WO2023204116A1 - ジオポリマー組成物とその製造方法 - Google Patents

ジオポリマー組成物とその製造方法 Download PDF

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WO2023204116A1
WO2023204116A1 PCT/JP2023/014812 JP2023014812W WO2023204116A1 WO 2023204116 A1 WO2023204116 A1 WO 2023204116A1 JP 2023014812 W JP2023014812 W JP 2023014812W WO 2023204116 A1 WO2023204116 A1 WO 2023204116A1
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mass
powder
geopolymer composition
geopolymer
powdered
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English (en)
French (fr)
Japanese (ja)
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雄大 大西
昂平 大村
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Tokuyama Corp
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Tokuyama Corp
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Priority to KR1020247030325A priority Critical patent/KR20250005978A/ko
Priority to US18/856,093 priority patent/US20250250198A1/en
Priority to AU2023255868A priority patent/AU2023255868A1/en
Priority to JP2024516219A priority patent/JPWO2023204116A1/ja
Priority to CN202380027726.1A priority patent/CN118871402A/zh
Publication of WO2023204116A1 publication Critical patent/WO2023204116A1/ja
Anticipated expiration legal-status Critical
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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
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
    • 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
    • C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
    • 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
    • C04B18/08—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
    • 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
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • 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
    • C04B20/023—Chemical treatment
    • 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
    • C04B20/023—Chemical treatment
    • C04B20/0232—Chemical treatment with carbon dioxide
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators or shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators or shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/10—Acids or salts thereof containing carbon in the anion, e.g. carbonates
    • 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
    • C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • 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
    • C04B5/00—Treatment of  metallurgical  slag ; Artificial stone from molten  metallurgical  slag 
    • C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0004—Compounds chosen for the nature of their cations
    • C04B2103/0006—Alkali metal or inorganic ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • C04B2103/0088—Compounds chosen for their latent hydraulic characteristics, e.g. pozzuolanes
    • 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 technology for retarding the setting of geopolymers.
  • Geopolymer does not use cement clinker and is made of raw materials mainly composed of amorphous aluminum silicate (active filler) and aqueous solutions of alkali metal silicates, carbonates, and hydroxides (alkali source). It is defined as a material cured using at least one type of cement, and is expected to be used as a construction material because it is more acid resistant, heat resistant, suppresses CO2 , and can use large amounts of industrial byproducts compared to hardened cement. It is an inorganic material.
  • fine slag powder has been used in addition to fly ash as an active filler to improve strength development and mass transfer resistance at room temperature, which are weaknesses of geopolymers that use only fly ash as an active filler. Used together.
  • the pot life (setting time) of the geopolymer is shortened to within about 15 to 40 minutes, resulting in a major drawback that sufficient time is not available for the implantation operation.
  • the strength may also decrease in the long term. Furthermore, since it is necessary to sinter the fine slag powder at a high temperature, a huge amount of thermal energy is required, and this is accompanied by CO2 emissions originating from thermal energy, which poses a large environmental burden.
  • Geopolymer compositions are often used as binders in concrete and mortar as an alternative to cement.
  • the allowable time from mixing the concrete to finishing pouring is Academia and the Architectural Institute of Japan have established standards for the duration to be within 120 minutes when the outside temperature is 25°C or less, and within 90 minutes when it exceeds 25°C. Therefore, in order to popularize geopolymer concrete, there is a need for a geopolymer composition that maintains fresh properties equivalent to cement concrete 120 minutes after mixing.
  • the present invention has been made based on the above circumstances, and its purpose is to provide a geopolymer composition that can significantly extend its pot life while maintaining strength development, and has a low environmental impact, and its production.
  • the purpose is to provide a method.
  • the present inventors have found that fine slag powder is subjected to carbonation treatment. It has been found that the effect of extending the pot life (setting time) of the geopolymer can be obtained. It has also been found that the bound water of the fine slag powder generated during the carbonation treatment of the fine slag powder contributes to extending the pot life.
  • a geopolymer composition that can significantly extend the pot life while maintaining strength development properties and has a low environmental impact, and a method for producing the same, are provided.
  • the first invention includes an active filler containing carbonated slag fine powder and a pozzolanic material, and an alkali source
  • the carbonated slag fine powder is a geopolymer composition containing 0.1% by mass or more and 2.0% by mass or less of CO 2 and 0.26% by mass or more and 1.0% by mass or less of bound water. .
  • the carbonated slag fine powder preferably contains 1.0% by mass or more and 2.0% by mass or less of CO 2 and contains 0.5% by mass or more and 1.0% by mass or less of bound water.
  • the carbonated slag fine powder contains 1.5% by mass or more and 2.0% by mass or less of CO 2 and contains 0.75% by mass or more and 1.0% by mass or less of bound water.
  • the carbonated slag fine powder is preferably carbonated under wet conditions in which 0.5 parts by mass or more of water is present per 1 part by mass of the fine slag powder.
  • the alkali source contained in the geopolymer composition is in powder form and contains at least one selected from alkali metal silicate powder and alkali metal carbonate powder.
  • a geopolymer composition is in powder form and contains at least one selected from alkali metal silicate powder and alkali metal carbonate powder.
  • the alkali source is an alkali metal silicate powder and an alkali metal carbonate powder.
  • the alkali metal silicate powder is sodium silicate powder.
  • the alkali metal carbonate powder is sodium carbonate powder.
  • a third aspect of the present invention is a geopolymer composition containing the powdered geopolymer composition and water.
  • a fourth aspect of the present invention is a method for producing a geopolymer composition, which comprises mixing the powdered geopolymer composition and water.
  • the fifth aspect of the present invention is a cured geopolymer that is a cured product of the geopolymer composition.
  • carbonated slag fine powder containing bound water as an active filler for geopolymers, it is possible to significantly extend the pot life (setting time) while maintaining strength development, and the geopolymers have a low environmental impact.
  • a composition can be obtained. Therefore, it can be used as a binder for concrete and the like as a substitute for cement, and can be used widely and suitably in the construction industry for the purposes of acid resistance, heat resistance, CO 2 suppression, and large-scale use of industrial by-products.
  • FIG. 1 is a schematic diagram of an apparatus for carbonating a slag fine powder slurry.
  • FIG. 2 is a schematic diagram of an apparatus for evaporating and drying a carbonated slag fine powder slurry.
  • the geopolymer composition of the present invention includes a fine carbonated slag powder, an active filler containing a pozzolanic material, an alkali source, and water, and the fine carbonated slag powder contains 0.1% by mass or more of CO2 . Contains 2.0% by mass or less, and contains 0.26% by mass or more and 1.0% by mass or less of bound water.
  • the active filler includes carbonated slag fine powder and pozzolanic material.
  • the active filler contains carbonated slag fine powder and pozzolan material as main components, and the total content of carbonated slag fine powder and pozzolan material in the entire active filler is preferably 90% by mass or more, and 95% by mass. It is more preferable that it is above, and it is especially preferable that it is substantially 100% by mass.
  • the carbonated slag fine powder contained in the active filler is produced by carbonating the slag fine powder, and contains 0.1% by mass or more and 2.0% by mass or less of CO2 , and contains bound water. Contains 0.26% by mass or more and 1.0% by mass or less. Unless both CO 2 and bound water satisfy this range, the pot life cannot be extended significantly. In order to further extend the pot life, the carbonated slag fine powder should contain 1.0% by mass or more and 2.0% by mass or less of CO 2 and 0.5% by mass or more and 1.0% by mass of bound water.
  • carbonated slag fine powder is preferably contained. preferably contains 1.5% by mass or more and 2.0% by mass or less of CO 2 and 0.75% by mass or more and 1.0% by mass or less of bound water.
  • the fine slag powder which is a raw material for the fine carbonated slag powder, is produced simultaneously with the production of pig iron, and contains CaO, SiO 2 , Al 2 O 3 , and MgO as main components.
  • the type of slag is not particularly limited and may be either blast furnace slag or steelmaking slag, but granulated blast furnace slag powder is preferable from the viewpoint of reactivity and is compliant with JIS A 6206, and gypsum is added. Carbonated granulated blast furnace slag powder containing 3% by mass or less of sulfur trioxide and 3% by mass or less of loss on ignition is used as a raw material. This is preferable from the viewpoint of strength development of a cured geopolymer obtained using fine slag powder.
  • Method for producing carbonated slag fine powder include a method of carbonating in air containing moisture, and a method of blowing CO2 gas into a fine slag powder immersed in water.
  • a method of carbonating in air since carbonation requires a considerable amount of time, productivity at an industrial level cannot be expected.
  • fine carbonated slag powder containing sufficient bound water cannot be obtained. Therefore, it is important to carry out the process under wet conditions such as a slurry state or a state immersed in water. In the wet method, carbonated slag fine powder can be obtained in about several hours, and carbonated slag fine powder containing sufficient bound water can be obtained reliably.
  • the mixing ratio of fine slag powder and water is preferably 0.5 parts by mass or more, and preferably 0.8 parts by mass or more, per 1 part by mass of fine slag powder. More preferably, the amount is 0.9 parts by mass or more.
  • the pozzolan material is a material having pozzolan activity, and specifically includes coal ash, biomass ash, silica fume, volcanic ash, and metakaolin.
  • fly ash such as coal ash and biomass ash is preferred, and fly ash for concrete is particularly preferred.
  • Fly ash is a fine ash that is recovered from the exhaust gas by a precipitator out of the coal ash produced by coal-fired power plants, etc. It has pozzolanic activity and contains SiO 2 and Al 2 O3 as its main components. It is a substance that According to JIS A 6201, it is preferable to use fly ash that is rated into classes I to IV based on particle size and flow value, and there are no particular restrictions on the standards for fly ash, but fly ash is classified into classes I and II, which have fine particle sizes and high reactivity. Seeds are more preferred. Also, other types of ash may be used in combination.
  • the content of the pozzolan material in the active filler is preferably 50 to 90% by mass, more preferably 60 to 85% by mass, based on the total mass of the pozzolanic material and the carbonated slag fine powder.
  • the content of the pozzolan material in the active filler is preferably 50 to 90% by mass, more preferably 60 to 85% by mass, based on the total mass of the pozzolanic material and the carbonated slag fine powder.
  • the content of the pozzolan material in the active filler is preferably 50 to 90% by mass, more preferably 60 to 85% by mass, based on the total mass of the pozzolanic material and the carbonated slag fine powder.
  • the alkali source may be either an alkali metal salt or an alkaline earth metal salt, and from the viewpoint of durability of the cured geopolymer, etc., it is preferable to use a salt of an alkali metal element.
  • the salt is a silicate, hydroxide, or carbonate, and the state thereof may be either liquid or powder, and the salt may be anhydrous, hydrated, or aqueous solution. From the viewpoint of cost and strength development, it is more preferable that the alkali source contains an alkali metal silicate. By using a mixture of an alkali metal silicate and other salts such as an alkali metal carbonate, the physical properties of the geopolymer composition can be adjusted as desired.
  • alkali metal silicates examples include sodium silicate (SiO 2 /NaO 2 molar ratio: about 1.95 to 3.4), sodium metasilicate (type 1, type 2), potassium silicate, potassium metasilicate, lithium silicate, etc. Can be mentioned.
  • the molar ratio of silicon (Si) contained in the alkali metal silicate to the alkali metal element (AL) contained in the alkali source is Si/AL from 0.05 to Preferably it is 0.85.
  • Si/AL silicon contained in the alkali metal silicate
  • the geopolymer composition can have fluidity that is easy to use in field work. Can be secured. From the above point, it is more preferable that Si/AL is 0.2 to 0.75.
  • the molar ratio AL/W of the alkali metal element (AL) contained in the alkali source of the geopolymer composition to water (W) is preferably 0.05 to 0.3.
  • AL/W is more preferably 0.05 to 0.18, and even more preferably 0.08 to 0.12.
  • various admixtures and admixtures can be added to the geopolymer composition of the present invention within a range that does not impair the effects of the present invention.
  • Examples include known materials used in concrete such as fluidizers, shrinkage reducers, rust preventives, waterproofing agents, setting retarders, antifoaming agents, dust reducers, pigments, calcium carbonate powder, and the like.
  • various aggregates can be added to the geopolymer composition of the present invention depending on the intended use of the geopolymer composition.
  • examples include known aggregates used in concrete, such as lightweight aggregate, normal aggregate, heavy aggregate, limestone aggregate, slag aggregate, and silica sand.
  • the geopolymer composition of the present invention includes an active filler containing the carbonated slag fine powder and pozzolan material, an alkali source, and water, and, if necessary, various admixtures and aggregates in predetermined amounts, simultaneously or sequentially. It can be manufactured by appropriately kneading with a kneading device.
  • the kneading device is not particularly limited, and includes, for example, a forced twin-screw mixer used for kneading concrete.
  • the method for producing a geopolymer composition includes a powder mixing step of mixing an active filler, a powdered alkali source, and aggregate, and adding water after the powder mixing step. This includes a kneading step of kneading.
  • the method includes a powder mixing step of mixing the active filler and aggregate in powder form, and a kneading step of adding and kneading an aqueous solution of the alkali source after the powder mixing step.
  • a secondary kneading step may be provided after the kneading step in which admixtures and admixtures such as fluidizers and setting retarders are mixed and kneaded.
  • the powdered geopolymer composition of the present invention is a powdered alkali source containing an active filler containing fine carbonated slag powder and pozzolan material powder, and at least one selected from alkali metal silicate powder and alkali metal carbonate powder. including.
  • the active filler of the powdered geopolymer composition of the present invention is an active filler used in the above-mentioned geopolymer composition, and has carbonated slag fine powder and pozzolan material powder as main components.
  • the powdered alkali source of the powdered geopolymer composition of the present invention contains at least one selected from alkali metal silicate powder and alkali metal carbonate powder.
  • alkali metal silicate powder examples include sodium silicate powder (SiO 2 /NaO 2 molar ratio: about 1.95 to 3.4), sodium metasilicate powder (type 1, type 2), potassium silicate powder, potassium metasilicate. Examples include powder, lithium silicate powder, and the like.
  • alkali metal carbonate powder examples include sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), lithium carbonate (Li 2 CO 3 ), and the like.
  • Sodium carbonate powder is preferred because it is inexpensive and shows high reactivity with fine slag powder.
  • the powdered alkali source may contain at least one selected from alkali metal silicate powder and alkali metal carbonate powder, but it is preferable that it is composed of alkali metal silicate powder and alkali metal carbonate powder for strength development. Preferable from a gender perspective.
  • the powdered geopolymer composition contains an alkali metal silicate powder and an alkali metal carbonate powder
  • silicon (Si) contained in the alkali metal silicate powder and alkali metal carbonate powder contained in the powdered alkali source is The molar ratio of Si/AL to the alkali metal element (AL) is preferably 0.05 to 0.85.
  • Si/AL is 0.2 to 0.75.
  • the production of the powdered geopolymer composition of the present invention includes at least one selected from carbonated slag fine powder and pozzolan material powder as an active filler, and alkali metal silicate powder and alkali metal carbonate powder as a powdered alkali source. It includes a powder mixing step of mixing one with the other in powder form. Note that, after the powder mixing step, a secondary powder mixing step may be provided in which various admixture materials such as a powdered fluidizing agent and a setting retarder, and aggregate are mixed.
  • the powdered geopolymer composition of the present invention can be used as a premix composition.
  • a premix composition it becomes possible to produce the geopolymer composition of the present invention simply by mixing the premix composition with water.
  • it contains an active filler containing carbonated slag fine powder and pozzolan material powder, a powdered alkali source containing at least one selected from alkali metal silicate powder and alkali metal carbonate powder, and water. I will do it.
  • the powdered geopolymer composition or geopolymer composition of the present invention may be present as part of the constituent raw materials when producing mortar, concrete, etc.
  • various powdered admixtures and admixtures can be added to the powdered geopolymer composition of the present invention within a range that does not impair the effects of the present invention.
  • Examples include known materials used in concrete such as fluidizers, shrinkage reducers, rust preventives, waterproofing agents, setting retarders, antifoaming agents, dust reducers, pigments, calcium carbonate powder, and the like.
  • various aggregates can be added to the powdered geopolymer composition of the present invention, depending on the use as a geopolymer composition.
  • examples include known aggregates used in concrete, such as lightweight aggregate, normal aggregate, heavy aggregate, limestone aggregate, slag aggregate, and silica sand.
  • the geopolymer composition of the present invention is produced by blending the above powdered geopolymer composition, water, and various admixtures and aggregates in predetermined amounts simultaneously or sequentially as necessary, and kneading the mixture using a kneading device as appropriate.
  • the kneading device is not particularly limited, and includes, for example, a forced twin-screw mixer used for kneading concrete.
  • the method for producing a geopolymer composition includes, for example, a powder mixing step of mixing the powdered geopolymer composition of the present invention with aggregate, and a kneading step of adding water and kneading after the powder mixing step. including.
  • a secondary kneading step may be provided after the kneading step in which admixtures and admixtures such as fluidizers and setting retarders are mixed and kneaded.
  • a cured geopolymer body which is a cured product of the geopolymer composition, can be obtained by curing the geopolymer composition in a temperature range of 5 ° C. to 90 ° C. can.
  • an alkali metal silicate and an alkali metal carbonate are used together as the alkali source of the geopolymer composition, it is possible to obtain a cured geopolymer composition with excellent compressive strength by curing at room temperature of 5 to 35°C. can.
  • Other curing conditions are not particularly limited, and may be any commonly used curing conditions. For example, steam curing, sealed curing, air curing, underwater curing, etc. are used.
  • the above geopolymer composition can extend the pot life to 120 minutes or more while maintaining strength development, so it has improved workability and Excellent workability. Therefore, like cement concrete, which is a general-purpose material, the geopolymer composition of the present invention can be kneaded in a factory, transported by a truck agitator, and placed at the site using a concrete pump truck or the like. Further, during the carbonation treatment of fine slag powder, calcium, magnesium, etc. and carbonate are formed on the surface of the slag particles. This has the advantage that CO 2 , which is a greenhouse gas, can be fixed and effectively used.
  • CO 2 which is a greenhouse gas
  • the CO 2 gas used as the carbon dioxide gas may include a certain amount of CO 2 such as industrial exhaust gas. Therefore, the cured geopolymer obtained using the geopolymer composition of the present invention has a lower environmental impact than conventional geopolymer compositions, and can be used in various applications as a binder for concrete in place of cement compositions. .
  • FIG. 1 shows an apparatus that carried out carbonation treatment of fine slag powder.
  • the inside of the gas cleaning bottle (4) was maintained at a predetermined temperature using a constant temperature water bath (3), and the inside of the gas cleaning bottle (4) was stirred at 300 min -1 (r.p.m.) using a stirrer (7).
  • carbonation treatment was carried out for a predetermined period of time to obtain a carbonated slag fine powder slurry.
  • the carbonated slag fine powder slurry (10) is put into a heat-resistant container (9), and the carbonated slag fine powder slurry (10) is turned into a carbonated slag fine powder slurry (10) in the dryer (8).
  • the purified water contained was evaporated to dryness. Note that the amount of CO 2 and the amount of bound water could be controlled by the flow rate of carbon dioxide gas, treatment temperature, mass ratio of fine slag powder to purified water, stirring speed, etc.
  • Table 1 below shows the carbonation treatment conditions for carbonated slag fine powder BFS-A and BFS-B.
  • the mass loss from room temperature to 500°C is taken as the amount of bound water, and the hydration product is assumed to be a gehlenite hydrate (2CaO ⁇ Al 2 O 3 ⁇ SiO 2 ⁇ 8H 2 O, molecular weight 418.3).
  • the amount of hydrate contained in the fine powder of chlorinated slag was also calculated.
  • *AL/W Molar ratio of alkali metal element (AL) to water (W) contained in soda ash and powdered silica.
  • Si/AL The molar ratio of silicon (Si) to alkali metal element (AL) contained in soda ash and powdered silica.
  • (AL+W)/P Volume ratio of a solution of soda ash, powdered silica and water to fly ash and various types of fine slag powder.
  • Comparative Example 1 is a mortar that uses ordinary Portland cement, which is a general-purpose material, as a binder, and its formulation and mixing method were in accordance with JIS R 5201:2015 (Physical Test Methods for Cement), 11.5.
  • Comparative Example 2 is a geopolymer composition using an active filler consisting of fine slag powder and fly ash that has not been subjected to carbonation treatment or heat treatment, and an alkali source consisting of soda ash, powdered silica, and water.
  • Comparative Examples 3 to 5 are the activated filler consisting of the heat-treated fine slag powder described in Patent Document 1 (in the case of BFS-400, it means that it was heated at 400°C for 3 hours) and fly ash, and soda ash.
  • This is a geopolymer composition using an alkali source consisting of powdered silica and silica powder.
  • the content of various fine slag powders which are said to contribute to pot life, compressive strength, and 15-stroke mortar flow value (fluidity), AL/W (mole ratio), Si/AL (mole ratio), and (AL+W )/P was the same as Comparative Example 2.
  • Example 1 includes an active filler consisting of carbonated slag fine powder (BFS-A) containing 1.26% by mass of CO 2 and 0.58% by mass of bound water and fly ash, and an active filler consisting of soda ash and powdered silica. These are a powdered geopolymer composition using an alkali source and a geopolymer composition using water. In addition, the content of various fine slag powders, which are said to contribute to pot life, compressive strength, and 15-stroke mortar flow value (fluidity), AL/W (mole ratio), Si/AL (mole ratio), and (AL+W )/P was combined with Comparative Examples 2 to 5.
  • BFS-A carbonated slag fine powder
  • Examples 2 to 6 used carbonated slag fine powder (BFS-B) with increased CO2 content and bound water content, an active filler made of fly ash, and an alkali source made of soda ash and powdered silica. These are the powdered geopolymer composition used and the geopolymer composition using water. In addition, the contents of various fine slag powders, AL/W (mole ratio), and Si/AL (mole ratio), which are said to contribute to pot life, compressive strength, and 15-stroke mortar flow value (fluidity), are compared. Together with Examples 2 to 5, (AL+W)/P was sequentially decreased in Examples 3 to 5.
  • BFS-B carbonated slag fine powder
  • the mortar cured to a predetermined age (1 day, 7 days, and 28 days) was subjected to a compressive strength test in accordance with the compressive strength test method described in JIS A 1108, and the compressive strength was measured. The results are shown in Table 3.
  • Examples 1 to 6 compared to Comparative Examples 2 to 5, a usable time that can secure enough working time of about 90 minutes or 120 minutes, which satisfies the guidelines of the Japan Society of Civil Engineers and the Architectural Institute of Japan, etc., is obtained, and First, the strength development property is 80% or more compared to a system using untreated fine slag powder. In addition, the 15-stroke mortar flow value also tends to be improved by carbonation treatment, indicating that the workability of the geopolymer composition is also greatly improved.

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JP2024076020A (ja) * 2022-11-24 2024-06-05 株式会社東芝 二酸化炭素固定方法、および、二酸化炭素固定装置
JP7720576B1 (ja) 2024-07-16 2025-08-08 学校法人大阪産業大学 混合物、アルカリ活性材料組成物、アルカリ活性材料硬化物およびその製造方法とアルカリ活性材料組成物から得られるプレキャスト製品とその製造方法
WO2025249263A1 (ja) * 2024-05-31 2025-12-04 株式会社トクヤマ ジオポリマー組成物
WO2025253902A1 (ja) * 2024-06-04 2025-12-11 株式会社トクヤマ ジオポリマー組成物の配合設計方法、ジオポリマーコンクリートの製造方法及びジオポリマーコンクリート製二次製品の製造方法

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CN111362606A (zh) * 2020-03-11 2020-07-03 新疆大学 精炼渣碳酸化优化的地质聚合物及其制备方法
JP2021031370A (ja) * 2019-08-29 2021-03-01 国立大学法人山口大学 ジオポリマー用凝結遅延型活性フィラー及びその製造方法、並びにジオポリマー固化体
JP2021054678A (ja) * 2019-09-30 2021-04-08 積水化学工業株式会社 ジオポリマー組成物及びその製造方法並びにコンクリート構造物の補修方法

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US20110132230A1 (en) * 2009-12-08 2011-06-09 Chan Han Geopolymer precursor dry mixture, package, processes and methods
JP2019532907A (ja) * 2016-11-04 2019-11-14 エン−テック コーポレーションＥｎ−Ｔｅｃｈ Ｃｏｒｐｏｒａｔｉｏｎ 非ポルトランドセメント系材料を調製して塗布するシステム及び方法
JP2021031370A (ja) * 2019-08-29 2021-03-01 国立大学法人山口大学 ジオポリマー用凝結遅延型活性フィラー及びその製造方法、並びにジオポリマー固化体
JP2021054678A (ja) * 2019-09-30 2021-04-08 積水化学工業株式会社 ジオポリマー組成物及びその製造方法並びにコンクリート構造物の補修方法
CN111362606A (zh) * 2020-03-11 2020-07-03 新疆大学 精炼渣碳酸化优化的地质聚合物及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024076020A (ja) * 2022-11-24 2024-06-05 株式会社東芝 二酸化炭素固定方法、および、二酸化炭素固定装置
WO2025249263A1 (ja) * 2024-05-31 2025-12-04 株式会社トクヤマ ジオポリマー組成物
WO2025253902A1 (ja) * 2024-06-04 2025-12-11 株式会社トクヤマ ジオポリマー組成物の配合設計方法、ジオポリマーコンクリートの製造方法及びジオポリマーコンクリート製二次製品の製造方法
JP7720576B1 (ja) 2024-07-16 2025-08-08 学校法人大阪産業大学 混合物、アルカリ活性材料組成物、アルカリ活性材料硬化物およびその製造方法とアルカリ活性材料組成物から得られるプレキャスト製品とその製造方法
JP2026013268A (ja) * 2024-07-16 2026-01-28 学校法人大阪産業大学 混合物、アルカリ活性材料組成物、アルカリ活性材料硬化物およびその製造方法とアルカリ活性材料組成物から得られるプレキャスト製品とその製造方法

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