JP4201677B2 - Fired product - Google Patents
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- JP4201677B2 JP4201677B2 JP2003346927A JP2003346927A JP4201677B2 JP 4201677 B2 JP4201677 B2 JP 4201677B2 JP 2003346927 A JP2003346927 A JP 2003346927A JP 2003346927 A JP2003346927 A JP 2003346927A JP 4201677 B2 JP4201677 B2 JP 4201677B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- 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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- Processing Of Solid Wastes (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
本発明は、コンクリート用骨材等として好適に使用できる焼成物に関し、特に、コンクリート用骨材として使用したときに、強度発現性や耐久性に優れたコンクリートを製造することができる焼成物に関する。 The present invention relates to a fired product that can be suitably used as an aggregate for concrete and the like, and more particularly to a fired product that can produce concrete having excellent strength and durability when used as an aggregate for concrete.
従来、コンクリート用骨材としては、天然産の石材や砂が使用されているが、これらは年々その産出量が逼迫し、良質のものが得られ難くなっており、天然資源や環境保護の面からも対策が求められている。天然産の石材や砂に代わるコンクリート用骨材として、例えば通常のセメントクリンカーを用いることが提案されている（特許文献１）。 Conventionally, natural stone and sand have been used as aggregates for concrete, but their production is getting tighter every year, making it difficult to obtain high quality products. Measures are also required. It has been proposed to use, for example, a normal cement clinker as a concrete aggregate to replace natural stone and sand (Patent Document 1).
特許文献１に記載されているコンクリートでは、コンクリートそのもののリサイクルは可能であるが、骨材として使用されている通常のセメントクリンカーは、石灰石等の天然資源を原料とするものであり、天然資源の保護の観点からは、未だ問題がある。 In the concrete described in Patent Document 1, it is possible to recycle the concrete itself, but ordinary cement clinker used as an aggregate is made from natural resources such as limestone. From a protection perspective, there are still problems.
また、近年、コンクリートの使用環境の多様化により、特にコンクリートの高耐久性が求められている。コンクリートの耐久性を低下させる原因のひとつに中性化が知られている。コンクリートの中性化により、鉄筋構造物に用いられている鉄筋に錆が生じ、そのときの膨張圧で、鉄筋とコンクリートとの付着が損なわれ、コンクリート片が剥落する等の問題が生じる。
しかして、通常のセメントクリンカーを骨材として使用したコンクリートでは、天然産の石材や砂を使用したコンクリートに比べ、強度発現性は向上するものの、耐中性化等の耐久性はほぼ同等であり、より高い耐久性が求められている。
However, in concrete using ordinary cement clinker as aggregate, strength development is improved compared to concrete using natural stone or sand, but durability such as neutralization resistance is almost the same. Higher durability is required.
従って、本発明の目的は、強度発現性や耐久性に優れ、コンクリート用骨材等として好適に使用できる焼成物を提供することにある。 Accordingly, an object of the present invention is to provide a fired product that is excellent in strength development and durability and can be suitably used as an aggregate for concrete.
かかる実情において、本発明者らは、鋭意研究を行った結果、2CaO・SiO2 及び2CaO・Al2O3・SiO2を特定の割合で含有し、3CaO・Al2O3と4CaO・Al2O3・Fe2O3の合計含有量が２０質量部以下焼成物が、コンクリート用骨材等として好適に使用でき、これを用いれば、強度発現性や耐久性に優れたコンクリートを製造することができることを見出し、本発明を完成した。 In such circumstances, the present inventors have found, after intense study, containing 2CaO · SiO 2 and 2CaO · Al 2 O 3 · SiO 2 in a specific ratio, 3CaO · Al 2 O 3 and 4CaO · Al 2 A calcined product with a total content of O 3 · Fe 2 O 3 of 20 parts by mass or less can be suitably used as an aggregate for concrete and the like, and if this is used, a concrete with excellent strength and durability can be produced. The present invention has been completed.
すなわち、本発明は、2CaO・SiO 2 、2CaO・Al 2 O 3 ・SiO 2 、3CaO・Al 2 O 3 及び4CaO・Al 2 O 3 ・Fe 2 O 3 からなる鉱物組成で、フリーライム量が１．０質量％以下である焼成物であって、2CaO・SiO2 １００質量部に対して、2CaO・Al2O3・SiO2を１００質量部を超え２０００質量部以下含有し、かつ、3CaO・Al2O3と4CaO・Al2O3・Fe2O3の合計含有量が０〜２０質量部であることを特徴とする焼成物を提供するものである。 That is, the present invention is a mineral composition consisting of 2CaO · SiO 2, 2CaO · Al 2 O 3 · SiO 2, 3CaO · Al 2 O 3 and 4CaO · Al 2 O 3 · Fe 2 O 3, the amount of free lime 1 .0 a calcined product or less by mass%, with respect to 2CaO · SiO 2 to 100 parts by mass, the 2CaO · Al 2 O 3 · SiO 2 contained less 2000 parts by mass exceeds 100 parts by weight, and, 3CaO · the total content of Al 2 O 3 and 4CaO · Al 2 O 3 · Fe 2 O 3 is intended to provide a baked product which is characterized in that 0 to 20 parts by weight.
本発明の焼成物は、コンクリート用骨材等として好適に使用でき、特に、強度発現性や、耐中性化等の耐久性に優れたコンクリートを製造することができる。
また、本発明の焼成物は、産業廃棄物、一般廃棄物、建設発生土を原料とすることができ、多量の廃棄物の有効利用が図れ、天然資源や環境保護の面からも好ましいものである。
The fired product of the present invention can be suitably used as an aggregate for concrete and the like, and in particular, a concrete excellent in durability such as strength development and neutralization resistance can be produced.
In addition, the fired product of the present invention can be made from industrial waste, general waste, and construction generated soil, so that a large amount of waste can be used effectively, which is preferable from the viewpoint of natural resources and environmental protection. is there.
本発明の焼成物は、2CaO・SiO2（Ｃ2Ｓ）及び 2CaO・Al2O3・SiO2（Ｃ2ＡＳ）を含有し、Ｃ2Ｓ１００質量部に対して、Ｃ2ＡＳを１０〜２０００質量部、好ましくは１００質量部を超え２０００質量部以下、特に好ましくは１５０〜２０００質量部含有するものである。
ここで用いるＣ2Ｓは水硬性を有し、コンクリート中でゆっくり反応してコンクリートを緻密化させ、強度を向上させる効果がある。また、Ｃ2ＡＳは水硬性はないが、炭酸化すると緻密化するため、中性化を抑制する効果がある。
Burned material of the present invention contains 2CaO · SiO 2 (C 2 S ) and 2CaO · Al 2 O 3 · SiO 2 (C 2 AS), relative to C 2 S100 parts by mass, 10 to the C 2 AS It contains 2000 parts by mass, preferably more than 100 parts by mass and 2000 parts by mass or less, particularly preferably 150 to 2000 parts by mass.
C 2 S used here is hydraulic and has an effect of reacting slowly in the concrete to densify the concrete and improving the strength. C 2 AS is not hydraulic, but becomes dense when carbonated, so it has the effect of suppressing neutralization.
Ｃ2ＡＳ含有量が１０質量部未満では、焼成物の吸水率が大きくなり、また、コンクリート用骨材として使用した場合に、耐中性化等の耐久性を十分向上させることができない。さらに、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、焼成物の焼成が困難になる。一方、Ｃ2ＡＳ含有量が２０００質量部を超えると、コンクリート用骨材として使用した場合に、十分な強度を得ることができない。 When the C 2 AS content is less than 10 parts by mass, the water absorption rate of the fired product is increased, and when used as a concrete aggregate, durability such as neutralization resistance cannot be sufficiently improved. Furthermore, even if the firing temperature is raised during firing, the amount of free lime is unlikely to decrease and firing of the fired product becomes difficult. On the other hand, when the C 2 AS content exceeds 2000 parts by mass, sufficient strength cannot be obtained when used as a concrete aggregate.
また、本発明の焼成物は、Ｃ2Ｓ１００質量部に対して、3CaO・Al2O3（Ｃ3Ａ）と4CaO・Al2O3・Fe2O3（Ｃ4ＡＦ）の合計含有量が２０質量部以下、好ましくは１０質量部以下である。２０質量部を超えると、焼成物の吸水率が大きくなり、また、コンクリート用骨材として使用した場合に、膨張破壊する可能性があり、耐久性に劣る。 The firing of the present invention, with respect to C 2 S100 parts by weight total content of 3CaO · Al 2 O 3 (C 3 A) and 4CaO · Al 2 O 3 · Fe 2 O 3 (C 4 AF) Is 20 parts by mass or less, preferably 10 parts by mass or less. When the amount exceeds 20 parts by mass, the water absorption of the fired product increases, and when used as an aggregate for concrete, there is a possibility of expansion failure, resulting in poor durability.
このような組成の焼成物を製造するための原料としては、一般のポルトランドセメントクリンカー原料、すなわち、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。 As a raw material for producing the burned material of such a composition, general Portland cement clinker raw material, i.e., limestone, burnt lime, CaO raw material such as slaked lime, silica, SiO 2 raw clay such, Al 2 O clay such as 3 Raw materials, Fe 2 O 3 raw materials such as iron cake and iron cake can be used.
また、本発明においては、焼成物の原料として、産業廃棄物、一般廃棄物及び建設発生土から選ばれる１種以上を用いることもでき、廃棄物の有効利用を促進させることができ、天然資源や環境保護の面からも好ましい。ここで、産業廃棄物としては、例えば石炭灰；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；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、コンクリート廃材などが挙げられ；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。 In the present invention, as the raw material of the baked product, one or more selected from industrial waste, general waste and construction generated soil can be used, and effective use of waste can be promoted. And from the viewpoint of environmental protection. Here, industrial waste includes, for example, coal ash; raw conslag; various sludges such as sewage sludge, purified water sludge, construction sludge, and iron sludge; Secondary ash, construction waste, concrete waste, and the like; examples of general waste include sewage sludge dry powder, municipal waste incineration ash, and shells. Examples of the soil generated from construction include soil and residual soil generated from construction sites and construction sites, and waste soil.
本発明の焼成物の鉱物組成は、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。
（１）ＣａＯ＞（1.87×SiO2＋1.41×Fe2O3）の場合：
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 baked product of the present invention can be determined from the following expressions from the contents (mass%) of CaO, SiO 2 , Al 2 O 3 , and Fe 2 O 3 in the raw materials used.
(1) In case of CaO> (1.87 × SiO 2 + 1.41 × Fe 2 O 3 ):
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
（２）ＣａＯ≦（1.87×SiO2＋1.41×Fe2O3）かつＣａＯ≧（1.87×SiO2）の場合：
Ｃ2Ｓ＝1.02×CaO＋0.95×SiO2−1.69×Al2O3−1.08×Fe2O3
Ｃ2ＡＳ＝−1.63×CaO＋3.05×SiO2＋2.69×Al2O3＋2.08×Fe2O3
Ｃ3Ａ＝1.61×CaO−3.01×SiO2
(2) When CaO ≦ (1.87 × SiO 2 + 1.41 × Fe 2 O 3 ) and CaO ≧ (1.87 × SiO 2 ):
C 2 S = 1.02 × CaO + 0.95 × SiO 2 −1.69 × Al 2 O 3 −1.08 × Fe 2 O 3
C 2 AS = -1.63 x CaO + 3.05 x SiO 2 + 2.69 x Al 2 O 3 + 2.08 x Fe 2 O 3
C 3 A = 1.61 × CaO−3.01 × SiO 2
（３）ＣａＯ＜（1.87×SiO2）の場合：
Ｃ2Ｓ＝3.84×CaO−4.3×SiO2−1.69×Al2O3−1.08×Fe2O3
Ｃ2ＡＳ＝2.69×Al2O3＋2.08×Fe2O3
Ｃ3Ｓ2＝4.8×SiO2−2.57×CaO
（Ｃ3Ｓ2は、3CaO・2SiO2である）
(3) In the case of CaO <(1.87 × SiO 2 ):
C 2 S = 3.84 × CaO−4.3 × SiO 2 −1.69 × Al 2 O 3 −1.08 × Fe 2 O 3
C 2 AS = 2.69 × Al 2 O 3 + 2.08 × Fe 2 O 3
C 3 S 2 = 4.8 × SiO 2 −2.57 × CaO
(C 3 S 2 is 3CaO · 2SiO 2 )
本発明の焼成物は、前記のような原料を適宜混合し、焼成することにより製造することができる。各原料を混合する方法は特に限定されず、慣用の装置等を用いて行なえばよい。また、焼成する際の焼成温度は、１０００〜１３５０℃が好ましく、特に１１５０〜１３５０℃であるのが好ましい。焼成温度が１０００℃未満では、フリーライム量を低減させることが困難であり、１３５０℃を超えると、原料混合物が溶融してしまうため好ましくない。 The fired product of the present invention can be produced by appropriately mixing and firing the above raw materials. The method for mixing the raw materials is not particularly limited, and may be performed using a conventional apparatus or the like. Moreover, 1000-1350 degreeC is preferable and the baking temperature at the time of baking has especially preferable 1150-1350 degreeC. If the calcination temperature is less than 1000 ° C, it is difficult to reduce the amount of free lime, and if it exceeds 1350 ° C, the raw material mixture will melt, which is not preferable.
焼成に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もできる。 The apparatus used for baking 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 also be used.
なお、焼成物中にフリーライムが多く存在すると、コンクリート用骨材として使用した場合に、膨張破壊する可能性がある。従って、焼成物中のフリーライム量は１．０質量％以下、特に０．５質量％以下であるのが好ましい。 If a large amount of free lime is present in the fired product, there is a possibility of expansion and destruction when used as a concrete aggregate. Therefore, the amount of free lime in the fired product is preferably 1.0% by mass or less, particularly preferably 0.5% by mass or less.
本発明の焼成物は、焼成物自体の強度と安定性、コンクリート用骨材として使用した場合のコンクリートの強度発現性、耐久性等の点から、「ＪＩＳ Ａ １１１０（粗骨材の密度及び吸水率試験方法）」に準じて測定される吸水率が５％以下、特に３．５％以下であるのが好ましい。 The fired product according to the present invention is based on “JIS A 1110 (density of coarse aggregate and water absorption) in terms of strength and stability of the fired product itself, strength development of concrete when used as a concrete aggregate, durability, and the like. The water absorption measured in accordance with the “rate test method)” is preferably 5% or less, particularly preferably 3.5% or less.
本発明の焼成物は、コンクリート用骨材、路盤材、埋め戻し材、セメントクリンカー用原料等として用いることができる。コンクリート用骨材としては、細骨材、粗骨材のいずれにも使用でき、粗骨材として使用する場合には、ふるい分け等により、粒度を５mm以上に調整して用いればよい。 The fired product of the present invention can be used as an aggregate for concrete, a roadbed material, a backfill material, a raw material for cement clinker, and the like. As the aggregate for concrete, it can be used for either fine aggregate or coarse aggregate, and when used as coarse aggregate, the particle size may be adjusted to 5 mm or more by sieving or the like.
次に、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらにより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 still in detail, this invention is not restrict | limited at all by these.
実施例１
（１）焼成物の製造：
石灰石、粘土、下水汚泥、建設発生土の原料を表１に示す組成で調合し、小型ロータリーキルンを用いて、表１に示す温度で焼成し、５〜１３mmにふるい分け、焼成物No.１〜７を得た。この際、燃料として、一般的な重油のほか、廃油や廃プラスチックを使用した。
用いた原料の化学組成は、表２に示すとおりである。
Example 1
(1) Production of fired product:
The raw materials of limestone, clay, sewage sludge and construction generated soil are prepared in the composition shown in Table 1, fired at a temperature shown in Table 1 using a small rotary kiln, sieved to 5 to 13 mm, and fired products Nos. 1 to 7 Got. At this time, in addition to general heavy oil, waste oil and waste plastic were used as fuel.
The chemical composition of the raw materials used is as shown in Table 2.
（２）焼成物の物性評価：
表１の各焼成物について、吸水率及びすりへり減量を評価した。結果を表３に示す。
（ｉ）吸水率：
ＪＩＳ Ａ １１１０（粗骨材の密度及び吸水率試験方法）に準じて測定した。
（ii）すりへり減量：
ＪＩＳ Ａ １１２１（ロサンゼルス試験機による粗骨材のすりへり試験方法）に準じて測定した。
(2) Physical property evaluation of fired product:
About each baked product of Table 1, the water absorption and the wear loss were evaluated. The results are shown in Table 3.
(I) Water absorption rate:
Measured according to JIS A 1110 (Drug and water absorption test method for coarse aggregate).
(Ii) Abrasive weight loss:
The measurement was performed according to JIS A 1121 (Coarse aggregate test method using a Los Angeles testing machine).
（３）コンクリートの調製：
下記材料を用い、表４に示す配合割合で、コンクリートを調製した。
セメント（Ｃ）；普通ポルトランドセメント（太平洋セメント社）
細骨材（Ｓ）；静岡県小笠郡産陸砂
粗骨材（Ｇ）；表１の焼成物No.１〜７
普通ポルトランドセメントクリンカー（普通クリンカー）
硬質砂岩砕石
水（Ｗ）；水道水
ＡＥ減水剤（ＷＲＡ）；リグニンスルホン酸系減水剤（ポゾリスNo.70、エヌエムビー社）
(3) Preparation of concrete:
Concrete was prepared using the following materials at the blending ratio shown in Table 4.
Cement (C): Ordinary Portland cement (Pacific Cement)
Fine aggregate (S); Coarse aggregate (G) from Ogasa-gun, Shizuoka Prefecture;
Ordinary Portland cement clinker (ordinary clinker)
Hard sandstone crushed water (W); tap water AE water reducing agent (WRA); lignin sulfonic acid water reducing agent (Pozoris No. 70, NM)
（４）コンクリートの物性評価：
表４で得られた各コンクリートについて、圧縮強度、中性化及び長さ変化を評価した。結果を表５に示す。
（ｉ）圧縮強度；
ＪＩＳ Ａ １１０８（コンクリートの圧縮強度試験方法）に準じて、材齢２８日、９１日及び１年の圧縮強度を測定した。
(4) Evaluation of physical properties of concrete:
About each concrete obtained in Table 4, compressive strength, neutralization, and length change were evaluated. The results are shown in Table 5.
(I) compressive strength;
In accordance with JIS A 1108 (concrete compressive strength test method), compressive strengths of ages 28 days, 91 days, and 1 year were measured.
（ii）中性化；
材齢２８日まで標準養生し、その後、温度２０℃、相対湿度６０％の室内で２８日間乾燥させた供試体について、ＣＯ2濃度５％、温度２０℃、相対湿度６０％の条件下で、促進中性化試験を行なった。フェノールフタレインの１％エタノール溶液を噴霧し、未着色部分の厚さから、中性化深さを求めた。
(Ii) neutralization;
For specimens that were standardly cured until the age of 28 days and then dried for 28 days in a room with a temperature of 20 ° C. and a relative humidity of 60%, under conditions of a CO 2 concentration of 5%, a temperature of 20 ° C., and a relative humidity of 60%, An accelerated neutralization test was conducted. A 1% ethanol solution of phenolphthalein was sprayed, and the neutralization depth was determined from the thickness of the uncolored portion.
（iii）長さ変化；
水中養生３ヶ月後のコンクリートの長さ変化を、ＪＩＳ Ａ １１２９−３に準じて測定した。
(Iii) length change;
The change in length of the concrete after 3 months of underwater curing was measured according to JIS A 1129-3.
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