JP2009084087A - Cement addition material and cement composition - Google Patents

Cement addition material and cement composition Download PDF

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JP2009084087A
JP2009084087A JP2007253215A JP2007253215A JP2009084087A JP 2009084087 A JP2009084087 A JP 2009084087A JP 2007253215 A JP2007253215 A JP 2007253215A JP 2007253215 A JP2007253215 A JP 2007253215A JP 2009084087 A JP2009084087 A JP 2009084087A
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cement
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JP4852506B2 (en
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Daisuke Kurokawa
大亮 黒川
Kenichi Honma
健一 本間
Makoto Kobayakawa
真 小早川
Yasuhiro Uchiyama
康広 内山
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Taiheiyo Cement Corp
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/24Cements from oil shales, residues or waste other than slag
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0068Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • C04B2103/0089Agents for reducing heat of hydration
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/34Flow improvers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034Physico-chemical characteristics of the mixtures
    • C04B2111/00215Mortar or concrete mixtures defined by their oxide composition
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cement addition material which uses industrial waste, domestic waste, construction waste soil or the like as raw material, undergoes low deterioration in strength development even when the addition to cement is increased, and has low heat of hydration and excellent flowability. <P>SOLUTION: The cement addition material includes a pulverized material of a fired material A having hydraulic modulus (H.M.) of 1.65-1.75, containing ≤8.0 mass% Al<SB>2</SB>O<SB>3</SB>and 2.2-5.0 mass% Fe<SB>2</SB>O<SB>3</SB>, containing as an essential component 2CaO-SiO<SB>2</SB>and 4CaO-Al<SB>2</SB>O<SB>3</SB>-Fe<SB>2</SB>O<SB>3</SB>and further containing 12CaO-7Al<SB>2</SB>O<SB>3</SB>and/or 4CaO-3Al<SB>2</SB>O<SB>3</SB>-SO<SB>3</SB>. The cement composition includes ≤50 mass% of the cement addition material internally to the cement. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、産業廃棄物、一般廃棄物、建設発生土等の廃棄物を原料とした焼成物を粉砕してなるセメント添加材、及び該セメント添加材を含有してなるセメント組成物に関する。   The present invention relates to a cement additive formed by pulverizing a fired product made from a waste such as industrial waste, general waste, and construction generated soil, and a cement composition containing the cement additive.

わが国では、経済成長、人口の都市部への集中に伴い、産業廃棄物や一般廃棄物等が急増している。従来、これらの廃棄物の大半は、焼却によって十分の一程度に減容化して埋め立て処分されているが、近年、埋め立て処分場の残余容量が逼迫していることから、新しい廃棄物処理方法の確立が緊急課題になっている。セメント産業では、産業廃棄物や一般廃棄物等を原料として多く使用しており、今後、さらなる使用量の増大が求められている。   In Japan, industrial waste, general waste, etc. are rapidly increasing with economic growth and population concentration in urban areas. Conventionally, most of these wastes have been landfilled by reducing their volume to one-tenth by incineration.Recently, the remaining capacity of landfill sites has become tight, so new waste disposal methods Establishment is an urgent issue. In the cement industry, industrial waste, general waste, etc. are used as raw materials, and further increase in the amount of use is required in the future.

しかしながら、産業廃棄物や一般廃棄物は、天然原料に比べAl2O3分に富むため、単純にこれらの使用量を増大すると、セメントクリンカー中の3CaO・Al2O3が増大し、モルタル・コンクリートとして使用した場合に、水和熱の増加、流動性の悪化等を引き起こすという問題が生じる。これに対処するため、産業廃棄物等をより多く原料として使用した焼成物を製造し、これをセメント添加材として使用することが提案されている(特許文献1、特許文献2)。 However, industrial waste and general waste are rich in Al 2 O 3 compared to natural raw materials. Therefore, simply increasing the amount used increases 3CaO · Al 2 O 3 in the cement clinker, resulting in mortar When used as concrete, there arises a problem of causing an increase in heat of hydration, deterioration of fluidity, and the like. In order to cope with this, it has been proposed to produce a fired product using a larger amount of industrial waste or the like as a raw material and use it as a cement additive (Patent Documents 1 and 2).

これらのセメント添加材は、石炭灰等の廃棄物を原料としたSiO2量が30〜50質量%、CaO量が25〜45質量%、Al2O3が5〜25質量%、f-CaO量が1.0質量%以下の焼結物の粉砕物である(特許文献1)か、SiO2量が50質量%を超え70質量%以下、CaO量が5〜45質量%、Al2O3が5〜45質量%、f-CaO量が1.0質量%以下の焼結物の粉砕物であり(特許文献2)、アノーサイト等のアルミノ珪酸塩鉱物を主体とするもので、2CaO・SiO2等のカルシウムシリケートや、3CaO・Al2O3等のカルシウムアルミネートをほとんど含まないものである。このため、セメントへの添加量が10質量%以上と大きくなると、セメント組成物の強度発現性が極端に低下してしまうため、セメントへの添加量が制限されるという問題があった。
特開2006−219347号公報 特開2006−219348号公報
These cement additives have a SiO 2 content of 30-50% by mass, a CaO content of 25-45% by mass, an Al 2 O 3 content of 5-25% by mass, and f-CaO. It is a pulverized product of a sintered product having an amount of 1.0% by mass or less (Patent Document 1), or the amount of SiO 2 exceeds 50% by mass and is 70% by mass or less, the amount of CaO is 5 to 45% by mass, Al 2 O 3 is a pulverized product of 5 to 45% by mass and f-CaO content of 1.0% by mass or less (Patent Document 2), mainly composed of aluminosilicate minerals such as anorthite. -Calcium silicate such as SiO 2 and calcium aluminate such as 3CaO · Al 2 O 3 are hardly included. For this reason, when the addition amount to the cement is as large as 10% by mass or more, the strength development property of the cement composition is extremely lowered, and there is a problem that the addition amount to the cement is limited.
JP 2006-219347 A JP 2006-219348 A

従って、本発明の目的は、産業廃棄物、一般廃棄物、建設発生土等を原料としたものであって、セメントへの添加量を多くした場合であっても、強度発現性の低下が小さく、かつ、水和熱が低く、流動性が良好なセメント添加材を提供することにある。   Accordingly, an object of the present invention is to use industrial waste, general waste, construction generated soil, etc. as a raw material, and even when the amount added to cement is increased, the decrease in strength development is small. Another object of the present invention is to provide a cement additive having a low heat of hydration and good fluidity.

本発明者らは、斯かる実情に鑑み、鋭意検討した結果、特定の化学成分と特定の鉱物を含有する焼成物の粉砕物であれば、セメントへの添加量を多くした場合であっても、セメント組成物の強度発現性の低下が小さく、かつ、セメントに混合した場合に水和熱が低減され、流動性も良好であることを見出し、本発明を完成した。   As a result of intensive investigations in view of such circumstances, the present inventors have found that a pulverized product containing a specific chemical component and a specific mineral is a pulverized product even when the amount added to cement is increased. The present inventors have found that the decrease in strength development of the cement composition is small, that the heat of hydration is reduced and the fluidity is good when mixed with cement, and that the present invention has been completed.

すなわち、本発明は、水硬率(H.M.)が1.65〜1.75、Al2O3量が8.0質量%以下、Fe2O3量が2.2〜5.0質量%で、かつ、2CaO・SiO2及び4CaO・Al2O3・Fe2O3を必須成分とし、さらに、12CaO・7Al2O3及び/又は4CaO・3Al2O3・SO3を含有する焼成物Aの粉砕物を含むセメント添加材を提供するものである。
また、本発明は、セメントに対して、当該セメント添加材を、内割で50質量%以下含有するセメント組成物を提供するものである。
That is, according to the present invention, the hydraulic modulus (HM) is 1.65 to 1.75, the amount of Al 2 O 3 is 8.0% by mass or less, and the amount of Fe 2 O 3 is 2.2 to 5.0% by mass. and was an essential component 2CaO · SiO 2 and 4CaO · Al 2 O 3 · Fe 2 O 3, furthermore, fired product a containing 12CaO · 7Al 2 O 3 and / or 4CaO · 3Al 2 O 3 · SO 3 A cement additive containing the pulverized product is provided.
The present invention also provides a cement composition containing 50% by mass or less of the cement additive relative to cement.

本発明のセメント添加材は、産業廃棄物、一般廃棄物等を原料として使用することができるので、廃棄物の有効利用の促進に貢献することができる。また、本発明のセメント添加材は、セメントへの添加量を10質量%以上と多くした場合であっても、セメント組成物の強度発現性の低下が小さい。さらに、本発明のセメント添加材を用いることにより、水和熱が低く、流動性が良好なセメント組成物を得ることができる。   Since the cement additive of the present invention can use industrial waste, general waste, etc. as a raw material, it can contribute to promotion of effective use of waste. Moreover, the cement additive of the present invention has a small decrease in strength development of the cement composition even when the amount added to the cement is increased to 10% by mass or more. Furthermore, by using the cement additive of the present invention, a cement composition having a low heat of hydration and good fluidity can be obtained.

本発明で用いる焼成物Aは、水硬率(H.M.)が1.65〜1.75、Al2O3量が8.0質量%以下、Fe2O3量が2.2〜5.0質量%で、かつ、2CaO・SiO2(C2S)及び4CaO・Al2O3・Fe2O3(C4AF)を必須成分とし、さらに、12CaO・7Al2O3(C12A7)及び/又は4CaO・3Al2O3・SO3(C4A3・SO3)を含有するものである。 The fired product A used in the present invention has a hydraulic modulus (HM) of 1.65 to 1.75, an Al 2 O 3 content of 8.0% by mass or less, and an Fe 2 O 3 content of 2.2 to 5.0. In addition, it contains 2CaO · SiO 2 (C 2 S) and 4CaO · Al 2 O 3 · Fe 2 O 3 (C 4 AF) as essential components, and further contains 12CaO · 7Al 2 O 3 (C 12 A 7 And / or 4CaO.3Al 2 O 3 .SO 3 (C 4 A 3 .SO 3 ).

このような化学成分と特定の鉱物を含有する焼成物の粉砕物であれば、セメントへの添加量を多くした場合であっても、セメント組成物の強度発現性の低下を小さくすることができる。また、セメント組成物の水和熱が低く、流動性も良好なものとすることができる。   If such a pulverized product containing a chemical component and a specific mineral is used, even if the amount added to the cement is increased, the decrease in strength development of the cement composition can be reduced. . In addition, the cement composition has a low heat of hydration and good fluidity.

焼成物Aの水硬率(H.M.)が1.65未満では、該焼成物中のC2S量が少なくなり、セメント組成物の強度発現性が低下する。一方、水硬率(H.M.)が1.75を超えると、C12A7やC4A3・SO3がほとんど生成せず、Al2O3の多くはC3Aとして存在し、さらに3CaO・SiO2(C3S)の生成量が多くなり、水和熱が高く、流動性が悪化する場合が多くなる。
焼成物Aの水硬率(H.M.)は、初期強度維持、水和熱低減、流動性改善の観点から、1.67〜1.73が好ましく、特に1.67〜1.72が好ましい。
水硬率(H.M.)は、焼成物A中のCaO、SiO2、Al2O3及びFe2O3の含有量から、CaO/(SiO2+Al2O3+Fe2O3)で算出される値である。
When the hydraulic modulus (HM) of the fired product A is less than 1.65, the amount of C 2 S in the fired product is reduced, and the strength development of the cement composition is lowered. On the other hand, when the hydraulic modulus (HM) exceeds 1.75, C 12 A 7 and C 4 A 3 · SO 3 are hardly generated, and most of Al 2 O 3 exists as C 3 A, and 3CaO・ The amount of SiO 2 (C 3 S) produced increases, the heat of hydration is high, and the fluidity deteriorates in many cases.
The hydraulic modulus (HM) of the fired product A is preferably 1.67 to 1.73, particularly preferably 1.67 to 1.72 from the viewpoint of maintaining initial strength, reducing heat of hydration, and improving fluidity.
The hydraulic modulus (HM) is calculated as CaO / (SiO 2 + Al 2 O 3 + Fe 2 O 3 ) from the contents of CaO, SiO 2 , Al 2 O 3 and Fe 2 O 3 in the fired product A. Value.

なお、水硬率(H.M.)が1.65〜1.75の場合、C12A7又はC4A3・SO3のいずれか一方が生成するが、クリンカ中のSO3量が0.6質量%以下ではC12A7が、それより多くなるとC4A3・SO3が生成しやすくなる。どちらも初期の強度発現性はC3Aと同様で、水和熱はC3Aより低く、流動性も良好であるため、いずれか一方あるいは両方が一定量以下存在することにより、廃棄物使用量が多く、Al2O3量が通常の普通ポルトランドセメントより多い場合でも、初期強度が低下せず、水和熱も増大せず、流動性が良好なセメントを得ることができる。 In addition, when the hydraulic modulus (HM) is 1.65 to 1.75, either C 12 A 7 or C 4 A 3 · SO 3 is produced, but the amount of SO 3 in the clinker is 0.6. If it is less than mass%, C 12 A 7 tends to be generated, and if it is more than that, C 4 A 3 · SO 3 is likely to be generated. In both cases, the initial strength development is the same as C 3 A, the heat of hydration is lower than that of C 3 A, and the flowability is also good. Even when the amount is large and the amount of Al 2 O 3 is larger than that of ordinary ordinary Portland cement, the initial strength is not lowered, the heat of hydration is not increased, and a cement having good fluidity can be obtained.

焼成物A中のAl2O3量は8.0質量%以下であるが、8.0質量%を超えると、焼成物中のC3A量、C12A7量やC4A3・SO3量の合計量が多くなり、セメント組成物の水和熱が高く、流動性も低下する。
焼成物A中のAl2O3量は、水和熱の低減、流動性改善や、廃棄物の使用量増加の観点から、6.0〜7.8質量%が好ましく、特に6.5〜7.5質量%が好ましい。
The amount of Al 2 O 3 in the fired product A is 8.0% by mass or less, but if it exceeds 8.0% by mass, the amount of C 3 A, C 12 A 7 and C 4 A 3 · The total amount of SO 3 is increased, the heat of hydration of the cement composition is high, and the fluidity is also lowered.
The amount of Al 2 O 3 in the fired product A is preferably 6.0 to 7.8% by mass, particularly 6.5 to 7.8% from the viewpoint of reducing heat of hydration, improving fluidity, and increasing the amount of waste used. 7.5 mass% is preferable.

焼成物A中のFe2O3量は2.2〜5.0質量%であるが、5.0質量%を超えると、焼成物中のC4AF量が多くなり、高温における融液が増加するため、焼成可能温度が狭まり、焼成物の製造が困難になる。また、C3AやC12A7などのカルシウムアルミネートの生成量が少なくなるため、初期強度の低下も大きくなる場合がある。一方、C4AFはC3AやC12A7などのカルシウムアルミネートの反応を制御する役割もあり、カルシウムアルミネートとC4AFが間隙層中で共存することにより、カルシウムアルミネートの水和がある程度抑えられる。従って、Fe2O3量が2.2質量%未満では、C3AやC12A7などのカルシウムアルミネート鉱物に対してC4AF量が少なくなり、石膏を加えても水和熱が上昇し、流動性が悪化する場合がある。また、廃棄物中にはFe2O3も含まれているため、Fe2O3量が少なくなると、廃棄物の使用量も制限される。 The amount of Fe 2 O 3 in the fired product A is 2.2 to 5.0% by mass. However, if it exceeds 5.0% by mass, the amount of C 4 AF in the fired product is increased, and the melt at high temperature is increased. Since it increases, the temperature at which baking can be performed is narrowed, making it difficult to produce a fired product. In addition, since the amount of calcium aluminate such as C 3 A or C 12 A 7 is reduced, the initial strength may be greatly reduced. On the other hand, C 4 AF also has a role in controlling the reaction of calcium aluminate such as C 3 A and C 12 A 7, and the calcium aluminate and C 4 AF coexist in the interstitial layer. The sum is suppressed to some extent. Therefore, when the amount of Fe 2 O 3 is less than 2.2% by mass, the amount of C 4 AF decreases with respect to calcium aluminate minerals such as C 3 A and C 12 A 7, and even when gypsum is added, the heat of hydration is reduced. May increase and liquidity may deteriorate. Moreover, since Fe 2 O 3 is also contained in the waste, when the amount of Fe 2 O 3 decreases, the amount of waste used is also limited.

焼成物A中のFe2O3量は、焼成物の焼成のしやすさ、廃棄物の使用量増加や、セメント組成物の強度維持、水和熱低減、流動性改善の観点から、2.2〜4.5質量%が好ましく、特に2.5〜4.0質量%が好ましい。
なお、本発明において、焼成物A中のCaO、SiO2、Al2O3及びFe2O3含有量は、「JIS R 5202(ポルトランドセメントの化学分析方法)」に準じて測定される値である。
The amount of Fe 2 O 3 in the fired product A is 2. from the viewpoints of ease of firing of the fired product, increase in the amount of waste used, maintenance of the strength of the cement composition, reduction of heat of hydration, and improvement of fluidity. 2-4.5 mass% is preferable, and 2.5-4.0 mass% is especially preferable.
In the present invention, the CaO, SiO 2 , Al 2 O 3 and Fe 2 O 3 content in the fired product A is a value measured according to “JIS R 5202 (chemical analysis method of Portland cement)”. is there.

焼成物Aは、鉱物として、C2S及びC4AFを必須成分とし、さらに、C12A7及び/又はC4A3・SO3を含有するものである。これらの鉱物を含有することにより、セメントへの添加量を10質量%以上と多くした場合であっても、セメント組成物の強度発現性の低下が少なく、水和熱が低いセメント添加材を得ることができる。 The fired product A contains C 2 S and C 4 AF as essential components and further contains C 12 A 7 and / or C 4 A 3 .SO 3 as minerals. By containing these minerals, even when the amount added to the cement is increased to 10% by mass or more, a cement additive having a low decrease in strength and low heat of hydration of the cement composition is obtained. be able to.

焼成物AがC2Sを含まない場合には、セメント組成物の強度発現性が低下する上、水和熱も高く、流動性も低下する。焼成物AがC4AFを含まない場合には、廃棄物の使用量が減少したり、焼成が困難になり、また、流動性を悪化させたり、水和熱が高くなることがある。なお、焼成物A中にC2S及びC4AFを含む場合には、C3Aも含むものとなる。
また、焼成物AがC12A7及び/又はC4A3・SO3を含有しない場合には、流動性が悪化し、水和熱が高くなる場合がある。
なお、C2S、C4AF及びC12A7を含有することは、粉末X線回折により、これらのメインピークが認められることにより、確認することができる。粉末X線回折は、通常の粉末X線回折装置を用い、通常の方法により行うことができる。
When the fired product A does not contain C 2 S, the strength development property of the cement composition is lowered, the heat of hydration is high, and the fluidity is also lowered. When the fired product A does not contain C 4 AF, the amount of waste used may be reduced, firing may be difficult, fluidity may be deteriorated, and heat of hydration may be increased. In the case where in the fired product A containing C 2 S and C 4 AF becomes intended to include C 3 A.
Moreover, when the baked product A does not contain C 12 A 7 and / or C 4 A 3 .SO 3 , fluidity may deteriorate and heat of hydration may increase.
The inclusion of C 2 S, C 4 AF and C 12 A 7 can be confirmed by the fact that these main peaks are observed by powder X-ray diffraction. Powder X-ray diffraction can be performed by a normal method using a normal powder X-ray diffractometer.

焼成物Aにおいて、C12A7及びC4A3・SO3の合計含有量は、10質量%以下(ただし、0質量%は含まない)が好ましく、特に6〜10質量%が好ましい。C12A7及びC4A3・SO3の合計含有量が10質量%を超えると、セメント組成物の水和熱が高く、流動性も低下する。
なお、C12A7量は、X線回折で2θ=18.1°付近に現れるC12A7の(211)ピーク、C4A3・SO3量は、2θ=23.6°付近に現れるC4A3・SO3の(422)ピーク強度を測定することにより定量可能であり、予め含有既知試料のピーク強度を測定しておき、そのときの強度比より、それぞれの値を定量することができる。
In the fired product A, the total content of C 12 A 7 and C 4 A 3 · SO 3 is preferably 10% by mass or less (however, 0% by mass is not included), and particularly preferably 6 to 10% by mass. When the total content of C 12 A 7 and C 4 A 3 · SO 3 exceeds 10% by mass, the heat of hydration of the cement composition is high and the fluidity is also lowered.
Incidentally, C 12 A 7 weight, (211) peak of C 12 A 7 appearing near 2 [Theta] = 18.1 ° in X-ray diffraction, C 4 A 3 · SO 3 amount is in the vicinity of 2 [Theta] = 23.6 ° It can be quantified by measuring the (422) peak intensity of C 4 A 3 · SO 3 that appears, and the peak intensity of a known sample contained in advance is measured, and each value is quantified from the intensity ratio at that time. be able to.

なお、本発明においては、焼成物A中のフリーライム量は、セメント組成物の水和熱や流動性、強度発現性等から、1.5質量%以下、特に1質量%以下であるのが好ましい。   In the present invention, the amount of free lime in the fired product A is 1.5% by mass or less, particularly 1% by mass or less, from the heat of hydration, fluidity and strength development of the cement composition. preferable.

焼成物Aは、さらに、2CaO・Al2O3・SiO2(C2AS)及び/又は3CaO・SiO2(C3S)を含有することができる。C2ASを含有することにより、セメント組成物の水和熱を低減させ、かつ流動性を向上させることができる。また、焼成物中のAl2O3量を増やすことができるため、産業廃棄物、一般廃棄物等の使用量を増加させることができる。また、C3Sを含有することにより、セメント組成物の強度発現性を向上させることができる。
なお、C2AS、C3Sを含有することは、粉末X線回折により、これらのメインピークが認められることにより、確認することができる。
The fired product A can further contain 2CaO · Al 2 O 3 · SiO 2 (C 2 AS) and / or 3CaO · SiO 2 (C 3 S). By containing C 2 AS, the heat of hydration of the cement composition can be reduced and the fluidity can be improved. Moreover, since the amount of Al 2 O 3 in the fired product can be increased, the amount of industrial waste, general waste, etc. used can be increased. Further, by containing the C 3 S, it is possible to improve the strength development of the cement composition.
The inclusion of C 2 AS and C 3 S can be confirmed by observing these main peaks by powder X-ray diffraction.

焼成物A中のC2AS量、C3S量は焼成物の製造の容易性や、セメント組成物の強度発現性の観点から、それぞれ10質量%以下が好ましく、特に5質量%以下、更に3質量%未満が好ましい。
なお、C2AS量は、X線回折で2θ=31.4°付近に現れるC2ASの(211)ピーク、C3S量は、2θ=51.4°付近に現れるC3Sの(14 2 4)ピーク強度を測定することにより定量可能であり、予め含有既知試料のピーク強度を測定しておき、そのときの強度比より、それぞれの値を定量することができる。
The amount of C 2 AS and C 3 S in the fired product A is preferably 10% by weight or less, particularly 5% by weight or less, respectively, from the viewpoint of ease of production of the fired product and strength development of the cement composition. Less than 3% by mass is preferred.
Incidentally, C 2 AS amount appears in the vicinity of 2 [Theta] = 31.4 ° in X-ray diffraction C 2 AS of (211) peak, C 3 S content is appearing near 2θ = 51.4 ° C 3 S in ( 14 2 4) It can be quantified by measuring the peak intensity, the peak intensity of the known sample contained in advance is measured, and the respective values can be quantified from the intensity ratio at that time.

焼成物Aは、産業廃棄物、一般廃棄物及び建設発生土から選ばれる1種以上を原料とし、これを焼成することにより製造することができる。産業廃棄物としては、例えば生コンスラッジ;下水汚泥、浄水汚泥、建設汚泥、製鉄汚泥等の各種汚泥;建設廃材、コンクリート廃材、ボーリング廃土;石炭灰、焼却飛灰、溶融飛灰等の各種焼却灰;鋳物砂、ロックウール、廃ガラス、高炉2次灰などが挙げられる。一般廃棄物としては、例えば下水汚泥乾粉、都市ごみ焼却灰、貝殻等が挙げられる。また、建設発生土としては、建設現場や工事現場等から発生する土壌や残土、さらには廃土壌等が挙げられる。   The fired product A can be produced by firing one or more selected from industrial waste, general waste, and construction generated soil as a raw material. Industrial waste includes, for example, raw conslag; various sludges such as sewage sludge, purified water sludge, construction sludge, and ironmaking sludge; construction wastes, concrete wastes, and boring waste soils; Ash; foundry sand, rock wool, waste glass, blast furnace secondary ash, etc. Examples of the general waste include sewage sludge dry powder, municipal waste incineration ash, and shells. In addition, examples of construction generated soil include soil and residual soil generated from construction sites and construction sites, and waste soil.

また、上記廃棄物等に加え、通常のポルトランドセメントクリンカー原料、例えば、石灰石、生石灰、消石灰等のCaO原料;珪石、粘土等のSiO2原料;粘土等のAl2O3原料;鉄滓、鉄ケーキ等のFe2O3原料を、焼成物の原料として使用することができる。 In addition to the above wastes, etc., ordinary Portland cement clinker raw materials, for example, CaO raw materials such as limestone, quicklime and slaked lime; SiO 2 raw materials such as silica and clay; Al 2 O 3 raw materials such as clay; An Fe 2 O 3 raw material such as a cake can be used as a raw material for the fired product.

上記各原料を、水硬率(H.M.)が1.65〜1.75、Al2O3量が8.0質量%以下、Fe2O3量が2.2〜5.0質量%となるように混合し、焼成することにより、焼成物Aを製造することができる。
本発明においては、廃棄物原料中にカルシウムが不足する場合には、その不足分を調整するために、石灰石等を混合して用いることができる。混合割合は、廃棄物原料の組成に応じて、得られる焼成物の組成が上記範囲内になるよう、適宜決定すれば良い。
The above raw materials have a hydraulic modulus (HM) of 1.65 to 1.75, an Al 2 O 3 amount of 8.0% by mass or less, and an Fe 2 O 3 amount of 2.2 to 5.0% by mass. By mixing and firing as described above, the fired product A can be manufactured.
In the present invention, when calcium is insufficient in the waste material, limestone or the like can be mixed and used in order to adjust the shortage. What is necessary is just to determine a mixing ratio suitably according to the composition of a waste raw material so that the composition of the baked product obtained may be in the said range.

焼成物Aを焼成する際の焼成温度は、1200〜1400℃、特に1250〜1370℃であるのが、目的とする鉱物組成の焼成物が得られる上、焼成工程の熔融相の状態が良好であるので好ましい。
各原料を混合する方法は特に制限されず、慣用の装置等を用いて行うことができる。
また、焼成に用いる装置も特に制限されず、例えばロータリーキルン等を用いることができる。ロータリーキルンで焼成する際には、燃料代替廃棄物、例えば廃油、廃タイヤ、廃プラスチック等を使用することができる。
The firing temperature when firing the fired product A is 1200 to 1400 ° C., particularly 1250 to 1370 ° C. In addition to obtaining a fired product of the desired mineral composition, the state of the molten phase in the firing process is good. This is preferable.
The method for mixing the raw materials is not particularly limited, and can be performed using a conventional apparatus or the like.
Moreover, the apparatus used for baking is not particularly limited, and for example, a rotary kiln or the like can be used. When firing in a rotary kiln, fuel substitute waste such as waste oil, waste tires, waste plastics and the like can be used.

本発明のセメント添加材は、上記のような焼成物Aの粉砕物のみからなるものでも良く、又は上記焼成物Aの粉砕物と石膏とからなるものでも良い。
焼成物Aの粉砕方法は特に制限されず、例えばボールミル等を用い、通常の方法で粉砕することができる。焼成物Aの粉砕物は、ブレーン比表面積が2500〜5000cm2/gであるのが、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、強度発現性の観点から好ましい。
The cement additive of the present invention may be composed only of the pulverized product of the baked product A as described above, or may be composed of the pulverized product of the baked product A and gypsum.
The pulverization method of the fired product A is not particularly limited, and can be pulverized by a normal method using, for example, a ball mill. The pulverized product of the fired product A preferably has a Blaine specific surface area of 2500 to 5000 cm 2 / g from the viewpoint of reducing bleeding of mortar and concrete, fluidity, and strength development.

石膏としては、二水石膏、α型又はβ型半水石膏、無水石膏等が挙げられ、これらを1種又は2種以上組み合わせて用いることができる。石膏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、強度発現性の観点から、2500〜10000cm2/gであるのが好ましい。 Examples of the gypsum include dihydrate gypsum, α-type or β-type hemihydrate gypsum, anhydrous gypsum, and the like, and these can be used alone or in combination. The specific surface area of the plaster of gypsum is preferably 2500 to 10000 cm 2 / g from the viewpoint of reducing bleeding of mortar and concrete, fluidity, and strength development.

本発明のセメント添加材において、石膏の含有量は、セメント組成物の強度発現性、水和熱や流動性の観点から、焼成物Aの粉砕物100質量部に対して、SO3換算で6質量部以下が好ましく、特に1〜5質量部であるのが好ましい。 In the cement additive of the present invention, the content of gypsum is 6 in terms of SO 3 with respect to 100 parts by mass of the pulverized product of fired product A from the viewpoint of strength development of the cement composition, heat of hydration and fluidity. The amount is preferably not more than part by mass, particularly preferably 1 to 5 parts by mass.

本発明のセメント添加材は、更に、C2S及びC2ASを必須成分とし、C2S100質量部に対して、C2AS+C4AFを10〜100質量部含有し、かつ、C3Aの含有量が20質量部以下である焼成物Bの粉砕物を含有することができる。このような焼成物Bの粉砕物を含有することにより、セメント組成物の水和熱を小さくすることができ、流動性を向上させることができる。また、廃棄物の有効利用を促進することができる。
焼成物Aは、焼成物Bより強度発現性が良好であるが、水和熱の面では、焼成物Bに劣るため、焼成物Aと焼成物Bを組み合わせて用いることにより、セメント添加材の混合量を増大でき、廃棄物の有効利用をより促進することができる。
The cement additive of the present invention further comprises C 2 S and C 2 AS as essential components, contains 10 to 100 parts by mass of C 2 AS + C 4 AF with respect to 100 parts by mass of C 2 S, and C 3 A The pulverized product of fired product B having a content of 20 parts by mass or less can be contained. By containing such a pulverized product of fired product B, the heat of hydration of the cement composition can be reduced, and the fluidity can be improved. In addition, effective use of waste can be promoted.
Although the fired product A has better strength development than the fired product B, it is inferior to the fired product B in terms of heat of hydration. Therefore, by using the fired product A and the fired product B in combination, The amount of mixing can be increased, and the effective use of waste can be further promoted.

焼成物Bは、C2S及びC2ASを必須成分とするもので、C2S100質量部に対して、C2AS+C4AFを10〜100質量部、好ましくは20〜90質量部含有するものである。C2AS+C4AF含有量が10質量部未満では、セメント組成物の流動性が悪くなる。また、焼成時に焼成温度を上げてもフリーライム量が低下しにくく、焼成が困難になり、また、生成するC2Sも水和活性のないγ型C2Sである可能性が高くなり、セメント組成物の強度発現性を大きく低下させることがある。一方、C2AS+C4AF含有量が100質量部を超えると、セメント組成物の強度発現性が低下する。 Calcined product B is for an essential component C 2 S and C 2 AS, with respect to C 2 S100 parts by 10 to 100 parts by weight of C 2 AS + C 4 AF, preferably contain from 20 to 90 parts by weight Is. When the content of C 2 AS + C 4 AF is less than 10 parts by mass, the fluidity of the cement composition is deteriorated. Also, even if the firing temperature is raised during firing, the amount of free lime is unlikely to decrease, making firing difficult, and the possibility that C 2 S produced is also γ-type C 2 S without hydration activity increases. The strength development property of the cement composition may be greatly reduced. On the other hand, when the C 2 AS + C 4 AF content exceeds 100 parts by mass, the strength development of the cement composition is lowered.

また、焼成物Bは、C2S100質量部に対するC3Aの含有量が20質量部以下、好ましくは10質量部以下のものである。20質量部を超えると、セメント組成物の水和熱が大きくなり、流動性も悪くなる。 In the fired product B, the content of C 3 A with respect to 100 parts by mass of C 2 S is 20 parts by mass or less, preferably 10 parts by mass or less. When it exceeds 20 parts by mass, the heat of hydration of the cement composition increases and the fluidity also deteriorates.

さらに、焼成物Bは、P2O5を0.2〜8質量%、特に0.5〜6質量%含有するのが好ましく、アルカリ(Na2O+K2O)を0.4〜4質量%、特に0.5〜3.5質量%含有するのが好ましい。P2O5やアルカリをこの範囲内で含有する場合、C2Sを活性化させるため、C3Aなどのカルシウムアルミネートがない場合でも、セメント組成物の強度発現性が良好になる。カルシウムアルミネートが少なくなるほど、セメント組成物の流動性も良好でかつ水和熱も低くなる。
なお、焼成物B中のフリーライム量は、セメント組成物の水和熱や流動性、強度発現性等の点から、1.5質量%以下、特に1質量%以下であるのが好ましい。
Furthermore, calcined product B is, P 2 O 5 and 0.2 to 8% by weight, particularly preferably contains 0.5 to 6 wt%, alkali (Na 2 O + K 2 O ) of 0.4 to 4 mass% In particular, the content is preferably 0.5 to 3.5% by mass. When P 2 O 5 or an alkali is contained within this range, C 2 S is activated, so that the strength development of the cement composition is improved even in the absence of calcium aluminate such as C 3 A. The less calcium aluminate, the better the fluidity of the cement composition and the lower the heat of hydration.
In addition, the amount of free lime in the fired product B is preferably 1.5% by mass or less, particularly 1% by mass or less from the viewpoint of heat of hydration, fluidity, strength development and the like of the cement composition.

焼成物Bは、産業廃棄物、一般廃棄物及び建設発生土から選ばれる1種以上を原料とし、これを焼成することにより製造することができる。産業廃棄物としては、例えば生コンスラッジ;下水汚泥、浄水汚泥、建設汚泥、製鉄汚泥等の各種汚泥;建設廃材、コンクリート廃材、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次灰などが挙げられ;一般廃棄物としては、例えば下水汚泥乾粉、都市ごみ焼却灰、貝殻等が挙げられる。また、建設発生土としては、建設現場や工事現場等から発生する土壌や残土、さらには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、例えば、石灰石、生石灰、消石灰等のCaO原料;珪石、粘土等のSiO2原料;粘土等のAl2O3原料;鉄滓、鉄ケーキ等のFe2O3原料を使用することができる。
The fired product B can be manufactured by firing one or more materials selected from industrial waste, general waste, and construction generated soil. Industrial wastes include, for example, raw conslag; various sludges such as sewage sludge, purified water sludge, construction sludge, steel sludge, etc .; Secondary ash etc. are mentioned; Examples of general waste include sewage sludge dry powder, municipal waste incineration ash, shells and the like. In addition, examples of construction generated soil include soil and residual soil generated from construction sites and construction sites, and waste soil.
Also, general Portland cement clinker raw materials such as CaO raw materials such as limestone, quicklime and slaked lime; SiO 2 raw materials such as silica and clay; Al 2 O 3 raw materials such as clay; Fe 2 O 3 such as iron cake and iron cake Raw materials can be used.

なお、焼成物Bの原料組成によっては、特に、前記産業廃棄物、一般廃棄物及び建設発生土から選ばれる1種以上(廃棄物原料)を原料として用いた場合、C4AFが生成することがあるが、本発明においては、焼成物BのC2ASの一部、好ましくはC2ASの70質量%以下がC4AFで置換されていても良い。C4AFがこの範囲を超えて置換されると、焼成の温度範囲が狭くなり、製造の管理が難しくなる。 Depending on the raw material composition of the fired product B, C 4 AF may be generated particularly when at least one selected from the industrial waste, general waste and construction waste soil (waste raw material) is used as the raw material. However, in the present invention, a part of C 2 AS of the fired product B, preferably 70% by mass or less of C 2 AS may be substituted with C 4 AF. If C 4 AF is substituted beyond this range, the temperature range for firing becomes narrow, and manufacturing control becomes difficult.

焼成物Bの鉱物組成は、使用原料中のCaO、SiO2、Al2O3、Fe2O3の各含有量(質量%)から、次式により求めることができる。
C4AF=3.04×Fe2O3
C3A=1.61×CaO−3.00×SiO2−2.26×Fe2O3
C2AS=−1.63×CaO+3.04×SiO2+2.69×Al2O3+0.57×Fe2O3
C2S=1.02×CaO+0.95×SiO2−1.69×Al2O3−0.36×Fe2O3
The mineral composition of the calcined product B can be obtained from the contents (mass%) of CaO, SiO 2 , Al 2 O 3 and Fe 2 O 3 in the raw materials used by the following formula.
C 4 AF = 3.04 × Fe 2 O 3
C 3 A = 1.61 × CaO−3.00 × SiO 2 −2.26 × Fe 2 O 3
C 2 AS = -1.63 x CaO + 3.04 x SiO 2 + 2.69 x Al 2 O 3 + 0.57 x Fe 2 O 3
C 2 S = 1.02 × CaO + 0.95 × SiO 2 −1.69 × Al 2 O 3 −0.36 × Fe 2 O 3

従って、例えば、廃棄物原料中にカルシウムが不足する場合には、その不足分を調整するために、石灰石等を混合して用いることができる。混合割合は、廃棄物原料の組成に応じて、得られる焼成物の組成が、前記範囲内になるよう、適宜決定すれば良い。   Therefore, for example, when calcium is insufficient in the waste material, limestone or the like can be mixed and used to adjust the shortage. What is necessary is just to determine a mixing ratio suitably according to the composition of a waste raw material so that the composition of the baked product obtained may be in the said range.

焼成物Bの焼成温度は、1000〜1350℃、特に1200〜1330℃であるのが、焼成工程の熔融相の状態が良好であるので好ましい。
用いる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際には、燃料代替廃棄物、例えば廃油、廃タイヤ、廃プラスチック等を使用することができる。
このような焼成により、C2ASが生成し、上記組成の焼成物Bを得ることができる。
The firing temperature of the fired product B is preferably 1000 to 1350 ° C., particularly 1200 to 1330 ° C., because the molten phase in the firing process is in good condition.
The apparatus to be used is not specifically limited, For example, a rotary kiln etc. can be used. Moreover, when baking with a rotary kiln, a fuel alternative waste, for example, waste oil, a waste tire, a waste plastic, etc. can be used.
By such firing, C 2 AS is produced, and a fired product B having the above composition can be obtained.

焼成物Bの粉砕物は、焼成物Aの粉砕物100質量部に対して20〜1000質量部、特に100〜400質量部含有させるのが、セメント組成物の水和熱や、流動性、強度発現性等の点から好ましい。
なお、焼成物Bの粉砕物は、ブレーン比表面積が2500〜5000cm2/gであるのが、セメント組成物の水和熱や、流動性、強度発現性の点から好ましい。粉砕方法は特に制限されず、例えばボールミル等を用い、通常の方法で粉砕することができる。
The pulverized product of the fired product B is contained in an amount of 20 to 1000 parts by weight, particularly 100 to 400 parts by weight, based on 100 parts by weight of the pulverized product of the fired product A. It is preferable from the viewpoint of expression.
The pulverized product of the fired product B preferably has a Blaine specific surface area of 2500 to 5000 cm 2 / g from the viewpoint of heat of hydration, fluidity and strength development of the cement composition. The pulverization method is not particularly limited, and for example, it can be pulverized by a usual method using a ball mill or the like.

本発明のセメント添加材は、上記各材料を混合して製造することができるが、その方法は特に制限されず、例えば、焼成物Aの粉砕物と石膏を混合しても良いし、焼成物Aと石膏を混合した後に粉砕しても良い。さらには、焼成物Aの粉砕物と石膏の混合物に、焼成物Bの粉砕物を混合しても良い。   The cement additive of the present invention can be produced by mixing the above materials, but the method is not particularly limited. For example, the pulverized product of the fired product A and gypsum may be mixed, or the fired product. You may grind | pulverize, after mixing A and gypsum. Furthermore, the pulverized product of the baked product B may be mixed with the mixture of the pulverized product of the baked product A and gypsum.

本発明のセメント組成物は、上記セメント添加材とセメントを混合することにより得ることができる。セメントとしては、普通ポルトランドセメント、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、フライアッシュセメント等の混合セメントを使用することができる。
セメント添加材は、セメントに対して、内割で50質量%以下含有され、好ましくは2〜50質量%、より好ましくは5〜40質量%含有される。セメント添加材の添加量が50質量%を超えると、セメント組成物の強度発現性が極端に低下する。
The cement composition of the present invention can be obtained by mixing the cement additive and cement. As the cement, various Portland cements such as ordinary Portland cement and low heat Portland cement; mixed cements such as blast furnace cement and fly ash cement can be used.
The cement additive is 50% by mass or less, preferably 2 to 50% by mass, and more preferably 5 to 40% by mass with respect to the cement. When the addition amount of the cement additive exceeds 50% by mass, the strength development property of the cement composition is extremely lowered.

本発明のセメント組成物には、石膏を配合することができ、セメント組成物中に全SO3換算で1〜5質量%、特に1.5〜4質量%、更に1.8〜3質量%配合するのが、セメント組成物の水和熱、凝結、流動性、耐久性や強度発現性等の観点から好ましい。 In the cement composition of the present invention, gypsum can be blended, and 1 to 5% by mass, particularly 1.5 to 4% by mass, and further 1.8 to 3 % by mass in terms of total SO 3 in the cement composition. It is preferable to blend from the viewpoint of heat of hydration, setting, fluidity, durability and strength development of the cement composition.

本発明のセメント組成物は、更に高炉スラグ粉末、フライアッシュ、石灰石粉末、珪石粉末及びシリカフュームから選ばれる1種以上の無機粉末を含有することができる。これらの無機粉末を含有することにより、セメント組成物の水和熱の低減や、流動性の向上、耐久性や長期強度発現性の向上等を図ることができる。   The cement composition of the present invention may further contain one or more inorganic powders selected from blast furnace slag powder, fly ash, limestone powder, silica stone powder, and silica fume. By containing these inorganic powders, it is possible to reduce the heat of hydration of the cement composition, improve fluidity, improve durability and long-term strength development, and the like.

これら無機粉末のうち、高炉スラグ粉末、フライアッシュ、石灰石粉末、珪石粉末は、入手のしやすさ、セメント組成物の流動性、強度発現性の観点から、ブレーン比表面積が2500〜10000cm2/gであるのが好ましく、特に強度発現性の観点から、3000〜10000cm2/g、更に4000〜9000cm2/gであるのが好ましい。
また、シリカフュームは、入手のしやすさ、セメント組成物の流動性、強度発現性の観点から、BET比表面積が5〜20m2/gであるのが好ましく、特に流動性、強度発現性の観点から、6〜18m2/g、更に7〜15m2/gであるのが好ましい。
Among these inorganic powders, blast furnace slag powder, fly ash, limestone powder, and quartzite powder have a brain specific surface area of 2500 to 10,000 cm 2 / g from the viewpoint of availability, fluidity of cement composition, and strength development. it is preferably at, particularly in view of the strength development, 3000~10000cm 2 / g, still more preferably from 4000~9000cm 2 / g.
Silica fume preferably has a BET specific surface area of 5 to 20 m 2 / g from the viewpoints of availability, fluidity and strength development of the cement composition, and particularly from the viewpoint of fluidity and strength development. from, 6~18m 2 / g, that is more 7~15m 2 / g preferred.

高炉スラグ粉末の含有量は、セメント組成物中、内割で70質量%以下、特に60質量%以下であるのが、セメント組成物の水和熱や、流動性、耐久性、強度発現性等の観点から好ましい。
フライアッシュ、石灰石粉末、珪石粉末、シリカフュームの含有量は、それぞれ、セメント組成物中、内割で40質量%以下、特に35質量%以下であるのが、セメント組成物の水和熱や、流動性、耐久性、強度発現性等の観点から好ましい。
The content of the blast furnace slag powder is 70% by mass or less, particularly 60% by mass or less in the cement composition. The heat of hydration of the cement composition, fluidity, durability, strength development, etc. From the viewpoint of
The contents of fly ash, limestone powder, silica stone powder, and silica fume are 40% by mass or less, particularly 35% by mass or less, respectively, in the cement composition. From the viewpoints of properties, durability, strength development and the like.

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することができるが、その方法は特に制限されず、例えば、セメント添加材をセメントクリンカー粉砕物やポルトランドセメントと混合しても良いし、ポルトランドセメントクリンカーと、セメント添加材用材料(焼成物A、石膏、焼成物B等)を混合した後粉砕するか、あるいは各成分を粉砕した後に混合しても良い。得られるセメント組成物は、ブレーン比表面積が、2500〜4500cm2/gであるのが、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、強度発現性の観点から好ましい。 The cement composition of the present invention can be produced by mixing a cement additive and cement, but the method is not particularly limited. For example, the cement additive may be mixed with a crushed cement clinker or Portland cement. The mixture may be pulverized after mixing the Portland cement clinker and the material for cement additive (fired product A, gypsum, fired product B, etc.), or may be mixed after each component is pulverized. The obtained cement composition preferably has a specific surface area of 2500 to 4500 cm 2 / g from the viewpoints of reducing bleeding of mortar and concrete, fluidity, and strength development.

次に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらに何ら制限されるものではない。   EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not restrict | limited to these at all.

実施例1
(1)焼成物Aの製造:
表1に示す化学組成の石灰石、下水汚泥、石炭灰、建設発生土を原料として、表2及び表3に示す化学組成及び鉱物組成の焼成物A1〜A6を製造した。焼成は、ロータリーキルンを用いて行った。焼成物1トン製造する際に使用した下水汚泥、石炭灰及び建設発生土の総量(廃棄物等の総量)と、焼成温度は、表2に示すとおりである。
Example 1
(1) Production of fired product A:
Using the limestone having the chemical composition shown in Table 1, sewage sludge, coal ash, and construction generated soil as raw materials, fired products A1 to A6 having the chemical composition and the mineral composition shown in Table 2 and Table 3 were produced. Firing was performed using a rotary kiln. Table 2 shows the total amount of sewage sludge, coal ash, and construction generated soil (total amount of waste, etc.) used in producing 1 ton of fired product, and the firing temperature.

Figure 2009084087
Figure 2009084087

Figure 2009084087
Figure 2009084087

Figure 2009084087
Figure 2009084087

(2)焼成物Bの製造:
表1に示す組成の化学組成の石灰石、下水汚泥、石炭灰を原料とし、C2S100質量部に対して、C2AS 32質量部、C4AF 15質量部、C3A 0質量部の焼成物B1(フリーライム量0.1質量%)を製造した。焼成は、ロータリーキルンを用い、1350℃で行った。焼成物1トンを製造する際に使用した下水汚泥及び石炭灰の総量(廃棄物等の総量)は、528kg/トンであった。
(2) Production of fired product B:
Using limestone, sewage sludge, and coal ash having the chemical composition shown in Table 1 as raw materials, 32 parts by mass of C 2 AS, 15 parts by mass of C 4 AF, and 0 parts by mass of C 3 A with respect to 100 parts by mass of C 2 S A fired product B1 (0.1% by mass of free lime) was produced. Firing was performed at 1350 ° C. using a rotary kiln. The total amount of sewage sludge and coal ash (total amount of waste, etc.) used in producing 1 ton of the calcined product was 528 kg / ton.

(3)焼成物の粉砕:
上記で得られた各焼成物(A1〜A6、B1)を粉砕して、ブレーン比表面積3200±50cm2/gの粉砕物を調製した。
(3) Grinding of the fired product:
Each fired product (A1 to A6, B1) obtained above was pulverized to prepare a pulverized product having a Blaine specific surface area of 3200 ± 50 cm 2 / g.

(4)焼成物以外の材料:
以下の材料を使用した。
・石膏:ブレーン比表面積4000cm2/gの2水石膏。
・無機粉末A:ブレーン比表面積4500cm2/gの高炉スラグ粉末。
・無機粉末B:ブレーン比表面積2900cm2/gのフライアッシュ。
・セメント:普通ポルトランドセメント(太平洋セメント社製)。
・細骨材:JIS R 5201(セメントの物理試験方法)の標準砂。
・減水剤A:ナフタレンスルホン酸系高性能減水剤(商品名:MT150)。
・減水剤B:ポリカルボン酸系高性能AE減水剤(商品名:SP8N)。
(4) Materials other than the fired product:
The following materials were used.
Gypsum: 2-water gypsum with a Blaine specific surface area of 4000 cm 2 / g.
Inorganic powder A: Blast furnace slag powder having a Blaine specific surface area of 4500 cm 2 / g.
Inorganic powder B: fly ash having a brain surface area of 2900 cm 2 / g.
Cement: Ordinary Portland cement (manufactured by Taiheiyo Cement).
・ Fine aggregate: Standard sand of JIS R 5201 (Cement physical test method).
Water reducing agent A: Naphthalenesulfonic acid-based high-performance water reducing agent (trade name: MT150).
Water reducing agent B: polycarboxylic acid-based high performance AE water reducing agent (trade name: SP8N).

(5)セメント組成物の製造:
普通ポルトランドセメントと、上記各材料を、表4に示す組成で混合し、セメント組成物を製造した。
(5) Production of cement composition:
Ordinary Portland cement and each of the above materials were mixed in the composition shown in Table 4 to produce a cement composition.

Figure 2009084087
Figure 2009084087

(6)評価:
得られたセメント組成物について、水和熱、モルタルフロー及びモルタル圧縮強さを評価した。結果を表5に示す。
(6) Evaluation:
About the obtained cement composition, the heat of hydration, the mortar flow, and the mortar compressive strength were evaluated. The results are shown in Table 5.

(評価方法)
(1)水和熱:
「JIS R 5203」に従って測定した。
(Evaluation methods)
(1) Heat of hydration:
It was measured according to “JIS R 5203”.

(2)モルタルフロー:
W/C=0.35、S/C=2、セメント組成物に対して(A)1.2質量%の減水剤Aを添加したもの、(B)0.65質量%の減水剤Bを混合したもの、を5分間混練したモルタルについて、「JIS R 5201−1997」に規定されているフローコーンを用い、「JIS R 5201」に従って、製造直後及び30分後のモルタルフローを測定した。
(2) Mortar flow:
W / C = 0.35, S / C = 2, (A) 1.2% by mass of water reducing agent A added to the cement composition, (B) 0.65% by mass of water reducing agent B About the mortar which knead | mixed what was mixed for 5 minutes, the mortar flow immediately after manufacture and 30 minutes after was measured according to "JISR5201" using the flow cone prescribed | regulated to "JISR5201-1997".

(3)モルタル圧縮強さ:
3日、7日及び28日後のモルタル圧縮強さを、「JIS R 5201」に従って測定した。
(3) Mortar compressive strength:
The mortar compressive strength after 3, 7 and 28 days was measured according to “JIS R 5201”.

Figure 2009084087
Figure 2009084087

表5の結果より、本発明のセメント添加材を含むセメント組成物では、水和熱が低く、流動性及び強度発現性が良好であった。
これに対し、C12A7及びC4A3・SO3を含まない焼成物A5を粉砕してなるセメント添加剤を含む比較例1〜2のセメント組成物では、水和熱が高く、流動性も低かった。また、カルシウムシリケートやカルシウムアルミネートを含まない焼成物A6を粉砕してなるセメント添加材を含む比較例3のセメント組成物では、強度発現性が低かった。
From the results in Table 5, the cement composition containing the cement additive of the present invention had a low heat of hydration and good fluidity and strength development.
On the other hand, in the cement compositions of Comparative Examples 1 and 2 including the cement additive formed by pulverizing the calcined product A5 not containing C 12 A 7 and C 4 A 3 · SO 3 , the heat of hydration is high, and the fluidity The nature was also low. Moreover, in the cement composition of Comparative Example 3 including the cement additive formed by pulverizing the fired product A6 not containing calcium silicate or calcium aluminate, strength development was low.

Claims (7)

水硬率(H.M.)が1.65〜1.75、Al2O3量が8.0質量%以下、Fe2O3量が2.2〜5.0質量%で、かつ、2CaO・SiO2及び4CaO・Al2O3・Fe2O3を必須成分とし、さらに、12CaO・7Al2O3及び/又は4CaO・3Al2O3・SO3を含有する焼成物Aの粉砕物を含むセメント添加材。 The hydraulic modulus (HM) is 1.65 to 1.75, the amount of Al 2 O 3 is 8.0% by mass or less, the amount of Fe 2 O 3 is 2.2 to 5.0% by mass, and 2CaO · SiO 2 and 2 and 4CaO · Al 2 O 3 · Fe 2 O 3 as essential components, further cements containing pulverized calcined product a containing 12CaO · 7Al 2 O 3 and / or 4CaO · 3Al 2 O 3 · SO 3 Additives. 焼成物Aが、更に、2CaO・Al2O3・SiO2及び/又は3CaO・SiO2を含有するものである請求項1記載のセメント添加材。 The cement additive according to claim 1, wherein the fired product A further contains 2CaO · Al 2 O 3 · SiO 2 and / or 3CaO · SiO 2 . 焼成物Aの粉砕物100質量部に対して、石膏をSO3換算で6質量部以下含有する請求項1又は2記載のセメント添加材。 The cement additive according to claim 1 or 2, comprising 6 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 A. 更に、2CaO・SiO2及び2CaO・Al2O3・SiO2を必須成分とし、2CaO・SiO2100質量部に対して、2CaO・Al2O3・SiO2+4CaO・Al2O3・Fe2O3を10〜100質量部含有し、かつ、3CaO・Al2O3の含有量が20質量部以下である焼成物Bの粉砕物を含有する請求項1〜3のいずれか1項記載のセメント添加材。 Furthermore, the 2CaO · SiO 2 and 2CaO · Al 2 O 3 · SiO 2 as essential components, with respect to 2CaO · SiO 2 100 parts by mass, 2CaO · Al 2 O 3 · SiO 2 + 4CaO · Al 2 O 3 · Fe 2 The pulverized product of the fired product B containing 10 to 100 parts by mass of O 3 and having a content of 3CaO · Al 2 O 3 of 20 parts by mass or less. Cement additive. セメントに対して、請求項1〜4のいずれか1項記載のセメント添加材を、内割で50質量%以下含有するセメント組成物。   The cement composition which contains 50 mass% or less of the cement additive of any one of Claims 1-4 with respect to cement by an internal split. 石膏を、SO3換算で1〜5質量%含有する請求項5記載のセメント組成物。 The cement composition according to claim 5, which contains 1 to 5% by mass of gypsum in terms of SO 3 . 更に、高炉スラグ粉末、フライアッシュ、石灰石粉末、珪石粉末及びシリカフュームから選ばれる1種以上の無機粉末を含有する請求項5又は6記載のセメント組成物。   The cement composition according to claim 5 or 6, further comprising at least one inorganic powder selected from blast furnace slag powder, fly ash, limestone powder, silica stone powder and silica fume.
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JP2004002155A (en) * 2002-03-22 2004-01-08 Taiheiyo Cement Corp Cement admixture
JP2007055843A (en) * 2005-08-24 2007-03-08 Taiheiyo Cement Corp Cement additive
JP2008222464A (en) * 2007-03-09 2008-09-25 Taiheiyo Cement Corp Fired product, cement additive and cement composition

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JP2004002155A (en) * 2002-03-22 2004-01-08 Taiheiyo Cement Corp Cement admixture
JP2007055843A (en) * 2005-08-24 2007-03-08 Taiheiyo Cement Corp Cement additive
JP2008222464A (en) * 2007-03-09 2008-09-25 Taiheiyo Cement Corp Fired product, cement additive and cement composition

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* Cited by examiner, † Cited by third party
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JP2009143755A (en) * 2007-12-13 2009-07-02 Taiheiyo Cement Corp Cement admixture and cement composition

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