JP2019052073A - Cement additive and cement composition - Google Patents
Cement additive and cement composition Download PDFInfo
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- 239000004568 cement Substances 0.000 title claims abstract description 118
- 239000000654 additive Substances 0.000 title claims abstract description 54
- 230000000996 additive effect Effects 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000003245 coal Substances 0.000 claims abstract description 50
- 238000002309 gasification Methods 0.000 claims abstract description 42
- 239000010883 coal ash Substances 0.000 claims abstract description 36
- 239000010881 fly ash Substances 0.000 claims abstract description 32
- 239000004567 concrete Substances 0.000 claims abstract description 20
- 239000002893 slag Substances 0.000 claims description 47
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 210000004556 brain Anatomy 0.000 claims 1
- 239000004570 mortar (masonry) Substances 0.000 description 25
- 239000011398 Portland cement Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010248 power generation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000009614 chemical analysis method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Abstract
Description
本発明は、セメント添加材及びセメント組成物に関する。 The present invention relates to a cement additive and a cement composition.
従来、モルタルやコンクリートにおいて、セメントの一部を石炭火力発電等によって発生するフライアッシュに置き換えたセメントが使われている。セメントの一部をフライアッシュに置き換えることによって、作業性や流動性の向上、発熱量の抑制、及び、廃棄物であるフライアッシュの有効利用等の利点がある。
しかし、「ＪＩＳ Ａ ６２０１：２０１５（コンクリート用フライアッシュ）」のフライアッシュＩ〜ＩＶ種の規定のいずれにも適合しない石炭灰は、モルタルやコンクリートの品質への悪影響が大きいことから、通常、モルタルやコンクリートに使うことができず、当該石炭灰の有効利用の方策が望まれている。
Conventionally, in mortar and concrete, cement in which part of the cement is replaced with fly ash generated by coal-fired power generation or the like has been used. By replacing part of the cement with fly ash, there are advantages such as improvement in workability and fluidity, suppression of heat generation, and effective use of fly ash as waste.
However, coal ash that does not conform to any of the fly ash types I to IV of “JIS A 6201: 2015 (fly ash for concrete)” has a great adverse effect on the quality of mortar and concrete. It cannot be used for concrete and concrete, and there is a need for a policy for effective use of the coal ash.
一方、次世代の石炭火力発電方式として検討及び実証が進められている石炭ガス化複合発電は、従来の石炭火力発電方式と比較して石炭の使用量が少なく、発電効率に優れ、石炭の利用炭種を拡大でき、環境負荷の低減を図ることができる等の利点を有することから、早期実用化が期待されている。
従来の石炭火力発電では、大量の石炭灰が発生するのに対して、石炭ガス化複合発電では、ガス化炉に投入された石炭中の灰成分が溶融してなるガラス状のスラグ（以下、「石炭ガス化スラグ」ともいう。）が大量に発生する。発生した石炭ガス化スラグは、セメント骨材やアスファルト舗装等に有効利用することができるものの、その発生量が大量であることから、更なる有効利用の方策が望まれている。
石炭ガス化スラグを用いたセメント組成物として、特許文献１には、ポゾランを３０〜７０重量％含有することを特徴とする水和反応遅延型セメント組成物において、上記ポゾランとして、石炭ガス化スラグ及び／又はフライアッシュを用いることが記載されている。
On the other hand, coal gasification combined power generation, which is being studied and verified as a next-generation coal-fired power generation system, uses less coal than conventional coal-fired power generation systems, has superior power generation efficiency, and uses coal. Since it has advantages such as the ability to expand the types of coal and the reduction of environmental burdens, early commercialization is expected.
In conventional coal-fired power generation, a large amount of coal ash is generated, whereas in coal gasification combined power generation, glassy slag (hereinafter referred to as slag) formed by melting the ash component in coal input to the gasification furnace is used. "Coal gasification slag") is generated in large quantities. Although the generated coal gasification slag can be effectively used for cement aggregate, asphalt pavement, and the like, since the amount of generation is large, further effective utilization measures are desired.
As a cement composition using coal gasification slag, Patent Document 1 discloses that the pozzolan is contained in an amount of 30 to 70% by weight. In the hydration delayed reaction cement composition, the coal gasification slag is used as the pozzolan. And / or the use of fly ash.
セメントの一部を「ＪＩＳ Ａ ６２０１：２０１５（コンクリート用フライアッシュ）」のフライアッシュＩ〜ＩＶ種の規定のいずれにも適合しない石炭灰に置き換えると、流動性や強度発現性（特に、材齢２８〜９１日における強度発現性）が低下するという問題がある。
本発明の目的は、「ＪＩＳ Ａ ６２０１：２０１５（コンクリート用フライアッシュ）」のフライアッシュＩ〜ＩＶ種の規定のいずれにも適合しない石炭灰を含むにもかかわらず、該石炭灰を含むセメント組成物の流動性（例えば、モルタルのフロー値）や強度（例えば、モルタルの圧縮強さ）発現性が良好であるセメント添加材を提供することである。
When a part of the cement is replaced with coal ash that does not conform to any of the fly ash types I to IV of “JIS A 6201: 2015 (Fly Ash for Concrete)”, fluidity and strength (particularly, age of the material) There is a problem in that the strength development on days 28 to 91 is reduced.
The object of the present invention is to provide a cement composition containing coal ash, although it contains coal ash that does not conform to any of the fly ash types I to IV of “JIS A 6201: 2015 (fly ash for concrete)”. An object of the present invention is to provide a cement additive having good fluidity (for example, mortar flow value) and strength (for example, mortar compressive strength).
本発明者は、上記課題を解決するために鋭意検討した結果、「ＪＩＳ Ａ ６２０１：２０１５（コンクリート用フライアッシュ）」のフライアッシュＩ〜ＩＶ種の規定のいずれにも適合しない石炭灰１００質量部、および、ブレーン比表面積及びＣａＯの含有率が特定の数値範囲内である石炭ガス化スラグ粉砕物１５〜４００質量部を含み、かつ、強熱減量が５．０質量％以下であるセメント添加材によれば、上記目的を達成できることを見出し、本発明を完成した。
すなわち、本発明は、以下の［１］〜［５］を提供するものである。
［１］ 「ＪＩＳ Ａ ６２０１：２０１５（コンクリート用フライアッシュ）」のフライアッシュＩ〜ＩＶ種の規定のいずれにも適合しない石炭灰１００質量部、および、ブレーン比表面積が３，０００〜１０，０００ｃｍ２／ｇである石炭ガス化スラグ粉砕物１５〜４００質量部を含むセメント添加材であって、上記石炭ガス化スラグ粉砕物中、ＣａＯの含有率が１１．０〜２３．０質量％であり、かつ、上記セメント添加材の強熱減量が５．０質量％以下であることを特徴とするセメント添加材。
［２］ 上記石炭ガス化スラグ粉砕物中、ＳｉＯ２の含有率が４３．０〜５５．０質量％であり、Ａｌ２Ｏ３の含有率が１５．０〜２５．０質量％である前記［１］に記載のセメント添加材。
［３］ 上記石炭ガス化スラグ粉砕物中、Ｆｅ２Ｏ３の含有率が３．０〜１５．０質量％であり、ＭｇＯの含有率が０．５〜５．０質量％である前記［１］又は［２］に記載のセメント添加材。
［４］ 前記［１］〜［３］のいずれかに記載のセメント添加材とセメントを含むセメント組成物。
［５］ 上記セメント組成物中、上記セメント添加材の含有率が５〜４０質量％である前記［４］に記載のセメント組成物。
As a result of intensive studies to solve the above problems, the present inventor has found that 100 parts by mass of coal ash that does not conform to any of the stipulations of fly ash types I to IV of “JIS A 6201: 2015 (fly ash for concrete)” And a cement additive containing 15 to 400 parts by mass of pulverized coal gasification slag whose specific surface area and CaO content are within a specific numerical range, and the ignition loss is 5.0% by mass or less. According to the present invention, the inventors have found that the above object can be achieved and completed the present invention.
That is, the present invention provides the following [1] to [5].
[1] 100 parts by mass of coal ash that does not conform to any of fly ash types I to IV of “JIS A 6201: 2015 (fly ash for concrete)”, and a specific surface area of branes of 3,000 to 10,000 cm It is a cement additive containing 15 to 400 parts by mass of a coal gasified slag pulverized product that is 2 / g, and the CaO content in the pulverized coal gasified slag is 11.0 to 23.0% by mass. And the ignition loss of the said cement additive is 5.0 mass% or less, The cement additive characterized by the above-mentioned.
[2] In the pulverized coal gasification slag, the content of SiO 2 is 43.0 to 55.0% by mass, and the content of Al 2 O 3 is 15.0 to 25.0% by mass. The cement additive according to [1].
[3] In the pulverized coal gasification slag, the content of Fe 2 O 3 is 3.0 to 15.0% by mass, and the content of MgO is 0.5 to 5.0% by mass [ The cement additive according to [1] or [2].
[4] A cement composition comprising the cement additive according to any one of [1] to [3] and cement.
[5] The cement composition according to [4], wherein the content of the cement additive is 5 to 40% by mass in the cement composition.
本発明のセメント添加材によれば、「ＪＩＳ Ａ ６２０１：２０１５（コンクリート用フライアッシュ）」のフライアッシュＩ〜ＩＶ種の規定のいずれにも適合しない石炭灰を含むにもかかわらず、該石炭灰を含むセメント組成物の流動性や強度発現性を良好にすることができる。また、石炭ガス化複合発電で大量に発生することから、新たな用途の開拓が望まれている石炭ガス化スラグを有効利用することができる。 According to the cement additive of the present invention, the coal ash is contained in spite of containing coal ash that does not conform to any of the fly ash types I to IV of “JIS A 6201: 2015 (concrete fly ash)”. The fluidity and strength development of the cement composition containing can be improved. Moreover, since it generate | occur | produces in large quantities by coal gasification combined cycle power generation, the coal gasification slag for which development of a new use is desired can be used effectively.
本発明のセメント添加材は、「ＪＩＳ Ａ ６２０１：２０１５（コンクリート用フライアッシュ）」のフライアッシュＩ〜ＩＶ種の規定のいずれにも適合しない石炭灰１００質量部、および、ブレーン比表面積が３，０００〜１０，０００ｃｍ２／ｇである石炭ガス化スラグ粉砕物１５〜４００質量部を含むセメント添加材であって、上記石炭ガス化スラグ粉砕物中、ＣａＯの含有率が１１．０〜２３．０質量％であり、かつ、上記セメント添加材の強熱減量が５．０質量％以下であるものである。
石炭灰のブレーン比表面積は、本発明のセメント添加材を含むセメント組成物の流動性や強度発現性をより向上させる観点から、好ましくは２，０００〜５，０００ｃｍ２／ｇ、より好ましくは２，２００〜４，５００ｃｍ２／ｇ、さらに好ましくは２，３００〜４，３００ｃｍ２／ｇ、特に好ましくは２，５００〜４，０００ｃｍ２／ｇである。
The cement additive of the present invention has 100 parts by mass of coal ash that does not conform to any of fly ash types I to IV of “JIS A 6201: 2015 (fly ash for concrete)”, A cement additive containing 15 to 400 parts by mass of a pulverized coal gasification slag of 000 to 10,000 cm 2 / g, wherein the CaO content in the pulverized coal gasification slag is 11.0 to 23. It is 0 mass%, and the ignition loss of the cement additive is 5.0 mass% or less.
The brane specific surface area of the coal ash is preferably 2,000 to 5,000 cm 2 / g, more preferably 2 from the viewpoint of further improving the fluidity and strength development of the cement composition containing the cement additive of the present invention. , 200-4,500 cm 2 / g, more preferably 2,300-4,300 cm 2 / g, particularly preferably 2,500-4,000 cm 2 / g.
石炭ガス化スラグは、通常、粒径が０．５〜１０ｍｍの粒状物である。
本発明で用いられる石炭ガス化スラグ粉砕物は、石炭ガス化スラグを粉砕してなるものである。石炭ガス化スラグ粉砕物のブレーン比表面積は、３，０００〜１０，０００ｃｍ２／ｇ、好ましくは３，５００〜９，０００ｃｍ２／ｇ、より好ましくは３，７００〜８，０００ｃｍ２／ｇ、さらに好ましくは３，８００〜７，５００ｃｍ２／ｇ、特に好ましくは４，０００〜７，０００ｃｍ２／ｇである。該ブレーン比表面積が３，０００ｃｍ２／ｇ未満であると、本発明のセメント添加材を含むセメント組成物の強度発現性が低下する。該ブレーン比表面積が１０，０００ｃｍ２／ｇを超えると、石炭ガス化スラグの粉砕に手間がかかることから、コストが高くなる。
The coal gasification slag is usually a granular material having a particle size of 0.5 to 10 mm.
The pulverized coal gasification slag used in the present invention is obtained by pulverizing coal gasification slag. The brane specific surface area of the pulverized coal gasification slag is 3,000 to 10,000 cm 2 / g, preferably 3,500 to 9,000 cm 2 / g, more preferably 3,700 to 8,000 cm 2 / g, More preferably, it is 3,800-7,500 cm < 2 > / g, Most preferably, it is 4,000-7,000 cm < 2 > / g. If the Blaine specific surface area is less than 3,000 cm 2 / g, strength development of the cement composition containing the cement additive of the present invention is lowered. If the Blaine specific surface area exceeds 10,000 cm 2 / g, it takes time to pulverize the coal gasification slag, which increases the cost.
石炭ガス化スラグ粉砕物中、ＣａＯの含有率は、１１．０〜２３．０質量％、好ましくは１３．０〜２１．０質量％、より好ましくは１４．０〜２０．０質量％、特に好ましくは１５．０〜１９．０質量％である。該含有率が１１．０質量％未満であると、本発明のセメント添加材を含むセメント組成物の強度発現性が、該含有率が１１．０質量％以上である場合と比べて小さくなる。該含有率が２３．０質量％を超える石炭ガス化スラグ粉砕物の入手は困難である。
石炭ガス化スラグ粉砕物中、ＳｉＯ２の含有率は、好ましくは４３．０〜５５．０質量％、より好ましくは４４．５〜５３．５質量％であり、特に好ましくは４６．０〜５１．０質量％である。該含有率が４３．０質量％未満である石炭ガス化スラグ粉砕物の入手は困難である。該含有率が５５．０質量％以下であれば、本発明のセメント添加材を含むセメント組成物の強度発現性が、該含有率が５５．０質量％を超える場合と比べて大きくなる。
石炭ガス化スラグ粉砕物中、Ａｌ２Ｏ３の含有率は、好ましくは１５．０〜２５．０質量％、より好ましくは１６．０〜２３．５質量％、特に好ましくは１７．０〜２２．０質量％である。該含有率が１５．０質量％以上であれば、本発明のセメント添加材を含むセメント組成物の強度発現性が、該含有率が１５．０質量％未満である場合と比べて大きくなる。該含有率が２５．０質量％を超える石炭ガス化スラグ粉砕物の入手は困難である。
In the pulverized coal gasification slag, the content of CaO is 11.0 to 23.0 mass%, preferably 13.0 to 21.0 mass%, more preferably 14.0 to 20.0 mass%, particularly Preferably it is 15.0-19.0 mass%. When the content is less than 11.0% by mass, the strength development of the cement composition containing the cement additive of the present invention is smaller than when the content is 11.0% by mass or more. It is difficult to obtain a pulverized coal gasification slag having a content of more than 23.0% by mass.
In the pulverized coal gasification slag, the content of SiO 2 is preferably 43.0 to 55.0% by mass, more preferably 44.5 to 53.5% by mass, and particularly preferably 46.0 to 51%. 0.0% by mass. It is difficult to obtain a pulverized coal gasification slag having a content of less than 43.0% by mass. If this content rate is 55.0 mass% or less, the strength development property of the cement composition containing the cement additive of this invention will become large compared with the case where this content rate exceeds 55.0 mass%.
In the pulverized coal gasification slag, the content of Al 2 O 3 is preferably 15.0 to 25.0% by mass, more preferably 16.0 to 23.5% by mass, and particularly preferably 17.0 to 22%. 0.0% by mass. If this content rate is 15.0 mass% or more, the strength development property of the cement composition containing the cement additive of this invention will become large compared with the case where this content rate is less than 15.0 mass%. It is difficult to obtain a pulverized coal gasification slag having a content of more than 25.0% by mass.
石炭ガス化スラグ粉砕物中、Ｆｅ２Ｏ３の含有率は、好ましくは３．０〜１５．０質量％、より好ましくは４．０〜１３．０質量％、特に好ましくは５．０〜１０．０質量％である。該含有率が３．０質量％以上であれば、本発明のセメント添加材を含むセメント組成物の強度発現性が、該含有率が３．０質量％未満である場合と比べて大きくなる。該含有率が１５．０質量％を超える石炭ガス化スラグ粉砕物の入手は困難である。
石炭ガス化スラグ粉砕物中、ＭｇＯの含有率は、好ましくは０．５〜５．０質量％、より好ましくは０．８〜４．０質量％、特に好ましくは１．０〜３．０質量％である。該含有率が０．５質量％以上であれば、本発明のセメント添加材を含むセメント組成物の強度発現性が、該含有率が０．５質量％未満である場合と比べて大きくなる。該含有率が５．０質量％を超える石炭ガス化スラグ粉砕物の入手は困難である。
In the pulverized coal gasification slag, the content of Fe 2 O 3 is preferably 3.0 to 15.0% by mass, more preferably 4.0 to 13.0% by mass, and particularly preferably 5.0 to 10%. 0.0% by mass. If this content rate is 3.0 mass% or more, the strength development property of the cement composition containing the cement additive of the present invention will be larger than when the content rate is less than 3.0 mass%. It is difficult to obtain a pulverized coal gasification slag having a content of more than 15.0% by mass.
The content of MgO in the pulverized coal gasification slag is preferably 0.5 to 5.0% by mass, more preferably 0.8 to 4.0% by mass, and particularly preferably 1.0 to 3.0% by mass. %. If this content rate is 0.5 mass% or more, the strength development property of the cement composition containing the cement additive of the present invention will be larger than when the content rate is less than 0.5 mass%. It is difficult to obtain a pulverized coal gasification slag having a content of more than 5.0% by mass.
上述した石炭灰１００質量部に対する、石炭ガス化スラグ粉砕物の量は、１５〜４００質量部、好ましくは２５〜３００質量部、より好ましくは３０〜２５０質量部、さらに好ましくは３５〜２００質量部、特に好ましくは５０〜１８０質量部である。該量が１５質量部未満であると、本発明のセメント添加材を含むセメント組成物の強度発現性及び流動性が低下する。また、石炭ガス化スラグの有効利用を図るという本発明の目的を十分に達成することができなくなる。該量が４００質量部を超えると、本発明のセメント添加材を含むセメント組成物の流動性及び強度発現性が低下する。 The amount of pulverized coal gasification slag with respect to 100 parts by mass of coal ash described above is 15 to 400 parts by mass, preferably 25 to 300 parts by mass, more preferably 30 to 250 parts by mass, and still more preferably 35 to 200 parts by mass. Particularly preferred is 50 to 180 parts by mass. When the amount is less than 15 parts by mass, strength development and fluidity of the cement composition containing the cement additive of the present invention are lowered. In addition, the object of the present invention to effectively use coal gasification slag cannot be achieved sufficiently. If the amount exceeds 400 parts by mass, the fluidity and strength developability of the cement composition containing the cement additive of the present invention will decrease.
本発明のセメント添加材の強熱減量は、５．０質量％以下、好ましくは０．５〜４．８質量％、より好ましくは０．８〜４．５質量％、特に好ましくは１．０〜４．０質量％である。該量が５．０質量％を超えると、本発明のセメント添加材を含むセメント組成物の流動性及び空気連行性が低下し、さらに、硬化後の意匠性が低下する（モルタル等の表面の黒色化が生じる）。 The ignition loss of the cement additive of the present invention is 5.0% by mass or less, preferably 0.5 to 4.8% by mass, more preferably 0.8 to 4.5% by mass, particularly preferably 1.0. It is -4.0 mass%. When the amount exceeds 5.0% by mass, the fluidity and air entrainment of the cement composition containing the cement additive of the present invention are lowered, and further, the designability after curing is lowered (the surface of the mortar or the like). Blackening occurs).
本発明のセメント添加材は、上述した石炭灰と石炭ガス化スラグ粉砕物を予め混合してなる混合物として使用してもよく、モルタル又はコンクリートを混練する際に、上述した石炭灰と石炭ガス化スラグ粉砕物を別々にミキサに投入して使用してもよい。
石炭灰と石炭ガス化スラグ粉砕物を混合するための混合手段としては、特に限定されるものではなく、例えば、パン型ミキサ、オムニミキサ、パドルミキサ等が挙げられる。
The cement additive of the present invention may be used as a mixture obtained by previously mixing the above-described coal ash and coal gasified slag pulverized material. When kneading mortar or concrete, the above-described coal ash and coal gasification are used. The slag pulverized product may be used separately in a mixer.
The mixing means for mixing the coal ash and the pulverized coal gasification slag is not particularly limited, and examples thereof include a pan mixer, an omni mixer, a paddle mixer, and the like.
本発明のセメント組成物は、上述したセメント添加材とセメントを含むものである。
セメントとしては、普通ポルトランドセメント、早強ポルトランドセメント等の各種ポルトランドセメントや、エコセメント等が挙げられる。中でも、セメント組成物の強度発現性がより向上する観点から、普通ポルトランドセメント又は早強ポルトランドセメントが好ましい。
セメント組成物中のセメント添加材の含有率は、好ましくは５〜４０質量％、より好ましくは７〜３５質量％、特に好ましくは１０〜３０質量％である。該含有率が５質量％以上であれば、石炭灰及び石炭ガス化スラグ粉砕物の有効利用をより促進することができる。該含有率が４０質量％以下であれば、セメント組成物の強度発現性の低下を抑制することができる。
The cement composition of the present invention includes the above-described cement additive and cement.
Examples of the cement include various Portland cements such as ordinary Portland cement and early-strength Portland cement, and eco-cement. Of these, ordinary Portland cement or early-strength Portland cement is preferable from the viewpoint of improving the strength development of the cement composition.
The content of the cement additive in the cement composition is preferably 5 to 40% by mass, more preferably 7 to 35% by mass, and particularly preferably 10 to 30% by mass. If this content rate is 5 mass% or more, the effective utilization of coal ash and coal gasification slag ground material can be promoted more. If this content rate is 40 mass% or less, the fall of the strength expression of a cement composition can be suppressed.
本発明のセメント組成物は、上述したセメント添加材とセメントを予め混合してなる混合物として使用してもよく、モルタル又はコンクリートを混練する際に、上述したセメント添加材及びセメント等の各材料を別々にミキサに投入して使用してもよい。
セメント添加材とセメントを混合するための混合手段は、特に限定されるものではなく、例えば、パン型ミキサ、オムニミキサ、パドルミキサ等が挙げられる。
The cement composition of the present invention may be used as a mixture obtained by previously mixing the above-mentioned cement additive and cement. When kneading mortar or concrete, each material such as the above-mentioned cement additive and cement is used. They may be used separately in a mixer.
The mixing means for mixing the cement additive and cement is not particularly limited, and examples thereof include a pan mixer, an omni mixer, and a paddle mixer.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
［使用材料］
（１）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）
（２）石炭灰；「ＪＩＳ Ａ ６２０１：２０１５（コンクリート用フライアッシュ）」のフライアッシュＩ〜ＩＶ種の規定のいずれにも適合しないもの、ブレーン比表面積：３，０００ｃｍ２／ｇ、強熱減量：６．３質量％、材齢２８日における活性度指数：７０、材齢９１日における活性度指数：７９
（３）石炭ガス化スラグ粉砕物Ａ〜Ｃ；表１参照
（４）細骨材；「ＪＩＳ Ｒ ５２０１：２０１５（セメントの物理試験方法）」に規定する標準砂
（５）水；水道水
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[Materials used]
(1) Cement: Ordinary Portland cement (manufactured by Taiheiyo Cement)
(2) Coal ash; not conforming to any of fly ash types I to IV of “JIS A 6201: 2015 (fly ash for concrete)”, Blaine specific surface area: 3,000 cm 2 / g, loss on ignition : 6.3% by mass, activity index at 28 days of age: 70, activity index at 91 days of age: 79
(3) Coal gasification slag pulverized products A to C; see Table 1 (4) Fine aggregate; Standard sand (5) water defined in “JIS R 5201: 2015 (physical test method for cement)”; tap water
［実施例１〜８、比較例１〜５、参考例２〜４］
石炭灰と、表２に示す種類の石炭ガス化スラグ粉砕物を、表２に示す配合で混合してセメント添加材を調製した。
得られたセメント添加材の強熱減量を 「ＪＩＳ Ｒ ５２０２：２０１０（セメントの化学分析方法）」に準拠して測定した。
普通ポルトランドセメントと、得られたセメント添加材を、普通ポルトランドセメント及びセメント添加材の合計１００質量％中、セメント添加材の含有率が２５質量％となるような配合で混合してセメント組成物を調製した。
得られたセメント組成物について「ＪＩＳ Ｒ ５２０１：２０１５（セメントの物理試験方法）」に準拠してモルタルを調製して、フロー値、及び、材齢２８日、９１日における圧縮強さを測定した。
結果を表２に示す。
［参考例１］
普通ポルトランドセメントについて、実施例１と同様にしてフロー値、及び、材齢２８日、９１日における圧縮強さを測定した。
結果を表２〜３に示す。
[Examples 1-8, Comparative Examples 1-5, Reference Examples 2-4]
A cement additive was prepared by mixing coal ash and the pulverized coal gasification slag of the type shown in Table 2 with the formulation shown in Table 2.
The ignition loss of the obtained cement additive was measured according to “JIS R 5202: 2010 (chemical analysis method of cement)”.
Cement composition is prepared by mixing ordinary Portland cement and the obtained cement additive in such a composition that the content of cement additive is 25% by mass in a total of 100% by mass of ordinary Portland cement and cement additive. Prepared.
For the obtained cement composition, a mortar was prepared according to “JIS R 5201: 2015 (cement physical test method)”, and the flow value and the compressive strength at the age of 28 days and 91 days were measured. .
The results are shown in Table 2.
[Reference Example 1]
About normal Portland cement, it carried out similarly to Example 1, and measured the flow value and the compressive strength in material age 28 days and 91 days.
The results are shown in Tables 2-3.
［実施例９〜１０］
石炭灰と石灰ガス化スラグ粉砕物Ａと普通ポルトランドセメントを含むセメント組成物について「ＪＩＳ Ｒ ５２０１：２０１５（セメントの物理試験方法）」に準拠して、モルタルを調製して、フロー値、及び、材齢２８日、９１日における圧縮強さを測定した。石炭灰、石灰ガス化スラグ粉砕物Ａ、及び普通ポルトランドセメントは、モルタルを混練する際に、別々にミキサに投入した。
石炭灰及び石灰ガス化スラグ粉砕物Ａの組み合わせであるセメント添加材は表３に示す配合に従った。また、セメント添加材の強熱減量を 「ＪＩＳ Ｒ ５２０２：２０１０（セメントの化学分析方法）」に準拠して測定した。
さらに、セメント組成物は、普通ポルトランドセメント及びセメント添加材の合計１００質量％中、セメント添加材の含有率が２５質量％となるような配合とした。
結果を表３に示す。
[Examples 9 to 10]
According to “JIS R 5201: 2015 (physical test method for cement)”, a mortar is prepared for a cement composition containing coal ash, lime gasified slag pulverized product A and ordinary Portland cement, and a flow value and The compressive strength at the age of 28 days and 91 days was measured. Coal ash, lime gasification slag pulverized product A, and ordinary Portland cement were separately charged into a mixer when kneading the mortar.
The cement additive which is a combination of coal ash and lime gasified slag pulverized product A was in accordance with the formulation shown in Table 3. The ignition loss of the cement additive was measured in accordance with “JIS R 5202: 2010 (Cement Chemical Analysis Method)”.
Furthermore, the cement composition was blended such that the content of cement additive was 25% by mass in a total of 100% by mass of ordinary Portland cement and cement additive.
The results are shown in Table 3.
表２から、比較例１（普通ポルトランドセメントと石炭灰からなるセメント組成物）と参考例１（普通ポルトランドセメントのみからなるセメント組成物）を比較すると、比較例１の各材齢におけるモルタルの圧縮強さは、各々、参考例１の各材齢におけるモルタルの圧縮強さよりも小さいことがわかる。
このことから、セメントの一部を石炭灰（「ＪＩＳ Ａ ６２０１：２０１５（コンクリート用フライアッシュ）」のフライアッシュＩ〜ＩＶ種の規定のいずれにも適合しないもの）に置き換えた場合、セメント組成物の強度発現性（特に、材齢２８日におけるモルタルの圧縮強さ）が低下することがわかる。
表２から、実施例１〜４（石炭灰及び石炭ガス化スラグ粉砕物Ａを用いたセメント組成物）の各材齢におけるモルタルの圧縮強さは、比較例１（普通ポルトランドセメントと石炭灰からなるセメント組成物）の各材齢におけるモルタルの圧縮強さよりも大きいことがわかる。
また、実施例５〜８（石炭灰及び石炭ガス化スラグ粉砕物Ｂを用いたセメント組成物）の各材齢におけるモルタル圧縮強さは、比較例１の各材齢におけるモルタルの圧縮強さよりも大きいことがわかる。
表２から、比較例３〜５（石炭灰及びブレーン比表面積が２，５００ｃｍ２／ｇの石炭ガス化スラグ粉砕物Ｃを用いたセメント組成物）の各材齢におけるモルタルの圧縮強さは、比較例１の各材齢におけるモルタルの圧縮強さと同程度であり、参考例１の各材齢におけるモルタルの圧縮強さよりも小さいことがわかる。
From Table 2, when comparing Comparative Example 1 (cement composition made of ordinary Portland cement and coal ash) and Reference Example 1 (cement composition made only of ordinary Portland cement), compression of mortar at each age of Comparative Example 1 It can be seen that the strength is smaller than the compressive strength of the mortar at each age in Reference Example 1.
Therefore, when a part of the cement is replaced with coal ash (one that does not conform to any of fly ash types I to IV of “JIS A 6201: 2015 (fly ash for concrete)”), the cement composition It can be seen that the strength development property (particularly the compressive strength of the mortar at the age of 28 days) decreases.
From Table 2, the compressive strength of the mortar in each age of Examples 1 to 4 (cement composition using coal ash and coal gasified slag pulverized product A) is from Comparative Example 1 (ordinary Portland cement and coal ash). It can be seen that the cement composition is greater than the compressive strength of the mortar at each age.
Moreover, the mortar compressive strength in each age of Examples 5-8 (cement composition using coal ash and coal gasified slag pulverized product B) is more than the compressive strength of mortar in each age of Comparative Example 1. You can see that it ’s big.
From Table 2, the compressive strength of mortar at each age of Comparative Examples 3 to 5 (cement composition using coal ash and pulverized coal gasified slag C having a specific surface area of 2500 cm 2 / g) is as follows. It can be seen that the compressive strength of the mortar at each age of Comparative Example 1 is similar to the compressive strength of the mortar at each age of Reference Example 1 and is smaller than the compressive strength of the mortar at each age of Reference Example 1.
これらのことから、本発明のセメント添加材によれば、「ＪＩＳ Ａ ６２０１：２０１５（コンクリート用フライアッシュ）」のフライアッシュＩ〜ＩＶ種の規定のいずれにも適合しない石炭灰を含むにもかかわらず、該石炭灰を含むセメント組成物の強度発現性を、比較例１と比べて、良好にしうることがわかる。
表２、３から、実施例２〜３（予め混合したセメント添加材と普通ポルトランドセメントを混合してなるセメント組成物を用いた場合）と、実施例９〜１０（モルタルを混練する際に各材料を別々にミキサに投入した場合）を比較すると、フロー値及びモルタルの圧縮強さは同程度であることがわかる。
From these facts, according to the cement additive of the present invention, although it contains coal ash that does not conform to any of the fly ash types I to IV of “JIS A 6201: 2015 (fly ash for concrete)”. It can be seen that the strength development of the cement composition containing coal ash can be made better than that of Comparative Example 1.
From Tables 2 and 3, Examples 2-3 (when using a cement composition formed by mixing pre-mixed cement additive and ordinary Portland cement) and Examples 9-10 (each when kneading mortar) When the materials are separately fed into the mixer, it can be seen that the flow value and the compressive strength of the mortar are comparable.
また、実施例１〜１０のフロー値（２１４〜２２４ｍｍ）は、比較例１のフロー値（１９５ｍｍ）よりも大きいことがわかる。このことから、本発明のセメント添加材によれば、「ＪＩＳ Ａ ６２０１：２０１５（コンクリート用フライアッシュ）」のフライアッシュＩ〜ＩＶ種の規定のいずれにも適合しない石炭灰を含むにもかかわらず、該石炭灰を含むセメント組成物の流動性を、比較例１と比べて、良好にしうることがわかる。
さらに、実施例１〜１０の各材齢におけるモルタルの圧縮強さ測定用供試体の表面を目視したところ、表面の黒色化は認められなかった。一方、比較例１〜２の各材齢におけるモルタルの圧縮強さ測定用供試体の表面を目視したところ、表面の一部の黒色化が認められた。
Moreover, it turns out that the flow value (214-224 mm) of Examples 1-10 is larger than the flow value (195 mm) of the comparative example 1. Therefore, according to the cement additive of the present invention, although it contains coal ash that does not conform to any of the fly ash types I to IV of “JIS A 6201: 2015 (Fly Ash for Concrete)”. It can be seen that the fluidity of the cement composition containing the coal ash can be improved as compared with Comparative Example 1.
Furthermore, when the surface of the specimen for measuring the compressive strength of the mortar at each age of Examples 1 to 10 was visually observed, no blackening of the surface was observed. On the other hand, when the surface of the specimen for measuring the compressive strength of mortar at each age of Comparative Examples 1 and 2 was visually observed, partial blackening of the surface was observed.
Claims (5)
上記石炭ガス化スラグ粉砕物中、ＣａＯの含有率が１１．０〜２３．０質量％であり、かつ、上記セメント添加材の強熱減量が５．０質量％以下であることを特徴とするセメント添加材。 100 parts by mass of coal ash not conforming to any of the specifications of fly ash types I to IV of “JIS A 6201: 2015 (fly ash for concrete)”, and a brain specific surface area of 3,000 to 10,000 cm 2 / g It is a cement additive containing 15 to 400 parts by mass of coal gasification slag pulverized product,
In the pulverized coal gasification slag, the CaO content is 11.0 to 23.0 mass%, and the ignition loss of the cement additive is 5.0 mass% or less. Cement additive.
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|---|---|---|---|---|
| KR102397193B1 (en) * | 2021-07-19 | 2022-05-12 | 문보경 | High-strength fly ash cement composition using coal gasification fly ash |
| WO2023003305A1 (en) * | 2021-07-19 | 2023-01-26 | 문보경 | High-strength fly ash cement composition using coal gasifier fly ash |
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