JP2007331976A - Cement admixture and cement composition - Google Patents

Cement admixture and cement composition Download PDF

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JP2007331976A
JP2007331976A JP2006165481A JP2006165481A JP2007331976A JP 2007331976 A JP2007331976 A JP 2007331976A JP 2006165481 A JP2006165481 A JP 2006165481A JP 2006165481 A JP2006165481 A JP 2006165481A JP 2007331976 A JP2007331976 A JP 2007331976A
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cement
raw material
waste
cement additive
firing
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JP4908072B2 (en
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Kenichi Honma
健一 本間
Masahiko Moriya
政彦 守屋
Shunichiro Uchida
俊一郎 内田
Masataka Uchida
雅隆 内田
Makihiko Ichikawa
牧彦 市川
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Taiheiyo Cement Corp
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • C04B2103/0079—Rheology influencing agents
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • C04B2103/0089—Agents for reducing heat of hydration
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1075—Chromium-free or very low chromium-content materials
    • C04B2111/1081—Chromium VI, e.g. for avoiding chromium eczema
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Sludge (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cement admixture lowering heat of hydration of a cement composition, improving the flowability and reducing elution of 6-valent chromium from a cement hardened body. <P>SOLUTION: The cement admixture is obtained by firing a CaO raw material, an SiO<SB>2</SB>raw material, an Al<SB>2</SB>O<SB>3</SB>raw material and an Fe<SB>2</SB>O<SB>3</SB>raw material under a reducing atmosphere or under the coexisting of a combustible substance and pulverizing the resultant fired material and has hydraulic modulus (H.M) of 0.8-1.5. The cement admixture is obtained by firing the CaO raw material, the SiO<SB>2</SB>raw material, the Al<SB>2</SB>O<SB>3</SB>raw material and the Fe<SB>2</SB>O<SB>3</SB>raw material and after that, cooling under the reducing atmosphere or under coexisting of a combustible substance to obtain a fired material and pulverizing the resultant fired material and has hydraulic modulus (H.M) of 0.8-1.5. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、セメントの水和熱を低下させ、かつ流動性を向上させることができ、さらにセメント硬化体からの６価クロムの溶出を低減することができるセメント添加材に関する。   The present invention relates to a cement additive that can reduce heat of hydration of cement and improve fluidity, and can further reduce elution of hexavalent chromium from a hardened cement.

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。この課題に対処するため、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、セメントクリンカーを製造することが提案されている（例えば、特許文献１）。   In Japan, industrial waste, general waste, etc. are increasing rapidly 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 order to cope with this problem, in the cement industry, it has been proposed to manufacture a cement clinker using industrial waste, general waste, or the like as a raw material (for example, Patent Document 1).

しかしながら、産業廃棄物や一般廃棄物等をセメント原料として大量に使用すると、セメント中の3CaO・Al2O3量が増加し、その結果、セメントの水和熱が上昇するという問題がある。また、そのようなセメントと混和剤を用いてモルタルやコンクリートを製造する場合には、モルタルフローやスランプが小さくなり、フローロスやスランプロスが大きくなるという欠点もある。
また、産業廃棄物や一般廃棄物等には、微量のクロムが含まれているものがあり、これらを原料としてセメントクリンカーを製造すると、得られるセメントクリンカー中に６価クロムが含まれることになる。このようなセメントクリンカーを粉砕してセメントとして使用した場合、６価クロムが、水質汚染や土壌汚染等を引き起こす可能性がある。
特開２００５−２５５４５６号公報 However, when industrial waste, general waste, or the like is used in large quantities as a raw material for cement, there is a problem that the amount of 3CaO · Al 2 O 3 in the cement increases, and as a result, the heat of hydration of the cement increases. In addition, when mortar or concrete is produced using such a cement and an admixture, there is a disadvantage that mortar flow and slump are reduced and flow loss and slump loss are increased.
In addition, some industrial wastes and general wastes contain a small amount of chromium. When cement clinker is produced using these as raw materials, hexavalent chromium is contained in the obtained cement clinker. . When such a cement clinker is crushed and used as cement, hexavalent chromium may cause water pollution, soil pollution, and the like.
JP 2005-255456 A

従って、本発明の目的は、セメント組成物の水和熱を低下させ、かつ流動性を向上させることができ、さらにセメント硬化体からの６価クロムの溶出を低減することができる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 provide a cement additive that can reduce the heat of hydration of a cement composition, improve fluidity, and reduce elution of hexavalent chromium from a hardened cement. It is to provide.

本発明者らは、斯かる実情に鑑み、種々検討した結果、水硬率（H.M.）を特定し、還元雰囲気又は可燃性物質共存下で焼成又は冷却した焼成物を粉砕したセメント添加材であれば、セメント組成物の水和熱を低下させ、かつ流動性を向上させることができるうえ、セメント硬化体からの６価クロムの溶出を低減することができることを見出し、本発明を完成した。   As a result of various studies in view of such circumstances, the present inventors have specified a hydraulic modulus (HM) and can be a cement additive obtained by pulverizing a fired product that has been fired or cooled in a reducing atmosphere or in the presence of a combustible substance. For example, the present inventors have found that the heat of hydration of the cement composition can be reduced and the fluidity can be improved, and the elution of hexavalent chromium from the hardened cement can be reduced.

すなわち、本発明は、CaO原料、SiO2原料、Al2O3原料及びFe2O3原料を還元雰囲気又は可燃性物質共存下で焼成して得られる焼成物を粉砕してなるセメント添加材であって、水硬率（H.M.）が0.8〜1.5であることを特徴とするセメント添加材を提供するものである。
また、本発明は、CaO原料、SiO2原料、Al2O3原料及びFe2O3原料を焼成後、還元雰囲気又は可燃性物質共存下で冷却して得られる焼成物を粉砕してなるセメント添加材であって、水硬率（H.M.）が0.8〜1.5であることを特徴とするセメント添加材を提供するものである。
また、本発明は、セメントと、上記セメント添加材とを含有してなるセメント組成物を提供するものである。 That is, the present invention is a cement additive obtained by pulverizing a calcined product obtained by calcining a CaO raw material, a SiO 2 raw material, an Al 2 O 3 raw material and a Fe 2 O 3 raw material in a reducing atmosphere or in the presence of a combustible substance. The present invention provides a cement additive having a hydraulic modulus (HM) of 0.8 to 1.5.
The present invention also relates to a cement obtained by firing a CaO raw material, SiO 2 raw material, Al 2 O 3 raw material, and Fe 2 O 3 raw material, and then pulverizing a fired product obtained by cooling in a reducing atmosphere or in the presence of a combustible substance. The present invention provides an additive having a hydraulic modulus (HM) of 0.8 to 1.5.
The present invention also provides a cement composition comprising cement and the cement additive.

本発明のセメント添加材を用いれば、水和熱が低く、かつ流動性が良好なセメント組成物を得ることができる。また、セメント硬化体からの６価クロムの溶出量を低減することができる。
また、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も貢献することができる。 If the cement additive of the present invention is used, a cement composition having a low heat of hydration and good fluidity can be obtained. Moreover, the elution amount of hexavalent chromium from a hardened cement body can be reduced.
Moreover, since the cement additive of this invention can use industrial waste, general waste, etc. as a raw material, it can also contribute to promotion of effective utilization of waste.

本発明のセメント添加材の原料としては、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。
また、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。
なお、上記原料のうち、粘土、鉄滓、産業廃棄物、一般廃棄物、建設発生土にはクロムが含まれるものがある。 As a raw material of the cement additive of the present invention, a general Portland cement clinker raw material, for example, a CaO raw material such as limestone, quicklime or slaked lime; a SiO 2 raw material such as silica or clay; an Al 2 O 3 raw material such as clay; Fe 2 O 3 raw materials such as iron cake can be used.
Moreover, it can manufacture by making 1 or more types chosen from an industrial waste, a general waste, and construction generation | occurrence | production soil as a raw material, and baking this. Industrial waste includes, for example, raw conslag; various sludges such as sewage sludge, purified water sludge, construction sludge, and iron sludge; construction waste, concrete waste, boring waste, various incineration ash, foundry sand, rock wool, waste glass, blast furnace 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.
Among the above raw materials, clay, iron slag, industrial waste, general waste, and construction generated soil include some containing chromium.

これらの原料を、水硬率（H.M.）が好ましくは0.8〜1.5、より好ましくは0.9〜1.45、特に好ましくは1.0〜1.4になるよう混合した後、還元雰囲気又は可燃性物質共存下で焼成するか、還元雰囲気又は可燃性物質共存下で冷却することにより、焼成物を製造する。
水硬率（H.M.）が0.8未満では、セメント組成物の強度発現性が低下するので好ましくない。また、セメント硬化体からの６価クロムの溶出量を低減する効果も低下する。一方、水硬率（H.M.）が1.5を超えると、セメント組成物の水和熱を低くすることが困難となる。
焼成温度が低い、あるいは、焼成時間が短いと、CaOがSiO2やAl2O3等と反応せず、焼成物中に遊離石灰として多量に残存する場合がある。遊離石灰が多い焼成物の粉砕物を普通ポルトランドセメントに混合し、コンクリート構造物に使用すると、遊離石灰が膨張してコンクリート構造物を破壊したり、減水剤等の混和剤の作用を阻害して流動性を悪化させる場合がある。そのため、焼成物中の遊離石灰量が1.0質量％以下になるように焼成温度、焼成時間を調整する必要がある。遊離石灰量を1.0質量％以下にするための焼成温度、焼成時間は、焼成物の組成や粒度にもよるが、それぞれ1000〜1400℃、10〜120分間である。 Whether these raw materials are mixed so that the hydraulic modulus (HM) is preferably 0.8 to 1.5, more preferably 0.9 to 1.45, and particularly preferably 1.0 to 1.4, and then fired in a reducing atmosphere or in the presence of a combustible substance. A fired product is produced by cooling in a reducing atmosphere or in the presence of a combustible substance.
A hydraulic modulus (HM) of less than 0.8 is not preferable because the strength development of the cement composition decreases. Moreover, the effect of reducing the elution amount of hexavalent chromium from the hardened cement body is also reduced. On the other hand, when the hydraulic modulus (HM) exceeds 1.5, it becomes difficult to lower the heat of hydration of the cement composition.
When the firing temperature is low or the firing time is short, CaO does not react with SiO 2 , Al 2 O 3 or the like, and a large amount of free lime may remain in the fired product. When pulverized products containing a large amount of free lime are mixed with ordinary Portland cement and used in concrete structures, the free lime expands, destroys the concrete structure, and inhibits the action of admixtures such as water reducing agents. The liquidity may be deteriorated. Therefore, it is necessary to adjust the firing temperature and the firing time so that the amount of free lime in the fired product is 1.0% by mass or less. The firing temperature and firing time for making the amount of free lime 1.0% by mass or less are 1000 to 1400 ° C. and 10 to 120 minutes, respectively, depending on the composition and particle size of the fired product.

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、焼成に使用する装置も特に制限されず、例えばロータリーキルンや電気炉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 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 an electric furnace 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.

本発明において、還元雰囲気下で焼成する方法としては、例えば、焼成に使用する装置（電気炉等）内を一酸化炭素ガス等で置換した後、焼成する方法等が挙げられる。   In the present invention, examples of the method of firing in a reducing atmosphere include a method of firing after replacing the inside of an apparatus (such as an electric furnace) used for firing with carbon monoxide gas or the like.

可燃性物質共存下で焼成する方法としては、例えば、焼成に使用する装置（ロータリーキルンや電気炉等）内に、可燃性物質（コークス、活性炭、廃木材、廃ブラスチック、重油スラッジ、都市ゴミ等の廃棄物を圧縮・固形化した廃棄物固形塊等）を供給する方法等が挙げられる。焼成に使用する装置としてロータリーキルンを使用する場合、可燃性物質は、プレヒーター側、ロータリーキルンの出口側や、ロータリーキルンの途中から供給することができるが、本発明では、ロータリーキルン内で最も高温になる位置よりロータリーキルンの出口までの途中で可燃性物質を供給することが好ましい。
この場合に用いる可燃性物質はロータリーキルン用の主燃料に比べて燃焼速度の遅いもの、あるいは主燃料と同様の燃焼速度を有しかつ主燃料よりも粗い粒の可燃性物質が使用される。
可燃性物質は、焼成物1ton当たり、5〜40kg使用することが好ましく、10〜40kg使用することがより好ましく、12〜40kg使用することが特に好ましい。可燃性物質の量が5kg未満では、セメント硬化体からの６価クロムの溶出量を低減する効果が低下する。一方、可燃性物質の量が40kgを超えると、焼成物中に未燃焼状態の可燃性物質が多量に残存して、セメント添加材の色調等に影響を及ぼす場合がある。
可燃性物質は、粒径が0.1〜5mmのものを使用するのが好ましい。可燃性物質の粒径が小さいと、焼成中の極初期で燃えきってしまうためセメント質硬化体からの６価クロムの溶出量を低減する効果が低下する。一方、粒径が大きいと焼成物中に未燃焼状態の可燃性物質が多量に残存する。
なお、可燃性物質は、原料に混合して用いても良い。この場合、可燃性物質は未燃焼状態で残存しない範囲であれば混合量は多い方が好ましく、粒径も大きいものを使用することができる。 As a method of firing in the presence of combustible substances, for example, in a device used for firing (rotary kiln, electric furnace, etc.), combustible substances (coke, activated carbon, waste wood, waste plastic, heavy oil sludge, municipal waste, etc.) For example, a waste solid lump obtained by compressing and solidifying the waste). When a rotary kiln is used as an apparatus used for firing, the combustible material can be supplied from the preheater side, the rotary kiln outlet side, or in the middle of the rotary kiln. It is preferable to supply a combustible substance on the way to the exit of the rotary kiln.
The combustible material used in this case has a combustion speed slower than that of the main fuel for the rotary kiln, or a combustible material having a combustion speed similar to that of the main fuel and coarser than the main fuel.
The combustible substance is preferably used in an amount of 5 to 40 kg, more preferably 10 to 40 kg, and particularly preferably 12 to 40 kg per ton of the fired product. If the amount of combustible material is less than 5 kg, the effect of reducing the elution amount of hexavalent chromium from the hardened cement body is reduced. On the other hand, if the amount of combustible material exceeds 40 kg, a large amount of unburned combustible material may remain in the fired product, which may affect the color tone of the cement additive.
It is preferable to use a combustible substance having a particle size of 0.1 to 5 mm. If the particle size of the combustible substance is small, the effect of reducing the elution amount of hexavalent chromium from the cementitious hardened body is reduced because it burns out at the very initial stage during firing. On the other hand, if the particle size is large, a large amount of unburned combustible material remains in the fired product.
The combustible substance may be used by mixing with the raw material. In this case, as long as the combustible substance is in an unburned state and does not remain, it is preferable that the mixing amount is large, and a substance having a large particle size can be used.

可燃性物質共存下で冷却する方法としては、例えば、焼成装置に接続されている冷却器（例えば、セメントクリンカー製造プラントにおけるクリンカークーラー等）内に、可燃性物質（コークス、活性炭、廃木材、廃ブラスチック、重油スラッジ、都市ゴミ等の廃棄物を圧縮・固形化した廃棄物固形塊等）を供給する方法等が挙げられる。この場合、可燃性物質は、クリンカークーラー入り口等焼成物の温度が1000℃以上の位置に供給することが好ましい。温度が低い場合は、セメント質硬化体からの６価クロムの溶出量を低減する効果が低下し、焼成物中に未燃焼状態の可燃性物質が多量に残存する。
なお、可燃性物質は冷却の初期の段階で効果を発揮すればよいので、粒径が小さい可燃性物質を使用することができる。 As a method of cooling in the presence of combustible substances, for example, in a cooler connected to a calciner (for example, a clinker cooler in a cement clinker manufacturing plant), combustible substances (coke, activated carbon, waste wood, waste) And a method of supplying waste solid lump obtained by compressing and solidifying waste such as plastic, heavy oil sludge, and municipal waste. In this case, the combustible material is preferably supplied to a position where the temperature of the fired product such as the entrance of the clinker cooler is 1000 ° C. or higher. When the temperature is low, the effect of reducing the elution amount of hexavalent chromium from the cementitious hardened body is reduced, and a large amount of unburned combustible material remains in the fired product.
In addition, since a combustible substance should just exhibit an effect in the initial stage of cooling, a combustible substance with a small particle size can be used.

本発明のセメント添加材は、1)上記焼成物を粉砕してなるセメント添加材、2)前記粉砕物100質量部に石膏をSO3換算で6質量部以下含有するセメント添加材、である。 The cement additive of the present invention is 1) a cement additive obtained by pulverizing the fired product, and 2) a cement additive containing gypsum in an amount of 6 parts by mass or less in terms of SO 3 in 100 parts by mass of the pulverized product.

焼成物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 pulverization method of the fired product 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 preferably has a Blaine specific surface area of 2500 to 5000 cm 2 / g from the viewpoints of reducing bleeding of mortar and concrete, fluidity, and strength development.

焼成物の粉砕物と石膏を含有する上記2)のセメント添加材は、焼成物の粉砕物と石膏を混合して製造してもよいし、焼成物と石膏を同時粉砕して製造してもよい。前者の場合、用いる石膏は、ブレーン比表面積が3000〜8000cm2/gであるのが、モルタルやコンクリートの流動性や、強度発現性の観点から好ましい。後者の場合は、セメント添加材の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。
なお、石膏としては、二水石膏、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。 The cement additive of the above 2) containing the pulverized product and gypsum of the fired product may be produced by mixing the pulverized product of the calcined product and gypsum, or may be produced by simultaneously grinding the fired product and gypsum. Good. In the former case, it is preferable that the gypsum used has a Blaine specific surface area of 3000 to 8000 cm 2 / g from the viewpoint of fluidity and strength development of mortar and concrete. In the latter case, the cement additive has a brane specific surface area of 2500 to 5000 cm 2 / g, which is preferable from the viewpoints of reducing bleeding of mortar and concrete, fluidity, and strength development.
Examples of gypsum include dihydrate gypsum, hemihydrate gypsum, anhydrous gypsum, and the like, and these can be used alone or in combination.

本発明のセメント添加材の使用量は、特に限定されるものではないが、通常、セメントとセメント添加材からなるセメント組成物100質量部中、1〜30質量部が好ましく、5〜20質量部がより好ましい。1質量部未満では、水和熱を低くする効果やセメント硬化体からの６価クロムの溶出量を低減する効果が低下する場合があり、30質量部を超えると、強度発現性が低下する場合がある。   The amount of the cement additive of the present invention is not particularly limited, but is usually 1 to 30 parts by mass, preferably 5 to 20 parts by mass in 100 parts by mass of the cement composition composed of cement and cement additive. Is more preferable. If the amount is less than 1 part by mass, the effect of lowering the heat of hydration and the effect of reducing the elution amount of hexavalent chromium from the hardened cement may be reduced. If the amount exceeds 30 parts by weight, the strength development will be reduced. There is.

本発明のセメント組成物とは、JIS R 5210に規定される各種ポルトランドセメント、JIS R 5211、JIS R 5212、あるいはJIS R 5213に規定される各種混合セメント、JISに規定された以上の混和材混合率にて製造した高炉セメント、フライアッシュセメント及びシリカセメント、石灰石粉末等を混合したフィラーセメント並びにアルミナセメント等のうちの１種又は２種以上と本発明のセメント添加材とを併用したものである。   The cement composition of the present invention includes various portland cements specified in JIS R 5210, various mixed cements specified in JIS R 5211, JIS R 5212, or JIS R 5213, and admixtures more than those specified in JIS. The cement additive of the present invention is used in combination with one or more of blast furnace cement, fly ash cement and silica cement, filler cement mixed with limestone powder, alumina cement, etc. .

本発明では、本発明のセメント添加材及びセメント組成物に、砂、砂利等の骨材の他に、減水剤、ＡＥ減水剤、高性能減水剤、高性能ＡＥ減水剤、消泡剤、増粘剤、防錆剤、防凍剤、膨張材、収縮低減剤、高分子エマルジョン、凝結調整剤、セメント急硬材、ベントナイトやゼオライト等の粘土鉱物、ハイドロタルサイト等のイオン交換体等のうちの１種又は２種以上を、本発明の目的を実質的に阻害しない範囲で使用することが可能である。   In the present invention, in addition to aggregates such as sand and gravel, the cement additive and cement composition of the present invention include a water reducing agent, AE water reducing agent, high performance water reducing agent, high performance AE water reducing agent, antifoaming agent, Of sticky agent, rust preventive agent, antifreeze agent, expansion agent, shrinkage reducing agent, polymer emulsion, setting modifier, cement hardener, clay mineral such as bentonite and zeolite, ion exchanger such as hydrotalcite, etc. It is possible to use 1 type (s) or 2 or more types in the range which does not substantially inhibit the objective of this invention.

本発明において、各材料の混合方法は特に限定されるものではなく、それぞれの材料を施工時に混合しても良いし、あらかじめ一部を、あるいは全部を混合しておいても差し支えない。混合装置としては、既存のいかなる装置も使用可能であり、例えば、傾胴ミキサ、オムニミキサ、ヘンシェルミキサ、パン型ミキサ、二軸ミキサ、Ｖ型ミキサ及びナウタミキサ等の使用が可能である。   In the present invention, the mixing method of each material is not particularly limited, and each material may be mixed at the time of construction, or a part or all of them may be mixed in advance. Any existing apparatus can be used as the mixing apparatus, and for example, a tilting mixer, an omni mixer, a Henschel mixer, a pan mixer, a biaxial mixer, a V mixer, and a Nauta mixer can be used.

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）焼成物の製造：
原料として、下水汚泥、建設発生土、石灰石等のポルトランドセメントクリンカー原料を用い、水硬率（H.M.）が1.35及び1.0となるよう、原料を調合した。調合原料を、ロータリーキルンを用いて、1)ロータリーキルン内で最も高温になる位置よりロータリーキルンの出口までの途中で可燃性物質（コークス(粒径0.1〜5mm)）を焼成物1ton当たり15kg供給しながら焼成、2)可燃性物質を供給しないで焼成して、焼成物を製造した。焼成温度は1350℃で焼成時間は30分間である。
なお、焼成物中の遊離石灰量は0.1〜0.2質量％であった。 Example 1
(1) Production of fired product:
Portland cement clinker raw materials such as sewage sludge, construction generated soil, and limestone were used as raw materials, and the raw materials were prepared so that the hydraulic modulus (HM) was 1.35 and 1.0. Using a rotary kiln, the blended raw material is fired while supplying 15 kg of combustible material (coke (particle size: 0.1 to 5 mm)) per 1 ton of fired product on the way from the highest temperature position in the rotary kiln to the exit of the rotary kiln. 2) Firing was carried out without supplying a combustible substance to produce a fired product. The firing temperature is 1350 ° C. and the firing time is 30 minutes.
The amount of free lime in the fired product was 0.1 to 0.2% by mass.

（２）セメント添加材の製造：
上記各焼成物をブレーン比表面積が3300cm2/gに粉砕した。該粉砕物100質量部に２水石膏(ブレーン比表面積3600cm2/g)をSO3換算で2質量部含有させたセメント添加材を製造した。 (2) Manufacture of cement additives:
Each fired product was pulverized to a Blaine specific surface area of 3300 cm 2 / g. A cement additive containing 2 parts by mass of 2-hydrate gypsum (Brain specific surface area of 3600 cm 2 / g) in terms of SO 3 in 100 parts by mass of the pulverized product was produced.

（３）セメント組成物の製造：
上記セメント添加材を、試製普通ポルトランドセメント(６価クロム含有量を高めたもの)と混合してセメント組成物を製造した。表１に、試製普通ポルトランドセメントの鉱物組成とセメント協会法1-51に記載された方法で測定した６価クロム含有量を示す。 (3) Production of cement composition:
The above cement additive was mixed with trial ordinary Portland cement (with increased hexavalent chromium content) to produce a cement composition. Table 1 shows the mineral composition of trial-made ordinary Portland cement and the hexavalent chromium content measured by the method described in Cement Association Method 1-51.

Figure 2007331976
Figure 2007331976

（４）試験：
上記セメント組成物を使用して、以下の試験を行った。
(a)水和熱
JIS R 5203に従って測定した。
(b)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0.8質量％のポリカルボン酸系高性能ＡＥ減水剤を混合したものを、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、モルタルフローを測定した。
(c)モルタル圧縮強さ
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。
(d)６価クロム溶出量
上記モルタル圧縮強さ試験用供施体(材齢28日)の６価クロム溶出量を環境庁告示第46号に従って測定した
その結果を表２に示す。 (4) Test:
The following tests were conducted using the cement composition.
(a) Heat of hydration
Measured according to JIS R 5203.
(b) Mortar flow W / C = 0.35, S / C = 2, mortar obtained by mixing 0.8% by mass of polycarboxylic acid-based high-performance AE water reducing agent with respect to cement composition for 5 minutes. Mortar flow was measured according to JIS R 5201 using a flow cone defined in R 5201-1997.
(c) Mortar compressive strength The mortar compressive strength after 7 and 28 days was measured according to JIS R 5201.
(d) Hexavalent chromium elution amount The hexavalent chromium elution amount of the mortar compressive strength test specimen (age 28 days) was measured in accordance with Environmental Agency Notification No. 46. The results are shown in Table 2.

Figure 2007331976
Figure 2007331976

表２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、かつ流動性が良好であることがわかる。また、セメント硬化体からの６価クロムの溶出量を低減できることがわかる。   From Table 2, it can be seen that the cement composition containing the cement additive of the present invention has a low heat of hydration and good fluidity. Moreover, it turns out that the elution amount of hexavalent chromium from a cement hardening body can be reduced.

Claims (5)

CaO原料、SiO2原料、Al2O3原料及びFe2O3原料を還元雰囲気又は可燃性物質共存下で焼成して得られる焼成物を粉砕してなるセメント添加材であって、水硬率（H.M.）が0.8〜1.5であることを特徴とするセメント添加材。 A cement additive obtained by pulverizing a calcined product obtained by calcining a CaO raw material, SiO 2 raw material, Al 2 O 3 raw material and Fe 2 O 3 raw material in a reducing atmosphere or in the presence of a combustible substance, and having a hydraulic modulus Cement additive characterized by having (HM) of 0.8 to 1.5. CaO原料、SiO2原料、Al2O3原料及びFe2O3原料を焼成後、還元雰囲気又は可燃性物質共存下で冷却して得られる焼成物を粉砕してなるセメント添加材であって、水硬率（H.M.）が0.8〜1.5であることを特徴とするセメント添加材。 A cement additive formed by pulverizing a calcined product obtained by calcining a CaO raw material, a SiO 2 raw material, an Al 2 O 3 raw material and a Fe 2 O 3 raw material and then cooling in a reducing atmosphere or in the presence of a combustible substance, A cement additive having a hydraulic modulus (HM) of 0.8 to 1.5. 産業廃棄物、一般廃棄物及び建設発生土から選ばれる１種以上を原料とする請求項１又は２に記載のセメント添加材。   The cement additive according to claim 1 or 2, wherein at least one selected from industrial waste, general waste, and construction generated soil is used as a raw material. 請求項１〜３のいずれか１項記載のセメント添加材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セメント添加材。 A cement additive containing 6 parts by mass or less of gypsum in terms of SO 3 with respect to 100 parts by mass of the cement additive according to any one of claims 1 to 3. セメントと、請求項１〜４のいずれか１項記載のセメント添加材とを含有してなるセメント組成物。   A cement composition comprising cement and the cement additive according to any one of claims 1 to 4.
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