WO2010143656A1 - Composition de ciment hydraulique - Google Patents

Composition de ciment hydraulique 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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WO
WIPO (PCT)
Prior art keywords
fine powder
mass
cement
cement composition
recycled
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/059763
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English (en)
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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Takenaka Corp
DC Co Ltd
Original Assignee
Takenaka Corp
DC Co Ltd
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Filing date
Publication date
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Publication of WO2010143656A1 publication Critical patent/WO2010143656A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention porte sur une composition de ciment hydraulique qui est applicable à une structure qui ne nécessite pas toujours une alcalinité, qui est principalement composée d'un laitier de haut fourneau et qui rejette du CO2 en une quantité considérablement réduite. La composition de ciment hydraulique comprend : 100 parties en masse d'un mélange comprenant 60 à 90 % en masse d'une micropoudre de laitier de haut fourneau ayant une finesse de poudre de 3 000 à 13 000 cm2/g, 5 à 20 % en masse de plâtre et 5 à 35 % en masse de ciment Portland ; et 10 à 30 parties en masse d'une micropoudre de béton recyclé qui est isolée à partir d'un béton démoli et qui contient 3 à 15 % en masse d'hydroxyde de calcium.
PCT/JP2010/059763 2009-06-09 2010-06-09 Composition de ciment hydraulique Ceased WO2010143656A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009138627A JP2010285302A (ja) 2009-06-09 2009-06-09 水硬性セメント組成物
JP2009-138627 2009-06-09

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WO2010143656A1 true WO2010143656A1 (fr) 2010-12-16

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CN103241966A (zh) * 2013-05-10 2013-08-14 浙江大学宁波理工学院 无熟料钢渣再生微粉复合水泥
CN106467368A (zh) * 2015-08-18 2017-03-01 武汉科技大学 一种钢渣水泥
CN109678369A (zh) * 2018-12-24 2019-04-26 铜陵上峰水泥股份有限公司 一种多元固废制备水泥的生产工艺及方法

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JP6579760B2 (ja) * 2015-02-24 2019-09-25 株式会社トクヤマ 水硬性組成物
JP6690273B2 (ja) * 2015-05-18 2020-04-28 宇部興産株式会社 セメント組成物およびその製造方法
JP2018112518A (ja) * 2017-01-13 2018-07-19 清水建設株式会社 セメント用混合材の活性度推定方法、活性度推定装置および混合セメントの製造方法
CN115734954A (zh) * 2020-06-29 2023-03-03 株式会社可乐丽 由纤维增强的固化体
JP7675542B2 (ja) * 2021-03-18 2025-05-13 Ｕｂｅ三菱セメント株式会社 水硬性材料
JP7850855B1 (ja) * 2025-10-29 2026-04-23 鹿島建設株式会社 地盤改良体

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JPS5547252A (en) * 1978-10-02 1980-04-03 Chichibu Cement Kk Manufacture of specific cement
JPH06285454A (ja) * 1993-03-31 1994-10-11 Onoda Cement Co Ltd コンクリート廃材の処理方法
JPH0834654A (ja) * 1994-07-27 1996-02-06 Nippon Steel Chem Co Ltd コンクリートの製造方法
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103241966A (zh) * 2013-05-10 2013-08-14 浙江大学宁波理工学院 无熟料钢渣再生微粉复合水泥
CN106467368A (zh) * 2015-08-18 2017-03-01 武汉科技大学 一种钢渣水泥
CN109678369A (zh) * 2018-12-24 2019-04-26 铜陵上峰水泥股份有限公司 一种多元固废制备水泥的生产工艺及方法

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