JP6292257B2 - Hydrated solidified product using desulfurized slag - Google Patents

Hydrated solidified product using desulfurized slag Download PDF

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JP6292257B2
JP6292257B2 JP2016133802A JP2016133802A JP6292257B2 JP 6292257 B2 JP6292257 B2 JP 6292257B2 JP 2016133802 A JP2016133802 A JP 2016133802A JP 2016133802 A JP2016133802 A JP 2016133802A JP 6292257 B2 JP6292257 B2 JP 6292257B2
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slag
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孝一 市川
孝一 市川
石田 匡平
匡平 石田
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JFE Steel Corp
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/10Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Description

この発明は、結合材としてセメントや消石灰を用いず、結合材の一部として脱硫スラグを用いる水和固化体に関する。   The present invention relates to a hydrated solid body that uses desulfurized slag as a part of the binder without using cement or slaked lime as the binder.

製鋼スラグを骨材とし、潜在水硬性の高炉スラグ微粉末などにアルカリ刺激剤を加えたものを結合材とし、これらに水を加えて混練し、打設して固化させた水和固化体は、港湾工事での捨石などのような海域用途の人工石材として広く用いられている。また、ブロックなどの二次製品としても用いられている。
この種の水和固化体は、結合材として高炉スラグ微粉末やポゾラン反応物質を用い、この結合材がアルカリ性の刺激を受けて水和固化する性質を利用している。アルカリ刺激としては、セメントや消石灰がよく用いられる。
A hydrated solidified body made of steelmaking slag as an aggregate, a mixture of latent hydraulic blast furnace slag fine powder added with an alkali stimulant, kneaded with water, and then cast and solidified. It is widely used as artificial stone for marine applications such as rubble in harbor construction. It is also used as secondary products such as blocks.
This type of hydrated solidified material uses blast furnace slag fine powder or pozzolanic reactant as a binder, and utilizes the property that this binder is hydrated and solidified under alkaline stimulation. Cement and slaked lime are often used as alkali stimuli.

しかし、セメントや消石灰を用いると製造コストが増大する。また、海域用途でセメントを用いる材料は、使用されたセメントからのアルカリ成分溶出のイメージがあり、敬遠される場合もある。
これに対して、アルカリ刺激剤に製鋼スラグの微粉末や脱硫スラグを用いる技術が知られている。
特許文献1には、脱硫スラグをアルカリ刺激剤代替として潜在水硬性物質やポゾラン反応性物質に配合したり、骨材代替として多量に配合することが記載されている。また、特許文献2には、脱硫スラグや他の製鋼スラグを最大粒径400μm以下にして、アルカリ刺激材的に配合することが記載されている。
However, the use of cement or slaked lime increases the manufacturing cost. In addition, materials that use cement in marine applications have an image of alkaline component elution from the used cement, and may be avoided.
On the other hand, a technique using fine powder of steelmaking slag or desulfurized slag as an alkali stimulant is known.
Patent Document 1 describes that desulfurized slag is blended with a latent hydraulic substance or a pozzolanic reactive substance as an alkali stimulant substitute, or a large amount is blended as an aggregate substitute. Further, Patent Document 2 describes that desulfurization slag and other steelmaking slag are blended like an alkali stimulant with a maximum particle size of 400 μm or less.

特開2003−34562号公報JP 2003-34562 A 特開2013−6743号公報JP 2013-6743 A

脱硫スラグは、その高いCaO含有量のために、高炉水砕スラグ微粉末を刺激して固化させる性能がある。一方、1〜4質量%という高い硫黄含有量のために、固化反応ではエトリンガイトのような高結晶水水和物を生成させることが、特許文献1にも記載されている。エトリンガイトは、硫酸イオンやカルシウムイオン、アルミニウムイオンが溶解している液中から容易に析出するが、硫酸イオンがゆっくり供給される場合は、時間経過してから固化組織中で生成して膨張崩壊を引き起こす場合がある。また、比重が小さく、溶解析出を繰り返して組織中の空隙に充填され、その空隙を埋めていくため、他の膨張反応物質があると、その膨張体積を逃す空間(空隙)がなくなり、膨張崩壊を助長する場合もある。また、脱硫スラグ粒が大きいと、局所的に集中してエトリンガイトが生成し、組織中の空隙に充填されるとともに、結合組織を膨張破壊させる。   Due to its high CaO content, desulfurized slag has the ability to stimulate and solidify ground granulated blast furnace slag powder. On the other hand, Patent Document 1 describes that a high crystal water hydrate such as ettringite is generated in the solidification reaction due to a high sulfur content of 1 to 4% by mass. Ettringite precipitates easily from a solution in which sulfate ions, calcium ions, and aluminum ions are dissolved, but when sulfate ions are supplied slowly, it will form in the solidified structure after a while and will expand and collapse. May cause. In addition, the specific gravity is small, and dissolution and precipitation are repeated to fill the voids in the tissue and fill the voids, so if there are other expansion reaction substances, there will be no space (voids) to escape the expansion volume, and expansion and collapse May be encouraged. In addition, when the desulfurized slag particles are large, ettringite is generated locally and is filled in the voids in the tissue, and the connective tissue is expanded and broken.

このように、脱硫スラグを固化体中に多量に用いることは、膨張崩壊が実用上のネックとなる。また、特許文献2のように、微粉砕してアルカリ刺激剤に用いる場合は、配合量が少ないため膨張に対する懸念は低いが、実際に最大粒径400μm以下に粉砕すると粉砕コストが増大するため、経済性を損なう。また、微粉の混合は、水和固化体の混練時の添加水量を押し上げる傾向があるため、強度を低下させる方向に作用する。これを抑制するために減水剤のような混和剤の添加量を増加させると、製造コストがさらに増大してしまう。   As described above, when a large amount of desulfurized slag is used in the solidified body, expansion and collapse become a practical bottleneck. In addition, as in Patent Document 2, when finely pulverized and used as an alkali stimulant, since the blending amount is small, concern about expansion is low, but when pulverized to a maximum particle size of 400 μm or less, the pulverization cost increases. Impair the economy. Further, the mixing of the fine powder tends to push up the amount of water added at the time of kneading the hydrated solidified product, and thus acts to reduce the strength. Increasing the amount of admixture such as a water reducing agent to suppress this further increases the manufacturing cost.

したがって本発明の目的は、以上のような従来技術の課題を解決し、結合材の一部として比較的多量の脱硫スラグを配合した水和固化体であって、十分な強度を有するとともに、脱硫スラグの配合に起因する膨張破壊が生じにくい水和固化体を提供することにある。   Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a hydrated solidified body in which a relatively large amount of desulfurized slag is blended as a part of the binder, and has sufficient strength and desulfurized. An object of the present invention is to provide a hydrated solid body that hardly causes expansion failure due to the blending of slag.

本発明者らは、上記課題を解決するために詳細な検討を行った結果、吸水率が所定値以上の製鋼スラグを骨材とし、高炉スラグ微粉末と所定粒度の脱硫スラグを結合材とすることにより、十分な強度を有し且つ膨張破壊を生じにくい水和固化体が得られることを見出した。
本発明は、このような知見に基づきなされたもので、以下を要旨とするものである。
As a result of detailed studies to solve the above-mentioned problems, the inventors of the present invention use steelmaking slag having a water absorption rate of a predetermined value or more as an aggregate, and blast furnace slag fine powder and desulfurized slag having a predetermined particle size as a binder. Thus, it was found that a hydrated solid body having sufficient strength and hardly causing expansion failure can be obtained.
The present invention has been made on the basis of such knowledge and has the following gist.

[1]吸水率が3.5%以上の製鋼スラグを骨材とし、
高炉スラグ微粉末または高炉スラグ微粉末およびポゾラン硬化性材料と、粒径が1mm以下であって、且つ粒径400μm以上の粒子の割合が25質量%以上である脱硫スラグを結合材とし、
脱硫スラグ/(高炉スラグ微粉末または高炉スラグ微粉末およびポゾラン硬化性材料)の質量比が0.02〜0.75であることを特徴とする水和固化体。
[2]上記[1]の水和固化体において、脱硫スラグが破砕後、磁選により鉄分を回収した後のスラグであることを特徴とする水和固化体。
[3]上記[1]又は[2]の水和固化体において、脱硫スラグ/(高炉スラグ微粉末または高炉スラグ微粉末およびポゾラン硬化性材料)の質量比が0.25〜0.75であることを特徴とする水和固化体。
[1] Steelmaking slag having a water absorption rate of 3.5% or more is used as an aggregate.
Blast furnace slag fine powder or blast furnace slag fine powder and pozzolanic curable material, and a desulfurized slag having a particle size of 1 mm or less and a ratio of particles having a particle size of 400 μm or more is 25% by mass or more as a binder,
A hydrated solidified product having a mass ratio of desulfurized slag / (fine blast furnace slag powder or fine blast furnace slag powder and pozzolanic curable material) of 0.02 to 0.75.
[2] The hydrated solidified product according to the above [1], wherein the desulfurized slag is a slag obtained by crushing and collecting iron by magnetic separation.
[3] In the above hydrated solidified product according to [1] or [2], the mass ratio of desulfurized slag / (fine blast furnace slag powder or fine blast furnace slag powder and pozzolanic curable material) is 0.25 to 0.75. Hydrated solidified product characterized by the above.

本発明の水和固化体は、海域用途の人工石材などに適用できる十分な強度を有するとともに、結合材の一部として比較的多量の脱硫スラグを配合するにも拘わらず膨張性が低く、膨張破壊が生じにくい優れた性能を有する。また、結合材としてセメントや消石灰を使用しないため、低コストに製造できる利点がある。   The hydrated solid body of the present invention has sufficient strength that can be applied to artificial stone materials for marine use and the like, and has low expansibility despite the incorporation of a relatively large amount of desulfurized slag as a part of the binder. It has excellent performance that is difficult to break. Moreover, since cement or slaked lime is not used as the binder, there is an advantage that it can be manufactured at low cost.

本発明の水和固化体は、骨材と結合材と水を混練し、この混練物を水和固化させたものであって、吸水率が3.5%以上の製鋼スラグを骨材とし、高炉スラグ微粉末または高炉スラグ微粉末+ポゾラン硬化性材料と、粒径が1mm以下であって、且つ粒径400μm以上の粒子の割合が25質量%以上である脱硫スラグを結合材とし、脱硫スラグ/(高炉スラグ微粉末または高炉スラグ微粉末+ポゾラン硬化性材料)の質量比を0.02〜0.75としたものである。   The hydrated solidified body of the present invention is an aggregate, binder and water kneaded, and this kneaded product is hydrated and solidified, and steelmaking slag having a water absorption of 3.5% or more is used as an aggregate. Blast furnace slag fine powder or blast furnace slag fine powder + pozzolanic curable material, and desulfurized slag having a particle size of 1 mm or less and a ratio of particles having a particle size of 400 μm or more of 25% by mass or more as a binder, / (Blast furnace slag fine powder or blast furnace slag fine powder + pozzolanic curable material) mass ratio is 0.02 to 0.75.

骨材である製鋼スラグは、鉄鋼製造プロセスの製鋼工程で発生するスラグであり、骨材として破砕加工、粒度調整したものである。
製鋼スラグとしては、転炉脱炭スラグ、溶銑予備処理スラグ(例えば、脱燐スラグ、脱珪スラグ)、電気炉スラグ、二次精錬スラグ、造塊スラグなどが挙げられ、これらの1種以上を用いることができる。また、製鋼スラグのなかでも溶銑予備処理スラグは、遊離CaOが少ないために大気エージングの終了が早いだけでなく、遊離MgO相が少ないため水和膨張による割れなどが生じにくいので、特に好ましい。また、そのなかでも、脱燐スラグは比重が適度にあるため水和固化体の比重を高めることができ、例えば海中用途に用いる場合に波濤を受けても移動、転倒しにくいという優位性が得られるので、特に好ましい。また、製鋼スラグは、事前に大気エージングや蒸気エージングを施したものや、炭酸化処理などの各種処理を施したものを用いてもよい。製鋼スラグは、スラグ粒子の粒径が大きいほど、内部に遊離CaOや遊離MgOの粒を含む可能性が高くなり、水和固化体の膨張安定性にとって問題が生じる可能性が高くなるので、粒径25mm以下のものが好ましい。
Steelmaking slag, which is an aggregate, is slag generated in the steelmaking process of the steel manufacturing process, and is crushed and aggregated as aggregate.
Steelmaking slag includes converter decarburization slag, hot metal pretreatment slag (eg dephosphorization slag, desiliconization slag), electric furnace slag, secondary refining slag, ingot slag, etc. Can be used. Among the steelmaking slags, the hot metal pretreatment slag is particularly preferable because not only the air aging is completed quickly because there is little free CaO, but also cracks due to hydration expansion are difficult to occur because there is little free MgO phase. Among them, dephosphorization slag has an appropriate specific gravity, so that the specific gravity of the hydrated solidified product can be increased. Is particularly preferable. Steelmaking slag may be one that has been subjected to air aging or steam aging in advance, or one that has been subjected to various treatments such as carbonation treatment. Steelmaking slag is more likely to contain free CaO and free MgO particles inside as the particle size of the slag particles is larger, and there is a higher possibility of problems in the expansion stability of the hydrated solidified body. Those having a diameter of 25 mm or less are preferred.

骨材として用いる製鋼スラグのうち多孔質なものは、粒内に伸びる空隙を有しており、水和物の溶解析出による充填に対して余裕を持っている(すなわち膨張体積を逃す空間がある)。ただし、密閉された気孔(閉気孔)では、水和物を内部に溶解析出させることは困難であり、外側から水が浸入しうる経路(連続気孔や亀裂)をもった空隙であることが必要である。JIS A1109(2006)、JIS A1110(2006)に従って測定された細骨材の吸水率、粗骨材の吸水率は、水が浸入しうる空隙量と相関しており、この吸水率が3.5%以上の製鋼スラグを骨材とすることにより、脱硫スラグを結合材として比較的多量に用いても、脱硫スラグの配合による水和固化体の膨張を抑えることができる。   Porous steelmaking slag used as an aggregate has voids extending in the grains and has a margin for filling by dissolution and precipitation of hydrates (that is, there is a space to escape the expansion volume). ). However, with closed pores (closed pores), it is difficult to dissolve and precipitate hydrates inside, and it is necessary to have voids with a path (continuous pores and cracks) through which water can enter from the outside. It is. The water absorption rate of fine aggregates and the water rate of coarse aggregates measured according to JIS A1109 (2006) and JIS A1110 (2006) correlate with the amount of voids into which water can enter, and this water absorption rate is 3.5. By using the steelmaking slag of at least% as an aggregate, even if a relatively large amount of desulfurized slag is used as a binder, expansion of the hydrated solidified body due to the blending of the desulfurized slag can be suppressed.

このため、本発明ではJIS A1109(2006)、JIS A1110(2006)で規定される吸水率試験方法で測定される吸水率が3.5%以上の製鋼スラグを骨材として用いる。この製鋼スラグは、粗骨材および/または細骨材として配合されるものであり、細骨材(例えば、粒度5mm以下)、粗骨材(例えば、粒度5mm超、25mm以下)について、それぞれ上記吸水率試験法で測定される吸水率が3.5%以上とする。
なお、骨材として吸水率が異なる2種以上の製鋼スラグを用いる場合(吸水率が異なる細粒(細骨材)と粗粒(粗骨材)からなる製鋼スラグの場合を含む。)には、上記吸水率は、それらの質量基準での配合比に基づいた重み付き平均値とする。
For this reason, in this invention, the steelmaking slag whose water absorption measured by the water absorption test method prescribed | regulated by JIS A1109 (2006) and JIS A1110 (2006) is 3.5% or more is used as an aggregate. This steelmaking slag is blended as coarse aggregate and / or fine aggregate, and for fine aggregate (for example, particle size of 5 mm or less) and coarse aggregate (for example, particle size of more than 5 mm, 25 mm or less), respectively. The water absorption measured by the water absorption test method shall be 3.5% or more.
When two or more types of steelmaking slag having different water absorption rates are used as aggregates (including the case of steelmaking slag composed of fine particles (fine aggregates) and coarse particles (coarse aggregates) having different water absorption rates). The water absorption rate is a weighted average value based on the blending ratio based on the mass.

一方、製鋼スラグのスラグ粒子は閉気孔も有しており、吸水率が高いスラグ粒子は相対的に閉気孔も多く含んでいる。このような閉気孔も多く含むと、骨材粒子自体が脆弱化して破壊起点となり、高強度の固化体を製造できなくなる恐れがある。また、高比重の水和固化体を製造しにくくなる。このため、過剰に吸水率が高い製鋼スラグは避けるのが望ましく、実用的には単種の製鋼スラグで吸水率は7%以下(すなわち、複数種の製鋼スラグを含む場合は、それぞれの製鋼スラグの吸水率が7%以下。吸水率が異なる細粒(細骨材)と粗粒(粗骨材)からなる製鋼スラグの場合は、細粒(細骨材)、粗粒(粗骨材)のそれぞれの吸水率が7%以下。)が望ましい。   On the other hand, slag particles of steelmaking slag also have closed pores, and slag particles having a high water absorption rate have relatively many closed pores. If many such closed pores are included, the aggregate particles themselves become brittle and become a starting point of destruction, which may make it impossible to produce a high-strength solidified body. In addition, it becomes difficult to produce a high specific gravity hydrated solidified product. For this reason, it is desirable to avoid steelmaking slag having an excessively high water absorption rate. Practically, a single type of steelmaking slag has a water absorption rate of 7% or less (that is, when multiple types of steelmaking slag are included, each steelmaking slag In the case of steelmaking slag consisting of fine particles (fine aggregate) and coarse particles (coarse aggregate) with different water absorption rates, fine particles (fine aggregate), coarse particles (coarse aggregate) It is desirable that each water absorption rate is 7% or less.

ここで、骨材スラグ自身が膨張性を持つと高結晶水水和物で充填性が高まった際に膨張崩壊を起すため、CaO/SiOが高く膨張性がある脱炭スラグの場合は、蒸気エージングで膨張を安定化させることが好ましい。一方、溶銑予備処理スラグ(脱珪スラグ、脱燐スラグなど)はCaO/SiOが2以下で膨張性が低く、また、これらのスラグは相対的に高粘性の状態で排出されるため、空気を巻き込んで多孔質化し易く、多くスラグの吸水率が本発明範囲の吸水率3.5%以上に達しているため利用が容易である。
製鋼スラグは、溶融した状態で排滓場に流し出した後に、表面に散水して強制的に冷却すると、組織内に亀裂等ができて水分が入り込めるようになり、吸水率を高めることができる。この手法は過剰に行うと粒子の脆弱化をも招くので、適正に調整して行う。
Here, when the aggregate slag itself has expansibility, it causes expansion and collapse when the filling property is increased with high crystal water hydrate. Therefore, in the case of decarburized slag with high CaO / SiO 2 , It is preferable to stabilize the expansion by steam aging. On the other hand, the hot metal pretreatment slag (desiliconized slag, dephosphorized slag, etc.) has a CaO / SiO 2 of 2 or less and low expansibility, and these slags are discharged in a relatively high viscosity state. It is easy to use because it is easy to be made porous by entraining and the water absorption rate of slag has reached the water absorption rate of 3.5% or more within the range of the present invention.
When steelmaking slag is melted and poured into the waste disposal field, if water is sprayed on the surface and forcibly cooled, cracks and the like can be formed in the structure, allowing moisture to enter, and the water absorption rate can be increased. . If this method is performed excessively, particle weakening will be caused.

結合材である高炉スラグ微粉末は、高炉水砕スラグを粉砕・乾燥して作る微粉末であり、アルカリ刺激により硬化する潜在水硬性を有する。この高炉スラグ微粉末は、ブレーン比表面積が3000cm/g以上のものが好ましく、特に、JIS A6206(2013)に適合したものが好ましい。細粒でより比表面積の大きいほうが強度発現に優れるが、粉砕コストは増大する。 Blast furnace slag fine powder, which is a binder, is a fine powder made by pulverizing and drying blast furnace granulated slag, and has latent hydraulic properties that harden by alkali stimulation. The blast furnace slag fine powder preferably has a Blaine specific surface area of 3000 cm 2 / g or more, and particularly preferably conforms to JIS A6206 (2013). A finer particle and a larger specific surface area are more excellent in strength development, but the pulverization cost increases.

結合材として、高炉スラグ微粉末に加えてポゾラン硬化性材料(微粉末)を配合してもよい。このポゾラン硬化性材料としては、例えば、シリカヒューム、フライアッシュなどが挙げられ、これらの1種以上を用いることができる。シリカヒュームは、アーク式電気炉などにおいて金属シリコンやフェロシリコンを精錬する際の排ガス中に含まれる二酸化珪素を主成分とする副産物であり、水の存在下で水酸化カルシウムと反応して硬化するポゾラン反応性を有し、長期材齢での強度向上に寄与する。また、フライアッシュは、石炭火力発電所などにおいて微粉炭をボイラ内で燃焼させることで生じた石炭灰のうち、電気集塵機で捕集された石炭灰であり、このフライアッシュも水の存在下で水酸化カルシウムと反応して硬化するポゾラン反応性を有し、長期材齢での強度向上に寄与する。   As a binder, a pozzolan curable material (fine powder) may be blended in addition to the blast furnace slag fine powder. Examples of the pozzolanic curable material include silica fume and fly ash, and one or more of these can be used. Silica fume is a by-product mainly composed of silicon dioxide contained in exhaust gas when refining metallic silicon and ferrosilicon in an arc electric furnace, etc., and cures by reacting with calcium hydroxide in the presence of water. It has pozzolanic reactivity and contributes to strength improvement at long-term ages. Fly ash is coal ash generated by burning pulverized coal in a boiler at a coal-fired power plant, etc., and is collected by an electric dust collector. This fly ash is also present in the presence of water. It has pozzolanic reactivity that hardens by reacting with calcium hydroxide, and contributes to strength improvement in long-term ages.

結合材(アルカリ刺激剤)である脱硫スラグは、鉄鋼製造プロセスの製鋼工程(脱硫プロセス)で発生するスラグであり、本発明では、粒径が1mm以下であって、且つ粒径400μm以上の粒子の割合が25質量%以上である脱硫スラグを用いる。このような粒度の脱硫スラグを用いるのは、(i)膨張源である遊離CaOや遊離MgOの粗大粒子が入り込み、水和固化体の膨張安定性を悪化させるのを回避するために、粒径1mm以下であることが必要であり、(ii)粒径400μm以下の微粉の割合が増大すると、混練時に添加しなければならない水分量が増大し、水和固化体の強度が低下するので、これを回避するために、粒径400μm以上の粒子の割合が25質量%以上であることが必要なためである。   The desulfurization slag as the binder (alkali stimulant) is slag generated in the steel making process (desulfurization process) of the steel manufacturing process. In the present invention, particles having a particle size of 1 mm or less and a particle size of 400 μm or more are used. A desulfurized slag having a ratio of 25% by mass or more is used. The desulfurization slag having such a particle size is used in order to avoid that (i) coarse particles of free CaO or free MgO which are expansion sources enter and deteriorate the expansion stability of the hydrated solidified body. (Ii) When the proportion of fine powder having a particle size of 400 μm or less increases, the amount of water that must be added during kneading increases, and the strength of the hydrated solidified body decreases. This is because the ratio of particles having a particle size of 400 μm or more needs to be 25% by mass or more in order to avoid the above.

脱硫スラグは脱硫プロセスで生成した直後は地金分を多量に含んでおり、通常は破砕して地金を回収する。脱硫スラグは、CaO/SiOが高く遊離CaOも多く含有するので、散水や雨水の水分と反応して膨張崩壊が進み、地金回収後の脱硫スラグは概して細粒となり、粒度は細骨材よりも細かい。遊離CaOまたは、それが消化した水酸化カルシウム分を含み、水分と接触すればアルカリ性を示すため、この粒度で十分に高炉スラグ微粉末の水和反応のアルカリ刺激作用を有する。磁選工程用に破砕される粒度で十分細粒を確保できる。ただし、この粒径よりも大きい場合は、脱硫スラグを粉砕処理してもよい。 Immediately after the desulfurization slag is produced in the desulfurization process, it contains a large amount of metal, and usually it is crushed to recover the metal. Since desulfurized slag is high in CaO / SiO 2 and contains a large amount of free CaO, it reacts with water spray and rainwater to cause expansion and collapse. The desulfurized slag after recovery of metal is generally fine, and the particle size is fine aggregate. Finer than. Since it contains free CaO or its digested calcium hydroxide and is alkaline when it comes in contact with moisture, it has sufficient alkali stimulating action for the hydration reaction of blast furnace slag fine powder at this particle size. Sufficiently fine particles can be secured with a particle size that is crushed for the magnetic separation process. However, when it is larger than this particle size, the desulfurized slag may be pulverized.

このように脱硫スラグは高炉スラグ微粉末の水和反応の刺激効果やポゾラン反応を起すアルカリのCaOを供給する効果を有するが、本発明では、脱硫スラグ/(高炉スラグ微粉末または高炉スラグ微粉末+ポゾラン硬化性材料)の質量比は0.02〜0.75とする。この質量比が0.02未満では、アルカリ刺激効果が十分に得られない。一方、本発明では、吸水率の高い骨材を使うことによって、脱硫スラグを多量に用いることが可能となるが、高結晶水の水和物の生成が増大すると、スラグ粒子内部の空隙に対する水和物の充填性が高くなり過ぎ、限界を超えて膨張崩壊を招く。このため上記質量比は0.75を上限とする。また、アルカリ刺激効果をより高めることにより、特に強度が高い水和固化体を得るには、上記質量比を0.25〜0.75とすることが好ましい。   In this way, desulfurization slag has the effect of stimulating the hydration reaction of blast furnace slag fine powder and supplying alkaline CaO causing pozzolanic reaction. In the present invention, desulfurization slag / (blast furnace slag fine powder or blast furnace slag fine powder + Pozzolanic curable material) mass ratio is 0.02 to 0.75. If this mass ratio is less than 0.02, the alkali stimulating effect cannot be sufficiently obtained. On the other hand, in the present invention, it is possible to use a large amount of desulfurized slag by using an aggregate having a high water absorption rate. However, if the production of hydrated high crystal water increases, The filling property of the Japanese product becomes too high, leading to expansion and collapse beyond the limit. For this reason, the mass ratio has an upper limit of 0.75. Moreover, in order to obtain a hydrated solid body having a particularly high strength by further enhancing the alkali stimulating effect, the mass ratio is preferably set to 0.25 to 0.75.

本発明で使用する骨材と結合材は、以上がすべてであり、したがって、セメント(普通ポルトランドセメント、高炉セメンなどト)や消石灰などの結合材も含まない。
なお、原料中には、さらに、ワーカビリティ(打設作業のしやすさ)改善や強度・耐久性の向上、凝結速度の調整などを目的として使用される混和剤を配合してもよい。
The aggregates and binders used in the present invention are all described above, and thus do not include binders such as cement (ordinary Portland cement, blast furnace cement, etc.) and slaked lime.
The raw material may further contain an admixture used for the purpose of improving workability (ease of placing work), improving strength and durability, and adjusting the setting speed.

本発明の水和固化体の製法は特に制限はなく、基本的な製法は従来法と同様でよい。すなわち、原料(骨材である製鋼スラグ、結合材である高炉スラグ微粉末または高炉スラグ微粉末+ポゾラン硬化性材料と脱硫スラグ)と水を混練し、この混練物を水和硬化させるが、この際、混練物を型枠に流し込んで水和硬化させて製品としてもよいし、混練物をヤードの広い範囲に打設し、水和硬化させた後、破砕・篩い分けを経て製品としてもよい。後者の製法では、例えば、原料と水の混練物をヤードの広い範囲に平に打設し、水和硬化後の水和固化体をコンクリートブレーカーなどの重機を用いて破砕し、必要に応じて、さらにジョークラッシャーなどを用いて破砕し、この破砕物を篩い分けして篩上を製品とする。篩い分けは、グリズリなどを用いて行うことができる。このような製法で得られる不定形な人工石材は、港湾土木材料である被覆石、根固め石、捨石、裏込め材、潜堤材などに特に適している。   The production method of the hydrated solid product of the present invention is not particularly limited, and the basic production method may be the same as the conventional method. That is, the raw material (steel slag as an aggregate, blast furnace slag fine powder or blast furnace slag fine powder + pozzolanic curable material and desulfurized slag as a binder) and water are kneaded, and this kneaded product is hydrated and cured. At this time, the kneaded product may be poured into a mold to be hydrated and cured to obtain a product, or after the kneaded product is placed in a wide area of the yard and hydrated and cured, the product may be crushed and sieved to obtain a product. . In the latter production method, for example, a kneaded mixture of raw material and water is laid flat over a wide area of the yard, and the hydrated solidified body after hydration and hardening is crushed using a heavy machine such as a concrete breaker, and if necessary. Further, the product is crushed using a jaw crusher or the like, and the crushed material is sieved to obtain a product on the sieve. The sieving can be performed using grizzly or the like. The amorphous artificial stone material obtained by such a manufacturing method is particularly suitable for covering stones, root-hardening stones, rubble stones, backfill materials, submerged levee materials and the like which are harbor civil engineering materials.

以下の条件で本発明例、比較例の水和固化体を製造した。
骨材としては、以下のスラグ骨材の1種以上を用いた。カッコ内はスラグ粒度を示す。スラグの吸水率は、JIS A1110(2006)、JIS A1109(2006)に準拠して測定した。具体的には、使用した下記の各スラグについて、粒度5mm以下を細骨材、粒度5mm超を粗骨材として、それぞれJIS A1109(2006)、JIS A1110(2006)で規定される吸水率試験方法により吸水率を測定した後、細骨材と粗骨材の質量比に基づいた重み付き平均値を求め、この平均値を各スラグの吸水率とした。また、吸水率が異なる2種以上の製鋼スラグを用いた場合の吸水率は、それらの質量基準での配合比に基づいた重み付き平均値とした。なお、転炉脱炭スラグ(3)は、排滓後に散水せずに12時間以上放置して徐冷し、緻密化させたものであり、転炉脱炭スラグ(1),(2)に較べて吸水率が低くなっている。
Under the following conditions, the hydrated solids of the inventive examples and comparative examples were produced.
As the aggregate, one or more of the following slag aggregates were used. The slag particle size is shown in parentheses. The water absorption rate of the slag was measured according to JIS A1110 (2006) and JIS A1109 (2006). Specifically, for each of the following slags used, a water absorption test method defined by JIS A1109 (2006) and JIS A1110 (2006), respectively, with a fine particle size of 5 mm or less and a coarse particle size of over 5 mm. After measuring the water absorption rate, a weighted average value based on the mass ratio of fine aggregate and coarse aggregate was determined, and this average value was taken as the water absorption rate of each slag. Moreover, the water absorption rate at the time of using 2 or more types of steelmaking slag from which a water absorption rate differs was made into the weighted average value based on the mixture ratio in those mass references | standards. The converter decarburization slag (3) was left to cool for 12 hours or more without being sprinkled after draining, and was densified, and the converter decarburization slag (1), (2) Compared to the water absorption rate.

・転炉脱炭スラグ(1)(0−10mm)、大気エージング10ヶ月、吸水率4.1%
・転炉脱炭スラグ(2)(0−10mm)、蒸気エージング(100℃で3日間保持)、吸水率3.5%
・転炉脱炭スラグ(3)(0−10mm)、大気エージング10ヶ月、吸水率3.2%
・脱燐スラグ(0−25mm)、大気エージング3ヶ月、吸水率4.1%
・脱珪スラグ(0−25mm)、大気エージング3ヶ月、吸水率3.8%
・高炉徐冷スラグ(0−25mm)、吸水率2.0%
・ Converter decarburization slag (1) (0-10mm), atmospheric aging 10 months, water absorption 4.1%
-Converter decarburization slag (2) (0-10mm), steam aging (held at 100 ° C for 3 days), water absorption 3.5%
・ Converter decarburization slag (3) (0-10mm), atmospheric aging 10 months, water absorption 3.2%
・ Dephosphorization slag (0-25mm), atmospheric aging 3 months, water absorption 4.1%
・ Silicon removal slag (0-25mm), air aging 3 months, water absorption 3.8%
・ Blast furnace annealing slag (0-25mm), water absorption 2.0%

結合材としては、高炉スラグ微粉末(ブレーン比表面積:4000cm/g)と、以下の脱硫スラグ(アルカリ刺激剤)の1種を用いた。
・脱硫スラグ(1):粒径が1mm以下であって、粒径400μm以上の粒子の割合が30質量%、磁選のみでエージング無し
・脱硫スラグ(2):粒径が5mm以下であって、粒径1mm以下の粒子の割合が20質量%、磁選のみでエージング無し
・脱硫スラグ(3):粒径が1mm以下であって、粒径400μm以上の粒子の割合が26質量%、磁選のみでエージング無し
・脱硫スラグ(4):粒径が5mm以下であって、粒径400μm〜1mmの粒子の割合が10質量%、磁選のみでエージング無し
・脱硫スラグ(5):粒径が1mm以下であって、粒径400μm以上の粒子の割合が14質量%、磁選のみでエージング無し
・脱硫スラグ(6):粒径が75μm以下、磁選のみでエージング無し
As the binder, blast furnace slag fine powder (Brain specific surface area: 4000 cm 2 / g) and one of the following desulfurized slag (alkali stimulant) were used.
Desulfurization slag (1): The particle size is 1 mm or less, the proportion of particles having a particle size of 400 μm or more is 30% by mass, and there is no aging by magnetic separation only. • Desulfurization slag (2): the particle size is 5 mm or less, The proportion of particles with a particle size of 1 mm or less is 20% by mass, and there is no aging only by magnetic separation. ・ Desulfurization slag (3): The particle size is 1 mm or less, and the proportion of particles with a particle size of 400 μm or more is 26% by mass. No aging ・ Desulfurized slag (4): The particle size is 5 mm or less, and the proportion of particles having a particle size of 400 μm to 1 mm is 10% by mass, and there is no aging only by magnetic separation. ・ Desulfurized slag (5): The particle size is 1 mm or less The ratio of particles having a particle size of 400 μm or more is 14% by mass, and there is no aging only by magnetic selection.

上記の骨材および結合材の配合条件を表1及び表2に示す。
原料の配合では水量を一定とし(但し、脱硫スラグ(5)、(6)を用いた比較例は水量を増量させた)、高性能減水剤添加量を加減して混練物のスランプを10〜15cmに調整した。混練物をφ100×200mmの型枠に打設して供試体を作製し、2日後に脱型した。この供試体について、以下のようにして強度の測定と膨張安定性試験を行った。
な試験を行った。
(1)強度の測定
供試体を20℃に保持した水槽に浸漬して養生し、7日後、28日後の圧縮強度を、JIS A1108(2006)に規定されたコンクリートの圧縮強度試験方法に準拠して測定した。
Tables 1 and 2 show the blending conditions of the above aggregate and binder.
In the blending of raw materials, the amount of water is constant (however, the comparative example using desulfurized slag (5), (6) has increased the amount of water), and the amount of high-performance water reducing agent added is adjusted to adjust the slump of the kneaded product to 10 to 10%. Adjusted to 15 cm. The kneaded product was placed in a mold of φ100 × 200 mm to prepare a specimen, and demolded after 2 days. The specimen was subjected to strength measurement and expansion stability test as follows.
Tests were conducted.
(1) Measurement of strength Immerse the specimen in a water tank maintained at 20 ° C., and cure the compressive strength after 7 and 28 days according to the compressive strength test method for concrete specified in JIS A1108 (2006). Measured.

(2)膨張安定性試験
膨張安定性試験は、「鐵鋼スラグ水和固化体技術マニュアル−製鋼スラグの有効利用技術−(改訂版)」(平成20年2月)の附属書2に記載された膨張性評価試験法に準拠して、以下のような試験を実施した。
・試験1:φ100×200mmの型枠に打設した供試体を、打設7日後から80℃に保持した水槽に水浸させて膨張挙動を観察し、試験後の供試体外観から膨張安定性を以下のように評価した。
〇:有害なひび割れは確認されず、ポップアウトも少ない。(合格)
×:有害なひび割れが確認される。若しくは、有害なひび割れは確認されないが、ポップアウトは多い。(不合格)
(2) Expansion Stability Test The expansion stability test is described in Annex 2 of “Technology Manual for Steel Slag Hydrated Solids-Effective Technology for Steelmaking Slag (Revised)” (February 2008). The following tests were conducted according to the expansibility evaluation test method.
Test 1: A specimen placed on a mold of φ100 × 200 mm was immersed in a water tank maintained at 80 ° C. from 7 days after placing and observed for expansion behavior. From the appearance of the specimen after the test, expansion stability was observed. Was evaluated as follows.
◯: No harmful cracks are confirmed, and pop-outs are few. (Pass)
X: A harmful crack is confirmed. Or, no harmful cracks are found, but there are many pop-outs. (failure)

・試験2:エトリンガイトは60℃程度で生成速度が最大になり、それ以上では分解して変質するため、膨張安定性試験の保持温度を60℃に変え、温度低下による反応速度の低下を見越して21日間浸漬して、エトリンガイトを主眼とした膨張挙動を観察し、試験後の供試体外観から膨張安定性を以下のように評価した。
〇:有害なひび割れは確認されず、ポップアウトも少ない。(合格)
×:有害なひび割れが確認される。若しくは、有害なひび割れは確認されないが、ポップアウトは多い。(不合格)
-Test 2: Ettringite has a maximum production rate at about 60 ° C, and decomposes and deteriorates at higher temperatures. Therefore, the retention temperature in the expansion stability test is changed to 60 ° C, and a decrease in reaction rate due to temperature decrease is anticipated. After immersing for 21 days, the expansion behavior focusing on ettringite was observed, and the expansion stability was evaluated from the appearance of the specimen after the test as follows.
◯: No harmful cracks are confirmed, and pop-outs are few. (Pass)
X: A harmful crack is confirmed. Or, no harmful cracks are found, but there are many pop-outs. (failure)

以上の試験結果を表1及び表2に併せて示すが、発明例はいずれも十分な強度と優れた膨張安定性が得られている。
発明例1、8は、結合材である脱硫スラグ(A)(粒径1mm以下)と高炉スラグ微粉末(B)の質量比A/Bを0.02としたものであり、7日強度が10N/mmに達し、型枠を外せるレベルに達した。発明例2〜4、9〜11は、結合材の質量比A/Bを、それぞれ0.26、0.50、0.75としたものであり、骨材である脱燐スラグをそれに合わせて低減した。これらは強度発現も問題なく、膨張安定性も試験1,2ともに問題なかった。また、発明例1、8に較べて強度レベルが高くなっている。発明例5、12は、発明例1、8の骨材の20容積%を転炉脱炭スラグ(1)で置換したものであり、強度がやや向上した。ただし、膨張安定性試験でわずかに表面に剥離(ポップアウト)が見られた。発明例6、13は、発明例1、8の脱燐スラグを脱珪スラグで置換したものであり、骨材の吸水率が上述した発明例より若干低い3.8%であるが、強度、膨張安定性ともに問題はなかった。発明例7、14は、冷却過程をやや徐冷傾向とした転炉脱炭スラグであって、蒸気エージング(100℃で3日間保持)した転炉脱炭スラグ(2)を骨材として用いたものであり、骨材の吸水率は3.5%である。膨張安定性試験で若干のポップアウトが見られ、強度も若干低下気味ではあるが、致命的なものはなく、人工石材としては使用可能なものであった。
The above test results are shown together in Tables 1 and 2, and all of the inventive examples have sufficient strength and excellent expansion stability.
Inventive Examples 1 and 8 are those in which the mass ratio A / B of desulfurized slag (A) (particle size of 1 mm or less) and blast furnace slag fine powder (B) as a binder is 0.02, and the strength for 7 days is It reached 10 N / mm 2 and reached a level where the formwork could be removed. Inventive Examples 2 to 4, 9 to 11 are those in which the mass ratio A / B of the binder is 0.26, 0.50, and 0.75, respectively, and the dephosphorization slag that is an aggregate is adjusted to that. Reduced. There was no problem in strength development, and there was no problem in expansion stability in both tests 1 and 2. Further, the strength level is higher than those of Invention Examples 1 and 8. Inventive Examples 5 and 12 were obtained by replacing 20% by volume of the aggregates of Inventive Examples 1 and 8 with converter decarburization slag (1), and the strength was slightly improved. However, slight exfoliation (pop-out) was observed on the surface in the expansion stability test. Invention Examples 6 and 13 are obtained by replacing the dephosphorization slag of Invention Examples 1 and 8 with desiliconization slag, and the water absorption rate of the aggregate is slightly lower than that of the above-described invention example, which is 3.8%. There was no problem in terms of expansion stability. Invention Examples 7 and 14 are converter decarburization slag whose cooling process has a tendency to be gradually cooled, and the converter decarburization slag (2) steam-aged (held at 100 ° C. for 3 days) is used as an aggregate. The aggregate has a water absorption of 3.5%. In the expansion stability test, a slight pop-out was observed, and the strength was slightly reduced, but none was fatal and could be used as an artificial stone.

比較例1は、結合材である脱硫スラグを添加しない水和固化体であり、アルカリ刺激に乏しく、7日での強度発現が低い。特に、水和固化体のブロック製作する場合、この強度では崩れるため型枠を外せない。比較例2、8は、脱硫スラグの最大粒径を5mmにしたものであるが、膨張性が残る粒子が大きいため、ポップアウトが多数起こり、供試体端部が一部欠落した。比較例3、4、9、10は、脱硫スラグを本発明の範囲を超えて過剰に配合したものであり、80℃での保持試験(試験1)でひび割れが生じた。比較例5、6、11、12は、吸水率が低い高炉徐冷スラグを配合して吸水率の平均を3.5%未満としたものであり、脱硫スラグ量は発明例3、10と同じであるが、骨材側の空隙が少ないため、60℃の保持試験(試験2)でひび割れが生じた。比較例7、13は、徐冷して緻密となり、その結果吸水率が低くなった転炉脱炭スラグ(3)を骨材として用いたものであり、ポップアウトも多い上に、60℃の保持試験(試験2)ではひび割れが見られた。比較例14、15は、粒径1mm以下ではあるものの、粒径400μm以上の粒子が割合が少ない(微粉の割合が多い)脱硫スラグ(5)を用いたものであるが、混練時に添加する水分量が増大するため、高炉スラグ微粉末量を増大させて強度指数を維持しても、十分な強度が得られず、特に7日での強度発現が低い。比較例16は、粒径75μm以下の脱硫スラグ(6)を用いたものであるが、比較例14、15と同様に混練時に添加する水分量が増大するため、高炉スラグ微粉末量を増大させて強度指数を維持しても、十分な強度が得られず、特に7日での強度発現が低い。   Comparative Example 1 is a hydrated solid body to which desulfurization slag, which is a binder, is not added, is poor in alkali stimulation, and has a low strength expression at 7 days. In particular, when producing a hydrated solid block, the mold cannot be removed because it collapses at this strength. In Comparative Examples 2 and 8, the maximum particle size of the desulfurized slag was 5 mm. However, since the particles that remained expandable were large, many pop-outs occurred, and part of the specimen end portion was missing. Comparative Examples 3, 4, 9, and 10 were obtained by excessively blending desulfurized slag beyond the scope of the present invention, and cracks occurred in the holding test (Test 1) at 80 ° C. Comparative Examples 5, 6, 11, and 12 were blended with blast furnace slow-cooled slag having a low water absorption rate so that the average water absorption rate was less than 3.5%, and the amount of desulfurized slag was the same as that of Invention Examples 3 and 10. However, since there were few voids on the aggregate side, cracks occurred in the 60 ° C. holding test (Test 2). In Comparative Examples 7 and 13, the converter decarburized slag (3), which is gradually cooled to become dense and consequently has a low water absorption, is used as an aggregate. In the holding test (Test 2), cracks were observed. Comparative Examples 14 and 15 use desulfurized slag (5) having a particle size of 1 mm or less but having a small proportion of particles having a particle size of 400 μm or more (a large proportion of fine powder). Since the amount increases, even if the amount of blast furnace slag fine powder is increased to maintain the strength index, sufficient strength cannot be obtained, and the strength development particularly at 7 days is low. Comparative Example 16 uses desulfurized slag (6) having a particle size of 75 μm or less, but the amount of water added during kneading increases as in Comparative Examples 14 and 15, so the amount of blast furnace slag fine powder was increased. Even if the strength index is maintained, sufficient strength cannot be obtained, and the strength expression at 7 days is particularly low.

Claims (4)

吸水率が3.5%以上の製鋼スラグを骨材とし、
高炉スラグ微粉末または高炉スラグ微粉末およびポゾラン硬化性材料と、粒径が1mm以下であって、且つ粒径400μm以上の粒子の割合が25質量%以上である脱硫スラグを結合材とし、
脱硫スラグ/(高炉スラグ微粉末または高炉スラグ微粉末およびポゾラン硬化性材料)の質量比が0.02〜0.75であることを特徴とする水和固化体。
Steelmaking slag with a water absorption rate of 3.5% or more is used as an aggregate,
Blast furnace slag fine powder or blast furnace slag fine powder and pozzolanic curable material, and a desulfurized slag having a particle size of 1 mm or less and a ratio of particles having a particle size of 400 μm or more is 25% by mass or more as a binder,
A hydrated solidified product having a mass ratio of desulfurized slag / (fine blast furnace slag powder or fine blast furnace slag powder and pozzolanic curable material) of 0.02 to 0.75.
骨材である製鋼スラグが、転炉脱炭スラグ、脱燐スラグ、脱珪スラグ、電気炉スラグ、二次精錬スラグ、造塊スラグの中から選ばれる1種以上からなることを特徴とする請求項1に記載の水和固化体。The steelmaking slag as an aggregate is composed of at least one selected from converter decarburization slag, dephosphorization slag, desiliconization slag, electric furnace slag, secondary refining slag, and ingot slag. Item 2. A hydrated solid product according to Item 1. 脱硫スラグが破砕後、磁選により鉄分を回収した後のスラグであることを特徴とする請求項1又は2に記載の水和固化体。 The hydrated solidified body according to claim 1 or 2 , wherein the desulfurized slag is slag after crushing and after recovering iron by magnetic separation. 脱硫スラグ/(高炉スラグ微粉末または高炉スラグ微粉末およびポゾラン硬化性材料)の質量比が0.25〜0.75であることを特徴とする請求項1〜3のいずれかに記載の水和固化体。 The hydration according to any one of claims 1 to 3, wherein a mass ratio of desulfurized slag / (fine blast furnace slag powder or fine blast furnace slag powder and pozzolanic curable material) is 0.25 to 0.75. Solidified body.
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