WO2018142661A1 - Method for producing coal ash, coal ash, and cement composition - Google Patents
Method for producing coal ash, coal ash, and cement composition Download PDFInfo
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- WO2018142661A1 WO2018142661A1 PCT/JP2017/033788 JP2017033788W WO2018142661A1 WO 2018142661 A1 WO2018142661 A1 WO 2018142661A1 JP 2017033788 W JP2017033788 W JP 2017033788W WO 2018142661 A1 WO2018142661 A1 WO 2018142661A1
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- Prior art keywords
- coal ash
- value
- cement
- pulverization
- mass
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/04—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with unperforated container
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/14—Mills in which the charge to be ground is turned over by movements of the container other than by rotating, e.g. by swinging, vibrating, tilting
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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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/10—Burned or pyrolised refuse
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/026—Comminuting, e.g. by grinding or breaking; Defibrillating fibres other than asbestos
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions 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
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions 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
- C04B28/08—Slag cements
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/28—Cements from oil shales, residues or waste other than slag from combustion residues, e.g. ashes or slags from waste incineration
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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
-
- 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
Definitions
- the present invention relates to a method for producing coal ash, coal ash, and a cement composition.
- Viscous soil has a very small particle size and is solidified, so it is not easy to mix and agitate with solidified material in improving the ground.
- a special stirring device is used, the water ratio is increased in order to improve the uniformity with the solidified material, or the dispersant acting on the soil particles is used in combination with the solidified milk. The method is taken.
- Patent Documents 1 to 3 have problems in that new equipment is required, running cost is high, and classification efficiency is low.
- an additive such as coal ash is mixed with the solidified material and its effective use can be achieved, the amount of solidified material can be reduced, and cost reduction such as a reduction in the amount of sludge can be expected.
- the object to be treated is soil such as viscous soil, as already mentioned, mixing and stirring with the solidifying material is not easy, so the currently known solidifying materials have problems such as cost increase and low efficiency. There is. From the viewpoint of effective use of coal ash, it is preferable that all of this can be used. In addition, it is very significant if it is possible to improve the homogeneity at the time of mixing in the improvement of the viscous ground by simple treatment without requiring treatment such as removal of unburned carbon, but such technology is currently known. Not.
- the present invention can use coal ash with a large amount of unburned carbon without performing treatment by classification, coal ash that can improve uniformity during mixing in ground improvement of viscous soil, and a method for producing the same, and
- An object is to provide a cement composition using the coal ash.
- the present inventor has pulverized coal ash having a high ignition loss by pulverizing it within a predetermined range. It was found that the obtained coal ash can improve the uniformity at the time of mixing in the soil improvement of cohesive soil and arrived at the present invention. That is, the present invention is as follows.
- [3] Coal ash before pulverization
- the particle size of 45 ⁇ m or more measured by the above measurement method of coal ash after pulverization with respect to the content (Vp) of particles having a particle size of 45 ⁇ m or more measured by laser diffraction scattering type particle size distribution measurement method The method for producing coal ash according to [1] or [2], wherein the pulverization is performed so that the particle content (Vg) ratio (Vg / Vp) is 0.85 or less.
- the ignition loss is 3.5% by mass or more, the content of particles having a particle size of 45 ⁇ m or more measured by a laser diffraction / scattering particle size distribution measurement method is 20% by volume or more and 45% by volume or less, and the brain ratio
- Coal ash according to [4] in which the loss on ignition is 8.0% by mass or less.
- a cement composition comprising the coal ash according to [4] or [5] and cement.
- the cement composition according to [6] wherein the cement is at least one cement selected from the group consisting of ordinary Portland cement, early-strength Portland cement, moderately hot Portland cement, and low heat Portland cement.
- coal ash containing a large amount of unburned carbon can be used without being treated by classification, coal ash that can improve uniformity during mixing in ground improvement of viscous soil, a method for producing the same, and A cement composition using the coal ash can be provided.
- a cement composition using the coal ash can be provided.
- Coal ash production method In the method for producing coal ash according to the embodiment of the present invention, the lightness (Lg) of coal ash after pulverization is compared with the lightness (Lp value) of coal ash before pulverization. Pulverization so that the ratio (Lg / Lp) is 0.9 or less.
- the present invention provides a coal ash that can improve the mixability with viscous soil when it is used for ground improvement of cohesive soil after predetermined pulverization of coal ash having a large loss on ignition of 3.5% by mass or more.
- Quality coal ash is proportional to the amount of unburned carbon in the coal ash, and “the ignition loss is 3.5 mass% or more larger” indicates that there is a large amount of so-called unburned carbon. Then, by subjecting the coal ash having a large loss on ignition to predetermined pulverization, at least a part of the unburned carbon contained in the coal ash particles is exposed to the surface side of the particles, thereby It can be used to improve the mixing of cement particles and clay particles.
- the unburned carbon exposed on the surface of the coal ash particles by pulverization shows the same properties as the unburned carbon in the powder particles existing before pulverization, and the properties are hydrophobic. That is, the predetermined pulverization increases the amount of unburned carbon exposed on the surface of the coal ash particles as compared to before pulverization, and thus the hydrophobicity becomes stronger.
- the predetermined pulverization increases the amount of unburned carbon exposed on the surface of the coal ash particles as compared to before pulverization, and thus the hydrophobicity becomes stronger.
- cement and this coal ash are mixed and used as a solidifying material, excessive water absorption is not shown at the time of cement kneading due to the hydrophobic unburned carbon exposed on the surface of the particles, and the water content is high.
- the dispersibility of clay particles and cement particles can be improved efficiently in the ground improvement of cohesive soil.
- the ignition loss of coal ash is related to the content of unburned carbon, and when the ignition loss is large, it can be assumed that the content of unburned carbon contained in the coal ash is also large. Therefore, if the ignition loss of coal ash is less than 3.5% by mass, the absolute amount of unburned carbon that exhibits hydrophobicity decreases, and thus the dispersibility of the clay particles cannot be improved.
- the ignition loss of coal ash is preferably 3.5% by mass or more and 9.0% by mass or less, and more preferably 6.0% by mass or more and 9.0% by mass or less. The ignition loss can be measured by the method described in Examples described later.
- Coal ash having a loss on ignition of 3.5% by mass or more is, for example, ash generated from a coal-fired power plant and generated by pulverized coal combustion.
- coal ash coal ash dropped from the combustion gas of the combustion boiler when passing through an air regenerator or coal saver, coal ash collected by an electric dust collector, coal ash dropped on the furnace bottom of the combustion boiler Etc.
- the ratio (Lg / Lp) of the lightness (Lg value) of the coal ash after pulverization to the lightness (Lp value) of the coal ash before pulverization of the coal ash whose ignition loss is 3.5% by mass or more is 0.9. It grind
- a pulverizer a ball mill, a vibration mill (which imparts vibration to the container and transmits vibration to the medium (ball or rod) inside the container to make the powder finer) can be used.
- the lightness (Lp value) of the coal ash before pulverization is measured, and the ratio (Lg / Lp) between this and the lightness (Lg value) of the coal ash after pulverization is 0.9 or less.
- the coal ash to be pulverized the entire amount of coal ash to be used may be pulverized, or a part of the coal ash may be pulverized. Further, the pulverized coal ash may be mixed with unpulverized coal ash and used as pulverized coal ash.
- the pulverized coal ash is obtained by pulverizing a part of the coal ash and mixing the pulverized coal ash, the lightness (Lp value) of the coal ash before pulverization and the pulverized coal containing the pulverized coal ash What is necessary is just to grind
- the brightness of the coal ash is related to the blackness, and is mainly an indicator of the amount of unburned carbon exposed on the surface. If the Lg / Lp ratio before and after pulverization exceeds 0.9, it is included.
- Lg / Lp is preferably 0.6 or more and 0.9 or less, and more preferably 0.6 or more and 0.85 or less. By setting it to 0.6 or more, pulverization of the spherical particles can be suppressed as much as possible to suppress a decrease in fluidity.
- the brightness of the coal ash can be determined by measuring by the method described in the examples described later.
- many particles with a particle size of 45 ⁇ m or more are non-spherical, and from the viewpoint of improving the fluidity by pulverizing them and exposing the spherical particles to be included, it is possible to improve the fluidity of the coal ash before pulverization.
- the ratio (Vg / Vp) is more preferably pulverized so as to be 0.6 or more and 0.80 or less.
- the coal ash may be used as pulverized coal ash by pulverizing particles having a particle size of 45 ⁇ m or more and mixing the pulverized coal ash with unpulverized coal ash.
- coal ash that can easily improve the dispersibility of clay particles by predetermined grinding is obtained.
- Coal ash The coal ash of the embodiment of the present invention has an ignition loss of 3.5% by mass or more, and the content of particles having a particle size of 45 ⁇ m or more measured by a laser diffraction scattering type particle size distribution measuring method is 20% by volume or more and 45% by volume. %,
- the specific surface area of branes is 3200 to 4200 cm 2 / g, and the lightness (Lg value) is 25.0 to 50.0.
- the ratio (Lg / Lp) of the lightness (Lg value) of the pulverized coal ash to the (value) is 0.9 or less.
- the ignition loss of coal ash is preferably 3.5% by mass or more and 9.0% by mass or less, and more preferably 6.0% by mass or more and 9.0% by mass or less.
- the content of particles having a particle size of 45 ⁇ m or more is preferably 20% by volume or more and 45% by volume or less, and more preferably 23% by volume or more and 43% by volume or less.
- the specific surface area of the brane is preferably 3200 to 4200 cm 2 / g, and more preferably 3300 to 4000 cm 2 / g.
- the lightness (Lg value) of the pulverized coal ash is less than 25.0, there is a lot of unburned carbon and blackness increases, resulting in a difference in color between the surrounding ground and the ground when improving the ground. In other words, if it exceeds 50.0, the amount of unburned carbon released is small, and when mixed with viscous soil, good fluidity cannot be obtained, and it may not be possible to mix uniformly.
- the brightness of the coal ash is preferably 30.0 to 50.0, and more preferably 35.0 to 45.0.
- the ratio is preferably 0.6 or more and 0.9 or less, and more preferably 0.6 or more and 0.85 or less.
- the coal ash according to the embodiment of the present invention can be produced by the method for producing coal ash according to the embodiment of the present invention.
- the coal ash production of the embodiment of the present invention is performed using a pulverizer such as a ball mill, a disk mill, etc., and the particle size distribution, the brain specific surface area, and the color difference measurement are performed each time, and a predetermined physical property value is obtained. It is preferable to confirm.
- the coal ash according to the embodiment of the present invention is preferably used as a cement composition to be described later, but can be applied to various other uses by making use of its characteristics.
- the cement composition of the embodiment of the present invention includes the coal ash of the embodiment of the present invention and cement.
- the type of cement is not particularly limited, and is preferably at least one selected from the group consisting of ordinary Portland cement, early-strength Portland cement, moderately hot Portland cement, and low heat Portland cement.
- the content of coal ash with respect to the total amount of the cement composition is preferably more than 5% by mass and 40% by mass or less. It can be used as a solidifying material by exceeding 5 mass% and 40 mass% or less. The content is more preferably 25% by mass or more and 35% by mass or less.
- gypsum, blast furnace slag, limestone powder, quicklime and the like can also be mixed in the cement composition.
- a V-type mixer, a rocking-type mixer, a pan-type mixer, a rotation / revolution mixer, or the like can be used.
- the cement composition of the embodiment of the present invention is preferably provided as a cement-based solidifying material, and more preferably as a cement-based solidifying material for improving the ground of cohesive soil.
- the water used for kneading may be 80 to 120 parts by mass with respect to 100 parts by mass of the cement composition.
- the amount is 85 to 110 parts by mass.
- the coal ash properties were determined as follows. (1) Loss on ignition: JISA6201: It calculated
- Vp Content (volume%) of particles having a particle size of 45 ⁇ m or more measured by laser diffraction scattering type particle size distribution measurement method of coal ash before pulverization and laser diffraction scattering type particle size distribution measurement method of coal ash after pulverization From the measured content (Vg) (volume%) of particles having a particle size of 45 ⁇ m or more, the content (Vp) of particles having a particle size of 45 ⁇ m or more measured by the laser diffraction scattering type particle size distribution measurement method of coal ash before pulverization.
- composition test according to Examples and Comparative Examples 30 g of each of the pulverized coal ash A to F, 70 g of cement (ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd.) and 100 g of kneaded water were sufficiently homogenized using a hand mixer to prepare cement milk. This was mixed in a rotating / revolving mixer with 1 L of kaolin (made by Kishida Chemical Co., Ltd.) as a viscous soil (wet density 1.846 g / cm 3 ) and kneaded. Specimens were produced in accordance with “Method for producing specimen without hardening”. Table 2 below shows the formulation (water content 35% by mass).
- coal ash E and the coal ash F are the same sample, and the degree of pulverization is different. The same applies to coal ash G and coal ash H.
- the mixing property of the solidified material and the clay was evaluated by a vane shear test.
- a vane shear test a vane blade having a stainless steel plate (0.5 cm ⁇ 3 cm) welded in the perpendicular direction was attached to the tip of a torque driver manufactured by Tohnichi Seisakusho Co., Ltd., and this was pushed into the sample and measured.
- the vane shear resistance value was determined from the maximum torque (see Table 2 below). The results are shown in Table 2 below. The evaluation index (see below) based on the resistance value is also shown.
- Examples 1 to 3 and 5 using pulverized coal ash had lower vane shear resistance and better kneadability. It was. As is clear from Example 4, good kneadability could be secured even if the amount of water was smaller than that in Example 1. Comparative Examples 4 and 6 were less pulverized than Examples 1 and 5, and kneadability was insufficient.
- the present invention as the amount of power generation at a coal-fired power plant increases, it is possible to effectively use coal ash whose generated amount has increased, and to improve uniformity during mixing in the soil improvement of cohesive soil. .
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Abstract
Description
石炭灰の大部分を占めるフライアッシュはコンクリートの混和材として用いられるが、JISによってその品質が細かく規定されており、一定の品質を維持するために分級等の処理が必要となる。分級によって除外された粗粉等は埋め立て処理される等、有効に利用されているとは言い難い。 On the other hand, the safety of nuclear power plants has been questioned, and the operating ratio of thermal power plants has increased, and the effective use of coal ash discharged along with its operation has become a further issue.
Fly ash, which occupies most of coal ash, is used as an admixture for concrete, but its quality is finely defined by JIS, and classification and other treatments are required to maintain a constant quality. It is difficult to say that the coarse powders excluded by classification are effectively used, such as being landfilled.
しかし、処理対象が粘性土のような土壌であると、既述のとおり、固化材との混合・攪拌が容易でないため、現状知られている固化材では、コストの上昇や低効率等の問題がある。石炭灰の有効利用の観点からは、これを全て利用できることが好ましい。また、未燃炭素の除去といった処理を必要とせず、簡易な処理で粘性土地盤改良における混合時の均一性改善が図れれば、非常に有意であるが、現状でそのような技術は知られていない。 Moreover, if an additive such as coal ash is mixed with the solidified material and its effective use can be achieved, the amount of solidified material can be reduced, and cost reduction such as a reduction in the amount of sludge can be expected.
However, if the object to be treated is soil such as viscous soil, as already mentioned, mixing and stirring with the solidifying material is not easy, so the currently known solidifying materials have problems such as cost increase and low efficiency. There is. From the viewpoint of effective use of coal ash, it is preferable that all of this can be used. In addition, it is very significant if it is possible to improve the homogeneity at the time of mixing in the improvement of the viscous ground by simple treatment without requiring treatment such as removal of unburned carbon, but such technology is currently known. Not.
[2] 前記粉砕前の石炭灰の明度(Lp値)に対する粉砕後の石炭灰の明度(Lg値)の比(Lg/Lp)が0.6以上となるように粉砕する、[1]に記載の石炭灰の製造方法。
[3] 粉砕前の石炭灰のレーザー回折散乱式粒度分布測定法で測定した粒径45μm以上の粒子の含有量(Vp)に対する粉砕後の石炭灰の前記測定法で測定した粒径45μm以上の粒子の含有量(Vg)の比(Vg/Vp)が0.85以下となるように粉砕する、[1]又は[2]に記載の石炭灰の製造方法。 [1] The ratio (Lg / Lp) of the brightness (Lg value) of the coal ash after pulverization to the brightness (Lp value) of the coal ash before pulverization of the coal ash whose ignition loss is 3.5% by mass or more. The manufacturing method of coal ash including grind | pulverizing so that it may become 0.9 or less.
[2] Pulverize so that the ratio (Lg / Lp) of the lightness (Lg value) of the coal ash after pulverization to the lightness (Lp value) of the coal ash before pulverization becomes 0.6 or more. The manufacturing method of coal ash of description.
[3] Coal ash before pulverization The particle size of 45 μm or more measured by the above measurement method of coal ash after pulverization with respect to the content (Vp) of particles having a particle size of 45 μm or more measured by laser diffraction scattering type particle size distribution measurement method The method for producing coal ash according to [1] or [2], wherein the pulverization is performed so that the particle content (Vg) ratio (Vg / Vp) is 0.85 or less.
[5] 強熱減量が8.0質量%以下である、[4]に記載の石炭灰。 [4] The ignition loss is 3.5% by mass or more, the content of particles having a particle size of 45 μm or more measured by a laser diffraction / scattering particle size distribution measurement method is 20% by volume or more and 45% by volume or less, and the brain ratio A pulverized coal ash having a surface area of 3200 to 4200 cm 2 / g and a lightness (Lg value) of 25.0 to 50.0, and pulverized coal with respect to the lightness (Lp value) of the coal ash before pulverization Coal ash having a ash brightness (Lg value) ratio (Lg / Lp) of 0.9 or less.
[5] Coal ash according to [4], in which the loss on ignition is 8.0% by mass or less.
[7] 前記セメントが、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント、及び低熱ポルトランドセメントからなる群より選ばれる少なくとも1種のセメントである、[6]に記載のセメント組成物。
[8] セメント組成物全量に対して、前記石炭灰の含有量が5質量%を超え40質量%以下である、[6]又は[7]に記載のセメント組成物。 [6] A cement composition comprising the coal ash according to [4] or [5] and cement.
[7] The cement composition according to [6], wherein the cement is at least one cement selected from the group consisting of ordinary Portland cement, early-strength Portland cement, moderately hot Portland cement, and low heat Portland cement.
[8] The cement composition according to [6] or [7], wherein the content of the coal ash is more than 5% by mass and 40% by mass or less with respect to the total amount of the cement composition.
(1)石炭灰の製造方法:
本発明の実施形態の石炭灰の製造方法は、強熱減量が3.5質量%以上である石炭灰を、粉砕前の石炭灰の明度(Lp値)に対する粉砕後の石炭灰の明度(Lg値)の比(Lg/Lp)が0.9以下となるように粉砕することを含む。 [Coal ash production method and coal ash]
(1) Coal ash production method:
In the method for producing coal ash according to the embodiment of the present invention, the lightness (Lg) of coal ash after pulverization is compared with the lightness (Lp value) of coal ash before pulverization. Pulverization so that the ratio (Lg / Lp) is 0.9 or less.
ここで、強熱減量は、石炭灰中の未燃炭素の量に比例し、「強熱減量が3.5質量%以上大きい」とは、いわゆる未燃炭素が多いことを示す。そして、強熱減量が大きい石炭灰に所定の粉砕を施すことで、石炭灰の粒子中に内包されている未燃炭素の少なくとも一部を粒子の表面側に露出させることによって、この石炭灰を用いて、セメント粒子と粘土粒子との混合性を改善することができる。粉砕によって石炭灰の粒子の表面に露出された未燃炭素は粉砕前から存在する粉体粒子中の未燃炭素と同一の性状を示し、その性状は疎水性である。つまり、所定の粉砕により、粉砕前に比べて石炭灰の粒子の表面に露出されている未燃炭素が多くなるため、疎水性がより強くなる。例えば、セメントとこの石炭灰とを混合して固化材として用いる場合には、粒子の表面に露出された疎水性の未燃炭素によって、セメント混練時に過剰な吸水性が示されず、含水比の高い粘性土の地盤改良において粘土粒子とセメント粒子との分散性を効率よく向上させることができる。 The present invention provides a coal ash that can improve the mixability with viscous soil when it is used for ground improvement of cohesive soil after predetermined pulverization of coal ash having a large loss on ignition of 3.5% by mass or more. Quality coal ash).
Here, the ignition loss is proportional to the amount of unburned carbon in the coal ash, and “the ignition loss is 3.5 mass% or more larger” indicates that there is a large amount of so-called unburned carbon. Then, by subjecting the coal ash having a large loss on ignition to predetermined pulverization, at least a part of the unburned carbon contained in the coal ash particles is exposed to the surface side of the particles, thereby It can be used to improve the mixing of cement particles and clay particles. The unburned carbon exposed on the surface of the coal ash particles by pulverization shows the same properties as the unburned carbon in the powder particles existing before pulverization, and the properties are hydrophobic. That is, the predetermined pulverization increases the amount of unburned carbon exposed on the surface of the coal ash particles as compared to before pulverization, and thus the hydrophobicity becomes stronger. For example, when cement and this coal ash are mixed and used as a solidifying material, excessive water absorption is not shown at the time of cement kneading due to the hydrophobic unburned carbon exposed on the surface of the particles, and the water content is high. The dispersibility of clay particles and cement particles can be improved efficiently in the ground improvement of cohesive soil.
粉砕装置としては、ボールミル、振動ミル(容器に振動を与えて、容器内部の媒体(ボールやロッド)に振動を伝えて粉体を細粒化させる)等を用いることができる。 The ratio (Lg / Lp) of the lightness (Lg value) of the coal ash after pulverization to the lightness (Lp value) of the coal ash before pulverization of the coal ash whose ignition loss is 3.5% by mass or more is 0.9. It grind | pulverizes, for example with a grinder so that it may become the following. Thereby, unburned carbon contained in the coal ash particles is exposed.
As a pulverizer, a ball mill, a vibration mill (which imparts vibration to the container and transmits vibration to the medium (ball or rod) inside the container to make the powder finer) can be used.
ここで、石炭灰の明度は黒色度と関連し、主に表面に露出させた未燃炭素の存在量の指標となり、粉砕前後の比であるLg/Lpが0.9を超えると、内包される未燃炭素が十分に表面に存在していないことになり、このような状態でセメントと混合した固化材とした場合には、粘土粒子とセメント粒子との分散性を効率よく向上させることができない。
Lg/Lpは0.6以上0.9以下となるようにすることが好ましく、0.6以上0.85以下となるようにすることがより好ましい。0.6以上とすることで球形粒子の粉砕をできるだけ抑制して流動性低下を抑制することができる。
石炭灰の明度は後述の実施例に記載の方法により測定して求めることができる。 In pulverization, first, the lightness (Lp value) of the coal ash before pulverization is measured, and the ratio (Lg / Lp) between this and the lightness (Lg value) of the coal ash after pulverization is 0.9 or less. To. As for the coal ash to be pulverized, the entire amount of coal ash to be used may be pulverized, or a part of the coal ash may be pulverized. Further, the pulverized coal ash may be mixed with unpulverized coal ash and used as pulverized coal ash. Even if the pulverized coal ash is obtained by pulverizing a part of the coal ash and mixing the pulverized coal ash, the lightness (Lp value) of the coal ash before pulverization and the pulverized coal containing the pulverized coal ash What is necessary is just to grind | pulverize so that ratio (Lg / Lp) with the brightness (Lg value) of ash may become 0.9 or less.
Here, the brightness of the coal ash is related to the blackness, and is mainly an indicator of the amount of unburned carbon exposed on the surface. If the Lg / Lp ratio before and after pulverization exceeds 0.9, it is included. When the solidified material mixed with cement in such a state is used, the dispersibility of clay particles and cement particles can be improved efficiently. Can not.
Lg / Lp is preferably 0.6 or more and 0.9 or less, and more preferably 0.6 or more and 0.85 or less. By setting it to 0.6 or more, pulverization of the spherical particles can be suppressed as much as possible to suppress a decrease in fluidity.
The brightness of the coal ash can be determined by measuring by the method described in the examples described later.
本発明の実施形態の石炭灰は、強熱減量が3.5質量%以上であり、レーザー回折散乱式粒度分布測定法で測定した粒径45μm以上の粒子の含有量が20体積%以上45体積%以下であり、ブレーン比表面積が3200~4200cm2/gであり、明度(Lg値)が25.0~50.0である粉砕された石炭灰であり、粉砕前の石炭灰の明度(Lp値)に対する粉砕後の石炭灰の明度(Lg値)の比(Lg/Lp)が0.9以下となっている。 (2) Coal ash:
The coal ash of the embodiment of the present invention has an ignition loss of 3.5% by mass or more, and the content of particles having a particle size of 45 μm or more measured by a laser diffraction scattering type particle size distribution measuring method is 20% by volume or more and 45% by volume. %, The specific surface area of branes is 3200 to 4200 cm 2 / g, and the lightness (Lg value) is 25.0 to 50.0. The ratio (Lg / Lp) of the lightness (Lg value) of the pulverized coal ash to the (value) is 0.9 or less.
粒径45μm以上の粒子の含有量は、20体積%以上45体積%以下であることが好ましく、23体積%以上43体積%以下であることがより好ましい。 When the content of particles having a particle diameter of 45 μm or more in coal ash measured by the laser diffraction / scattering particle size distribution measurement method is less than 20% by volume, there are few non-spherical particles, and unburned carbon particles are released by pulverization and dispersed. If the effect of improving the property is reduced and the amount exceeds 45% by volume, the amount of non-spherical particles is increased and the fluidity is lowered or the hydration activity of the coal ash itself is lowered.
The content of particles having a particle size of 45 μm or more is preferably 20% by volume or more and 45% by volume or less, and more preferably 23% by volume or more and 43% by volume or less.
ブレーン比表面積は、3200~4200cm2/gであることが好ましく、3300~4000cm2/gであることがより好ましい。 If the Blaine specific surface area of coal ash is less than 3200 cm 2 / g, the hydration activity may be reduced and a predetermined strength may not be obtained, and if it exceeds 4200 cm 2 / g, the fluidity will be reduced.
The specific surface area of the brane is preferably 3200 to 4200 cm 2 / g, and more preferably 3300 to 4000 cm 2 / g.
石炭灰の明度は、30.0~50.0であることが好ましく、35.0~45.0であることがより好ましい。 In addition, if the lightness (Lg value) of the pulverized coal ash is less than 25.0, there is a lot of unburned carbon and blackness increases, resulting in a difference in color between the surrounding ground and the ground when improving the ground. In other words, if it exceeds 50.0, the amount of unburned carbon released is small, and when mixed with viscous soil, good fluidity cannot be obtained, and it may not be possible to mix uniformly.
The brightness of the coal ash is preferably 30.0 to 50.0, and more preferably 35.0 to 45.0.
当該比は0.6以上0.9以下であることが好ましく、0.6以上0.85以下であることがより好ましい。 When the ratio (Lg / Lp) of the lightness (Lg value) of the coal ash after pulverization to the lightness (Lp value) of the coal ash before pulverization exceeds 0.9, the unburned carbon contained is sufficiently present on the surface Therefore, when the solidified material is mixed with cement in such a state, the dispersibility between the clay particles and the cement particles cannot be improved efficiently.
The ratio is preferably 0.6 or more and 0.9 or less, and more preferably 0.6 or more and 0.85 or less.
本発明の実施形態のセメント組成物は、本発明の実施形態の石炭灰と、セメントとを含む。
セメントの種類は特に限定されず、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント、及び低熱ポルトランドセメントからなる群より選ばれる少なくとも1種であることが好ましい。 [Cement composition]
The cement composition of the embodiment of the present invention includes the coal ash of the embodiment of the present invention and cement.
The type of cement is not particularly limited, and is preferably at least one selected from the group consisting of ordinary Portland cement, early-strength Portland cement, moderately hot Portland cement, and low heat Portland cement.
粘性土の地盤改良用のセメント系固化材とする場合、また、混練する際に使用される水(混練水)は、セメント組成物100質量部に対して、80~120質量部とすることが好ましく、85~110質量部とすることがより好ましい。 The cement composition of the embodiment of the present invention is preferably provided as a cement-based solidifying material, and more preferably as a cement-based solidifying material for improving the ground of cohesive soil.
In the case of using a cement-based solidifying material for improving the ground of cohesive soil, the water used for kneading (kneading water) may be 80 to 120 parts by mass with respect to 100 parts by mass of the cement composition. Preferably, the amount is 85 to 110 parts by mass.
国内の火力発電所にて発生した石炭灰A~Fのそれぞれを、試験用ボールミル(内容積100L)により、粉砕した。なお、粉砕の度合は、レーザー回折粒度分布計、ブレーン比表面積測定装置、色彩色差計により紛体物性を確認することで調整した。
粉砕前後の石炭灰A~Fの石炭灰性状(強熱減量、炭素量、MT-45μR及び粉砕前後のMT-45μRの比、ブレーン比表面積、L値及び粉砕前後のL値の比)を下記表1に示す。
(Production of coal ash A to F)
Each of the coal ash A to F generated in a domestic thermal power plant was pulverized by a test ball mill (internal volume 100 L). The degree of pulverization was adjusted by confirming powder physical properties using a laser diffraction particle size distribution meter, a Blaine specific surface area measuring device, and a color difference meter.
Coal ash properties of coal ash A to F before and after pulverization (ignition loss, carbon content, ratio of MT-45μR and MT-45μR before and after pulverization, Blaine specific surface area, L value and ratio of L value before and after pulverization) Table 1 shows.
(1)強熱減量:
JISA6201:コンクリート用フライアッシュ(975℃15分強熱)に準拠して求めた。
(2)カーボン量(炭素量):
株式会社堀場製作所製固体中炭素・硫黄分析装置(EMIA-320V)により測定して求めた。
(3)MT-45μR(粒径45μm以上の粒子の含有量):
レーザー回折式粒度分布計(日機装株式会社製マイクロトラックMT-3300EX)により測定して求めた。粉砕前の石炭灰のレーザー回折散乱式粒度分布測定法で測定した粒径45μm以上の粒子の含有量(Vp)(体積%)と、粉砕後の石炭灰のレーザー回折散乱式粒度分布測定法で測定した粒径45μm以上の粒子の含有量(Vg)(体積%)とから、粉砕前の石炭灰のレーザー回折散乱式粒度分布測定法で測定した粒径45μm以上の粒子の含有量(Vp)(体積%)に対する粉砕後の石炭灰のレーザー回折散乱式粒度分布測定法で測定した粒径45μm以上の粒子の含有量(Vg)(体積%)の比(Vg/Vp:MT-45μR比)を求めた。 The coal ash properties were determined as follows.
(1) Loss on ignition:
JISA6201: It calculated | required based on the fly ash for concrete (975 degreeC 15 minute ignition).
(2) Carbon content (carbon content):
It was determined by measurement with a solid carbon / sulfur analyzer (EMIA-320V) manufactured by HORIBA, Ltd.
(3) MT-45 μR (content of particles having a particle size of 45 μm or more):
It was determined by measuring with a laser diffraction particle size distribution meter (Microtrack MT-3300EX manufactured by Nikkiso Co., Ltd.). Content (Vp) (volume%) of particles having a particle size of 45 μm or more measured by laser diffraction scattering type particle size distribution measurement method of coal ash before pulverization and laser diffraction scattering type particle size distribution measurement method of coal ash after pulverization From the measured content (Vg) (volume%) of particles having a particle size of 45 μm or more, the content (Vp) of particles having a particle size of 45 μm or more measured by the laser diffraction scattering type particle size distribution measurement method of coal ash before pulverization. Ratio (Vg / Vp: MT-45 μR ratio) of the content (Vg) (volume%) of particles having a particle diameter of 45 μm or more measured by a laser diffraction scattering particle size distribution measurement method of coal ash after pulverization to (volume%) Asked.
JISR5201:セメントの物理試験方法に準拠して求めた。
(5)色差(L値):
コニカミノルタジャパン(株)製の色彩色差計(CR-300)を用いて、CIE(国際照明委員会)で規定された明度(L値)を測定し求めた。粉砕前の石炭灰の明度(Lp値)と粉砕後の石炭灰の明度(Lg値)とから、粉砕前の石炭灰の明度(Lp値)に対する粉砕後の石炭灰の明度(Lg値)の比(Lg/Lp:L値比)を求めた。 (4) Blaine specific surface area JISR5201: It calculated | required based on the physical test method of cement.
(5) Color difference (L value):
Using a color difference meter (CR-300) manufactured by Konica Minolta Japan Co., Ltd., the brightness (L value) defined by the CIE (International Lighting Commission) was measured and determined. From the lightness (Lp value) of the coal ash before pulverization and the lightness (Lg value) of the coal ash after pulverization, the lightness (Lg value) of the coal ash after pulverization with respect to the lightness (Lp value) of the coal ash before pulverization The ratio (Lg / Lp: L value ratio) was determined.
粉砕後の石炭灰A~Fそれぞれ30gと、セメント(住友大阪セメント(株)製普通ポルトランドセメント)70gと、混練水100gとをハンドミキサーを用いて十分に均一化してセメントミルクを作製した。これを自転・公転式のミキサーに、粘性土としてのカオリン(キシダ化学(株)製)1L(湿潤密度1.846g/cm3)と共に入れて混練して、JGS0821-2009「安定処理土の締固めをしない供試体作製方法」に準拠して供試体を作製した。
下記表2に配合(含水比35質量%)について示す。 (Composition test according to Examples and Comparative Examples)
30 g of each of the pulverized coal ash A to F, 70 g of cement (ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd.) and 100 g of kneaded water were sufficiently homogenized using a hand mixer to prepare cement milk. This was mixed in a rotating / revolving mixer with 1 L of kaolin (made by Kishida Chemical Co., Ltd.) as a viscous soil (wet density 1.846 g / cm 3 ) and kneaded. Specimens were produced in accordance with “Method for producing specimen without hardening”.
Table 2 below shows the formulation (water content 35% by mass).
G(良い:good):ベーンせん断抵抗値<10.0kN/m2
Av(普通:average):10.0kN/m2≦ベーンせん断抵抗値≦12.0kN/m2
P(悪い:poor)×:ベーンせん断抵抗値>12.0kN/m2 After kneading, the mixing property of the solidified material and the clay was evaluated by a vane shear test. In the vane shear test, a vane blade having a stainless steel plate (0.5 cm × 3 cm) welded in the perpendicular direction was attached to the tip of a torque driver manufactured by Tohnichi Seisakusho Co., Ltd., and this was pushed into the sample and measured. The vane shear resistance value was determined from the maximum torque (see Table 2 below). The results are shown in Table 2 below. The evaluation index (see below) based on the resistance value is also shown.
G (good): Vane shear resistance value <10.0 kN / m 2
Av (ordinary: average): 10.0 kN / m 2 ≦ Vane shear resistance value ≦ 12.0 kN / m 2
P (poor: poor) x: vane shear resistance value> 12.0 kN / m 2
According to the present invention, as the amount of power generation at a coal-fired power plant increases, it is possible to effectively use coal ash whose generated amount has increased, and to improve uniformity during mixing in the soil improvement of cohesive soil. .
Claims (8)
- 強熱減量が3.5質量%以上である石炭灰を、粉砕前の石炭灰の明度(Lp値)に対する粉砕後の石炭灰の明度(Lg値)の比(Lg/Lp)が0.9以下となるように粉砕することを含む、石炭灰の製造方法。 The ratio (Lg / Lp) of the lightness (Lg value) of the coal ash after pulverization to the lightness (Lp value) of the coal ash before pulverization of the coal ash whose ignition loss is 3.5% by mass or more is 0.9. The manufacturing method of coal ash including grind | pulverizing so that it may become the following.
- 前記粉砕前の石炭灰の明度(Lp値)に対する粉砕後の石炭灰の明度(Lg値)の比(Lg/Lp)が0.6以上となるように粉砕する、請求項1に記載の石炭灰の製造方法。 The coal according to claim 1, wherein the coal ash is pulverized so that a ratio (Lg / Lp) of the brightness (Lg value) of the coal ash after pulverization to the brightness (Lp value) of the coal ash before pulverization becomes 0.6 or more. Ash production method.
- 粉砕前の石炭灰のレーザー回折散乱式粒度分布測定法で測定した粒径45μm以上の粒子の含有量(Vp)に対する粉砕後の石炭灰の前記測定法で測定した粒径45μm以上の粒子の含有量(Vg)の比(Vg/Vp)が0.85以下となるように粉砕する、請求項1又は2に記載の石炭灰の製造方法。 Inclusion of particles having a particle size of 45 μm or more measured by the above-described measurement method of coal ash after pulverization with respect to the content (Vp) of particles having a particle size of 45 μm or more measured by the laser diffraction scattering particle size distribution measurement method of coal ash before pulverization The manufacturing method of the coal ash of Claim 1 or 2 grind | pulverized so that ratio (Vg / Vp) of quantity (Vg) may be 0.85 or less.
- 強熱減量が3.5質量%以上であり、レーザー回折散乱式粒度分布測定法で測定した粒径45μm以上の粒子の含有量が20体積%以上45体積%以下であり、ブレーン比表面積が3200~4200cm2/gであり、明度(Lg値)が25.0~50.0である粉砕された石炭灰であり、粉砕前の石炭灰の明度(Lp値)に対する粉砕後の石炭灰の明度(Lg値)の比(Lg/Lp)が0.9以下である、石炭灰。 The ignition loss is 3.5% by mass or more, the content of particles having a particle size of 45 μm or more measured by a laser diffraction scattering type particle size distribution measuring method is 20% by volume or more and 45% by volume or less, and the Blaine specific surface area is 3200. ~ 4200Cm a 2 / g, a coal ash is crushed lightness (Lg value) is 25.0 to 50.0, the lightness of coal ash after grinding for brightness coal ash before pulverization (Lp value) Coal ash having a (Lg value) ratio (Lg / Lp) of 0.9 or less.
- 強熱減量が8.0質量%以下である、請求項4に記載の石炭灰。 Coal ash according to claim 4, wherein the ignition loss is 8.0% by mass or less.
- 請求項4又は5に記載の石炭灰と、セメントとを含むセメント組成物。 A cement composition comprising the coal ash according to claim 4 or 5 and cement.
- 前記セメントが、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント、及び低熱ポルトランドセメントからなる群より選ばれる少なくとも1種のセメントである、請求項6に記載のセメント組成物。 The cement composition according to claim 6, wherein the cement is at least one cement selected from the group consisting of ordinary Portland cement, early-strength Portland cement, moderately hot Portland cement, and low heat Portland cement.
- セメント組成物全量に対して、前記石炭灰の含有量が5質量%を超え40質量%以下である、請求項6又は7に記載のセメント組成物。 The cement composition according to claim 6 or 7, wherein a content of the coal ash is more than 5% by mass and 40% by mass or less based on the total amount of the cement composition.
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2017
- 2017-02-02 JP JP2017017452A patent/JP6323579B1/en active Active
- 2017-09-19 AU AU2017396650A patent/AU2017396650B2/en active Active
- 2017-09-19 KR KR1020187036007A patent/KR102202526B1/en active IP Right Grant
- 2017-09-19 NZ NZ755774A patent/NZ755774A/en unknown
- 2017-09-19 WO PCT/JP2017/033788 patent/WO2018142661A1/en active Application Filing
- 2017-09-19 CN CN201780042909.5A patent/CN109414704B/en active Active
- 2017-09-19 SG SG11201900713XA patent/SG11201900713XA/en unknown
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2018
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JP2007002100A (en) * | 2005-06-23 | 2007-01-11 | Tohoku Electric Power Co Inc | Plastic grouting material using coal ash and method for grouting the plastic grouting material |
JP2011133344A (en) * | 2009-12-24 | 2011-07-07 | Taiheiyo Cement Corp | Evaluation method of expression property of strength of coal ash and improvement method of expression property of strength |
JP2016113319A (en) * | 2014-12-15 | 2016-06-23 | 株式会社トクヤマ | Hydraulic composition containing furnace bottom ash |
Also Published As
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CN109414704A (en) | 2019-03-01 |
JP2018122260A (en) | 2018-08-09 |
JP6323579B1 (en) | 2018-05-16 |
PH12018501223B1 (en) | 2019-02-04 |
CN109414704B (en) | 2021-01-26 |
PH12018501223A1 (en) | 2019-02-04 |
AU2017396650B2 (en) | 2019-10-03 |
KR20190113527A (en) | 2019-10-08 |
SG11201900713XA (en) | 2019-02-27 |
KR102202526B1 (en) | 2021-01-13 |
AU2017396650A1 (en) | 2019-04-18 |
NZ755774A (en) | 2020-05-29 |
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