では、副生成物である鉄鋼スラグが生成される。鉄鋼スラグは、例えば、脱炭スラグ、溶銑脱燐スラグ、溶銑脱硫スラグ、溶銑脱珪スラグ、取鍋精錬スラグ、電気炉鉄鋼スラグなどである。鉄鋼スラグには精錬処理によってある程度の差はあるものの、酸化カルシウム（ＣａＯ）、二酸化珪素、酸化アルミニウム、鉄などが含まれている。この鉄鋼スラグは、精錬処理後に外部に排滓して様々な用途に用いられるが、精錬処理後の鉄鋼スラグ中には、ｆ−ＣａＯやＣａ（ＯＨ）２が含まれている。
Hereinafter, the surface modification method of the slag material according to the present invention will be described with reference to the drawings.
In steelworks, hot metal pretreatment such as desulfurization and desiliconization is generally performed on hot metal discharged from a blast furnace, and dephosphorization and decarburization are performed after the hot metal pretreatment is completed. In various refining processes in which hot metal or the like is refined into molten steel, steel slag as a by-product is generated. Examples of the steel slag include decarburization slag, hot metal dephosphorization slag, hot metal desulfurization slag, hot metal desiliconization slag, ladle refining slag, and electric furnace steel slag. Steel slag contains calcium oxide (CaO), silicon dioxide, aluminum oxide, iron, and the like, although there are some differences depending on the refining treatment. This steel slag is discharged to the outside after the refining treatment and used for various purposes. The steel slag after the refining treatment contains f-CaO and Ca (OH) 2 .
各精錬処理後に排滓した鉄鋼スラグに対して、何ら処理もせずにそのまま海洋に使用すると、鉄鋼スラグ中に含まれるｆ−ＣａＯやＣａ（ＯＨ）２が海水などの水分と反応［ＣａＯ＋Ｈ２Ｏ→Ｃａ２＋＋２ＯＨ−、Ｃａ（ＯＨ）２＋Ｈ２Ｏ→Ｃａ２＋＋２ＯＨ−］により、海水がアルカリ化してしまい、海洋環境に影響を与える可能性がある。
本発明では、鉄鋼スラグを含むスラグ材を、海洋環境修復材などとして使用できるように、スラグ材の改質を行うこととしている。なお、スラグ材とは、鉄鋼スラグを含むものであればよく、鉄鋼スラグのみで構成したもの（鉄鋼スラグが１００％）であっても、鉄鋼スラグと他の骨材やバインダーとを合わせて塊成化した材料であっても、鉄鋼スラグを土砂等と混合した材料であってもよい。また、排滓後の鉄鋼スラグに対して蒸気エージング処理を行ってＣａＯやＣａ（ＯＨ）２を変質させたものをスラグ材としてもよい。
When steel slag discharged after each refining process is used as it is in the ocean without any treatment, f-CaO and Ca (OH) 2 contained in the steel slag react with moisture such as seawater [CaO + H 2 O. → Ca 2+ + 2OH − , Ca (OH) 2 + H 2 O → Ca 2+ + 2OH − ], the seawater may be alkalized, which may affect the marine environment.
In the present invention, the slag material is modified so that the slag material including the steel slag can be used as a marine environment restoration material or the like. In addition, the slag material should just contain steel slag, and even if it is comprised only with steel slag (steel slag is 100%), the steel slag and other aggregates and binders are combined together. Even if it is materialized, the material which mixed steel slag with earth and sand etc. may be sufficient. Moreover, it is good also as a slag material what performed the steam aging process with respect to the steel slag after a waste, and modified CaO and Ca (OH) 2 .
以下、スラグ材の表面改質方法について詳しく説明する。
スラグ材の表面改質方法では、鉄鋼スラグに含まれているｆ−ＣａＯやＣａ（ＯＨ）２を利用して、スラグ材の表面をコーティングし、このコーティングによって鉄鋼スラグからのアルカリ溶出を抑制することとしている。なお、鉄鋼スラグのみによってスラグ材を構成したものを例にとり説明する。
Hereinafter, the surface modification method of the slag material will be described in detail.
In the surface modification method for slag material, the surface of the slag material is coated using f-CaO or Ca (OH) 2 contained in the steel slag, and alkali elution from the steel slag is suppressed by this coating. I am going to do that. In addition, it demonstrates taking the case of what comprised the slag material only with the steel slag.
例えば、精錬処理後に鉄鋼スラグをスラグパンなどに排滓し、排滓した鉄鋼スラグ（スラグ材）に、水を噴霧して鉄鋼スラグの表面に水膜を形成する。そうすると、鉄鋼スラグ中にｆ−ＣａＯやＣａ（ＯＨ）２が含まれるため、水膜にＣａイオンやＣＯ３イオンが溶け出し、炭酸化反応が進み、鉄鋼スラグの表面に炭酸化カルシウムが形成されることになる。しかしながら、鉄鋼スラグの表面に形成された水膜の厚さが厚過ぎる場合、鉄鋼スラグの表面に形成された炭酸カルシウムは最終的に皮膜とはならず、当該炭酸カルシウムによって鉄鋼スラグの表面をコーティングすることができない。一方、鉄鋼スラグの表面に形成された水膜の厚さが薄過ぎる場合、水膜に溶け込むＣａイオンやＣＯ３イオンが少なく炭酸化反応が十分に進まないため、炭酸カルシウムが鉄鋼スラグの表面をコーティングできる十分な皮膜にならない。 For example, steel slag is discharged into a slag pan after refining treatment, and water is sprayed on the discharged steel slag (slag material) to form a water film on the surface of the steel slag. Then, since f-CaO and Ca (OH) 2 are contained in the steel slag, Ca ions and CO 3 ions are dissolved in the water film, the carbonation reaction proceeds, and calcium carbonate is formed on the surface of the steel slag. Will be. However, when the thickness of the water film formed on the surface of the steel slag is too thick, the calcium carbonate formed on the surface of the steel slag does not eventually become a film, and the surface of the steel slag is coated with the calcium carbonate. Can not do it. On the other hand, if the thickness of the water film formed on the surface of the steel slag is too thin, since Ca ions and CO 3 ions to blend into the water film less carbonation reaction does not proceed sufficiently, calcium carbonate the surface of steel slag Not enough film to coat.
このようなことから、本発明では、後述するような工程を採用することにより、炭酸カルシウムによって鉄鋼スラグの表面を十分にコーティングできるようにしている。
具体的には、図１の排滓処理工程に示すように、まず、スラグ材の元材料である鉄鋼ス
ラグ１をスラグパンに排滓して冷却した後、鉄鋼スラグ１を、例えば、１〜１００ｍｍに粉砕する。
For this reason, in the present invention, the surface of the steel slag can be sufficiently coated with calcium carbonate by adopting a process as described later.
Specifically, as shown in the waste disposal process of FIG. 1, first, after steel slag 1 that is the original material of the slag material is drained and cooled, the steel slag 1 is, for example, 1 to 100 mm. Grind into.
次に、第１工程に示すように、粉砕した鉄鋼スラグ１を相対湿度が１００％となる湿潤環境下にある容器２等に入れ、湿潤環境下で保持する。このように、相対湿度が１００％となる湿潤環境下に鉄鋼スラグ１を設置すると、時間が経過するに伴い、鉄鋼スラグ１の表面全体が次第に濡れた状態になり、鉄鋼スラグ１の表面に水膜が形成され、この水膜にＣａイオンやＣＯ３イオンを溶け込ませることができる。 Next, as shown in the first step, the pulverized steel slag 1 is put in a container 2 or the like in a humid environment where the relative humidity becomes 100% and held in the humid environment. As described above, when the steel slag 1 is installed in a humid environment where the relative humidity is 100%, the entire surface of the steel slag 1 gradually gets wet as time passes, and the surface of the steel slag 1 becomes water. A film is formed, and Ca ions and CO 3 ions can be dissolved in the water film.
第１工程では、鉄鋼スラグ１の表面全体が十分に濡れていることが目視で分かるまで鉄鋼スラグ１を湿潤環境で保持する。第１工程では、鉄鋼スラグ１の表面が十分に濡れるまで当該鉄鋼スラグを保持すればよく、保持時間は限定されないが、２時間以上であることが好ましい。
第１工程においては、鉄鋼スラグ１の周囲の相対湿度を１００％に保持するために、環境全体（容器２内）の湿度の制御を行ってもよいし、高温多湿の大気雰囲気下に鉄鋼スラグ１を置いてもよい。また、ＣＯ３イオンの溶け出しを推進するために、ＣＯ２ガスを容器２内に吹き込んでＣＯ２ガス濃度を上昇させてもよい。また、鉄鋼スラグ１の周囲の相対湿度が１００％とするために、例えば、水道水、蒸留水、塩水、海水、炭酸水等を、直接、鉄鋼スラグ１の表面に散布したり噴霧することにより、当該鉄鋼スラグ１に水分を供給して、表面全体の水膜の形成を促進してもよい。或いは、湿潤環境下で分級した鉄鋼スラグの塊を設置台などに載せて、上下左右から当該鉄鋼スラグの表面に大気等の水分が付着するようにしてもよいし、鉄鋼スラグ１の表面を結露させてもよい。
In the first step, the steel slag 1 is held in a wet environment until it is visually confirmed that the entire surface of the steel slag 1 is sufficiently wet. In the first step, the steel slag may be held until the surface of the steel slag 1 is sufficiently wet, and the holding time is not limited, but is preferably 2 hours or more.
In the first step, in order to keep the relative humidity around the steel slag 1 at 100%, the humidity of the entire environment (in the container 2) may be controlled, or the steel slag is kept in a high-temperature and high-humidity atmosphere. 1 may be placed. Further, in order to promote the leaching of CO 3 ions, it may increase the CO 2 gas concentration by blowing CO 2 gas into the container 2. Further, in order to set the relative humidity around the steel slag 1 to 100%, for example, tap water, distilled water, salt water, seawater, carbonated water, etc. are directly sprayed or sprayed on the surface of the steel slag 1. The water may be supplied to the steel slag 1 to promote the formation of a water film on the entire surface. Alternatively, a lump of steel slag classified in a wet environment may be placed on an installation table so that moisture such as air adheres to the surface of the steel slag from above, below, left, and right, or the surface of the steel slag 1 is condensed. You may let them.
第１工程において、鉄鋼スラグ１の表面温度が高いと、水膜に溶け込むＣａイオンやＣＯ３イオンの溶け込み速度が低下し、低温では、水膜中のイオンの拡散速度が低下する。このようなことから、第１工程においては、鉄鋼スラグ１の表面温度が高過ぎず低過ぎないのがよく、表面温度が５〜６０℃となる範囲となるように雰囲気の温度調整することが好ましく、より好ましくは表面温度が１０〜５０℃にするのがよい。 In the first step, when the surface temperature of the steel slag 1 is high, the penetration rate of Ca ions and CO 3 ions that dissolve in the water film decreases, and at low temperatures, the diffusion rate of ions in the water film decreases. Therefore, in the first step, the surface temperature of the steel slag 1 should not be too high and not too low, and the temperature of the atmosphere can be adjusted so that the surface temperature is in the range of 5 to 60 ° C. The surface temperature is preferably 10 to 50 ° C., more preferably.
次に、第１工程が終了すると、鉄鋼スラグ１を湿潤環境とは別の環境に移す。具体的には、第２工程に示すように、鉄鋼スラグ１を相対湿度が８０％以下となる乾燥環境下にある容器２に入れ、乾燥環境下で保持する。相対湿度が８０％以下となる乾燥環境下に鉄鋼スラグ１を設置すると、鉄鋼スラグ１の表面全体が徐々に乾いていき、水膜が徐々に薄くなっていく。水膜が徐々に薄くなっていく過程では、水膜に溶け込んだＣａイオンやＣＯ３イオンが濃縮していくと共に、鉄鋼スラグ１と水膜との境界部分で炭酸化反応が進み、鉄鋼スラグ１の表面に炭酸カルシウムからなる皮膜を形成させることができる。第２工程における相対湿度は６０％以下にすることが好ましい。 Next, when the first step is finished, the steel slag 1 is moved to an environment different from the wet environment. Specifically, as shown in the second step, the steel slag 1 is placed in a container 2 in a dry environment where the relative humidity is 80% or less, and held in a dry environment. When the steel slag 1 is installed in a dry environment where the relative humidity is 80% or less, the entire surface of the steel slag 1 is gradually dried, and the water film is gradually thinned. In the process of gradually thinning the water film, the Ca ions and CO 3 ions dissolved in the water film are concentrated, and the carbonation reaction proceeds at the boundary between the steel slag 1 and the water film. A film made of calcium carbonate can be formed on the surface of the film. The relative humidity in the second step is preferably 60% or less.
第２工程では、鉄鋼スラグ１の表面全体が十分に乾いていることが目視で分かるまで鉄鋼スラグ１を乾燥環境で保持する。第２工程では、鉄鋼スラグ１の表面が十分に乾くまで当該鉄鋼スラグ１を保持すればよいため、保持時間は限定されないが５時間以上が好ましい。
第２工程においては、鉄鋼スラグ１の周囲の相対湿度を８０％以下に保持するために、環境全体（容器２内）の湿度の制御を行ってもよいし、低湿となるように風を当てるようにしてもよい。
In the second step, the steel slag 1 is held in a dry environment until it is visually confirmed that the entire surface of the steel slag 1 is sufficiently dry. In the second step, since the steel slag 1 may be held until the surface of the steel slag 1 is sufficiently dried, the holding time is not limited, but 5 hours or more is preferable.
In the second step, in order to keep the relative humidity around the steel slag 1 at 80% or less, the humidity of the entire environment (in the container 2) may be controlled, or wind is applied so as to reduce the humidity. You may do it.
第２工程において、鉄鋼スラグ１の表面温度が高いと、鉄鋼スラグ１の表面全体が乾燥するのが速く、水膜が一挙に無くなるため、当該工程における１回当たりの成膜量が小さくなる。一方、鉄鋼スラグ１の表面温度が低いと、乾燥するまで非常に長い時間がかかる。このようなことから、第２工程においても、鉄鋼スラグ１の表面温度が高過ぎず低過ぎないのがよく、表面温度が５〜６０℃となる範囲となるように雰囲気の温度調整することが好ましく、より好ましくは表面温度が３０〜５０℃にするのがよい。なお、第２工程における温度や湿度は、上述した範囲内であれば変動させてもよい。 In the second step, when the surface temperature of the steel slag 1 is high, the entire surface of the steel slag 1 dries quickly and the water film disappears at a stroke, so the amount of film formation per time in the step becomes small. On the other hand, if the surface temperature of the steel slag 1 is low, it takes a very long time to dry. Therefore, also in the second step, the surface temperature of the steel slag 1 should not be too high and too low, and the temperature of the atmosphere can be adjusted so that the surface temperature is in the range of 5 to 60 ° C. Preferably, the surface temperature is preferably 30 to 50 ° C. Note that the temperature and humidity in the second step may be varied as long as they are within the above-described ranges.
以上、第１工程及び第２工程をまとめると、第１工程では、鉄鋼スラグ（スラグ材）１を相対湿度が１００％となる湿潤環境で保持して、鉄鋼スラグ(スラグ材)１の表面全体を濡らすこととし、表面に形成した水膜にＣａイオンやＣＯ３イオンを溶け込ませている。
第２工程では、鉄鋼スラグ（スラグ材）１を相対湿度が８０％以下となる乾燥環境で保持して、鉄鋼スラグ(スラグ材)１の表面全体を徐々に乾かし、鉄鋼スラグ１の表面に炭酸カルシウムからなる皮膜を形成させている。
As described above, the first step and the second step are summarized. In the first step, the steel slag (slag material) 1 is held in a humid environment where the relative humidity becomes 100%, and the entire surface of the steel slag (slag material) 1 is obtained. , And Ca ions and CO 3 ions are dissolved in the water film formed on the surface.
In the second step, the steel slag (slag material) 1 is held in a dry environment where the relative humidity is 80% or less, the entire surface of the steel slag (slag material) 1 is gradually dried, and the surface of the steel slag 1 is carbonated. A film made of calcium is formed.
このように、本発明では、鉄鋼スラグの周囲の湿度の環境をかえることによって、鉄鋼スラグ１の表面全体に水分を供給し、その後に徐々に乾燥させることによって鉄鋼スラグ１の表面に炭酸カルシウムからなる皮膜を形成させるようにしているが、鉄鋼スラグ１の表面に確実に皮膜を形成させるため、第１工程と第２工程とからなる湿乾処理を３回以上行うこととしている。なお、上述したように、第１工程及び第２工程、即ち、湿乾処理は、鉄鋼スラグの表面温度が５〜６０℃となる範囲で行うことが好ましい。 As described above, in the present invention, moisture is supplied to the entire surface of the steel slag 1 by changing the humidity environment around the steel slag, and then gradually dried, so that the surface of the steel slag 1 is made of calcium carbonate. However, in order to reliably form a film on the surface of the steel slag 1, the wet and dry treatment including the first step and the second step is performed three times or more. In addition, as above-mentioned, it is preferable to perform a 1st process and a 2nd process, ie, a wet-dry process, in the range from which the surface temperature of steel slag will be 5-60 degreeC.
湿乾処理を１回で終わらすのではなく、繰り返し３回以上行うことによって、繰り返す毎に鉄鋼スラグ１に形成した皮膜が大きくなると共に、皮膜が鉄鋼スラグ１の表面から剥がれにくくなり、さらに、皮膜は鉄鋼スラグ１の全体に亘って形成されるため、鉄鋼スラグ１の表面全体を炭酸カルシウムの皮膜によりコーティングすることができる。
表１、２は、本発明のスラグ材の表面改質方法をおこなった例と、本発明とは異なる方法でスラグ材の表面改質を行った例とをまとめたものである。
Rather than finishing the wet-drying process once, the film formed on the steel slag 1 increases each time it is repeated three times or more, and the film becomes difficult to peel off from the surface of the steel slag 1. Is formed over the entire steel slag 1, so that the entire surface of the steel slag 1 can be coated with a coating of calcium carbonate.
Tables 1 and 2 summarize an example in which the method for modifying the surface of the slag material of the present invention and an example in which the surface modification of the slag material is performed by a method different from the present invention.
スラグ材の表面改質を行うには、まず、ＣａＯ、Ｃａ（ＯＨ）２、Ｃａ２ＳｉＯ４の合計が５０質量％以上となる鉄鋼スラグを用意して、この鉄鋼スラグを１０〜６０ｍｍの粒度で分級する。そして、分級した鉄鋼スラグを乾湿複合サイクル試験機に入れて、湿潤環境に相当する処理（第１環境処理）を行うと共に、乾燥環境に相当する処理（第２環境処理）を実施した。この乾湿複合サイクル試験機は、スガ試験機株式会社製で、温度、湿度、水分供給（水噴霧）が行えるものである。第１環境処理では、鉄鋼スラグの表面に向けて適宜、水噴霧した。 In order to perform the surface modification of the slag material, first, a steel slag in which the total of CaO, Ca (OH) 2 , and Ca 2 SiO 4 is 50 mass% or more is prepared, and the steel slag has a particle size of 10 to 60 mm. Classify by. Then, the classified steel slag was put into a dry / wet combined cycle tester to perform a process corresponding to a wet environment (first environmental process) and a process corresponding to a dry environment (second environmental process). This dry / wet combined cycle tester is manufactured by Suga Test Instruments Co., Ltd. and can supply temperature, humidity, and moisture (water spray). In the first environmental treatment, water was sprayed as appropriate toward the surface of the steel slag.
鉄鋼スラグの処理量は５ｋｇであり、無作為に鉄鋼スラグを５個取り出し、第１環境処理では全面が濡れているか、第２環境処理では全面が乾いているかを確認した。鉄鋼スラグの乾きの程度は、表面全体が乾いている場合を「全面」とし、表面一部が乾いている場合を「一部」とした。
また、第１環境処理と第２環境処理とを連続して１回行った後、その繰り返し回数を１回、３回、５回、７回、１０回の５パターンに分けて処理を実施した。各パターンの終了毎に鉄鋼スラグを１ｋｇ取り出してアルカリ溶出評価試験を行った。
The processing amount of steel slag was 5 kg, and five steel slags were randomly taken out, and it was confirmed whether the entire surface was wet in the first environmental treatment or whether the entire surface was dry in the second environmental treatment. The degree of drying of the steel slag was defined as “entire surface” when the entire surface was dry, and “partial” when part of the surface was dry.
Further, after the first environmental treatment and the second environmental treatment were performed once in succession, the number of repetitions was divided into five patterns of 1, 3, 5, 7, and 10 times. . At the end of each pattern, 1 kg of steel slag was taken out and subjected to an alkali elution evaluation test.
アルカリ溶出評価試験では、取り出した１ｋｇの鉄鋼スラグを約３００ｇの３つに分け
、３個の試験片（鉄鋼スラグ）を、それぞれ１．５ｋｇの人工海水（マリンアートＳＦ−１を１０％硫酸にてｐＨ８．２に調整したもの）に沈める。そして、試験片を沈めた人工海水をそれぞれ３時間放置し、３時間後に人工海水を１回／ｓｅｃの速さで１０回攪拌し、各人工海水のｐＨを測定した。試験片を入れた人工海水のうち、最も高いｐＨを示した人工海水のｐＨ値を記録し、ｐＨ９．０以上の場合を不可「××」とし、ｐＨ８．８以上９．０未満の場合を不良「×」とし、ｐＨ８．６以上８．８未満の場合をやや不良「△」とし、ｐＨ８．４以上８．６未満の場合を良好「○」とし、ｐＨ８．４未満の場合を最良「◎」として、人工海水の評価、即ち、鉄鋼スラグからのアルカリ溶出の評価を行った。なお、ｐＨの評価は、2008年9月に(社)日本鉄鋼連盟から刊行されている「転炉系製鋼スラグ 海域利用の手引き」P50に記載されている「表5-6 pH、白濁試験方法」に準じて実施した。
In the alkali elution evaluation test, the 1 kg of steel slag taken out was divided into three parts of about 300 g, and three test pieces (steel slag) were each 1.5 kg of artificial seawater (Marine Art SF-1 in 10% sulfuric acid). And adjusted to pH 8.2). The artificial seawater in which the test piece was submerged was left for 3 hours, and after 3 hours, the artificial seawater was stirred 10 times at a rate of 1 time / sec, and the pH of each artificial seawater was measured. Record the pH value of the artificial seawater that showed the highest pH among the artificial seawater containing the test piece. If the pH is 9.0 or higher, it is determined as “No”, and the pH is 8.8 or higher and lower than 9.0. The case where the pH is 8.6 or less and less than 8.8 is rated as “Poor”, the case where the pH is 8.4 or more and less than 8.6 is determined as “Good”, and the case where the pH is less than 8.4 is best. As for “”, artificial seawater was evaluated, that is, alkali elution from steel slag was evaluated. The evaluation of pH is described in “Table 5-6 pH and cloudiness test methods” described in P50, “Guide for Utilization of Converter Steelmaking Slag Sea Area” published by the Japan Iron and Steel Federation in September 2008. It implemented according to.
実施番号１〜４に示すように、第１環境処理にて、相対湿度を１００％として鉄鋼スラグを保持しつつ当該鉄鋼スラグの表面全体を濡らした後、第２環境処理にて、相対湿度を８０％以下として鉄鋼スラグを保持しつつ当該鉄鋼スラグの全面を乾かし、これらの第１環境処理及び第２環境処理を３回以上繰り返した場合、アルカリ溶出評価試験でのｐＨを良好「○」又は最良「◎」とすることができた。 As shown in operation numbers 1 to 4, in the first environmental treatment, the relative humidity is set to 100%, and the entire surface of the steel slag is wetted while holding the steel slag. When the entire surface of the steel slag is dried while holding the steel slag as 80% or less, and the first environmental treatment and the second environmental treatment are repeated three times or more, the pH in the alkali elution evaluation test is good. It was possible to be the best “◎”.
実施番号５、６に示すように、第１環境処理にて相対湿度を１００％として鉄鋼スラグを保持したものの当該鉄鋼スラグの表面一部しか濡らさなかったり、相対湿度を１００％ではなく９５％にした場合、第２環境処理にて鉄鋼スラグの表面全体を乾燥させたとしても、アルカリ溶出評価試験でのｐＨは不可「××」又は不良「×」となった。
実施番号７に示すように、第２環境処理にて相対湿度を８０％以下とせずに鉄鋼スラグを保持して当該鉄鋼スラグの表面一部しか乾かさなかった場合、第１環境処理にて鉄鋼スラグの表面全体を濡らしたとしても、アルカリ溶出評価試験でのｐＨは不可「××」又は不良「×」となった。
As shown in operation numbers 5 and 6, although the steel slag was held with relative humidity of 100% in the first environmental treatment, only a part of the surface of the steel slag was wetted, or the relative humidity was set to 95% instead of 100%. In this case, even if the entire surface of the steel slag was dried by the second environmental treatment, the pH in the alkali elution evaluation test was not possible “XX” or defective “X”.
As shown in the execution number 7, when the steel slag is held in the second environmental treatment without reducing the relative humidity to 80% or less and only a part of the surface of the steel slag is dried, the steel slag is obtained in the first environmental treatment. Even when the entire surface of the sample was wetted, the pH in the alkali elution evaluation test was unsatisfactory “XX” or poor “X”.
実施番号８、９に示すように、第２環境処理にて鉄鋼スラグの表面を乾かすことを行わなかったり、第１環境処理にて鉄鋼スラグの表面を濡らさなかったりした場合、繰り返し処理を３回以上行ったとしても、アルカリ溶出評価試験でのｐＨは不可「××」となった。
これから分かるように、第１環境処理（第１工程）では、鉄鋼スラグを相対湿度が１００％となる湿潤環境で保持しつつ当該鉄鋼スラグの表面全体を濡らし、第２環境処理（第２工程）では、鉄鋼スラグを相対湿度が８０％以下となる乾燥環境で保持しつつ当該鉄鋼スラグの表面全体を乾かし、これら第１工程及び第２工程を湿乾処理として、この湿乾処理を３回以上行うと、鉄鋼スラグの表面全体に炭酸カルシウムの皮膜ができ、アルカリ溶出を抑えることができる。
As shown in execution numbers 8 and 9, when the surface of the steel slag is not dried in the second environmental treatment or the surface of the steel slag is not wetted in the first environmental treatment, the treatment is repeated three times. Even if it carried out above, pH in an alkali elution evaluation test was impossible "XX".
As can be seen, in the first environmental treatment (first step), the entire surface of the steel slag is wetted while holding the steel slag in a humid environment where the relative humidity becomes 100%, and the second environmental treatment (second step). Then, while maintaining the steel slag in a dry environment where the relative humidity is 80% or less, the entire surface of the steel slag is dried, and these wet and dry processes are performed three or more times as the first and second processes. When performed, a calcium carbonate film is formed on the entire surface of the steel slag, and alkali elution can be suppressed.
なお、今回開示された実施形態において、明示的に開示されていない事項、例えば、運転条件や操業条件、各種パラメータ、構成物の寸法、重量、体積などは、当業者が通常実施する領域を逸脱するものではなく、通常の当業者であれば、容易に想定することが可能な事項を採用している。 In the embodiment disclosed this time, matters not explicitly disclosed, for example, operating conditions and operating conditions, various parameters, dimensions, weights, volumes, etc. of components deviate from the areas normally practiced by those skilled in the art. However, matters that can be easily assumed by those skilled in the art are employed.
１ 鉄鋼スラグ
２ 容器
1 Steel slag 2 Container
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| JPS5041772A (en) * | 1973-08-20 | 1975-04-16 | ||
| JPH08259282A (en) * | 1995-03-20 | 1996-10-08 | Kawasaki Steel Corp | Stabilization method for steelmaking slag |
| KR100732732B1 (en) * | 2003-06-09 | 2007-06-29 | 신닛뽄세이테쯔 카부시키카이샤 | Method for stabilization treatment of steel making slag, stabilized steel making slag, and material and method for environmental preservation of water area using said slag |
| JP3828897B2 (en) * | 2003-06-09 | 2006-10-04 | 新日本製鐵株式会社 | Method for stabilizing steelmaking slag and stabilized steelmaking slag |
| JP2009028581A (en) * | 2007-07-24 | 2009-02-12 | Shimizu Corp | Carbon dioxide immobilization method |
| JP2009057257A (en) * | 2007-09-03 | 2009-03-19 | Nippon Steel Corp | Carbonated slag and carbonation method of slag |
| JP5473494B2 (en) * | 2009-09-01 | 2014-04-16 | 日新製鋼株式会社 | Method for producing modified steel slag |
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