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WO2018198392A1 - Ciment mixte - Google Patents

Ciment mixte Download PDF

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Publication number
WO2018198392A1
WO2018198392A1 PCT/JP2017/033785 JP2017033785W WO2018198392A1 WO 2018198392 A1 WO2018198392 A1 WO 2018198392A1 JP 2017033785 W JP2017033785 W JP 2017033785W WO 2018198392 A1 WO2018198392 A1 WO 2018198392A1
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WIPO (PCT)
Prior art keywords
coal ash
mass
amount
content
sio
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PCT/JP2017/033785
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English (en)
Japanese (ja)
Inventor
賢司 宮脇
金井　謙介
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Sumitomo Osaka Cement Co Ltd
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Sumitomo Osaka Cement Co Ltd
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Application filed by Sumitomo Osaka Cement Co Ltd filed Critical Sumitomo Osaka Cement Co Ltd
Priority to AU2017411817A priority Critical patent/AU2017411817B2/en
Priority to SG11201900709QA priority patent/SG11201900709QA/en
Priority to CN201780042999.8A priority patent/CN109415263B/zh
Priority to KR1020187036004A priority patent/KR102241949B1/ko
Priority to NZ755775A priority patent/NZ755775A/en
Priority to PH12018500748A priority patent/PH12018500748A1/en
Publication of WO2018198392A1 publication Critical patent/WO2018198392A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
    • 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
    • C04B28/04—Portland 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
    • C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
    • 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
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
    • C04B7/42—Active ingredients added before, or during, the burning process
    • C04B7/428—Organic materials
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/05—Materials having an early high strength, e.g. allowing fast demoulding or formless casting
    • 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 mixed cement mixed with coal ash.
  • coal ash discharged from thermal power plants is broadly divided into fly ash and clinker ash, and fly ash is collected by a dust collector out of coal ash generated when coal is burned at a coal thermal power plant. It means fine ash.
  • Clinker ash is obtained by crushing massive coal ash that has fallen into the water tank at the bottom of the boiler in a red hot state with a crusher. About 90% of coal ash is fly ash.
  • fly ash cement using fly ash as a mixed material is manufactured and sold.
  • a part of fly ash used as a cement admixture is stipulated in JIS A6201 “Fly Ash for Concrete”.
  • coal ash refers to fly ash.
  • Coal ash contains pozzolans containing silicon dioxide (SiO 2 ) and aluminum oxide (Al 2 O 3 ) as main components. Pozzolana in coal ash reacts slowly with calcium hydroxide (Ca (OH) 2 ) produced by cement hydration reaction (Pozzolanic reaction) to produce hydrate, Contributes to strength development.
  • Ca (OH) 2 calcium hydroxide
  • Pozzolanic reaction cement hydration reaction
  • a strength enhancer in order to supplement the strength development of the short-term age of the cured product, as a strength enhancer, a composition containing a reaction product obtained by reacting glycerin and formaldehyde, or mannose, galactose, talose, ribose, and erythrose A composition containing a specific amount of one or more compounds selected from the group has been proposed (Patent Documents 1 and 2).
  • an object of the present invention is to provide a mixed cement containing coal ash, maintaining the properties as an admixture of coal ash, and having high short-term strength development.
  • the present inventors have, as a result of intensive studies to achieve the object, among the pozzolanic contained in coal ash, silica and the content of (SiO 2), alumina (Al 2 O 3) to silica (SiO 2 ) Mass ratio (SiO 2 / Al 2 O 3 ), these mixed cements containing coal ash in a specific range maintain the properties of coal ash as an admixture, while exhibiting short-term strength development properties.
  • the present inventors have found that a high mixed cement can be obtained and completed the present invention. That is, the present invention is as follows.
  • Coal ash having a SiO 2 content of 55 to 60% by mass and a SiO 2 / Al 2 O 3 mass ratio of 2.3 to 2.7 with respect to the total amount of coal ash and Portland cement is 20 A blended cement containing 100 to 300 mg / kg of trialkanolamine containing 3 to 40% by weight of Portland cement and 60 to 80% by weight of Portland cement and having 3 straight-chain alkanol groups having 3 or less carbon atoms.
  • the mixed cement according to [1] or [2], wherein the total content of SiO 2 and Al 2 O 3 in the coal ash is 70 to 82% by mass.
  • the SiO 2 content is 55 to 60% by mass and the SiO 2 / Al 2 O 3 mass ratio is 2.3 to 2.7 based on the total amount of coal ash and Portland cement.
  • Mixed cement containing 20 to 40% by mass of coal ash and 60 to 80% by mass of Portland cement and 100 to 300 mg / kg of trialkanolamine having 3 linear alkanol groups having 3 or less carbon atoms It is a composition.
  • Coal ash has a SiO 2 content of 55 to 60% by mass and a SiO 2 / Al 2 O 3 mass ratio of 2.3 to 2.7.
  • the coal ash is preferably generated from a coal-fired power plant.
  • the mechanism is not clear, but the content of SiO 2 , which is one of the main components of pozzolans, and the main components of pozzolans (SiO 2 , Al 2 O 3 ) It was found that the mass ratio (SiO 2 / Al 2 O 3 ) contributes to, for example, the short-term strength development of a 3-day age.
  • Pozzolana in coal ash reacts slowly with calcium hydroxide (Ca (OH) 2 ) produced by cement hydration reaction (Pozzolanic reaction) to produce hydrate, It is known to contribute to strength development.
  • the hydration reaction of Portland cement contained in the mixed cement is promoted by a chelating action of a trialkanolamine having three linear alkanol groups having 3 or less carbon atoms, and at a relatively early stage.
  • Pozzolanic reaction between calcium hydroxide (Ca (OH) 2 ) produced by hydration reaction of Portland cement and pozzolanic components (Al 2 O 3 , SiO 2 ) in coal ash occurs, and short-term strength development is Presumed to improve.
  • the SiO 2 content in the coal ash is 55 to 60% by mass, preferably 55.0 to 59.5% by mass, and more preferably 55.0 to 59.0% by mass. If the SiO 2 content in the coal ash is less than 55.0% by mass, the SiO 2 content, which is one of the pozzolanic components contained in the coal ash, is too small, and the mixed cement containing the coal ash is desired long-term May not exhibit the strength development of When SiO 2 content in the coal ash exceeds 60.0 wt%, since it is often SiO 2 content in the coal ash, the content of relatively Al 2 O 3 is reduced, SiO 2 / Al The mass ratio of 2 O 3 exceeds 2.7.
  • the content of SiO 2 contained in coal ash has a correlation with the content of other components contained in coal ash, such as Al 2 O 3 , Fe 2 O 3 , CaO, and MgO contained in coal ash. Yes, when the SiO 2 content in the coal ash increases, the content of other components tends to decrease relatively.
  • the mass ratio of SiO 2 / Al 2 O 3 in the coal ash is 2.3 to 2.7, preferably 2.30 to 2.65.
  • the mass ratio of SiO 2 / Al 2 O 3 in coal ash exceeds 2.7, the content of silica (SiO 2 ) in coal ash is large, and the content of alumina (Al 2 O 3 ) is high.
  • the pozzolanic reaction is promoted at an early stage because there are few aluminum ions in the pozzolanic component of coal ash. Therefore, it becomes difficult to increase short-term strength development.
  • the total of SiO 2 content and Al 2 O 3 content in the coal ash is preferably 70 to 82% by mass, more preferably 72.0 to 82.0% by mass, and further preferably 75.0 to 81.5%. % By mass.
  • the trialkanolamine can be used together with a mild pozzolanic reaction that contributes to long-term strength development.
  • the hydration reaction of Portland cement is promoted by the chelating action.
  • the mixed cement When the cation in the Portland cement is masked by the chelating action of the trialkanolamine, the mixed cement has a pozzolanic component (SiO 2 , in the coal ash to maintain the equilibrium state of the hydration reaction of the mixed cement. Cations contained in (Al 2 O 3 ) are likely to react.
  • the mixed cement reacts with calcium hydroxide (Ca (OH) 2 ) produced by the hydration reaction of Portland cement by pozzolanic components (Al 2 O 3, SiO 2 ) contained in coal ash at a relatively early stage.
  • the pozzolanic reaction is promoted, which is considered to contribute to the improvement of short-term strength development.
  • the coal ash has an Fe 2 O 3 content of preferably 5.0 to 8.0% by mass, more preferably 5.1 to 7.9% by mass.
  • Fe 2 O 3 content in the coal ash mechanism contributing to short term strength development is not clear, Fe 2 O 3 content in the coal ash is 5.0 to 8.0 mass% , SiO 2 content contained in coal ash and other components other than SiO 2 contained in coal ash, such as Al 2 O 3 , Fe 2 O 3 , CaO, MgO, etc. in coal ash from relationship, SiO 2 / Al 2 mass ratio of O 3 tends to be from 2.3 to 2.7, the weight ratio of SiO 2 / Al 2 O 3 tends to become a suitable range contributes to the short-term strength development It is guessed.
  • the mass ratio (the amount of Fe in the crystalline phase / the amount of Fe in the coal ash) of the amount of iron in the crystalline phase (the amount of Fe in the crystalline phase) contained in the coal ash to the amount of iron in the coal ash (the amount of Fe in the coal ash) is: It is preferably 0.10 to 0.17, more preferably 0.110 to 0.170.
  • the mass ratio of the amount of iron in the crystalline phase contained in the coal ash to the amount of iron in the coal ash (the amount of Fe in the crystalline phase / the amount of Fe in the coal ash) is the amount of crystalline phase contained in the coal ash and the amorphous phase It becomes an index representing the mass ratio of the quantity.
  • the amount of Fe in the crystalline phase is determined by the method for measuring the crystalline phase and the amorphous phase (mass%) in coal ash described in the examples described later, and includes the total amount including unburned carbon.
  • “the amount of crystalline phase Fe calculated taking into account the total amount of amorphous phase G total (% by mass) including unburned carbon” is also referred to as “the amount of Fe in the crystalline phase”.
  • the amount of Fe in the crystalline phase / the amount of Fe in the coal ash is 0.10 to 0.17, the amount of iron in the crystalline phase is relatively small.
  • the amount of crystalline phase that does not contribute to the pozzolanic reaction in the coal ash It is presumed that the amount of amorphous phase including alumina (Al 2 O 3 ) and silica (SiO 2 ) contributing to the pozzolanic reaction is relatively small and relatively large.
  • the amount of Fe in the crystal phase / the amount of Fe in the coal ash exceeds 0.17, it is presumed that the content of the crystal phase in the coal ash increases, and an amorphous phase that is relatively easy to contribute to the pozzolanic reaction Less.
  • the crystalline phases in the coal ash such as quartz or cristobalite (SiO 2), mullite (3Al 2 O 3 ⁇ 2SiO 2 or 2Al 2 O 3 ⁇ SiO 2) , hematite (Fe 2 O 3), magnetite (Fe 3 O 4 ) and the like. If the mass ratio of the amount of Fe in the crystal phase / the amount of Fe in the coal ash representing the index of the amount of crystalline phase and the amount of amorphous phase in the coal ash is 0.17 or less, the amount of crystal phase in the coal ash is small, The amount of the amorphous phase is relatively increased.
  • the mixed cement When the mass ratio of the amount of Fe in the crystal phase of coal ash / the amount of Fe in coal ash contained in the mixed cement is 0.17 or less, the mixed cement has a relatively early stage due to the chelating action of the trialkanolamine. Hydration reaction is promoted to produce calcium hydroxide (Ca (OH) 2 ), and this calcium hydroxide (Ca (OH) 2 ) and the pozzolanic component (Al 2 O 3 ) contained in the amorphous phase. , SiO 2 ), a pozzolanic reaction occurs, and it is estimated that short-term strength development is improved.
  • the mixed cement has a pozzolanic component (SiO2) in the coal ash to maintain an equilibrium state of the hydration reaction of the mixed cement.
  • SiO2 a pozzolanic component
  • cations contained in Al 2 O 3 are likely to react, and the reactivity of the pozzolanic reaction, which reacts relatively slowly, is promoted even at an early stage, which is considered to contribute to the improvement of short-term strength development.
  • the mass ratio of Fe amount in the crystalline phase / Fe amount in the coal ash which indicates the index of the crystalline phase and the amorphous phase of the coal ash, the smaller the numerical value, the less the crystalline phase in the coal ash and the more the amorphous phase.
  • the pozzolanic component Al 2 O 3 , SiO 2 .
  • the mass ratio of the amount of crystalline phase Fe in coal ash / the amount of Fe in coal ash is 0.10 or more.
  • the coal ash has an insoluble residue content (insol) of preferably 75 to 87% by mass, more preferably 75.5 to 86.5% by mass. It is considered that the insoluble residue in the coal ash includes a crystalline phase and an amorphous phase (glass phase) constituting silicic acid and silicate.
  • the mechanism by which the insoluble residue (insol) in the coal ash contained in the mixed cement contributes to the short-term strength development is not clear. If the insoluble residue (insol) in the coal ash contained in the mixed cement is 75.0 to 87.0% by mass, the pozzolanic component (Al 2 O 3 , SiO 2) that contributes to the pozzolanic reaction contained in the coal ash. ) Is contained in a relatively large amount.
  • the insoluble residue in coal ash refers to the insoluble residue of coal ash measured according to the method described in JIS R5202 “Chemical chemical analysis method of cement”.
  • the coal ash has a brane specific surface area of preferably 2500 to 4000 cm 2 / g, more preferably 2600 cm 2 / g or more, further preferably 2700 cm 2 / g or more, and even more preferably 2800 to 4000 cm 2 / g. is there.
  • the Blaine specific surface area of coal ash is large, the activity becomes high, and in a relatively early stage, the pozzolanic component (Al 2 O 3 , SiO 2 ) contained in the coal ash is generated by the hydration reaction of Portland cement. It easily reacts with calcium oxide (Ca (OH) 2 ).
  • the Blaine specific surface area of the coal ash is 2500 to 4000 cm 2 / g
  • the coal ash and Portland cement can be mixed uniformly, and the chelating action of the trialkanolamine is a pozzolanic component in Portland cement and coal ash. It reaches alumina (Al 2 O 3 ), and the pozzolanic reaction proceeds at a relatively early stage, so that the short-term strength development can be increased.
  • the brane specific surface area of coal ash refers to a value measured according to JIS R5201 “Cement physical test method”.
  • Coal ash is contained in the mixed cement in an amount of 20 to 40% by mass and more preferably 25 to 35% by mass with respect to the total amount of coal ash and Portland cement. If the mixed cement contains less than 20% by mass of coal ash with respect to the total amount of coal ash and Portorado cement, the amount of coal ash is too small to effectively use the coal ash. If the mixed cement contains more than 40% by mass of coal ash with respect to the total amount of coal ash and Portorado cement, the amount of coal ash that has almost no hydraulic property in the short-term age is too much and mixed. The short-term strength development of cement decreases.
  • the mixed cement contains 20 to 40% by mass of coal ash with 100 to 300 mg / kg of the trialkanolamine with respect to the total amount of coal ash and Portland cement, and the coal ash has a SiO 2 content of 55%. If it is ⁇ 60 mass% and the mass ratio of SiO 2 / Al 2 O 3 is 2.3 to 2.7, it can contribute to improvement of short-term strength development.
  • Portland cement The type of Portland cement contained in the mixed cement is not particularly limited. Examples of Portland cement include ordinary Portland cement, early-strength Portland cement, moderately hot Portland cement, and low heat Portland cement.
  • the mixed cement contains 60-80% by mass of Portland cement and preferably 65-75% by mass with respect to the total amount of coal ash and Portland cement.
  • the content of Portland cement is less than 60% by mass with respect to the total amount of coal ash and Portland cement, a hardened product having a desired strength cannot be obtained because the amount of cement is small. If the content exceeds 80% by mass, the amount of coal ash contained in the mixed cement decreases, and the coal ash cannot be used effectively.
  • the mixed cement contains 100 to 300 mg / kg, preferably 150 to 250 mg / kg, of a trialkanolamine having 3 linear alkanol groups having 3 or less carbon atoms with respect to the total amount of coal ash and Portland cement. It is.
  • the trialkanolamine the hydration reaction of Portland cement is promoted by chelating action against Portland cement, and calcium hydroxide (Ca (OH) 2 ) is generated at a relatively early stage.
  • Trialkanolamine has three linear alkanol groups having 3 or less carbon atoms, and specific examples thereof include trimethanolamine, triethanolamine, and tripropanolamine. Of these, triethanolamine is preferable.
  • triisopropanolamine and triethanolamine may have higher short-term strength (for example, mortar strength) when using triisopropanolamine, for example. .
  • mortar strength for example, mortar strength
  • the effect of increasing strength in a short period is greater when triethanolamine is used than when triisopropanolamine is used.
  • the mixed cement contains 20 % coal ash having a SiO 2 content of 55 to 60% by mass and a SiO 2 / Al 2 O 3 mass ratio of 2.3 to 2.7 with respect to the total amount of coal ash and Portland cement.
  • Manufactured by mixing ⁇ 40 mass% and 60-80 mass% of Portland cement, and further mixing 100-300 mg / kg of trialkanolamine having 3 linear alkanol groups having 3 or less carbon atoms can do.
  • the mixed cement can be used as a mixed cement composition by blending an admixture in addition to coal ash and Portland cement.
  • the admixture include blast furnace slag powder, limestone powder, quartz powder, gypsum and the like.
  • the loss on ignition (ig.loss) and insoluble residue (insol) in coal ash refer to the insoluble residue of coal ash measured according to JIS R5202 “Chemical chemical analysis method”.
  • the brane specific surface area of coal ash was measured according to JIS R5201 “Physical test method for cement”. The results are shown in Table 1.
  • the amount of the amorphous phase of the coal ash of Examples 1 to 6 was in the range of 66.7 to 68.2% by mass.
  • the amount of amorphous phase of the coal ash of Examples 7 to 9 was in the range of 60.5 to 61.9% by mass.
  • the amount of amorphous phase (mass%) in each coal ash of Examples 1 to 9 is shown in Table 1.
  • the amount of amorphous phase GFA (mass%) in coal ash in Table 1 is calculated from the amount of amorphous phase G total (mass%) of coal ash by Rietveld analysis and the amount of unburned carbon (mass of mass) of coal ash. %) Is subtracted.
  • a method for measuring the amount of crystalline phase and amorphous phase (mass%) in coal ash is described below.
  • Measurement conditions X-ray tube: Cu Tube voltage: 40 kV Tube current: 40 mA Measurement range of diffraction angle 2 ⁇ : start angle 5 °, end angle 70 ° / 75 ° *
  • rutile type titanium dioxide is added as an internal standard substance, if the end angle is 70 °, the peak shape of titanium dioxide around 70 ° cannot be obtained correctly. Therefore, the end angle of the sample added with titanium dioxide was set to 75 °.
  • Step width 0.025 ° / step
  • Counting time 60 sec. / Step Internal standard: Rutile type titanium dioxide Rietveld analysis conditions Rietveld analysis software: TOPAS Ver.
  • coal ash (sample 1) to which 20% by mass of rutile type titanium dioxide was added and coal ash (sample 2) to which no internal standard substance was added were prepared.
  • Coal ash (sample 2) to which no internal standard substance was added was measured using a powder X-ray diffractometer, and the obtained powder ash (sample 2) powder X-ray diffraction pattern and the target mineral quartz , Mullite, anhydrous gypsum, limestone, magnetite, and hematite, and fitting each theoretical profile, quantitative analysis of each mineral to be analyzed contained in coal ash, the amount of each mineral (% by mass) ) was calculated.
  • the amount (mass%) of magnetite and hematite in the coal ash was calculated only from the coal ash (sample 2) to which no internal standard substance was added.
  • Sample 2 to which no internal standard substance is added is used for quantitative analysis of magnetite and hematite.
  • the diffraction angle 2 ⁇ of magnetite and hematite is about 35.5 ° to 35.6 °, and the diffraction angle 2 ⁇ of rutile titanium dioxide. This is because the peak near 36.1 ° is close.
  • Analytical minerals such as quartz, mullite, anhydrous gypsum, limestone, hematite, magnetite, and titanium dioxide were fitted to each theoretical profile, and each of the minerals included in the coal ash (sample 1) with the internal standard added.
  • the mass ratio of the amount of iron in the crystal phase contained in the coal ash to the amount of iron in the coal ash of Examples 1 to 9 was calculated as follows.
  • the amount of Fe in coal ash is a measured value 1 of the iron content in terms of oxide (iron (III) oxide: Fe 2 O 3 ) measured in accordance with JIS R5204 “Method for X-ray fluorescence analysis of cement” From the following formula (2), the iron content was converted and calculated.
  • Iron content in coal ash Measured value 1 ⁇ 2 Fe / Fe 2 O 3 (111.6 / 159.7) (mass%) (2) (ii)
  • the amount of iron in the crystalline phase contained in the coal ash is the hematite in the crystalline phase calculated in consideration of the total amount of amorphous phase G total (% by mass) containing unburned carbon contained in the coal ash.
  • the content (mass%) of the magnetite in the crystal phase calculated taking the total amorphous phase quantity G total (mass%) including unburned carbon into account, with the content (mass%) of The measured value 3 was calculated by the following formula (3).
  • Iron amount (Fe amount) in crystal phase considering total amorphous phase amount G total including unburned carbon contained in coal ash [measured value 2 ⁇ ⁇ 2Fe / Fe 2 O 3 (111.6 / 159 .7) ⁇ ] + [measured value 3 ⁇ ⁇ 3Fe / Fe 3 O 4 (167.4 / 231.5) ⁇ ] (3) (Iii) Total amount of amorphous phase including the amount of iron in coal ash (Fe amount in coal ash) determined by the above formula (2) and unburned carbon contained in the coal ash determined by the above formula (3) From the amount of iron in the crystalline phase considering G total (the amount of Fe in the crystalline phase), the amount of Fe in the crystalline phase considering the total amount of amorphous phase G total including unburned carbon relative to the amount of Fe in coal ash The mass ratio (the amount of Fe in the crystal phase / the amount of Fe in coal ash) was determined. The results are shown in Tables 1 and 2.
  • Examples 1 to 8 and Comparative Examples 1 to 6 Ordinary Portland cement, Examples 1 to 9, and a mixture shown in Table 2 using a kind of additive selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA) and diethylene glycol (DEG) Cement was produced.
  • the content of coal ash is a mixing ratio with respect to 100% by mass of the total amount of coal ash and ordinary Portland cement.
  • the addition amount of one kind of additive selected from triethanolamine (TEA), triisopropanolamine (TIPA) and diethylene glycol (DEG) is the addition amount (mg / kg) with respect to the total amount of 1000 kg of coal ash and ordinary Portland cement. It is.
  • Table 2 shows the amount of chemical components (mass%) of silica (SiO 2 ) and alumina (Al 2 O 3 ) and the mass ratio of silica to alumina (SiO 2 / Al 2 O 3 ) for coal ash used in the mixed cement. ), Fe 2 O 3 chemical component amount (mass%), mass ratio of Fe amount in crystal phase / Fe amount in coal ash considering total amorphous phase amount G total including unburned carbon, Blaine specific surface area ( cm 2 / g).
  • Mortar Strength For the mixed cements of Examples 1 to 8 and Comparative Examples 1 to 6, the mortar compressive strength at 3 days of age (in accordance with “11 Strength Test” in JIS R5201 “Physical Test Method for Cement” ( N / mm 2 ).
  • the mortar compressive strength of the mortar specimen using the mixed cement having a coal ash content of 25% by mass in Comparative Example 6 was set to 1.00, and the mortar compressive strength of Examples 1 to 8 and Comparative Examples 1 to 6 was used.
  • the relative value of mortar strength was calculated. Further, for some examples and comparative examples, the mortar compressive strength (N / day) of 28-day or 91-day age was determined in accordance with “11 Strength Test” in JIS R5201 “Physical Test Method for Cement”.
  • Example 1 having a coal ash content of 25% by mass with a SiO 2 content of 55-60% by mass and a SiO 2 / Al 2 O 3 mass ratio of 2.3-2.7.
  • the relative value of the mortar strength at the age of 3 days with respect to Comparative Example 6 is 1.14 or more, respectively, and the short-term strength The expression was improved.
  • the mixed cements of Examples 1 to 6 having a SiO 2 content of 55 to 60% by mass and a SiO 2 / Al 2 O 3 mass ratio of 2.3 to 2.7 and a coal ash content of 30% by mass
  • the relative value of the mortar strength at 3 days of age relative to Comparative Example 6 was 1.06 or more, respectively, and short-term strength development was improved. I was able to confirm.
  • the mixed cements of Examples 6 to 8 having a coal ash content of 25% by mass all have a mortar strength of 28-day age relative to Comparative Example 6 (coal ash content 25% by mass, additive 0 mg / kg).
  • the relative value and the relative value of the mortar strength of the 91-day age were 1.15 or more, and the coal ash contained in the mixed cement maintained characteristics that contribute to long-term strength development.
  • the SiO 2 content and the mass ratio of SiO 2 / Al 2 O 3 satisfy the above range, include 200 mg / kg of triethanolamine (TEA), and consider the total amorphous phase amount G total including unburned carbon.
  • the mixed cements of Examples 1 to 8 using coal ash having a mass ratio of Fe amount in crystal phase / Fe amount in coal ash in the range of 0.10 to 0.17 have a coal ash content of 25 mass. %, 30% by mass, and 35% by mass, the relative value of the mortar strength at 3 days relative to Comparative Example 6 (coal ash content 25% by mass, additive 0 mg / kg) is Comparative Example 1.
  • the coal ash content of the mixed cements of 5 to 5 was larger than the respective relative values of 25% by mass, 30% by mass, and 35% by mass, and the short-term strength development was improved.
  • Table 1 an example in which the mass ratio of the Fe amount in the crystalline phase / the Fe amount in the coal ash in consideration of the total amorphous phase amount G total including unburned carbon is in the range of 0.10 to 0.17.
  • the coal ash of 1 to 6 has a mass ratio of Fe amount in the crystal phase / Fe amount in the coal ash in consideration of the total amorphous phase amount G total including unburned carbon exceeding 0.17. Examples 7 to 8 amorphous phase amount G FA in the coal ash was often compared to the coal ash.
  • the mixed cement of No. 3 is a three-day material for Comparative Example 6 (coal ash content 25% by mass, additive 0 mg / kg) in any case where the coal ash content is 25% by mass, 30% by mass, and 35% by mass.
  • the relative values of the mortar strength of the ages were as low as less than 1.14, less than 1.06 and less than 0.98, respectively, and the short-term strength development was not improved as compared with the mixed cements of Examples 1 to 6.
  • the mixed cement of Comparative Example 3 having a coal ash content of 25% by mass has a relative value of the mortar strength at 28 days of age and 91 relative to Comparative Example 6 (coal ash content of 25% by mass, additive 0 mg / kg).
  • the relative value of the mortar strength of the day age is 1.09, and the coal ash contained in the mixed cement has maintained the characteristics contributing to the long-term strength development, but compared with Examples 6-8 The long-term strength development was slightly lower.
  • Comparative Examples 4 and 5 in Table 2 when coal ash having a SiO 2 content of 55 to 60% by mass and a SiO 2 / Al 2 O 3 mass ratio of 2.3 to 2.7 is used. Even so, when triisopropanolamine (TIPA) or diethylene glycol (DEG) is used as an additive, the chelating action of the additive on ordinary Portland cement is not appropriate, and the mixed cements of Comparative Examples 4 and 5 are In all cases where the coal ash content is 25% by mass, 30% by mass, and 35% by mass, the mortar strength of the 3-day age relative to Comparative Example 6 (coal ash content 25% by mass, additive 0 mg / kg) Are less than 1.14, less than 1.06, and less than 0.98, respectively, and the short-term strength development was not improved as compared with the mixed cements of Examples 1 to 6.
  • TIPA triisopropanolamine
  • DEG diethylene glycol
  • Comparative Example 6 of Table 2 the case where coal ash having a SiO 2 content of 55 to 60% by mass and a SiO 2 / Al 2 O 3 mass ratio of 2.3 to 2.7 was used. However, when the additive is not used, as the coal ash content increases to 25 mass%, 30 mass%, and 35 mass%, Comparative Example 6 (coal ash content 25 mass%, additive 0 mg / The relative value of 3-day age mortar strength relative to kg) decreased. Since the coal ash itself has almost no hydraulic property in the short-term age, it is presumed that the relative value of the mortar strength of the 3-day age became lower as the coal ash increased.
  • coal ash whose generation amount is increasing can be effectively used with the increase in power generation amount at a coal-fired power plant, and coal having a specific component with high short-term strength development.
  • Mixed cement containing ash can be provided.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Civil Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Processing Of Solid Wastes (AREA)
  • Seal Device For Vehicle (AREA)
  • Glass Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention concerne un ciment mixte qui comprend des cendres de charbon, qui conserve des caractéristiques en tant que mélange de cendres de charbon et qui présente une apparition de résistance initiale élevée. Ce ciment mixte comprend 20 à 40 % en masse de cendres de charbon qui présentent une teneur en SiO2 de 55 à 60 % en masse et un rapport massique SiO2/Al2O3 de 2,3 à 2,7 et 60 à 80 % en masse de ciment Portland par rapport à la quantité totale des cendres de charbon et du ciment Portland et 100 à 300 mg/kg de trialcanolamine présentant trois groupes alcanol à chaîne droite comprenant trois atomes de carbone ou moins.
PCT/JP2017/033785 2017-04-28 2017-09-19 Ciment mixte Ceased WO2018198392A1 (fr)

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AU2017411817A AU2017411817B2 (en) 2017-04-28 2017-09-19 Mixed cement
SG11201900709QA SG11201900709QA (en) 2017-04-28 2017-09-19 Mixed cement
CN201780042999.8A CN109415263B (zh) 2017-04-28 2017-09-19 混合水泥
KR1020187036004A KR102241949B1 (ko) 2017-04-28 2017-09-19 혼합 시멘트
NZ755775A NZ755775A (en) 2017-04-28 2017-09-19 Mixed cement containing coal ash
PH12018500748A PH12018500748A1 (en) 2017-04-28 2018-04-05 Mixed cement

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WO2020170467A1 (fr) * 2019-02-21 2020-08-27 太平洋セメント株式会社 Composition de ciment pour environnements à haute température et béton pour environnements à haute température

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JP6966012B1 (ja) * 2021-03-26 2021-11-10 住友大阪セメント株式会社 セメント組成物及びその製造方法
JP7180742B1 (ja) * 2021-12-23 2022-11-30 住友大阪セメント株式会社 セメント組成物及びその製造方法

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JPS5722146A (en) * 1980-06-06 1982-02-05 Grace W R & Co Strength increasing mixture for concrete composition
JPH05186251A (ja) * 1991-05-20 1993-07-27 Idemitsu Petrochem Co Ltd モルタルまたはコンクリート遠心力成形用添加材
JPH08100403A (ja) * 1994-10-03 1996-04-16 Mitsubishi Materials Corp 透水性コンクリート舗装体
JP2001330574A (ja) * 2000-05-23 2001-11-30 Taiheiyo Cement Corp 石炭灰の評価方法
JP2006256919A (ja) * 2005-03-18 2006-09-28 Denki Kagaku Kogyo Kk セメント組成物およびその使用方法
WO2014077251A1 (fr) * 2012-11-14 2014-05-22 太平洋セメント株式会社 Composition de ciment et son procédé de production

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CN1228269C (zh) * 2002-09-29 2005-11-23 赖兆平 粉煤灰水泥辅料及其用途
US8133317B2 (en) * 2005-10-17 2012-03-13 Taiheiyo Cement Corporation Cement additive and cement composition
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JP6016686B2 (ja) 2013-03-26 2016-10-26 花王株式会社 水硬性粉体用強度向上剤組成物
JP6371574B2 (ja) 2013-05-09 2018-08-08 花王株式会社 水硬性粉体用強度向上剤組成物
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JPS5443008B1 (fr) * 1970-12-28 1979-12-18
JPS5722146A (en) * 1980-06-06 1982-02-05 Grace W R & Co Strength increasing mixture for concrete composition
JPH05186251A (ja) * 1991-05-20 1993-07-27 Idemitsu Petrochem Co Ltd モルタルまたはコンクリート遠心力成形用添加材
JPH08100403A (ja) * 1994-10-03 1996-04-16 Mitsubishi Materials Corp 透水性コンクリート舗装体
JP2001330574A (ja) * 2000-05-23 2001-11-30 Taiheiyo Cement Corp 石炭灰の評価方法
JP2006256919A (ja) * 2005-03-18 2006-09-28 Denki Kagaku Kogyo Kk セメント組成物およびその使用方法
WO2014077251A1 (fr) * 2012-11-14 2014-05-22 太平洋セメント株式会社 Composition de ciment et son procédé de production

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WO2020170397A1 (fr) * 2019-02-21 2020-08-27 太平洋セメント株式会社 Composition de ciment pour environnements haute température et béton pour environnements haute température

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CN109415263A (zh) 2019-03-01
SG11201900709QA (en) 2019-02-27
AU2017411817B2 (en) 2019-10-31
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NZ755775A (en) 2020-01-31
JP2018188346A (ja) 2018-11-29

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