WO2010143656A1 - Hydraulic cement composition - Google Patents

Hydraulic cement composition Download PDF

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Publication number
WO2010143656A1
WO2010143656A1 PCT/JP2010/059763 JP2010059763W WO2010143656A1 WO 2010143656 A1 WO2010143656 A1 WO 2010143656A1 JP 2010059763 W JP2010059763 W JP 2010059763W WO 2010143656 A1 WO2010143656 A1 WO 2010143656A1
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Prior art keywords
fine powder
mass
cement
cement composition
recycled
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PCT/JP2010/059763
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French (fr)
Japanese (ja)
Inventor
悦郎 坂井
真 西川
剛史 安齋
清 鯉渕
貴之 蛯名
信和 二戸
敏男 米澤
健郎 三井
陽作 池尾
孝志 ▲蓮▼見
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株式会社竹中工務店
株式会社 デイ・シイ
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Publication of WO2010143656A1 publication Critical patent/WO2010143656A1/en

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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
    • C04B28/08—Slag cements
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • 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

Definitions

  • the present invention relates to a hydraulic cement composition, and more particularly to a hydraulic cement composition in which CO 2 emissions during the manufacture of cement mainly composed of blast furnace slag are drastically reduced.
  • the amount of CO 2 generated by the production of Portland cement is about 350 kg / ton in terms of calcining energy per ton of cement and about 450 kg / ton from the raw material limestone, totaling about 750 kg / ton.
  • the cement industry as a whole is equivalent to about 4% of Japan.
  • blast furnace cement As cement using blast furnace slag fine powder, blast furnace cement has already been standardized to Japanese Industrial Standard JISR5211. According to this, the content of fine blast furnace slag powder in blast furnace cement type A is 5-30% by mass, in type B 30-30% by mass, and in class C 60-70% by mass. However, the B type cement having a blast furnace slag fine powder content of about 50% by mass accounts for the majority.
  • the blast furnace cement type A For the purpose of reducing CO 2 during cement production, the blast furnace cement type A is insufficient.
  • the B type is not sufficient, but apart from this, the blast furnace cement B type has a problem that it is neutralized and has a large drying shrinkage compared with concrete using ordinary Portland cement, and its use expansion is not necessarily progressing.
  • the blast furnace cement type C has a greater CO 2 reduction effect, the problems of neutralization and drying shrinkage in the type B are more strongly expressed and are hardly used at present.
  • high sulfate slag cement cement obtained by adding gypsum and an alkali stimulant to blast furnace slag fine powder exhibits high strength.
  • alkali stimulating material necessary for the hydration reaction of the cement include industrial raw materials such as calcium hydroxide, sodium hydroxide, and sodium carbonate.
  • This cement has a high blast furnace slag fine powder content of 80 to 90% by mass, and has a very large CO 2 reduction effect.
  • the present invention is used for a structure that does not necessarily require alkalinity, and a CO 2 emission amount during production mainly composed of blast furnace slag is reduced, and a structure with high compressive strength is formed. It is an object of the present invention to provide a hydraulic cement composition that can be used.
  • the invention proposed in each of the above patent documents is the problem of the amount of resources and production energy / cost of the conventional alkali stimulating material in that recycled concrete fine powder is used as the alkali stimulating material of cement mainly composed of blast furnace slag fine powder. It shows the first step to solve the problem.
  • the present invention is an extension of this technology that uses recycled concrete fine powder as an alkali stimulant, and shows the relationship between the amount of blast furnace slag fine powder, gypsum and Portland cement, and the amount of recycled concrete fine powder and strength development. It has been completed by finding out that excellent physical properties that have never been achieved can be achieved by an optimal combination.
  • the conventional recycled concrete fine powder simply uses the crushed material of the demolished concrete
  • the recycled concrete fine powder the calcium hydroxide content is appropriate.
  • a composition having a more stable quality as a cement has been found.
  • a Portland cement to be used together with a conventional Portland cement made of limestone as a raw material and produced by a rotary kiln, as a part thereof, instead of a specific means, By using the produced recycled cement, further reduction of CO 2 emissions was achieved.
  • the hydraulic cement composition of the present invention has the following configuration.
  • ⁇ 1> Disassembling with respect to 100 parts by mass of a mixture containing 60 to 90% by mass of fine blast furnace slag powder having a fineness of 3000 to 13000 cm 2 / g, 5 to 20% by mass of gypsum and 5 to 35% by mass of Portland cement
  • gypsum is anhydrous gypsum.
  • ⁇ 3> The hydraulic cement composition according to any one of ⁇ 1> or ⁇ 2>, wherein the Portland cement is a recycled cement obtained by recovering the hydration activity of the recycled concrete fine powder.
  • the Portland cement is a recycled cement obtained by recovering the hydration activity of the recycled concrete fine powder.
  • the recycled cement is manufactured using recycled concrete fine powder as a raw material for Portland cement.
  • the recycled cement is obtained by heat-treating recycled concrete fine powder at 400 to 800 ° C.
  • the blast furnace slag fine powder occupies a high content, and the Portland cement content is low, so that it is possible to drastically reduce CO 2 emissions during cement production, Recycled concrete fine powder containing calcium hydroxide in a specific ratio separated from demolition concrete is used.
  • This reclaimed concrete fine powder is suitable as an alkali stimulant for blast furnace slag fine powder, and this cement composition should be used.
  • a structure having a high strength can be formed, and the quality of the cement composition can be easily controlled.
  • CO 2 emissions during production mainly composed of blast furnace slag is drastically reduced, and, hydraulic cement composition which can form a structure of high compressive strength is provided.
  • the hydraulic cement composition of the present invention is a mixture 100 containing 60 to 90% by mass of fine blast furnace slag powder having a fineness of 3000 to 13000 cm 2 / g, 5 to 20% by mass of gypsum, and 5 to 35% by mass of Portland cement. It is characterized by containing 10 to 30 parts by mass of recycled concrete fine powder containing 3 to 15% by mass of calcium hydroxide separated from demolition concrete with respect to parts by mass. That is, the mixture used for the hydraulic cement composition of the present invention is a mixture containing the blast furnace slag fine powder, gypsum and Portland cement in the above-mentioned content.
  • the hydraulic cement composition of the present invention contains 10 to 30 parts by mass of recycled concrete fine powder separated from demolition concrete and containing calcium hydroxide in a specific ratio. It is.
  • the most different point from the above-mentioned known cement composition is that a recycled concrete fine powder containing 3 to 15% by mass of calcium hydroxide obtained by separating from demolition concrete is used.
  • recycled concrete fine powder In the cement composition using the recycled concrete fine powder as an alkali stimulant for the blast furnace slag fine powder, it is effective to control the quality of the recycled concrete fine powder in controlling the quality of the obtained cement. I found out. That is, as a result of various studies on recycled concrete fine powder as an alkali stimulant, among the components of calcium hydroxide, cement hydrate, unhydrated cement, and aggregate powder contained in recycled concrete fine powder, calcium hydroxide It has been found that the regenerated concrete fine powder containing 3 to 15% by mass of calcium hydroxide is extremely effective in determining the cement quality.
  • the content of calcium hydroxide in the recycled concrete fine powder is less than 3% by mass, the amount of the active ingredient is small and the alkali stimulating effect is not exhibited effectively, and the resulting cement composition is inferior in curability.
  • a recycled concrete fine powder having a calcium hydroxide content of more than 15% by mass an alkali stimulating effect can be sufficiently obtained, but such a recycled concrete fine powder having a calcium hydroxide content is obtained.
  • Recycled concrete fine powder such as recycled concrete fine powder manufactured from demolition concrete lumps, etc., which is not easily obtained and has a remarkably large amount of cement is limited. If the rate is too high, the amount of recycled concrete fine powder used in the cement composition decreases.
  • the content of calcium hydroxide contained in the recycled concrete fine powder is required to be 3 to 15% by mass. Further, in order to control the quality of the cement composition, 6 to 12% by mass is more preferable.
  • the fineness of the recycled concrete fine powder is not particularly limited as long as the content of calcium hydroxide is 3 to 15% by mass. However, from the efficiency of the alkali stimulating effect and the fluidity when mortar or concrete is used. A range of 2000 to 7000 cm 2 / g is preferred. When the fineness is in the above range, a sufficient alkali stimulating effect is obtained, and suitable fluidity is achieved even when used in mortar and concrete.
  • the recycled concrete fine powder separated from the demolished concrete can be obtained, for example, by removing coarse aggregate or fine aggregate from the demolished concrete. At this time, coarse aggregates and fine aggregates separated from the demolished concrete can also be used as recycled products.
  • a mechanical rubbing method is preferred, and an eccentric rotor method among mechanical rubbing methods Is more preferable.
  • a method for producing such recycled concrete fine powder will be described.
  • the preferred recycled concrete fine powder in the present invention is preferably produced by a mechanical rubbing method without heating from the viewpoint of reducing carbon dioxide during production and ensuring that the quality of the fine powder obtained does not vary.
  • a mechanical rubbing apparatus such as an eccentric rotor type or a planetary mill
  • a mechanical grinding process is performed in a sealed space to remove CO 2 in the air in the space, or nitrogen gas, etc.
  • Recycled concrete fine powder that suppresses the decrease in the content of calcium hydroxide due to carbonation during the treatment by using the method of enclosing the inert gas is optimal for use as an alkali stimulant as in the present invention.
  • a fine powder having a calcium hydroxide content can be obtained.
  • the content of the recycled concrete fine powder is required to be 10 to 30 parts by mass, and more preferably 15 to 25 parts per 100 parts by mass of the mixture of the blast furnace slag fine powder, gypsum and Portland cement described below. It is the range of mass parts. If the content of the recycled concrete fine powder in the hydraulic cement composition is less than 10 parts by mass relative to the mixture, the strength of the structure obtained using this cement composition is not sufficient, and exceeds 30 parts by mass. In some cases, no further improvement in the strength of the structure obtained using this cement composition was observed. On the other hand, the amount of powder of the cement composition increased relatively, and the mortar using the cement composition increased. Or the fluidity of concrete is not preferred.
  • the hydraulic cement composition of the present invention contains a mixture in which fine powder of blast furnace slag having a fineness of 3000 to 13000 cm 2 / g, gypsum and Portland cement are mixed at a specific ratio.
  • the gypsum that can be used in the present invention may be, for example, dihydrate gypsum, anhydrous gypsum, or semi-water gypsum, and one or more of these can be used. Among these, anhydrous gypsum is preferable.
  • the amount of gypsum contained in the mixture of blast furnace slag fine powder and gypsum having a fineness of 3000 to 13000 cm 2 / g is 5 to 20% by mass with respect to the whole mixture of blast furnace slag fine powder, gypsum and Portland cement. is there.
  • the content of gypsum in the mixture is in the range of 5 to 20% by mass, preferably in the range of 10 to 15% by mass.
  • blast furnace slag fine powder contained in the mixture general-purpose blast furnace slag fine powder can be used if the fineness is 3000 to 13000 cm 2 / g, but the fineness is 4000 to 8000 cm 2 / g. Is preferred.
  • the fineness of the blast furnace slag fine powder can be measured according to the cement fineness measuring method described in JIS R 5201 (1997) [ISO 679 (1989)]. The fineness can be controlled by the pulverization method, pulverization conditions, and classification after pulverization when blast furnace granulated slag is pulverized.
  • the fineness of the blast furnace slag fine powder is less than 3000 cm 2 / g, the hardening reaction of the cement composition does not proceed easily.
  • the fineness exceeds 13000 cm 2 / g the reaction proceeds rapidly and the calorific value increases. Drying shrinkage becomes large, and problems such as generation of cracks and reduction in dimensional stability are likely to occur in the obtained molded article.
  • the blending amount of the blast furnace slag fine powder with respect to the mixture is preferably large in terms of CO 2 reduction at the time of cement production, but if it exceeds 90% by mass, the content of gypsum and Portland cement will be relatively lowered, and sufficient It is difficult to obtain strength, and this is not preferable because the rate of strength development tends to be particularly slow.
  • the content of fine blast furnace slag powder in the mixture is in the range of 60 to 90% by mass, preferably 70 to 80% by mass.
  • Portland cement in the hydraulic cement composition various Portland cements stipulated in JIS can be used, but generally Portland cement may be used. However, although it is a small amount, since Portland cement is used, it works in the direction of increasing the amount of CO 2 generated during cement production. From the viewpoint of reducing the amount of CO 2 emission, in the present invention, the following is shown. It is desirable to use Portland cement obtained from such recycled concrete.
  • most of the recycled concrete fine powder produced from demolition concrete is a material containing a large amount of cement raw material, although it is a cement hydrate, and this material has the same hydraulic properties as Portland cement. It has been found that the production of recycled cement can further reduce the amount of CO 2 generated during cement production. That is, it has been found that the same cement as Portland cement can be produced by using recycled concrete fine powder as a part of the cement raw material. In this case, although not be expected the reduction of CO 2 emissions from the firing energy, it becomes possible to reduce the CO 2 emissions from raw materials. As another method for producing recycled cement that can be used in the present invention, there is a method of heat treating recycled concrete fine powder at 400 to 800 ° C.
  • the recycled cement obtained by this heat treatment is treated with the Portland cement in the present invention.
  • the method for producing recycled cement is described in, for example, JP-A-2005-320202, JP-A-10-114556, etc., and the techniques described therein can be applied as the method for producing recycled cement in the present invention.
  • the firing temperature during the production of the above-mentioned recycled cement is considerably lower than the firing temperature of Portland cement (1450 ° C.), and it is possible to achieve further CO 2 emission reduction from the viewpoint of energy consumption during production. it can.
  • the Portland cement content in the mixture is required to be 5 to 35% by mass, and preferably in the range of 10 to 30% by mass. If the content of Portland cement in the mixture is less than 5% by mass, the strength of the molded product obtained from the cement composition is not sufficient, and even if it exceeds 35% by mass, no further improvement in strength is observed. This is not preferable because the amount of powder with respect to water increases and the fluidity of the mixture with water such as mortar and concrete decreases. Moreover, since the CO 2 reduction amount when the content is increased in the Portland cement is increased with it, from this point of view, it is preferable that 35 mass% or less.
  • the hydraulic cement composition of the present invention containing 10 to 30 parts by mass of the recycled concrete fine powder with respect to 100 parts by mass of the mixture of the blast furnace slag fine powder, gypsum and Portland cement has an extremely low content of Portland cement. Therefore, the amount of carbon dioxide emitted during production can be reduced, and a high-strength structure can be produced despite the low content of Portland cement.
  • the hydraulic cement composition of the present invention is a concrete structure that does not necessarily require alkalinity, that is, a structure using a reinforcing material such as rust-proof iron or stainless steel, or a rust-proof iron or stainless steel. It is suitably used for producing a precast concrete molded body using a frame material. In addition to the above essential components, various additives that are usually used in cement compositions may be added to the cement composition of the present invention as necessary.
  • the amount of carbon dioxide discharged when the following cement composition was produced was calculated by the following method.
  • the amount of CO 2 generated during the production of Portland cement is 750 kg / ton. Of these, the amount generated from raw materials is 450 kg, and the amount generated from manufacturing energy and others is 300 kg. About 5% (15 kg) of the latter generation amount is CO 2 generated from pulverization and the like. These amounts are common to all cements.
  • production energy of recycled concrete fine powder 30 kg ⁇ CO 2 / ton ⁇ fine powder. Using these values, the amount of carbon dioxide (CO 2 ) generated during the production of the cement composition was calculated. These results are shown in Table 2 below.
  • Recycled concrete fine powder 1 Calcium hydroxide content 8.2 mass% Fineness 5860cm 2 / g
  • Recycled concrete fine powder 2 Calcium hydroxide content 4.7% by mass Fineness 5710 cm 2 / g
  • Recycled concrete fine powder 3 Calcium hydroxide content 13.6% by mass Fineness 5650 cm 2 / g
  • Recycled concrete fine powder 4 Calcium hydroxide content 1.4% by mass Fineness 5690 cm 2 / g
  • Recycled concrete fine powder 5 Recycled fine powder under 5 mm produced by crushing the same demolition concrete lump as the raw material of recycled concrete fine powder 1 with a jaw crusher. And the same as the recycled concrete fine powder used in the examples of JP-A-63-2842. (Calcium hydroxide content: 2.6% by mass)
  • Table 2 shows material configurations and test results of Examples 1 to 12 and Comparative Examples 1 to 12. As shown in Table 2, in the molded body using the hydraulic cement composition of the present invention, it is estimated that the curing reaction has sufficiently progressed from the calorific value at the time of curing. It can be seen that the body is superior in compressive strength as compared with those of Comparative Examples 1 to 10 having a low carbon dioxide gas generation amount.
  • Comparative Examples 9 and 10 have the same composition as in Example 3, but the fineness of the blast furnace slag fine powder is outside the scope of the present invention, and Comparative Example 9 having a small fineness does not exhibit sufficient strength and has a fineness.
  • the large comparative example 10 has a remarkably large calorific value, and cracking of the structure becomes a problem.
  • the comparative examples 11 and 12 containing Portland cement improve compressive strength, it turns out that the amount of carbon dioxide generation increases remarkably.
  • the amount of carbon dioxide consumed in the production of a cement composition containing a general Portland cement (Comparative Example 12) is 750 kg / ton, and the cement composition according to the present invention achieves sufficient compressive strength. It can be seen that the carbon dioxide emission during production is reduced.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
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  • Organic Chemistry (AREA)
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Abstract

Disclosed is a hydraulic cement composition which is applicable to a structure that does not always require alkalinity, is mainly composed of a blast-furnace slug, and discharges CO2 in a drastically reduced amount. The hydraulic cement composition comprises: 100 parts by mass of a mixture comprising 60 to 90% by mass of a blast-furnace slug micropowder having a powder fineness of 3000 to 13000 cm2/g, 5 to 20% by mass of plaster and 5 to 35% by mass of Portland cement; and 10 to 30 parts by mass of a recycled concrete micropowder that is isolated from a demolished concrete and contains 3 to 15% by mass of hydroxide calcium.

Description

水硬性セメント組成物Hydraulic cement composition
　本発明は水硬性セメント組成物に係り、特に高炉スラグを主体とするセメント製造時のＣＯ２排出量が抜本的に削減された水硬性セメント組成物に関する。 The present invention relates to a hydraulic cement composition, and more particularly to a hydraulic cement composition in which CO 2 emissions during the manufacture of cement mainly composed of blast furnace slag are drastically reduced.
　ポルトランドセメントの製造によって発生するＣＯ２は、セメント１トン当り焼成エネルギーで約３５０kg／トン、原料の石灰石から約４５０kg／トン、合計約７５０kg／トンであり膨大な量となっている。セメント産業全体ではわが国全体の約４％に相当する。 The amount of CO 2 generated by the production of Portland cement is about 350 kg / ton in terms of calcining energy per ton of cement and about 450 kg / ton from the raw material limestone, totaling about 750 kg / ton. The cement industry as a whole is equivalent to about 4% of Japan.
　現在の鉄筋コンクリート構造物はポルトランドセメントの水和によって生ずる高いアルカリ性がもたらす鋼材の防食作用を不可欠の要件としているが、これを必ずしも必要としない構造体であれば高炉スラグを主体とした焼成不要のセメントを利用することができる。 Current reinforced concrete structures require the anticorrosive action of steel materials brought about by the high alkalinity generated by the hydration of Portland cement, but if the structure does not necessarily require this, it is a cement that does not require firing, mainly blast furnace slag. Can be used.
　高炉スラグ微粉末を用いたセメントとしては、既に日本工業規格ＪＩＳＲ５２１１に高炉セメントが規格化されている。これによれば、高炉セメントＡ種では高炉スラグ微粉末の含有量が５～３０質量％、Ｂ種では３０～６０質量％、Ｃ種では６０～７０質量％と定められており、実際に流通し、使用されているのは、高炉スラグ微粉末の含有量が５０質量％前後のＢ種セメントが大半を占める。 As cement using blast furnace slag fine powder, blast furnace cement has already been standardized to Japanese Industrial Standard JISR5211. According to this, the content of fine blast furnace slag powder in blast furnace cement type A is 5-30% by mass, in type B 30-30% by mass, and in class C 60-70% by mass. However, the B type cement having a blast furnace slag fine powder content of about 50% by mass accounts for the majority.
　セメント製造時のＣＯ２を削減する目的からは、前記高炉セメントＡ種は不十分である。Ｂ種も十分ではないが、これとは別に高炉セメントＢ種は普通ポルトランドセメントを用いたコンクリートに比べて中性化が速く乾燥収縮が大きいといった課題があり、その利用拡大は必ずしも進んでいない。高炉セメントＣ種ではＣＯ２削減効果はより大きくなるものの、上記のＢ種における中性化、乾燥収縮の問題がさらに強く発現し、ほとんど利用されていないのが現状である。 For the purpose of reducing CO 2 during cement production, the blast furnace cement type A is insufficient. The B type is not sufficient, but apart from this, the blast furnace cement B type has a problem that it is neutralized and has a large drying shrinkage compared with concrete using ordinary Portland cement, and its use expansion is not necessarily progressing. Although the blast furnace cement type C has a greater CO 2 reduction effect, the problems of neutralization and drying shrinkage in the type B are more strongly expressed and are hardly used at present.
　一方、高炉スラグ微粉末にセッコウとアルカリ刺激材を添加したセメントが高い強度を発現することは、古くから、高硫酸塩スラグセメントとして知られている。このセメントの水和反応に必要なアルカリ刺激材としては水酸化カルシウム、水酸化ナトリウム、炭酸ナトリウム等の工業原料がある。このセメントは、高炉スラグ微粉末の含有量が８０～９０質量％と高くＣＯ２の削減効果はきわめて大きい。しかし、アルカリ反応刺激材の資源量、コスト、製造エネルギー・ＣＯ２等の面で本発明の目的とするセメントとすることは難しい。 On the other hand, it has long been known as high sulfate slag cement that cement obtained by adding gypsum and an alkali stimulant to blast furnace slag fine powder exhibits high strength. Examples of the alkali stimulating material necessary for the hydration reaction of the cement include industrial raw materials such as calcium hydroxide, sodium hydroxide, and sodium carbonate. This cement has a high blast furnace slag fine powder content of 80 to 90% by mass, and has a very large CO 2 reduction effect. However, it is difficult to obtain a cement that is the object of the present invention in terms of the amount of resources, cost, production energy, CO 2, etc. of the alkali reaction stimulating material.
　一方、解体コンクリートの中には、セメントの水和によって生成した水酸化カルシウムや未水和のセメントが残留しており、これらの副産物をアルカリ刺激材として利用することが考えられる。また、解体コンクリートのリサイクルにおいては、再生粗骨材を回収する技術は確立しているものの、再生コンクリート微粉末の用途が限られているため、再生細骨材と再生コンクリート微粉末のリサイクルが進んでいない。再生コンクリート微粉末をセメントの原料として利用できるようになれば、コンクリートのリサイクルが全体として進展することになる。
　そのような観点から、高炉スラグ微粉末５０～８０質量部、セッコウ２～５質量部に解体コンクリート破砕物の５ｍｍ以下のものを２０～５０質量部を添加した水硬性セメントが提案されている（例えば、特許文献１参照。）。しかし、このセメントは２８日強度が１０～１４Ｎ／ｍｍ２程度に過ぎず、実用性を有するものではなかった。 On the other hand, in the demolished concrete, calcium hydroxide produced by cement hydration and unhydrated cement remain, and these by-products can be used as alkali stimulants. In recycling demolition concrete, although the technology to recover recycled coarse aggregate has been established, the use of recycled concrete fine powder is limited, so recycling of recycled fine aggregate and recycled concrete fine powder has progressed. Not. If recycled concrete fine powder can be used as a raw material for cement, concrete recycling will progress as a whole.
From such a viewpoint, hydraulic cement has been proposed in which 50 to 80 parts by mass of blast furnace slag fine powder, 2 to 5 parts by mass of gypsum, and 20 to 50 parts by mass of 5 mm or less of crushed demolition concrete are added ( For example, see Patent Document 1.) However, this cement had a 28-day strength of only 10 to 14 N / mm 2 and was not practical.
　さらに、前記水硬性セメントの強度を改善するために上記組成物に、さらに、５～３０質量部のポルトランドセメントを添加する方法が記載され、２８日強度が２０～２５Ｎ／ｍｍ２を得ることを示している（例えば、特許文献２参照。）。しかし、このセメントは、初期強度の発現が低い点、コンクリート破砕物の５ｍｍ以下のものが、本質的に組成の変動の大きいものである点、ポルトランドセメントの使用量が相当量必要でありＣＯ２の削減効果に限界がある点等の課題を有している。
特開昭６２－１５８１４６号公報 特開昭６３－２８４２号公報 Furthermore, in order to improve the strength of the hydraulic cement, a method of further adding 5 to 30 parts by mass of Portland cement to the above composition is described, and the 28-day strength is 20 to 25 N / mm 2. (For example, refer to Patent Document 2). However, this cement are that expression of the early strength is low, the following 5mm concrete crushed is, the point is greater variability essentially composition, the amount of Portland cement is required substantial amount CO 2 There is a problem such as the point that there is a limit to the reduction effect.
JP-A-62-158146 Japanese Unexamined Patent Publication No. 63-2842
　本発明は、上記した課題に鑑み、アルカリ性を必ずしも必要としない構造体に使用される、高炉スラグを主体とする製造時のＣＯ２排出量が削減され、且つ、高圧縮強度の構造体を形成しうる水硬性セメント組成物を提供しようとするものである。 In view of the above-mentioned problems, the present invention is used for a structure that does not necessarily require alkalinity, and a CO 2 emission amount during production mainly composed of blast furnace slag is reduced, and a structure with high compressive strength is formed. It is an object of the present invention to provide a hydraulic cement composition that can be used.
　上記各特許文献に提案の発明は、高炉スラグ微粉末を主体にしたセメントのアルカリ刺激材として再生コンクリート微粉末を使用している点で従来のアルカリ刺激材の資源量や製造エネルギー・コストの問題を解決する第一歩を示したものである。
　本発明は、再生コンクリート微粉末をアルカリ刺激材として使用するこの技術を発展させたものであり、高炉スラグ微粉末とセッコウとポルトランドセメントの量および再生コンクリート微粉末の量と強度発現との関係の最適な組み合せとすることで、従来にない優れた物性が達成されることを見いだして完成したものである。
　さらに、従来の再生コンクリート微粉末が、単に解体コンクリートの破砕物を用いていたのに対し、本発明の好適な態様においては、再生コンクリート微粉末として、水酸化カルシウムの含有率が適正なものを使用することにより、セメントとしてより安定した品質の組成物を見出したものである。
　また、本発明のセメント組成物中の好ましい態様においては、使用するポルトランドセメントとして、石灰石を原料としロータリーキルンで製造された従来のポルトランドセメントとともに、その一部として、これに替えて、特定の手段で製造した再生セメントを用いることで、さらなるＣＯ２排出量の削減を達成したものである。 The invention proposed in each of the above patent documents is the problem of the amount of resources and production energy / cost of the conventional alkali stimulating material in that recycled concrete fine powder is used as the alkali stimulating material of cement mainly composed of blast furnace slag fine powder. It shows the first step to solve the problem.
The present invention is an extension of this technology that uses recycled concrete fine powder as an alkali stimulant, and shows the relationship between the amount of blast furnace slag fine powder, gypsum and Portland cement, and the amount of recycled concrete fine powder and strength development. It has been completed by finding out that excellent physical properties that have never been achieved can be achieved by an optimal combination.
Further, while the conventional recycled concrete fine powder simply uses the crushed material of the demolished concrete, in the preferred embodiment of the present invention, as the recycled concrete fine powder, the calcium hydroxide content is appropriate. By using the composition, a composition having a more stable quality as a cement has been found.
Further, in a preferred embodiment in the cement composition of the present invention, as a Portland cement to be used, together with a conventional Portland cement made of limestone as a raw material and produced by a rotary kiln, as a part thereof, instead of a specific means, By using the produced recycled cement, further reduction of CO 2 emissions was achieved.
　すなわち、本発明の水硬性セメント組成物は、以下に示す構成である。
＜１＞　粉末度が３０００～１３０００ｃｍ２／ｇの高炉スラグ微粉末６０～９０質量％とセッコウ５～２０質量％とポルトランドセメント５～３５質量％とを含有する混合物１００質量部に対して、解体コンクリートから分離した、水酸化カルシウムを３～１５質量％含む再生コンクリート微粉末を１０～３０質量部含有する水硬性セメント組成物である。
＜２＞　前記セッコウが無水セッコウであることを特徴とする前記＜１＞に記載の水硬性セメント組成物である。 That is, the hydraulic cement composition of the present invention has the following configuration.
<1> Disassembling with respect to 100 parts by mass of a mixture containing 60 to 90% by mass of fine blast furnace slag powder having a fineness of 3000 to 13000 cm 2 / g, 5 to 20% by mass of gypsum and 5 to 35% by mass of Portland cement A hydraulic cement composition containing 10-30 parts by mass of recycled concrete fine powder separated from concrete and containing 3-15% by mass of calcium hydroxide.
<2> The hydraulic cement composition according to <1>, wherein the gypsum is anhydrous gypsum.
＜３＞　前記ポルトランドセメントが、再生コンクリート微粉末の水和活性を回復して得られる再生セメントである前記＜１＞又は＜２＞のいずれか１項に記載の水硬性セメント組成物である。
＜４＞　前記再生セメントが、再生コンクリート微粉末をポルトランドセメントの原料として製造されたものである前記＜３＞に記載の水硬性セメント組成物である。
＜５＞前記再生セメントが、再生コンクリート微粉末を４００～８００℃で加熱処理することにより得られたものである前記＜３＞に記載の水硬性セメント組成物である。 <3> The hydraulic cement composition according to any one of <1> or <2>, wherein the Portland cement is a recycled cement obtained by recovering the hydration activity of the recycled concrete fine powder.
<4> The hydraulic cement composition according to <3>, wherein the recycled cement is manufactured using recycled concrete fine powder as a raw material for Portland cement.
<5> The hydraulic cement composition according to <3>, wherein the recycled cement is obtained by heat-treating recycled concrete fine powder at 400 to 800 ° C.
　本発明の水硬性セメント組成物は、高炉スラグ微粉末が高い含有率を占め、ポルトランドセメントの含有率が低いので、セメント製造時におけるＣＯ２排出量を抜本的に削減することができ、また、解体コンクリートから分離した、水酸化カルシウムを特定の割合で含む再生コンクリート微粉末を用いており、この再生コンクリート微粉末は高炉スラグ微粉末のアルカリ刺激材として適しており、このセメント組成物を用いることで、高い強度の構造体を形成することができ、セメント組成物の品質のコントロールが容易であるという利点をも有する。 In the hydraulic cement composition of the present invention, the blast furnace slag fine powder occupies a high content, and the Portland cement content is low, so that it is possible to drastically reduce CO 2 emissions during cement production, Recycled concrete fine powder containing calcium hydroxide in a specific ratio separated from demolition concrete is used. This reclaimed concrete fine powder is suitable as an alkali stimulant for blast furnace slag fine powder, and this cement composition should be used. Thus, a structure having a high strength can be formed, and the quality of the cement composition can be easily controlled.
　本発明によれば、高炉スラグを主体とする製造時のＣＯ２排出量が抜本的に削減され、且つ、高圧縮強度の構造体を形成しうる水硬性セメント組成物が提供される。 According to the present invention, CO 2 emissions during production mainly composed of blast furnace slag is drastically reduced, and, hydraulic cement composition which can form a structure of high compressive strength is provided.
　以下、本発明を詳細に説明する。
　本発明の水硬性セメント組成物は、粉末度が３０００～１３０００ｃｍ２／ｇの高炉スラグ微粉末６０～９０質量％とセッコウ５～２０質量％とポルトランドセメント５～３５質量％とを含有する混合物１００質量部に対して、解体コンクリートから分離した、水酸化カルシウムを３～１５質量％含む再生コンクリート微粉末を１０～３０質量部含有することを特徴とする。
　即ち、本発明の水硬性セメント組成物に用いられる混合物は、高炉スラグ微粉末とセッコウとポルトランドセメントとを上記の含有量で含有する混合物である。
　　このような混合物１００質量部に対して、本発明の水硬性セメント組成物においては、解体コンクリートから分離した、水酸化カルシウムを特定の割合で含む再生コンクリート微粉末を１０～３０質量部含有するものである。
　本発明において、上記公知のセメント組成物と最も異なる点は、解体コンクリートから分離して得られる水酸化カルシウムを３～１５質量％含む再生コンクリート微粉末を用いることである。 Hereinafter, the present invention will be described in detail.
The hydraulic cement composition of the present invention is a mixture 100 containing 60 to 90% by mass of fine blast furnace slag powder having a fineness of 3000 to 13000 cm 2 / g, 5 to 20% by mass of gypsum, and 5 to 35% by mass of Portland cement. It is characterized by containing 10 to 30 parts by mass of recycled concrete fine powder containing 3 to 15% by mass of calcium hydroxide separated from demolition concrete with respect to parts by mass.
That is, the mixture used for the hydraulic cement composition of the present invention is a mixture containing the blast furnace slag fine powder, gypsum and Portland cement in the above-mentioned content.
With respect to 100 parts by mass of such a mixture, the hydraulic cement composition of the present invention contains 10 to 30 parts by mass of recycled concrete fine powder separated from demolition concrete and containing calcium hydroxide in a specific ratio. It is.
In the present invention, the most different point from the above-mentioned known cement composition is that a recycled concrete fine powder containing 3 to 15% by mass of calcium hydroxide obtained by separating from demolition concrete is used.
（再生コンクリート微粉末）
　本発明者らは、再生コンクリート微粉末を高炉スラグ微粉末に対するアルカリ刺激材として使用したセメント組成物では、得られるセメントの品質をコントロールするうえで、再生コンクリート微粉末の品質をコントロールすることが有効であることを見出した。すなわち、アルカリ刺激材としての再生コンクリート微粉末について種々検討した結果、再生コンクリート微粉末に含まれる水酸化カルシウム、セメント水和物、未水和セメント、骨材粉の各成分のうち、水酸化カルシウムの作用がセメントの品質を決定する上で支配的であり、水酸化カルシウムを３～１５質量％含む再生コンクリート微粉末が極めて有効であることを見出した。 (Recycled concrete fine powder)
In the cement composition using the recycled concrete fine powder as an alkali stimulant for the blast furnace slag fine powder, it is effective to control the quality of the recycled concrete fine powder in controlling the quality of the obtained cement. I found out. That is, as a result of various studies on recycled concrete fine powder as an alkali stimulant, among the components of calcium hydroxide, cement hydrate, unhydrated cement, and aggregate powder contained in recycled concrete fine powder, calcium hydroxide It has been found that the regenerated concrete fine powder containing 3 to 15% by mass of calcium hydroxide is extremely effective in determining the cement quality.
　再生コンクリート微粉末中の水酸化カルシウムの含有率が３質量％未満では有効成分の量が少なくアルカリ刺激効果が効果的に発揮されず、得られるセメント組成物は硬化性に劣る。また、再生コンクリート微粉末として水酸化カルシウムの含有率が１５質量％を上回るものを用いる場合には、アルカリ刺激作用は十分に得られるものの、このような水酸化カルシウム含有率の再生コンクリート微粉末が容易に得られず、セメント量の著しく多い解体コンクリート塊等から製造した再生コンクリート微粉末等、利用可能な再生コンクリート微粉末が限定され再生コンクリート微粉末の活用効率が悪くなるとともに、水酸化カルシウム含有率が多すぎると、セメント組成物に利用される再生コンクリート微粉末量が減少する。このため、コンクリート廃材を有効な資源として再生利用し、廃棄量を減少させるというリサイクル上の観点からも好ましくない事態となる。したがって、再生コンクリート微粉末に含まれる水酸化カルシウムの含有率としては３～１５質量％であることを要する。また、セメント組成物の品質をコントロールするうえでは６～１２質量％のものがより好ましい。 When the content of calcium hydroxide in the recycled concrete fine powder is less than 3% by mass, the amount of the active ingredient is small and the alkali stimulating effect is not exhibited effectively, and the resulting cement composition is inferior in curability. In addition, when a recycled concrete fine powder having a calcium hydroxide content of more than 15% by mass is used, an alkali stimulating effect can be sufficiently obtained, but such a recycled concrete fine powder having a calcium hydroxide content is obtained. Recycled concrete fine powder, such as recycled concrete fine powder manufactured from demolition concrete lumps, etc., which is not easily obtained and has a remarkably large amount of cement is limited. If the rate is too high, the amount of recycled concrete fine powder used in the cement composition decreases. For this reason, it becomes an unpreferable situation also from the viewpoint of recycling that the waste concrete is recycled as an effective resource and the amount of waste is reduced. Therefore, the content of calcium hydroxide contained in the recycled concrete fine powder is required to be 3 to 15% by mass. Further, in order to control the quality of the cement composition, 6 to 12% by mass is more preferable.
　再生コンクリート微粉末の粉末度は、水酸化カルシウムの含有率が３～１５質量％であれば特に限定されるものではないが、アルカリ刺激効果の効率やモルタルやコンクリートにした時の流動性からは２０００～７０００ｃｍ２／ｇの範囲が好ましい。粉末度が上記範囲であると、十分なアルカリ刺激効果が得られ、モルタルやコンクリートに使用した時も好適な流動性が達成される。 The fineness of the recycled concrete fine powder is not particularly limited as long as the content of calcium hydroxide is 3 to 15% by mass. However, from the efficiency of the alkali stimulating effect and the fluidity when mortar or concrete is used. A range of 2000 to 7000 cm 2 / g is preferred. When the fineness is in the above range, a sufficient alkali stimulating effect is obtained, and suitable fluidity is achieved even when used in mortar and concrete.
　解体コンクリートから分離された再生コンクリート微粉末は、例えば、解体コンクリートから粗骨材や細骨材を取り除くことにより得ることができる。このとき解体コンクリートから分離された粗骨材や細骨材も再生品として使用することができる。
　解体コンクリートから分離した再生コンクリート微粉末であって、水酸化カルシウムを上記の含有率で含む再生コンクリート微粉末を得る手段としては、機械擦りもみ方式が好ましく、機械擦りもみ方式のなかでは偏心ロータ方式がより好ましい。以下、このような再生コンクリート微粉末の製造方法について説明する。 The recycled concrete fine powder separated from the demolished concrete can be obtained, for example, by removing coarse aggregate or fine aggregate from the demolished concrete. At this time, coarse aggregates and fine aggregates separated from the demolished concrete can also be used as recycled products.
As a means for obtaining reclaimed concrete fine powder separated from demolition concrete and containing calcium hydroxide at the above-mentioned content rate, a mechanical rubbing method is preferred, and an eccentric rotor method among mechanical rubbing methods Is more preferable. Hereinafter, a method for producing such recycled concrete fine powder will be described.
　本発明における好ましい再生コンクリート微粉末は、加熱を行わない機械擦りもみ方式により製造されることが、製造時の二酸化炭素の削減及び得られる微粉末の品質にばらつきがないという観点から好適である。特に、偏心ロータ方式や遊星ミル等の機械擦りもみ装置で製造する際に、機械すりもみプロセスを密閉された空間内で行い、空間内の空気中のＣＯ２を除去する方法、或いは、チッソガスなどの不活性ガスを封入する方法をとることで、処理中の炭酸化による水酸化カルシウム含有率の減少を抑制した再生コンクリート微粉末は、本発明における如き、アルカリ刺激材として使用するのに最適な水酸化カルシウム含有率の微粉末を得ることができる。 The preferred recycled concrete fine powder in the present invention is preferably produced by a mechanical rubbing method without heating from the viewpoint of reducing carbon dioxide during production and ensuring that the quality of the fine powder obtained does not vary. In particular, when manufacturing with a mechanical rubbing apparatus such as an eccentric rotor type or a planetary mill, a mechanical grinding process is performed in a sealed space to remove CO 2 in the air in the space, or nitrogen gas, etc. Recycled concrete fine powder that suppresses the decrease in the content of calcium hydroxide due to carbonation during the treatment by using the method of enclosing the inert gas is optimal for use as an alkali stimulant as in the present invention. A fine powder having a calcium hydroxide content can be obtained.
　他方、解体コンクリート塊をジョークラッシャーやインペラーブレーカー等の破砕機を用いて破砕する方法においては、骨材とモルタル・ぺーストが同時に破砕されるため、再生コンクリート微粉末中に骨材粉が多くなり易く、また、微粉中の骨材粉とモルタル・ぺースト粉の比率もコンクリートの配合（調合）によっては相当変化することとなり、高炉スラグ微粉末のアルカリ刺激材として用いるには、品質のコントロールが極めて困難であり、また、加熱と機械擦りもみによって骨材を取り出す加熱すりもみ方式で製造した微粉末は骨材粉が少なく、アルカリ刺激材として適しているものの、加熱によって解体コンクリート中の水和物が変化する懸念があり、また、製造エネルギーが大きくなり、セメント製造時のＣＯ２を削減するという観点からも好適とは言い難い。
　再生コンクリート微粉末中の水酸化カルシウム含有率は、熱重量分析法により測定することができる。 On the other hand, in the method of crushing demolition concrete lump using a crusher such as jaw crusher or impeller breaker, aggregate and mortar paste are crushed simultaneously, so that aggregate powder increases in recycled concrete fine powder. In addition, the ratio of aggregate powder to mortar paste powder in the fine powder varies considerably depending on the blending (mixing) of the concrete, and quality control is necessary to use it as an alkali stimulant for blast furnace slag fine powder. It is extremely difficult, and the fine powder produced by the heated grinding method, which takes out the aggregate by heating and mechanical rubbing, is low in aggregate powder and suitable as an alkali stimulating material, but it is hydrated in demolition concrete by heating. There is concern that things will change, and manufacturing energy will increase, reducing CO 2 during cement production. It is difficult to say that it is preferable from the viewpoint of the above.
The calcium hydroxide content in the recycled concrete fine powder can be measured by thermogravimetric analysis.
　再生コンクリート微粉末の含有量は、以下に説明する高炉スラグ微粉末とセッコウとポルトランドセメントとの混合物１００質量部に対して、１０～３０質量部であることを要し、より好ましくは１５～２５質量部の範囲である。
　水硬性セメント組成物における再生コンクリート微粉末の含有量が、前記混合物に対して１０質量部未満ではこのセメント組成物を用いて得られた構造体の強度が十分でなく、３０質量部を超えた場合には、このセメント組成物を用いて得られた構造体のさらなる強度の向上は見られず、却って、セメント組成物の粉体量が相対的に増加して、セメント組成物を用いたモルタルやコンクリートの流動性が低下するため好ましくない。 The content of the recycled concrete fine powder is required to be 10 to 30 parts by mass, and more preferably 15 to 25 parts per 100 parts by mass of the mixture of the blast furnace slag fine powder, gypsum and Portland cement described below. It is the range of mass parts.
If the content of the recycled concrete fine powder in the hydraulic cement composition is less than 10 parts by mass relative to the mixture, the strength of the structure obtained using this cement composition is not sufficient, and exceeds 30 parts by mass. In some cases, no further improvement in the strength of the structure obtained using this cement composition was observed. On the other hand, the amount of powder of the cement composition increased relatively, and the mortar using the cement composition increased. Or the fluidity of concrete is not preferred.
（高炉スラグ微粉末とセッコウとポルトランドセメントとの混合物）
　本発明の水硬性セメント組成物は、粉末度が３０００～１３０００ｃｍ２／ｇの高炉スラグ微粉末とセッコウとポルトランドセメントとを特定の比率で混合した混合物を含有する。
　本発明に用いうるセッコウは、例えば、二水セッコウ、無水セッコウ、半水セッコウのいずれでもよく、これらの一種又は二種以上を用いることができるが、これらの中では無水セッコウが好ましい。 (A mixture of ground granulated blast furnace slag, gypsum and Portland cement)
The hydraulic cement composition of the present invention contains a mixture in which fine powder of blast furnace slag having a fineness of 3000 to 13000 cm 2 / g, gypsum and Portland cement are mixed at a specific ratio.
The gypsum that can be used in the present invention may be, for example, dihydrate gypsum, anhydrous gypsum, or semi-water gypsum, and one or more of these can be used. Among these, anhydrous gypsum is preferable.
　粉末度が３０００～１３０００ｃｍ２／ｇの高炉スラグ微粉末とセッコウとの混合物中に含まれるセッコウの量は、高炉スラグ微粉末とセッコウとポルトランドセメントとの混合物全体に対し、５～２０質量％である。混合物中のセッコウの含有量が５～２０質量％の範囲を外れた場合、コンクリートの高い強度と強度発現速度を得るのが困難となる。混合物中のセッコウの含有量は５～２０質量％の範囲であり、好ましくは１０～１５質量％の範囲である。 The amount of gypsum contained in the mixture of blast furnace slag fine powder and gypsum having a fineness of 3000 to 13000 cm 2 / g is 5 to 20% by mass with respect to the whole mixture of blast furnace slag fine powder, gypsum and Portland cement. is there. When the gypsum content in the mixture is outside the range of 5 to 20% by mass, it becomes difficult to obtain high strength and strength development rate of the concrete. The content of gypsum in the mixture is in the range of 5 to 20% by mass, preferably in the range of 10 to 15% by mass.
　該混合物に含まれる高炉スラグ微粉末としては、粉末度が３０００～１３０００ｃｍ２／ｇであれば、汎用の高炉スラグ微粉末を使用することができるが、粉末度が４０００～８０００ｃｍ２／ｇのものが好ましい。
　高炉スラグ微粉末の粉末度はＪＩＳ　Ｒ　５２０１（１９９７年）〔ＩＳＯ　６７９（１９８９年）〕記載のセメントの粉末度の測定方法に準じて測定することができる。粉末度は、高炉水砕スラグを粉砕する時の粉砕方法、粉砕条件や粉砕後の分級により制御することができる。
　高炉スラグ微粉末の粉末度が３０００ｃｍ２／ｇ未満では、セメント組成物の硬化反応が進行し難く、１３０００ｃｍ２／ｇを超える場合には、反応が急速に進行して発熱量が増加するとともに、乾燥収縮が大きくなり、得られる成形体におけるクラックの発生や寸法安定性の低下などの問題が生じやすくなる。 As the blast furnace slag fine powder contained in the mixture, general-purpose blast furnace slag fine powder can be used if the fineness is 3000 to 13000 cm 2 / g, but the fineness is 4000 to 8000 cm 2 / g. Is preferred.
The fineness of the blast furnace slag fine powder can be measured according to the cement fineness measuring method described in JIS R 5201 (1997) [ISO 679 (1989)]. The fineness can be controlled by the pulverization method, pulverization conditions, and classification after pulverization when blast furnace granulated slag is pulverized.
When the fineness of the blast furnace slag fine powder is less than 3000 cm 2 / g, the hardening reaction of the cement composition does not proceed easily. When the fineness exceeds 13000 cm 2 / g, the reaction proceeds rapidly and the calorific value increases. Drying shrinkage becomes large, and problems such as generation of cracks and reduction in dimensional stability are likely to occur in the obtained molded article.
　混合物に対する高炉スラグ微粉末の配合量は、セメント製造時のＣＯ２削減という点では多い方が好ましいが、９０質量％を超えると、相対的にセッコウやポルトランドセメントの含有量が低下し、十分な強度を得るのが難しく、特に強度の発現速度が遅くなる傾向にあり好ましくない。
　混合物に対する高炉スラグ微粉末の含有量は６０～９０質量％の範囲であり、好ましくは７０～８０質量％である。 The blending amount of the blast furnace slag fine powder with respect to the mixture is preferably large in terms of CO 2 reduction at the time of cement production, but if it exceeds 90% by mass, the content of gypsum and Portland cement will be relatively lowered, and sufficient It is difficult to obtain strength, and this is not preferable because the rate of strength development tends to be particularly slow.
The content of fine blast furnace slag powder in the mixture is in the range of 60 to 90% by mass, preferably 70 to 80% by mass.
　水硬性セメント組成物中のポルトランドセメントとしては、ＪＩＳに規定された各種のポルトランドセメントを使用することができるが、一般には普通ポルトランドセメントを使用すればよい。ただし、少量とはいえ、ポルトランドセメントを使用するため、セメント製造時のＣＯ２発生量を多くする方向に働くので、ＣＯ２排出量を少なくするという観点からは、本発明においては、以下に示すような再生コンクリートから得られるポルトランドセメントを用いることが望ましい。 As the Portland cement in the hydraulic cement composition, various Portland cements stipulated in JIS can be used, but generally Portland cement may be used. However, although it is a small amount, since Portland cement is used, it works in the direction of increasing the amount of CO 2 generated during cement production. From the viewpoint of reducing the amount of CO 2 emission, in the present invention, the following is shown. It is desirable to use Portland cement obtained from such recycled concrete.
　本発明者らが検討した結果、解体コンクリートから製造した再生コンクリート微粉末の多くはセメント水和物とはいえ、セメント原料を多く含む材料であり、この材料からポルトランドセメントと同様な水硬性を有する再生セメントを製造することにより、セメント製造時のＣＯ２発生量をさらに少なくすることができることを見いだした。
　即ち、再生コンクリート微粉末をセメント原料の一部として使用することによりポルトランドセメントと同様のセメントが製造できることを見出した。この場合、焼成エネルギーからのＣＯ２排出量の削減は望めないものの、原料からのＣＯ２排出量が削減できることになる。
　また、本発明に使用しうる再生セメントの他の製造方法としては、再生コンクリート微粉末を４００～８００℃に加熱処理する方法が挙げられ、この加熱処理により得られた再生セメントを本発明におけるポルトランドセメントの代替品として使用しうる。再生セメントの製造方法については、例えば、特開２００５－３２０２０２公報、特開平１０－１１４５５６号公報などに記載され、これらに記載の技術を本発明における再生セメントの製造方法として適用できる。
　上記の再生セメントの製造時の焼成温度はポルトランドセメントの焼成温度（１４５０℃）よりも相当に低いのであり、製造時のエネルギー消費量の観点からもさらなるＣＯ２排出量の削減を達成することができる。 As a result of the examination by the present inventors, most of the recycled concrete fine powder produced from demolition concrete is a material containing a large amount of cement raw material, although it is a cement hydrate, and this material has the same hydraulic properties as Portland cement. It has been found that the production of recycled cement can further reduce the amount of CO 2 generated during cement production.
That is, it has been found that the same cement as Portland cement can be produced by using recycled concrete fine powder as a part of the cement raw material. In this case, although not be expected the reduction of CO 2 emissions from the firing energy, it becomes possible to reduce the CO 2 emissions from raw materials.
As another method for producing recycled cement that can be used in the present invention, there is a method of heat treating recycled concrete fine powder at 400 to 800 ° C. The recycled cement obtained by this heat treatment is treated with the Portland cement in the present invention. Can be used as a substitute for The method for producing recycled cement is described in, for example, JP-A-2005-320202, JP-A-10-114556, etc., and the techniques described therein can be applied as the method for producing recycled cement in the present invention.
The firing temperature during the production of the above-mentioned recycled cement is considerably lower than the firing temperature of Portland cement (1450 ° C.), and it is possible to achieve further CO 2 emission reduction from the viewpoint of energy consumption during production. it can.
　該混合物中のポルトランドセメントの含有量は５～３５質量％であることを要し、好ましくは、１０～３０質量％の範囲である。
　混合物中のポルトランドセメントの含有量が５質量％未満では、セメント組成物から得られる成形体の強度が十分ではなく、また、３５質量％を超えてもそれ以上の強度向上は認められず、却って、水に対する粉体量が増加し、モルタル・コンクリート等の水との混合物の流動性が低下するため好ましくない。また、ポルトランドセメントの含有量が増加するとＣＯ２削減量がそれに伴って大きくなるため、このような観点からも、３５質量％以下であることが好ましい。 The Portland cement content in the mixture is required to be 5 to 35% by mass, and preferably in the range of 10 to 30% by mass.
If the content of Portland cement in the mixture is less than 5% by mass, the strength of the molded product obtained from the cement composition is not sufficient, and even if it exceeds 35% by mass, no further improvement in strength is observed. This is not preferable because the amount of powder with respect to water increases and the fluidity of the mixture with water such as mortar and concrete decreases. Moreover, since the CO 2 reduction amount when the content is increased in the Portland cement is increased with it, from this point of view, it is preferable that 35 mass% or less.
　前記高炉スラグ微粉末とセッコウとポルトランドセメントとの混合物１００質量部に対し、前記再生コンクリート微粉末を１０～３０質量部含有する本発明の水硬性セメント組成物は、ポルトランドセメントの含有量が極めて少ないため、製造時の二酸化炭素の排出量が削減され、また、ポルトランドセメントの含有量が少ないにも拘わらず高強度の構造体を作製しうる。
　本発明の水硬性セメント組成物は、アルカリ性を必ずしも必要としないコンクリート構造体、即ち、防錆処理した鉄やステンレス綱などの補強材を用いた構造物や防錆処理した鉄やステンレス綱などの枠材を用いたプレキャストコンクリート成形体などの製造に好適に用いられる。
　本発明のセメント組成物には、上記必須成分に加え、通常、セメント組成物に用いられる各種添加剤を必要に応じて添加してもよい。 The hydraulic cement composition of the present invention containing 10 to 30 parts by mass of the recycled concrete fine powder with respect to 100 parts by mass of the mixture of the blast furnace slag fine powder, gypsum and Portland cement has an extremely low content of Portland cement. Therefore, the amount of carbon dioxide emitted during production can be reduced, and a high-strength structure can be produced despite the low content of Portland cement.
The hydraulic cement composition of the present invention is a concrete structure that does not necessarily require alkalinity, that is, a structure using a reinforcing material such as rust-proof iron or stainless steel, or a rust-proof iron or stainless steel. It is suitably used for producing a precast concrete molded body using a frame material.
In addition to the above essential components, various additives that are usually used in cement compositions may be added to the cement composition of the present invention as necessary.
　以下、実施例を挙げて本発明を詳細に説明するが、本発明はこれらに制限されない。
　表１に示す組成の５種類の高炉スラグ微粉末と無水セッコウ、および下に示す再生コンクリート微粉末を用いて、下記表２に示す組成の水硬性セメント組成物を用いて水／セメント比５０％のセメントペーストを調整し、その水和発熱量（１週間の発熱量の総量）をコンダクションカロリーメーターで測定した。
　また、得られた水硬性セメント組成物を用い、ＪＩＳ　Ｒ５２０１に定める方法でセメントと標準砂の質量比１：３、水セメント比５０％のモルタルによる成形体を作製して、その圧縮強度を測定した。
　下記セメント組成物を製造する際に排出される炭酸ガス量を、以下の方法により算出した。
　ポルトランドセメント製造時のＣＯ２発生量を７５０ｋｇ／トンとする。このうち原料からの発生量は４５０ｋｇ、製造エネルギー他からの発生量３００ｋｇである。後者の発生量の約５％（１５ｋｇ）が、粉砕その他から発生するＣＯ２である。これらの量は全てのセメントで共通とする。ここで、再生コンクリート微粉末の製造エネルギー＝３０ｋｇ・ＣＯ２／トン・微粉末である。これらの値を用いてセメント組成物製造時の炭酸ガス（ＣＯ２）発生量を算出した。
　これらの結果を下記表２に示す。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not restrict | limited to these.
Using 5 types of blast furnace slag fine powder and anhydrous gypsum having the composition shown in Table 1 and the recycled concrete fine powder shown below, a hydraulic cement composition having the composition shown in Table 2 below is used, and the water / cement ratio is 50%. The cement paste was prepared, and the hydration calorific value (total calorific value for one week) was measured with a conduction calorimeter.
Further, using the obtained hydraulic cement composition, a molded body made of mortar with a mass ratio of cement to standard sand of 1: 3 and a water cement ratio of 50% was prepared by the method defined in JIS R5201, and the compression strength was measured. did.
The amount of carbon dioxide discharged when the following cement composition was produced was calculated by the following method.
The amount of CO 2 generated during the production of Portland cement is 750 kg / ton. Of these, the amount generated from raw materials is 450 kg, and the amount generated from manufacturing energy and others is 300 kg. About 5% (15 kg) of the latter generation amount is CO 2 generated from pulverization and the like. These amounts are common to all cements. Here, production energy of recycled concrete fine powder = 30 kg · CO 2 / ton · fine powder. Using these values, the amount of carbon dioxide (CO 2 ) generated during the production of the cement composition was calculated.
These results are shown in Table 2 below.
再生コンクリート微粉末としては下記５種類を使用した。
　（１）　再生コンクリート微粉末１：水酸化カルシウム含有率　８．２質量％
　　　　　　　　　　　　　　　　　　粉末度　５８６０ｃｍ２／ｇ
　（２）　再生コンクリート微粉末２：水酸化カルシウム含有率　４．７質量％
　　　　　　　　　　　　　　　　　　粉末度　５７１０ｃｍ２／ｇ
　（３）　再生コンクリート微粉末３：水酸化カルシウム含有率　１３．６質量％
　　　　　　　　　　　　　　　　　　粉末度　５６５０ｃｍ２／ｇ
　（４）　再生コンクリート微粉末４：水酸化カルシウム含有率　１．４質量％
　　　　　　　　　　　　　　　　　　粉末度　５６９０ｃｍ２／ｇ
　（５）　再生コンクリート微粉末５：再生コンクリート微粉末１の原料とした解体コンクリート塊と同一の解体コンクリート塊をジョークラッシャーで破砕して製造した５mmアンダーの再生微粉であり、特開昭６２－１５８１４６および特開昭６３－２８４２の実施例で使用された再生コンクリート微粉末と同様の方法で製造したもの。（水酸化カルシウム含有率：２．６質量％） The following five types of recycled concrete fine powder were used.
(1) Recycled concrete fine powder 1: Calcium hydroxide content 8.2 mass%
Fineness 5860cm 2 / g
(2) Recycled concrete fine powder 2: Calcium hydroxide content 4.7% by mass
Fineness 5710 cm 2 / g
(3) Recycled concrete fine powder 3: Calcium hydroxide content 13.6% by mass
Fineness 5650 cm 2 / g
(4) Recycled concrete fine powder 4: Calcium hydroxide content 1.4% by mass
Fineness 5690 cm 2 / g
(5) Recycled concrete fine powder 5: Recycled fine powder under 5 mm produced by crushing the same demolition concrete lump as the raw material of recycled concrete fine powder 1 with a jaw crusher. And the same as the recycled concrete fine powder used in the examples of JP-A-63-2842. (Calcium hydroxide content: 2.6% by mass)
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記の材料を用いて、実施例として表２に材料構成を示す実施例１～実施例１２及び比較例１～比較例１２の２４種類のセメント組成物で調整したセメントペーストとモルタルを用いて反応熱量と圧縮強度を測定した。また、セメント組成物を製造する際に消費される炭酸ガス量を算出した。なお、下記表２においては普通ポルトランドセメントを「ＯＰＣ」と表記している。これらの結果を下記表２に示す。 Using the above materials, the reaction was carried out using cement paste and mortar prepared with 24 types of cement compositions of Examples 1 to 12 and Comparative Examples 1 to 12 whose composition is shown in Table 2 as examples. The amount of heat and compressive strength were measured. Further, the amount of carbon dioxide consumed when producing the cement composition was calculated. In Table 2 below, ordinary Portland cement is expressed as “OPC”. These results are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２には、実施例１～実施例１２及び比較例１～比較例１２の材料構成と試験結果を示す。表２に示すように、本発明の水硬性セメント組成物を用いた成形体は、硬化時の発熱量から、十分に硬化反応が進行していることが推定され、実際に、得られた成形体は、炭酸ガス発生量が低い比較例１～１０のものに比べ、圧縮強度に優れることがわかる。
　他方、実施例と同じ再生コンクリート微粉末を用いたものであっても、セメントの組成が本発明の範囲外である比較例１～比較例４、再生コンクリート微粉末であって水酸化カルシウムの含有率が本発明の好ましい範囲外のものを用いた比較例５、６及び、特開昭６２－１５８１４６に記載の再生コンクリート微粉末を含有するセメント組成物を用いた比較例７、高炉スラグ微粉末の含有量が少ない比較例８のいずれも、実施例に比べて得られた成形体の圧縮強度が劣るものであった。
　比較例９、１０は実施例３と同じ組成であるが、高炉スラグ微粉末の粉末度が本発明の範囲外であり、粉末度の小さい比較例９は強度発現が十分でなく、粉末度が大きい比較例１０は、発熱量が著しく大きく、構造体のひび割れが問題となる。
　また、ポルトランドセメントを含有する比較例１１及び１２は圧縮強度が向上するが、炭酸ガス発生量が著しく増加するのがわかる。一般的なポルトランドセメントを含有するセメント組成物（比較例１２）の製造に消費される炭酸ガス量は７５０ｋｇ／トンであり、本発明によるセメント組成物は、これに比べ十分な圧縮強度を達成しうるセメント組成物であり、且つ、製造時の炭酸ガス排出量が削減されていることがわかる。 Table 2 shows material configurations and test results of Examples 1 to 12 and Comparative Examples 1 to 12. As shown in Table 2, in the molded body using the hydraulic cement composition of the present invention, it is estimated that the curing reaction has sufficiently progressed from the calorific value at the time of curing. It can be seen that the body is superior in compressive strength as compared with those of Comparative Examples 1 to 10 having a low carbon dioxide gas generation amount.
On the other hand, even if the same recycled concrete fine powder as in the examples is used, the composition of the cement is outside the scope of the present invention, Comparative Examples 1 to 4, the recycled concrete fine powder containing calcium hydroxide Comparative Examples 5 and 6 using a ratio outside the preferred range of the present invention, Comparative Example 7 using a cement composition containing recycled concrete fine powder described in JP-A-62-158146, blast furnace slag fine powder In any of Comparative Examples 8 having a small content of, the compression strength of the obtained molded body was inferior to that of the Examples.
Comparative Examples 9 and 10 have the same composition as in Example 3, but the fineness of the blast furnace slag fine powder is outside the scope of the present invention, and Comparative Example 9 having a small fineness does not exhibit sufficient strength and has a fineness. The large comparative example 10 has a remarkably large calorific value, and cracking of the structure becomes a problem.
Moreover, although the comparative examples 11 and 12 containing Portland cement improve compressive strength, it turns out that the amount of carbon dioxide generation increases remarkably. The amount of carbon dioxide consumed in the production of a cement composition containing a general Portland cement (Comparative Example 12) is 750 kg / ton, and the cement composition according to the present invention achieves sufficient compressive strength. It can be seen that the carbon dioxide emission during production is reduced.

Claims (9)

  1. 　粉末度が３０００～１３０００ｃｍ２／ｇの高炉スラグ微粉末６０～９０質量％とセッコウ５～２０質量％とポルトランドセメント５～３５質量％とを含有する混合物１００質量部に対して、解体コンクリートから分離した、水酸化カルシウムを３～１５質量％含む再生コンクリート微粉末を１０～３０質量部含有する水硬性セメント組成物。 Separated from demolition concrete with respect to 100 parts by mass of a mixture containing 60 to 90% by mass of fine powder of blast furnace slag having a fineness of 3000 to 13000 cm 2 / g, 5 to 20% by mass of gypsum and 5 to 35% by mass of Portland cement A hydraulic cement composition containing 10 to 30 parts by mass of recycled concrete fine powder containing 3 to 15% by mass of calcium hydroxide.
  2. 　前記セッコウが無水セッコウであることを特徴とする請求項１に記載の水硬性セメント組成物。 The hydraulic cement composition according to claim 1, wherein the gypsum is anhydrous gypsum.
  3. 　前記ポルトランドセメントが、再生コンクリート微粉末の水和活性を回復して得られる再生セメントである請求項１または請求項２に記載の水硬性セメント組成物。 The hydraulic cement composition according to claim 1 or 2, wherein the Portland cement is a recycled cement obtained by restoring the hydration activity of the recycled concrete fine powder.
  4. 　前記再生コンクリート微粉末の粉末度が２０００～７０００ｃｍ２／ｇの範囲である請求項１または請求項２に記載の水硬性セメント組成物。 The hydraulic cement composition according to claim 1 or 2, wherein the fineness of the recycled concrete fine powder is in the range of 2000 to 7000 cm 2 / g.
  5. 　前記再生コンクリート微粉末中の、水酸化カルシウムの含有量が６～１２質量％である請求項１または請求項２に記載の水硬性セメント組成物。 The hydraulic cement composition according to claim 1 or 2, wherein the content of calcium hydroxide in the recycled concrete fine powder is 6 to 12% by mass.
  6. 　前記再生セメントが、再生コンクリート微粉末を原料としたポルトランドセメントである請求項３に記載の水硬性セメント組成物。 The hydraulic cement composition according to claim 3, wherein the recycled cement is Portland cement made from recycled concrete fine powder.
  7. 　前記再生セメントが、再生コンクリート微粉末を４００～８００℃で加熱処理することにより得られたものである請求項３に記載の水硬性セメント組成物。 The hydraulic cement composition according to claim 3, wherein the recycled cement is obtained by heat-treating recycled concrete fine powder at 400 to 800 ° C.
  8. 　前記高炉スラグの粉末度が４０００～８０００ｃｍ２／ｇの範囲である請求項１に記載の水硬性セメント組成物。 The hydraulic cement composition according to claim 1, wherein the fineness of the blast furnace slag is in the range of 4000 to 8000 cm 2 / g.
  9. 　前記再生コンクリート微粉末中が、機械擦りもみ方式により製造されたものである請求項１または請求項２に記載の水硬性セメント組成物。 The hydraulic cement composition according to claim 1 or 2, wherein the recycled concrete fine powder is produced by a mechanical rubbing method.
PCT/JP2010/059763 2009-06-09 2010-06-09 Hydraulic cement composition WO2010143656A1 (en)

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