WO2015198380A1 - Bonding material for carbonated construction materials, and method for producing same - Google Patents

Bonding material for carbonated construction materials, and method for producing same Download PDF

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WO2015198380A1
WO2015198380A1 PCT/JP2014/066574 JP2014066574W WO2015198380A1 WO 2015198380 A1 WO2015198380 A1 WO 2015198380A1 JP 2014066574 W JP2014066574 W JP 2014066574W WO 2015198380 A1 WO2015198380 A1 WO 2015198380A1
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raw material
binder
sio
mass
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PCT/JP2014/066574
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French (fr)
Japanese (ja)
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慎 庄司
盛岡 実
樋口 隆行
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電気化学工業株式会社
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Priority to PCT/JP2014/066574 priority Critical patent/WO2015198380A1/en
Priority to JP2016528773A priority patent/JP6383417B2/en
Publication of WO2015198380A1 publication Critical patent/WO2015198380A1/en

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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions 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
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/02Selection of the hardening environment
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04GSCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G21/00Preparing, conveying, or working-up building materials or building elements in situ; Other devices or measures for constructional work
    • E04G21/02Conveying or working-up concrete or similar masses able to be heaped or cast
    • 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
    • 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
    • Y02P40/121Energy efficiency measures, e.g. improving or optimising the production methods

Definitions

  • SiO 2 raw material quartzite fine powder, SiO 2 component: 97.0%, Al 2 O 3 component: 2.0%, Fe 2 O 3 component: 0.1%, SiO 2 raw material, Al 2 O 3 raw material, and Fe 2 O 3 raw material: fly ash, CaO component: 5.2%, SiO 2 component: 62.5%, Al 2 O 3 component: 21.8%, Fe 2 O 3 component: 4.8%, loss on ignition: 3.2%.
  • Fe 2 O 3 raw material iron oxide raw material, Fe 2 O 3 component: 90.0%
  • CaO raw material (1) limestone fine powder, CaO 55.4%, MgO 0.37%, Al 2 O 3 0.05%, Fe 2 O 3 0.02%, SiO 2 0.10 %, Loss on ignition is 43.57%.
  • 150 ⁇ m passage rate is 97. %, 100 ⁇ m passage rate is 91.9%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Civil Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The purpose of the present invention is to provide: a bonding material for carbonated construction materials, which has a high bending strength following carbonation hardening, exhibits excellent resistance to freezing and melting, and has a reduced length change rate; and a method for producing the same. Provided are: a bonding material for carbonated construction materials, in which the content of β-2CaO·SiO2 is 40-70 mass%, the overall quantity of 3CaO·SiO2 and interstitial phases is 30-60 mass%, and the content of gypsum is less than 1 mass% in terms of SO3; and a method for producing the same.

Description

炭酸化建材用の結合材およびその製造方法Binder for carbonized building materials and method for producing the same
 本発明は、主に、土木・建築分野において使用される炭酸化建材用の結合材およびその製造方法に関する。 The present invention mainly relates to a binder for carbonized building materials used in the field of civil engineering and construction, and a method for producing the same.
 住宅建材としてスレート板はよく知られており、従来から多用されている。そして、スレート板の建材としての歴史は古く、初期のスレート板は繊維材料としてアスベストを使用してきた。
 しかし、アスベストの健康被害が深刻化するのに伴い、アスベストはパルプ繊維に置き換わってきている。これは、スレート板がオートクレーブ養生を施されて生産されるため、高温条件に耐える繊維としてパルプ繊維が選定されているためである。
Slate plates are well known as a housing building material and have been widely used in the past. And the history as a building material of a slate board is old, and the early slate board has used asbestos as a fiber material.
However, asbestos health has become more serious, asbestos has been replaced by pulp fibers. This is because the pulp fiber is selected as the fiber that can withstand high temperature conditions because the slate plate is produced by autoclave curing.
 オートクレーブ養生を施されて生産されたスレート板は、寸法変化が小さいという利点がある。一方、供用開始後に空気中の二酸化炭素と反応して中性化すると、強度低下が起こり、炭酸化に伴う収縮も惹起されて耐久性が低下することも明らかになってきている。
 また、オートクレーブ養生は重油消費量が大きく、環境負荷の大きな養生方法である。近年では、寸法安定性や長期の耐久性に加え、環境負荷低減の性能も重要視されている。特に、最近では、環境負荷の小さいスレート板の生産方法が強く求められている。
The slate plate produced by autoclave curing has the advantage that the dimensional change is small. On the other hand, when it reacts with carbon dioxide in the air after the start of service and becomes neutral, the strength is lowered and shrinkage due to carbonation is also induced, resulting in a decrease in durability.
Autoclave curing is a curing method that consumes a large amount of heavy oil and has a large environmental load. In recent years, in addition to dimensional stability and long-term durability, the performance of reducing the environmental load is also regarded as important. In particular, recently, there is a strong demand for a method for producing a slate plate with a low environmental load.
 炭酸化養生による建材の製造方法に関連して、例えば、木質系セメント硬化体は、炭酸化処理することにより反り返りが発生しにくくなり、寸法安定性に優れたものとなる(特許文献1)。
 しかしながら、この建材の寸法安定性は、未だ十分ではなく、また、二酸化炭素の固定化能力も、環境負荷低減の性能も十分ではなかった。さらに、可燃性の木材チップが配合されているため、耐火性にも課題があった。
In relation to a method for producing a building material by carbonation curing, for example, a wood-based cement hardened body is less likely to warp and is excellent in dimensional stability by being carbonized (Patent Document 1).
However, the dimensional stability of this building material is not yet sufficient, and the ability to fix carbon dioxide and the performance of reducing the environmental load are not sufficient. Furthermore, since flammable wood chips are blended, there is a problem in fire resistance.
 一方、高炉セメント、高炉スラグ、モノサルフェートおよびセッコウを主成分とするスラリーを成形し、養生して、乾燥させる無機質製品において、廃熱ガスを用いて、乾燥と炭酸化を行う方法も提案されている(特許文献2)。
 しかしながら、この方法で得られる製品は、強度発現性が十分でなく、寸法安定性も未だ十分ではなかった。さらに、表面が脆弱であり、粉吹き現象を呈しやすく、耐久性や美観にも課題があった。
On the other hand, a method of drying and carbonation using waste heat gas is proposed for inorganic products that are formed, cured, and dried from blast furnace cement, blast furnace slag, monosulfate, and gypsum. (Patent Document 2).
However, the product obtained by this method does not have sufficient strength development and dimensional stability is still insufficient. Furthermore, the surface is fragile, it is easy to exhibit a powder blowing phenomenon, and there are problems in durability and aesthetics.
 また、中性化による白華の発生を抑制する目的で、相対湿度80%以上、二酸化炭素濃度5~25体積%で炭酸化させたセメント硬化体も提案されている(特許文献3)。
 上記の方法は、アルカリの溶出を抑え、エフロ(Efflorescence)も防止できるが、強度発現性が十分でなく、寸法安定性も不十分であり、さらに、二酸化炭素の固定化能力も十分でなく、環境負荷低減の性能も十分ではなかった。
Further, for the purpose of suppressing the generation of white flower due to neutralization, a hardened cement body that has been carbonated at a relative humidity of 80% or more and a carbon dioxide concentration of 5 to 25% by volume has been proposed (Patent Document 3).
The above method can suppress elution of alkali and prevent efflorescence, but also has insufficient strength development, insufficient dimensional stability, and insufficient carbon dioxide immobilization ability, The environmental load reduction performance was not sufficient.
 本発明者は、既に、ビーライト(Belite)を38質量%以上含有する炭酸化建材用セメントを提案した。このセメントは炭酸化養生することで高強度となり、特に曲げ強度が高いものであった。その組成は、ビーライト含有量が38%~60質量%、エーライトとアルミネートとフェライトの合計が少なくとも40質量%以下、加えて、アルミネートとフェライトはそれぞれ10質量%以下であり、セッコウ類をSO換算で1~5質量%含むものであった(特許文献4)。 The present inventor has already proposed a cement for carbonated building materials containing 38% by mass or more of Belite. This cement became high strength by carbonation curing, and particularly had high bending strength. Its composition is that belite content is 38% to 60% by mass, the total of alite, aluminate and ferrite is at least 40% by mass, in addition, aluminate and ferrite are each 10% by mass or less. In an amount of 1 to 5% by mass in terms of SO 3 (Patent Document 4).
 上記の組成に当てはまるセメントとして、日本では、低熱ポルトランドセメントがJIS化されている。
 しかし、建材には曲げ強度のほか、寸法安定性や長期耐久性が求められ、その観点からは、従来の炭酸化建材用のセメント組成物は改良の余地を残している。
In Japan, low heat Portland cement is JISed as a cement applicable to the above composition.
However, in addition to bending strength, building materials are required to have dimensional stability and long-term durability. From that viewpoint, conventional cemented compositions for carbonized building materials leave room for improvement.
日本特開2000-7466号公報Japanese Unexamined Patent Publication No. 2000-7466 日本特開昭56-22688号公報Japanese Unexamined Patent Publication No. 56-22688 日本特開平11-278961号公報Japanese Unexamined Patent Publication No. 11-278961 日本特開平10-194798号公報Japanese Unexamined Patent Publication No. 10-194798
 そこで、本発明は、炭酸化養生を行うことにより、高い曲げ強度を発現し、オートクレーブ養生を行わなくても寸法安定性に優れ、供用後の炭酸化に伴う強度低下や収縮も起こさず、凍結融解抵抗性にも優れ、長期耐久性を有する建材用の結合材、および環境負荷低減が可能な該結合材の製造方法を提供することを目的とする。 Therefore, the present invention expresses a high bending strength by performing carbonation curing, is excellent in dimensional stability without performing autoclave curing, does not cause a decrease in strength and shrinkage due to carbonation after use, and freezes. It is an object of the present invention to provide a binding material for building materials that is excellent in melting resistance and has long-term durability, and a method for producing the binding material that can reduce the environmental load.
 各種のポルトランドセメントには、SO換算で1~5質量%のセッコウが必須成分として含まれる。セッコウはポルトランドセメント中のアルミネート相の初期水和を制御して流動性や作業性を確保する目的で添加され、さらに、強度発現性にも貢献する。このため、セッコウは必須成分として用いられてきた。
 しかし、本発明者らは、曲げ強度が高く、寸法安定性や耐久性に優れる建材の製造方法として、セッコウをSO換算で1質量%未満の範囲とした結合材を適用し、炭酸化養生を施すことによって、曲げ強度の更なる向上と、寸法安定性や耐久性の向上が実現できることを知見した。
Various Portland cements contain 1 to 5% by weight of gypsum as an essential component in terms of SO 3 . Gypsum is added to control the initial hydration of the aluminate phase in Portland cement to ensure fluidity and workability, and also contributes to strength development. For this reason, gypsum has been used as an essential component.
However, the present inventors applied a binder in which gypsum is less than 1% by mass in terms of SO 3 as a method for producing a building material having high bending strength and excellent dimensional stability and durability. It has been found that further improvement of the bending strength and improvement of dimensional stability and durability can be realized by applying.
 さらに、炭酸化建材用の結合材を製造する際に、副生の消石灰を用いることにより、セメント生産時の燃料消費量を著しく低減でき、低温焼成が可能となること、CO排出量を大幅に低減できることを見出した。 In addition, when manufacturing binders for carbonated building materials, by-product slaked lime can be used to significantly reduce fuel consumption during cement production, enable low-temperature firing, and greatly reduce CO 2 emissions. It was found that it can be reduced.
 本発明は、上記の知見の基づくものであり、以下の要旨を有する。
(1)β-2CaO・SiOの含有量が40~70質量%であり、3CaO・SiOと間隙相(3CaO・Alと4CaO・Al・Fe)との合計量が30~60質量%であり、セッコウ含有量がSO換算で1質量%未満であることを特徴とする炭酸化建材用の結合材。
(2)間隙相が10質量%以下であり、3CaO・Alの含有量が5質量%以下である上記(1)に記載の炭酸化建材用の結合材。
(3)結合材の粉末度が、ブレーン比面積値で2,000~8,000cm/gである、上記(1)または(2)に記載の炭酸化建材用の結合材。
The present invention is based on the above findings and has the following gist.
(1) The content of β-2CaO · SiO 2 is 40 to 70% by weight, of the 3CaO · SiO 2 and a gap phase (3CaO · Al 2 O 3 and 4CaO · Al 2 O 3 · Fe 2 O 3) A binder for carbonated building materials, characterized in that the total amount is 30 to 60% by mass and the gypsum content is less than 1% by mass in terms of SO 3 .
(2) The binder for carbonated building materials according to the above (1), wherein the interstitial phase is 10% by mass or less and the content of 3CaO.Al 2 O 3 is 5% by mass or less.
(3) The binder for carbonated building materials according to the above (1) or (2), wherein the fineness of the binder is 2,000 to 8,000 cm 2 / g in terms of Blaine area.
(4)上記(1)~(3)のいずれかに記載の結合材の製造方法であって、
CaO原料、SiO原料、Al原料、およびFe原料を、撹拌混合し、熱処理を行う製造方法。
(5)CaO原料の一部または全部に副生消石灰を用いる上記(4)に記載の製造方法。
(6)SiO原料、Al原料、およびFe原料がフライアッシュである、上記(4)または(5)に記載の製造方法。
(4) A method for producing the binder according to any one of (1) to (3) above,
A manufacturing method in which a CaO raw material, a SiO 2 raw material, an Al 2 O 3 raw material, and an Fe 2 O 3 raw material are mixed by stirring and heat-treated.
(5) The manufacturing method as described in said (4) using byproduct slaked lime for some or all of CaO raw material.
(6) SiO 2 raw material, Al 2 O 3 raw material, and Fe 2 O 3 raw material is fly ash, the production method according to (4) or (5).
(7)熱処理温度が、1200~1600℃である、上記(4)~(6)のいずれかに記載の製造方法。
(8)副生消石灰が、カーバイドからアセチレンを発生させる際に生じたものである、上記(5)~(7)のいずれかに記載の製造方法。
(9)結合材生産時のCO排出量原単位が200kg-CO/ton以下である、上記(4)~(8)のいずれかに記載の製造方法。
(7) The production method according to any one of (4) to (6), wherein the heat treatment temperature is 1200 to 1600 ° C.
(8) The production method according to any one of (5) to (7), wherein the by-product slaked lime is produced when acetylene is generated from carbide.
(9) The production method according to any one of the above (4) to (8), wherein the CO 2 emission basic unit during production of the binder is 200 kg-CO 2 / ton or less.
 本発明の炭酸化建材用の結合材は、製造時の環境負荷も小さく、該結合材を用いて炭酸化養生を施したセメント硬化体などは、従来のセメント組成物を用いてオートクレーブ養生を施した建材などと比較して、強度発現性に優れ、寸法安定性に優れ、供用後の炭酸化に伴う強度低下や収縮も起こさず、凍結融解抵抗性も向上し、かつ長期耐久性を有し、住宅建材分野で有用である。 The binding material for carbonated building materials of the present invention has a small environmental load during production, and the hardened cement body subjected to carbonation curing using the binding material is subjected to autoclave curing using a conventional cement composition. Compared to building materials, etc., it has excellent strength development, excellent dimensional stability, no reduction in strength and shrinkage due to carbonation after use, improved freeze-thaw resistance, and long-term durability Useful in the field of residential building materials.
 本発明における、「部」や「%」は、実施例の記載を含めて特に規定しない限り全て質量基準で示す。
 また、本発明でいうセメントコンクリートとは、セメントペースト、セメントモルタル、およびコンクリートの総称である。
In the present invention, “parts” and “%” are all shown on a mass basis unless otherwise specified including the description of Examples.
The cement concrete as used in the present invention is a general term for cement paste, cement mortar, and concrete.
 本発明で使用する炭酸化建材用の結合材は、β-2CaO・SiOの含有量が40~70%、好ましくは50~60%であり、3CaO・SiOと間隙相(3CaO・Alと4CaO・Al・Fe)との合計量が30~60%、好ましくは40~50%であり、セッコウ含有量がSO換算で1%未満、好ましくは0.5%未満であることを特徴とする。 The binder for carbonated building materials used in the present invention has a content of β-2CaO · SiO 2 of 40 to 70%, preferably 50 to 60%, and 3CaO · SiO 2 and a gap phase (3CaO · Al 2 The total amount of O 3 and 4CaO.Al 2 O 3 .Fe 2 O 3 ) is 30 to 60%, preferably 40 to 50%, and the gypsum content is less than 1% in terms of SO 3 , preferably 0.8. It is characterized by being less than 5%.
 間隙相の含有量は10%以下が好ましく、より好ましくは6%以下である。また、3CaO・Alの含有量は5%以下が好ましく、より好ましくは3%以下である。
 間隙相が10%を超えたり、3CaO・Al含有量が5%を超えると、流動性が悪くなったり、炭酸化養生後の曲げ強度が十分でない場合がある。
The interstitial phase content is preferably 10% or less, more preferably 6% or less. Further, the content of 3CaO · Al 2 O 3 is preferably 5% or less, and more preferably 3% or less.
If the interstitial phase exceeds 10% or the 3CaO · Al 2 O 3 content exceeds 5%, the fluidity may deteriorate or the bending strength after carbonation curing may not be sufficient.
 β-2CaO・SiOの含有量が40%未満では、炭酸化養生後の曲げ強度が十分でない場合や、流動性が悪くなる場合がある。逆に、70%を超えると、脱型強度の確保が難しくなり、生産性が悪くなる場合がある。
 3CaO・SiOと間隙相との合計量が30%未満では、脱型強度の確保が難しくなり、逆に、60%を超えると、炭酸化養生後の曲げ強度が十分でない場合や、流動性が悪くなる場合がある。
If the content of β-2CaO · SiO 2 is less than 40%, the bending strength after carbonation curing may not be sufficient, or the fluidity may deteriorate. On the other hand, when it exceeds 70%, it is difficult to secure the mold release strength, and the productivity may deteriorate.
If the total amount of 3CaO.SiO 2 and the interstitial phase is less than 30%, it is difficult to ensure the demolding strength. Conversely, if it exceeds 60%, the bending strength after carbonation curing is insufficient, or the fluidity May get worse.
 本発明において、セッコウは、CaSOなる分子式で示される硫酸カルシウムを主成分とする鉱物の総称である。具体的には、CaSO、CaSO・1/2HO、及びCaSO・2HOなる分子式でそれぞれ示される無水、半水、および二水の各セッコウを総称するもので特に限定されるものではない。
 本発明では、セッコウ含有量は、SO換算で1%未満である。本発明において、セッコウ含有量は重要であり、セッコウ含有量をSO換算で1%未満とすることで、炭酸化養生後の曲げ強度をさらに高めることができる。また、寸法安定性や耐久性も向上させることができる。耐久性の具体例としては、供用後の強度低下がないこと、凍結融解抵抗性が向上すること等が挙げられる。
 より好ましくは、セッコウの含有量は、SO換算で0.5%以下であり、0.3%以下が最も好ましい。なお、本発明においては、セッコウは含有されなくてもよい。
In the present invention, gypsum is a general term for minerals mainly composed of calcium sulfate represented by the molecular formula CaSO 4 . Specifically, it is specifically limited to generic names of anhydrous, half-water, and two-water gypsum represented by molecular formulas of CaSO 4 , CaSO 4 .1 / 2H 2 O, and CaSO 4 .2H 2 O, respectively. It is not a thing.
In the present invention, the gypsum content is less than 1% in terms of SO 3 . In the present invention, the gypsum content is important, and the bending strength after carbonation curing can be further increased by setting the gypsum content to less than 1% in terms of SO 3 . Also, dimensional stability and durability can be improved. Specific examples of durability include no decrease in strength after in-service, and improvement in freeze-thaw resistance.
More preferably, the content of gypsum is 0.5% or less in terms of SO 3 , and most preferably 0.3% or less. In the present invention, gypsum may not be contained.
 本発明の結合材を製造する際の原料としては、特に限定されるものではないが、CaO原料としては、例えば、石灰石や炭酸カルシウムの他、水酸化カルシウムを用いることもできる。
 本発明では、CaO原料の一部または全部に、副生消石灰を用いて製造することが望ましい。CaO原料として、副生消石灰を用いることにより、本発明の結合材を製造する際のCO排出量の原単位を著しく低減することが可能である。特に、副生消石灰が、カーバイドからアセチレンを発生させる際に生じたものであることが望ましい。
Although it does not specifically limit as a raw material at the time of manufacturing the binder of this invention, As a CaO raw material, calcium hydroxide can also be used other than limestone or calcium carbonate, for example.
In the present invention, it is desirable to produce by-product slaked lime for some or all of the CaO raw material. By using by-product slaked lime as a CaO raw material, it is possible to remarkably reduce the basic unit of CO 2 emission when producing the binder of the present invention. In particular, it is desirable that the byproduct slaked lime is generated when acetylene is generated from carbide.
 上記の副生消石灰を用いることで、本発明の結合材を生産する際のCO排出量の原単位が200kg-CO/ton以下となる。通常、ポルトランドセメントのCO排出量の原単位は750kg-CO/ton程度とされ、副産物である高炉スラグを多量に混和した高炉セメントのCO排出量の原単位でも450kg-CO/ton程度とされている(土木学会:コンクリート技術シリーズ No.44、コンクリートの環境負荷評価、p.I-25(2002)参照)。かくして、本発明の結合材は環境負荷低減性が顕著に高い。 By using the above-mentioned byproduct slaked lime, the basic unit of CO 2 emission amount when producing the binder of the present invention is 200 kg-CO 2 / ton or less. Usually, the basic unit of CO 2 emission of Portland cement is about 750 kg-CO 2 / ton, and the basic unit of CO 2 emission of blast furnace cement mixed with a large amount of by-product blast furnace slag is 450 kg-CO 2 / ton. (See Japan Society of Civil Engineers: Concrete Technology Series No. 44, Environmental Impact Assessment of Concrete, p.I-25 (2002)). Thus, the binding material of the present invention has a significantly high environmental load reduction.
 SiO原料としては、特に限定されるものではないが、ケイ石微粉末、粘土、シリカフューム、フライアッシュ、非晶質シリカ、またはその他の各産業から副生するシリカ質の物質から選定できる。なかでも、ケイ石微粉末、粘土、またはフライアッシュが好ましい。
 Al原料としては、特に限定されるものではないが、フライアッシュ、粘土、明礬石、ボーキサイト、またはその他の各産業から副生するアルミ質の物質から選定できる。なかでも、フライアッシュ、粘土、またはボーキサイトが好ましい。
 Fe原料としては、特に限定されるものではないが、フライアッシュ、ヘマタイト、リモナイト、マグネタイト、 ウスタイト、マグヘマイト、またはその他の各産業から副生する鉄質の物質から選定できる。なかでも、ヘマタイト、リモナイトまたはマグネタイトが好ましい。
The SiO 2 raw material is not particularly limited, it can be selected quartzite powder, clay, silica fume, fly ash, amorphous silica or other siliceous by-produced from the industrial materials. Of these, quartzite fine powder, clay, or fly ash is preferable.
The Al 2 O 3 raw material is not particularly limited, but can be selected from fly ash, clay, alunite, bauxite, or other aluminum-based substances by-produced from other industries. Among these, fly ash, clay, or bauxite is preferable.
The Fe 2 O 3 raw material is not particularly limited, but can be selected from fly ash, hematite, limonite, magnetite, wustite, maghemite, or other ferrous substances by-produced from other industries. Among these, hematite, limonite or magnetite is preferable.
 本発明の結合材は、CaO原料、SiO原料、あるいは、CaO原料、SiO原料、Al原料、Fe原料を、コニカルミル、らせん型混合機、櫂型攪拌機等を用いて撹拌しながら混合し、その後、熱処理することによって得られる。
 結合材の製造時の各原料の混合の仕方は、すべての原料を撹拌混合器内に投入した後でもよいし、順次上記原料を投入してもよい。これらの原料の投入順序には制限はないが、まとめて原料を投入し混合するのが、生産効率上は好ましい。
The binding material of the present invention is a CaO raw material, SiO 2 raw material, or a CaO raw material, SiO 2 raw material, Al 2 O 3 raw material, Fe 2 O 3 raw material, using a conical mill, a helical mixer, a vertical stirrer, or the like. It is obtained by mixing with stirring and then heat-treating.
The method of mixing the respective raw materials at the time of manufacturing the binder may be after all the raw materials have been charged into the stirring mixer, or the above raw materials may be sequentially added. Although there is no restriction | limiting in the injection | throwing-in order of these raw materials, it is preferable on production efficiency to input and mix a raw material collectively.
 熱処理方法は、キルンでの焼成や電気炉での溶融等が挙げられる。なかでもキルンを用いる熱処理方法が好ましい。
 熱処理温度は、原料の配合にもよるが1200~1600℃が好ましく、1250~1500℃がより好ましい。1200℃未満では効率良く反応が進まず、遊離石灰が多く生成する場合がある。また、熱処理温度が1600℃を超えた場合は、得られるクリンカーの生成反応の更なる改善は期待できず、消費エネルギーが大きくなり、コスト高となり、環境負荷も大きくなるため望ましくない。
Examples of the heat treatment method include baking in a kiln and melting in an electric furnace. Of these, a heat treatment method using a kiln is preferred.
The heat treatment temperature is preferably 1200 to 1600 ° C., more preferably 1250 to 1500 ° C., although it depends on the composition of the raw materials. If it is less than 1200 degreeC, reaction may not advance efficiently and may produce | generate much free lime. On the other hand, when the heat treatment temperature exceeds 1600 ° C., further improvement of the resulting clinker formation reaction cannot be expected, and this is undesirable because energy consumption increases, costs increase, and environmental impact increases.
 CaO原料、SiO原料、Al原料、Fe原料などの混合物を熱処理して得られたクリンカーは、ボールミルを用いて粉砕し、粉末にすることで結合材としても利用できる。
 結合材の粉末度は、ブレーン比表面積値(以下、ブレーン値という)で2,000~8,000cm/gが好ましく、3,000~6,000cm/gがより好ましく、4,000~5,000cm/gが最も好ましい。2000cm/g未満では充分な強度発現性が得られない場合があり、8,000cm/gを超えるように微粉化しても、さらなる効果の向上は期待できず、消費エネルギーが大きくなり、コスト高となり、環境負荷も大きくなる。
The clinker obtained by heat-treating a mixture of CaO raw material, SiO 2 raw material, Al 2 O 3 raw material, Fe 2 O 3 raw material and the like can be used as a binder by pulverizing with a ball mill to form a powder.
Fineness of binder, Blaine specific surface area value (hereinafter, referred to as Blaine) 2,000 ~ 8,000cm 2 / g are preferred, the more preferred 3,000 ~ 6,000cm 2 / g, 4,000 ~ Most preferred is 5,000 cm 2 / g. If it is less than 2000 cm 2 / g, sufficient strength development may not be obtained, and even if pulverized to exceed 8,000 cm 2 / g, further improvement in the effect cannot be expected, energy consumption increases, and the cost High and environmental impact increases.
 本発明では、セッコウはSO換算で1%未満の範囲で添加できる。セッコウはクリンカーと同時粉砕しても良いし、別々に粉砕した後、混合してもよい。これらの混合機としては、ボールミル、らせん型混合機、回転混合機等が挙げられ、ボールミル、またはらせん型混合機が好ましい。 In the present invention, gypsum can be added in a range of less than 1% in terms of SO 3 . Gypsum may be pulverized simultaneously with the clinker, or may be pulverized separately and then mixed. Examples of these mixers include a ball mill, a helical mixer, and a rotary mixer, and a ball mill or a helical mixer is preferable.
 本発明では、本発明の結合材の他に、高炉スラグ、フライアッシュ、シリカフューム、石灰石粉末、高炉徐冷スラグ微粉末、都市ゴミ焼却灰、下水汚泥焼却灰、砂等の細骨材、砂利等の粗骨材、膨張材、急硬材、減水剤、AE減水剤、高性能減水剤、高性能AE減水剤、消泡剤、増粘剤、従来の防錆剤、防凍剤、収縮低減剤、凝結調整剤、ベントナイトなどの粘土鉱物、ハイドロタルサイトなどのアニオン交換体、および繊維物質からなる群から選ばれる一種以上の材料を、本発明の目的を実質的に阻害しない範囲で併用することが可能である。
 上記した材料の混合装置としては、既存の如何なる装置も使用可能であり、例えば、傾胴ミキサ、オムニミキサ、ヘンシェルミキサ、V型ミキサ、ナウタミキサ等の使用が可能である。好ましくは、傾胴ミキサ、オムニミキサ、またはナウタミキサが用いられる。
In the present invention, in addition to the binder of the present invention, blast furnace slag, fly ash, silica fume, limestone powder, blast furnace slow-cooled slag fine powder, municipal waste incineration ash, sewage sludge incineration ash, fine aggregates such as sand, gravel, etc. Coarse aggregate, expansion material, rapid hardening material, water reducing agent, AE water reducing agent, high performance water reducing agent, high performance AE water reducing agent, antifoaming agent, thickener, conventional rust preventive agent, antifreeze agent, shrinkage reducing agent A combination of one or more materials selected from the group consisting of a coagulation modifier, a clay mineral such as bentonite, an anion exchanger such as hydrotalcite, and a fiber substance, as long as the object of the present invention is not substantially inhibited. Is possible.
As the above-described material mixing apparatus, any existing apparatus can be used. For example, a tilting cylinder mixer, an omni mixer, a Henschel mixer, a V-type mixer, and a Nauta mixer can be used. Preferably, a tilting cylinder mixer, an omni mixer, or a nauta mixer is used.
 本発明においては、炭酸化養生は、オートクレーブ養生を行わなくても高い曲げ強度を発現し、寸法安定性に優れ、供用後の炭酸化に伴う強度低下や収縮も起こさず、凍結融解抵抗性を向上させる目的で実施される。
 本発明の結合材を用いた炭酸化養生は、温度10℃以上70℃以下、相対湿度10%以上90%以下、CO濃度10%以上の条件で行うことが好ましく、温度20℃以上50℃以下、相対湿度40%以上90%以下、CO濃度20%以上の条件がより好ましい。
 得られた建材は盛土・擁壁工事、スラブ等の土木分野、壁材、屋根材等の建築分野で好ましく用いられる。
In the present invention, the carbonation curing exhibits high bending strength without performing autoclave curing, is excellent in dimensional stability, does not cause reduction in strength or shrinkage due to carbonation after use, and exhibits freeze-thaw resistance. It is implemented for the purpose of improving.
Carbonation curing using the binder of the present invention is preferably performed under conditions of a temperature of 10 ° C. or more and 70 ° C. or less, a relative humidity of 10% or more and 90% or less, and a CO 2 concentration of 10% or more, and a temperature of 20 ° C. or more and 50 ° C. Hereinafter, conditions of relative humidity of 40% to 90% and a CO 2 concentration of 20% or more are more preferable.
The obtained building materials are preferably used in the field of civil engineering such as embankment and retaining wall construction, slabs, and the building field such as wall materials and roofing materials.
 以下、実施例、および比較例を挙げてさらに詳細に内容を説明するが、本発明はこれらに限定して解釈されるものではない。 Hereinafter, the contents will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not construed as being limited thereto.
「実験例1」
 炭酸化建材用の結合材は、CaO原料として石灰石微粉末を、SiO原料としてケイ石微粉末を、SiO原料、Al原料、およびFe原料としてフライアッシュを、Al原料としてボーキサイトをFe原料として鉄鉱石を使用して製造した。
 上記の原料を所定の割合で、室温下、ボールミル(古河産機システムズ社製)中に、同時に投入して混合粉砕した。次いで、パン型造粒機により造粒し、ロータリーキルンを用いて熱処理を行い、表1に示すようなクリンカーを製造した。
 熱処理温度は、バーナーの焼点温度で1450±30℃で行った。得られたクリンカーを粉砕し、セッコウを添加することなく、そのまま炭酸化建材用の結合材とした。
"Experiment 1"
Binder for carbonation building material, limestone powder as CaO material, a quartzite powder as SiO 2 raw material, SiO 2 material, Al 2 O 3 raw material, and the fly ash as Fe 2 O 3 raw material, Al 2 bauxite as O 3 raw material was prepared using the iron ore as Fe 2 O 3 raw material.
The above raw materials were simultaneously charged at a predetermined ratio into a ball mill (manufactured by Furukawa Industrial Systems Co., Ltd.) at room temperature and mixed and ground. Subsequently, it granulated with the bread | pan type granulator, and it heat-processed using the rotary kiln, and manufactured the clinker as shown in Table 1.
The heat treatment temperature was 1450 ± 30 ° C. as the burning point temperature of the burner. The obtained clinker was pulverized and used as a binder for carbonated building materials without adding gypsum.
 この結合材を用いて、水/結合材の質量比率50%、結合材と砂の質量比率が1/3のモルタルを調製した。50℃で4時間の蒸気養生(蒸気養生槽内、相対湿度100%)を施した後、脱型し、脱型時の強度を測定した。さらに、脱型後から炭酸化養生を施し、所定の材齢で強度を測定し、さらに、凍結融解、長さ変化を測定した。
 炭酸化養生の条件は、30℃、相対湿度60%、COガス濃度10体積%の条件で、装置として中性化試験装置(朝日科学社製)を用い、7日間行った。
Using this binder, a mortar having a water / binder mass ratio of 50% and a binder / sand mass ratio of 1/3 was prepared. After steam curing at 50 ° C. for 4 hours (in a steam curing tank, relative humidity 100%), the mold was removed and the strength at the time of removal was measured. Furthermore, carbonation curing was applied after demolding, the strength was measured at a predetermined age, and freeze-thaw and length change were further measured.
Carbonation curing conditions were 30 ° C., relative humidity 60%, CO 2 gas concentration 10% by volume, and a neutralization test apparatus (manufactured by Asahi Kagaku) was used as the apparatus for 7 days.
<使用材料>
 CaO原料(1):石灰石微粉末、CaOが55.4%、MgOが0.37%、Alが0.05%、Feが0.02%、SiOが0.10%、強熱減量が43.57%。150μm通過率が97.%、100μm通過率が91.9%。
 SiO原料:ケイ石微粉末、SiO成分:97.0%、Al成分:2.0%、Fe成分:0.1%、
 SiO原料、Al原料、およびFe原料:フライアッシュ、CaO成分:5.2%、SiO成分:62.5%、Al成分:21.8%、Fe成分:4.8%、強熱減量:3.2%。
 Fe原料:酸化鉄原料、Fe成分:90.0%
<Materials used>
CaO raw material (1): limestone fine powder, CaO 55.4%, MgO 0.37%, Al 2 O 3 0.05%, Fe 2 O 3 0.02%, SiO 2 0.10 %, Loss on ignition is 43.57%. 150 μm passage rate is 97. %, 100 μm passage rate is 91.9%.
SiO 2 raw material: quartzite fine powder, SiO 2 component: 97.0%, Al 2 O 3 component: 2.0%, Fe 2 O 3 component: 0.1%,
SiO 2 raw material, Al 2 O 3 raw material, and Fe 2 O 3 raw material: fly ash, CaO component: 5.2%, SiO 2 component: 62.5%, Al 2 O 3 component: 21.8%, Fe 2 O 3 component: 4.8%, loss on ignition: 3.2%.
Fe 2 O 3 raw material: iron oxide raw material, Fe 2 O 3 component: 90.0%
(測定方法)
 鉱物組成:化学成分値からボーグの式を用いて求めた。
S=(4.07×CaO)-(7.60×SiO)-(6.72×Al)-(1.43×Fe)-(2.85×SO
S=(2.87×SiO)-(0.754×CS)
A=(2.65×Al)-(1.69×Fe
AF=(3.04×Fe
 なお、本発明では、CSは3CaO・SiOを示し、CSは2CaO・SiOを示し、CAは3CaO・Alを示し、CAFは4CaO・Al・Feを示す。
(Measuring method)
Mineral composition: It was determined from the chemical component value using the Borg formula.
C 3 S = (4.07 × CaO) − (7.60 × SiO 2 ) − (6.72 × Al 2 O 3 ) − (1.43 × Fe 2 O 3 ) − (2.85 × SO 3 )
C 2 S = (2.87 × SiO 2 ) − (0.754 × C 3 S)
C 3 A = (2.65 × Al 2 O 3 ) − (1.69 × Fe 2 O 3 )
C 4 AF = (3.04 × Fe 2 O 3 )
In the present invention, C 3 S represents a 3CaO · SiO 2, C 2 S indicates 2CaO · SiO 2, C 3 A shows a 3CaO · Al 2 O 3, C 4 AF are 4CaO · Al 2 O 3 · Fe 2 O 3 is shown.
 モルタルの脱型強度:JIS R 5201に準じて圧縮強さを測定した。
 炭酸化養生後のモルタルのCO含有量:クーロメータ(日本アンス社製)を用いて、CO量を測定して求めた。
 炭酸化養生後のモルタル曲げ強度:供試体サイズは縦4cm×横4cm×長さ16cmの直方体であり、それ以外はJIS A 1106に準じて曲げ強度を測定した。
Demolding strength of mortar: Compressive strength was measured according to JIS R 5201.
CO 2 content of the mortar after carbonation curing: coulometer (manufactured by Nippon ans Co.) was determined by measuring the amount of CO 2.
Mortar bending strength after carbonation curing: The specimen size is a rectangular parallelepiped of 4 cm long × 4 cm wide × 16 cm long. Otherwise, the bending strength was measured according to JIS A1106.
 炭酸化養生後のモルタルの凍結融解:JIS A 1148に準じて行った。評価は、500サイクルまで動弾性係数の相対値が60%以上を確保した場合は○、300サイクルまで動弾性係数の相対値が60%以上を確保した場合は△、300サイクル未満で動弾性係数の相対値が60%未満に低下した場合は×とした。
 炭酸化養生後のモルタルの長さ変化率:JIS A 1129-3に準拠して測定した。
Freezing and thawing of mortar after carbonation curing: Measured according to JIS A 1148. The evaluation is ○ when the relative value of the dynamic elastic modulus is 60% or more up to 500 cycles, Δ when the relative value of the dynamic elastic modulus is 60% or higher up to 300 cycles, and the dynamic elastic modulus is less than 300 cycles. When the relative value of was reduced to less than 60%, it was marked as x.
Change rate of mortar length after carbonation curing: Measured according to JIS A 1129-3.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 表1より、β-2CaO・SiOの含有量が40~70%であり、3CaO・SiOと間隙相(3CaO・Alと4CaO・Al・Fe)との合計量が30~60%であり、セッコウ含有量がSO換算で0%であると、炭酸化養生後の曲げ強度が大きく、凍結融解抵抗性に優れ、長さ変化率も小さくなることがわかる。中でも、間隙相が10%以下であり、3CaO・Alの含有量が5%以下であるものが特に優れることが分かる。 From Table 1, a content of β-2CaO · SiO 2 40 to 70% of the 3CaO · SiO 2 and a gap phase (3CaO · Al 2 O 3 and 4CaO · Al 2 O 3 · Fe 2 O 3) When the total amount is 30 to 60% and the gypsum content is 0% in terms of SO 3 , the bending strength after carbonation curing is large, the resistance to freezing and thawing is excellent, and the rate of change in length is also small. Recognize. In particular, it can be seen that those having a gap phase of 10% or less and a content of 3CaO.Al 2 O 3 of 5% or less are particularly excellent.
「実験例2」
 実験No.1-4のクリンカーを使用し、SO含有量が表2のようになるように二水セッコウ(試薬、市販品)を添加したこと以外は実験例1と同様に行った。結果を表2に示す。
"Experimental example 2"
Experiment 1 was carried out in the same manner as in Experimental Example 1 except that the clinker of No. 1-4 was used and dihydrate gypsum (reagent, commercially available product) was added so that the SO 3 content was as shown in Table 2. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 表2より、SO換算で1%未満のセッコウ添加量であると、炭酸化養生後の曲げ強度が大きく、凍結融解抵抗性に優れ、長さ変化率も小さくなることが分かる。
 なお、セッコウ添加量が2.0%は、ポルトランドセメントの標準的なSO添加率に相当する。
From Table 2, it can be seen that when the amount of gypsum added is less than 1% in terms of SO 3 , the bending strength after carbonation curing is large, the freeze-thaw resistance is excellent, and the length change rate is also small.
A gypsum addition amount of 2.0% corresponds to the standard SO 3 addition rate of Portland cement.
「実験例3」
 実験No.1-4のクリンカー組成比となるように原料を配合し、CaO原料として、下記するCaO原料(1)~(5)を使用したこと以外は実験例1と同様に行った。結果を表3に示す。なお、CaO原料(2)~(5)はその一部又は全部に副生の消石灰を使用したものである。
"Experiment 3"
The raw materials were blended so that the clinker composition ratio of Experiment No. 1-4 was obtained, and the same procedures as in Experimental Example 1 were performed except that the following CaO raw materials (1) to (5) were used as CaO raw materials. The results are shown in Table 3. The CaO raw materials (2) to (5) are obtained by using by-product slaked lime as a part or all of them.
 <使用材料>
 CaO原料(1):石灰石微粉末、CaOが55.4%、MgOが0.37%、Alが0.05%、Feが0.02%、SiOが0.10%、強熱減量が43.57%。150μm通過率が97.%、100μm通過率が91.9%。
 CaO原料(2):副生消石灰、カルシウムカーバイドと水を反応させてアセチレンを発生させた後に副生する消石灰、CaOが73.1%、MgOが0.07%、Alが0.55%、Feが0.28%、SiOが0.95%、SOが1.31%、NaOが0.03%、KOが0.02%、強熱減量が23.80%。150μm通過率が99.5%、100μm通過率が96.9%。
 CaO原料(3):CaO原料(1)30%とCaO原料(2)70%の混合物。
 CaO原料(4):CaO原料(1)50%とCaO原料(2)50%の混合物。
 CaO原料(5):CaO原料(1)70%とCaO原料(2)30%の混合物。
<Materials used>
CaO raw material (1): limestone fine powder, CaO 55.4%, MgO 0.37%, Al 2 O 3 0.05%, Fe 2 O 3 0.02%, SiO 2 0.10 %, Loss on ignition is 43.57%. 150 μm passage rate is 97. %, 100 μm passage rate is 91.9%.
CaO raw material (2): by-product slaked lime, slaked lime produced as a by-product after the reaction of calcium carbide and water to generate acetylene, CaO 73.1%, MgO 0.07%, Al 2 O 3 0. 55%, Fe 2 O 3 0.28%, SiO 2 0.95%, SO 3 1.31%, Na 2 O 0.03%, K 2 O 0.02%, loss on ignition Is 23.80%. The 150 μm pass rate is 99.5%, and the 100 μm pass rate is 96.9%.
CaO raw material (3): A mixture of 30% CaO raw material (1) and 70% CaO raw material (2).
CaO raw material (4): Mixture of CaO raw material (1) 50% and CaO raw material (2) 50%.
CaO raw material (5): a mixture of 70% CaO raw material (1) and 30% CaO raw material (2).
(測定方法)
 焼成エネルギー:CaO原料として、石灰石(CaO原料(1))を用いた際の重油使用量と電力使用量の総和エネルギーを100とし、相対値で示した。
 収率:ロータリーキルンにフィード(feed)した原料の質量を100とし、焼成後に得られた焼成物の質量の比率を100分率で示した。
(Measuring method)
Firing energy: The total energy of the amount of heavy oil used and the amount of power used when using limestone (CaO raw material (1)) as a CaO raw material was taken as 100 and expressed as a relative value.
Yield: The mass of the raw material fed to the rotary kiln was defined as 100, and the mass ratio of the calcined product obtained after calcination was shown as 100 fractions.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 表3より、副生消石灰をCaO原料の一部又は全部に用いた場合に(実験No.3-1~3-4)には、焼成エネルギーを大幅に削減でき、収率も著しく向上することが分かる。また、得られたクリンカーから調製した結合材の物性も良好であることが分かる。 From Table 3, when by-product slaked lime is used for some or all of the CaO raw material (Experiment Nos. 3-1 to 3-4), the burning energy can be greatly reduced and the yield is also significantly improved. I understand. Moreover, it turns out that the physical property of the binder prepared from the obtained clinker is also favorable.
「実験例4」
 実験例3の結合材の製造において、かかる原料由来と燃料由来のCO排出量の原単位を算出した。なお、重油や電力のCO排出量の原単位は、土木学会のコンクリート技術シリーズ62、コンクリートの環境負荷評価(その2)、p.39に記載されるインベントリデータ(各種エネルギーの原単位)を用いて算出した。すなわち、重油は2.97kg-CO/リットル、電力は0.407kg-CO/kWhを用いた。また、炭酸化養生後の供試体を用いてCO吸収量を定量した。結果を表4に示す。
"Experimental example 4"
In the production of the binder of Experimental Example 3, the basic unit of the CO 2 emission amount derived from the raw material and the fuel was calculated. The basic unit of CO 2 emissions of heavy oil and electric power is the same as the concrete technology series 62 of the Japan Society of Civil Engineers, the environmental load evaluation of concrete (Part 2), p. It was calculated using the inventory data described in No. 39 (unit values of various energies). That is, 2.97 kg-CO 2 / liter for heavy oil and 0.407 kg-CO 2 / kWh for electric power were used. Moreover, the amount of CO 2 absorption was quantified using the specimen after carbonation curing. The results are shown in Table 4.
(測定方法)
 CO吸収量:クーロメータ(日本アンス社製)を用いてCO量を測定した。
 強熱減量を差し引いた結合材100部に対するCO量に換算し、結合材1tあたりのCO吸収量を定量した。
 CO排出量:原料由来のCO排出量と燃料由来のCO排出量を計算した。
 ここで、原料由来のCO排出量は石灰石微粉末を使用した場合、脱炭酸分を計算した値となり、副生消石灰を使用した場合、0kg-CO/tである。燃料由来のCO排出量の原単位は実際に使用した燃料量から算出した。
(Measuring method)
CO 2 absorption amount: The CO 2 amount was measured using a coulometer (manufactured by Nippon Anse Co., Ltd.).
The amount of CO 2 absorbed per 1 ton of binding material was quantified by converting the amount of CO 2 to 100 parts of the binding material after subtracting the loss on ignition.
CO 2 emissions: calculated CO 2 emissions from the raw material and CO 2 emissions from the fuel.
Here, the CO 2 emission amount derived from the raw material is a value obtained by calculating the decarboxylation content when using limestone fine powder, and is 0 kg-CO 2 / t when using by-product slaked lime. The basic unit of fuel-derived CO 2 emissions was calculated from the amount of fuel actually used.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 表4より、副生消石灰をCaO原料の一部又は全部に用いた場合に(実験No.3-1~3-4)には、CO排出量の原単位が著しく小さいことが分かる。また、CaO原料に占める副生消石灰の割合が一定以上になると、炭酸化養生後のCO吸収量の方が大きな値となっていることも分かる。 From Table 4, it can be seen that when the by-product slaked lime is used for some or all of the CaO raw material (Experiment Nos. 3-1 to 3-4), the basic unit of CO 2 emission is extremely small. It can also be seen that when the proportion of by-product slaked lime in the CaO raw material exceeds a certain level, the amount of CO 2 absorbed after carbonation curing is larger.
 本発明の炭酸化建材用の結合材は、炭酸化養生後の曲げ強度が大きく、凍結融解抵抗性に優れ、長さ変化率も小さく、主として土木・建築分野において、使用することができる。 The binder for carbonated building materials of the present invention has a high bending strength after carbonation curing, is excellent in freeze-thaw resistance, has a small rate of change in length, and can be used mainly in the civil engineering and construction fields.

Claims (9)

  1.  β-2CaO・SiOの含有量が40~70質量%であり、3CaO・SiOと間隙相(3CaO・Alと4CaO・Al・Fe)との合計量が30~60質量%であり、セッコウ含有量がSO換算で1質量%未満であることを特徴とする炭酸化建材用の結合材。 beta-2CaO · SiO 2 content is 40 to 70 mass%, the total amount of the 3CaO · SiO 2 and a gap phase (3CaO · Al 2 O 3 and 4CaO · Al 2 O 3 · Fe 2 O 3) A binder for carbonated building materials, wherein the binder is 30 to 60% by mass and the gypsum content is less than 1% by mass in terms of SO 3 .
  2.  間隙相が10質量%以下であり、3CaO・Alの含有量が5質量%以下である請求項1に記載の炭酸化建材用の結合材。 The binder for carbonized building materials according to claim 1, wherein the interstitial phase is 10% by mass or less, and the content of 3CaO · Al 2 O 3 is 5% by mass or less.
  3.  結合材の粉末度が、ブレーン比面積値で2,000~8,000cm/gである、請求項1または2に記載の炭酸化建材用の結合材。 The binder for carbonated building materials according to claim 1 or 2, wherein the fineness of the binder is 2,000 to 8,000 cm 2 / g in terms of Blaine specific area.
  4.  請求項1~3のいずれかに記載の結合材の製造方法であって、
    CaO原料、SiO原料、Al原料、およびFe原料を、撹拌混合し、熱処理を行う製造方法。
    A method for producing the binding material according to any one of claims 1 to 3,
    A manufacturing method in which a CaO raw material, a SiO 2 raw material, an Al 2 O 3 raw material, and an Fe 2 O 3 raw material are mixed by stirring and heat-treated.
  5.  CaO原料の一部または全部に副生消石灰を用いる請求項4に記載の製造方法。 The manufacturing method of Claim 4 which uses byproduct slaked lime for some or all of CaO raw materials.
  6.  SiO原料、Al原料、およびFe原料がフライアッシュである、請求項4または5に記載の製造方法。 SiO 2 raw material, Al 2 O 3 raw material, and Fe 2 O 3 raw material is fly ash, the production method according to claim 4 or 5.
  7.  熱処理温度が、1200~1600℃である、請求項4~6のいずれかに記載の製造方法。 The manufacturing method according to any one of claims 4 to 6, wherein the heat treatment temperature is 1200 to 1600 ° C.
  8.  副生消石灰が、カーバイドからアセチレンを発生させる際に生じたものである、請求項5~7のいずれかに記載の製造方法。 The production method according to any one of claims 5 to 7, wherein the by-product slaked lime is produced when acetylene is generated from carbide.
  9.  結合材生産時のCO排出量原単位が200kg-CO/ton以下である、請求項4~8のいずれかに記載の製造方法。 The production method according to any one of claims 4 to 8, wherein the CO 2 emission basic unit during the production of the binder is 200 kg-CO 2 / ton or less.
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CN111072295A (en) * 2019-12-17 2020-04-28 福建源鑫环保科技有限公司 High-activity composite ferronickel slag cementing material and preparation method thereof
JP7490862B2 (en) 2019-03-13 2024-05-27 太平洋セメント株式会社 Method for producing cement powder composition

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JP2000072497A (en) * 1998-08-19 2000-03-07 Taiheiyo Cement Corp Cement for highly fluid shotcrete
JP2004018298A (en) * 2002-06-14 2004-01-22 Denki Kagaku Kogyo Kk Cement composition for carbonated/hardened body, cement concrete composition for carbonated/hardened body and method for manufacturing carbonated/hardened body

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JP5501717B2 (en) * 2009-09-29 2014-05-28 太平洋セメント株式会社 Cement clinker and cement

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JP2000072497A (en) * 1998-08-19 2000-03-07 Taiheiyo Cement Corp Cement for highly fluid shotcrete
JP2004018298A (en) * 2002-06-14 2004-01-22 Denki Kagaku Kogyo Kk Cement composition for carbonated/hardened body, cement concrete composition for carbonated/hardened body and method for manufacturing carbonated/hardened body

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7490862B2 (en) 2019-03-13 2024-05-27 太平洋セメント株式会社 Method for producing cement powder composition
CN111072295A (en) * 2019-12-17 2020-04-28 福建源鑫环保科技有限公司 High-activity composite ferronickel slag cementing material and preparation method thereof

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