JP7198604B2 - Firing products, cement additives, and cement compositions - Google Patents

Firing products, cement additives, and cement compositions Download PDF

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JP7198604B2
JP7198604B2 JP2018143399A JP2018143399A JP7198604B2 JP 7198604 B2 JP7198604 B2 JP 7198604B2 JP 2018143399 A JP2018143399 A JP 2018143399A JP 2018143399 A JP2018143399 A JP 2018143399A JP 7198604 B2 JP7198604 B2 JP 7198604B2
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JP2020019668A (en
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大亮 黒川
健一 本間
俊一郎 内田
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Taiheiyo Cement Corp
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/10Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

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Description

本発明は、特定の化学組成を有する焼成物、該焼成物を粉砕してなるセメント添加材、および該セメント添加材を含むセメント組成物に関する。 TECHNICAL FIELD The present invention relates to a fired product having a specific chemical composition, a cement additive obtained by pulverizing the fired product, and a cement composition containing the cement additive.

セメント産業は、古くからセメント原料の一部に産業廃棄物、一般廃棄物、および建設発生土等を用いてきたが、近年、資源循環型社会の構築の機運の高まりから、産業廃棄物等の使用量をさらに増やすことが望まれている。一般に、セメント原料として入手できるこれらの廃棄物はAlを多く含むため、おもに粘土代替原料として使用されてきた。したがって、これらの廃棄物をセメント原料として多用すると、セメントクリンカー中の3CaO・Al(以下「CA」という。)が増加する。
しかし、CAは水和活性が他のセメント鉱物に比べて高いため、CAが増加したセメントは水和熱が高く、また流動性が低下して経時変化(フローロスやスランプロス)が大きくなるという問題がある。
The cement industry has long used industrial waste, general waste, and soil from construction as raw materials for cement. It is desired to further increase the amount used. In general, these wastes, which are available as raw materials for cement, contain a large amount of Al 2 O 3 and have been mainly used as substitute raw materials for clay. Therefore, when these wastes are used extensively as raw materials for cement, 3CaO.Al 2 O 3 (hereinafter referred to as “C 3 A”) in cement clinker increases.
However, since C 3 A has a higher hydration activity than other cement minerals, cement with increased C 3 A has a high heat of hydration and a decrease in fluidity, resulting in deterioration over time (flow loss and slump loss). There is the problem of growing up.

また、TiOはアルミナを製造する過程で生じる赤泥中に含まれるなど、産業廃棄物や産業副産物、および建設発生土中に多く含まれている場合がある。TiOが多く含まれている産業廃棄物等を、セメントクリンカー用原料として多用すると、セメントの色調が変化(黄色味の増加)し初期強度発現性が低下する場合があるため、同様に、これらの使用量は限られていた。 Also, TiO 2 is often contained in industrial wastes, industrial by-products, and construction soil, such as red mud generated in the process of producing alumina. If industrial waste containing a large amount of TiO 2 is used extensively as a raw material for cement clinker, the color tone of cement may change (increase in yellowness) and the initial strength development may decrease. was used in a limited amount.

そこで、AlやTiOを多く含む産業廃棄物等を大量に再利用できる技術として、本願出願人は、先に、2CaO・SiOと2CaO・Al・SiOを必須成分とし、TiOを特定量含む焼成物であって、2CaO・SiO100質量部に対して、2CaO・Al・SiOおよび4CaO・Al・Feを特定量含む焼成物と、該焼成物を粉砕してなるセメント添加材と、該セメント添加材を含み、水和熱が低く、流動性や強度発現性が高いセメント組成物を提案した(特許文献1)。
そして、10年たった現在でも、さらに多くの産業廃棄物等を再利用でき、資源循環型社会の進展に資する技術が望まれている。
Therefore, as a technology that can reuse a large amount of industrial waste containing a large amount of Al 2 O 3 and TiO 2 , the applicant of the present application has previously proposed the use of 2CaO.SiO 2 and 2CaO.Al 2 O 3.SiO 2 as essential components. and a fired product containing a specific amount of TiO 2 , which contains specific amounts of 2CaO.Al 2 O 3.SiO 2 and 4CaO.Al 2 O 3.Fe 2 O 3 with respect to 100 parts by mass of 2CaO.SiO 2 A calcined product, a cement additive obtained by pulverizing the calcined product, and a cement composition containing the cement additive, having a low heat of hydration, and high fluidity and strength development have been proposed (Patent Document 1).
Even now, 10 years later, there is a demand for a technology that can reuse a larger amount of industrial waste and contribute to the development of a recycling-oriented society.

特開2008-290926号公報JP 2008-290926 A

したがって、本発明は、より多くの産業廃棄物等を再利用でき、水和熱が低く、流動性に優れ、気中養生でも長期の強度発現性が高いセメント組成物等を提供することを目的とする。 Therefore, an object of the present invention is to provide a cement composition, etc. that can reuse more industrial waste, etc., has a low heat of hydration, has excellent fluidity, and has high long-term strength development even when cured in air. and

本発明者は、前記目的にかなうポルトランドセメントを検討したところ、2CaO・SiO、2CaO・Al・SiO、および4CaO・Al・Feを特定量含み、[Al×(MgO+TiO+P)]/MnOの質量比が特定の範囲にある焼成物の粉砕物(セメント添加材)と、該セメント添加材を含むセメント組成物は、前記目的にかなうことを見い出し、本発明を完成させた。すなわち、本発明は以下の構成を有する焼成物等である。 The present inventors have investigated a Portland cement that meets the above object, and found that it contains specific amounts of 2CaO·SiO 2 , 2CaO·Al 2 O 3 ·SiO 2 , and 4CaO·Al 2 O 3 ·Fe 2 O 3 , [Al 2 O 3 × (MgO + TiO 2 + P 2 O 5 )]/MnO pulverized product (cement additive) having a mass ratio within a specific range, and a cement composition containing the cement additive are provided for the above purpose. The inventors have found that it can be achieved, and have completed the present invention. That is, the present invention is a fired product and the like having the following constitutions.

[1]2CaO・SiO、2CaO・Al・SiO、および4CaO・Al・Feを必須成分とし、下記(A))の条件を満たす焼成物。
(A)2CaO・SiO100質量部に対し、2CaO・Al・SiOおよび4CaO・Al・Feを合計で44.3~52質量部含む。
(B)前記焼成物中の[Al×(MgO+TiO+P)]/MnOの質量比が206~671である。
(C)前記焼成物中のTiO の含有率が0.3質量%以上である。
[2]焼成物中のSOの含有率が0.3質量%以上である、前記[1]に記載の焼成物。
[3]前記[1]または[2]に記載の焼成物の粉砕物からなるセメント添加材。
[4]前記[1]または[2]に記載の焼成物の粉砕物100質量部に対して、石膏をSO換算で3.5質量部以下含む、前記[3]に記載のセメント添加材。
[5]セメントとセメント添加材の合計を100質量%として、前記[]または[]に記載のセメント添加材を25~40質量%含むセメント組成物。
[6]石膏を、SO換算で1.0~5.0質量%含む、、前記[]に記載のセメント組成物。
[1] A fired product containing 2CaO.SiO 2 , 2CaO.Al 2 O 3 .SiO 2 , and 4CaO.Al 2 O 3 .Fe 2 O 3 as essential components and satisfying the following conditions (A) to ( C ).
(A) 2CaO.Al 2 O 3 .SiO 2 and 4CaO.Al 2 O 3 .Fe 2 O 3 are contained in a total of 44.3 to 52 parts by mass based on 100 parts by mass of 2CaO.SiO 2 .
(B) The mass ratio of [Al 2 O 3 ×(MgO+TiO 2 +P 2 O 5 )]/MnO in the fired product is 206-671.
(C) The content of TiO 2 in the fired product is 0.3% by mass or more.
[2] The fired product according to [ 1] above, wherein the content of SO 3 in the fired product is 0.3% by mass or more.
[3] A cement additive comprising a pulverized product of the fired product according to [1] or [2] .
[4] The cement additive according to [3] above, which contains 3.5 parts by mass or less of gypsum in terms of SO 3 with respect to 100 parts by mass of the pulverized product of the fired product according to [1] or [2] above. .
[5] A cement composition containing 25 to 40% by mass of the cement additive according to [ 3 ] or [ 4 ], with the total of cement and cement additive being 100% by mass.
[6] The cement composition according to [ 5 ] above, containing 1.0 to 5.0% by mass of gypsum in terms of SO 3 .

本発明の、焼成物を粉砕したセメント添加材を含むせセメント組成物は、水和熱が低く、流動性に優れ、気中養生でも長期の強度発現性が高い。また、本発明の焼成物は、多くの産業廃棄物、産業副産物、および建設発生土等を原料として再利用できる。 The cement composition of the present invention containing a cement additive obtained by pulverizing a fired product has a low heat of hydration, excellent fluidity, and high long-term strength development even when cured in air. In addition, the fired product of the present invention can be reused as a raw material from many industrial wastes, industrial by-products, construction soil, and the like.

以下、本発明を、焼成物、焼成物の製造方法、セメント添加材、およびセメント組成物に分けて詳細に説明する。
1.焼成物
本発明の焼成物は、2CaO・SiO(以下「CS」と略す。)、2CaO・Al・SiO(以下「CAS」と略す。)、および4CaO・Al・Fe(以下「CAF」と略す。)を必須成分とし、(A)CS100質量部に対し、CASおよびCAFを合計で10~100質量部含み、かつ、(B)前記焼成物中の[Al×(MgO+TiO+P)]/MnOの質量比は130~1000である。
前記焼成物中のCASおよびCAFの合計の含有率が10質量部未満では、焼成温度を高くしてもフリーライム(未反応のCaO)が減らず焼成が困難になり、しかも、生成するCSは水和活性がないγ型CSが多くなって、強度発現性が低下する場合がある。また、CASおよびCAFの合計の含有率が100質量部を超えると、高温における融液が多くなり焼成可能温度が狭まり、また、CSの生成が少ないため、セメント組成物の初期と長期の強度発現性がともに低下する場合がある。なお、CASおよびCAFの合計の含有率は、CS100質量部に対し、好ましくは20~90質量部である。なお、焼成物の製造のし易さ等から、C2ASおよびC4AFの合計100質量%として、C2ASの含有率は、好ましくは10~99質量%、より好ましくは20~90質量%である。
また、前記焼成物中の[Al×(MgO+TiO+P)]/MnOの質量比が前記範囲を外れると、気中養生すると長期の強度発現性が低下する。なお、前記[Al×(MgO+TiO+P)]/MnOの質量比は、好ましくは140~900であり、より好ましくは150~800である。
Hereinafter, the present invention will be described in detail by dividing into a fired product, a method for producing a fired product, a cement additive, and a cement composition.
1. Fired Product The fired product of the present invention includes 2CaO.SiO 2 (hereinafter abbreviated as “C 2 S”), 2CaO.Al 2 O 3 .SiO 2 (hereinafter abbreviated as “C 2 AS”), and 4CaO.Al. 2 O 3 ·Fe 2 O 3 (hereinafter abbreviated as “C 4 AF”) is an essential component, and (A) 10 to 100 parts by mass of C 2 AS and C 4 AF in total per 100 parts by mass of C 2 S and (B) the mass ratio of [Al 2 O 3 ×(MgO+TiO 2 +P 2 O 5 )]/MnO in the fired product is 130-1000.
If the total content of C 2 AS and C 4 AF in the fired product is less than 10 parts by mass, free lime (unreacted CaO) does not decrease even if the firing temperature is increased, making firing difficult. The C 2 S that is produced is often γ-type C 2 S that does not have hydration activity, which may reduce the strength development. In addition, when the total content of C 2 AS and C 4 AF exceeds 100 parts by mass, the amount of melt at high temperatures is increased, the temperature at which firing is possible is narrowed, and the generation of C 2 S is small. Both initial and long-term strength development may decrease. The total content of C 2 AS and C 4 AF is preferably 20 to 90 parts by mass with respect to 100 parts by mass of C 2 S. From the viewpoint of ease of production of the fired product, the content of C 2 AS is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, assuming that the total of C 2 AS and C 4 AF is 100% by mass. %.
Further, if the mass ratio of [Al 2 O 3 ×(MgO+TiO 2 +P 2 O 5 )]/MnO in the calcined product is out of the above range, the long-term strength development will be degraded after air curing. The mass ratio of [Al 2 O 3 ×(MgO+TiO 2 +P 2 O 5 )]/MnO is preferably 140-900, more preferably 150-800.

また、前記焼成物中のMgOの含有率は、好ましくは0.9~1.7質量%であり、前記焼成物中のPの含有率は、好ましくは0.3~1.5質量%である。
また、前記焼成物中のTiOの含有率は、水和熱が低下するため、好ましくは0.3質量%以上である。なお、前記TiOの含有率は、より好ましくは0.31~0.8質量%であり、さらに好ましくは0.32~0.7質量%である。また、前記焼成物中のMnOの含有率は、好ましくは0.03~0.155質量%であり、より好ましくは0.04~0.15質量%である。
Further, the content of MgO in the fired product is preferably 0.9 to 1.7% by mass, and the content of P 2 O 5 in the fired product is preferably 0.3 to 1.5. % by mass.
Moreover, the content of TiO 2 in the fired product is preferably 0.3% by mass or more because the heat of hydration decreases. The content of TiO 2 is more preferably 0.31 to 0.8% by mass, still more preferably 0.32 to 0.7% by mass. Also, the content of MnO in the fired product is preferably 0.03 to 0.155% by mass, more preferably 0.04 to 0.15% by mass.

また、本発明の焼成物中のSOの含有率は、強度発現性が向上するため、好ましくは0.3質量%以上である。なお、前記SOの含有率は、より好ましくは0.35~1.5質量%であり、さらに好ましくは0.4~1.2質量%である。 In addition, the content of SO 3 in the fired product of the present invention is preferably 0.3% by mass or more in order to improve strength development. The SO 3 content is more preferably 0.35 to 1.5% by mass, and still more preferably 0.4 to 1.2% by mass.

2.焼成物の製造方法
本発明の焼成物の原料は、産業廃棄物、一般廃棄物、および建設発生土から選ばれる1種以上であり、これらを焼成して製造する。これらのうち、産業廃棄物は、生コンスラッジ、下水汚泥、浄水汚泥、建設汚泥、製鉄汚泥、および赤泥等の各種汚泥や、石炭灰、ボーリング廃土、各種焼却灰、鋳物砂、ロックウール、廃ガラス、高炉2次灰、建設廃材、およびコンクリート廃材などが挙げられ、一般廃棄物は、下水汚泥乾粉、都市ごみ焼却灰、および貝殻等が挙げられ、建設発生土は、建設現場や工事現場等から発生する土壌、残土、および廃土壌等が挙げられる。
また、一般のポルトランドセメントクリンカー原料である、石灰石、生石灰、および消石灰等のCaO原料、珪石、および粘土等のSiO原料、粘土等のAl原料、鉄滓、および鉄ケーキ等のFe原料も、本発明において焼成物の原料として使用できる。
2. Method for producing calcined product The raw material for the calcined product of the present invention is one or more selected from industrial waste, general waste, and soil generated from construction, and is produced by calcining these materials. Of these, industrial waste includes raw concrete sludge, sewage sludge, purified water sludge, construction sludge, iron-making sludge, various sludges such as red sludge, coal ash, boring waste soil, various incineration ash, foundry sand, rock wool, Examples include waste glass, secondary blast furnace ash, construction waste, and concrete waste. General waste includes dry powder of sewage sludge, municipal waste incineration ash, and shells. Examples include soil, surplus soil, waste soil, and the like generated from, etc.
In addition, CaO raw materials such as limestone, quicklime, and slaked lime, which are general Portland cement clinker raw materials, SiO2 raw materials such as silica stone and clay , Al2O3 raw materials such as clay, iron slag, iron cake, and other Fe A 2 O 3 raw material can also be used as a raw material for the fired product in the present invention.

本発明の焼成物中のセメント鉱物の組成は、原料または焼成物中のCaO、SiO、Al、およびFeの各含有率(単位は質量%)から、次式により求めることができる。
AF=3.04×Fe
A=1.61×CaO-3.00×SiO-2.26×Fe
AS=-1.63×CaO+3.04×SiO+2.69×Al+0.57×Fe
S=1.02×CaO+0.95×SiO-1.69k×Al-0.36×Fe
例えば、廃棄物原料中にカルシウムが不足する場合、その不足分を調整するために、石灰石等を混合する。混合割合は、廃棄物原料の化学組成に応じて、得られる焼成物の鉱物組成が、本発明において規定する前記範囲内になるよう、適宜決定する。
The composition of the cement mineral in the fired product of the present invention is obtained by the following formula from each content of CaO, SiO 2 , Al 2 O 3 , and Fe 2 O 3 in the raw material or fired product (unit: mass %) be able to.
C4AF = 3.04 x Fe2O3
C 3 A=1.61×CaO−3.00×SiO 2 −2.26×Fe 2 O 3
C 2 AS=−1.63×CaO+3.04×SiO 2 +2.69×Al 2 O 3 +0.57×Fe 2 O 3
C 2 S=1.02×CaO+0.95×SiO 2 −1.69 k×Al 2 O 3 −0.36×Fe 2 O 3
For example, if there is a shortage of calcium in the waste raw material, limestone or the like is mixed to adjust the shortage. The mixing ratio is appropriately determined according to the chemical composition of the waste raw material so that the mineral composition of the resulting fired product is within the range specified in the present invention.

成分を調整した原料を焼成する際の焼成温度は、焼成工程の熔融相の状態が良好であるため、好ましくは1000~1350℃、より好ましくは1200~1330℃である。
用いる焼成装置は、特に限定されず、例えばロータリーキルン等を用いることができる。また、ロータリーキルンで焼成する場合、例えば、廃油、廃タイヤ、および廃プラスチック等の燃料代替廃棄物を使用できる。このような焼成により、CAS等の鉱物が生成して、本発明において規定する鉱物組成を有する焼成物が得られる。
The sintering temperature for sintering the raw material with adjusted components is preferably 1000 to 1350° C., more preferably 1200 to 1330° C., since the state of the molten phase in the sintering process is good.
The baking apparatus to be used is not particularly limited, and for example, a rotary kiln or the like can be used. In addition, when burning in a rotary kiln, for example, fuel substitute wastes such as waste oil, waste tires, and waste plastics can be used. By such firing, minerals such as C 2 AS are generated to obtain a fired product having the mineral composition specified in the present invention.

3.セメント添加材
本発明のセメント添加材は、前記焼成物の粉砕物、または前記焼成物の粉砕物と石膏の混合物である。焼成物の粉砕方法は、特に限定されず、例えばボールミル等を用い、通常の方法で粉砕する。
焼成物の粉砕物のブレーン比表面積は、モルタルやコンクリートのブリーディングの低減や、流動性および強度発現性の向上のため、好ましくは2500~5000cm/gである。また、石膏のブレーン比表面積は、同じくモルタルやコンクリートのブリーディングの低減や、流動性および強度発現性の向上のため、好ましくは2500~10000cm/gである。用いる石膏の種類は、特に限定されず、例えば、二水石膏、α型半水石膏、β型半水石膏、および無水石膏から選ばれる1種以上が挙げられる。
本発明のセメント添加材中の石膏の含有率は、セメント組成物の強度発現性および流動性の向上や水和熱の低減のため、焼成物の粉砕物100質量部に対し、SO換算で好ましくは3.5質量部以下である。
3. Cement Additive The cement additive of the present invention is a pulverized product of the fired product or a mixture of the pulverized product of the fired product and gypsum. The method of pulverizing the fired product is not particularly limited, and pulverization is performed by a conventional method using, for example, a ball mill or the like.
The Blaine specific surface area of the pulverized product of the fired product is preferably 2500 to 5000 cm 2 /g in order to reduce bleeding of mortar or concrete and improve fluidity and strength development. Also, the Blaine specific surface area of gypsum is preferably 2500 to 10000 cm 2 /g in order to reduce bleeding of mortar and concrete and improve fluidity and strength development. The type of gypsum to be used is not particularly limited, and examples thereof include one or more selected from dihydrate gypsum, α-hemihydrate gypsum, β-type hemihydrate gypsum, and anhydrous gypsum.
The content of gypsum in the cement additive of the present invention is, in terms of SO3 conversion , per 100 parts by mass of the pulverized fired product in order to improve the strength development and fluidity of the cement composition and to reduce the heat of hydration. Preferably, it is 3.5 parts by mass or less.

4.セメント組成物
本発明のセメント組成物は、前記セメント添加材とセメントの混合物である。用いるセメントは、普通ポルトランドセメント、中庸熱ポルトランドセメント、および低熱ポルトランドセメント等の各種ポルトランドセメント、高炉セメントおよびフライアッシュセメント等の混合セメント、並びに、石灰石粉末等を混合した石灰石フィラーセメント等から選ばれる1種以上である。
前記セメント組成物中のセメント添加材の含有率は、好ましくは25~40質量%である。セメント添加材の含有率が前記範囲を外れると、気中養生した場合にセメント組成物の強度発現性が低下するおそれがある。なお、前記セメント添加材の含有率は、モルタルおよびコンクリートのブリーディングの低減や、流動性および強度発現性の向上のためには、より好ましくは26~37質量%、さらに好ましくは27~35質量%である。
4. Cement Composition The cement composition of the present invention is a mixture of the cement additive and cement. The cement to be used is selected from various Portland cements such as ordinary Portland cement, moderate heat Portland cement, and low heat Portland cement, mixed cement such as blast furnace cement and fly ash cement, and limestone filler cement mixed with limestone powder etc. 1 more than seeds.
The content of the cement additive in the cement composition is preferably 25-40 mass %. If the content of the cement additive is out of the above range, the strength development of the cement composition may deteriorate when cured in the air. The content of the cement additive is more preferably 26 to 37% by mass, more preferably 27 to 35% by mass, in order to reduce bleeding of mortar and concrete and improve fluidity and strength development. is.

また、本発明のセメント組成物中の石膏の含有率は、通常の凝結性状が得られるため、セメント中に元々含まれている石膏も含めた全SO換算で、好ましくは1.0~3.0質量%、より好ましくは1.5~3.0質量%、さらに好ましくは1.5~2.5質量%である。 In addition, the content of gypsum in the cement composition of the present invention is preferably 1.0 to 3 in terms of total SO 3 including the gypsum originally contained in the cement, since normal setting properties can be obtained. 0% by mass, more preferably 1.5 to 3.0% by mass, and even more preferably 1.5 to 2.5% by mass.

本発明のセメント組成物は、セメント添加材とセメントを混合して製造できるが、その方法は特に限定されず、例えば、セメントクリンカー、焼成物、および石膏を混合した後に粉砕するか、または前記各成分を粉砕した後に混合してもよい。また、焼成物、または焼成物と石膏を粉砕して得られたセメント添加材を、セメントクリンカー粉砕物、ポルトランドセメント、または混合セメントに混合して製造することもできる。セメント組成物のブレーン比表面積は、モルタルやコンクリートのブリーディングの低減や、流動性および強度発現性の向上のため、好ましくは2500~4500cm/gである。 The cement composition of the present invention can be produced by mixing a cement additive and cement, but the method is not particularly limited. The ingredients may be ground and then mixed. Alternatively, a cement additive obtained by pulverizing a calcined product or a calcined product and gypsum can be mixed with pulverized cement clinker, Portland cement, or mixed cement. The Blaine specific surface area of the cement composition is preferably 2,500 to 4,500 cm 2 /g in order to reduce bleeding of mortar or concrete and improve fluidity and strength development.

以下、本発明を実施例により説明するが、本発明はこれらの実施例に限定されない。
1.使用した材料
焼成物の製造以外で使用した材料を以下に示す。
(1)普通ポルトランドセメント(太平洋セメント社製)
Sを60質量%、CSを18質量%、CAを9質量%、およびCAFを9質量%含む。また、[Al×(MgO+TiO+P)]/MnOは113である。
(2)細骨材
JIS R 5201「セメントの物理試験方法」に規定する標準砂
(3)減水剤
ポリカルボン酸系高性能AE減水剤で、商品名はレオビルドSP8N(登録商標、BASFジャパン社製)である。
(4)水道水
EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.
1. Materials used Materials other than the production of fired products are shown below.
(1) Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd.)
It contains 60% by weight C 3 S, 18% by weight C 2 S, 9% by weight C 3 A and 9% by weight C 4 AF. Also, [Al 2 O 3 ×(MgO+TiO 2 +P 2 O 5 )]/MnO is 113.
(2) Fine aggregate Standard sand specified in JIS R 5201 “Physical test method for cement” (3) Water reducing agent Polycarboxylic acid-based high-performance AE water reducing agent, trade name: Leobuild SP8N (registered trademark, manufactured by BASF Japan) ).
(4) Tap water

2.焼成物の製造
石灰石、生コンクリートスラッジ、下水汚泥、および建設発生土を原料に用いて、表1に示す焼成物を製造した。焼成は箱型電気炉を用いて、1350℃で30分間行なった。
2. Production of Burnt Material Limestone, ready-mixed concrete sludge, sewage sludge, and soil generated from construction were used as raw materials to produce baked materials shown in Table 1. Firing was performed at 1350° C. for 30 minutes using a box type electric furnace.

Figure 0007198604000001
Figure 0007198604000001

3.セメント添加材の製造
前記焼成物A、B、およびRを、ブレーン比表面積が3200±50cm/gに粉砕した後、該焼成物の粉砕物100質量部に対し、ブレーン比表面積が6000cm/gの二水石膏をSO換算で2質量部混合して、焼成物Aを含むセメント添加材A、焼成物Bを含むセメント添加材B、および焼成物Rを含むセメント添加材Rを製造した。
3. Production of Cement Additive Material After pulverizing the fired products A, B, and R to a Blaine specific surface area of 3200±50 cm 2 /g, the Blaine specific surface area is 6000 cm 2 /g with respect to 100 parts by mass of the ground product of the fired product. 2 parts by mass of gypsum dihydrate in terms of SO 3 are mixed to produce cement additive A containing fired product A, cement additive B containing fired product B, and cement additive R containing fired product R. .

4.前記セメント添加材を含むセメント組成物の発熱特性(水和熱)の評価
前記普通ポルトランドセメント70質量部と、前記セメント添加材AおよびBを、ぞれぞれ30質量部混合して、セメント添加材Aを含むセメント組成物A、およびセメント添加材Bを含むセメント組成物Bを製造した。次に、セメント組成物AおよびBと、比較のため普通ポルトランドセメントの水和熱を、JIS R 5203「セメントの水和熱測定方法(溶解熱方法)」に準拠して測定した。その結果を表2に示す。
表2に示すように、セメント組成物AおよびBの水和熱は、普通ポルトランドセメントの水和熱と比べ、7日および20日のいずれの場合も約8割と低い。
4. Evaluation of exothermic properties (heat of hydration) of a cement composition containing the cement additive 70 parts by mass of the ordinary Portland cement and 30 parts by mass of the cement additives A and B were mixed, and the cement was added. A cement composition A containing material A and a cement composition B containing cement additive B were produced. Next, the heats of hydration of cement compositions A and B and ordinary Portland cement for comparison were measured according to JIS R 5203 "Method for measuring heat of hydration of cement (heat of solution)". Table 2 shows the results.
As shown in Table 2, the heats of hydration of cement compositions A and B are about 80% lower than that of ordinary Portland cement for both 7 days and 20 days.

Figure 0007198604000002
Figure 0007198604000002

5.モルタルの流動性の評価
前記普通ポルトランドセメントと前記セメント添加材を、表3の含有率になるように混合して、セメント組成物を製造した。次に、水/セメント組成物の質量比が0.35、細骨材/セメント組成物の質量比が2.0、および減水剤/セメント組成物の質量比が0.006のモルタルを混練して、モルタルのフロー値を以下の手順で測定した。その結果を表3に示す。
[フロー値の測定]
混練直後と、混練後30分経過した時点で、前記モルタルをフローコーン(上面の内径は5cm、下面の内径は10cm、高さは15cm)に投入し、フローコーンを上方に取り去った後、拡大が止まったときのモルタルの広がり(フロー値)を測定した。
5. Evaluation of Fluidity of Mortar The ordinary Portland cement and the cement additive were mixed so as to have the content shown in Table 3 to produce a cement composition. Next, mortar having a water/cement composition mass ratio of 0.35, a fine aggregate/cement composition mass ratio of 2.0, and a water reducing agent/cement composition mass ratio of 0.006 was kneaded. Then, the mortar flow value was measured by the following procedure. Table 3 shows the results.
[Measurement of flow value]
Immediately after kneading and 30 minutes after kneading, the mortar was put into a flow cone (upper surface inner diameter: 5 cm, lower inner diameter: 10 cm, height: 15 cm), the flow cone was removed upward, and then expanded. The spread of the mortar (flow value) was measured when the flow stopped.

6.圧縮強度の測定
前記セメント組成物を用いて、水/セメント組成物の質量比が0.5、および細骨材/セメント組成物の質量比が3.0のモルタルを混練して型枠に打設した後、1日間、湿空養生して脱型して、直径10cm、長さ20cmの供試体を作製した。
該供試体は、20℃、相対湿度60%で、1年、5年、および10年間、気中養生して、それぞれの養生期間の供試体の圧縮強度を、JIS R 5201「セメントの物理試験方法」の準拠して測定した。その結果を表3に示す。
表3に示すように、実施例1および2は、フロー値が大きく流動性に優れ、特に材齢10年の圧縮強度は、比較例1および2や参考例と比べ、約2割高い。
6. Measurement of Compressive Strength Using the cement composition, mortar having a water/cement composition mass ratio of 0.5 and a fine aggregate/cement composition mass ratio of 3.0 was kneaded and cast into a mold. After setting, it was cured in wet air for 1 day and removed from the mold to prepare a specimen having a diameter of 10 cm and a length of 20 cm.
The specimens were air-cured at 20° C. and a relative humidity of 60% for 1 year, 5 years, and 10 years, and the compressive strength of the specimens for each curing period was measured according to JIS R 5201 "Physical test of cement. Measured in accordance with "Method". Table 3 shows the results.
As shown in Table 3, Examples 1 and 2 have large flow values and excellent fluidity, and in particular, the compressive strength at 10 years of age is about 20% higher than those of Comparative Examples 1 and 2 and Reference Example.

Figure 0007198604000003
Figure 0007198604000003

Claims (6)

2CaO・SiO、2CaO・Al・SiO、および4CaO・Al・Feを必須成分とし、下記(A))の条件を満たす焼成物。
(A)2CaO・SiO100質量部に対し、2CaO・Al・SiOおよび4CaO・Al・Feを合計で44.3~52質量部含む。
(B)前記焼成物中の[Al×(MgO+TiO+P)]/MnOの質量比が206~671である。
(C)前記焼成物中のTiO の含有率が0.3質量%以上である。
A baked product containing 2CaO.SiO 2 , 2CaO.Al 2 O 3 .SiO 2 , and 4CaO.Al 2 O 3 .Fe 2 O 3 as essential components and satisfying the following conditions (A) to ( C ).
(A) 2CaO.Al 2 O 3 .SiO 2 and 4CaO.Al 2 O 3 .Fe 2 O 3 are contained in a total of 44.3 to 52 parts by mass based on 100 parts by mass of 2CaO.SiO 2 .
(B) The mass ratio of [Al 2 O 3 ×(MgO+TiO 2 +P 2 O 5 )]/MnO in the fired product is 206-671.
(C) The content of TiO 2 in the fired product is 0.3% by mass or more.
焼成物中のSOの含有率が0.3質量%以上である、請求項1に記載の焼成物。 The fired product according to claim 1 , wherein the content of SO3 in the fired product is 0.3% by mass or more. 請求項1または2に記載の焼成物の粉砕物からなるセメント添加材。 A cement additive comprising a pulverized product of the fired product according to claim 1 or 2 . 請求項1または2に記載の焼成物の粉砕物100質量部に対して、石膏をSO換算で3.5質量部以下含む、請求項3に記載のセメント添加材。 4. The cement additive according to claim 3, which contains 3.5 parts by mass or less of gypsum in terms of SO3 per 100 parts by mass of the pulverized product of the fired material according to claim 1 or 2 . セメントとセメント添加材の合計を100質量%として、請求項またはに記載のセメント添加材を25~40質量%含むセメント組成物。 A cement composition containing 25 to 40% by mass of the cement additive according to claim 3 or 4 , with the total amount of cement and cement additive being 100% by mass. 石膏を、SO換算で1.0~5.0質量%含む、請求項に記載のセメント組成物。
6. The cement composition according to claim 5 , comprising 1.0 to 5.0% by mass of gypsum in terms of SO 3 .
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Citations (2)

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JP2008222475A (en) 2007-03-12 2008-09-25 Taiheiyo Cement Corp Fired product, cement additive and cement composition
JP2008290926A (en) 2007-05-28 2008-12-04 Taiheiyo Cement Corp Fired product, cement additive, and cement composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008222475A (en) 2007-03-12 2008-09-25 Taiheiyo Cement Corp Fired product, cement additive and cement composition
JP2008290926A (en) 2007-05-28 2008-12-04 Taiheiyo Cement Corp Fired product, cement additive, and cement composition

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