JP4833415B2 - Method for producing cured body by carbonation - Google Patents
Method for producing cured body by carbonation Download PDFInfo
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- JP4833415B2 JP4833415B2 JP2001003664A JP2001003664A JP4833415B2 JP 4833415 B2 JP4833415 B2 JP 4833415B2 JP 2001003664 A JP2001003664 A JP 2001003664A JP 2001003664 A JP2001003664 A JP 2001003664A JP 4833415 B2 JP4833415 B2 JP 4833415B2
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- JP
- Japan
- Prior art keywords
- lime
- based material
- carbonation
- curing
- magnesium carbonate
- 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.)
- Expired - Lifetime
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- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/10—Lime cements or magnesium oxide cements
- C04B28/105—Magnesium oxide or magnesium carbonate cements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
【０００１】
【産業の属する技術分野】
本発明は、石灰系材料を炭酸化により硬化させる際に炭酸ガスを使わずに炭酸化させて硬化体を得る方法に関するものである。
【０００２】
【従来の技術】
水と混練した消石灰は空地中の炭酸ガスと徐々に反応して炭酸カルシウムに変化して硬化し耐水性のある材料となる。この現象を利用して昔からしっくいあるいは石灰プラスターとして塗装材料などに使用されてきた。また近年、製鋼スラグのＣａＯに着目し、これを炭酸ガスで炭酸化して硬化体を製造する方法も公表されている。例えば、▲１▼特開昭５８−７４５５９号公報に示されるように、粒径２.５ｍｍ以下の製鋼風砕スラグに高炉水砕スラグ、セメントおよび石膏の少なくとも１つを添加し、所定量の水を加えて混練した混練物を所定形状に加圧成形した後、炭酸ガス雰囲気中で養生し炭酸化反応を行って硬化体を得ている。
【０００３】
【発明が解決しようとする課題】
本発明者らは、上記の方法を石灰系材料の硬化体製造に適用しようと試みた。その結果、硬化体が大きくなるほど炭酸ガスによって中心部まで確実に炭酸化させることが困難になることが判明した。これは、硬化体の外部から炭酸ガスが内部へ拡散することで炭酸化するのであるが、硬化体が大きくなるほど炭酸ガスの必要量を中心部まで供給するのに時間が掛かるからである。また、上記の方法では加圧成形が必要であるが、これも硬化体の大きさや形状に対する制約条件となる。
【０００４】
本発明はこの問題を解決し、大きさや形状によらずに硬化体内部のどの部位も物性的に均一な硬化体を短時間かつ加圧成形無しで製造することを目的とする。
【０００５】
【課題を解決するための手段】
本発明は、石灰系材料を炭酸化により硬化させて硬化体を得る製造方法において、前記石灰系材料が製鋼スラグであり、該石灰系材料に固体の炭酸マグネシウム系物質と水を配合して混練・養生することにより加圧成形無しで硬化させることを特徴とする炭酸化による硬化体の製造方法である。
【０００６】
【発明の実施の形態】
以下、本発明を詳細について説明する。
【０００７】
石灰系材料と固体の炭酸マグネシウム系物質を適当な粒度に調整し、該石灰系材料と炭酸マグネシウム系化合物に所定量の水を配合して混練し、適当な型枠に流し込んで養生する。石灰系材料、炭酸マグネシウム系物質、水の配合比は目的の強度に応じて選んでよい。例えば、高強度を求める場合は石灰系材料と炭酸マグネシウム系物質の配合量を近づけ、また混練可能な限り水の配合量を下げる方がよい。炭酸の供給源としての炭酸マグネシウム系物質の配合量としては、石灰系材料と炭酸マグネシウム系物質の合計の質量に対して、１０〜５０質量％が望ましい。炭酸マグネシウム系物質の配合量が１０質量％未満の場合は炭酸の供給が不足し、５０質量％を超えると炭酸の供給が過剰となる。また、水の配合量は固形物１００質量％に対して、混練上５〜３５質量％をさらに添加することが望ましい。ここで、固形物とは、石灰系材料と炭酸マグネシウム系物質とを混練したものを意味する。養生中に石灰系材料からはＣａ2+とＯＨ-、炭酸マグネシウム系物質からはＭｇ2+とＣＯ3 2-が水中に溶出する。これらは以下のような反応により炭酸カルシウムと水酸化マグネシウムを生成し、これら生成物は水に対する溶解度が小さいので析出する。
【０００８】
Ｃａ２＋＋ＣＯ３ ２−→ＣａＣＯ３↓・・・・・・・・・・・・・・（１）
Ｍｇ２＋＋２ＯＨ−→Ｍｇ（ＯＨ）２↓・・・・・・・・・・・・・（２）
上記の析出物が粒子間の空隙に充填され、空隙が徐々に減少して緻密で高強度の硬化体を形成する。石灰系材料とは、ＣａＯを主要成分の１つとして含むものであり、製鋼スラグである。一方、炭酸マグネシウム系物質とは、ＭｇＣＯ３を主要成分の１つとして含むものであり、例えば、炭酸マグネシウムの無水物または水和物、ドロマイト、水酸化炭酸マグネシウム、ＭｇＯ−ＳｉＯ２系鉱物（蛇紋岩、滑石、かんらん石等）と炭酸ガスまたは炭酸塩を反応させて炭酸マグネシウム含有物にしたものなどである。ここで主要成分としては、ＣａＯやＭｇＣＯ３を１５質量％程度以上含んでいることが望ましい。
【０００９】
本発明で固体の炭酸マグネシウム系物質に限定する理由は、炭酸源が固体であれば石灰系材料と直接混合することができるので、石灰系材料の粒子のごく近傍に炭酸源があることになり、炭酸化速度が速くなる。従来用いられているガス状のＣＯ2では、石灰系材料の外側からガスが材料の細孔を通って内部へ拡散しながら炭酸化が進行するので、炭酸化に時間がかかる。
【００１０】
通常、混練は常温で行い、必要により加熱、好ましくは６０℃迄昇温して行うことができる。加熱した場合には硬化反応促進の効果が得られる。
【００１１】
また、養生には、水中養生、空中養生、連結硬化養生（水中養生後に空中養生する）などがある。本発明は、これらの養生のうち、特定の方法に限定されるものではない。
【００１２】
【実施例】
以下、本発明を実施例に基づいて説明する。
【００１３】
本実施例では、石灰系材料として製鋼スラグ、炭酸マグネシウム系物質として炭酸マグネシウムの無水物、すなわちマグネサイトを選んだ。製鋼スラグの化学組成を表１に示す。製鋼スラグを冷却・凝固させた後、２.５ｍｍアンダーに破砕するか、あるいは２.５ｍｍよりも粗い粒度で破砕して分級し２.５ｍｍアンダー品を得た。また、マグネサイトを０.１ｍｍアンダーに破砕した。両者を表２の条件で配合し、大気中において常温で混練して、１×１×１ｍの型枠に流し込み養生した。
【００１４】
従来法は特開昭５８−７４５５９号公報に示されるように、製鋼スラグの２.５ｍｍアンダー破砕品に水を加えて混練し、１×１×１ｍの型枠に流し込んで１０ＭＰａの圧力で加圧成形し、炭酸ガス１００％の雰囲気で、温度５０℃により養生し、炭酸化反応により硬化させた。養生期間と圧縮強度の関係を図１に示す。図１で、マグネサイト配合量２０％、３０％、４０％が本発明例、マグネサイト配合量０％＋炭酸ガス処理が従来法である。図１より、本発明例では、養生期間が３０日程度以下で強度がほぼ飽和に達するのに対し、従来法では強度が飽和に達するのに１５０日以上かかった。従って、本発明例は比較例に対して養生期間が大幅に短縮された。
【００１５】
【表１】
【表２】
【発明の効果】
本発明により、製鋼スラグを炭酸化により硬化させる際に、炭酸ガスを使わずに短い養生期間で硬化させることが可能となった。
【図面の簡単な説明】
【図１】 本発明と従来法について養生期間と強度の関係を示すグラフ[0001]
[Technical field to which industry belongs]
The present invention relates to a method for obtaining a cured product by carbonizing a lime-based material by carbonation without using carbon dioxide when it is cured by carbonation.
[0002]
[Prior art]
The slaked lime kneaded with water gradually reacts with carbon dioxide in the open space and changes to calcium carbonate, which hardens and becomes a water-resistant material. Using this phenomenon, it has been used for paint materials as plaster or lime plaster for a long time. In recent years, a method for producing a hardened body by focusing on CaO of steelmaking slag and carbonating it with carbon dioxide gas has been announced. For example, (1) as disclosed in JP-A-58-74559, at least one of blast furnace granulated slag, cement and gypsum is added to a steelmaking-pulverized slag having a particle size of 2.5 mm or less, and a predetermined amount of A kneaded product added with water and pressure-molded into a predetermined shape is cured in a carbon dioxide atmosphere and subjected to a carbonation reaction to obtain a cured product.
[0003]
[Problems to be solved by the invention]
The present inventors tried to apply the above method to the production of a cured body of a lime-based material. As a result, it has been found that the larger the cured body, the more difficult it is to carbonate to the central portion with carbon dioxide gas. This is because the carbon dioxide gas diffuses from the outside of the cured body to the inside, and it takes longer to supply the required amount of carbon dioxide gas to the center as the cured body becomes larger. In addition, the above method requires pressure molding, which is also a constraint on the size and shape of the cured body.
[0004]
An object of the present invention is to solve this problem, and to produce a cured body having a uniform physical property in any part of the cured body in a short time and without pressure molding regardless of the size and shape.
[0005]
[Means for Solving the Problems]
The present invention provides a method for producing a cured product by curing a lime-based material by carbonation, wherein the lime-based material is steel slag, and the lime-based material is kneaded by mixing a solid magnesium carbonate-based substance and water. -It is the manufacturing method of the hardening body by carbonation characterized by making it harden | cure without pressure molding by curing.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0007]
A lime-based material and a solid magnesium carbonate-based material are adjusted to an appropriate particle size, and a predetermined amount of water is blended and kneaded into the lime-based material and the magnesium carbonate-based compound, and then poured into an appropriate mold and cured. The mixing ratio of the lime-based material, the magnesium carbonate-based material, and water may be selected according to the target strength. For example, when high strength is required, it is better to bring the blending amount of the lime-based material and the magnesium carbonate-based material close to each other and reduce the blending amount of water as much as possible. As a compounding quantity of the magnesium carbonate type substance as a carbonic acid supply source, 10-50 mass% is desirable with respect to the total mass of a lime type material and a magnesium carbonate type substance. When the amount of the magnesium carbonate-based material is less than 10% by mass, the supply of carbonic acid is insufficient, and when it exceeds 50% by mass, the supply of carbonic acid is excessive. Moreover, it is desirable that the amount of water is further added in an amount of 5 to 35% by mass for 100% by mass of the solid. Here, the solid material means a material obtained by kneading a lime-based material and a magnesium carbonate-based material. During the curing, Ca 2+ and OH − are eluted from the lime-based material, and Mg 2+ and CO 3 2− are eluted from the magnesium carbonate-based material into the water. These produce calcium carbonate and magnesium hydroxide by the following reaction, and these products are precipitated because of their low solubility in water.
[0008]
Ca 2+ + CO 3 2− → CaCO 3 ↓ (1)
Mg 2+ + 2OH − → Mg (OH) 2 ↓ (2)
The precipitates are filled in the voids between the particles, and the voids are gradually reduced to form a dense and high-strength cured body. The lime-based material, which contains a CaO as one of the major components, a steelmaking slag. On the other hand, the magnesium carbonate-based material is one containing MgCO 3 as one of main components. For example, magnesium carbonate anhydride or hydrate, dolomite, magnesium hydroxide carbonate, MgO—SiO 2 -based mineral (serpentine) Rocks, talc, olivine, etc.) and carbon dioxide or carbonate to react with magnesium carbonate. Here, as a main component, it is desirable to contain about 15% by mass or more of CaO and MgCO 3 .
[0009]
The reason for limiting to the solid magnesium carbonate material in the present invention is that if the carbonate source is solid, it can be mixed directly with the lime material, so that the carbonate source is in the immediate vicinity of the particles of the lime material. , Carbonation rate is faster. In the case of gaseous CO 2 that has been conventionally used, since carbonation proceeds while diffusing gas from the outside of the lime-based material into the inside through the pores of the material, it takes time for carbonation.
[0010]
Usually, the kneading is performed at room temperature, and can be performed by heating if necessary, preferably by raising the temperature to 60 ° C. When heated, the effect of accelerating the curing reaction can be obtained.
[0011]
Curing includes underwater curing, aerial curing, and linked curing curing (air curing after underwater curing). The present invention is not limited to a specific method among these curing methods.
[0012]
【Example】
Hereinafter, the present invention will be described based on examples.
[0013]
In this example, steelmaking slag was selected as the lime-based material, and magnesium carbonate anhydride, that is, magnesite, was selected as the magnesium carbonate-based material. Table 1 shows the chemical composition of the steelmaking slag. After the steelmaking slag was cooled and solidified, it was crushed to under 2.5 mm, or crushed with a particle size coarser than 2.5 mm and classified to obtain a 2.5 mm under product. Moreover, the magnesite was crushed to 0.1 mm under. Both were blended under the conditions shown in Table 2, kneaded at normal temperature in the atmosphere, poured into a 1 × 1 × 1 m mold and cured.
[0014]
As disclosed in Japanese Patent Laid-Open No. 58-74559, the conventional method is to add water to a 2.5 mm under-crushed product of steelmaking slag, knead it, pour it into a 1 × 1 × 1 m mold and apply it at a pressure of 10 MPa. It was pressed, cured in an atmosphere of 100% carbon dioxide at a temperature of 50 ° C., and cured by a carbonation reaction. The relationship between the curing period and the compressive strength is shown in FIG. In FIG. 1, 20%, 30%, and 40% of magnesite content are examples of the present invention, and magnesite content is 0% + carbon dioxide treatment is the conventional method. From FIG. 1, in the example of the present invention, the strength almost reached saturation when the curing period is about 30 days or less, whereas in the conventional method, it took 150 days or more to reach the saturation. Accordingly, the curing period of the inventive example was significantly shortened compared to the comparative example.
[0015]
[Table 1]
[Table 2]
【The invention's effect】
The present invention, the steel slag when curing by carbonation, it has become possible to cure in a short curing period without carbon dioxide.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between curing period and strength for the present invention and the conventional method.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001003664A JP4833415B2 (en) | 2001-01-11 | 2001-01-11 | Method for producing cured body by carbonation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001003664A JP4833415B2 (en) | 2001-01-11 | 2001-01-11 | Method for producing cured body by carbonation |
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| Publication Number | Publication Date |
|---|---|
| JP2002211962A JP2002211962A (en) | 2002-07-31 |
| JP4833415B2 true JP4833415B2 (en) | 2011-12-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001003664A Expired - Lifetime JP4833415B2 (en) | 2001-01-11 | 2001-01-11 | Method for producing cured body by carbonation |
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| JP5998582B2 (en) * | 2012-03-30 | 2016-09-28 | 新日鐵住金株式会社 | Civil engineering materials processing method |
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|---|---|---|---|---|
| JPS5080313A (en) * | 1973-11-20 | 1975-06-30 | ||
| JPS557547A (en) * | 1978-07-03 | 1980-01-19 | Asahi Chemical Ind | Manufacture of carbonic hardening article |
| JPH05345650A (en) * | 1992-06-16 | 1993-12-27 | Kubota Corp | Production of flame-resistant fiber-reinforced cement board |
| JP2574212B2 (en) * | 1994-02-23 | 1997-01-22 | ニチハ株式会社 | Method and apparatus for producing inorganic plate |
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| JP2002211962A (en) | 2002-07-31 |
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Free format text: JAPANESE INTERMEDIATE CODE: R350 |
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| EXPY | Cancellation because of completion of term |